Synthesis of Some Epiminocyclohexanes by Hydride Reduction of α,β-Unsaturated Cyclohexanone Oximes and the Pyrolytic cis-Elimination of N-Acetylepiminocyclohexanes

1973 ◽  
Vol 51 (3) ◽  
pp. 427-432 ◽  
Author(s):  
J. R. Dimmock ◽  
W. A. Turner ◽  
P. J. Smith ◽  
R. G. Sutherland
Keyword(s):  
Mass Spectrum ◽  
Reaction Mechanism ◽  
Acetic Anhydride ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Fragmentation Pathways ◽  
Hydride Reduction

Reduction of several 2-benzylidenecyclohexanone oximes with lithium aluminum hydride gave the corresponding 1-benzyl-1,2-epiminocyclohexanes. Reduction of 2-benzylidenecyclohexanone oxime with lithium aluminum deuteride gave an epiminocyclohexane (8) which had incorporated two deuterium atoms. A reaction mechanism for the reduction is postulated. The major fragmentation pathways in the mass spectrum of 8 are outlined. Acetylation of 1-benzyl-1,2-epiminocyclohexane with acetic anhydride (15 min reflux) gave 3-acetamido-2-benzyl-1-cyclohexene by a pyrolytic cis elimination.

Free Radical Substitution Reactions of Sulfur Monochloride. A Limited Synthesis of Mercaptans

1973 ◽  
Vol 51 (20) ◽  
pp. 3366-3372 ◽  
Author(s):  
Dennis D. Tanner ◽  
Brian G. Brownlee
Keyword(s):  
Free Radical ◽  
Lithium Aluminum Hydride ◽  
Elemental Sulfur ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Substitution Reactions ◽  
Sulfur Monochloride ◽  
Hydride Reduction ◽  
Abstraction Reaction ◽  
Radical Substitution

The photolysis of sulfur monochloride with a series of saturated aliphatic hydrocarbons yielded alkyl chlorides, di- and polysulfides, hydrogen chloride, and elemental sulfur. The free radical substitution reactions leading to the production of alkyl chloride and the di- and polysulfides were shown to proceed via a chlorine atom abstraction reaction. The major products, the di- and polysulfides could be transformed quantitatively, by lithium aluminum hydride reduction into their corresponding mercaptans. The reaction describes a simple free radical route to the synthesis of a variety of alkyl mercaptans.

Preparation and Spectral Analysis of 3,3',4,4'-Tetrachloroazobenzene and the Corresponding Azoxy and Hydrazo Analogs

1979 ◽  
Vol 62 (4) ◽  
pp. 746-750
Author(s):  
M T Stephen Hsia ◽  
Charles F Burant
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Chromatographic Method ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Reverse Phase ◽  
High Pressure Liquid Chromatographic ◽  
Hydride Reduction ◽  
Liquid Chromatographic Method ◽  
Liquid Chromatographic

Abstract An efficient preparation was developed for 3,3',4,4'-tetrachloroazobenzene and the corresponding azoxy and hydrazo derivatives, based on the lithium aluminum hydride reduction of 3,4-dichIoronitrobenzene. Batches were analyzed for purity by using a reverse phase high pressure liquid chromatographic method. All 3 compounds can be synthesized in gram quantities with 97–99% purity. Detailed mass, infrared, and nuclear magnetic resonance spectral analyses are presented.

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