PHOTOCHEMISTRY OF ALPHA-OXO-OXIMES .6. IRRADIATION OF 3-ETHOXYIMINO-1,7,7-TRIMETHYLBICYCLO[2.2.1]HEPTAN-2-ONE

被引：11

作者：

BAAS, P ^{[1
]}

CERFONTAIN, H ^{[1
]}

机构：

[1] UNIV AMSTERDAM,ORGAN CHEM LAB,NL-1018 WS AMSTERDAM,NETHERLANDS

来源：

TETRAHEDRON | 1979年 / 35卷 / 09期

关键词：

D O I：

10.1016/S0040-4020(01)93735-4

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The photolysis of 3-ethoxyimino-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one 1 with λ 254 nm has been investigated in acetonitrile as solvent. Photoexcited 1 undergoes N-O bond homolysis with formation of a cyclic α-oxo-iminyl and an ethoxy radical. Cage recombination of these radicals affords the ethyl cyanocyclopentanecarboxylate 9. The formation of the products 6-8 is explained by decarbonylation of the α-oxo-iminyl radical, followed by disproportionation and H-abstraction. The occurrence of the α-oxo-iminyl radical and (by loss of CO) the tertiary cyanocyclopentyl radical is substantiated by an ESR photoexperiment in the presence of 2-methyl-2-nitrosopropane. © 1979.

引用

页码：1135 / 1137

页数：3

共 20 条

[1]

ANDREWS RS, 1969, THESIS U ALABAMA

[2] PHOTOCHEMISTRY OF ALPHA-OXO-OXIMES .1. PHOTOISOMERIZATION OF BIACETYL MONO-OXIME ETHYL ETHER [J].

BAAS, P ;

CERFONTAIN, H .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1977, (10) :1351-1353

[3]

BAAS P, UNPUBLISHED

[4]

BAAS P, 1977, THESIS U AMSTERDAM, P91

[5]

BAAS VP, UNPUBLISHED

[6] PERESTERS .5. DI-TERT-BUTYLPEROXYOXALATE [J].

BARTLETT, PD ;

BENZING, EP ;

PINCOCK, RE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1960, 82 (07) :1762-1768

[7] ADDITIVITY RULES FOR ESTIMATION OF THERMOCHEMICAL PROPERTIES [J].

BENSON, SW ;

CRUICKSHANK, FR ;

GOLDEN, DM ;

HAUGEN, GR ;

ONEAL, HE ;

RODGERS, AS ;

SHAW, R ;

WALSH, R .

CHEMICAL REVIEWS, 1969, 69 (03) :279-+

[8] PREPARATION AND REACTIONS OF SOME 1-CYANO-STEROIDS [J].

GLEN, AT ;

LAWRIE, W ;

MCLEAN, J .

JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1966, (07) :661-&

[9]

GRELLMANN KH, 1974, TETRAHEDRON LETT, P3707

[10] MECHANISM FOR NOVEL HOMOLYTIC AROMATIC-SUBSTITUTION BY DIPHENYLMETHANIMINYL RADICAL IN PHOTOLYSIS OF BENZOPHENONE O-ACYLOXIMES IN AROMATIC SOLVENTS [J].

ISHIKAWA, SI ;

SAKURAGI, H ;

YOSHIDA, M ;

INAMOTO, N ;

TOKUMARU, K .

CHEMISTRY LETTERS, 1975, (08) :819-822

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