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Pd / C 촉매에 의한 디페닐유도체의 합성반응
Synthesis of Diphenylamine Derivatives on Pd / C Catalyst
김병삼 , 정동근 , 김기석 ( Byong Sam Kim , Dong Geun Jung , Kiseok Kim )
응용화학 1권 1호 87-90(4pages)
UCI I410-ECN-0102-2009-570-007340697
이 자료는 4페이지 이하의 자료입니다.

2-methyl-3`-hydroxy-1, 1`-diphenylamine was synthesized from the mixture consisting of 3-aminophenol, 3-nitrophenol, and 2-methyl cyclohexanone via vapor phase reaction on 5% Pd/C catalyst. Reaction was allowed to proceed at 203℃ for 5 to 10 hrs in an autoclave-type high pressure reactor. The optimal composition of the reaction mixture was 1 : 2 : 48 in the molar ratio of 3-aminophenol : 3-nitrophenol : 2-methyl cyclohexanone, and the highest yield of diphenylamine derivative was ca. 90% after 6 hrs of reaction time, based on the moles of aminophenol plus nitrophenol introduced. The rate-determining step of overall reaction was lydrogen-abstraction of the intermediate, N-cyclohexylideneaniline species, which was readily formed via condensation of aminophenol and excess cyclohexanone derivative. The hydrogen abstracted was transferred to nitrophenol, which was easily converted to aminophenol via reduction, thus replenishing the aromatic amine reactant for formation of the intermediate. The mechanism of overall reaction was in essence identical to that previously observed in formation of 2-methyl-4-methoxy diphenylamine, a raw-material of fluoran heat-sensitive dye.

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