Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 4, pp. 691−694.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
E.G. Mamedbeili, T.G. Kyazimova, S.B. Zeinalov, Kh.I. Gasanov, Z.M. Nagiev, 2010, published in Zhurnal Prikladnoi Khimii, 2010,
Vol. 83, No. 4, pp. 638−641.
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of 1,4,5,6-Tetrachloro-7,7-dimethoxy-
of p-Substituted Benzoic Acids
E. G. Mamedbeili, T. G. Kyazimova, S. B. Zeinalov, Kh. I. Gasanov, and Z. M. 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 June 24, 2009
Abstract—The possibility of preparing 1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.1]hepta-2,5-dienyl-methyl
esters of p-substituted benzoic acids by [4+2]cycloaddition of tetrachlorodimethoxycyclo-pentadine to propargyl
esters of the corresponding acids was examined. The optimal synthesis conditions were found. The structure of
the compounds synthesized was conﬁ rmed by independent synthesis and by IR and
H NMR spectroscopy.
[4+2]-Cycloaddition involving polychlorocyclo-
pentadienes is a convenient and promising route
to chlorine-substituted norbornene derivatives .
Functionally substituted polychlorinated norbornenes, in
turn, are of interest as starting compounds for preparing
Proceeding with studies in the ﬁ eld of synthesis of
polyhalogenated bicyclic esters [4–10], we prepared in
this work 1,4,5,6-tetrachloro-7,7-dimethoxybicyclo[2.2.
1]hepta-2,5-dienylmethyl esters of p-substituted benzoic
acids. By esteriﬁ cation of propargyl aclohol I with
benzoic acids IIa–IIg, we synthesized the corresponding
starting dienophiles IIIa–IIIg:
where R = H (IIa, IIIa), Me (IIb, IIIb), OH (IIc, IIIc),
MeO (IId, IIId), Cl (IIe, IIIe), Br (IIf, IIIf), NO
The physicochemical data for propargyl esters of
p-substituted benzoic acids IIIa–IIIg are given in
The ﬁ nal products Va–Vg were prepared by [4+2]-
cycloaddition of dimethoxytetrachlorocyclopentadiene
IV to IIIa–IIIg. The reaction follows the scheme
where R = H (Va), Me (Vb), OH (Vc), MeO (Vd), Cl
(Ve), Br (Vf), NO
The physicochemical parameters of the compounds
synthesized are given in Table 2.