Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 3, pp. 410−414.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © M.K. Mamedov, V.S. Kadyrly, Dzh.G. Ismailova, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86, No. 3, pp. 441−445.
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of 5-Methyl-5-octyloxycarbonylnorborn-2-yl
M. K. Mamedov, V. S. Kadyrly, and Dzh. G. Ismailova
Mamedaliev Institute of Petrochemical Processes, Baku, Azerbaijan
Received December 18, 2012
Abstract—[4+2]-Cycloaddition of cyclopentadiene to octyl methacrylate with dicyclopentadiene used as starting
compound, and also thermal and catalytic addition of (meth)acrylic acids to 5-methyl-5-octyloxycarbonylnorborn-
2-ene in the presence of a catalyst, BF
, were studied. 5-Methyl-5-octyloxycarbonylnorborn-2-yl (meth)
acrylates, new monomers for polymer synthesis, were prepared.
Cycloalkyl acrylates are starting compounds for
preparing paint-and-varnish materials, printing paints,
optical lenses that do not transmit UV and laser beams,
and liquid crystal displays for modern TV and computer
monitors [1–3]. Acrylates are also used as monomers for
preparing hybrid polymers of high thermal and chemical
stability, which allows their use for preparing dental
It has been practically proved that functional
substituents (Cl, CN, COOH, RO, etc.) impart special
properties to polymers and considerably improve their
physicomechanical characteristics. Therefore, synthesis
of new monomers, 5-methyl-5-octyloxycarbonylnorborn-
2-yl (meth)acrylates (MOCN(M)A), is a topical
problem. Previously we studied the addition of acrylic
(AA) and methacrylic (MAA) acids to bicycloheptene,
dicyclopentadiene, and 5-acetoxymethylnorborn-2-ene
and synthesized the corresponding (meth)acrylates,
which are reactive monomers for preparing valuable
macromolecular compounds [5, 6].
This study deals with the addition of AA and MAA
to 5-methyl-5-octyloxycarbonylnorborn-2-ene (MOCN).
To this end, we first synthesized MOCN from
dicyclopentadiene (DCPD) and n-octyl methacrylate
It should be noted that DCPD under the reaction
conditions decomposes to cyclopentadiene (CPD), which
reacts with OMA to form the exo adduct as major product:
This may be due to steric hindrance produced by
the methyl and octyloxycarbonyl groups at the double
bond and methylene group of CPD. It is assumed that
the [4+2]-cycloaddition occurs via an unsymmetrical
transition state in which the formation of the exo isomer
prevails over that of the endo isomer.
The physicochemical properties of the isomer mixture
are as follows: bp 142–144°С (2 mm Hg), d
To ﬁ nd the optimal conditions for the synthesis of
MOCN from DCPD and OMA, we studied how the target
product yield depends on various factors: reactant molar
I II III IV