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Title: Deamination of 1-amino-4-bromo-7, 7-dimethylbicyclo[2.2.1]heptan-2-ol: A cyclic hydroxamic acid from 1,3-cyclo-hexanedione and β-nitrostyrene 
Author: Ooi, Thean-Chit
Date: 1969
Publisher: [Honolulu]
Abstract: PART I: Deamination of l-amino-4-bromo-7,7-dimethylbicyclo_ [2.2.1]heptan-2-ol (1) with nitrous acid formed 4-bromo-5, 5-dimethylbicyclo[2.1.1]hexane-l-carboxaldehyde (2). The structure of 2 was elucidated with infrared and nmr spectra. The corresponding carboxylic acid, semicarbazone, and p-toluenesulfonylhydrazone derivatives of 2 were prepared. The ring contraction during the deamination of 1 is similar to that of l-amino-3,3-dimethylbicyclo[2.2.1]heptan-2-ol (3), which formed 5,5-dimethylbicyclo[2.1.1]hexane-l-carboxaldehyde (4). Compounds 1 and 3 are different in the configuration of the hydroxyl groups and the substitution feature at C-3. Therefore, the successful deamination of 1 and 3 to the bicyclo[2.1.1]hexane derivatives demonstrates that the deamination of l-aminobicyclo[2.2.1]heptan-2-ols may be of general utility. During the ring contraction, the migrating group is anti-coplanar to the leaving group. PART II: Condensation of β-nitrostyrene with 1,3-cyclohexanedione in the presence of sodium methoxide did not yield a normal Michael addition product. The product was proved, with the support of spectral data, to be N-hydroxy-3-phenyl-4,5,6,7-tetrahydrooxindol-4-one (5). The acetyl derivative of 5, which gave a band in the infrared spectrum that is characteristic of an ester, ruled out the isomeric structure 6 as an alternative structure for 5. Upon hydrolysis, compound 5 could be converted into keto acid Z, from which a known compound, 2-phenyloctanedioic acid, could be obtained through Wolff-Kishner reduction. Hydrogenation of 5 over Raney nickel catalyst produced 3phenyl- 2,3,4,5,6,7-hexahydroindol-4-one (9), which was then dehydrogenated with Raney nickel in hot ethanol to form 3phenyl- 4,5,6,7-tetrahydroindol-4-one (2). Structures 8 and 9 were fully elucidated, and an authentic sample of 9 was synthesized. Stetter and Hoehne proposed oxazine 10 as the structure of the condensation product. This structure is reassigned as 5.
Description: Typescript. Thesis (Ph. D.)--University of Hawaii, 1969. Bibliography: leaves 111-115. ix, 115 l illus
URI: http://hdl.handle.net/10125/11409
Rights: All UHM dissertations and theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission from the copyright owner.
Keywords: Amines, Chemistry, Organic

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