ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 2, pp. 326!327. + Pleiades Publishing, Ltd., 2008.
Original Russian Text + L.M. Popova, I.N. Gaidukov, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81, No. 2, pp. 338!339.
Preparation of 1,1,5-Trihydrooctafluoropentyl Dehydroabietate
L. M. Popova and I. N. Gaidukov
St. Petersburg State Technological University of Plant Polymers, St. Petersburg, Russia
Received December 25, 2007
Abstract-1,1,5-Trihydrooctafluoropentyl dehydroabietate was prepared by esterification of dehydroabietic
acid with 1,1,5-trihydrooctafluoropentanol.
Rosin esters are widely used in the production of
varnishes, paints, and adhesive composites, thanks to
diversity of their properties dependent on the kind of
a raw material and alcohol . The use of straight
rosin for this purpose is restricted by its acidity, low
melting point, poor moisture resistance, and tendency
toward polymerization .
To impart water- and oil-repellent properties to
fibers and paper, these materials are treated with com-
pounds containing long-chain fluoroalkyl groups in
their molecule. This treatment is efficiently used in
industry. Furthermore, fibrous materials treated with
fluorinated compounds almost fully preserve their gas
permeability, softness, color, strength, and other char-
Therefore, the development of new fluorinated
compounds based on esters of rosin and polyfluori-
nated telomeric alcohols for treatment of fibrous ma-
terials is a promising line of organic synthesis.
Various procedures for preparing esters from resin
acids of rosin and various alcohols have been reported
, but these do not include esterification with
polyfluorinated telomeric alcohols.
The goal of this study was to synthesize of 1,1,5-tri-
hydrooctafluoropentyl dehydroabietate, a potentially
effective hydrooleophobizing agent for fibrous materi-
als. As synthesis procedure we chose esterification of
dehydroabietic acid with 1,1,5-trihydrooctafluoropen-
tanol in the presence of catalytic amounts of concen-
trated sulfuric acid.
The promising source of dehydroabietic acid is
tall rosin, a by-product from kraft pulp production.
The ester is a noncrystallizing red-brown resinous
F NMR spectra of the dehydroabietic
acid ester were recorded on a Bruker WH-400 spec-
trometer (400.13 MHz) from 5% solutions in CDCl
The chemical shifts were determined relative to in-
ternal reference, tetramethylsilane (
H) and trifluoro-
acetic acid (
The purity of the starting dehydroabietic acid and
the reaction progress were monitored by TLC on Silu-
fol UV 254 plates (eluent hexane3methylene chloride3
acetone, 1 : 1 : 0.5).
Dehydroabietic acid was recovered from tall rosin
(Segezha Pulp and Paper Combine, Karelia, Russia)
by the procedure described in .
Synthesis of 1,1,5-trihydrooctafluoropentyl dehy-
droabietate. To a solution of 3 g (9.9 0 10
dehydroabietic acid in 50 ml of hexane, we added
1.6 ml (11.5 0 10
mol) of 1,1,5-trihydrooctafluoro-
pentanol and a catalytic amount of concentrated sul-
furic acid. The reaction mixture was stirred for 10 h
at 70oC and then cooled to room temperature. The
solvent was distilled off at reduced pressure (5 mm
Hg), the reaction mixture was extracted with ether,
and the extract was washed with water to neutral reac-
tion and dried over MgSO
. The solvent was removed
on a rotary evaporator, and the product was dried in
a vacuum. Yield of the ether 80385%.
H NMR spectrum, d, ppm: 7.2 d, 7.0 d
21 Hz); 6.89 s (=C
H3); 5.9 t
52 Hz); 4.5 m (3OCH
F NMR spectrum, d
, ppm: 3124.3 s, 3127.2 s,
3132 s (3C
3); 3139.5 d (F