Fluoro-organic sulphur-containing compounds. IV. Haloalkylation reactions of polyfluorinated thiophenols with CHal3R compounds in the presence of AlCl3: Synthesis and some reactions of polyfluorophenylthio derivatives of halomethanes

Article abstract of DOI:10.1016/S0022-1139(99)00080-9

The haloalkylation of polyfluorothiophenols with CHal₃R compounds (Hal=Cl, F; R=Cl, H, C₆H₅, C₆F₅) in the presence of AlCl₃ has been investigated. The reactions of polyfluorothiophenols 4-XC₆F₄SH (X=F, H, CH₃) with CCl₄ and AlCl₃ lead to dichloromethane derivatives (4-XC₆F₄S)₂CCl₂. The reaction of pentafluorothiophenol with CHCl₃ in the presence of AlCl₃ gave (C₆F₅S)₂CHCl and (C₆F₅S)₃CH (ratio by GLC 8:1). In the reaction of pentafluorothiophenol with ArCX₃ (Ar=C₆H₅, C₆F₅; X=Cl, F) compounds (C₆F₅S)₂CClAr (Ar=C₆H₅, C₆F₅) together with C₆F₅SCCl₂Ar (Ar=C₆H₅, C₆F₅) are formed. Peculiarities of these processes are considered. The hydrolysis of (C₆F₅S)₂CCl₂ and C₆F₅SCCl₂C₆H₅ leads to bis(pentafluorophenyl)dithiocarbonate and the S-(pentafluorophenyl) ester of thiobenzoic acid, respectively. Compounds (C₆F₅S)₂CF₂ and (C₆F₅S)₂CClF were obtained from (C₆F₅S)₂CCl₂ by the action of caesium fluoride. An attempt to produce these compounds through the action of antimony fluorides was unsuccessful. The compounds (C₆F₅S)₂CCl₂, (C₆F₅S)₂CClF and (C₆F₅S)₂CF₂ are stable to oxidation. The reactions of (C₆F₅S)₂CF₂ and (C₆F₅S)₂CClF with CrO₃ in acetic acid proceeded only with the formation of mono-sulphoxide. The conversion is low in the former case.

Full text of DOI:10.1016/S0022-1139(99)00080-9

Journal of Fluorine Chemistry 98 (1999) 17±28
Fluoro-organic sulphur-containing compounds. IV. Haloalkylation
reactions of poly¯uorinated thiophenols with CHal3R
compounds in the presence of AlCl3
Synthesis and some reactions of poly¯uorophenylthio
derivatives of halomethanes1
T.D. Petrova, V.E. Platonov*, A.M. Maksimov
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division of Russian Academy of Science, 9,
Lavrentiev ave., Novosibirsk, 630090, Russian Federation
Received 17 December 1998; accepted 10 March 1999
Abstract
The haloalkylation of poly¯uorothiophenols with CHal3R compounds (HalˆCl, F; RˆCl, H, C6H5, C6F5) in the presence of AlCl3 has
been investigated. The reactions of poly¯uorothiophenols 4-XC6F4SH (XˆF, H, CH3) with CCl4 and AlCl3 lead to dichloromethane
derivatives (4-XC6F4S)2CCl2. The reaction of penta¯uorothiophenol with CHCl3 in the presence of AlCl3 gave (C6F5S)2CHCl and
(C6F5S)3CH (ratio by GLC 8:1). In the reaction of penta¯uorothiophenol with ArCX3 (ArˆC6H5, C6F5; XˆCl, F) compounds
(C6F5S)2CClAr (ArˆC6H5, C6F5) together with C6F5SCCl2Ar (ArˆC6H5, C6F5) are formed. Peculiarities of these processes are considered.
The hydrolysis of (C6F5S)2CCl2 and C6F5SCCl2C6H5 leads to bis(penta¯uorophenyl)dithiocarbonate and the S-(penta¯uorophenyl) ester of
thiobenzoic acid, respectively. Compounds (C6F5S)2CF2 and (C6F5S)2CClF were obtained from (C6F5S)2CCl2 by the action of caesium
¯uoride. An attempt to produce these compounds through the action of antimony ¯uorides was unsuccessful. The compounds
(C6F5S)2CCl2, (C6F5S)2CClF and (C6F5S)2CF2 are stable to oxidation. The reactions of (C6F5S)2CF2 and (C6F5S)2CClF with CrO3 in acetic
acid proceeded only with the formation of mono-sulphoxide. The conversion is low in the former case. # 1999 Elsevier Science S.A. All
rights reserved.
Keywords: Poly¯uorothiophenols; Haloalkylation reaction; AlCl3; Poly¯uorophenylthiohalomethanes
1. Introduction
along with trichloromethyl penta¯uorophenyl ether and
tris(penta¯uorophenoxy)chloromethane. The ratio of these
compounds depends on the reaction conditions. The reaction
of aliphatic poly¯uorinated alcohols leads only to carbo-
nates [3].
It was of interest to study the possibility of a haloalkyl-
ation reaction of poly¯uoroaromatic thio derivatives with
compounds of the formula CHal3R in the presence of AlCl3.
The alkylation or arylation of thiols with RHal is usually
accomplished in the presence of a strong base, e.g. NaOH,
tertiary amines, etc., in order to promote the nucleophilicity
of the sulphur atom and to remove the halide ion as it is
released. In the case of penta¯uorothiophenol (1) the pre-
sence of an inorganic or even weak organic base causes
extensive polymerization as a result of repeated nucleophilic
substitution of the p-¯uorine atoms by the thiolate anion.
Alkylation or arylation of (1) therefore presents problems
We have previously described the haloalkylation reaction
of poly¯uoroaromatic amino and hydroxy derivatives with
compounds of the formula CHal3R (HalˆCl, F; RˆCl,
C6H5, C6F5) in the presence of AlCl3. The reaction proceeds
at the heteroatom and leads to compounds of various classes.
The products of the reactions of poly¯uoroaromatic amines
with CCl4/AlCl3 have been shown to be poly¯uoroaromatic
carbonimidoyl dichlorides [1]. The products of the reactions
with CHal3Ar(Arf)/AlCl3 are poly¯uoroaromatic imidoyl
chlorides [1,2]. The reaction of penta¯uorophenol with
CCl4/AlCl3 under similar conditions leads to the formation
of bis(penta¯uorophenyl)carbonate as the main product
*Corresponding author. Fax: +7-3832-34-4752.
1For Part III, see Russ. Chem. Bull. 45 (1996) 153.
0022-1139/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 0 8 0 - 9

18
T.D. Petrova et al. / Journal of Fluorine Chemistry 98 (1999) 17±28
Scheme 1.
[4]. However, compounds containing activated halide atoms
combined with (1) in DMF without the necessity of adding a
base. The reaction of (1) with iodoform in DMF occurs to
afford tris(penta¯uorophenylthio)methane (2) and a higher
molecular weight material as a result of further reactions of
(1) at the para position of the former product. Octa¯uoro-
toluene (3) reacts with (1) in DMF at room temperature to
give the product which resulted from reaction of (1) at the
para position of (3) [4].
In the present paper we describe the reactions of
penta¯uorothiophenol (1), 2,3,5,6-tetra¯uorothiophenol
(4) and 4-methyl-2,3,5,6-tetra¯uorothiophenol (5) with
CCl4, CHCl3, benzotrichloride (6) and penta¯uorobenzo-
trichloride (7) or benzotri¯uoride (8) and octa¯uorotoluene
(3) in the presence of AlCl3.2 The reactions of hydrolysis,
replacement of chlorine by ¯uorine, using antimony ¯uor-
ides and caesium ¯uoride, and the oxidation of the com-
pounds obtained have been studied.
of (1), but only as an impurity, in very small amounts.
Compounds (9±11) are stable to hydrolysis under the reac-
tion conditions.
We have studied the interaction of compound (1) and
CCl4 in the presence of AlCl3 under various conditions. We
tried to produce mainly penta¯uorophenylthiotrichloro-
methane (19) or tris(penta¯uorophenylthio)chloromethane
(12) by varying the amounts of CCl4 and AlCl3 or tem-
perature, but these attempts failed. Dichloromethane deri-
vative (9) was formed as the main product irrespective of the
amount of CCl4 and AlCl3 at 608C and at room temperature,
but much deca¯uorodiphenyl disulphide (13) was formed in
the latter case probably as a result of competitive transfor-
mation of (1) under the action of AlCl3. A mixture con-
sisting of unreacted starting material (1), disulphide (13)
and derivative (9) (5:3:1 according to 19F NMR data) was
formed at 08C. Hence, lowering the temperature of the
reaction favours only the formation of disulphide (13). A
temperature rise up to 808C also leads to compound (9) as a
main product. According to MS and 19F NMR data, one
fraction after column chromatography of the reaction mix-
ture on silica gel contained (12), but in very small amounts.
The suggested reaction Scheme 2 can explain a formation
of observed products and can help an understanding of the
difference in the end products formation in the reactions of
poly¯uoroaromatic hydroxy and thio derivatives with CCl4
and AlCl3. The scheme involves a primary attack on (1) by
CCl4 activated by AlCl3 to form trichloromethylthio deri-
vative (19) which is then further converted to the compound
2. Results and discussion
2.1. Reactions of polyfluorinated thiophenols with
CHal3R/AlCl3
The results obtained in the reactions of compounds (1, 4,
5) with CCl4, CHCl3 and ArCHal3 in the presence of AlCl3
are shown in Scheme 1 and Table 1.
2.1.1. Reactions with CCl4 and AlCl3
Poly¯uorinated thiophenols, like penta¯uorophenol,
undergo polychloroalkylation at the heteroatom in reaction
with CCl4 in the presence of AlCl3. However, as opposed to
penta¯uorophenol, the reactions of penta¯uorothiophenol
(1) and para-substituted tetra¯uorothiophenols (4, 5) lead to
bis(poly¯uoroarylthio)dichloromethanes (9±11) in high
yields. At times the formation of tris(penta¯uorophe-
nylthio)chloromethane (12) was observed in the reactions
2Preliminary communications [5,6].
Scheme 2.

T.D. Petrova et al. / Journal of Fluorine Chemistry 98 (1999) 17±28
19
Table 1
Interaction of polyfluorothiophenols with compounds of the CHal3R type in the presence of AlCl3
Experiment
Thiocompound
g (mmol)
CHal3R g
(mmol)
AlCl3
(mmol)
g
CHCl3
(ml)
Reaction
temperature
8C (time, h)
Weight of
residue after
reaction (g)
Content of main products in residue
after reaction
Compound
% by
GLC
Ratio by
19F NMR
Reaction with CCl4 (ml)
1
2
(1) 1.52 (7.6)
(1) 1.21 (6)
10
85
3.04 (22.8)
2.42 (18)
60±70 (6)
60±70 (6)
2.0
1.52
(9)
(9)
90
90
4
(13)
(9)
3
4
5
(1) 1.0 (5)
10
120
10
0.67 (5)
60±70 (6)
60±70 (9)
20 (6)
1.17
23.56
0.7
91
4
(13)
(9)
(1) 20 (100)
(1) 0.73 (3.65)
26.6 (100)
1.46 (10.1)
90
3
(13)
(9)
82
10
(13)
6
7
(1) 1.9 (9)
80
80
1.27 (9)
20 (6)
0 (6)
(9)
(13)
(1)
8
1
(1) 1.3 (65)
0.87 (6.5)
5
(9)
1
(13)
(9)
3
8
(1) 1.05 (5.25)
10
2.10 (15.7)
80 (6)
1.45a
Main
traces
(12)
(10)
(11)
9
(4) 1.89 (10)
(5) 1.57 (5)
100
80
4 (30)
60±70 (6)
60±70 (6)
2.3
1.7
10
2.9 (15)
Reaction with CHCl3
11
(1) 3.72 (18.6)
7 (55.8)
±
20
10
60±70 (7)
60±70 (6)
3.89
1.05
(2)b
(13)
(14)c
(1)
9
2
82
12
(1) 0.96 (4.8)
12
1
(13)
Reaction with Ar(Arf)CF3
13
(1) 1.98 (10)
(8) 1.45 (10)
(3) 2.12 (9)
3.96 (30)
3.5 (27)
80
80
60±70 (6)
60±70 (6)
3.25
2.77
(15)d
(20)
(16)
3
1
14
(1) 1.83 (9)
Reaction with Ar(Arf)CCl3
15
(1) 2.33 (11.6) (6) 2.28 (11.6)
4.67 (34.9) 80
60±70 (6)
3.8
4.3
(15)
(17)
(15)
(17)
(20)
(13)
(15)
(20)
(17)
(1)
1
2
16
(1) 2.08 (10.4) (6) 2.01 (10.3)
4.1 (31)
45
80
60±70 (6)
2.25
39
1
17
18
(1) 2.22 (11)
(1) 1.5 (7.5)
(6) 2.17 (11)
(6) 1.52 (7.7)
4.44 (33)
20 (6)
20 (6)
3.6
0.5
2.7
1
1
1.04 (7.7)
60
2.75
1
(15)
(17)
(20)
(7)
19
3.5
3.5
1
19
20
21
22
(1) 1.6 (8)
(1) 1.0 (5)
(1) 1.05 (5)
(1) 5 ml
(7) 2.26 (8)
(7) 1.42 (5)
(7) 3.76 (12)
(7) 1.48 (5)
3.2 (24)
0.67 (5)
2.1 (15)
2.1 (15)
80
10
60±70 (6)
20 (6)
3.5
2
(16)
(18)
(7)
1.5
1.5
1.5
1
(16)
(18)
(7)
1.3
7.5
1
20 (6)
3.10
8
(16)
(18)
(13)
(14)
(16)
2.6
1
2
60±70 (6)
1.5
1

20
T.D. Petrova et al. / Journal of Fluorine Chemistry 98 (1999) 17±28
Table 1 (continued )
Experiment
Thiocompound
CHal3R g
(mmol)
AlCl3
g
CHCl3
(ml)
Reaction
Weight of
Content of main products in residue
after reaction
g (mmol)
(mmol)
temperature
8C (time, h)
residue after
reaction (g)
Compound
% by
GLC
Ratio by
19F NMR
23
(1) 1 (5)
(7) 1.42 (5)
2 (15)
80
5±10 (6)
2.07
(7)
(13)
(16)
(18)
16
1.5
16
1
a Compound (9) (0.9 g), the mixture of compounds (9) and (21) (0.09 g), compound (21) (0.15 g) and the mixture of compounds (21) and (12) (0.3 g, ratio by
19F NMR 1:1.3) were obtained from the residue by column chromatography (eluent hexane).
b 0.2 g of (2) was isolated from 1.35 g residue by column chromatography (eluent hexane).
c 1.4 g of (15) was isolated from 2.5 g residue by distillation at 165±1678C/10 mm Hg.
d 1.38 g of (16) was isolated from 2.5 g residue by filtration and washing with small amount of hexane.
(9). In the thiophenols series the conversion to dichloro-
methane derivatives seems to be easier due to higher
nucleophility of thiophenols as compared to phenols, and
the trichloromethylthio derivative may not be detected. The
different behaviour of derivative (9) in a further reaction
with (1) or in hydrolysis as compared to the oxygen
analogue may be explained by the different ability of
oxygen and sulphur atoms to stabilize the adjacent carbo-
cationic centre [7]. The sulphur atom is less effective and
this could explain the stability of (9) towards hydrolysis or
further reaction with (1) to (12).
presence of more reactive compounds of the ArCHal3 type.
Therefore, itwas possibletouseCHCl3 as a solvent. Attempts
touseexcessof(1)inthereactionof(1)with(7)inCHCl3 (exp.
22)gavecompound(16),butthereactioniscomplicateddueto
the formation of by-products (13) and (14).
2.2. Hydrolysis of dichloromethane derivatives (9, 17)
The dichloromethane derivatives formed in the polyha-
loalkylation reactions of (1) are stable to hydrolysis but they
react with water when an excess of 10% HCl in dioxane
(1008C) was used (Scheme 3). Thus, bis(penta¯uorophe-
nyl)dithiocarbonate (21) and compound (20) were obtained
from compounds (9) and (17) under these conditions. The
derivative (20) was identical with that described in the
literature [8].
2.1.2. Reaction with CHCl3 and AlCl3
Penta¯uorothiophenol (1) did not react with CHCl3 at
608C in the absence of AlCl3. The reaction mixture con-
tained only disulphide (13) together with unreacted starting
material (1) (ratio of (1) and (13) 16:1 deduced from
19F NMR data). In the presence of AlCl3 reaction of (1)
and CHCl3 gave bis(penta¯uorophenylthio)chloromethane
(14) as main product and tris(penta¯uorophenylthio)-
methane (2) (ratio by GLC 8:1).
2.3. Reactions of halogen exchange
It is known [9] that the ¯uorinated sulphides of the (4-
FC6H4S)2(CF2)n type are starting compounds to bis-sul-
phone monomers which react with bis-phenols to give
¯uorinated poly-(ether sulphone)s as new polymers. In this
respect it was of interest to study bis(penta¯uorophe-
nylthio)di¯uoromethane (22) as the simplest compound
of the per¯uorinated series. For this reason chlorine atoms
exchange with ¯uorine under the action of the antimony
¯uorides and caesium ¯uoride has been studied for chloro
compound (9). The main results of this investigation are
shown in Scheme 4 and Tables 2 and 3.
2.1.3. Reaction with ArCHal3 and AlCl3
Reactions of (1) with aryltrihalomethanes and AlCl3
proceeded similarly. Bis(penta¯uorophenylthio)arylchloro-
methanes were formed, but, in contrast, in these reactions
the primary dichloromethane derivatives have also been
isolated and characterized (see Table 1). Reaction of (1)
with benzotri¯uorides (8, 3) and AlCl3 at 608C gave as
the main products bis(penta¯uorophenylthio)arylchloro-
methanes (15, 16). In the reaction mixture with (8) a small
amount of S-penta¯uorophenyl thiobenzoate (20) was iden-
ti®ed which probably forms as a result of a side reaction
involving hydrolysis of the primary product (17). Reactions
of (1) with benzotrichlorides (6, 7) gave (15, 16) and
penta¯uorophenylthioaryldichloromethanes (17, 18). Pro-
duct ratios depended on the temperature and amount of
reagents. Reactions of (1), ArCHal3 and AlCl3 proceeded in
excess of ArCHal3 as well as with equimolar amounts of (1)
and ArCHal3 in CHCl3. It should be noted that compound
(1) and CHCl3 reacted with no or low conversion in the
2.3.1. Reactions with antimony fluorides
It is known that RSCCl3 compounds transform into
RSCF3 derivatives with SbF3 [10] or SbF3‡SbCl5 [11].
Scheme 3.

T.D. Petrova et al. / Journal of Fluorine Chemistry 98 (1999) 17±28
21
Scheme 4.
The reaction is usually realized by heating with simulta-
neous distillation of reaction products.
Dichloromethane derivative (9) reacts with a threefold
molar excess of anhydrous caesium ¯uoride without solvent
at 1808C to give chloro¯uoromethane derivative (23) as
main product. Di¯uoromethane derivative (22), disulphide
(13) and polysulphides of the (25) type were also identi®ed
among the reaction products (see Table 3). An increase of
reaction temperature favours the formation of compound
(22) and polysulphides. At 2258C (exp. 4) from GLC data
the reaction mixture not only contained ꢀ5% chloro¯uoro-
methane derivative (23) and 43% di¯uoromethane deriva-
tive (22) but also 34% polysulphides (25) and 8% disulphide
(13). Compound (22) was not obtained pure and was
identi®ed according to 19F NMR , GC±MC and GLC data.
Separation of a mixture of (22), (23) and (13) was dif®cult.
The compounds show close chromatographic retention
times. An unseparated mixture of these compounds was
isolated by column chromatography. An attempt to distil off
compound (22) from the reaction mixture was also unsuc-
cessful. An unseparated mixture of polysulphides (25) was
identi®ed by 19F NMR data. The determination of the
amount of each component was dif®cult. The compounds
show coincident 19F NMR signals. The 19F NMR signals at
115.5±117 ppm were attributed to the ¯uorine atoms of CF2
and CFCl groups, the signals at 30±34 ppm to the ortho-
¯uorine atoms, the signals at 2.3±2.7 ppm to the meta-
¯uorine atoms and the signals at 12.6±12.9 ppm to the
Reaction of (9) with an excess of SbF3 similar to the
transformation of PhSCCl3 to PhSCF3 [10] at 1508C (exp. 1,
Table 2) gave dithiocarbonate (21) as the main product,
small amounts of di¯uoromethane derivative (22) and dis-
ulphide (13) (75%, 16% and 6%, GLC data). Lowering of
the temperature of the reaction to 1108C did not change the
result. Compound (9) did not react with SbF3 at 458C.
Disulphide (13) was the main product in the reaction of
compound (9) with SbF3/SbCl5 at 120±1408C/25 mm Hg.
Derivative (22) and dithiocarbonate (21) were among the
reaction products, but in small amounts. Unreacted starting
compound (9) remained in the mixture (exp. 5, Table 2).
The use of SbF5 favours the exchange process. The reaction
of (9) with SbF5 at 908C (exp. 6, Table 2) resulted in an
increase in formation of di¯uoromethane derivative (22) but
the main product was disulphide (13). Chloro¯uoromethane
derivative (23) and dithiocarbonate (21) were also identi®ed
among the reaction products. Penta¯uorophenylthiotri¯uor-
omethane (24) previously described in [12] is likely
formed in this reaction according to 19F NMR and GC±
MS data.
The formation of compound (21) in the reactions with
antimony ¯uorides is presumably a result of partial hydro-
lysis of the dihalomethanes in the presence of traces of
moisture. This hydrolysis occurs most easily for starting
material (9) and is more favourable than the exchange
process. Di¯uoromethane derivative (22) and chloro¯uoro-
methane derivative (23) are stable to the action of SbF3 and
traces of moisture to 1608C (exp. 7 and 8, Table 2). The
transformation of dihalomethane derivatives by SbF5 with a
rupture of the C±S bond and formation of a penta¯uoro-
phenylthiodihalomethyl cation and a penta¯uorophenylthio
radical as intermediates could be the explanation of the
reaction pathway into tri¯uoromethane derivative (24) and
disulphide (13) (Scheme 5, compare [13]).
Disulphide (13) could be also formed from dithiocarbo-
nate (21) under the reaction conditions (exp. 9, Table 2).
2.3.2. Reactions with caesium fluoride
The results obtained in the reactions of compound (9)
with caesium ¯uoride are shown in Scheme 4.
Scheme 5.

Table 2
Interaction of dihalomethanes with antimony fluorides
Experiment
1
Starting compound
g (mmol)
Antimony fluoride
g (mmol)
Reaction temperature
Method
A
Weight of product
after reaction (g)
Reaction products
8C (time, h)
Content in mixture
Compound
Ratio by 19F NMR
(9) 0.48 (1)
SbF3 0.16 (0.85)
150 (2)
110 (3)
0.41
(9)
(13)
(21)
(22)
(9)
0.3
1
9.3
2
2
(9) 0.15 (0.31)
SbF3 0.05 (0.28)
C
0.1
0.5
0.75
(13)
(21)
(22)
(9)
13.2
3
3
4
(9) 0.15 (0.31)
(9) 0.48 (1)
SbF3 0.05 (0.28)
45 (1.5)
C
B
0.1
0.1a
SbF3 0.17 (0.8), SbCl5 (5 drops)
120±140/15 mm Hg (45 min)
(13)
(21)
(22)
(13)
(21)
(9)
41
2.4
1
19
1
0.05
5
6
(9) 0.15 (0.31)
(9) 0.15 (0.31)
SbF3 0.05 (0.28), SbCl5 (2 drops)
55 (4)
C
C
1.5
(13)
(21)
(22)
(23)
(9)
1.5
1
b
b
SbF5 0.03 (0.14)
90 (4)
0.11
1.5
6
(13)
(21)
(22)
(23)
(24)
(22)
(23)
1.5
3
1
4
7
8
(22)
(23)
1
SbF3
0.06
110 (4)
160 (6)
C
C
0.06
0.08
1
5
8
0.1 (19F NMR)
(13)
(22)
(23)
2
10
SbF3
0.06
(13)
(21)
(22)
(23)
(13)
2.5
2
81
14
0.08 (% GLC)
77 (% GLC)
93 (% GLC)
9
(21) 0.08 (0.19)
SbF3 0.03 (0.17), SbCl5 (2 drops)
140 (1.5)
C
0.05
a A solid which sublimed on the condenser.
b Traces, the ratio of (22) and (23) is approximately 1:2.

T.D. Petrova et al. / Journal of Fluorine Chemistry 98 (1999) 17±28
23
Table 3
Interaction of dihalomethanes with caesium fluoride
Experiment
Substrate g
(mmol)
Caesium fluoride,
g (mmol)
Reaction temperature,
8C (time, h)
Weight of residue
after reaction (g)
Reaction products
Compound
Ratio by 19F NMR
1
(9) 0.96 (2)
1.92 (12)
180 (19)
180 (27)
0.85a
(13)
(22)
(23)
(25)
(9)
1.5
7
18
6
2b
(9) 8 (17)
16 (100)
3.2c
1
(13)
(22)
(23)
(13)
(23)
(25)
(13)
(22)
(23)
(25)
(13)
(22)
(23)
(25)
(13)
(22)
(23)
(25)
1.1
1
11
1.65
1
19
63 (% GLC)
1
3
4
5
(9) 1.2 (2.5)
(9) 1.2 (2.5)
(23) 0.93 (2)
2.28 (15)
2.28 (15)
1 (6)
210 (19)
225 (22)
220 (18)
1.05d
2
3
1.8
1
1.06e
0.8
4
1
6
1.5
19.5
55.5
20 (% GLC)
a A mixture (0.38 g) of 2% of (13), 10% of (22) and 84% of (23) (GLC) was obtained from residue by sublimation at 1108C/15 mm Hg.
b Carried out in argon.
c The solid product sublimed on the flask from which compound (23) was separated and purified.
d A mixture (0.35 g) of 10% of (13), 33.5% of (22) and 50% of (23) (GLC) was obtained from products after reaction by sublimation at 105±1108C/
15 mm Hg.
e This mixture was treated with petroleum ether (70±1008C), organic layer was filtered, solvent distilled off. From 0.72 g of solid residue by column
chromatography (eluent hexane) a mixture (0.21 g) of 15% of (13), 70% of (22) and 7% of (23) (GLC) was isolated.
para-¯uorine atoms. The signals coincide with those for
similar polysulphide fragments in the compounds described
previously [14]. Polysulphides (25) probably result from a
side reaction involving para-¯uorine atom displacement by
the penta¯uorophenylthio group. Formation of compounds
(25) may be represented in Scheme 6.
The scheme involves an attack by ¯uoride anion at
aliphatic carbon atom with substitution of chlorine by
¯uorine and a rupture of C±S bond and further transforma-
tions by the penta¯uorophenylthio anion. An attempt to
obtain pure di¯uoromethane derivative (22) from chloro-
¯uoromethane derivative (23) by heating with caesium
¯uoride at 2208C did not gave a positive result (exp. 5,
Table 3).
2.4. Reactions with oxidants
Dihalomethane derivatives (9, 23) did not react with
potassium permanganate in acetone. Treatment of (23) with
potassium permanganate in boiling acetic acid resulted in
formation of disulphide (13) (see 1 of Section 3.5). Dis-
ulphide (13) probably results from dithiocarbonate (21)
formed by hydrolysis of starting material (23). Such a
pathway was con®rmed by the transformation of (21) into
(13) on heating with potassium permanganate in acetic acid
(2 of Section 3.5). Compound (22) did not react with
potassium permanganate under these conditions. Chromium
trioxide/acetic acid as oxidant was more effective, but
insuf®cient. Previously, this oxidant was used for oxidation
of the ¯uoro-containing sulphides to sulphones [9,15]. By
boiling ¯uorochloromethane derivative (23) with threefold
molar excess of chromium trioxide in acetic acid, only
mono-sulphoxide (26) was obtained (Scheme 7). The
19F NMR spectrum of (26) shows two different C6F5-
groups, and changes with the CFCl-group and aromatic
¯uorine atoms on going from sulphide to sulphoxide. In the
Scheme 6.

24
T.D. Petrova et al. / Journal of Fluorine Chemistry 98 (1999) 17±28
spectra were measured on a Specord M-80 instrument for
a 5% CCl4 solution. GLC analyses were carried out on a
LHM-7a instrument with a thermal conductivity detector
and a linear temperature programme of 108C min 1, using
internal normalization (80±2708C, a 4000Â4 mm column
packed with methylsilicon E-30, ¯uorosilicon QF-1/Chro-
mosorb W, silicon SKTFT-50 and SKTFV-803/Celite, 5:100
and 15:100 with He carrier at 60 ml min 1). Column chro-
matography was carried out on silica gel 100±160 mesh.
GC±MS analysis of the reaction mixtures was carried out on
a GCHP 5890 with an HP 5971 mass spectrometer, ioniza-
tion potential 70 eV. Molecular weights and molecular
formulae were determined mass spectrometrically on a
GC±MS Finnigan MAT-8200 instrument. The nominal
energy of the ionizing electrons was 70 eV. Newly synthe-
sized compounds were puri®ed by recrystallization from
petroleum ether (b.p. 70±1008C) and hexane or by sublima-
tion in a vacuum, or by column chromatography. All these
compounds have correct analytical data. The reaction con-
ditions and the results of experiments are presented in
Tables 1, 2±4. Spectroscopic and analytical data for new
synthesized compounds are presented in Table 5.
Scheme 7.
MS spectra of this compound fragment ions with structure
of sulphide (C6F5SCFCl, C6F5S) and sulphoxide (C6F5SO)
were observed. The ions containing sulphone groups and the
molecular ion were not observed. Unfortunately, we have
not managed to obtain single crystals of compound (26)
suitable for X-ray structure analysis.
Di¯uoromethane derivative (22) is the least reactive
substrate in the reactions with oxidants.
Only a small amount of derivative (22) reacted with
chromium trioxide in acetic acid to give compound (27)
which was identi®ed spectroscopically in the reaction
mixture. GC±MS and 19F NMR data for (27) are similar
to those for (26). Increasing amounts of chromium trioxide
gave a mixture of two main products ± unreacted
starting compound (22) and a poly¯uoroaromatic compound
which probably results from a reaction with acetic acid
and containing one penta¯uorophenyl group (exp. 3,
Table 4).
3.1. Reactions with RCHal3 and AlCl3
Corresponding thiophenol was added to a vigorously
stirred suspension of AlCl3 in RCHal3. The reaction mixture
was stirred at the temperature indicated in Table 1, poured
into cold water and extracted with ether. The ether layer was
dried over CaCl2, the solvents distilled off and the residue
1
analysed by 19F and H NMR spectroscopy, GC±MS, IR
3. Experimental
spectroscopy and GLC. Compounds (9±11, 15, 16, 17, 18)
were puri®ed by recrystallization from CCl4 or hexane and
sublimed at 100±1408C/10 mm Hg. Compound (15) was
puri®ed by distillation at 164±1668C/13 mm Hg. Com-
pound (2) was separated by column chromatography on
1
19F and H NMR spectra were recorded on a Bruker WP-
200SY instrument in CCl4 solution. The internal standards
were hexa¯uorobenzene and hexamethyldisiloxane. IR
Table 4
Reactions with chromium trioxide in acetic acid
Experiment
Starting compound
Chromium
trioxide (g)
AcOH (ml)
Reaction
time (h)
Reaction products
Compound Content in mixture
g
Content in mixture
(% GLC)
g
(% GLC)
1
(13)
(22)
(23)
0.22
10
33
50
0.4
4
6.5
(13)
(22)
(26)
(27)
2
20
44
25
0.09a
0.31b
0.05c
2
3
(23) 0.72
(13)
(22)
0.9
5
4
6
(26)
15
70
7
0.71
15
(23)
0.19
a A mixture (0.02 g) of (26) and (27) (76% and 21% by GLC) was obtained from the solid residue after washing with petroleum ether (70±1008C).
b The compound was purified by recrystalization from petroleum ether (70±1008C).
c A mixture of two main products: compound (22) and compound with unknown structure (1.5:1 from 19F NMR data).

Table 5
Analytical data and spectroscopic characteristics of new compounds
Compound
M.p. (8C)
C
H
Cl Found (%)
Calculated
F
S
M±Cl (35Cl)
Found
Composition
C19HF15S3
19F NMR
1H NMR
IR spectrum
1
spectrum, ꢀ,
ppm (solvent)
spectrum ꢀ,
ppm (solvent)
n (cm )
Calculated
(2)
120±122
37.84; 37.84
0.16; 0.46
0.16
46.50; 47.12
46.72
15.42; 15.30
15.74
608.88942a
608.89225
30.67 (6Fo)
13.92 (3Fp)
2.55 (6Fm)
(CHCl3)
5.51 (H)
(CCl4)
855(vs)
980(vs)
(134±135 [4]) 37.38
1080(vs)
1490±1510(vs)
1630(m)
2900(w)
870(s)
(9)
120±122.5b
32.96; 32.64
32.43
15.21; 15.40
14.76
39.91; 40.00
39.50
13.14; 13.46
13.30
444.8976
444.8970
C13Cl2F10S2
35.8 (4Fo)
17.75 (2Fp)
3.05 (4Fm)
(Ether‡CCl4)
995(vs)
1100(vs)
1500±1515(vs)
1630(m)
870(s)
(10)
141.5±143.5b
34.98; 34.59
35.05
0.49; 0.48
0.45
16.29; 16.36
15.95
34.21; 34.48
34.16
14.82; 15.10
14.38
408.9160
408.9159
C13H2Cl2F8S2 34.6 (4Fo)
25.6 (4Fm)
7.4 (HAr)
(Ether‡CCl4)
920(vs)
(Ether‡CCl4)
1190(s)
1235(s)
1390(s)
1500(vs)
1610(w)
3090(w)
920(vs)
(11)
135±137
38.10; 38.25
38.13
1.14; 1.20
1.14
14.25; 14.51
15.04
31.65; 31.80
32.20
13.64
13.56
436.9466
436.9471
C
15H6Cl2F8S2 33.51 (4Fo)
21.10 (4Fm)
(CCl4)
2.37
(6H, 2CH3)
(CCl4)
1080(vs)
1280(vs)
1490(vs)
1630(w)
2880(w)
2935(w)
(12)c
(14)
608.89007
608.89223
C19ClF15S3
36.79 (6Fo)
16.88 (3Fp)
2.39 (6Fm)
(CCl4)
d
35.48; 35.61
35.0
0.50; 0.57
0.22
7.90; 8.20
7.82
42.77; 42.83
42.82
14.10; 14.40
14.35
410.93485
410.93595
C13HClF10S2
31.92 (4Fo)
14.38 (2Fp)
2.45 (4Fm)
(CCl4)
6.25 (H)
(CCl4)
835(s)
975(vs)
1100(s)
1490±1540(vs)
1640(m)
3000(w)
875(m)
(15)
94±96
43.19; 42.93
43.68
1.31; 1.17
0.96
6.56; 6.53
6.80
36.17
36.40
12.33; 12.50
12.26
486.9673
486.9673
C
19H5ClF10S2 35.09 (4Fo)
7.9 (2HAr
7.3 (3HAr
(CCl4)
)
)
15.34 (2Fp)
1.80 (4Fm)
995(vs)
1100(vs)

Table 5 (continued )
Compound
M.p. (8C)
C
H
Cl Found (%)
Calculated
F
S
M±Cl (35Cl)
Found
Composition
19F NMR
1H NMR
IR spectrum
1
n (cm )
spectrum, ꢀ,
ppm (solvent)
spectrum ꢀ,
ppm (solvent)
Calculated
(CHCl3)
1495±1520(vs)
1630(m)
3075(w)
880(m)
(16)
59±60
37.36; 37.40
37.20
6.34; 6.30
6.04
46.74; 46.57
46.56
10.51; 10.42
10.46
576.9241
576.9202
C19ClF15S2
34.75 (4Fo)
32.27 (2Fo)
17.02 (2Fp)
12.41 ꢁFp0 †
2.57 (4Fm)
1.77 (2Fm0 )
(CCl4)
995(vs)
1010(m)
1100(vs)
1125(m)
1495±1520(vs)
1635(m)
980(vs)
(17)
101±102
44.15; 43.88
43.57
1.71; 1.67
1.40
19.77; 20.06
19.55
26.02; 25.82
26.54
9.10; 9.30
8.94
322.97157
322.97206
C13H5Cl2F5S
34.28 (2Fo)
15.84 (Fp)
1.95 (2Fm)
(CCl4)
7.89 (2HAr
7.40 (3HAr
(CCl4)
)
)
1095(vs)
1175(m)
1400(m)
1445(m)
1488(vs)
1512(vs)
1630(m)
3040(w)
(18)
67±68
412.92328
412.92495
C
13Cl2F10
S
34.50 (2Fo)
17.59 (Fp)
2.74 (2Fm)
(S±C6F5)
30.96 ꢁ2Fo0 †
12.68 (Fp0 )
1.76 (2Fm0 )
(C±C6F5)
(CCl4)
990±1020(vs)
1100(vs)
1135(vs)
1310(m)
1490±1520(vs)
1640(m)
1650(m)
e
(20)
34±37
C13H5F5OS
31.51 (2Fo)
12.60 (Fp)
1.30 (2Fm)
(CCl4)
7.99 (2HAr
7.55 (3HAr
(CCl4)
)
960(vs)
(34±37) [8]
)
1075(vs)
1490±1500(vs)
1650(vs)
1690(vs)
2915±2925(w)
990(vs)
(21)
50±52
36.17; 35.92
36.62
44.69; 44.86
44.60
15.60; 15.90
15.02
425.92428f
425.92308
C13F10OS2
32.50 (4Fo)
15.48 (2Fp)
2.59 (4Fm)
(CCl4)
1100(vs)
1495±1520(vs)
1640(m)
1730(m)
(22)g
448h
448
C13F12S2
114.78 (2F, CF2)
33.39 (4Fo)

Table 5 (continued )
Compound
M.p. (8C)
C
H
Cl Found (%)
Calculated
F
S
M±Cl (35Cl)
Found
Composition
19F NMR
1H NMR
IR spectrum
1
n (cm )
spectrum, ꢀ,
ppm (solvent)
spectrum ꢀ,
ppm (solvent)
Calculated
16.41 (2Fp)
2.66 (4Fm)
(CH2Cl2)
(23)
80±84
33.26
33.62
8.30; 8.00
8.64
45.29; 45.53
44.99
14.00; 14.28
13.78
428.92600
428.92657
C13ClF11S2
116.65 (1F, CFCl)
33.90 (4Fo)
16.91 (2Fp)
2.78 (4Fm)
(CH2Cl2)
975(vs)
1100(vs)
1175(vs)
1375(m)
1500±1525(vs)
1640(m)
(24)i
(26)
120.27 (3F, CF3)
33.39 (2Fo)
16.83 (Fp)
2.76 (2Fm)
(CH2Cl2)
74.60 (1F, CFCl)
35.50 (2Fo, SC6F5)
120±121
32.55; 32.75
32.47
8.00; 8.19
7.39
43.0; 42.70
43.5
13.56; 13.76
13.3
535; 539e,j
480.5
C13ClF11OS2
965(s)
970(vs)
1100(vs)
1175(s)
18.05 (Fp)
2.94 (2Fm)
1375(m)
1500±1525(vs)
1640(m)
32.66 (2Fo, SOC6F5)
24.39 (Fp)
5.25 (2Fm)
(CH2Cl2)
(27)
82.34 (2F, CF2)
35.46 (2Fo, SC6F5)
18.05 (Fp)
2.92 (2Fm)
31.79 (2Fo, SOC6F5)
24.81 (Fp)
5.21 (2Fm)
(CH2Cl2)
a The ion M±H.
b In a sealed capillary.
c This compound was identified in the mixture with (9) from GC±MS and 19F NMR data.
d B.p. 164±1668C/13 mm Hg.
e The molecular ion was absent.
f The molecular ion.
g A mixture of 15% of (13), 70% of (22) and 7% of (23) (GLC).
h The molecular ion with low intensity. Found composition was determined for the fragment ion C7F7S (M±SC6F5) (found 248.96080; calculated 248.96089).
i This compound was previously described in [12]. The literature chemical shifts for the signals corresponding to aromatic fluorines (2Fo 54.6, Fp 72.6, 2Fm 86.5 ppm with external trifluoroacetic acid as the
reference) and our data for this signals are different, but this difference could be attributed to the use of external and internal references.
j Molecular weights was determined by the vapour-phase osmometry in acetone.

28
T.D. Petrova et al. / Journal of Fluorine Chemistry 98 (1999) 17±28
silica gel (eluent hexane) and then recrystallized from
petroleum ether (70±1008C).
(13, 22, 23) (2%, 10.5% and 84% according to GLC
data) was added. The mixture was re¯uxed for 6 h, then
0.04 g potassium permanganate was added and the
mixture was re¯uxed for a further 3 h. After reaction,
the mixture was poured into water and extracted with
ether. The ether layer was washed with water, dried over
CaCl2, the solvents distilled off and the residue (0.09 g)
was analysed by 19F NMR spectroscopy and GLC. The
residue contained (13), (22) and (23) in the ratio 6:4.7:1
according to 19F NMR data or 30%, 38% and 7%,
respectively, by GLC.
3.2. Hydrolysis of compounds (9, 17)
To a solution of 1.1 g of compound (9) in 20 ml dioxane,
35 ml of 10% HCl was added. A mixture was re¯uxed for
7 h. After reaction the mixture was extracted with ether, the
organic layer was washed with water and dried over CaCl2,
the solvents were distilled off. The solid residue was ®ltered,
washed with small amount of petroleum ether (70±1008C)
and 0.31 g of compound (21) was obtained which was
puri®ed by sublimation at 1108C/15 mm Hg.
The reaction with (19) was carried out by a procedure
similar to that for (9) (0.34 g of (19), 4 ml of dioxane and
6 ml of 10% HCl were used). 0.16 g of compound (18) was
obtained which was puri®ed by sublimation at 708C/
15 mm Hg.
2. Boiling of 0.04 g of (21) with 0.06 g of KMnO4 and
1.5 ml AcOH (3.5 h) gave 0.11 g of the reaction mixture
containing AcOH and disulphide (13).
3. To a suspension of chromium trioxide in acetic acid, a
dihalomethane was added. The mixture was refluxed,
then acetic acid distilled off, the residue was poured into
water and extracted with methylene chloride. The
organic layer was washed with water, dried over CaCl2,
the solvents distilled off, the residue analysed by
19F NMR spectroscopy, GC±MS, GLC and purified by
recrystallization. The conditions and results are shown in
Table 4.
3.3. Reactions with antimony fluorides ± see Table 2
Antimony tri¯uoride was dried at 210±2208C.
Method A. The reaction was carried out in a ¯ask con-
nected via a condenser to a trap immersed in a cooling bath.
Antimony halogenide was added to corresponding substrate.
The reaction mixture was further heated. Products did not
distil off during the reaction. After reaction, the mixture was
cooled to room temperature, extracted with methylene
chloride, the precipitate was ®ltered off. Then a solution
was washed with water, organic layer was dried over CaCl2,
the solvent distilled off and a residue analysed by 19F NMR
spectroscopy, GLC and GC±MS.
References
[1] T.I. Savchenko, I.V. Kolesnikova, T.D. Petrova, V.E. Platonov, J.
Fluorine Chem. 22 (1983) 439.
[2] T.D. Petrova, I.S. Popova, I.V. Kolesnikova, V.E. Platonov, Russ.
Chem. Bull. 43 (1994) 1027.
[3] T.D. Petrova, A.G. Ryabitchev, T.I. Savchenko, I.V. Kolesnikova,
V.E. Platonov, Zh. Org. Khim. 24 (1988) 1513.
[4] R.T. Wragg, Tetrahedron Lett. (1971) 2475.
[5] T.D. Petrova, V.E. Platonov, A.M. Maksimov, I.S. Popova, Russ.
Chem. Bull. 40 (1991) 1938.
Method B. The reaction was carried out by a procedure
similar to that for A, but in vacuo.
Method C. The reaction was carried out in the closed steel
vessel. After reaction, the mixture was worked up as in A.
[6] T.D. Petrova, V.E. Platonov, I.S. Popova, I.V. Kolesnikova, J.
Fluorine Chem. 54 (1991) 300.
[7] S. Oae, Chemistry of Organic Compounds of Sulphur, Khimiya,
Moscow, 1975, p. 20 (in Russian).
3.4. Reactions with caesium fluoride
[8] M.E. Peach, H.G. Spinney, Can. J. Chem. 49 (1971) 644.
[9] A.F. Feiring, E.R. Wonchoba, S.D. Arthur, J. Polym. Sci. A 28
(1990) 2809.
Caesium ¯uoride was dried at 2708C. The reactions were
carried out in the closed steel vessel or in the ¯ask. The
reaction conditions are indicated in Table 3.
[10] L.M. Yagupolsky, M.S. Marenec, Zh. Obshchei Khim. 24 (1954)
887.
A substrate was added to a caesium ¯uoride and the
mixture was heated. Work-up of the reaction mixture by a
procedure similar to that for Method A for antimony
¯uorides afforded a residue which was puri®ed by column
chromatography or sublimation and recrystallization.
[11] M. Hudlicky, Chemistry of Organic Compounds of Fluorine, GNTI,
Moscow, 1961, p. 137 (in Russian).
[12] R.N. Haszeldine, R.B. Rigby, A.E. Tipping, J. Chem. Soc., Perkin I
(1972) 2180.
[13] E. Laurent, B. Marquet, Ch. Roze, F. Ventalon, J. Fluorine Chem. 87
(1998) 215.
[14] T.D. Petrova, V.E. Platonov, L.N. Shchegoleva, A.M. Maksimov, A.
Haas, M. Schelvis, M. Lieb, J. Fluorine Chem. 79 (1996) 13.
[15] L.M. Yagupolskii, N.V. Kondratenko, V.P. Sambur, Synthesis (1975)
721.
3.5. Reaction with oxidants
1. To a suspension of 0.26 g potassium permanganate in
3 ml of acetic acid, 0.12 g of the mixture of compounds