Artículos de revistas
A Carbon-13 Nmr Study Of 2-substituted-5-n′,n′-dimethylaminophenyl-n,n-dimethylcarbamates: Correlations Of Substituent-induced Chemical Shifts With Substituent Parameters
Registration in:
Canadian Journal Of Analytical Sciences And Spectroscopy. , v. 44, n. 6, p. 180 - 185, 1999.
12056685
2-s2.0-0033234302
Author
Rittner R.
Barbarini J.E.
Hoehr N.F.
Institutions
Abstract
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). 44 6 180 185 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