New synthesis of 1,2,4-trithiolane derivatives

Full text of DOI:10.1134/S1070428008090303

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 9, pp. 1403–1405. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.A. Dorofeev, L.G. Shagun, I.A. Tokareva, M.G. Voronkov, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 9,
pp. 1420–1422.
SHORT
COMMUNICATIONS
New Synthesis of 1,2,4-Trithiolane Derivatives
I. A. Dorofeev, L. G. Shagun, I. A. Tokareva, and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail:shag@irioch.irk.ru
Received January 5, 2008
DOI: 10.1134/S1070428008090303
1
Classical reactions of carbonyl compounds with
nucleophilic reagents are catalyzed by acids, generally
by hydrogen chloride. Hydrogen iodide (which is
a stronger acid than hydrogen chloride) was not used
to catalyze such reactions.
C–S–C fragment. The H NMR spectrum of this com-
pound contained one signal from methyl protons at
δ 1.87 ppm, and signals at δC 31.08 and 53.43 ppm
from the methyl carbon atoms and C3 (C5), respec-
tively, were present in the 13C NMR spectrum.
A strong peak from the molecular ion (m/z 180) was
observed in the mass spectrum of 3,3,5,5-tetramethyl-
1,2,4-trithiolane (I), which is consistent with published
data [1, 2].
We were the first to accomplish acid-catalyzed ad-
dition of hydrogen sulfide to aliphatic, alicyclic, aro-
matic–aliphatic, and aromatic ketones in the presence
of hydrogen iodide generated in situ. For this purpose,
a required amount of molecular iodine was dissolved
in the corresponding ketone or its solution in chloro-
form, and hydrogen sulfide was passed through the
mixture. Hydrogen iodide liberated during the process
catalyzed nucleophilic addition of hydrogen sulfide at
the ketone carbonyl group. The products were readily
isolated by column chromatography on silica gel.
Unlike the known method of synthesis of com-
pound I [2] via reaction of acetone with hydrogen
sulfide and sulfur in the presence of diisobutylamine
(yield 44%), the described one-step procedure is ad-
vantageous due to simple manipulations and fast and
easy isolation of the target product.
Likewise, cyclohexanone reacted with hydrogen
sulfide in the presence of iodine to produce 35.5%
of 7,14,15-trithiadispiro[5.1.5.2]pentadecane (II)
Thus the reaction of acetone with hydrogen sulfide
and iodine at –30°C gave 2-sulfanylpropan-2-ol as
primary adduct which was converted into 3,3,5,5-tetra-
methyl-1,2,4-trithiolane (I) in 52% yield (Scheme 1).
The structure of I was confirmed by the IR, 1H and 13C
NMR, and mass spectra. In the IR spectrum of I (film)
we observed an absorption band at 554 cm–1, which
may be assigned to stretching vibrations of the S–S
bond, and a band at 646 cm–1, corresponding to the
1
(Scheme 2). Compound II displayed in the H NMR
spectrum signals from the cyclohexane methylene pro-
tons as a multiplet in the region δ 1.43–2.40 ppm. The
corresponding carbon signals appeared in the 13C NMR
spectrum at δC 25.22, 26.16, and 39.82 ppm, and the
spiro carbon nuclei resonated at δC 80.96 ppm. The
known procedure for the synthesis of 7,14,15-trithia-
Scheme 1.
O
Me
Me
Me
Me
Me
Me
Me
Me
I2
I2
H2S
S
S
S
S
HO
Me
SH
Me
2
+ H2S
Me
Me
OH HO
SH HO
S
S
Me
Me
Me
Me
–H2O
S
I
I2
+
H2S
2HI + S
1403

DOROFEEV et al.
1404
Scheme 2.
O
S
S
SH
OH
S
S
I2
I2, H2S
2
+ H2S
–H2O
S
SH HO
II
Scheme 3.
O
HO
SH
Me
S
S
I2
I2, H2S
Me
2
+ H2S
Me SH HO Me
S
S
–H2O
S
Me
Me
III
dispiro[5.1.5.2]pentadecane (II) is based on the reac-
tion of 1-morpholinocyclohexene with hydrogen sul-
fide in the presence of sulfur [2].
3,3,5,5-Tetramethyl-1,2,4-trithiolane (I). Iodine,
8.74 g (6.8 mmol), was added to a solution of 2 g
(3.4 mmol) of acetone in 5 ml of chloroform. The mix-
ture was cooled to –30°C, and hydrogen sulfide was
passed through the mixture until the initial ketone dis-
appeared completely (30 min). The mixture was then
purged with nitrogen to remove hydrogen sulfide,
allowing it to gradually warm up to room temperature,
and evaporated under reduced pressure, and the residue
(~3 ml) was subjected to column chromatography on
silica gel using chloroform as eluent. Yield 1.6 g
(52%), colorless oil. IR spectrum, ν, cm–1: 554 (S–S),
646 (C–S–C) (cf. [1]). 1H NMR spectrum: δ 1.87 ppm,
s (CH3). 13C NMR spectrum, δC, ppm: 31.08 (CH3),
53.43 (C3, C5). Mass spectrum: m/z 180 [M]+.
Following the proposed procedure, from acetophe-
none we obtained previously unknown 3,5-dimethyl-
3,5-diphenyl-1,2,4-trithiolane (III) in 52% yield
(Scheme 3). The structure of III was confirmed by the
1
13
IR, H and C NMR, and mass spectra. The IR spec-
trum of III (film) contained an absorption band at
545 cm–1, which corresponds to stretching vibrations
of the S–S bond, and the band at 673 cm–1 may be as-
signed to the C–S–C moiety. In the 1H NMR spectrum
of this compound we observed a signal at δ 2.12 ppm
from the methyl groups, and aromatic protons reso-
nated as a multiplet in the region δ 7.31–7.70 ppm.
Signals at δC 26.75 and 70.96 ppm in the 13C NMR
spectrum were typical of the methyl and quaternary
(C3, C5) carbon atoms, respectively. In the mass spec-
trum of 3,5-dimethyl-3,5-diphenyl-1,2,4-trithiolane
(III) a strong peak from the molecular ion (m/z 304)
was present.
7,14,15-Trithiadispiro[5.1.5.2]pentadecane (II)
was synthesized in a similar way from 2 g (2.0 mmol)
of cyclohexanone in the presence of 5.18 g (4.0 mmol)
of iodine (hydrogen sulfide was passed over a period
of ~1 h). Yield 0.94 g (35.5%), colorless crystals,
mp 50–51°C [2]. IR spectrum, ν, cm–1: 534 (S–S), 700
1
(C–S–C). H NMR spectrum: δ 1.43–2.40 ppm, m
Under analogous conditions, benzophenone was
converted into 3,3,5,5-tetraphenyl-1,2,4-trithiolane
(IV) in a poor yield (5–10%). Compound IV was syn-
thesized previously by reaction of thiobenzophenone
with 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione
[3], primary or secondary amines [4, 5], or Chlor-
amine-T [6].
Thus we have developed a new simple and con-
venient procedure for the synthesis of 1,2,4-trithiolane
derivatives by reaction of aliphatic, alicyclic, and
aromatic–aliphatic ketones with hydrogen sulfide in
the presence of molecular iodine.
(CH2). 13C NMR spectrum, δC, ppm: 25.22 (CH2),
26.16 (CH2), 39.82 (CH2), 80.96 (C3, C5).
3,5-Dimethyl-3,5-diphenyl-1,2,4-trithiolane (III)
was synthesized in a similar way from 1.5 g
(1.2 mmol) of acetophenone in the presence of 3 g
(2.4 mmol) of iodine (hydrogen sulfide was passed
over a period of ~1.5 h). Yield 1 g (52%), colorless
thick oil. IR spectrum, ν, cm–1: 545 (S–S), 673
1
(C–S–C). H NMR spectrum, δ, ppm: 2.12 s (6H,
CH3), 7.31–7.70 m (10H, Harom). 13C NMR spectrum,
δC, ppm: 26.75 (CH3), 70.96 (C3, C5), 126.38–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

NEW SYNTHESIS OF 1,2,4-TRITHIOLANE DERIVATIVES
1405
133.14 m (Carom). Found, %: C 62.85; H 5.16; S 32.03.
C16H16S3. Calculated, %: C 63.15; H 5.26; S 31.58.
nos. 05-03-32041, 05-05-64191) and by the Council
for Grants at the President of the Russian Federation
(project no. NSh-4575,2006.3).
The H and 13C NMR spectra were recorded from
1
solutions in CDCl3 on a Bruker DPX-400 spectrometer
at 400 and 100 MHz, respectively. The IR spectra were
measured from samples pelleted with KBr or neat sub-
stances on an IFS-25 spectrometer. The mass spectra
(electron impact, 70 eV) were obtained on a GCMS-
QP5050A instrument (quadrupole mass analyzer). The
progress of reactions and the purity of products were
monitored by TLC on Silufol UV-254 plates using
chloroform as eluent; spots were visualized under UV
light or by treatment with iodine vapor. Silica gel L
(70–230 mesh) was used for column chromatography
(eluent chloroform).
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This study was performed under financial support
by the Russian Foundation for Basic Research (project
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008