Synthesis of Ethyl Methylphenylglycidate

27 Apr.,2023

 

Author: Subject: Synthesis of Ethyl Methylphenylglycidate Synthesis of Ethyl Methylphenylglycidate


I am interested in synthesizing ethyl methylphenylglycidate to make "bubblegum" scented perfume. I plan to do so by condensing acetophenone and diethyl malonate and then epoxidizing the carbon-carbon double bond. What reagent would I need for the epoxidation? Also, what equipment would I need? I think NileRed had a video about something similar to the first step (the cinnamic acid video).

Glacial Acetic acid/H2O2/Na2CO3 stirred in an ice bath would be a good try (?

Hi Russianwannabe76, pls post your experiments, I'm very interested in everything nice smelling :-)
If you have monochloroacetic acid, esterify it with ethanol and then this another way to go:
https://en.wikipedia.org/wiki/Darzens_reaction
here 250 g of monochloroacetic acid for 7 EUR, good price:
https://chemcraft.su/product/25266?field_packaging%5B0%5D=25...





Quote: Originally posted by Russianwannabe76  I am interested in synthesizing ethyl methylphenylglycidate to make "bubblegum" scented perfume. I plan to do so by condensing acetophenone and diethyl malonate and then epoxidizing the carbon-carbon double bond. What reagent would I need for the epoxidation? Also, what equipment would I need? This looks like a cool compound. I actually hadn't heard of it before. Judging by how new you are to chemistry, and the fact that you don't know what equipment you will need for this reaction, I would recommend trying out making some simple esters by Fischer esterification first, before you take on this more complex molecule. I agree with Fery's suggestion of the Darzens condensation, though, and that would involve performing a Fischer esterification to make the ethyl chloroacetate that you'll need. If you go that route, you could try an esterification using less valuable materials first, as a practice. Methyl salicylate is a really nice one. Also, with either the Darzens or the malonic ester, you'll need sodium ethoxide to generate the enolate from the ester. Have you made a plan to obtain that? The best way is to use sodium metal, though there are also makeshift methods of making it from sodium hydroxide. See a recent thread here: https://www.sciencemadness.org/whisper/viewthread.php?tid=15...

Quote: Originally posted by Garry63566  Glacial Acetic acid/H2O2/Na2CO3 stirred in an ice bath would be a good try? Why include sodium carbonate? If the goal is to produce peracetic acid in-situ to affect the epoxidation, adding a base seems counter-intuitive to me. Unless you're referring to another method that I am unaware of or blanking on...




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Quote: Originally posted by Texium (zts16)  This looks like a cool compound. I actually hadn't heard of it before.

It's well known on the drug forums (like the buffered peracetic/formic), being a hydrolysis and decarboxylation away from phenylacetone.

Understand everything now?

Accounts opened in 18 or 19 that had lain dormant until the past few months sure have a lot of similarities.

Maybe you need a bug up your butt to see things as clearly.



"You're going to be all right, kid...Everything's under control." Yossarian, to Snowden



Cool your jets SC. I also thought this thread was about benzyl glycidate (the compound you're thinking of). This is phenyl glycidate, 1 carbon shorter.



Reflux condenser?? I barely know her!



I think the phenylacetone precursor is what is meant with methyl phenylglycidate.
The glycidic acid ester moiety is already counted, so thats why it isn't a benzylglycidate ester.

Yes, my mistake. The precursor compound is sold as a phenylacetone precursor under the name "BMK glycidate" (BMK for benzyl methyl ketone, where I took benzyl from).



Reflux condenser?? I barely know her!



Quote: Originally posted by Texium (zts16)  I agree with Fery's suggestion of the Darzens condensation, though, and that would involve performing a Fischer esterification to make the ethyl chloroacetate that you'll need. If you go that route, you could try an esterification using less valuable materials first, as a practice. How dangerous is monochloroacetic acid? I'm new but I have taken a Chemistry class at a college before and apparently it is a very bad idea for me to get around chemicals that are toxic via skin absorption (I have a funny story about that, maybe I'll share it some time). Also, what equipment would I need? Please assume that I have absolutely nothing, I'm still new to Chemistry as a hobby. Like Fery, I am also interested in "nice smelling" chemicals. I want to make my own perfumes.

You're clearly going to need some experience with simpler stuff before you pursue this. If you want to get into organic chemistry like this, you should buy an inexpensive organic glassware kit from Deschem on eBay. Like this: https://www.ebay.com/itm/233642376874?epid=28012078542&h... It has all the essentials but it's not a huge investment. With a kit like that, you can run reactions under reflux, run simple and fractional distillations, and perform solvent extractions using the sep funnel. First thing you should do if you haven't run a distillation before is distill some water. I know it sounds silly, but I'm serious. It's really good practice. It'll ensure that the kit you get doesn't leak or break when heated, and it'll allow you to calibrate your thermometer too. Get some aspirin and HCL, make salicylic acid. Get some methanol and sulfuric or phosphoric acid, make methyl salicylate. Lovely wintergreen aroma. That's a good starter project, and you'll have to find several really useful chemicals that you'll need for other things in the future. Once you do that, you'll have enough experience to consider this synthesis again. I won't go into further details about salicylic acid and methyl salicylate because you can find everything you need on here and/or YouTube.




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Work with the simple and safe stuff before trying to work with the chlorinated stuff. Try a selection of esters, if you like nice smells.



Please remember: "Filtrate" is not a verb.
Write up your lab reports the way your instructor wants them, not the way your ex-instructor wants them.



Quote: Originally posted by Russianwannabe76   Quote: Originally posted by Texium (zts16)  I agree with Fery's suggestion of the Darzens condensation, though, and that would involve performing a Fischer esterification to make the ethyl chloroacetate that you'll need. If you go that route, you could try an esterification using less valuable materials first, as a practice. How dangerous is monochloroacetic acid? I'm new but I have taken a Chemistry class at a college before and apparently it is a very bad idea for me to get around chemicals that are toxic via skin absorption (I have a funny story about that, maybe I'll share it some time). Also, what equipment would I need? Please assume that I have absolutely nothing, I'm still new to Chemistry as a hobby. Like Fery, I am also interested in "nice smelling" chemicals. I want to make my own perfumes.
AFAIK monochloroacetic acid is the less toxic alkylating compound I have ever used in any of my synthesis according the risk carcinogenicity. It is crystalline, its ethyl ester should be more volatile. For producing ethyl ester you need a flask, condenser, separatory funnel (if no sep. funnel, you can use with some difficulties any vessel and a pipette to remove the bottom layer or a larger plastic medicinal syringe which is even cheaper than a pipette). Wearing gloves should be satisfactory to prevent skin absorption and covering working bench with few layers of plastic foil to prevent spilling drops to your workspace. Have a few old newspaper at hand to soak anything and an old bucket to throw anything into it.
Here studies concerning carcinogenicity / genotoxicity of monochloroacetic acid, just use the word "carcinogenicity" or "genotoxicity" as a search pattern - no such effect found using bacteria / mices.
https://www.epa.gov/sites/production/files/2016-09/documents...
https://ntp.niehs.nih.gov/ntp/htdocs/lt_rpts/tr396.pdf?utm_s...

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Quote: Originally posted by njl  Cool your jets SC. I also thought this thread was about benzyl glycidate (the compound you're thinking of).

Quote: Originally posted by karlos³  I think the phenylacetone precursor is what is meant with methyl phenylglycidate.
The glycidic acid ester moiety is already counted, so thats why it isn't a benzylglycidate ester.

Ethyl methylphenylglycidate is the ethyl ester of methylphenylglycidic acid. Methyl methylphenylglycidate is the methyl ester. Both hydrolyze to the same acid, it does not matter which ester. This IS the glycidic acid which decarboxylates to phenylacetones, read some more on the subject. Just because I say it (e.g. aq. IPA is a great recrystallization solvent, Ca(OH)2 doesn't melt, fractionation columns work by having a vertical rather than horizontal temperature gradient derisively aka "steam pipe" etc) doesn't mean it's not true.

Explosive and drug precursors subvert forums, sources, and general welfare (most toxic cpd OTC, seriously? We need videos for idiots to make cyanide, really?); this was well known at RS and the-hive. It's so fucked up of me to take such things into consideration.

[Edited on 1-5-2021 by S.C. Wack]



"You're going to be all right, kid...Everything's under control." Yossarian, to Snowden



You might want to double-check the reactions you’re proposing, wack. The actual phenylacetone precursor found in clandestine meth, BMK glycidate, is 2-methyl-3-phenylglycidic acid, while the acid in the compound being discussed here (which is also well-known as strawberry aldehyde in the fragrance world) is 3-methyl-3-phenylglycidic acid. I understand why your alarm went off, it’s an honest enough mistake.

[Edited on 5-1-2021 by Amos]

Quote: Originally posted by Amos   The actual phenylacetone precursor found in clandestine meth, BMK glycidate, is 2-methyl-3-methylglycidic acid, while the acid in the compound being discussed here (which is also well-known as strawberry aldehyde in the fragrance world) is 3-methyl-3-phenylglycidic acid.

I think you mean BMK glycidate is 2-methyl-3-phenylglycidic acid, but yeah. To be fair I don't think SC really made a mistake, the post says "ethyl methylphenylglycidate" which has 2 isomers, and it isn't immediately clear which one is being discussed until you read further into the thread. Either way though, valuable chemistry is being discussed.



Reflux condenser?? I barely know her!



Yep, thanks for help fixing the typo. And if you’re going to raise a big stink and suggest that nobody is as enlightened as you for not knowing drug precursors, while not even knowing the most commercially relevant and generally interesting isomer, when maybe your confidence itself is a mistake.

[Edited on 5-1-2021 by Amos]

Quote: Originally posted by Amos   while not even knowing the most commercially relevant and generally interesting isomer, when maybe your confidence itself is a mistake.

There wasn't much overconfident really about not googling and going with the first thing that comes to mind as I said; (AFAIK you can't do chemistry and be overconfident)...it's shallowness plus underconfidence in the quality of let's say post-Dr. Bob accounts. I apologize for this mischaracterization.

[Edited on 2-5-2021 by S.C. Wack]



"You're going to be all right, kid...Everything's under control." Yossarian, to Snowden



Glad we got past that, cheers.

Quote: Originally posted by Texium (zts16)  You're clearly going to need some experience with simpler stuff before you pursue this. If you want to get into organic chemistry like this, you should buy an inexpensive organic glassware kit from Deschem on eBay. Like this: https://www.ebay.com/itm/233642376874?epid=28012078542&h... Texium, I once bought something similar, only it was just a distillation kit). I had trouble propping up the distillation kit. I also had trouble heating it so I bought a stand for bunsen burners with the intention of instead using an alcohol burner or oil lamp, both of which I already had. How would I prop up the equipment?

Seriously? Buy a ring stand or two and some utility clamps, and while you’re at it, we’re in the 21st century, so get a hotplate to use instead of an open flame.

You could easily find the answers you’re looking for if you search the forum. The forum search engine isn’t the best though, so instead, type what you’re looking for into Google, followed by site:sciencemadness.org. I’m going to close this thread now to discourage you from asking for more hand-holding.




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Texium

Administrator Thread Closed
1-5-2021 at 18:58

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