Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Reactions of Trimethyl-and Triphenyl-Metal(Ⅳ) Methoxide with Phenylisocyanate

Trimethyl- 및 Triphenyl-metal(Ⅳ) methoxide와 phenylisocyanate의 반응

  • Ghap-Ju Kim (Department of Chemistry, Catholic Medical College) ;
  • Bae Seok Seo (Department of Chemistry, Catholic Medical College) ;
  • Myung Jae Lee (Department of Chemistry, Catholic Medical College) ;
  • Sung Woo Park (Chemistry Section, The National Institute of Scientific Investigation) ;
  • Il-Kyu Lee (Department of Chemistry, Chung-Ang University)
  • 김갑주 (카톨릭대학 의학부 화학교실) ;
  • 서배석 (카톨릭대학 의학부 화학교실) ;
  • 이명재 (카톨릭대학 의학부 화학교실) ;
  • 박성우 (국립과학수사연구소 화학실) ;
  • 이일규 (중앙대학교 문리대 화학과)
  • Published : 1987.02.20
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Abstract

Trimethyl-and triphenyl-metal (IVA) methoxides were reacted with phenylisocyanate at various temperatures. Even at 100$^{\circ}C$, methyltrimethylsilyl ether, methyltriphenylsilyl ether and triphenyltin methoxide produced the cyclic dimer of phenylisocyanate, N,N'-diphenyluretidine-2,4-dione. But the other compounds produced only the cyclic trimer of phenylisocyanate, phenylisocyanurate. And above 200$^{\circ}C$, considerable amounts of diphenylcarbodiimide was formed by all the organometallic compounds. From these results, the mechanism of cyclic polymerization of phenylisocyanate by the organometal catalysts, and the correlation of substituents with the reactivity were discussed.

Triphenylmetal(IVA) methoxide 또는 triphenylmetal(IVA) methoxide와 phenylisocyanate를 1 : 500mole비로 혼합하여 여러온도에서 반응시켰다. Methyltrimethylsilyl ether, methyltriphenylsilyl ether 및 triphenyltin methoxide는 100$^{\circ}C$에서도 phenylisocyanate의 cyclid dimer(N,N'-diphenyluretidine-2,4-dione)를 생성하였으나, 다른 화합물들은 주로 cyclic trimer(phenylisocyanate)만을 생성하였다. 또한 200$^{\circ}C$이상에서는 모든 화합물들이 상당량의 diphenylcarbodiimide를 생성하였다. 이와 같은 반응결과로부터 phenylisocyanate의 cyclic polymerization의 mechanism과 (p-d)$\pi$ overlap에 대한 금속의 치환기 효과를 고찰하였다.

Keywords

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