ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 10, pp. 1803–1807. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © T.G. Kyazimova, E.G. Mamedbeili, A.V. Nagiev, E.I. Suleimanova, Kh.S. Khalilov, 2008, published in Zhurnal Prikladnoi Khimii,
2008, Vol. 81, No. 10, pp. 1679–1683 .
Synthesis of Bicyclo[2.2.1]Hept-5-Enyl Methyl Esters
of Haloacetic Acids
T. G. Kyazimova, E. G. Mamedbeili, A. V. Nagiev, E. I. Suleimanova, and Kh. S. Khalilov
Institute of Chemical Problems, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Baku Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,
Received January 22, 2008
Abstract—Synthesis of norbornenyl methyl esters of a number of haloacetic acids via [4 +2] cycloaddition of
cyclopentadiene to allyl esters of these acids was examined. The yield and isomer composition of the
synthesized compounds were examined in relation to the reaction conditions, and the best conditions for their
preparation were found.
The structure of bicyclo[2.2.1]heptane, or norbor-
nane, is a basis of many important natural compounds
like borneal, camphor, etc. . Similarly to norbornane
and adamantane moieties, the norbornene moiety is a part
of amines, many of which are medical preparations .
Significant interest in norbornene compounds
also stems from their availability increased due to im-
provement of diene synthesis techniques. In most cases,
this reaction does not involve side processes, which
makes it possible to reveal factors governing the rate,
direction, and equilibrium of the process with and
without catalysts .
Halogenated functionally substituted norbornenes
are good synthons for preparation of important inter-
mediate halogenated sterically hindered phenols [4–8].
These compounds are also suitable as stanting materi-
als for preparation of α-diketones and γ-lactones [9–12].
This study continues a series dedicated to synthe-
sis of halogen-containing esters of norbornene com-
pounds [13–16]. Here, we prepared bicyclo[2.2.1]-
hept-5-enylmethyl esters of a number of haloacetic acids
by the reaction of cyclopentadiene (CPD) with allyl
esters of haloacetic acids 11–19. The allyl esters 10–18
were synthesized by the well-known technique of esterifi-
cation of corresponding acids 1–9 with allyl alcohol
R = CH
Cl (1, 10); CHCl
(2, 11); CCl
Br (4, 13); CHBr
(5, 14); CBr
(6, 15); CF
(7, 16); CH
–CHCl (8, 17); CH
Table 1 lists the physicochemical parameters of
the starting allyl esters (10–18).
The target products (19–27) were prepared by
[4+2] cycloaddition of CPD to allyl esters of haloace-
tic acids (10–18) by the scheme
AND INDUSTRIAL ORGANIC CHEMISTRY
R = CH
Cl (19), CHCl
The reaction was carried out at temperatures
within 100–180°С in the course of 6–10 h at the diene-
to-dienophile molar ratio of 1 : (1–4).