Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 7, pp. 1305−1309.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
V.F. Gareev, T.A. Yangirov, V.P. Volodina, R.M. Sultanova, R.Z. Biglova, V.A. Dokichev, 2009, published in Zhurnal Prikladnoi
Khimii, 2009, Vol. 82, No. 7, pp. 1209−1212.
AND POLYMERIC MATERIALS
as an Effective Catalyst
of Functionalization of Isobutylene Oligomers
and 1,2-Polybutadiene with Methyl Diazoacetate
V. F. Gareev, T. A. Yangirov, V. P. Volodina, R. M. Sultanova, R. Z. Biglova, and V. A. Dokichev
Institute of Organic Chemistry, Ufa Scientiﬁ c Center, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Bashkir State University, State Educational Institution of Higher Professional Education, Ufa, Bashkortostan, Russia
Received April 20, 2009
Abstract—The possibility of [1+2]-cycloaddition of methoxycarbonylcarbene generated by catalytic
decomposition of methyl diazoacetate in the presence of the Cu(OAc)
system to the
carbon–carbon double bound in isobutylene oligomers and syndiotactic 1,2-polybutadiene was examined.
A comparative analysis of physicochemical properties of the starting compounds and their functionalized
products was performed.
One of important lines in the development of
macromolecular chemistry is chemical modiﬁ cation of
polymers, allowing the physical and chemical properties
of products to be varied in a wide range. Addition reactions
as a functionalization route occupy a particular place in
the chemistry of diene polymers because of high activity
of the C=C bond in the macromolecule unit .
Syndiotactic 1,2-polybutadiene and isobutylene
oligomers are convenient unsaturated substrates for
chemical modiﬁ cation. The presence of reactive double
bonds in pendant substituents in syndiotactic 1,2-
polybutadiene and of terminal or trisubstituted C=C
bonds in oligoisobutylene allows introduction of various
chemical groups and preparation of products with new
properties on the basis of these polymers. Substances of
diverse classes, e.g., epoxides and aromatic amines, can
be used as addition reagents .
Of particular interest are polymers containing along
with unsaturated bonds cyclopropane rings. To such
polymers belong polycyclopropane derivatives of fatty
acids isolated form Streptoverticillium fervens and
A cyclopropane fragment can be introduced into
a macromolecule by cyclocopolyisomerization
of 1,3-butadiene and ethylene . This procedure,
however, is very complex, and chemical modiﬁ cation of
a macromolecular compound is preferable.
This paper deals with the reaction of syndiotactic
1,2-polybutadiene and of isobutylene oligomers
with methyl diazoacetate in the presence of the
catalytic system Cu(OAc)
comparative analysis of the properties of the starting
compounds (isobutylene oligomers and syndiotactic
1,2-polybutadiene) and their functionalized derivatives.
C NMR spectra were recorded
on a Bruker AM-300 spectrometer (300.13 and 75.47
MHz, respectively) in CDCl
, and the IR spectra, on
a Shimadzu IR-Prestige-21 Fourier spectrometer, with
samples prepared as liquid films. In our study we
(Vekton), anhydrous ZnCl
isobutylene oligomers I (n = 7, M
≈ 504, n
and II (n = 10, M
≈ 700, n
= 1.4701), and syndiotactic
1,2-polybutadiene (III) (Efremov Synthetic Rubber Plant,
Joint-Stock Company; M
= 52600, M
= 116600, degree
of crystallinity 18%, syndiotacticity 53%). The solvents
used in this study (Et
petroleum ether, EtOH, CHCl
) and 2,4-lutidine were
puriﬁ ed by standard procedures [5, 6].