The nucleophilic displacements at carbonyl center are remarkable. Mainly stepwise mechanism was found in these reactions. The stepwise mechanism with rate-limiting addition of the nucleophilie to the carbonyl group to form zwitterionic tetrahedral intermediate was a common type of mechanism. Such as, Dey et al. [1] proposed the pyridinolyses of α-chloroacetanilides proceed via a stepwise mechanism with rate-limiting addition of the nucleophile to the carbonyl group to form zwitterionic tetrahedral intermediate (T±). In some cases concerted mechanism was found. Oh and coworkers [9] reported that a concerted mechanism with a hydrogen bonded cyclic transition state for the aminolysis of aryl N-allyl thiocarbamates with benzylamines in acetonitrile The mechanism change from stepwise to concerted was also found in some cases. It was concluded that the change of the amine from benzylamines to anilines causes a shift of the aminolysis mechanism from a concerted to a stepwise process. This paper includes an exclusive review of literature from 1997 to 2015.
| Published in | Science Journal of Chemistry (Volume 3, Issue 3) |
| DOI | 10.11648/j.sjc.20150303.14 |
| Page(s) | 57-61 |
| Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
| Copyright |
Copyright © The Author(s), 2024. Published by Science Publishing Group |
Nucleophilic Substitution, Carbonyl Compound, Stepwise, Concerted
| [1] | (a) Shuchismita Dey, Keshab Kumar Adhikary, Chan Kyung Kim, Bon-Su Lee, and Hai Whang Lee, Nucleophilic Substitution Reactions of α-Chloroacetanilides with Pyridines in Dimethyl Sulfoxide, Bull. Korean Chem. Soc. 2005, Vol. 26, No. 5, 776-780. (b) Lee, I.; Shim, C. S.; Chung, S. Y.; Lee, H. W. J. Chem. Soc., Perkin Trans. 2 1988, 975. (c) Lee, K. S.; Adhikary, K. K.; Lee, H. W.; Lee, B.-S.; Lee, I. Org. Biomol. Chem. 2003, 1, 1989. |
| [2] | Enrique a. Castro, monica andujar, paola campodonico, jos´e g. Santos, Kinetics and Mechanism of the Aminolysis of 4-Nitrophenyl and 2,4- Dinitrophenyl 4-Methylphenyl Carbonates in Aqueous Ethanol, Int J Chem Kinet 34: 309–315, 2002. |
| [3] | (a) Han Joong Koh, Ok Sun Kim, Hai Whang Lee And Ikchoon Lee, Kinetics And Mechanism Of The Aminolysis Of P-Nitrophenyl N- Phenylcarbamates, Journal Of Physical Organic Chemistry, VOL. 10, 725–730 (1997). (b) I. Lee, H. J. Koh, D. S. Sohn and B. C. Lee, Bull. Korean Chem. Soc. 12, 101 (1991). (c) I. Lee, H. J. Koh, B. S. Lee, D. S. Sohn and B. C. Lee,. J. Chem. Soc., Perkin Trans. 2 1714 (1991). |
| [4] | Dae Dong Sung, Hee Man Janga, Dae Il Jung and Ikchoon Lee, Kinetics and mechanism of the anilinolysis of S-aryl N-arylthiocarbamates in acetonitrile, J. Phys. Org. Chem. 2008, 21 1014–1019. |
| [5] | Han Joong Koh, Ji-Won Lee, Hai Whang Lee, and Ikchoon Lee, Kinetics and mechanism of the aminolysis of ethyl aryl carbonates in acetonitrile, Can. J. Chem. Vol. 76, 1998, 710-716. |
| [6] | D. RAJARATHNAM, J. BABU, P. ANANTHAKRISHNA NADAR, Enhanced Reactivity in the Ammonolysis of Phenyl Thiolacetates in Aqueous Medium, Int J Chem Kinet 34: 18– 26, 2002. |
| [7] | (a) Ik-Hwan Um, Eun-Ju Lee and Sang-Eun Jeon, Effect of Solvent and Basicity: Aminolyses of p-nitrophenyl acetate in H2O and DMSO, J. Phys. Org. Chem. 2002; 15: 561–565. (b) Um IH, Chung EK, Lee SM. Can. J. Chem. 1998; 76: 729; (c) Um IH, Min JS, Lee HW. Can. J. Chem. 1999; 77: 659; (d) Um IH, Kwon HJ, Kwon DS, Park JY. J. Chem. Res. 1995; (M) 1801. (S) 301; (e) Um IH, Yeon ES, Kwon HJ, Kwon DS. Bull. Korean Chem. Soc. 1997; 18: 865; (f) Um IH, Kim MJ, Min JS, Kwon DS. Bull. Korean Chem. Soc. 1999; 20: 392. |
| [8] | Enrique A. Castro, Leonardo Leandro, Nicolas Quesieh, and Jose´ G. Santos, Kinetics and Mechanisms of the Reactions of 3-Methoxyphenyl, 3-Chlorophenyl, and 4-Cyanophenyl 4-Nitrophenyl Thionocarbonates with Alicyclic Amines, J. Org. Chem. 2001, 66, 6130- 6135. |
| [9] | Hanna Lee and Hyuck Keun Oh, Kinetics and Mechanism of the Aminolysis of Aryl N-Allyl Thiocarbamates in Acetonitrile, Bull. Korean Chem. Soc. 2010, Vol. 31, No. 2 475-478. |
| [10] | Ik-Hwan Um, Min-Young Kim, Ae-Ri Bae, Julian M. Dust, and Erwin Buncel, Evidence for a Catalytic Six-Membered Cyclic Transition State in Aminolysis of 4‑ Nitrophenyl 3,5-Dinitrobenzoate in Acetonitrile: Comparative Brønsted-Type Plot, Entropy of Activation, and Deuterium Kinetic Isotope Effects, J. Org. Chem. 2015, 80, 217−222. |
| [11] | (a) Dae Dong Sung, Hee Man Jang, Dae Il Jung and Ikchoon Lee, Kinetics and mechanism of the anilinolysis of S-aryl N-arylthiocarbamates in acetonitrile, J. Phys. Org. Chem. 2008, 21, 1014–1019. (b) H. K. Oh, Y. C. Jin, D. D. Sung, I. Lee, Org. Biomol. Chem. 2005, 3, 1240. (c) H. K. Oh, J. E. Park, D. D. Sung, I. Lee, J. Org. Chem. 2004, 69, 9285. (d) H. K. Oh, J. E. Park, D. D. Sung, I. Lee, J. Org. Chem. 2004, 69, 3150. (e) D. D. Sung, I. S. Han, I. Lee, J. Sulfur Chem. 2007, 28, 483. |
APA Style
Shuchismita Dey. (2015). Nucleophilic Displacements at Carbonyl Compounds. Science Journal of Chemistry, 3(3), 57-61. https://doi.org/10.11648/j.sjc.20150303.14
ACS Style
Shuchismita Dey. Nucleophilic Displacements at Carbonyl Compounds. Sci. J. Chem. 2015, 3(3), 57-61. doi: 10.11648/j.sjc.20150303.14
AMA Style
Shuchismita Dey. Nucleophilic Displacements at Carbonyl Compounds. Sci J Chem. 2015;3(3):57-61. doi: 10.11648/j.sjc.20150303.14
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Download@article{10.11648/j.sjc.20150303.14,
author = {Shuchismita Dey},
title = {Nucleophilic Displacements at Carbonyl Compounds},
journal = {Science Journal of Chemistry},
volume = {3},
number = {3},
pages = {57-61},
doi = {10.11648/j.sjc.20150303.14},
url = {https://doi.org/10.11648/j.sjc.20150303.14},
eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20150303.14},
abstract = {The nucleophilic displacements at carbonyl center are remarkable. Mainly stepwise mechanism was found in these reactions. The stepwise mechanism with rate-limiting addition of the nucleophilie to the carbonyl group to form zwitterionic tetrahedral intermediate was a common type of mechanism. Such as, Dey et al. [1] proposed the pyridinolyses of α-chloroacetanilides proceed via a stepwise mechanism with rate-limiting addition of the nucleophile to the carbonyl group to form zwitterionic tetrahedral intermediate (T±). In some cases concerted mechanism was found. Oh and coworkers [9] reported that a concerted mechanism with a hydrogen bonded cyclic transition state for the aminolysis of aryl N-allyl thiocarbamates with benzylamines in acetonitrile The mechanism change from stepwise to concerted was also found in some cases. It was concluded that the change of the amine from benzylamines to anilines causes a shift of the aminolysis mechanism from a concerted to a stepwise process. This paper includes an exclusive review of literature from 1997 to 2015.},
year = {2015}
}
TY - JOUR T1 - Nucleophilic Displacements at Carbonyl Compounds AU - Shuchismita Dey Y1 - 2015/05/27 PY - 2015 N1 - https://doi.org/10.11648/j.sjc.20150303.14 DO - 10.11648/j.sjc.20150303.14 T2 - Science Journal of Chemistry JF - Science Journal of Chemistry JO - Science Journal of Chemistry SP - 57 EP - 61 PB - Science Publishing Group SN - 2330-099X UR - https://doi.org/10.11648/j.sjc.20150303.14 AB - The nucleophilic displacements at carbonyl center are remarkable. Mainly stepwise mechanism was found in these reactions. The stepwise mechanism with rate-limiting addition of the nucleophilie to the carbonyl group to form zwitterionic tetrahedral intermediate was a common type of mechanism. Such as, Dey et al. [1] proposed the pyridinolyses of α-chloroacetanilides proceed via a stepwise mechanism with rate-limiting addition of the nucleophile to the carbonyl group to form zwitterionic tetrahedral intermediate (T±). In some cases concerted mechanism was found. Oh and coworkers [9] reported that a concerted mechanism with a hydrogen bonded cyclic transition state for the aminolysis of aryl N-allyl thiocarbamates with benzylamines in acetonitrile The mechanism change from stepwise to concerted was also found in some cases. It was concluded that the change of the amine from benzylamines to anilines causes a shift of the aminolysis mechanism from a concerted to a stepwise process. This paper includes an exclusive review of literature from 1997 to 2015. VL - 3 IS - 3 ER -
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