MISC

2002年8月

trans-2,2 '-bi(1-phenyladamantylidene): The most twisted biadamantylidene

JOURNAL OF ORGANIC CHEMISTRY
  • T Okazaki
  • ,
  • K Ogawa
  • ,
  • T Kitagawa
  • ,
  • K Takeuchi

67
17
開始ページ
5981
終了ページ
5986
記述言語
英語
掲載種別
DOI
10.1021/jo020247+
出版者・発行元
AMER CHEMICAL SOC

The Grignard coupling of 2,2-dibromo-1-phenyladamantane gave trans-2,2'-bi(1-phenyladamantylidene) (1-Ph). Single-crystal X-ray analysis indicated that 1-Ph has a 23.2degrees twisted double bond, which is much more distorted than that of parent 2,2'-biadamantylidene (1-H) and that of the ethyl-substituted derivative (1-Et). A cyclic voltammogram showed a reversible electron oxidation wave at 0.87 V vs Fc/Fc(+), which is 0.19 V lower than 1-H, indicating a significant increase in the HOMO energy level due to the distortion. The reaction of 1-Ph with 0.9 equiv of bromine gave an intramolecular Friedel-Crafts alkylation product, while bromination of 1-H and 1-Me has been reported to give a bridged bromonium ion and a rearranged product, 2-(1-methyl-2-adamantylidene)4-bromotricyclo[5,3,1,0(3.9)]undec-4-ene, respectively.

Web of Science ® 被引用回数 : 6

リンク情報
DOI
https://doi.org/10.1021/jo020247+
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000177559800019&DestApp=WOS_CPL

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