Absolute rate constants of alkene addition reactions of a fluorinated radical in water

被引:21
|
作者
Zhang, L
Dolbier, WR [1 ]
Sheeller, B
Ingold, KU
机构
[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
[2] Natl Res Council Canada, Ottawa, ON K1A 0R6, Canada
关键词
D O I
10.1021/ja0256010
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Absolute rate constants of .RfSO(3)(-) radical addition to a series of water-soluble alkenes containing ionic, carboxylate substituents were measured by laser flash photolysis experiments in water. The observed rate constants were all considerably larger than those of structurally similar analogues in a nonpolar organic solvent, with rate factors of 3-9-fold being observed. It is concluded that such rate enhancements derive at least in part from stabilization of the polar transition state for addition of the electrophilic fluorinated radical to alkenes by the polar solvent water.
引用
收藏
页码:6362 / 6366
页数:5
相关论文
共 50 条
  • [41] Prediction of rate constants for reactions of the hydroxyl radical in water at high temperatures and pressures
    Ghandi, K
    Percival, PW
    JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (17): : 3005 - 3008
  • [42] Rate constants for reactions of ethylbenzene with hydroperoxyl radical
    Altarawneh, Mohammednoor Khalil
    Dlugogorski, Bogdan Z.
    Kennedy, Eric M.
    Mackie, John C.
    COMBUSTION AND FLAME, 2013, 160 (01) : 9 - 16
  • [43] Rate constants for anilidyl radical cyclization reactions
    Martinez, E
    Newcomb, M
    JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (02): : 557 - 561
  • [44] RATE CONSTANTS FOR REACTIONS OF PERFLUOROBUTYLPEROXYL RADICAL WITH ALKENES
    NAHOR, GS
    NETA, P
    INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1991, 23 (10) : 941 - 946
  • [45] REACTIVITY IN INTRAMOLECULAR RADICAL REACTIONS - A COMPARISON OF HYDROGEN TRANSFER WITH ALKENE ADDITION
    BERTI, C
    GRIERSON, L
    GRIMES, JAM
    PERKINS, MJ
    TEREM, B
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1990, 29 (06): : 653 - 655
  • [46] ABSOLUTE RATE CONSTANTS FOR REACTIONS OF HYDROGEN ATOMS WITH OLEFINS
    COWFER, JA
    KEIL, DG
    MICHAEL, JV
    YEH, C
    JOURNAL OF PHYSICAL CHEMISTRY, 1971, 75 (10): : 1584 - &
  • [47] Absolute rate constants for reactions of α-carbethoxy and α-cyano radicals
    Newcomb, M.
    Horner, J.H.
    Filipkowski, M.A.
    Ha, C.
    Park, S.-U.
    1600, ACS, Washington, DC, USA (117):
  • [48] Rate constants of intermolecular carbon-hydrogen abstraction reactions by fluorinated radicals in water.
    Dolbier, WR
    Zhang, L
    Shtarev, AB
    Smart, BE
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2000, 219 : U176 - U176
  • [49] RATE CONSTANTS FOR OZONE-ALKENE REACTIONS UNDER ATMOSPHERIC CONDITIONS
    ADENIJI, SA
    KERR, JA
    WILLIAMS, MR
    INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1981, 13 (02) : 209 - 217
  • [50] Absolute rate constants for the addition of malonyl radicals to alkenes in solution
    Weber, M
    Fischer, H
    HELVETICA CHIMICA ACTA, 1998, 81 (04) : 770 - 780