CHEMISTRY OF DIOXACYCLANES: VII.
was then added, and CCl4 was distilled off with a
545
O
Dean Stark trap. p-Toluenesulfonic acid, 0.1 g (0.3%
per aldehyde, by weight) and 42.3 g diol I were added
to the residue (3,4-dibromocyclohexanecarboxal-
dehyde and toluene). The water formed was azeo-
tropically distilled at 130 C for 5 h. Further workup
was performed as described for compound VII.
2.95 d (2H, CH CH ), 3.25 4.30 m (7H, CH2O
CH2CHCH2), 4.80 5.60 m (2H, CH2=C), 4.65 d (1H,
trans-OC2HO, J 7 Hz), 5.70 d (1H, cis-OC2HO, J
7 Hz), 5.80 6.10 m (1H, C=CH).
2-[4(3)-Chloro-3(4)-hydroxycyclohexyl]-4-(2-
propenyloxymethyl)-1,3-dioxolane (XIX). Hydrogen
chloride was barboted into a mixture of 24 g of di-
oxolane XVIII and 30 ml of diethyl ether at 7 to
5 C. Removal of the ether followed by vacuum dis-
tillation gave compound XIX. The IR spectrum of
2-(p-Chlorophenyl)-4-(2,2-dichlorocyclohexyl-
propylmethoxymethyl)-1,3-dioxolane (XI). Chloro-
form, 22.3 g, was added dropwise with stirring to a
mixture of 50 ml of 50% aqueous NaOH, 10 ml of
benzene, 0.4 g of triethylbenzylammonium chloride,
and 25.5 g of dioxolane VII. The reaction mixture
warmed up to 30 C. After all chloroform had been
added, the mixture was stirred for an additional 3 h,
diluted with diethyl ether, washed with 1% aqueous
acetic acid and water, dried with MgSO4. Removal of
the solvent by distillation followed by vacuum dis-
tillation gave 16.3 g (48%) of compound XI. 1H NMR
spectrum, , ppm: 0.88 1.20 m (1H, CH), 1.40
1.90 m (2H, CH2), 3.20 4.40 m (7H, CH2OCH2
CHCH2), 5.45 s (1H, trans-OC2HO, J 6 Hz), 5.57 s
(1H, cis-OC2HO, J 6 Hz), 7.25 s (4H, C6H4).
1
dioxolane XIX lacks bands at 800 and 920 cm and
1
contains a broad band at 3450 3500 cm characteris-
tic of associated OH group.
REFERENCES
1. Kerimov, A.Kh., Zh. Org. Khim., 2001, vol. 37, no. 1,
pp. 144 147.
2. Richard, S.P., J. Label. Comp., 1974, vol. 10, no. 3,
pp. 381 387.
3. Rohm, R., Wiss. Z. Univ., 1980, vol. 29, no. 2,
pp. 97 106.
4. Jpn. Patent 55-87733, 1981, Ref. Zh. Khim., 1981,
23H113p.
Compounds X, XII XV were prepared in a similar
way.
5. Jpn. Patent 56-139196, 1984, Ref. Zh. Khim., 1984,
4N27p.
4-(2,3-Dibromopropoxymethyl)-2-(p-chloro-
phenyl)-1,3-dioxolane (XVII). Bromine, 17.6 g, was
added dropwise with stiriing to a mixture of 25.5 of
dioxolane VII and 80 ml of chloroform at 10 to
5 C. The resulting mixture was stirred for an addi-
tional 1.5 2 h at that temperature and then washed
with 5% aqueous NaOH and water. The aqueous layer
was treated with chloroform, the extract was com-
bined with the organic layer, and dried with MgSO4.
Removal of the solvent by distillation followed by
vacuum distillation gave compound XVII. IR spec-
6. Hibbert, H. and Timm, J.A., J. Am. Chem. Soc., 1924,
vol. 46, no. 5, pp. 1283 1290.
7. Burt, C.P. and Howlang, F., J. Am. Chem. Soc., 1930,
vol. 52, no. 1, pp. 217 219.
8. Ol’shanova, K.M., Potapova, M.A., and Morozo-
va, N.M., Praktikum po khromatograficheskomu
analizu (Manual on Chromatogaraphic Analysis),
Moscow: Vysshaya Shkola, 1970, pp. 64 66.
9. Kerimov, A.Kh., Babaev, M.G., Alieva, E.S., and
Mishiev, D.E., Zh. Obshch. Khim., 1991, vol. 61,
no. 10, pp. 2328 2332.
10. Kerimov, A.Kh., Babaev, M.G., and Mishiev, D.E.,
Zh. Org. Khim., 1985, vol. 21, no. 3, pp. 645 648.
11. Polyanskii, N.G., Kozova, G.Ya., and Chernyshe-
va, D.A., Khim. Prom st., 1970, no. 2, pp. 87 91.
12. Shostakovskii, S.M., Kolesnikov, R.V., Grigore-
va, V.A., and Grigorev, A.A., Abstracts of Papers,
Vsesoyuznaya konferentsiya Perspektivy razvitiya
khimii karkasnykh soedinenii i ikh primenenie v otras-
lyakh promyshlennosti (All-Union Conf. Prospects
of Chemistry of Skeleton Compounds and Their Indus-
trial Application, Kiev, 1986, p. 97.
1
trum, , cm : 650, 670 (C Br), 780, 810 (C Cl),
1010, 1200 (C O C), 1590 (aromatic ring). Other
absorption bands in the spectrum belong to stretching
1
1
(2820 2880 cm ) and bending (1340 1460 sm )
vibrations of C H bonds in CH and CH2 groups [15].
Compound XVI was prepared in a similar way.
2-(3,4-Epoxycyclohexyl)-4-(2-propenyloxy-
methyl)-1,3-dioxolane (XVIII). To a mixture of
22.4 g of compound VIII and 50 ml of chloroform,
30.4 g of 55% peracetic acid was added with stirring
at 18 20 C over the course of 30 min. The mixture
was stirred for an additional 1.5 2 h at that tempera-
ture and then treated with 5% aqueous sodium car-
bonate, washed with water, and dried with MgSO4.
Removal of the solvent by distillation followed by
13. Yanovskaya, L.A., Dombrovskii, V.A., and Khu-
sid, A.Kh., Tsiklopropany s funktsional’nymi grup-
pami (Cyclopropanes with Functional Groups),
Moscow: Nauka, 1980, pp. 79 95.
14. Rakhmankulov, D.L., Kantor, E.A., and Nurie-
va, R.Kh., Available from VINITI, 1979, Moscow,
no. 4353-79.
1
vacuum distillation gave compound XVIII. H NMR
spectrum, , ppm: 1.25 2.25 m (7H, CH2CH2CHCH2),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 4 2001