Sciencemadness Discussion Board

Methyl Phenyl Butanone to Methyl Benzyl Ketone

evil_lurker - 14-8-2006 at 12:04

I just managed to stumble onto this reaction in which benzaldehyde is condensed with MEK to form methyl phenyl butanone.

The ketone is then subjected to a baeyer-villiger type oxidation using a peracid, such as performic, to the corresponding ester then hydrolyzed to form methyl benzyl ketone.

Does anyone have any references or information relating to this reaction?

Nicodem - 14-8-2006 at 12:15

I assume you are looking for this:

Phenylacetone by Bayer-Villiger Oxidation of 2-acetyl-1-phenylprop-1-ene
Boeeseken & Jacobs
Recl. Trav. Chim. Pays-Bas 55, 786 (1936)

Peracetic acid treatment of 2-acetyl-propenylbenzene (3-methyl-4-phenyl-but-3-en-2-one) below 30°C resulted in the formation of phenylacetone enol acetate (2-acetoxy-1-phenylprop-1-ene), mp 131°C and bp 103°C/3mmHg. Heating the crude reaction mixture with aqueous HCl at 80°C gave phenylacetone.

For more information check the old Twodogs' thread from The Hive (post No 245942).

matagaska - 9-8-2007 at 00:35

Quote:

The Baeyer-Villiger Oxidation
The reaction of the above unsaturated ketone with peracetic acid was first done by Boesken reported in Rec. Trav. Chim. 55, 786 (1936). There is some discussion of this also in Patent US3980708. Also see Organic Reactions Vols 9 43 I think. By following the directions in Patent US5670661 you will get about 35% ketone based on the weight of the unsaturated ketone used. In that patent it is suggested that by recycling a higher percentage can be achieved.

To a 1 litre flask is added 625 ml of Glacial acetic acid and 143 grms of Sodium Perborate. To this is added 100 grms of the methyl phenyl butenone with stirring and the mixture is heated to 50°C. The mixture will heat up so care has to be taken ie cooling. However if the mix gets too cool it solidifies. Stirring and heating continued for about 6 hours. Cooled poured into 1 litre H2O and extracted with toluene or DCM. The solvent is distilled leaving a yellow oil that has a pleasant smell. This is added to 500 mls of 10% NaOH solution (50/50 H20:EtOH) and stirred for 1-2 hours extracted with toluene or DCM and distilled and the fraction boiling between 210-220°C collected Phenyl-2-Propanone (About 35 gms)

In the Organic Reactions review of the Baeyer-Villiger there is a reference to the oxidation of alpha Methyl Cinnamaldehyde using H2O2 catalysed by a nitrobenzene selenic acid or something like that to give the same enol ester as above but in 90% yield



I can't get hold of Glacial Acetic Acid and need some help performing the above synth with Peracetic Acid ("Peracetic Acid - Hydrogen Peroxide and peroxyacetic acid mix. 25% w/v H202")

Anyone able to explain this to me??

Cheers

Polverone - 9-8-2007 at 08:06

I'm sure you can find information about peracetic acid oxidations without forum members providing a "recipe" for working with this particular substrate.

Sergei_Eisenstein - 9-8-2007 at 08:10

Are you certain you cannot get hold of GAA? It sounds somewhat peculiar to me.

Peracetic acid can be made by mixing hydrogen peroxide with GAA and allowing the mixture to stand for a while (several days) in the dark at RT. The concentration of peracetic acid depends, inter alia, on the strenght of your hydrogen peroxide. This is how it was done in Böseken's time.

Alternatively, you may want to try performic acid or oxone (in combination with e.g. GAA).

roamingnome - 9-8-2007 at 13:53

Always curious about the novelity ( if that’s even a word) of things

I saw on
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv8...

that a vaguely similar creature
3-Hydroxy-3-methyl-1-phenyl-1-butanone is too unstable to be purified by distillation, and decomposes to acetophenone and acetone.


An exhaustive degradation study of methyl phenyl butenone might well yield interesting intermediates in higher yield then 30% ..say allybenzene under Ultraviolet rays…

I know I know shut up gnome

Sergei_Eisenstein - 10-8-2007 at 00:21

That's just the retro-aldol reaction. It can be expected to occur, just as dehydration might be an option when you heat the reaction mixture. I'm not convinced that compound stability problems will arise when distilling 2-acetyl-propenylbenzene. You have an a,b-unsaturated ketone conjugated with an aromatic nucleus. These usually is a stabile type of product.

tina_craig - 20-9-2007 at 11:49

So can sodium percarbonate be substituted for sodium perborate for this procedure?

zgoat65 - 27-7-2012 at 19:18

Ammonium persulphate has been used with success in the bv oxidation. Also forming Caro's acid has been proven to increase yields.

zed - 28-8-2012 at 18:50

But then of course, you might be able to produce your unsaturated ester by the direct coupling of a diazonium salt, say Benzene Diazonium Chloride (or possibly FluoroBorate) with Methyl-Methacrylate.

Making P2P is a questionable hobby, so I assume your interest is purely academic.

The use of Methyl-Methacrylate as a substrate.... bears consideration, because like Styrene monomer, it can be generated by the thermal decomposition of a commonly available plastic.....In this case Lucite.

Moreover, under some conditions, the above mentioned coupling can result in the formation of a halo-ester. The halogen function of such esters, can then be reacted directly with ammonia or an amine.....To form a unique aminoacid. Yawn.

Now, if a guy/or gal were able to Diazotize 2-5-Dimethoxy Aniline, couple it with ethylacrylate to form the haloester, and then react that, with ammonia to produce the corresponding amino acid. That amino acid might be readily decarboxylated to form
2-5-Dimethoxyphenethylamine. Much more interesting than P2P.

Of course, I have no idea whether or not 2-5-Dimethoxy Aniline can be diazotized, but it is an interesting speculation.


popi - 29-10-2012 at 12:26

Can't help you evil but Antocho could, if you remember where? a dozen yrs ago.He's around these days again. . Good luck! Ou8e2

UnintentionalChaos - 29-10-2012 at 12:29

Quote: Originally posted by popi  
Can't help you evil but Antocho could, if you remember where? a dozen yrs ago.He's around these days again. . Good luck! Ou8e2


The OP is from 6 years ago. Antocho has showed up on this forum before and somewhat recently, but that is largely irrelevant.

popi - 29-10-2012 at 13:23

Thanks uc, Just trying to relate to some old Prof,'s of Chemistry. Alot have died and as you get older you miss them and miss the op date's.Like the oringal Wizard 1970...Ian and Rhodi who never ever not returned a post. I got respect for worlds best chemist's that answer questions from a student kid for free.When I grew up you had to pay for any of the information here. Now it's free..all you guys are unreal! It's a great site!

It's aliiiiiiiive.......

Johnny Windchimes - 6-5-2020 at 12:22

Quite the necropost, but I feel its warranted:

Everything you wanted to know about the Baeyer-Villiger 1-Phenyl-2-Propanone from Methyl Ethyl Ketone and Benzaldehyde reaction, but were afraid to ask....

They even formally cite "The Hive" for the above mentioned 'twodogs' method as executed by 'twodogs' and 'bio', with lots of commentary from Rhodium among other distinguished underground chemists during that time period.... Truly a detailed and OTC style set of papers.

As an aside, one of the references mentioned in the two attached papers is essentially off limits; it's a law enforcement only journal it seems.

Davis SF, Culshaw PN, Wermuth UD. The production of phenyl-2-propanone from benzaldehyde via a Baeyer-Villiger reaction. Journal of the Clandestine Laboratory Investigating Chemists Association 2008;18(1):28-31. [Editor’s Notes: Presents the title study (details not provided, in accordance with DEA Microgram policy). JCLICA is a law enforcement restricted publication. Contact: Forensic Chemistry, Queensland and Health Scientific Services, 39Kessels Rd., Coopers Plains, QLD 4108, Australia.]

I couldn't find it anywhere, anyone else craftier than me?



Be safe out there~!







Filename: doughty2016 - Baeyer-Villiger P2P Part 1 - Copy.pdf
Filename: doughty2018 - Baeyer-Villiger P2P Part 2 - Copy.pdf

[edit] files removed
[Edited on 7-5-2020 by Johnny Windchimes]

[Edited on 8-5-2020 by j_sum1]

karlos³ - 6-5-2020 at 20:05

I've got something in my front pocket for you
Why don't you reach on in my pocket and see what it is?
There, grab onto it, it's just for you
Give it a little squeeze and say: "How do you do?" :D

I took it out of said pocket and attached it instead :P
Its on the last pages.
But to me it doesn't look as informative as you might have hoped for.

And yes, that is only for LE use, or rather their forensical chemists.

But in my opinion, some of the best papers come from forensical chemists who tried out if something can be accomplished in a simplified manner.
And how well it does work in special, so the cops can adjust the possible yield produced in a clandestine lab and punish the chemist accordingly.
There is real gold among those studies.

They even use an OTC product in the attached paper as perborate source
Or like this from I believe it was Melbourne, where they published an unbelievably simple method for L-PAC, not long ago.
Those sort of papers always look like they tried to make it incredibly simple as if its meant as a gift to clandestine chemists(do they really think those wouldn't read their papers as well?).


Filename: JCLIC Vol 18 No 1 januar 2008.pdf

[edit] file removed

[Edited on 8-5-2020 by j_sum1]

Johnny Windchimes - 7-5-2020 at 04:26

Quote: Originally posted by karlos³  
I've got something in my front pocket for you
Why don't you reach on in my pocket and see what it is?
There, grab onto it, it's just for you
Give it a little squeeze and say: "How do you do?" :D

I took it out of said pocket and attached it instead :P
Its on the last pages.
But to me it doesn't look as informative as you might have hoped for.

And yes, that is only for LE use, or rather their forensical chemists.

But in my opinion, some of the best papers come from forensical chemists who tried out if something can be accomplished in a simplified manner.
And how well it does work in special, so the cops can adjust the possible yield produced in a clandestine lab and punish the chemist accordingly.
There is real gold among those studies.

They even use an OTC product in the attached paper as perborate source
Or like this from I believe it was Melbourne, where they published an unbelievably simple method for L-PAC, not long ago.
Those sort of papers always look like they tried to make it incredibly simple as if its meant as a gift to clandestine chemists(do they really think those wouldn't read their papers as well?).



YOU SIR..... Are a gentleman and a scholar!!

THANK YOU~!:D:D:D

j_sum1 - 7-5-2020 at 16:09

@karlos and Johnny Windchimes

Although these papers are bona fide scientific articles, they are likely to be used simply as recipes for illicit substances. There is a reason why they were restricted to law enforcement only.

We do not support low-level spoonfeed requests here. For consistency we should not be providing the same information unsolicited. Feel free to take this conversation up on a different board.
Refer to Polverone's post upthread.

This thread will be closed.

[Edited on 8-5-2020 by j_sum1]