European Journal of Chemistry

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

Article Sidebar

PDF
Published: Sep 30, 2012
DOI: https://doi.org/10.5155/eurjchem.3.3.267-272.624
Keywords:
Solvolysis, Ionization, Addition-elimination, Activation parameters, tert-Butyl chlorothioformate, Grunwald-Winstein equations
Section
Research Article
Issue
Vol. 3 No. 3 (2012): September 2012
Dates
Received 2012-04-24
Accepted 2012-05-19
Published 2012-09-30


Main Article Content

Jin Burm Kyong
Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-Do, 426-791, Korea
Yelin Lee
Department of Chemistry and Applied Chemistry, Hanyang University, Ansan-si, Gyeonggi-Do, 426-791, Korea
Malcolm John D'Souza
Department of Chemistry, Wesley College, Dover, DE, 19901, USA
Brian Patrick Mahon
Department of Chemistry, Wesley College, Dover, DE, 19901, USA
Dennis Neil Kevill
Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL, 60115, USA

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.

3_3_267_272_800


icon graph This Abstract was viewed 2162 times | icon graph Article PDF downloaded 762 times

How to Cite
(1)
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.

Article Details

Share
Links for Article


Crossref - Scopus - Google - European PMC
Crossref
Scopus
Google Scholar
Europe PMC
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)
Most read articles by the same author(s)
TrendMD

Dimensions - Altmetric - scite_ - PlumX

Downloads and views

Downloads

Download data is not yet available.

Metrics

Metrics Loading ...
License Terms

License Terms

by-nc

Copyright © 2024 by Authors. This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at https://www.eurjchem.com/index.php/eurjchem/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution, or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License (https://www.eurjchem.com/index.php/eurjchem/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry).