Abstract
The quality of predictions of reactivity coming from alternative theoretical approaches as related to the experimental values is examined for the hydrolysis of phenyl N-methylcarbamates. We have combined literature kinetic data for phenyl N-phenylcarbamates with our own kinetic data and have correlated them all with theoretically estimated reactivity indices: i.e. Hirshfeld and NBO atomic charges, the Parr electrophilicity index (Ω), and the electrostatic potential at the carbon and oxygen atoms of the reaction centre (VC, VO). The results show that the best correlation coefficients are obtained with the electrostatic potentials VO and VC and the electrophilicity index Ω. The variations of electronic structure in the phenolate ions (leaving groups) were also analysed. The results obtained illustrate the accuracy of theoretical description of local properties as provided by the electrostatic potential at the nuclei.
References
1.
Wolfe N.L.
,
Zeep R.G.
, and
Paris D.F.
(1987 ) Water Res. , 12 , 565 .
2.
Corbett J.R.
,
Wright K.
,
Baillic A.C.
(1984 ) The biochemical mode of action of pesticides. Academic Press , New York .
3.
Latrous L.
,
Ben Hamida N.
, and
Sabbah S.
(2001 ) J. Soc. Chim. Tun. , 4 , 977 .
4.
Ben Hamida N.
,
Latrous L.
, and
Sabbah S.
(2001 ) J. Soc. Chim. Tun. , 4 , 1185 .
5.
Ben Hamida N.
,
Samaali M.
, and
Sabbah S.
(2005 ) J. Soc. Chim. Tun. , 7 , 143 .
6.
Boujelbane F.
, and
Ben Hamida N.
(2007 ) J. Soc. Chim. Tun. , 9 , 121 .
7.
Boujelbane F.
, and
Ben Hamida N.
(2010 ) J. Soc. Chim. Tun. , 12 , 43 .
8.
Boujelbane F.
, and
Ben Hamida N.
(2008 ) J. Soc. Chim. Tun. , 10 , 39 .
9.
Ouertani R.
,
Latrous L.
, and
Ben Hamida N.
(2012 ) Prog. React. Kinet. Mec. , 37 , 1 .
10.
Frisch M.J.
,
Trucks G.W.
,
Schlegel H.B.
2003 ) Gaussian 03 (Revision A.1). Gaussian Inc : Pittsburgh PA.
11.
Becke A.D.
(1993 ) J. Chem. Phys. , 98 , 5648 .
12.
Becke A.D.
(1996 ) J. Chem. Phys. , 104 , 1040 .
13.
Lee C.T.
,
Yang W.T.
, and
Parr R.G.
(1988 ) Phys. Rev. B , 37 , 785 .
14.
Curtiss L.A.
,
McGrath M.P.
,
Blaudeau J.P.
1995 ) J. Chem. Phys. , 103 , 6104 .
15.
Clark T.
,
Chandrasekar J.
,
Spitznagel G.W.
, and
Schleyer P.V.R.
(1983 ) J. Comput. Chem. , 4 , 294 .
16.
Wilson E.B.
(1962 ) J. Chem. Phys. , 36 , 2232 .
17.
Politzer P.
, and
Truhlar D.G.
(1981 ) In: Chemical applications of atomic and molecular electrostatic potentials. Plenum Press , New York .
18.
Reed A.E.
,
Weinstock R.B.
, and
Weinhold F.
(1985 ) J. Chem. Phys. , 83 , 735 .
19.
Reed A.E.
,
Curtiss L.A.
, and
Weinhold F.
(1988 ) Chem. Rev. , 88 , 899 .
20.
Hirshfeld F.L.
(1977 ) Theor. Chem. Acta. , 44 , 129 .
21.
Ritchie J.P.
(1985 ) J. Am. Chem. Soc. , 107 , 1829 .
22.
Ritchie J.P.
, and
Bachrach S.M.
(1987 ) J. Comp. Chem. , 8 , 499 .
23.
Parr R.G.
,
Szentplay L.V.
, and
Liu S.
(1999 ) J. Am. Chem. Soc. , 121 , 1922 .
24.
Mulliken R.S.
(1955 ) J. Chem. Phys. , 23 , 1833 .
25.
Carpenter J.E.
, and
Weinhold F.
(1988 ) J. Phys. Chem. , 92 , 4295 .
26.
Glendening E.D.
,
Reed A.E.
,
Carpenter J.E.
, and
Weinhold F.
NBO version 3.1.
27.
Bultinck P.
,
Langenaeker W.
,
Lahorte
2002 ) J. Phys. Chem. A , 106 , 7895 .
28.
Bobadova-Parvanova P.
, and
Galabov B.
(1998 ) J. Phys. Chem. A , 102 , 1815 .
29.
Galabov B.
, and
Bobadova-Parvanova P.
(1999 ) J. Phys. Chem. A , 103 , 6793 .
30.
Dimitrova V.
,
Ilieva S.
, and
Galabov B.
(2002 ) J. Phys. Chem. A , 106 , 11801 .
31.
Galabov B.
,
Ilieva S.
,
Hadjieva B.
, and
Atanasov Y.
(2008 ) J. Phys. Chem. A , 112 , 6700 .
32.
Galabov B.
,
Cheshmedzhieva D.
,
Ilieva S.
, and
Hadjieva B.
(2004 ) J. Phys. Chem. A , 108 , 11457 .
33.
Galabov B.
,
Nikolova V.
,
Wilke J.J.
2008 ) J. Am. Chem. Soc. , 130 , 9887 .
34.
Koleva G.
,
Galabov B.
,
Wu J.I.
2009 ) J. Am. Chem. Soc. , 131 , 14722 .
35.
Alia J.M.
, and
Edwards H.G.
(2005 ) J. Phys. Chem. A , 109 , 7977 .
36.
Alia J.M.
, and
Edwards H.G.
(2007 ) Int. J. Quant. Chem. , 107 , 1170 .
37.
Karpfen A.
, and
Kryachko E.S.
(2005 ) J. Phys. Chem. A , 109 , 8930 .
38.
Zheng W.X.
,
Wong N.B.
, and
Tian A.
(2004 ) J. Phys. Chem. A , 108 , 1172 .
39.
Zheng W.X.
,
Wong N.B.
, and
Tian A.
(2005 ) J. Phys. Chem. A , 109 , 1926 .
40.
Sadlej-Sosnowska N.
(2007 ) J. Phys. Chem. A , 111 , 11134 .
41.
Sadlej-Sosnowska
(2007 ) N. Pol. J. Chem. , 81 , 1123 .
42.
Sadlej-Sosnowska N.
(2007 ) Chem. Phys. Lett. , 447 , 192 .
43.
Cedillo A.
,
Contreras R.
,
Galvan M.
2007 ) J. Phys. Chem. A , 111 , 2442 .
44.
Novakovic S.B.
,
Fraisse B.
,
Bogdanovic G.A.
, and
Spasojevic-de Bire A.
(2007 ) Cryst. Growth Des. , 7 , 191 .
45.
Novakovic S.B.
,
Fraisse B.
,
Ghermani N.
2007 ) J. Phys. Chem. A , 111 , 13492 .
46.
Chattaraj P.K.
,
Sarkar U.
, and
Roy D.R.
(2006 ) Chem. Rev. , 106 , 2065 .
47.
Chattaraj P.K.
, and
Roy D.R.
(2007 ) Chem. Rev. , 107 , PR46 .
48.
Hammett L.P.
(1937 ) J. Am. Chem. Soc. , 59 , 96 .
49.
Hammett L.P.
(1938 ) Trans. Faraday Soc. , 34 , 156 .
50.
Hansch C.
,
Leo A.
, and
Taft W.
(1991 ) Chem. Rev. , 91 , 165 .
51.
Exner O.
, and
Böhm S.
(2006 ) Curr. Org. Chem. , 10 , 7638 .
52.
Exner O.
, and
Böhm S.
(2006 ) J. Phys. Org. Chem. , 19 , 393 .
53.
Exner O.
, and
Böhm S.
(2009 ) J. Comp. Chem. , 30 , 1069 .
54.
Krygowski T.M.
, and
Stepien B.T.
(2005 ) Chem. Rev. , 105 , 3482 .
55.
Wiberg K.B.
(2002 ) J. Org. Chem. , 67 , 1613 .
56.
Krygowski T.M.
,
Ejsmont K.
,
Stepień B.T.
2004 ) J. Org. Chem. , 69 , 6634 .
57.
Galabov B.
,
Ilieva S.
, and
Schaefer H.F.
(2006 ) J. Org. Chem. , 71 , 6382 .
58.
Williams A.
(1972 ) J. Chem. Soc. Perkin Trans II , 808 .
59.
Nalbantova D.
,
Cheshmedzhieva D.
,
Hadjieva B.
2011 ) J. Phys. Org. Chem. , 24 , 1166 .
60.
Leffler J.E.
, and
Grunwald E.
(1963 ) Rates and equilibria of organic reactions. p. 178 . Wiley , New York .