서지주요정보
Mechanistic studies on the photoaddition reaction of conjugated polialkynes with olefins = 컨쥬게이트된 폴리알카인과 올레핀과의 광부가 반응에 대한 메카니즘 연구
서명 / 저자 Mechanistic studies on the photoaddition reaction of conjugated polialkynes with olefins = 컨쥬게이트된 폴리알카인과 올레핀과의 광부가 반응에 대한 메카니즘 연구 / Geon-Soo Kim.
발행사항 [대전 : 한국과학기술원, 1997].
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8008134

소장위치/청구기호

학술문화관(문화관) 보존서고

DCH 97016

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초록정보

The photolysis of 3-phenyl-4-phenylethynylcyclobut-3-en-trails-1,2-dicarboxylic acid dimethyl ester (PPCB) in methanol yields 1:1 photoadducts (la-Id, 2a, and 2b) and an acetylene reduction product (3). The major products are 2a and 2b under neutral conditions, whereas la and lb are the major products under acidic conditions and/or in the presence of electron donors, such as 1,4-dimethoxybenzene. The fluorescence of PPCB decreases as the concentration of sulfuric acid is increased. Azulene quenching studies suggest that la-2b are formed from the singlet excited state, while the triplet excited state yields 3. The formation of the photoadducts la-1d can be correlated with the atomic charge of excited PPCB. Photolysis of 1,3-diphenyldiazopropyne (DPP-N2) in methanol and olefins was carried out as model reactions of substituted propargylenes. Major products are OH insertion product (4) in methanol and cyclopropane ring compounds in olefins (5-7). No difference was observed when the reaction is sensitized with benzophenone indicating that the reaction proceeds in the singlet excited state. The energy gap between the higher lying singlet state and the ground triplet state is very small and intersystem crossing between the two states is very fast. No compound containing epoxy ring was detected from the photolysis of DPP-N2 in methyl acrylate, and attempt to trap DPP with acetone is failed. These results show that the singlet state carbene does not react with C=0 double bond but reacts with C=C double bond. To compare the reactivity of methanol and olefins with DPP, DPP-N2 was photolyzed in the mixture of methanol and olefins. The reactivities of methanol and olefins to DPP are in the order of methyl acrylate (MA) acrylonitrile (AN) >> methanol > 2,3-dimethyl-2-butene (DMB) suggesting that the singlet state of DPP has nucleophilic character. Methanol quenching of photoreaction of DPB-DMB yields compound 8. To verify the participation of cyclobutene from the reaction of DPB-DMB, photolysis of cyclobutene compound in methanol was carried out, but compound 8 was not detected. The results show that an exciplex and a carbocation intermediate is involved in the formation of cyclopropane ring in DPB-dimethyl frmarate (DMFu) system and a carbene intermediate is involved in DPB-DMB system.

서지기타정보

서지기타정보
청구기호 {DCH 97016
형태사항 xiii, 81 p. : 삽도 ; 26 cm
언어 영어
일반주기 저자명의 한글표기 : 김건수
지도교수의 영문표기 : Sang-Chul Shim
지도교수의 한글표기 : 심상철
학위논문 학위논문(박사) - 한국과학기술원 : 화학과,
서지주기 Reference : p. 72-76
주제 Photoaddition Reaction
Polialkyne
Olefin
Propargylene
Cyclopropane
광첨가반응
폴리알카인
올레핀
프로파질렌
시클로프로판
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