HETEROCYCLIC STUDIES .47. REARRANGEMENTS OF 1-ACYL-4-(ACYLOXY)-1,2-DIAZEPINES - FORMATION AND PROPERTIES OF A 1-ACYL-5-(ACYLOXY)-1,3-DIAZEPINE

被引：12

作者：

MOORE, JA ^{[1
]}

YOKELSON, HB ^{[1
]}

FREEMAN, WJ ^{[1
]}

BLOUNT, JF ^{[1
]}

机构：

[1] HOFFMANN LA ROCHE INC,DEPT CHEM RES,NUTLEY,NJ 07110

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1979年 / 44卷 / 15期

关键词：

D O I：

10.1021/jo01329a018

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

1-Acyl-1, 5-dihydrodiazepinones 9 undergo enolization and ring contraction to 3-hydroxy-6-benzamidopyridines 14. The enol 13 was characterized by NMR. The enol esters 11 rearrange thermally to a mixture of (acyl-oxy)pyridines 15 and 1-acyl-1l, 3-diazepines 16. The isomeric enol acetate 12 in the 2, 3-dihydrodiazepinone series rearranges to the 2, 3-disubstituted pyridine 17, indicating parallel and separate pathways for the formation of 2-and 6-aminopyridines from 1, 2-diazepines. The relative rates of rearrangements of ketones and enol esters suggest that the oxygen substituent is a dominant factor in these reactions. The 1, 3-diazepine 16 undergoes facile hydrolytic ring opening to the l, 4-bis(acylamido)butadiene 22, whose structure was established by crystallography. Alkaline hydrolysis of 16 causes ring contraction via the enol to the 6-benzamidopyridine 14. © 1979, American Chemical Society. All rights reserved.

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页码：2683 / 2688

页数：6

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