dormouse (Member)
04-22-00 18:00
No 108705
      Synthesis of allylpyrocatechol through Friedel-Crafts reaction. -psychokitty  Bookmark   

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Author  Topic:   Synthesis of allylpyrocatechol through Friedel-Crafts reaction. 
Member   posted 04-25-99 08:36 PM          
I just found this reference. Supposedly it details the synthesis of 4-allylcatechol by way of catechol and allylchloride through a Friedel-Crafts reaction.
Someone with access to a better library, please locate it and post the experimental details. I believe that the article is not printed in English so a translation may be in order.

Author: S.G. Mel'Kanoviiskaya

Publication: Zh. Org. Khim. vol.1, p325 (1965)

-- PK

Member   posted 04-26-99 12:12 AM          
Hey psychokitty, you might also want to check out this thread: 

I think its kind of along the same lines.



Member   posted 04-26-99 12:24 AM          
Psychokitty : Long time no post my feline friend. I can get the english translation of this (Russian) journal, probably not for a day or two, but I can dig it up.

Administrator   posted 04-26-99 06:28 PM          
Speaking of catechol, why have I never seen any formylation/methylenation of this to give piperonal?
Would a vilsmeyer yield the 2,3-substituted benzaldehyde instead (seems strange, as a bromination puts the halogen right on the spot).

If it works, piperonal is only a few hours away from catechol.

Member   posted 04-26-99 07:06 PM          
Well, it seems now everbee is putting on his/her thinking cap. Fuck safrole. It's soon to be obsolete.
-- PK

Member   posted 04-27-99 11:52 AM          
Psychokitty : I have the paper, here is a very brief summary of the main part of the (slightly) relevant experimental.
A mixture of 0.79g of copper powder, 9 g of allyl chloride and 175 g of guaiacol acetate was heated in a glycerol bath for 14 hrs at 150-160 degrees C. After this time, a further 20 g of allyl chloride was added at such a rate that the temperature remained in the range given. After the completion of the heating process, the mixture was passed through a column containing 50 g of anion-exchanger (to remove HCl [my note]), and this was washed with 50 mL of ether three times. The filtrate was dried with MgSO4 and fractionated. (My notes : The authors analysed their different fractions by GC and never isolated their compounds individually. There was apparently much [~131 g] unchanged starting material (guaiacol acetate).
In this paper the authors do not actually perform the allyation of catechol. The reference they give appears to be
W.H. Perkin and V.M. Trikojus, J. Chem Soc., 1927, pg 1663.
I think that you would be better off looking at Org. Synth., III, pg 418 for a related synthesis (in good yield) of o-eugenol, or the above reference which I have not yet investigated.


Member   posted 05-10-99 11:12 PM          
This proceedure details the claisen rearrangement. If it truly works, catechol could become a direct precursor to allypyrocatechol, and the method employed to synthesize it would be simple.

Administrator   posted 05-10-99 11:22 PM          
The synth is also in The Complete Book of Ecstasy. Unfortunately, the main product is 3-allylcatechol (say 2/3 or so).
Member   posted 05-27-99 01:44 AM          
What about one of the techniques that oxidizes phenol to catechol used on chavicol to produce allylpyrocatechol? Isn't chavicol (found in West Indian Bay oil) phenol but with that ever-so-desirable allyl side chain?
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(Distinctive Doe)
04-05-02 04:47
No 292799
      Friedel-Crafts acylations
(Rated as: excellent)

This reference could bee interesting.

Friedel-Crafts acylations with little or no catalyst.
Pearson, D. E.; Buehler, Calvin A.   
Synthesis  (1972),   (10),  533-42. 
Review with 61 refs. on Friedel-Crafts acylations with min. amts. of catalyst.  Thus 4-(p-RC6H4)C6H4COC6H4R1-p (R = R1 = H; R = Bz, R1 = H; R = H, R1 = Me, Bz, COC6H4Ph-p) were prepd. in 5-78% yield by acylating biphenyl with BzCl, p-MeC6H4COCl, p-PhCOC6H4COCl, or p-(ClCO)2C6H4 in the presence of a trace of FeCl3 until no more HCl evolved.  PhOMe was acylated to 45% p-MeOC6H4COPh in the absence of catalyst by heating it with BzCl at 176-255 for 4 days.
(Official Hive Translator)
04-05-02 06:50
No 292833
(Rated as: excellent)

Actually, i have that 1st article Rhenium sited. Its main drawback is the huge qtty of phenol as compared to allylchloride.

That copper catalysis thing looks interesting, tho.

Another couple of articles from the same author deals with allylation of phenol ethers - and two of them are from an Uzbekian journal (Rhodium, are you reading this?smile) - but one is from Russian Journal of General Chemistry, 32, 2232, 1952 (or 1962? - a typo there)

Someone, look it up if you can.

Then, again, here is an absolutely awesome Patent US4048236.

This is the Example 14 (the best conversion , yield and selectivity), figures calculated and pasted into the typical procedure.

A mixture of 10 g of guaiacol, 3.22 g of sodium hydroxide, 6.90 g of allyl chloride, 2.010 g of CuSO4*5H2O, 3.7 g of 28% aqueous ammonia and 34 ml of water was reacted at 25 C and with stirring, for 15 minutes. When the CuSO4 and aq. ammonia were introduced, a deep violet-blue color occurred, indicating formation of (Cu(II)(NH3)2)++ ion. The reaction solution was then neutralized with hydrochloric acid and extracted with five portions of 30 ml of ether. The resulting ethereal extract was distilled to give 6.78 g of the desired eugenol and 1,46 g of the unreacted guaiacol. There was also obtained 2.44 g of by-product O-allylguaiacol.

Note that allylation takes place mostly para- to hydroxy group. Which is good, since this probably can bee applied to catechol too, with all the resulting consequences.

I can't wait to see any details on allylation of fully methylated phenols. Imagine this done to p-diMeO-benzene! Or 1,3-benzodioxole!

An interesting detail on Claisen rearrangement: it proceeds surprisingly well even when the both ortho-positions are substituted - namely, syringol. Allylation takes place para to hydroxy. Can post the proc, if interested.

(Hive Bee)
04-12-02 11:50
No 296103
      Antoncho!!!  Bookmark   

This is great!! I'm thinking about the possibility of using catechol in this rxn, but I haven't fully read the patent yet.

Why do you think it could also be succesfully applied to phenolethers? Don't take me wrong, I have a ~15grs of 1,4-DMBz that I would be glad to use in this reaction.

(Hive Bee)
04-12-02 14:25
No 296151
      hot shit  Bookmark   

This would be a very hot procedure if it can be applied to 1,3-benzodioxole (or even catechol) with similare yields as seen in that example. SWIM will see is she can dream up such a thing this summer. Any bees are welcome to post their dream their dream reports.

Can a bee be visa vis its entity when half a bee philosophically must ipso facto half not be?
(Hive Bee)
04-13-02 06:58
No 296418
      DOX and 2C-X  Bookmark   

I'm not sure about p-DiMeOBenzene, but p-MeOPhenol will do just fine.

Let's not play games. 2C-B is but footsteps away.wink
(Official Hive Translator)
04-13-02 08:49
No 296448
      Actually....  Bookmark   

... i am quite confident that the procedure would need to bee seriously modified both for catechol and benzodioxole.

Phenol nuclei are much more activated towards electrophylic substitution then their ethers - e.g., Reimer-Tiemann and Duff formylations go well w/phenols, but methyl ethers are completely unreactive under the same conditions.

There is a Russian article i mentioned earlier, about allylation of ethers - but it hasn't been retrieved thus far....  frown Maybee, someone at The Hive could find it... i would very dearly like to see it...


P.S. Rhodium, Osmium or some other high-class chemist - what do you think about allylating benzodioxole in this way - namely, what direction will the substitution take place?
(Chief Bee)
04-13-02 11:41
No 296485
      ortho-safrole  Bookmark   

I believe a mixture of the both possible isomers will result, with no more than 50% of the desired isomer. However, ortho-safrole would be interesting as a starting material for ortho-MDA, untasted, as far as I know.
(Hive Bee)
04-16-02 09:43
No 297747
      It would seem that research into this application ...  Bookmark   

It would seem that research into this application to mda would be two fold then, however it will be greatly recieved once I synth ortho-mda and be the fisrt to discover it is 20x more active! BWAHAHAHAHAH *sinister laugh*

Can a bee be visa vis its entity when half a bee philosophically must ipso facto half not be?
(Hive Prodigy)
04-16-02 17:34
No 297863
      Hey  Bookmark   

I was told by people here that the 2,3-MDA/MDMA is of like properties, but of decreased potency, when I had asked about such things during the craze of Antoncho's manganese triacetate acetonylation finding! crazy

Are you now telling me that 2,3-MDA/MDMA has never been synthesized?


Vivent Longtemps La Ruche!
(Chief Bee)
04-16-02 18:27
No 297892
      ortho-MDMA  Bookmark   

It has been made in some forensic journal, but I do not know of any syntheses outside law enforcement, and definitely no controlled trials.