The reactions of some ortho-substituted anilines with various α,β-acetylenic ketones. A route to substituted quinolines |
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| Authors: | M S Sinsky R G Bass |
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| Institution: | 1. Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284
Taken from the thesis submitted by M. S. Sinsky in partial fulfillment of the requirements for a Master's degree, Virginia Commonwealth University, Richmond, Virginia. Presented in part at the 60th annual meeting of the Virginia Academy of Science, Blacksburg, Virginia, April 1982. Virginia J. Sci., 33, 131 (1982).;2. Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284 |
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| Abstract: | The reactions of some ortho-substituted anilines with various α,β-acetylenic ketones were investigated as a route to 4-alkyl-, 4-aryl-, 4-hydroxy-, and 4-amino-3-quinolyl ketones. The anilines examined were 2-aminoacetophenone ( 1 ), 2-aminobenzophenone ( 2 ), anthranilonitrile ( 3 ), methyl anthranilate ( 4 ), and ethyl anthranilate ( 5 ). The acetylenic ketones used were 1,4-diphenyl-2-butyne-1,4-dione ( 6 ), 3-butyn-2-one (7), 1,3-diphenyl-2-propyn-1-one ( 8 ), and 4-phenyl-3-butyn-2-one ( 9 ). The acetylenic ketones typically reacted with the anilines to give enamines; however, exceptions were found. Acetylene 6 reacts with 3 to give the enamine ( 13 ) along with a small amount of 2,3-dibenzoyl-4-quinolamine ( 14 ). The reactions of 1 or 2 with 6 give the respective quinoline derivatives directly. Acetylene 8 reacts with 2 to give 3-benzoyl-2,4-diphenylquinoline ( 22 ) directly, whereas no reaction occurs between 8 and 1 or 3 . Acetylene 9 does not react with 1, 2 , or 3 . The enamines exist as the intramolecularly hydrogen bonded isomers and usually undergo cyclization with 5 molar equivalents of methanolic sodium methoxide to give quinoline derivatives. The 4-quinolinols exist predominantly as the 4-quinolinone tautomer. |
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