Marked difference between 1,1,3,3-tetramethyl-2-oxobutyl and 1,3,3-trimethyl-2-oxocyclopentyl systems in the Grunwald-Winstein relationships in solvolysis

Chemistry Letters

Volumn , Issue 9, 1996, Pages 763-764

  Takeuchi, Ken'ichi ^a   Ohga, Yasushi ^a   Ushino, Takuhiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0030355818     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1996.763     Document Type: Article

References (18)

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9. 2: C, 67.57; H, 9.92%.
10. 1a
11. In this communication the errors are given by standard errors.
12. 2
13. D. J. Raber, W. C. Neal, Jr., M. D. Dukes, J. M. Harris, and D. L. Mount, J. Am. Chem. Soc., 100, 8137 (1978).
14. T parameters much improves the linearity (1 = 0.58 ± 0.02, m = 0.67 ± 0.02, c = 0.04 ± 0.03, r = 0.998): D. N. Kevill and S. W. Anderson, J. Org. Chem., 56, 1845 (1991).
15. 2
16. The large solvolysis rate ratio of 22 in 80% ethanol at 25 °C between 2-chloro-2,4,4-trimethylpentane and 2-chloro-2-methylpropane has been attributed to relief of B-strain in the former: see, H. C. Brown and R. S. Fletcher, J. Am. Chem. Soc., 71, 1845 (1949); H. C. Brown, "The Nonclassical Ion Problem," with comments by P. v. R. Schleyer, Plenum Press, New York (1977), p. 22.
17. The large solvolysis rate ratio of 22 in 80% ethanol at 25 °C between 2-chloro-2,4,4-trimethylpentane and 2-chloro-2-methylpropane has been attributed to relief of B-strain in the former: see, H. C. Brown and R. S. Fletcher, J. Am. Chem. Soc., 71, 1845 (1949); H. C. Brown, "The Nonclassical Ion Problem," with comments by P. v. R. Schleyer, Plenum Press, New York (1977), p. 22.
18. We have found that the nucleophilic solvent assistance is negligible in the solvolysis of a homologous compound 2-chloro-2,4,4-trimethylpentane: the result will be reported elsewhere.