서지주요정보
Activation of superoxide with organophosphorus halide compounds = 유기인 할로겐을 이용한 슈퍼옥사이드의 활성화
서명 / 저자 Activation of superoxide with organophosphorus halide compounds = 유기인 할로겐을 이용한 슈퍼옥사이드의 활성화 / Sang-Chul Lim.
저자명 Lim, Sang-Chul ; 임상철
발행사항 [대전 : 한국과학기술원, 1990].
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등록번호

8000262

소장위치/청구기호

학술문화관(문화관) 보존서고

DAC 9006

SMS전송

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초록정보

Phosphorus oxychloride, phenylphosphonic dichloride, diphenylphosphinic chloride, and other diarylphosphinic chloride were used to develope new peroxyphosphorus inter mediates which showed stronger oxidizing ability than superoxide itself. Various sulfides and sulfoxides were readily oxidized to the corresponding sulfoxides and sulfones respectively by peroxyphosphorus intermediate which is generated $\underline{in}$ $\underline{situ}$ by the treatment of phosphorus oxychloride with potassium superoxide. It was found that phenylphosphonic dichloride reacted with superoxide to form a peroxyphosphorus intermediate to convert the various aryl and alkyl thioamides into the corresponding amides in excellent yields. Various sulfoxides which have a α-hydrogen gave the corresponding sulfones and α-chlorosulfoxides in same system and the ratio of α-chlorination was depended upon by the p-substitutents of sulfoxide in aromatic ring. Oxidation of a series of p-substituted phenyl methyl sulfides was carried out to compare the relative reactivities of oxidation. The relative reactivity order was p-methoxyphenyl- > p-methylphenyl- > phenyl- > pchloro- phenyl methyl sulfide (ρ =-1.14, γ =0.994 against $\sigma_ρ^+$ values). The value shows a strong electrophilicity. Both trans- and cis-stilbene were treated with the peroxyphosphorus intermediate to give only transstilbene oxide (from trans-stilbene ; 28%, from cisstilbene ; 12 %) through the electrophilic radical epoxidation. The spin trapping studies were carried out for the system, $O_2\cdot$+2-nitrobenzenesulfonyl chloride, 2-nitro-benzenesulfinyl chloride, diphenylphospinic chloride, diphenylphosphoryl chloride, 2-nitrobenzoyl chloride. The DMPO spin adducts have the coupling constants, $a_N$ = 12.6-12.8 G and $a_H$ = 10.0-10.3 G in agrement with those of the DMPO spin adducts of alkylperoxy radicals. The spin trapping studies with the use of DMPO have revealed that organic chlorides readily react with $O_2\bar{\cdot}$ to give their peroxy radicals. To develope a new activator of superoxde, various substituted diarylphosphinic chloride were synthesized and examined as activator for the oxidation of sulfide. The reactivity and selectivity on the oxidation of sulfide by 2-nitrophenyl (phenyl)peroxyphosphorus intermediate are poor, but the 4-nitrophenyl(phenyl)phosphinic chloride shows best selectivity among the various diaryl-phosphinic chloride.

서지기타정보

서지기타정보
청구기호 {DAC 9006
형태사항 x, 140 p. : 삽도 ; 26 cm
언어 영어
일반주기 저자명의 한글표기 : 임상철
지도교수의 영문표기 : Yong-Hae Kim
지도교수의 한글표기 : 김용해
학위논문 학위논문(박사) - 한국과학기술원 : 화학과,
서지주기 Reference : p. 125-140
주제 Organophosphorous compounds.
Oxidizing agents.
활성화. --과학기술용어시소러스
산화제. --과학기술용어시소러스
Superoxide.
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