Structure-reactivity relationships in the rate of esterification by acetylimidazole: The influence of the second hydroxy group and of the length of the N-ω-hydroxy-n-alkyl chain in 3-(N-methyl, N-ω-hydroxy-n-alkyl)ammo-2-tert-butylpropan-1-ols

Journal of the Chemical Society. Perkin Transactions 2

Volumn , Issue 5, 1997, Pages 851-852

  Madder, Annemieke ^a   De Clercq, Pierre J ^a   Maskill, Howard ^b  

^a GHENT UNIVERSITY   (Belgium)

^b NEWCASTLE UNIVERSITY   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0347173875     PISSN: 03009580     EISSN: None     Source Type: Journal    
DOI: 10.1039/a608033b     Document Type: Article

References (20)

1. I. Steels, P. J. De Clercq and H. Maskill, J. Chem. Soc., Chem. Commun., 1993, 294.
2. For examples of the hydrolysis of AcIm involving amino alcohols, see (a) D.G. Oakenfull and W. P. Jencks, J. Am. Chem. Soc., 1971 ,93, 178; (b) D. G. Oakenfull, K. Salvesen and W. P. Jencks, J. Am. Chem. Soc., 1971, 93, 188; for examples of esterification of amino alcohols with AcIm, see (c) L. Anoardi and U. Tonellato, J. Chem. Soc., Chem. Commun., 1977, 401.
3. For examples of the hydrolysis of AcIm involving amino alcohols, see (a) D.G. Oakenfull and W. P. Jencks, J. Am. Chem. Soc., 1971 ,93, 178; (b) D. G. Oakenfull, K. Salvesen and W. P. Jencks, J. Am. Chem. Soc., 1971, 93, 188; for examples of esterification of amino alcohols with AcIm, see (c) L. Anoardi and U. Tonellato, J. Chem. Soc., Chem. Commun., 1977, 401.
4. For examples of the hydrolysis of AcIm involving amino alcohols, see (a) D.G. Oakenfull and W. P. Jencks, J. Am. Chem. Soc., 1971 ,93, 178; (b) D. G. Oakenfull, K. Salvesen and W. P. Jencks, J. Am. Chem. Soc., 1971, 93, 188; for examples of esterification of amino alcohols with AcIm, see (c) L. Anoardi and U. Tonellato, J. Chem. Soc., Chem. Commun., 1977, 401.
5. For a recent review on hydrogen bonding, see F. Hibbert and J. Emsley, Adv. Phys. Org. Chem., 1990, 26, 255.
6. For studies of intramolecular hydrogen bonding in some substituted amino alcohols, see (a) A. M. De Roos and G. A. Bakker, Rec. Trav. Chim. Pays-Bas, 1962, 81, 219; (b) M. G. Zaitseva, S. V. Bogatkov and E. M. Cherkasova, Zh. Obs. Khim., 1964, 35, 2056;
7. For studies of intramolecular hydrogen bonding in some substituted amino alcohols, see (a) A. M. De Roos and G. A. Bakker, Rec. Trav. Chim. Pays-Bas, 1962, 81, 219; (b) M. G. Zaitseva, S. V. Bogatkov and E. M. Cherkasova, Zh. Obs. Khim., 1964, 35, 2056;
8. A. F. Casy and M. M. A. Hassan, Can. J. Chem., 1969, 47, 1587;
9. (d) R. Mathis, M.-T. Maurette, C. Godechot and A. Lates, Bull. Soc. Chim. Fr., 1970, 3047;
10. (e) P. Gilli, V. Bertolasi, V. Ferrelti and G. Gilli, J. Am. Chem. Soc., 1994, 116, 909;
11. (f) J. Hine and M. N. Khan, Ind. J. Chem., Sect. B, 1992, 31, 427.
12. For studies on the basicity of amino alcohols, see (a) S. V. Bogatkov, V. N. Romaslov, N. I. Kholdyakov and E. M. Cherkasova, Zh. Obsch. Khim., 1959, 39, 247; (b) S. V. Bogatkov, E. Y. Skobeleva and E. M. Cherkasova, Zh. Obsch. Khim., 1966, 36, 138; B. A. Koralev, M. A. Mal'tseva, A. I. Tarasov and V. A. Vasnev, Zh. Obsch. Khim., 1974, 44, 833;
13. For studies on the basicity of amino alcohols, see (a) S. V. Bogatkov, V. N. Romaslov, N. I. Kholdyakov and E. M. Cherkasova, Zh. Obsch. Khim., 1959, 39, 247; (b) S. V. Bogatkov, E. Y. Skobeleva and E. M. Cherkasova, Zh. Obsch. Khim., 1966, 36, 138; B. A. Koralev, M. A. Mal'tseva, A. I. Tarasov and V. A. Vasnev, Zh. Obsch. Khim., 1974, 44, 833;
14. For studies on the basicity of amino alcohols, see (a) S. V. Bogatkov, V. N. Romaslov, N. I. Kholdyakov and E. M. Cherkasova, Zh. Obsch. Khim., 1959, 39, 247; (b) S. V. Bogatkov, E. Y. Skobeleva and E. M. Cherkasova, Zh. Obsch. Khim., 1966, 36, 138; B. A. Koralev, M. A. Mal'tseva, A. I. Tarasov and V. A. Vasnev, Zh. Obsch. Khim., 1974, 44, 833;
15. (d) G. Stevens, S. Chen, P. Huyskens and S. De Jaegere, Bull. Soc. Chim. Belg., 1991, 100, 493.
16. a values in water have been reported for the conjugate acids of 1,2-, 1,3-, 1,4- and 1,5-amino alcohols: 9.50, 10.09, 10.38 and 10.61 respectively (see ref. 5d); the relative order follows the reduced influence of the inductive effect of HO as the chain lengthens,
17. The hydrogen is not counted in the ring size designation in accord with a linear proton transfer.
18. Six-membered ring transition states are particularly favoured for linear hydrogen transfers: (a) E. A. Dorigo and K. N. Houk, J. Am. Chem. Soc., 1987, 109, 2195;
19. (b) P. Camilleri, C. A. Marby, B. Odell, H. S. Rzepa, R. N. Shepard, J. J. P. Stervart and D. J. Williams, J. Chem. Soc., Chem. Commun., 1989, 1722.
20. Fig. 2 shows the minimum energy conformation of several low-energy conformations found. Geometry calculated using Macromodel V3.0: W. C. Still, F. Mohamadi, N. G. J. Richards, W. C. Guida, M. Lipton, R. Liskamp, G. Chang, T. Hendrickson, F. DeGunst and W. Hasel, Department of Chemistry, Columbia University, New York, NY 10027, USA.