836
B. LIU, H. J. SHINE AND W. ZHAO
2. M. A. Khuddus and D. Swern, J. Am. Chem. Soc. 95, 8393 (1973).
3. J. March, Advanced Organic Chemistry, 4th ed., p. 1194. Wiley–
Interscience, New York (1992).
4. C. R. Johnson and W. G. Phillips, J. Org. Chem. 32, 1926 (1967).
5. W. Zhao and H. J. Shine, Tetrahedron Lett. 37, 1749 (1996).
6. W. Zhao, H. J. Shine and B. R. Whittlesey, J. Org. Chem. 62, 8693
(1997).
7. W. Zhao and H. J. Shine, Can. J. Chem. 76, 695 (1998).
8. S. Oae, Organic Sulfur Chemistry: Structure and Mechanism, pp.
86–87, 161–167. CRC Press, Boca Raton, FL (1991).
9. N. J. Leonard and C. R. Johnson, J. Am. Chem. Soc. 84, 3701
(1962).
10. C. R. Johnson, J. Am. Chem. Soc. 85, 1020 (1963).
11. C. R. Johnson and D. McCants Jr, J. Am. Chem. Soc. 87, 23 (1965).
12. C. R. Johnson and W. G. Phillips, J. Am. Chem. Soc. 91, 682
(1969).
13. E. J. Corey and C. U. Kim, J. Am. Chem. Soc. 94, 7586 (1972).
14. E. J. Corey, C. U. Kim and M. Takeda, Tetrahedron Lett. 4339
(1972).
15. E. J. Corey and C. U. Kim, Tetrahedron Lett. 919 (1973).
16. E. J. Corey and C. U. Kim, J. Org. Chem. 38, 1233 (1973).
17. (a) D. Landini, G. Modena, F. Montanari and G. Scorrano, J. Am.
Chem. Soc. 92, 7168 (1970); (b) D. Landini, G. Modena, U.
Quintily and G. Scorrano, J. Chem. Soc. 2041 (1971); (c) S.
Tamagaki, M. Mizuno, H. Yoshida, H. Hirota and S. Oae, Bull.
Chem. Soc. Jpn. 44, 2456 (1971).
18. (a) K. Mislow, T. Simmons, J. T. Melillo and A. L. Ternay Jr, J.
Am. Chem. Soc. 86, 1452 (1964); (b) H. Yoshida, T. Numata and S.
Oae, Bull. Chem. Soc. Jpn. 44, 2875 (1971).
19. C. R. Johnson and J. J. Rigau, J. Am. Chem. Soc. 91, 5398 (1969).
20. S. Oae and Y. H. Kim, Bull. Chem. Soc. Jpn. 42, 3528 (1969).
21. K. Tsumori, H. Minato and M. Kobayashi, Bull. Chem. Soc. Jpn.
46, 3503 (1973).
in 10 ml of MeCN containing toluene as GC standard was
stirred for 30 min. GC on column E failed to detect MeOH.
PhSH (71 mg, 0.645 mmol) was injected into the suspen-
sion and stirring was continued for 30 min. GC again
failed to detect MeOH. Water (0.2 ml) was injected and
stirring was continued for 30 min. A small amount of solid
remained. GC gave 0.269 mmol (105%) of MeOH. A
similar experiment with 10.5 mg (0.194 mmol) of NaOMe
and 1.22 g (11.1 mmol) of PhSH again gave MeOH
(0.185 mmol, 95%) only after the addition of 0.2 ml of
water. The same type of experiments were carried out with
EtSH. With 10.5 mg (0.194 mmol) of NaOMe and 36 ml
(0.484 mmol) of EtSH, MeOH (0.192 mmol, 99%) was
obtained only after the addition of water. When a larger
amount of EtSH (11.2 mmol) was used, MeOH was
detectable again only after the addition of water, but assay
was thwarted by overlap of the MeOH peak with the very
large peak from EtSH.
(b) The sodium salt of cyclohexanol was prepared by
heating Na with cyclohexanol under reflux. The white
precipitate was filtered, washed with dry diethylether and
dried under vacuum. To 20.7 mg (0.170 mmol) of the salt
was added 10 ml of dry MeCN containing naphthalene as
GC standard. Most of the salt dissoved. After stirring for
30 min, GC assay on column A gave 0.162 mmol (95%)
of cyclohexanol. The experiment was repeated with
redried (P2O5) MeCN and again cyclohexanol (98%) was
found without the need to add PhSH or water.
22. H. Minato, T. Miura and M. Kobayashi, Chem. Lett. 701 (1975).
23. S. Winstein, D. Darwish and N. J. Holness, J. Am. Chem. Soc. 78,
2915 (1956).
24. W. T. Ford, Acc. Chem. Res. 6, 410 (1975).
25. D. J. McLennan, Tetrahedron 31, 2999 (1975).
26. J. March, Advanced Organic Chemistry, 4th ed., pp. 997, 998.
Wiley–Interscience, New York (1992).
27. E. L. Eliel and R. G. Haber, J. Am. Chem. Soc. 81, 1249 (1959).
28. D. J. McLennan, J. Chem. Soc. B 705 (1966).
29. C. R. Johnson and M. P. Jones, J. Org. Chem. 32, 2014 (1967).
30. H. Meerwein, K.-F. Zenner and R. Gipp, Justus Liebigs Ann.
Chem. 688, 67 (1965).
31. J. L. Kice, Acc. Chem. Res. 1, 58 (1968).
32. D. Cook, R. E. J. Hutchinson, J. K. MacCleod and A. J. Parker, J.
Org. Chem. 39, 534 (1974).
33. F. G. Bordwell and S. R. Mrozack, J. Org. Chem. 47, 4813 (1982).
34. C. Arnone, G. Consiglio, V. Frenna and D. Spinelli, J. Org. Chem.
62, 3093 (1997).
Reaction of 1b with PhSH. A solution of 16.2 mg
(0.039 mmol) of 1b and 28.3 mg (0.257 mmol) of PhSH
was made in 3 ml of CD3CN containing napthalene as
GC standard. Reaction (decrease of the peaks of 1b at 8.4
and 4.54 ppm) had not occurred after 18 h. After the
solution had been heated for 1 h at 100°C, GC showed
cyclohexene, ThO, PhSH and DPDS. A solution of 1b in
MeCN gave ThO (105%) and cyclohexene (100%) when
injected into the hot GC inlet.
35. R. G. Pearson and J. Songstad, J. Org. Chem. 32, 2899 (1967).
36. R. G. Pearson, H. Sobel and J. Songstad, J. Am. Chem. Soc. 90, 319
(1968).
Acknowledgements
37. W. Galezowski and E. S. Lewis, J. Phys. Org. Chem. 7, 90 (1994).
38. D. Landini and F. Montanari, J. Chem. Soc. Chem. Commun. 86
(1968).
39. J. L. Kice and T. E. Rogers, J. Org. Chem. 41, 255 (1976).
40. J. O. Edwards and R. G. Pearson, J. Am. Chem. Soc. 84, 16 (1962).
41. S. M. Bachrach and D. C. Mulhearn, J. Phys. Chem. 100, 3535
(1996), and references cited therein.
We thank the Robert A. Welch Foundation for support
(Grant D-0028) and Professors J. L. Kice, E. S. Lewis, C.
J. Stirling, N. Furukawa and J. Drabowicz for helpful
discussions.
42. M. E. Jung and P. L. Ornstein, Tetrahedron Lett. 30, 947 (1973).
43. L. Ruzicka, P. A. Plattner and H. Wild, Helv. Chim. Acta 28, 395
(1945).
REFERENCES
44. E. L. Eliel and R. S. Ro, J. Am. Chem. Soc. 79, 5995 (1967).
45. K. Iwai and H. J. Shine, J. Org. Chem. 46, 271 (1981).
46. H. J. Shine and W. Yueh, J. Org. Chem. 59, 3553 (1994).
1. H. Meerwein, E. Battenberg, H. Gold, E. Pfeil and G. Wilfang, J.
Prakt Chem. 154, 83 (1939).
Copyright 1999 John Wiley & Sons, Ltd.
J. Phys. Org. Chem. 12, 827–836 (1999)