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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 28, Number 5
JKCSEZ 28(5)
October 20, 1984 

Synthesis of Conjugated Dienals by Palladium-Catalyzed Vinyl Substitution Reaction

팔라듐 촉매화 비닐 치환 반응을 이용한 Conjugated Dienals의 합성
Jong Tae Lee, Jin Il Kim

이종태, 김진일
α,β-불포화 알데히드의 아세탈은 브롬화 방향족화합물들과 팔라듐 촉매와 트리에틸아민 존재하에서 쉽게 반응하여 방향족의 conjugated enals을 생성하였다. 불포화 아세탈로서 acrolein diethyl acetal과 methacrolein diethyl acetal을 사용하여 이들을 메틸기와 이소프로필기로 치환된 브롬화 방향족화합물들과 100℃에서 반응시킨 뒤 생성물들을 옥살산 수용액으로 처리하여 방향족의 conjugated enals를 합성하였다. o-bromotoluene과 methacrolein diethyl acetal과의 반응을 제외하고는 모두 60% 이상의 좋은 수득율을 얻을 수 있었으며 생성물의 구조는 proton NMR과 IR스펙트럼으로 확인하였다. 3-bromopropenal dimethyl acetal 및 (E)-3-bromo-2-methylpropenal diethyl acetal을 할로겐화 비닐화합물의 반응 부위로 하고 1-알켄과 ethyl acrylate등을 올레핀 반응 부위로 하는 반응물들의 역조합(reverse combination)에 의하여 지방족의 2,4-dienals를 50% 이상의 수득율로 합성 할 수 있다.

Acetals of α,β-unsaturated aldehydes reacted readily with aryl bromides in the presence of palladium catalyst and triethylamine to form aryl conjugated enals. Acrolein diethyl acetal and methacrolein diethyl acetal were reacted with phenyl bromides with substituents such as methyl and isopropyl groups at 100℃. The reaction products yields except the reaction of o-bromotoluene with methacrolein diethyl acetal. The products were identified by proton nuclear magnetic resonance and infrared spectroscopy. In the reverse combination of reactants to prepare aliphatic 2,4-dienals in good yield of above 50%, 3-bromopropenal dimethyl acetal and (E)-3-bromo-2-methylpropenal diethyl acetal were used as vinylic halide reactants and 1-alkenes and ethyl acrylate as olefin reactants.

335 - 341
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