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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 27, Number 2
JKCSEZ 27(2)
April 20, 1983 

The Synthesis of Carbamoylsulfenyl Chloride and its Derivatives

염화카바모일술페닐과 그 유도체의 합성
Surk Sik Moon, Dong Young Oh

문석식, 오동영
N-Methylidene-2,6-diethylaniline (Ⅲ)은 2,6-diethylaniline (Ⅱ)과 과량의 paraformaldehyde와의 반응으로 만들었으며, 이 화합물 Ⅲ에서 N=CH2 프로톤은 AB 스핀계를 나타냈다. 화합물 Ⅲ과 chlorocarbonylsulfenyl chloride(Ⅳ)를 반응시켜서 N-(chloromethyl)-N-(2,6-diethylphenyl)-carbamoylsulfenyl chloride(Ⅴ)를 합성하였다. 화합물 Ⅴ와 여러 종류의 알콜을 반응시켜서 Alkyl N-(chloromethyl)-N-(2,6-diethylphenyl)-carbamoylsulfenate esters(Ⅵ∼ⅩⅥ)를 71~95%의 수득률로 합성하였다. Ⅵ∼ⅩⅥ은 서서히 분해되지만 S-O 결합이 S=O결합으로 변하지는 않았다. 과량의 알콜은 V의 2가 황과 N-chloromethyl기의 α-탄소에 대해 친핵성 공격을 할 수 있었으며, 이렇게 하여 생긴 화합물 (ⅩⅦ, ⅩⅧ)은 상당한 안정성을 가지고 있었다.

N-Methylidene-2,6-diethylaniline (Ⅲ) was prepared by the reaction of 2,6-diethylaniline (Ⅱ) with an excess paraformaldehyde. The protons of N=CH2 in the compound Ⅲ exhibited a second order NMR spectrum. The compound Ⅲ reacted with bifunctional chlorocarbonylsulfenyl chloride(Ⅳ) to give N-(chloromethyl)-N-(2,6-diethylphenyl)-carbamoylsulfenyl chloride(Ⅴ). The reaction of the compound V with various alcohols resulted in the formation of Alkyl N-(chloromethyl)-N-(2,6-diethylphenyl)-carbamoylsulfenate esters(Ⅵ∼ⅩⅥ) in 71~95% yields. The compound Ⅵ∼ⅩⅥ decomposed gradually, but the thermal rearrangement of S-O bonding to S=O bonding was not found. The nucleophilic attack of an excess alcohol to the compound Ⅴ was made on both divalent sulfur and α-carbon of N-chloromethyl group. The corresponding substituted products(ⅩⅦ, ⅩⅧ) had considerable stability.

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