Journal of the American Chemical Society p. 14 - 20 (1993)
Update date:2022-08-11
Topics:
Casamassina, Thomas E.
Huskey, W. Phillip
Primary hydrogen isotope effects are reported for the elimination of 4-nitrophenol from 4-(4-nitrophenoxy)-2-butanone in methanolic methoxide at 20°C and in aqueous hydroxide at 25°C. The isotope effects do not change significantly when the isotopic composition of the solvents is changed: (kH/kD)MeOH = 6.48 ± 0.22, (kHkD)MeOD = 6.40 ± 0.24; and (kH/kD)HOH = 7.54 ± 0.11, (kH/kD)DOD = 7.48 ± 0.21. Kinetic solvent isotope effects (using the undeuterated substrate) are kMeOD/kMeOH = 2.195 ± 0.064 and kDOD/kHOH = 1-526 ± 0.029. The experimental results are compared with model vibrational analysis calculations and about 60 literature examples of related solvent isotope effects on proton-transfer rates. The observations of primary hydrogen isotope effects that are unchanged upon isotopic substitution in protonic sites of the solvent were used to conclude that solvent reorganization is not coupled to proton transfer in the reaction coordinate.
View MoreJiangsu Fengshan Group Co., Ltd.
Contact:86-25-86558671
Address:1903,Central International Mansion 105-6 North Zhongshan Road, Nanjing, China
Contact:+86-21-56338808
Address:799 Dunhuang Road, Putuo
Guangzhou Flower's Song Fine Chemical CO,. Ltd
Contact:+86-20-87475199
Address:No.12, Fenghuang 3 Road, Jiulong Industrial Park, Luogang District, Guangzhou. China
SuZhou Bichal Biological Technology CO.,LTD
Contact:+86-512-68051130
Address:NO.32 huoju road HI-TECH Industrial development zone SuZhou China
Wuhan Soleado Technology Co.,Ltd.
Contact:86-2783341481 18971291927
Address:RM2405 Unit 1 Builing 1, Taiyin Tower, Changqing Road,Wuhan China
Doi:10.1016/j.catcom.2016.02.011
(2016)Doi:10.1016/j.tetlet.2012.10.085
(2013)Doi:10.1039/c9nj04076e
(2019)Doi:10.1016/S0040-4039(01)82106-7
(1981)Doi:10.1124/jpet.105.084426
(2005)Doi:10.1002/hlca.19330160175
(1933)