NMR of sterols and sphingolipids
Extensive 1H and 13C NMR data for sterols and sphingolipid bases are presented in the following papers:
Wilson, W.K., Sumpter, R.M., Warren, J.J., Rogers, P.S., Ruan, B., and Schroepfer, G.J., Jr., Analysis of unsaturated C27 sterols by nuclear magnetic resonance spectroscopy, J. Lipid Res. 37, 1529-1555 (1996).
Kisic, A., Tsuda, M., Kulmacz, R.J., Wilson, W.K., and Schroepfer, G.J., Jr., Sphingolipid bases. A revisitation of the O-methyl derivatives of sphingosine. Isolation and characterization of diacetate derivatives, with revised 13C nuclear magnetic resonance assignments for D-erythro-sphingosine, J. Lipid Res. 36, 787-803 (1995).
Some useful NMR data for unsaturated sterols are also given below.
1
H NMR chemical shifts of unsaturated sterolsData updated to July 1997
Chemical shifts from 500-MHz spectra collected at 25 degrees C, in dilute CDCl3 solution (generally <10 mM)
C27 free sterols
|
Double bond |
H-18 |
H-19 |
H-21 |
|
D 0 |
.647 |
.802 |
.897 |
|
D 4 |
.677 |
1.048 |
.900 |
|
D 5 (cholesterol) |
.678 |
1.008 |
.914 |
|
D 6 |
.691 |
.780 |
.906 |
|
D 7 |
.534 |
.796 |
.920 |
|
D 8 |
.609 |
.950 |
.923 |
|
D 8(14) |
.840 |
.689 |
.929 |
|
D 14 |
.899 |
.822 |
.910 |
|
D 4,6 |
.725 |
.997 |
.909 |
|
D 5,7 |
.620 |
.946 |
.941 |
|
D 5,8 |
.652 |
1.188 |
.934 |
|
D 5,8(14) |
.877 |
.889 |
.941 |
|
D 5,20E |
.545 |
1.010 |
1.628 |
|
D 5,22E |
.693 |
1.010 |
1.009 |
|
D 5,22Z |
.719 |
1.017 |
.956 |
|
D 5,24 |
.680 |
1.009 |
.937 |
|
D 5,25 |
.681 |
1.009 |
.928 |
|
D 6,8 |
.576 |
.793 |
.939 |
|
D 6,8(14) |
.893 |
.643 |
.942 |
|
D 7,9(11) |
.505 |
.902 |
.915 |
|
D 7,14 |
.829 |
.788 |
.925 |
|
D 7,24 |
.536 |
.797 |
.942 |
|
D 8,14 |
.818 |
.991 |
.938 |
|
D 8,24 |
.610 |
.951 |
.946 |
|
D 5,7,9(11) |
.566 |
1.246 |
.922 |
|
D 5,7,9-19-nortriene |
.588 |
.995 |
|
|
Vitamin D3 |
.543 |
.919 |
|
|
D 5,22E,24 |
.709 |
1.012 |
1.045 |
|
D 6,8,14 |
.817 |
.854 |
.955 |
Boldface indicates estimated values
C27 sterol acetates
|
Double bond |
H-18 |
H-19 |
H-21 |
|
D 0 |
.646 |
.816 |
.897* |
|
D 4 |
.676 |
1.061 |
.901* |
|
D 5 (cholesterol Ac) |
.677 |
1.019 |
.914* |
|
D 6 |
.689 |
.794 |
.906* |
|
D 7 |
.533 |
.810 |
.919* |
|
D 8 |
.606 |
.963 |
.923* |
|
D 8(14) |
.838 |
.704 |
.929* |
|
D 14 |
.898 |
.836 |
.910* |
|
D 4,6 |
.724 |
1.010 |
.910* |
|
D 5,7 |
.618 |
.953 |
.941* |
|
D 5,8 |
.650 |
1.200 |
.934* |
|
D 5,8(14) |
.875 |
.899 |
.941* |
|
D 5,20E |
.544 |
1.020 |
1.628* |
|
D 5,22E |
.692 |
1.020 |
1.009* |
|
D 5,22Z |
.720 |
1.027 |
.956* |
|
D 5,24 |
.678 |
1.019 |
.936* |
|
D 6,8 |
.573 |
.806 |
.939* |
|
D 6,8(14) |
.892 |
.657 |
.941* |
|
D 7,9(11) |
.503 |
.916 |
.915* |
|
D 7,14 |
.827 |
.801 |
.924* |
|
D 7,24 |
.533 |
.810 |
.941* |
|
D 8,14 |
.816 |
1.004 |
.938* |
|
D 8,24 |
.607 |
.963 |
.945* |
|
D 5,7,9(11) |
.563 |
1.256 |
.922* |
|
Vitamin D3 Ac |
.540 |
.919* |
|
|
D 5,7,9-19-nortriene |
.594 |
.997* |
|
|
D 5,22E,24 |
.706 |
1.021 |
1.045* |
|
D 6,8,14 |
.814 |
.867 |
.956* |
Methyl resonances sorted in order of increasing chemical shift
C27 free sterols
|
Double bond |
Chemical shift |
|
D 7,9(11) |
.505 |
|
D 7 |
.534 |
|
Vitamin D3 |
.543 |
|
D 5,20E |
.545 |
|
D 5,7,9(11) |
.566 |
|
D 6,8 |
.576 |
|
D 5,7,9-19-nortriene |
.588 |
|
D 8 |
.609 |
|
D 8,24 |
.610 |
|
D 5,7 |
.620 |
|
D 6,8(14) |
.643 |
|
D 0 |
.647 |
|
D 0 |
.647 |
|
D 5,8 |
.652 |
|
D 4 |
.677 |
|
D 5 |
.678 |
|
D 5,24 |
.680 |
|
D 5,25 |
.681 |
|
D 8(14) |
.689 |
|
D 6 |
.691 |
|
D 5,22E,24 |
.709 |
|
D 4,6 |
.725 |
|
D 6 |
.780 |
|
D 7,14 |
.788 |
|
D 6,8 |
.793 |
|
D 7 |
.796 |
|
D 6,8,14 |
.817 |
|
D 8,14 |
.818 |
|
D 14 |
.822 |
|
D 7,14 |
.829 |
|
D 8(14) |
.840 |
|
D 6,8,14 |
.854 |
|
D 5,8(14) |
.877 |
|
D 5,8(14) |
.889 |
|
D 6,8(14) |
.893 |
|
D 0 |
.897 |
|
D 14 |
.899 |
|
D 4 |
.900 |
|
D 7,9(11) |
.902 |
|
D 6 |
.906 |
|
D 4,6 |
.909 |
|
D 14 |
.910 |
|
D 5 |
.914 |
|
D 7,9(11) |
.915 |
|
Vitamin D3 |
.919 |
|
D 7 |
.920 |
|
D 5,7,9(11) |
.922 |
|
D 8 |
.923 |
|
D 7,14 |
.925 |
|
D 5,25 |
.928 |
|
D 8(14) |
.929 |
|
D 5,8 |
.934 |
|
D 5,24 |
.937 |
|
D 8,14 |
.938 |
|
D 6,8 |
.939 |
|
D 5,7 |
.941 |
|
D 5,8(14) |
.941 |
|
D 6,8(14) |
.942 |
|
D 5,7 |
.946 |
|
D 8,24 |
.946 |
|
D 8 |
.950 |
|
D 8,24 |
.951 |
|
D 6,8,14 |
.955 |
|
D 8,14 |
.991 |
|
D 5,7,9-19-nortriene |
.995 |
|
D 4,6 |
.997 |
|
D 5 |
1.008 |
|
D 5,24 |
1.009 |
|
D 5,25 |
1.009 |
|
D 5,20E |
1.010 |
|
D 5,22E,24 |
1.012 |
|
D 5,22E,24 |
1.045 |
|
D 4 |
1.048 |
|
D 5,8 |
1.188 |
|
D 5,7,9(11) |
1.246 |
|
D 5,20E |
1.628 |
Methyl resonances sorted in order of increasing chemical shift
C27 sterol acetates
|
Double bond |
Chemical shift |
|
D 7,9(11) |
.503 |
|
D 7 |
.533 |
|
D 7,24 |
.533 |
|
Vitamin D3 Ac |
.540 |
|
D 5,7,9(11) |
.563 |
|
D 6,8 |
.573 |
|
D 5,7,9-19-nortriene |
.594 |
|
D 8 |
.606 |
|
D 8,24 |
.607 |
|
D 5,7 |
.618 |
|
D 0 |
.646 |
|
D 5,8 |
.650 |
|
D 6,8(14) |
.657 |
|
D 4 |
.676 |
|
D 5 |
.677 |
|
D 5,24 |
.678 |
|
D 6 |
.689 |
|
D 5,22E |
.692 |
|
D 8(14) |
.704 |
|
D 5,22Z |
.720 |
|
D 4,6 |
.724 |
|
D 6 |
.794 |
|
D 7,14 |
.801 |
|
D 6,8 |
.806 |
|
D 7 |
.810 |
|
D 7,24 |
.810 |
|
D 8,14 |
.816 |
|
D 0 |
.816 |
|
D 7,14 |
.827 |
|
D 14 |
.836 |
|
D 8(14) |
.838 |
|
D 6,8,14 |
.867 |
|
D 6,8,14 |
.867 |
|
D 5,8(14) |
.875 |
|
D 6,8(14) |
.892 |
|
D 0 |
.897* |
|
D 14 |
.898 |
|
D 5,8(14) |
.899 |
|
D 4 |
.901* |
|
D 6 |
.906* |
|
D 14 |
.910* |
|
D 4,6 |
.910* |
|
D 5 |
.914* |
|
D 7,9(11) |
.915* |
|
D 7,9(11) |
.916 |
|
D 7 |
.919* |
|
Vitamin D3 Ac |
.919* |
|
D 5,7,9(11) |
.922* |
|
D 8 |
.923* |
|
D 7,14 |
.924* |
|
D 8(14) |
.929* |
|
D 5,8 |
.934* |
|
D 5,24 |
.936* |
|
D 8,14 |
.938* |
|
D 6,8 |
.939* |
|
D 5,7 |
.941* |
|
D 5,8(14) |
.941* |
|
D 6,8(14) |
.941* |
|
D 7,24 |
.941* |
|
D 8,24 |
.945* |
|
D 5,7 |
.953 |
|
D 5,22Z |
.956* |
|
D 6,8,14 |
.956* |
|
D 8 |
.963 |
|
D 8,24 |
.963 |
|
D 5,7,9-19-nortriene |
.997* |
|
D 8,14 |
1.004 |
|
D 5,22E |
1.009* |
|
D 4,6 |
1.010 |
|
D 5 |
1.019 |
|
D 5,24 |
1.019 |
|
D 5,22E |
1.020 |
|
D 5,22E,24 |
1.021 |
|
D 5,22E,24 |
1.021 |
|
D 5,22Z |
1.027 |
|
D 5,22E,24 |
1.045* |
|
D 4 |
1.061 |
|
D 5,8 |
1.200 |
|
D 5,7,9(11) |
1.256 |
Asterisk (*) indicates H-21 (shown for acetate data only)