

Correlation analysis of the rates of solvolysis of 4-bromopiperidine: A reaction following a Grob fragmentation pathway
Dennis Neil Kevill (1)



(1) Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, Illinois 60115-2862, USA
(2) Department of Chemistry, Dong-Eui University, 995 Eomgwango, Busan-Jin-Gu, Busan 614-714, Republic of Korea
(3) Department of Chemistry, Wesley College, 120 North State Street, Dover, Delaware 19901-3875, USA
(*) Corresponding Author
Received: 13 Mar 2017 | Revised: 11 Apr 2017 | Accepted: 19 Apr 2017 | Published: 30 Jun 2017 | Issue Date: June 2017
Abstract
A Grunwald-Winstein treatment of the specific rates of solvolysis of 4-bromopiperidine gives for aqueous ethanol, methanol, acetone, and dioxane a very good logarithmic correlation against the YBr solvent ionizing power values with a slope (m value) of 0.46±0.02, consistent with the operation of a synchronous Grob fragmentation mechanism. When the organic component of the solvent is 2,2,2-trifluoroethanol (TFE), the data points show a negative deviation, consistent with an appreciable deactivating interaction of the acidic TFE component of the solvent with the lone-pair of electrons present on the nitrogen.
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European Journal of Chemistry
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DOI: 10.5155/eurjchem.8.2.162-167.1566
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Funding information
The American Chem. Soci. Petroleum Res. Fund (PRF#38163-AC4); the National Inst. of General Med. Sci.-NIGMS (P20GM103446), IDeA prog. from the National Inst. of Health (DE-INBRE); the National Sci. Found. (NSF) EPSCoR IIA-1301765
Citations
[1]. Dennis Neil Kevill, Chang-Bae Kim, Malcolm John D’Souza
Correlation of the rates of solvolysis of α-bromoisobutyrophenone using both simple and extended forms of the Grunwald-Winstein equation and the application of correlation analysis to related studies
European Journal of Chemistry 9(1), 1, 2018
DOI: 10.5155/eurjchem.9.1.1-6.1680

[2]. Xhenti Ferhati, Marina Salas-Cubero, Pablo Garrido, Josune García-Sanmartín, Ana Guerreiro, Alberto Avenoza, Jesús H. Busto, Jesús M. Peregrina, Alfredo Martínez, Ester Jiménez-Moreno, Gonçalo J. L. Bernardes, Francisco Corzana
Bioorthogonal Self-Immolative Linker Based on Grob Fragmentation
Organic Letters 23(21), 8580, 2021
DOI: 10.1021/acs.orglett.1c03299

References
[1]. D'Arcy, R.; Grob, C. A.; Kaffenberger, T.; Krasnobajew, V. Helv. Chim. Acta. 1966, 49, 185-203.
https://doi.org/10.1002/hlca.660490125
[2]. Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700-2707.
https://doi.org/10.1021/ja01150a078
[3]. Kevill, D. N.; D'Souza, M. J. J. Chem. Res. 2008, 61-66.
https://doi.org/10.3184/030823408X293189
[4]. Bentley, T. W.; Llewellyn, G. Prog. Phys. Org. Chem. 1990, 17, 121-158.
https://doi.org/10.1002/9780470171967.ch5
[5]. Kevill, D. N. in Advances in Quantitative Structure-Property Relationships; Charton, M. Ed.; JAI Press: Greenwich, CT, USA, 1996; Volume 1, pp. 81-115.
https://doi.org/10.1016/S1874-527X(96)80006-5
[6]. Grob, C. A.; Schiess, P. W. Angew. Chem. 1967, 79, 1-14; Angew. Chem. Int. Ed. 1967, 6, 1-15.
https://doi.org/10.1002/anie.196700011
[7]. Grob, C. A. Angew. Chem. 1969, 81, 543-554; Angew. Chem. Int. Ed. 1969, 8, 535-546.
https://doi.org/10.1002/anie.196905351
[8]. Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd. ed.; Harper and Row: New York, NY, USA, 1987; pp. 373-375.
[9]. Jasti, R.; Rychonovsky, S. D. Org. Lett. 2006, 8, 2175-2178.
https://doi.org/10.1021/ol0606738
[10]. Snider, B. B. The Prins Reaction and Carbonyl Ene Reactions, eds. Trost, B. M., Fleming, I., and Heathcock, C. H. Pergamon Press, New York, NY, 1991, Vol. 2, pp. 527-561.
[11]. Lee, C. L. K.; Lee, C. H. A.; Tan K. T.; Loh, T. P. Org. Lett. 2004, 6, 1281-1283.
https://doi.org/10.1021/ol049633z
[12]. Kevill, D. N.; Kolwyck K. C.; Weitl, F. L. J. Am. Chem. Soc. 1970, 92, 7300-7306.
https://doi.org/10.1021/ja00728a012
[13]. Kevill, D. N.; Dorsey, J. E. J. Org. Chem. 1969, 34, 1985-1987.
https://doi.org/10.1021/jo01258a108
[14]. Rappoport, Z.; Kaspi, J. J. Am. Chem. Soc. 1974, 96, 4518-4530.
https://doi.org/10.1021/ja00821a027
[15]. Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741-5747.
https://doi.org/10.1021/ja00385a031
[16]. Lee, I.; Lee, H. W.; Uhm, T. S.; Sung D. D.; Ryu, Z. H. J. Korean Chem. Soc. 1988, 32, 85-93.
https://doi.org/10.12925/jkocs.2015.32.1.85
[17]. Koh, H. J.; Han, K. L.; Lee H. W.; Lee, I. J. Org. Chem. 1998, 63, 9834-9839.
https://doi.org/10.1021/jo9814905
[18]. Grunwald, E.; Winstein, S. J. Am. Chem. Soc. 1948, 70, 846-854.
https://doi.org/10.1021/ja01182a117
[19]. Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667-7675.
https://doi.org/10.1021/ja00440a037
[20]. Kevill, D. N.; Anderson, S. W. J. Org. Chem. 1991, 56, 1845-1850.
https://doi.org/10.1021/jo00005a034
[21]. Kevill, D. N.; Rissmann, T. J. J. Chem. Soc., Perkin Trans. 2 1984, 717-720.
https://doi.org/10.1039/p29840000717
[22]. Kevill, D. N.; D'Souza, M. J. J. Org. Chem. 1998, 63, 2120-2128.
https://doi.org/10.1021/jo9714270
[23]. D'Souza, M. J.; Sandosky, B.; Fernandez-Bueno, G. A.; McAneny M. J.; Kevill, D. N. Can. Chem. Trans. 2014, 2, 160-174.
[24]. Kevill, D. N.; D'Souza M. J.; Ren, H. Can. J. Chem. 1998, 76, 751-757.
https://doi.org/10.1139/v98-059
[25]. Kevill, D. N.; D'Souza, M. J. J. Chem Res. (S) 1994, 190-191.
[26]. McManus, S. P.; Neamati-Mazrach, N.; Hovanes, B. A.; Paley M. S.; Harris, J. M. J. Am. Chem. Soc. 1985, 107, 3392-3393.
https://doi.org/10.1021/ja00297a081
[27]. McManus, S. P.; Sedaghat-Herati, M. R.; Karaman, R. M.; Neamati-Mazrach, N.; Cowell, S. M.; Harris, J. M. J. Org. Chem. 1989, 54, 1911-1918.
https://doi.org/10.1021/jo00269a030
[28]. McManus, S. P.; Sedaghat-Herati, M. R.; Harris, J. M. Tetrahedron Lett. 1987, 28, 5299-5300.
https://doi.org/10.1016/S0040-4039(00)96712-1
[29]. McManus, S. P.; Neamati-Mazrach, N.; Karaman, R. M.; Harris, J. M. J. Org. Chem. 1986, 51, 4876-4878.
https://doi.org/10.1021/jo00375a022
[30]. McManus, S. P.; Lam, D. H. J. Org. Chem. 1978, 43, 650-651.
https://doi.org/10.1021/jo00398a028
[31]. Neamati-Mazrach, N.; McManus, S. P. Tetrahedron Lett. 1987, 28, 837-840.
https://doi.org/10.1016/S0040-4039(01)81002-9
[32]. Kevill, D. N.; Abduljaber, M. H. Croatica Chemica Acta 1992, 65, 539-546.
[33]. Bentley, T. W.; Schleyer, P. v. R. J. Am Chem. Soc. 1976, 98, 7658-7666.
https://doi.org/10.1021/ja00440a036
[34]. Harris, J. M.; McManus, S. P.; Sedaghat-Herati, M. R.; Neamati-Mazrach, N.; Kamlet, M. J.; Doherty, R. M.; Taft, R. W. Abraham, M. H. in Nucleophilicity, ed. Harris, J. M. and McManus, S. P. Advances in Chemistry No 215, American Chemical Society, Washington, D. C. , 1987, pp. 249.
[35]. Jursic, B.; Ladika, M.; Sunko, D. E. Tetrahedron 1986, 42, 911-916.
https://doi.org/10.1016/S0040-4020(01)87497-4
[36]. Chechik, V. O.; Bobylev, V. A. J. Gen. Chem. USSR. (Engl. Transl.) 1992, 62, 814-820.
[37]. Chechik, V. O.; Bobylev, V. A. Acta. Chem. Scand. 1994, 48, 837-842.
https://doi.org/10.3891/acta.chem.scand.48-0837
[38]. D'Souza, M. J.; Kevill, D. N. Recent Res. Devel. Organic Chem. 2013, 13, 1-38.
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