218
BREDIKHINA et al.
Method B. (4R)-4-(2-Allyphenoxymethyl)-1,3,2-
(S)-1-(tert-Butylamino)-3-[(4-morpholino-1,2,5-
thiadiazol-3-yl)oxy]-2-propanol [(S)-thymolol (S)-
(Ic)] was synthesized similarly from dioxathiolanes
(4R)-(VIIc) and t-BuNH2. The reaction product was
characterized as hemimaleate, yield 85%, mp 197
198 C (from ethanol), [ ]2D0 7.0 (c 5, 1 N HCl)
{publ.: mp 198 199 C, [ ]2D0 7.5 (c 20, 1 N HCl)
[26]}.
dioxathiolane 2-oxide (4R)-(VIId). To a stirred solu-
tion of 2.08 g (10 mmol) of (S)-3-(2-allylphenoxy)-
propane-1,2,-diol (S)-(VId) in 10 ml of dichloro-
methane was added within 15 min dropwise at 20 C
1.19 g (10 mmol) of thionyl chloride in 5 ml of
dichloromethane. The stirring was continued for 1 h,
then the solvent was distilled off; an isomeric mixture
of (R)-4-(2-allyphenoxymethyl)-1,3,2-dioxathiolane
2-oxides (VIId) was obtained in quantitative yield.
REFERENCES
(4R)-4-[(4-Morpholino-1,2,5-thiadiazol-3-yl)oxy-
methyl]-1,3,2-dioxathiolane 2-oxides (4R)-(VIIc)
were prepared similarly to sulfites (4R)-VIId along
method B using 2 equiv of triethylamine for binding
HCl. Yield 75%. The spectral characteristics are the
same as published in [14].
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(4R)-4-Naphthyloxymethyl-1,3,2-dioxathiolane
2-oxides (4R)-(VIIb) were prepared as a mixture of
diastereomers similarly to sulfites (4R)-VIId along
method B in quantitative yield. The spectra pattern is
identical to superimposed spectra of individual iso-
mers published in [14].
trans-4-(4-bromophenyloxymethyl)-1,3,2-di-
oxathiolane 2-oxides (trans)-(VIIh) were prepared
similarly from rac-3-(4-bromophenyloxy)propane-
1,2-diol (VIh) and thionyl chloride along method B.
From the reaction mixture separated the trans-dia-
stereomer (yield 78%0, mp 100 101 C. IR spectrum,
1
, cm : 1595 (Ar), 975, 1050 (C O, S O), 1227
(S=O). 13C NMR spectrum, , ppm: 66.90 (OCH2),
68.72 (OCH2), 77.76 (CH); 114.20, 116.55, 132.58,
157.13 (Ar).
(S)-1-(2-(Allylphenoxy)-3-isopropylamino-2-
propanol [(S)-alprenol (S)-(Id)]. A mixture of 0.4 g
(0.075 mmol) of dioxathiolanes (4R)-VIId, 1.6 g
(27 mmol) of i-PrNH2, and 6 ml of DMF was heated
to 60 70 C for 45 h. On completion of reaction the
mixture was washed with 20 ml of 1 N NaOH water
solution, and the product was extracted into ethyl
acetate (3 60 ml). The extract was dried with
MgSO4, the solvent was removed in a vacuum.
(S)-alprenol was isolated as a base, [ ]2D0 14.1 (c 3.8,
EtOH) {publ.: [ ]D20 15.2 (4%, EtOH) [20]}.
(S)-3-Isopropylamino-1-(naphthyl-1-oxy)-2-
propanol [(S)-propanolol (S)-(Ib)] was prepared in a
similar way. The residue after removing ethyl acetate
was dissolved in ether, and dry HCl was passed
through the solution. The precipitate was filtered off.
We isolated (S)-propanolol hydrochloride in 80%
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1996, vol. 19, no. 5, pp. 517 522; Lamm, B.,
Ankner, K., and Frantsi, M., Acta Nhem. Scand.,
yield, mp 193 194 C. [ ]D20
24.5 (c 1.0,
EtOH) {publ.: mp 194 196 C, [ ]2D0 25.1 (c 1.05,
EtOH) [25]}.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 2 2002