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
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