Substituent Effects on 13C NMR Chemical Shift of Aliphatic Chain Ethers

Abstract

Abstract:

The ¹³C NMR chemical shift for a given carbon atom in aliphatic ether molecules was related to the atomic electronegativity, polarizability and steric effects of the substituents. In this study, the relationship between ¹³C NMR chemical shift (δ_C) and the above parameters were established by multiple variable regression using 153 chemical shift values from 23 aliphatic ethers as the training set. The following formula was obtained: δ_C = 121.134 8+94.365 1Q_i-2.082 3Q_iΣα_x-7.634 7S_H-47.614 9S_O, where Q_i is the partial net charge on the given atom, Σα_xis the polarizability of the atoms near the given atom, S_H and S_O are the steric effect parameters. The stability and prediction capacity of the formula were tested using leave-one-out (LOO) cross-validation (cv) method (R_cv=0.998 0, R₂ cv=0.997 7 and S_cv=0.89), and confirmed by predictions of ¹³C NMR chemical shift of 43 different carbon atoms in 4 compounds.

Key words: ¹³C NMR, chemical shift, electronegativity, atomic polarizability, steric effect, aliphatic ethers

CLC Number:

O482.53

YI Gui-Yuan, CAO Chen-Zhong. Substituent Effects on ¹³C NMR Chemical Shift of Aliphatic Chain Ethers[J]. Chinese Journal of Magnetic Resonance, 2010, 27(2): 172-184.

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Substituent Effects on ¹³C NMR Chemical Shift of Aliphatic Chain Ethers

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