Hydrosilylation of unsaturated fluorinated esters and ethers with hydrochlorosilanes

Article abstract of DOI:10.1134/S1070363209120123

Hydrosilylation of allyl esters of fluoro acids and ethers of fluoro alcohols with hydrochlorosilanes in the presence of the Speier's catalyst was studied. Yields of adducts with ethers reach 62-68%, and with esters, 27-45%. By etherification of the addut

Full text of DOI:10.1134/S1070363209120123

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 12, pp. 2634–2636. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © Z.V. Belyakova, M.G. Pomerantseva, E.A. Chernyshev, P.A. Storozhenko, 2009, published in Zhurnal Obshchei Khimii, 2009,
Vol. 79, No. 12, pp. 2008–2010.
Hydrosilylation of Unsaturated Fluorinated Esters
and Ethers with Hydrochlorosilanes
Z. V. Belyakova, M. G. Pomerantseva, E. A. Chernyshev, and P. A. Storozhenko
State Research Institute of Chemistry and Technology of Organoelemental Compounds,
sh. Entuziastov 38, Moscow, 111123 Russia
e-mail: eos2004@inbox.ru
Received June 25, 2009
Abstract—Hydrosilylation of allyl esters of fluoro acids and ethers of fluoro alcohols with hydrochlorosilanes
in the presence of the Speier’s catalyst was studied. Yields of adducts with ethers reach 62–68%, and with
esters, 27–45%. By etherification of the adduts with ethers the respective ethoxysilanes were obtained in 41–
43% yield. The latter reaction even in very mild conditions is complicated by the formation of a large amount
of siloxanes. Yield of siloxanes is 22–32%.
DOI: 10.1134/S1070363209120123
In order to obtain new monomeric silicon
compounds, we continued to study the hydrosilylation
of unsaturated fluorine-containing esters and ethers
[1].
(1)
RfCOOCH2CH CH2 + HSiMenCl3−n
RfCOO(CH2)3SiMenCl3−n
,
I
II
III
IIIa: Rf = C2F5, n = 1; IIIb: Rf = CF3OCF2CF2, n = 1; IIIc: Rf = CF3(CF2)5; IIId: Rf =
F
COO, n = 1;
F
O
F
O
F
COO,
n = 2; IIIf: Rf =
CF2COO, n = 2.
IIIe: Rf =
CF2COO, n = 1; IIIg: Rf =
(2)
H(CF2)nCH2O(CH2)3SiMeCl2,
H(CF2)nCH2OCH2CH
CH2 + MeSiHCl2
IV
IVa: n = 2, IVb: n = 4.
Yields of products at the hydrosilylation of ethers
in the presence of the Speier’s catalyst reached 62–
68%, and of esters, 27–45% (see Tables 1 and 2).
Lower yields in the case of esters are explained, as was
shown earlier [2], by the side processes of splitting of
ester bond and the formation of acyloxysilanes that
earlier have not been isolated from the reaction
mixture but were obtained in an independent synthesis.
At the hydrosilylation of allyl perfluorofurancar-
boxylate with dimethylchlorosilane we isolated and
characterized the corresponding acyloxysilane Va.
F
O
F
O
CF2COOO(CH2)3SiMe2(OCOCF2
)
Va
EtOH split off ethyl trifluoroacetate [3]. In this study
we found that upon further heating of the remainder
after the removal of the ester at 270°C quantitative
liberation occurred of a mixture of propylene and
cyclopropane with the formation of brittle resin (see
the figure). The acethoxypropyltriethoxysilane behaved
similarly.
RCOO(CH2)3Si(OEt)3
We studied also transformations of acyloxypropyl-
alkoxysilanes at heating. We previously showed that γ-
trifluoroacetoxypropyltriethoxysilane when heated to
110–115°C in the presence of Et3N, HCl, FeCl3, and
110−120°C
RCOOEt + [−(CH2)3Si(OEt)2-O-]n
270°C
(3)
C4H6 + [−Si(OEt)2-O-]n.
2634

HYDROSILYLATION OF UNSATURATED FLUORINATED ESTERS
Table 1. Conditions of synthesis, yields, and properties of compounds
2635
Conditions of synthesis
Comp.
no.
Yield, %
bp, °С/mm Hg
d420
n2D0
duration of boiling, h final temperature, ° C
5
120
120
45
63–69/2
73/3
1.3717
1.4106
1.5373
1.5424
1.4501
1.5038
1.4080
1.3822
1.3705
1.3635
1.3835
1.3790
1.3808
1.3720
1.4038
1.3458
1.3525
1.3890
1.3764
1.3940
1.3780
IIIа
IIIb
IIIc
IIId
IIIe
IIIf
IIIg
IVа
IVb
V
5
41
6
115
60
110–115/2
82/2
2
140
42
4
160
33.5
113/4
3
140
27
103–104/4
100–105/4
83/1–2
6
140
31a
62
5
170
5
170
68
103–105/4
134–135
115–119/9
132–135/3
190–200/6
205–212/3
1.4185
1.5510
1.1170
1.2350
6
140
31
1.5
1.5
1.5
1.5
45–50
45–50
45–50
45–50
41
VIа
VIb
VIIа
VIIb
43
32.4
22.3
1.3274
a
with bp 134–135°С/1 mm Hg, d420 1.5510; nD20 1.3525. Found: C 29.42, H 1.80, F
F
F
Isolated
F
CF2COOO(CH2)3SiMe2(OCOC
)
2
O
O
50.4, Si 4.0. C17H12O6F18Si. Calculated,%: C 29.3, H 1.76, F 50.2, Si 4.2.
Table 2. Analytical data of compounds
Comp.
no.
Found, %
Cl
Calculated, %
Formula
C
H
F
Si
C
H
Cl
F
Si
26.37
24.95
25.34
27.68
31.32
26.87
30.13
27.89
27.66
42.87
38.36
39.01
34.56
2.63
2.46
1.94
1.82
2.71
1.92
2.92
3.35
3.17
7.12
5.31
5.47
4.41
C7H9Cl2F5O2Si
C8H9Cl2F7O3Si
C11H9Cl2F13O2Si
C11H9Cl2F11O2Si
C12H12ClF11O2Si
C10H9Cl2F9O3Si
C11H12ClF9O3Si
C7H12Cl2F4OSi
C7H12Cl2F8OSi
C11H22F9O3Si
26.30
25.0
25.4
27.45
31.2
26.35
30.9
29.27
27.91
43.1
38.4
37.8
35.8
2.84
2.36
1.7
22.2
18.4
13.7
14.7
7.7
29.07 8.8
IIIа
IIIb
IIIc
IIId
IIIe
IIIf
18.7
13.9
14.5
35.00
48.65
47.8
7.48
5.3
5.7
7.2
6.2
7.6
34.5
47.6
7.52
5.4
1.88
2.6
47.38 5.8
45.4 6.1
45.6
16.3
7.6
41.2
2.02
2.80
4.18
3.10
7.12
5.42
6.35
4.6
15.9
38.22 6.3
40.05 6.6
40.7
IIIg
IVа
IVb
VIа
VIb
VIIа
VIIb
23.6
25.72
9.09
23.9
37.2
9.2
7.0
24.8
37.4
9.1
6.9
C13H22F8O3Si
10.1
8.9
C18H34F8O5Si2
C28H34F16O5Si2
10.5
7.6
41.9
41.2
The etherification with ethanol of chlorosilanes IV
containing a fluorinated organic group and an ether
bond is not complicated by side processes of C–O
bond splitting. Yield of products of etherification is
about 40%, even in very mild conditions formed up to
20–30% siloxanes and ethyl chloride.
H(CF2)nCH2O(CH2)3SiMeCl2 + C2H5OH → H(CF2)nCH2O(CH2)3SiMe(OC2H5)2 + HCl
VI
+ [H(CF2)nCH2O(CH2)3SiMe]2O + C2H5Cl,
VII
VIа: n = 2, VIb: n = 4; VIIа: n = 2, VIIb: n = 4.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 12 2009

2636
V, ml
BELYAKOVA et al.
Reaction of methyldichlorosilanes with allyl
ethers of fluorinated alcohols. To a mixture of
0.1 mol of allyl ether and 0.15 ml of Speier’s catalyst
heated to 100°C was added dropwise within one hour
0.11 mol of methyldichlorosilane. Then the mixture
was maintained at boiling point for 0.5 hours and
distilled.
800
700
600
500
400
300
200
100
0
Transformations of γ-(acyloxypropyl)triethoxy-
silane under the action of iron chloride. 0.31 mol of
γ-acyloxypropyltriethoxysilane and 0.5 g of anhydrous
iron chloride was placed into a Claisen flask connected
through a condenser and a receiver with a gas meter,
and then the device was maintained in an oil bath at
110–120°C. After 10 min boiling started in the flask.
Ethyl ester of acid was distilled off (yield 95–97%).
▲ – 1
– 2
0
2
4
6
8
10
The residue consisted of a viscous resin. The gas
evolution was not observed. On heating the residue to
270–300°C vigorous evolution of gas started (a mix-
ture of propylene with cyclopropane, totally 670 ml,
96%). In the flask remained a brittle resin (4.3 g).
t, h
Evolution of propylene and cyclopropane upon heating of
RCOO(CH3)Si(OEt)3 in the presence of FeCl3: (1) R = CH3
and (2) R = CF3.
Etherification of ethers. Into a flask with stirrer,
thermometer, dropping funnel and rflux condenser
cooled at the top with dry ice in acetone and connect
through the column filled with calcium chloride with a
water-jet pump was placed 0.1 mol of chlorosilane,
and at the reaction mixture temperature 45–50°C was
added in 1 hour 0.2 mol of anhydrous ethanol. The
mixture was maintained then at the same temperature
for another half an hour, and distilled.
EXPERIMENTAL
Thr reaction products were analyzed on a LHM-72
chromatograph with a detector katharometer, column
4×2000 mm, stationary phase Chromaton N-AW +
15% PMS 20000, flow rate of carrier gas (helium)
60 ml min–1. The temperature of the evaporator 550°C,
of oven from 50 to 250°C, the programmed rate of
heating 20 deg min–1.
REFERENCES
Reaction of hydrosilanes with allyl esters of
fluorinated acids. To a mixture of 0.1 mol of
unsaturated ester and 0.1 ml of 0.1 M solution of pla-
tinumhydrochloric acid in isopropyl alcohol (Speier’s
catalyst) was added 0.1 mol of hydrosilane at a rate
that ensures the continuous increase in the boiling
temperature of the mixture. The mixture was kept for a
few hours until the boiling temperature remained
unchanged, and then it was distilled.
1. Belyakova, Z.V., Pomerantseva, M.G., Golubtsov, S.A.,
and Popkov, K.K., Zh. Obshch. Khim., 1967, vol. 37,
no. 4, p. 922.
2. Belyakova, Z.V., Pomerantseva, M.G., and Golub-
tsov, S.A., Zh. Obshch. Khim., 1974, vol. 44, no. 8,
p. 1780.
3. Pomerantseva, M.G., Belyakova, Z.V., Golubtsov, S.A.,
Zubkov, V.I., Ainshtein, A.A., and Baranova, G.G., Zh.
Obshch. Khim., 1972, vol. 42, no. 4, p. 862.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 12 2009