Reaction of unsaturated nitriles with hydrosilanes

Article abstract of DOI:10.1134/S1070363210050105

Reaction of acrylonitrile and 1,4-dicyanobut-1-ene with hydrosilanes in the presence of various catalysts was studied. In the presence of triallylamine, allyl-bis(triethoxypropyl)amine, diallylaminopropyltriethoxysilane, HMPA, NiCl₂ + 2MePh₂PO, CuCl + 2MePh₂PO, [(Me ₂N)₂CCl]₂CuCl₄, and [(Me ₂N)₂CCl]₂PtCl₆, the addition of trichlorosilane to acrylonitrile proceeded with the yield of 36 to 97%. Triethoxy-and tributoxysilane were added to acrylonitrile in the presence of rhodium dicarbonyl acetylacetonate with the formation of α-isomer in 56-58% yield. Attempted addition of hydrosilanes to 1,4-dicyanobutene failed. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070363210050105

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 5, pp. 927–929. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © Z.V. Belyakova, M.G. Pomerantseva, E.N. Chekrii, E.A. Chernyshev, P.A. Storozhenko, 2010, published in Zhurnal Obshchei
Khimii, 2010, Vol. 80, No. 5, pp. 757–759.
Reaction of Unsaturated Nitriles with Hydrosilanes
Z. V. Belyakova, M. G. Pomerantseva, E. N. Chekrii, 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―Reaction of acrylonitrile and 1,4-dicyanobut-1-ene with hydrosilanes in the presence of various
catalysts was studied. In the presence of triallylamine, allyl-bis(triethoxypropyl)amine, diallylamino-
propyltriethoxysilane, HMPA, NiCl2 + 2MePh2PO, CuCl + 2MePh2PO, [(Me2N)2CCl]2CuCl4, and
[(Me2N)2CCl]2PtCl6, the addition of trichlorosilane to acrylonitrile proceeded with the yield of 36 to 97%.
Triethoxy- and tributoxysilane were added to acrylonitrile in the presence of rhodium dicarbonyl
acetylacetonate with the formation of α-isomer in 56–58% yield. Attempted addition of hydrosilanes to 1,4-
dicyanobutene failed.
DOI: 10.1134/S1070363210050105
Owing to practical value of silicon monomers
containing nitrile groups the interest to the search for
new catalysts of hydrosilylation of cyanoalkenes, the
most useful reaction for the synthesis of such
compounds, remains continuously unabated.
catalyst can be easily separated from the adduct by
distillation, and provide a pure β-cyanoethyltri-
chlorosilane.
In the literature a catalytic system for hydro-
silylation of simple olefins, NiX2 + 2R3P=O, has been
described [1]. We carried out reaction of
trichlorosilane with acrylonitrile in the presence of the
While hydrosilylation of allyl cyanide proceeds
smoothly in the presence of H2PtCl6·6H2O, hydro-
solylation of acrylonitrile, the most accessible among
the unsaturated nitriles, is not practicable in these
conditions. In this communication we report on the
results of the search of catalysts for the hydrosilylation
of acrylonitrile.
mixtures NiCl2
+
2MePh2P=O and CuCl
+
2MePh2P=O, by heating the reagents in a sealed
ampule at 90–95°C. In contrast to the reactions
catalyzed by phosphines, in both cases formed a
mixture of β- and α-isomers. It seems that this is due to
the change in the polarization of the double bond in
acrylonitrile under the action of phosphine oxide,
which is of more acid nature (see the table).
As known, the addition of hydrosilanes to
acrylonitrile may result in the formation of both α- and
β-isomers, and basic catalysts (amines, phosphine)
promote formation of a more valuable β-isomer.
Addition to the acrylonitrile of trichlorosilane
occurs also in the presence of dimethylaminochloro-
carbenium tetrachlorocuprate and hexachloroplatinate.
The yield of β-cyanoethyltrichlorosilane is 60 and 20%
respectively. Analogous Co, Ni, and Mn salts are not
active. Attempts of applying any of the above-
mentioned catalysts except bisdimethylaminochloro-
carbenium hexachloroplatinate in the reaction of
methyldichlorosilane and dimethylchlorosilane addi-
tion to acrylonitrile failed. In the presence of
[(Me2N)2SCl]2PtCl6, methyldichlorosilane is added to
acrylonitrile in 12% yield (see the table). There are
practically no published data on the addition to
acrylonitrile of hydroalkoxysilanes. A formation of β-
→ CNCH2CH2Si
HSi + CH2=CHCN –
→ CNCH(CH3)Si
We found that in the presence of triallylamine,
allylbis(triethoxysililpropyl)amine, diallylaminopropyltri-
ethoxysilane and HMPA, acrylonitrile added trichlo-
rosilane with the formation of only β-cyanoethyltri-
chlorosilane; in the presence of triallylamine and
HMPA the yield reaches 97 and 75% respectively (see
the table, nos. 1–4). The reaction proceeds at heating
the mixture of components to boiling. All four new
927

928
BELYAKOVA et al.
Hydrosilylation of acrylonitrile
Reaction conditions
Addition product
formula
Hydrosilane
Run
Catalysts
moles per 1 mol of acrylonitrile
moles per 1 mol
no.
temperature,
duration,
h
yield, %
of acrylonitrile
°С
1
2
3
4
HSiCl3, 1.5
HSiCl3, 1.5
HSiCl3, 1.5
HSiCl3, 1.3
Triallylamine,0.05
120
120
120
120
36
36
36
3
NCCH2CH2SiCl3
97
49
40
75
Allylbis(triethoxypropyl)amine, 0.05
Diallylaminopropyltriethoxysilane, 0.05
HMPA
NCCH2CH2SiCl3
NCCH2CH2SiCl3
NCCH2CH2SiCl3
NCCH2CH2SiCl3
NCCHMeSiCl3
32.0
23.0
5а
6а
7а
HSiCl3, 1.0
HSiCl3, 1.0
HSiCl3, 1.0
NiCl2+2MePh2PO, 0.015 + 0.02
CuCl+2MePh2PO, 0.006 + 0.02
[(Me2N)2CCl]2CuCl4, 0.01
90–95
90–95
100
10
10
14.0
22.0
NCCH2CH2SiCl3
NCCHMeSiCl3
10
24
35.0
60.0
NCCH2CH2SiCl3
8а
HSiCl3, 1.0
[(Me2N)2CCl]2PtCl6, 1×10–5
[(Me2N)2CCl]2PtCl6, 1×10–5
Rh(acac)2(CO)2, 3×10–2
Rh(acac)2(CO)2, 3×10–2
100
100
120
120
20
16
3
NCCH2CH2SiCl3
NCCHMeSiMeCl2
NCCHMeSi(OEt)3
20.1
12.1
56.0
58.0
9а
MeSiHCl2, 1.0
HSi(OEt)3, 1.0
HSi(OBu)3, 1.0
b
10
11
c
3
NCCHMeSi(OBu)3
a In a sealed ampule. b bp. 70–73°С (3 mm Hg), n2D0 1.4100. c bp 122–123°С (3.5 mm Hg), n2D0 1.4205.
cyanoethyltriethoxysilane in the presence of poly(p-
diphenylphosphinostyrene)bis(triphenylphosphine)-
rhodium with 10% yield has been described [2] and of
α-cyanoethyltriethoxysilane in the presence of
Ph3PRhCl in 66% yield [3].
H2PtCl6, H2O, Pd/C, tetramethylethylendiamine, benzoyl
peroxide, and tert-butyl peroxides. However, in the
presence of the first three catalysts formed an isomeric
compound, 1,4-dicyanobut-1-ene; in the presence of
the last two catalysts interactions did not proceed.
Applying as a catalyst rhodium dicarbonyl acetyl-
acetonate, we performed addition of triethoxysilane to
acrylonitriles and obtained α-isomer with 56% yield.
CN
EXPERIMENTAL
Chromatographic analysis was carried out on a
Color-100 chromatograph with a detector on the
thermal conductivity, a glass column 3 x 3000 mm and
with evaporator containing a glass tube. Phase 15% E-
301 on the carrier “Cromaton-N-AW.” Evaporator
temperature 150°C, detector temperature 180°C,
column temperature from 30 to 130°C, the prog-
rammed increase rate 20°C per 1 min. The detector
current 130 mA, the rate of helium flow 60 ml min–1.
The NMR spectra were registered on a Varian
spectrometer with an operating frequency 60 MHz.
CH3CH−Si(OCH2CH3)3
1
2
3
4
In the NMR spectrum was detected: (a) a protons,
(b) a quadruplet at 1.9–2.4 ppm of CH2 protons, and
(c) a complex signal in the region of 1.2–1.6 ppm from
the doublet of CH31 protons and triplet of CH34 protons.
The ratio of integral intensities of the signals is a:b:c =
1:6:12. Since the reaction is accompanied by strong
spontaneous heating it is recommended to perform it
by means of gradual adding acrylonitrile to a mixture
of silane and catalyst. Similarly was prepared α-
cyanoethyltributoxysilane (see the table).
Hydrosolylation with trichlorosilane in the
presence of amines. A mixture of acrylonitrile and
trichlorosilane (mole ratio 1:1) with a catalyst in a
flask with reflux condenser was boiled for 18 h, the
remaining trichlorosilane was then added, and the
boiling was continued for another 18 h. The
An attempt was made to obtain cyano-containing
silicon monomers by addition of hydrosilanes to 1,4-
dicyanobut-2-ene. The following catalysts were tested:
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 5 2010

REACTION OF UNSATURATED NITRILES WITH HYDROSILANES
929
temperature of the mixture reached 120°C. After
cooling, dry HCl was passed to precipitate the amine.
The mixture was filtered and filtrate was subjected to
the fractional distillation.
Hydrosilylation in the presence of rhodium
dicarbonyl acetylacetonate. To a mixture of tri-
alkoxysilane and a catalyst heated to 95–100°C
acrylonitrile was slowly added over 0.5 h. At the
beginning of the additions there was a sharp rise in
temperature to 150°C. The remaining acrylonitrile was
added at a temperature of 120°C, and after adding the
mixture was maintained at this temperature for 1 h.
Hydrosilylation in the presence of HMPA. To the
catalyst 1/10 part of a mixture of trichlorosilane with
acrylonitrile was added, the mixture was heated to
boiling and then at of 80–90°C the remaining mixture
was added over 3 hours. The boiling was continued
until the temperature of the mixture reached 120°C.
The mixture was maintained at this temperature for 1 h
and then it was distilled.
REFERENCES
1. Moldavskaya, N.A., Skvortsov, N.K., Voloshina, N.F.,
and Reikhsfel’d, V.O., Zh. Obshch. Khim., 1981,
vol. 51, no. 7, p. 1621.
Hydrosilylation in the presence of salts of nickel
and copper and phosphinoxides, as well as in the
presence of carbenium salts was carried out in
ampules.
2. Svoboda, P., Capka, M., Chvalovsky, V., Bazant, V.,
and Hetfleijs, J., Z. Chem., 1972, vol. 12, no. 4, p. 153.
3. Oijma, I., Kumada, M., and Nagai, Y., J. Oganomet.
Chem., 1976, vol. 43, p. 37.
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