Author Topic: Mescaline synthesis-lets make it home friendly!  (Read 1619 times)

Baba_McKensey

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Re: Mescaline synthesis-lets make it home friendly!
« Reply #40 on: June 04, 2012, 10:57:41 PM »

Sol Invictus

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Re: Mescaline synthesis-lets make it home friendly!
« Reply #41 on: June 06, 2012, 01:35:13 PM »
  Hmmm... Are you sure that's the correct Hyperlab translation, Lugh? Because after reading over it several times I could find no mention of the Russian paper you mentioned, & while some of the chemistry discussed in the translation was relevant to converting allylbenzenes to aldehydes, it did not employ the use of the reagents specifically mentioned by shroomedalice.

Also, the two patents linked discuss exclusively the synthesis of 3,4,5-tmbenzoic acid from various tannins & do not mention the conversion of allylbenzenes to aldehydes. And while the synthesis in question of the benzoic acid derivative is interesting/relevant, I did not see one route that didn't rely upon dimethyl sulfate as the methylating agent, so at least in Sol's opinion this route(s) from tannins is not necessarily any more 'home friendly' than the 5-bromovanillin route from the Rhodium Archives.

  Did I miss something? Admittedly I did not register at Hyperlab (yet) to view the original page...

I think I'll request both the Russian & the Chinese paper- hopefully a translation or readily translatable version can be tracked down. I don't recall seeing a DOI # for either one. Perhaps there's an English language paper involving a largely similar synthesis (?). Sol will have to do some digging...

EDIT: Perhaps isomerization to the propenylbenzene via KOH, then proceed w KMnO4 on alumina ala the paper on Rhodium? It even notes that ring substitutions such as those present in (iso-)elemicin would not be damaged. Sol is wondering how this compares with the aforementioned dichromate process...

http://www.erowid.org/archive/rhodium/chemistry/benzaldehydes.kmno4.html
« Last Edit: June 06, 2012, 02:31:37 PM by Sol Invictus »

lugh

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Re: Mescaline synthesis-lets make it home friendly!
« Reply #42 on: June 06, 2012, 04:24:39 PM »
That Hyperlab thread is mostly a discussion of various methods of synthesizing piperonal from piperine  ;) The part that shroomedlalice was referring to is in response to what Zolvox posted:

syspylacopa

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Apr 19 2009, 22:00
[post = 526289]
   

 

quote (said: Zolvox)
 
Condensate all gathered in one container and put in refrigerator for 12 hours. The solution became completely transparent, and at the bottom grew white translucent crystals. But they were so small that the young chemist upset and did not conduct any further manipulation
 


Good job, next time better to lead the recording is fixed more carefully what he was doing as something laid. For example, it seems suspicious that the IRS could dissolve 20% KOH and do not specify the volume of solution taken, well, all right, now in effect.

1. Condensate was necessary to extract something, because piperonal solubility in water is 0.2 g per 100 ml of water.

2. You can try other oxidants such as dichromate in sulfuric acid in the presence of sulfanilic acid (protects aldehydes derived from further oxidation), such as making an example here (http://www.chemister.pp.ru/Database/search.dbp?action = synthesis & dbid = 1 & id = 119). Without sulfanilic acid output usually falls at least twice.


as an alternative to permanganate since the yield is approximately doubled when sulfanilic acid is employed to protect the aldehyde ;)  Sulfanilic acid is prepared by heating aniline with an excess of sulfuric acid for four to five hours and is an important reagent in the dye industry  :-X The attached article should clarify matters 8)
« Last Edit: June 06, 2012, 08:04:24 PM by lugh »
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carl_nnabis

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Re: Mescaline synthesis-lets make it home friendly!
« Reply #43 on: June 08, 2012, 01:02:31 AM »
Had a quick search through the whole thread and it seems everyone claims the lack of methylation agent (for me it is also a problem to get a good one) but no one has ever mentioned the option of halogenating another aldehyde?
I am speaking of anisaldehyde to be more precisely. This will dibrominate on position 3 and 5, which in consequent reaction with sodium methoxide gives the wanted starting 3,4,5-trimethoxbenzaldehyde. From there everything is common knowledge.
Why hasnt anyone came up with this way easier route? Is anisaldehyde hard to obtain where you live? It should bee as satisfactoy easy as it can bee as the two reactions used first give very high yields
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Sol Invictus

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Re: Mescaline synthesis-lets make it home friendly!
« Reply #44 on: June 08, 2012, 02:00:22 PM »
Hmmm... Anisealdehyde brominated via HBr perhaps (?) to 4-MeO-3,5-DiBr-Benzaldehyde, followed by the methylation utilizing Na Methoxide formed ala Ullmann w/ NaOH, MeOH, & molsieves. Now THAT'S starting to sound more accessible- both the synths/reagents as well as the starting aldehyde, which is certainly more available than Elemicin. I can see why they call you 'Friendly Stranger', Mr. carl_nnabis...  ;) The halogenation of the 3 & 5 positions on Anisealdehyde seems logical, but I have to ask if you have either a reference or firsthand anecdotal evidence (for example how likely is either 'over-bromination' or only partial bromination of the Anisealdehyde, leaving one with a mix of variously brominated products which would have to be separated from the desired 3,5-DiBr-Anisealdehyde -?). If anything, it would certainly help to lend weight to this particular route indeed being the most 'home friendly'!

And Lugh thanks for pointing out the relevant section in that translated Hyperlab thread, as well as the tips for sulfanilic acid preparation. I'll check out the article you posted over the next few days.  :)

Thanks everyone for continuing to contribute to this interesting & informative thread!
« Last Edit: June 08, 2012, 04:06:12 PM by Sol Invictus »

carl_nnabis

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Re: Mescaline synthesis-lets make it home friendly!
« Reply #45 on: June 10, 2012, 03:11:54 AM »
Actually after I posted this I wanted to add the reference where it was stated, but then I saw it was actually not what I thought of, but I do have some first hand experience with it: Used a bit more 2 molar NaOCl solution to chlorinate less than 2g anisaldehyde in aqueos "solution", while stirrer was turned on heavy stirring for about one hour, while keeping the plate handwarm (didnt used a thermo as it was just for entertainment), and upon standing and acidification a white hard precipitate formed, which was filtered off and dried. Melting point wasnt measured as trying to do so filled the house with an even more sweeter odor than anisaldehyde itself, just like someone threw a whole pound TLC reagent into his overchlorinated pool.
It was then simply discarded as reagents were dirt-cheap.
Wouldt have done it when it would be the dibrominated derivative.
But heres a reference for the 2 step synthesis from p-hydroxybenzaldehyd (which ones hydroxy group has such a stronger ortho-directing that it can be used for dihalogenation und afterwards can be methylated on 4-. I think a methoxy group has the same directing effect, only less strong than that of a hydroxy.

Reference will be uploaded in short time as soon as i find out how to do
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carl_nnabis

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Re: Mescaline synthesis-lets make it home friendly!
« Reply #46 on: June 23, 2012, 12:34:49 AM »
hmm thought i edited the post to say the reference was not of use, there was a two-step synthesis example where they dichlorinated 4-hydroxybenzaldehyd on position 3 and 5, and some other sources that state this or similiar reactionslike monohalogenation occuring in anisaldehyd on position 3.
There is even a simple fungus who can in occurence of chloride, bromide or iodide salts dihalogenate his own selfmade aromatic aldehydes (mainly 4-OH and 4-MeO benzaldehyde) in a similiar manner first on 3, then on 5. This fungus seemed not to care which of both benzaldehydes, both became 3,5-dihalosubstituted

The not measured melting point was btw above 100° from that precipitate i have made once, and its smell was also noticeable different, it really smelled like someone familiar with anisaldehyd and chlorous smelling stuff would expect it ;D
Nothing like anisaldehyde at all, just a memory of anisaldehyde is left it that stuff, but it had its own smell, i doubt if it would become overoxidized to (dichloro)anisic acid that it still would at all.
But summarized what does this say about if it works or not? just that anisaldehyde reacts tp a solid with way higher melting point before with its own smell that implicates just that my anisaldehyde had get a dichloro substitution without getting oxidized all the way down to anisic acid.
Also possible would be after it got his first chlorine attached, that the other ones will attach opposed to the first, so one would end up with the 3,4,6-tri-MeO mescaline, dont know if that is a good one?

Anyway this would be too much work for mescaline itself, have you considered oxidizing calamus oil yet to asaronaldehyde? the mescaline analogue out of it is a bit potenter too
« Last Edit: June 23, 2012, 12:39:32 AM by carl_nnabis »
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Sol Invictus

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Re: Mescaline synthesis-lets make it home friendly!
« Reply #47 on: June 24, 2012, 09:34:41 AM »
Cool thanks for elaborating Carl_nnabis.

Just to throw it out there does anyone have any thought on the potential of an Oxone-type halogenation being successful in doing the job on positions 3 & 5? Might be worth some experimentation...
 
With regard to asarone, PIHKAL indicates the amphetamine derivative is markedly superior to the phenethylamine, & in Sol's opinion going through the aldehyde is an unnecessary additional step if one's target compound is the former.