Abstract
A new topological approach to predicting the13C NMR chemical shifts of polysubstituted benzenes has been proposed (in the example case of compounds with substituents of one kind of the type C6H6−nXn). The collective interactions of several substituents X [X=CH3, C2H5, iso-C3H7, CF3, COOH, f, Cl, Br, Si(CH3)3] have been expressed in the framework of a regression treatment in terms of two-particle increments. The chemical shift of each carbon atom has been represented in the form of an equation containing 17 parameters. The calculation scheme can be transformed and expanded for use even in the calculation of the spectra of compounds not previously studied. The calculated shifts for some previously investigated compounds and some compounds not previously investigated have been presented. The error in reproducing chemical shifts is equal to 0.2–0.3 ppm (and may be as high as 0.8 ppm for only a few measurements).
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Literature Cited
J. B. Stothers, Carbon-13 NMR Spectroscopy, Academic Press, New York (1972).
F. W. Wehrli and T. Wirthlin, Interpretation of Carbon-13 NMR Spectra, Heyden, London (1976).
W. Bremser, Angew. Chem., Int. Ed. Engl.,27, No. 2, 247–260 (1988).
G. C. Levy and G. L. Nelson, Carbon-13 Nuclear Magnetic Resonance for Organic Chemists, Wiley-Interscience, New York (1972) [Russian translation: Mir, Moscow (1975)].
E. Breitmaier and W. Voelter, Carbon-13 NMR Spectroscopy. High-Resolution Methods and Applications in Organic Chemistry and Biochemistry, Chimie, New York (1987).
V. I. Dostovalova, F. K. Velichko, T. T. Vasil'eva, et al., Org. Magn. Reson.,16, No. 4, 251–260 (1981).
D. F. Ewing, Org. Magn. Reson.,12, No. 9, 499–524 (1979).
J. Bromilov, R. T. C. Brownlee, D. Craik, et al., U. Org. Chem.,45, No. 12, 2429–2438 (1980).
J. Bromilov, R. T. C. Brownlee, D. Craik, and M. Sadek, Magn. Reson. Chem.,24, No. 10, 862–871 (1986).
H. M. Relles, J. Magn. Reson.,39, No. 3, 481–485 (1980).
J. Knuutinen, R. Laatikainen, and J. Paasivirta, and J. PaasivirtaOrg. Magn. Reson.,14, No. 5, 360–365 (1980).
D. K. Dalling, K. H. Ladner, D. M. Grant, and W. R. Woolfenden, J. Am. Chem. Soc.,99, No. 22, 7142–7150 (1977).
Y. Takeuchi, H. Furuyama, S. Fukushi, and S. Fujiwara, J. Chem. Soc. Perkin Trans. II, No. 2, 175–177 (1985).
O. Sudmeijer, A. E. Wilson, and G. R. Hays, Org. Magn. Reson.,22, No. 7, 459–463 (1984).
W. R. Woolfenden and D. M. Grant, J. Am. Chem. Soc.,88, No. 7, 1496–1502 (1966).
13C Data Bank, Vol. 1, Bruker Physik (1976).
H. Nery, D. Canet, B. Azoui, et al., Org. Magn. Reson.,10, 240–244 (1977).
M. Mishima, J. Fujio, R. Takeda,and T. Tsuno, Mem. Fac. Sci., Kyushu Univ., Sec. C,11 No. 1, 97–118 (1978).
T. Kaneda, T. Otsubo, H. Horita, and S. Misumi, Bull. Chem. Soc. Jpn.,53, No. 4, 1015–1018 (1980).
D. J. Iverson, G. Hunter, J. F. Blount, et al., J. Am. Chem. Soc.,103, No. 20 6073–6083 (1981).
W. B. Smith and D. L. Deavenport, J. Magn. Reson.,7, No. 3, 364–369 (1972).
J. M. Briggs and E. W. Randall, J. Chem. Soc. Perkin Trans. II, No. 13, 1789–1791 (1973).
L. Ernst and V. Wrya, J. Magn. Reson.,28, No. 3, 373–375 (1977).
M. A. Hamza, G. Serratrice, and J.-J. Delpuech, Org. Magn. Reson.,16, No. 2, 98–102 (1981).
K. Takahashi, A. Yoshino, K. Hosokawa, and H. Muramatsu, Bull. Chem. Soc. Jpn.,58, No. 2, 755–756 (1985).
J. Siegel, A. Gutierrez, W. B. Schweizer, et al., J. Am. Chem. Soc.,108, No. 7, 1569–1575 (1986).
D. Bruck and M. Rabinovitz, Tetrahedron Lett., No. 47, 4121–4124 (1977).
J. Schraml, V. Chvalovsky, M. Mägi, et al., J. Organomet. Chem.,120, No. 1, 41–47 (1976).
V. I. Dostovalova, T. T. Vasil'eva, F. K. Velichko, Izv. Akad. Nauk SSSR, Ser. Khim., No. 12, 2770–2776 (1988).
V. I. Dostovalova, F. K. Velichko, and R.Kh. Freidlina, Izv. Akad. Nauk SSSR, Ser. Khim., No. 4, 773–778 (1987).
S. Fliszar, Charge Distributions and Chemical Effects, Springer Verlag, New York (1983).
S. Ueji, Tetrahedron Lett.,21, No. 5, 475–478 (1980).
V. I. Dostovalova, Izv. Akad. Nauk SSSR, Ser. Khim., No. 1, 58–60 (1990).
Additional information
V. I. Vernadskii Institute of Geochemistry and Analytical Chemistry, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 2, pp. 62–71, March–April, 1991.
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Dostovalova, V.I., Fedorov, L.A. Topological incremental scheme for calculating13C NMR chemical shifts in polysubstituted benzenes with substituents of one kind. J Struct Chem 32, 208–214 (1991). https://doi.org/10.1007/BF00777189
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DOI: https://doi.org/10.1007/BF00777189