3. Electronic effects of groups containing C C or C O double bonds |
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5. J. Shorter, in The Chemistry of Hydroxyl, Ether and Peroxide Groups, Supplement E2 (Ed.
S.Patai), Chap. 9, Wiley, Chichester, 1993.
6.J. Shorter, in The Chemistry of Triple-bonded Functional Groups, Supplement C2 (Ed. S. Patai), Chap. 5, Wiley, Chichester, 1994.
7.J. Shorter, in The Chemistry of Amino, Nitroso, Nitro and Related Groups, Supplement F2 (Ed.
S.Patai), Wiley, Chichester, 1996.
8.M. Charton, in The Chemistry of Double-bonded Functional Groups (Ed. S. Patai), Chap. 5, Wiley, Chichester, 1989.
9.This section is largely based on previous accounts in References 1,2,5,6 and 7, in which certain material was adapted (by kind permission of Oxford University Press) from J. Shorter, Correlation Analysis in Organic Chemistry; An Introduction to Linear Free-Energy Relationships, Chap. 2, Oxford Chemistry Series, 1973.
10.J. Shorter, Correlation Analysis of Organic Reactivity, Chap. 1, Research Studies Press, Wiley, Chichester, 1982.
11.L. P. Hammett, Physical Organic Chemistry, Chap. 7, McGraw-Hill, New York, 1940.
12.L. P. Hammett, Physical Organic Chemistry, 2nd edn., Chap. 11, McGraw-Hill, New York, 1970.
13.O. Exner, in Advances in Linear Free Energy Relationships (Eds. N. B. Chapman and J. Shorter), Chap. 1, Plenum Press, London, 1972.
14.Reference 10, Chap. 3.
15.J. Shorter, in Similarity Models in Organic Chemistry, Biochemistry, and Related Fields (Eds.
R.I. Zalewski, T. M. Krygowski and J. Shorter), Chap. 2, Elsevier, Amsterdam, 1991.
16.O. Exner, Correlation Analysis of Chemical Data, Plenum, New York and SNTL, Prague, 1988.
17. O. Exner, in Correlation Analysis in Chemistry: Recent Advances (Eds. N. B. Chapman and
J. Shorter), Chap. 10, Plenum Press, New York, 1978.
18.J. Shorter, Pure Appl. Chem., 66, 2451 (1994).
19.H. H. Jaffe,´ Chem. Rev., 53, 191 (1953).
20.The symbol and sign conventions used for substituent effects in this chapter are those most frequently used by writers on correlation analysis in organic chemistry. I or R effects which withdraw electrons from the ring are regarded as positive. The sign convention is the opposite of that used by Ingold. See Reference 10, pp. 229 230 for a more detailed discussion of symbol and sign conventions.
21.H. C. Brown and Y. Okamoto, J. Am. Chem. Soc., 80, 4979 (1958).
22.H. van Bekkum, P. E. Verkade and B. M. Wepster, Recl. Trav. Chim. Pays-Bas, 78, 815 (1959).
23.J. Shorter, in Reference 17, Chap. 4.
24.Y. Yukawa and Y. Tsuno, Bull. Chem. Soc. Jpn., 32, 971 (1959).
25.Y. Yukawa, Y. Tsuno and M. Sawada, Bull. Chem. Soc. Jpn., 39, 2274 (1966).
26.R. W. Taft and I. C. Lewis, J. Am. Chem. Soc., 80, 2436 (1958).
27.R. W. Taft and I. C. Lewis, J. Am. Chem. Soc., 81, 5343 (1959).
28.R. W. Taft, in Steric Effects in Organic Chemistry (Ed. M. S. Newman), Chap. 13, Wiley, New York, 1956.
29.R. W. Taft, S. Ehrenson, I. C. Lewis and R. E. Glick, J. Am. Chem. Soc., 81, 5352 (1959).
30.S. Ehrenson, Prog. Phys. Org. Chem., 2, 195 (1964).
31.S. Ehrenson, R. T. C. Brownlee and R. W. Taft, Prog. Phys. Org. Chem., 10, 1 (1973).
32.It should be mentioned that the expression ‘ value’ or ‘ constant’ has acquired both a specialized and a more general meaning. The former denotes substituent constants based on the ionization of benzoic acids; the latter signifies polar (electronic) substituent constants in general. Thus the meaning of often has to be understood in context, but expressions such as ‘sigma value’ or ‘ -type constant’ are preferable when the more general meaning is intended.
33.O. Exner, Collect. Czech. Chem. Commun., 31, 65 (1966).
34.See, for example, M. Charton, J. Am. Chem. Soc., 91, 6649 (1969).
35.R. W. Taft, E. Price, I. R. Fox, I. C. Lewis, K. K. Andersen and G. T. Davis, J. Am. Chem. Soc., 85, 709 (1963).
36.R. W. Taft, E. Price, I. R. Fox, I. C. Lewis, K. K. Andersen and G. T. Davis, J. Am. Chem. Soc., 85, 3146 (1963).
37.D. F. Ewing, in Reference 17, Chap. 8.
38.D. J. Craik and R. T. C. Brownlee, Prog. Phys. Org. Chem., 14, 1 (1983).
39.A. R. Katritzky and R. D. Topsom, in Reference 13, Chap. 3.
40.G. P. Ford, A. R. Katritzky and R. D. Topsom, in Reference 17, Chap. 3.
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41.J. D. Roberts and W. T. Moreland, J. Am. Chem. Soc., 75, 2167 (1953).
42.Reference 10, Chap. 4.
43.J. Shorter, in Reference 13, Chap. 2.
44.Reference 9, Chap. 3.
45.R. W. Taft, J. Am. Chem. Soc., 79, 1045 (1957).
46.R. T. C. Brownlee, R. E. J. Hutchinson, A. R. Katritzky, T. T. Tidwell and R. D. Topsom, J. Am. Chem. Soc., 90, 1757 (1968).
47.J. Bromilow, R. T. C. Brownlee, V. O. Lopez and R. W. Taft, J. Org. Chem., 44, 4766 (1979).
48.W. F. Reynolds, A. Gomes, A. Maron, D. W. MacIntyre, A. Tanin, G. K. Hamer and I. R. Peat, Can. J. Chem., 61, 2376 (1983).
49.D. A. R. Happer, J. Chem. Soc., Perkin Trans. 2, 1673 (1984).
50.C. Laurence, M. Berthelot, M. Lu¸con, M. Helbert, D. G. Morris and J.-F. Gal, J. Chem. Soc., Perkin Trans. 2, 705 (1984).
51.C. Laurence, in Reference 15, Chap. 5.
52.G. G. Smith and F. W. Kelly, Prog. Phys. Org. Chem., 8, 75 (1971).
53.K. A. Holbrook, in Supplement B: The Chemistry of Acid Derivatives, Vol. 2, (Ed. S. Patai), Chap. 12, Wiley, Chichester, 1992.
54.R. Taylor, in Supplement B: The Chemistry of Acid Derivatives, (Ed. S. Patai), Wiley, Chichester, 1979, p. 860.
55.M. Fujio, R. T. McIver and R. W. Taft, J. Am. Chem. Soc., 103, 4017 (1981).
56.M. Mashima, R. T. McIver, R. W. Taft, F. G. Bordwell and W. N. Olmstead, J. Am. Chem. Soc., 106, 2717 (1984).
57.R. W. Taft and R. D. Topsom, Prog. Phys. Org. Chem., 16, 1 (1987).
58.S. Marriott and R. D. Topsom, J. Am. Chem. Soc., 106, 7 (1984).
59.S. Marriott and R. D. Topsom, J. Chem. Soc., Perkin Trans. 2, 1045 (1985).
60.S. Marriott, A. Silvestro and R. D. Topsom, J. Chem. Soc., Perkin Trans. 2, 457 (1988).
61.S. Marriott, A. Silvestro and R. D. Topsom, J. Mol. Struct. (Theochem), 184, 23 (1989).
62.Cai Jinfeng and R. D. Topsom, J. Mol. Struct. (Theochem), 204, 353 (1990).
63.Jinfeng Cai and R. D. Topsom, J. Mol. Struct. (Theochem), 228, 181 (1991).
64.Tony Silvestro and R. D. Topsom, J. Mol. Struct. (Theochem), 206, 309 (1990).
65.R. D. Topsom, Prog. Phys. Org. Chem., 17, 107 (1990).
66.R. D. Topsom, Prog. Phys. Org. Chem., 16, 125 (1987).
67.T. Sotomatsu, Y. Murata and T. Fujita, J. Comput. Chem., 10, 94 (1989).
68.K. H. Kim and Y. C. Martin, J. Org. Chem., 56, 2723 (1991).
69.V. I. Galkin, A. R. Cherkasov, R. D. Sayakhov and R. A. Cherkasov, Zh. Obshch. Khim., 65, 458, 469, 474 (1995).
70.M. Ludwig, V. Baron, K. Kalfus, O. Pytela and M. VeceM rMa, Collect. Czech. Chem. Commun., 51, 2135 (1986).
71.O. Pytela, M. Ludwig and M. VeceM rMa, Collect Czech. Chem. Commun., 51, 2143 (1986).
72.O. Pytela, Collect. Czech. Chem. Commun., 59, 159 (1994).
73.O. Pytela, Collect. Czech. Chem. Commun., 59, 381 (1994).
M´
74.O. Pytela, J. Kulhanek,´ M. Ludwig and V. Riha, Collect. Czech. Chem. Commun., 59, 627 (1994).
75.O. Pytela, J. Kulhanek´ and M. Ludwig, Collect. Czech. Chem. Commun., 59, 1637 (1994).
76.O. Pytela and J. Liska, Collect. Czech. Chem. Commun., 59, 2005 (1994).
77.W. Ostwald, Z. Phys. Chem., 3, 170, 241, 369 (1889).
78.C. K. Ingold, Chem. Rev., 15, 225 (1934).
79.Except where a more specific reference is given, pKa values quoted explicitly, or quoted implicitly through correlations, in this chapter, have been taken from the following compilations:
(a)G. Kortum,¨ W. Vogel and K. Andrussow, Dissociation Constants of Organic Acids in Aqueous Solution, Butterworths, London, 1961 (for I.U.P.A.C.). This is a reprint from Pure and Applied Chemistry, Vol. 1, Nos. 2 and 3.
(b)E. P. Serjeant and B. Dempsey, Ionisation Constants of Organic Acids in Aqueous Solution, Pergamon Press, Oxford, 1979 (I.U.P.A.C. Chemical Data Series, No. 23).
(c)V. A. Palm (Ed.), and several compilers (from the Laboratory of Chemical Kinetics and Catalysis, Tartu State University, Estonia), Tables of Rate and Equilibrium Constants of Heterolytic Organic Reactions, Moscow, 1975 79, in 5 volumes, each being in two parts (10 books in all).
Six supplementary volumes were published in 1984 90. Information about pKa values may be found in particular in the first volume of each series. These volumes are especially useful for
3. Electronic effects of groups containing C C or C O double bonds |
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pKa values determined in aqueous organic or purely organic solvents. Detailed references may be found in the above sources. Some use has also been made of Tables in Charton’s review80, where detailed references are also given. Reference 79c has also been used as a source of rate constants in the present chapter, where no more specific reference is given.
80.M. Charton, Prog. Phys. Org. Chem., 13, 119 (1981).
81.In 4-X-bicyclo[2.2.2]octane-1-carboxylic acid and related systems the influence of X reaches the acidic centre either by induction through the bonds of the molecular skeleton or through the electric field of the substituent as moderated by the dielectric behaviour of the molecular cavity and solvent. The respective roles of these two modes of transmission have long been a matter of controversy. See J. Shorter in Reference 15, especially pp. 117 120; see also K. Bowden and E. J. Grubbs, Prog. Phys. Org. Chem., 19, 183 (1993); O. Exner and Z. Friedl, Prog. Phys. Org. Chem., 19, 259 (1993). Both modes of transmission are ‘inductive’ in the most general meaning of this term in physics and we shall continue the traditional practice of describing them collectively as the ‘inductive effect’, cf Reference 48 in Section II.C.1.
82.M. Charton, J. Org. Chem., 29, 1222 (1964).
83.C. A. Grob and M. G. Schlageter, Helv. Chim. Acta, 59, 264 (1976).
84.C. A. Grob and M. G. Schlageter, Helv. Chim. Acta, 60, 1884 (1977).
85.C. Hansch and A. Leo, Substituent Constants for Correlation Analysis in Chemistry and Biology, Wiley, New York, 1979.
86. C. Hansch, A. Leo and D. Hoekman, Exploring QSAR |
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Constants, American Chemical Society, Washington, DC, 1995. This is the second part of a two- |
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Chemistry and Biology. The second part is effectively the print-out from an enormous data-base. The volume is a mine of information and has been much consulted by the present contributor since he acquired it. It is important to note that in their preface the authors write that they have tried to be comprehensive rather than critical, i.e. they have not attempted to pass judgement on the quality of all values, although they indicate the ones they normally prefer. When there is an obvious discrepancy, they leave it to the user to consult the original literature to decide whether the model system is appropriate, or whether experimental conditions cast doubt on its validity.
87.G. B. Ellam and C. D. Johnson, J. Org. Chem., 36, 2284 (1971).
88.A. J. Hoefnagel and B. M. Wepster, Collect. Czech. Chem. Commun., 55, 119 (1990).
89.The 50% ethanol water of Hoefnagel and Wepster was made by mixing V dm3 of ethanol with water and making up to 2V dm3. It contains 22.4 mol% ethanol. It must be carefully distinguished from the 50% ethanol water solvent used by many other authors, which is obtained by mixing equal volumes of ethanol and water. It contains 23.6 mol% ethanol.
90.A. J. Hoefnagel and B. M. Wepster, J. Chem. Soc., Perkin Trans. 2, 977 (1989).
91.M. Charton, J. Org. Chem., 30, 552 (1965), as quoted in Reference 85.
92.C. Hansch, A. Leo and R. W. Taft, Chem. Rev., 91, 165 (1991).
93.M. Decouzon, P. Ertl, O. Exner, J.-F. Gal and P.-C. Maria, J. Am. Chem. Soc., 115, 12071 (1993).
94.K. Bowden, Can. J. Chem., 43, 3354 (1965).
95.B. Szyszkowski, Z. Phys. Chem., 22, 173 (1897).
96.E. A. McCoy and L. L. McCoy, J. Org. Chem., 33, 2354 (1968).
97.Reference 6, p. 273.
98.K. Bowden, Can. J. Chem., 41, 2781 (1963).
99.K. Bowden, N. B. Chapman and J. Shorter, Can. J. Chem., 42, 1979 (1964).
100.N. B. Chapman, J. Shorter and J. H. P. Utley, J. Chem. Soc., 1824 (1962).
101.M. Charton. Prog. Phys. Org. Chem., 10, 81 (1973).
102.A. J. Hoefnagel and B. M. Wepster, J. Am. Chem. Soc., 95, 5357 (1973).
103.K. P. Ang, J. Phys. Chem., 62, 1109 (1958).
104.O. Exner, personal communication to J. Shorter, 1991.
105.B. J. Thamer and A. F. Voigt, J. Phys. Chem., 56, 225 (1952); 59, 450 (1955).
106.H. B. Watson, Modern Theories of Organic Chemistry, 2nd ed., Oxford University Press, Oxford, 1941, p. 241.
107.Reference 10, Chap. 4.
108.M. H. Aslam, A. G. Burden, N. B. Chapman, J. Shorter and M. Charton, J. Chem. Soc., Perkin Trans. 2, 500 (1981).
109.M. H. Aslam, N. B. Chapman, J. Shorter and M. Charton, J. Chem. Soc., Perkin Trans. 2, 720 (1981).
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110.M. Charton and B. I. Charton, J. Org. Chem., 43, 1161 (1978) and earlier papers referred to therein.
111.M. Charton, in Topics in Current Chemistry 114; Steric Effects in Drug Design (Eds. M. Charton and I. Motoc), Springer-Verlag, Berlin, 1983, pp. 57 91.
112.M. Charton, in Reference 15, Chap. 11.
113.Reference 5, pp. 433 436.
114.M. H. Aslam, Ph.D. thesis, University of Hull, 1978. Also deposited material associated with References 108 and 109.
115.K. Bowden, Chem. Soc. Rev., 24, 431 (1995).
116. |
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O. Exner and M. BudeLsMinsky,´ Magn. Reson. Chem., 27, 27 (1989). |
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117. |
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M. BudeLsMinsky´ and O. Exner, Magn. Reson. Chem., 27, 585 (1989). |
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118. |
M. Ludwig, S. Wold and O. Exner, Acta. Chem. Scand., 46, 549 (1992). |
119. |
C. G. Swain and E. C. Lupton, J. Am. Chem. Soc., 90, 4328 (1968). |
120. |
C. Hansch, A. Leo, S. H. Unger, K. H. Kim, D. Nakaitani and E. J. Lien, J. Med. Chem., 16, |
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1207 (1973). |
121. |
C. G. Swain, S. H. Unger, N. R. Rosenquist and M. S. Swain, J. Am. Chem. Soc., 105, 492 |
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(1983). |
122. |
W. F. Reynolds and R. D. Topsom, J. Org. Chem., 49, 1989 (1984). |
123. |
A. J. Hoefnagel, W. Oosterbeek and B. M. Wepster, J. Org. Chem., 49, 1993 (1984). |
124. |
M. Charton, J. Org. Chem., 49, 1997 (1984). |
125. |
C. G. Swain, J. Org. Chem., 49, 2005 (1984). |
126. |
C. Hansch, in Reference 17. Chap. 9. |
127. |
W. J. Hehre, C.-F. Pau, A. D. Headley, R. W. Taft and R. D. Topsom, J. Am. Chem. Soc., 108, |
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1711 (1986). |
128. |
J.-L. M. Abboud, J. Catalan,´ J. Elguero and R. W. Taft, J. Org. Chem., 53, 1137 (1988). |
129. |
R. W. Taft, J. L. M. Abboud, F. Anvia, M. Berthelot, M. Fujio, J.-F. Gal, A. D. Headley, |
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W. G. Henderson, I. Koppel, J. H. Qian, M. Mishima, M. Taagepera and S. Ueji, J. Am. Chem. |
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Soc., 110, 1797 (1988). |
130.M. Charton, Prog. Phys. Org. Chem., 16, 287 (1987).
131.M. Charton and B. Charton, Bull. Soc. Chim. France, 199 (1988).
132.Reference 130, p. 288.