SYNTHETIC APPLICATIONS OF INTRA-MOLECULAR INSERTION IN ARYLCARBENES .4. ORTHO-ALKOXY-1-PHENYLETHYLIDENES, DIALKYLAMINO-1-PHENYLETHYLIDENES AND ALKYLTHIO-1-PHENYLETHYLIDENES

被引:24
作者
CROW, WD [1 ]
MCNAB, H [1 ]
机构
[1] AUSTRALIAN NATL UNIV,DEPT CHEM,CANBERRA 2600,ACT,AUSTRALIA
关键词
D O I
10.1071/CH9790123
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A series of 1-phenylethylidenes, substituted in the ortho-position by alkoxy, dialkylamino and alkylthio side chains containing up to three carbon atoms, has been generated in the gas phase and pyrolysed at 250-750°/0. 05-0.30 mm. Carbene insertion to form five-membered heterocyclic rings predominates, with up to 20% Bamford-Stevens insertion, to give the styrenes; little or no formation of six-membered rings is observed. In cases where stereoselective insertion is possible, the trans-disubstituted heterocycle is formed preferentially, the selectivity being greatest in the case of dialkylamino substitution. The mechanisms involved are discussed in terms of transition state geometry. © 1979 Australian Journal of Chemistry, All rights reserved.
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页码:123 / 131
页数:9
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