dormouse
(Member) 04-22-00 18:00 No 108705 |
Synthesis of allylpyrocatechol through Friedel-Crafts reaction. -psychokitty | Bookmark | ||||||
the Hive BB Novel Discourse Synthesis of allylpyrocatechol through Friedel-Crafts reaction. profile | register | preferences | faq | search next newest topic | next oldest topic Author Topic: Synthesis of allylpyrocatechol through Friedel-Crafts reaction. psychokitty 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 I think its kind of along the same lines. Peace TheCat If it works, piperonal is only a few hours away from catechol. Rhenium Contact Us | the Hive Powered by: Ultimate Bulletin Board, Version 5.39a |
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foxy2 (Distinctive Doe) 04-05-02 04:47 No 292799 |
Friedel-Crafts acylations (Rated as: excellent) |
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This reference could bee interesting. Friedel-Crafts acylations with little or no catalyst. Pearson, D. E.; Buehler, Calvin A. Synthesis (1972), (10), 533-42. Abstract 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. |
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Antoncho (Official Hive Translator) 04-05-02 06:50 No 292833 |
Allylations. (Rated as: excellent) |
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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?) - 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. Antoncho |
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element109 (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. e109 |
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alchemy_bee (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? |
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cilliersb (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. |
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Antoncho (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.... Maybee, someone at The Hive could find it... i would very dearly like to see it... Antoncho 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? |
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Rhodium (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. |
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alchemy_bee (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? |
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PrimoPyro (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! Are you now telling me that 2,3-MDA/MDMA has never been synthesized? PrimoPyro Vivent Longtemps La Ruche! |
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Rhodium (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. |
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