ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 12, pp. 2085!2089. + Pleiades Publishing, Ltd., 2007.
Original Russian Text + M.K. Mamedov, A.G. Piraliev, R.A. Rasulova, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 12,
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Bicyclo[2.2.1]hept-2-yloxyethyl Acrylates
and Saturated Acid Esters Derived from Them
M. K. Mamedov, A. G. Piraliev, and R. A. Rasulova
Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received February 15, 2007; in final form, July 2007
Abstract-New reactive monomers, bicyclo[2.2.1]hept-2-yloxyethyl acrylates, were prepared by esterification
of monoethers derived from ethylene glycol and bicyclic alcohols with acrylic acid, using naphthalene-1,5-
disulfonic acid as a new effective catalyst. The related propionates and isobutyrates were prepared by
hydrogenation of these acrylates.
Esters of alicyclic alcohols and acrylic acids are
widely used as reactive monomers for preparing plas-
tics [1, 2], superadhesives , printer’s inks , and
lenses for protection from UV radiation . Previous-
ly, we have developed procedures for preparing acrylic
and methacrylic acid esters of bi- and tricyclic alcohols
 and showed that these compounds can be used
as monomers for preparing valuable macromolecular
In this study, we performed esterification of mono-
ethers derived from ethylene glycol and bicyclic al-
cohols with acrylic acidwith the aim to prepare new
reactive alicyclic functional monomers. We found that
the reaction mainly follows the pathway of formation
of bicyclo[2.2.1]hept-2-yloxyethyl acrylates:
where R = H (I, VI, IX), CH
(II, VII, X), CH
(III, VIII, XI); R` =H(VI!VIII), CH
To choose an effective esterification catalyst, and
study its catalytic activity for the example of the reac-
tion of bicyclo[2.2.1]hept-2-yloxyethanol (BEL) with
acrylic acid (AA), we tested sulfuric acid, naphtha-
lenesulfonic acid (NSA), KU-2 and KU-2-8 ion-ex-
change resins, p-toluenesulfonic acid (TSA), and
naphthalene-1,5-disulfonic acid (NDSA), which were
taken in an amount of 2.5 wt % (in terms of sulfo
groups) relative to the starting compounds. The reac-
tion was performed until the water evolution ceased.
The results are listed in Table 1.
We found (Table 1) that, among the catalysts tested
in synthesis of bicyclo[2.2.1]hept-2-yloxyethyl acry-
late, NDSA is the most effective, because it provides
a product yield as high as 91.2%, whereas with
the other esterification catalysts the yield is 52374%.
Therefore, experiments on the synthesis of other
related monomers by esterification of bicyclo[2.2.1]-
hept-2-yloxyethanol and its alkyl derivatives with
acrylic and methacrylic acids were performed with
NDSA as catalyst. The results are listed in Table 2.
The results obtained show (Table 2) that, with
NDSA as catalyst, the yield of acrylates and methac-
rylates reaches 50.2355.0 g (87394%)
It should be noted that, with alkyl-substituted bicy-
cloheptyl monoether of ethylene glycol as starting
compound, the yield of acrylates and methacrylates
tends to decrease with increasing molecular weight.
This is caused by steric hindrance and a certain de-
crease in the activity of the OH group.
We determined the physicochemical constants and
elemental composition of the synthesized 2-(bicyclo-