PEROXYDICARBONATE-MEDIATED OXIDATION OF N-(ORTHO-ARYLOXYPHENYL) AND N-(ORTHO-ARYLAMINOPHENYL)ALDIMINES

被引:28
作者
LEARDINI, R
MCNAB, H
NANNI, D
机构
[1] UNIV BOLOGNA,DIPARTIMENTO CHIM ORGAN A MANGINI,I-40136 BOLOGNA,ITALY
[2] UNIV EDINBURGH,DEPT CHEM,EDINBURGH EH9 3JJ,MIDLOTHIAN,SCOTLAND
关键词
D O I
10.1016/0040-4020(95)00769-5
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Imidoyl radicals 5, obtained from imines 1 by hydrogen abstraction with di-iso-propyl peroxydicarbonate (DPDC), give dibenzoxazepines through 7-membered ring closure. A competitive 6-membered cyclisation leads to intermediate spirocyclohexadienyl radicals that rearrange to aryloxy radicals; this process entails a novel 1,5-aryl radical translocation from an oxygen to a carbon atom and leads to benzophenones,benzoxazoles, and biphenyls. The possibility that the oxazepines arise from rearrangement of the 6-membered-ring-closure intermediates is discussed With imine le, the formation of 5e occurs to a minor extent owing to a side-reaction of the iso-propoxycarbonyloxy radicals, which give rise to an intermolecular aromatic ipso-substitution on the benzenic ring linked to the two oxygen atoms. The 1,5-aryl migration can also be observed with imidoyl radicals generated by radical addition to 2-phenoxyisocyanobenzene. In contrast, the reactions of imines 2 with DPDC do not afford imidoyl radicals, as abstraction of the iminic hydrogen is slower than oxidation of the methyl group: this process entails the formation of carbamoyl radicals, which cyclise onto the carbon-nitrogen double bond, furnishing quinoxalinone derivatives, or loose carbon monoxide to yield benzimidazoles through ring closure of aminyl radicals. A novel cyclisation of a nitrogen-centred radical onto a formamido group could account for the formation of a benzimidazolinone derivative.
引用
收藏
页码:12143 / 12158
页数:16
相关论文
共 58 条
  • [1] CHEMICAL AND ELECTROCHEMICAL REDUCTION OF ORTHO-NITROANILIDES - A COMBINED CHEMICAL, POLAROGRAPHIC AND EPR STUDY
    ALBERTI, A
    CARLONI, P
    GRECI, L
    STIPA, P
    ANDRUZZI, R
    MARROSU, G
    TRAZZA, A
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1991, (07): : 1019 - 1023
  • [2] INTRAMOLECULAR ADDITION OF CARBON-CENTERED TINTHIOIMIDOYL RADICALS TO CARBON CARBON DOUBLE-BONDS - SYNTHESIS OF GAMMA-THIOLACTAMS AND DELTA-THIOLACTAMS
    BACHI, MD
    DENENMARK, D
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1990, 55 (11) : 3442 - 3444
  • [3] CYCLIZATIONS OF ENE RADICALS - IMIDOYL RADICALS AS INTERMEDIATES IN THE SYNTHESIS OF HETEROCYCLIC-COMPOUNDS
    BACHI, MD
    DENENMARK, D
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (05) : 1886 - 1888
  • [4] BANKS RE, 1972, TETRAHEDRON LETT, P3699
  • [5] BECKWITH ALJ, 1988, J AM CHEM SOC, V100, P2565
  • [6] FREE-RADICAL ADDITION OF ALKANETHIOLS TO ALKYNES - REARRANGEMENTS OF THE INTERMEDIATE BETA-THIOVINYL RADICALS
    BENATI, L
    CAPELLA, L
    MONTEVECCHI, PC
    SPAGNOLO, P
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1994, 59 (10) : 2818 - 2823
  • [7] ELECTRON-SPIN RESONANCE STUDY OF RADICAL-ADDITION TO ALKYL ISOCYANIDES
    BLUM, PM
    ROBERTS, BP
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1976, (14) : 535 - 536
  • [8] ELECTRON-SPIN RESONANCE STUDY OF RADICAL-ADDITION TO ALKYL ISOCYANIDES
    BLUM, PM
    ROBERTS, BP
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1978, (12): : 1313 - 1319
  • [9] HETEROCYCLIC DERIVATIVES OF 1-2-5-6-DIBENZOCYCLOHEPTA-1-3-5-TRIENE .1. 2-3-6-7-DIBENZ-1-OXA-4-AZACYCLOHEPTA-2-4-6-TRIENES
    BRODRICK, CI
    DONALDSON, ML
    NICHOLSON, JS
    SHORT, WF
    WIBBERLEY, DG
    [J]. JOURNAL OF THE CHEMICAL SOCIETY, 1953, (APR): : 1079 - 1085
  • [10] DECOMPOSITION OF BENZOYL PEROXIDE IN THIOPHENE
    CAMAGGI, CM
    LEARDINI, R
    TUNDO, A
    TIECCO, M
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1974, (02): : 271 - 274