1070-4272/05/7806-1000 C 2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 6, 2005, pp. 1000!1002. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 6, 2005,
Original Russian Text Copyright + 2005 by Khimich, Slabospitskaya, Korzhikov, Tennikova.
AND POLYMERIC MATERIALS
Synthesis of an Unsaturated >-Alanine Derivative
G. N. Khimich, M. Yu. Slabospitskaya, V. A. Korzhikov, and T. B. Tennikova
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received July 26, 2004; in final form, January 2005
Abstract-A procedure was developed for preparing an acrylic derivative of b-alanine. A terpolymer of this
compound with glycidyl methacrylate and ethylene glycol dimethacrylate was prepared.
Preparation of novel supports and sorbents for
the analysis and isolation of biologically active sub-
stances is an actively developing field of polymer
The surface of supports used in affinity chromatog-
raphy can be modified with ligands specific to target
products . An ideal case is direct synthesis of
a peptide ligand on an appropriate matrix and its
subsequent use for analytical or preparative separa-
tion [2, 3]. In so doing, the matrix should meet the re-
quirements both to solid phases for peptide synthesis
and to sorbents for chromatography.
Synthesis of acrylic derivatives of amino acids,
capable of terpolymerization with glycidyl methac-
rylate (GMA) and ethylene glycol dimethacrylate
(EDMA), is important in view of their use for pre-
paration of monolithic porous sorbents  ready
for analysis and use in solid-phase peptide synthesis.
The capacity of the monolith, as determined by the
amino group content, can be controlled by varying
the monomer ratio.
Previously, we have demonstrated the possibility
of preliminary covalent binding of a peptide with
glycidyl methacrylate, followed by copolymerization
of the resulting conjugate with GMA and EDMA .
A direct peptide synthesis was made on the GMA3
EDMA monolithic sorbent modified with b-alanine,
a stable and convenient anchor amino acid .
In this context, our goal was to prepare an acrylic
derivative of b-alanine and to examine the possibility
of preparing a terpolymer of this monomer with
GMA and EDMA in the presence of a porogenic sol-
We used the following chemicals: glycidyl methac-
rylate (Fluka Chemie AG, Switzerland), 2,2-dimethyl-
2-hydroxyacetophenone (Merck3Schuchard, Germa-
ny), ethylene glycol dimethacrylate, di-tert-butyl pyro-
carbonate, b-alanine, cyclohexanol (all Sigma3Ald-
rich, Germany), 2,2`-azobis(isobutyronitrile) (Merck3
Schuchard), dodecanol, ethylenediamine, 2-propanol,
and acryloyl chloride (all Reakhim, Russia).
H NMR spectra were recorded on a Bruker
AC 300 spectrometer (300 MHz) in acetone-d
The IR spectra were taken on a Bruker IFS 88
UV irradiation was performed with a 125-W mer-
cury lamp with a broad radiation spectrum and con-
III. b-Alanine methyl ester hydrochloride (3.03 g,
21.6 mmol) was dissolved in 7 ml of MeOH. To
the resulting solution, we added 60 ml of a 10%
solution of triethylamine in methanol and then,
in small portions, a 1.57 g (7.2 mmol) of di-tert-
butyl pyrocarbonate. The mixture was heated to
50oC and kept at this temperature for 30 min. After
that, it was left overnight at room temperature.
Then the mixture was evaporated, diluted with 50 ml
of ethyl acetate, and acidified with 2% KHSO
The resulting mixture was washed with water.
The organic layer was dried over Na
. The prod-
uct was obtained as a colorless oil; yield 3.48 g