628 JOUrNAL OF CHEMICAL rESEArCH 2007
(3 ¥ 300 ml). The organic extracts were combined, dried (Na2SO4),
and the solvent removed in vacuo to give 3,6-dimethoxycyclohex-
4-ene-1,2-diol 6 as a colourless crystals (4.3 g, 87%); m.p. 49–50°C
(79), 129 (67), 114 (98), 99 (40), 87 (100), 75 (31); Found: C, 51.02;
H, 6.37. C16H24O10 requires: C, 51.06; H, 6.43%.
dl-1,4-di-O-methyl-myo-inositol: rac-liriodendritol (12): 154 mg
(0.4 mmol) of tetraacetate 11 (0.11 g, 0.199 mmol) was dissolved
in 5 ml of 0.5 N H2SO4. The resulting mixture was stirred at room
temperature for 6 h. The acid was neutralised with BaCO3. The solid
material was filtered and the filtrate was concentrated under reduced
pressure to yield 1,4-di-O-methyl-myo-inositol: rac-liriodendritol 12
(67 mg, 83%). M.p. 226–228°C (recrystallised from CH3CH2OH):
1H NMr and 13C NMr are agreement with data given in the
literature.7a 1H NMr (400 MHz CD3OD ppm): d 4.17–4.21 (br s,
4H, –OH), 3.81 (br s, 1H, –CHO), 3.63 (s, 3H, –OMe), 3.53 (br s,
1H, –CHO), 3.39 (br s, 1H, –CHO), 3.34 (s, 3H, –OMe), 3.14 (br s,
1H, –CHO), 3.05 (dd, 1H, J = 9.9 and 2.8 Hz, –CHO), 2.63 (t, 1H,
J = 9.5 Hz, –CHO); 13C NMr (100 MHz CD3OD ppm): δ 82.5, 80.9,
74.4, 72.5, 71.3, 68.4, 54.6 (x2, –OMeC-1 and –OMeC-4).
1
(Lit16; 48–49°C) (recrystallised from CH2Cl2/Et2O): H NMr (400
MHz CDCl3 ppm) d 5.65 (s, 2H, –CH=CH), 4.56 (s, 2H, –OH), 3.75
(br d, A part of AA'XX' system, JAX = 5.9 Hz, 2H, –CH–OH), 3.55
(br d, ¥ part of AA'XX' system, JAX = 5.9 Hz, 2H, –CH–OCH3), 3.36
(s, 6H, -OCH3); 13C NMr (100 MHz CDCl3 ppm) δ 127.1 (x2), 81.2
(x2), 74.2 (x2), 57.2 (x2).
(1RS,2RS,3RS,6RS)-3,6-diisopropoxycyclohex-4-ene-1,2-diol
(7): In a 250 ml round-bottomed flask fitted with a stirring bar at
room temperature, sodium metal (ca 2.23 g) was added to dry 2-
propanol (150 ml) and the resulting suspension was stirred until all
the sodium had disappeared and hydrogen liberation ceased. 5,6-
dibromocyclohex-2-ene-1,4-diol 5 (2.85 g, 10.5 mmol) was added
slowly and the mixture was stirred for 24 h at room temperature to
provide complete conversion. The reaction mixture was quenched
with saturated aqueous NH4Cl (20 ml) and extracted with EtOAc
(3 ¥ 300 ml). The organic extracts were combined, dried (Na2SO4),
and the solvent removed in vacuo to give 3,6-diisopropoxycyclohex-
4-ene-1,2-diol 7 (4.23 g, 67%). Colourless crystals, m.p. 125–127°C
(recrystallised from CH2Cl2/Et2O): Ir (KBr): 3399, 2972, 2896,
1651, 1598, 1488, 1381, 1212, 1121, 1097, 1068, 983, 784 cm-1;
1H NMr (400 MHz CDCl3 ppm): d 5.64 (s, 2H, –CH=CH), 3.92 (br
d, A part of AA'XX' system, JAX = 5.1 Hz, 2H, –CH–OH), 3.62 (br
d, ¥ part of AA'XX' system, JAX = 5.1 Hz, 2H, –CH–OCH(CH3)2),
3.84 (heptet, 2H, OCH(CH3)2), 3.10 (s, 2H, –OH), 1.18 (d, 6H,
J = 6.2 Hz, –(CH3)2), 1.17 (d, 6H, J = 5.9 Hz, –(CH3)2); 13C NMr
(100 MHz CDCl3 ppm): δ 128.3 (x2), 77.3 (x2), 74.7 (x2), 71.6 (x2),
23.2 (x2), 22.7 (x2); EIMS m/z (%): 230 (0.5), 201 (4), 190 (7), 170
(79), 141 (34), 128 (67), 110 (48), 99 (46), 86 (100), 83 (46), 81 (16),
70 (11), 57 (14); Found: C, 62.90; H, 9.75. C12H22O4 requires: C,
62.58; H, 9.63%.
The author is indebted to Department of Chemistry and
Atatürk University for financial support and Res. Assistant
Baris Anil for the NMr spectra, Dr. Ebru Mete for mass
spectra and elemental analyses.
Received 15 October 2007; accepted 12 November 2007
Paper 07/4890
doi: 10.3184/030823407X262463
References
1
2
3
(a) S. Posternak, C. R. Acad. Sci., 1919, 169, 138; (b) T. Posternak,
Chemistry of the cyclitols–the cyclitols, 1965. Hermann, Paris.
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(1RS,2RS,3RS,6RS)-3,6-dimethoxycyclohex-4-ene-1,2-diyl
diacetate (9): 3,6-dimethoxycyclohex-4-ene-1,2-diol
6 (2.5 g,
14.4 mmol) of was dissolved in 20 ml of acetyl chloride and the
resulting solution was stirred at room temperature during overnight.
The excess of unreacted acetyl chloride was evaporated (60°C,
20 mmHg). The residue was dissolved in CH2Cl2 and filtered over
silica gel. Evaporation of solvent gave 3,6-dimethoxycyclohex-4-ene-
1,2-diyl diacetate 9 (3.5 g, 95%). M.p. 44–45°C (recrystallised from
CH2Cl2/Et2O): Ir (KBr): 2949, 2831, 1753, 1371, 1242, 1222, 1097,
1048, 953, 784 cm-1; 1H NMr (400 MHz CDCl3 ppm): d 5.74 (s,
2H, –CH=CH), 5.13 (m, 2H, –CHOAc), 4.03 (br d, 2H, –CHOCH3),
3.29 (s, 6H, –OCH3), 1.99 (s, 6H, –OCOCH3); 13C NMr (100 MHz
CDCl3 ppm): δ 170.3 (x2), 127.9 (x2), 78.7 (x2), 72.3 (x2), 56.5 (x2),
21.0 (x2); EIMS m/z (%): 258 (0.5), 198 (10), 156 (45), 155 (65),
142 (13), 138 (17), 127 (48), 114 (100), 113 (58), 100 (48), 99 (42),
95 (18), 81 (14), 71 (19), 55 (7); Found: C, 55.73; H, 7.26 C12H18O6
requires: C, 55.81; H, 7.02%;
4
5
6
7
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8
9
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G. Vogel, J. Med. Chem., 1999, 42, 1262.
dl-2,3,5,6-tetra-O-acetyl-1,4-di-O-methyl-myo-inositol (11): A 100 ml
two-necked, round-bottomed flask, equipped with a magnetic stirrer
and a nitrogen inlet, was charged with 1.16 g (14.2 mmol) of NMO,
4 ml of water, and 4 ml of acetone. To this solution were added ca.
10 mg of OsO4 (0.08 mmol) and 3.66 g (14.2 mmol) of diacetate
9. The resulting mixture was stirred vigorously under nitrogen at
0°C. During the overnight stirring, the reaction mixture became
homogeneous. After stirring 18 h, sodium bisulfite (100 mg) and 2 g
of Florisil slurried in 1 ml of water were added, the slurry was stirred
for 1 h, and the mixture was filtered through a short pad 2 g of celite
in a 50 ml sintered glass funnel. The celite cake was washed with
acetone (3 ¥ 10 ml). The filtrates were combined and solvent was
removed to give the crude diacetate-diol 11. The same procedure
as described above was applied for acetylation of 11 (4.75 g, 85%).
M.p. 130–132°C (Lit6d; 139 or 155–156°C) (recrystallised from
Ethyl acetate/hexane): Ir (KBr): 2978, 2942, 2845, 1749, 1486,
1434, 1372, 1229, 1103, 1143, 1047, 945, 919, 718 cm-1; 1H NMr
(400 MHz CDCl3 ppm): d 5.67 (t, 1H, J = 2.6 Hz, H-2, –CHOAc),
5.25 (t, 1H, J = 10.0 Hz, H-6, –CHOAc), 5.02 (t, 1H, J = 9.9 Hz, H-5,
–CHOAc), 4.83 (dd, 1H, J = 10.3 and 2.9 Hz, H-3, –CHOAc), 3.66 (t,
1H, J = 10.0 Hz, H-4, –CH-OMe), 3.42 (s, 3H, –OCH3), 3.34 (dd, 1H,
J = 9.9 and 2.9 Hz, H-1, –CH–OMe), 3.30 (s, 3H, –OCH3), 2.14 (s,
3H, –OCOCH3), 2.05 (s, 3H, –OCOCH3), 2.04 (s, 3H, –OCOCH3),
2.02 (s, 3H, –OCOCH3); 13C NMr (100 MHz CDCl3 ppm): δ 170.5,
170.2, 170.1, 170.0, 78.6, 77.3, 72.7, 71.5, 71.3, 66.8, 60.9, 58.5,
21.1 (x2), 21.0 (x2); EIMS m/z (%): 376 (0.5), 334 (3), 317 (3), 243
(10), 224 (22), 213 (59), 182 (98), 171 (38), 158 (45), 155 (78), 140
15 (a) O. Plettenburg, S. Adelt, G. Vogel and H.J. Altenbach, Tetrahedron
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16 V. Cerè, G. Matovani, F. Peri, S. Pollicino and A. ricci, Tetrahedron,
2000, 56, 1225.
PAPER: 07/4890