기관회원 [로그인]
소속기관에서 받은 아이디, 비밀번호를 입력해 주세요.
개인회원 [로그인]

비회원 구매시 입력하신 핸드폰번호를 입력해 주세요.
본인 인증 후 구매내역을 확인하실 수 있습니다.

회원가입
서지반출
The α-Effect in SNAr Reaction of 1-Fluoro-2,4-dinitrobenzene with Hydrazine: Ground-State Destabilization versus Transition-State Stabilization
[STEP1]서지반출 형식 선택
파일형식
@
서지도구
SNS
기타
[STEP2]서지반출 정보 선택
  • 제목
  • URL
돌아가기
확인
취소
  • The α-Effect in SNAr Reaction of 1-Fluoro-2,4-dinitrobenzene with Hydrazine: Ground-State Destabilization versus Transition-State Stabilization
  • The α-Effect in SNAr Reaction of 1-Fluoro-2,4-dinitrobenzene with Hydrazine: Ground-State Destabilization versus Transition-State Stabilization
저자명
Cho. Hyo-Jin,Um. Ik-Hwan
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2014년|35권 8호|pp.2371-2374 (4 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
PDF텍스트
주제분야
기타
이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
서지반출

기타언어초록

A kinetic study is reported on SNAr reaction of 1-fluoro-2,4-dinitrobenzene with a series of primary amines including hydrazine in $H_2O$ at $25.0^{circ}C$. The plots of $k_{obsd}$ vs. [amine] are linear and pass through the origin, indicating that general-base catalysis by a second amine molecule is absent. The Br${o}$nsted-type plot exhibits an excellent linear correlation with ${eta}_{nuc}$ = 0.46 when hydrazine is excluded from the correlation. The reaction has been suggested to proceed through a stepwise mechanism, in which expulsion of the leaving group occurs after the rate-determining step (RDS). Hydrazine is ca. 10 times more reactive than similarly basic glycylglycine (i.e., the ${alpha}$-effect). A five-membered cyclic intermediate has been suggested for the reaction with hydrazine, in which intramolecular H-bonding interactions would facilitate expulsion of the leaving group. However, the enhanced leaving-group ability is not responsible for the ${alpha}$-effect shown by hydrazine because expulsion of the leaving group occurs after RDS. Destabilization of the ground-state of hydrazine through the electronic repulsion between the nonbonding electron pairs is responsible for the ${alpha}$-effect found in the current $S_NAr$ reaction.