Thermal rearrangements of 7,7-dihalo-trans-bicyclo[4.1.0]hept-3-enes.

被引:7
作者
Gassman, PG
Han, SD
Chyall, LJ
机构
[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA
[2] Univ Chicago, Dept Chem, Chicago, IL 60637 USA
关键词
D O I
10.1016/S0040-4039(98)01110-1
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Derivatives of trans-bicyclo[4.1.0]hept-3-ene with chlorine and bromine substituents the 7 position were synthesized and their thermal rearrangements were examined. Thermolysis of the dichloride leads to the formation of the cis-fused isomer, while heating the dibromide results in ring-expanded products. Thermal rearrangement of the bromochloro derivative provided a mixture of ring-isomerized and ring-expanded products. The halogenated compounds are very labile relative to the unsubstituted molecule with rate accelerations on the order of 1000 or more at 120 degrees C. When solvents of widely varying polarity were employed, the isomerization rate coefficients for the halogenated derivatives vary by a factor of 1.0-3.2. Therefore, it is unlikely that these compounds rearrange via ionic intermediates. (C) 1998 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:5459 / 5462
页数:4
相关论文
共 14 条
[1]  
CHYALL LJ, 1991, THESIS U MINNESOTA
[2]  
DESELMS RC, 1963, J ORG CHEM, V28, P2206
[3]   THE ELECTRONIC-STRUCTURES OF TRANS-BICYCLO[4.1.0]HEPT-3-ENE AND CIS-BICYCLO[4.1.0]HEPT-3-ENE - EVIDENCE FOR A TWIST, BENT SIGMA-BOND [J].
DIXON, DA ;
GASSMAN, PG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (07) :2309-2310
[4]  
FRIEDRICH EC, 1987, CHEM CYCLOPROPYL G 1, pCH11
[5]   MOLECULES WITH TWIST BENT BONDS - THE SYNTHESIS, PROPERTIES, AND REACTIONS OF TRANS-BICYCLO[4.1.0]HEPT-3-ENE AND CERTAIN METHYLATED DERIVATIVES [J].
GASSMAN, PG ;
BONSER, SM ;
MLINARICMAJERSKI, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (07) :2652-2662
[6]   MOLECULES WITH TWIST BENT BONDS - A COMPARISON OF THE THERMAL AND TRANSITION-METAL-COMPLEX PROMOTED REARRANGEMENTS OF DERIVATIVES OF TRANS-BICYCLO[4.1.0]HEPT-3-ENE [J].
GASSMAN, PG ;
MLINARICMAJERSKI, K .
TETRAHEDRON LETTERS, 1988, 29 (38) :4803-4806
[7]   SYNTHESIS AND THERMAL-ISOMERIZATION OF TRANS-BICYCLO[4.1.0]HEPT-3-ENE [J].
GASSMAN, PG ;
BONSER, SM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (03) :667-669
[8]  
GASSMAN PG, 1967, J CHEM SOC CHEM COMM, P793
[9]  
HAN S, 1997, THESIS U MINNESOTA
[10]   RING-CLOSURE REACTIONS .13. CONVENIENT SYNTHESIS OF MANY-MEMBERED THIACYCLOALKANES [J].
MANDOLINI, L ;
VONTOR, T .
SYNTHETIC COMMUNICATIONS, 1979, 9 (09) :857-861