Author Topic: Catalytic Hydrogenation for mescaline  (Read 3795 times)

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mottaman420

  • Guest
Catalytic Hydrogenation for mescaline
« on: April 29, 2002, 10:22:00 PM »
Can you magnetically stir a hydrogenation such as the ones described here (Krz's write up)--->

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mescaline.cathyd.html


or do you have to shake like a vibrator to accomplish this goal???

Blue Horses + Red Donkeys = Purple Mules

Rhodium

  • Guest
Shaking is the way to go.
« Reply #1 on: April 29, 2002, 10:33:00 PM »
Shaking is the way to go.

Osmium

  • Guest
Unless your reaction is small and your stirrer ...
« Reply #2 on: April 30, 2002, 12:47:00 AM »
Unless your reaction is small and your stirrer magnet and flask are quite big, then magnetic will work ok too.
Another possibility is surface stirring. You want to get as much turbulence and liquid to gas contact as possible.

I'm not fat just horizontally disproportionate.

mottaman420

  • Guest
hmmm
« Reply #3 on: April 30, 2002, 11:40:00 PM »
anyone know of a stirrer that can be just dropped in and is fully self contained??

Or any ideas on how one could make one. It sure would make life a lot easier. Prolly just a stupid idea though.

Since overhead stirring is almost completely out of the question. And the use of glass is the same (don't feel safe making a glass bomb). Is stainless steel impossible to run a magnetic stirrer through?? What metals could one use and still be able to magnetically stir? What is the largest volume that a magnetic stirrer could stir through one of those metals.

Corny kegs come in 3, 5 ,And 10 gal sizes and to me seem like they would work perfect for a hydrogenator. They open up real easily and are very easy to find as well as to pressurize and do all that shit with. 3 gal seems like all the room one would need for most catalytic hydrogenations, so would a 3 gal work with a mag stir assuimng it was like between 1/4 and 1/2 inch thick stainless steel?

Blue Horses + Red Donkeys = Purple Mules

obia

  • Guest
I think there used to be vibrating stirrers that ...
« Reply #4 on: May 01, 2002, 12:08:00 AM »
I think there used to be vibrating stirrers that were totally sealed they were attached to the top of containers and used an internal plunger moved by an external electromagnet. I guess these could be worked onto the holes on a cask/keg. if i can be bothered i'll draw one
a word of warning about using unlined 304 stainless steel kegs, I have seen them suffer from weld failure probly due to hydrogen embrittlement and attack by dissolved chloride ions. even at 60psi there is a lot of force released plus it is kinda difficult to recover catalyst from the ceiling.

hest

  • Guest
Hydrogenation
« Reply #5 on: May 01, 2002, 09:00:00 AM »
mottaman420, Don't think the hydrogenator will solve all your problems. It's grath for turning nitrostyrenes into oximes (who cares) but not so greath for turning them into amines (atleast not for mee) An extreme high cat. load might solve the problem, but then it's to ekspensive to run.


mottaman420

  • Guest
teflon
« Reply #6 on: May 01, 2002, 07:19:00 PM »
what if i coated the inside with 3 or 4 coats of a teflon based paint?

Blue Horses + Red Donkeys = Purple Mules

hest

  • Guest
Won't work
« Reply #7 on: May 01, 2002, 11:30:00 PM »
That is not the problem. The problem is that cat. hydrogenation of nitrostyrens to alkylamines does not work.

josef_k

  • Guest
Won't work??
« Reply #8 on: May 02, 2002, 01:22:00 AM »
So whomever wrote that writeup on rhodiums page is lying?
And the ones who wrote the us patent 3458576 is also lying?

Rhodium

  • Guest
catalytic reduction of nitrostyrenes
« Reply #9 on: May 02, 2002, 02:14:00 AM »
Hest is wrong - catalytic reductions of nitrostyrenes work satisfactorily, but phenylnitropropenes react very sluggishly (which is what he has experience from).

Rhodium

  • Guest
catalytic reduction of nitrostyrenes
« Reply #10 on: May 02, 2002, 02:15:00 AM »
Hest is wrong - catalytic reductions of nitrostyrenes work satisfactorily, but phenylnitropropenes react very sluggishly (which is what he has experience from), unless very high catalyst loads are employed.

hest

  • Guest
Hydrogenation
« Reply #11 on: May 02, 2002, 08:52:00 PM »
Sorry for the short answer.
My personal experience with catalytic hydrogenations of penylnitropropen, phenylnitropropan, trimethoxynitroethen and trimethoxynitroethan was bad, I always ended up with the oxime. I know that the literature says that it is possible, especially with an extreme high catalytic load (usual g to g). If anyone has a personal ekspiriens of success I would love to hear and learn from it.
And yes patents are full of lies.
(Don’t come with 10-15 refs. where they say it works. I have only respect for personal experience
My point is that hydrogenation at 4-6 bar wont substitute LAH

mottaman420

  • Guest
best way
« Reply #12 on: May 03, 2002, 06:47:00 AM »
So the best way to make mescaline from 3,4,5-trimethoxybenzaldehyde is to make it into the nitrostyrene and the use electrosynthesis?
Any other ideas on doing it while using the most easily available chems?
Anyone here actually made mesc? (extracting don't count)

Blue Horses + Red Donkeys = Purple Mules

hest

  • Guest
Mescalin
« Reply #13 on: May 03, 2002, 08:24:00 AM »
Yes, but only with the LAH reduction of the nitroethen and the nitroethan. Next time ill try the mandelonitril

https://www.thevespiary.org/rhodium/Rhodium/chemistry/2cb.mandelonitrile.html

. Also used alot in the chemical litt.

mottaman420

  • Guest
???
« Reply #14 on: May 03, 2002, 11:23:00 AM »
Don't know which question you are answering. I assume it is the "has anybody made it question" and not the "is this the best way question"

Blue Horses + Red Donkeys = Purple Mules

zed

  • Guest
I wouldn't admit to doing it.
« Reply #15 on: May 11, 2002, 02:37:00 AM »
But, I might admit to seeing it. It has been a while, but....in the experiments I observed.....Electro-reductions did not work very well for producing Mescaline....poor yields.

Never tried producing it via H2/Pt, I assumed it was possible, but I must defer to hest. In my experiments, I used H2/Pt to produce P2Ps from Nitro-propenylbenzenes via the oxime. This works well, and it scales well.

The LAlH4 reduction does work fairly well, but it isn't the highest yielding of LAlH4 reductions. This I have seen.

Regarding Hydrogenations:

Shaking, it has it's advantages.

Stirring also has something to be said for it; It is easy, and it can be done with stuff you already have, a filter flask with a balloon on it will work nicely. Further, there are stir bars that are designed to help entrain gases, and since it is a stationary setup, successive charges of reactant can be siphoned through the system, through fixed siphon tubes. Best point might be, that you could experiment with it tomorrow afternoon.

Those stationary systems, that provide agitation via an isolated solenoid, might provide the best of both worlds. Alas, I never had the pleasure of working with one.

But, from what we are hearing, hydrogenation, may not be the best answer for this one.

As for lying on patents and research papers, I concur with hest. They lie.

Now, my question. Has anyone tried to circumvent this nasty reduction problem via using 3,5-Di-iodo(or Di-Bromo) tyrosine as a starting material?

Hest, do you think this is possible? No reductions, Just methoxylation, methylation, and decarboxylation?

psycosmo

  • Guest
A protecting group might be necessary for the ...
« Reply #16 on: May 11, 2002, 05:42:00 AM »
A protecting group might be necessary for the methylation. I dunno how much trouble that is.

hest

  • Guest
tyrosine
« Reply #17 on: May 11, 2002, 11:14:00 AM »
Can' see why it should'nt work, you will end up with the ester after the methoxylation, but who cares. Mice thought. But the Iodation of tyrosine is not posible unless you protect the amine. On the other hand, I'm quite sure that the bromination will work werrye well. Nice thought's

moo

  • Guest
Re: Electro-reductions did not work very well for ...
« Reply #18 on: May 11, 2002, 10:26:00 PM »

Electro-reductions did not work very well for producing Mescaline....poor yields.




Yes, but please tell us more about your apparatus.


psycosmo

  • Guest
Even if bromine doesnt require protection of the ...
« Reply #19 on: May 12, 2002, 01:21:00 AM »
Even if bromine doesnt require protection of the amine, wouldnt the methylation require it so as not to get the n-methyl product?

zed

  • Guest
Patent. 2835700
« Reply #20 on: May 12, 2002, 11:11:00 AM »
The Iodation-Bromination looks possible, via US. Pat. 2,835,700. Coulumn 4, Wherein Tyrosine is Iodated.

I'm concerned most about the methylation step. Wherein the Na/K phenolate, might be reacted with a controlled amount of Methyl Iodide. True, it might like to methylate that amino function if unprotected.

But, would it prefer that amino, over interacting with those delicious Alkalie Metal phenolates, and carboxylates?

What do you think?

zed

  • Guest
Apparatus....Not that simple!
« Reply #21 on: May 12, 2002, 01:55:00 PM »
Aside from poor yields, there were scaling problem; These reductions can require a lot of current. That's not to say a clever Bee, couldn't make a breakthrough.

Master Researcher, Polyethylene Sam, has a topic posted just below this one. It is on electroreductions. Try posts 299552 and 306860. He claims the cited patents contain apparatus construction details.

Good luck...........zed

moo

  • Guest
The Electrolytic Apparatus
« Reply #22 on: May 12, 2002, 10:01:00 PM »

Aside from poor yields, there were scaling problem; These reductions can require a lot of current. That's not to say a clever Bee, couldn't make a breakthrough.




Unless the clever bee manages to raise the cell resistance to such a value that he/she can use lower currents with appropriate voltages to effect the reduction, although having to wait longer. Details on apparatus for reducing nitrostyrenes efficiently has been around since the thirties, in fact the translation of the article is located at

https://www.thevespiary.org/rhodium/Rhodium/chemistry/electromesc.txt

, the illustration has been posted here on the Hive. But please, share some information on your own apparatus, even if it didn't work so well. There is very little information on experiments conducted by bees and the key to success is avoiding the mistakes.


zed

  • Guest
Sorry Moo!
« Reply #23 on: May 13, 2002, 12:12:00 PM »
Sorry Moo, a couple of fellow Bees built the apparatus. I didn't build or design the apparatus myself, I didn't own it, and it was a long time ago.

It was copied from a design reported in literature. It was about the size of a car battery, and contained a series of flat metal plates. I don't remember a lot more about it.

It wasn't working well, there was talk of needing a $1,000 power supply, and It's ~15% yields, were disheartening. As I recall, there was also, gas build up on the electrodes, which interfered with performance....a problem which Sam's patent's, rotating electrode with wiper might help solve.

I was involved with this project for reasons other than genius at electrochemistry. I had other talents.

Anyway, reducing agents were readily available at that time, and there were more rewarding projects awaiting.

Electroreduction would have been nice, but it was a sticky problem.

I'm afraid you need someone who is well versed in this arcane craft, and has successfully practiced electroreduction. Wish I could be more helpful, but I'm not the guy.

I wish you well .........................zed

P.S. We would have been happy to accept longer reaction times. But, longer reaction times did not seem to help yields. We concluded that if we overcame other problems, we would still need a huge power supply, to provide the current density needed. Further, even the literature reported yields, for the ring substituted phenethylamines that we were interested in, were modest.

Were I to take on such a project, I would try to make sure there was some payoff, even if things went poorly.

I used to find a co-operative chemistry/physics professor, create my own independent studies course, use free college equiptment, and reagents, get college credits, and collect every cent of student grant money I could.

I then restricted myself to legal projects, that might have other applications. My projects usually failed, but my grades were good, it didn't cost me much, and the only stress involved was in trying to accomplish the impossible.

It is quite possible, none of this applies to you, but I guess my point is, this might be a pretty demanding project.

PolytheneSam

  • Guest
oxime reduction
« Reply #24 on: May 15, 2002, 12:55:00 AM »
I found this in a book today.  It seems oximes can be reduced catalytically.

http://community.webshots.com/scripts/editPhotos.fcgi?action=showMyPhoto&albumID=28229010&photoID=38035795&security=iPyrNq



http://www.geocities.com/dritte123/PSPF.html
The hardest thing to explain is the obvious

Rhodium

  • Guest
error
« Reply #25 on: May 15, 2002, 08:12:00 PM »
Sam: That link doesn't work for people not logged into webshots.

PolytheneSam

  • Guest
Chemtext3 folder
« Reply #26 on: May 16, 2002, 02:40:00 AM »
OK.  Try going here

http://community.webshots.com/user/pleistocene1

and look at the last picture in the Chemtext3 folder.

http://www.geocities.com/dritte123/PSPF.html
The hardest thing to explain is the obvious

zed

  • Guest
Perhaps?
« Reply #27 on: May 16, 2002, 12:54:00 PM »
Perhaps something is poisoning hest's catalyst. The reduction of Nitro-olefin to Oxime is very easy. The reduction of the Oxime, is less easy.

A Catalyst that quickly reduces the Nitro-olefin, might none-the-less be too compromised, to reduce the Oxime.

While there are few viable reports of reducing Nitro-propenylbenzenes, directly to Amines via PtorPd/H2....There have been many reports of B-Nitro-Styrenes being reduced to Phenyethylamines by this means. Maybe something is wrong.

Of course, it is probably possible, to take the Aldehydes, or Ketones that are easily produced by this reduction, and hydrogenated them with Benzylamine, to produce the Psychedelic N-unsubstituted Amphetamines or Phenethylamines desired. The reduction first produces, the N-Benzylamine, which I believe is cleaved by reduction to toluene, and the desired Amine.

It might avoid hydrides, and produce good yields.

TFSE still doesn't like me, but I'll see if I can find a reference.

zed

  • Guest
Ah, TFSE does work!
« Reply #28 on: May 16, 2002, 02:08:00 PM »
Ah! Zed's Megalomaniacal Euphoria, was causing zed to type his own name in the user Id box. Since this proceedure could only call up items that zed had posted himself, this usually resulted in 0 results. It is much more entertaining when that space is left blank.

hest

  • Guest
Pd/C
« Reply #29 on: May 16, 2002, 06:17:00 PM »
The Pd/C was just fine. several batch's from aldrich was used. They all work in different reductions.
The redution off nitroethens is not that common. A quick beilsten end up with 30-40 hits (200-300for the LAH) And they usual have low yeald (<60%) or a HIGH Pd/C load (g/g)

hest

  • Guest
off topic
« Reply #30 on: May 16, 2002, 07:45:00 PM »
Is there a rehab to the Hive ??

zed

  • Guest
Hest, In a related matter.
« Reply #31 on: May 17, 2002, 11:30:00 AM »
Hest, in a related matter, this Oxime resistance to reduction might actually be useful. A few bees have expressed interest in Indole-3-acetaldehyde as a DMT precurser, but producing this material via Oxidation of Tryptophane is touchy. It might be produced as follows.

The sequence is:

1. Indole.....To Indole-3-Carboxaldehyde.

2. Carboxaldehyde+Nitromethane.....To the Indole Analog of B-Nitrostyrene.

3. Followed by reduction of the Nitro-olefin to Oxime. This should produce the Oxime of Indole-3-Acetaldehyde.

The advantage being that fairly large amounts of this material, might be synthesised in this manner; the reagents, and reactions are well known, and proceed in reasonable yields.

Shulgin provides pertinent reaction information in his #48 alpha-MT synthesis recorded in Tihkal.

You have been battling to reduce the Oxime of a phenylacetaldehyde. Were your craft applied to Indoles, the Oxime of Indoleacetaldehyde would actually be your goal.

When your current battle is over, that hydrogenator, might be used for such an experiment.

Warmest Regards .................................Zed