Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 1, pp. 164−166.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © I.S. Polevaya, N.M. Karpyak, M.D. Fedevich, O.I. Marshalok, I.J. Pyrig, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85,
No. 1, pp. 171−173.
of 1,3,4-Trimethylcyclohex-3-en-1-Carboxylic Acid Allyl Ester
I. S. Polevaya, N. M. Karpyak, M. D. Fedevich,
O. I. Marshalok, and I. J. Pyrig
Lviv Polytechnical National University, Lviv, Ukraine
Received November 12, 2010
Abstract—The process of diene cyclization of 2,3-dimethylbutadiene with allyl methacrylicate was investigated.
Effects of temperature, reaction duration, and ratio of reagents on the yield of 1,3,4-trimethylcyclohex-3-en-1-
carboxylic acid allyl ester was studied. Optimal conditions of passing the process were found.
Esters of alkyl-substutited cyclohexenecarboxylic ac-
ids are valuable raw material for the synthesis of a number
of compounds including medical preparations, some of
which inhibit cholesterin biosynthesis and noticeably
reduce its level in blood . Furthermore esters of alkyl-
substutited cyclohexenecarboxylic acids are used for the
synthesis of tertiary alcohols applied in perfumery com-
positions . Owing to the dielectric anisotropy, esters
are used as components of liquid-crystal compositions for
electro-optical instruments. They are also widely applied
as softening modiﬁ ers of epoxy resins. Multifunctional
monomers of various structures with a certain complex
physicochemical characteristics are obtained on the ba-
sis of esters of alkyl-substutited cyclohexenecarboxylic
In the literature there are data on the cyclization
of some dienes with acrylates. Ethyl ester of
3,4-dimethylcyclohex-3-en-1-carboxylic acid is
obtained by the reaction of 2,3-dimethylbutadiene
(DMB) with ethyl acrylate by the Diels–Alder reaction
. Methyl ester of 2-methylcyclohex-3-en-1-carboxylic
acid is obtained by the condensation of piperylene
with methyl acrylate, using equimolar amounts of
piperylene and methyl acrylate. The mixture is stirred,
put in an autoclave, and heated up for 6 h at 200°С in
the presence of hydroquinone. The yield of the ester
is 65% . Methyl ester of 1,3,4-trimethylcyclohex-
3-en-1-carboxylic acid is obtained by the cyclization
of DMB with methyl metacrylate, using a solution of
methyl metacrylate and DMB in toluene. The mixture
is stirred, put in a glass ampoule, and heated up within
12 h at 140°С in the presence of pyrogallol. The yield
of the ester is 70% . No published information on the
procedures of preparation of 1,3,4-trimethylcyclohex-
3-en-1-carboxylic acid allyl esters (TMCHC AE) is
The aim of this work was the extension of the assort-
ment of esters of cyclohexenecarboxylic acids due to
obtaining new monomers, unsaturated esters of alkyl-
substutited cyclohexenecarboxylic acids.
To prepare TMCHC AE, we have chosen its synthesis
from DMB with methacrylic acid allyl ester (MA AE)
has been selected.
In the work we have studied the process of TMCHC
AE preparation by DMB diene cyclization with MA AE
according to the reaction according to the scheme
To obtain TMCHC AE, we used DMB synthesized by
a catalytic dehydration of 2,3-dimethyl-2,3-butanediol [4,
5] and chemically-pure grade MA AE.
Reaction products were analyzed on a “Chrom-5”
chromatograph with a DTP thermal conduction detector
and a chromatograph column of 1 m in length and diam-