Journal of the Chemical Society. Perkin transactions II p. 983 - 990 (1985)
Update date:2022-08-29
Topics:
Bentley, T. William
Carter, Gillian E.
Harris, H. Carl
The further development of a convenient, conductimetric method for studying the rates of relatively fast solvolytic reactions in highly aqueous media is described.Rate and product data are reported for solvolyses of benzoyl chloride at 25 deg C in water and in binary aqueous mixtures with acetone, ethanol, methanol, trifluoroethanol, and hexafluoropropan-2-ol.Comparison of these kinetic data with rate data for the SN1 model, 1-adamantyl chloride, reveals sensitivity to solvent nucleophilicity even for highly aqueous media.In constrast with other nucleophilically solvent-assisted processes, the solvent effects are not satisfactorily correlated by one linear free energy relationship.Gas-phase thermochemical data show the feasibility of a direct heterolytic cleavage of the C-Cl bond in benzoyl chloride.Rate-product correlations for hydrolysis and aminolysis in 50percent w/w acetone-water are observed, providing that allowance is made for the medium effect of the added o-nitroaniline.These results are consistent with an SN2 mechanism, not SN1 and/or ion-pair mechanisms previously discussed.Another pathway, dominant in less aqueous media, is much less sensitive to changes in solvent ionizing power, consistent with earlier proposals for a carbonyl addition-elimination mechanism.
View MoreShanghai shibo Chemical Co., Ltd
Contact:+86-021-60753516
Address:688 Qiushi Road, Jinshan High-tech Park, Shanghai, China,201512
Contact:410-273-7300; 800-221-3953
Address:4609 Richlynn Dr., PO Box 369, Belcamp, MD, 21017-0369, USA
PharmaResources(Kaiyuan)CO,.Ltd
Contact:+86-21-50720028
Address:No.3, Beihuan Road, Economic Development District, Kaiyuan City, Tieling City, Liaoning Province, China 112300
Contact:+86-531-58668191 58668193 58668196 58661173
Address:No 55,Beixiaoxinzhuang West Street,Jinan City, Shandong Province
Jinzhou Jiutai Pharmaceutical Co.,Ltd
Contact:+86-0416-5179890
Address:No.41, Taianli, Taihe District, Jinzhou, Liaoning
Doi:10.1055/s-1986-31839
(1986)Doi:10.1002/anie.201900995
(2019)Doi:10.1007/BF02252292
(1998)Doi:10.1016/j.cclet.2017.07.016
(2017)Doi:10.1021/jacs.5b13458
(2016)Doi:10.1039/c5ta00606f
(2015)
