Journal of the Chemical Society. Perkin transactions II p. 500 - 508 (1981)
Update date:2022-08-03
Topics:
Aslam, Hanif M.
Burden, Alan G.
Chapman, Norman B.
Shorter, John
Charton, Marvin
The main results now discussed are rate coefficients for the reactions of benzoic acid and 32 ortho-substituted benzoic acids with diazodiphenylmethane (DDM) at 30.0 deg C in 11 alcohols including 2-methoxyethanol.The reaction involves a rate-determining proton transfer.The results have been subjected to correlation analysis in two ways. (a) For the reactions of a given acid in the various alcohols, the log k values are correlated through multiple regression on appropriate solvent parameters. (b) For reactions in a given alcohol, the log k values for the various acids are correlated by using the appropriate form of the extended Hammett equation involving inductive, resonance, and steric parameters.Analyses of type (a), as in earlier work, involve the ?* value of the group R in the alcohol ROH, the Kirkwood function of dielectric constant, f(ε)=(ε-1)/(2ε+1) and nγH, the number of hydrogen atoms in the γ-position in the alcohol.These correlations yield information on the influence of ortho-substituents on the relative importance of specific and non-specific solvent effects.In analyses of type (b) the correlation equations are established with a limited set of substituents (up to 18), whose characteristic parameters ?I, ?R, and υ (determined by Charton) are well established, and are unlikely to show effects due to hydrogenbonding or substituent conformation.The results for other substituents are then interpreted by comparing log k(calc.) from a correlation expression with log k(obs.).
View MoreShanghai Dianyang Industry Co.,ltd
Contact:+86 21 6492 4669
Address:Chejing RD, Songjiang District, Shanghai, China
Suzhou Time-chem Technologies Co., Ltd.
Contact:0512-63983931/68086856
Address:No. 1326 of Binhe Road, New District, Suzhou, Jiangsu, P. R. China
Hunan Haili Chemical Industry Co.,Ltd.
Contact:+86-731-85521860
Address:No.251, 2nd Section, Furong Road, Changsha,Hunan,China
Changzhou LanXu Chemical Co.,ltd.(expird)
Contact:86-0519-86330911,13656129734,15261186386
Address:Room 524, Depart.Chemical, Changzhou Science and Eductaion town, Jiangsu, China;Factory: Haian Fine Chemical Industry Park,Nantong,Jiangsu,China
Contact:86-574-26865651
Address:529 YuanBaoShan Road, Beilun District
Doi:10.1016/S0960-894X(96)00262-4
(1996)Doi:10.1039/cc9960001835
(1996)Doi:10.1016/0040-4020(96)00561-3
(1996)Doi:10.1021/acs.orglett.1c00288
(2021)Doi:10.1016/0957-4166(94)80119-3
(1994)Doi:10.1248/cpb.44.1484
(1996)
