European Journal of Chemistry

Correlation of the rates of solvolysis of tert-butyl chlorothioformate and observations concerning the reaction mechanism



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Jin Burm Kyong
Yelin Lee
Malcolm John D'Souza
Brian Patrick Mahon
Dennis Neil Kevill

Abstract

The “parent” tertiary alkyl chloroformate, tert-butyl chloroformate, is unstable, but the tert-butyl chlorothioformate (1) is of increased stability and a kinetic investigation of the solvolyses is presented. Analyses in terms of simple and extended Grunwald-Winstein equations are carried out. The original one-term equation satisfactorily correlates the data with sensitivity towards changes in solvent ionizing power of 0.73±0.03. When the two-term equation is applied, the sensitivity towards changes in solvent nucleophilicity of 0.13±0.09 is associated with a high (0.17) probability that the term that it governs is not statistically significant.

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Kyong, J. B.; Lee, Y.; D’Souza, M. J.; Mahon, B. P.; Kevill, D. N. Correlation of the Rates of Solvolysis of Tert-Butyl Chlorothioformate and Observations Concerning the Reaction Mechanism. Eur. J. Chem. 2012, 3, 267-272.

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References

[1]. Kevill D. N. Chloroformate Esters and Related Compounds. In: Patai S. editor. The Chemistry of the Functional Groups: The Chemistry of Acyl Halides. Wiley; New York: 1972, pp. 381-453, Chapter 12.

[2]. Grunwald, E.; Winstein, S. J. Am. Chem. Soc. 1948, 70, 846-854.
http://dx.doi.org/10.1021/ja01182a117

[3]. Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700-2707.
http://dx.doi.org/10.1021/ja01150a078

[4]. Kevill, D. N.; D’Souza, M. J. J. Chem. Res. 2008, 61-66.

[5]. Kevill, D. N.; Bond, M. W.; D’Souza, M. J. J. Org. Chem. 1997, 62, 7869-7871.
http://dx.doi.org/10.1021/jo970657b

[6]. Kevill, D. N.; D’Souza, M. J. J. Org. Chem. 1998, 63, 2120-2124.
http://dx.doi.org/10.1021/jo9714270

[7]. D’Souza, M. J.; Hailey, S. M.; Kevill, D. N. Int. J. Mol. Sci. 2010, 11, 2253-2266.
http://dx.doi.org/10.3390/ijms11052253
PMid:20559514 PMCid:2885106

[8]. D’Souza M. J.; Mahon, B. P.; Kevill, D. N. Int. J. Mol. Sci. 2010, 11, 2597-2611.
http://dx.doi.org/10.3390/ijms11072597
PMid:20717524 PMCid:2920554

[9]. D’Souza, M. J.; McAneny, M. J.; Kevill, D. N.; Kyong, J. B.; Choi, S. H. Beilstein J. Org. Chem. 2011, 7, 543-552.
http://dx.doi.org/10.3762/bjoc.7.62
PMid:21647255 PMCid:3107482

[10]. Bentley, T. W.; Carter, G. E.; Roberts, K. J. Org. Chem. 1984, 49, 5183-5189.
http://dx.doi.org/10.1021/jo00200a034

[11]. Bentley, T. W.; Schleyer, P. v. R. Adv. Phys. Org. Chem. 1977, 14, 1-67.
http://dx.doi.org/10.1016/S0065-3160(08)60107-0

[12]. Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667-7674.
http://dx.doi.org/10.1021/ja00440a037

[13]. Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121-158.
http://dx.doi.org/10.1002/9780470171967.ch5

[14]. Bentley, T. W.; Schadt, F. L.; Schleyer, P. v. R. J. Am. Chem. Soc. 1972, 94, 992-995.
http://dx.doi.org/10.1021/ja00758a049

[15]. Kevill, D. N.; Lin, G. M. L. J. Am. Chem. Soc. 1979, 101, 3916-3919.
http://dx.doi.org/10.1021/ja00508a032

[16]. Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845-1850.
http://dx.doi.org/10.1021/jo00005a034

[17]. 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.
http://dx.doi.org/10.1016/S1874-527X(96)80006-5

[18]. Kevill, D. N.; Kim, J. C.; Kyong, J. B. J. Chem. Res. Synop. 1999, 150-151.

[19]. Kyong, J. B.; Won, H.; Kevill, D. N. Int. J. Mol. Sci. 2005, 6, 87-96.
http://dx.doi.org/10.3390/i6010087

[20]. D’Souza, M. J.; Carter, S. E.; Kevill, D. N. Int. J. Mol. Sci. 2011, 12, 1161-1174.
http://dx.doi.org/10.3390/ijms12021161
PMid:21541050 PMCid:3083697

[21]. Kevill, D. N.; D’Souza, M. J. J. Chem. Soc., Perkin Trans. 2 2002, 240-243.
http://dx.doi.org/10.1039/b109169g

[22]. Kyong, J. B.; Kim, Y. -G.; Kim, D. K.; Kevill, D. N. Bull. Korean Chem. Soc. 2000, 21, 662-664.

[23]. D’Souza, M. J.; Reed, D. N.; Erdman, K. J.; Kyong, J. B.; Kevill, D. N. Int. J. Mol. Sci. 2009, 10, 862-879.
http://dx.doi.org/10.3390/ijms10030862
PMid:19399225 PMCid:2672006

[24]. Kyong, J. B.; Yoo, J. -S.; Kevill, D. N. J. Org. Chem. 2003, 68, 3425-3432.
http://dx.doi.org/10.1021/jo0207426
PMid:12713342

[25]. Kevill, D. N.; D’Souza, M. J. J. Chem. Soc. Perkin Trans. 2 1997, 1721-1724.
http://dx.doi.org/10.1039/a701140g

[26]. D’Souza, M. J.; Shuman, K. E.; Carter, S. E.; Kevill, D. N. Int. J. Mol. Sci. 2008, 9, 2231-2242.
http://dx.doi.org/10.3390/ijms9112231
PMid:19330071 PMCid:2635616

[27]. D’Souza, M. J.; Knapp, J. A.; Fernandez-Bueno, G. A.; Kevill, D. N. Int. J. Mol. Sci. 2012, 13, 665-682.
http://dx.doi.org/10.3390/ijms13010665
PMid:22312278 PMCid:3269712

[28]. Choppin, A. R.; Rodgers, J. W.; J. Am. Chem. Soc. 1948, 70, 2967-2967.
http://dx.doi.org/10.1021/ja01189a040

[29]. Sakakibara, S.; Shin. M.; Fujino, M.; Shimonishi, Y.; Inove, S.; Inukai, N. Bull. Chem. Soc. Jpn. 1965, 38, 1522-1525.
http://dx.doi.org/10.1246/bcsj.38.1522
PMid:5831768

[30]. Kevill, D. N.; Weitl, F. L. Tetrahedron Lett. 1971, 707-710.
http://dx.doi.org/10.1016/S0040-4039(01)96537-2

[31]. Kevill, D. N.; Kyong, J. B.; Weitl, F. L. J. Org. Chem. 1990, 55, 4304-4311.
http://dx.doi.org/10.1021/jo00301a019

[32]. Kevill, D. N.; Weitl, F. L. J. Chem. Soc. Perkin Trans. 1 1972, 2162-2164.

[33]. Kevill, D. N.; Weitl, F. L. J. Chem. Res. Synop. 1989, 318-319.

[34]. Kevill, D. N.; Weitl, F. L. J. Am. Chem. Soc. 1968, 90, 6416-6420.
http://dx.doi.org/10.1021/ja01025a030

[35]. Haas, W. L.; Krumkalns, E. V.; Gerzon, K. J. Am. Chem. Soc. 1966, 88, 1988-1992.
http://dx.doi.org/10.1021/ja00961a024

[36]. Kevill, D. N.; Kyong, J. B. J. Org. Chem. 1992, 57, 258-265.
http://dx.doi.org/10.1021/jo00027a046

[37]. Hoshiko, T.; Ozaki, S.; Watanabe, Y.; Ogasawara, T.; Yamauchi, S.; Fujiwara, K.; Hoshi, A.; Iigo, M. Chem. Pharm. Bull. 1985, 33, 2832-2837.
http://dx.doi.org/10.1248/cpb.33.2832

[38]. Lee, Y. H.; Seong, M. H.; Lee, E. S.; Lee, Y. -W.; Won, H.; Kyong, J. B.; Kevill, D. N. Bull. Korean Chem. Soc. 2010, 31, 1209-1214.
http://dx.doi.org/10.5012/bkcs.2010.31.5.1209

[39]. Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741-5747.
http://dx.doi.org/10.1021/ja00385a031

[40]. Kevill, D. N.; D’Souza, M. J. J. Chem. Res. Synop. 1993, 174-175.

[41]. Lomas, J. S.; D’Souza, M. J.; Kevill, D. N. J. Am. Chem. Soc. 1995, 117, 5891-5892.
http://dx.doi.org/10.1021/ja00126a045

[42]. Kevill, D. N.; Ryu, Z. H. Int. J. Mol. Sci. 2006, 7, 451-455.
http://dx.doi.org/10.3390/i7100451

[43]. Ingold, C. K. Structure and Mechanism in Organic Chemistry, 2nd Ed. Cornell University Press, Ithaca, New York, 1969, pp. 471-473.

[44]. Koh, H. J.; Kang, S. J.; Kevill, D. N. Bull. Korean Chem. Soc. 2010, 31, 835-839.
http://dx.doi.org/10.5012/bkcs.2010.31.04.835

[45]. Kevill, D. N.; Miller, B. J. Org. Chem. 2002, 67, 7399-7406.
http://dx.doi.org/10.1021/jo020467n
PMid:12375970

[46]. Lee, Y. -W.; Seong, M. H.; Kyong, J. B.; Kevill, D. N. Bull. Korean Chem. Soc. 2010, 31, 3366-3370.
http://dx.doi.org/10.5012/bkcs.2010.31.11.3366

[47]. Olah, G. A.; Schilling, P. Bollinger, J. M.; Nishimura, J. J. Am. Chem. Soc. 1974, 96, 2221-2228.
http://dx.doi.org/10.1021/ja00814a036

[48]. Bentley, T. W. J. Org. Chem. 2008, 73, 6251-6257.
http://dx.doi.org/10.1021/jo800841g
PMid:18630963

[49]. Kevill, D. N.; Koyoshi, F.; D’Souza, M. J. Int. J. Mol. Sci. 2007, 8, 346-362.
http://dx.doi.org/10.3390/i8040346

[50]. D’Souza, M. J.; Shuman, K. E.; Omondi, A. O.; Kevill, D. N. Eur. J. Chem. 2011, 2, 130-135.
http://dx.doi.org/10.5155/eurjchem.2.2.130-135.405

[51]. Bentley, T. W.; Bowen, C. T.; Parker, W.; Watt, C. I. F. J. Chem. Soc., Perkin Trans. 2 1980, 1244-1252.
http://dx.doi.org/10.1039/p29800001244

Supporting Agencies

National Center for Research Resources-NCRR (5P20RR016472-12) and the National Institute of General Medical Sciences - NIGMS (8 P20 GM103446-12) from the National Institutes of Health (NIH), a National Science Foundation (NSF)
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