Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 2, pp. 282−286.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
E.G. Mamedbeili (Mamedov), T.G. Kyazimova, Kh.I. Gasanov, O.B. Abdiev, I.M. Mamedova, 2009, published in Zhurnal Priklad-
noi Khimii, 2009, Vol. 82, No. 2, pp. 288−292.
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Hexachlorobicyclo[2.2.1]hept-5-enylmethyl
E. G. Mamedbeili (Mamedov), T. G. Kyazimova, Kh. I. Gasanov, O. B. Abdiev,
and I. M. Mamedova
Institute of Chemical Problems, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received June 3, 2008
Abstract—The possibility of preparing hexachlorobicyclo[2.2.1]hept-5-enylmethyl haloacetates by reactions of
hexachlorocyclopentadiene with allyl haloacetates was examined. The optimal conditions for preparing the esters
were found. The structures of the compounds prepared were proved by IR and
H NMR spectroscopy.
Hexachlorocyclopentadiene (HCCPD) and related
compounds are peculiar objects in the modern organic
chemistry. Studies of HCCPD gave an impetus to
the development of the theory of X-philic reactions
in theoretical organic chemistry, and the theory of
pericyclic reactions was supplemented by the reverse
Diels–Alder reaction. The syn–anti isomerism of adducts
of diene condensation involving HCCPD derivatives was
substantiated . Hexachlorocyclopentadiene and related
compounds are of scientiﬁ c interest for understanding the
mechanism of the Diels–Alder reaction .
Halogen-containing bicyclic esters are widely used for
imparting the ﬁ re resistance to polymeric materials, as
modiﬁ ers and curing agents for epoxy resins, as modiﬁ ers
for biologically active substances , and as synthetic
precursors of halogen-substituted sterically hindered
phenols [4–6] and α-diketones [7, 8].
Proceeding with studies in the ﬁ eld of synthesis of
polyhalogenated norbornene esters [9–11], we examined
the reactions of formation of hexachlorobicyclo[2.2.1]-
heptenylmethyl haloacetates. These compounds were
prepared by the Diels–Alder reaction of HCCPD with
allyl haloacetates 2–8 following Scheme 1.
The physicochemical characteristics of adducts 9–15
are given in Table 1.
The reaction was performed in the temperature range
100–160°C for 2–14 h. The diene : dienophile molar
ratio was varied from 1 : 1 to 4 : 1. We examined the
effect of the above parameters on the yield and isomeric
composition of the ﬁ nal products. The results are given
in Table 2.
Studies of the inﬂ uence of the reaction temperature
on the adduct yield, performedby the condensation of
HCCPD with allyl monochloroacetate as an example,
showed that the yield of adduct 9 increased from 21.6 to
85.1% with increasing temperature from 100 to 160°C.
With an increase in the diene : dienophile molar ratio
from 1 : 1 to 2 : 1, the yield of adduct 9 increased from
48.2 to 85.1%. Further increase in the molar ratio to 3 :
1 and 4 : 1 is unfavorable for the yield, which decreased
R = CH
Cl (2, 9), CHCl
(3, 10), CCl
(4, 11), CH
(6, 13), CBr
(7, 14), CF