A Carbon-13 Nmr Study Of 2-substituted-5-n′,n′-dimethylaminophenyl-n,n-dimethylcarbamates: Correlations Of Substituent-induced Chemical Shifts With Substituent Parameters

The Carbon-13 NMR spectra of seven 2-substituted-5-N′,N′-dimethylaminophejiyl N,N-dimethylcarbamates and of the parent compound were recorded, and unequivocal assignments of the chemical shifts through the use of HETCOR and COLOC sequences were performed. Large intramolecular interaction chemical shifts (ICS) were observed for C-1 (-9.3 to +3.4 ppm) and moderate values for C-2 to C-6 (-3.0 to +3.8), mostly for the oxygen-bearing derivatives [OCH3, NO2 and C(O)CH3]. Correlation analyses for the substituent-induced chemical shifts (SCS) with several sets of substituent parameters were carried out, through SSP (Single Substituent Parameter), DSP (Dual Substituent Parameter) and DSP-NLR (Dual Substituent Parameter Non-Linear Resonance) treatments, as well as through multiple regression analysis. Good correlations were found for C-1, C-4, C-5 and C-6 (r>0.97), while for C-2, C-3 and C-10 (the carbonyl carbon) just rough trends were observed (r>0.89). The resonance contribution is predominant for C-4 and C-6 (unsubstituted carbons) and for C-5, while for C-2 and C-3 (and C-10) the electronegativity parameter is the prevailing component and for C-1 both contributions are relevant. Negative p values were found for several correlations (reverse substituent effect).

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Taylor, P., (1985) Goodman and Gilman's "The Pharmacological Basis of Therapeutics", p. 110. , A. G. Gilman, L. S. Goodman, T. W. Rall and F. Murad (eds.), 7a ed., Macmillan Publishing Co., New York

Aeschlimann, J.A., Reinert, M., (1931) J. Pharmacol.Exp.Ther., 43, p. 413

Millner O.E., Jr., Stanley, J.W., Purcell, W.P., (1974) J. Med. Chem., 17, p. 13

Hetnarski, B., O'Brien, R.D., (1975) J. Agric. Food Chem., 23, p. 709

Yamagami, C., Takao, N., Nishioka, T., Fujita, T., Takeuchi, Y., (1984) Org. Magn. Res., 22, p. 439

Yamagami, C., Sonoda, C., Takao, N., Tanaka, M., Yamada, J., Horisaka, K., Fujita, T., (1982) Chem. Pharm. Bull., 30, p. 4175

Perjessy, A., Jones, R.G., McClair, S.L., Wilkins, M., (1983) J. Org. Chem., 48, p. 1266

Barbarini, J.E., Rittner, R., Höehr, N.F., Suwinski, J., (1997) Bioorg. Chem., 25, p. 37

Höehr, N.F., (1993), Ph. D. Thesis, Universidade Estadual de CampinasJackman, L.M., Sternhell, S., (1969) "Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry," 2nd Ed., , Pergamon Press, Oxford

Laplanche, L.A., Rogers, M.T., (1963) J. Am. Chem. Soc., 85, p. 3728

Martins, M.A.P., Rittner, R., (1980) Org. Magn. Res., 14, p. 522

Breitmaier, E., Voelter, W., (1987) "Carbon-13 NMR Spectroscopy," 3rd Ed., , VCH, Weinheim

Rittner, R., Barbarini, J.E., (1998) Can. J. Anal. Sci. Spectrosc., 43, p. 14

Duddeck, H., (1987) Top. Stereochem., 16, p. 219

Charton, M., (1983) Top. Curr. Chem., 114, p. 57

Shorter, J., (1994) Pure Appl. Chem., 66, p. 2451

Charton, M., (1981) Prog. Phys. Org. Chem., 13, p. 119

Yamagami, C., Sai, T., Takao, N., (1987) Aust. J. Chem., 40, p. 2005

Bromilow, J., Brownlee, R.T.C., Craik, D.J., Sadek, M., Taft, R.W., (1980) J. Org. Chem., 45, p. 2429

Exner, O., Dahn, H., Péchy, P., (1992) Magn. Reson. Chem., 30, p. 381

Exner, O., (1988) Correlation Analysis of Chemical Data, , Plenum, New York

Bromilow, J., Brownlee, R.T.C., Craik, D.J., Fiske, P.R., Rowe, J.E., Sadek, M., (1981) J. Chem. Soc., Perkin Trans., 2, p. 753

Canto, E.L., (1996), Ph. D. Thesis, Universidade Estadual de CampinasLewin, A.H., Frucht, M., (1975) Org. Magn. Res., 7, p. 206

(1985) Statgraphics, Statiscal Graphics System, , STSC Inc., Utah

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