Yei, thanks for your input, but the point was that we
need and want that methyl group to stay there. Maybe in all this excitation I failed to express myself clearly. That methyl is one of the crucial reasons why carvacrol and thymol look so promising. The goal is to prepare either 4-
methyl-3-methoxy-phenylacetone or 4-
methyl-2,5-dimethoxy-phenylacetone since these two yield psychedelics that are otherwise synthesized from difficult to obtain precursors. This proposal is in my opinion the most OTC and kitchen chemist friendly that I ever saw (if it works!). As you can see the chemicals needed on the way to the two P2P’s are all OTC except maybe for Oxone which is needed for the
in situ generation of DMDO (well, at least in my country Oxone is not OTC, but I heard that elsewhere it can be obtained and if not, maybe ammonium persulphate might substitute it). However, now we first have to hold down the wishful thinking and examine that benzylic DMDO oxidation review to see its applicability in the reaction in question as well as its kitchen chemistry potential. If it turns out as theoretically possible we will have the opportunity to add DOM and MMA to the list of “essential amphetamines” but unlike the others on that list the essential oils needed would bee literally uncontrollable as they are everywhere around (oregano, thyme, camphor, carvone, turpentine and who know how many other ubiquitous essential oils can bee a potential source).
Yei, BTW, the oxidation of thymole/carvacrol would unlikely go the route you described. The methyl group would not be oxidized that easily. It would probably be left intact and the quinone would break into a maleic acid and other degradation products. Also the isopropyl groups tend to be quite easily oxidatively cleaved. However, if you are interested in the benzylic vs. ring oxidations you can check this review: DOI:
10.1016/S0040-4020(02)01492-8
. But if you would still want to use this method for 2,5-dimethoxy-phenylacetone you can already start with 2- or 3-isopropyl-phenol though I have not check their availability. Or furthermore it might be possible to “isopropylate” p-dimethoxybenzene or 2,5-dimethoxy-halobenzene as can be done for benzene in
Post 517569
(Organikum: "Cumene by H2SO4 catalyzed Friedel-Crafts reaction", Chemistry Discourse) (thanks to Moo for reminding me about it).
Your question about benzylic halogenation has already been discussed and it was said that ring halogenation was unavoidable. See
Post 530677
(moo: "Nice thinking Nicodem, very nice!", Methods Discourse) and the replies. Though DMDO is somewhat electrophylic and we still have to see if it leaves the highly activated benzene ring intact, we already know that the halogens and halogantion reagents are all too electrophylic to not cause ring halogenation. There are other methods, off course, to make a double bond on that isopropyl and other oxidants like KMnO
4 or air in the presence of Co(AcO)
2 might also be useful. It’s just that this DMDO thing caught my attention as it seams so easy, available and selective.
I must also apologize for
a misinformation in one of my posts above. I confused DMDO with the “acetone peroxide”. Apparently the later is the cyclic trimer of DMDO. While acetone peroxide (
[-Me2C-O2-]3) forms easily from acetone and hydrogen peroxide in the presence of an acid as a catalyst the acetone solution of DMDO (
Me2C=O2) is prepared with Oxone. Acetone peroxide
* is also a shock sensitive explosive while DMDO doesn’t have to be isolated. For those with access to Oxone it seams to be the best choice for peroxidations, certainly superior to the performic or other similar methods which require more chemicals and work.
* those of us who were fascinated with dangerous stuff in the early years already know what acetone peroxide is (see http://www.worldhistory.com/wiki/a/acetone-peroxide.htm
)
while the structure and some typical reactions with DMDO are depicted in http://www.unibas.ch/mdpi/ecsoc/e0004/e0004.htm