Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 1, pp. 102−106.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
T.G. Kyazymova, E.G. Mamedbeili (Mamedov), O.B. Abdiev, Z.M. Nagiev, S.T. Alieva, A.V. Nagiev, 2009, published in Zhurnal
Prikladnoi Khimii, 2009, Vol. 82, No. 1, pp. 103−107.
ORGANIC SYNTHESIS AND INDUSTRIAL
Synthesis of 1,4,5,6-Tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-
T. G. Kyazymova, E. G. Mamedbeili (Mamedov), O. B. Abdiev, Z. M. Nagiev,
S. T. Alieva, and A. V. Nagiev
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 February 21, 2008
Abstract—The possibility of preparing 1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hept-5-enylmethyl
haloacetates by the reaction of tetrachlorodimethoxycyclopentadiene with allyl haloacetates was examined. The
effect of various factors on the product yield was studied, and the optimal synthesis conditions were found.
Halogenated bicyclic compounds containing various
substituents are widely used as fire retardants for
commercially important polymeric materials  and
are convenient starting compounds for preparing
halogen-substituted sterically hindered phenols [2–4]
and α-diketones [5, 6]. Therefore, the development of
synthesis procedures and study of properties of new
polyhalogenated bicyclic compounds of the norbornene
series are topical problems.
Here we report on the synthesis of 1,4,5,6-
enylmethyl haloacetates by the Diels–Alder reaction
of tetrachlorodimethoxycyclopentadiene with allyl
haloacetates. The initial allyl esters IX–XV were prepared
by common esteriﬁ cation of haloacetic acids II–VIII
with allyl alcohol I:
where R = CH
Cl (XVII), CHCl
Br (XX), CHBr
The physicochemical characteristics of the synthesized
adducts XVII–XXIII are given in Table 2.
The reaction was performed in the temperature interval
80–160°C for 2–14 h. The diene : dienophile molar
ratio was 1 : 1 to 4 : 1. We examined the effect of these
parameters on the product yield. The results are given
in Table 3.
With allyl mono-, di-, and trichloroacetates as
examples, we examined how the number of halogen
atoms in dienophile molecules affects the yield of the
adducts (XVII, XVIII, XIX, respectively). We found
that, with an increase in the number of chlorine atoms
where R = CH
Cl (II, IX), CHCl
(III, X), CCl
Br (V, XII), CHBr
(VI, XIII), Br
The physicochemical data for IX–XV are given in
Target products XVII–XXIII were prepared by the