Journal of the Chemical Society. Perkin Transactions 2 (2001) p. 2537 - 2547 (1996)
Update date:2022-08-10
Topics:
Born, Monique
Ingemann, Steen
Nibbering, Nico M. M.
The gas-phase reactions of mono-halogen substituted carbene radical anions, CHX- (X = F, Cl and Br) and the corresponding carbanions, CH2X- (X = Cl and Br) with halomethanes and organic esters have been examined with the use of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The chlorine and bromine containing (radical) anions react by SN2 substitution with the parent chloro- and bromo-methanes, whereas an SN2 and/or a BAC2 reaction occurs with the methyl ester of trifluoroacetic acid and dimethyl carbonate. The main features of the results are: (i) the SN2 substitution of a given carbene radical anion with CH3C1 or CH3Br is less efficient than this reaction of the corresponding carbanion, (ii) the radical anions react less efficiently with dimethyl carbonate than the carbanions, (iii) the SN2 substitution is less important for the radical anions than for the carbanions in the reactions with the two carbonyl compounds, (iv) for both types of ions, the BAC2 pathway becomes relatively more important as the halogen atom is changed from chlorine to bromine. These findings are discussed in terms of the thermodynamics of the overall processes in combination with considerations of the potential energy surfaces which can describe these gas-phase processes.
View MoreMedicalChem(Yancheng)Manuf.Co.,Ltd.
Contact:+86-515-84383366
Address:Touzeng BinHai, YanCheng City, JiangSu Province, China
Jiangsu Cale New Material Co.ltd
Contact:+86-515-88334667/88203550
Address:Zhongshan 3rd Road, Coastal Chemical Industry Park, Yancheng, Jiangsu, China
shandong zhongke taidou chemical co.,ltd
Contact:86-531-88682301
Address:Jinan shandong Province CHina
Shandong Topscience Biotech Co., Ltd.
Contact:0633-2619278
Address:No. 98 Lanshan West Road, Lanshan District, Rizhao, Shandong Province, P.R. of China
Contact:+86-21-38122007
Address:2, Lane 1123, Kangqiao Road, Pudong New Area, Shanghai
Doi:10.1021/ci100112s
(2010)Doi:10.1016/S0223-5234(02)01377-6
(2002)Doi:10.14233/ajchem.2014.17759
(2014)Doi:10.1016/j.phytochem.2010.05.008
(2010)Doi:10.1039/c9nj04058g
(2019)Doi:10.2165/00019053-200119110-00003
(1910)