European Journal of Chemistry 2017, 8(2), 162-167 | doi: https://doi.org/10.5155/eurjchem.8.2.162-167.1566 | Get rights and content

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Correlation analysis of the rates of solvolysis of 4-bromopiperidine: A reaction following a Grob fragmentation pathway


Dennis Neil Kevill (1) , Zoon Ha Ryu (2) , Malcolm John D’Souza (3,*)

(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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Keywords


Solvolysis; Mechanism; Correlation; 4-Bromopiperidine; Grob fragmentation; Grunwald-Winstein equation

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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

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[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
/

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How to cite


Kevill, D.; Ryu, Z.; D’Souza, M. Eur. J. Chem. 2017, 8(2), 162-167. doi:10.5155/eurjchem.8.2.162-167.1566
Kevill, D.; Ryu, Z.; D’Souza, M. Correlation analysis of the rates of solvolysis of 4-bromopiperidine: A reaction following a Grob fragmentation pathway. Eur. J. Chem. 2017, 8(2), 162-167. doi:10.5155/eurjchem.8.2.162-167.1566
Kevill, D., Ryu, Z., & D’Souza, M. (2017). Correlation analysis of the rates of solvolysis of 4-bromopiperidine: A reaction following a Grob fragmentation pathway. European Journal of Chemistry, 8(2), 162-167. doi:10.5155/eurjchem.8.2.162-167.1566
Kevill, Dennis, Zoon Ha Ryu, & Malcolm John D’Souza. "Correlation analysis of the rates of solvolysis of 4-bromopiperidine: A reaction following a Grob fragmentation pathway." European Journal of Chemistry [Online], 8.2 (2017): 162-167. Web. 28 May. 2023
Kevill, Dennis, Ryu, Zoon, AND D’Souza, Malcolm. "Correlation analysis of the rates of solvolysis of 4-bromopiperidine: A reaction following a Grob fragmentation pathway" European Journal of Chemistry [Online], Volume 8 Number 2 (30 June 2017)

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European Journal of Chemistry 2017, 8(2), 162-167 | doi: https://doi.org/10.5155/eurjchem.8.2.162-167.1566 | Get rights and content

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