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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 23, Number 1
JKCSEZ 23(1)
February 20, 1979 

Kinetic Studies on the Reaction of Benzyl m-Nitrobenzenesulfonate with N,N-Dimethylanilines

벤질 m-술폰산니트로벤젠과 N,N-디메틸아닐린류와의 반응에 관한 반응속도론적 연구
Soo-Dong Yoh, Mu-Sang Lee

여수동, 이무상
Benzyl m-nitrobenzenesulfonate와 N,N-dimethylaniline류와의 반응속도를 아세톤 용매에서 전기전도도법으로 측정하였다. N,N-디메틸아닐린의 반응성에 관한 치환기효과와 직선 자유에너지 관계를 고찰하였다. 반응속도상수 k는 2.55∼487 × 10-4l·mol-l·sec-1 (35℃)였으며 치환기가 전자를 주는 능력이 클수록 반응은 빨랐다. Hammett 도시에서 치환기상수 σ와 σp-MeO = -0.35의 새로운 값을 사용했을때 ρ = -1.37의 좋은 직선이 얻어졌다. 본반응의 경우 r값은 브롬화벤질에 비해 큰 값을 가졌다. Bronsted 도시에서 용매효과에 기인된 p-MeO기를 제외하고는 좋은 직선이 얻어졌으며 C…O 결합의 쪼개짐이 결합 형성보다 우선적인 Sn2 전이상태를 갖는다고 추정된다.

The kinetics of the reaction of benzyl m-nitrobenzenesulfonate with m-and p-substituted N,N-dimethylanilines in acetone have been investigated by an electric conductivity method. The effects of substituents on the reactivity of N,N-dimethylaniline and the existence of linear free energy relationship were discussed. The rate constants k were in the range 2.55∼487 × 10-4l·mol-l·sec-1 (35℃) and increased with the electron donating ability of substituents. In the present reaction, the Hammett plot was correlated with σ substituent constant, especially using the new a value of 0.35 in p-MeO and it's ρ value was found to be -1.37. r value for the reaction was very large than the value obtained in the reaction of benzyl bromide. Bronsted linear relationship was shown between rate constant and basicites except for p-MeO resulted from solvent effect. From the Bronsted plot, this reaction was suggested that the cleavage of the C…O bond in the SN2 transition state proceed the bond formation.

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