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Author Topic: Oxidation of 9-10-dihydrolysergic Acid  (Read 142 times)

no1uno

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Oxidation of 9-10-dihydrolysergic Acid
« on: December 15, 2009, 04:31:20 AM »
Righto, now the 9-10-dihydrolysergic acid's (and the various amides) are the ones that can be accessed from the Sclerotia of Claviceps Africanus, the ergot that grows wild on sorghum and is a major problem in Australia (and most of the world).


Woodward's total synthesis of Lysergic acid went via the 9-10-dihydrolysergic acid, which was then oxidized to the 'standard' lysergic acid:

Quote
Under these conditions generation of the desired indole system was accomplished, but reduction of the double bond in ring D took place as well.

Subsequent studies obviated these difficulties; in similar experiments in which heat-deactivated Raney nickel was used as dehydrogenation catalyst in the presence of sodium arsenate, dl-lysergic acid (78) was the sole product isolated.
(Taken from the last two paragraphs of page 9 of Hoffman's paper)

That means that the researcher could quite happily and LEGALLY, run around collecting their dihydroergosides/etc, extract them and just do whatever, in the knowledge that the 9-10 dihydro-derivatives are not under the scope in terms of laws, they aren't drugs or analogues thereof, nor are they precursors to drugs.
« Last Edit: December 15, 2009, 04:34:58 AM by no1uno »
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shroomedalice

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Re: Oxidation of 9-10-dihydrolysergic Acid
« Reply #1 on: December 16, 2009, 01:44:51 AM »
very interesting thats a new one to me.

I wonder if you would get away with copperchromate instead of raney nickel.

no1uno

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Re: Oxidation of 9-10-dihydrolysergic Acid
« Reply #2 on: December 16, 2009, 09:22:37 AM »
I'd be more likely to consider Zn/Ni-Urushibara type catalysts - precipitate the finely divided nickel (or use nickel acetate and get finely divided nickel on Al2O3 - digest the alumina with NaOH same as with RaNi). The Arsenate is the biatch, I'm tipping that arsine is going to get given off, so it would have to be done in scuba gear somewhere, then again, playing with LSD25 without it wouldn't be too easy either (imagine what that'd do for your lab technique)...

Although, reading this (Brossi, "The Alkaloids: Chemistry and Pharmacology", Vol.38, pp.120-125), apparently the 'Actual' reagent used was Raney Nickel (heat deactivated by refluxing in xylene) and hydrated sodium arsenate, but after that the others used MnO2...

What the fuck does that mean? I wonder if they mean that 9-10 double bond could be affected by MnO2 in this substrate, or whether that is just a standard approach that doesn't work with Lysergic acids?...

Kinda hard to tell, no?
« Last Edit: December 16, 2009, 09:36:36 AM by no1uno »
"...     "A little learning is a dang'rous thing;
    Drink deep, or taste not the Pierian spring:
    There shallow draughts intoxicate the brain,
    And drinking largely sobers us again.
..."

shroomedalice

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Re: Oxidation of 9-10-dihydrolysergic Acid
« Reply #3 on: December 27, 2009, 04:31:54 PM »
I would say that heat deactivation of nickel would be to change the poors of the metal so as
it will not split H2 into nascant hydrogen. there for stoping it from working as a reducing agent.

simular to poisoning.

what I find interesting is that you can oxidize the "acid" with out fucking up its
stereo configuration.

there would have to be a million and one things that will oxidize acid then.

I think they chose nickel as its common in research labs.

this also means that reducing agent can be used to dehalogenate acid too.
as all you have to do is oxidize it latter to fix any reduction of the double bond.

I like the idea of using palladium on carbon.
this will work for both compounds that are not ergot.

this way you can diversify your starting reagent a little without using to many chems.

realy all your doing is using the ergot as your hydrogen source so I would say there is
a good chance of getting arsine from sodium arsinate.

I would also think it would be possible to use platinum electrodes to do either reaction
dehalogenate or oxidize to alkene.

expensive experiment though.
way out of my price range as a poor ass student at the moment.

realy we need ftir to do these kind of reactions as we need to know what is going on.
I dont think taste testing is realy a wise solution.

maby next year I will be able to afford one :)
« Last Edit: December 27, 2009, 04:46:46 PM by shroomedalice »

JustDreaming

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Re: Oxidation of 9-10-dihydrolysergic Acid
« Reply #4 on: April 14, 2012, 10:52:40 PM »
Hate to see good idea's die out, even if it means bumping an old thread.

The Dehydrogenation of Indolines to Indoles with Manganese Dioxide.
By A. B. A. JANSEN, M. JOHNSON, J. R. SURTEES
1964

References relevent to woodwards article:
RAMEY NICKEL AS AN ORGANIC OXIDATION-REDUCTION CATALYST
E. Kleiderer a n d E. Kornfeld, J . Org. Chem., 13, 455 (1948)

Anyone know german ;D?
Eine neue Sgnthese des 2,6-Dimethyl-l, 5-anthrazolins (Benzo-dipicolins) und hydrierter Derivate
 P. Ruggli and E. Girod, HeIu. Chim. Acta, 27, 1464 (1944)

Also, see: hxxp://books.google.com/books?id=BkDyhc-RrKkC&pg=PA120&lpg=PA120&dq=raney+nickel+dehydrogenation+sodium+arsenate&source=bl&ots=780bcSXFJo&sig=ClRE470IzbgnuJ1NL9fIF2jwKns&hl=en&sa=X&ei=9PqJT46RJMOYOpbvhdIJ&ved=0CBwQ6AEwAA
The Alkaloids: Chemistry and Pharmacology
by Richard Helmuth Fred Manske, Arnold Brossi
Page 120 and on for more information
« Last Edit: April 14, 2012, 10:54:54 PM by JustDreaming »
This never really happens, but an eye still see's these things. It keeps happening. You just don't see it.

JustDreaming

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Re: Oxidation of 9-10-dihydrolysergic Acid
« Reply #5 on: April 15, 2012, 03:06:23 AM »
Sorry to bump again but eye could use some help digging up an article :)

SYNTHESIS OF SUBSTITUTED INDOLES VIA INDOLINES
M. N.Preobrazhenskaya
October 1967
RUSSIAN CHEMICAL REVIEWS
Vol.36 No. 10

Quote
The classical dehydrogenating agent Hg(OCOCH3)2 is
relatively unsuitable for the indoline series, since indole
compounds are mercurated by mercury salts, probably with
formation of 1,3-dimercuri-derivatives 190 .
However, in some cases dehydrogenation has been achieved. The
dehydrogenation of dihydrolysergic acid derivatives(57)
(XXXVm) with Hg(OCOCH3)2 has been described
Quote
57. P.Stadler, A.Frey, and F.Troxler, Angew.Chem., 73_, 738 (1961).

Perhaps they are referring to 2,3 dihydro or some other dihydro derivative, though, there is only one way to find out.

Now I checked for anything by frey, troxler, or stadler, in 1961. however, I could only find an article with stadler in 1962 with A. Hofmann :). And one in 1964 with the three people as well as again A. Hoffman. None of which are in Angew. chemie and all are in Helvetic Chemica Acta, and the reference makes no mention to the beloved Mr Hofmann. Must say, reading through what I can understand of Hofmann and co-workers work is heart warming. To say the very least. I am sure the references in the article I posted below have more hints but I am done digging for the day.

Selektive Reduktions- und Oxydationsreaktionen an lysergsaure-Derivaten. 2,3-Dihydro- und 12-Hydroxy-lysergsaureamide
P.Stadler, A.Frey, and F.Troxler, A. Hofmann
Helvetic Chemica Acta(1964)
This never really happens, but an eye still see's these things. It keeps happening. You just don't see it.
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