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Correlation of the Rates of Solvolysis of t-Butyl Fluoroformate Using the Extended Grunwald-Winstein Equation
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  • Correlation of the Rates of Solvolysis of t-Butyl Fluoroformate Using the Extended Grunwald-Winstein Equation
  • Correlation of the Rates of Solvolysis of t-Butyl Fluoroformate Using the Extended Grunwald-Winstein Equation
저자명
Lee. Yong-Woo,Seong. Mi-Hye,Kyong. Jin Burm,Kevill. Dennis N.
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2010년|31권 11호|pp.3366-3370 (5 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

The specific rates of solvolysis of t-butyl fluoroformate (1) have been measured at $40.0^{circ}C$ in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation, with incorporation of the solvent nucleophilicity and the solvent ionizing power, is applied. The actual values are very similar to those obtained in earlier studies of the solvolyses of isopropyl chloroformate and ethyl chlorothioformate in the more ionizing and least nucleophilic solvents, which are believed to proceed by an ionization pathway. The small negative values for the entropies of activation are consistent with the ionization nature of the proposed rate-determining step. These observations are also compared with those previously reported for the corresponding primary and secondary alkyl haloformate esters.