SYNTHESIS OF DIOXOLANYLMETHYL METHACRYLATES
523
reduced pressure in a nitrogen atmosphere on a 60-cm
column. Separation gave two low-boiling fractions
(68 70 C at 5 7 mm Hg and 72 74 C at 5 6 mm Hg)
and bottoms.
mined by reaction conditions, mainly by the nature of
the acid catalyst. Thus, to prepare dioxolanylmethyl
methacrylates from glycerol, MMA, and aldehydes,
there is no need to separate the isomers formed in the
first stage. The yield of DMM based on glycerol is
about 60%. The physicochemical characteristics of
one of DMMs, 2-methyl-1,3-dioxolan-4-ylmethyl
methacrylate, are as follows: colorless transparent liq-
Chromatographic analysis of the fractions per-
formed on two different stationary phases showed that
the first fraction was a practically individual sub-
stance (92 95% purity). The second fraction was,
apparently, a mixture of cis and trans isomers (ap-
proximately 66 and 28%) with an impurity of a third
isomer. Published data on isomerism of heterocyclic
compounds suggest the possibility of formation of cis
and trans isomers; with different substituents, the
number of isomers increases to four (two isomers for
each of the cis and trans forms) [3, 4]. The first frac-
tion, practically consisting of a single isomer, was
20
3
uid; bp 84 86 C at 5 6 mm Hg; d = 1.079 g cm ;
4
20
n
= 1.4540; molecular refraction: calculated 46.35,
D
found 46.40.
CONCLUSIONS
(1) Dioxolanylmethyl methacrylates are formed
from aldehydes, glycerol, and methyl methacrylate
as mixtures of two isomers, irrespective of whether
the intermediate 4-hydroxymethyl-1,3-dioxolane was
taken as individual isomer or isomeric mixture.
1
analyzed by H NMR spectroscopy (Tesla BS-567
spectrometer, 100 MHz). The spectrum was consistent
with the structure of 1,3-dioxolane containing one
hydroxy group. The signal at 3.4 4.2 ppm (relative to
HMDS) corresponds to the 1,3-dioxolane ring [5].
(2) 1,3-Dioxan-5-ol is not formed in reaction of
aldehydes with glycerol.
1
Thus, the H NMR and GLC data showed that a rather
complex mixture of isomers was formed. Detailed
study of its composition is beyond the scope of this
work.
REFERENCES
1. RF Patent 2089545.
The second stage involving reaction of HMDs with
methyl methacrylate (MMA) was performed under
conditions of ester interchange with HMDs based on
ketones [1]. The reaction vessel was equipped with a
distillation column. HMD was taken as a single iso-
mer and as an isomeric mixture. The results were as
follows. After removal of unchanged reactants by dis-
tillation under reduced pressure in a nitrogen atmos-
phere, DMM was obtained as a mixture of two iso-
mers, irrespective of whether the initial HMD was an
individual isomer or an isomeric mixture. It should
be noted that the ratio of the HMD isomers is deter-
2. Shevchuk, A.S., Podgornova, V.A., and Piskaiki-
na, E.G., Zh. Prikl. Khim., 1999, vol. 72, no. 5,
pp. 815 818.
3. Shabarov, Yu.S., Organicheskaya khimiya (Organic
Chemistry), Moscow: Khimiya, 1996, part 2.
4. March, J., Advanced Organic Chemistry. Reactions,
Mechanisms, and Structure, New York: Wiley Inter-
science, 1987, vol. 1.
5. Chernyshova, A.T., Rol’nik, L.E., Zlotskii, S.S., and
Rakhmankulov, D.L., Zh. Org. Khim., 1994, vol. 30,
no. 5, pp. 787 788.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 74 No. 3 2001