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Subject:
Reduction of Ketones in presence of Amines
Category: Science > Chemistry Asked by: albing-ga List Price: $15.00 |
Posted:
13 Jun 2006 14:44 PDT
Expires: 13 Jul 2006 14:44 PDT Question ID: 737901 |
I would like to reduce a ketone to a secondary alcohol with an unprotected amine function in the molecule. Those should the only functional groups that would limit my choice of reducing agents. Suggestions? Pls suggest approximate conditions also. |
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There is no answer at this time. |
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Subject:
Re: Reduction of Ketones in presence of Amines
From: mhitar-ga on 15 Jun 2006 11:50 PDT |
Amine groups are normally not affected by the reduction agents, do you have any specific reasons to worry? Also, you need to tell more details about your system, if you want a more specific answer than the recipes from an organic chemistry textbook, like "try lithium tetrahydridoaluminate in ethoxyethane" or "sodium borohydride in ethanol". |
Subject:
Re: Reduction of Ketones in presence of Amines
From: eugene123-ga on 16 Jun 2006 16:14 PDT |
Can you tell us what the molecule is? |
Subject:
Re: Reduction of Ketones in presence of Amines
From: albing-ga on 22 Jun 2006 05:55 PDT |
eugene-123: Sorry, structure is confidential. But it is jus alky and aryl stuff. |
Subject:
Re: Reduction of Ketones in presence of Amines
From: albing-ga on 22 Jun 2006 05:58 PDT |
mhitar: Basic organic textbook may work, but I was concerned about the hydride ions abstracting protons from the amine. Maybe that's no problem. Maybe I just add an extra molar equivalent of hydride? Could you cite a reference? |
Subject:
Re: Reduction of Ketones in presence of Amines
From: michalski-ga on 07 Jul 2006 15:47 PDT |
In 30 ml of heated methanol, dissolve 4.9 mmol of aminoketone and 29.4 mmol of cerium chloride heptahydrate. Cool the mixture to -20C and while stirring add 14.7 mmol of sodium borohydride by portions within 20-30 min. After the mixture is stirred for 1h, slowly warm to room temperature, stir for 5 h and boil for 2 h. Distill the solvent off, to the residue add 30 ml of 2 N hydrochloric acid and extract the reaction product into dichloromethane (2x15 ml). Wash the organic solution with 10 ml of 20% aqueous ammonia, dry with sodium sulfate, and distill the solvent off in a vacuum. Subject the residue to chromatography on a column charged with 10 g of silica gel (eluent benzene). This will obtain a mixture containing diastereomeric alcohols. Procedure taken from I. L. Lysenko, A. V. Bekish, and O.G. Kulinkovich. 2001. Stereoelective Conversion of Ethyl Pipecolinate into (+)-a- and (+)-b-Conhydrins. Belorussian State University, Minsk. |
Subject:
Re: Reduction of Ketones in presence of Amines
From: iwannahelp-ga on 07 Jul 2006 18:09 PDT |
For a system with a ketone and an aniline: "LiBEt3H, THF, -78oC" Pilli, R. A.; Russowsky, D.; Dias, L. C.; J Chem Soc, Perkin Trans 1 [JCPRB4] 1990, 1213. "Baker's yeast, Saccharose, H2O/EtOH" Fujisawa, T.; Kishioka, Y.; Hayashi, H.; Chem Lett [CMLTAG] 1987, 129. For a system with a ketone and an amine: "NaBH4, EtOH" Winkler, J. D.; Hershberger, P. M.; J Am Chem Soc [JACSAT] 1989, 111 (13), 4852. Lamant, M.; Guignard, A.; Helv Chim Acta [HCACAV] 1987, 70, 1279. "RhCl(COD), MCCPM, NEt3, MeOH" Takeda, H.; Tachinami, T.; Aburatani, M.; Tetrahedron Lett [TELEAY] 1989, 30 (3), 363. "Pt, EtOH, H2O" Tramontini, M.; Synthesis [SYNTBF] 1982 (8), 605. "1)ZnBr2/MeOH (Zinc bromide and aziridine give a complex which can be crystallized out) then 2)NaBH4/MeOH" Bartnik, R.; Lesniak, S.; Laurent, A.; Tetrahedron Lett [TELEAY] 1981, 22, 4811. "LiAlH(O-tBu)3, THF" TANDON, V. K.; SINGH, K. A.; AWASTHI, A. K.; KHANNA, J. M.; LAL, B.; ANAND, N.; Bioorg Med Chem Lett [BMCLE8] 2004, 14 (11), 2867-2870. "LiBH4, CeCl3, THF" BARTOLI, G.; BARTOLACCI, M.; CORTESE, M.; MARCANTONI, E.; MASSACCESI, M.; PELA, R.; SAMBRI, L.; Eur J Org Chem [EJOCFK] 2004, (11), 2359-2366. "BH3.Py, TiCl4, CH2Cl2" BARTOLI, G.; BARTOLACCI, M.; CORTESE, M.; MARCANTONI, E.; MASSACCESI, M.; PELA, R.; SAMBRI, L.; Eur J Org Chem [EJOCFK] 2004, (11), 2359-2366. "Zn(BH4)2, THF" ORDONEZ, M.; DE LA CRUZ-CORDERO, R.; QUINONES, C.; GONZALEZ-MORALES, A.; Chem Commun (Cambridge) [CHCOFS] 2004, (6), 672-673. |
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