Hydrolysis of Bis[5,5-dimethyl-3-(4-oxa-1-azonia-cyclohexylidene)-1-cyclohexenyl] sulfide diperchlorate

Article abstract of DOI:10.1023/A:1013100209089

Hydrolysis of bis[5,5-dimethyl-3-(4-oxa-1-azoniacyclohexylidene)-1-cyclohexenyl] sulfide diperchlorate, as well as of bis(5,5-dimethyl-3-thioxo-1-cyclohexenyl) sulfide, in the system MeCN-Et₃N yields a mixture of bis(5,5-dimethyl-3-oxo-1-cyclohexenyl) sulfide and isomeric 5,5-dimethyl-3-oxo-1-cyclohexenyl 3,3-dimethyl-5-oxo-1-cyclohexenyl sulfide. The structure of the products and their ratio were established by ¹H and ¹³C NMR and IR spectroscopy.

Full text of DOI:10.1023/A:1013100209089

Russian Journal of Organic Chemistry, Vol. 37, No. 9, 2001, pp. 1335 1337. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 9, 2001,
pp. 1400 1402.
Original Russian Text Copyright
2001 by Timokhina, Panova, Kanitskaya, Toryashinova, Sokol’nikova, Fedorov, Voronkov.
Hydrolysis of Bis[5,5-dimethyl-3-(4-oxa-1-azonia-
cyclohexylidene)-1-cyclohexenyl] Sulfide Diperchlorate*
L. V. Timokhina, G. M. Panova, L. V. Kanitskaya, D.-S. D. Toryashinova,
O. V. Sokol’nikova, S. V. Fedorov, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
Received December 20, 2000
Abstract Hydrolysis of bis[5,5-dimethyl-3-(4-oxa-1-azoniacyclohexylidene)-1-cyclohexenyl] sulfide diper-
chlorate, as well as of bis(5,5-dimethyl-3-thioxo-1-cyclohexenyl) sulfide, in the system MeCN Et3N yields
a mixture of bis(5,5-dimethyl-3-oxo-1-cyclohexenyl) sulfide and isomeric 5,5-dimethyl-3-oxo-1-cyclohexenyl
3,3-dimethyl-5-oxo-1-cyclohexenyl sulfide. The structure of the products and their ratio were established by
1H and 13C NMR and IR spectroscopy.
We previously [1] synthesized bis(5,5-dimethyl-3-
thioxo-1-cyclohexenyl) sulfide (II) by the action of
hydrogen sulfide on bis[5,5-dimethyl-3-(4-oxa-1-
azoniacyclohexylidene)-1-cyclohexenyl] sulfide (I).
described in [2]. The resulting dioxo sulfide III also
had mp 80 C. When the hydrolysis was carried out
with a threefold amount of triethylamine, we obtained
a mixture of sulfide III and its isomer with a different
With the goal of synthesizing its oxygen-containing location of the double bond in one of the cyclohexene
analog, bis(5,5-dimethyl-3-oxo-1-cyclohexenyl) sul-
fide (III), we have studied hydrolysis of diperchlorate
I. The formation of dioxo sulfide III in the reaction
of 3-chloro-5,5-dimethyl-2-cyclohexenone with Na2S
was reported in [2], but its yield was as low as 5%.
The structure of III was confirmed by the IR and
UV spectra.
rings, namely 5,5-dimethyl-3-oxo-1-cyclohexenyl
3,3-dimethyl-5-oxo-1-cyclohexenyl sulfide (IV); the
isomer ratio was 8:2 (Scheme 2).
The structure of products III and IV and their
1
ratio were established by the H and 13C NMR spectra
using APT multipulse sequence and two-dimensional
techniques (HETCOR and NOESY), as well as quan-
titative approaches to analysis of mixtures of organic
compounds [3]. The spectral parameters of dioxo
sulfides III and IV are given in table. An independent
proof for the structure of IV was obtained by the IR
spectrum of its mixture with isomer III; three car-
bonyl absorption bands were present at 1717, 1649,
The hydrolysis of diperchlorate I was carried out in
acetonitrile at 50 60 C in the presence of a catalytic
amount of triethylamine. As a result, we isolated
dioxo sulfide III in 45% yield (Scheme 1). The struc-
1
ture of III was proved by the H NMR, IR, and UV
spectra. However, its melting point (mp 80 81 C) was
considerably different from that given in [2] (mp 176
177 C). Therefore, we have reproduced the procedure
1
and 1668 cm . The first of these belongs to the
unconjugated carbonyl group in IV, and the two latter,
Scheme 1.
____________
*
This study was financially supported by the Russian Founda-
tion for Basic Research (project no. 98-03-32863a).
1070-4280/01/3709-1335$25.00 2001 MAIK Nauka/Interperiodica

1336
TIMOKHINA et al.
Scheme 2.
to the conjugated carbonyl groups in III and IV. The
hydrolysis of dithioxo sulfide II in the system aceto-
nitrile triethylamine at 0 5 C gave a mixture of the
same isomers III and IV at a ratio of 8.7:1.3.
with ice water, dried over Na2SO4, and evaporated.
The yellow oily residue was kept for 5 days at 5 C,
and the crystals thus formed were washed with hexane
and dried under reduced pressure. We isolated 0.3 g
(45%) of bis(5,5-dimethyl-3-oxo-1-cyclohexenyl)
sulfide (III) as colorless crystals with mp 80 81 C
EXPERIMENTAL
1
(published data [2]: mp 176 177 C). H NMR spec-
1
The H and 13C NMR spectra of mixtures of com-
trum (CDCl3), , ppm: 1.08 s (12H, CH3), 2.28 s (4H,
4
C4H2), 2.42 d (4H, C6H2, J = 1.3 Hz), 6.16 t (2H,
pounds III and IV were recorded on a Varian VXR-
500S spectrometer at 500.1 (1H) and 125.5 MHz (13C)
using CDCl3 as solvent. Quantitative 13C NMR data
were obtained with a pulse delay of 2.5 s (90 pulse);
Chromium tris(acetylacetonate), c = 0.02 M, was used
as relaxant. The relative error in determination of the
components was 4.6%. The two-dimensional NMR
spectra (HETCOR and NOESY) were obtained on
a Bruker DPX-400 spectrometer at 400.13 (1H) and
100.6 MHz (13C). The IR spectra were measured on
an IFS 25 instrument in KBr. The UV spectra were
recorded on a Specord UV-Vis spectrophotometer.
The progress of reactions was monitored, and the
purity of products was checked, by TLC on Silufol
UV-254 plates using chloroform ethyl acetate (3:1)
as eluent.
Reaction of bis[5,5-dimethyl-3-(4-oxa-1-azonia-
cyclohexylidene)-1-cyclohexenyl] sulfide diper-
chlorate (I) with H2O. a. To a solution of 1.5 g
(2.4 mmol) of diperchlorate I in 36 ml of acetonitrile,
heated to 40 C, we added dropwise while stirring
18 ml of water and then 0.02 ml of triethylamine.
The mixture was stirred for 6 h at 50 60 C, cooled,
and poured into 120 ml of ice water. The product was
4
1
HC C, J = 1.3 Hz). IR spectrum, , cm : 1582
(C C S), 1658 (C O); published data [2]: IR spec-
1
trum (CHCl3), , cm : 1580 (C C S), 1660 (C O).
UV spectrum (MeCN), max, nm (log ): 214 (4.18),
275 (4.16), 309 (4.12). Published data [2]: UV spec-
trum (EtOH), max, nm (log ): 232 (3.96), 278 (3.97),
313 (3.90). Found, %: C 69.20; H 8.06; S 11.15.
C16H22O2S. Calculated, %: C 69.06; H 7.91; S 11.51.
b. The reaction was carried out with 1.5 g
(2.4 mmol) of salt I in 36 ml of acetonitrile, 9 ml
of H2O, and 0.06 ml of triethylamine as described
above in a. The product was extracted into diethyl
ether, and the extract was washed with ice water,
dried over Na2SO4, and evaporated. The residue,
an orange thick oil, was treated with hexane and dried
under reduced pressure. We isolated 0.58 g (87%) of
a mixture of bis(5,5-dimethyl-3-oxo-1-cyclohexenyl)
sulfide (III) and 5,5-dimethyl-3-oxo-1-cyclohexenyl
3,3-dimethyl-5-oxo-1-cyclohexenyl sulfide (IV) as
a light yellow powder with mp 68 70 C. IR spectrum,
1
, cm : 1582 (C C S); 1649, 1668, 1717 (C O).
Found, %: C 69.01; H 7.81; S 11.69. C16H22O2S.
extracted into benzene, and the extract was washed Calculated, %: C 69.06; H 7.91; S 11.51.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001

HYDROLYSIS OF BIS[5,5-DIMETHYL-3-(4-OXA-1-AZONIA-. . .
1H and 13C NMR spectra of compounds II, III, and IV
1337
II
III
IV
Atom
no.
C, ppm
, ppm (J, Hz)
C, ppm
, ppm (J, Hz)
C, ppm
, ppm (J, Hz)
C1
C2
148.53
138.56
155.11
129.00
161.53
119.58
6.92 t
6.10 t
5.70 t
(4J2, 6 = 1.2)
(4J2, 6 = 1.3)
(4J2, 6 = 1.2)
C3
C4
C5
C6
232.61
59.70
34.58
45.12
196.21
50.69
34.01
44.56
195.59
50.83
33.94
43.72
2.77 s
2.28 s
2.18 s
2.34 d
2.39 d
2.25 br.s
(4J2, 6 = 1.2)
(4J2, 6 = 1.3)
C7
C8
148.53
138.56
155.11
129.00
122.05
43.27
2.95 d
(4J8, 12 = 1.7)
C9
232.61
59.70
34.58
45.12
196.21
50.69
34.01
44.56
206.34
52.15
37.49
C10
C11
C12
2.35 s
151.09
6.30 t
(4J12, 8 = 1.7)
1.08 s
C13
C14
27.10
27.10
1.07 s
27.77
27.77
1.06 s
27.78a
28.74a
0.99 s
a
Alternative assignment is possible.
Hydrolysis of bis(5,5-dimethyl-3-thioxo-1-cyclo-
cyclohexenyl sulfide (IV) as a light yellow powder
with mp 71 73 C. IR spectrum, , cm : 1582
(C C S); 1656, 1670, 1718 (C O).
1
hexenyl) sulfide (II). To a suspension of 0.1 g
(0.3 mmol) of dithioxo sulfide II in 10 ml of aceto-
nitrile, cooled to 0 5 C, we added dropwise with
stirring 2 ml of water and then a solution of 0.01 ml
of triethylamine in 1 ml of acetonitrile. The mixture
was stirred for 8 h at 0 5 C, left overnight at 5 C,
filtered, and poured into 30 ml of ice water. The prod-
uct was extracted into diethyl ether, and the extract
was washed with ice water, dried over Na2SO4, and
evaporated. The residue, a yellow thick oil, was
treated with hexane and dried under reduced pressure.
We obtained 0.05 g (60%) of a mixture of bis(5,5-di-
methyl-3-oxo-1-cyclohexenyl) sulfide (III) and 5,5-di-
methyl-3-oxo-1-cyclohexenyl 3,3-dimethyl-5-oxo-1-
REFERENCES
1. Timokhina, L.V., Panova, G.M., Toryashino-
va, D.-S.D., Albanov, A.I., Sokol’nikova, O.V., and
Voronkov, M.G., Russ. J. Org. Chem., 1999, vol. 35,
no. 9, pp. 1408 1409.
2. Dalgaard, L. and Lawesson, S.-O., Acta Chem. Scand.,
Ser. B, 1974, vol. 28, pp. 1077 1090.
3. Kanitskaya, L.V., Cand. Sci. (Chem.) Dissertation,
Irkutsk, 1990.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 9 2001