Features of the reaction of polyfluoroalkyl chlorolsulfites with allyl alcohol

Article abstract of DOI:10.1134/S107036321108010X

Unlike the saturated aliphatic and aromatic alcohols, allyl alcohol under the same conditions reacts with polyfluoroalkyl chlorosulfites to form not ethers, but polyfluorinated alcohols. The exception is polyfluoroalkyl chlorosulfites with the chain length of more than five carbon atoms. Allyl ethers of polyfluorinated alcohols of general formula CH₂=CHCH ₂OCH₂(CF₂CF₂)_nH (n = 1-3) were obtained, when the reaction proceeded in the presence of potassium carbonate, owing to its participation in a specific orientation of the reaction centers in the resulting intermediate structure, which is easily transformed into allyl ethers of polyfluorinated alcohols. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S107036321108010X

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 8, pp. 1640–1642. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.I. Rakhimov, A.V. Miroshnichenko, Do Duong Phuong Thao, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 8,
pp. 1295–1297.
Features of the Reaction of Polyfluoroalkyl Chlorolsulfites
with Allyl Alcohol
A. I. Rakhimov, A. V. Miroshnichenko, and Do Duong Phuong Thao
Volgograd State Technical University, pr. Lenina 28, Volgograd, 400131 Russia
e-mail: rakhimov@sprint-v.com.ru
Received July 13, 2010
Abstract—Unlike the saturated aliphatic and aromatic alcohols, allyl alcohol under the same conditions reacts
with polyfluoroalkyl chlorosulfites to form not ethers, but polyfluorinated alcohols. The exception is
polyfluoroalkyl chlorosulfites with the chain length of more than five carbon atoms. Allyl ethers of
2 2 2 2 2 n
polyfluorinated alcohols of general formula CH =CHCH OCH (CF CF ) H (n = 1–3) were obtained, when the
reaction proceeded in the presence of potassium carbonate, owing to its participation in a specific orientation of
the reaction centers in the resulting intermediate structure, which is easily transformed into allyl ethers of
polyfluorinated alcohols.
DOI: 10.1134/S107036321108010X
The monohydric saturated and aromatic alcohols
react with polyfluoroalkyl chlorosulfites to afford
ethers [1–5]. But the attempt to synthesize in these
conditions (catalysis with N,N-dimethylformamide) the
allyl ethers of polyflurinated alcohols failed. The
reaction of allyl alcohol with polyfluoroalkyl chloro-
sulfite gives rise to polyfluorinated alcohol. Perhaps,
the hydrolysis of chlorosulfite proceeds as follows:
H(CF CF ) CH OSOCl + CH =CHCH OH
2
2 n
2
2
2
CH2
H
HC
H C
O
CH2 (CF CF ) H
2
2 n
H(CF CF ) CH OH
2
2 n
2
Cl
O
2
SO2, CH =CHCH Cl
2 2
S
O
I
n = 1, 2, 3.
The chlorine atom of chlorosulfite group attacks the
methylene carbon atom of allyl fragment with
simultaneous nucleophilic substitution of chlorosulfite
groups with hydroxy one via the transition state I. The
substitution is accompanied by the simultaneous
release of sulfur dioxide. Allyl ether of the poly-
fluorinated alcohol is formed as a by-product. In the
case of low-molecular chlorosulfite (n = 1) only traces
of allyl ether were observed. When the chlorsulfite
with n = 3 was used, the ether content increased to
substituent increases, it prevents the complex I forma-
tion, leading to the polyfluorinated alcohol.
We studied a possibility to change the reaction
direction using potassium carbonate. As expected, its
molecule can interact with the polar group of both
reagents and orient the reaction centers appropriately
to form the structure II. The latter transforms readily
into the reaction products, the allyl ethers IIIa–IIIc.
3
0%. This is probably due to the increasing influence
As a result of the reaction of allyl alcohol with
polyfluoroalkyl chlorosulfites in the presence of
of the steric factor: as the bulk of thrpolyfluoroalkyl
1
640

FEATURES OF THE REACTION OF POLYFLUOROALKYL CHLOROLSULFITES
H(CF CF ) CH OSOCl + CH =CHCH OH
1641
2
2 n
2
2
2
(
CH2 CH2
O
CF CF ) H
2
2 n
HC
O
S
K CO3
2
H(CF CF ) CH OCH CH=CH
2
2
2 n
2
2
H C
2
H
KCl, SO2, KHCO3
O
C
Cl
K
O
KO
O
II
n = 1 (IIIа), 2 (IIIb), 3 (IIIc).
1
potassium carbonate the yield of allyl ethers IIIa–IIIc
In the H NMR spectra of the obtained allyl ethers
IIIa–IIIc there are triplet of triplet signals of the
protons of HCF CF group at 5.8 (IIIa, IIIb) and
was increased to 40.4–66.2%.
2
2
Since the reaction of polyfluoroalkylchlorosulfites
with monohydric alcohols (catalysis with DMF)
proceeds via two stages (in the first stage at –10 to –5°C
a complex is formed, and in the second at 30°C it
decomposes to alkylpolyfluoroalkyl ether) [4], the
reaction with allyl alcohol was also performed in two
stages. Initially the reagents (allyl alcohol, potassium
carbonate, and polyfluoroalkyl chlorosulfite) were
mixed in chloroform at from –10 to –5°C, and then the
reaction mixture was heated to 30°C and kept for 3–
1
.6 ppm (IIIc) with the spin-spin coupling
constants JHF 4.2–5.5 and 51.9–52.5 Hz, which corres-
ponds to the published data [7]. α-Methylene group in
H(CF CF ) CH -fragment appears as a triplet with the
2
2 n
2
spin–spin coupling constant JHF 13.2–14.1 Hz. The
spectral analysis of the allyl group in the synthesized
ethers IIIa–IIIc allows us to identify the cor-
responding protons.
H
H(A)
5
h. The potassium chloride and potassium hydrogen
C
C
carbonate precipitates were filtered off. The solvent
was removed and the residue was distilled in a
vacuum. The resulting allyl ethers were colorless
heavy liquids. The synthesized allyl ethers were
H
CH −OCH (CF CF ) H
2
2
2
2 n
(
B2)
(C2)
δ
А
5.81 ppm (multiplet), δВ2 5.23 ppm (multiplet), δC2
4.39 ppm (doublet).
1
identified by the IR and H NMR spectroscopy. A
characteristic feature of the IR spectra of the ethers is a
strong absorption band originating from the stretching
vibrations of CH –O–CH bonds [6]. Moreover, the
The known approach to allyl ethers of poly-
fluorinated alcohols via the reaction of allyl bromide
and iodide with potassium alcoholates [8] is less
effective. The disadvantages of this method are low
accessibility of allyl iodide (bromide) and the longer
reaction time as compared with the synthesis of the
ethers by the new method, the reaction of polyalkyl
chlorosulfites with allyl alcohol in the presence of
potassium carbonate.
2
2
introduction of allyl group has no significant effect on
–
1
a narrow absorption range (1000–1150 cm ). In the IR
spectra of ethers IIIa and IIIc the stretching vibrations
–
1
of C–O–C bond are observed at 1154 and 1163 cm ,
respectively, as strong absorption bands. The
absorption band of an isolated double bond usually
–
1
occurs in the range of 1680–1620 cm [6]. For the
synthesized ethers IIIa–IIIc the respective absorption
EXPERIMENTAL
–
1
band of medium intensity is observed at 1686 cm ,
which is caused by the inductive effect of the electron-
withdrawing perfluorinated carbon chain. In the IR
spectra of the ether IIIa there is an absorption band at
1
The H NMR spectra (300 MHz) were taken on a
Varian Mercury-300 instrument in CCl , internal
reference tetramethylsilane. The IR spectra were
obtained on a Specord-M82 from a thin layer (liquid
film). The fluorine content was determined by the
direct potentiometry with a fluoride-selective electrode.
4
–
1
–1
3
023 cm , which is shifted to the region of 3040 cm
(IIIb, IIIc) as the perfluorocarbon chain increases. It
belongs to the stretching vibrations of C–H bond in
CHF -group.
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011

1
642
RAKHIMOV et al.
51.6%, bp 90°С (6 mm Hg), n 1.3560, d 1.4816. IR
2
D
0
20
4
3-(2,2,3,3-Tetrafluoro)propoxy-1-propene (IIIa). In
–
1
a three-neck reactor equipped with a thermometer,
reflux condenser, and a stirrer, was placed a solution of
1
spectrum, ν, cm : 520 m. narrow, 614 w, 640 v.w, 700
br.s, 743 br.s, 769 br.s, 811 w, 837 w, 889 s. narrow,
931 s. narrow, 991 s. narrow, 1077 s. narrow, 1086 s.
narrow, 1129 w, 1189 br.s (С–О–С), 1240 br.s (CF2),
1334 w, 1420 w, 1437 m, 1497 m, 1574 br.w, 1644
.49 g (0.0256 mol) of allyl alcohol in 30 ml of
chloroform and 3.54 g (0.0256 mol) of K CO . To the
2
3
mixture cooled to –15°C was added a solution of 5.5 g
0.02564 mol) of 1,1,3-trihydroperfluoropropyl chloro-
(
br.m (С=С), 2886 v.w (CH –O), 2929 v.w, 3006 m
2
1
sulfite in 10 ml of chloroform. Then the reaction
mixture was heated to 30°C and kept under stirring for
(CH , CH), 3049 br.w (CHF ), 3143 w. Н NMR
2
2
spectrum, δ, ppm (J, Hz): 6.017 t.t (HCF , J 51.6, 5.1),
2
3
h. After the removal of the precipitate, solvent and
3.931 t (СF СН , J 14.1), 4.39 d (CН C=, J 22.5),
2
2
2
unreacted alcohol, the target product was distilled in a
5.814 m (CН=), 5.259 m (=CН ). Found F, %: 60.77.
2
vacuum. Yield 2.92 g (66.2%), bp 95–98°С (15 mm
C H F O. Calculated F, %: 61.29.
1
0
7 12
20
20
–1
Hg), nD 1.3660, d 1.4286. IR spectrum, ν, cm : 520
4
m. narrow, 666 m, 760 br.m, 749 br.s, 880 s. narrow,
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1
br.m (С=С), 2886 v.w (CH –O), 2920 v.w, 2997 m
2
2
317 m, 1386 w, 1446 s, 1480 m, 1574 br.w, 1686
2
2
(CH , CH), 3023 br.w (CHF ), 3134 w.
2
2
3
-(2,2,3,3,4,4,5,5-Octafluoro)pentoxy-1-propene
(IIIb) was obtained similarly to IIIа. Yield 40.4%, bp
2
0
20
9
8–100°С (15 mm Hg), n 1.3635, d 1.4418. IR
D 4
–
1
spectrum, ν, cm : 520 m. narrow, 666 m, 760 br.m,
8
1
03 br.s, 887 s. narrow, 940 s. narrow, 991 s. narrow,
043 m, 1069 w, 1112 w, 1163 br.s (С–О–С), 1197
br.s (CF ), 1249 br.s, 1317 m, 1386 w, 1437 s, 1489 m,
2
1
566 br.w, 1686 br.m (С=С), 2886 v.w (CH –O), 2920
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2
v.w, 2989 m (CH , CH), 3040 br.w (CHF ), 3126 w.
2
2
1
Н NMR spectrum, δ, ppm (J, Hz): 5.803 t. t (HCF , J
2
7
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2
5
1.6, 5.4), 4.285 t (СF СН , J 14.1), 4.46 d (CН C=, J
2 2 2
6.7), 5.894 m (CН=), 5.296 m (=CН ). Found F, %:
2
4.29. C H F O. Calculated F, %: 55.88.
8
7 8
8
. Rakhimov, A.I., Shurubtsova, E.V., and Storozhako-
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3
-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro)heptoxy-
1
-propene (IIIc) was obtained similarly to IIIа. Yield
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 8 2011