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Author Topic: lysergic acid methyl ester hcl hydrolysis  (Read 309 times)

overunity33

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lysergic acid methyl ester hcl hydrolysis
« on: January 06, 2011, 01:10:36 PM »
So I was looking into methods for converting mixed LSA's into LA.. Standard hydrolysis seems to work well but im interested in this patent: http://www.freepatentsonline.com/4524208.html

It seems pretty easy to make the lysergic acid methyl ester hcl, which also happens to be a good way to store it without needing tartaric acid.  also anytime you precipitate something from a solution as opposed to a liquid phase extraction many impurities get left behind.  The main thing I am interested in is that the iso-LSA gets converted to a usable form so yields are much higher.

Does anyone have any input for hydrolysing the LA methyl ester hcl after this reaction to usable LA?  Does this seem like a viable route?

Naphyrone

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #1 on: January 20, 2011, 06:11:55 PM »
Just noticed this thread, yes it seems like a viable route, without the need to for an extra step of hydrolysis again. I wouldn't use hcl, maybe maleic acid?
My thought is you could a similar procedure as the one to dmt from indolacetic acid.

A La rhodium:
A mixture of 16.0 g of methyl-3-indoleacetate, 100 ml of ethylene glycol and 19.4 of anhydrous dimethylamine was stirred at RT for 40 hrs. The mixture was poured into 100 ml of water and extracted with 5 100ml-portions of ethylacetate:ether (1:1). The extract was washed with a little water, dried and evaporated to give a red oil. This was taken up in warm EtOAc and on chilling, three crops of colorless cryst weighting a total of 12.5 g (70%) were obtained, mp 126-128°C.

I wonder if propylene glycol can be used ???
« Last Edit: January 20, 2011, 06:15:48 PM by Naphyrone »

overunity33

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #2 on: January 21, 2011, 09:53:51 PM »
Yeah it would  be great to be able to proceed from the ester with the hydrolysis but nobody that knows their salt has said anything about this method.  Seems like if it worked well we would hear about it...

jon

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #3 on: January 21, 2011, 10:43:49 PM »
Quote
Just noticed this thread, yes it seems like a viable route, without the need to for an extra step of hydrolysis again. I wouldn't use hcl, maybe maleic acid?
My thought is you could a similar procedure as the one to dmt from indolacetic acid.

A La rhodium:
A mixture of 16.0 g of methyl-3-indoleacetate, 100 ml of ethylene glycol and 19.4 of anhydrous dimethylamine was stirred at RT for 40 hrs. The mixture was poured into 100 ml of water and extracted with 5 100ml-portions of ethylacetate:ether (1:1). The extract was washed with a little water, dried and evaporated to give a red oil. This was taken up in warm EtOAc and on chilling, three crops of colorless cryst weighting a total of 12.5 g (70%) were obtained, mp 126-128°C.

I wonder if propylene glycol can be used

that would be the dimethylamide not N,N dimethylamine it would have to be reduced using LiAlH4 or something similar like borane.
very clever it's a reaction known as aminolysis of esters.
i did'nt know it could be done under subtle conditions like that.
also the czechs are good at lsd chemistry
i found this patent using the 8-pentachlorylphenylester of lysergic acid
it undergoes aminolysis at room temperature too and in good yeild i had problems finding the relavent patents for preparing the ester.
good stuff though see attached.
« Last Edit: January 21, 2011, 10:53:34 PM by jon »

Naphyrone

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #4 on: January 22, 2011, 12:44:10 AM »
Yes jon it forms dimethyltryptamide which as you said needs to be reduced to get dmt. However, if you want the amide in the case of lsd then no reduction is needed.

jon

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #5 on: January 22, 2011, 01:12:04 AM »
right because there is another process where diethylamine and lysergic acid methyl ester is reacted in a bomb to get 60% but if mild conditions like this can be used then yeilds will be higher.
the methyl ester of lysergic acid can be made from ergine via partial hydrolysis of ergotamine and a weak base milder conditions.
but the only hitch is that ergine would have to isolated via chromatography but if your making lsd better get used to chromatography.
the yeild of the methyl ester from ergine is very good almost 100% and the milder conditions of hydrolysis of ergotamine probably minimize loss too.
the other advantage is it gives a higher proportion of the r-epimer close to 80/20 r/s

Naphyrone

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #6 on: January 22, 2011, 03:12:40 AM »
but if you start from ergine via the lsa bioreactor thread, then no need for the ET step, higher yeilds overall.

jon

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #7 on: January 22, 2011, 03:18:57 AM »
no because you always end up with other alkaloids ergovaline for example so some type of hydrolysis is needed unless you chromatograph the ergine which is definitely possible.
but i'll have to lookup hoffmann and stoll's old work hoffman figured out that lower ph of 9 or so less heat and so on yeilded ergine instead of lysergic acid.
i suspect the yeilds are better because the conditions are milder that's a real yeild buster, the hydrolysis step.
it would be fun to expiriment with.

akcom

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #8 on: January 23, 2011, 11:14:09 PM »
Convert all those useless ergot alkaloids to precious (R,R)-LSA. 

Quote
Lysergic acids are readily purified from naturally occurring ergot alkaloids, crude alkaloid mixts., mother liquors, etc., by alk. hydrolysis at high temp. in an inert atm., pptn. by concn. and cooling, and sepn. by column chromatog. on silica gel or Sephadex G-10.  Thus, 28 g waste ergot bases contg. 75.9% alkaloids was hydrolyzed for 1 hr at 98 (inert atm., darkness) in 300 ml 7N KOH contg. 3 g Na2S2O4.  After cooling to 40, the hydrolyzate was reduced to half the starting vol. in vacuo and cooled overnight at 0-5.  The pptd. resinous material was dissolved in 120 ml H2O; the soln. was adjusted to pH 10 with HOAc, placed on a column of Sephadex G-10, and eluted with H2O.  The fluorescent fraction was treated with charcoal, acidified with satd. NaHSO3, and cooled overnight at 0-5 to ppt. d-lysergic acid (I) [82-58-6], [.alpha.]20D = + 34 (c 0.41, pyridine).  With concn. and recrystn. of the mother liquor, a total yield of 81% was obtained. 
Lysergic acids.     Rucman, Rudolf.  Ger. Offen., 2610859, 23 Sep 1976

jon

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #9 on: December 12, 2012, 11:16:14 AM »
here is the ref i was talking about rather the whole enchillada

dream0n

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Re: lysergic acid methyl ester hcl hydrolysis
« Reply #10 on: December 13, 2012, 05:14:20 AM »
Jon Delivers good on old bars, much appreciated.
off to bigger and better things - don't worry I will visit from time to time
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