OXIDATION OF TERPENOID DIOLS WITH CHLORINE DIOXIDE
1545
completeness for θ < 30.51° was of 98.8%. The
structure was solved by the direct method and refined
using full-matrix PLS along F2 using SHELХTL
software package [17]. Nonhydrogen atoms were
refined under anisotropic approximation; hydrogen
atoms, besides those of OH group, were localized
according to the space electron density peaks and were
included into refinement under isotropic approxima-
tion in the rider model. The OH hydrogen position was
refined independently under isotropic approximation.
Final parameters of the structure refinement were as
follows: R1 = 0.0278, wR2 = 0.0650 for reflections with
I > 2σ(I); R1 = 0.0419, wR2 = 0.0666 for all reflections,
GOOF = 1.002, absolute structural parameter of
0.00(6), maximal and minimal peaks of space electron
density were 0.185/–0.171 е Å–3.
J 3.2, 4.7, 8.0, 15.3), 1.57 d.d (1Н, Н2, J 9.3, 14.3),
2.00 d.d.d (1Н, Н5, J 6.3, 9.0, 15.3), 3.22 d.d.d (1Н,
Н4, J 4.0, 8.0, 9.0), 3.88 s (1Н, ОН3), 4.15 d (1Н, ОН4,
J 4.0). 13С NMR spectrum (DMSO-d6), δС, ppm: 15.82
(С10), 17.83 (С7), 17.83 (С6), 18.73 (С1), 25.98 (С5),
26.75 (С9), 29.25 (С8), 29.84 (С2), 70.12 (С3), 71.24 (С4).
Caranediol-3β,4α (IV). [α]D –1.7° (c 1.6, acetone),
mp 81–82°С. IR spectrum, ν, cm–1: 3374, 2984, 2926,
2864, 1449, 1121, 1067, 949. 1Н NMR spectrum
(DMSO-d6), δ, ppm (J, Hz): 0.60–0.67 m (2Н, Н1, Н6),
0.93 s (3Н, С10Н3), 0.95 s (2Н, С8Н3), 1.03 s (3Н,
С9Н3), 1.08 d.d (1Н, Н2, J 4.0, 15.0), 1.52 d.d.d (1Н,
Н5, J 7.8, 9.9, 13.0), 1.80 m (1Н, Н2, J 15.0), 1.86 d.d
(1Н, Н5, J 7.2, 13.0), 3.11 d.d.d (1Н, Н4, J 3.9, 7.2,
9.9), 4.03 s (1Н, ОН3), 4.24 d (1Н, ОН4, J 3.9). 13С
NMR spectrum (DMSO-d6), δС, ppm: 16.14 (С7),
19.92 (С6), 20.02 (С9), 20.91 (С1), 28.42 (С5), 28.99
(С8), 34.10 (С2), 71.67 (С3), 73.44 (С4).
The X-ray diffraction data were deposited in the
Cambridge Crystallographic Data Centre.
Pinanediol-2α,3α (V). Mp 56–57°С, [α]D +3.1° (c
8.3, CHCl3). IR spectrum, ν, cm–1: 3468 (ОН), 3292,
2920, 1480, 1376, 1266, 1164, 1122, 1086, 1052,
Caranediol-3α,4α (I). [α]D +14° (acetone), mp 69–
70°С. IR spectrum, ν, cm–1: 3323, 2990, 2959, 2930,
1441, 1375, 1140, 1061, 930, 868. Н NMR spectrum
1
1
(DMSO-d6), δ, ppm (J, Hz): 0.51 d.d.d (1Н, Н1, J 4.3,
9.5, 13.8), 0.70 d.d.d (1Н, Н6, J 2.5, 6.3, 9.5), 0.87 s
(3Н, С10Н3), 0.96 s (3Н, С8Н3), 1.04 s (3Н, С9Н3), 1.06
d.d (1Н, Н2, J 4.3, 15), 1.62–1.75 m (2Н, Н5), 1.92 d.d
(1Н, Н2, J 9.5, 15), 2.95 d.d.d (1Н, Н4, J 7.1, 9.3,
13.8), 3.66 s (1Н, ОН3), 4.10 d (1Н, ОН4, J 7.1). 13С
NMR spectrum (DMSO-d6), δС, ppm: 72.51 (С4),
69.09 (С3), 33.96 (С2), 29.29 (С8), 27.18 (С5), 27.02
(С9), 22.53 (С6), 17.63 (С1), 17.03 (С7), 15.84 (С10).
1014, 956, 949, 906. Н NMR spectrum (CDCl3), δ,
ppm (J, Hz): 0.92 s (3Н, С8Н3), 1.26 s (3Н, С9Н3),
1.29 s (3Н, С10Н3), 1.37 d (1Н, Н7, J 10.5), 1.63
d.d.d.d (1Н, Н4, J 2.5, 5.1, 7.4, 13.9), 1.90 m (1Н, Н5),
1.99 d.d (1Н, Н1, J 5.7, 5.9), 2.17 m (1Н, Н7), 2.42 m
(1Н, Н4), 3.24 s (1Н, ОН), 3.63 d (1Н, ОН, J 5.9),
3.97 d.d (1Н, Н3, J 5.4, 9.3). 13С NMR spectrum
(CDCl3), δС, ppm: 73.7 (С2), 68.9 (С3), 53.8 (С1), 40.4
(С5), 38.8 (С6), 37.9 (С4), 29.5 (С10), 27.9 (С7), 27.7
(С9), 24.0 (С8).
Caranediol-3α,4β (II). Pale-yellow oily substance,
nD 1.4750, [α]D +62.9 (с 0.8, CHCl3). IR spectrum, ν,
cm–1: 3421, 2932, 2868, 1454, 1377, 1140, 1045, 926.
1Н NMR spectrum, (CDCl3), δ, ppm (J, Hz): 0.57–0.71
m (2Н, Н1, Н6), 1.02 s (3Н, С8Н3), 1.05 s (3Н, С9Н3),
1.18 s (3Н, С10Н3), 1.39 m (1Н, Н2), 1.42 m (1Н, Н5),
1.77 d.d (1Н, Н2, J 8.8, 15), 1.84 br.s (1Н, ОН), 2.12
br.s (1Н, ОН), 2.31 m (1Н, Н5), 3.53 d.d (1Н, Н4, J
3.3, 7.0). 13C NMR spectrum (CDCl3), δС, ppm: 71.75
(С4), 71.13 (С3), 28.72 (С8), 28.36 (С2), 25.60 (С5),
25.00 (С10), 18.00 (С7), 17.80 and 17.48 (С1, С6),
15.07 (С9).
Pinanediol-2α,3β (VI). Mp 165–168°С, [α]D +49.0°
(с 13, CHCl3). IR spectrum, ν, cm–1: 3332 (ОН), 2920,
1456, 1390, 1372, 1356, 1166, 1124, 1088, 1058, 1024,
1
1000, 920, 898, 852. H NMR spectrum (CDCl3), δ,
ppm (J, Hz): 0.94 s (3Н, С10Н3), 1.25 s (3Н, С8Н3),
1.35 s (3Н, С9Н3), 1.46 d (1Н, Н7, J 10.2), 1.64 d.d
(1Н, Н4, J 6.6, 14.3), 1.88–1.97 m (3Н, Н1, Н5), 2.13
m (1Н, Н7, J 10.5), 2.46 d.d.d (1Н, Н4, J 4.5, 10.2,
14.3), 4.17 d.d (1Н, Н3, J 6.6, 10.2). 13С NMR spec-
trum (CDCl3), δС, ppm: 78.5 (С2), 73.9 (С3), 54.9 (С1),
40.2 (С5), 39.1 (С6), 34.8 (С4), 27.5 (С8), 25.4 (С7),
24.7 (С9), 22.8 (С10).
Caranediol-3β,4β (III). [α]D +42.7° (с 1.0, CHCl3),
mp 43–44°С. IR spectrum, ν, cm–1: 3451, 2994, 2934,
Metal acetylacetonates were prepared according to
[21].
1
2864, 1373, 1125, 1051, 984, 908. Н NMR spectrum
(DMSO-d6), δ, ppm (J, Hz): 0.47 d.d.d (1Н, Н6, J 3.2,
9.2, 12.3), 0.57 d.d.d (1Н, Н1, J 4.9, 9.2, 14.2), 0.96 s
(3Н, С8Н3), 1.10 and 1.11 s (3Н each, С10Н3, С9Н3),
1.40 d.d (1Н, Н2, J 4.9, 14.3), 1.46 d.d.d.d (1Н, Н5,
General procedure of terpenoid diols oxidation
with chromic acid. The oxidizer solution (1 g of
Na2Cr2O7·2H2O, 1.27 ml of conc. H2SO4, and 12 ml of
H2O) was added during 30 min to the solution of 1 g
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 8 2013