1070-4272/02/7502-0310 $27.00 C 2002 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 75, No. 2, 2002, pp. 310!314. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 2, 2002,
Original Russian Text Copyright + 2002 by A. Radbil’, Zolin, Shkapova, B. Radbil’.
AND POLYMERIC MATERIALS
Reaction of ===-Pinene with Haloacetic Acids
A. B. Radbil’, B. A. Zolin, Yu. A. Shkapova, and B. A. Radbil’
Lesma Research and Promotion Limited Liability Company, Nizhni Novgorod, Russia
Lesosibirsk Rosin Extraction Plant, Open Joint-Stock Company, Lesosibirsk, Krasnoyarsk krai, Russia
Received September 25, 2001
Abstract-The reactions of a-pinene with chloro-, bromo-, and trichloroacetic acids, accompanied by isom-
erization of a-pinene, were studied.
a-Pinene I, one of the major components of turpen-
tine, is an important representative of unsaturated
monoterpene hydrocarbons. Esters derived from
a-pinene show a wide spectrum of scents  and are
used as components of diverse perfume formulations.
Also, these compounds are components of plastics,
rubbers, drugs, cosmetics, and disinfectants .
Monoterpene esters show particular promise in pro-
duction of detergents to impart to them pleasant odor
and to mask the odor originating from petroleum raw
materials used for detergent manufacture .
Esters derived from a-pinene are widely used as
intermediates in synthesis of biologically and physio-
logically active substances [2, 4, 5]. Of most inter-
est in this respect is the report  on synthesis of
borneol with high yield and selectivity by reaction of
a-pinene with chloroacetic acid, followed by saponi-
fication of the reaction mixture with NaOH. Accord-
ing to other papers , the yield of borneol esters
in reactions of a-pinene with some haloacetic acids
does not exceed 20%, with low reaction selectivity.
In this work, we studied the reaction of a-pinene
with chloro-, bromo-, and trichloroacetic acids. The
results are given in the table and in Figs. 1 and 2.
We found that addition of haloacetic acids to
a-pinene is accompanied by its isomerization and
yields both mono- and bicyclic terpenoids. As seen
from the table, the qualitative composition of the
isomerization products is similar in all cases: cam-
phene II, dipentene III, a-terpinene IV, b-terpinene
V, terpinolene VI, and fenchene VII are detected.
With chloro- and bromoacetic acids, the correspond-
ing fenchol, borneol, and a-terpineol esters are formed,
and with trichloroacetic acid, a minor amount of the
isoborneol ester is also detected. Furthermore, with
Fig. 1. Curves of product accumulation in reactions of a-pinene with (a) chloro-, (b) trichloro-, and (c) bromoacetic acids
(70oC, molar ratio a-pinene : acid = 1 : 1). (x) Product content and (t) time. (1) Terpene esters, (2) terpene hydrocarbons,
and (3) polyterpenes; the same for Fig. 2.