DC Field | Value | Language |
---|---|---|
dc.contributor.advisor | Oh, Dong-Young | - |
dc.contributor.advisor | 오동영 | - |
dc.contributor.author | Lee, Kil-Sung | - |
dc.contributor.author | 이길성 | - |
dc.date.accessioned | 2011-12-13T04:25:42Z | - |
dc.date.available | 2011-12-13T04:25:42Z | - |
dc.date.issued | 1991 | - |
dc.identifier.uri | http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=61611&flag=dissertation | - |
dc.identifier.uri | http://hdl.handle.net/10203/31348 | - |
dc.description | 학위논문(박사) - 한국과학기술원 : 화학과, 1991.2, [ vii, 138 p. ] | - |
dc.description.abstract | A convenient synthetic methods for the preparation of a variety of $\beta$ -keto phosphonate derivatives, enamine phosphonates, and 1,2-epoxyalkane phosphonates were studied. Various $\alpha$ -alkyl or $\alpha$ -hetero atom substituted $\beta$ -keto and enamine phosphonates are obtained by the nucleophilic addition of $\alpha$ -lithioalkane phosphonates to nitriles as an acyl cation equivalent, followed by treatment with electrophiles and hydrolysis or ketimine enamine isomerization. 1,2-Epoxyalkane phosphonates are prepared by the combination of chlorination of diethylalkane phosphonates and intramolecular substitution reaction in the presence of 2eq. HMPT. In this reaction benzenesulfonyl chloride is used as a chlorenium source. It is also studied the reactions to obtain $\alpha$, $\beta$ -unsaturated ketones, deoxybenzoin derivatives,$\beta$ -keto sulfides, and 1,1-dichloro olefins. The preparation of $\alpha$, $\beta$ -unsaturated ketones is carried out through the nucleophilic addition of $\alpha$ -lithiomethane phosphonate to nitriles and subsequent witting-Horner reaction without isolation of $\beta$ -keto phosphonates. The deoxybenzoin and $\beta$ -keto sulfide derivatives are prepared by the nucleophilic addition of $\alpha$ -lithioanion of the phosphonates bearing an electron stabilizing group to aromatic nitriles and subsequent treatment with 5N-NaOH solution, and two possible mechanisms are proposed. A variety of 1,1-dichloro olefins are prepared by combination of the dichlorination and Wittig-Horner condensation starting from diethyl methylphosphonate and benzenesulfonyl chloride in the presence of 3eq. of n-BuLi in THF. The present method is useful both aldehydes and ketones and no reaction occurred with use of LDA as a base. | eng |
dc.language | eng | - |
dc.publisher | 한국과학기술원 | - |
dc.title | Study on the synthetic reactions of β-activated phosphonates | - |
dc.title.alternative | β-활성화된 포스네이트 유도체들의 합성반응에 관한 연구 | - |
dc.type | Thesis(Ph.D) | - |
dc.identifier.CNRN | 61611/325007 | - |
dc.description.department | 한국과학기술원 : 화학과, | - |
dc.identifier.uid | 000865292 | - |
dc.contributor.localauthor | Oh, Dong-Young | - |
dc.contributor.localauthor | 오동영 | - |
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