Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Kinetic and Mechanism of the Addition of Benzylamines to α-Phenyl-β-thiophenylacrylonitriles in Acetonitrile

  • Hwang, Jae-young (Department of Chemistry, Gyeongsang National University) ;
  • Yang, Ki-yull (Department of Chemistry Education and the Research Institute of Natural Science, Gyeongsang National University) ;
  • Koo, In-Sun (Department of Chemistry Education and the Research Institute of Natural Science, Gyeongsang National University) ;
  • Sung, Dae-Dong (Department of Chemistry, Dong-A University) ;
  • Lee, Ik-choon (Department of Chemistry, Inha University)
  • Published : 2006.05.20
Download PDF
⟨ Previous Next ⟩

Abstract

Nucleophilic addition reactions of p-substitutedbenzylamines $(XC _6H_4CH _2NH _2)$ to $\alpha$-phenyl-$\beta$-thiophenyl-acrylonitriles ($YC _4SH _2CH=C(CN)C_6H_4$Y') have been studied in acetonitrile at 25.0, 30.0, and 35.0 ${^{\circ}C}$. The reactions take place in single step in which the $C_\beta$ -N bond formation and proton transfer to $C_\alpha$ of $\alpha$-phenyl-$\beta$-thiophenylacrylonitriles occur concurrently with four-membered cyclic transition structure. These mechanistic conclusions are drawn based on (i) the large negative $\rho$x and large positive $\rho$Y' values and also large magnitude of $\rho$X, (ii) the negative sign and large magnitude of the cross-interaction constants ($\rho$XY), (iii) the normal kinetic isotope effects ($k_H/k_D$ > 1.0), and (iv) relatively low $\Delta H ^\neq$ and large negative $\Delta S ^\neq$ values.

Keywords

References

  1. Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301 https://doi.org/10.1021/ar00140a006
  2. Bernasconi, C. F. Tetrahedron 1989, 45, 4017 https://doi.org/10.1016/S0040-4020(01)81304-1
  3. Oh, H. K.; Yang, J. H.; Sung, D. D.; Lee, I. J. Chem. Soc.,Perkin Trans. 2 2000, 101
  4. Oh, H. K.; Yang, J. H.; Lee, H. W.;Lee,I. J. Org. Chem. 2000, 65, 2188 https://doi.org/10.1021/jo991823d
  5. Oh, H. K.; Yang, J. H.;Lee, H. W.;Lee, I. J. Org. Chem. 2000, 65, 5391 https://doi.org/10.1021/jo000512w
  6. Oh, H. K.;Kim, I. K.; Sung, D. D.; Lee, I. Org. Biomol. Chem. 2004, 2, 1213 https://doi.org/10.1039/b401239a
  7. Oh, H. K.; Kim, I. K.; Sung, D. D.; Lee, I. Bull. Korean Chem.Soc. 2005, 26, 641 https://doi.org/10.1007/s11814-009-0107-9
  8. Lee, I. Adv. Phys. Org. Chem.1992, 27, 57
  9. Lee, I.; Lee, H. W. Collect. Czech. Chem. Commun. 1999, 64, 1529 https://doi.org/10.1135/cccc19991529
  10. Lee, I. Chem. Soc. Rev. 1990, 19, 317 https://doi.org/10.1039/cs9901900317
  11. Oh, H. K.; Kim,T. S.; Lee, H. W.; Lee, I. Bull. Korean Chem. Soc. 2003, 24, 193 https://doi.org/10.5012/bkcs.2003.24.2.193
  12. Imoto, E.; Motoyama, R. Bull. Naniwa Univ. 2A 1954, 127
  13. Imoto, E.; Motoyama, R. Chem. Abs. 1955, 49, 9614
  14. Charton,M. Correlation Analysis in Chemistry; Plenum Press: New Yorkand London, 1978; pp 199-200
  15. Ritchie, C. D. In Solute-Solvent Interactions; Coetzee, J. F.,Ritchie, C. D., Eds.; Marcel Dekker: New York, 1969; Chapter 4
  16. Coetzee, J. F. Progress in Physical Organic Chemistry;Streitwieser, A., Jr., Taft, R. W., Eds.; Wiley; New York, 1967;Vol. 4, pp 54-92
  17. Spillane, W. J.; Hogan, G.; McGrath, P.; King,J.; Brack, C. J. Chem. Soc., Perkin Trans. 2 1996, 2099
  18. Lee,I.; Kim, C. K.; Han, I. S.; Lee, H. W.; Kim, W. K.; Kim, Y. B. J. Phys. Chem. B 1999, 103, 7302 https://doi.org/10.1021/jp991115w
  19. Lee, I.; Rhee, S. K.; Kim, C. K.; Chung, D. S.; Kim, C. K. Bull. Korean Chem. Soc. 2000, 21, 882 https://doi.org/10.1007/BF02705534
  20. Lee, I. Chem. Soc. Rev. 1990, 19, 317 https://doi.org/10.1039/cs9901900317
  21. Lee, I. Chem. Soc. Rev. 1995, 24, 223 https://doi.org/10.1039/cs9952400223

Cited by

  1. Effects of substituents on activation parameter changes in the Michael-type reactions of nucleophilic addition to activated alkenes and alkynes in solution vol.147, pp.2, 2016, https://doi.org/10.1007/s00706-015-1622-5
  2. Kinetics and Mechanism of the Addition of Anilines to β-Nitrostilbenes in Acetonitrile vol.28, pp.10, 2006, https://doi.org/10.5012/bkcs.2007.28.10.1670
  3. Aminolyses of 2,4-Dinitrophenyl 2-Furoate and Benzoate: Effect of Nonleaving Group on Reactivity and Mechanism vol.28, pp.2, 2006, https://doi.org/10.5012/bkcs.2007.28.2.220
  4. Aminolyses of Y-substituted Phenyl 2-Furoates and Cinnamates: Effect of Nonleaving Group Substituent on Reactivity and Mechanism vol.28, pp.8, 2006, https://doi.org/10.5012/bkcs.2007.28.8.1353
  5. Alkali Metal Ion Catalysis in Nucleophilic Substitution Reactions of 5-Nitro-8-quinolyl Benzoate with Alkali Metal Ethoxides in Anhydrous Ethanol: Unusually High Na+ Ion Selectivity vol.29, pp.1, 2006, https://doi.org/10.5012/bkcs.2008.29.1.117
  6. Kinetic Study on Michael-type Reactions of 1-Phenyl-2-propyn-1-one with Alicyclic Secondary Amines: Effect of Medium on Reactivity and Mechanism vol.29, pp.10, 2006, https://doi.org/10.5012/bkcs.2008.29.10.1911
  7. Physical Chemistry Research Articles Published in the Bulletin of the Korean Chemical Society: 2003-2007 vol.29, pp.2, 2008, https://doi.org/10.5012/bkcs.2008.29.2.450
  8. Aminolysis of Y-Substituted Phenyl 2-Thiophenecarboxylates and 2-Furoates: Effect of Modification of Nonleaving Group from 2-Furoyl to 2-Thiophenecarbonyl on Reactivity and Mechanism vol.29, pp.3, 2006, https://doi.org/10.5012/bkcs.2008.29.3.585
  9. Kinetic Studies on the Nucleophilic Substitution Reaction of 4-X-Substituted-2,6-dinitrochlorobenzene with Pyridines in MeOH-MeCN Mixtures vol.30, pp.7, 2006, https://doi.org/10.5012/bkcs.2009.30.7.1579
  10. Kinetic Studies on the Aminolysis of 2-(p-Substitutedbenzoyl)-4,5-dichloropyridazin-3-ones vol.30, pp.11, 2006, https://doi.org/10.5012/bkcs.2009.30.11.2779
  11. Kinetic Studies on the Aminolysis of 2-(p-Substitutedbenzoyl)-4,5-dichloropyridazin-3-ones vol.30, pp.11, 2006, https://doi.org/10.5012/bkcs.2009.30.11.2779
  12. Single Electron Transfer (SET) Pathway: Nucleophilic Substitution Reaction of 4-Chloro-7-nitrobenzofurazan with Anilines in MeOH-MeCN Mixtures vol.31, pp.10, 2006, https://doi.org/10.5012/bkcs.2010.31.10.2801
  13. Kinetics and Mechanism of Nucleophilic Substitution Reaction of 4-Substituted-2,6-dinitrochlorobenzene with Benzylamines in MeOH-MeCN Mixtures vol.31, pp.11, 2006, https://doi.org/10.5012/bkcs.2010.31.11.3279
  14. Kinetics and Mechanism of Nucleophilic Substitution Reaction of 4-Substituted-2,6-dinitrochlorobenzene with Benzylamines in MeOH-MeCN Mixtures vol.31, pp.11, 2006, https://doi.org/10.5012/bkcs.2010.31.11.3279