Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
권호 표지
DOI QR코드

DOI QR Code

Limitations of the Transition State Variation Model. Part 8. Dual Reaction Channels for Solvolyses of 3,4-Dimethoxybenzenesulfonyl Chloride

  • Koo, In-Sun (Department of Chemistry Education and The Research Institute of Natural Science, Gyeongsang National University) ;
  • Kwon, Eun-Ju (Department of Chemistry Education and The Research Institute of Natural Science, Gyeongsang National University) ;
  • Choi, Ho-June (Department of Chemistry, Gyeongsang National University) ;
  • Yang, Ki-Yull (Department of Chemistry Education and The Research Institute of Natural Science, Gyeongsang National University) ;
  • Park, Jong-Keun (Department of Chemistry Education and The Research Institute of Natural Science, Gyeongsang National University) ;
  • Lee, Jong-Pal (Department of Chemistry, Dong-A University) ;
  • Lee, Ikc-Hoon (Department of Chemistry, Inha University) ;
  • Bentley, T. William (Department of Chemistry, University of Wales)
  • Published : 2007.12.20
Download PDF
⟨ Previous Next ⟩

Abstract

Solvolyses of 3,4-dimethoxybenzenesulfonyl chloride (DSC) in water, D2O, CH3OD, and in aqueous binary mixtures of acetone, acetonitrile, 1,4-dioxane, ethanol, methanol, and 2,2,2-trifluoroethanol (TFE) have been investigated at 25.0 oC. Kinetic solvent isotope effects (KSIE) in water and in methanol and product selectivities in alcohol-water mixtures are also reported. The Grunwald-Winstein plot of first-order rate constants for the solvolyic reaction of DSC with YCl shows marked dispersions into separated lines for various aqueous mixtures. With use of the extended Grunwald-Winstein equation, the l and m values obtained are 1.12 and 0.58 respectively for the solvolyses of DSC. The relatively large magnitude of l is consistent with substantial nucleophilic solvent assistance. From Grunwald-Winstein plots the rate data are dissected approximately into contributions from two competing reaction channels. This interpretation is supported for alcohol-water mixtures by the trends of product selectivities, which show a maximum for ethanol-water mixtures. From the KSIE of 1.45 in methanol, it is proposed that the reaction channel favored in methanolwater mixtures and in all less polar media is general-base catalysed and/or is possibly (but less likely) an addition-elimination pathway. Also, the KISE value of 1.35 for DSC in water is expected for SN2-SN1 processes, with minimal general base catalysis, and this mechanism is proposed for solvolyses in the most polar media.

Keywords

References

  1. Barker, J. W.; Nathan, W. W. J. Chem. Soc. 1936, 236 https://doi.org/10.1039/jr9360000236
  2. Swain, C. G.; Langsdorf, W. P. J. Am. Chem. Soc. 1951, 73, 2813 https://doi.org/10.1021/ja01150a113
  3. Rossel, J. B. J. Chem. Soc. 1963, 5183 https://doi.org/10.1039/jr9630005183
  4. Yoh, S. D.; Tsuno, Y.; Yukawa, Y. J. Kor. Chem. Soc. 1984, 28, 433
  5. Yoh, S. D. J. Kor. Chem. Soc. 1975, 19, 240
  6. Lee, I.; Rhyu, K. B.; Lee, B. C. J. Kor. Chem. Soc. 1979, 23, 277
  7. Rogne, O. J. Chem. Soc. (B) 1968, 1294
  8. Kim, W. K.; Lee, I. J. Kor. Chem. Soc. 1974, 18, 8
  9. Kevill, D. N.; Park, B.-C.; Park, K.-H.; D'Souza, M. J.; Yaakoubd, L.; Milynarski, S. L.; Kyong, J. B. Org. Biomol. Chem. 2006, 4, 1580 https://doi.org/10.1039/b518129a
  10. Ciuffarin, E.; Senatore, L.; Isola, M. J. Chem. Soc. Perkin Trans. 2 1972, 468
  11. Stangeland, L. J.; Senatore, L.; Ciuffarin, E. J. Chem. Soc. Perkin Trans. 2 1972, 852
  12. Hall, H. K. Jr. J. Am. Chem. Soc. 1956, 78, 1450 https://doi.org/10.1021/ja01588a048
  13. Robertson, R. E.; Laughton, P. M. Can. J. Chem. 1957, 35, 1319 https://doi.org/10.1139/v57-175
  14. Rossall, B.; Robertson, R. E. Can. J. Chem. 1971, 49, 1451 https://doi.org/10.1139/v71-237
  15. Ballistreri, F. P.; Cantona, A.; Maccarone, E.; Tomaselli, G. A.; Tripolone, M. J. Chem. Soc. Perkin Trans. 2 1981, 438
  16. Koo, I. S.; Yang, K.; Kang, K.; Lee, I.; Bentley, T. W. J. Chem. Soc. Perkin Trans. 2 1998, 1175
  17. Koo, I. S.; Yang, K.; Kang, K.; Lee, I. Bull. Kor. Chem. Soc. 1998, 19, 968
  18. Koo, I. S.; Lee, J. S.; Yang, K.; Kang, K.; Lee, I. Bull. Kor. Chem. Soc. 1999, 20, 573
  19. Bentley, T. W.; Koo, I. S. J. Chem. Soc. Perkin Trans. 2 1989, 1385
  20. Bentley, T. W.; Carter, G. E. J. Am. Chem. Soc. 1982, 104, 5741 https://doi.org/10.1021/ja00385a031
  21. Bentley, T. W.; Harris, H. C.; Koo, I. S. J. Chem. Soc. Perkin Trans. 2 1988, 783
  22. Bentley, T. W.; Harris, H. C. J. Chem. Soc. Perkin Trans. 2 1986, 619
  23. Koo, I. S.; An, S. K.; Yang, K.; Koh, H. J.; Choi, M. H.; Lee, I. Bull. Korean Chem. Soc. 2001, 22, 842
  24. Bentley, T. W.; Bowen, C. T.; Morten, D. H.; Schleyer, P. v. R. J. Am. Chem. Soc. 1981, 103, 5466 https://doi.org/10.1021/ja00408a031
  25. Winstein, S.; Grunwald, E. J. Am. Chem. Soc. 1948, 70, 846 https://doi.org/10.1021/ja01182a117
  26. Bentley, T. W.; Dau-Schmidt, J.-P.; Llewllyn, G.; Mayr, H. J. Org. Chem. 1992, 57, 2387
  27. Winstein, S.; Fainberg, A.; Grunwald, E. J. Am. Chem. Soc. 1957, 79, 4146 https://doi.org/10.1021/ja01572a046
  28. Fainberg, A. H.; Winstein, S. J. Am. Chem. Soc. 1957, 79, 1957
  29. Winstein, S.; Grunwald, E.; Jones, H. W. J. Am. Chem. Soc. 1951, 73, 2700 https://doi.org/10.1021/ja01150a078
  30. Kevill, D. N.; Ismail, NHJ.;.D'Souza, M. J. J. Org. Chem. 1994, 59, 6303 https://doi.org/10.1021/jo00100a036
  31. Kevill, D. N.; D'Souza, M. J. J. Chem. Soc. Perkin Trans. 2 1995, 973
  32. Kevill, D. N.; D'Souza, M. J. J. Chem. Soc. Perkin Trans. 2 1997, 257
  33. Kevill, D. N.; Bond, M. W.; D'Souza, M. J. J. Org. Chem. 1997, 62, 7869 https://doi.org/10.1021/jo970657b
  34. Harris, J. M.; Clark, D. C.; Becker, A.; Fagan, J. F. J. Am. Chem. Soc. 1974, 96, 4478 https://doi.org/10.1021/ja00821a021
  35. Harris, J. M.; Becker, A.; Fagan, J. F.; Walden, F. A. J. Am. Chem. Soc. 1974, 96, 4484 https://doi.org/10.1021/ja00821a022
  36. Koo, I. S.; Yang, K.; Park, J. K.; Woo, M. Y.; Cho, J. M.; Lee, J. P.; Lee, I. Bull. Kor. Chem. Soc. 2005, 26, 1241 https://doi.org/10.5012/bkcs.2005.26.8.1241
  37. Dey, S.; Adhikary, K. K.; Kim, C. K.; Lee, B.-S.; Lee, H. W. Bull. Kor. Chem. Soc. 2005, 26, 776
  38. Oh, H. K.; Ku, M. H.; Lee, H. W. Bull. Kor. Chem. Soc. 2005, 26, 935 https://doi.org/10.5012/bkcs.2005.26.6.935
  39. Karton, Y.; Pross, A. J. Chem. Soc. Perkin Trans. 2 1977, 1860
  40. McLennan, D. J.; Martin, P. L. J. Chem. Soc. Perkin Trans. 2 1982, 1099
  41. Bentley, T. W.; Ryu, Z. H. J. Chem. Soc. Perkin Trans. 2 1994, 761
  42. Koo, I. S.; Yang, K.; Kang, K.; Lee, I.; Bentley, T. W. J. Chem. Soc. Perkin Trans. 2 1998, 1179
  43. Bentley, T. W.; Harris, H. C. J. Org. Chem. 1988, 53, 724 https://doi.org/10.1021/jo00239a004
  44. Bentley, T. W.; Jones, R. O. J. Chem. Soc., Perkin Trans. 2 1993, 2351
  45. Bentley, T. W.; Jones, R. O.; Koo, I. S. J. Chem. Soc. Perkin Trans. 2 1994, 753
  46. Jones, R. O. M. Phil. Thesis; University of Wales: 1991
  47. Koo, I. S.; Bentley, T. W.; Lee, I. J. Kor. Chem. 1990, 34, 304
  48. Bentley, T. W.; Llewellyn, G.; Ryu, Z. H. J. Org. Chem. 1998, 63, 4654 https://doi.org/10.1021/jo980109d
  49. Koo, I. S.; Kang, D. H.; Bentley, T. W.; Lee, I. J. Chem. Soc. Perkin Trans. 2 1991, 175
  50. Koo, I. S.; Yang, K.; An, S. K.; Lee, C.-K.; Lee, I. Bull. Kor. Chem. Soc. 2000, 21, 1011
  51. Bentley, T. W.; Koo, I. S.; Norman, S. J. J. Org. Chem. 1991, 56, 1604 https://doi.org/10.1021/jo00004a048
  52. Schadt, F. L.; Bentley, T. W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1976, 98, 7667 https://doi.org/10.1021/ja00440a037
  53. Kevil, D. N.; Lin, G. M. L. J. Am. Chem. Soc. 1979, 101, 3916 https://doi.org/10.1021/ja00508a032
  54. Senatore, L.; Sagramora, L.; Ciuffarin, E. J. Chem. Soc. Perkin Trans. 2 1974, 722
  55. Rogne, O. J. Chem. Soc. (B) 1969, 663
  56. Gordon, I. M.; Maskill, H.; Ruasse, M. F. Chem. Soc. Rev. 1989, 18, 123 https://doi.org/10.1039/cs9891800123
  57. Kice, J. L. Adv. Phys. Org. Chem. 1980, 17, 156
  58. Aronovitch, H.; Pross, A. J. Chem. Soc. Perkin Trans. 2 1978, 540
  59. Arcoria, A.; Ballistreri, F. P.; Spina, E.; Tomaselli, G. A.; Maccarone, E. J. Chem. Soc. Perkin Trans. 2 1988, 1793
  60. Robertson, R. E. Prog. Phys. Org. Chem. 1967, 4, 213 https://doi.org/10.1002/9780470171837.ch5

Cited by

  1. Correlation of the Rates of Solvolysis of Two Arenesulfonyl Chlorides and of trans-β-Styrenesulfonyl Chloride — Precursors in the Development of New Pharmaceuticals vol.9, pp.12, 2008, https://doi.org/10.3390/ijms9122639
  2. Concerted Solvent Processes for Common Sulfonyl Chloride Precursors used in the Synthesis of Sulfonamide-based Drugs vol.9, pp.5, 2008, https://doi.org/10.3390/ijms9050914
  3. Aminolysis of Y- Substituted Phenyl Benzenesulfonates in MeCN: Effect of Medium on Reactivity and Reaction Mechanism vol.32, pp.spc8, 2011, https://doi.org/10.5012/bkcs.2011.32.8.2955
  4. Correlation of the Rates of Solvolyses of 4-Methylthiophene-2-carbonyl Chloride Using the Extended Grunwald-Winstein Equation vol.33, pp.2, 2012, https://doi.org/10.5012/bkcs.2012.33.2.499
  5. 2 spectrum. Rate constants and product selectivities for solvolyses of benzenesulfonyl chlorides in aqueous alcohols vol.22, pp.9, 2009, https://doi.org/10.1002/poc.1522
  6. Evaluation of Methylthio and Phenylthio Group Effects in the Solvolyses of 2-Chloro-2-(methylthio)acetone and 2-Chloro-2-(phenylthio)acetophenone Using Extended Grunwald-Winstein Equations vol.29, pp.11, 2007, https://doi.org/10.5012/bkcs.2008.29.11.2145
  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. Effect of Leaving Group in the Hydrolyses of N-Cyclopropanecarbonylimidazoles vol.29, pp.7, 2007, https://doi.org/10.5012/bkcs.2008.29.7.1403
  9. N-Propionylbenzimidazole과 N-Propionyl-5-nitrobenzimidazole의 가수분해반응 vol.52, pp.4, 2007, https://doi.org/10.5012/jkcs.2008.52.4.450
  10. N-Cyclopropanecarbonylimidazole과 N-Propionylimidazole의 가수분해반응 vol.53, pp.2, 2007, https://doi.org/10.5012/jkcs.2009.53.2.213
  11. N-Cyclopropanecarbonyl-4-methylimidazole과 N-Propionyl-4-methylimidazole의 가수분해반응 vol.53, pp.6, 2009, https://doi.org/10.5012/jkcs.2009.53.6.814
  12. Evidence for Existence of Intermediate in Acid Hydrolyses of Sulfinamide and Carboxamide vol.31, pp.6, 2007, https://doi.org/10.5012/bkcs.2010.31.6.1773
  13. Correlation of the Rates of Solvolysis of 4-Morpholinecarbonyl Chloride Using the Extended Grunwald-Winstein Equation vol.31, pp.7, 2010, https://doi.org/10.5012/bkcs.2010.31.7.1963
  14. Correlation of the Rates of Solvolysis of 1-Piperidincarbonyl Chloride Using the Extended Grunwald-Winstein Equation vol.32, pp.11, 2007, https://doi.org/10.5012/bkcs.2011.32.11.3941