Synthesis of Halomethyl-Substituted
M. K. Mamedov, A. G. Piraliev, and R. A. Rasulova
Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received December 27, 2007
Abstract―Bicyclic esters, which are reactive monomers for the synthesis of new polymeric products and also
of organic compounds, were synthesized by the reaction of thermal addition of (met)acrylic acids to 5-halogen-
substituted bicyclo[2.2.1]hept-2-en hydrocarbons in the presence of the inhibitor anthraquinone.
ISSN 1070-4272, Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 3, pp. 515–517. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © M.K. Mamedov, A.G. Piraliev, R.A. Rasulova, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 3, pp. 521–523.
In recent years alkyl-and cycloalkyl (met)acrylic
esters are successfully used as reactive monomers for
obtaining practically valuable polymeric products
which are applied as superglues, optical lenses, and
paintwork materials [1–4].
Earlier effective procedures have been developed
for the synthesis of alicyclic esters with a framework
structure by thermal, and also catalytic addition of
(met)acrylic acids to bi- and tricyclic olefin hydro-
carbons [5–7] and for the preparation of practically
valuable polymeric products of interest as paintwork
materials on the basis of these esters .
To obtain the monomers, i.e. halogen-containing ali-
cyclic acrylates of a framework structure adding to
polymeric products such specific properties as flexibility
and frost- and wear-resistance, we have studied the
reaction of the thermal addition of acrylic acids to 5-hali-
methylsubstituted bicyclo[2.2.1]hept-2-en hydrocarbons:
To prevent side oligomerization reactions of initial
acrylic (AA) and methacrylic (MAA) acids, and also
of resulting halomethylbicyclic esters of acrylates, we
applied anthraquinone (AN) as an inhibitor. Unlike the
known inhibitor hydroquinone this inhibitor in-creases
the yield of target products (met)acrylates ap-
proximately by 15–22%. It results from the fact that in
this reaction π-bonds of acrylic acids with anthra-
quinone form a stable quinhydrone-type intermediate
To optimize reaction conditions, we have studied
the effects of temperature, molar ratio of reacting com-
ponents, using AA and 5-chloromethylbicyclo [2.2.1]-
hept-2-en (CB) as an example, and reaction duration
on the yield of 5-chlorometylbicyclo [2.2.1] hept-2-
ylacrilate (CBА). The results of these studies have
shown that the optimal conditions of the reaction are as
follows: temperature 120°С, duration 3 h, ratio of the
initial components CB:AA=1:1.2 (mol), and AN
content 0.01% to an AA weight. Under these
conditions the thermal addition of MAA to CB was
studied, and 5-chloromethylbicyclo[2.2.1]hept-2-ylmetha-
crylate (CBМAC) was synthesized.
It was found that the optimal conditions for the reac-
tion of AA and MAA addition to 5-bromo-
methylbicyclo-[2.2.1] hept-2-en (BB) are the same as
for the reaction of the CBА synthesis. The results of
the synthesis of halogen-containing bicyclic (met)ac-
rylates under optimal conditions are given in Table 1.
X = Cl, R = H (III); X = Cl, R = CH
(IV); X = Br, R = H
(V); X = Br, R = CH