Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 2, pp. 327−330.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © M.K. Mamedov, R.A. Rasulova, S.A. Velieva, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 2, pp. 341−344.
Synthesis of Acrylates Based on Tetracyclododecene
and Its Methyl Derivative
M. K. Mamedov, R. A. Rasulova, and S. A. Velieva
Institute of Petrochemical Processes, National Azerbaijan Academy of Sciences, Baku, Azerbaijan
Received July 7, 2011
Abstract—The reaction of catalytic and thermal addition of acrylic acid to tetracyclo[4.4.1
and its 8-methyl-substituted derivative was studied. The reaction is intended for the synthesis of corresponding
acrylates, which are reactive monomers suitable for producing high-molecular compounds.
Acrylates are known to be reactive monomers suitable
for obtaining practically valuable polymeric products
applicable as organic glass, optical lenses, paintwork
materials, printing inks, and for the preparation of dental
artiﬁ cial limbs [1–4].
Earlier reactions of acrylic acid (AA) addition to
bicyclo[2.2.1]hept-2-en, its 5-alkyl-[5, 6], 5-cyanohalide-
methyl-, and acetoxy-substituted derivatives [7–9], to
]deca-3,8-dien [10, 11], and also to other
unsaturated polycyclic hydrocarbons have been studied.
As a result new monomers and practically valuable poly-
mer products [12, 13] were synthesized.
With the aim of synthesizing new reactive alicyclic
monomers, in the present work we have studied the reac-
tion of AA addition to tetracyclo-[4.4.12,5.17,10.01,6]
dodec-3-en (TCD) and its 8-methyl-substituted derivative
(МTCD) in the presence and absence of BF
and KU-2×8 (H-form) catalysts. As a result tetracy-
]dodec-3-ylacrylate (TCDА) and its
8-methyl derivative (МTCDА) were synthesized (see
To ﬁ nd optimal conditions of tetracyclic acrylates
formation, we have studied effects of temperature, molar
ratio of reacting components, amount of a catalyst, and
reaction duration on the yield of TCDА. Optimal condi-
tions of the reaction in the presence of BF
KU-2×8 (H-form) catalysts are temperature of 80 and
120°С, molar ratio AA : TCD = 2 : 1, catalyst amount
of 1.0 and 5.0%, and duration of 4 and 5 h, respectively.
In this case the yield of TCDА ester is 80.5 and 70.4%,
In spite of the fact that hydroquinone was applied in
the reactions as a polymerization inhibitor, a resin (5-8%)
is formed as a result of oligomerization of the initial acid
and a formed acrylate.
To develop more effective and ecologically pure meth-
od of synthesizing tetracyclic acrylates, we have carried
out a thermal addition of AA to TCD. The results of the
experiments have shown that the thermal AA addition to
TCD with the TCDА formation is stereo-selective. Op-
O C CH=CH
R = H, CH