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Author: Subject: 3-quinuclidinol synthesis?
Douchermann
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[*] posted on 30-1-2006 at 16:23
3-quinuclidinol synthesis?


Would anyone happen to know a synthesis to this material? Or could think of one?
Its formual is C7H13NO and here is its structure
http://williestop.tripod.com/orgysynpages/3quinuclidinol.bmp
you have to copy and paste the link because tripod is gay.



[Edited on 31-1-2006 by Douchermann]

[Edited on 31-1-2006 by Douchermann]

[Edited on 31-1-2006 by Douchermann]




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[*] posted on 1-2-2006 at 04:30


Hmmm why do you want this?
So far as http://dtirp.dtra.mil/products/CWC/129p.htm is concerned 3-quinuclidinol or Quinuclidine-3-ol is a "Scheduled precursor to BZ and Arsenic trichloride".
BZ is the benzilic acid ester of 3-quinuclidinol and is a chemical weapon. But 4-quinuclidinol is used as in legit in pharmacuticals. Also see http://www.fas.org/nuke/control/ag/docs/auslist.htm.
I couldnt find any infor on its synthesis, probably due to this restriction from the risk of chemical weapons development and i dont have any thoughts on how it could be done.

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[*] posted on 1-2-2006 at 05:18


I would be interested in synthesis of 3-quinuclidinol too... simply because of theoretical interest.
I read something about biotechnical synthesis once... don't know where though.
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[*] posted on 1-2-2006 at 07:28


Here is an interesting synthesis of ketone which can easily be turned into alcohol with NaBH4 or simillar.

http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p0989
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[*] posted on 1-2-2006 at 08:29


Interesting synthesis. Nicotinic acid can be produced by oxidation of nicotine with nitric acid. But what about iso-nicotinic acid? I know very little about reactions involving pyridine (yet) but would a Friedel-Crafts alkylation work on pyridine, followed by oxidation of the methyl group to the carboxylic acid? Obviously this should be followed by separation of the isomers which would form.

It's still difficult to accomplish, at least for me. I'm sort of afraid of dealing with pyridine anyways, because of its toxicity and its possible effect on my offspring (if you know what I mean), although I with a very good ventilation this should not be such a problem.




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[*] posted on 1-2-2006 at 08:30


That's it! Thanks, Sandmeyer!
I'm sure that the ketone is the immediate precursor for the alcohol.

The isonicotinic acid would be very easy to get from the pharmacy or a chemical supplier since it is not particularly hazardous.
The reagents don't seem too hard to get... except for the potassium.
Could the potassium perhaps be replaced by sodium? Since the potassium is used to make the ethoxide, I don't see any reason why sodium shouldn't work equally well.

[Edited on 1-2-2006 by garage chemist]
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[*] posted on 1-2-2006 at 08:45


Polarity wise, pyridine would prefer to be Friedel-Crafts alkylated on position 3; oxidizing subsequently yields nicotinic acid. Picolinic and isonicotinic acid I believe are synthesized via different routes.

If not sodium or potassium, how about lithium, given that it's more accessible to some in the form of batteries?

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[*] posted on 1-2-2006 at 09:17


It would be foolish to think that this synthesis could actually be done with OTC materials (in theory it would be possible), as it would be very expensive (think of the price of Lithium batteries!) and would take forever due to the many steps involved.

Go to the pharmacy and order your isonicotinic acid and sodium if you actually want to synthesize 3-quinuclidinol.

The ethyl bromoacetate should better be synthesized (bromination of acetic acid, followed by esterification) instead of bought, since it is very toxic and the pharmacy most likely won't sell it to you.

Potassium is extremely expensive if bought from a chemical supplier, it should be replaced by sodium if possible.
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[*] posted on 1-2-2006 at 09:27


Quote:
Originally posted by sparkgap
Polarity wise, pyridine would prefer to be Friedel-Crafts alkylated on position 3


Sorry but Friedel-Crafts on pyridine is impossible under standard conditions as it is even more electron-deficient than nitrobenzene (often used as solvent in Friedel-Crafts). A direct way to introduce acyl group on a pyridine-like systems can be done by Minisci reaction (i.e nucleophilic radicals/acidic conditions). In case there is interest in practical details on this I can dig them up.
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[*] posted on 2-2-2006 at 05:19


I didn't say it can be done at standard conditions. :) But you're right, Sandy. I was drunk and sleep-deprived yesterday when I posted, but hey, at least I remembered the polarity alternation rule! :D

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[*] posted on 6-2-2006 at 05:48


Quote:
Originally posted by Esplosivo
Interesting synthesis. Nicotinic acid can be produced by oxidation of nicotine with nitric acid. But what about iso-nicotinic acid?


permanganate oxidation of y-picoline, easy as that.
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[*] posted on 5-12-2006 at 07:56


Old topic, but I just found out that quinine, the bitter ingredient in Schweppes, contains the quinuclidine skeleton.
Here is an article about quinine, if you scroll down you can see its structure:

http://dc2.uni-bielefeld.de/dc2/tip/09_00.htm

Making quinuclidine derivatives from this would require oxidative degradation of the quinine molecule.
Schweppes contains less than 80mg/l quinine, which makes it unsuitable as a source (to extract it, basify and extract the freebase with chloroform).

It is still interesting that this molecule has often been right under your nose in walmart.

Some medicaments (muscle relaxants like Limptar) contain quinine sulfate as the active principle. It should be possible to extract those.




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[*] posted on 7-12-2006 at 15:30


Quote:
Originally posted by garage chemist
It would be foolish to think that this synthesis could actually be done with OTC materials (in theory it would be possible), as it would be very expensive (think of the price of Lithium batteries!) and would take forever due to the many steps involved.

Go to the pharmacy and order your isonicotinic acid and sodium if you actually want to synthesize 3-quinuclidinol.

The ethyl bromoacetate should better be synthesized (bromination of acetic acid, followed by esterification) instead of bought, since it is very toxic and the pharmacy most likely won't sell it to you.

Potassium is extremely expensive if bought from a chemical supplier, it should be replaced by sodium if possible.


Clearly, an ethanolic ethoxide soln. do induce the Dieckmann cyclization on the di-ester -- no need to hassle obtaining potassium, it should work with sodium methoxide too, maybe the authors use potassium salt for solubility reasons. Old fart Organikum has posted some interesting stuff from a patent on 100% OTC preparation of potassium (or sodium?) ethoxide if I remember correctly, I think both here and at the Hive (R.I.P)... utfse...

4-picolinic acid is presumably cheap, otherwise it can be made easily by permanganate oxidation of 4-picoline, I have done this reaction on a picoline derivative and esterified in (sort of) one pot -- it is really easy and the yield is high...

Edit: Is someone here trying to make 3-quinuclidinyl benzilate or am I missing something...? :D ;)

[Edited on 8-12-2006 by Sandmeyer]




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[*] posted on 19-12-2006 at 04:59


Some time back, the BBC made a documentry that had a lot of footage of US soldiers on various different battlefield drugs. The guy on PCP was bad, the guys on LSD were just laughing but the guy they SHOWED on that stuff looked very ill. Couldn't stand up, had to have his rifle taken off him, couldn't recognize people or see properly. The program pointed out that this should be considered as a semi-lethal weapon because on a battlefield so many would die in accidents or by suicide. Nice!
Have you tried Datura? Well this is much stronger and longer lasting than that.
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[*] posted on 19-12-2006 at 08:40


This might just be a viable source of quinine OTC.

http://www.sodastream.co.uk/gbretail/productmoreinfo.asp?cat...


[Edited on 19-12-2006 by unionised]
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[*] posted on 22-12-2006 at 23:41


First things first. You will need to make some ethyl bromoacetate, for which there is a reliable Org.Syn. procedure,

Next, get yourself some 4-picoline (4-methylpyridine) and oxidize it with KMnO4 to isonicotinic acid. This is easy but tedious and there is an analogous Org.Syn. procedure for nicotinic acid from 3-picoline q.v.

NOW you have the starting materials for the Org.Syn.prep of 3-quinuclidinone. This compound is NOT a listed chemical under the CWC, it is on the unofficial Australian Group list, which so far means nothing.

You will need a hydrogenation apparatus to reduce the aromatic ring but note that in one of the footnotes the authors say that 100 psig and 90 C will do the trick rapidly and exothermically. This is not much above the very conservative recommended limit for a Parr shaker type apparatus (glass bottle) and well below the tested pressure (150 psig) at which they test their bottles. The Parr gauge reads to 100 psi. My guess is that the H2 uptake will proceed at still lower pressures and temperatures if you want to stick to the Parr manual's 60 psi and 80C.

The Dieckmann condensation step calls for potassium, but will still work with sodium,

The quinuclidine cage ius a beautiful thing (bicyclo2.2.2]octane) and 3-quinuclidinol in and of itself is harmless, unless and until it is esterified with a certain analog of benzilic acid. BZ was a failure as a military agent, it was mass produced and weaponized as a nonlethal incapacitant and then found to be unreliable for military purposes. Now being very expensively destroyed. It is a muscarine antagonist and produces a prolonged terrifying delerium state, night,marish like a super scopalomine. The 3-one by the way is reduced to the racemic 3-ol with LAH quite facilely. Closely related compounds have found numerous applications in pharmacology and experimental medicine. THERE IS NO POTENTIAN FOIR "recreational" USE OF this family of psychoactive compounds. Some years ago an attempt was made to exploit the related 3-hydroxy-N-alkylpiperidine benzilates in this fashion but it was a black market flop, even the damned fools who take phemcyclidine and ketimine for fun found these things to be less than a fun ride.

You might want to check the laws where you are but I think if you stop at the ketone you are in the clear. Let your conscience be your guide (per J.Cricket.)

Another thing, the range between the ED50 and the LD50 for BZ was IIRC a wee bit narrow.
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[*] posted on 22-12-2006 at 23:53


By the way the lead scientist on all this psychopharm was Dr Leo Abood. Much info (but not synthetic) can be found in SOLDIERS AT RISK, National Academy Press and available online free, it's in two volumes and the psychoactives (LSD, PCP and BZ and its many variants) are in Vol 2.

The antidote for BZ intoxication is tetrahydroacridine. Thorazine is NOT advised.
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