SOLVENT EFFECT ON SOLVOLYTIC REACTIVITIES OF 1-ARYL-2,2-DIMETHYL-1-PROPYL TOSYLATES CONTAINING ORTHO-METHYL GROUPS - INCONSISTENCY BETWEEN THEORETICAL CALCULATIONS AND EXPERIMENTAL RESULTS

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题名:	SOLVENT EFFECT ON SOLVOLYTIC REACTIVITIES OF 1-ARYL-2,2-DIMETHYL-1-PROPYL TOSYLATES CONTAINING ORTHO-METHYL GROUPS - INCONSISTENCY BETWEEN THEORETICAL CALCULATIONS AND EXPERIMENTAL RESULTS
作者:	LIU,KT;TANG,CS;CHIN,CP
贡献者:	中央大學
关键词:	RATES
日期:	1994
上传时间:	2010-06-29 19:49:01 (UTC+8)
出版者:	化學研究所
摘要:	Solvolyses of tosylates IIB and IIC in a variety of solvents were found to give excellent linear log k - Y(BnOTs) plots (R = 0.997 and SD = 0.022) and negative DELTAS(not-equal) for IIB, but slight deviations (R = 0.987 and SD = 0.047) from lineation and positive DELTAS(not-equal) for several cases for IIC. Limiting S(N)1 mechanisms with steric hindrance to resonance and solvent intervention at the cationic transition state could thus be confirmed. The inconsistency between theoretical and observed trend of DELTAH(not-equal) is attributed to the neglect of solvent effect in MO calculations. Deductions linking theoretical calculation and solvolytic experiments should be drawn with caution.
關聯:	JOURNAL OF THE CHINESE CHEMICAL SOCIETY
显示于类别:	[化學研究所] 期刊論文

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