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Author Topic: YUP - FINALLY A SYNTHESIS OF SAFROLE  (Read 740 times)

no1uno

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YUP - FINALLY A SYNTHESIS OF SAFROLE
« on: September 18, 2009, 08:56:05 AM »
Yes, finally - it is here a methylenation of dihydroxyallylbenzene to 3,4-methylenedioxyallylbenzene (aka 1,2-Methylenedioxy-4-allylbenzene) - after all this fucking time, finally an article dealing with the synthesis thereof (fuck, did I just finally win the fucking safrole comp? ???)

Quote
General Synthetic Procedure

The materials, the methylene diiodide, the anhydrous potassium carbonate, and the catalysts were added to the solvents; then the mixture was reacted on an oil bath with stirring, as is shown in the tables. The reaction mixture was extracted with ether, washed with 3% HCl, 3% NaOH and water successively, and dehydrated with anhydrous Na2SO4. Then the product obtained by distillation in vacuo after the removal of the solvent.

1,2-Methylenedioxy-4-allylbenzene (Safrole).

Bp 94.0-94.5'C/4mmHg (lit bp 100-101.5C/10-11mmHg). Beilstein's test for halogen: negative. n20D 1.5380 (lit n20D 1.5381). IR (KBr): 2786, 929 717 cm-1 (O-CH2-O). (Found: C, 74.08; H 6.26%. Calcd for C10H10O2: C, 74.05; H, 6.22%).

..........

"...     "A little learning is a dang'rous thing;
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    There shallow draughts intoxicate the brain,
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Douchermann

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #1 on: September 18, 2009, 05:12:21 PM »
no1uno, this is not news.  I have even suggested multiple times on this board that methyleneation should be done with methylene iodide as opposed to methylene chloride.  The problem with synthing safrole is the 4-allylcatechol.  It's remarkably unstable, turning from a clear ether solution into a black tarry liquid within hours.  I thank you for posting the reference up, however.  It is a good read.

no1uno

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #2 on: September 18, 2009, 09:48:08 PM »
Kind of an "in" joke within a small group perhaps... Simply put, when challenged by Chi IIRC over at WD NOBODY could actually come up with a single article that actually dealt with the synthesis of Safrole, many came close, none actually dealt with it precisely...
"...     "A little learning is a dang'rous thing;
    Drink deep, or taste not the Pierian spring:
    There shallow draughts intoxicate the brain,
    And drinking largely sobers us again.
..."

Sedit

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #3 on: September 18, 2009, 11:35:48 PM »
Chi has never seen a synthesis of Safrole? You gotta be kidding me... I assumed chi was a learned man that reads alot. I have seen a few of them.
There once were some bees and you took all there stuff!
You pissed off the wasp now enough is enough!!!

no1uno

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #4 on: September 19, 2009, 02:17:24 AM »
Learned or not, have a GOOD look - see what journal articles (professional ones) deal with the synthesis of Safrole itself - not the 3,4-methylenedioxypropylbenzene or the propenyl, but the actual methylenedioxyallylbenzene...

Chi is learned as all hell (bit starchy perhaps ;)), the closest I could find was one dealing with the synthesis of radiolabelled safrole derivatives, even that only went to the propylbenzene/propenylbenzene IIRC.
"...     "A little learning is a dang'rous thing;
    Drink deep, or taste not the Pierian spring:
    There shallow draughts intoxicate the brain,
    And drinking largely sobers us again.
..."

Douchermann

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #5 on: September 19, 2009, 07:05:11 PM »
Aha, makes sense.  Well, I said it in my first post and I'll say it again, good find no1uno.

Formula409

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #6 on: September 24, 2009, 10:08:34 AM »
Good find but I don't think making safrole from eugenol is the best way to get to MD(M)A. Following Psychokitty's work, I propose this:

eugenol > isoeugenol (Psychokitty's PTC isomerisation) > 3-methoxy-4-hydroxy-phenyl-2-nitropropene (pseudonitrosite) > 1-(3-methoxy-4-hydroxyphenyl)isopropylamine (Al/Hg, Urushibara, etc) > 1-(3,4-dihydroxyphenyl)isopropylamine  (Thiourea/AlCl3, etc)> 1-(3,4-methylenedioxyphenyl)isopropylamine (DCM/NaOH, etc) > MDA  > MDMA.

Alternatively you could make methyl vanillyl ketone from the nitropropene with Fe/HCl if it is easier to do a reductive amination with methylamine instead of methylating mda.

Psychokitty proposed that you should make the ketone through peracid treatment of isoeugenol, but from reading his posts at the hive, he had problems with very low yields. The pseudonitrosites never seem to get looked at, but in this case they are perfect!

I can start a thread, but I would prefer to wait until I have actually tried these synths before posting! If you would like refs, PM me!

Formula409

jon

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #7 on: October 03, 2009, 03:57:29 AM »
have fun with that eugenol !!!!
swij never fucked with eugenol but it's legened to be a serious pain in the ass from certain members on other boards.

hypnos

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #8 on: December 16, 2009, 02:46:56 AM »
aaah,,its a bit hard to pm someone who is not a member ::) go on,  be a devil and become member# 61? ;D
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Quantum Dude

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #9 on: August 10, 2010, 07:18:17 AM »
Quote from: Formula409 on September 24, 2009, 10:08:34 AM

eugenol > isoeugenol (Psychokitty's PTC isomerisation) > 3-methoxy-4-hydroxy-phenyl-2-nitropropene (pseudonitrosite) > 1-(3-methoxy-4-hydroxyphenyl)isopropylamine (Al/Hg, Urushibara, etc) > 1-(3,4-dihydroxyphenyl)isopropylamine  (Thiourea/AlCl3, etc)> 1-(3,4-methylenedioxyphenyl)isopropylamine (DCM/NaOH, etc) > MDA  > MDMA.
I was a defender once of a similar but more convenient route but jon lucidly pointed out to me that making the amine before methylenation to the piperonyl is unwise as undesired N-methylation to higher amines will surely result. I couldnt agree more. Therefore the amino group should be protected prior to methylenation.

drone1240

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #10 on: August 10, 2010, 11:51:38 PM »
Here is another one by psycho chemist and then one thats a little more formal.
acting in accordance with the dictates of reason....

shroomedalice

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #11 on: August 22, 2010, 09:43:39 AM »
I still think IBX is the go for both eugenol and vanillin.

personaly I would work with vanillin if I wanted to use a demethylation methylation

route.

atara

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Re: YUP - FINALLY A SYNTHESIS OF SAFROLE
« Reply #12 on: September 13, 2010, 10:36:08 PM »
I still say: eugenol + MeBr ---> methyleugenol. Any number of routes can take this to 3,4-dimethoxyphenyl-2-propanone. Demethylate with HBr.

Working with eugenol is asking for failure. Protect the hydroxy and you're fine. EtBr is probably okay as is MeI.
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