The company has a group of cooperation teams engaged in the Tristyrylphenol Ethoxylates industry for many years, with dedication, innovation spirit and service awareness, and has established a sound quality control and management system to ensure product quality.
Disclosed are compounds of Formula 1, including all stereoisomers, N-oxides, and salts thereof,wherein A, Z, R1 R2, R3 and m are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling undesired vegetation comprising contacting the undesired vegetation or its environment with an effective amount of a compound or a composition of the invention.
FIELD OF THE INVENTION
[0001] This invention relates to certain pyrimidinyloxy benzene derivatives, their N-oxides, salts and compositions, and methods of their use for controlling undesirable vegetation.
BACKGROUND OF THE INVENTION
[0002] The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, maize, potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.
SUMMARY OF THE INVENTION
[0003] This invention is directed to compounds of Formula 1 (including all all geometric and stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides:
[0000]
[00002]
[0000] wherein
[0000]
[0004]
A is;[0000]
[00003]
[0000]
[0005]
B is O or S;[0006]
R1 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 halocycloalkylalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 alkylamino, C1-C6 haloalkylamino, C2-C10 dialkylamino, C2-C10 halodialkylamino, C3-C6 cycloamino, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C4-C8 halocycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C3-C7 cyanoalkoxyalkyl, C1-C6 hydroxyalkyl, C1-C6 nitroalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkenylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C2-C6 alkylthioalkyl, C2-C6 haloalkylthioalkyl, benzyl, —N(R7)(OR8), —ON(R9a)(R9b) or —N(R7)N(R9a)(R9b);[0007]
Z is O or S;[0008]
R2 is halogen, cyano, nitro, C1-C6 alkoxy, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C6 cycloalkyl or —SOnR10;[0009]
each R3 is independently halogen, cyano, nitro, CHO, C(═O)NH2, C(═S)NH2, SO2NH2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C7 cycloalkylcarbonyl, C2-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C2-C4 alkylthioalkyl, —C(═O)N(R11a)(R11b), —C(═NOR12)H, —C(═N(R13))H or —SOnR14;[0010]
m is 0, 1, 2 or 3;[0011]
each n is independently 0, 1 or 2;[0012]
R4 is H, C1-C6 alkyl or C1-C6 haloalkyl;[0013]
R5 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C1-C6 hydroxyalkyl, C1-C6 nitroalkyl, C2-C6 alkylthioalkyl, C2-C6 haloalkylthioalkyl or benzyl;[0014]
each R6a and R6b is independently H, C1-C6 alkyl or C1-C6 haloalkyl;[0015]
R7 is H, C1-C6 alkyl or C1-C6 haloalkyl;[0016]
R8 is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl or C2-C6 cyanoalkyl;[0017]
each R9a and R9b is independently H, C1-C6 alkyl or C1-C6 haloalkyl;[0018]
R10 is independently C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylamino or C2-C10 dialkylamino;[0019]
each R11a is independently C1-C4 alkyl or C1-C4 haloalkyl;[0020]
each R11b is independently H, C1-C4 alkyl or C1-C4 haloalkyl;[0021]
each R12 is independently H or C1-C4 alkyl;[0022]
each R13 is independently H, amino, C1-C4 alkyl or C1-C4 alkylamino;[0023]
each R14 is independently C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylamino or C2-C10 dialkylamino; and[0024]
R15 is H or C1-C6 alkyl;[0025]
provided that[0026]
(i) when A is A-1 then R1 is other than H, C1-C6 alkyl or C2-C6 alkenyl;[0027]
(ii) when A is A-6, then R1 is other than C1-C6 alkylsulfonyl;[0028]
(iii) when A is A-1, R2 is Cl and R3 is 3-Br, then R1 is other than C2 alkylthio, C2 alkylsulfinyl or C2 alkylsulfonyl; and[0029]
(iv) the compound of Formula 1 is other than methyl 2-[(5-chloro-2-pyrimidinyl)oxy]benzoate (CAS Registry No. 854215-38-6), methyl 2-[(5-bromo-2-pyrimidinyl)oxy]benzoate (CAS Registry No. 1086397-52-5), 1-[2-[(5-bromo-2-pyrimidinyl)oxy]phenyl]-ethanone (CAS Registry No. 1147704-06-0) and 2-[(5-bromo-2-pyrimidinyl)oxy]-benzeneacetonitrile (CAS Registry No. 138193-83-6).[0030] More particularly, this invention pertains to a compound of Formula 1 (including all stereoisomers), an N-oxide or a salt thereof. This invention also relates to a herbicidal composition comprising a compound of the invention (i.e. in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of the invention (e.g., as a composition described herein).
[0031] This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (b1) through (b16); and salts of compounds of (b1) through (b16), as described below.
DETAILS OF THE INVENTION
[0032] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
[0033] The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
[0034] The transitional phrase “consisting essentially of” is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.
[0035] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of” or “consisting of”.
[0036] Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
[0037] Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
[0038] As referred to herein, the term “seedling”, used either alone or in a combination of words means a young plant developing from the embryo of a seed.
[0039] As referred to herein, the term “broadleaf” used either alone or in words such as “broadleaf weed” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.
[0040] In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl” includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
[0041] “Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. “Alkoxyalkoxy” denotes alkoxy substitution on alkoxy. Examples of “alkoxyalkoxy” include CH3OCH2O, (CH3)2CHOCH2O, CH3OCH2CH2O and CH3CH2OCH2CH2CH2O. “Alkenyloxy” includes straight-chain or branched alkenyloxy moieties. Examples of “alkenyloxy” include H2C═CHCH2O, (CH3)2C═CHCH2O, (CH3)CH═CHCH2O, (CH3)CH═C(CH3)CH2O and CH2═CHCH2CH2O. “Alkynyloxy” includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC═CCH2O, CH3C═CCH2O and CH3C≡CCH2CH2O. “Alkylthio” includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. “Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH3S(O)—, CH3CH2S(O)—, CH3CH2CH2S(O)—, (CH3)2CHS(O)— and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of “alkylsulfonyl” include CH3S(O)2—, CH3CH2S(O)2—, CH3CH2CH2S(O)2—, (CH3)2CHS(O)2—, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. “Alkylthioalkyl” denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. “Cyanoalkyl” denotes an alkyl group substituted with one cyano group. “Cyanoalkoxy” denotes an alkoxy group substituted with one cyano group. “Cyanoalkoxyalkyl” denotes an alkoxyalkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. The term “hydroxyalkyl” denotes an alkyl group substituted with one hydroxy group. Examples of “hydroxyoalkyl” include HOCH2—, HOCH2CH2— and CH3CH(OH)CH2—. The term “nitroalkyl” denotes an alkyl group substituted with one nitro group. Examples of “nitroalkyl” include O2NCH2—, O2NCH2CH2— and CH3CH(NO2)CH2—. “Alkylamino”, “dialkylamino”, “alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl”, and the like, are defined analogously to the above examples.
[0042] “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term “alkylcycloalkyl” denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term “cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. The term “cycloalkylalkoxy” denotes cycloalkyl substitution on an alkoxy moiety. The term “cycloalkylcarbonyl” denotes cycloalkyl substitution bonded through a carbonyl moiety. Examples of “cycloalkylcarbonyl” include c-Pr(C═O)—, cyclopentyl(C═O)—. The term “cycloalkylsulfonyl” denotes cycloalkyl substitution bonded through a sulfonyl moiety. Examples of “cycloalkylsulfonyl” include c-Pr(S═O2)—, cyclopentyl(S═O2)—. The term “cycloalkylthio” denotes cycloalkyl substitution bonded through a sulfer atom. Examples of “cycloalkylthio” include c-Pr(S)-, cyclopenty(S)-. Examples of “cycloalkylalkoxy” include cyclopropylmethoxy, cyclopentylethoxy. The term “cycloalkoxy” denotes cycloalkyl linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy. The term “cycloamino” denotes a cyclic amine moiety bonded through nitrogen. Examples of “cycloamino” include —N[CH2CH2CH2 (i.e. azetidine) and —N[CH2CH2CH2CH2, (i.e. pyrrolidine).
[0043] The term “halogen”, either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F3C, ClCH2, CF3CH2 and CF3CCl2. The terms “halocycloalkyl”, “haloalkoxy”, “haloalkylthio”, “haloalkylsulfinyl”, “haloalkylsulfonyl”, “haloalkenyl”, “haloalkynyl”, “haloalkoxyalkoxy”, “alkoxyhaloalkyl” and the like, are defined analogously to the term “haloalkyl”. Examples of halocycloalkyl include c-Pr(2-Cl), c-Bu(2,2-di-Br) and c-Hex(3,5-di-Cl). Examples of “haloalkoxy” include CF3O—, CCl3CH2O—, HCF2CH2CH2O— and CF3CH2O—. Examples of “haloalkylthio” include CCl3S—, CF3S—, CCl3CH2S— and ClCH2CH2CH2S—. Examples of “haloalkylsulfinyl” include CF3S(O)—, CCl3S(O)—, CF3CH2S(O)— and CF3CF2S(O)—. Examples of “haloalkylsulfonyl” include CF3S(O)2—, CCl3S(O)2—, CF3CH2S(O)2— and CF3CF2S(O)2—. Examples of “haloalkenyl” include (Cl)2C═CHCH2— and CF3CH2CH═CHCH2—. Examples of “haloalkynyl” include HC═CCHCl—, CF3C≡C—, CCl3C≡C— and FCH2C≡CCH2—. Examples of “haloalkoxyalkoxy” include CF3OCH2O—, ClCH2CH2OCH2CH2O—, Cl3CCH2OCH2O— as well as branched alkyl derivatives. Examples of “alkoxyhaloalkyl” include CH3OCF2CH2—, CH3CH2OCH2CCl2—, CF3CH2CH2OCH2— as well as branched alkyl derivatives.
[0044] The term “haloalkenyloxy” refers to a haloalkenyl group bonded through oxygen. Examples of “haloalkenyloxy” include (Cl)2C═CHCH2O— and CF3CH2CH═CHCH2O—. The term “haloalkylamino” refers to a haloalkyl group bonded through a nitrogen atom (i.e. as a secondary amine). Examples of “haloalkylamino” include CF3NH—, CCl3CH2NH—, HCF2CH2CH2NH— and CF3CH2NH—. The term “haloalkylcarbonyl” refers to a haloalkyl group bonded through a carbonyl moiety. Examples of “haloalkylcarbonyl” include CH2ClC(═O)—, CH3CHClCH2C(═O)— and (CH3)2CCl(═O)—. The term “haloalkylthioalkyl” refers to a haloalkylthio group bonded through an alkyl moiety. Examples of “haloalkylthioalkyl” include CCl3SCH2—, CF3SCH2—, CCl3CH2SCH2— and ClCH2CH2CH2SCH2—. The term “haloalkynyloxy” refers to a haloalkynyl group bonded through an oxygen atom. Examples of “haloalkynyloxy” include HC≡CCHClO—, CF3C≡CO—, CCl3C≡CO— and FCH2C≡CCH2O— haloalkynyloxy. The term “haloalkoxyalkyl” refers to a haloalkoxy group bonded through an alkyl moiety. Examples of “haloalkoxyalkyl” include CF3OCH2—, C1CH2CH2OCH2CH2—, Cl3CCH2OCH2— as well as branched alkyl derivatives. The term “halocycloalkoxy” refers to a halocycloalkyl group bonded through an oxygenatom. Examples of “halocycloalkoxy” include c-Pr(2-Cl) CH2O— and c-Bu(1-Cl) CH2CH2O—. The term “halodialkylamino” indicate two haloalkyl groups bonded through nitrogen. Examples of “halodialkylamino” include (CH2Cl)2N—, (CH2CH2Cl)2N— and (CH2CH2Cl)(CH2Br)N—.
[0045] “Alkylcarbonyl” denotes a straight-chain or branched alkyl moieties bonded to a C(═O) moiety. Examples of “alkylcarbonyl” include CH3C(═O)—, CH3CH2CH2C(═O)— and (CH3)2CHC(═O)—. Examples of “alkoxycarbonyl” include CH3OC(═O)—, CH3CH2OC(═O)—, CH3CH2CH2OC(═O)—, (CH3)2CHOC(═O)— and the different butoxy- or pentoxycarbonyl isomers. Examples of “alkylcarbonyloxy” include CH3C(═O)O—, CH3CH2CH2C(═O)O— and (CH3)2CHC(═O)O—
[0046] The total number of carbon atoms in a substituent group is indicated by the “Ci-Cj” prefix where i and j are numbers from 1 to 10. For example, C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C2 alkoxyalkyl designates CH3OCH2—; C3 alkoxyalkyl designates, for example, CH3CH(OCH3)—, CH3OCH2CH2— or CH3CH2OCH2—; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2— and CH3CH2OCH2CH2—.
[0047] When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents, e.g., (R3)m, where m is 0, 1, 2 or 3). Further, when the subscript indicates a range, e.g. (R)i-j, then the number of substituents may be selected from the integers between i and j inclusive. When a group contains a substituent which can be hydrogen, for example (R1 or R4), then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a variable group is shown to be optionally attached to a position, for example (R3)m wherein m may be 0, then hydrogen may be at the position even if not recited in the variable group definition. When one or more positions on a group are said to be “not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.
[0048] Unless otherwise indicated, a “ring” ˜ or “ring system” as a component of Formula 1 is carbocyclic or heterocyclic. The term “ring system” denotes two or more fused rings. The term “ring member” refers to an atom or other moiety (e.g., C(═O), C(═S), S(O) or S(O)2) forming the backbone of a ring or ring system.
[0049] A compound of Formula 1 in the Summary of the Invention can alternatively be represented by the following
[0000]
[00004]
[00005]
[0050] The terms “carbocyclic ring”, “carbocycle” or “carbocyclic ring system” denote a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies Hückel's rule, then said ring is also called an “aromatic ring”. “Saturated carbocyclic” refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
[0051] The terms “heterocyclic ring”, “heterocycle” or “heterocyclic ring system” denote a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hückel's rule, then said ring is also called a “heteroaromatic ring” or “aromatic heterocyclic ring”. Unless otherwise indicated, heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
[0052] “Aromatic” indicates that each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and that (4n+2) π electrons, where n is a positive integer, are associated with the ring to comply with Hückel's rule. The term “aromatic ring system” denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic. The term “aromatic carbocyclic ring system” denotes a carbocyclic ring system in which at least one ring of the ring system is aromatic. The term “aromatic heterocyclic ring system” denotes a heterocyclic ring system in which at least one ring of the ring system is aromatic. The term “nonaromatic ring system” denotes a carbocyclic or heterocyclic ring system that may be fully saturated, as well as partially or fully unsaturated, provided that none of the rings in the ring system are aromatic. The term “nonaromatic carbocyclic ring system” in which no ring in the ring system is aromatic. The term “nonaromatic heterocyclic ring system” denotes a heterocyclic ring system in which no ring in the ring system is aromatic.
[0053] The term “optionally substituted” in connection with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.” Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.
[0054] A wide variety of synthetic methods are known in the art to enable preparation of aromatic and nonaromatic heterocyclic rings and ring systems; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of Comprehensive Heterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.
[0055] Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.
[0056] Compounds of this invention can exist as one or more conformational isomers due to restricted rotation about the amide bond (e.g., C(=A)-R1 wherein R1 is alkylamino) in Formula 1. This invention comprises mixtures of conformational isomers. In addition, this invention includes compounds that are enriched in one conformer relative to others.
[0057] Compounds of Formula 1 typically exist in more than one form, and Formula 1 thus include all crystalline and non-crystalline forms of the compounds they represent. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound of Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound of Formula 1. Preparation and isolation of a particular polymorph of a compound of Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.
[0058] One skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
[0059] One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of a compound of Formula 1 are useful for control of undesired vegetation (i.e. are agriculturally suitable). The salts of a compound of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.
[0060] Embodiments of the present invention as described in the Summary of the Invention include:
[0000]
[0061]
Embodiment 1. A compound of Formula 1 including all all geometric and stereoisomers, N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides.[0062]
Embodiment 2. A compound of Embodiment 1 wherein A is A-1, A-2, A-3 or A-5.[0063]
Embodiment 3. A compound of Embodiment 2 wherein A is A-1, A-2 or A-5.[0064]
Embodiment 4. A compound of Embodiment 3 wherein A is A-1 or A-2.[0065]
Embodiment 5. A compound of Embodiment 1 wherein A is A-1 or A-3.[0066]
Embodiment 6. A compound of Embodiment 1 wherein A is A-1.[0067]
Embodiment 7. A compound of Embodiment 1 wherein A is A-2.[0068]
Embodiment 8. A compound of Embodiment 1 wherein A is A-3.[0069]
Embodiment 9. A compound of Embodiment 1 wherein A is A-4.[0070]
Embodiment 10. A compound of Embodiment 1 wherein A is A-5.[0071]
Embodiment 11. A compound of Embodiment 1 wherein A is A-6.[0072]
Embodiment 12. A compound of Embodiment 1 wherein A is A-7.[0073]
Embodiment 13. A compound of any one of Embodiments 1, 2, 5 or 8 wherein B is O.[0074]
Embodiment 14. A compound of Formula 1 or any one of Embodiments 1 through 14 either alone or in combination, wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 halocycloalkylalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 alkylamino, C1-C6 haloalkylamino, C2-C10 dialkylamino, C2-C10 halodialkylamino, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C4-C8 halocycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C3-C7 cyanoalkoxyalkyl, C1-C6 hydroxyalkyl, C1-C6 nitroalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkenylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C2-C6 alkylthioalkyl, C2-C6 haloalkylthioalkyl, benzyl, —N(R7)(OR8), —ON(R9a)(R9b) or —N(R7)N(R9a)(R9b).[0075]
Embodiment 15. A compound of Embodiment 14 wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 halocycloalkylalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 alkylamino, C1-C6 haloalkylamino, C2-C10 dialkylamino, C2-C10 halodialkylamino, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C4-C8 halocycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C3-C7 cyanoalkoxyalkyl, C1-C6 hydroxyalkyl, C1-C6 nitroalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkenylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C2-C6 alkylthioalkyl or C2-C6 haloalkylthioalkyl.[0076]
Embodiment 16. A compound of Embodiment 15 wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 cycloalkoxy, C4-C8 cycloalkylalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio or C1-C6 alkenylthio.[0077]
Embodiment 17. A compound of Embodiment 16 wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio or C1-C6 alkenylthio.[0078]
Embodiment 18. A compound of Embodiment 17 wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio or C1-C6 alkenylthio.[0079]
Embodiment 19. A compound of Embodiment 17 wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy or C3-C6 haloalkenyloxy.[0080]
Embodiment 20. A compound of Embodiment 19 wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy.[0081]
Embodiment 21. A compound of Embodiment 20 wherein R1 is C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy.[0082]
Embodiment 22. A compound of Embodiment 21 wherein R1 is C1-C6 alkyl.[0083]
Embodiment 23. A compound of Embodiment 21 wherein R1 is C1-C6 haloalkyl.[0084]
Embodiment 24. A compound of Embodiment 21 wherein R1 is C1-C6 alkoxy.[0085]
Embodiment 25. A compound of Embodiment 21 wherein R1 is C2-C6 haloalkoxy.[0086]
Embodiment 26. A compound of Embodiment 21 wherein R1 is C4-C6 alkyl, C3-C6 haloalkyl, C3-C6 alkoxy or C3-C6 haloalkoxy.[0087]
Embodiment 27. A compound of Embodiment 26 wherein when A is A-3 then R1 is C3-C6 haloalkyl.[0088]
Embodiment 28. A compound of Embodiment 26 wherein when A is A-1 then R1 is C4-C6 haloalkyl.[0089]
Embodiment 29. A compound of Embodiment 28 wherein when A is A-1 then R1 is C4-C5 haloalkyl.[0090]
Embodiment 30. A compound of Embodiment 29 wherein when A is A-1 then R1 is CH2CH2CH2CF3.[0091]
Embodiment 31. A compound of Embodiment 29 wherein when A is A-1 then R1 is CH2CH2CF2CF3.[0092]
Embodiment 32. A compound of Embodiment 19 wherein when A is A-3 then R1 is C4-C6 haloalkenyloxy.[0093]
Embodiment 33. A compound of Embodiment 26 wherein when A is A-3 then R1 is C4-C5 haloalkoxy.[0094]
Embodiment 34. A compound of Embodiment 23 wherein R1 is CH2CH2CH2CH2CH2CF3.[0095]
Embodiment 35. A compound of Embodiment 23 wherein R1 is CH2CH2CH2CH2CF3.[0096]
Embodiment 36. A compound of Embodiment 23 wherein R1 is CH2CH2CH2CF3.[0097]
Embodiment 37. A compound of Embodiment 23 wherein R1 is CH2CH2CF3.[0098]
Embodiment 38. A compound of Embodiment 25 wherein R1 is OCH2CH2CH2CH2CF3.[0099]
Embodiment 39. A compound of Embodiment 25 wherein R1 is OCH2CH2CH2CF3.[0100]
Embodiment 40. A compound of Embodiment 25 wherein R1 is OCH2CH2CF3.[0101]
Embodiment 41. A compound of Embodiment 25 wherein R1 is OCH2CF2CF3.[0102]
Embodiment 42. A compound of any one Embodiments 1 through 13 wherein R1 is other than H.[0103]
Embodiment 43. A compound of any one Embodiments 1 through 14 wherein R1 is other than benzyl (unsubstituted).[0104]
Embodiment 44. A compound of any one Embodiments 1 through 22 wherein R1 is other than CH3, CH2CH3 or CH2CH2CH3.[0105]
Embodiment 45. A compound of any one Embodiments 1 through 20 or wherein R1 is other than CH2CH═CH2, CH═CHCH3, C(═CH2)CH3 or CH═C(CH3)2[0106]
Embodiment 46. A compound of Embodiment 1 wherein R1 is other than propen-2-yl, propen-1-yl, n-propyl, ethyl, 1-methylethen-2-yl or 2-methylpropen-1-yl (i.e. R1 is other than CH2CH═CH2, CH2CH2CH3, CH═CHCH3, CH2CH3, C(═CH2)CH3 or CH═C(CH3)2.[0107]
Embodiment 47. A compound of any one Embodiments 1 through 22 or 24 wherein R1 is other than OCH3.[0108]
Embodiment 48. A compound of Formula 1 or any one of Embodiments 1 through 47 either alone or in combination, wherein Z is O.[0109]
Embodiment 49. A compound of Formula 1 or any one of Embodiments 1 through 48 either alone or in combination, wherein R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl.[0110]
Embodiment 50. A compound of Embodiment 49 wherein R2 is halogen or C1-C4 alkyl.[0111]
Embodiment 51. A compound of Embodiment 50 wherein R2 is halogen or CH3.[0112]
Embodiment 52. A compound of Embodiment 51 wherein R2 is halogen.[0113]
Embodiment 53. A compound of Embodiment 52 wherein R2 is F, Cl or Br.[0114]
Embodiment 54. A compound of Embodiment 53 wherein R2 is Cl.[0115]
Embodiment 55. A compound of Formula 1 or any one of Embodiments 1 through 54 either alone or in combination, wherein m is 0, 1 or 2.[0116]
Embodiment 56. A compound of Embodiment 55 wherein m is 0 or 1.[0117]
Embodiment 57. A compound of Embodiment 56 wherein m is 1.[0118]
Embodiment 58. A compound of Embodiment 57 wherein m is 1, at the 3, 4 or 6-position.[0119]
Embodiment 59. A compound of Embodiment 58 wherein m is 1, at the 3 or 4-position.[0120]
Embodiment 60. A compound of Embodiment 59 wherein m is 0 (i.e. each of the 3-, 4-, 5- and 6-positions are unsubstituted by R3).[0121]
Embodiment 61. A compound of Formula 1 or any one of Embodiments 1 through 60 either alone or in combination, wherein each R3 is independently halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, —C(═O)N(R11aR11b), —C(═NOR12)H or —SOnR14.[0122]
Embodiment 62. A compound of Embodiment 61 wherein each R3 is independently halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl or —SOnR14.[0123]
Embodiment 63. A compound of Embodiment 62 wherein each R3 is independently halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.[0124]
Embodiment 64. A compound of Embodiment 63 wherein each R3 is independently halogen, cyano, C1-C3 alkyl or C1-C3 haloalkyl.[0125]
Embodiment 65. A compound of Embodiment 64 wherein each R3 is independently halogen, cyano, C1-C2 alkyl or C1-C2 haloalkyl.[0126]
Embodiment 66. A compound of Embodiment 65 wherein each R3 is independently halogen, cyano, CH3, CH2CH3 or CF3.[0127]
Embodiment 67. A compound of Embodiment 66 wherein each R3 is independently halogen, cyano or CF3.[0128]
Embodiment 68. A compound of Embodiment 67 wherein each R3 is independently F, Cl, Br or cyano.[0129]
Embodiment 69. A compound of Embodiment 68 wherein each R3 is independently Br or cyano.[0130]
Embodiment 70. A compound of Embodiment 69 wherein each R3 is independently halogen or cyano.[0131]
Embodiment 71. A compound of Embodiment 70 wherein each R3 is independently cyano.[0132]
Embodiment 72. A compound of Embodiment 70 wherein each R3 is independently halogen.[0133]
Embodiment 73. A compound of Embodiment 72 wherein each R3 is independently Br.[0134]
Embodiment 74. A compound of Formula 1 or any one of Embodiments 1 through 73 either alone or in combination, wherein m is at least 1 and one R3 is located at the 3-position (i.e. adjacent to the -AR1 group) represented by the compound of Formula 1D[0000]
[00006]
[0000]
[0135]
wherein A, R1, R2 and Z are as defined in the Summary of the Invention or in any one of Embodiments 1 through 59;[0136]
R3a is as defined for R3 in any one of Embodiments 61 through 73;[0137]
R3b is as defined for R3 in any one of Embodiments 61 through 73; and[0138]
p is is 0 or 1.[0139]
Embodiment 75. A compound of Embodiment 74 wherein p is 1; R3a is halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy; and R3b is halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy.[0140]
Embodiment 76. A compound of Embodiment 75 wherein p is 0 and R3a is halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy.[0141]
Embodiment 77. A compound of Embodiment 76 wherein R3a is halogen or cyano.[0142]
Embodiment 78. A compound of Embodiment 77 wherein R3a is Br or cyano.[0143]
Embodiment 79. A compound of Formula 1 or any one of Embodiments 1 through 28 either alone or in combination, wherein R5 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C2-C6 alkylthioalkyl or C2-C6 haloalkylthioalkyl.[0144]
Embodiment 80. A compound of Embodiment 79 wherein R5 is C1-C6 alkyl or C1-C6 haloalkyl.[0145]
Embodiment 81. A compound of Embodiment 1 wherein when A is A-5, then R3 is in the 4-, 5- or 6-position.[0146]
Embodiment 82. A compound of Embodiment 1 wherein when A is A-3, B is 0, R3 is 3-Br then R1 is other then 3-bromopropane.[0147]
Embodiment 83. A compound of Embodiment 1 wherein when A is A-3, R3 is halogen at the 3-position.[0148]
Embodiment 84. A compound of Embodiment 1 wherein when A is A-1, R3 is cyano at the 3-position.[0149]
Embodiment 85. A compound of Embodiment 1 wherein R1 is other than C3-C6 cycloamino.[0150]
Embodiment 86. A compound of Embodiment 1 wherein each R11a is independently C1-C2 alkyl C1-C2 haloalkyl.[0151]
Embodiment 87. A compound of Embodiment 1 wherein each R11b is independently C1-C2 alkyl or C1-C2 haloalkyl.[0152]
Embodiment 88. A compound of Embodiment 1 wherein each R12 is independently H or C1-C3 alkyl.[0153]
Embodiment 89. A compound of Embodiment 1 wherein each R14 is independently C1-C3 alkyl or C1-C3 haloalkyl.[0154]
Embodiment 90. A compound of Embodiment 1 wherein each R14 is independently C1-C3 alkyl.[0155]
Embodiment 91. A compound of Embodiment 1 wherein m is 1, 2 or 3.[0156]
Embodiment 92. A compound of Embodiment 1 wherein m is 1 or 2.Embodiments of this invention, including Embodiments 1-92 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-92 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.[0157] Combinations of Embodiments 1-92 are illustrated by:
[0000] Embodiment A. A compound of Formula 1 wherein
[0000]
[0158]
A is A-1, A-2, A-3 or A-5;[0159]
R1 is R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 halocycloalkylalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 alkylamino, C1-C6 haloalkylamino, C2-C10 dialkylamino, C2-C10 halodialkylamino, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C4-C8 halocycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C3-C7 cyanoalkoxyalkyl, C1-C6 hydroxyalkyl, C1-C6 nitroalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkenylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C2-C6 alkylthioalkyl or C2-C6 haloalkylthioalkyl;[0160]
R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl;[0161]
each R3 is independently halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, —C(═O)N(R11aR11b), —C(═NOR12)H or —SOnR14.[0162]
R5 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C2-C6 alkylthioalkyl or C2-C6 haloalkylthioalkyl;[0163]
R11a is C1-C2 alkyl C1-C2 haloalkyl;[0164]
R11b is C1-C2 alkyl or C1-C2 haloalkyl;[0165]
R12 is H or C1-C3 alkyl; and[0166]
R14 is C1-C3 alkyl or C1-C3 haloalkyl.Embodiment B. A compound of Embodiment A wherein[0167]
A is A-1, A-2 or A-5;[0168]
R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 cycloalkoxy, C4-C8 cycloalkylalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio or C1-C6 alkenylthio;[0169]
R2 is halogen or C1-C4 alkyl;[0170]
each R3 is independently halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl or —SOnR14.[0171]
R5 is C1-C6 alkyl or C1-C6 haloalkyl;[0172]
each R14 is independently C1-C3 alkyl; and[0173]
m is 0, 1 or 2.Embodiment C. A compound of Embodiment B wherein[0174]
A is A-1 or A-2;[0175]
R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio or C1-C6 alkenylthio;[0176]
R2 is halogen or CH3; and[0177]
each R3 is independently halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.Embodiment D. A compound of Embodiment C wherein[0178]
A is A-1;[0179]
R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C1-C6 alkylthio, C1-C6 haloalkylthio or C1-C6 alkenylthio;[0180]
Z is O;[0181]
R2 is halogen;[0182]
each R3 is independently halogen, cyano, C1-C3 alkyl or C1-C3 haloalkyl; and[0183]
m is 1 or 2.Embodiment E. A compound of Embodiment C wherein[0184]
A is A-2;[0185]
R1 is C1-C6 alkyl, C2-C6 alkenyl, C1-C6 haloalkyl, C1-C6 alkoxy or C1-C6 haloalkoxy;[0186]
Z is O;[0187]
R2 is F, Cl or Br;[0188]
each R3 is independently halogen, cyano, C1-C2 alkyl or C1-C2 haloalkyl; and[0189]
m is 0 or 1.Embodiment F. A compound of Embodiment A wherein[0190]
A is A-3;[0191]
R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 cycloalkoxy, C4-C8 cycloalkylalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio or C1-C6 alkenylthio;[0192]
R2 is halogen or C1-C4 alkyl;[0193]
each R3 is independently halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl; and[0194]
m is 1 or 2.Embodiment G. A compound of Embodiment F wherein[0195]
B is O;[0196]
R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio or C1-C6 alkenylthio;[0197]
Z is O;[0198]
R2 is halogen or CH3;[0199]
each R3 is independently halogen, cyano, C1-C3 alkyl or C1-C3 haloalkyl; and[0200]
m is 1 or 2.[0201] Specific embodiments include compounds of Formula 1 selected from the group consisting of:
[0202]
3,3,3-trifluoropropyl 2-chloro-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 15);[0203]
3,3,3-trifluoro-1-methylpropyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 16);[0204]
propyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 13);[0205]
4,4,4-trifluorobutyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 20);[0206]
2-propen-1-yl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 22);[0207]
3-buten-1-yl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 21);[0208]
2,2,3,3,3-pentafluoropropyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 23);[0209]
3,3,3-trifluoropropyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 26);[0210]
1-[2-chloro-6-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-4,4,4-trifluoro-1-butanone (Compound 107); and[0211]
3-[(5-chloro-2-pyrimidinyl)oxy]-2-(5,5,5-trifluoropentyl)benzonitrile (Compound 73).[0212] Embodiments of the present invention as described in the Summary of the Invention include (where Formula 1P as used in the following Embodiments includes N-oxides and salts thereof):
[0000]
[00007]
[0000]
[0213]
Embodiment P1. A compound of Formula 1P wherein A is H2, O, S or N(OR5).[0214]
Embodiment P2. A compound of Embodiment P1 wherein A is H2, O or N(OR5).[0215]
Embodiment P3. A compound of Embodiment P2 wherein A is O or N(OR5).[0216]
Embodiment P4. A compound of Embodiment P3 wherein A is O.[0217]
Embodiment P5. A compound of Embodiment P3 wherein A is N(OR5).[0218]
Embodiment P6. A compound of Formula 1P or any one of Embodiments P1 through P5 either alone or in combination, wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 alkylamino, C1-C6 haloalkylamino, C2-C10 dialkylamino, C2-C10 halodialkylamino, C3-C6 cycloamino, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C4-C8 halocycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C3-C7 cyanoalkoxyalkyl, C1-C6 hydroxyalkyl, C1-C6 nitroalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C2-C6 alkylthioalkyl, C2-C6 haloalkylthioalkyl, benzyl, —NR7OR8, —ON(R9aR9b) or —NR7N(R9aR9b).[0219]
Embodiment P7. A compound of Embodiment P6 wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 alkylamino, C1-C6 haloalkylamino, C2-C10 dialkylamino, C2-C10 halodialkylamino, C3-C6 cycloamino, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C4-C8 halocycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C3-C7 cyanoalkoxyalkyl, C1-C6 hydroxyalkyl, C1-C6 nitroalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C2-C6 alkylthioalkyl or C2-C6 haloalkylthioalkyl.[0220]
Embodiment P8. A compound of Embodiment P7 wherein R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy or C3-C6 cycloalkoxy.[0221]
Embodiment P9. A compound of Embodiment P8 wherein R1 is C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy or C3-C6 cycloalkoxy.[0222]
Embodiment P10. A compound of Formula 1P or any one of Embodiments P1 through P9 either alone or in combination, wherein Z is O.[0223]
Embodiment P11. A compound of Formula 1P or any one of Embodiments P1 through P10 either alone or in combination, wherein R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl.[0224]
Embodiment P12. A compound of Embodiment P11 wherein R2 is halogen or C1-C4 alkyl.[0225]
Embodiment P13. A compound of Embodiment P12 wherein R2 is halogen or CH3.[0226]
Embodiment P14. A compound of Embodiment P13 wherein R2 is halogen.[0227]
Embodiment P15. A compound of Embodiment P14 wherein R2 is F, Cl or Br.[0228]
Embodiment P16. A compound of Formula 1P or any one of Embodiments P1 through P15 either alone or in combination, wherein m is 0, 1 or 2.[0229]
Embodiment P17. A compound of Embodiment P16 wherein m is 0 or 1.[0230]
Embodiment P18. A compound of Embodiment P17 wherein m is 1.[0231]
Embodiment P19. A compound of Embodiment P17 wherein m is 0 (i.e. the 3-, 4-, 5- and 6-positions are unsubstituted by R3).[0232]
Embodiment P20. A compound of Formula 1P or any one of Embodiments P1 through P19 either alone or in combination, wherein each R3 is independently halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, —C(═O)N(R11aR11b), —C(═NOR12)H or —SOnR14.[0233]
Embodiment P21. A compound of Embodiment P20 wherein each R3 is independently halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl or —SOnR14.[0234]
Embodiment P22. A compound of Embodiment P21 wherein each R3 is independently halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl.[0235]
Embodiment P23. A compound of Embodiment P22 wherein each R3 is independently halogen or cyano.[0236]
Embodiment P24. A compound of Embodiment P23 wherein each R3 is independently cyano.[0237]
Embodiment P25. A compound of Embodiment P23 wherein each R3 is independently halogen.[0238]
Embodiment P26. A compound of Embodiment P23 wherein each R3 is independently Br.[0239]
Embodiment P27. A compound of Formula 1P or any one of Embodiments P1 through P26 either alone or in combination, wherein m is 1 and R3 is located at the 3-position (i.e. adjacent to the C(=A)R1 group).[0240]
Embodiment P28. A compound of Formula 1P or any one of Embodiments P1 through P26 either alone or in combination, wherein m is 2 and R3 is located at the 3- and the 6-position (i.e. adjacent to the C(=A)R1 group and the Z(pyrimidine group).[0241]
Embodiment P29. A compound of Formula 1P or any one of Embodiments P1 through P28 either alone or in combination, wherein R5 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C2-C6 alkylthioalkyl or C2-C6 haloalkylthioalkyl.[0242]
Embodiment P30. A compound of Embodiment P29 wherein R5 is C1-C6 alkyl, or C1-C6 haloalkyl.Embodiments of this invention, including Embodiments P1-P30 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1P but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1P. In addition, embodiments of this invention, including Embodiments P1-P30 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.[0243] Combinations of Embodiments P1-P30 are illustrated by:
[0000] Embodiment PA. A compound of Formula 1P wherein
[0000]
[0244]
A is H2, O, S or N(OR5);[0245]
R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C1-C6 alkylamino, C1-C6 haloalkylamino, C2-C10 dialkylamino, C2-C10 halodialkylamino, C3-C6 cycloamino, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C4-C8 halocycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C3-C7 cyanoalkoxyalkyl, C1-C6 hydroxyalkyl, C1-C6 nitroalkyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C3-C8 cycloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C8 cycloalkylsulfonyl, C2-C6 alkylthioalkyl or C2-C6 haloalkylthioalkyl;[0246]
Z is O;[0247]
R2 is halogen, C1-C4 alkyl or C1-C4 haloalkyl;[0248]
each R3 is independently halogen, cyano, CHO, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl or —SOnR14; and[0249]
m is 0, 1 or 2.Embodiment PB. A compound of Embodiment PA wherein[0250]
A is H2, O or N(OR5);[0251]
R1 is C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy or C3-C6 cycloalkoxy;[0252]
R2 is halogen or C1-C4 alkyl;[0253]
each R3 is independently halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl;[0254]
R5 is H, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, C3-C7 cyanoalkoxyalkyl, C2-C6 alkylthioalkyl or C2-C6 haloalkylthioalkyl; and[0255]
m is 0 or 1.Embodiment PC. A compound of Embodiment PB wherein[0256]
A is O or N(OR5);[0257]
R1 is C1-C6 alkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, C1-C6 haloalkoxy, C3-C6 haloalkenyloxy, C3-C6 haloalkynyloxy or C3-C6 cycloalkoxy;[0258]
R2 is halogen or CH3;[0259]
R3 is independently halogen or cyano; and[0260]
R5 is C1-C6 alkyl, or C1-C6 haloalkyl.Embodiment PD. A compound of Embodiment PC wherein[0261]
A is O;[0262]
R2 is halogen; and[0263]
each R3 is independently halogen.[0264] Specific embodiments include compounds of Formula 1 selected from the group consisting of:
[0265]
3,3,3-trifluoropropyl 2-chloro-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 15),[0266]
3,3,3-trifluoro-1-methylpropyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 16),[0267]
propyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 13), 4,4,4-trifluorobutyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 20),[0268]
2-propen-1-yl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 22),[0269]
3-buten-1-yl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 21),[0270]
2,2,3,3,3-pentafluoropropyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 23), and[0271]
3,3,3-trifluoropropyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 26).[0272] This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein). Of note as embodiments relating to methods of use are those involving the compounds of embodiments described above. Compounds of the invention are particularly useful for selective control of weeds in crops such as wheat, barley, maize, soybean, sunflower, cotton, oilseed rape and rice, and specialty crops such as sugarcane, citrus, fruit and nut crops.
[0273] Also noteworthy as embodiments are herbicidal compositions of the present invention comprising the compounds of embodiments described above.
[0274] This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (b13) homogentisate solenesyltransererase (HST) inhibitors, (b14) cellulose biosynthesis inhibitors, (b15) other herbicides including mitotic disruptors, organic arsenicals, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanid, flurenol, fosamine, fosamine-ammonium, hydantocidin, metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid and pyributicarb, and (b16) herbicide safeners; and salts of compounds of (b1) through (b16).
[0275] “Photosystem II inhibitors” (b1) are chemical compounds that bind to the D-1 protein at the QB-binding niche and thus block electron transport from QA to QB in the chloroplast thylakoid membranes. The electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cellular destruction. The QB-binding niche has three different binding sites: binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, binding site B binds the phenylureas such as diuron, and binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate. Examples of photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazon, bromacil, bromofenoxim, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxuron, cumyluron, cyanazine, daimuron, desmedipham, desmetryn, dimefuron, dimethametryn, diuron, ethidimuron, fenuron, fluometuron, hexazinone, ioxynil, isoproturon, isouron, lenacil, linuron, metamitron, methabenzthiazuron, metobromuron, metoxuron, metribuzin, monolinuron, neburon, pentanochlor, phenmedipham, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn and trietazine.
[0276] “AHAS inhibitors” (b2) are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thus kill plants by inhibiting the production of the branched-chain aliphatic amino acids such as valine, leucine and isoleucine, which are required for protein synthesis and cell growth. Examples of AHAS inhibitors include amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, cloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron-sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide), mesosulfuron-methyl, metazosulfuron (3-chloro-4-(5,6-dihydro-5-methyl-1,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-1-methyl-1H-pyrazole-5-sulfonamide), metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone-sodium, propyrisulfuron (2-chloro-N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-6-propylimidazo[1,2-b]pyridazine-3-sulfonamide), prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thifensulfuron-methyl, triafamone (N-[2-[(4,6-dimethoxy-1,3,5-triazin-2-yl)carbonyl]-6-fluorophenyl]-1,1-difluoro-N-methylmethanesulfonamide), triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl and tritosulfuron.
[0277] “ACCase inhibitors” (b3) are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an early step in lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production leads to losses in cell membrane integrity, especially in regions of active growth such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die back. Examples of ACCase inhibitors include alloxydim, butroxydim, clethodim, clodinafop, cycloxydim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxydim, propaquizafop, quizalofop, sethoxydim, tepraloxydim and tralkoxydim, including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P and quizalofop-P and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl and fenoxaprop-P-ethyl.
[0278] Auxin is a plant hormone that regulates growth in many plant tissues. “Auxin mimics” (b4) are chemical compounds mimicking the plant growth hormone auxin, thus causing uncontrolled and disorganized growth leading to plant death in susceptible species. Examples of auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl-4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazolin-ethyl, chloramben, clacyfos, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid), halauxifen-methyl (methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), MCPA, MCPB, mecoprop, picloram, quinclorac, quinmerac, 2,3,6-TBA, triclopyr, and methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate.
[0279] “EPSP synthase inhibitors” (b5) are chemical compounds that inhibit the enzyme, 5-enol-pyruvylshikimate-3-phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant foliage and translocated in the phloem to the growing points. Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate).
[0280] “Photosystem I electron diverters” (b6) are chemical compounds that accept electrons from Photosystem I, and after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys cell membrane integrity, so that cells and organelles “leak”, leading to rapid leaf wilting and desiccation, and eventually to plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.
[0281] “PPO inhibitors” (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, quickly resulting in formation of highly reactive compounds in plants that rupture cell membranes, causing cell fluids to leak out. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, trifludimoxazin (dihydro-1,5-dimehyl-6-thioxo-3-[2,2,7-trifluoro-3,4-dihydro-3-oxo-4-(2-propyn-1-yl)-2H-1,4-benzoxazin-6-yl]-1,3,5-triazine-2,4(1H,3H)-dione) and tiafenacil (methyl N-[2-[[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]thio]-1-oxopropyl]-β-alaninate).
[0282] “GS inhibitors” (b8) are chemical compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia into glutamine. Consequently, ammonia accumulates and glutamine levels decrease. Plant damage probably occurs due to the combined effects of ammonia toxicity and deficiency of amino acids required for other metabolic processes. The GS inhibitors include glufosinate and its esters and salts such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P ((2S)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid) and bilanaphos.
[0283] “VLCFA elongase inhibitors” (b9) are herbicides having a wide variety of chemical structures, which inhibit the elongase. Elongase is one of the enzymes located in or near chloroplasts which are involved in biosynthesis of VLCFAs. In plants, very-long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethenamid, diphenamid, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro-5,5-dimethylisoxazole), fentrazamide, flufenacet, indanofan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)—N,N-diethyl-2-(1-naphthalenyloxy)propanamide), pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor, including resolved forms such as S-metolachlor and chloroacetamides and oxyacetamides.
[0284] “Auxin transport inhibitors” (b10) are chemical substances that inhibit auxin transport in plants, such as by binding with an auxin-carrier protein. Examples of auxin transport inhibitors include diflufenzopyr, naptalam (also known as N-(1-naphthyl)phthalamic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).
[0285] “PDS inhibitors” (b11) are chemical compounds that inhibit carotenoid biosynthesis pathway at the phytoene desaturase step. Examples of PDS inhibitors include beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone norflurzon and picolinafen.
[0286] “HPPD inhibitors” (b12) are chemical substances that inhibit the biosynthesis of synthesis of 4-hydroxyphenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include benzobicyclon, benzofenap, bicyclopyrone (4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinotrione (2-[[8-chloro-3,4-dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-1,3-cyclohexanedione), isoxachlortole, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate (1-[[1-ethyl-4-[3-(2-methoxyethoxy)-2-methyl-4-(methylsulfonyl)benzoyl]-1H-pyrazol-5-yl]oxy]ethyl methyl carbonate), topramezone, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, 5-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)-4(3H)-pyrimidinone, 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide and 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide.
[0287] “HST inhibitors” (b13) disrupt a plant's ability to convert homogentisate to 2-methyl-6-solanyl-1,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include haloxydine, pyriclor, cyclopyrimorate (6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.
[0288] HST inhibitors also include compounds of Formulae A and B.
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See Also
Flumioxazin; Pesticide TolerancesLes types des herbicides pdf - Canada Guidelines Working TutorialsUS Patent for Bacillus isolates and uses thereof Patent (Patent # 11,560,342 issued January 24, 2023)Plants having increased tolerance to herbicides - US11306322B2[00008]
[0289]
wherein Rd1 is H, Cl or CF3; Rd2 is H, Cl or Br; Rd3 is H or Cl; Rd4 is H, Cl or CF3; Rd5 is CH3, CH2CH3 or CH2CHF2; and Rd6 is OH, or —OC(═O)-i-Pr; and Re1 is H, F, Cl, CH3 or CH2CH3; Re2 is H or CF3; Re3 is H, CH3 or CH2CH3; Re4 is H, F or Br; Re5 is Cl, CH3, CF3, OCF3 or CH2CH3; Re6 is H, CH3, CH2CHF2 or C≡CH; Re7 is OH, —OC(═O)Et, —OC(═O)-i-Pr or —OC(═O)-t-Bu; and Ae8 is N or CH.[0290] “Cellulose biosynthesis inhibitors” (b14) inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied preemergence or early postemergence on young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include chlorthiamid, dichlobenil, flupoxam, indaziflam (N2-[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-(1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaben and triaziflam.
[0291] “Other herbicides” (b15) include herbicides that act through a variety of different modes of action such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl), organic arsenicals (e.g., DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors. Other herbicides include those herbicides having unknown modes of action or do not fall into a specific category listed in (b1) through (b14) or act through a combination of modes of action listed above. Examples of other herbicides include aclonifen, asulam, amitrole, bromobutide, cinmethylin, clomazone, cumyluron, daimuron, difenzoquat, etobenzanid, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone (1-(2,4-dichlorophenyl)-N-(2,4-difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb and 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole.
[0292] “Herbicide safeners” (b16) are substances added to a herbicide formulation to eliminate or reduce phytotoxic effects of the herbicide to certain crops. These compounds protect crops from injury by herbicides but typically do not prevent the herbicide from controlling undesired vegetation. Examples of herbicide safeners include but are not limited to benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride, oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide.
[0293] An embodiment of the present invention is a herbicidal mixture comprising (a) a compound of Formula 1, and (b) at least one additional active ingredient selected from (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b4) auxin mimics, (b5) 5-enol-pyruvylshikimate-3-phosphate (EPSP) synthase inhibitors, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors and (b12) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors.
[0294] The compounds of Formula 1 can be prepared by general methods known in the art of synthetic organic chemistry. One or more of the following methods and variations as described in Schemes 1-10 can be used to prepare the compounds of Formula 1. The definitions of (A, Z, R1, R2, R3, R4, R5, R6a and R6b) in the compounds of Formulae 1-17 below are as defined above in the Summary of the Invention unless otherwise noted.
[0295] Compounds of Formulae 1a-1b are various subsets of the compounds of Formula 1, and all substituents for Formulae 1a-1b are as defined above for Formula 1 unless otherwise noted.
[0296] As shown in Scheme 1 a compound of Formula 1 can be prepared by nucleophilic substitution by heating a compound of Formula 2 in a suitable solvent, such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide in the presence of a base such as potassium or cesium carbonate, with a compound of Formula 3 (wherein LG is halogen or SO2Me). The reaction is typically conducted at temperatures ranging from 20 to 110° C.
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[00009]
[0297] As shown in Scheme 2, compounds of Formula 1b (wherein A is S) can be prepared by reacting compounds of Formula 1a (wherein A is A-3 and B is 0) with a thionation reagent such as Lawesson's reagent, tetraphosphorus decasulfide or diphosphorus pentasulfide in a solvent such as tetrahydrofuran or toluene. Typically, the reaction is carried out at temperatures ranging from 0 to 115° C.
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[00010]
[0298] As shown in Scheme 3, a compound of Formula 2a (wherein A is A-3, B is 0 and Z is 0) can be prepared by deprotection of a compound of Formula 4 (wherein R20 is CH3 or C(═O)CH3) with a suitable deprotecting agent. Suitable methoxy (i.e. when R20 is CH3) deprotecting reagents such as BBr3, AlCl3 and HBr in acetic acid can be used in the presence of solvents such as toluene, dichloromethane and dichloroethane at a temperature of from −80 to 120° C. Suitable acetoxy (i.e. when R20 is C(═O)CH3) deprotecting agents include potassium carbonate in methanol or ammonium acetate in aqueous methanol at room temperature can be used as discussed in Das, et al., Tetrahedron 2003, 59, 1049-1054 and methods cited therein. Alternatively, a compound of Formula 4 can be combined with Amberlyst 15© in methanol (as discussed in Das, et al. Tet. Lett. 2003, 44, 5465-5468) or combined with sodium acetate in ethanol (as discussed in Narender, T., et al. Synthetic Communications 2009, 39(11), 1949-1956) to obtain a compound of Formula 2a. Other useful phenolic protecting groups suitable for use in preparing a compound of Formula 2a can be found in Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 4th ed.; Wiley: Hoboken, N.J., 1991.
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[00011]
[0299] As shown in Scheme 4 compounds of Formula 5 (wherein R1a is alkyl, alkenyl, or alkynyl) can be prepared by reaction of organometallic reagents such as organomagnesium or organolithium reagents of Formula 6 with amides of the Formula 7. This reaction is typically carried out in a solvent such as tetrahydrofuran or diethyl ether at temperatures ranging from −78 to 25° C. To those skilled in the art, Amides such as Formula 7 are commonly referred to as a ‘Weinreb Amide’ and this type of transformation is commonly referred to as the ‘Weinreb-Nahm ketone synthesis.’ See Synthesis 2008, 23, 3707-3738 and references cited therein.
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[00012]
[0300] As shown in Scheme 5 compounds of Formula 8 can be prepared by reaction of acids of Formula 9 with alkylamines, alcohols or thiols of Formula 10 (wherein Rib is alkoxy, alkylthio or alkylamino) in the presence of a dehydrative coupling reagent such as propylphosphonic anhydride, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-N-ethylcarbodiimide, N,N-carbonyldiimidazole, 2-chloro-1,3-dimethylimidazolium chloride or 2-chloro-1-methylpyridinium iodide. Polymer-supported reagents, such as polymer-supported cyclohexylcarbodiimide, are also suitable. These reactions are typically run at temperatures ranging from 0-60° C. in a solvent such as dichloromethane, acetonitrile, N,N-dimethylformamide or ethyl acetate in the presence of a base such as triethylamine, N,N-diisopropylamine, or 1,8-diazabicyclo[5.4.0]undec-7-ene. See Organic Process Research & Development 2009, 13, 900-906 for coupling conditions employing propylphosphonic anhydride.
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[00013]
[0301] In Scheme 6 a compounds of Formula 11 (wherein Rx is R4, OR5 or NR6aR6b) can readily be prepared by condensation of an organoamine, organohydroxylamine, or organohydrazine with a compound of Formula 8, typically in the presence of either an acid or base. Reactions are typically run in solvents such as methanol, ethanol, dichloromethane, or toluene at temperatures ranging from 20-110° C. Suitable acids for the reactions include, but are not limited to, inorganic acids such as hydrochloric acids and organic acids such as acetic acid and trifluoroacetic acid. Suitable bases for the reaction include, but are not limited to, hydroxides such as sodium hydroxide, carbonates such as sodium and potassium carbonate, and organic bases such as sodium acetate and pyridine.
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[00014]
[0302] As shown in Scheme 7 benzylic alcohols of Formula 12 can be prepared by reduction of aldehydes of Formula 13 by a wide variety of methods well known to those skilled in the art. Suitable reducing agents for the reaction include, but are not limited to, sodium borohydride, lithium aluminum hydride, and diisobutylaluminium hydride. A variety of solvents are also suitable for this reaction and include, but are not limited to, methanol, ethanol, and tetrahydrofuran with typically reaction temperatures ranging from −10° C. to 25° C.
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[00015]
[0303] As shown in Scheme 8 benzylic halides of Formula 14 (wherein X is Cl, Br or I) can be prepared by substitution of alcohol with a halide on compounds of Formula 12 by a wide variety of methods well known to those skilled in the art. One such method employs thionyl chloride, optionally with N,N-dimethyl formamide, in solvents including, but not limited to dichloromethane, toluene, chloroform and no solvent at temperatures typically between 0-80° C. Alternatively compounds of the Formula 14 can be prepared from benzyl alcohols of the Formula 12 employing a phosphorus reagent and a halide regent. A typical phosphorus reagent is triphenyl phosphine and halide reagents include, but are not limited to, carbon tetrahalide, N-halosuccinimide, dihalide, and tetrahalomethane. Solvents suitable for this reaction include, but are not limited to, dichloromethane, tetrahydrofuran, and acetonitrile and typical reaction temperatures range from −78-50° C. This latter reaction is well known to those skilled in the art and is referred to as an ‘Appel Reaction’. For examples see Smith, M. B.; March, J. March's Advanced Organic Chemistry, 6th ed., pages 576-580; John Wiley & Sons. Hoboken, N.J. and references therein.
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[00016]
[0304] In Scheme 9 a benzylic heterateroatom containing compound of Formula 15 (wherein Rib is alkoxy, alkylthio or alkylamino) can readily be prepared by those skilled in the art by a displacement reaction with a compound of the Formula 14 using an appropriate heteroalkyl reagent of Formula 10 (alcohol, alkylamine, or thiol), typically in the presence of a base. Suitable solvents for the reaction include, but are not limited to, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, toluene and dichloromethane. Suitable bases for the reaction include, but are not limited to, hydroxides such as sodium hydroxide and potassium hydroxide, hydride bases such as sodium hydride, carbonate bases such as sodium and potassium carbonate, and organic bases such as triethylamine and N,N-diethylisopropylamine. Additionally this reaction can be optionally substituted with an iodide, for example sodium iodide or tetrabutylammonium iodide.
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[00017]
[0305] As shown in Scheme 10 sulfone (n=1) and sulfoxides (n=2) of the Formula 16 can be readily prepared by the oxidation of a compound of Formula 17 (wherein A is A-1 and R21 is alkyl or haloalkyl) by a wide variety of methods well known to those skilled in the art. Suitable reagents for this reaction include but are not limited to, dihydrogen peroxide, 3-chloro-benzenecarboxylic acid, sodium periodate, and Oxone. Typical solvents for this reaction include dichloromethane, methanol, tetrahydrofuran, and acetic acid and a typical reaction temperature range between −78 to 50° C. The sulfur is first oxidized to the sulfoxide (n=1) followed by oxidation to the sulfone (n=2). Careful monitoring reaction progress with well-established analytical methods (i.e. thin layer chromotagraphy, nuclear magnetic resonance, etc.) allows for selection of the sulfoxide or sulfone.
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[00018]
[0306] In Scheme 11 a compound of Formula 18 can readily be prepared by alkylation of a compound of Formula 19. This can be accomplished using an appropriate alkylating reagent in the presence of an appropriate base. Suitable solvents for this reaction generally include polar solvents including but not limited to N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, or tetrahydrofuran. Suitable bases generally include but are not limited to sodium hydride, sodium amide, sodium hydroxide, and lithium diisopropyl amide. Reaction temperatures range from 0° C. to 100° C. as described in synthesis Example 5.
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[00019]
[0307] As shown in Scheme 12 a compound of Formula 20 can be prepared through deoxygenation of a compound of Formula 21. One method utilizes a transition metal catalyst in the presence of a hydride source optionally in the presence of an acid utilizing a number of solvents including methanol and ethanol. A typical transition metal catalyst is palladium on carbon, and standard hydride sources include hydrogen gas, either at atmospheric or elevated pressure, or ammonium formate. Acids utilized for this reaction can include hydrochloric acid, sulfuric acid, and para-toluenesulfonic acid. An example of this reaction can be found in J. Med. Chem. 1992, 35, 1818. A second method employs a hydride source in combination with an acid. Typical hydride sources include triethylsilane and sodium borohydride, in combination with Brönsted acids such as trifluoroacetic acid and acetic acid, or Lewis acids such as boron trifluoride etherate. The solvent for these reactions can be the acid alone or as a mixture with a number of other common solvents such as dichloromethane or acetonitrile. An example of this reaction can be found in US 2007/0003539 or in Step B of synthesis Example 6.
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[00020]
[0308] As shown in Scheme 13 a compound of Formula 22 (where R1a is alkyl, alenyl, or alkynyl) can be prepared by reaction of organometallic reagents such as organomagnesium or organolithium reagents with aldehydes of the Formula 23. This reaction is typically carried out in a solvent such as tetrahydrofuran or diethyl ether at temperatures ranging from −78 to 25° C. An example of this reaction can be found in Synlett, 2016, 27, 789 or as described in Step A of synthesis Example 6.
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[00021]
[0309] As shown in Scheme 14, compounds of Formula 25 can be prepared by a transition metal catalyzed coupling of a cyano group with a compound of Formula 24 (R3a═Br or I). Conditions for this reaction generally include a cyanide source and a copper catalyst or palladium catalyst with a co-catalyst. This reaction is typically carried out with a copper(I) halide in the presence of a ligand such as 2-(methylamino)ethylamine or trans-N,N′-dimethylcyclohexane-1,2-diamine with a metal cyanide salt. This reaction can be utilized in a range of polar aprotic solvents such as N,N-dimethylformamide, tetrahydrofuran, acetonitrile, N-methyl-2-pyrrolidone or toluene at temperatures ranging from 100 to 210° C. This reaction is known to those skilled in the art as the Rosenmund-von Braun reaction. Similar conditions can be utilized with copper(I) cyanide with or without the presence of added ligand and cyanide source. The analogous coupling can be affected by using a palladium catalyst such as tetrakis(triphenylphosphine)palladium, palladium diacetate, or tris(dibenzylideneacetone)dipalladium with optional phosphine ligands and a co-catalyst such as zinc cyanide. These reactions can be carried out in a range of polar aprotic solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, acetonitrile and 1,4-dioxane at temperatures ranging from 80 to 150° C. Alternatively a palladium co-catalyst such as copper(I) halide and a cyanide salt can be used in place of the zinc cyanide under similar conditions. An example of this reaction can be found in J. Am. Chem. Soc. 2003, 125, 2890 and as described in Step C of synthesis Example 6.
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[00022]
[0310] Compounds of Formulae 24, 22 and 20 can readily be converted to a compound of Formula 1 using the methods discussed for Scheme 3 and Scheme 1; by deprotection of the PG group and subsequent alkylation with a compound of Formula 3. It is recognized by one skilled in the art that various functional groups can be converted into others to provide different compounds of Formula 1. For a valuable resource that illustrates the interconversion of functional groups in a simple and straightforward fashion, see Larock, R. C., Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Ed., Wiley-VCH, New York, 1999. For example, intermediates for the preparation of compounds of Formula 1 may contain aromatic nitro groups, which can be reduced to amino groups, and then be converted via reactions well known in the art such as the Sandmeyer reaction, to various halides, providing compounds of Formula 1. The above reactions can also in many cases be performed in alternate order It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular presented to prepare the compounds of Formula 1.
[0311] One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
[0312] Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following non-limiting Examples are illustrative of the invention. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1H NMR spectra are reported in ppm downfield from tetramethylsilane; “s” means singlet, “d” means doublet, “t” means triplet, “q” means quartet, “m” means multiplet, “dd” means doublet of doublets, “dt” means doublet of triplets, and “br s” means broad singlet. Mass spectra (MS) are reported as the molecular weight of the highest isotopic abundance parent ion (M+1) formed by addition of H+(molecular weight of 1) to the molecule, or (M−1) formed by the loss of H+(molecular weight of 1) from the molecule, observed by using liquid chromatography coupled to a mass spectrometer (LCMS) using either atmospheric pressure chemical ionization (AP+) where “amu” stands for unified atomic mass units.
Example 1
Preparation of 2-[(5-chloro-2-pyrimidinyl)oxy]-N-(2,2,2-trifluoroethyl)benzamide (Compound 28)
Step A: Preparation of 2-methoxy-N-(2,2,2-trifluoroethyl)benzamide
[0313] A solution of 2,2,2-Trifluoroethylamine (1.28 g, 12.89 mmoles) and triethylamine (4.1 mL, 29.31 mmoles) in dichloromethane (30 mL) was cooled to 0° C. The reaction mixture was treated with a solution of 2-methoxybenzoyl chloride (2.0 g, 11.72 mmoles) in in dichloromethane (8 mL) at a temperature below 5° C. The reaction mixture was allowed to slowly warm to room temperature. De-ionized water was added and the mixture partitioned. The aqueous phase was extracted with dichloromethane. The combined organic phases were washed with 1N HCl and saturated aqueous sodium chloride solution and dried with magnesium sulfate and concentrated under vacuum to a white solid. The solid was filtered from hexanes to obtain the title compound (2.24 g) as a solid.
[0314] 1H NMR (400 MHz, CDCl3) δ 8.20 (d, 2H), 7.49 (t, 1H), 7.10 (t, 1H), 7.00 (d, 1H), 4.10 (q, 2H), 3.99 (s, 3H).
Step B: Preparation of 2-hydroxy-N-(2,2,2-trifluoroethyl)benzamide
[0315] A solution of 2-methoxy-N-(2,2,2-trifluoroethyl)benzamide (i.e. the product of Step A) (1.0 g, 4.28 mmoles) in anhydrous dichloromethane (20 mL) was cooled with an ice-water bath to 0° C. The solution was treated with 1 M boron tribromide solution (4.72 mL, 4.72 mmoles) in dichloromethane dropwise and stirred for 3 hours. The reaction mixture was then poured into ice-water and partitioned. The aqueous phase was extracted with dichloromethane and then ethyl acetate. The combined organic phases were washed with saturated aqueous sodium chloride solution, dried with magnesium sulfate and concentrated under vacuum to a solid. The solid was filtered from hexanes to obtain the title compound (475 mg) as a solid.
[0316] 1H NMR (400 MHz, CDCl3) δ 7.44 (t, 1H), 7.40 (d, 1H), 7.01 (d, 1H), 6.89 (t, 1H), 6.53 (bs, 1H), 4.13 (m, 2H).
Step C: Preparation of 2-[(5-chloro-2-pyrimidinyl)oxy]-N-(2,2,2-trifluoroethyl)-benzamide
[0317] To a solution of 2-hydroxy-N-(2,2,2-trifluoroethyl)benzamide (i.e. the product of Step B) (100 mg, 0.456 mmoles) in acetonitrile (3 mL) was added 2,5-dichloropyrimidine (71 mg, 0.48 mmoles) and potassium carbonate (190 mg, 1.37 mmoles). The reaction mixture was heated to 80° C. for 12 hours. The reaction was partitioned between water and ethyl acetate, the organic phase was separated, dried with magnesium sulfate, and concentrated under vacuum. The residue was purified by chromatography on silica gel with a 5 gram Bond elut column, eluting with 20% ethyl acetate/hexanes to afford the title compound, a compound of the present invention, as an oil (0.30 g).
[0318] 1H NMR (400 MHz, CDCl3) δ 8.30 (s, 2H), 7.65 (d, 1H), 7.48 (t, 1H), 7.31 (t, 1H), 7.21 (bs, 1H), 7.00 (d, 1H), 4.75 (q, 2H).
Example 2
Preparation of 3-buten-1-yl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 21)
Step A: Preparation of 3-butenyl 2-bromo-6-hydroxybenzoate
[0319] To a stirred solution of 2-bromo-6-hydroxybenzoic acid (0.200 g, 0.921 mmol) in dry dichloromethane (3 mL) was added oxalyl chloride (94.8 μL, 1.11 mml) and 2 drops of N,N′-dimethylformamide. The reaction mixture was stirred at room temperature for 3 hours. The reaction mixture was then concentrated under vacuum and the residue was dissolved in dry dichloromethane (3 mL) and treated with 3-buten-1-ol (86.9 μL, 1.01 mmol) and 3 drops of triethylamine. The reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was concentrated under vacuum onto Celite® diatomaceous earth filter aid and purified by column chromatography on silica gel, eluting with 0 to 20% ethyl acetate in hexanes to afford the title compound (0.117 g).
[0320] 1H NMR (500 MHz, CDCl3) δ 10.96 (s, 1H), 7.24-7.17 (m, 2H), 6.98-6.93 (m, 1H), 5.95-5.87 (m, 1H), 5.22-5.18 (m, 1H), 5.15-5.12 (m, 1H), 4.47 (t, 2H), 2.62-2.57 (m, 2H).
Step B: Preparation of 3-buten-1-yl 2-bromo-6[(5-chloro-2-pyrimidinyl)oxy]benzoate
[0321] To a stirred solution of 3-butenyl 2-bromo-6-hydroxybenzoate (i.e. the product of Step A) (0.117 g, 0.431 mmol) and 5-chloro-2-(methylsulfonyl)-pyrimidine (i.e. 5-chloro-2-methylsulfonylpyrimidine) (99.8 mg, 0.518 mmol) in N,N′-dimethylformamide (2 mL) was added potassium carbonate (85.9 mg, 0.646 mmol). The reaction mixture was stirred at room temperature for 18 hours. The reaction mixture was then filtered through a pad of Celite® diatomaceous earth filter aid and the filtrate was concentrated under vacuum. The crude residue was purified by column chromatography on silica gel, eluting with 0 to 30% ethyl acetate in hexanes to afford the title compound, a compound of the present invention, as a solid (0.104 g).
[0322] 1H NMR (500 MHz, CDCl3) δ 8.48 (s, 2H), 7.53 (dd, 1H), 7.35 (t, 1H), 7.17 (dd, 1H), 5.75-5.65 (m, 1H), 5.11-4.99 (m, 2H), 4.29 (t, 2H), 2.39-2.34 (m, 2H).
Example 3
Preparation of 3,3,3-trifluoropropyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)oxy]benzoate (Compound 26)
Step A: Preparation of 3,3,3-trifluoropropyl 2-bromo-6-hydroxybenzoate
[0323] To a stirred solution of 2-bromo-6-hydroxybenzoic acid (0.500 g, 2.30 mmol) and molecular sieves in 3,3,3-trifluoropropan-1-ol (15 mL) was added concentrated sulfuric acid (0.300 mL). The reaction mixture was heated at 78° C. for 24 hours. The reaction mixture was cooled to room temperature and filtered through a small pad of Celite® diatomaceous earth filter aid. The filtrate was diluted with ethyl acetate and washed with water, and saturated aqueous sodium chloride solution. The organic phase was separated, dried over magnesium sulfate and concentrated under vacuum. The crude material was purified by column chromatography on silica gel, eluting with 0 to 20% ethyl acetate in hexanes to afford the title compound (0.268 g).
[0324] 1H NMR (500 MHz, CDCl3) δ 10.79 (s, 1H), 7.26-7.20 (m, 2H), 7.00-6.94 (m, 1H), 4.63 (t, 2H), 2.70 (m, 2H).
Step B: Preparation of 3,3,3-trifluoropropyl 2-bromo-6-[(5-chloro-2-pyrimidinyl)-oxy]benzoate
[0325] To a stirred solution of 3,3,3-trifluoropropyl 2-bromo-6-hydroxybenzoate (i.e. the product of Step A) (0.124 g, 0.396 mmol) and 5-chloro-2-(methylsulfonyl)-pyrimidine (i.e. 5-chloro-2-methylsulfonylpyrimidine) (95.1 mg, 0.475 mmol) in N,N′-dimethylformamide (2 mL) was added potassium carbonate (82.1 mg, 0.594 mmol). The reaction was stirred at room temperature for 18 hours. The reaction mixture was filtered through a pad of Celite® diatomaceous earth filter aid and filtrate was concentrated under vacuum. The crude material was purified by column chromatography on silica gel, eluting with 0 to 30% ethyl acetate in hexanes to afford the title compound, a compound of the present invention, as a solid (55.0 mg).
[0326] 1H NMR (500 MHz, CDCl3) δ 8.49 (s, 2H), 7.54 (dd, 1H), 7.38 (t, 1H), 7.20 (dd, 1H), 4.46 (t, 2H), 2.50 (m, 2H).
Example 4
Preparation of 1-[2-chloro-6-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-4,4,4-trifluoro-1-butanone (Compound 107)
Step A: Preparation of 2-chloro-6-methoxy-α-(3,3,3-trifluoropropyl)benzenemethanol
[0327] A reaction flask was charged with 1.92 g (79.18 mmol) of magnesium, a catalytic amount of iodine, and 50 mL of diethyl ether. The mixture was heated to reflux and 1,1,1-trifluoro-3-iodo-propane (10.64 g, 47.51 mmol) was added over 30 min. The mixture was allowed to cool to room temperature and transferred to a second reaction flask charged with 2-chloro-6-methoxy-benzaldehyde (6.75 g, 39.59 mmol) and 75 mL of tetrahydrofuran at −78° C. The reaction mixture was allowed to warm to room temperature, quenched with 1 N hydrochloric acid, and partitioned between diethyl ether and brine. The organic phase was dried over MgSO4, filtered, and concentrated to provide 9.4 g of crude product that was used in the subsequent step without purification.
Step B: Preparation of 1-(2-chloro-6-methoxyphenyl)-4,4,4-trifluoro-1-butanone
[0328] To a solution of 2-chloro-6-methoxy-α-(3,3,3-trifluoropropyl)benzenemethanol (i.e. the crude material obtained in Step A, 9.4 g) in 175 mL of acetone was added 15.7 mL (42 mmol) of 2.64 M Jones reagent over 15 min. The reaction mixture was stirred for an additional 30 min., quenched with 0.5 mL of isopropanol, and partitioned between diethyl ether and water. The organic phase was dried over MgSO4, filtered, and concentrated. The crude material was purified by silica gel chromatography eluting with a hexane:ethyl acetate gradient to provide 7.0 g of the title compound.
[0329] 1H NMR (CDCl3) δ 7.32-7.24 (m, 1H), 7.00 (d, 1H), 6.84 (d, 1H), 3.82 (s, 3H), 3.09-3.01 (m, 2H), 2.64-2.51 (m, 2H).
Step C: Preparation of 1-(2-chloro-6-hydroxyphenyl)-4,4,4-trifluoro-1-butanone
[0330] To a solution of 1-(2-chloro-6-methoxyphenyl)-4,4,4-trifluoro-1-butanone (i.e. the product from Step B, 3.5 g, 13.2 mmol) of in 100 mL of dichloromethane was added boron tribromide (1.0 M in dichloromethane, 15.79 mL) at 0° C. The reaction solution was stirred for 2 h while warming to room temperature, which was then poured into ice cold dilute aqueous hydrochloric acid, and extracted with dichloromethane. The organic phase was dried over MgSO4, filtered, and concentrated. The crude material was purified by silica gel chromatography eluting with a gradient of hexanes/ethyl acetate to provide 2.6 g of the title compound.
[0331] 1H NMR (CDCl3) δ 11.88 (s, 1H), 7.35-7.30 (m, 1H), 7.01-6.98 (m, 1H), 6.96-6.92 (m, 1H), 3.55-3.49 (m, 2H), 2.65-2.53 (m, 2H).
Step D: Preparation of 1-[2-chloro-6-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-4,4,4-trifluoro-1-butanone
[0332] A reaction flask was charged with 1-(2-chloro-6-hydroxyphenyl)-4,4,4-trifluoro-1-butanone (i.e. the product obtained in Step C, 2.6 g, 10.3 mmol), 5-chloro-2-(methylsulfonyl)-pyrimidine (2.7 g, 14.0 mmol), potassium carbonate (1.7 g, 12.36 mmol), and 50 mL of isopropanol. The reaction mixture was heated to 50° C. for 1 h, poured into dilute ice cold aqueous hydrochloric acid, and extracted with diethyl ether repeatedly. The combined organic extracts were washed with brine, dried over MgSO4, filtered, and concentrated. The crude material was purified by silica gel chromatography eluting with a gradient of hexanes/ethyl acetate to provide 3.0 g of the title compound, a compound of the invention.
[0333] 1H NMR (CDCl3) δ 8.49 (s, 2H), 7.45-7.40 (m, 1H), 7.37-7.33 (m, 1H), 7.15-7.11 (m, 1H), 3.14-3.08 (m, 2H), 2.57-2.46 (m, 2H).
Example 5
Preparation of 2-[(5-chloro-2-pyrmidinyl)oxy]-α-pentylbenzeneacetonitrile (Compound 141)
Step A: Preparation of 2-methoxy-α-pentylbenzeneacetonitrile
[0334] To a solution of 2-methoxy-benzeneacetonitrile (500 mg, 3.39 mmol) in dimethylsulfoxide (5 mL) was added aqueous sodium hydroxide (50%, 0.75 mL) followed by 1-bromopentane (559 mg, 0.458 mL, 3.76 mmol) and the reaction mixture was stirred at ambient temperature for 18 h. The reaction mixture was partitioned between ethyl acetate and water, the organic phase was washed with water (3×). The organic phase was dried over MgSO4 and concentrated under vacuum. The resulting residue was purified by chromatography on silica gel eluting with a gradient of 0 to 50% ethyl acetate in hexanes to afford the desired product in quantitative yield.
[0335] 1H NMR (500 MHz, CDCl3) δ 7.38-7.41 (m, 1H), 7.27-7.31 (m, 1H), 6.96-7.01 (m, 1H), 6.87-6.91 (m, 1H), 4.15-4.20 (m, 1H), 3.85 (s, 3H), 1.77-1.90 (m, 2H), 1.41-1.58 (m, 2H), 1.27-1.37 (m, 4H), 0.84-0.94 (m, 3H).
Step B: Preparation of 2-hydroxy-α-pentylbenzeneacetonitrile
[0336] To a solution of 2-methoxy-α-pentylbenzeneacetonitrile (i.e. the product of Step A, 440 mg, 2.02 mmol) in dichloromethane (10 mL) at 0° C. was added boron tribromide (1.0 M in dichloromethane, 10 mL, 10 mmol) and the reaction was allowed to warm to room temperature over 18 h. The reaction mixture was quenched with a saturated solution of sodium carbonate, the phases were separated and the organic layer was dried over MgSO4. The solvent was removed under vacuum and purified by chromatography on silica gel, eluting with a gradient of 0 to 50% ethyl acetate in hexanes to afford the desired product (232 mg) 1H NMR (500 MHz, CDCl3) δ 7.35-7.39 (m, 1H), 7.15-7.20 (m, 1H), 6.93-6.98 (m, 1H), 6.76-6.79 (m, 1H), 5.28-5.40 (bs, 1H), 4.14-4.20 (m, 1H), 1.84-1.93 (m, 2H), 1.42-1.58 (m, 2H), 1.25-1.38 (m, 4H), 0.85-0.91 (m, 3H).
Step C: Preparation of 2-[(5-chloro-2-pyrmidinyl)oxy]-α-pentylbenzeneacetonitrile
[0337] To a solution of 2-hydroxy-α-pentylbenzeneacetonitrile (208 mg, 1.02 mmol) in N,N′-dimethylformamide (2.0 mL) was added potassium carbonate (169 mg, 1.22 mmol) followed by 5-chloro-2-(methylsulfonyl)-pyrimidine (137 mg, 1.07 mmol) and the reaction was heated to 35° C. for 5 h. The reaction was partitioned between ethyl acetate and water. The organic phase was washed with water (3×), followed by drying over MgSO4 and concentrating. The resulting residue was purified by chromatography on silica gel eluting with a gradient of 0 to 30% ethyl acetate in hexanes to afford the title product, a compound of the invention (171 mg).
[0338] 1H NMR (500 MHz, CDCl3) δ 8.51 (s, 2H), 7.56-7.58 (m, 1H), 7.38-7.42 (m, 1H), 7.31-7.35 (m, 1H), 7.12-7.15 (m, 1H), 3.99-4.03 (m, 1H), 1.80-1.96 (m, 2H), 1.36-1.55 (m, 2H), 1.20-1.28 (m, 4H), 0.81-0.87 (m, 3H).
Example 6
Preparation of 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(5,5,5-trifluoropentyl)benzonitrile (Compound 73)
Step A: Preparation of 2-bromo-6-methoxy-α-(4,4,4-trifluorobutyl)benzenemethanol
[0339] To magnesium metal shavings (0.254 g, 10.5 mmol, 1.5 eq.) in dry diethyl ether (2 mL) was added a crystal of iodine. The mixture was warmed to 35° C. and stirred for 15 min. To this mixture was added 1-bromo-4,4,4-trifluorobutane (1.30 mL, 10.5 mmol, 1.5 eq.) over 30 min. The reaction mixture continued to stir at 35° C. until all the magnesium was consumed. The resulting Grignard reagent was taken up by syringe. In separate reaction vial 2-bromo-6-methoxy-benzaldehyde (1.50 g, 6.97 mmol, 1.0 eq.) was dissolved in dry tetrahydrofuran (20 mL) and cooled to 0° C. The previously prepared Grignard reagent was added dropwise to the aldehyde. The reaction mixture was stirred at room temperature for 18 h. The reaction was quenched with 1 N hydrochloric acid and diluted with ethyl acetate. The organic layer was separated, dried and concentrated. The crude material was purified by column chromatography, eluting with a gradient of 0 to 20% ethyl acetate in hexanes to afford the desired product (2.15 g).
[0340] 1H NMR (500 MHz, CDCl3) δ 7.21-7.16 (m, 1H), 7.09 (t, 1H), 6.90-6.87 (m, 1H), 5.17-5.09 (m, 1H), 3.90 (s, 3H), 3.72 (d, 1H), 2.24-2.10 (m, 2H), 2.02-1.75 (m, 3H), 1.73-1.61 (m, 1H).
Step B: Preparation of 1-bromo-3-methoxy-2-(5,5,5-trifluoropentyl)benzene
[0341] To a stirred solution of 2-bromo-6-methoxy-α-(4,4,4-trifluorobutyl)benzenemethanol (i.e. the product of Step A, 2.15 g, 6.58 mmol, 1.0 eq.) in dry dichloromethane (22 mL) was added triethylsilane (4.20 mL, 26.3 mmol, 4.0 eq.). After stirring for 15 min. trifluoroacetic acid (2.01 mL, 26.3 mmol, 4.0 eq.) was added and the reaction was heated to 40° C. After 2 h, another 4.0 eq. of trifluoroacetic acid was added and the reaction mixture was stirred at 40° C. for another 18 h. The reaction was cooled to room temperature and concentrated onto Celite® diatomaceous earth filter aid for purification by column chromatography, eluting with a gradient of 0 to 10% ethyl acetate in hexanes to afford the desired product (1.82 g).
[0342] 1H NMR (500 MHz, CDCl3) δ 7.20-7.12 (m, 1H), 7.07-7.00 (m, 1H), 6.81-6.78 (m, 1H), 3.81 (s, 3H), 2.85-2.78 (m, 2H), 2.20-2.07 (m, 2H), 1.69-1.55 (m, 4H)
Step C: Preparation of 3-methoxy-2-(5,5,5-trifluoropentyl)benzonitrile
[0343] A solution of 1-bromo-3-methoxy-2-(5,5,5-trifluoropentyl)benzene (i.e. the product of Step B, 1.82 g, 5.86 mmol, 1.0 eq.) in N,N-dimethylformamide (20 mL) was deoxygenated by bubbling N2 through the reaction mixture for −10 min. To this mixture was added copper(I) cyanide (1.57 g, 17.6 mmol, 3.0 eq.). The reaction was refluxed at 160° C. under nitrogen for 18 h. The reaction was cooled to ambient temperature and filtered through a pad of Celite® diatomaceous earth filter aid. The filtrate was diluted with ethyl acetate and washed several times with water, then once with brine. The organic layer was dried and concentrated in vacuo. The crude material was purified by column chromatography, eluting with 0 to 30% ethyl acetate in hexanes to afford the desired product (1.38 g).
[0344] 1H NMR (500 MHz, CDCl3) δ 7.29-7.24 (m, 1H), 7.22-7.19 (m, 1H), 7.08-7.04 (m, 1H), 3.86 (s, 3H), 2.94-2.82 (m, 2H), 2.24-2.07 (m, 2H), 1.75-1.60 (m, 4H).
Step D: Preparation of 3-hydroxy-2-(5,5,5-trifluoropentyl)benzonitrile
[0345] A solution of 3-methoxy-2-(5,5,5-trifluoropentyl)benzonitrile (i.e. the product of Step C, 1.38 g, 5.36 mmol, 1.0 eq.) in dichloroethane (17 mL) was treated with boron tribromide (1.0 M in dichloromethane, 10.7 mL, 10.7 mmol, 2.0 eq.). The reaction mixture was heated to 60° C. for 18 h. The reaction was cooled to ambient temperature and quenched with saturated aqueous sodium bicarbonate. The organic phase was separated, dried and concentrated onto Celite® diatomaceous earth filter aid for purification by column chromatography, eluting with a gradient of 0 to 30% ethyl acetate in hexanes to afford the desired product (1.16 g).
[0346] 1H NMR (500 MHz, CDCl3) δ 7.25-7.21 (m, 1H), 7.19-7.15 (m, 1H), 6.98-6.95 (m, 1H), 5.05-5.01 (m, 1H), 2.92-2.86 (m, 2H), 2.20-2.08 (m, 2H), 1.78-1.62 (m, 4H).
Step E: Preparation of 3-[(5-chloro-2-pyrimidinyl)oxy]-2-(5,5,5-trifluoropentyl)benzonitrile
[0347] A mixture of 3-hydroxy-2-(5,5,5-trifluoropentyl)benzonitrile (i.e. the product of Step D, 1.16 g, 4.79 mmol, 1.0 eq.), 5-chloro-2-(methylsulfonyl)-pyrimidine (1.11 g, 5.75 mmol, 1.2 quiv) and potassium carbonate (0.993 g, 7.18 mmol, 1.5 eq.) in N,N-dimethylformamide (16 mL) was stirred at room temperature for 18 h. The reaction mixture was heavily diluted with ethyl acetate and washed several times with water, then once with brine. The organic phase was dried and concentrated onto Celite® diatomaceous filter aid for purification by column chromatography, eluting with a gradient of 0 to 30% ethyl acetate in hexanes to afford the desired product (1.65 g).
[0348] 1H NMR (500 MHz, CDCl3) δ 8.52-8.48 (m, 2H), 7.61-7.56 (m, 1H), 7.42-7.36 (m, 1H), 7.35-7.31 (m, 1H), 2.87-2.78 (m, 2H), 2.16-2.00 (m, 2H), 1.74-1.64 (m, 2H), 1.63-1.54 (m, 2H).
[0349] By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 585 can be prepared. The following abbreviations are used in the Tables which follow: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, i-Pr means isopropyl, Bu means butyl, c-Pr cyclopropyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, NHMe methylamino, —CN means cyano, S(O)Me means methylsulfinyl, and S(O)2Me means methylsulfonyl.
[0000]
[00001]
TABLE 1[00023]
[00024]
[00025]
[00026]
[00027]
R2 = F, (R3)m = 3-F, Z = O and A = A-3AR1R1butyl3,3,4,4,4-pentafluorobutoxytert-butyl2,2,3,3,3-pentafluoropropoxyethyl3,3,4,4-tetrafluorobutoxyhexyl2,2,3,3-tetrafluoropropoxyisobutyl3,3,3-trichloropropoxyisopentyl4,4,4-trifluorobutoxymethyl2,2,2-trifluoroethoxypentyl6,6,6-trifluorohexoxypropyl4,4,4-trifluoro-2-methyl-butoxybenzyl3,3,3-trifluoropropoxyallyl4-bromobut-3-ynoxy3-buten-1-y14-chlorobut-3-ynoxy3-methy1-2-buten-1-y13-chloroprop-2-ynoxy3-methy1-3-buten-1-y14,4-difluorobut-2-ynoxy4-methy1-3-penten-1-y15,5,5-trifluoropent-2-ynoxy3-penten-1-y15,5,5-trifluoropent-3-ynoxy3-butyn-1-y1cyclobutylmethoxy4-methy1-2-pentyn-1-y1cyclohexoxy3-pentyn-1-y1cyclopentoxy2-propyn-1-y12-cyclopropylethoxy5-hexyn-1-y1cyclopropylmethoxy4-pentyn-1-y1(2-bromo-2-chloro-cyclopropyl)methoxy3-bromopropyl(2,2-dibromocyclopropyl)methoxy3-chlorobutyl(2,2-dichloro-1-methyl-cyclopropyl)methoxy3-chloropropyl(3,3-difluorocyclobutyl)methoxy4,4-difluorobutyl2-(2,2-difluorocyclopropyl)ethoxy2,2-difluoroethyl(2,2-difluorocyclopropyl)methoxy3,3-difluoropropyl2-chloroethoxymethyl3,3,4,4,4-pentafluorobutyl2,3-dichloro-5-methoxy-pentyl2,2,3,3,3-pentafluoropropyl3,3-difluoro-5-methoxy-pentyl3,3,4,4-tetrafluorobutyl2-isopropoxyethyl2,2,3,3-tetrafluoropropyl2-methoxyethyl3,3,3-trichloropropyl5-methoxypentyl4,4,4-trifluorobutyl2-methoxypropyl2,2,2-trifluoroethyl1,1,2,2-tetrafluoroethoxymethyl6,6,6-trifluorohexyl2,2,2-trifluoroethoxymethyl4,4,4-trifluoro-2-methyl-butyl2-(trifluoromethoxy)ethyl3,3,3-trifluoropropyl2-isopropoxyethoxy4-bromo-3-buten-1-y14-methoxybutoxy2-chloroally12-methoxyethoxy3-chloroally12-methoxypropoxy3-chloro-3-buten-l-y14-cyanobutyl4-chloro-3-buten-l-y13-cyano-1,2-dimethyl-propyl5,5-difluoro-3-penten-l-y12-cyanoethyl4,4,4-trifluoro-2-buten-l-y13-cyano-2-methyl-propyl5,5,5-trifluoro-3-methy1-2-penten-l-y1cyanomethyl5,5,5-trifluoro-3-penten-l-y15-cyanopentyl4-bromo-3-butyn-1-y13-cyanopropyl3-butyn-l-y14-cyanobutoxy4-chloro-3-butyn-1-y13-cyano-1,2-dimethyl-propoxy3-chloro-2-propyn-l-y12-cyanoethoxy4,4-difluoro-2-butyn-l-y1cyanomethoxy5,5,5-trifluoro-1-methy1-2-pentyn-l-y13-cyano-2-methyl-propoxy5,5,5-trifluoro-2-pentyn-l-y15-cyanopentoxy5,5,5-trifluoro-3-pentyn-l-y13-cyanopropoxy2-cyclobutylethyl2-(cyanomethoxy)ethylcyclohexyl3-(cyanomethoxy)-2-methyl-propylcyclopentylmethylcyanomethoxymethyl2-cyclopropylethyl1,2-dimethyl-3-nitro-propyl3-cyclopropylpropyl4-hydroxybutyl(2,2-dimethylcyclopropyl)methyl3-hydroxy-1,2-dimethyl-propyl(1-methylcyclopropyl)methyl2-hydroxyethyl(2-methylcyclopentyl)methyl3-hydroxy-2-methyl-propyl(2-bromo-2-chloro-cyclopropyl)methylhydroxymethyl(2,2-dibromocyclopropyl)methyl5-hydroxypentyl2-(2,2-dichloro-1-methyl-cyclopropyl)ethyl3-hydroxypropyl(2,2-dichloro-1-methyl-cyclopropyl)methyl2-methyl-3-nitro-propyl2-(3,3-difluorocyclobutyl)ethyl4-nitrobutyl2-(2,2-difluorocyclopropyl)ethyl2-nitroethyl(2,2-difluorocyclopropyl)methylnitromethylbutyl(methyl)amino5-nitropentyldimethylamino3-nitropropylethyl(propyl)aminobutylthioisopropyl(methyl)aminotert-butylthioisopropyl(propyl)amino1,3-dimethylbutylthiomethyl(propyl)amino3,3-dimethylbutylthio2-chloroethyl(2,2,2-trifluoroethyl)aminoethylthio3-chloropropyl(methyl)aminoisopentylthiomethyl(2,2,2-trifluoroethyl)aminomethylthiomethyl(3,3,3-trifluoropropyl)aminopentylthiobutylaminopropylthio3-chloropropylamino3-bromopropylthioisopentylamino3-chlorobutylthiopropylamino3-chloropropylthio3,3,3-trifluoropropylamino2,2-difluoroethylthio1-piperidyl3,3,3-trichloropropylthio1-pyrrolidinyl4,4,4-trifluorobutylthiobutoxy2,2,2-trifluoroethylthiotert-butoxy6,6,6-trifluorohexylthio1,3-dimethylbutoxy3,3,3-trifluoropropylthio3,3-dimethylbutoxycyclobutylmethylthioethoxycyclohexylthiohexylcyclopentylthioisopentyloxy2-cyclopropylethylthiomethoxycyclopropylmethylthiopropoxy2-chloroethylthiomethylallyloxy2,3-dichloro-5-methylthio-pentyl3-butenoxy3,3-difluoro-5-methylthio-pentyl3-methy1-2-butenoxy2-isopropylthioethyl3-methy1-3-butenoxy2-methylthioethyl4-methyl-3-pentenoxy5-methylthiopentyl4-bromo-3-butenoxy2-methylthiopropyl2-chloroallyloxy1,1,2,2-tetrafluoroethylthiomethyl3-chloroallyloxy2,2,2-trifluoroethylthiomethyl3-chloro-3-butenoxy2-(trifluoromethylthio)ethyl4-chloro-3-butenoxybis(2-chloroethyl)aminooxy5,5-difluoro-3-pentenoxycyanomethoxy(methyl)amino4,4,4-trifluoro-2-butenoxydiethylamino(methyl)amino5,5,5-trifluoro-3-methy1-2-pentenoxyethoxy(methyl)amino5,5,5-trifluoro-3-pentenoxyethoxy(2,2,2-trifluoroethyl)amino3-butynoxyethylamino(methyl)amino]5-hexynoxyethylamino(2,2,2-trifluoroethyl]amino4-methyl-2-pentynoxyethyl(methyl)amino]-(2,2,2-trifluoroethy)amino3-pentynoxyethyl(3,3,3-trifluoropropyl)amino]-methyl-amino4-pentynoxyisobutyl(methylamino]oxy2-propynoxy2-methoxyethoxy(methyl)amino3-bromopropoxymethyl(propyl)amino]oxy3-chlorobutoxymethyl(2,2,2-trifluoroethoxy)amino3-chloropropoxymethyl(2,2,2-trifluoroethyl)amino]oxy4,4-difluorobutoxymethyl(3,3,3-trifluoropropoxy)amino2,2-difluoroethoxymethyl-(3,3,3-trifluoropropylamino)amino3,3-difluoropropoxy[0350] The present disclosure also includes Tables 2 through 292. Each Table is constructed in the same manner as Table 1 above, except that the row heading in Table 1 (i.e. “R2═F, (R3)m=3-F, Z═O and A=A-3A”) is replaced with the respective row heading shown below. For example, the first entry in Table 2 is a compound of Formula 1 wherein R2 is Cl, (R3)m is 3-F, Z is 0, A is A-3A and R1 is butyl. Tables 3 through 292 are constructed similarly.
[0000]
[00002]
Header RowTableR2(R3)mZA2Cl3-FOA-3A3Br3-FOA-3A4I3-FOA-3A5CF33-FOA-3A6OMe3-FOA-3A7Me3-FOA-3A8F3-ClOA-3A9Cl3-ClOA-3A10Br3-ClOA-3A11I3-ClOA-3A12CF33-ClOA-3A13OMe3-ClOA-3A14Me3-ClOA-3A15F3-BrOA-3A16Cl3-BrOA-3A17Br3-BrOA-3A18I3-BrOA-3A19CF33-BrOA-3A20OMe3-BrOA-3A21Me3-BrOA-3A22F3-IOA-3A23Cl3-IOA-3A24Br3-IOA-3A25I3-IOA-3A26CF33-IOA-3A27OMe3-IOA-3A28Me3-IOA-3A29F3-CNOA-3A30Cl3-CNOA-3A31Br3-CNOA-3A32I3-CNOA-3A33CF33-CNOA-3A34OMe3-CNOA-3A35Me3-CNOA-3A36F3-CF3OA-3A37Cl3-CF3OA-3A38Br3-CF3OA-3A39I3-CF3OA-3A40CF33-CF3OA-3A41OMe3-CF3OA-3A42Me3-CF3OA-3A43F4-ClOA-3A44Cl4-ClOA-3A45Br4-ClOA-3A46I4-ClOA-3A47CF34-ClOA-3A48OMe4-ClOA-3A49Me4-ClOA-3A50F5-ClOA-3A51Cl5-ClOA-3A52Br5-ClOA-3A53I5-ClOA-3A54CF35-ClOA-3A55OMe5-ClOA-3A56Me5-ClOA-3A57F6-ClOA-3A58Cl6-ClOA-3A59Br6-ClOA-3A60I6-ClOA-3A61CF36-ClOA-3A62OMe6-ClOA-3A63Me6-ClOA-3A64F3-Br, 4-FOA-3A65Cl3-Br, 4-FOA-3A66Br3-Br, 4-FOA-3A67I3-Br, 4-FOA-3A68CF33-Br, 4-FOA-3A69OMe3-Br, 4-FOA-3A70Me3-Br, 4-FOA-3A71F3-F, 4-FOA-3A72Cl3-F, 4-FOA-3A73Br3-F, 4-FOA-3A74I3-F, 4-FOA-3A75CF33-F, 4-FOA-3A76OMe3-F, 4-FOA-3A77Me3-F, 4-FOA-3A78F3-Cl, 4-FOA-3A79Cl3-Cl, 4-FOA-3A80Br3-Cl, 4-FOA-3A81I3-Cl, 4-FOA-3A82CF33-Cl, 4-FOA-3A83OMe3-Cl, 4-FOA-3A84Me3-Cl, 4-FOA-3A85F3-BrSA-3A86Cl3-BrSA-3A87Br3-BrSA-3A88I3-BrSA-3A89CF33-BrSA-3A90OMe3-BrSA-3A91Me3-BrSA-3A92F3-ClSA-3A93Cl3-ClSA-3A94Br3-ClSA-3A95I3-ClSA-3A96CF33-ClSA-3A97OMe3-ClSA-3A98Me3-ClSA-3A99Cl3-FOA-3B100Br3-FOA-3B101I3-FOA-3B102CF33-FOA-3B103OMe3-FOA-3B104Me3-FOA-3B105F3-ClOA-3B106Cl3-ClOA-3B107Br3-ClOA-3B108I3-ClOA-3B109CF33-ClOA-3B110OMe3-ClOA-3B111Me3-ClOA-3B112F3-BrOA-3B113Cl3-BrOA-3B114Br3-BrOA-3B115I3-BrOA-3B116CF33-BrOA-3B117OMe3-BrOA-3B118Me3-BrOA-3B119F3-IOA-3B120Cl3-IOA-3B121Br3-IOA-3B122I3-IOA-3B123CF33-IOA-3B124OMe3-IOA-3B125Me3-IOA-3B126F3-CNOA-3B127Cl3-CNOA-3B128Br3-CNOA-3B129I3-CNOA-3B130CF33-CNOA-3B131OMe3-CNOA-3B132Me3-CNOA-3B133F3-CF3OA-3B134Cl3-CF3OA-3B135Br3-CF3OA-3B136I3-CF3OA-3B137CF33-CF3OA-3B138OMe3-CF3OA-3B139Me3-CF3OA-3B140F4-ClOA-3B141Cl4-ClOA-3B142Br4-ClOA-3B143I4-ClOA-3B144CF34-ClOA-3B145OMe4-ClOA-3B146Me4-ClOA-3B147F5-ClOA-3B148Cl5-ClOA-3B149Br5-ClOA-3B150I5-ClOA-3B151CF35-ClOA-3B152OMe5-ClOA-3B153Me5-ClOA-3B154F6-ClOA-3B155Cl6-ClOA-3B156Br6-ClOA-3B157I6-ClOA-3B158CF36-ClOA-3B159OMe6-ClOA-3B160Me6-ClOA-3B161F3-Br, 4-FOA-3B162Cl3-Br, 4-FOA-3B163Br3-Br, 4-FOA-3B164I3-Br, 4-FOA-3B165CF33-Br, 4-FOA-3B166OMe3-Br, 4-FOA-3B167Me3-Br, 4-FOA-3B168F3-F, 4-FOA-3B169Cl3-F, 4-FOA-3B170Br3-F, 4-FOA-3B171I3-F, 4-FOA-3B172CF33-F, 4-FOA-3B173OMe3-F, 4-FOA-3B174Me3-F, 4-FOA-3B175F3-Cl, 4-FOA-3B176Cl3-Cl, 4-FOA-3B177Br3-Cl, 4-FOA-3B178I3-Cl, 4-FOA-3B179CF33-Cl, 4-FOA-3B180OMe3-Cl, 4-FOA-3B181Me3-Cl, 4-FOA-3B182F3-BrSA-3B183Cl3-BrSA-3B184Br3-BrSA-3B185I3-BrSA-3B186CF33-BrSA-3B187OMe3-BrSA-3B188Me3-BrSA-3B189F3-ClSA-3B190Cl3-ClSA-3B191Br3-ClSA-3B192I3-ClSA-3B193CF33-ClSA-3B194OMe3-ClSA-3B195Me3-ClSA-3B196Cl3-FOA-1197Br3-FOA-1198I3-FOA-1199CF33-FOA-1200OMe3-FOA-1201Me3-FOA-1202F3-ClOA-1203Cl3-ClOA-1204Br3-ClOA-1205I3-ClOA-1206CF33-ClOA-1207OMe3-ClOA-1208Me3-ClOA-1209F3-BrOA-1210Cl3-BrOA-1211Br3-BrOA-1212I3-BrOA-1213CF33-BrOA-1214OMe3-BrOA-1215Me3-BrOA-1216F3-IOA-1217Cl3-IOA-1218Br3-IOA-1219I3-IOA-1220CF33-IOA-1221OMe3-IOA-1222Me3-IOA-1223F3-CNOA-1224Cl3-CNOA-1225Br3-CNOA-1226I3-CNOA-1227CF33-CNOA-1228OMe3-CNOA-1229Me3-CNOA-1230F3-CF3OA-1231Cl3-CF3OA-1232Br3-CF3OA-1233I3-CF3OA-1234CF33-CF3OA-1235OMe3-CF3OA-1236Me3-CF3OA-1237F4-ClOA-1238Cl4-ClOA-1239Br4-ClOA-1240I4-ClOA-1241CF34-ClOA-1242OMe4-ClOA-1243Me4-ClOA-1244F5-ClOA-1245Cl5-ClOA-1246Br5-ClOA-1247I5-ClOA-1248CF35-ClOA-1249OMe5-ClOA-1250Me5-ClOA-1251F6-ClOA-1252Cl6-ClOA-1253Br6-ClOA-1254I6-ClOA-1255CF36-ClOA-1256OMe6-ClOA-1257Me6-ClOA-1258F3-Br, 4-FOA-1259Cl3-Br, 4-FOA-1260Br3-Br, 4-FOA-1261I3-Br, 4-FOA-1262CF33-Br, 4-FOA-1263OMe3-Br, 4-FOA-1264Me3-Br, 4-FOA-1265F3-F, 4-FOA-1266Cl3-F, 4-FOA-1267Br3-F, 4-FOA-1268I3-F, 4-FOA-1269CF33-F, 4-FOA-1270OMe3-F, 4-FOA-1271Me3-F, 4-FOA-1272F3-Cl, 4-FOA-1273Cl3-Cl, 4-FOA-1274Br3-Cl, 4-FOA-1275I3-Cl, 4-FOA-1276CF33-Cl, 4-FOA-1277OMe3-Cl, 4-FOA-1278Me3-Cl, 4-FOA-1279F3-BrSA-1280Cl3-BrSA-1281Br3-BrSA-1282I3-BrSA-1283CF33-BrSA-1284OMe3-BrSA-1285Me3-BrSA-1286F3-ClSA-1287Cl3-ClSA-1288Br3-ClSA-1289I3-ClSA-1290CF33-ClSA-1291OMe3-ClSA-1292Me3-ClSA-1[0000]
[00003]
TABLE 293[00028]
R2 = F, (R3)m = 3-F and Z = OR1R1butylsulfinyl3,3-difluoropropoxytert-butylsulfinylethylsulfonyl1,3-dimethylbutylsulfinylisopentylsulfonyl3,3-dimethylbutylsulfinylmethylsulfonylethylsulfinylpentylsulfonylisopentylsulfinylpropylsulfonylmethylsulfinyl3-bromopropylsulfonylpentylsulfinyl3-chlorobutylsulfonylpropylsulfinyl3-chloropropylsulfonyl3-bromopropylsulfinyl2,2-difluoroethylsulfonyl3-chlorobutylsulfinyl3,3,3-trifluoropropylsulfonyl3-chloropropylsulfinyl3,3,3-trichloropropylsulfonyl2,2-difluoroethylsulfinyl4,4,4-trifluorobutylsulfonyl3,3,3-trifluoropropylsulfinyl2,2,2-trifluoroethylsulfonyl3,3,3-trichloropropylsulfinyl6,6,6-trifluorohexylsulfonyl4,4,4-trifluorobutylsulfinylcyclobutylmethylsulfonyl2,2,2-trifluoroethylsulfinylcyclohexylsulfonyl6,6,6-trifluorohexylsulfinylcyclopentylsulfonyl1,3-dimethylbutylsulfonyl2-cyclopropylethylsulfonyl3,3-dimethylbutylsulfonylcyclopropylmethylsulfonyl[0351] The present disclosure also includes Tables 294 through 390. Each Table is constructed in the same manner as Table 293 above, except that the row heading in Table 293 (i.e. “R2═F, (R3)m=3-F and Z═O”) is replaced with the respective row heading shown below. For example, the header row in Table 294 is “R2═Cl, (R3)m=3-F and Z═O” and the first entry in Table 294 is a compound of Formula 1 wherein R1=butylsulfinyl, R2═Cl, (R3)m=3-F and Z═O. Tables 295 through 390 are constructed similarly.
[0000]
[00004]
Header RowTableR2(R3)mZ294Cl3-FO295Br3-FO296I3-FO297CF33-FO298OMe3-FO299Me3-FO300F3-ClO301Cl3-ClO302Br3-ClO303I3-ClO304CF33-ClO305OMe3-ClO306Me3-ClO307F3-BrO308Cl3-BrO309Br3-BrO310I3-BrO311CF33-BrO312OMe3-BrO313Me3-BrO314F3-IO315Cl3-IO316Br3-IO317I3-IO318CF33-IO319OMe3-IO320Me3-IO321F3-CNO322Cl3-CNO323Br3-CNO324I3-CNO325CF33-CNO326OMe3-CNO327Me3-CNO328F3-CF3O329Cl3-CF3O330Br3-CF3O331I3-CF3O332CF33-CF3O333OMe3-CF3O334Me3-CF3O335F4-ClO336Cl4-ClO337Br4-ClO338I4-ClO339CF34-ClO340OMe4-ClO341Me4-ClO342F5-ClO343Cl5-ClO344Br5-ClO345I5-ClO346CF35-ClO347OMe5-ClO348Me5-ClO349F6-ClO350Cl6-ClO351Br6-ClO352I6-ClO353CF36-ClO354OMe6-ClO355Me6-ClO356F3-Br, 4-FO357Cl3-Br, 4-FO358Br3-Br, 4-FO359I3-Br, 4-FO360CF33-Br, 4-FO361OMe3-Br, 4-FO362Me3-Br, 4-FO363F3-F, 4-FO364Cl3-F, 4-FO365Br3-F, 4-FO366I3-F, 4-FO367CF33-F, 4-FO368OMe3-F, 4-FO369Me3-F, 4-FO370F3-Cl, 4-FO371Cl3-Cl, 4-FO372Br3-Cl, 4-FO373I3-Cl, 4-FO374CF33-Cl, 4-FO375OMe3-Cl, 4-FO376Me3-Cl, 4-FO377F3-BrS378Cl3-BrS379Br3-BrS380I3-BrS381CF33-BrS382OMe3-BrS383Me3-BrS384F3-ClS385Cl3-ClS386Br3-ClS387I3-ClS388CF33-ClS389OMe3-ClS390Me3-ClS[0000]
[00005]
TABLE 391[00029]
[00030]
[00031]
[00032]
[00033]
R2 = F, (R3)m = 3-F and Z = OAAA = A-4; R4 = 3-bromopropylA = A-5; R5 = 4-chloro-3-butyn-1-ylA = A-4; R4 = tert-butyl)A = A-5; R5 = 3-chloro-2-propyn-1-ylA = A-4; R4 = 3-chlorobutylA = A-5; R5 = 4,4-difluoro-2-butyn-1-ylA = A-4; R4 = 3-chloropropylA = A-5; R5 = 5,5,5-trifluoro-1-methyl-2-pentyn-1-ylA = A-4; R4 = 4,4-difluorobutylA = A-5; R5 = 5,5,5-trifluoro-2-pentyn-1-ylA = A-4; R4 = 2,2-difluoroethylA = A-5; R5 = 5,5,5-trifluoro-3-pentyn-1-ylA = A-4; R4 = 3,3-difluoropropylA = A-5; R5 = 2-cyclobutylethylA = A-4; R4 = ethylA = A-5; R5 = cyclohexylA = A-4; R4 = hexylA = A-5; R5 = cyclopentylmethylA = A-4; R4 = isobutylA = A-5; R5 = 2-cyclopropylethylA = A-4; R4 = isopentylA = A-5; R5 = 3-cyclopropylpropylA = A-4; R4 = methylA = A-5; R5 = 2,2-dimethylcyclopropyl)methylA = A-4; R4 = 3,3,4,4,4-pentafluorobutylA = A-5; R5 = 1-methylcyclopropyl)methylA = A-4; R4 = 2,2,3,3,3-pentafluoropropylA = A-5; R5 = 2-methylcyclopentyl)methylA = A-4; R4 = pentylA = A-5; R5 = (2-bromo-2-chloro-cyclopropyl)methylA = A-4; R4 = propylA = A-5; R5 = (2,2-dibromocyclopropyl)methylA = A-4; R4 = 3,3,4,4-tetrafluorobutylA = A-5; R5 = 2-(2,2-dichloro-1-methyl-1-cyclopropyl)ethylA = A-4; R4 = 2,2,3,3-tetrafluoropropylA = A-5; R5 = (2,2-dichloro-1-methyl-cyclopropyl)methylA = A-4; R4 = 3,3,3-trichloropropylA = A-5; R5 = 2-(3,3-difluorocyclobutyl)ethylA = A-4; R4 = 4,4,4-trifluorobutylA = A-5; R5 = 2-(2,2-difluorocyclopropyl)ethylA = A-4; R4 = 2,2,2-trifluoroethylA = A-5; R5 = (2,2-difluorocyclopropyl)methylA = A-4; R4 = 6,6,6-trifluorohexylA = A-5; R5 = 2-chloroethoxymethylA = A-4; R4 = 4,4,4-trifluoro-2-methyl-butylA = A-5; R5 = 2,3-dichloro-5-methoxy-pentylA = A-4; R4 = 3,3,3-trifluoropropylA = A-5; R5 = 3,3-difluoro-5-methoxy-pentylA = A-4; R4 = 3-bromopropylA = A-5; R5 = 2-isopropoxyethylA = A-5; R5 = butylA = A-5; R5 = 2-methoxyethylA = A-5; R5 = tert-butylA = A-5; R5 = 5-methoxypentylA = A-5; R5 = ethylA = A-5; R5 = 2-methoxypropylA = A-5; R5 = hexylA = A-5; R5 = 1,1,2,2-tetrafluoromethoxymethylA = A-5; R5 = isobutylA = A-5; R5 = 2,2,2-trifluoroethoxymethylA = A-5; R5 = isopentylA = A-5; R5 = 2-(trifluoromethoxy)ethylA = A-5; R5 = pentylA = A-5; R5 = 4-cyanobutylA = A-5; R5 = propylA = A-5; R5 = 3-cyano-1,2-dimethyl-propylA = A-5; R5 = benzyl)A = A-5; R5 = 2-cyanoethylA = A-5; R5 = allylA = A-5; R5 = 3-cyano-2-methyl-propylA = A-5; R5 = 3-buten-1-ylA = A-5; R5 = cyanomethylA = A-5; R5 = 3-methyl-2-lbuten-1-ylA = A-5; R5 = 5-cyanopentylA = A-5; R5 = 3-methyl-3-buten-1-ylA = A-5; R5 = 3-cyanopropylA = A-5; R5 = 4-methyl-3-penten-1-ylA = A-5; R5 = 2-(cyanomethoxy)ethylA = A-5; R5 = 3-penten-1-ylA = A-5; R5 = 3-(cyanomethoxy)-2-methyl-propylA = A-5; R5 = 3-butyn-1-ylA = A-5; R5 = cyanomethoxymethylA = A-5; R5 = 4-methyl-2-pentyn-1-ylA = A-5; R5 = 1,2-dimethyl-3-nitro-propylA = A-5; R5 = 3-pentyn-1-ylA = A-5; R5 = 4-hydroxybutylA = A-5; R5 = 2-propyn-1-ylA = A-5; R5 = 3-hydroxy-1,2-dimethyl-propylA = A-5; R5 = 5-hexyn-1-ylA = A-5; R5 = 3-hydroxy-2-methyl-propylA = A-5; R5 = 4-pentyn-1-ylA = A-5; R5 = hydroxymethylA = A-5; R5 = 3-bromopropylA = A-5; R5 = 5-hydroxypentylA = A-5; R5 = 3-chlorobutylA = A-5; R5 = 3-hydroxypropylA = A-5; R5 = 3-chloropropylA = A-5; R5 = 2-methyl-3-nitro-propylA = A-5; R5 = 4,4-difluorobutylA = A-5; R5 = 4-nitrobutylA = A-5; R5 = 2,2-difluoroethylA = A-5; R5 = 2-nitroethylA = A-5; R5 = 3,3-difluoropropylA = A-5; R5 = nitromethylA = A-5; R5 = 3,3,4,4,4-pentafluorobutylA = A-5; R5 = 5-nitropentylA = A-5; R5 = 2,2,3,3,3-pentafluoropropylA = A-5; R5 = 3-nitropropylA = A-5; R5 = 3,3,4,4-tetrafluorobutylA = A-5; R5 = 2-chloroethylthiomethylA = A-5; R5 = 2,2,3,3-tetrafluoropropylA = A-5; R5 = 2,3-dichloro-5-methylthio-pentylA = A-5; R5 = 3,3,3-trichloropropylA = A-5; R5 = 3,3-difluoro-5-methylthio-pentylA = A-5; R5 = 4,4,4-trifluorobutylA = A-5; R5 = 2-isopropylthioethylA = A-5; R5 = 2,2,2-trifluoroethylA = A-5; R5 = 2-methylthioethylA = A-5; R5 = 6,6,6-trifluorohexylA = A-5; R5 = 5-methylthiopentylA = A-5; R5 = 4,4,4-trifluoro-2-methyl-butylA = A-5; R5 = 2-methylthiopropylA = A-5; R5 = 3,3,3-trifluoropropylA = A-5; R5 = 1,1,2,2-tetrafluoroethylthiomethylA = A-5; R5 = 4-bromo-3-buten-1-ylA = A-5; R5 = 2,2,2-trifluoroethylthiomethylA = A-5; R5 = 2-chloroallylA = A-5; R5 = 2-(trifluoromethylthio)ethylA = A-5; R5 = 3-chloroallylA = A-6; R6a = Me); R6b = butylA = A-5; R5 = 3-chloro-3-buten-1-ylA = A-6; R6a = Me; R6b = tert-butylA = A-5; R5 = 4-chloro-3-buten-1-ylA = A-6; R6a = Me; +Rhu 6b = ethylA = A-5; R5 = 5,5-difluoro-3-penten-1-ylA = A-6; R6a = Me; R6b = IsobutylA = A-5; R5 = 4,4,4-trifluoro-2-buten-1-ylA = A-6; R6a = Me; R6b = propylA = A-5; R5 = 5,5,5-trifluoro-3-methyl-2-A = A-6; R6a = ethyl)(; R6b = ethylpenten-1-ylA = A-5; R5 = 5,5,5-trifluoro-3-penten-1-ylA = A-6; R6a = Me; R6b = 3,3,3-trifluoropropylA = A-5; R5 = 4-bromo-3-butyn-1-ylA = A-6; R6a = Me; R6b = 2,2,3,3,3-pentafluoropropylA = A-5; R5 = 3-butyn-1-ylA = A-6; R6a = 3,3,3-trifluoropropyl; R6b = 3,3,3-trifluoropropylA = A-7; R15 = isopentylA = A-7; R15 = ethylA = A-7; R15 = pentylA = A-7; R15 = hexylA = A-7; R15 = propylA = A-7; R15 = isobutylA = A-7; R15 = HA = A-7; R15 = methyl[0352] The present disclosure also includes Tables 392 through 585. Each Table is constructed in the same manner as Table 391 above, except that the row heading in Table 391 (i.e. “R2═F, (R3)m=3-F and Z═O”) is replaced with the respective row heading shown below. For example, the header row in Table 392 is “R2═Cl, (R3)m=3-F and Z═O” and the first entry in Table 392 is a compound of Formula 1 wherein R1=3-bromopropyl, R2═Cl, (R3)m=3-F and Z═O. Tables 392 through 585 are constructed similarly.
[0000]
[00006]
Header RowTableR2(R3)mZ392Cl3-FO393Br3-FO394I3-FO395CF33-FO396OMe3-FO397Me3-FO398F3-ClO399Cl3-ClO400Br3-ClO401I3-ClO402CF33-ClO403OMe3-ClO404Me3-ClO405F3-BrO406Cl3-BrO407Br3-BrO408I3-BrO409CF33-BrO410OMe3-BrO411Me3-BrO412F3-IO413Cl3-IO414Br3-IO415I3-IO416CF33-IO417OMe3-IO418Me3-IO419F3-CNO420Cl3-CNO421Br3-CNO422I3-CNO423CF33-CNO424OMe3-CNO425Me3-CNO426F3-CF3O427Cl3-CF3O428Br3-CF3O429I3-CF3O430CF33-CF3O431OMe3-CF3O432Me3-CF3O433F4-ClO434Cl4-ClO435Br4-ClO436I4-ClO437CF34-ClO438OMe4-ClO439Me4-ClO440F5-ClO441Cl5-ClO442Br5-ClO443I5-ClO444CF35-ClO445OMe5-ClO446Me5-ClO447F6-ClO448Cl6-ClO449Br6-ClO450I6-ClO451CF36-ClO452OMe6-ClO453Me6-ClO454F3-Br, 4-FO455Cl3-Br, 4-FO456Br3-Br, 4-FO457I3-Br, 4-FO458CF33-Br, 4-FO459OMe3-Br, 4-FO460Me3-Br, 4-FO461F3-F, 4-FO462Cl3-F, 4-FO463Br3-F, 4-FO464I3-F, 4-FO465CF33-F, 4-FO466OMe3-F, 4-FO467Me3-F, 4-FO468F3-Cl, 4-FO469Cl3-Cl, 4-FO470Br3-Cl, 4-FO471I3-Cl, 4-FO472CF33-Cl, 4-FO473OMe3-Cl, 4-FO474Me3-Cl, 4-FO475F3-BrS476Cl3-BrS477Br3-BrS478I3-BrS479CF33-BrS480OMe3-BrS481Me3-BrS482F3-ClS483Cl3-ClS484Br3-ClS485I3-ClS486CF33-ClS487OMe3-ClS488Me3-ClS489Cl3-FO490Br3-FO491I3-FO492CF33-FO493OMe3-FO494Me3-FO495F3-ClO496Cl3-ClO497Br3-ClO498I3-ClO499CF33-ClO500OMe3-ClO501Me3-ClO502F3-BrO503Cl3-BrO504Br3-BrO505I3-BrO506CF33-BrO507OMe3-BrO508Me3-BrO509F3-IO510Cl3-IO511Br3-IO512I3-IO513CF33-IO514OMe3-IO515Me3-IO516F3-CNO517Cl3-CNO518Br3-CNO519I3-CNO520CF33-CNO521OMe3-CNO522Me3-CNO523F3-CF3O524Cl3-CF3O525Br3-CF3O526I3-CF3O527CF33-CF3O528OMe3-CF3O529Me3-CF3O530F4-ClO531Cl4-ClO532Br4-ClO533I4-ClO534CF34-ClO535OMe4-ClO536Me4-ClO537F5-ClO538Cl5-ClO539Br5-ClO540I5-ClO541CF35-ClO542OMe5-ClO543Me5-ClO544F6-ClO545Cl6-ClO546Br6-ClO547I6-ClO548CF36-ClO549OMe6-ClO550Me6-ClO551F3-Br, 4-FO552Cl3-Br, 4-FO553Br3-Br, 4-FO554I3-Br, 4-FO555CF33-Br, 4-FO556OMe3-Br, 4-FO557Me3-Br, 4-FO558F3-F, 4-FO559Cl3-F, 4-FO560Br3-F, 4-FO561I3-F, 4-FO562CF33-F, 4-FO563OMe3-F, 4-FO564Me3-F, 4-FO565F3-Cl, 4-FO566Cl3-Cl, 4-FO567Br3-Cl, 4-FO568I3-Cl, 4-FO569CF33-Cl, 4-FO570OMe3-Cl, 4-FO571Me3-Cl, 4-FO572F3-BrS573Cl3-BrS574Br3-BrS575I3-BrS576CF33-BrS577OMe3-BrS578Me3-BrS579F3-ClS580Cl3-ClS581Br3-ClS582I3-ClS583CF33-ClS584OMe3-ClS585Me3-ClS[0353] The present disclosure also includes Tables 586 through 684. Each Table is constructed in the same manner as Table 1 above, except that the row heading in Table 1 (i.e. “R2═F, (R3)m=3-F, Z═O and A=A-4”) is replaced with the respective row heading shown below. For example, the first entry in Table 586 is a compound of Formula 1 wherein R2 is Cl, (R3)m is 3-F, Z is 0, A is A-3A and R1 is butyl. Tables 587 through 684 are constructed similarly.
[0000]
[00007]
Header RowTableR2(R3)mZA586F3-FOA-4587F3-FOA-1588F3-FOA-2589Cl3-FOA-2590Br3-FOA-2591I3-FOA-2592CF33-FOA-2593OMe3-FOA-2594Me3-FOA-2595F3-ClOA-2596Cl3-ClOA-2597Br3-ClOA-2598I3-ClOA-2599CF33-ClOA-2600OMe3-ClOA-2601Me3-ClOA-2602F3-BrOA-2603Cl3-BrOA-2604Br3-BrOA-2605I3-BrOA-2606CF33-BrOA-2607OMe3-BrOA-2608Me3-BrOA-2609F3-IOA-2610Cl3-IOA-2611Br3-IOA-2612I3-IOA-2613CF33-IOA-2614OMe3-IOA-2615Me3-IOA-2616F3-CNOA-2617Cl3-CNOA-2618Br3-CNOA-2619I3-CNOA-2620CF33-CNOA-2621OMe3-CNOA-2622Me3-CNOA-2623F3-CF3OA-2624Cl3-CF3OA-2625Br3-CF3OA-2626I3-CF3OA-2627CF33-CF3OA-2628OMe3-CF3OA-2629Me3-CF3OA-2630F4-ClOA-2631Cl4-ClOA-2632Br4-ClOA-2633I4-ClOA-2634CF34-ClOA-2635OMe4-ClOA-2636Me4-ClOA-2637F5-ClOA-2638Cl5-ClOA-2639Br5-ClOA-2640I5-ClOA-2641CF35-ClOA-2642OMe5-ClOA-2643Me5-ClOA-2644F6-ClOA-2645Cl6-ClOA-2646Br6-ClOA-2647I6-ClOA-2648CF36-ClOA-2649OMe6-ClOA-2650Me6-ClOA-2651F3-Br, 4-FOA-2652Cl3-Br, 4-FOA-2653Br3-Br, 4-FOA-2654I3-Br, 4-FOA-2655CF33-Br, 4-FOA-2656OMe3-Br, 4-FOA-2657Me3-Br, 4-FOA-2658F3-F, 4-FOA-2659Cl3-F, 4-FOA-2660Br3-F, 4-FOA-2661I3-F, 4-FOA-2662CF33-F, 4-FOA-2663OMe3-F, 4-FOA-2664Me3-F, 4-FOA-2665F3-Cl, 4-FOA-2666Cl3-Cl, 4-FOA-2667Br3-Cl, 4-FOA-2668I3-Cl, 4-FOA-2669CF33-Cl, 4-FOA-2670OMe3-Cl, 4-FOA-2671Me3-Cl, 4-FOA-2672F3-BrSA-2673Cl3-BrSA-2674Br3-BrSA-2675I3-BrSA-2676CF33-BrSA-2677OMe3-BrSA-2678Me3-BrSA-2679F3-ClSA-2680Cl3-ClSA-2681Br3-ClSA-2682I3-ClSA-2683CF33-ClSA-2684OMe3-ClSA-2[0354] A compound of this invention will generally be used as a herbicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
[0355] Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
[0356] The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
[0357] Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting.
[0358] The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
[0000]
[00008]
Weight PercentActiveSurfac-IngredientDiluenttantWater-Dispersible and Water-soluble0.001-900-99.9990-15Granules, Tablets and PowdersOil Dispersions, Suspensions, 1-5040-99 0-50Emulsions, Solutions (includingEmulsifiable Concentrates)Dusts 1-2570-99 0-5 Granules and Pellets0.001-995-99.9990-15High Strength Compositions 90-990-10 0-2[0359] Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.
[0360] Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
[0361] The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
[0362] Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
[0363] Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as NN-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.
[0364] Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
[0365] Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
[0366] Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
[0367] The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 μm can be wet milled using media mills to obtain particles with average diameters below 3 μm. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. Pat. No. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 μm range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. Nos. 4,144,050, 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.
[0368] For further information regarding the art of formulation, see T. S. Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture” in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments informulation technology, PJB Publications, Richmond, U K, 2000.
[0369] In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Table A. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated.
Example A
[0370]
[0000]
[00009]
High Strength ConcentrateCompound 198.5%silica aerogel0.5%synthetic amorphous fine silica1.0%Example B
[0371]
[0000]
[00010]
Wettable PowderCompound 165.0%dodecylphenol polyethylene glycol ether2.0%sodium ligninsulfonate4.0%sodium silicoaluminate6.0%montmorillonite (calcined)23.0%Example C
[0372]
[0000]
[00011]
GranuleCompound 110.0%attapulgite granules (low volatile matter, 0.71/0.30 mm;90.0%U.S.S. No. 25-50 sieves)Example D
[0373]
[0000]
[00012]
Extruded PelletCompound 125.0%anhydrous sodium sulfate10.0%crude calcium ligninsulfonate5.0%sodium alkylnaphthalenesulfonate1.0%calcium/magnesium bentonite59.0%Example E
[0374]
[0000]
[00013]
Emulsifiable ConcentrateCompound 110.0%polyoxyethylene sorbitol hexoleate20.0%C6-C10 fatty acid methyl ester70.0%Example F
Microemulsion
[0375]
[0000]
[00014]
Compound 15.0%polyvinylpyrrolidone-vinyl acetate copolymer30.0%alkylpolyglycoside30.0%glyceryl monooleate15.0%water20.0%Example G
Suspension Concentrate
[0376]
[0000]
[00015]
Compound 1 35%butyl polyoxyethylene/polypropylene block copolymer4.0%stearic acid/polyethylene glycol copolymer1.0%styrene acrylic polymer1.0%xanthan gum0.1%propylene glycol5.0%silicone based defoamer0.1%1,2-benzisothiazolin-3-one0.1%water53.7%Example H
Emulsion in Water
[0377]
[0000]
[00016]
Compound 110.0%butyl polyoxyethylene/polypropylene block copolymer4.0%stearic acid/polyethylene glycol copolymer1.0%styrene acrylic polymer1.0%xanthan gum0.1%propylene glycol5.0%silicone based defoamer0.1%1,2-benzisothiazolin-3-one0.1%aromatic petroleum based hydrocarbon20.0water58.7%Example I
[0378]
[0000]
[00017]
Oil DispersionCompound 125%polyoxyethylene sorbitol hexaoleate15%organically modified bentonite clay2.5% fatty acid methyl ester57.5%[0379] The present disclosure also includes Examples A through I above except “Compound 1” is replaced with “Compound 2”, “Compound 3”, “Compound 4”, “Compound 5”, “Compound 6”, “Compound 7”, “Compound 8”, “Compound 9”, “Compound 10”, “Compound 11”, “Compound 12”, “Compound 13”, “Compound 14”, “Compound 15”, “Compound 16”, “Compound 17”, “Compound 18”, “Compound 19”, “Compound 20”, “Compound 21”, “Compound 22”, “Compound 23”, “Compound 24”, “Compound 25”, “Compound 26”, “Compound 27”, “Compound 28”, “Compound 29”, “Compound 30”, “Compound 31”, “Compound 32”, “Compound 33”, “Compound 34”, “Compound 35”, “Compound 36”, “Compound 37”, “Compound 38”, “Compound 39”, “Compound 40”, “Compound 41”, “Compound 42”, “Compound 43”, “Compound 44”, “Compound 45”, “Compound 46”, “Compound 47”, “Compound 48”, “Compound 49”, “Compound 50”, “Compound 51”, “Compound 52”, “Compound 53”, “Compound 54”, “Compound 55”, “Compound 56”, “Compound 57”, “Compound 58”, “Compound 59”, “Compound 60”, “Compound 61”, “Compound 62”, “Compound 63”, “Compound 64”, “Compound 65”, “Compound 66”, “Compound 67”, “Compound 68”, “Compound 69”, “Compound 70”, “Compound 71”, “Compound 72”, “Compound 73”, “Compound 74”, “Compound 75”, “Compound 76”, “Compound 77”, “Compound 78”, “Compound 79”, “Compound 80”, “Compound 81”, “Compound 82”, “Compound 83”, “Compound 84”, “Compound 85”, “Compound 86”, “Compound 87”, “Compound 88”, “Compound 89”, “Compound 90”, “Compound 91”, “Compound 92”, “Compound 93”, “Compound 94”, “Compound 95”, “Compound 96”, “Compound 97”, “Compound 98”, “Compound 99”, “Compound 100”, “Compound 101”, “Compound 102”, “Compound 103”, “Compound 104”, “Compound 104”, “Compound 106”, “Compound 107”, “Compound 108”, “Compound 109”, “Compound 110”, “Compound 111”, “Compound 112”, “Compound 113”, “Compound 114”, “Compound 115”, “Compound 116”, “Compound 117”, “Compound 118”, “Compound 119”, “Compound 120”, “Compound 121”, “Compound 122”, “Compound 123”, “Compound 124”, “Compound 125”, “Compound 126”, “Compound 127”, “Compound 128”, “Compound 129”, “Compound 130”, “Compound 131”, “Compound 132”, “Compound 133”, “Compound 134”, “Compound 135”, “Compound 136”, “Compound 137”, “Compound 138”, “Compound 139”, “Compound 140”, “Compound 141”, “Compound 142”, “Compound 143”, “Compound 144”, “Compound 145” or “Compound 146”.
[0380] Test results indicate that the compounds of the present invention are highly active preemergent and/or postemergent herbicides and/or plant growth regulants. The compounds of the inention generally show highest activity for postemergence weed control (i.e. applied after weed seedlings emerge from the soil) and preemergence weed control (i.e. applied before weed seedlings emerge from the soil). Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. Many of the compounds of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can readily be determined by performing routine biological and/or biochemical assays. Compounds of this invention may show tolerance to important agronomic crops including, but is not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Compounds of this invention can be used in crops genetically transformed or bred to incorporate resistance to herbicides, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits. Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.
[0381] As the compounds of the invention have both preemergent and postemergent herbicidal activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth, the compounds can be usefully applied by a variety of methods involving contacting a herbicidally effective amount of a compound of the invention, or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the undesired vegetation or to the environment of the undesired vegetation such as the soil or water in which the undesired vegetation is growing or which surrounds the seed or other propagule of the undesired vegetation.
[0382] A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is about 0.001 to 20 kg/ha with a preferred range of about 0.004 to 1 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
[0383] In one common embodiment, a compound of the invention is applied, typically in a formulated composition, to a locus comprising desired vegetation (e.g., crops) and undesired vegetation (i.e. weeds), both of which may be seeds, seedlings and/or larger plants, in contact with a growth medium (e.g., soil). In this locus, a composition comprising a compound of the invention can be directly applied to a plant or a part thereof, particularly of the undesired vegetation, and/or to the growth medium in contact with the plant.
[0384] Plant varieties and cultivars of the desired vegetation in the locus treated with a compound of the invention can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the plant's genome. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
[0385] Genetically modified plant cultivars in the locus which can be treated according to the invention include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics. Plants can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance. Useful genetically modified plants containing single gene transformation events or combinations of transformation events are listed in Exhibit C. Additional information for the genetic modifications listed in Exhibit C can be obtained from publicly available databases maintained, for example, by the U.S. Department of Agriculture.
[0386] The following abbreviations, T1 through T37, are used in Exhibit C for traits. A “-” means the entry is not available; “tol.” means “tolerance” and “res.” means resistance.
[0000]
[00018]
TraitDescriptionT1Glyphosate tol.T2High lauric acid oilT3Glufosinate tol.T4Phytate breakdownT5Oxynil tol.T6Disease res.T7Insect res.T9Modified flower colorT11ALS Herbicide tol.T12Dicamba tol.T13Anti-allergyT14Salt tol.T15Cold tol.T16Imidazolinone herb. tol.T17Modified alpha-amylaseT18Pollination controlT192,4-D tol.T20Increased lysineT21Drought tol.T22Delayed ripening/senescenceT23Modified product qualityT24High celluloseT25Modified starch/carbohydrateT26Insect & disease resist.T27High tryptophanT28Erect leaves semidwarfT29SemidwarfT30Low iron tol.T31Modified oil/fatty acidT32HPPD tol.T33High oilT34Aryloxyalkanoate tol.T35Mesotrione tol.T36Reduced nicotineT37Modified product[0000]
[00019]
Exhibit CCropEvent NameEvent CodeTrait(s)Gene(s)AlfalfaJ101MON-00101-8T1cp4 epsps (aroA:CP4)AlfalfaJ163MON-ØØ163-7T1cp4 epsps (aroA:CP4)Canola*23-18-17 (Event 18)CGN-89465-2T2teCanola*23-198 (Event 23)CGN-89465-2T2teCanola*61061DP-Ø61Ø61-7T1gat4621Canola*73496DP-Ø73496-4T1gat4621Canola*GT200 (RT200)MON-89249-2T1cp4 epsps (aroA:CP4); goxv247Canola*GT73 (RT73)MON-ØØØ73-7T1cp4 epsps (aroA:CP4); goxv247Canola*HCN10 (Topas 19/2)—T3barCanola*HCN28 (T45)ACS-BNØØ8-2T3pat (syn)Canola*HCN92 (Topas 19/2)ACS-BNØØ7-1T3barCanola*MON88302MON-883Ø2-9T1cp4 epsps (aroA:CP4)Canola*MPS961—T4phyACanola*MPS962—T4phyACanola*MPS963—T4phyACanola*MPS964—T4phyACanola*MPS965—T4phyACanola*MS1 (B91-4)ACS-BNØØ4-7T3barCanola*MS8ACS-BNØØ5-8T3barCanola*OXY-235ACS-BNØ11-5T5bxnCanola*PHY14—T3barCanola*PHY23—T3barCanola*PHY35—T3barCanola*PHY36—T3barCanola*RF1 (B93-101)ACS-BNØØ1-4T3barCanola*RF2 (B94-2)ACS-BNØØ2-5T3barCanola*RF3ACS-BNØØ3-6T3barBeanEMBRAPA 5.1EMB-PV051-1T6ac1 (sense and antisense)Brinjal #EE-1—T7cry1AcCotton19-51aDD-Ø1951A-7T11S4-HrACotton281-24-236DAS-24236-5T3, T7pat (syn); cry1FCotton3006-210-23DAS-21Ø23-5T3, T7pat (syn); cry1AcCotton31707—T5, T7bxn; cry1AcCotton31803—T5, T7bxn; cry1AcCotton31807—T5, T7bxn; cry1AcCotton31808—T5, T7bxn; cry1AcCotton42317—T5, T7bxn; cry1AcCottonBNLA-601—T7cry1AcCottonBXN10211BXN10211-9T5bxn; cry1AcCottonBXN10215BXN10215-4T5bxn; cry1AcCottonBXN10222BXN10222-2T5bxn; cry1AcCottonBXN10224BXN10224-4T5bxn; cry1AcCottonCOT102SYN-IR102-7T7vip3A(a)CottonCOT67BSYN-IR67B-1T7cry1AbCottonCOT202—T7vip3ACottonEvent 1—T7cry1AcCottonGMF Cry1AGTL-GMF311-7T7cry1Ab-AcCottonGHB119BCS-GH005-8T7cry2AeCottonGHB614BCS-GH002-5T12mepspsCottonGK12—T7cry1Ab-AcCottonLLCotton25ACS-GH001-3T3barCottonMLS 9124—T7cry1CCottonMON1076MON-89924-2T7cry1AcCottonMON1445MON-01445-2T1cp4 epsps (aroA:CP4)CottonMON15985MON-15985-7T7cry1Ac; cry2Ab2CottonMON1698MON-89383-1T7cp4 epsps (aroA:CP4)CottonMON531MON-00531-6T7cry1AcCottonMON757MON-00757-7T7cry1AcCottonMON88913MON-88913-8T1cp4 epsps (aroA:CP4)CottonNqwe Chi 6 Bt—T7—CottonSKG321—T7cry1A; CpTICottonT303-3BCS-GH003-6T3, T7cry1Ab; barCottonT304-40BCS-GH004-7T3, T7cry1Ab; barCottonCE43-67B—T7cry1AbCottonCE46-02A—T7cry1AbCottonCE44-69D—T7cry1AbCotton1143-14A—T7cry1AbCotton1143-51B—T7cry1AbCottonT342-142—T7cry1AbCottonPV-GHGT07 (1445)—T1cp4 epsps (aroA:CP4)CottonEE-GH3—T1mepspsCottonEE-GH5—T7cry1AbCottonMON88701MON-88701-3T3, T12Modified dmo; barCottonOsCr11—T13Modified Cry jFlaxFP967CDC-FL001-2T11alsLentilRH44—T16alsMaize3272SYN-E3272-5T17amy797EMaize5307SYN-05307-1T7ecry3.1AbMaize59122DAS-59122-7T3, T7cry34Ab1; cry35Ab1; patMaize676PH-000676-7T3, T18pat; damMaize678PH-000678-9T3, T18pat; damMaize680PH-000680-2T3, T18pat; damMaize98140DP-098140-6T1, T11gat4621; zm-hraMaizeBt10—T3, T7cry1Ab; patMaizeBt176 (176)SYN-EV176-9T3, T7cry1Ab; barMaizeBVLA430101—T4phyA2MaizeCBH-351ACS-ZM004-3T3, T7cry9C; barMaizeDAS40278-9DAS40278-9T19aad-1MaizeDBT418DKB-89614-9T3, T7cry1Ac; pinII; barMaizeDLL25 (B16)DKB-89790-5T3barMaizeGA21MON-00021-9T1mepspsMaizeGG25—T1mepspsMaizeGJ11—T1mepspsMaizeFl117—T1mepspsMaizeGAT-ZM1—T3patMaizeLY038REN-00038-3T20cordapAMaizeMIR162SYN-IR162-4T7vip3Aa20MaizeMIR604SYN-IR604-5T7mcry3AMaizeMON801 (MON80100)MON801T1, T7cry1Ab; cp4 epsps (aroA:CP4); goxv247MaizeMON802MON-80200-7T1, T7cry1Ab; cp4 epsps (aroA:CP4); goxv247MaizeMON809PH-MON-809-2T1, T7cry1Ab; cp4 epsps (aroA:CP4); goxv247MaizeMON810MON-00810-6T1, T7cry1Ab; cp4 epsps (aroA:CP4); goxv247MaizeMON832—T1cp4 epsps (aroA:CP4); goxv247MaizeMON863MON-00863-5T7cry3Bb1MaizeMON87427MON-87427-7T1cp4 epsps (aroA:CP4)MaizeMON87460MON-87460-4T21cspBMaizeMON88017MON-88017-3T1, T7cry3Bb1; cp4 epsps (aroA:CP4)MaizeMON89034MON-89034-3T7cry2Ab2; cry1A.105MaizeMS3ACS-ZM001-9T3, T18bar; barnaseMaizeMS6ACS-ZM005-4T3, T18bar; barnaseMaizeNK603MON-00603-6T1cp4 epsps (aroA:CP4)MaizeT14ACS-ZM002-1T3pat (syn)MaizeT25ACS-ZM003-2T3pat (syn)MaizeTC1507DAS-01507-1T3, T7cry1Fa2; patMaizeTC6275DAS-06275-8T3, T7mocry1F; barMaizeVIP1034—T3, T7vip3A; patMaize43A47DP-043A47-3T3, T7cry1F; cry34Ab1; cry35Ab1; patMaize40416DP-040416-8T3, T7cry1F; cry34Ab1; cry35Ab1; patMaize32316DP-032316-8T3, T7cry1F; cry34Ab1; cry35Ab1; patMaize4114DP-004114-3T3, T7cry1F; cry34Ab1; cry35Ab1; patMelonMelon A—T22sam-kMelonMelon B—T22sam-kPapaya55-1CUH-CP551-8T6prsv cpPapaya63-1CUH-CP631-7T6prsv cpPapayaHuanong No. 1—T6prsv repPapayaX17-2UFL-X17CP-6T6prsv cpPlumC-5ARS-PLMC5-6T6ppv cpCanola**ZSR500—T1cp4 epsps (aroA:CP4); goxv247Canola**ZSR502—T1cp4 epsps (aroA:CP4); goxv247Canola**ZSR503—T1cp4 epsps (aroA:CP4); goxv247Rice7Crp#242-95-7—T137crpRice7Crp#10—T137crpRiceGM Shanyou 63—T7cry1Ab; cry1AcRiceHuahui-1/TT51-1—T7cry1Ab; cry1AcRiceLLRICE06ACS-OS001-4T3barRiceLLRICE601BCS-OS003-7T3barRiceLLRICE62ACS-OS002-5T3barRiceTarom molaii + cry1Ab—T7cry1Ab (truncated)RiceGAT-OS2—T3barRiceGAT-OS3—T3barRicePE-7—T7Cry1AcRice7Crp#10—T137crpRiceKPD627-8—T27OASA1DRiceKPD722-4—T27OASA1DRiceKA317—T27OASA1DRiceHW5—T27OASA1DRiceHW1—T27OASA1DRiceB-4-1-18—T28Δ OsBRI1RiceG-3-3-22—T29OSGA2ox1RiceAD77—T6DEFRiceAD51—T6DEFRiceAD48—T6DEFRiceAD41—T6DEFRice13pNasNa800725atAprt1—T30HvNAS1; HvNAAT-A; APRTRice13pAprt1—T30APRTRicegHvNAS1-gHvNAAT-1—T30HvNAS1; HvNAAT-A; HvNAAT-BRicegHvIDS3-1—T30HvIDS3RicegHvNAAT1—T30HvNAAT-A; HvNAAT-BRicegHvNAS1-1—T30HvNAS1RiceNIA-OS006-4—T6WRKY45RiceNIA-OS005-3—T6WRKY45RiceNIA-OS004-2—T6WRKY45RiceNIA-OS003-1—T6WRKY45RiceNIA-OS002-9—T6WRKY45RiceNIA-OS001-8—T6WRKY45RiceOsCr11—T13Modified Cry jRice17053—T1cp4 epsps (aroA:CP4)Rice17314—T1cp4 epsps (aroA:CP4)RoseWKS82/130-4-1IFD-52401-4T95AT; bp40 (f3′5′h)RoseWKS92/130-9-1IFD-52901-9T95AT; bp40 (f3′5′h)Soybean260-05 (G94-1, G94-19,—T9gm-fad2-1 (silencing locus)G168)SoybeanA2704-12ACS-GM005-3T3patSoybeanA2704-21ACS-GM004-2T3patSoybeanA5547-127ACS-GM006-4T3patSoybeanA5547-35ACS-GM008-6T3patSoybeanCV127BPS-CV127-9T16csr1-2SoybeanDAS68416-4DAS68416-4T3patSoybeanDP305423DP-305423-1T11, T31gm-fad2-1 (silencing locus); gm-hraSoybeanDP356043DP-356043-5T1, T31gm-fad2-1 (silencing locus);gat4601SoybeanFG72MST-FG072-3T32, T12mepsps; hppdPF W336SoybeanGTS 40-3-2 (40-3-2)MON-04032-6T1cp4 epsps (aroA:CP4)SoybeanGU262ACS-GM003-1T3patSoybeanMON87701MON-87701-2T7cry1AcSoybeanMON87705MON-87705-6T1, T31fatb1-A (sense & antisense); fad2-1A (sense & antisense); cp4 epsps(aroA:CP4)SoybeanMON87708MON-87708-9T1, T12dmo; cp4 epsps (aroA:CP4)SoybeanMON87769MON-87769-7T1, T31Pj.D6D; Nc.Fad3; cp4 epsps(aroA:CP4)SoybeanMON89788MON-89788-1T1cp4 epsps (aroA:CP4)SoybeanW62ACS-GM002-9T3barSoybeanW98ACS-GM001-8T3barSoybeanMON87754MON-87754-1T33dgat2ASoybeanDAS21606DAS-21606T34, T3Modified aad-12; patSoybeanDAS44406DAS-44406-6T1, T3, T34Modified aad-12; 2mepsps; patSoybeanSYHT04RSYN-0004R-8T35Modified avhppdSoybean9582.814.19.1—T3, T7cry1Ac, cry1F, PATSquashCZW3SEM-ØCZW3-2T6cmv cp, zymv cp, wmv cpSquashZW20SEM-0ZW20-7T6zymv cp, wmv cpSugar BeetGTSB77 (T9100152)SY-GTSB77-8T1cp4 epsps (aroA:CP4); goxv247Sugar BeetH7-1KM-000H71-4T1cp4 epsps (aroA:CP4)Sugar BeetT120-7ACS-BV001-3T3patSugar BeetT227-1—T1cp4 epsps (aroA:CP4)SugarcaneNXI-1T—T21EcbetASunflowerX81359—T16alsPepperPK-SP01—T6cmv cpTobaccoC/F/93/08-02—T5bxnTobaccoVector 21-41—T36NtQPT1 (antisense)SunflowerX81359—T16alsWheatMON71800MON-718ØØ-3T1cp4 epsps (aroA:CP4)*Argentine (Brassica napus),**Polish (B. rapa),# Eggplant[0387] Although most typically, compounds of the invention are used to control undesired vegetation, contact of desired vegetation in the treated locus with compounds of the invention may result in super-additive or synergistic effects with genetic traits in the desired vegetation, including traits incorporated through genetic modification. For example, resistance to phytophagous insect pests or plant diseases, tolerance to biotic/abiotic stresses or storage stability may be greater than expected from the genetic traits in the desired vegetation.
[0388] An embodiment of the present invention is a method for controlling the growth of undesired vegetation in genetically modified plants that exhibit traits of glyphosate tolerance, glufosinate tolerance, ALS herbicide tolerance, dicamba tolerance, imidazolinone herbicide tolerance, 2,4-D tolerance, HPPD tolerance and mesotrione tolerance, comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Formula 1.
[0389] Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including herbicides, herbicide safeners, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Mixtures of the compounds of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. Thus the present invention also pertains to a composition comprising a compound of Formula 1 (in a herbicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
[0390] A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanafos, bispyribac and its sodium salt, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, catechin, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clefoxydim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam-methyl, cumyluron, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-P, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate), halauxifen, halauxifen-methyl, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, hydantocidin, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, isoxachlortole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium, esters (e.g., MCPA-2-ethylhexyl, MCPA-butotyl) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyldymron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, pethoxyamid, phenmedipham, picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, tiafenacil, tiocarbazil, tolpyralate, topramezone, tralkoxydim, tri-allate, triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifludimoxazin, trifluralin, triflusulfuron-methyl, tritosulfuron, vernolate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 5-chloro-3-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-1-(4-methoxyphenyl)-2(1H)-quinoxalinone, 2-chloro-N-(1-methyl-1H-tetrazol-5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole (previously methioxolin), 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2-methyl-1,2,4-triazine-3,5(2H,4H)-dione, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, 2-methyl-3-(methylsulfonyl)-N-(1-methyl-1H-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl-N-(4-methyl-1,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides also include bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
[0391] Compounds of this invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-1H-purin-6-amine, epocholeone, gibberellic acid, gibberellin A4 and A7, harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.
[0392] General references for agricultural protectants (i.e. herbicides, herbicide safeners, insecticides, fungicides, nematocides, acaricides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U. K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U. K., 2001.
[0393] For embodiments where one or more of these various mixing partners are used, the mixing partners are typically used in the amounts similar to amounts customary when the mixture partners are used alone. More particularly in mixtures, active ingredients are often applied at an application rate between one-half and the full application rate specified on product labels for use of active ingredient alone. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual. The weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of weeds controlled beyond the spectrum controlled by the compound of Formula 1 alone.
[0394] In certain instances, combinations of a compound of this invention with other biologically active (particularly herbicidal) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect on weeds and/or a less-than-additive effect (i.e. safening) on crops or other desirable plants. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. Ability to use greater amounts of active ingredients to provide more effective weed control without excessive crop injury is also desirable. When synergism of herbicidal active ingredients occurs on weeds at application rates giving agronomically satisfactory levels of weed control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load. When safening of herbicidal active ingredients occurs on crops, such combinations can be advantageous for increasing crop protection by reducing weed competition.
[0395] Of note is a combination of a compound of the invention with at least one other herbicidal active ingredient. Of particular note is such a combination where the other herbicidal active ingredient has different site of action from the compound of the invention. In certain instances, a combination with at least one other herbicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise (in a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar spectrum of control but a different site of action.
[0396] Compounds of this invention can also be used in combination with herbicide safeners such as allidochlor, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, daimuron, dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)-2-fluorobenzenesulfonamide, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4-(dichloroacetyl)-1-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 191), ethyl 1,6-dihydro-1-(2-methoxyphenyl)-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3-carboxamide, and 3-oxo-1-cyclohexen-1-yl 1-(3,4-dimethylphenyl)-1,6-dihydro-6-oxo-2-phenyl-5-pyrimidinecarboxylate, 2,2-dichloro-1-(2,2,5-trimethyl-3-oxazolidinyl)-ethanone and 2-methoxy-N-[[4-[[(methylamino)carbonyl]amino]phenyl]sulfonyl]-benzamide to increase safety to certain crops. Antidotally effective amounts of the herbicide safeners can be applied at the same time as the compounds of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a compound of this invention and an antidotally effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control, because it physically restricts antidoting to the crop plants. Therefore a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of the crop with a herbicidally effective amount of a compound of this invention wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation.
[0397] Compounds of the invention cans also be mixed with: (1) polynucleotides including but not limited to DNA, RNA, and/or chemically modified nucleotides influencing the amount of a particular target through down regulation, interference, suppression or silencing of the genetically derived transcript that render a herbicidal effect; or (2) polynucleotides including but not limited to DNA, RNA, and/or chemically modified nucleotides influencing the amount of a particular target through down regulation, interference, suppression or silencing of the genetically derived transcript that render a safening effect.
[0398] Of note is a composition comprising a compound of the invention (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
[0399] Preferred for better control of undesired vegetation (e.g., lower use rate such as from synergism, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds are mixtures of a compound of this invention with a herbicide selected from the group 2,4-D, acetochlor, alachlor, atrazine, bromoxynil, bentazon, bicyclopyrone, carfentrazone-ethyl, cloransulam-methyl, dicamba, dimethenamid-p, florasulam, flufenacet, flumioxazin, flupyrsulfuron-methyl, fluroxypyr-meptyl, glyphosate, halauxifen-methyl, isoxaflutole, MCPA, mesotrione, metolachlor, metsulfuron-methyl, nicosulfuron, pyrasulfotole, pyroxasulfone, pyroxsulam, rimsulfuron, saflufenacil, tembotrione, thifensulfuron-methyl, topramazone and tribenuron.
[0400] Table A1 lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention. Compound 13 in the Component (a) column is identified in Index Table A. The second column of Table A1 lists the specific Component (b) compound (e.g., “2,4-D” in the first line). The third, fourth and fifth columns of Table A1 lists ranges of weight ratios for rates at which the Component (a) compound is typically applied to a field-grown crop relative to Component (b) (i.e. (a):(b)). Thus, for example, the first line of Table A1 specifically discloses the combination of Component (a) (i.e. Compound 13 in Index Table A) with 2,4-D is typically applied in a weight ratio between 1:192-6:1. The remaining lines of Table A1 are to be construed similarly.
[0000]
[00020]
TABLE A1Component (a)TypicalMore TypicalMost Typical(Compound 13)Component (b)Weight RatioWeight RatioWeight Ratio132,4-D1:192-6:11:64-2:11:24-1:313Acetochlor1:768-2:11:256-1:2 1:96-1:1113Acifluorfen 1:96-12:11:32-4:11:12-1:213Aclonifen1:857-2:11:285-1:3 1:107-1:1213Alachlor1:768-2:11:256-1:2 1:96-1:1113Ametryn1:384-3:11:128-1:1 1:48-1:613Amicarbazone1:192-6:11:64-2:11:24-1:313Amidosulfuron 1:6-168:1 1:2-56:1 1:1-11:113Aminocyclopyrachlor 1:48-24:11:16-8:1 1:6-2:113Aminopyralid 1:20-56:1 1:6-19:1 1:2-4:113Amitrole1:768-2:11:256-1:2 1:96-1:1113Anilofos 1:96-12:11:32-4:11:12-1:213Asulam1:960-2:11:320-1:3 1:120-1:1413Atrazine1:192-6:11:64-2:11:24-1:313Azimsulfuron 1:6-168:1 1:2-56:1 1:1-11:113Beflubutamid1:342-4:11:114-2:1 1:42-1:513Benfuresate1:617-2:11:205-1:2 1:77-1:913Bensulfuron-methyl 1:25-45:1 1:8-15:1 1:3-3:113Bentazone1:192-6:11:64-2:11:24-1:313Benzobicyclon 1:85-14:11:28-5:11:10-1:213Benzofenap1:257-5:11:85-2:11:32-1:413Bicyclopyrone 1:42-27:11:14-9:1 1:5-2:113Bifenox1:257-5:11:85-2:11:32-1:413Bispyribac-sodium 1:10-112:1 1:3-38:1 1:1-7:113Bromacil1:384-3:11:128-1:1 1:48-1:613Bromobutide1:384-3:11:128-1:1 1:48-1:613Bromoxynil 1:96-12:11:32-4:11:12-1:213Butachlor1:768-2:11:256-1:2 1:96-1:1113Butafenacil 1:42-27:11:14-9:1 1:5-2:113Butylate1:1542-1:2 1:514-1:5 1:192-1:2213Carfenstrole1:192-6:11:64-2:11:24-1:313Carfentrazone-ethyl1:128-9:11:42-3:11:16-1:213Chlorimuron-ethyl 1:8-135:1 1:2-45:1 1:1-9:113Chlorotoluron1:768-2:11:256-1:2 1:96-1:1113Chlorsulfuron 1:6-168:1 1:2-56:1 1:1-11:113Cincosulfuron 1:17-68:1 1:5-23:1 1:2-5:113Cinidon-ethyl1:384-3:11:128-1:1 1:48-1:613Cinmethylin 1:34-34:1 1:11-12:1 1:4-3:113Clacyfos 1:34-34:1 1:11-12:1 1:4-3:113Clethodim 1:48-24:11:16-8:1 1:6-2:113Clodinafop-propargyl 1:20-56:1 1:6-19:1 1:2-4:113Clomazone1:384-3:11:128-1:1 1:48-1:613Clomeprop1:171-7:11:57-3:11:21-1:313Clopyralid1:192-6:11:64-2:11:24-1:313Cloransulam-methyl 1:12-96:1 1:4-32:1 1:1-6:113Cumyluron1:384-3:11:128-1:1 1:48-1:613Cyanazine1:384-3:11:128-1:1 1:48-1:613Cyclopyrimorate 1:17-68:1 1:5-23:1 1:2-5:113Cyclosulfamuron 1:17-68:1 1:5-23:1 1:2-5:113Cycloxydim 1:96-12:11:32-4:11:12-1:213Cyhalofop 1:25-45:1 1:8-15:1 1:3-3:113Daimuron1:192-6:11:64-2:11:24-1:313Desmedipham1:322-4:11:107-2:1 1:40-1:513Dicamba1:192-6:11:64-2:11:24-1:313Dichlobenil1:1371-1:2 1:457-1:4 1:171-1:2013Dichlorprop1:925-2:11:308-1:3 1:115-1:1313Diclofop-methyl1:384-3:11:128-1:1 1:48-1:613Diclosulam 1:10-112:1 1:3-38:1 1:1-7:113Difenzoquat1:288-4:11:96-2:11:36-1:413Diflufenican1:857-2:11:285-1:3 1:107-1:1213Diflufenzopyr 1:12-96:1 1:4-32:1 1:1-6:113Dimethachlor1:768-2:11:256-1:2 1:96-1:1113Dimethametryn1:192-6:11:64-2:11:24-1:313Dimethenamid-P1:384-3:11:128-1:1 1:48-1:613Dithiopyr1:192-6:11:64-2:11:24-1:313Diuron1:384-3:11:128-1:1 1:48-1:613EPTC1:768-2:11:256-1:2 1:96-1:1113Esprocarb1:1371-1:2 1:457-1:4 1:171-1:2013Ethalfluralin1:384-3:11:128-1:1 1:48-1:613Ethametsulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:113Ethoxyfen 1:8-135:1 1:2-45:1 1:1-9:113Ethoxysulfuron 1:20-56:1 1:6-19:1 1:2-4:113Etobenzanid1:257-5:11:85-2:11:32-1:413Fenoxaprop-ethyl 1:120-10:11:40-4:11:15-1:213Fenoxasulfone 1:85-14:11:28-5:11:10-1:213Fenquinotrione 1:17-68:1 1:5-23:1 1:2-5:113Fentrazamide 1:17-68:1 1:5-23:1 1:2-5:113Flazasulfuron 1:17-68:1 1:5-23:1 1:2-5:113Florasulam 1:2-420:1 1:1-140:1 2:1-27:113Fluazifop-butyl1:192-6:11:64-2:11:24-1:313Flucarbazone 1:8-135:1 1:2-45:1 1:1-9:113Flucetosulfuron 1:8-135:1 1:2-45:1 1:1-9:113Flufenacet1:257-5:11:85-2:11:32-1:413Flumetsulam 1:24-48:1 1:8-16:1 1:3-3:113Flumiclorac-pentyl 1:10-112:1 1:3-38:1 1:1-7:113Flumioxazin 1:25-45:1 1:8-15:1 1:3-3:113Fluometuron1:384-3:11:128-1:1 1:48-1:613Flupyrsulfuron-methyl 1:3-336:1 1:1-112:1 2:1-21:113Fluridone1:384-3:11:128-1:1 1:48-1:613Fluroxypyr 1:96-12:11:32-4:11:12-1:213Flurtamone1:857-2:11:285-1:3 1:107-1:1213Fluthiacet-methyl 1:48-42:1 1:16-14:1 1:3-3:113Fomesafen 1:96-12:11:32-4:11:12-1:213Foramsulfuron 1:13-84:1 1:4-28:1 1:1-6:113Glufosinate1:288-4:11:96-2:11:36-1:413Glyphosate1:288-4:11:96-2:11:36-1:413Halosulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:113Halauxifen 1:20-56:1 1:6-19:1 1:2-4:113Halauxifen methyl 1:20-56:1 1:6-19:1 1:2-4:113Haloxyfop-methyl 1:34-34:1 1:11-12:1 1:4-3:113Hexazinone1:192-6:11:64-2:11:24-1:313Hydantocidin1:1100-16:11:385-8:1 1:144-4:1 13Imazamox 1:13-84:1 1:4-28:1 1:1-6:113Imazapic 1:20-56:1 1:6-19:1 1:2-4:113Imazapyr 1:85-14:11:28-5:11:10-1:213Imazaquin 1:34-34:1 1:11-12:1 1:4-3:113Imazethabenz-methyl1:171-7:11:57-3:11:21-1:313Imazethapyr 1:24-48:1 1:8-16:1 1:3-3:113Imazosulfuron 1:27-42:1 1:9-14:1 1:3-3:113Indanofan1:342-4:11:114-2:1 1:42-1:513Indaziflam 1:25-45:1 1:8-15:1 1:3-3:113Iodosulfuron-methyl 1:3-336:1 1:1-112:1 2:1-21:113Ioxynil1:192-6:11:64-2:11:24-1:313Ipfencarbazone 1:85-14:11:28-5:11:10-1:213Isoproturon1:384-3:11:128-1:1 1:48-1:613Isoxaben1:288-4:11:96-2:11:36-1:413Isoxaflutole 1:60-20:11:20-7:1 1:7-2:113Lactofen 1:42-27:11:14-9:1 1:5-2:113Lenacil1:384-3:11:128-1:1 1:48-1:613Linuron1:384-3:11:128-1:1 1:48-1:613MCPA1:192-6:11:64-2:11:24-1:313MCPB1:288-4:11:96-2:11:36-1:413Mecoprop1:768-2:11:256-1:2 1:96-1:1113Mefenacet1:384-3:11:128-1:1 1:48-1:613Mefluidide1:192-6:11:64-2:11:24-1:313Mesosulfuron-methyl 1:5-224:1 1:1-75:1 1:1-14:113Mesotrione 1:42-27:11:14-9:1 1:5-2:113Metamifop 1:42-27:11:14-9:1 1:5-2:113Metazachlor1:384-3:11:128-1:1 1:48-1:613Metazosulfuron 1:25-45:1 1:8-15:1 1:3-3:113Methabenzthiazuron1:768-2:11:256-1:2 1:96-1:1113Metolachlor1:768-2:11:256-1:2 1:96-1:1113Metosulam 1:8-135:1 1:2-45:1 1:1-9:113Metribuzin1:192-6:11:64-2:11:24-1:313Metsulfuron-methyl 1:2-560:1 1:1-187:1 3:1-35:113Molinate1:1028-2:1 1:342-1:3 1:128-1:1513Napropamide1:384-3:11:128-1:1 1:48-1:613Napropamide-M1:192-6:11:64-2:11:24-1:313Naptalam1:192-6:11:64-2:11:24-1:313Nicosulfuron 1:12-96:1 1:4-32:1 1:1-6:113Norflurazon1:1152-1:1 1:384-1:3 1:144-1:1613Orbencarb1:1371-1:2 1:457-1:4 1:171-1:2013Orthosulfamuron 1:20-56:1 1:6-19:1 1:2-4:113Oryzalin1:514-3:11:171-1:2 1:64-1:813Oxadiargyl1:384-3:11:128-1:1 1:48-1:613Oxadiazon1:548-3:11:182-1:2 1:68-1:813Oxasulfuron 1:27-42:1 1:9-14:1 1:3-3:113Oxaziclomefone 1:42-27:11:14-9:1 1:5-2:113Oxyfluorfen1:384-3:11:128-1:1 1:48-1:613Paraquat1:192-6:11:64-2:11:24-1:313Pendimethalin1:384-3:11:128-1:1 1:48-1:613Penoxsulam 1:10-112:1 1:3-38:1 1:1-7:113Penthoxamid1:384-3:11:128-1:1 1:48-1:613Pentoxazone 1:102-12:11:34-4:11:12-1:213Phenmedipham 1:102-12:11:34-4:11:12-1:213Picloram 1:96-12:11:32-4:11:12-1:213Picolinafen 1:34-34:1 1:11-12:1 1:4-3:113Pinoxaden 1:25-45:1 1:8-15:1 1:3-3:113Pretilachlor1:192-6:11:64-2:11:24-1:313Primisulfuron-methyl 1:8-135:1 1:2-45:1 1:1-9:113Prodiamine1:384-3:11:128-1:1 1:48-1:613Profoxydim 1:42-27:11:14-9:1 1:5-2:113Prometryn1:384-3:11:128-1:1 1:48-1:613Propachlor1:1152-1:1 1:384-1:3 1:144-1:1613Propanil1:384-3:11:128-1:1 1:48-1:613Propaquizafop 1:48-24:11:16-8:1 1:6-2:113Propoxycarbazone 1:17-68:1 1:5-23:1 1:2-5:113Propyrisulfuron 1:17-68:1 1:5-23:1 1:2-5:113Propyzamide1:384-3:11:128-1:1 1:48-1:613Prosulfocarb1:1200-1:2 1:400-1:4 1:150-1:1713Prosulfuron 1:6-168:1 1:2-56:1 1:1-11:113Pyraclonil 1:42-27:11:14-9:1 1:5-2:113Pyraflufen-ethyl 1:5-224:1 1:1-75:1 1:1-14:113Pyrasulfotole 1:13-84:1 1:4-28:1 1:1-6:113Pyrazolynate1:857-2:11:285-1:3 1:107-1:1213Pyrazosulfuron-ethyl 1:10-112:1 1:3-38:1 1:1-7:113Pyrazoxyfen 1:5-224:1 1:1-75:1 1:1-14:113Pyribenzoxim 1:10-112:1 1:3-38:1 1:1-7:113Pyributicarb1:384-3:11:128-1:1 1:48-1:613Pyridate1:288-4:11:96-2:11:36-1:413Pyriftalid 1:10-112:1 1:3-38:1 1:1-7:113Pyriminobac-methyl 1:20-56:1 1:6-19:1 1:2-4:113Pyrimisulfan 1:17-68:1 1:5-23:1 1:2-5:113Pyrithiobac 1:24-48:1 1:8-16:1 1:3-3:113Pyroxasulfone 1:85-14:11:28-5:11:10-1:213Pyroxsulam 1:5-224:1 1:1-75:1 1:1-14:113Quinclorac1:192-6:11:64-2:11:24-1:313Quizalofop-ethyl 1:42-27:11:14-9:1 1:5-2:113Rimsulfuron 1:13-84:1 1:4-28:1 1:1-6:113Saflufenacil 1:25-45:1 1:8-15:1 1:3-3:113Sethoxydim 1:96-12:11:32-4:11:12-1:213Simazine1:384-3:11:128-1:1 1:48-1:613Sulcotrione 1:120-10:11:40-4:11:15-1:213Sulfentrazone1:147-8:11:49-3:11:18-1:313Sulfometuron-methyl 1:34-34:1 1:11-12:1 1:4-3:113Sulfosulfuron 1:8-135:1 1:2-45:1 1:1-9:113Tebuthiuron1:384-3:11:128-1:1 1:48-1:613Tefuryltrione 1:42-27:11:14-9:1 1:5-2:113Tembotrione 1:31-37:1 1:10-13:1 1:3-3:113Tepraloxydim 1:25-45:1 1:8-15:1 1:3-3:113Terbacil1:288-4:11:96-2:11:36-1:413Terbuthylazine1:857-2:11:285-1:3 1:107-1:1213Terbutryn1:192-6:11:64-2:11:24-1:313Thenylchlor 1:85-14:11:28-5:11:10-1:213Thiazopyr1:384-3:11:128-1:1 1:48-1:613Thiencarbazone 1:3-336:1 1:1-112:1 2:1-21:113Thifensulfuron-methyl 1:5-224:1 1:1-75:1 1:1-14:113Tiafenacil 1:17-68:1 1:5-23:1 1:2-5:113Thiobencarb1:768-2:11:256-1:2 1:96-1:1113Tolpyralate 1:31-37:1 1:10-13:1 1:3-3:113Topramzone 1:6-168:1 1:2-56:1 1:1-11:113Tralkoxydim 1:68-17:11:22-6:1 1:8-2:113Triafamone 1:2-420:1 1:1-140:1 2:1-27:113Triallate1:768-2:11:256-1:2 1:96-1:1113Triasulfuron 1:5-224:1 1:1-75:1 1:1-14:113Triaziflam1:171-7:11:57-3:11:21-1:313Tribenuron-methyl 1:3-336:1 1:1-112:1 2:1-21:113Triclopyr1:192-6:11:64-2:11:24-1:313Trifloxysulfuron 1:2-420:1 1:1-140:1 2:1-27:113Trifludimoxazin 1:25-45:1 1:8-15:1 1:3-3:113Trifluralin1:288-4:11:96-2:11:36-1:413Triflusulfuron-methyl 1:17-68:1 1:5-23:1 1:2-5:113Tritosulfuron 1:13-84:1 1:4-28:1 1:1-6:1[0401] Table A2 is constructed the same as Table A1 above except that entries below the “Component (a)” column heading are replaced with the respective Component (a) Column Entry shown below. Compound 15 in the Component (a) column is identified in Index Table A. Thus, for example, in Table A2 the entries below the “Component (a)” column heading all recite “Compound 15” (i.e. Compound 15 identified in Index Table A), and the first line below the column headings in Table A2 specifically discloses a mixture of Compound 15 with 2,4-D. Tables A3 through A146 are constructed similarly.
[0000]
[00021]
Table NumberComponent (a) Column EntriesA2Compound 15A3Compound 16A4Compound 21A5Compound 22A6Compound 23A7Compound 24A8Compound 27A9Compound 1A10Compound 2A11Compound 3A12Compound 4A13Compound 5A14Compound 6A15Compound 7A16Compound 8A17Compound 9A18Compound 10A19Compound 11A20Compound 12A21Compound 14A22Compound 17A23Compound 18A24Compound 19A25Compound 20A26Compound 25A27Compound 26A28Compound 28A29Compound 29A30Compound 30A31Compound 31A32Compound 32A33Compound 33A34Compound 34A35Compound 35A36Compound 36A37Compound 37A38Compound 38A39Compound 39A40Compound 40A41Compound 41A42Compound 42A43Compound 43A44Compound 44A45Compound 45A46Compound 46A47Compound 47A48Compound 48A49Compound 49A50Compound 50A51Compound 51A52Compound 52A53Compound 53A54Compound 54A55Compound 55A56Compound 56A57Compound 57A58Compound 58A59Compound 59A60Compound 60A61Compound 61A62Compound 62A63Compound 63A64Compound 64A65Compound 65A66Compound 66A67Compound 67A68Compound 68A69Compound 69A70Compound 70A71Compound 71A72Compound 72A73Compound 73A74Compound 74A75Compound 75A76Compound 76A77Compound 77A78Compound 78A79Compound 79A80Compound 80A81Compound 81A82Compound 82A83Compound 83A84Compound 84A85Compound 85A86Compound 86A87Compound 87A88Compound 88A89Compound 89A90Compound 90A91Compound 91A92Compound 92A93Compound 93A94Compound 94A95Compound 95A96Compound 96A97Compound 97A98Compound 98A99Compound 99A100Compound 100A101Compound 101A102Compound 102A103Compound 103A104Compound 104A105Compound 104A106Compound 106A107Compound 107A108Compound 108A109Compound 109A110Compound 110A111Compound 111A112Compound 112A113Compound 113A114Compound 114A115Compound 115A116Compound 116A117Compound 117A118Compound 118A119Compound 119A120Compound 120A121Compound 121A122Compound 122A123Compound 123A124Compound 124A125Compound 125A126Compound 126A127Compound 127A128Compound 128A129Compound 129A130Compound 130A131Compound 131A132Compound 132A133Compound 133A134Compound 134A135Compound 135A136Compound 136A137Compound 137A138Compound 138A139Compound 139A140Compound 140A141Compound 141A142Compound 142A143Compound 143A144Compound 144A145Compound 145A146Compound 146[0402] The compounds of the present invention are useful for the control of weed species that are resistant to herbicides with the AHAS-inhibitor or (b2) [chemical compound that inhibits acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS)] mode of action.
[0403] The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Tables A-C for compound descriptions. The following abbreviations are used in the Index Tables which follow: t is tertiary, s is secondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, i-Pr is isopropyl, Bu is butyl, c-Pr is cyclopropyl, t-Bu is tert-butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, TFP is trifluoropropyl (i.e. —CH2CH2CF3), Bn is benzyl and —CN is cyano. The abbreviation “Cmpd. No.” stands for “Compound Number”. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared. Mass spectra are reported with an estimated precision within ±0.5 Da as the molecular weight of the highest isotopic abundance parent ion (M+1) formed by addition of H+ (molecular weight of 1) to the molecule. The presence of molecular ions containing one or more higher atomic weight isotopes of lower abundance (e.g., 37Cl, 81Br) is not reported. The alternate molecular ion peaks (e.g., M+2 or M+4) that occur with compounds containing multiple halogens are not reported. The reported M+1 peaks were observed by mass spectrometry using atmospheric pressure chemical ionization (AP+) or electrospray ionization (ESI).
[0000]
[00022]
INDEX TABLE A[00034]
[00035]
[00036]
[00037]
[00038]
[00039]
M.S.(AP+)Cmpd. No.AR1R2R3or m.p.1A-3AOCH2CH(CH3)2Cl3-Br*2A-3AOCH2C(Cl)═CH2Cl3-Br*3A-3AOCH2C(CH3)═CH2Cl3-Br*4A-3AOCH2CF2CFBr3-F4475A-3AOCH2CF2CF3Cl3-F4016A-3AOCH(cyclo-pentyl)Cl3-Br4117A-3AOCH2CH2CNCl3-Br3828A-3AOCH2(cyclo-butyl)Cl3-Br3979A-3AOCH2(cyclo-propyl)Cl3-Br39310A-3AOCH2(2,2-di-F-cyclo-propyl)Cl3-Br41911A-3AOCH2CH═C(CH3)2Cl3-Br39712A-3ACH3Cl3-Br*13A-3AOCH2CH2CH3Cl3-Br*14A-3AOC(CH3)3Cl3-Br*15A-3AOCH2CH2CF3Cl3-Cl38116A-3AOCH(CH3)CH2CF3Cl3-Br43917A-3AOCH2CH2CF3Cl(m = 0)34718A-3AN(CH3)CH2CH(CH3)(CF3)Cl3-Br45219A-3AN(CH3)CH2CH2CF3Cl3-Br43820A-3AOCH2CH2CH2CF3Cl3-Br*21 (Ex. 2)A-3AOCH2CH2CH═CH2Cl3-Br*22A-3AOCH2CH═CH2Cl3-Br36923A-3AOCH2CF2CF3Cl3-Br46124A-3AN(CH3)OCH2CF3Br3-Br48425A-3AN(CH3)OCH2CF3Cl3-Br44026 (Ex. 3)A-3AOCH2CH2CF3Cl3-Br42527A-3ANHCH2CF3Br(m = 0)*28 (Ex. 1)A-3ANHCH2CF3Cl(m = 0)*29A-3ACH2ClCl(m = 0)283 (65-70)30A-3AOCH2CH2CF3Cl3-CN37231A-3AOCH2CF3CN3-Br*32A-3AOCH2CF3Cl3-CN35833A-3AOCH2CH2CF3Br3-Br46734A-3AOCH2CF3Br3-Br45535A-3AOCH2CF3Cl3-Br41136A-3AOCH(CH2Cl)2Cl3-Br43937A-3AOCH2CH(CH3)CH═CH2Cl3-Br39738A-3AOCH2CH2C≡CHCl3-Br38139A-3AOCH2CNCl3-CN31540A-3AOCH2CNCl3-Br*41A-3AOCH2CH2CF3Br3-F40942A-3AOCH2CH2CF3Cl3-F36543A-3AOC(CH3)3Cl3-F32544A-3AO(cyclo-pentyl)Cl3-Br39745A-3AOCH2CCl3Cl3-Br45946A-3AOCH2CH2ClCl3-Br39147A-3AOCH2CF3Br3-F39648A-3AOCH2CF3Cl3-F35149A-3AOCH2CNCl3-F308(80-83)50A-3AE-OCH2CH═CHCF3Cl3-Br43751A-3ACH3Cl3-OMe27952A-3ACH3Cl(m = 0)24955A-5; R5 is MeCH3Cl(m = 0)27856A-5; R5 is i-PrCH3Cl(m = 0)30657A-5; R5 is i-PrHCl(m = 0)29258A-5; R5 is BnCH3Cl(m = 0)35459A-5; R5 is t-BuCH3Cl(m = 0)32060A-5; R5 is HCH3Cl(m = 0)26461A-3AOCH2C(Br)═CH2Cl3-Br87-9162A-1OCH2CF3Cl3-Br63-6663A-1OCH2CF2CF3Cl3-Br49-5364A-3AOCH2CH2CF3Cl4-CN117-12065A-3AOCH2CH2CH2CF3Cl3-CF342966A-1OCH2CH2CF3Cl3-Br63-6767A-3ACH2CH2CH3Cl3-CN85-8868A-3ACH2CH2CH2CH3Cl3-CN 98-10269A-5; R5 is i-PrCH3Cl3-CN80-8470A-3ASCH2CH2CH3Cl3-Br38771A-3ASCH2CH2CF3Cl3-Br121-12572A-1CH2CH2CF3Cl3-CN34273A-1(CH2)3CF3Cl3-CN35674A-1O(CH2)3CF3Cl3-Br42575A-3ACH2CH2CH3Cl3-Br88-9276A-5; R5 is i-PrCH3Cl3-F62-6677A-3A(CH2)3CF3Cl3-Br42378A-3AO(c-Bu)Cl3-Br100-10379A-3A(CH2)3CH3Cl3-Br77-8180A-1O(CH2)2CF3Cl3-CN35881A-1O(CH2)3CF3Cl3-CN37282A-3A(CH2)4CF3Cl3-Br43783A-3ASCH2CH3Cl3-Br37384A-3AOCH(CH3)CH2CH3Cl3-Br38585A-3ASCH2CF3Cl3-Br90-9386A-1(CH2)2CH3Cl3-CN28887A-1(CH2)3CH3Cl3-CN30288A-3AO(CH2)2CF3Cl4-Cl87-9089A-1(CH2)2CF3Cl3-Br39590A-3AOCH2CH2C(═CH2)CH3Cl3-Br39791A-3ASCH2CH═CH2Cl3-Br38592A-3A(CH2)2CF3Cl3-Br40993A-3ANH(CH2)2CF3Cl3-Br42494A-3AO(CH2)2CF3Cl4-Br88-9195A-5; R5 is EtCH3Cl3-Br37096A-3AO(CH2)2C(CH3)3Cl3-Br41397A-3AOCH2CHClCH2ClCl3-Br43998A-5; R5 is TFPCH3Cl3-Br*99A-3AO(CH2)2CF3Cl3-CH351-53100A-3AO(CH2)3CH3Cl3-Br385101A-3AO(CH2)4CH3Cl3-Br399102A-3AOCH2CH2CH2CH2BrCl3-Br449103A-3AOCH2CF2CHF2Cl3-Br443104A-5; R5 is i-PrCH3Cl3-Cl340105A-5; R5 is i-PrCH3Cl3-Br384106A-1OCH2CH3Cl3-Br343107 (Ex. 4)A-3A(CH2)2CF3Cl3-Cl**108A-3AOCH2C≡CHCl3-Br108-112109A-3A(CH2)4CF3Cl3-CN384110A-3ACH2CH2CF2CF3Cl3-Br459111A-3ACH2CH2CF2CF3Cl3-CN406112A-3AO(CH2)2CF3Cl3-OCH3109-113113A-3AO(CH2)2CF3Cl3-CF3415114A-2(CH2)3CH3Cl3-Br380115A-3AO(CH2)2CF3Cl3-O-i-Pr405116A-3AO(CH2)2CF3Cl3-OCH2CH3391117A-3AO(CH2)2CF3Cl3-OCH2CF3445118A-2(CH2)2CH3Cl3-Br366119A-3Acis-OCH2CCl═CClCl3-Br114-117120A-3Atrans-OCH2CCl═CClCl3-Br84-88121A-1(CH2)4CF3Cl3-Br423122A-1(CH2)2CF3Cl3-Cl351123A-3AO(CH2)2c-PrCl3-Br397124A-1(CH2)4CF3Cl3-Cl379125A-3A(CH2)3CF3Cl3-CF3413126A-7; R15 is Me(CH2)3CF3Cl3-CN371127A-3Acis-OCH2C═C(CH3)ClCl3-Br59-63128A-3Atrans-OCH2C≡C(CH3)ClCl3-Br82-86129A-2(CH2)3CH3Cl(m = 0)302130A-3A(CH2)3CH3Cl3-CF3359131A-1OCH2CF3Cl3-CN344132A-1OCH2CF2CF3Cl3-CN70-73133A-3A(CH2)3CF3Cl3-CN94-96134A-1(CH2)3CF3Cl3-CH2CH3359135A-1(CH2)3CF3Cl3-c-Pr371136A-3A(CH2)2CH3Cl3-CF3345137A-1(CH2)3CF3Cl3-Cl365138A-1(CH2)3CF3Cl3-Br409139A-3AHCl3-Cl*140A-2HCl(m = 0)*141 (Ex. 5)A-2(CH2)4CH3Cl(m = 0)**142A-3A(CH2)2CF3Cl3-CN354143A-3A(CH2)3CF3Cl3-Cl379144A-2(CH2)3CF3Cl(m = 0)356145A-2(CH2)4CF3Cl(m = 0)370146A-7; R15 is H(CH2)3CF3Cl3-CN358*See Index Table C for 1H NMR data.**See Synthesis Example for 1H NMR data.E indicates E stereochemistry of double bond[0000]
[00023]
INDEX TABLE BM.S.(AP+)INCodeCmpdStructureor m.p.TLU0853[00040]
415 (80-83) TKV3854[00041]
361 (78-81)INDEX TABLE CCmpd1H NMR (CDCl3 solution unless indicated otherwise)18.48 (s, 2H), 7.53 (dd, 1H), 7.35 (t, 1H), 7.18 (dd, 1H), 4.02 (d, 2H), 1.98-1.83 (m, 1H), 0.89 (d, 6H).28.48 (m, 2H), 7.55 (dd, 1H), 7.38 (t, 1H), 7.26 (s, 1H), 7.20 (dd, 1H), 5.55-5.46 (m, 1H), 5.38 (m,1H), 4.80-4.78 (m, 2H).38.47 (s, 2H), 7.54 (dd, 1H), 7.36 (t, 1H), 7.19 (dd, 1H), 4.99-4.93 (m, 1H), 4.91-4.89 (m, 1H), 4.63(s, 2H), 1.71 (s, 3H).128.48 (s, 2H), 7.51 (dd, 1H), 7.32 (t, 1H), 7.15 (dd, 1H), 2.55 (s, 3H).138.49 (s, 2H), 7.53 (dd, 1H), 7.35 (t, 1H), 7.18 (dd, 1H), 4.20 (t, 2H), 1.58-1.67 (m, 2H), 0.82-0.93(m, 3H).148.49 (s, 2H), 7.51 (dd, 0.95 Hz, 1H), 7.32 (t, 1H), 7.16 (dd, 1H), 1.43 (s, 9 H).208.49 (s, 2H), 7.54 (dd, 1H), 7.37 (t, 1H), 7.20 (dd, 1H), 4.31 (t, 2H), 2.20-2.04 (m, 2H), 1.93-1.85(m, 2H).218.48 (s, 2H), 7.53 (dd, 1H), 7.35 (t, 1H), 7.17 (dd, 1H), 5.75-5.67 (m, 1H), 5.09-5.05 (m, 1H), 5.03-5.00 (m, 1H), 4.29 (t, 2H), 2.39-2.34 (m, 2H).278.37 (s, 2H), 7.64 (d, 1H), 7.46 (t, 1H), 7.32 (t, 1H), 7.19 (bs, 1H), 7.00 (d, 1H), 4.75 (q, 2H).288.30 (s, 2H), 7.65 (d, 1H), 7.48 (t, 1H), 7.31 (t, 1H), 7.21 (bs, 1H), 7.00 (d, 1H), 4.75 (q, 2H).318.81 (s, 2H), 7.63 (dd, 1H), 7.45 (t, 1H), 7.22 (dd, 1H), 4.58 (q, 2H).408.50 (s, 2H), 7.57 (dd, 1H), 7.43 (t, 1H), 7.24 (dd, 1H), 4.87 (s, 2H).99500 MHz) 8.47 (s, 2H) 7.53-7.56 (m, 1H) 7.29-7.33 (m, 1H) 7.14-7.18 (m, 1H) 4.19 (t, 2H) 2.26-2.36 (m, 1H) 2.09 (s, 3H).13910.39 (s, 1H), 8.46 (s, 2H), 7.62-7.56 (m, 1H), 7.47-7.42 (m, 1H), 7.22-7.17 (m, 1H).140(500 MHz) 8.49 (s, 2H), 7.54-7.58 (m, 1H), 7.40-7.45 (m, 1H), 7.30-7.36 (m, 1H), 7.16-7.20 (m,1H), 3.72 (s, 2H).1H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singletBiological Examples of the Invention
Test A
[0404] Seeds of plant species selected from barnyardgrass (Echinochloa crus-galli), kochia (Kochia scoparia), ragweed (common ragweed, Ambrosia elatior), Italian ryegrass (Lolium multiflorum), large (Lg) crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberii), morningglory (Ipomoea spp.), pigweed (Amaranthus retroflexus), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), and corn (Zea mays) were planted into a blend of loam soil and sand and treated preemergence with a directed soil spray using test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
[0405] At the same time, plants selected from these crop and weed species and also blackgrass (Alopecurus myosuroides), and galium (catchweed bedstraw, Galium aparine) were planted in pots containing the same blend of loam soil and sand and treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 10 cm and were in the one- to two-leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately 10 days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, are based on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
[0000]
[00024]
TABLE A1000 g ai/haCompoundsPostemergence125556575859Barnyardgrass800502040 0Blackgrass50—————Corn20030203020Crabgrass, Large—040308010Foxtail, Giant7010 70206010Galium80—————Kochia80—————Morningglory———1030 0Pigweed10006040100 30Ragweed60—————Ryegrass, Italian50—————Velvetleaf—10 100 —90—Wheat 0010202030500 g ai/haCompoundsPostemergence678910111314151617182021Barnyardgrass40904090100 20100401009000100 100 Blackgrass308020809020 707010090005080Corn107020506010 9010 906020 04060Crabgrass, Large——————————————Foxtail, Giant50100 6090100 20100601009000100 100 Galium90100 90100 100 20100100 100100 009090Kochia90100 8090100 4010070100100 010 100 100 Morningglory——————————————Pigweed90100 90100 100 60100100 100100 40 20 100 100 Ragweed3090401050 0 20 0 4030004040Ryegrass, Italian4070305060 010070 9030004090Velvetleaf——————————————Wheat1020 05040 0 304010020002040500 g ai/haCompoundsPostemergence2223242526272830313233343539Barnyardgrass100 5010 10100020 2000100 20800Blackgrass9050030100——30009070800Corn50200201000070009030300Crabgrass, Large—————00———————Foxtail, Giant100 800101000010000100 80100 0Galium90100 20 50100——10000100 100 100 0Kochia100 100 050100——10000100 90100 0Morningglory—————00———————Pigweed100 100 10 60100020 100030 100 100 100 0Ragweed3010020 60——00040 0 00Ryegrass, Italian60700 0 80——00080 0400Velvetleaf—————030 ———————Wheat3010010 9000300060 0200500 g ai/haCompoundsPostemergence4041424748496164657273757879Barnyardgrass20000300100070100 100100 100 100 Blackgrass2000020010004050100606090Corn20030 0 00 4002060 60906090Crabgrass, Large——————————————Foxtail, Giant40000200100090100 100100 8080Galium40000100100070100 100100 100 100 Kochia100 60 60 0 00—0—100 100100 100 100 Morningglory——————————————Pigweed100 90 90 04001000100 100 100100 90100 Ragweed 010 00 00 3003030 30403040Ryegrass, Italian 0000 00 800 040100703090Velvetleaf——————————————Wheat20000 00 300 040 90703030500 g ai/haCompoundsPostemergence83848591106125130136139Barnyardgrass904020100 100 90100 800Blackgrass40 0 030209090100 0Corn30404050103050500Crabgrass, Large—————————Foxtail, Giant806060100709090900Galium2040909010100 100 100 0Kochia907080100 —100 100 100 0Morningglory—————————Pigweed707070100 20100 100 100 0Ragweed 0 0 020 04060600Ryegrass, Italian 0 0 030 090907020 Velvetleaf—————————Wheat 0202030 03030200125 g ai/haCompoundsPostemergence1234567891011131516Barnyardgrass30406000103010202010809010Blackgrass203030001030030200309020Corn20203000010020100305020Foxtail, Giant60608000105030203020809020Galium709070006010060701001010010090Kochia3090400040100405090010010080Pigweed708010000601005010090109010090Ragweed100000104010010002010Ryegrass, Italian02030000200010006010Wheat000000001000202020125 g ai/haCompoundsPostemergence1718192021222324252630313233Barnyardgrass000307060100010000080Blackgrass0003060601000100100060Corn000303030100060300030Foxtail, Giant00050708030001006000100Galium0001080309010201006000100Kochia0009090908001010010000100Pigweed20101010080100100030100100020100Ragweed00000000103000030Ryegrass, Italian00000010007000030Wheat0000000004000020125 g ai/haCompoundsPostemergence3435363738394041424344454647Barnyardgrass01003060000010020300Blackgrass104003000100000000Corn3020010100200200020100Foxtail, Giant204004090010000020400Galium50600408003000400100700Kochia609004060070203010050900Pigweed100100608010007090804001001000Ragweed0000100000001000Ryegrass, Italian00000000000000Wheat00000000000000125 g ai/haCompoundsPostemergence4849505153546162636465666768Barnyardgrass00200001004010030100030Blackgrass002000030400020100030Corn001000020303001070020Foxtail, Giant0070000604030040100030Galium00901000608030020100060Kochia0090000—100500—50040Pigweed200100000409060090100090Ragweed000000100001020020Ryegrass, Italian00200002000005000Wheat000000000003000125 g ai/haCompoundsPostemergence6970717273747576777879808182Barnyardgrass7030408090409009060909050100Blackgrass302030305030400502050904040Corn201020503020800304080604030Foxtail, Giant30304070100709009050809070100Galium6070908010080809010070909080100Kochia407050100100401000100701007050100Pigweed8020701001001001003010080100100100100Ragweed020201020103000030301040Ryegrass, Italian0202010802040060090501060Wheat00010201020010202040030125 g ai/haCompoundsPostemergence8384858687888990919293949596Barnyardgrass000401000903030100003010Blackgrass000207006002050001010Corn2010103050020102040001020Foxtail, Giant00030900506030100006010Galium30303070700802070100004020Kochia30303010010009050601000000Pigweed303030406009050100100002010Ragweed0000001000200000Ryegrass, Italian000203003000500000Wheat0004030020020200000125 g ai/haCompoundsPostemergence979899100101102103104105106107108109110Barnyardgrass201080502003000409010060Blackgrass20108040001020100900050Corn101050100020100060202050Foxtail, Giant6020907020070100109010090Galium10050707040010030200904030100Kochia40040802001001010—904020100Pigweed509040706001004030101005060100Ragweed2010300000000300200Ryegrass, Italian30050201000000800020Wheat010300000000300020125 g ai/haCompoundsPostemergence111112113114115116117118119120121122123124Barnyardgrass010401001010100040505060Blackgrass03040102001000030605060Corn0020201010101020010201020Foxtail, Giant030502002010100070405070Galium08080802060100309030806010090Kochia03010080010506030080809080Pigweed0701001004050706010020100100100100Ragweed040202000201010050101020Ryegrass, Italian00301000000020202020Wheat002010000000100010125 g ai/haCompoundsPostemergence125126127128129130131132133134135136137138Barnyardgrass3003020100901050302010306090Blackgrass3002020805003002020503090Corn100201020203030201020201060Foxtail, Giant5005020100402050302020306090Galium1000908090100506050408040100100Kochia10006060100100907020606080100100Pigweed100103050701008090508090100100100Ragweed300000300001010204060Ryegrass, Italian200006020200010101030100Wheat2001010103020200100101040125 g ai/haCompoundsPostemergence139140141142143144145146Barnyardgrass0020070908090Blackgrass0010080906090Corn00201030805080Foxtail, Giant0040070907090Galium00602010010080100Kochia030601010010090100Pigweed020702010010010070Ragweed00202050102030Ryegrass, Italian0010080804070Wheat00002060302031 g ai/haCompoundsPostemergence12345193637384344454650Barnyardgrass2030200000010002000Blackgrass00000000000000Corn0100000000000010Foxtail, Giant30303000000400020020Galium50604000001050200505060Kochia20500000003000203060Pigweed406070001002080100806080Ragweed000000000001000Ryegrass, Italian00000000000000Wheat0000000000000031 g ai/haCompoundsPostemergence5153546263666768697071747677Barnyardgrass00020040010100010030Blackgrass00000100101001010020Corn000010200100101010010Foxtail, Giant00000300202001020030Galium0003003002040303020090Kochia000602020020202010200100Pigweed000502040020401030600100Ragweed00000000000000Ryegrass, Italian000000000000020Wheat0000000000000031 g ai/haCompoundsPostemergence8081828687888990929394959697Barnyardgrass3010302040030040000010Blackgrass30104001002001000000Corn1010203040010010000010Foxtail, Giant30203010400201050000010Galium603090303003009000100100Kochia50308090100080301000000—Pigweed80501003040090101000010020Ragweed100400001000000010Ryegrass, Italian00400001000000020Wheat0010302000000000031 g ai/haCompoundsPostemergence9899100101102103104105107108109110111112Barnyardgrass0301010000040003000Blackgrass0300000005000000Corn00100020003010102000Foxtail, Giant0502000100070003000Galium1020201007010109020070060Kochia020600070009020010000Pigweed301030200901010100202090040Ragweed01000000020000020Ryegrass, Italian000000002000000Wheat0000000000000031 g ai/haCompoundsPostemergence113114115116117118119120121122123124126127Barnyardgrass10000000020101010010Blackgrass0000000020201020010Corn10100010010010101010010Foxtail, Giant10000000010102030010Galium40502030601010070309070060Kochia802000203030020805050010Pigweed90501040304070080707070020Ragweed0000000020001000Ryegrass, Italian000000001000000Wheat000000001000100031 g ai/haCompoundsPostemergence128129131132133134135137138140141142143144Barnyardgrass0200301000209001002040Blackgrass02000010010400003050Corn1020202001010103001001020Foxtail, Giant1020030101010109002003060Galium20302020301050407004009040Kochia1040404002010909005009090Pigweed2020506030404080100040010090Ragweed000000010300002010Ryegrass, Italian000000010300002030Wheat0000000020000101031 g ai/haCompoundsPostemergence145146Barnyardgrass3030Blackgrass4030Corn3020Foxtail, Giant5030Galium4070Kochia7070Pigweed9060Ragweed100Ryegrass, Italian100Wheat10201000 g ai/haCompoundsPreemergence125556575859Barnyardgrass80090509020Corn—000200Crabgrass, Large—0100100100 80Foxtail, Giant100 010090100 30Kochia 0—————Morningglory———0 00Pigweed100 0100605030Ragweed80—————Ryegrass, Italian40—————Velvetleaf—09020200Wheat—000200500 g ai/haCompoundsPreemergence678910111314151617182021Barnyardgrass60100100 9010030 1006010010000100100Corn——————————————Crabgrass, Large——————————————Foxtail, Giant100 100100 100100100 100100 10010000100100Kochia 0100 0100100010070100 80010 100100Morningglory——————————————Pigweed701006010010020 100100 10010010 40 100100Ragweed 0 50 0 0 00 010 10 000 0 0Ryegrass, Italian70 3030 30 300 9020 90 2000 90 90Velvetleaf——————————————Wheat——————————————500 g ai/haCompoundsPreemergence2223242526272830313233343539Barnyardgrass1007030 3010002000010090900Corn—————0 0———————Crabgrass, Large—————050———————Foxtail, Giant100100 20 60100020100 00100100 100 0Kochia10050050100——100 0010040 800Morningglory—————0 0———————Pigweed100100 90 80100080100 030 100100 100 0Ragweed 0100 0 20——000 200 00Ryegrass, Italian90 400 0100——0001000300Velvetleaf—————020———————Wheat—————0 0———————500 g ai/haCompoundsPreemergence4041424748496164657273757879Barnyardgrass5000010 01000100 100100100100100Corn——————————————Crabgrass, Large——————————————Foxtail, Giant100 00010 01000100 100100100100100Kochia9030 0000100090100100100 60100Morningglory——————————————Pigweed100 40 30 0001000100 100100100100100Ragweed 080 0000 20080 10 50 10 0 90Ryegrass, Italian 000000 80030 30 90100 20100Velvetleaf——————————————Wheat——————————————500 g ai/haCompoundsPreemergence83848591106125130136139Barnyardgrass90 90 10 100100 1001001000Corn—————————Crabgrass, Large—————————Foxtail, Giant100 100 70 100100 1001001000Kochia000100901001001000Morningglory—————————Pigweed90 100 60 100701001001000Ragweed000 0 0 40 90 800Ryegrass, Italian000 80101001001000Velvetleaf—————————Wheat—————————125 g ai/haCompoundsPreemergence1234567891011131516Barnyardgrass305080001050304040010010030Foxtail, Giant701001000060901001001004010010090Kochia407040000500709009010090Pigweed7090100001010010100100010010090Ragweed000000—0000000Ryegrass, Italian01030000001010010400125 g ai/haCompoundsPreemergence1718192021222324252630313233Barnyardgrass000100100402000100000100Foxtail, Giant0001001001007001010010000100Kochia0020304030000100900060Pigweed01020100100100100040100100030100Ragweed000000000200000Ryegrass, Italian0003030300007000040125 g ai/haCompoundsPreemergence3435363738394041424344454647Barnyardgrass0700309000004000200Foxtail, Giant70100070100020006040101000Kochia2030004006030010000700Pigweed4010000100040300900701000Ragweed000000050000000Ryegrass, Italian00000000000000125 g ai/haCompoundsPreemergence4849505153546162636465666768Barnyardgrass00100005070100030100070Foxtail, Giant00100000100100900100100080Kochia0000009070006040030Pigweed009000010090900100100080Ragweed0000000000010000Ryegrass, Italian000000301000103000125 g ai/haCompoundsPreemergence6970717273747576777879808182Barnyardgrass9020109010060100701006010010090100Foxtail, Giant7060100901001001007010090100100100100Kochia30009010010080010020801009080Pigweed100040100100901005010080100100100100Ragweed000010000003020060Ryegrass, Italian00010502080070090502080125 g ai/haCompoundsPreemergence8384858687888990919293949596Barnyardgrass300090100090409010000700Foxtail, Giant900050100050707010000500Kochia00010090050020900000Pigweed3000100100010004010000400Ragweed00000000000000Ryegrass, Italian000202002000800000125 g ai/haCompoundsPreemergence979899100101102103104105106107108109110Barnyardgrass103010010010050303001003020100Foxtail, Giant7040100100400604020801008040100Kochia0080000700030100100100Pigweed2009060001004020301007060100Ragweed0010000000020000Ryegrass, Italian00300000000800070125 g ai/haCompoundsPreemergence111112113114115116117118119120121122123124Barnyardgrass0809020000020030907080Foxtail, Giant07010090030202090010040100100Kochia05060100000000701010Pigweed0100100300703050100009080100Ragweed0008000050000000Ryegrass, Italian004000000000302020125 g ai/haCompoundsPreemergence125126127128129130131132133134135136137138Barnyardgrass1000605010010010010030804010090100Foxtail, Giant100010010010010090100909050100100100Kochia1000300100100100601010010070100Pigweed100070301001001001001005020100100100Ragweed20000020000008000Ryegrass, Italian700101060802030020102020100125 g ai/haCompoundsPreemergence139140141142143144145146Barnyardgrass0060010010080100Foxtail, Giant001000100100100100Kochia0402001001004080Pigweed010900—100100100Ragweed500300010300Ryegrass, Italian0101007070505031 g ai/haCompoundsPreemergence145146Barnyardgrass4020Foxtail, Giant9080Kochia060Pigweed10060Ragweed00Ryegrass, Italian10031 g ai/haCompoundsPreemergence12345193637384344454650Barnyardgrass201060000002000000Foxtail, Giant307070000020300004050Kochia03000000001000000Pigweed20405000000603000500Ragweed00000000000000Ryegrass, Italian0000000000000031 g ai/haCompoundsPreemergence5153546263666768697071747677Barnyardgrass000304090010700010020Foxtail, Giant00030107001040040400100Kochia0002000000000080Pigweed000600200204000200100Ragweed00000000000000Ryegrass, Italian0000000000000031 g ai/haCompoundsPreemergence8081828687888990929394959697Barnyardgrass601050070020070001000Foxtail, Giant90309006001010100000040Kochia100070103001009000000Pigweed100100902040010010000000Ragweed00000000000000Ryegrass, Italian00000000300000031 g ai/haCompoundsPreemergence9899100101102103104105107108109110111112Barnyardgrass0704000000901004000Foxtail, Giant090500010001001008000Kochia04000000090001000Pigweed05000040001000040060Ragweed00000000000000Ryegrass, Italian000000003000001031 g ai/haCompoundsPreemergence113114115116117118119120121122123124126127Barnyardgrass000000000302010020Foxtail, Giant601000005003004060030Kochia100700000020100000Pigweed100005002020004004000Ragweed0202030010000000000Ryegrass, Italian100000000100000031 g ai/haCompoundsPreemergence128129131132133134135137138140141142143144Barnyardgrass20700300000700002080Foxtail, Giant30100040010070900100100100Kochia0301010000050010010090Pigweed090907070001080000—100Ragweed00000000000000Ryegrass, Italian0200000001010002020Test B
[0406] Plant species in the flooded paddy test selected from rice (Oryza sativa), sedge, umbrella (small-flower umbrella sedge, Cyperus difformis), ducksalad (Heteranthera limosa), and barnyardgrass (Echinochloa crus-galli) were grown to the 2-leaf stage for testing. At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test. Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
[0000]
[00025]
TABLE B250 g ai/haCompoundsFlood1234567891011121318Barnyardgrass000000002000000Ducksalad20303000000758000700Rice000000000000300Sedge, Umbrella80100100000070758000750250 g ai/haCompoundsFlood1920212223242526303335363738Barnyardgrass0030000060000000Ducksalad030704030001004080500040Rice0000150020000000Sedge, Umbrella040100509500100095600030250 g ai/haCompoundsFlood4344454647484950515354565758Barnyardgrass00000202001500000Ducksalad0007500065000000Rice000100202001500000Sedge, Umbrella03008000080000000250 g ai/haCompoundsFlood6162636465666768697071747576Barnyardgrass20404500300000040400Ducksalad100100100070100007570901009585Rice002500000200003510Sedge, Umbrella1009010008595008080951009570250 g ai/haCompoundsFlood7778798081828384858687888990Barnyardgrass15206075453500040500400Ducksalad857090100100100800010010009530Rice0154555030000203520400Sedge, Umbrella1008010010010095800010010009560250 g ai/haCompoundsFlood919293949596979899100101102103104Barnyardgrass02500000060400000Ducksalad10010000300700100900809575Rice20000000040000200Sedge, Umbrella95100000075090700809575250 g ai/haCompoundsFlood105106107108109110111112113114115116117118Barnyardgrass0050002502065003000Ducksalad400958007501008040075200Rice0035002504020007000Sedge, Umbrella009560090010090900906050250 g ai/haCompoundsFlood119120121122123124125126127128129130131132Barnyardgrass00508040454590402045551545Ducksalad1000010095100700909090408090Rice0035403540350151540351545Sedge, Umbrella9007010095100900908580989080250 g ai/haCompoundsFlood133134135136137138139140141142143144145146Barnyardgrass0004575500020050705040Ducksalad09585609510030070090100100100Rice3020203550450010040353035Sedge, Umbrella09585809585005009010010085Test C
[0407] Seeds of plant species selected from blackgrass (Alopecurus myosuroides), ryegrass, Italian (Italian ryegrass, Lolium multiflorum), wheat (winter wheat, Triticum aestivum), galium (catchweed bedstraw, Galium aparine), corn (Zea mays), crabgrass, large (large crabgrass, Digitaria sanguinalis), foxtail, giant (giant foxtail, Setaria faberii), johnsongrass (Sorghum halepense), lambsquarters (Chenopodium album), morningglory (Ipomoea coccinea), nutsedge, yellow (yellow nutsedge, Cyperus esculentus), pigweed (Amaranthus retroflexus), ragweed (common ragweed, Ambrosia elatior), soybean (Glycine max), barnyardgrass (Echinochloa crus-galli), oilseed rape (Brassica napus), pigweed, palmer (palmer pigweed, Amaranthus palmeri), waterhemp (common waterhemp, Amaranthus rudis), velvetleaf (Abutilon theophrasti), kochia (Kochia scoparia), surinam grass (Brachiaria decumbens), nightshade (eastern black nightshade, Solanum ptycanthum), wild poinsettia (Euphorbia heterophylla), windgrass (Apera spica-venti), and oat, wild (wild oat Avena fatua), were planted into a blend of loam soil and sand or a silt loam soil and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
[0408] At the same time, plants selected from these crop and weed species and also chickweed (common chickweed, Stellaria media), buckwheat, wild (wild buckwheat, Polygonum convolvulus), wild mustard (Sinapis arvensis), field poppy (Papaver rhoeas), field violet (Viola arvensis), geranium, cutleaf (cutleaf geranium, Geranium dissectum), Canada thistle (Cirsium arvense), and speedwell (bird's-eye speedwell, Veronica persica), were planted in pots containing Sunshine Redi-Earth© planting medium comprising spaghnum peat moss, vermiculite, starter nutrients and dolomitic limestone and treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for 13 to 15 d, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
[0409] Plant species in the flooded paddy test consisted of rice (Oryza sativa), sedge, umbrella (small-flower umbrella sedge Cyperus difformis), ducksalad (Heteranthera limosa), and barnyardgrass (Echinochloa crus-galli) grown to the 2-leaf stage for testing. At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test.
[0000]
[00026]
TABLE C125 g ai/haCompoundsPostemergence715162021222326333572737577Barnyardgrass102020202010203025151030—30Blackgrass 510 510 5 52035201030353025Buckwheat, Wild————————————85—Canada Thistle————————————100—Chickweed50908075806085988550988598100 Corn1520202020151025302020152025Crabgrass, Large1525251535252565151050602530Field Poppy————————————100—Field Violet————————————100—Foxtail, Giant1535352515253025202020252570Galium4095559880708095856098988098Geranium, Cutleaf————————————65—Johnsongrass——————20252010102070—Kochia209590100 905085959590100 100 98100 Lambsquarters5595608585758098907085989090Morningglory5590757070503585656070756580Mustard, Wild—————————————Nightshade————————————98—Nutsedge, Yellow 520201010 5101010 51530515Oat, Wild 51010 5 5 5 53530 010103515Oilseed Rape 5 0706030803580956565509585Pigweed70985095909585100 100 98100 100 —100 Pigweed, Palmer————————————85—Poinsettia, Wild————————————80—Ragweed2565406055505090602075656070Ryegrass, Italian30 5 5 515 5 51030 51520510Soybean7090506060753575553570608565Speedwell————————————100—Surinam Grass————————————20—Velvetleaf4085507070854080754070757565Waterhemp65——98858095100 100 9590100 95100 Wheat 5 0 0 5 0 0 0105 0 5 51030Windgrass————————————5—125 g ai/haCompoundsPostemergence7980828992107110125130136137138143144Barnyardgrass——60—20—3010201040—2010Blackgrass3025454520602530301540654015Buckwheat, Wild909510085—100809880809010010095Canada Thistle100859885—90959098851009510090Chickweed989090100100 1009098908010010010085Corn2025252020301520202025303025Crabgrass, Large6530209035606020203070953025Field Poppy10085100100—10010010010090100100100100Field Violet909590100—100100981001008510010090Foxtail, Giant4015202050252525302535652540Galium95909090100 959090807585859590Geranium, Cutleaf65606055—756055604535607540Johnsongrass8553085—98152515152590205Kochia98809595100—— 98100989890989810090Lambsquarters100859010085100981009580901009585Morningglory3060755585955075553520656560Mustard, Wild—90100——10010010010010010010010095Nightshade1007510095—1009890908090989090Nutsedge, Yellow55105205510555302510Oat, Wild3555030 5455515151010702035Oilseed Rape100709510070989595988010010010085Pigweed————100 —————————Pigweed, Palmer85609885—10095856570709810080Poinsettia, Wild85757590—909085757575907560Ragweed6535552570456055503530755515Ryegrass, Italian305251030502015151010352020Soybean6595407075953570954040556565Speedwell10010095100—1009598988510010010095Surinam Grass35252520—352520201020352025Velvetleaf9055757085907530757070757065Waterhemp98909595100 10095908575751009075Wheat151530151030152530520353015Windgrass30303535—50303535304550403062 g ai/haCompoundsPostemergence715162021222326333572737577Barnyardgrass152020102010102010101020—25Blackgrass 010 0 5 5 01515101010401020Buckwheat, Wild————————————80—Canada Thistle————————————75—Chickweed30905065506550858545909090100 Corn1020151015 5 520252010151520Crabgrass, Large2025251525252025101510251530Field Poppy————————————80—Field Violet————————————98—Foxtail, Giant1020301020152510101020201025Galium10955580756055958055 5757095Geranium, Cutleaf————————————35—Johnsongrass——————15202010102010—Kochia259580100 908555909560100 100 90100 Lambsquarters3075407065706598806575907070Morningglory4085407040356065756040852090Mustard, Wild——————————————Nightshade————————————85—Nutsedge, Yellow 5 510 5 5 5 510 5 01020 015Oat, Wild 5 5 5 5 5 0101525 0 5 54010Oilseed Rape 0100 6050505550755550 0988070Pigweed6095859890707098989085100 —100 Pigweed, Palmer————————————95—Poinsettia, Wild————————————80—Ragweed2050105545504055501040605035Ryegrass, Italian3010 010 0 0 510 5 510101010Soybean4080505560357065303540758570Speedwell————————————100 —Surinam Grass————————————20—Velvetleaf3560304060553575653540707055Waterhemp60——9090858598100 9090100 90100 Wheat 5 0 0 5 0 0 0 5 0 0 05 010Windgrass————————————10—62 g ai/haCompoundsPostemergence7980828992107110125130136137138143144Barnyardgrass——10—15—205101020—1010Blackgrass2054030 5202015201015101515Buckwheat, Wild857510075—75957575909810010080Canada Thistle70758585—909890988598909090Chickweed95759085100 9895908075901008585Corn2015251515202015152015252020Crabgrass, Large7010308525302515101040851520Field Poppy100 85100100—98100100100801001009090Field Violet859090100—9895989595851009880Foxtail, Giant2510101025202510101040301030Galium85858580100 907580856075808085Geranium, Cutleaf55354050—604055455030556035Johnsongrass6051010—3510101010108010 5Kochia90809580100 95100959585989510090Lambsquarters908085100501009595858085959070Morningglory3055302565806050652020655050Mustard, Wild—80100100—95100981008510010010080Nightshade95709595—9895858570901009075Nutsedge, Yellow 5520010555501010510Oat, Wild45104040 5354515151010501030Oilseed Rape9865959050958590958090959570Pigweed————98—————————Pigweed, Palmer70709880—1009880457050908040Poinsettia, Wild80708580—908075607065757050Ragweed7515601060356045553030355525Ryegrass, Italian255205102015101055301015Soybean6590356570955065755045605550Speedwell9810095100—100909898801001008595Surinam Grass30152520—201510151010251020Velvetleaf8030504060757060653515506550Waterhemp958598909010090757555701007575Wheat1001010 510152015510201510Windgrass30203050—50351035303035351531 g ai/haCompoundsPostemergence713151620212223263335727375Barnyardgrass51015101010 51010 5 5 515—Blackgrass0 5 5 0 5 0 0 515 5 010 5 5Buckwheat, Wild—————————————60Canada Thistle—————————————75Chickweed570802060506050805540858085Corn10 5101510 5 5 5252510152015Crabgrass, Large51520151020151020 510101010Field Poppy—————————————80Field Violet—————————————98Foxtail, Giant525302010101035101010302510Galium050605060802555807035807070Geranium, Cutleaf—————————————40Johnsongrass———————152010 5101010Kochia30 30955095508050909540100 100 85Lambsquarters25 55755080607055907040858055Morningglory25 30753065251055606550657515Mustard, Wild——————————————Nightshade—————————————80Nutsedge, Yellow0 5 0 5 5 0 0 010 5 01015 0Oat, Wild0 5 5 5 0 0 0 51010 0 5 535Oilseed Rape0359535504040 5754530608080Pigweed40 709075957570759895708585—Pigweed, Palmer—————————————90Poinsettia, Wild—————————————70Ragweed20 54010501035355530 5505510Ryegrass, Italian0 0 5 0 5 0 0 0 5 5 0 5 510Soybean25 35453565404030556525707065Speedwell—————————————95Surinam Grass—————————————15Velvetleaf20 25502550604035555030506035Waterhemp70 ———95857590988080809890Wheat0 0 0 0 0 0 0 0 0 0 0 0 5 5Windgrass————————————— 531 g ai/haCompoundsPostemergence777980828992107110125130136137138143Barnyardgrass25——10—10—1055510—10Blackgrass20105351510201520510103515Buckwheat, Wild—80707075—7585659060758085Canada Thistle—65758580—8590857575858085Chickweed8090758595100 9095757565558580Corn1525102015202020102010152020Crabgrass, Large25251530601010201010520655Field Poppy—98758595—9810095100859510090Field Violet—758570100—9895988590709580Foxtail, Giant2020101010201010101020202010Galium9880757575858075708065708085Geranium, Cutleaf—50353035—3530303525253550Johnsongrass—6552010—101055510255Kochia100 80759575100 851009085809085100Lambsquarters7585757575608590989075759090Morningglory8520354015856050452515155570Mustard, Wild——8095——909095909585100100Nightshade—95658090—9085758075808085Nutsedge, Yellow10 501001055500005Oat, Wild 56004010 5403010105105510Oilseed Rape7098609595508060858580958580Pigweed98————90————————Pigweed, Palmer—80358075—9595856555458075Poinsettia, Wild—75656560—7565657065656065Ragweed402010355403550354520353050Ryegrass, Italian 530015515351051055510Soybean5070756040404040605540305540Speedwell—9010085100—100957085808010080Surinam Grass—25102010—252010105102010Velvetleaf5075354535506540354550153555Waterhemp9895809570859890807570609880Wheat 0 501010 0555555510Windgrass—3553510—152515151010153531 g ai/haCompoundPostemergence144Barnyardgrass5Blackgrass10Buckwheat, Wild55Canada Thistle60Chickweed55Corn15Crabgrass, Large25Field Poppy80Field Violet65Foxtail, Giant10Galium70Geranium, Cutleaf20Johnsongrass5Kochia90Lambsquarters75Morningglory20Mustard, Wild7031 g ai/haCompoundPostemergence144Nightshade75Nutsedge, Yellow0Oat, Wild30Oilseed Rape35Pigweed—Pigweed, Palmer35Poinsettia, Wild35Ragweed15Ryegrass, Italian10Soybean30Speedwell70Surinam Grass20Velvetleaf30Waterhemp60Wheat5Windgrass1016 g ai/haCompoundsPostemergence713151620212223263335727375Barnyardgrass51020 51010 51010 55 510—Blackgrass0 0 0 0 5 0 0 010 50 5100Buckwheat, Wild—————————————45Canada Thistle—————————————70Chickweed5403520604020 555505658060Corn51015 5 5 5 5 520205101010Crabgrass, Large5 530101010101010 510 101510Field Poppy—————————————70Field Violet—————————————80Foxtail, Giant51025101010101010 55301510Galium065704570551050555035 807040Geranium, Cutleaf—————————————30Johnsongrass——————— 010100 5 55Kochia0309040956050 590905100 9875Lambsquarters550704065656525756050 757550Morningglory52065 57510 510655540 75705Mustard, Wild——————————————Nightshade—————————————75Nutsedge, Yellow0 5 0 0 0 0 0 0 5 50 5 50Oat, Wild0 0 5 0 0 0 0 510 50 5 55Oilseed Rape0 04515503035 5403520 50 560Pigweed35 75905085856060759580 8090—Pigweed, Palmer—————————————75Poinsettia, Wild—————————————65Ragweed10 530203010 5154040035505Ryegrass, Italian10 0 0 0 0 0 0 0 5 00 5 50Soybean25 30451525304020652525 604550Speedwell—————————————90Surinam Grass—————————————10Velvetleaf520502020405010302540 404030Waterhemp35 ———75757580959065 858585Wheat0 0 0 0 0 0 0 0 0 00 0 00Windgrass—————————————016 g ai/haCompoundsPostemergence777980828992107110125130136137138143Barnyardgrass15——10—10—1055510—5Blackgrass 52003010 551010555510Buckwheat, Wild—75708070—4585703550707075Canada Thistle—55758580—8065807565758085Chickweed8095605565100 8060707555707580Corn151515201510101010105101515Crabgrass, Large1010101055201010105510355Field Poppy—85705090—808590100658510080Field Violet—707560100—9580908085659075Foxtail, Giant101051010101010101010201020Galium7575705075807560657550556575Geranium, Cutleaf—45303035—255252515103030Johnsongrass—40555—2055555105Kochia9575558070100 8095858080857598Lambsquarters5575507070408075707555556575Morningglory501025255202030201010101015Mustard, Wild——7595100—8590909885100100100Nightshade—90608575—7575507570607565Nutsedge, Yellow 5 00100 050500000Oat, Wild 01502515 552055551010Oilseed Rape1080507060 56560807065907085Pigweed95————85————————Pigweed, Palmer—60307555—9075403550207545Poinsettia, Wild—30654055—7040655540153055Ragweed403054003525405252020020Ryegrass, Italian 0——50551055550555Soybean2560602535305040254030203530Speedwell—85907595—10060558075759580Surinam Grass—25102010—101551055205Velvetleaf3530303520356050202520101035Waterhemp9595806570809585756570409875Wheat 0 5050 0555100555Windgrass—2001010—520101051003016 g ai/haCompoundPostemergence144Barnyardgrass5Blackgrass10Buckwheat, Wild70Canada Thistle90Chickweed50Corn15Crabgrass, Large10Field Poppy60Field Violet60Foxtail, Giant5Galium50Geranium, Cutleaf15Johnsongrass5Kochia85Lambsquarters40Morningglory30Mustard, Wild7016 g ai/haCompoundPostemergence144Nightshade65Nutsedge, Yellow0Oat, Wild20Oilseed Rape35Pigweed—Pigweed, Palmer25Poinsettia, Wild30Ragweed10Ryegrass, Italian5Soybean30Speedwell60Surinam Grass10Velvetleaf25Waterhemp35Wheat5Windgrass108 g ai/haCompoundPostemergence13Barnyardgrass5Blackgrass0Chickweed5Corn5Crabgrass, Large5Foxtail, Giant5Galium5Kochia5Lambsquarters60Morningglory5Nutsedge, Yellow0Oat, Wild0Oilseed Rape0Pigweed60Ragweed5Ryegrass, Italian0Soybean20Velvetleaf15Wheat04 g ai/haCompoundPostemergence13Barnyardgrass5Blackgrass0Chickweed5Corn5Crabgrass, Large5Foxtail, Giant5Galium10Kochia0Lambsquarters30Morningglory5Nutsedge, Yellow0Oat, Wild0Oilseed Rape0Pigweed30Ragweed5Ryegrass, Italian0Soybean15Velvetleaf15Wheat0125 g ai/haCompoundsPreemergence1516202126303361727375777980Barnyardgrass100 758598100 25100 65100100100100 95100Blackgrass8010100 9090 090510010075100 9090Corn2510302040 5100 60 505353020Crabgrass, Large100 100 100 100 100 98100 9010010098100 9898Foxtail, Giant100 100 100 909875100 6510010098100 98100Galium——95100 100 859515100100098598Johnsongrass————98153520100 9570—7060Kochia———————30——100—100100Lambsquarters955090709555856010010070988598Morningglory602510109535400 95 7510656075Nightshade———————75——80—9590Nutsedge, Yellow50 010 045 5 50 0 102030035Oat, Wild———————5——5—4030Oilseed Rape100 100 50100100 100 100 10100 6540100 95100Pigweed100 95100 100100 100 100 —100100—100 ——Pigweed, Palmer———————75——100—9098Poinsettia, Wild———————0——35—4085Ragweed20 0 0 050 05030 45 255453020Ryegrass, Italian50 5709095 585510010015903525Soybean55 510 0—603010 90 405025585Surinam Grass———————25——80—8598Velvetleaf100 7550100 100 40100 5100 9525100 75100Waterhemp100 100 9898100 100 100 10010010098100 100100Wheat 5 0 5 01510 510 80 7010 01515Windgrass———————70——100—100100125 g ai/haCompoundsPreemergence828992107125130136138143144Barnyardgrass90100100100———95—95Blackgrass59010090908595907530Corn510 4045525552030Crabgrass, Large989810010010010010098100100Foxtail, Giant988510098100100100100100100Galium800—9580909058055Johnsongrass8560—80758570608070Kochia9590—1009898988090100Lambsquarters706510095959580709575Morningglory1020 7085501030102520Nightshade8585—90———80—100Nutsedge, Yellow00 5005050570Oat, Wild510—6555604530510Oilseed Rape501510098809598209890Pigweed——100———————Pigweed, Palmer10098—10010085100100100100Poinsettia, Wild2040—70304550502580Ragweed3050 605035104010510Ryegrass, Italian540 9590857065804560Soybean010 604520304052060Surinam Grass3575—986580100755060Velvetleaf106010098658565507045Waterhemp10010010010010010010098100100Wheat05 203550101005Windgrass90100—1001001001001001009062 g ai/haCompoundsPreemergence1516202126303361727375777980Barnyardgrass100 303090100 10955080100 80987570Blackgrass50 5855590 070098100 80907570Corn10 0 0 525 01010204002055Crabgrass, Large100 909898100 80100 75100 100 98100 100100Foxtail, Giant100 9090959865986075100 65100 8085Galium——80 59560601090100 5987075Johnsongrass————80 0250708030—5055Kochia———————5——90—90100Lambsquarters8520102595308050909035100 7095Morningglory3525 5 58510250556020351040Nightshade———————50——75—8085Nutsedge, Yellow 5 0 0 015 0 50 0 00 000Oat, Wild———————5——0—510Oilseed Rape100 605075100 100 850805010100 7070Pigweed100 50100 98100 100 100 —100 100 —100 ——Pigweed, Palmer———————70——95—90100Poinsettia, Wild———————0——35—1040Ragweed30 5 0 060 04054010040205Ryegrass, Italian15 5301585 03004585535305Soybean40 0 0 03510—2015251015540Surinam Grass———————60——35—5060Velvetleaf100 50 5708510555557535702070Waterhemp100 85100 95100 100 100 90100 100 98100 95100Wheat 0 0 0 0 5 0 05303010 050Windgrass———————40——100—10010062 g ai/haCompoundsPreemergence828992107125130136138143144Barnyardgrass2090 98100———80—70Blackgrass58510090606060808040Corn00 3515555505Crabgrass, Large9010010010010010010098100100Foxtail, Giant90601009898987085100100Galium00—9030905058050Johnsongrass4030—70607035505040Kochia9085—1009065858090100Lambsquarters20010085603525259565Morningglory05 6040102050510Nightshade4065—80———80—90Nutsedge, Yellow00 500000060Oat, Wild530—30103555510Oilseed Rape50100855040705805Pigweed——100———————Pigweed, Palmer10090—100100100100100100100Poinsettia, Wild020—4025102552040Ragweed205 6050550000Ryegrass, Italian515 557040603520300Soybean05 70350101501530Surinam Grass2565—98406510653570Velvetleaf02510098607515204015Waterhemp10010010010010010010010010098Wheat00 015050500Windgrass8065—10090100851001008031 g ai/haCompoundsPreemergence1315162021263033617273757779Barnyardgrass408515 55575154009080606060Blackgrass 0 0040 3590 0100989851510Corn10 000 0 0 0 0020200150Crabgrass, Large85100 75 50 75100 359810100 100 85100 98Foxtail, Giant95100 25 50 809830955080100 25100 70Galium———0 0901060075100 00Johnsongrass—————50 0 5065400—5Kochia————————5——50—90Lambsquarters157020 530852560158090106010Morningglory 52000 01010 00401002010Nightshade————————60——75—65Nutsedge, Yellow 5 000 0 0 0 00 0 00 00Oat, Wild————————0——0—0Oilseed Rape50100 50 0 0855580080200550Pigweed60100 055 55100 95100 —100 95—100 —Pigweed, Palmer————————50——100—85Poinsettia, Wild————————0——40—0Ragweed101000 030 0350 0 00 00Ryegrass, Italian 0 5001075 0300453553010Soybean 51000 010——20 0 00 50Surinam Grass————————10——30—30Velvetleaf7085504030 030560305305Waterhemp100 100 60 85 75100 100 100 75100 100 95100 98Wheat 5 000 020 0 00 0 00 05Windgrass————————5——45—8031 g ai/haCompoundsPreemergence80828992107125130136138143144Barnyardgrass305358585———40—40Blackgrass100158090603035507510Corn500150000000Crabgrass, Large807098100 9898100859510098Foxtail, Giant40805100 98857065809885Galium500—60550003050Johnsongrass30540—305102502510Kochia955060—100606580758090Lambsquarters70200100 75303030351040Morningglory20004001050000Nightshade702075—60———50—65Nutsedge, Yellow000 500000020Oat, Wild0010—50150005Oilseed Rape8000100 405105050Pigweed———100 ———————Pigweed, Palmer858570—100100757560100100Poinsettia, Wild3000—10005055Ragweed000553010020000Ryegrass, Italian005 53530353010200Soybean20054020000000Surinam Grass501035—6020502565105Velvetleaf550207575510525100Waterhemp1005085100 98100100100859898Wheat000 01000050—Windgrass603050—100857030100853016 g ai/haCompoundsPreemergence1315162021263033617273757779Barnyardgrass 10100010 4010 20 025 15 520 5Blackgrass0 00054500060 5055Corn5 0000 000050000Crabgrass, Large 60955520 98075 0100 98 6598 65Foxtail, Giant0100 535 20 95560 055 98 095 40Galium———10 — 580 0055000Johnsongrass—————55000500—0Kochia————————0——0—5Lambsquarters 50600007010 25 565 85 050 0Morningglory52010 002000010 0010 20Nightshade————————60 ——40—30Nutsedge, Yellow0 0000 000000000Oat, Wild————————0——0—0Oilseed Rape0300008010 50 050000Pigweed598055 5100 90 80 —100 90 —85 —Pigweed, Palmer————————40 ——70—75Poinsettia, Wild————————0——10—0Ragweed01000020055 000000Ryegrass, Italian0 00003500010 30 000Soybean5 0000—015 —00050Surinam Grass————————0——0—5Velvetleaf 20600010 005010 0010 10Waterhemp 809010 30 70 100 85 100 50 100 65 7595 100Wheat0 0000 000000000Windgrass————————0——5—6016 g ai/haCompoundsPreemergence80828992107125130136138143144Barnyardgrass10553565———20—10Blackgrass505456053001055Corn000 00050050Crabgrass, Large556075100 98359850757085Foxtail, Giant5200100 60305025352070Galium000—5000000Johnsongrass500—1051010050Kochia70060—1005105053070Lambsquarters3030090301035250550Morningglory500100000000Nightshade55510—30———40—35Nutsedge, Yellow000 00050000Oat, Wild005—0500000Oilseed Rape3500855005000Pigweed———100 ———————Pigweed, Palmer1005565—100908595406585Poinsettia, Wild500—0000050Ragweed000300000000Ryegrass, Italian000 5100155050Soybean000 00000000Surinam Grass104010—15510030510Velvetleaf3001050401050500Waterhemp956070100 100705065758598Wheat000 05000000Windgrass54060—8020300702508 g ai/haCompoundPreemergence13Barnyardgrass0Blackgrass0Corn0Crabgrass, Large30Foxtail, Giant0Lambsquarters5Morningglory0Nutsedge, Yellow0Oilseed Rape0Pigweed10Ragweed0Ryegrass, Italian0Soybean0Velvetleaf10Waterhemp10Wheat04 g ai/haCompoundPreemergence13Barnyardgrass0Blackgrass0Corn0Crabgrass, Large25Foxtail, Giant0Lambsquarters0Morningglory0Nutsedge, Yellow0Oilseed Rape0Pigweed5Ragweed0Ryegrass, Italian0Soybean0Velvetleaf5Waterhemp5Wheat0250 g ai/haCompoundsFlood616692119Barnyardgrass40804025Ducksalad909510050Rice2020150Sedge, Umbrella859510090125 g ai/haCompoundsFlood61626692119Barnyardgrass202025200Ducksalad9075859540Rice20100150Sedge, Umbrella856585908062 g ai/haCompoundsFlood61626692119Barnyardgrass00000Ducksalad754080600Rice2000150Sedge, Umbrella806075605531 g ai/haCompoundsFlood61626692119Barnyardgrass00000Ducksalad50040300Rice2000100Sedge, Umbrella8004020016 g ai/haCompoundFlood62Barnyardgrass0Ducksalad0Rice0Sedge, Umbrella0Want more 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