Helv. Chim. Acta 2016, 99, 373 – 377
377
+
þ
2
3
04.2392 (M , C H O ; calc. 304.2397). cis-Fusion of
M. Agarwal, A. Azam, I. Choi, A. R. Bhat, Eur. J. Med. Chem.
011, 46, 4742.
[5] A. Erm, K. Siirde, T. Pehk, K. Leets, Zhur. Org. Khimii 1979,
5, 1593 (Chem. Abstr. 1980, 92, 22612); K. Siirde, T. Valimae,
T. Pehk, A. Erm, H. Rang, K. Leets, Zhur. Org. Khimii 1979,
5, 2028 (Chem. Abstr. 1980, 92, 129086).
[6] K. Kimura, I. Iwata, H. Nishimura, Agric. Biol. Chem. 1982, 46,
387.
2
0
32
2
rings of 7 was established similar to our previous work
3
15a]. The coupling constants J(6,7) = 13.2 and 3.2 sug-
gest that the H–C(6) is axial in the cyclohexene ring,
hence the H–C(1) has an equatorial conformation ( J
1,10) = 5.5). The coupling constants J(3,4) = 11.4 and
.5 suggest that the H–C(3) is axial in the pyran ring.
Based on these data and taking into account the rings
fusion, one can assume only cis-arrangement of H–C(6)
and H–C(3).
To a suspension of K10 clay (10.0 g) in 100 ml of
CH Cl at 10 °C, a solution of citral (12.0 g in 200 ml of
CH Cl ) was added. The mixture was stirred for 3 h at
room temperature and then AcOEt (50 ml) was added.
K10 clay was filtered off and the solvent was distilled off.
The residue was distilled at 69 – 72 °C (2 Torr) to isolate
geranial (1) (3.28 g, 55% based on the content of isomer
in initial mixture) containing 4% neral (2) as impurity
H-NMR data). The distillation residue consisted of ca.
0 compounds (m/z ≥ 268, GC/MS).
[
1
3
1
3
(
1
2
[
[
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2
2
2
2
[
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2
[
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(
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Received October 16, 2015
Accepted February 4, 2016
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2016 Verlag Helvetica Chimica Acta AG, Z u€ rich
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