60
CHERNYSHEV et al.
acrylate VIII. Previously [14] we used the example
of hydrosilylation of allyl phenyl ether with triethoxy-
silane to show that Speier’s catalyst modified with
triethoxy(vinyl)silane slows down isomerization. In
our case, too, additives probably act by the same
mechanism.
water (3 30 ml), ethanol (3 30 ml), and ether
(2 30 ml) and dried first in air and then in a vacuum
(1 mm Hg) at 20 C for 6 h. A reddish-brown catalyst
with a platinum content of 0.06% was obtained.
Catalysts XVIII and XIX were obtained analog-
ously. Catalyst XVI was prepared according to [20].
EXPERIMENTAL
Hydrosilylation of allyl glycidyl ether in the
presence of Speier’s catalyst. All the reactions were
carried out under nitrogen.
Gas chromatography was carried out on a Tsvet-
500 chromatograph with a thermal conductivity de-
tector, using 3000x3-mm metallic column packed
with 5% of SE-300 on Chromaton N-AW-DMCS;
injector and detector temperatures 300 C. The oven
temperature was programmed from 60 to 290 C at a
rate of 16 C/min with 1- and 3-min isotherms at the
initial and final temperatures, respectively. Carrier gas
a. A 0.1 M solution of H2PtCl6 6H2O in 2-pro-
panol, 0.02 ml, was mixed with 1.5 3 ml of a mixture
of 5.9 ml of allyl glycidyl ether and 9.2 ml of tri-
ethoxysilane and the mixture was heated to 60
110 C. After 0.5 6 min, vigorous heat evolution took
place, and the reaction mixture warmed up to 120
160 C. When the temperature began to decrease, the
rest reagent mixture was added dropwise at 110
130 C, and the resulting mixture was heated at 120
130 C until complete reaction (GLC monitoring).
1
helium, flow rate 40 mlmin .
Identification of admixtures in the reaction product
was carried out by adding reference substances and
by mass spectrometry. The mass spectra were ob-
tained on a Hewlett Packard HP-5971 A GC MS
system, ionizing voltage 70 V. Gas chromatography
was carried out on a 25000 0.32-mm quartz capillary
column, stationary phase DB-5, film thickness 25 m.
The oven temperature was programmed from 50 to
280 C at a rate 7 C/min. Carrier gas helium, flow rate
b. The reagent and catalysts amount were the same
as in the above procedure. A mixture of the catalyst
and allyl glycidyl ether was heated to 60 70 C, and
triethoxysilane was added at a rate providing maintain-
ing a preset temperature (90 100 C). After the addi-
tion was complete, the resulting mixture was heated
for 1 3 h at 90 145 C until complete reaction.
1
0.8 mlmin .
c. The reaction was carried out by adding allyl
glycidyl ether to a mixture of triethoxysilane and the
catalyst. The reagent amounts were the same as in the
above procedures.
Platinum bisdicarbollyl complex was prepared ac-
cording to [15] and iron and nickel bisdicarbollyl
complexes, according to the Hawthorn method [16].
Platinum and nickel dimethylglyoximates were ob-
taimed by treating NiCl2 6H2O and K2PtCl4 with
dimethylglyoxime [17, 18]. The carbenium salt was
prepared according to [19].
Hydrosilylation in presence of a modified Speier’s
catalyst and complex compounds was carried out
analogously. The amounts of additives were 0.02
0.05 ml (g) per 0.02 ml of Speier’s catalyst. The
Synthesis of supported catalysts. a. Modification
of porous glass with functionalyzed organosilicon
compounds. Porous glass containing 96% of SiO2 and
4% of B2O3 was used, pore diameter 40 50 . specific
4
4
catalyst concentration was 1.3 10 7.6 10 M.
Hydrosilylation of allyl glycidyl ether in pres-
ence of supported catalysts. A mixture of 1.5 g of
a catalyst, 1.2 ml of allyl glycidyl ether, and 1.95 ml
of triethoxysilane was heated at 110 120 C until
complete reaction. The liquid was decanted, and the
catalyst was washed with hexane (2 3 ml). A new
portion of the reagents was added to the catalyst, and
the procedure was repeated.
1
surface 100 50 m2 g , porosity 30%. Before treatment
it was dried for 2.5 h at 200 250 C; adsorbed water
content was controlled by IR spectroscopy.
b. Catalyst XVII. Porous glass, 30 g, was treated
with a solution of 32.5 g of (diallylaminopropyl)tri-
ethoxysilane in 150 ml of toluene and refluxed for
26 h. The glass was filtered, washed with benzene
(3 20 ml), and extracted in a Soxhlet apparatus for
7 h with hexane. After that it was filtered, washed
with ether (2 10 ml), and dried in a vacuum (1 mm
Hg) for 2 h at 50 C. The modified porous glass was
treated with a solition of 2.34 g of H2PtCl6 6H2O in
30 ml of 2-propanol and kept for 1.5 months at room
temperature. The glass was filtered off, washed with
REFERENCES
1. Jpn. Patent 56-90092, Ref. Zh. Khim., 1982, 14C407P.
2. Jpn. Patent 56-7796, Ref. Zh. Khim., 1982, 3N70P.
3. Jpn. Patent 50-5696, Ref. Zh. Khim., 1976, 10N91P.
4. US Patent 4083856, Ref. Zh. Khim., 1979, 2S374P.
5. Kuli-Zade, F.A., Ragimov, A.A., Khudayarov, M.A.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 1 2007