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Nucleophilicities of Amines and Amino Acids

Frank Brotzel ,  Herbert Mayr 

LMU München, Department Chemie und Biochemie, Butenandtstrasse 5-13, München 81377, Germany


Rate constants for the reactions of amines and amino acids with substituted benzhydrylium ions have been determined photometrically [1]. The correlation equation log k20 °C = s(N + E), where s and N are nucleophile specific parameters and E is an electrophile specific parameter has been used to determine the nucleophilicity parameters N of various amines and amino acids in aqueous solution and to compare them with N of other nucleophiles [2]. It is found that diethylamine and pyrrolidine have widely differing nucleophilicities despite of comparable Brønsted basicities. Moreover it is shown that α-effect amines [3] like semicarbazide, hydroxylamine or hydrazine do not show enhanced reactivity toward benzhydrylium ions in water. These reactivity parameters are suggested as guidelines for the nucleophilic reactivities of these important molecules in biological and organic chemistry.

[1] S. Minegishi, H. Mayr, J. Am. Chem. Soc. 2003, 125, 286-295.

[2] a) H. Mayr, T. Bug, M. F. Gotta, N. Hering, B. Irrgang, B. Janker, B. Kempf, R. Loos, A. R. Ofial, G. Remennikov, H. Schimmel, J. Am. Chem. Soc. 2001, 123, 9500-9512; b) H. Mayr, B. Kempf, A. R. Ofial, Acc. Chem. Res. 2003, 36, 66-77; c) H. Mayr, A. R. Ofial in Carbocation Chemistry (Eds.: G. A. Olah, G. K. S. Prakash), Wiley, Hoboken, NJ, 2004, Chapt. 13, pp 331-358; d) H. Mayr, A. R. Ofial, Pure Appl. Chem. 2005, 77, 1807-1821; e) For a comprehensive listing of nucleophilicity parameters N and electrophilicity parameters E, see:

[3] Reviews: a) N. J. Fina, J. O. Edwards, Int. J. Chem. Kinet. 1973, 5, 1-26; b) A. P. Grekov, V. Ya. Veselov, Russ. Chem. Rev. 1978, 47, 631-648; c) E. Buncel, I.-H. Um, Tetrahedron 2004, 60, 7801-7825.


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Presentation: poster at 18th Conference on Physical Organic Chemistry, Posters, by Frank Brotzel
See On-line Journal of 18th Conference on Physical Organic Chemistry

Submitted: 2006-05-29 17:05
Revised:   2009-06-07 00:44