pashov (Stranger)
03-19-03 13:05
No 419150
      DMT from T with urushibara Nickel  Bookmark   

I'm researching the DMT synthesis from Tryptamine. I saw Rhodium confirmed and gave a literature reference to KrZ's higher yielding synthesis. Very nice, I got sorta confused when people started calling it a hoax in another thread.

Now, the use of Urushibara nickel as a substitute for NaCNBH3 has been discussed in another thread. No definite, or semi-definite answer was found for that question, though. So, I want to bring the topic up again - would using U-Nickel instead of NaCNBH3 in KrZ's higher yielding synthesis be possible?
 
 
 
 
    pashov
(Stranger)
03-20-03 08:59
No 419448
      Literature about U-Nickel  Bookmark   

Does somebody know some good literature references about Urushibara Nickel? Google doesn't know too much about it. :) Something describing various known working reactions and uses...
 
 
 
 
    Rhodium
(Chief Bee)
03-20-03 13:37
No 419517
      Try my page, I have long documents of U-Ni...  Bookmark   

Try my page, I have long documents of U-Ni there.
 
 
 
 
    pashov
(Stranger)
03-20-03 13:55
No 419526
      Sure, I did read this one already: ...  Bookmark   

Sure, I did read this one already: ../rhodium/chemistry /urushibara.html
Besides ../rhodium/chemistry /amph.urushibara.html that's the only document dealing with U-Ni I could find on rhodium.ws... Well, what I'd like to see of course is something describing a reaction similar to that of t->dmt being catalyzed with U-Ni, that's mainly why I was asking...

I don't know how easy or how hard it is to get Tryptamine in other places, but the little I might get access to I do not want to waste senselessly. T->DMT with U-Ni would be such a nice thing if it worked! I'd try if I knew I had some positive chances of success, yet I really can't judge that...
 
 
 
 
    Rhodium
(Chief Bee)
03-20-03 14:07
No 419529
      U-Ni  Bookmark   

This is very likely applicable to U-Ni: ../rhodium/chemistry /zn-ni.couple.html

I don't think there has been anything published on something as specific as reductive alkylation of tryptamines with U-Ni.
 
 
 
 
    pashov
(Stranger)
03-21-03 15:59
No 419970
      Hm, ok. So, what would you say, just some wild  Bookmark   

Hm, ok. So, what would you say, just some wild guess...

"Probably works, but low yield...", "Probably doesn't work", "Probably works well", "Impossible to tell"...

Do you think there's a good chance of success, that is, getting to DMT?
 
 
 
 
    Rhodium
(Chief Bee)
03-22-03 11:31
No 420244
      My best guess is that U-Ni is too strong a...  Bookmark   

My best guess is that U-Ni is too strong a reducing agent for this operaton, but that is nothing more than a hunch.
 
 
 
 
    pashov
(Stranger)
03-22-03 14:17
No 420273
      From ../rhodium/chemistry /urushibar...  Bookmark   

From ../rhodium/chemistry /urushibara.html:

"[...]it is worth noting that the more vigorous the reaction between the nickel chloride solution and the zinc dust, the more likely the activity of the catalyst will be promoted; a mild and lengthy reaction which is brought about by the gradual addition of the reagents will reduce the activity."

So, do you think a catalyst with 'reduced activity' would be better suited for this particular task? The above cited passage seems to imply that you can pretty much create a catalyst of arbitrary activity... Will a less active catalyst just mean the reaction will proceed slower, or does  it mean the catalyst is 'softer' on the compound being reduced... If U-Ni is too strong, what will the main product of the reaction be? The corresponding dimethylated indoline? The quaternized product?
 
 
 
 
    Rhodium
(Chief Bee)
03-23-03 11:20
No 420534
      U-Ni DMT?  Bookmark   

If it is really too strong, then you'd get the indoline, and if it is somewhat too strong, then the formaldehyde might be reduced to methanol before it has a chance to add to the tryptamine nitrogen and form the intermediate imines necessary for DMT synthesis.

If you intend to use an untested reducing system like U-Ni, prepare yourself to do quite a few small-scale test runs, and analyze your products with TLC and color test reagents like van Urk etc. Lilienthal has posted a lot on such tests.

Also read this for an introduction to Tryptamine alkylation: Post 419195 (Rhodium: "Why it is hard to reductively alkylate Tryptamine", Newbee Forum)
 
 
 
 
    pashov
(Stranger)
03-24-03 09:23
No 420858
      OK. I guess I'll go with NaCNBH3 as a reducing  Bookmark   

OK. I guess I'll go with NaCNBH3 as a reducing agent first... And later do some fun experimentation with U-Ni. Getting frustared long before seeing any product is always bad :)

One question about the reduction with sodium cyanoborohydride... AFAIK the addition of formaldehyde, yielding the imine R-N=CH2 needs acidic conditions to proceed. Isn't that going to release some HCN when adding NaCNBH3... Cause then that's something I do not really need to tamper with...
 
 
 
 
    Rhodium
(Chief Bee)
03-24-03 14:04
No 420900
      no problem  Bookmark   

The cyanide is tightly bound to the boron, so it will not be released by such mildly acidic conditions.
 
 
 
 
    Potter
(Stranger)
04-07-03 05:53
No 424527
      see the  Bookmark   

Chem. Communs 1970,23 1605-1608
 
 
 
 
    pashov
(Stranger)
04-07-03 09:23
No 424549
      What's "Chem. Communs"?  Bookmark   

What's "Chem. Communs"? I can't manage to find the ISSN. There's a journal called "Chemical Communications" but that was first published 1996. There are some references to "Chem. Communs" though that are a lot older, says google.

What exactly is the publication about anyway?
 
 
 
 
    moo
(Hive Bee)
04-07-03 14:23
No 424591
      Chemical Communications has been published...  Bookmark   

Chemical Communications has been published much longer. Just take a look at the Wanted references thread.
 
 
 
 
    Rhodium
(Chief Bee)
04-08-03 14:17
No 424847
      J Chem Soc Chem Commun 1605 (1970)  Bookmark   

J Chem Soc Chem Commun 1605 (1970) (../rhodium/pdf /spiroindolineproline.pdf)
 
 
 
 
    Lilienthal
(Moderator)
04-08-03 14:56
No 424863
      Great, they don't give the reaction conditions  Bookmark   

Great, they don't give the reaction conditions frown. At least they say it must be anhydrous.
 
 
 
 
    urushibara
(Hive Bee)
04-17-03 06:44
No 427573
      indole-3-acetic acid route?  Bookmark   

I thought I'd post this here since it is relevant...

On rhodium there is a synthesis which looks rather nice:

IAA --[MeOH + H2SO4]--> indolemethylacetate --[Me2NH]--> nn dimethyltryptamide --[LAH]--> nn dimethyltryptamine

reading this again I realised that the second intermediate is an ester... anyway, the point is that other than LAH, this whole reaction scheme is so OTC it is not funny.

Would urushibara nickel work here? Since it would be nice to see the reaction totally involving unsuspicious and uncontrollable chemicals, I'm keen on U-Ni as the catalyst, and preferably with electrogeneration of hydrogen, which probably would be best not generated in situ but piped in and out to a spark free environment.

Another potential reducing mechanism I have thought of is using Al/Hg. This would make the reaction much simpler and involving less fiddly apparatus and preparations of materials. Would that work?

we can't stop here, this is bat country
 
 
 
 
    Noid
(Hive Bee)
07-28-03 21:25
No 450507
      Anyone check it out?  Bookmark   

Another potential reducing mechanism I have thought of is using Al/Hg. This would make the reaction much simpler and involving less fiddly apparatus and preparations of materials. Would that work?

That would be real nice. Anyone know if it's possible?

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