I.

Preparation of Abietic Acid from Wood Rosin and Its Dehydrogenatlon to Retene

1.

Introduction

The oleoresinous exudate of conifers, mainly pines, can be separated into two components - rosin and turpentine.
Turpentine is generally removed from oleoresin by steam distillation, and rosin remains in the still as a
nonvolatile residue. Rosin is known as naval stores, as it was used for caulking the hulls of ships.
Rosin consists mainly of isomeric diterpenoid acids having an empirical formula C20H30O2. Abietic acid is the
most abundant resin acid; it can also be prepared by acid-catalyzed isomerization of other natural resin acids (1).
Abietic acid has been purified through its diamylamine, piperidine, and brucine salts (2).
The nature of the ring system of abietic acid was established by dehydrogenation with sulphur to retene (3), and
was identified as 1-methyl-7-isopropylphenanthrene by oxidative degradation and by synthesis.

2.

Principle

Rosin is isomerized by refluxing in a solution of ethanol-hydrochloric acid for 2 hours (4). Abietic acid is then
isolated from the isomerized rosin by formation of the diamylamine salt; its crystallization and acidification with
acetic acid affords pure abietic acid. On dehydrogenation with sulphur, abietic acid forms retene, identified as a
picrate.

3.

Materials
Acetic acid
Acetone
Carbon dioxide
Diamylamine

4.

Ethanol, 95%
Ether
Hydrochloric acid

Sodium hydroxide
Sulphur
Wood rosin

Time
5-6 hours

5.

Procedure

a. Preparation of abietic acid

Into a 2-litre round-bottomed flask fitted with a 35-cm reflux condenser are introduced 250 g wood rosin, 740
ml 95% ethanol, and 42 ml hydrochloric acid. A stream of carbon dioxide is passed over the surface of the
solution through a glass tube during this reaction. The mixture is boiled under reflux for 2 hr. At the end of this
period, the ethanol and acid are removed by steam distillation, and the water is decanted. The residue is cooled
to room temperature and dissolved in 1 litre ether. The ether solution is extracted with water and dried over
anhydrous sodium sulphate. Evaporation of ether in vacuo yields 245 g isomerized rosin, which is placed in a 1litre Erlenmeyer flask and dissolved in 375 ml acetone by heating the mixture on a steam bath. To this solution
at incipient boiling are added slowly, with vigorous agitation, 127 g diamylamine. Upon cooling to room
temperature, crystals appear in the form of rosettes. The mass in agitated, cooled well in an ice bath, and filtered
by suction. The crystalline salt is washed on a Buchner funnel with 150 ml acetone and dried in a vacuum oven
at 50C for 1 hour. The solid is recrystallized four times from acetone. Each time a sufficient quantity (20 ml per
gram) of acetone is used to ensure complete solution, and the solvent is evaporated until incipient precipitation
of the salt; yield, 118 g; [a]D24-60.
The amine salt is placed in a 4-litre Erlenmeyer flask and dissolved in 1 litre 95% ethanol by heating the mixture
on a steam bath. To the solution, which has been cooled to room temperature, is added 36 ml glacial acetic acid.
The resulting solution is stirred, 900 ml water is added, at first cautiously and with vigorous agitation, until
crystals of abietic acid begin to appear; the remainder of the water is then added more rapidly. The abietic acid
is collected on a Buchner funnel and washed with water until the acetic acid has been removed completely, as
indicated by tests with indicator paper. Recrystallization can be effected by dissolving the crude product in 700
ml 95% ethanol, adding 600 ml water as described above, and cooling the solution. The yield of abietic acid is
98 g (40% based on the weight of isomerized rosin); [a]D24 -106.

b. 1H-NMR

c. Abietic Acid

d. 13C NMR
C-l
C-2
C-3
C-4
C-5
C-6
C-7

38.3
18.1
37.2
46.3
44.9
25.6
120.5

C-8
C-9
C-10
C-11
C-12
C-13
C-14

135.5
51.0
34.5
22.5
27.5
145.1
122.5

C-15
C-16
C-17
C-18
C-19
C-20

34.8
20.9
21.4
185.4
16.7
14.0

e. Mass Spectrum
Abietic Acid C20H30O2, Mol. wt. 302.
m/z
302(62%)
105(78%)
121(49%)
93(49%)

91(100%)
79(55%)

77(56%)
67(45%)

f. UV Spectrum of abietic acid (Ethanol)

lmax 237 mm (loge 4.2)
Abietic acid is a heteroannular conjugated diene in which the two double bonds are conjugated, but located in
two adjoining rings; the parent homoannular diene has an absorption maximum at 253 mm.

g. Dehydrogenation of abietic acid to retene

Abietic acid, 50 g, and 25 g sulphur are heated at 200C (in a hood) until hydrogen sulphide begins to evolve
more slowly; heating at 250C is then continued for a short period. The crude product is distilled under reduced
pressure; BP 260-270C/20 mm; yield, 11-12 g.
The solid distillate is extracted with ether, and the ethereal solution is washed with alkaline solution.
Crystallization of the residue (after removal of ether) from ethanol yields 3 g crystals of MP 98-99C; the
picrate melts at 127C.

References
1.
2.
3.
4.

Ruzicka, L., and Meyer, J. (1922). Helv. Chim. Acta 5, 315.

Lombard, R., and Frey, J. M. (1948). Bull. Soc. Chim. France 1194.
Vesterberg, A. (1903). Ber. 36, 4200.
Wheeler, T. S. (1963). Org. Synth. Coll. 4, 478.

Recommended Reviews
1.
2.
3.

Barton, D. H. R. (1949). The chemistry of the diterpenoids. Quart. Revs. 3, 36.

McCrindte, R., and Overtone, K. H. (1965). The chemistry of the cyclic diterpenoids. In "Advances in Organic Chemistry" (R. A.
Raphael, E. C. Taylor, and H. Wynberg, eds.), Vol. 5, p. 472. Interscience, New York.
Weaver, J. C. (1982). Natural resins. In "Kirk-Othmer Encyclopedia of Chemical Technology" Vol. 20, p. 197. Wiley, New York.