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  #1  
Old 07-07-2009, 01:32 AM
Fractals Fractals is offline
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Default OTC Mescaline Synthesis from Vanillin

I'm not much for words, so here's the synthesis I've been working on (slightly plagiarized, see sources):

Vanillin + NaOH(aq) + NaI3.NaI + H2SO4 -> 5-iodovanillin (99% yield *)

5-iodovanillin + NaOH + Cu -> 5-hydroxyvanillin (99% yield, iodine can be recovered *)

5-hydroxyvanillin + acetone + dimethylsulfate + Na2CO3.H2O + KOH -> 3,4,5-trimethoxybenzaldehyde (94% yield *)

3,4,5-trimethoxybenzaldehyde + nitromethane + ammonium acetate -> 3,4,5-trimethoxynitrostyrene (*)

3,4,5-trimethoxynitrostyrene + Pd/C + EtOH + HCl -> mescaline (*)

This is the first synth that I've designed (okay, pieced together), so go easy on me. Click on the *'s for the sources. AFAIK, this is untested.
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  #2  
Old 07-07-2009, 02:02 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Nice.

I'm not sure how accessible these reagents are, but here's what I think.

Vanillin: Obviously. Essence of Vanilla.
Iodine: Sort of, only in 10-100 g quantaties
NaI: Yes, can be purchased without hazard
NaOH: Lye, quite accessible
Copper: Yes.
Acetone: Can find 1 gal quantaties
Dimethylsulfate: Maybe.... Perhaps MeOH + H2SO4 then something else?
Bases: Yea, pretty much all of those are easy to obtain


Well almost everything here is accessible. I'd be worried about Pd/C and dimethylsulfate.

Someone give it a shot!
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Old 07-07-2009, 02:14 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fractals View Post
...dimethylsulfate...
Bad voodoo. [1] I'd look inta alts. [2][3]

The rest is legit/well documented.

...

Isoelemicin [4][5]+ KMnO4 -> 3,4,5-TMB?
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Old 07-07-2009, 02:38 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Ford Prefect View Post
Bad voodoo. [1] I'd look inta alts. [2][3]

The rest is legit/well documented.

...

Isoelemicin [4][5]+ KMnO4 -> 3,4,5-TMB?
Damn, I though it would be easy when wikipedia said "the simplest being the esterification of sulfuric acid with methanol."

Quote:
Originally Posted by Aperson444 View Post
Well almost everything here is accessible. I'd be worried about Pd/C and dimethylsulfate.
Pd/C can be made from palladium chloride, HCl, carbon, and sodium acetate trihydrate(*).

Edit:

Quote:
Originally Posted by Aperson444 View Post
Iodine: Sort of, only in 10-100 g quantaties
At least you can recycle the I2, or you could use bromine and GAA(*).

Edit2:
Ford, in your thread, trimethylphosphate was talked about. Is there any problem using/acquiring it? One of the SM links said it's easy to get, but I couldn't find any consumer uses on google.
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Last edited by Fractals; 07-07-2009 at 03:04 AM.
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Old 07-07-2009, 05:16 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Dimethyl cabonate (MSDS) might work as the methylating agent. It is much less toxic than DMS, and can be made from methanol and carbon dioxide. It's also environmentally friendly.
Quote:
Abstract: Dimethylcarbonate (DMC) is a valuable methylating reagent which can replace
methyl halides and dimethylsulfate in the methylation of a variety of nucleophiles. It couples
tunable reactivity and unprecedented selectivity toward mono-C- and mono-N-methylation in
the reactions of acidic CH2 and primary aromatic amines, respectively. In addition, it is a pro-
totype example of a green reagent, since it is nontoxic, made by a clean process, and
biodegradable
, and it reacts in the presence of a catalytic amount of base thereby avoiding
the formation of undesirable inorganic salts as by-products. Other remarkable reactions are
those where DMC behaves as an oxidant: cyclic ketones are transformed into α,ω-dimethyl
esters with a reaction of atom efficiency of 1.0.
Source of quote
http://pubs.acs.org/doi/abs/10.1021/ie9806444
http://www.sciencedirect.com/science...37afe4132a286e does anyone have a sciencedirect account?
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Old 07-07-2009, 05:31 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fractals View Post
Dimethyl cabonate (MSDS) might work as the methylating agent. It is much less toxic than DMS, and can be made from methanol and carbon dioxide. It's also environmentally friendly.

Source of quote
http://pubs.acs.org/doi/abs/10.1021/ie9806444
http://www.sciencedirect.com/science...37afe4132a286e does anyone have a sciencedirect account?
Anything a little more practical? Syntheses of DMC aren't hugely difficult, the problem is with how it reacts.

A cool did you know: beta-phenylnitroethane reacts with dimethylcarbonate to yield alpha-methyl, beta-phenylnitroethane. A common error among less-informed chemists is that amphetamines can be made from the Henry reaction with nitromethane (they can't, you need nitroethane); but with this process it would be much more practical to make phenylisopropylamines from reaction with nitromethane and DMC. 2 immediately obvious options:
1) Partial reduction of the olefin followed by reaction with DMC. Then reduction of the nitro group. Hydrogenation by 2 different methods should be able to achieve both tasks (perhaps even a simultaneous approach could be worked out since one would likely be working with pressure, which is how DMC usually reacts--massive potential here provided someone can assure me that in nitroalkene reductions, the olefin is targeted first, or that a practical hydrogenation reaction exists that would allow that to occur).
2) Full reduction to the ethylamine, then oxidation to the nitroethane, reaction with DMC, and reduction back to the amine (the interconversion between the 2 oxidation stages of the nitrogen can be nearly quantitative with several OTC reagents, making this process particularly useful although more tedious).

If there are easy ways of making this reagent react (Montmorillonite/K2CO3 anyone?), then it could be of massive use to clandestine chemists.

Last edited by nshanin; 07-07-2009 at 05:44 AM.
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Old 07-07-2009, 06:21 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Looks feasible at first glance... Here's your ScienceDirect article.

High performance method for O-methylation of phenol with dimethyl carbonate
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Old 07-07-2009, 07:22 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by nshanin View Post
Anything a little more practical? Syntheses of DMC aren't hugely difficult, the problem is with how it reacts.
What is the problem, exactly? According to the ScienceDirect article (thanks, Zip!), they were able to perform the reaction at standard atmospheric pressure at 130C, and get a 100% conversion. It uses TBAB (I'm not sure how easy this is to make/get) as a catalyst, which can be regenerated after the reaction.

Quote:
Originally Posted by nshanin View Post
A cool did you know: beta-phenylnitroethane reacts with dimethylcarbonate to yield alpha-methyl, beta-phenylnitroethane. A common error among less-informed chemists is that amphetamines can be made from the Henry reaction with nitromethane (they can't, you need nitroethane); but with this process it would be much more practical to make phenylisopropylamines from reaction with nitromethane and DMC. 2 immediately obvious options:
1) Partial reduction of the olefin followed by reaction with DMC. Then reduction of the nitro group. Hydrogenation by 2 different methods should be able to achieve both tasks (perhaps even a simultaneous approach could be worked out since one would likely be working with pressure, which is how DMC usually reacts--massive potential here provided someone can assure me that in nitroalkene reductions, the olefin is targeted first, or that a practical hydrogenation reaction exists that would allow that to occur).
2) Full reduction to the ethylamine, then oxidation to the nitroethane, reaction with DMC, and reduction back to the amine (the interconversion between the 2 oxidation stages of the nitrogen can be nearly quantitative with several OTC reagents, making this process particularly useful although more tedious).

If there are easy ways of making this reagent react (Montmorillonite/K2CO3 anyone?), then it could be of massive use to clandestine chemists.
Interesting!

Edit: TBAB looks pretty hard to get, but the paper did mention a few other catalysts. Only TBAB got 100% yields though.
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Last edited by Fractals; 07-07-2009 at 07:30 AM.
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  #9  
Old 07-07-2009, 10:35 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fractals View Post
3,4,5-trimethoxybenzaldehyde + nitromethane + ammonium acetate -> 3,4,5-trimethoxynitrostyrene (*)
Does this work with piperonal or do you absolutely need nitroethane?
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Old 07-07-2009, 10:59 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fra View Post
Does this work with piperonal or do you absolutely need nitroethane?
need nitroethane.
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Old 07-07-2009, 12:07 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

Is there any way to add that missing carbon atom? Or is it easier to just buy/make nitroetane?
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Old 07-07-2009, 01:05 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

dimethylsulfate and pd/c would be my biggest qualms with this, i got this little graph that turns vanillin into lots of things (dma, or mmda) so its good to see a rxn for mescaline.

curious whether you can just start from styrene and cut off a few steps because of it, i really didnt put enough effort into finding styrene sources but if worst comes to worst just buy a block of it retail
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Old 07-07-2009, 02:32 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fractals View Post
What is the problem, exactly? According to the ScienceDirect article (thanks, Zip!), they were able to perform the reaction at standard atmospheric pressure at 130C, and get a 100% conversion. It uses TBAB (I'm not sure how easy this is to make/get) as a catalyst, which can be regenerated after the reaction.
Didn't read that article (since it wasn't provided yet) but after looking at the review it just seemed impractical. Good to know that there are better methods out there. Anybody seen anything similar for mono N-methylation?

Quote:
Edit: TBAB looks pretty hard to get, but the paper did mention a few other catalysts. Only TBAB got 100% yields though.
I have 90 or so grams of TBAB with me but it is trickier to get than many chemicals. From the mechanism they lay out it seems like a good lewis acid could do the trick well enough to react--lithium salts perhaps?
Quote:
Originally Posted by Fra View Post
Is there any way to add that missing carbon atom? Or is it easier to just buy/make nitroetane?
Well I just made a huge post about it...
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Old 07-07-2009, 04:41 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fra View Post
Is there any way to add that missing carbon atom? Or is it easier to just buy/make nitroetane?
buy/make
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Old 07-07-2009, 05:55 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fra View Post
Is there any way to add that missing carbon atom? Or is it easier to just buy/make nitroetane?
DiMethylCarbonate
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Old 07-09-2009, 11:35 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

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How difficult is Pd/C to get? Can it be easily made from PdCl from a photography store?
Heat 7.5g activated charcoal (Note 2) on a steam bath for 2-3 hours with conc. hydrochloric acid (5 ml) and water (150 ml). Wash the charcoal by decantation with hot water until free of acid, filter it off, and dry it in an oven below 100C. Heat palladium chloride (0.5 g) in conc. hydrochloric acid (0.75 ml) and water (5 ml) on the steam bath for ~20 min. Add the solution to AnalaR sodium acetate (17.5 g) in water (50 ml) contained in a hydrogenation flask. Introduce the purified charcoal (5.8 g) and hydrogenate the mixture until no more hydrogen is absorbed (~2 h). Collect the catalyst on a 7 cm Buchner filter (3 thicknesses of Whatman No. 1 filter paper), wash it with water (5 x 100 ml) and drain it on the filter with suction. Dry the catalyst over fresh silica gel in a vacuum desiccator and store it in a tightly stoppered bottle. [1]

Aluminum amalgum is an alternative.

...

No thoughts on elemicin?
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Old 07-09-2009, 11:37 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fractals View Post
Sorry I havn't been posting too much lately. I've been busy with work and a cow pasture full of mushrooms. I'm looking into TBAB alternatives and more on DMC. How difficult is Pd/C to get? Can it be easily made from PdCl from a photography store?
Pd/c is easily aquired or can be made easily (look on the rhodium archive). I have made some and it works fine
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Old 07-10-2009, 01:23 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

In that SD paper about DCM, 4-Dimethylaminopyridine was also used as a catalyst, with 67% yields.
Quote:
Originally Posted by wikipedia
DMAP can be prepared in a two-step procedure from pyridine, which is first oxidized to 4-pyridylpyridinium cation. This cation then reacts with dimethylamine:[4]
In that SD article, they talked about the "molar space velocity of anisole formation per mole of catalyst." What is velocity, in regards to chemistry?

Edit:
Quote:
Originally Posted by Ford Prefect View Post
No thoughts on elemicin?
Hmmmm, elemicin does look interesting. It only is 2.4% of nutmeg essential oil (according to the wiki page), but it can be synthed from eugenol. Is there any way to aminate it to mescaline without forming the nitrile? KCN is pretty hard to get, isn't it?
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Last edited by Fractals; 07-10-2009 at 01:36 AM.
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Old 07-10-2009, 02:30 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Fractals View Post
Hmmmm, elemicin does look interesting. It only is 2.4% of nutmeg essential oil (according to the wiki page), but it can be synthed from eugenol. Is there any way to aminate it to mescaline without forming the nitrile? KCN is pretty hard to get, isn't it?
Rumor has it that there are tea tree oils with significantly higher levels... Purely theoretical and I have exactly zero refs to back it up, but perhaps a mw isomerization followed by an oxidative cleavage could yield your benzaldehyde intermediate.

Or... oxidation of the double bond (it's late, there is a double bond, no?) to a molozide intermediate, which rearranges rapidly to an ozonide, which'd then be reduced. Again, just thoughts.
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Old 07-10-2009, 05:16 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by Ford Prefect View Post
oxidative cleavage
I've looked into OTC methods of doing this and the easiest I've found so far is to generate your own ozone into wet acetone and reduce with zinc. That's not at all practical and I don't know of other reagents (save permanganate, but we all know the problem with that) that will do this. Any refs or precise reagents?
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Old 07-15-2009, 08:13 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

Why MeI (methyliodide, iododomethane) could not be used instead of nasty DMS?
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Old 07-15-2009, 11:54 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

Quote:
Originally Posted by micro View Post
Why MeI (methyliodide, iododomethane) could not be used instead of nasty DMS?
It looks like it would work, but it would need RP and more I2. Maybe bromomethane? It would be cheaper than MeI and easier than DMC.
http://www.sciencemadness.org/talk/v...0507#pid126542
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Old 07-16-2009, 05:40 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

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Originally Posted by nshanin View Post
I've looked into OTC methods of doing this and the easiest I've found so far is to generate your own ozone into wet acetone and reduce with zinc. That's not at all practical and I don't know of other reagents (save permanganate, but we all know the problem with that) that will do this. Any refs or precise reagents?
Nahh, like I said it's lla speculative. But shit, I'd prefer to generate ozone electrolytically, I'd prefer most anything to working with the mutagens commonly used in methylations. And while KMnO4 is often rather blunt, by simply adjusting the PH or temp it might prove effective, I dunno, it'd have to be tested.

Anyways, the oil mentioned earlier would be that of the black tea-tree...

A number of the oils examined contained from 85 to 90 per cent of methyl eugenol, whereas other oils contained equivalent percentages of methyl iso- eugenol and elemicin, respectively. This is the first recorded occurrence of methyl isoeugenol in Australian essential oils, and the first time elemicin has been identified in oil of Melaleuca bracteata. [1]

...

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Old 07-16-2009, 08:38 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Related, but not entirely:
I've been seriously considering a process for a mescaline analogue for several months now and was wondering what you guys thought. It's a pretty blunt synthesis, you just brute force your way to the molecule, but if I'm correct then it should do the job well enough. The idea was to try and get to pentamethoxy PEA (aka dimethoxy mescaline), which is several times more potent than mescaline itself in multiple animal models. The initial thought was to use PEA and "halogenate the shit out of" (technical term) the ring. There exist several forms of very active halogens--FCl, H3C-CN-I+ (the cation of N-iodoacetonitrile), and really any halogen cation. I've looked into the papers of the two that I've mentioned and the former is not practical (fluorine gas n' stuff) and the latter degrades amines and produces rather poor yields when taken all the way to the fully substituted compound. It also turns out that PEA is far too weak of an activator for this process to be done the normal way, with dihalogens rather than the activated forms mentioned above.

So, assuming that a highly active halogen derivative is not found (I've googled it pretty heavily but only with a limited amount of search terms; if you could find something that's feasible for this I would thank you endlessly ), it may be easier to start from highly activated aryl compounds, like pyrogallol, catechol or hydroquinone, and proceed to make the aldehyde via a choice of aldehyde synthesis (I for one am hopelessly confused as to why the Duff reaction isn't more popular)--before or after methylation, it really depends on the reaction, conditions, other crap on your molecule, etc. Then you would follow this up with a lengthy reflux in a large excess of diatomic halogen and a lewis acid catalyst (though one may not be necessary--certainly not with the trihydroxylated varieties and perhaps not with the others--I couldn't find much info on it).

THEN you do some sort of crazy electrosynthesis the ref for which is in Fry and I have stored somewhere wherein methanol replaces a halogen on a benzene ring. This avoids the need for methylating agents after you hydroxylate. Now of course you'll still need to methylate the rest of your hydroxyls, which is why Ford's idea with regards to cleaving methyl eugenol is plausible, though I don't know about working with ozone. I don't think there are many dimethoxybenzene compounds that are as readily available as the polyoxygenated ones mentioned above along with the possibilities of cleavage of propenylbenzenes and of course, vanillin; but IMO working with MeBr would be less of a drag than basically having to innovate an entire clandestine methodology for working with ozone, the use of which has yet to be documented--to my knowledge--by home chemists. Ozone generators are available but are bloody expensive and I don't know how one could replicate one--though admittedly I haven't looked into it as much as I should have.

Anyway, that's my story; I'm sure you guys know what to do with the aldehyde once you get there. Oh, and to add to the incentive--this compound hasn't been tasted by man (at least not when I looked into it last), so in case you were wondering--it is a VERY important synthesis.
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Old 07-17-2009, 04:38 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

Sorry to lead off on a tangent, but has anyone heard of any oils containing significant amounts of elemicin?

It says here (http://chestofbooks.com/health/aroma.../Elemicin.html) that treatment with permanganate will yield the corresponding carboxylic acid (TriMeGallic acid). I'm sure one of the O-Chem students will know a way from here to the aldehyde or maybe even better route to mescaline off the top of their head...

However, in the case of eugenol, that open HO may do something....

Bulk elemicin would be so much nicer than vanillin.... man, O-methylations are a bitch
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Old 07-17-2009, 09:41 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

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Originally Posted by HeaT View Post
a way from here to the aldehyde or maybe even better route to mescaline off the top of their head...
There aren't any good ones. You're better off decarboxylating and then F-Cing or formylating. Unless you have access to a hydrogenator, LAH, acid chlorinators, etc. Cleaving the double bond to the aldehyde (most likely with ozone, unless y'all have better ideas) is another option but it almost definitely won't be done with permanganate. There are methods of cleaving diols and epoxides which you may want to look into--you may even be able to make the 2-step cleavage one-pot, but making the acid is useless unless you have thionyl/phthaloyl/oxalyl/triazine-tri/etc. chloride or just really, really want to avoid that methylation.
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Old 07-17-2009, 09:46 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

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Originally Posted by Fractals View Post
3,4,5-trimethoxynitrostyrene + Pd/C + EtOH + HCl -> mescaline (*)
Can someone propose something else for this step? This could be replaced with a Al/Hg correct? Anyone have anything about it? Amounts etc?
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Old 07-18-2009, 03:29 AM
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This could be replaced with a Al/Hg correct?
Yes.
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Old 07-19-2009, 12:54 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

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Yes.
Cookies if you find me something about it

If am crusing in the hive archives and nothing relevant so far
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Old 07-19-2009, 06:46 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

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Originally Posted by stateofhack View Post
Cookies if you find me something about it

If am crusing in the hive archives and nothing relevant so far
http://www.erowid.org/archive/rhodiu...reductions.txt

And MOAR: http://designer-drugs.com/pte/12.162...roalkenes.html

A veritable treasure trove of reductions: http://www.sciencemadness.org/talk/v...id=11&tid=4629
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Old 07-21-2009, 10:56 AM
VisualDistortion VisualDistortion is offline
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Default Re: OTC Mescaline Synthesis from Vanillin

Mescaline is soooo easy to extract. I guess the challenge in synthesizing it is what makes it fun.
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Old 07-21-2009, 11:26 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Unless you wanted to sell it, and you were REALLY interested in heavy profits. Generally syntheses work out cheaper than extractions at larger and larger scales, although in this case the very starting precursor is semi organic, which would obviously put a lid on lowering the costs.

But you are correct, its the challenge that interests us.
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Old 07-22-2009, 08:43 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

Anybody heard of a beta-ketone analogue of mescaline or its amphetamine homologue? Or any active beta-keto PEAs (without alpha carbons) for that matter?

One idea that I had that has relevance for the synthesis of both above compounds and mescaline proper is the use of nitroacetic acid (which sources tell me decomposes spontaneously in a manner not unique among nitro compounds, but I dunno) in an F-C (there's an OTC way for this that does not involve halogens, I promise) with your target compound to yield 2-nitro acetophenones. These can then be reduced (think high-pressure H2 or some creative electrochemistry) straight to your PEA. Hey, it beats the hell out of using chloroacetaldehyde. This nitro compound has a very highly activated methylene handle which can be used for any number of things (but only reasonably for alkylations w/ 1-4 carbons).

That was for those who like to see a universal path for a given group of compounds, like the alpha-i-propyl homologue which AFAIK wasn't tested in the SAR of this series (though please do prove me wrong with a more expansive article) (EDIT: NVM, just do it with valine). More practically, an F-C with glycine would take you straight to the B-keto PEA. This is highly prone to dimerization however, so there are a few things one can do to salvage their product: 1) Quick hands 2) Simultaneous reduction. The F-C technique I'm thinking of just requires a solid support so electrochemistry could easily be performed in such a medium. Benzyl ketone reduction can be highly selective to your target product over any of the other things in your reaction medium (namely acids). 3) Form an imine of glycine as a protecting group. Alkylation/Dealkylation would probably be a bad idea. 4) Some reducing agent that reacts with benzyllic ketones and not with acids. Borohydride could be used but one would need quite a large excess and some would probably react with the amino acid. 5) Fuck mescaline. Go for N-methyl, beta-keto mescaline, which doesn't dimerize and will probably be rated as <1 MU but should have nice CNS effects. It's a crapshoot. 6) Do a barrel roll.

Yeah, just throw this in the bullshit thread. I'm procrastinating.

Oh, and in other news, the above outlines pretty damn well a one-stepper to cathinone. See if you can pick it out.

Last edited by nshanin; 07-22-2009 at 08:50 AM.
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Old 09-06-2009, 02:08 PM
2bfrank 2bfrank is offline
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Default Re: OTC Mescaline Synthesis from Vanillin

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Originally Posted by nshanin View Post
Anything a little more practical? Syntheses of DMC aren't hugely difficult, the problem is with how it reacts.

A cool did you know: beta-phenylnitroethane reacts with dimethylcarbonate to yield alpha-methyl, beta-phenylnitroethane. A common error among less-informed chemists is that amphetamines can be made from the Henry reaction with nitromethane (they can't, you need nitroethane); but with this process it would be much more practical to make phenylisopropylamines from reaction with nitromethane and DMC. 2 immediately obvious options:
1) Partial reduction of the olefin followed by reaction with DMC. Then reduction of the nitro group. Hydrogenation by 2 different methods should be able to achieve both tasks (perhaps even a simultaneous approach could be worked out since one would likely be working with pressure, which is how DMC usually reacts--massive potential here provided someone can assure me that in nitroalkene reductions, the olefin is targeted first, or that a practical hydrogenation reaction exists that would allow that to occur).
2) Full reduction to the ethylamine, then oxidation to the nitroethane, reaction with DMC, and reduction back to the amine (the interconversion between the 2 oxidation stages of the nitrogen can be nearly quantitative with several OTC reagents, making this process particularly useful although more tedious).

If there are easy ways of making this reagent react (Montmorillonite/K2CO3 anyone?), then it could be of massive use to clandestine chemists.
Just to add on this selective reduction to a betanitrostyrne...

Kodukulla, K. R. P.; Trivedi, G. K.; Vora, J. D.; Mathur, H. H., Synth. Commun. ,1994, 24,

re, To an efficiently stirred mixture of b-nitrostyrene 224 (5.775 g, 0.0276 mole), silica gel (52.72 g), 2-propanol (50 ml) and chloroform (400 ml), was added sodium
borohydride (4.36 g, 0.1153 mole) over a period of 15 min at 25 oC
(disappearance of yellow colour). The excess borohydride was decomposed
with dilute HCl followed by the washing of the silica gel cake with methylene
chloride. The resultant solution was washed with brine and dried over Na2SO4. Evaporation of the solvent gave the 2-aryl-1-nitroethane 223 (5.2 g, 89.19%) as a colorless oil.
Interesting prep I thought, and basically about establishing a compound that could be used in a condensation reaction. ie. the formation of 1,2-diarylpropylamine. could have some useful inhibitive effects. also the diarylnitropropene could be turned into a diarylketone that leads to more theoretical/practical scope..

2b

Last edited by 2bfrank; 09-13-2009 at 09:34 AM. Reason: to be clear
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  #35  
Old 09-06-2009, 11:55 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

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Originally Posted by 2bfrank View Post
Just to add on this selective reduction to a betanitrostyrne...

Kodukulla, K. R. P.; Trivedi, G. K.; Vora, J. D.; Mathur, H. H., Synth. Commun. ,1994, 24,

re, To an efficiently stirred mixture of b-nitrostyrene 224 (5.775 g, 0.0276 mole), silica gel (52.72 g), 2-propanol (50 ml) and chloroform (400 ml), was added sodium
borohydride (4.36 g, 0.1153 mole) over a period of 15 min at 25 oC
(disappearance of yellow colour). The excess borohydride was decomposed
with dilute HCl followed by the washing of the silica gel cake with methylene
chloride. The resultant solution was washed with brine and dried over Na2SO4. Evaporation of the solvent gave the 2-aryl-1-nitroethane 223 (5.2 g, 89.19%) as a colorless oil.
Any help with the dimethylcarbonate prep would be helpful,, He was thinking of trying to see if the phenylnitroethane could via henry reaction, and do so with the use of paraformaldehyde,, Looking at a microwave prep.. Anyother ideas for selective reduction, ones that dont require the borohydride would also be good.. My first post here, and its a long one..


2b
Hey Frank, nice to see you discovering the smaller boards

Baker's yeast will reduce alpha, beta unsaturated nitroalkanes. No ref with me, but it does exist ().
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  #36  
Old 09-07-2009, 10:43 AM
2bfrank 2bfrank is offline
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Default Re: OTC Mescaline Synthesis from Vanillin

Thats great news if it is so.. I initially thought yeast, as I know it generates NADPH, or NADH, hence hydride, but my searches all ended in NO2>NH3. I just accepted no selectivity. I am pleased to be wrong, and I found that prep that I posted in light of what I considered a difficulty.. GOOD< my last 100g of Borohydride lives another day.. . I lost my database access due to health, hence not enrolled in units this part of year, DAM It, so ill look for freebies and friends. So if that can get sorted, and/or another thing been experimenting with, oxone, dmdo for pea. but regardless, do you feel that its possibile to condense phenylnitroethane with formaldehyde(para) to 3-phenyl-2-nitroprop-1-ene.?
Just for the novelty of it all Thinking loading silicon gel/bentonite looks mighty good. And yes, nice site, found by searching this thing in fact.

2b/Frank.

ps, but perhaps there are just some things in life, that one has to find out for one self..Im like a little kid sometimes, CAN I< CAN I,question,, typical newbee at a forum i suppose

Last edited by 2bfrank; 09-07-2009 at 10:50 AM.
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  #37  
Old 09-07-2009, 10:15 PM
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Default Re: OTC Mescaline Synthesis from Vanillin

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Originally Posted by 2bfrank View Post
Thats great news if it is so.. I initially thought yeast, as I know it generates NADPH, or NADH, hence hydride, but my searches all ended in NO2>NH3. I just accepted no selectivity. I am pleased to be wrong, and I found that prep that I posted in light of what I considered a difficulty
True story; I think biocatalysis is the wave of the future--not only in clandestine chemistry . here's a ref that a simple google search turned up; I'm sure there are plenty more.

Quote:
.. GOOD< my last 100g of Borohydride lives another day.. . I lost my database access due to health, hence not enrolled in units this part of year, DAM It, so ill look for freebies and friends.
*becomes friend*
Quote:
So if that can get sorted, and/or another thing been experimenting with, oxone, dmdo for pea.
Be sure to tell us how this goes, I was considering this route as well but PEA is pretty expensive and has... other uses.
Quote:
but regardless, do you feel that its possibile to condense phenylnitroethane with formaldehyde(para) to 3-phenyl-2-nitroprop-1-ene.?
I have seen condensations with formaldehyde but they've been with smaller nitroalkanes only, although these two refs should have something interesting to say on the subject (using bulky phenylseleno groups, if I'm not mistaken):
T. Sakakibira, I. Takai, E. Ohara, R. Sudah, J. Chem. Soc., Chem. Commun. 1981, 261
T. Sakakibira, S. Ikuta, R. Sudah, Synthesis 1982, 261

Also, a condensation agent is absolutely crucial for this reaction as you're not conjugating with the aromatic group in this situation so you're likely to get stuck with the alcohol. This should also produce less of the di-reacted product.

Last edited by nshanin; 09-07-2009 at 10:18 PM.
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Old 09-08-2009, 04:52 AM
2bfrank 2bfrank is offline
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Thanks muchly nshanin, I checked the yeast mediated file, and a bit of a look in the others, didn;t think youd mind/hope not,(got some VERY cool and interesting bits)(Im sorting some file sharing shortly and will offer some of mine/if interested) anyway the yeast reduces, but that paper, it seems to require a methyl group or larger attatched to the beta Carbon..and all the products were at least phenyl-2-nitropropane/butane, etc. I might be wrong, as its easy to miss things, and I Know I have seen this elsewhere, but as said, all my searches(without access to lit) so far haven't found selective for beta-nitrostyrene.and not touching the nitro.Please tell me Im hallucinating my new friend Also those references,(Henry style)with big/bulky nitro derivatives - and HCOH, I presume, I can get a friend to do so, but he wont unless I provide a doi number, hes busy as hell. I have had a quick attempt to hunt it up, but if you have them, could you enclose. I tell you, I took access to Sc literature for granted. So the problem with b-nitrostyrne (bNS) is I am assuming that the beta pos proton, is not acidic/or enough, due to unsaturation.(Im a learner chemer here) so the alpha carbon proton might be? hence this is giving me some ideas.which have got me back to the books, and get a better handle on this, rather than paper dependant..How absurd, that just sounded..lol's ......tick tick,,,just got back,check this out, soz if youve got it, frreee good books from http://scientist-at-work.blogspot.com/. Scroll back to find the better ones.

2b

Last edited by 2bfrank; 09-08-2009 at 07:46 AM.
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  #39  
Old 09-08-2009, 07:49 AM
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Default Re: OTC Mescaline Synthesis from Vanillin

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Originally Posted by 2bfrank View Post
Thanks muchly nshanin, I checked the yeast mediated file, and a bit of a look in the others, didn;t think youd mind/hope not,(got some VERY cool and interesting bits)(Im sorting some file sharing shortly and will offer some of mine/if interested)
Did I give you the whole folder? Silly me. Oh well, live and let learn

Quote:
anyway the yeast reduces, but that paper, it seems to require a methyl group or larger attatched to the beta Carbon..and all the products were at least phenyl-2-nitropropane/butane, etc. I might be wrong, as its easy to miss things, and I Know I have seen this elsewhere, but as said, all my searches(without access to lit) so far haven't found selective for beta-nitrostyrene.and not touching the nitro.Please tell me Im hallucinating my new friend
No you're right, but I think that was only the case because they wanted to test out stereoselectivity; they specifically state substituted nitrostyrenes, not just methyl-substituted ones, although you're right in saying that that's all that they tested. I would assume it would still work with this particular substrate, even if I only had this paper to go off of.
Quote:
Also those references,(Henry style)with big/bulky nitro derivatives - and HCOH, I presume, I can get a friend to do so, but he wont unless I provide a doi number, hes busy as hell. I have had a quick attempt to hunt it up, but if you have them, could you enclose.
I don't ATM but I'll search for it when I get the time... also overloaded and not really any time for chemistry, barely even been checking into this forum let alone the others.

Quote:
So the problem with b-nitrostyrne (bNS) is I am assuming that the beta pos proton, is not acidic/or enough, due to unsaturation.(Im a learner chemer here) so the alpha carbon proton might be? hence this is giving me some ideas.which have got me back to the books, and get a better handle on this, rather than paper dependant..How absurd, that just sounded..lol's
Both protons of beta-nitro styrene are acidic to some extent for varying reasons but the alpha proton is more acidic because it's alpha to a nitro group and thus has a resonance stability similar to that of a carbonyl (hopefully you're familiar with aldol reactions) which is all that makes the Henry reaction (also known as a nitroaldol for just this particular reason) work. Either way it's not a good idea to do it with the styrene because the product will be the alcohol and you'd need an additional, separate dehydrating step to convert it to the nitroalkene.

Consider this:
1) 2-Nitrostyrene
--Reduction--
2) 2-phenyl, 1-nitroethane
--Henry w/ CH2O--
3) Iso-P2NP (there may be isomerization so maybe some P2NP in there as well)
--Reduction, works the same for both substrates--
4) Amphetamine

I was going to write your pathway when I realized I had forgotten 90% of IUPAC nomenclature and have a 7:30 class tomorrow. Anyway, that method is inefficient if it even works in the first place. If you really want details I can give them to you at a later date but honestly--no nitroaldol with nitroalkenes, it's a waste of time.

Last edited by nshanin; 09-08-2009 at 07:54 AM.
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Old 09-08-2009, 08:54 AM
2bfrank 2bfrank is offline
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Default Re: OTC Mescaline Synthesis from Vanillin

Yeah, I agree the use of paraformaldehyde should work,their is also the possibility to make the dianion and then alkylate, but that would be troublesome, less OTC etc. I was toying with other possibilities, but looking at it, I think your correct. Id much prefer to look at the use of paraformaldehyde than God knows what. I do have a reasonable understanding of a nitroaldol reaction, and yet very much learning, and forgetting things what not..Id like to look at this via microwaves. Perhaps not the reduction, but for most parts yes..Obviously I would like confirmation that a nitroaldol, or perhaps any molecule able to be acidic, or made etc,type reaction would work for a bulky nitro, and paraformaldehyde, but I cannot see at ALL, why not. The only question in my mind is the the reduction with yeast..I have also seen it before, and your saying it, and it would certainly be a big deal somewhat if this is as easy as easy, as the ability to add an extra carbon(s) at the alpha position with respect to nitro derivatives is very attractive.It all looks too fucking easy..Oh well some fun to be had, experiments to be done..I'm not into big yields with this sort of thing, etc. getting right into the loading things on clay and gel. its all good. If you haven't checked out that site I gave, do so, as its got some really good chem books..2bfrank.

Last edited by 2bfrank; 09-21-2009 at 01:56 AM.
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