Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 3, pp. 371−375.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © L.M. Popova, A.N. Gorbenko, Yu.V. Chernetsova, S.V. Vershilov, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86, No. 3,
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of Abietinol and Dehydroabietinol
L. M. Popova
, A. N. Gorbenko
, Yu. V. Chernetsova
, and S. V. Vershilov
St. Petersburg State Technological University of Plant Polymers, St. Petersburg, Russia
Federal State Unitary Enterprise Lebedev's Institute of Synthetic Rubber, St. Petersburg, Russia
Received June 28, 2012
Abstract—New polyﬂ uorinated acylates of diterpene alcohols were prepared by reactions of sodium abietinolate
and dihydroabietinolate with perﬂ uoro(2-methyl-3-oxahexanoyl), perﬂ uoro(2,5-dimethyl-3,6-dioxanonanoyl),
and perﬂ uoro(2,5,8-trimethyl-3,6,9-trioxaundecanoyl) ﬂ uorides, and also of abietinol and dehydroabietinol with
heptadecaﬂ uorononanoic acid in the presence of catalytic amounts of concentrated sulfuric acid.
Rosin and its esters are widely used in various branch-
es [1, 2]. In turn, diterpene alcohols and their derivatives
also ﬁ nd use. For example, abietyl acetate, abietyl iso-
butyrate, abietyl stearate, and abietyl hydroxystearate as
coating agents for paper, textile, wood, and porous stone
are components of linoleum plastics, adhesives, cements,
and sealing waxes . The products of esteriﬁ cation,
condensation, and amidation are ingredients of formula-
tions with dry oils, cellulose derivatives, or polymers .
Additions of abietinol and dehydroabietinol mono- and
diesters enhance the elasticity of polycarbonate ﬁ lms .
Abietinol, dehydroabietinol, and tetrahydroabietinol are
used as components of lubricants for application of im-
ages onto nonferrous metals (aluminum and its alloys)
. Diterpene alcohols and their esters are also used for
preparing varnishes [6, 7] and coagulants for treatment
of oil spillages ; Eucommia bark extract containing
abietinol exhibits estrogen properties .
Surfactant properties of compounds containing long-
chain ﬂ uoroalkyl groups are well known. Therefore, esters
of diterpene alcohols and perﬂ uoroacyl ﬂ uorides can be
valuable hydro- and oleophobizing agents for ﬁ brous
Published procedures for preparing esters of diterpene
alcohols involve the use of carboxylic acids themselves,
their anhydrides, chlorides, and esters with other alcohols
as acid components [1–8]. However, data on synthesis of
esters of abietinol-series alcohols and polyﬂ uoroalkyl-
containing acids are lacking.
As a continuation of our studies on the synthesis of
new tall rosin derivatives [10–12], we performed in this
study esteriﬁ cation of a mixture of sodium abietinolate
and dehydroabietinolate with perﬂ uoroacyl ﬂ uorides and
of a mixture of diterpene alcohols (containing about 70%
abietinol) with heptadecaﬂ uorononanoic acid .
There are two principal ways to obtain alcohols of
abietane series: isolation from natural raw materials by
preparative chromatography [13, 14–18] and synthesis by
reduction of the corresponding acids and their derivatives
with various agents [1, 19, 20–30]: sodium borohydride
, lithium aluminum hydride in diethyl ether [19, 20,
22, 25, 26] or tetrahydrofuran , Grignard reagent
(with subsequent hydrolysis) , lithium metal in liq-
uid ammonia  sodium metal in xylene (120–135°С,
yield 78%) [27, 28], or hydrogen on copper–chromium or
nickel–chromium catalyst at 150–225°C, 1–50 MPa 
or at 250°С, 7–8 MPa for 2 days (yield 73%) . In ad-
dition, abietinol was isolated as by-product in preparation
of retene from resin acids by treatment with hydrogen on
metal oxide catalysts (Ni–Mo and Co–Mo) .