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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 41, Number 2
JKCSEZ 41(2)
April 20, 1997 

 
Title
Nucleophilic Substitution Reactions of Benzoic Anhydrides with Aniline in Methanol-Acetonitrile Mixtures

메탄올-아세토니트릴 혼합용매에서 벤조산 무수물과 아닐린의 친핵성 치환반응
Author
Byung Choon Lee, Young-Kook Shin, Seung Woo Lee, IkChoon Lee, Won Heui Lee

이병운,신영국,이승우,이익춘,이원해
Keywords
Abstract
메탄올-아세토니트릴 혼합용매에서 벤조산 무수물의 아닐린에 의한 친핵성 치환반응을 35.0℃에서 속도론적으로 연구하여 반응 메카니즘을 밝혔다. 벤조산 무수물에있는 두 개의 카르보닐 탄소에서 경쟁적으로 치환반응이 일어나므로 반응 생성물의 비율로부터 각각의 반응속도 kxy와 kxz를 구하였다. Hammett ρi 값과 교차작용상수 ρij를 이용하여 전이상태구조 및 반응메카니즘을 규명하였다. 현저히 큰 ρx, ρxy, ρxz 및 양의 값을 갖는 ρy의 크기로부터, 본 반응이 사각고리 전이상태를 갖는 전면공격 Sn2메카니즘으로 진행됨을 알았다.

Kinetic studies for the nucleophilic substitution reactions of the benzoic anhydrides with anilines in methanol-acetonitrile mixtures at 35.0 ℃ have been carried out in order to elucidate the reaction mechanism. Individual rate constants kXY and kXZ were decided from the ratios of the reaction products for the competitive substitution reaction at either one of the two carbonyl carbons in benzoic anhydride. Transition state structure and reaction mechanism were elucidated by the Hammett ρx, ρy and ρz values and cross interaction constant ρx, ρy and ρz values. The reaction of the benzoic anhydride has been proposed to proceed by a frontside attack SN2 mechanism with four-membered ring transition state from unusually large magnitude of the ρX, ρXY, ρXZ and positive ρY values.

Page
69 - 76
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