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 MoreContact:+86-021-6989-5597
Address:No.80 Yichuan Rd., Putuo District,Shanghai,P.R.China
Winchem Industrial Co. Ltd.(expird)
Contact:86-574-83851061 86-574-87083208
Address:Room 905, No.3 Building,East Business Center, 456 Xingning Road, Ningbo City,China
ShangHai BMG Chemical Co., Ltd
Contact:+86-13524845543
Address:Room 602, no 291 sikai road shanghai
Contact:+86-571-86025531 / 86024803
Address:1218-24 Guangyin Mansion,42 Fengqi East Road
Hangzhou Ocean Chemical Co., Ltd.
website:http://www.hzoceanchem.com
Contact:+86-571-88025872, 28272092, 28272096
Address:Room 623 ,Building No 1 , COFCO Radius Commercial Center Xiwen Road, Xiacheng District, Hangzhou, Zhejiang Province, China
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)
