ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 2, pp. 207−213. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © D.O. Anashkin, I.M. Raigorodskii, V.M. Kopylov, V.A. Kovyazin, V.V. Boev, V.N. Sokolik, 2014, published in Zhurnal Prikladnoi Khimii,
2014, Vol. 87, No. 2, pp. 227−233.
AND INDUSTRIAL ORGANIC CHEMISTRY
Reaction of γ-(Aminopropyl)siloxanes with Phenolphthalein
as a Route to New Siloxane-containing Phenols
D. O. Anashkin
, I. M. Raigorodskii
, V. M. Kopylov
, V. A. Kovyazin
V. V. Boev
, and V. N. Sokolik
Lomonosov Moscow State University of Fine Chemical Technologies, pr. Vernadskogo 86, Moscow, 119571 Russia
Penta-91 Limited Liability Company, Volgogradskii pr., Moscow, 109216 Russia
Received May 18, 2013
Abstract—The reaction of γ-aminopropylorganosiloxanes with phenolphthalein yields monomeric and oligomeric
N-alkylsiloxy-3,3-bis(4-hydroxyphenyl)phthalimidines. Their structures and compositions were conﬁ rmed by
IR and NMR spectroscopy and by HPLC–MS. Studies by GLC and MALDI mass spectrometry showed that the
action of the amine and of the water released in the reaction leads to the rearrangement of the siloxane bond in
the course of the synthesis with the formation of linear and cyclic carbofunctional oligomeric siloxanephenols
and mixed oligophenolaminosiloxanes. The possibility of modiﬁ cation of epoxy resins with the synthesized
oligomers was revealed.
Carbofunctional siloxane-containing phenols (CSPs)
are demanded monomeric and oligomeric organosili-
con compounds for the synthesis of copolymers  and
block copolymers [2, 3] and for modiﬁ cation of organic
polymers [4, 5]. CSP-based copolymers have diverse
applications. They are used as modiﬁ ers of commercial
polycarbonates and as materials for high-performance
gas-permeable and pervaporation membranes, electro-
technical coatings, adhesive ﬁ lms for triplex, and con-
ducting matrices for current sources, and also as various
materials for medicobiological purpose .
The ﬁ rst representatives of organosilicon phenols
with the Si–aryl bond were prepared by Speier et al.
 by organometallic synthesis from halophenoxysilyl-
chlorosilanes and chlorosilanes with the subsequent hy-
drolysis of the reaction products to the desired phenols.
Later, such phenols were prepared by hydrosilation of
alkenylphenols with hydridosilanes in the presence of
as catalyst . After that, the hydrosilation re-
action was successfully applied to the synthesis of CSPs
from unsaturated phenols or their silyl ethers and hydri-
doorganosilanes [9–12]. Mironov et al.  also sug-
gested preparation of CSPs by intramolecular hydrosila-
tion of vinylphenoxyhydridosilanes to cyclic products,
followed by hydrolysis to obtain the desired organosili-
Continuing the search for facile routes to new CSPs,
which are of interest as monomers for polycondensation
copolymers and as modiﬁ ers for organic resins and
polymers, we studied possible procedures for preparing
phenols with a grafted siloxane group.
RESULTS AND DISCUSSION
For our experiments we chose γ-aminopropylorgano-
siloxanes and phenolphthalein, which is a readily
available compound containing, along with two phenoxy
groups, also a reactive lactone functional group.
It is known [14–16] that reactions of phenolphthalein
with primary organic amines yield N-phthalimidines.
However, we found no data on the corresponding
reactions with organosilicon amines.
We expected that the use of aminoalkylsiloxanes in
reaction with phenolphthalein would yield siloxane-