Use of the simple and extended grunwald-winstein equations in the correlation of the rates of solvolysis of highly hindered tertiary alkyl derivatives

Current Organic Chemistry

Volumn 14, Issue 10, 2010, Pages 1037-1049

  Kevill, Dennis N ^a   D'Souza, Malcolm J ^b  

^a NORTHERN ILLINOIS UNIVERSITY   (United States)

^b Wesley College Dover   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC COMPOUNDS; CARBON; CHLORINE COMPOUNDS; FREE ENERGY;

ALKYL DERIVATIVES; ALKYLHALIDES; AROMATIC RINGS; EXTENDED GRUNWALD-WINSTEIN EQUATIONS; GRUNWALD-WINSTEIN EQUATION; IONIZING POWER; LINEAR FREE ENERGY RELATIONSHIPS; NUCLEOPHILICITIES; SIMPLE++; SOLVOLYSES;

SOLVENTS;

EID: 77953374045     PISSN: 13852728     EISSN: None     Source Type: Journal    
DOI: 10.2174/138527210791130505     Document Type: Article

References (48)

1. Grunwald, E.; Winstein, S. The correlation of solvolysis rates. J. Am. Chem. Soc., 1948, 70, 846-854.
2. Kevill, D.N.; D'Souza, M.J. Sixty years of the Grunwald-Winstein equation: Development and recent applications. J. Chem. Res., 2008, 61-66.
3. Schleyer, P.V.R.; Nicholas, R.D. The reactivity of bridgehead compounds of adamantane. J. Am. Chem. Soc., 1961, 83, 2700-2707.
4. Bentley, T.W.; Schleyer, P.V.R. Medium effects on the rates and mecha-nisms of solvolytic reactions. Adv. Phys. Org. Chem., 1977, 14, 32-40.
5. Bentley, T.W.; Llewellyn, G. Yx scales of solvent ionizing power. Prog. Phys. Org. Chem., 1990, 17, 121-158.
6. Bentley, T.W.; Carter, G.E. The SN2-SN1 spectrum. 4. Mechanism for sol-volyses of tert-butyl chloride: A revised Y scale of solvent ionizing power ased on solvolyses of 1-adamantyl chloride. J. Am. Chem. Soc., 1982, 104, 5741-5747.
7. Kevill, D.N.; Anderson, S.W. Essentially solvent-independent rates of sol-volysis of the 1-adamantyldimethylsulfonium ion. Implications regarding nu-cleophilic assistance in solvolyses of tert-butyl derivatives and the NKL solvent nucleophilicity scale. J. Am. Chem. Soc., 1986, 108, 1579-1585.
8. Bentley, T.W.; Roberts, K. Weakly nucleophilic leaving groups. Solvolyses of 1-adamantyl and t-butyl heptafluorobutyrates and trifluoroacetates. J. Chem. Soc. Perkin II., 1989, 1055-1060.
9. Fǎrcasciu, D.; Jähme, J.; Rüchardt, C. Relative reactivity of bridgehead adamantyl and homoadamantyl substrates from solvolyses with heptafluoro-butyrate as a highly reactive carboxylate leaving group. Absence of SN2 character of solvolysis of tert-butyl derivatives. J. Am. Chem. Soc., 1985, 107, 5717-5722.
10. Gajewski, J.J. Is the tert-butyl chloride solvolysis the most misunderstood reaction in organic chemistry? Evidence against nucleophilic solvent partici-pation in the tert-butyl chloride transition state and for increased hydrogen bond donation to the 1-adamantyl chloride solvolysis transition state. J. Am. Chem. Soc., 2001, 123, 10877-10883.
11. Dvorko, G. F.; Ponomareva, E.A.; Ponomarev, M.E. Role of nucleophilic solvation and the mechanism of covalent bond heterolysis. J. Phys. Org.Chem., 2004, 17, 825-836.
12. McManus, S.P.; Somani, S.; Harris, J.M.; McGill, R.A. A solvolysis model for 2-chloro-2-methyladamantane based on the linear solvation energy ap-proach. J. Org. Chem., 2004, 69, 8865-8873.
13. Kevill, D.N.; Kamil, W.A.; Anderson, S.W. Nucleophilic participation in the solvolysis of the t-butyldimethylsulfonium ion. Tetrahedron Lett., 1982, 23, 4635-4638.
14. Bentley, T.W.; Garley, M.S. Correlations and predictions of solvent effects on reactivity: some limitations of multi-parameter equations and comparisons with similarity models based on one solvent parameter. J. Phys. Org. Chem., 2006, 19, 341-349.
15. Wells, P.R. Linear free energy relationships; Academic Press: New York, 1968, p. 67.
16. Fainberg, A.H.; Winstein, S. Correlation of solvolysis rates. III. t-Butyl chloride in a wide range of solvent mixtures. J. Am. Chem. Soc., 1956, 78, 2770-2777.
17. Streitwieser, A. Solvolytic displacement reactions; McGraw - Hill: New York, 1964.
18. Winstein, S.; Grunwald, E.; Jones, H.W. The correlation of solvolyses rates and the classification of solvolysis reactions into mechanistic categories. J. Am. Chem. Soc., 1951, 73, 2700-2707.
19. Kevill, D.N. Development and uses of scales of solvent nucleophilicity. In Advances in quantitative structure-property relationships, Charton, M. Ed; JAI Press: Greenwich, CT, 1996, Vol. 1, pp. 81-115.
20. Bentley, T.W.; Schadt, F.L.; Schleyer, P.V.R. Correlation of solvolysis rates with three- and four-parameter relations. Scale of solvent nucleophilicities. J. Am. Chem. Soc., 1972, 94, 992-995.
21. Schadt, F.L.; Bentley, T.W.; Schleyer, P.V.R. The SN2-SN1 spectrum. 2. Quantitative treatments of nucleophilic solvent assistance. A scale of solvent nucleophilicities. J. Am. Chem. Soc., 1976, 98, 7667-7674.
22. Kevill, D.N.; Anderson, S.W. An improved scale of solvent nucleophilicitybased on the solvolysis of the S-methyldibenzothiophenium ion. J. Org.Chem., 1991, 56, 1845-1850.
23. Fainberg, A.H.; Winstein, S. Correlation of solvolysis rates. VII. Neophyl chloride and bromide. J. Am. Chem. Soc., 1957, 79, 1608-1612.
24. Winstein, S.; Fainberg, A.H.; Grunwald, E. Correlation of solvolysis rates. VIII. Benzhydryl chloride and bromide. Comparison of mY and Swain's cor-relations. J. Am. Chem. Soc., 1957, 79, 4146-4155.
25. Liu, K.-T. Nucleophilic solvent intervention in benzylic solvolyses. The use of YBnX scales in Grunwald-Winstein type correlation analysis. J. Chin.Chem. Soc., 1995, 42, 607-615.
26. Kevill, D.N.; D'Souza, M.J. Concerning the development of scales of solvent ionizing power based on solvolyses of benzylic substrates. J. Phys. Org.Chem., 1992, 5, 287-294.
27. Kevill, D.N.; Ismail, N. H.J.; D'Souza, M.J. Solvolysis of the (p-Methoxybenzyl)dimethyl sulfonium ion. Development and use of a scale tocorrect for dispersion in Grunwald-Winstein plots. J. Org. Chem., 1994, 59, 6303-6312.
28. Minegishi, S.; Kobayashi, S.; Mayr, H. Solvent nucleophilicity. J. Am. Chem.Soc., 2004, 126, 5174-5181.
29. Kevill, D.N.; D'Souza, M.J. Application of the aromatic ring parameter (I) to solvolyses of -arylalkyl toluene-p-sulfonates. J. Chem. Soc. Perkin II, 1997, 257-263.
30. Fujio, M.; Goto, M.; Funatsu, K.; Yoshino, T.; Saeki, Y.; Yatsugi, K.; Tsuno, Y. Solvent effects on the solvolysis of neophyl tosylates. Bull. Chem. Soc.Jpn., 1992, 65, 46-54.
31. Fujio, M.; Saeki, Y.; Nakamoto, K.; Yatsugi, K.; Goto, M.; Kim, S.H.; Tsuji, Y.; Rappoport, Z.; Tsuno, Y. The solvent effects on anchimerically assisted solvolyses. 2. Solvent effects in solvolyses of threo-2-aryl-1-methylpropyl p-toluenesulfonates. Bull. Chem., Soc. Jpn., 1995, 68, 2603-2617.
32. Fujio, M.; Saeki, Y.; Nakamoto, K.; Kim, S.H.; Rappoport, Z.; Tsuno, Y.Solvent effects on anchimerically assisted solvolyses. III. Solvent effects on the solvolyses of (1-arylcycloalkyl) methyl p-toluenesulfonates Bull. Chem. Soc. Jpn., 1996, 69, 751-764.
33. Liu, K.-T.; Hou, S.-J.; Tsao, M.-L. B-strain and solvolytic reactivity revis-ited. Nucleophilic solvent participation and abnormal rate ratios for tertiary chloroalkanes. J. Org. Chem., 1998, 63, 1360-1362.
34. da Roza, D.A.; Andrews, L.J.; Keefer, R.M. Solvent system ethanol-2,2,2-trifluoroethanol as a medium for solvolytic displacement. J. Am. Chem. Soc.,1973, 95, 7003-7009.
35. Takeuchi, K.; Takasuka, M.; Shiba, E.; Tokunaga, H., Endo, T.; Ushino, T.; Tokunaga, K.; Okazaki, T.; Kinoshita, T.; Ohga, Y. The Grunwald-Winstein relationship in the solvolysis of crowded tertiary alkyl chlorides. Hindered hydration and hydrophobic effect. J. Phys. Org. Chem., 2001, 14, 229-238.
36. Bentley, T.W.; Dau-Schmidt, J.-P.; Llewellyn, G.; Mayr, H. Solvation effects adjacent to the reaction site. Differences in solvation between alkyl, alkenyl or alkynyl, and aryl groups in binary aqueous mixtures. J. Org. Chem., 1992, 57, 2387-2392.
37. Kevill, D.N.; D'Souza, M.J. Additional YCl values and correlation of the specific rates of solvolysis of tert-butyl chloride in terms of NT and YCl scales. J. Chem. Res. Synop., 1993, 174-175.
38. Reis, M.C.; Elvas-Leitão, R.; Martins, F. The influence of carbon-carbon multiple bonds on the solvolyses of tertiary alkyl halides: A Grunwald-Winstein analysis. Int. J. Mol. Sci., 2008, 9, 1704-1716.
39. Takeuchi, K.; Ohga, Y.; Ushino, T.; Takasuka, M. Structural effects of the Grunwald-Winstein correlations in the solvolysis of some simple tertiary alkyl chlorides. J. Phys. Org. Chem., 1997, 10, 717-724.
40. Takeuchi, K.; Ohga, Y.; Ushino, T.; Takasuka, M. Grunwald Winstein relations in the solvolyses of highly congested simple secondary and tertiary alkyl systems. Evidence for the Brønsted base-type solvation in the standard 1- and 2-adamantyl systems. J. Org. Chem., 1997, 62, 4904-4905.
41. Brown, H.C.; Fletcher, R.S. Chemical effects of steric strains. I. The effect of structure upon the hydrolysis of tertiary aliphatic chlorides. J. Am. Chem. Soc., 1949, 71, 1845-1854.
42. Liu, K.-T.; Hou, S.-J.; Tsao, M.-L. Nucleophilic solvent participation in the solvolysis of tertiary bromoalkanes. J. Chin. Chem. Soc., 2009, 56, 425-430.
43. Fainberg, A.H.; Winstein, S. Correlation of solvolysis rates. VI. t-Butyl and -phenylethyl bromides. J. Am. Chem. Soc., 1957, 79, 1602-1608.
44. Harris, J.M.; Mount, D.L.; Smith, M.R.; Neal, W.C. Jr. Dukes, M.D. Raber, D.J. Application of the ethanol-trifluoroethanol method to solvolyses for which nucleophilic involvement is questioned. J. Am. Chem. Soc., 1978, 100, 8147-8156.
45. Bentley, T.W.; Bowen, C.T.; Parker, W.; Watt, C.I.F. SN2 character of sol-volyses of tert-butyl halides and of trifluoroacetolyses of secondary alkyl sul-fonates. J. Am. Chem. Soc., 1979, 101, 2486-2488.
46. Kevill, D.N.; D'Souza, M.J. Application of the aromatic ring parameter (I) to solvolyses of extremely crowded alkyl derivatives. Tetrahedron Lett., 1998, 39, 3973-3976.
47. Allard, B.; Casadevall, E. Comparative study of the electrophilic properties of some protic solvents characterized by spectroscopic and kinetic solvent-sensitive standard process. Nouv. J. Chim., 1985, 9, 565-568.
48. Abraham, M.H.; Grellier, P.L.; Abboud, J.-L.M.; Doherty, R.M.; Taft, R.W. Solvent effects in organic chemistry. Recent developments. Can. J. Chem., 1988, 66, 2673-2686.