(Stranger)
11-24-03 02:16
No 472752
(Rated as: good read)
High bees!
I want to share with you this part of the experimental of the article J.Med.Chem. 39(16) 1996, 3148-3157. (hosted by Pharmacist here: http://pharmacist.the-hive.tripod.com/ju
) They synthetise from 2,5-dimethoxy-3,6-dimethylbenzaldehyde (precursor to JUNO) another methylated benzaldehyde: the 2,4,5-trimethoxy-3,6-dimethylbenzaldehyd
Also the route can bee followed to achieve other strange and atypical PEAs, like some 2,3,5- and 2,3,6- analogs, lets make 'em and taste 'em too!
Here we go:
General Procedure for the Synthesis of the Aldehydes 10, 14, and 17: Representative Route to the Aldehyde 10a.
2,5-Dimethoxy-3,6-dimethylphenol (8a).
m-Chloro-perbenzoic acid (70%, 130 g, 0.53 mol) was added portionwise to a solution of 2,5-dimethoxy-3,6-dimethylbenzaldehyde (7a) (94 g, 0.48 mol) in dichloromethane (660 mL) with stirring at room temperature. The mixture was heated to reflux for 30 min, then ice (Z00 g) and a saturated solution of sodium thiosulfate (200 mL) were added. The resulting solid were filtered off and washed with a small amount of dichloromethane. The combined organic layer was washed successively with 1 N sodium hydroxide and brine, dried, and evaporated. The residue was dissolved in methanol (250 mL). To the solution was added 28% sodium methoxide in methanol (120 mL, 0.59 mol), and the mixture was stirred at room temperature for 30 min. Ice-water (300 mL) was added to the reaction mixture, and then the mixture was neutralized with 2 N hydrochloric acid affording white precipitate. The solid was collected by filtration, washed with water, and dried to afford crude 8a (75 g, 0.41 mol, 81%) as a white solid, which was used for the next step without further purification: 1H NMR (400 MHz, CDCl3) S 2.13 (s, 3H), 2.27 (s, 3H), 3.75 (s, 3H), 3.77 (s, 3H), 5.73 (br s, 1H), 6.29 (s, 1H).
4-Hydroxy-2,5-dimethoxy-3,6-dimethylbenz
To the solution of 2,5-dimethoxy-3,6-dimethylphenol (8a) (31 g, 0.28 mol) in dichloromethane (330 mL) was added titanium(IV) chloride (40 mL, 0.36 mol) under 10 °C, and the resulting deep purple solution was stirred for an additional 15 min at 0 °C. a,a-Dichloromethyl methyl ether (39 mL, 0.43 mol) was added to the solution under 15 °C, and the mixture was stirred at room temperature for 2.5 h. The reaction was quenched carefully with 300 mL of ice-water and the mixture extracted with ethyl acetate twice. The organic layer was washed successively with saturated sodium hydrogen carbonate and brine, dried, and evaporated. The residue was treated with ether, and the resulting solid was collected by filtration and washed with a small amount of ethanol and n-hexane (1:1) to afford 9a (38 g, 0.18 mol, 65%) as a white solid, which was used for the next step without further purification: mp 168-169 °C (EtOH-n-hexane); 1H NMR (400 MHz, CDCl3) d 2.20 (s, 3H), 2.52 (s, 3H), 3.75 (s, 3H), 3.81 (s, 3H), 6.40 (s, 1H), 10.39 (s, 1H).
2,4,5-Trimethoxy-3,6-dimethylbenzaldehyd
To the solution of 4-hydroxy-2,5-dimethoxy-3,6-dimethylbenz
Liszt + Buta = Beauty/Luxury
(Chief Bee)
11-24-03 11:05
No 472843
They aren't telling where they got the starting benzaldehyde from, and the only literature prep in Beilstein was through Gattermann formylation of para-Xyloquinone, found in J. Org. Chem. 6, 427-431 (1941) and J. Amer. Chem. Soc. 59, 673-678 (1937).
The starting material, para-Xyloquinone, is commercially available but pretty expensive, as it is relatively hard to make [sad]
(Hive Bee)
11-24-03 21:23
No 472920
ning appologizes in advance if this is out of place, but since ning has been studying quinones so much of late, a thought came to the fingers...
p-xyloquinone is quinone of p-xylene, right?
assuming you had p-xylene, ning can't see why it would bee so hard too:
mononitrate p-xylene (can't miss on this one...only one place to go!)
reduce to 2-amino p-xylene with zinc or iron powder
oxidize thru to quinone using one of the many methods in posession of the hive, preferably something involving bleach.
Now that doesn't sound like such an expensive route to ning...hope it's not too obvious to all you master chemists
(Chief Bee)
11-24-03 23:19
No 472941
I made a literature search once on that (hydro)quinone and it seemed like most of the usual routes were very low-yielding
(Hive Bee)
11-25-03 01:18
No 472965
(Rated as: excellent)
The above mentioned hydroquinone (2,6-dimethyl-hydroquinone) can bee made with reasonable yield (20-30%) through Elbs-persulfate oxydation of 2,6-Xylenol, I have the paper somewhere, IIRC it is J. Chem. Soc. 2303 1948W. Baker, N. C. Brown found from this old thread Post 122784 (dormouse: "Bromo-benzodifuranyl-isopropylamine
I agree with what you said in this thread Rhodium:
Still, making 2,5-dimethoxy-4,6-methyl-amphetamine (6-Me-DOM) from 2,6-dimethyl-p-hydroquinone would be very interesting. The compound should be really active.
as, AFAIK the 6-methyl group push the side chain downward in a good conformation, contrary to the 2-methyl group which push it upward in a less good conformation (also 2-ethoxy tweetios are less potent too). I remember this from somewhere i dont remember, I think it was from some paper on ring-methylated MDA analogs, and I also think the 3-methyl didnt have such a strong steric effect (as it is located further from the side chain). In every compound to be found in the 2C-X family, there are two methoxy groups, one at the 2-position and one at the 5-position. There are thus three possible tweetio compounds, a 2-EtO-, a 5-EtO- and a 2,5-di-EtO-. Those that have been evaluated in man are included after each of the 2C-X's that has served as the prototype. In general, the 2-EtO- compounds have a shorter duration and a lower potency, the 5-EtO- compounds have a relatively unchanged potency and a longer time duration; the 2,5-di-EtO- homologues are very weak, if active at all. And, finally, JUNO (3,6-dimethoxy-2,4-dimethylamphetamine) has been made (from 2,5-dimethoxy-m-xylene, which was reacted with POCl3 and N-methylformanilide to the benzaldehyde, mp 53-54 °C, and to the nitrostyrene with nitroethane, mp 73-74 °C from cyclohexane, and to the final amine hydrochloride with LAH in THF). Rather amazingly, I have had JUNO on the shelf for almost 14 years and have not yet gotten around to tasting it.
In conclusion AFAIK:
- 2-methyl-DOM (if it existed, but only the tweetio (methoxy replaced by ethoxy) can exist, it is called Florence in Pihkal and has not been bioassayed yet) should be less potent than DOM:
Quote from Pihkal, 2C-D entry: (http://www.erowid.org/library/books_onl
The 2-EtO-homologue of 2C-D is 2-ethoxy-5-methoxy-4-methylphenethylamin
2CD-2ETO is the 2C, phenethylamine homologue of Florence (3C, amphetamine homologue)
- 3-methyl-DOM exist, it is Ganesha (http://www.erowid.org/library/books_onl
Its potency is a bit lowered, but not too much vs DOM (DOM: 3-10mg vs Ganesha: 20-32mg), and is a bit more long lived (DOM: 14-20h vs Ganesha: 18-24h).
So, I conclude the 3-methyl change slightly the duration and require 2 or 3x the same dosage, which is still quite good IMHO.
- 6-methyl-DOM exist, it is Juno in Pihkal, but sadly it is untested:
Quote from Pihkal, Ariadne entry (http://www.erowid.org/library/books_onl
Personally I think Juno will bee, by extrapolation of the work on side chain configuration of methylated MDA analogs:
-Slighty more potent or at least equal potency than DOM.
-Slighty more long lived (wild guess from Ganesha).
-Of course very interesting.
Also, I have in this ref: Journal of Organic Chemistry, 48(17), 2932-3, 1983
the preparation of the above mentioned quinone (2,6-dimethyl-quinone) from 2,6-xylenol, by bichromate oxydation, easily, in good yield and big scale.
The abstract of this paper is:
Jones oxidn. of alkylphenols was a simple effective method for the large scale (30-60 g) prepn. of p-quinones, which usually gave quinones of reasonably high purity without chromatog. purifn. Six quinones thus prepd. included I-III.
And they claim the reaction 2,6-dimethyl-phenol ---Na2Cr2O7, H2SO4---> 2,6-dimethyl-quinone in 84% yield.
(in general alkylated quinones are easier to prepare than non alkylated ones btw)
This quinone can be reduced to the hydroquinone easily by shaking with sodium dithionite aqueous solution. Trimethylphosphate or any other methylating agent can then alkyl both phenols. For DMS check this ref, it could be interesting: Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry (1997), 36B(11), 1044-1046.
The real problem is in the formylation, as i have found no refs for this except the one from Pihkal. Further research is needed, it must exist a preparation somewhere!
As a side note, an alternative attractive procedure someone has to try is to use the beautiful reactivity of the quinone to our advantage. With a bit of luck, the 2,6-dimethyl-quinone will react with allyl-oxalate in the presence of AgNO3/Persulfate, to yield the allyl quinone in one step! (see Post 471656 (Chimimanie: "Why i prefer p-Meo-phenol?", Novel Discourse) and Chem. lett. 1992 7 1299)
2,6-xylenol --Jones Oxydation--> 2,6-dimethyl-quinone --allyl-oxalate, AgNO3/persulfate--> the allyl-quinone --1.dithionite, 2.methylation--> 2,5-dimethoxy-4,6-dimethyl-allylbenzene --> to Juno
...will obviate the need to use POCl3 which is a watched chem.
Please someone find some formylation refs for the 2,5-dimethoxy-m-xylene! Rhodium: your refs seems interesting, I will check them, thx!
(Chief Bee)
11-25-03 01:35
No 472971
(Rated as: good read)
Simple, inexpensive procedure for the large-scale production of alkyl quinones
Dennis Liotta, Jack Arbiser, James W. Short, Manohar Saindane
J. Org. Chem.; 1983; 48(17); 2932-2933 (1983) (../rhodium/pdf /alkylphenol2
(Hive Bee)
11-25-03 12:07
No 473053
(Rated as: good read)
Process for the preparation of quinones
Patent EP0249289
Phenols are oxidated to quinones with hydrogen peroxide in the presence of catalytic amounts of bromine, iodine, hydrogen bromide and hydrogen iodide.
2,6-dimethylbenzoquinone from 2,6-dimethoxyphenol, yield 85%.
fear fear hate hate
(Chief Bee)
11-25-03 15:25
No 473079
(Rated as: good read)
Checking out Gattermann formylations, I found that 2,5-dimethoxybenzaldehyde is prepared with that method in the following articles:
· Justus Liebigs Ann. Chem. 357, 373 (1907)
· Chem.Ber. 40, 840 (1907)
· Chem.Ber. 40, 2357 (1907)
· J.Chem.Soc. 1482 (1928)
A superior method seems to be the one used in Patent FR1415670 but as I cannot read french, I could only see some bragging about "rendement supériurs à 90.5% et souvent quantitatif" which sounds nice, regardless of what language it was written in. Maybe someone can decrypt and post the essential improvements they made to the method?
(Official Hive Translator)
11-25-03 17:07
No 473100
i can't read French either
, but what i managed to read witnesses the fact that they use liquid HCN, which isn't the nicest of all alternatives, definitely
A-cho
(Hive Bee)
12-10-03 02:33
No 475803
To convert that hydroquinone to an allylbenzene? Use the allyl chloride, and then heat. As far as I know, when the claisen rearrangement is blocked, it moves to the next available position. Though whether that includes the meta position, not sure.
Catching a buzz @ the Hive
(Chief Bee)
12-10-03 19:05
No 475961
It doesn't - only ortho/para.
12-16-03 22:34
(Rated as: misinforming)
(Chief Bee)
12-17-03 01:00
No 477275
Even if we pretend that no side reactions occur in that wild soup, the methyl groups would add in 2,5-orientation as the position para to the first introduced methyl group would be the most activated one after the first was introduced.
The Hive - Clandestine Chemists Without Borders
(Hive Addict)
12-17-03 02:54
No 477298
ning, I really admire your enthusiasm and commitment towards chemistry, but I have to ask you...
...are you sponsored by a company that produces acetaminophen?
You seem to have quite some affection towards using acetaminophen as a precursor for just about anything. A query on TFSE showed that you already made 23 posts on the subject.
If you keep this trend going, one day you'll probably earn the title 'acetaminophen'.
The Other War (http://www.markfiore.com/animation/drug
(acetaminophanatic)
12-17-03 23:30
No 477483
Shh! Don't let the word get out, or all the tylenol codeine people will lynch me! Looks like somebody on high thought your suggestion was a good idea...
Seriously, with 50 grams of the stuff, almost pure, off the shelf, so close to quinone and who knows what else, just begging to bee experimented with, who couldn't resist? Unless you're not enough of an acetaminophanatic...
Rhodium, I have a paper that might make you reconsider that "misinforming" rating...Admittedly, they use a catalyst, but they do just what we want.
aniline --> 2,6 dimethyl aniline with MeI and Pd(OAc)2.
[mol]c1ccccc1NC(=O)C>>c1cc(C)c(NC(
Turns out the palladium acetate will selectively ortho-alkylate all manner of things in high yields. Pretty cool.
And of course, you're right, the activation will change, I know. But there must bee a way to make this xyloquinone, without catalysts...I will keep searching.
The paper will bee posted shortly.
Catching a buzz @ the Hive
(Chief Bee)
12-18-03 00:37
No 477494
Turns out the palladium acetate will selectively ortho-alkylate all manner of things in high yields.
And if you have both an OH and a NH2 on the ring, which will it ortho-alkylate?
I have a paper that might make you reconsider that "misinforming" rating...
Even if you have a palladium-catalyzed aromatic alkylation procedure up your sleeve it still doesn't change the fact that you incorrectly stated that FC alkylation of acetaminophen would give 4-hydroxy-2,6-dimethylaniline. As an aromatic OH group is more activated (and a lot less sterically hindered) than an aromatic NHAc, the first alkylation would very likely end up ortho to the phenol, even... As backwards as can be.
You will continue to recieve misinforming ratings if you in the future don't check the literature more closely before posting long ranting essays about "possibilities". It is a lot more useful to people if you post one single well-researched synthesis than if you post 20 "possible" syntheses which haven't been tried in any lab ever...
A bird in the hand is worth ten in the bush, or what they say...
The Hive - Clandestine Chemists Without Borders
(Hive Bee)
12-18-03 03:51
No 477520
If you keep this trend going, one day you'll probably earn the title 'acetaminophen'.
Hahaha
it is not acetaminophen but acetaminophanatic !Ning: cannot you get xylenol? please stop propagandising for the big pharm houses in this thread...
What do you think is easier to get? Pd-diacetate or xylenol??? Really do you think xylenol or acetaminophen is more suitable here, to make xyloquinone?
btw i find it astounding nobody still posted the Chem. lett. 1992 7 1299 article, which ref I gave one month ago. Finally as noone seemed interested, I decided to post it there Post 477519 (Chimimanie: "convenient procedure for allylation of quinone", Novel Discourse), as a valuable article for a possible route, that might bee very useful in this case, as we have to pass trough the quinone nonetheless, better to exploit the chemistry at its best here I think...
Please Ning, restrain your posting.... You dont have to bee in such a rush you known, you should photocopy plenty ref, keep them for yourself, think about them, compare with other, rethink about the former, then, if they finally seem worthy, you can post them... literature is huge, dont clutter the hive with useless rambling, stim bee have a hard time enough to follow, so keep it clean and simple.
hahaha acetaminophanatic!
suit you well
(Newbee)
12-18-03 11:30
No 477594
(Rated as: good idea!)
Ning: Congratulations for your new title, he, he...
But, I don't really get the point of all this theoretisizing about (alkyl)quinones synth. What is the purpose? If you would want to make DOM, Ganesha and all the other DOM positional isomers, what could be easier than electroanodic oxidation of toluene. This has already been covered a few times, check Post 473897 (Lego: "2,5-Dimethoxyprecursors from benzene or anisole", Chemistry Discourse). I know everybody gets scared away when they hear about electrochemistry, don't know why.
Well, instead of seeing these p-benzoquinone-bis-dimethylketals just as precursors to the p-dimetoksibenzenes try thinking of them as a beutiful substrates for 1,4-additions of carboanions that can lead directly to x-methyl-2,5-dimethoxy-P2P (where x=3, 4 or 6).
Nobody ever heard about the Nenitzescu reaction? It is used to make 5-hydroxy-indoles and 5-hydroxy-benzofuranes. The key point in its mechanism is the 1,4-addition of ethylacetoacetate (or its imine or similar) carboanion and then the cyclisation to the aforementioned cmpnds. Now if you react the ethylacetoacetate carboanion with a p-benzoquinone-bis-dimethylketal, the last step - cyclisation, is impossible and you get a product that after hydrolysis/decarboxylation gives a 2,5-dimethoxy-P2P. To all those Bees that have troubles visualizing structures (draw the other two positional isomers by yourself):
Molecule: what do you think of this? ("C/1=C/C(\C(=C/C\1(OC)OC)C)(OC)OC.C(C(=
I really don’t know why nobody posted this before? I don’t believe nobody envisioned this. Maybe some egoism at work, or everybody except me knows it does not work, or I just don’t know how to UTFSE? Ideas are made to be shared, aren’t they? Almost everything is in Lego’s post, including the examples of nucleophilic additions to these weird ketales in the Synthesis articles and all the necessary patents in the link to Bottleneck’s and PolytheneSam’s posts.
OK, if anybody knows an easier and more OTC way to DOM and its isomers, I’ll shut up and beg for forgiveness
.Thanks to prof. Nenitzescu for the idea... http://www.arkat-usa.org/ark/journal/200
“The real drug-problem is that we need more and better drugs.” – J. Ott
(acetaminophanatic)
12-18-03 22:28
No 477686
First, I think the MeI would methylate the OH group.
It seems to only alkylate ortho to the acetylamino group.
This has something to do with the metal complex it forms, which has limited "reach", and also something to do with the acetate on the palladium. Or maybe not. See for yourself:
JACS 1984, 5759
And Rhodium, I said you were right and I was wrong. Did you miss that?
They also used this process to cyclize acetaniline with allyl iodide to give an indole derivative, which might be of some interest.
Here is the reactions of interest:
Molecule: will it alkylate twice? Yes. ("CC(=O)Nc1ccccc1>>CC(=O)Nc1c(C)cc
81% yield. 15x excess MeI, 1.5x excess Pd(OAc)2 (yuck), 100 C
Molecule: what about phenol group? ("CC(=O)Nc1c(OC)cccc1>>CC(=O)Nc1c(
79.7% yield.
I would bee posting more "real world" results if I was in a position to do so right now. But I'm not. Sometimes it's a time for theory, sometimes it's a time for experiment, and now is my time for theory. I hope that is understandable.
Catching a buzz @ the Hive
(Hive Addict)
12-27-03 15:12
No 479285
(Rated as: good read)
A couple of posts back Chimimanie stated in this thread:
The real problem is in the formylation, as i have found no refs for this except the one from Pihkal. Further research is needed, it must exist a preparation somewhere!
So we learned that we can easily oxidize 2,6-xylenol to 2,6-dimethyl-1,4-benzoquinone in high yields using either dichromate (Post 472971 (Rhodium: "alkyl quinones from alkyl phenols", Novel Discourse)) or H2O2 with a catalytic amount of halogen (the Patent EP0249289 moo provided), and reducing this compound to the corresponding hydroquinone is pretty straightforward, as pointed out by Chimimanie in the abovementioned post.
What I would suggest is, instead of fully methylating the substituted hydroquinone, why not monomethylate it?
I found only 1 reference on this matter (I will dig it up after the weekend):
2,6-dimethylhydroquinone --(MeOH, H2SO4)--> 4-methoxy-2,6-dimethylphenol
Chem. Ber. 36 (1903), 2033
Considering that it is similar to the preparation of p-methoxyphenol from hydroquinone/benzoquinone via the hemiketal as described in:
Post 267698 (Antoncho: "P-MeO-phenol from hydroquinone: part II", Novel Discourse)
Patent GB1557237
it would not be so unreasonable to assume that this procedure could give acceptable yields for 2,6-dimethylhydroquinone too, as it does for unsubstituted hydroquinone.
However, if this proposed procedure would turn out to be not viable, the 2,6-dimethylhydroquinone can still be monomethylated with Me2SO4 using one of these procedures:
Post 268898 (foxy2: "Re: P-MeO-phenol from hydroquinone: part II", Novel Discourse)
Post 267779 (moo: "Re: P-MeO-phenol from hydroquinone: part II", Novel Discourse)
When we have obtained the 4-methoxy-2,6-dimethylphenol my next suggestion would be to perform a Reimer-Tiemann formylation on it. As there is only the ortho- position that can be formylated, a Reimer-Tiemann on this phenol should give decent yields of 2-hydroxy-5-methoxy-4,6-dimethylbenzalde
Post 454518 (Rhodium: "Two Syntheses of 2,5-Dimethoxybenzaldehyde", Chemistry Discourse)
Post 330714 (Antoncho: "A patented improvement", Chemistry Discourse)
Alternatively, the phenol could also be formylated with Mg(OCH3)2 or paraformaldehyde/amine/SnCl2, methods that have been discussed before here.
References can be found here:
Post 273718 (Osmium: "Re: P-MeO-phenol from hydroquinone: part II", Novel Discourse)
(Ah yes, and if one is really desperate, there is always the Duff formylation to try too , or if you happen to have some trifluoroacetic acid around..)
2-Hydroxy-5-methoxy-4,6-dimethylbenzalde
Post 475637 (Rhodium: "Synthesis of 2C-B from Anise Oil (Anethole)", Novel Discourse)
Post 425432 (Vitus_Verdegast: "J. Chem. Soc. (1923) 123, page 1587 and 1588", Methods Discourse)
I really hope that the more OTC approach, the monomethylation with MeOH/H2SO4 followed by a Reimer-Tiemann, will work, as this will facilitate the route to JUNO alot.
Comments, thoughts, suggestions... ?
The Other War (http://www.markfiore.com/animation/drug
(Hive Bee)
12-28-03 09:53
No 479439
When we have obtained the 4-methoxy-2,6-dimethylphenol my next suggestion would be to perform a Reimer-Tiemann formylation on it. As there is only the ortho- position that can be formylated, a Reimer-Tiemann on this phenol should give decent yields of 2-hydroxy-5-methoxy-4,6-dimethylbenzalde
Here is a mistake, unfortunately. There are two methyls both ortho to the phenolic hydroxyl group, so that position cannot be formylated by these methods. 4-methoxy-3,5-dimethylphenol is needed for that. Some time ago it occurred to me that it would be cool if it was possible to prepare 4-methoxy-3-methylphenol from toluhydroquinone through methylation with H2SO4/MeOH as this compound would have been a nice precursor for a DOM synth via phenol ortho-formylation. After drawing a few resonance structures it was obvious that the product would more likely be 4-methoxy-2-methylphenol, ruining the plan. I guess that this 2,6-dimethylhydroquinone methylation ref proves it, in addition to finding no such preparations in literature. Too bad.
fear fear hate hate
(Hive Addict)
12-28-03 23:44
No 479533
(Rated as: excellent)
Thanks moo!
I did a quick literature search for 4-methoxy-3,5-dimethylphenol but didn't came up with anything..
This could be an alternative approach, although allyltributyl stannate is pretty expensive (20 euro/gram):
Reactants: 2,6-dimethyl-[1,4]benzoquinone and allyl-tributyl-stannane
Product: 2-allyl-3,5-dimethylhydroquinone
Yield: 82 percent
Reagent: BF3*OEt2
Solvent: CH2Cl2
Temperature: -78 C
Naruta, Yoshinori; J.Amer.Chem.Soc.; EN; 102; 11 (1980) 3774-3783.
http://pubs.acs.org/cgi-bin/sample.cgi/jacsat/19 80/102/i 11/pdf/j a00531a0 19.pdf
Methylation will give 2,5-dimethoxy-4,6-dimethyl-allylbenzene.
Mmm, this is probably a better way:
2-allyl-3,5-dimethylphenol is prepared by Claisen rearrangement of allyl-(3,5-dimethylphenyl)-ether using either:
* allyl bromide: Wehrli,R. et al.; Helv.Chim.Acta 60 (1977) 2034-2061.
* allyl chloride: Le Noble,W.J. et al.; J.Org.Chem. 36 (1971) 193-196.
http://pubs.acs.org/cgi-bin/sample.cgi/j
EDIT: The title of the article starts with "Chemical reactions under high pressure", so I guess we better scratch this one.
Next, 2-allyl-3,5-dimethyl-1,4-benzoquinone is prepared from 2-allyl-3,5-dimethylphenol by oxidation with O2 and Co(II) salts according to:
Matsumoto, Masakatsu; Watanabe, Nobuko; Mori, Eiko; Aoyama, Misao; Kusunoki, Jun and Yamaura, Tetsuaki; Heterocycles 38; 12 (1994) 2589-2592.
This paper also describes the reduction of the benzoquinone to 2-allyl-3,5-dimethylhydroquinone using NaBH4.
The Other War (http://www.markfiore.com/animation/drug