dormouse (Member)
04-25-00 00:45
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      TMA-2: electrochemical nitropropene questions ?! -element 109  Bookmark   


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Author  Topic:   TMA-2: electrochemical nitropropene questions ?! 
element 109
NewBee   posted 01-10-2000 10:01 AM           
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OK, here's something that's been haunting me for days now. It was a sudden "eureka" that hit me when I thought this one up, but my knowledge of chemistry falls way too short, I'm still learning this and I know I could be all wrong.
Now, in his book PiHKaL Shulgin synthesizes much (if not all) of his PEA's and amphetamines starting from their corresponding benzaldehydes. This benzaldehyde is then reacted with nirtomethane or nitroethane to give the beta-nitrostyrene or the phenyl-2-nitropropene respectively. Then he uses LAH on these creatures for reductive amination to give the phenethylamine or amphetamine.

In another article, the synthesis of mescaline from gallic acid (found at Rhodium's page), the authors use an awesome piece of electrochemical reductive amination; after 12 hours mescaline.HCl is obtained from 3,4,5-trimethoxy-beta-nitrostyrene in 77% yield. (J.Prakt.Chem 137, 339 (1933))

"Yeah, so what the fuck ?",you may ask yourselves now.

Well, in another article found at Rhodium's fine page, "TMA-2 from Sweet Flag root by Randolph Carter", the author distills asarone from calamus root (185-200C) and went on reacting this with NaNO2 and H2SO4, to get an 78% yield of 2,4,5-trimethoxyphenyl-2-nitropropene. Now Shulgin would probably do a LAH job here, but the author went on oxidizng it into the ketone and did a Leukart.

Where am I getting at? Phenyl-2-nitropropene differs from beta-nitrostyrene by having an extra CH3 just like final product amphetamine differs from the PEA; so I don't see why a electrochemical reductive amination
similar to the one in the mescaline paper shouldn't work.

The cathode liquor is a solution of this nitropropene in acetic acid/EtOH/HCl and the anode liguor is H2O/H2SO4. The reaction requires 12 hours, using a current of 5-6 A.
Check it yourselves.

What I think is happening here, is that the O2 from the nitro-group leaves for a better place at the anode while being replaced by a H2 from shitloads of hydrogen accumulating at the cathode, leaving us with the oh-so-wanted amine. The description of the apparatus in the paper is not so detailled, so if someone can give a more clear explenation of it's setup it would be very much appreciated. It can't be that hard though, I remember those electrolysis experiments from my Merit (tm) Junior Chem Kit [now banned] I did as a kid so this must be something simuilar , i hope

Element 109


Teonanacatl
Hive Bee   posted 01-10-2000 06:36 PM           
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I wondered about this extra step that R.C. put in his write up as well for awhile since reduction of nitropropenes is nothing special, I came to the (assumed) conclusion that the addition of an extra step through this alternate route was probably chosen for it's ease in comparison to a reduction and the availability of most of the chemicals used in it...is this right Randolph? Anyways, reductions via NaBH4 or LAH seem inaccesible to many bees, catalytic reduction may seem too complex and expensive? (or maybe it's the slightly low yields it tends to produce) and the method you suggest has it's own problems as well as having been noted to be "not chemistry oriented enough" (or something to that regard) somewhere on the Hive in the past...anyways, I think if this is a method you feel confident in pursuing it should work...
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Danger...ethnic digestion tabernacles on now; privacy robotic doubles, rolling rehab threat machines, reformulators, heightened insensitivity vehicles, erotic invisible empires on now...


element 109
NewBee   posted 01-11-2000 08:39 AM           
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Not chemistry-orientated enough? Why is it called electroCHEMISTRY then ?
I'm really interested in this, but i can't seem to find any decent info about it's setup and mechanism. I was actually hoping that at least some of you would be interested in this.

Can i find decent info elsewhere on the net about electrochem ?


 
Wizard X
PimpBee   posted 01-13-2000 07:49 PM           
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Look at my Profiles, the box with the ? in it, and link to my website. Download XFile3.zip, Electrochemical reduction of nitropropenes.
 
Night Trojan
Hive Bee   posted 01-13-2000 08:17 PM           
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Its in Psychedelic Chemistry by M. V. Smith available at Mind Books and Lampoonics.
 
Skink
Hive Bee   posted 01-16-2000 12:55 AM           
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Uncle Fester's books discuss many electrochemical techniques. I would start there; I think you'll find it useful. You can find them in the loompmanics catalog online. You'll need to get the newest editions.
Skink


sparks
Hive Bee   posted 01-18-2000 04:16 AM           
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Electrolytic reduction of nitropropenes has been used for decades by non trained chemists in europe to manufacture basement amph. at least until the supplies of nitroethane dried up about ten years ago.
Hg catode and Pb anode with the traditional flowerpot as a cell divider was used.
From what i've heard it was a high yielding procedure, extremely simple too.
I once saw a photo from a lab bust not very far from where i live.
They had eight 15 liters electrolytic baths running at the same time.
That was a big scale operation.
It was the neighbors living half a kilometer away that couldn't stand the acetic smell and called the police.
I did a write up on the technique on the old board long ago.
I don't know if it's still available in some archive or something.
I think it was called eltrolytic reduction (yes, i misspelled electrolytic)
Basically it's the same method as in psychedelic chemistry, only a bit more low-tech.
Anyway, if one had access to the bensaldehydes the process could be used on the mescaline family.
Nitromethane is readily available, so the nitrostyrenes are extremely easy to make with good yields.
 
element 109
NewBee   posted 02-28-2000 12:06 PM           
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Sparks: Thanks for the info. So the flowerpot does work. I have done a complete search but i didn't find any write-up. Wizard's site is down for now (02-28) and i don't have the money to buy any books .
Can someone please just outline the thing ?

Also, how to coat the Pb cathode with lead peroxide prior to reduction ?


 
sparks
Hive Bee   posted 03-01-2000 03:35 AM           
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The flowerpot is the classic way of doing this reduction, but a custom made thinwalled cheramic vessel may be better.
I don't see the point in covering the Pb electrode with anything.
It's only purpose is to get oxidised to provide e-, then it needs good contact with the anolyte.
 
randolph carter
Hive Bee   posted 03-01-2000 10:53 AM           
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howdy swarm.....
i'll take a quick stab at an outline from memory here....

Electroshock Reduction of 2,4,5 trimethoxy pheny-2-nitropropene

as channeled by: randolph carter

4 g of the nitropropene are added to 100 ml ethanol and 50l glacial acetic acid; then add 10 ml concentrated hydrochloric acid or alternately 50 ml concentrated sulphuric for the catholyte in a 40 cm3 Hg-cathode in a porous cell surrounded by 3n sulphuric acid anolyte with a water cooled Pb anode and reduce at 4 amps (approx 0.07 amps/cm2 cathode surface area...)at 30-40 deg c for 20 hours or until solution is colourless. Evaporate in vacuum to about 20 ml; cool with ice, basify with sodium hydroxide and extract with ether. wash, dry and dilute the ether (or dry, evaporate in vacuum) to get NOT-2,4,5 trimethoxyamphetamine.....synonymous with high energy sexual fun in dream dimensions......

enjoy.....
hope this is of some interest all.......


------------------
randolph carter...
the perennial dream questor...
"remember, love is real(but so are gunz and ammo...), not fade-away, so, pass some on today...'cause it's the end of the world as we know it and i feel FINE!!!..."


 
randolph carter
Hive Bee   posted 03-01-2000 10:55 AM           
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quote:
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Originally posted by randolph carter:
howdy swarm.....
i'll take a quick stab at an outline from memory here....

Electroshock Reduction of 2,4,5 trimethoxy phenyl-2-nitropropene

as channeled by: randolph carter

4 g of the nitropropene are added to 100 ml ethanol and 50 ml glacial acetic acid; then add 10 ml concentrated hydrochloric acid or alternately 50 ml concentrated sulphuric for the catholyte in a 40 cm3 Hg-cathode in a porous cell surrounded by 3n sulphuric acid anolyte with a water cooled Pb anode and reduce at 4 amps (approx 0.07 amps/cm2 cathode surface area...)at 30-40 deg c for 20 hours or until solution is colourless. Evaporate in vacuum to about 20 ml; cool with ice, basify with sodium hydroxide and extract with ether. wash, dry and dilute the ether (or dry, evaporate in vacuum) to get NOT-2,4,5 trimethoxyamphetamine
make the acid salt as covered ad nauseum elsewhere...
.....synonymous with high energy sexual fun in dream dimensions......

enjoy.....
hope this is of some interest all.......

--------------------------------------------------------------------------------


------------------
randolph carter...
the perennial dream questor...
"remember, love is real(but so are gunz and ammo...), not fade-away, so, pass some on today...'cause it's the end of the world as we know it and i feel FINE!!!..."


 
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