1,7-DITHIOXO SYSTEMS.
1657
100.6 MHz (13C). The IR spectra were recorded on
an IFS-25 spectrometer from samples pelleted with
KBr. The progress of reactions was monitored, and
the purity of products was checked, by TLC on Silufol
UV-254 plates.
Reaction of bis(5,5-dimethyl-3-oxo-1-cyclo-
hexenyl) sulfide (VII) with hydrogen sulfide. A so-
lution of 0.8 g (3 mmol) of dioxo sulfide VII in 40 ml
of anhydrous methanol was saturated with gaseous
HCl for 1 h at 40 C, and hydrogen sulfide was
passed through the solution for 10 h at 40 to 30 C.
The mixture was left to stand for 12 h at 70 C,
purged with argon at 30 C to remove HCl and H2S,
filtered, poured onto ice, and extracted with ether.
The extract was washed with ice water to pH 4 5,
dried over Na2SO4 at 5 C, and evaporated under
reduced pressure. The residue, 0.31 g, was a dark
violet thick oil with an unpleasant odor. It contained
26 1.7% of sulfide VIII. 1H NMR spectrum (CDCl3),
, ppm: 2.22 (4H, 10-H), 2.35 (4H, 6-H), 2.36 (4H,
3-(4-Oxa-1-azoniacyclohexylidene)-3 -thioxobis-
(5,5-dimethyl-1-cyclohexenyl) sulfide perchlorate
(III). A cooled solution of 0.86 g (5 mmol) of 3-mer-
capto-5,5-dimethyl-2-cyclohexenethione (V) in a mix-
ture of 10 ml of dry acetonitrile and 3 ml of dry
chloroform was added dropwise to a solution of
1.64 g (5 mmol) of 1-(3-chloro-5,5-dimethyl-2-cyclo-
hexenylidene)morpholinium perchlorate (IV) in 10 ml
of dry acetonitrile, while stirring under argon at 10 C.
The mixture was stirred for 2.5 h (until hydrogen
chloride no longer evolved) and was poured into ice
water. The product was extracted into chloroform, and
the extract was washed with ice water and dried over
CaCl2 at 5 C. The solvent was removed, and the
residue (a red brown oily substance) was washed
with cold methanol and dried in a vacuum at reduced
temperature. Yield 0.9 g (39%); dark orange powder,
decomposing at 117 121 C. The decomposition point
and 1H NMR and IR spectral parameters of the
product were identical to those reported in [1].
Found, %: C 50.91; H 7.04; Cl 7.62; N 2.27; S 13.48.
C20H30ClNO5S2. Calculated, %: C 51.78; H 6.47;
Cl 7.66; N 3.02; S 13.81.
4
12-H), 2.74 (4H, 4-H), 6.08 t (1H, 8-H, J = 1.3 Hz),
4
6.93 t (1H, 2-H, J = 1.3 Hz). 13C NMR spectrum
(CDCl3), C, ppm: 27.19 (C13), 27.55 (C14), 33.99
(C12), 34.32 (C5), 42.22 (C11), 42.37 (C6), 50.27
(C10), 59.36 (C4), 123.12 (C8), 134.14 (C2), 157.78
(C1), 158.15 (C7), 195.21 (C9), 230.67 (C3).
Reaction of 3-(4-oxa-1-azoniacyclohexylidene)-
3 -thioxobis(5,5-dimethyl-1-cyclohexenyl) sulfide
perchlorate (III) with hydrogen sulfide. Dry hydro-
gen sulfide was passed over a period of 10 min
through a solution of 0.46 g (1 mmol) of perchlorate
III in 15 ml of dry acetonitrile, cooled to 40 C.
Triethylamine, 0.02 ml, was added, and hydrogen
sulfide was passed through the mixture over a period
of 4 h at 40 C. The mixture was allowed to gradually
warm up to 15 C, and hydrogen sulfide was passed
through the mixture for an additional 4 h at that tem-
perature. The progress of the reaction was monitored
by TLC using chloroform ethyl acetate (3:1) as
eluent. The mixture was purged with argon to remove
hydrogen sulfide and was evaporated under reduced
pressure. The dark red solid residue was dissolved in
ethyl acetate, and the solution was passed through
a column charged with silica gel (40/100 mesh). The
column was eluted with ethyl acetate to isolate 0.09 g
(40%) of 5,5-dimethyl-3-morpholino-2-cyclohexene-
thione (VI) as orange crystals with mp 160 162 C
(published data [5]: mp 161 162 C). Found, %:
C 64.67; H 8.59; N 6.19; S 13.83. C12H19NOS. Cal-
culated, %: C 64.00; H 8.45; N 6.22; S 14.22.
Reaction of 3-chloro-5,5-dimethyl-2-cyclohexene-
thione (IX) with Na2S2O3. Anhydrous sodium thio-
sulfate, 0.16 g (1 mmol), was added in portions over
a period of 15 min to a solution of 0.37 g (2 mmol)
of chlorothione IX in 10 ml of anhydrous methanol,
stirred at 45 C. The mixture was allowed to slowly
warm up to 20 to 30 C and was stirred for 7 h at
that temperature. TLC analysis (eluent chloroform)
revealed formation of dithioxo sulfide I in 40 min
after the reaction started. The unreacted Na2S2O3 was
filtered off, and the filtrate was poured into 60 ml
of ice water and extracted with benzene. The extract
was washed with ice water and dried over Na2SO4.
Removal of the solvent left 0.18 g of a residue which
contained dithioxo sulfide I, initial chlorothione IX,
and a number of unidentified products. IR spectrum,
1
, cm : 1110 (C S), 1545 (C C S) (compound I);
1123 (C S), 1579 (C C) (compound IX).
Condensation of 3-mercapto-5,5-dimethyl-2-
cyclohexenethione (V). a. Compound V, 0.1 g, was
placed in a flask which was then purged with argon
and left to stand for 20 days at 10 C. TLC analysis
(eluent chloroform ethyl acetate, 3:1) showed the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 11 2001