ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 3, pp. 438!442. + Pleiades Publishing, Ltd., 2008.
Original Russian Text + T.G. Kyazimova, E.G. Mamedov, R.S. Babaev, I.M. Mamedova, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81,
No. 3, pp. 453!457.
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis and Photostabilizing Properties
of Hexachlorobicyclo[2.2.1]hept-5-enylmethyl Esters
of Substituted Benzoic Acids
T. G. Kyazimova, E. G. Mamedov, R. S. Babaev, and I. M. Mamedova
Institute of Chemical Problems, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Insitute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received January 24, 2007
Abstract-Polychlorinated bicyclic esters of p-substituted benzoic acids were prepared by the Diels3Alder
reaction of hexachlorocyclopentadiene with allyl esters of p-substitutted benzoic acids. Some of the adducts
synthesized were tested as photostabilizers for polyethylene-based polymer formulations.
Hexachlorocyclopentadiene (HCCPD, I) and re-
lated compounds are among unusual objects of the
modern organic chemistry. Thanks to HCCPD, the
theory of X-philic reactions was developed, and the
theory of pericyclic reactions was supplemented by
the reversed Diels3Alder reaction. The syn!anti iso-
merism of diene condensation adducts was substanti-
ated using data for HCCPD derivatives . Simple
synthesis of dihomocubane compounds from poly-
halogenated cyclopentadienes attracts attention. Hexa-
chlorocyclopentadiene and related compounds, along
with practical significance, are of interest for elucidat-
ing the mechanism of the Diels3Alder reaction .
Halogen-containing bicyclic esters with other
unique fragments are widely used for imparting flame
resistance to polymeric materials, and also as modi-
fiers and curing agents for epoxy resins and biologi-
cally active substances .
Synthesis of various polyhalogenated bicyclic
esters from unsaturated esters of substituted benzoic
acids attracts researchers’ attention [4, 5].
Proceeding with studies in the field of synthesis of
polyhalogenated bicyclic esters , we prepared,
identified, and examined polyhalonorbornenylmethyl
esters of p-substituted benzoic acids. First, we pre-
pared by a common esterification procedure allyl
esters of p-substituted benzoic acids II!VIII. Their
physicochemical properties are given in Table 1.
Target products IX!XV were prepared by diene
condensation of HCCPD I with allyl esters of p-sub-
stituted benzoic acids II!VIII. The reaction follows
where R = H (II, IX), CH
(III, X), HO (IV, XI),
MeO (V, XII), Cl (VI, XIII), Br (VII, XIV), NO
The reaction was performed in the temperature
range 100 3160oC for 4312 h; the diene : dienophile
molar ratio was from 1 : 1 to 4 : 1. The physicochemi-