Doesn't that produce a lot of dibenzylketone that isn't easily removed with a single simple distillation? Or am I thinking of another reaction like decarboxylative arylation?
Use a really, really big vacuum jacketed and silvered fractionating column? Maybe steam distill, the partial pressure of p2p might be a lot higher than dbk at boiling water temp?
I tended to save station's posts even before they made it to the chief's archive. Found some cool references and had a unique style. Other's here I also miss.
the Hive BB
General Discussion
Resolution references
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Author Topic: Resolution references
station posted 08-12-99 04:51 PM
Junior
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This manuscript is being offered for its informational and educational value only, and it is intended and expected that the information will be used solely by legitimate researchers and forensic chemists investigating these compounds. No synthesis of these substances, the manufacture of which is illegal without governmental license, should be undertaken without approval from the appropriate governmental authorities. The authors do not want to assist, counsel, urge, otherwise encourage or cause a criminal act, particularly in view of the fact that manufacture of amphetamine(s) and methamphetamine(s) is punishable by sentences up to life in prison.
RESOLUTION OF AMPHETAMINE AND METHAMPHETAMINE
The dextro isomer of amphetamine and methamphetamine is the d, (+), D or S isomer; the levo isomer is the l, (-), L or R isomer. The racemic mixtures may be referred to as d,l or (+,-) or DL or (R)(S).
Classical resolution techniques are often tedious and usually afford poor yields. The best published procedure seems to be that of Rusznak et al. below which utilizes a selective extraction rather than the usual crystallization.
Selective Extraction of d-Methamphetamine with d-Tartaric Acid:
Rusznak et al., Resolution of Phenylisopropylamines, Hung. Teljes, 12,208 (Cl. C07B), 28 Sep. 1976, Appl. 1,516, 08 Nov. 1974; C.A. 85: 192337q, p. 518 (1976).
Phenylisopropylamines and phenylisopropylmethylamines and various substituted amines were resolved with 0.5 mole tartaric acid in benzene- water containing 0.5 mole sodium hydroxide or potassium hydroxide by selective extraction of either enantiomer.
A mixture of 0.1 mole (13.52 g.) phenylisopropylamine (or 14.92 g. methamphetamine base) in 60 ml benzene, 0.05 mole d-tartaric acid (7.50 g.) in 30 ml water, and 2 g sodium hydroxide (reagent grade or titrated equivalent) in 3 ml water was kept 4 hours with intermittent shaking, and the organic phase evaporated to give 98% L-phenylisopropylamine. The aqueous phase was extracted with benzene at pH 13 and evaporated to give 96% D-enantiomer.
Selective Crystallization of Methamphetamine with d-Tartaric Acid:
Rusznak et al., Resolution of 1-Phenylisopropyl methyl amine, Hung. Teljes, 12,210 (Cl. C07B), 28 Sep. 1976, Appl. 1,520, 04 Dec. 1974; C.A. 85: 192335n, p. 518 (1976).
Phenylisopropylmethylamine was resolved by treatment with 0.4-6 moles of dextro tartaric acid in water or aqueous ethanol containing 0.4-6 moles hydrogen chloride. A mixture of phenylisopropylmethylamine 150, d-tartaric acid 82.5, and H2O 330 g was treated with HCl to pH 4 to deposit 120 g L- phenylisopropylmethylamine-d-tartrate salt, which gave 88 g L- phenylisopropylmethylamine. The D-enantiomer (58 g as the HCl salt) was isolated from the filtrate.
Osmium posted 08-13-99 05:05 AM
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I like that extraction. Didn't know it was that easy!
cicada posted 08-13-99 06:13 AM
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Interesting. What's the mechanism here? The solution is roughly neutral (.5 moles each of the acid and base. But (I'm guessing here) the d-amine preferentially combines with the d-acid and thus stays in solution leaving the remaining l-amine to seperate. Is that your take?
What a handy tool.
LaBTop posted 08-14-99 03:26 PM
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Thank god, at last a good reference researcher AND one who posts the contents, readable, instead of just the ref !!!!
My eternal thanks for doing this.
You are now on my Christmas list, and I believe now that it's you! who composed the refs in the 2 other posts on reductive amination/alkylation. HAT OFF ! LT/
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Use a really, really big vacuum jacketed and silvered fractionating column? Maybe steam distill, the partial pressure of p2p might be a lot higher than dbk at boiling water temp?
I tended to save station's posts even before they made it to the chief's archive. Found some cool references and had a unique style. Other's here I also miss.
the Hive BB
General Discussion
Resolution references
[Post New Topic] [Post A Reply]
profile | register | preferences | faq | search
next newest topic | next oldest topic
Author Topic: Resolution references
station posted 08-12-99 04:51 PM
Junior
Member [Click Here to See the Profile for station]
----------------------------------------------------------
This manuscript is being offered for its informational and educational value only, and it is intended and expected that the information will be used solely by legitimate researchers and forensic chemists investigating these compounds. No synthesis of these substances, the manufacture of which is illegal without governmental license, should be undertaken without approval from the appropriate governmental authorities. The authors do not want to assist, counsel, urge, otherwise encourage or cause a criminal act, particularly in view of the fact that manufacture of amphetamine(s) and methamphetamine(s) is punishable by sentences up to life in prison.
RESOLUTION OF AMPHETAMINE AND METHAMPHETAMINE
The dextro isomer of amphetamine and methamphetamine is the d, (+), D or S isomer; the levo isomer is the l, (-), L or R isomer. The racemic mixtures may be referred to as d,l or (+,-) or DL or (R)(S).
Classical resolution techniques are often tedious and usually afford poor yields. The best published procedure seems to be that of Rusznak et al. below which utilizes a selective extraction rather than the usual crystallization.
Selective Extraction of d-Methamphetamine with d-Tartaric Acid:
Rusznak et al., Resolution of Phenylisopropylamines, Hung. Teljes, 12,208 (Cl. C07B), 28 Sep. 1976, Appl. 1,516, 08 Nov. 1974; C.A. 85: 192337q, p. 518 (1976).
Phenylisopropylamines and phenylisopropylmethylamines and various substituted amines were resolved with 0.5 mole tartaric acid in benzene- water containing 0.5 mole sodium hydroxide or potassium hydroxide by selective extraction of either enantiomer.
A mixture of 0.1 mole (13.52 g.) phenylisopropylamine (or 14.92 g. methamphetamine base) in 60 ml benzene, 0.05 mole d-tartaric acid (7.50 g.) in 30 ml water, and 2 g sodium hydroxide (reagent grade or titrated equivalent) in 3 ml water was kept 4 hours with intermittent shaking, and the organic phase evaporated to give 98% L-phenylisopropylamine. The aqueous phase was extracted with benzene at pH 13 and evaporated to give 96% D-enantiomer.
Selective Crystallization of Methamphetamine with d-Tartaric Acid:
Rusznak et al., Resolution of 1-Phenylisopropyl methyl amine, Hung. Teljes, 12,210 (Cl. C07B), 28 Sep. 1976, Appl. 1,520, 04 Dec. 1974; C.A. 85: 192335n, p. 518 (1976).
Phenylisopropylmethylamine was resolved by treatment with 0.4-6 moles of dextro tartaric acid in water or aqueous ethanol containing 0.4-6 moles hydrogen chloride. A mixture of phenylisopropylmethylamine 150, d-tartaric acid 82.5, and H2O 330 g was treated with HCl to pH 4 to deposit 120 g L- phenylisopropylmethylamine-d-tartrate salt, which gave 88 g L- phenylisopropylmethylamine. The D-enantiomer (58 g as the HCl salt) was isolated from the filtrate.
Osmium posted 08-13-99 05:05 AM
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[Click Here to See the Profile for Osmium]
----------------------------------------------------------
I like that extraction. Didn't know it was that easy!
cicada posted 08-13-99 06:13 AM
Member
[Click Here to See the Profile for cicada]
----------------------------------------------------------
Interesting. What's the mechanism here? The solution is roughly neutral (.5 moles each of the acid and base. But (I'm guessing here) the d-amine preferentially combines with the d-acid and thus stays in solution leaving the remaining l-amine to seperate. Is that your take?
What a handy tool.
LaBTop posted 08-14-99 03:26 PM
Member
[Click Here to See the Profile for LaBTop]
----------------------------------------------------------
Thank god, at last a good reference researcher AND one who posts the contents, readable, instead of just the ref !!!!
My eternal thanks for doing this.
You are now on my Christmas list, and I believe now that it's you! who composed the refs in the 2 other posts on reductive amination/alkylation. HAT OFF ! LT/
------------------
EMOTIONSwill always beFREE!
All times are CT (US) next newest topic | next oldest topic
Administrative Options: Close Topic | Archive/Move | Delete Topic
[Post New Topic] [Post A Reply]
Hop to:
Contact Us | the Hive
Powered by: Ultimate Bulletin Board, Version 5.39a
(c) Infopop Corporation (formerly Madrona Park, Inc.), 1998 - 1999.