A new method for the synthesis of organosulfur trifluorides

Article abstract of DOI:10.1081/SCC-120021841

Simple, convenient and universal method of the different types of organosulfur trifluorides synthesis, with common formula RSF3 where R = dialkylamino group, aromatic or heterocyclic radical, was elaborated. The method consists in the reaction of thiosulf

Full text of DOI:10.1081/SCC-120021841

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A New Method for the Synthesis of Organosulfur
Trifluorides
V. E. Pashinnik a , E. G. Martyniuk a , M. R. Tabachuk a , Yu. G. Shermolovich a & L. M.
Yagupolskii a
a Institute of Organic Chemistry of the NAS of Ukraine , Murmanska, Kyiv, Ukraine
Published online: 20 Aug 2006.
To cite this article: V. E. Pashinnik , E. G. Martyniuk , M. R. Tabachuk , Yu. G. Shermolovich & L. M. Yagupolskii (2003) A
New Method for the Synthesis of Organosulfur Trifluorides, Synthetic Communications: An International Journal for Rapid
Communication of Synthetic Organic Chemistry, 33:14, 2505-2509, DOI: 10.1081/SCC-120021841
To link to this article: http://dx.doi.org/10.1081/SCC-120021841
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 14, pp. 2505–2509, 2003
A New Method for the Synthesis of
Organosulfur Trifluorides
V. E. Pashinnik, E. G. Martyniuk, M. R. Tabachuk,
*
Yu. G. Shermolovich, and L. M. Yagupolskii
Institute of Organic Chemistry of the NAS of Ukraine,
Murmanska, Kyiv, Ukraine
ABSTRACT
Simple, convenient and universal method of the different types of
organosulfur trifluorides synthesis, with common formula RSF3
where R ¼ dialkylamino group, aromatic or heterocyclic radical,
was elaborated. The method consists in the reaction of thiosulfurous
acid diamides, diaryldisulfides or diheteryldisulfides with chlorine in
the presence of potassium fluoride excess.
Key Words: Disulfide; Dialkylaminotrifluoro sulfurane; Aryl tri-
fluoro sulfurane.
*Correspondence: Yu. G. Shermolovich, Institute of Organic Chemistry of
the NAS of Ukraine, Murmanska, 5, Kyiv, 02094, Ukraine; E-mail: sherm@
ukrpack.net.
2505
DOI: 10.1081/SCC-120021841
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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2506
Pashinnik et al.
Dialkylaminosulfur trifluorides are widely used in the organic synthe-
sis for substitution of different functional groups in the molecules for
fluorine atoms, and also as starting compounds in the synthesis of various
types of organosulfur compounds.[1–5] The usage of arylsulfur trifluorides
as fluorinating agents is also known.[4]
The method based on reaction of dialkylamino trimethylsilanes with
sulfur tetrafluoride in autoclave[6–8] or in the solution of ether at
low temperature[1] is widely used for the synthesis of dialkylaminosulfur
trifluorides, and arylsulfur trifluorides were obtained by the reaction of
fluorine or silver difluoride with diaryldisulfides.[9–11]
To the best of our knowledge heterylsulfur trifluorides containing
SF3 group at carbon atom of heterocycle were not obtained till now.
As one can see, the methods of organosulfur trifluorides synthesis are
not universal and can be used only for the synthesis of certain type of
fluorosulfuranes. They are based upon the usage of highly reactive,
toxic, and hardly available reagents (sulfur terafluoride, fluorine, silver
difluoride), what restricts the possibility of these methods application.
We have found a simple and convenient on the synthetic point of
view method of different types of organosulfur trifluoride synthesis,
namely: dialkylaminosulfur trifluorides, arylsulfur trifluorides and benzo-
thiazolyl-2-sulfur trifluorides. The method consists in the reaction of
thiosulfurous acid diamides or diaryl disulfides or di(benzothiazolyl-2)
disulfide with chlorine at presence of potassium fluoride excess.
The reaction proceeds at addition of chlorine solution in acetonitrile
to the suspension of potassium chloride and corresponding disulfide in
acetonitrile, or at passing through of gaseous chlorine in calculated quan-
tity. The optimal yields of dialkylamino-, aryl-, and heterylsulfur trifluor-
ides are obtained at the molar relation of disulfide:chlorine 1:5. The yields
of dialkylaminosulfur trifluorides are 60–67% and yields of arylsulfur
trifluorides and benzothiazolylsulfur trifluoride are near quantitative
taking into consideration the starting disulfide.
Scheme 1.

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Organosulfur Trifluorides
2507
EXPERIMENTAL
1
All melting points are uncorrected. H NMR and 19F NMR spectra
were recorded at 300 and 288 MHz on Varian VXR-300 spectrometer
using TMS and CCl3F as internal standards. All works were conducted
in argon-atmosphere using dry solvents and spray dried potassium
fluoride.
Piperidinosulfur trifluoride (Ia). The solution of chlorine (28.4 g,
0.4 mol) in acetonitrile (270 mL) was added at 10–15ꢀC during 3.5 h to
the stirred suspension of the bispiperidide of thiosulfurous acid (18.6 g,
0.08 mol) and potassium fluoride (58.0 g, 1.0 mol) in acetonitrile
(100 mL). Reaction mixture was stirred 2 h at 20ꢀC, the precipitate was
filtered and filtrate was evaporated in vacuum 10–20 mm Hg at 20–25ꢀC.
The desired product (Ia) was obtained by the distillation of the residue in
vacuum. Yield 18.6 g. (67%). B.p. 75–76ꢀC (12 mm Hg), nD20 1.4515.[1]
19F NMR (diethyl ether): ꢀ ¼ 57.97 (2Fa), 20.77 (Fe).
Morpholinosulfur trifluoride (Ib) was obtained from bismorpholide of
thiosulfurous acid (11.8 g, 0.05 mol), potassium fluoride (93 g, 1.6 mol),
and chlorine (17.8 g, 0.25 mol) as described for compound (Ia). Yield
10.5 g (60%). B.p. 41–42ꢀC (0.5 mm Hg), n2D0 1.4540.[1] 19F NMR (ether):
ꢀ ¼ 56.74 (d, JFa ¼ 55 Hz, 2Fa), 18.08 (T, JFe ¼ 55 Hz, 1Fe).
e
a
–F
–F
Phenylsulfur trifluoride (Ic). a). The solution of chlorine (3.55 g,
0.05 mol) in acetonitrile (40 mL) was added at 20ꢀC during 3.5 h to the
stirred suspension of diphenyl disulfide (2.2 g, 0.01 mol) and potassium
fluoride (10.4 g, 0.18 mol) in acetonitrile (30 mL). Reaction mixture was
stirred 1 h at 20ꢀC, the precipitate was filtered and filtrate was evaporated
in vacuum 10–20 mmHg at 20ꢀC. The residuary fuming liquid was distilled
in vacuum. Yield 2.71 g (87.5%). b). The chlorine (42.6 g, 0.6 mol)
was passed through the stirred suspension of diphenyldisulfide (24.0 g,
0.11 mol) and potassium fluoride (65.0 g, 1.12 mol) in acetonitrile at
10ꢀC till the intermediately formed red color of the reaction mixture
was disappeared (ꢁ4 h). The precipitate was filtered, the filtrate was
evaporated in vacuum 10–20 mm Hg at 20ꢀC and residue was distilled in
vacuum. Yield 33.2 g (98%). B.p. 70–71ꢀC (12 mm Hg). Found: C 44, 10;
H 3, 12; S 19,60. Calcd. for C6H5F3S: C 43.37; H 3.03; S 19,29. 19F NMR
(ether): ꢀ ¼ 57.24 (d, JFa ¼ 65 Hz, 2Fa), ꢂ42.58 (t, JFe ¼ 65 Hz, 1Fe).
e
a
–F
–F
p-Nitrophenylsulfur trifluoride (Id) was obtained from di( p-nitro-
phenyl)disulfide (11.0 g, 0.035 mol), potassium fluoride (34.8 g, 0.6 mol),
and chlorine (12.0 g, 0.17 mol) in acetonitrile (200 mL) as described for
compound (Ic) (method a). Yield 12.7 g. (98%). M.p. 57–58ꢀC (from
CCl4).[11] 19F NMR (CD3CN): ꢀ ¼ 60.34 (d, Ja ¼ 70 Hz, 2Fa), ꢂ45.60
e
–F
F
(t, J eF ¼ 70 Hz, 1Fe).
a
–F

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2508
Pashinnik et al.
Benzothiazolyl-2-sulfur trifluoride (Ie). The solution of chlorine
(10.7 g, 0.15 mol) in acetonitrile (100 mL) was added at 20ꢀC during 3 h
to the stirred suspension of di(benzothiazolyl-2) disulfide (11.0 g,
0.033 mol) and potassium fluoride (34.8 g, 0.6 mol) in acetonitrile
(100 mL). Reaction mixture was stirred 1 h at 20ꢀC, the precipitate was
filtered and filtrate was evaporated in vacuum 10–20 mm Hg at 20ꢀC. The
solid residue was purified by crystallization from hexane. Yield 14.1 g.
(95.5%). M.p. 76–77ꢀC. 19F NMR (CD3CN): ꢀ ¼ 60.03 (d, Ja ¼ 51 Hz,
e
–F
F
2Fa), ꢂ29.00 (T, JFe ¼ 51 Hz, 1Fe). H NMR (CD3CN): ꢀ ¼ 7.64–7.70
a
1
–F
(m, 2H); 8.04–8.07 (m, 1H); 8.32–8.35 (m, 1H). Found: C 37.70; H 1.82;
S 28.55. Calcd. for C7H4F3NS2: C 37.66; H 1.80; S 28.72.
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Organosulfur Trifluorides
2509
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Received in the Netherlands November 14, 2002

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