-ALKYLTHIO- -CHLORO- , -DICARBONYL COMPOUNDS
743
The mixture was acidified with 10% hydrochloric acid
to pH 5 6, the organic phase was separated, and the
aqueous phase was extracted with two portions of
diethyl ether. The extracts were combined with the
organic phase, dried over MgSO4, and evaporated, and
the residue was subjected to fractional distillation to
isolate compounds V and IVa.
(OCH2), 83.50 (CHCl), 168.63 (OC O), 187.69
(C O). Found, %: Cl 15.50; S 14.37. C8H13ClO3S.
Calculated, %: Cl 15.78; S 14.25.
Reaction of dichloroaldehyde semithioacetals
IIa and IIb with sodium hydride. 1-Propanethiol,
0.1 mol, was added dropwise with stirring at 8 to
5 C to a solution of 0.15 mol of aldehyde Ia or Ib
in 50 ml of dry diethyl ether. The mixture was kept
for 2 h at that temperature and cooled to 15 C, and
0.22 mol of sodium hydride was added in portions.
The mixture was allowed to slowly warm up to room
temperature, the precipitate was filtered off, the sol-
vent was removed from the filtrate, and the residue
was subjected to fractional distillation. The reaction
of compound IIa with sodium hydride gave products
IVa and V, and from compound IIb ester IVc was
obtained.
Dichloroacetophenone (V). Yield 40%. bp 80
81 C (0.09 mm) [5].
3-Chloro-1-phenyl-3-propylthio-1,2-propanedi-
one (IVa). Yield 40%. bp 128 130 C (0.08 mm),
n2D0 = 1.5784. IR spectrum, , cm : 1685 (C O),
1
1
1750 (C O). H NMR spectrum (acetone-d6), , ppm:
0.97 t (3H, CH3), 1.50 m (2H, CH2), 2.55 m (2H,
SCH2), 7.65 m (3H, Harom), 8.20 m (2H, Harom),
9.50 s (1H, CHCl). Found, %: Cl 13.65; S 12.65.
C12H13ClO2S. Calculated, %: Cl 13.84; S 12.47.
Compounds IVb and IVc were synthesized in
a similar way.
REFERENCES
3-Chloro-3-isopropylthio-1-phenyl-1,2-propane-
1. Guseinov, F.I. and Moskva, V.V., Zh. Org. Khim.,
dione (IVb). Yield 40%. bp 120 C (0.09 mm), nD20
=
1994, vol. 30, p. 360.
1.5672 [1].
2. Guseinov, F.I., Tagiev, S.Sh., and Moskva, V.V.,
Ethyl 3-chloro-2-oxo-3-propylthiopropionate
Russ. J. Org. Chem., 1995, vol. 31, p. 86.
(IVc). Yield 80%. bp 66 68 C (10 mm), n2D0 = 1.4607.
3. Guseinov, F.I., Burangulova, R.N., and Moskva, V.V.,
1
IR spectrum, , cm : 1680 (C O), 1755 (C O).
Russ. J. Org. Chem., 1997, vol. 33, p. 415.
1H NMR spectrum (acetone-d6), , ppm: 0.95 t (3H,
CH3), 1.20 t (3H, CH3), 1.60 q (2H, CH2), 2.50 t
(2H, SCH2), 4.30 q (2H, OCH2), 9.40 s (1H, CHCl).
4. Guseinov, F.I., Izv. Ross. Akad. Nauk, Ser. Khim.,
1998, p. 747.
5. Svoistva organicheskikh soedinenii (Properties of
Organic Compounds), Potekhin, A.A., Ed., Leningrad:
Khimiya, 1984, p. 34.
13C NMR spectrum (acetone-d6), C, ppm: 16.36 and
17.28 (CH3), 25.02 (CH2), 66.88 (SCH2), 69.57
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 5 2003