Synthesis of polyfluoroalkyl chlorosulfites and new polyfluoroalkylation reactions with their participation

Article abstract of DOI:10.1134/S107036321008013X

Regularities were revealed of polyfluoroalkyl chlorosulfites synthesis by reaction of thionyl chloride with associates polyflorinated alcohol- triethylamine and of a new reaction with polyfluorinated alcohols (catalysis by amides), resulting in symmetrica

Full text of DOI:10.1134/S107036321008013X

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 8, pp. 1626–1645. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.I. Rakhimov, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 8, pp. 1315–1334.
Synthesis of Polyfluoroalkyl Chlorosulfites
and New Polyfluoroalkylation Reactions
with Their Participation
A. I. Rakhimova,b
a Volgograd State Technical University, pr. Lenina 28,Volgograd, 400131 Russia
e-mail: organic@vstu.ru
b Institute of Ecological Problems, Russian Academy of Sciences, Volgograd, Russia
Received September 4, 2009
Abstract—Regularities were revealed of polyfluoroalkyl chlorosulfites synthesis by reaction of thionyl
chloride with associates polyflorinated alcohol–triethylamine and of a new reaction with polyfluorinated
alcohols (catalysis by amides), resulting in symmetrical simple polyfluoroalkyl ethers. New polyfluoro-
alkylation reactions of aliphatic (including polyfluorinated) alicyclic, benzyl alcohols, phenol, carboxylic acids
and their salts with polyfluoroalkyl chlorosulfites through substitution of chlorosilfite moiety by halogen,
alkoxy- (or polyfluoroalcoxy-), phenoxy-, and acyloxy-groups were studied. Novel synthesis approaches to F-
oligo- and polymeric materials with new properties were developed.
DOI: 10.1134/S107036321008013X
1. Synthesis of polyfluoroalkyl chlorosulfites by
reaction of thionyl chloride with associates alcohol–
tertiary amine.
Bispolyfluoroalkyl sulfite is the reaction by-
product. Two-fold increase in alcohol excess relative
to thionyl chloride leads to yield growth to 65–81%
[5]:
Polyfluoroalkyl chlorosulfites (PFACS) were first
obtained in 1960 by reaction of thionyl chloride with
perfluoroalkylhypohalogenites (oxidative substitution
method) [1]:
2RFOH·NEt3 + SOCl2 → (RFO)2SO + Et3N·HCl,
RF = CF3CH2, HC(CF3)2, CH3C(CF3)2, C(CF3)3.
Bis(1,1,3-trihydroperfluoropropyl) and (1,1,7-
trihydroperfluoroheptyl) sulfites were obtained in 65–
66% yield by reaction of a mixture of pyridine and
1,1,3-trihydroperfluoropropanol-1 (PFA-1) or 1,1,7-
trihydroperfluoropentanol-1 (PFA-2) with thionyl
chloride in diethyl ether at 20°С [6]. When the
synthesis was carried out at 25°С, appreciable amounts
(about 5%) of chloroderivatives formed [7]. Thionyl
chloride is recommended to add to the previously
prepared and cooled to –196°С complex alcohol–
amine in molar ratio; then temperature was slowly
raised to ambient in approximately 14 h.
RFOCl + SOCl2 → RFOS(O)Cl + Cl2.
The perfluoroalkyl hypochlorites (highly explosive)
are obtained by reaction of perfluorinated aldehydes
and ketones with chlorine monofluoride. The process
is catalyzed by Lewis acids (HF, CoF3, and AsF5)
[2, 3]. This method has not found a wide application
due to low availability of the reagents. Furthermore the
reaction is accompanied with a side reaction of sul-
fur(IV) oxidation into sulfur(VI) leading to low yields
of PFACS.
Fifteen years later De Marco et al. [4] synthesized
PFACS in 30–70% yield by the action of four-fold
excess of thionyl chloride on associates of
polyfluorinated alcohols (PFA) with triethylamine at
–78°С (alcohol and TEA were mixed in molar ratio).
Reaction of thionyl chloride with associates of
polyfluorinated alcohols and triethylamine was
examined at the Organic Chemistry Department of
Volgograd State Technical University [8–16]. It was
confirmed that the amount of triethylamine used for
the complex preparation significantly affects the yields
RFOH·NEt3 + SOCl2 → RFOS(O)Cl + Et3N·HCl,
RF = CF3CH2, HC(CF3)2, CH3C(CF3)2.
1626

SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
1627
Table 1. Dependence of product yield on triethylamine
amount
of the reaction products. Maximal yield was achieved
using complex alcohol–TEA (1:1). Raising the amine
amount over the equimolar ratio did not increase the
yield of 2,2,3,3-tetrafluoropropylchlorosulfite [12]
(Table 1).
TEA
1:0
Yield of HCF2CF2CH2OS(O)Cl, %
5.0
15.1
30.2
84.3
84.2
84.3
1:0.2
1:0.5
1:1.0
1:1.2
1:1.4
The reaction of thionyl chloride with the alcohol–
amine associate proceeds with a great exothermal
effect. In this connection it is necessary to use solvent
in order to regulate heat conditions. Use of chloroform
or diethyl ether provides a possibility to maintain the
temperature about –10°С. This circumstance and
decrease of the ratio thionyl chloride–alcohol to 2.5:1
makes it possible to increase the yield of PFACS to
84.3%.
in the (in comparison with alcohol solution in
tetrachloromethane in the absence of triethylamine).
The influence of the length of the alcohol
perfluorinated chain on associative properties of
protons of HCF2- and HO-groups was estimated by the
Further decrease in the molar ratio thionyl
chloride–alcohol to 1.5:1 and 1:1 leads to the
appearance of bis(polyfluoroalkyl)sulfite among the
reaction products. Thus, it forms in the synthesis of
2,2,3,3-tetrafluoropropylchlorosulfite in yields of 0.8
and 2.0% respectively. The single bis(2,2,3,3-
tetrafluoropropyl)sulfite forms (76%), if the ratio
thionyl chloride–alcohol is 0.5:1.
1
change in the chemical shift of H in diluted alcohol
solutions in tetrachloromethane (concentration 0.177
and 0.354 mol l–1) in the absence and the presence of
equimolar acetone quantity. In this case location of
central peak of HCF2-moiety (the more intensive peak
in the triplet of triplets) was compared with the
location of the signal trichloromethane proton, which
was added into the studied system. The following
equation was applied: Δδ = δН (HCF2 in CCI4 +
acetone) – δН (HCF2 in CCI4) [11, 16], for PFA-1 Δδ =
0.09 ppm, for PFA-2 Δδ = 0.13 ppm, for PFA-3 Δδ =
0.05 ppm, for HСCl3 Δδ = 0.04 ppm.
The complex formation process was studied by
calorimetry using the molar ratio alcohol–amine 1:1
[10, 12, 14]. The study was carried out at 303K. The
heat of the complex formation for complexes TEA–
PFA-1 and TEA–PFA-2 equals 19.81 and 21.62 kJ mol–1
respectively. The complex formation time for PFA-1
(3700 sec) is shorter than for PFA-2 (5250 sec).
In accordance with Δδ values, HCF2-group in PFA-
2 (Δδ 0.13 ppm) possesses maximal associative ability,
and alcohol PFA-3 has a minimal of associative ability
close to that of НС-group in the trichloromethane.
The heat of complex formation depends somewhat
on the number of difluoromethylene groups in alcohol
and correlates with acidity of polyfluorinated alcohols,
which is determined by their proton-donor properties.
In these experiments proton-donor properties of
HO-group in the polyfluorinated alcohols are similar:
for PFA-1 Δδ is 1.90 ppm and for PFA-2 Δδ is
1.86 ppm. However PFA-1 and PFA-2 are more active
proton-donors, than PFA-3, where Δδ is 1.20 ppm. The
high electron density on the oxygen atom in the
complex PFA–TEA favors the nucleophilic
substitution of chlorine by polyfluoroalkoxy group in
thionyl chloride by bimolecular mechanism [17, 18],
as confirmed by kinetic studies [10, 12, 14].
The IR spectroscopy was used to determine the
structure of complexes PFA-1 and PFA-2 with TEA. A
sharp decrease in the intensity of absorption band of
OH-group is observed in the IR spectra apparently due
to the formation of triethylammonium cations [17].
The latter absorb in the range of 2800–2300 cm–1 and
form a salt structure:
HCF2CF2CH2OH + N(C2H5)3
→ HCF2CF2CH2O– +NH(C2H5)3.
The experiment showed that thionyl chloride
reacted with complex alcohol–amine quickly and
virtually irreversibly. Therefore method of heat flow
calorimetry was seemed to be suitable for kinetic
study. It allows to determine heat generation rate WE =
f(τ) in a direct registration mode.
HCF2-groups of PFA are involved into association
with proton-acceptor substrate atoms along with HO-
moiety. This fact is confirmed by the shift to the low-
frequencies by Δν 8 cm–1 of the absorption band of the
stretching vibrations of H–CF2-moiety of the alcohol
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1628
RAKHIMOV
The determination of kinetic parameters of
(1) Formation of equimolar amount (relative to
theoretic yield of PFACS) of the reaction by-product,
triethylamine hydrochloride, and the need for its
separation from PFACS followed by regeneration into
triethylamine.
chemical reactions by this method is based on an
existence of the mutually unambiguous correspond-
dence between reagents concentrations and the change
in the enthalpy of system, where the chemical process
occurs. This correspondence is observed in the case of
both simple and complex chemical reactions, which
may be considered as an array of several simple
reactions. Since the liberated heat is proportional to
quantity of the reacted substance, the heat generation
rate is proportional to the rate of the change in the
concentration of reacting substances.
(2) Difficulties connected with purification of
PFACS. Use of gas-liquid chromatography method,
suggested by De Marco, is not suitable for large-scale
production, and rectification in a vacuum does not
result in sufficient purification: the product grows dark
at standing due to the presence of admixtures.
2. Catalytic synthesis of polyfluoroalkyl chloro-
sulfites by reaction of thionyl chloride with poly-
fluorinated alcohols.
The reaction of the alcohol with thionyl chloride
involves two consecutive stages: The first stage of АВ
complex formation is reversible. But since contribution
of this stage is little owing to high rate of the following
conversion of AB into the final reaction products, the
simpler model including only direct reaction was
taken. Then at the equality of initial concentrations of
thionyl chloride А and complex of alcohol with amine
В the kinetic model takes the form:
2.1. Synthesis features of PFACS under
conditions of catalysis with carboxylic acid amides of
the reaction between thionyl chloride and poly-
fluorinated alcohols.
The catalytic effect of carboxylic acids amides first
found by us [19–27] in the reaction of PFA with
thionyl chloride provides a possibility:
dcA
= –k1сA2,
dτ
(a) to synthesize PFACS in the yield up to 90%;
(b) to decrease the molar ratio of reagents thionyl
chloride–PFA;
dcA
dτ
= k1сA2 – k2cAB
.
(c) to carry out at milder temperature;
For all experiments at various temperatures the
adequacy dispersion for the chosen model was within
1%. The error in evaluation of the constants comprises
10–12%. Due to small temperature range and low
sensitivity of the reaction to temperature change the
calculated constants are close in values (difference in
values is in acceptable divergence range). Therefore
the simulation results are represented as two constants
k1 0.02±0.003 l mol–1 s–1 and k2 0.03±0.003 s–1
according to the given equations in the range of 25–
35°С.
(d) to obtain the end product of high quality by
evaporating excess thionyl chloride followed by the
vacuum distillation of PFACS.
Reaction was carried out by adding the amide
solution into thionyl chloride at from –15 to –5ºС. The
optimal ratio PFA–thionyl chloride–amide is
1:2:0.005. The formed hydrogen chloride was blown
out from the reaction mixture by dry nitrogen or air.
Catalytic activity of carboxamide was found to be
determined by its structure (Table 2). Within similar
reaction time and other equal conditions the yield of
polyfluoroalkyl chlorosulfite decreases in the fol-
lowing series of carboxamides:
Models, in which both reactions have an order
subject to determining, and models with reverse and
autocatalytic reactions were also included into the
program system. They were checked in order to obtain
more reliable results. From 13 models the better
coincidence with experimental data was found for
model describing interactions by bimolecular
mechanism.
HC(O)N(CH3)2
> CH3C(O)N(C2H5)2 > CH3C(O)N(CH3)2
> C6H5C(O)N(CH3)2 > HC(O)NHC6H5 = HC(O)N(C6H5)2
> C6H5C(O)NH2 > ClCH2C(O)NH2.
The maximal yield of PFACS (n = 2) of 90% was
achieved at catalysis with N,N-dimethylformamide
(DMF) at the temperature of the reagents mixing from
Synthesis method of PFACS using reaction of
thionyl chloride with PFA–triethylamine complex has
the following drawbacks:
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SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
1629
Table 2. Dependence of the yield of polyfluoroalkyl chlorosulfites H(CF2CF2)nCH2OS(O)Cl on reaction conditions
Amide R1C(O)NR2R3
n
Dosage temperature, ºС
Reaction time, h
PFACS yield, %
R1
H
R2
R3
2
CH3
CH3
–15
0.5
2
72
90
75
56
36
63
77
41
79
87
86
85
80
80
72
58
3
4
–5
3
1
H
CH3
CH3
–15
0.5
2
3
3
2
H
CH3
C2H5
CH3
CH3
H
CH3
C2H5
CH3
CH3
C6H5
C6H5
H
–15
–15
3
CH3
CH3
C6H5
H
2
H
C6H5
H
C6H5
ClCH2
H
H
–10 to –15ºС followed by temperature increase to 25ºС
and also at maintaining for 2 h at this temperature.
Minimal yield of PFACS was obtained for amides of
benzoic (72%) and monochloroacetic acids (58%).
Thus, at 25ºС the initial reaction rates ν0 for various
alcohols are 0.125 (PFA-1), 0.083 (PFA-2) and
0.050 min–1 (PFA-3). Therefore the initial reaction rate
decreases 1.3 to 2 times as the perfluorinated chain
increases again proving the maximum reactivity of
PFA-1. As seen the reactivity of PFA-2 is intermediate
between PFA-1 and PFA-3.
The increase in the initial reaction temperature to
–5°С (Table 2) leads to significant decrease in the
yield. The increased reaction time also decreases
PFACS yield and leads to the formation of side-
products, bis(polyfluoroalkyl) sulfite and poly-
fluoroalkyl chloride:
The initial reaction rate of PFA-1 grows
proportionally to the temperature rise from 5 to 15ºС:
ν0 (5ºС) 0.042 min–1, ν0 (15ºС) 0.125 min–1. Further
temperature increase to 25ºС does not cause the
H(CF2CF2)nCH2OS(O)Cl + H(CF2CF2)nCH2OH
Table 3. Influence of conditions of reaction of thionyl
chloride with PFA (catalysis with DMF) on the initial rate, ν0
→ [H(CF2CF2)nCH2O]2SO + HCl,
H(CF2CF2)nCH2OS(O)Cl → H(CF2CF2)nCH2Cl + SO2.
Reaction
Catalyst concentration,
Bis(polyfluoroalkyl) sulfite was isolated in the
yield of 10–28%, and at the increased temperature
polyfluorochloroalkane was obtained in 10% yield.
PFA, n
ν0, min–1
temperature, ºС mol/mol of alcohol
1
2
3
1
1
2
2
2
2
25
25
25
15
5
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.010
0.015
0.125
0.083
0.050
0.125
0.042
0.021
0.014
0.020
0.021
We studied the influence of the alcohol nature,
temperature, and catalyst amount on the initial rate ν0
of the catalytic reaction of polyfluorinated alcohol with
thionyl chloride (Table 3), which was determined by
differentiation of the curves of HCl release. The initial
rate of hydrogen chloride release depends on PFA
nature and decreases in the following series:
15
5
5
HCF2CF2CH2OH > H(CF2CF2)2CH2OH
> H(CF2 CF2)3CH2OH.
5
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1630
RAKHIMOV
growth of the initial reaction rate. For PFA-2 the initial
reaction rate rises not that quickly as the temperature
increases: ν0(5ºС) 0.014 min–1, ν0(15ºС) 0.021 min–1,
ν0(25ºС) 0.083 min–1.
The IR spectra of diluted solutions of PFA-1, PFA-
2, DMF, amide of monochloroacetic acid, and their
mixture with alcohols in molar ratio 1:1 were
compared with those of propyl alcohol (PA) and its
mixture with DMF.
In order to determine the optimal amount of
catalyst, the DMF content was increased from 0.005 mol
per 1 mol of PFA-2 to 0.01 and 0.015 mol per 1 mol of
PFA-2 (2- and 3-fold). In this case the initial reaction
rates are as follows: ν0(0.005) 0.014 min–1, ν0(0.01)
0.020 min–1, ν0(0.015) 0.024 min–1.
Alcohol ОH-groups have two characteristic
absorption bands in the IR spectrum. “Free” (non-
bonded hydroxy groups) gave a narrow band in the
range of large wavenumbers (“monomeric”, νОНm),
hydroxy moieties bonded into intermolecular hydrogen
bonds in the starting alcohol gave a wide band at lower
wave numbers (”polymeric,” νОНp).
We failed to obtain PFACS in the absence of some
catalysts or acceptors of hydrogen chloride. Here,
reaction of PFA-2 with thionyl chloride yields bis
(polyfluoroalkyl)sulfite (34.6%), PFACS (3.9%), and
1,1,5-trihydro-1-chloroperfluoropentane (1.5%).
Intermolecular associates are destructed in diluted
solutions of CCl4. HO-Absorption of non-associated
molecules was observed; further dilution does not
affect the position of the absorption band. Thus, for
PFA-1 νОНm in CCl4 solution is 3623 (0.4 mol l–1),
3623 (0.2 mol l–1), and 3624 cm–1 (0.08 mol l–1) [12].
The increase in the alcohol acidity is accompanied by a
small, but regular change of νОНm, cm–1: PA, 3644;
PFA-1, 3624; PFA-2, 3608. The absorption bands
characteristic of the hydroxy groups involved into the
hydrogen bonds appear in the IR spectra of associates
with amides. Moreover, on addition of amide intensity
of polymeric band increases sharply and shifts to lower
wavenumbers (Table 4). The strength of the inter-
molecular hydrogen bond (alcohol–amide association)
was estimated by a shift value Δν, which is the
difference between absorption of free and associated
hydroxy group. Value Δν < 50 cm–1 was considered
H(CF2CF2)2CH2OH + SOCL2
25oC, 120 min
H(CF2CF2)2CH2Cl
+ [H(CF2CF2)2CH2O + H(CF2CF2)2CH2OS(O)Cl.
The reasons of the high catalytic activity of car-
boxylic acid amides may be the activation of PFA mole-
cule due to associative interaction with the amide, par-
ticipation of amide molecule directly in the reaction act.
2.2 Activation of PFA with amides of carboxylic
acids.
Associative interactions of PFA with carboxylic
acid amides were studied by means of IR and PMR
spectroscopy.
Table 4. Location of absorption band of hydroxy group νОН in monomers, self-associates, and associates with amides
Absorption νОН, cm-1
Concentration, mol/l
in initial alcohol
Compound
in associate with
amide
(solvent)
Δν
monomer
self-association
H(CF2)4CH2OН
0.109 (СCl4)
3608
3604
3460
3436
–
–
148
168
0.064 (CHCl3)
H(CF2)2CH2OH
0.084 (CCl4)
0.089 (CCl4)
0.042 (CCl4)
3624
3644
–
3499
3537
–
–
–
125
107
233
СH3CH2CH2OH
H(CF2)2CH2OН
HC(O)N(CH3)2
H(CF2)4CH2OН
HC(O)N(CH3)2
3391
0.063 (CCl4)
0.064(CHCl3)
–
–
–
–
3365
3333
243
271
CH3CH2CH2OH
HC(O)N(CH3)2
H(CF2)4CH2OН
ClCH2C(O)NH2
0.045 (CCl4)
–
–
3494
150
0.055 (CHCl3)
–
–
3357
247
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SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
1631
[28] as an indication of weak hydrogen bond. Value Δν
50–200 cm–1 corresponds to the bond of moderate
strength as observed for PFA and amide molecules
(Table 4).
showed that even low concentration (from 0.005 to
0.01 mol per 1 mol of PFA) is enough to obtain the
product in 90% yield. At the same time the existence
of associative interactions between PFA and
carboxylic acids amides, which lead to the formation
of strong associates, were established by IR and PMR
spectroscopy. It determines the strategy of the
synthesis: first complex PFA–amide was prepared
[Eq. (1)], and then it was reacted with thionyl chloride
to give PFACS [Eq. (2)]. The formed hydrogen
chloride was blown out by dry nitrogen or air. Catalyst
was regenerated during the process:
As follows from Table 4, in tetrachloromethane
PFA forms stronger hydrogen bonds with amide
moiety (for PFA-1 Δν 233 cm–1 and for PFA-2
Δν 243 cm–1), than propyl alcohol (Δν = 150 cm–1).
Furthermore, the increase in the length of the
perfluorinated chain is seen to increase the associates
strength, although insignificantly.
The amide structure also affects the hydrogen bond
strength. Maximal value Δν is observed with DMF: in
CCl4 and in CHCl3, 243 and 271 cm–1 respectively.
The bond strength growth in associate with DMF in
comparison with amide of monochloroacetic acid (Δν
247 cm–1, CHCl3) is due to the presence of p-π-
conjugation of N(CH3)2-group of amide and to the
increase in the electron density on the amide oxygen
atom. The incorporation of electronegative substituent
into the amide of monochloroacetic acid decreases
electron density on the oxygen atom resulting in the
decrease in the hydrogen bond strength. As seen,
polarity of the solvent (chloroform) also is significant.
RFOH + amide → RFOH·amide,
(1)
RFOH·amide + SOCl2 → RFOS(O)Cl + amide + HCl. (2)
The mechanism of the catalytic reaction was
considered by means of quantum-chemical method.
For quantum-chemical calculations we choose semi-
empirical method АМ1 of GAMESS program package
[28–31] taking into account the hydrogen bonding
between reagents. Several reaction stages of PFA-2
and SOCl2 in the presence DMF were considered.
In the first stage PFA-2 and catalyst (DMF) form
associated complex represented in Fig. 1.
Quantum-chemical computation for this complex
and starting components shows that the formation of
the complex trough associative interactions between
Н1–О2 and Н–О2 atoms is preferable by energy of
0.352 eV. Bond lengths and bond orders are as
follows: R(Н1–О2) 2.136 Å, R(Н–О2) 2.536 Å,
Р(Н1–О2) 0.0078, P(Н–О2) 0.0008.
Results of PMR spectral study of PFA–amide
association were compared with the data on PFA–TEA
[12] and PFA–acetone association [16].
The PMR spectrum of PFA-2 (0.109 mol l–1, CCl4)
contains a triplet of triplets signal of proton of
(CF2CF2)2H-moiety at δ 5.97 ppm with intensity ratio
1:3:1; the coupling constants are 52.1 and 5.4 Hz.
Protons of –СН2– group appear at δ 3.99 ppm as a
triplet of doublets (J 13.95 and 7.05 Hz). The signal of
the hydroxy group proton was observed at δ 1.98 ppm.
On addition of equimolar amount of DMF HO-group
signal is shifted downfield (δ 4.31 ppm).
In the second stage the complex PFA-2–DMF in
solution of PFA-2 was added to thionyl chloride
cooled to –15ºС, which results in new complex
represented in Fig. 2.
In this complex charges on the atoms involved into
the associative interactions are changed owing to the
formation of new hydrogen bonds H1–O3, O1–S3, H2–
O3. The charge on the oxygen atom q(O2) is changed
Differences between chemical shift values for НО-
group in “free” and associated state for various
associates are presented in Table 5.
In all considered cases we observed formation of
associates of moderate strength by НО-group and
weak by HCF2-group. Comparable change of δH for
HO-group occurs at association of PFA with DMF and
TEA causing its polarization.
1
Table 5. Change in Н chemical shift (Δδ, ppm) in PFA
associates
Δδ, ppm
Associate; concentration in CCl4,
mol l–1
НО group
HCF2 group
0.07
PFA-2–DMF; 0.063
2.32
2.49
1.86
1.94
2.3. Mechanism of catalytic reaction of thionyl
chloride with PFA.
PFA-2–ТEА; 0.173
0.08
PFA-2–acetone; 0.177
0.13
Estimation of optimal amount of catalyst (DMF) for
reaction of thionyl chloride with PFA to form PFACS
PFA-1–acetone; 0.177
0.09
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RAKHIMOV
O1 –0.31
H1 +0.23
H
F
H2 +0.13
C2 +0.26
H
F
H
F
H
F
O2 –0.40
N2 –0.34
H
F
F
F
H
H
F
H
H
Fig. 1. Structure of associated complex PFA-2–DMF (first stage).
Cl
Cl
S3 +0.95
O3 –0.55
O1 –0.33
H
F
H1 +0.24
H2 +0.16
H
F
2 +0.26
H
F
O2 –0.42
C
H
F
N2 –0.34
F
H
F
F
H
H
F
H
Fig. 2. Structure of associated complex PFA-2–DMF–SOCl2 (second stage).
from –0.35 to –0.40, and q(H1), from +0.22 to + 0.23.
The energy gain for this complex is 0.553 eV. Bond
lengths are R(Н1–О2) 2.098 Å, R(Н1–О3) 2.7 Å,
R(H2–O3) 2.246 Å, R(O1–S3) 3.168 Å; bond orders are
Р(Н1–О2) 0.0095, Р(Н1–О3) 0.0007, Р(Н2–О3) 0.0036,
Р(O1–S3) 0.0004.
HCl + H(CF2)4OS(O)Cl + HC(O)N(CH3)2.
To model the chlorine atom rotation and the
formation of HCl molecule, the bond Н1–Сl(3) was
chosen as the reaction coordinate. It was decreased
from 4.212 to 1.3 Å (the length of the covalent bond)
at 0.1Å interval. The calculation results showed that
this reaction is characterized by two low barriers. The
first is 0.135 eV at 3.0Å and is caused by Н1–O1
hydrogen bond rupture. The second appears in the
moment of HCl formation in transition point of this
reaction, when R(H1–Cl3) 1.6Å and ЕА 0.183 eV.
The third stage (Fig. 3) is barrier reaction of
hydrogen Н1 exchange between PFA-2 molecule and
DMF.
It is characterized by Н1–O1 covalent bond cleavage
and by the formation of covalent Н1–O2 and hydrogen
Н1–O1 bonds. Bond Н1–O1 was chosen as reaction
coordinate, whose value was fixed in each point on
energy curve. All the others calculation parameters
were optimized.
Reaction probability in the absence of catalyst is
low since both atoms Cl3 and S3 cannot simultaneously
be near atoms Н1 and O1. It is experimentally
confirmed: yield of PFACS using catalyst is 90%.
Reaction does not virtually proceeds without catalyst.
In the fourth reaction stage due to the chlorine atom
turning in the –OS(O)Cl group the hydrogen bond
Н1–O1 in H(CF2)4OS(O)Cl2 is broken as shown with an
arrow in Fig. 3, and then chlorine atom Cl3 is ruptured
and the formation of the end reaction product occurs
and the catalyst is regenerated (Fig. 4):
3. Synthesis of polyfluoroalkanes, polyfluori-
nated ethers and esters.
New promising reagents for the synthesis of
polyfluoroalkanes, polyfluorinated ethers and esters
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
1633
Cl3
Cl
S3
O3
H
O1
H2
C2
F
H
H
H1
F
F
H
O2
N2
H
F
F
F
H
F
H
H
F
H
Fig. 3. Structure of transition complex H(CF2)4CH2OS(O)Cl2–HC(OH)N(CH3)2 (third stage).
Cl
S3
H
F
O3
F
O1
F
F
H
Cl3
H1
H
F
H
H2
F
H
F
C2
H
F
N2
H
O2
H
H
Fig. 4. Srtucture of the complex formed in the final reaction stage.
are PFACS. Unlike unsubstituted alkylchlorosulfites,
they are thermally stable compounds.
sulfites at room temperature results in the substitution
of a chlorine atom by an alkoxy group to form
symmetric bis(polyfluoroalkyl) sulfites [57]. The
replacement of the chlorine atom by fluorine proceeds
by the action of chlorine monofluoride:
The nucleophilic substitution of S(O)OCl-group in
PFACS in reactions with metal halides, carboxylic acid
salts, hydroxy groups of alcohols, phenol and with
carboxylic groups of acids was studied in detail at the
Organic Chemistry Department of Volgograd State
Technical University. In these reactions polyfluoro-
alkanes, polyfluorinated ethers and esters were ob-
tained [12, 27, 32–56].
RFOS(O)Cl + ClF → RFOS(O)F + Cl2,
RF = CH2CF3, HC(CF3)2, CH3C(CF3)2.
The formation of some amounts of thionyl fluoride
was observed. This reaction proceeds through elec-
trophilic addition of chlorine monofluoride to the S=O
group followed by dechlorination of hypochlorite. We
failed to replace the chlorine atom with fluorine in the
reaction of the above mentioned PFACS with
potassium or sodium fluoride.
3.1. Synthesis of polyfluoroalkanes and esters by
reactions with metal halides and carboxylic acid
salts.
Substitution on the sulfur atom in PFACS has some
special features. The chlorine atom in polyfluoroalkyl
sulfites is less reactive than that in alkyl chlorosulfites
leading to greater stability of PFACS relative to
hydrolysis. Continuous heating of PFACS with alcohol
does not yield bis(polyfluoroalkyl). However the
treatment with metal mercury of the polyfluoroalkyl
Later [12, 13] it was established that the reaction of
PFACS with alkali metals halides has some
peculiarities. Thus, they do not react at temperature
below 120°С. If 2,2,3,3-tetrafluoropropylchlorosulfite
is heated with potassium fluoride in diethylene glycol
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1634
RAKHIMOV
Table 6. Acryl and methacryl esters of PFA
Compound
Yield, %
bp, °С (p, mm Hg)
d420
nD20
CH2=CHCOOCH2(CF2)2H
76.2
34.0а
76.0
38.5а
76.1
45.2а
76.4
56.0а
76.5
50.8а
56 (60)
75 (110)а
85 (40)
1.2860
1.2858а
1.4460
1.4884а
1.5892
1.5974а
1.4210
1.4106а
1.5360
1.5390а
1.3666
1.3668а
1.3462
1.3460а
1.3402
1.3400а
1.3578
1.3580а
1.3506
1.3500а
CH2=CHCOOCH2(CF2)4H
CH2=CHCOOCH2(CF2)6H
CH2=C(CH3)COOCH2(CF2)4H
84 (40)а
110 (40)
107 (40)а
100 (40)
87 (40)а
104 (20)
112 (40)а
CH2=C(CH3)COOCH2(CF2)6H
a Published data.
at 130°С, 1,1,2,2,3-pentafluoropropane is obtained in
75% yield, the product of chlorosulfite moiety
substitution with fluorine. Under similar conditions
various PFACS react with potassium fluoride, lithium
chloride, potassium bromide, and potassium iodide in
diethylene glycol with distilling off the reaction
product to obtain the corresponding polyfluorohalo-
alkanes:
sulfites [17]. The reaction of n-butyl chlorosulfite with
sodium benzoate gives rise to n-butyl benzoylsulfite,
which undergoes decomposition into n-butyl benzoate.
Therefore PFACS are very promising for the use
in the organic synthesis of polyfluorohaloalkanes,
polyfluorinated ethers and esters.
3.2. Catalytic synthesis of polyfluorinated ethers
of aliphatic, alicyclic, and aliphatic-aromatic
alcohols.
H(CF2)nCH2OS(O)Cl + MeX
→ H(CF2)nCH2X + MeCl + SO2,
Reaction of PFACS with saturated monohydric
alcohols in the presence of DMF gives rise to ethers of
1,1,3-trihydroperfluoropropanol, 1,1,5-trihydroperfluoro-
pentanol with n- and iso-butyl, pentyl and n-hexyl
alcohols [39–43, 45]:
n = 2, 4, 6; X = F, Cl, Br, I; Me = K, Li, Na.
Apparently the substitution of chlorosulfite group
with halogen by the action of alkali metals halides in
diethylene glycol occurs by bimolecular nucleophilic
substitution. This approach to polyfluoroalkyl halides
is simpler than the hydroxy group replacement in PFA
with fluorine by the action of sulfur tetrafluoride
(≤ 300°С) or with bromine by the action of trichloro-
dibromophosphorus [58].
RFCH2OS(O)Cl + R1CH2OH
HC(O)N(CH3)2
RFCH2OCH2R1 + SO2 + HCl,
RF = H(CF2)2, H(CF2)4; R1 = n-С4H9, (СH3)2СHСH2,
(СH3)2СH(СH2)2, n-С5H11, n-С6H13.
The reaction of polyfluoroalkyl chlorosilfites with
salts of acrylic and methacrylic acids results in the
corresponding PFA ethers, important monomers in
synthesis of specialty polymers [59]:
The catalytic amount of DMF (0.005–0.001 mol per
mol of alcohol) was prepared in alcohol and then
dissolved in chloroform [13]. The solution of PFACS
in the same solvent (molar ratio to alcohol 1.04:1) was
added into the prepared solution at –5ºС. Then the
temperature was raised to 45–50ºС and the reaction
mixture was allowed to stand for 6 h. The hydrogen
chloride was continually blown out by inert gas
(nitrogen). After solvent removal the reaction product
was distilled. Physicochemical properties and yields of
polyfluorinated ethers are given in Table 7.
CH2=C(R)COOK + H(CF2)nCH2OS(O)Cl
→ CH2=C(R)C(O)O–СH2(CF2)nH + SO2 + KCl,
R = H, CH3; n = 2, 4, 6.
Polyfluoroalkyl acrylates and methacrylates were
obtained by the new method (Table 6) in higher yields
(76.0–76.5%) than in [60] (34.0–54.0%). It was found
that mixed anhydrides form as intermediates in
reactions of carboxylic acid salts with alkyl chloro-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
Table 7. Polyfluoroalkyl ethers of monohydric saturated alcohols
1635
Compound
Yield, %
bp, °С (p, mm Hg)
95–97 (4)
d420
nD20
n-С4H9OCH2CF2CF2H
90
85
56
60
70
71
1.2770
1.4165
1.304
1.102
1.098
1.299
1.4180
1.3700
1.352
1.345
1.355
1.360
1.365
1.348
n-С4H9OCH2(CF2CF2)2H
(СH3)2СHСH2OCH2(CF2)2H
(СH3)2СHСH2OCH2( CF2)2H
(СH3)2СH(СH2)2OCH2(CF2)2H
(СH3)2СH(СH2)2OCH2(CF2)4H
102–104 (4)
106–110 (3)
95–100 (3)
100–102 (3)
113–115 (3)
n-С6H13OCH2CF2CF2H
60
55
100–117 (2)
118–120 (2)
1.087
1.213
n-С6H13OCH2 (CF2CF2)2H
Table 8. Some physicochemical properties of cyclohexyl ethers of PFA
Ether
Yield, %
bp, °С (p, mm Hg)
105–107
d420
nD20
С6Н11OCH2 (CF2CF2 )2H
С6Н11OCH2 CF2CF2 H
С6Н11OCH2 (CF2CF2 )3H
1.3733
1.1005
1.4067
1.3865
1.3798
1.3891
75
82
65
95–98
123–127
The elongation of the carbon chain and isomeriza-
tion of carbon skeleton of the saturated monohydric
alcohol leads to the decrease in the ether yield. The
secondary hydroxy group in the alcohol molecule does
not react with PFACS is evidently because of the
mechanism of this reaction.
Unlike secondary aliphatic alcohols, reaction of
PFACS with cyclohexanol is explained by the absence
of steric hindrances owing to equatorial position of the
reacting hydroxy group.
Kinetic parameters of the reaction of PFACS with
aliphatic alcohols were determined by the rate of
simultaneous release of hydrogen chloride and sulfur
dioxide at 25–35°С. The results were compared with
kinetic parameters for cyclohexanol and PFA-1 (Table 9).
OH + H(CF2)nCH2OS(O)Cl
DMF
OCH2(CF2)nH
_SO2, _HCl
It was established that the reaction rate constant
decreases and activation energy rises (1-butanol Еа
31.0 kcal mol–1, 1-pentanol Еа 32.2 kcal mol–1, 1-
hexanol Еа 33.0 kcal mol–1) as carbon chain length
increases in a series 1-butanol, 1-pentanol, 1-hexanol.
Incorporation of electron-acceptor fluorine atoms into
the alcohol molecule raises essentially the reaction rate
and decreases the activation barrier (for PFA-1 Еа
25.4 kcal mol–1). It demonstrates the higher reactivity
of polyfluorinated alcohols in the reactions of alcohols
with PFACS in comparison with aliphatic alcohols.
In this relation the reaction of cyclohexanol with
PFACS is unusual. Cyclohexanol reacts with PFACS
in the presence of DMF to give polyfluoroalkyl
cyclohexyl ethers.
Cyclohexyl ethers of PFA obtained for the first
time in 65–82% yield are colorless high-boiling liquids
(Table 8).
Yield of cyclohexyl ethers decreases appreciably in
going from PFACS with n = 1 to n = 3. Taking into
account similar reaction conditions, this fact can be
explained by the decrease in reactivity of PFACS as
the perfluorinated chain length increases.
The study of kinetics of the reaction of chlorosulfite
with cyclohexanol under similar conditions showed
that reactivity of cyclohexanol is lower than in the case
Ether density also rises from 1.1005 (tetrafluoro-
propyl ether) to 1.4067 g cm–3 (dodecafluoroheptyl
ether) as perfluorinated carbon chain elongates.
of aliphatic alcohols: for hexanol-1
k 0.140×
10–3 (mol l–1 s–1) at 30°С, and for cyclohexanol
k 0.102×10–-3 (mol l–1 s–1) at the same temperature.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1636
RAKHIMOV
Table 9. Kinetic parameters of reaction of aliphatic alcohols,
PFA-1, with 1,1,3-trihydroperfluoropropyl chlorosulfite
OH
+ H(CF2CF2)nCH2OS(O)Cl
CH2OCH2(CF2CF2)nH
Parametera
Butanol-1 Pentanol-1 Hexanol-1 PFA-1
R
DMF
k×10–3, mol–1 l s–1
25°С
(3)
_SO2, _HCl
0.06
0.21
0.33
31.0
0.04
0.18
0.25
32.2
0.03
0.14
0.21
33.0
0.09
0.30
0.41
25.4
R
n = 1, 2, R = H; p-Cl; p-CH3O; m-NO2.
30°С
35°С
Еа, kcal mol–1
a At 30°С for cyclohexanol k = 0.102×10–3 mol–1 l s–1.
The influence of the substituent in the aromatic ring
on the yield of the polyfluoroalkyl benzyl ether was
revealed. The incorporation of electron-acceptor
substituents into the aromatic ring considerably
increases the ether yield in comparison with the
unsubstituted aromatic compound. And vice versa, the
introduction of the electron-donor substituents leads to
a decrease in the product yield. Thus, maximal yield is
in case of m-nitrobenzyl alcohol (90%) and minimal,
for p-methoxybenzyl alcohol (63%). Physicochemical
properties and yields of polyfluoroalkyl benzyl ethers
are given in Table 10.
An example of the reaction of PFACS with HO-
group of polycyclic compounds is the reaction of 1-
adamantol with 2,2,3,3-tetrafluoropropyl chlorosulfite
and 2,2,3,3,4,4,5,5-octafluoropentyl chlorosulfite in
the dioxane medium to give the corresponding ethers
[37]:
OH + H(CF2)nCH2OS(O)Cl
Polyfluoroalkyl benzyl ethers are heavy high-
boiling liquids, which are distilled in a vacuum without
decomposition. For example, tetrafluoropropyl and
octafluoropentyl ethers of m-nitrobenzyl alcohol boil
in a vacuum of 3 mm Hg at 130–133 and 140–143°С,
respectively.
OCH2(CF2)nH
n = 2, 4.
Reactions of PFACS with substituted benzyl
alcohols were studied [38, 39, 45]. Benzene was used
as a solvent. All others reaction conditions were
similar to those in the case of aliphatic alcohols.
It is seen from the kinetic data of reaction of
PFACS with benzyl alcohols that m-nitrobenzyl
alcohol is the most reactive (Table 11), and it has
higher acidity of HO-group in comparison with benzyl
alcohol. Thus, reaction rate constants are as follows,
mol l–1 s–1: benzyl alcohol, 0.08 (25°С), 0.25 (30°С),
0.38 (35°С); m-nitrobenzyl alcohol, 0.10 (25°С), 0.31
Benzyl alcohols react with PFACS under catalysis
with DMF. In this case chlorosulfite group is
substituted by ArCH2O-moiety to form polyfluoroalkyl
benzyl ethers.
Table 10. Polyfluoroalkylbenzyl ethers
Compound
Yield, %
bp, °С (p, mm Hg)
d420
nD20
PhCH2OCH2(CF2)2H
85
83
90
85
70
63
90
84
120–122
125–127
130–133
135–137
110–112
116–120
130–133
140–143
1.5065
1.6382
1.4025
1.5002
1.2856
1.3643
1.3570
1.5002
1.3580
1.3730
1.4580
1.4100
1.4440
1.3995
1.4760
1.4310
PhCH2OCH2(CF2)4H
p-Cl–PhCH2OCH2(CF2)2H
p-Cl–PhCH2OCH2(CF2)4H
p-СН3О–PhCH2OCH2(CF2)2H
p-СН3О–PhCH2OCH2(CF2)4H
m-NO2PhCH2OCH2(CF2)2H
m-NO2PhCH2OCH2(CF2)4H
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SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
1637
Table 11. Influence of substituents in aromatic ring on the rate of reaction of PFACS with benzyl alcohols
Benzyl alcohol
p-Methoxybenzyl alcohol
p-Chlorobenzyl alcohol
m-Nitrobenzyl alcohol
Parameter
k×10–3, mol–1 l s–1
25°С
0.08
0.25
0.05
0.21
0.10
0.29
0.10
0.31
30°С
35°С
0.38
0.32
0.40
0.41
Еа, kcal mol–1
25.50
28.61
21.40
21.05
(30°С), 0.41 (35°С). The activation energy of the
reaction of PFACS with m-nitrobenzyl alcohol
(21.05 kcal mol–1) is appreciably lower than for benzyl
alcohol (25.50 kcal mol–1). Therefore, as in the case of
PFA, in the benzyl alcohols the electron-acceptor
substituents are favor the catalytic reaction giving
polyfluoroalkyl ethers, HCl and SO2.
proton and СН2 group carbon atom of PFACS are
favorable for the complex formation.
The transfer of alcohol proton to the polar chlorine
atom, the simultaneous cleavage of С3–O5 and S–Cl
bonds, the liberation of SO2 and HCl molecules, the
regeneration of DMF molecule from its associate with
alcohol and the formation of ether occur in this
complex.
On the contrary, the incorporation of electron-donor
methoxy group decreases the acidity of the benzyl
alcohol and the reaction rate. The activation energy of
the reaction of PFACS with p-methoxybenzyl alcohol
increases to 28.61 kcal mol–1.
The structure of six-membered complex was
investigated by PMR spectroscopy (Table 12) at –30°С
by the example of reaction of butanol-1 and PFACS
(n = 2). Owing to the direct interaction of the Н2 atom
of the alcohol hydroxy group with the oxygen atom in
DMF and chlorine atom in PFACS, the signal of this
proton is shifted downfield (Δδ 0.17 ppm) in the PMR
spectrum. The signal of the СН2 group proton of
PFACS located at the carbon atom reacting with the
nucleophilic alcohol oxygen atom is shifted upfield in
comparison with isolated PFACS molecule; the
coupling constant value increases. These facts indicate
the formation of the complex. In this connection the
lability and transfer of proton to give HCl and the
simultaneous bonding of alkoxy group oxygen to
release SO2 is the factor, which determines the ease of
the reaction products formation.
The observed experimental facts are understandable
in the context of mechanism of nucleophilic
bimolecular substitution of chlorosulfite group in
PFACS by ArCH2O group. This process is
accompanied with simultaneous liberation of SO2 and
HCl with identical rate.
Most probably the reaction occurs through
formation of six-membered complex:
HF2C
CF2
H
H
O5
C
1
O
R
3
CH
H
The alcohol acidity decreases and steric factor
increases as aliphatic chain elongates, what leads to
higher activation barriers.
2 H
O
S
H3C
H3C
Cl
N
C
H
O
Therefore catalyst (DMF) role is in alcohol
molecule activation in associates alcohol–DMF, which
appears due to hydrogen bonding between О4 atom in
DMF molecule and Н2 and Н3 atoms in alcohol
molecules, and in involving these associates in the
formation of complexes with PFACS molecules.
Polarization of Н2–O1 bond occurs in the associate.
The bond is stretched and the proton becomes more
mobile. Due to the stronger polarization of Н2–O1
bond the proton mobility increases still further as
The chlorosulfite carbon atom and the oxygen atom
of alcohol RCH2OH take part in the complex forma-
tion (1,1,3-trihydroperfluorochlorosulfite was taken as
an example) to give a bond O1–С3. Chloro-sulfite
chlorine atom and hydroxy proton bonded in associate
with DMF also are involved into this process to form
Н2–Cl bond. The high nucleophilicity of the chlorine
atom, considerable positive charges on HO group
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1638
RAKHIMOV
Table 12. 1Н NMR spectra parameters for PFACS, butanol-1, and transition complex
Chemical shift, δ and spin-spin coupling constant, J
Compound
HCF2
O–CH2–CF2
HO–
δ, ppm
J, Hz
δ, ppm
J, Hz
δ, ppm
Complex
PFACS
5.73 t.t
51.9
5.4
52.5
3.9
–
3.85 t
3.64 t
4.06 t
4.51 t
–
14.6
12.6
12.0
12.3
–
3.10 s
5.90 t.t
–
–
Butanol-1
2.93 s
fluorine or chlorine atoms and electron-accepor nitro-
group is incorporated into aliphatic or benzyl alcohol
molecule [Eq. (3)]. It makes easier the proton transfer
in the formed polar six-membered complex.
(3) The decay of the six-membered structure to H
(CF2)2CH2OR, SO2, HCl and (CH3)2NCHO has an
energy barrier Еа, kcal mol–1: 38.058 (R = С3H7),
21.898 (R = HCF2CF2CH2), 25.341 (R = PhCH2).
The character of activation energy variation for the
reaction of PFACS with alcohols obtained by
quantum-chemical method is in agreement with the
results of kinetic studies (Table 11). It should be noted
that increase in polarity of alcohol НО group in the
forming complexes and the charge increase rise on Cl
atom in comparison with PFACS favor the formation
of thereaction end-products [42].
Quantum-chemical analysis was performed for
starting reagents, intermediates, and end-products of
the reaction PFACS with alcohols catalyzed with
DMF. The computation of PFACS reaction model by
the example of reaction of H(CF2)2CH2OS(O)Cl with
different alcohols in the presence of DMF was made
by quantum-chemical ab initio method using 3-21G
basis (from H to Ar). Electronic and geometric
structures of the compounds H(CF2)2CH2OS(O)C1,
ROH, (CH3)2NCHO, (R = С3H7, HCF2CF2CH2,
PhCH2) were calculated. The computation was per-
formed with optimization of all geometric parameters.
All stages were successively analyzed.
The incorporation of aromatic ring also makes the
reaction easier. The reactivity of 1-propanol is
substantially lower due to the weak polarization of
О–Н bond in the complex. The computational and
experimental values of activation energy are close
(Table 13). It indicates that the suggested mechanism
is fairly probable.
(1) The association in the system ROH–(CH3)2·
NCHO is accompanied with energy gain ΔЕ
–3.12 kcal mol–1 (R = С3H7), ΔЕ –4.844 kcal mol–1
(R = HCF2CF2CH2), ΔЕ –6.0956 kcal mol–1 (R = PhCH2).
Based on the kinetic study and quantum-chemical
calculations, it is possible to conclude that the reaction
of PFACS with alcohols occurs through bimolecular
nucleophilic substitution of chlorosulfite group by
alkoxy moiety. The incorporation of electron-acceptor
fluorine atoms into aliphatic alcohols and of electron-
acceptor substituents into the aromatic ring of benzyl
alcohols increases the reaction rate and decreases the
activation energy.
(2) The formation of a six-membered structure
involving simultaneously H(CF2)2CH2OS(O)C1, ROH,
and (CH3)2NCHO proceeds with energy gain ΔЕ,
kcal mol–1: 1.945 (R=С3H7), –3.078 (R
=
HCF2CF2CH2), –2.8764 (R = PhCH2).
Table 13. Atomic charges in the reaction complexes
3.3. Catalytic synthesis of symmetrical and unsym-
metrical di(polyfluoroalkyl) ethers.
Atomic charge
The high rate of the reaction of PFA-1 with 1,1,3-
trihydroperfluoropropylchlorosulfite (Table 8) led us
to the idea of the synthesis of symmetrical di-
(polyfluoroalkyl) ethers by mixing of PFA with thionyl
chloride and avoiding the stage of PFACS isolation.
Indeed, DMF catalysis allows to obtain for the first
time the symmetrical di(polyfluoroalkyl) ethers
without PFACS isolation [44]:
PFACS, alcohol and its
complex
O
H
Cl, PFACS
alcohol OH group
butanol, PFACS
complex
–0.330 +0.197
–0.363 +0.223
–0.325 +0.197
–0.380 +0.235
–0.361
–0.393
–0.361
–0.398
benzyl alcohol, PFACS
complex
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
Table 14. Yields and physicochemical properties of di(polyfluoroalkyl) ethers
1639
Ether
Yield, %
bp, °С (p, mm Hg)
d420
nD20
HCF2CF2CH2OCH2СF2CF2H
75.8
96.4
77.3
65 (1)
103 (2)
130 (1)
1.3575
1.3385
1.3370
1.6251
1.7344
1.8014
H(CF2CF2)2CH2OCH2(CF2CF2)2H
H(CF2CF2)3CH2OCH2(CF2CF2)3H
Table 15. Dependence of yield of di(polyfluoroalkyl) ethers [H(CF2CF2)nCH2]2O from reaction conditions (complex forma-
tion at –15°С)
Reagents ratio, mol
thionyl chloride
Complex decay time, h
Ether yield, %
alcohol (n)
DMF
at 20–30°С
at 30–50°C
1 (n = 1)
1 (n = 2)
1 (n = 3)
1 (n = 1)
1 (n = 1)
1 (n = 1)
1.0
0.005
0.006
0.009
0.006
0.015
0.007
1
5
2
1
1
1
4 (30–40)
5 (30–40)
6 (40–50)
3 (35)
75.8
96.4
77.3
44.7
61.1
69.6
1.06
1.1
0.5
0.57
1.0
3 (35)
3 (35)
H(CF2CF2)2CH2OS(O)Cl + H(CF2CF2)2CH2OH
2H(CF2CF2)nCH2OH + SOCl2
→ H(CF2CF2)nCH2OCH2(CF2CF2)nH + SO2 + 2HCl.
DMF
[H(CF2CF2)2CH2O]2SO
−HCl
This new reaction occurs using equimolar reagents
ratio in the presence of catalytic amount of DMF (0.05
mol) to give the corresponding di(polyfluoroalkyl)
ethers, whose yields and some physicochemical
properties are presented in Table 14.
+ [H(CF2CF2)2CH2]2O +SO2.
to meet strictly optimal parameters for the synthesis of
di(polyfluoroalkyl) ethers:
Even during PFACS synthesis it was found that the
increase in the temperature of reagents mixing up to
5°С and the increase in reaction time led to an
essential decrease in the target product yield owing to
the formation of by-products, bis(polyfluoroalkyl)-
sulfite and polyfluoroalkyl chloride.
(а) equimolar reagents ratio (thionyl chloride–
PFA);
(b) catalyst (DMF) should not exceed 0.005 mol per
1 mol of reagent;
(c) PFA dosage temperature at the complex
formation stage should not exceed −15°С;
H(CF2CF2)nCH2OS(O)Cl + H(CF2CF2)nCH2OH
(d) optimal reaction time at the complex ther-
molysis stage at 20–30°С should be 1.5 h.
→ [H(CF2CF2)nCH2O]2SO + HCl,
H(CF2CF2)nCH2OS(O)Cl → H(CF2CF2)nCH2Cl + SO2.
It is obvious from Table 15 that the divergence
from the mentioned process parameters of di(poly-
fluoroalkyl) ethers synthesis leads to the decrease in
their yields. The isolation of the target product by
vacuum distillation is not difficult since the boiling
temperature of di(polyfluoroalkyl) ethers substantially
differs from that of the others components of the
reaction mixture.
Moreover, the increase in the catalyst concentration
in the reaction of thionyl chloride with PFA-2 causes
the rise in the rate of hydrogen chloride and SO2
release; PFACS yield decreases to 59%. In this case
the reaction mixture contains about 1% of bis(poly-
fluoroalkyl) sulfite and 34% of symmetrical di(1,1,5-
trihydroperfluoropentyl) ether:
Unsymmetrical di(polyfluoroalkyl) ethers were
obtained by catalysis with DMF through reaction of
Therefore variety of possible by-products formed in
catalytic reaction of PFA with thionyl chloride requires
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1640
RAKHIMOV
Table 16. Yields and physicochemical properties of unsymmetrical di(polyfluoroalkyl) ethers
Ether
Yield, %
85.0
bp, °С (p, mm Hg)
d420
nD20
HCF2CF2CH2OCH2(CF2CF2)2H
83 (2)
1.6790
1.3500
HCF2CF2CH2OCH2(CF2CF2)3H
HCF2CF2CH2OCH2(CF2CF2)4H
H(CF2CF2)2CH2OCH2(CF2CF2)3H
53.1
34.5
61.5
95 (1)
130 (1)
110 (1)
1.7310
(mp 49°С)
1.7647
1.3450
–
1.3380
Table 17. Yields and physicochemical properties of polyfluoroalkyl ethers of phenol
Ether
Yield, %
43.0
bp, °С (p, mm Hg)
d420
nD20
53 (3)
HCF2CF2CH2OC6H5
1.4378
1.4508
51.0
H(CF2CF2)2CH2OC6H5
68 (3)
1.5760
1.3980
PFACS with PFA containing various polyfluoroalkyl
moieties in the molecules. Furthermore, non-catalytic
method, reaction of PFACS with PFA in the presence
of triethylamine, was also used [32]:
product along with economic profit. And triethyl-
ammonium salt formed by the second method (5) es-
sentially contaminates the target product.
4. Synthesis of polyfluoroalkyl ethers and esters
of phenol and carboxylic acids.
'
RFCH2OS(O)Cl + RFCH2OH
DMF
Polyfluoroalkyl ethers of phenol were obtained
earlier by the action of brombenzene on PFA
alcoholates in the presence of copper in pyridine [61].
Recently they were synthesized through reaction of
phenol with PFACS in the presence of triethylamine
[33, 52]:
'
(4)
RFCH2OCH2RF + SO2 + HCl,
'
RFCH2OS(O)Cl + RFCH2OH
NEt3
'
RFCH2OCH2RF + SO2 + NEt3HCl,
(5)
RF = HCF2CF2, R' = H(CF2CF2)2, RF = HCF2CF2, R' =
F
F
H(CF2CF2)3, RF = H(CF2CF2)2, R' = H(CF2CF2)3.
F
RFCH2OS(O)Cl + C6H5OH
NEt3
.
RFCH2OC6H5 + SO2 + NEt3 HCl.
According to catalytic method [Eq. (4)], the
solution of PFACS was added to PFA with catalyst in
molar ratio 1:(0.005–0.01) at –10ºС. The reaction
mixture was kept for one day at room temperature.
Then the solvent (chloroform, diethyl ether) was
removed and reaction product was distilled. Yield 59–
98%. By the second method [Eq. (5)], the solution of
PFACS was added to the previously prepared complex
of alcohol with triethylamine at –10ºС. Then the
reaction mixture was allowed to stand for one day at
room temperature (solvent IS pentane or hexane). The
formed triethylammonium chloride was filtered off,
and the ether obtained was purified by vacuum
distillation in yield of 34–85% (Table 16).
In this case the reaction was carried out using
equimolar ratio of PFACS and associated phenol and
triethylamine at –10°С in pentane. Then the reaction
mixture was kept at room temperature for one day.
After triethylamine hydrochloride separation and
pentane removal the corresponding polyfluoroalkyl
ethers of phenol were isolated by vacuum distillation
(Table 17).
The reaction carried out in the presence of catalyst
(DMF) leads to similar results. One of the possible reasons
of decrease in the yield of phenol polyfluoroalkyl
ethers are, in our opinion, steric factors affecting the for-
mation of six-membered polar complex considered earlier.
Though both methods allow to obtain ethers in
comparatively similar yields, the catalytic method is
the most reasonable to use, since it results in more pure
However polyfluoroalkyl ethers were not isolated
in the reaction of tetrafluoropropyl- and octafluoro-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
1641
pentylchlorosulfites I and II with salicylic aldehyde
III. The reaction was carried out by different methods:
in the presence of DMF as catalyst and in its absence
or with triethylamine using equimolar reagents ratio
and hexane as solvent. The main reaction product was
acyclic sulfite of (2-hydroxyphenyl)chloromethanol
IV. The latter was obtain in 57% yield as colorless
crystalline substance, mp 131–131.5°С (chloroform).
Polyfluorinated alcohol was also obtained [50]. The
scheme of the reaction is as follows:
O
O
S(O)CH2(CF2CF2)nH
H
ClS(O)OCH2(CF2CF2)nH +
OH
O
Cl
O
S
O
_H(CF2CF2)nCH2OH
O
Cl
IV
The existence of intramolecular hydrogen bond in
the initial salicylic aldehyde molecule favors the first
stage of nucleophilic substitution of chlorine in
PFACS with further ring closure to form sulfite and to
eliminate PFA molecule.
To avoid the rapid heat generation and tarring of
the reaction products, reaction is preferably carried out
using previous mixing of the equimolar amounts of
carboxylic acid and TEA in hexane. Then to this
solution PFACS solution in hexane is added at –10°С.
Vigorous release of SO2 is observed at refluxing.
Carboxylic acids in the presence of triethylamine
react, involving НООС-group, with PFACS to give
polyfluoroalkyl esters:
The formation of polyfluoroalkyl ester VII, TEA
hydrochloride, and SO2 can be explained by the
reaction through a six-membered polar complex. The
formation of the latter is favoring the nucleophilic
substitution at the α-methylene group of PFACS V
involving the carboxy group of VI [51]:
R−C(O)OH + H(CF2CF2)nCH2OS(O)Cl
NEt3
.
.
R−C(O)OCH2(CF2CF2)nH + SO2 + NEt3 HCl,
R = CH3, n = 2; R = CH3, n = 1; R = Pr, n = 2; R = Bu,
n = 1.
(CF2CF2)nH
O
CH2
NEt3
O
O
V + VI
VII +
Et3N HCl + SO2
R
C
O
H
S
Cl
Et3N:
Similar result was obtained, when reaction of
PFACS with carboxylic acid was catalyzed with DMF.
or in DMF involving prevailingly the carboxy group
similarly to the carboxylic acids, resulting in the
oligomer OCA-IV [51, 62, 63].
5. Polyfluoroalkylation of oligomers and poly-
mers at HO- and HOOC-groups.
The existence of ester group in oligomer OCA is
confirmed by the absorption in the IR spectrum in the
range of the stretching vibrations of this group at νC=O
1748–1752 cm–1. Microdoping of polyfluorinated
compounds including F-oligomers into polycapro-
Reaction of PFACS with oligomers of ε-
aminocapronic acid (OCA), H[HN(CH2)5C(O)]mOH
(m = 60–80), proceeds in the presence of triethylamine
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

1642
RAKHIMOV
the terminal HO groups in the presence of DMF was
OCA + H(CF2CF2)2CH2OS(O)Cl
carried out to reveal features of polyfluoroalkylation of
oligodiols:
N(C2H5)3
(CF2)4H
+δ
CH2
HO
OH
+ 2 RFCH2OS(O)Cl
O
O
_
H[HN(CH2)5C(O)]n 1HN(CH2)5
O
+
DMF
O_
O
H
RFO
ORF
O
S
_
_SO2, _HCl
+δ
_[(C2H5)3NH]+Cl , _SO2
Cl
:N(C2H5)3
RF = HCF2CF2CH2, H(CF2CF2)2CH2.
O
Diethers were obtained in 79–80% yield. They are
high-boiling liquids (Table 18).
H[HN(CH2)5C(O)]n 1HN(CH2)5
_
O CH2 (CF2)4H
We failed to obtain the monosubstitution product.
Owing to the capability of the diethylene glycol to
polymerize in acidic media, polyethers containing
terminal polyfluoroalkyl groups were obtained as by-
products. They are viscous liquids of the structure
RFCH2O(CH2OCH2)nOCH2CH2OH insoluble in water
and non-distillable in a vacuum. It is necessary to
remove quickly hydrogen chloride from the reaction
mixture to decrease the polyether formation.
OCA-IV
amide compositions increase their heat and light
stability, improves tribologic characteristics [63, 64].
The reaction of PFACS with oligomeric diols
catalyzed with DMF was studied [38] by the example
of isoprene-butadiene oligomers containing terminal
hydroxy groups with monomers ratio 20:80, average
molecular mass 3000–3500, and hydroxy groups
content 0.7–1.1 wt %. Perfluoroalkylated oligomers of
the following structure were obtained:
The existence of unsaturated fragments in the
oligomer structure makes it possible to incorporate
various functionalities. Hydroperoxides are known
[66] to be added readily to the double bond in the
presence of acids, which was used for the synthesis of
di(polyfluoroalkyl)-containing oligomers with tert-
butylperoxy-groups [67].
RFCH2O−[CH2−C(CH3)=CH−CH2)x
−[CH2−CH=CH−CH2)y−OCH2RF,
.
RF = HCF2CF2, H(CF2CF2)2, H(CF2CF2)3.
The reaction proceeds involving more reactive 2-
methyl-2-butene fragment under mild conditions in
organic solvent medium at 30-40°С over 2 h. The formed
di(polyfluoroalkyl)oligo-tert-butylperoxide is white
pasty substance containing 0.4% of active oxygen,
which is well combined with polymers and monomers
and can be used as an active component of poly-
merization system and in co-vulcanization process.
IR spectroscopy method indicates that the obtained
oligomer contains no hydroxy groups. The fluorine
content is 2.3 (RF = HCF2CF2) and 4.0% [RF =
H(CF2CF2)2] respectively confirming almost quanti-
tative substitution of НО-groups with polyfluoroalkyl
fragments.
The reaction of PFACS with diethylene glycol at
RFO−[CH2−C(CH3)=CH−CH2)x] − (CH2−CH=CH−CH2)y−ORF
(CH3)3COOH
RFO{CH2C(CH3)[O2C(CH3)3]CH2CH2}x(CH2CH=CHCH2)yORF,
RF = H(CF2)nCH2, n = 2–6; x = 10, y = 51.
Table 18. Yields and physico-chemical properties of polyfluoroalkyl diethers
RF
Yield, %
79
bp, °С (p, mm Hg)
d420
nD20
HCF2CF2
122–125 (3)
1.3460
1.2990
80
Н(CF2CF2)2
160–163 (3)
1.3320
1.4260
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 8 2010

SYNTHESIS OF POLYFLUOROALKYL CHLOROSULFITES
1643
The hydrochlorination of the starting fluorine-
containing oligomer was carried out [67]. Addition of
HCl occurs through electrophilic addition mechanism
in accordance with the Markownikoff’s rule:
RFO−[CH2−C(CH3)=CH−CH2)x] − (CH2−CH=CH−CH2)y−ORF
HCl
RFO−{CH2(Cl)C(CH3)CH2−CH2−]x − [CH2−CH(Cl)CH2−CH2)y − ORF,
RF = H(CF2)nCH2, n = 2–6; x = 10, y = 51.
6. Cohen, W., J. Org. Chem., 1961, vol. 26, no. 10,
The hydrogen chloride adds to all double bonds.
The reaction was performed in organic solvent
medium. Through the reaction mixture the hydrogen
chloride was bubbled for 40 min at 50°С. It was
established that hydrogen chloride addition occurs
virtually quantitatively. The IR spectra of the hydro-
chlorination product contain no intensive absorption
band, which is characteristic of double carbon–carbon
bond (1640 cm–1) of the starting oligomer.
p. 4021.
7. Grakauskas, V., J. Org. Chem., 1970, vol. 35, no. 9,
p. 3030.
8. Rakhimov, A.I. and Vostrikova, O.V., Abstracts of
Papers, IV Mezhdunarodnaya konferentsiya
“Naukoyemkie khimicheskie tekhnologii” (IV
International Conference “Science Intensive Techno-
logies”), Volgograd, 1996, p. 65.
9. Rakhimov, A.I. and Vostrikova, O.V., Zh. Org. Khim.,
Anther alcohol of wide practical importance is the
polyvinyl alcohol (PVA). Its modification was
performed by the reaction with PFACS [46]. Owing to
high reactivity of PFACS relative to water, dry DMF
was chosen as medium the for modification. DMF is
also a catalyst for this process.
1999, vol. 35, no. 5, p. 815.
10. Rakhimov, A.I., Popov, Yu.V., Volchkov, V.M., and
Vostrikova, O.V., Khimiya i tekhnologiya elemento-
organicheskikh monomerov i polimernykh materialov
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R–OH + RFCH2OS(O)Cl → R–O–CH2RF,
11. Storozhakova, N.A., Cand. Sci. (Chem.) Dissertation,
RF = HCF2CF2, H(CF2CF2)2; ROH = PVA.
Volgograd, 1998.
12. Vostrikova, О.V., Cand. Sci. (Chem.) Dissertation,
Volgograd, 1999.
13. Rakhimov, A.I. and Vostrikova, O.V., Khimiya i
The incorporation of fluorine into polyvinyl alcohol
molecule in little amounts (≤ 5%) is a necessary
condition to retain the water-solubility of poly-
fluorinated polyvinyl alcohol.
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i
polimernykh materialov (Chemistry and Technology of
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The use of polyfluorinated peroxide initiators and
polyfluorine-containing polyvinyl alcohol at suspend-
sion polymerization of vinyl chloride allows to obtain
poly(vinylchloride) with increased heat and light stab-
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high operational reliability [68].
14. Rakhimov, A.I. and Vostrikova, O.V., Zh. Org. Khim.,
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