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Derivatives of dehydroabietic acid as polymer additives

Thesis · April 2009

DOI: 10.13140/RG.2.1.2898.0000/1

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Sandip Maurya
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 Master’s Dissertation

The Maharaja Sayajirao University of Baroda, Vadodara

Faculty of Technology and Engineering
Department of Applied Chemistry

Partial M.S. Dissertation

Derivatives of dehydroabietic acid as polymer additives

By
Sandip Maurya

1
INTRODUCTION

2
1. INTRODUCTION.
Gum rosin is the purified and distilled rosin from the balsam of various species of pine. Their
biosphere is determined by climate, weathering, soil composition, and other botanical and
[1]
meteorogical factors .

Collection:

The living tree is systematically wounded so that if the wound is sufficiently long pathological
resin flows arises. The tree is wounded, by a Number of V-shaped groove like cuts. Such a wound
is known as a “lachte”. Irritants (Irritants are chemicals which causes irritation), such as sulfuric
acid, significantly increase the resin flow from the tree. Rosin harvesting begins when the pine
trunks have a diameter of 20 cm and can then continue for about 20-30 years [1].

Composition:
The rosin acids have molecular formula C20H30O2 and they belong to the class of diterpenes. A
large number of isomeric tricyclic rosin acids exist that differ in the positions of the two double
bond. Gum rosin is a mixture of acids, these acids are in equilibrium with each other, and their
composition is depending on the country of origin and plant species.

This acid mixture contains between 30 and 50% levopimaric acid(1) which is thermally sensitive
isomer and readily isomerizes to stable Abietic acid(4) at 100-200oC. (Table-1)

Composition of gum rosin is listed below [1].

3
TABLE-1

No. Name Structural formula m.p.(oC) Content in gum rosin,%

1 Levopimaric acid 150-152oC 0.1-15%

COOH

2 Neoabietic acid 167-169 oC 10-60%

COOH

3 Palustric acid 162-167 oC ~20%

COOH

4 Abietic acid 173-175 oC 10-40%

COOH

5 Dehydroabietic acid 171-173 oC 1-10%

COOH

6 Tetrahydroabietic 1%
acid

COOH

4
7 Dihydroabietic acid 4%

COOH

8 Dextropimaric acid 217-219 oC 8%

COOH

9 Isodextropimaric 162-164 oC 8%
acid

COOH

5
AIM & OBJECTIVE

6
2. Aim & Objectives:

Derivatives of abietic acid such as esters show a very good compatibility with many elastomers,
such as ethylene-vinyl acetate, styrene-isoprene-styrene (SIS), natural rubber, etc. They increase
the crystallinity of polymer which is responsible for strength of polymer. [1]

Hydroabietylalcohol used in adhesives as tackifiers and, as plasticizers in paints, coatings,

adhesives, and polymers.

Dehydroabietylamine and its reaction products are used to combat fungi, bacteria, and algae; as
corrosion inhibitors in water systems; and as process materials in ore floatation and
pharmaceuticals [7].

Amide derivatives of dehydroabietic acid are reported as nucleating and clarifying agents such as
cyclohexyldehydroabietamide in polymer processing, and they are also reported as cholesterol
reducing agents [3, 4].

With this knowledge, it was thought to prepare amides of dehydroabietic acid.

Our efforts in this direction & the results obtained are discussed in the subsequent section.

1. Disproportionation of gum rosin.

2. Isolation of dehydroabietic acid from disproportionated gum rosin.

3. Preparation of amides from isolated dehydroabietic acid.

7
1. Disproportionation of gum rosin:

What is Disproportionation?

A chemical reaction (reversible or irreversible), in which a species are simultaneously reduced and
oxidized so as to form two different products, this types reactions are famous as
Disproportionation. E.g. The disproportionation of hydrogen peroxide into water [1].

2H2O2 → 2H2O + O2

As we know that gum rosin is the mixture of various acids which are shown in table-1, which show
content of dehydroabietic acid (5) was very lesser then other rosin acids in gum rosin.
Disproportionation is the reaction which increases the % of dehydroabietic acid (5) in gum rosin
by simultaneous reduction and oxidation of abietic acid into dehydroabietic acid (5) and
dihydroabietic acid (7).

This process can be carried out thermally (without catalyst) or catalytically, but performance is
high in process which uses catalysts.

2. Isolation of dehydroabietic acid from disproportionated gum rosin:

Disproportionated gum rosin contains mainly dehydroabietic acid and dihydroabietic acid (7) with
traces of Tetrahydroabietic acid (6). Both the major constituent of gum rosin have same functional
group therefore separation of dehydroabietic acid (5) from mixture, is difficult. But dihydroabietic
acid (7) is isomerizes on further heating. The Isomerized acid is much easier to separate from
dehydroabietic acid (5) [4].

8
 H

COOH
C O
(7)
O

Isomerization of dihydroabietic acid

Due to the isomerization, % of dihydroabietic acid (7) is decreases in disproportionated gum rosin.
Selective precipitation of dehydroabietic acid (5) can be done by using agents like 2-ethanol amine
which formed salt with dehydroabietic acid (5) and increase the rate of crystallization. 2-ethanol
amine cannot form salt with Isomerized dihydroabietic acid [6].

During crystallization of amine salt of dehydroabietic acid (5), dihydroabietic acid (7) was also
crystallizing in some extent; these can be removed by recrystallisation [10].

Amine salt was further treated with diluted hydrochloric acid, which gave pure dehydroabietic
acid.

3. Preparation of amides from isolated dehydroabietic acid:

Amide from acid can easily prepared by reaction of thionyl chloride or phosphorus pentachloride
and it was followed by amine [5, 7].

O O
SOCl2 R'-NH2 O
R C +
R C R C + HCl
OH PCl5 Cl NH

SO2 R'
+ HCl
POCl3 +

9
It can also be prepared by using phosgene and followed by amine.

O O O
R'-NH2 R C + HCl
R C + COCl2 R C + CO2 + HCl
NH
OH Cl
R'

Where R, R’ are alkyl or aromatic group.

10
EXPERIMENTAL

11
3. Experimental:

Preparation of disproportionated gum rosin:

It can be disproportionated at 280oC with 0.2% of 5% palladium on carbon. Take about 500gm
gum rosin and 1.0gm of palladium on carbon, was charged to a flask blanketed with nitrogen and
heated rapidly to 280oC. The charge was held at 280oC with stirring under a slow current of
nitrogen for 1 Hour. The slightly exothermic reaction starts at 280oC with Pd as catalyst, 50-60%
of Dehydroabietic acid and 25-35% of Dihydroabietic acid and dihydropimaric acid together with
traces of Tetrahydroabietic acid were formed [2].

Isolation of Dehydroabietic acid (DAA) from disproportionated gum rosin: [2]

A solution of 100 g of the disproportionated gum rosin in 250 ml of ethanol was filtered to remove
impurities. The solution was warmed to 70oC and 18 g of 2-amino ethanol was added, followed
by 250 ml of water at 70-80oC. The hot solution was extracted with five portion of Cyclohexane,
each portion contain 200 ml cyclohexane. The solution was heated between extractions as
necessary to keep the temperature above 60oC. The solution was refrigerated and crystals were
collected, washed with 250 ml of cold 50 % ethanol, and again collected.

Compound was recrystallised by using minimum quantity of absolute ethanol. Yield: 46.5 g.

The ethanolamine salt was dissolved in 50 ml of ethanol and acidified to PH 2-3 with 10 % diluted
hydrochloric acid, after that 100 ml of water added for precipitation. The Dehydroabietic acid (5)
was collected, washed with hot water and recrystallised from 75 % ethanol. Yield: 31.870 g.

HCl
H2N +
+ OH
Cl H3N
OH
COO COOH
COOH
H3N (5)
OH

Synthesis of tert-butyl dehydroabietamide:

12
 SOCl2 tert-butyl amine
triethylamine
COOH CONH
COCl
(5) (10)
Preparation of tert-butyl dehydroabietamide

A solution of Dehydroabietic acid (3 g, 0.01 moles) and thionyl chloride (1.5 g, 0.0127 moles) in
distilled toluene (~30 ml) and 2-3 drops of DMF used as catalyst, placed in RBF. This reaction
mixture was stirred for two hours at 40oC. Removal of excess of thionyl chloride at 60oC, under
vacuum gave viscous yellow colored oily substance which is acid chloride of Dehydroabietic acid.
Complete removal of thionyl chloride was followed by addition of 30 ml of toluene and
evaporation of it. Procedure of Removal of this thionyl chloride was repeated by 3 times.

A solution of tert-butyl amine (0.7314 g, 0.01 moles) and Triethyl amine (1.518 g, 0.015 moles)
in distilled acetone was placed in 150 ml RBF. Distilled acetone (20 ml) was added into acid
chloride and it was taken in addition funnel. The reaction mixture was stirred for one hour after,
addition of acid chloride into amine solution. Reaction mixture was poured on ice-water mixture,
acidified to PH 2-3 by using 10 % diluted HCl. Precipitates were filtered and washed with hot water
and dried it. Recrystallised it with acetone. Recrystallisation gave the tert-butyl dehydroabietamide
(10) as a white, needle shaped crystals (Yield 2.21 g, 62.08 % yield, m.p.152oC from DSC).

Synthesis of 2-methyl cyclohexyl dehydroabietamide:

13
 2-methyl cyclohexyl
SOCl2 amine
triethylamine CONH
COOH COCl (11)
(5)
Preparation of 2-methyl cyclohexyl dehydroabietamide

A solution of Dehydroabietic acid (3 g, 0.01 moles) and thionyl chloride (1.5 g, 0.0127 moles) in
distilled toluene (~30 ml) and 2-3 drops of DMF used as catalyst, placed in RBF. This reaction
mixture was stirred for two hours at 40oC. Removal of excess of thionyl chloride at 60oC gave
viscous yellow colored oily substant which is acid chloride of Dehydroabietic acid. Complete
removal of thionyl chloride was followed by addition of 30 ml of toluene and evaporation of it.
Procedure of Removal of this thionyl chloride was repeated by 3 times.

A solution of 2-methyl cyclohexyl amine (1.132 g, 0.01 moles) and Triethyl amine (1.518 g, 0.015
moles) in distilled acetone was placed in 150 ml RBF. Distilled acetone (20 ml) was added into
acid chloride and it was taken in addition funnel. The reaction mixture was stirred for one hour
after, addition of acid chloride into amine solution. Reaction mixture was poured on ice-water
mixture, acidified to PH 2-3 by using 10 % diluted HCl. Precipitates were filtered and washed with
hot water and dried it. Recrystallised it with acetone.

From the Recrystallisation with acetone, 2-methyl cyclohexyl dehydroabietamide (11) obtained as
white colored crystals which had not shiny surface. (Yield 2.85 g, 72.04 % yield, m.p.208.1oC
from DSC).

14
RESULTS AND DISCUSSION

15
4. RESULTS AND DISCUSSION:

A. Dehydroabietic acid:

Thermal analysis of dehydroabietic acid (5):

DSC shows melting point of dehydroabietic acid (5), is 174.19oC.

16
B. tert-butyl dehydroabietamide:

Thermal analysis of tert-butyl dehydroabietamide (10):

DSC shows melting point of tert-butyl dehydroabietamide (10) is 152.6oC, and it has no other
impurity which has low melting point.

IR Spectra of tert-butyl dehydroabietamide (10):

White needle shaped crystals of tert-butyl dehydroabietamide (10) show following observation in
IR analysis.

Wave number (cm-1) Functional group

3444.1 N-H stretch (amide)

2967.8,2937.4,2868.1,2834.2 C-H stretch

1648.6 C=O group

1516.6,1448.5 C=C stretch (aromatic)

Mass spectra of tert-butyl dehydroabietamide:

From mass spectra of tert-butyl dehydroabietamide (10):

m/z Value Fragmented ions

355.75 Molecular ion peak (shows molecular weight) C24H37NO+

340.83 C23H34NO+

298.62 C20H28NO+

284.63 C20H26O+

17
239.56 C18H23+

197.42 C15H17+

186.47 C14H17+

131.38 C10H11+

117.36 C9H10+

18
C. 2-methyl cyclohexyl dehydroabietamide:

Thermal analysis of 2-methyl cyclohexyl dehydroabietamide (11):

DSC shows melting point of 2-methyl cyclohexyl dehydroabietamide (11) is 210.20oC.

IR Spectra of 2-methyl cyclohexyl dehydroabietamide (11):

Wave number (cm-1) Functional group

3338.7 N-H stretch

2927.6, 2853.1 C-H stretch (methyl)

1621.5 C=O group

1532.9, 1456.2 C=C Ring stretch

Mass Spectra of 2-methyl cyclohexyl dehydroabietamide (11):

m/z Value Fragmented ions

395.88 Molecular ion peak (shows molecular weight) C27H41NO+

380.96 C26H38NO+

338.83 C23H32NO+

284.66 C20H27O+

239.57 C18H23+

197.50 C15H17+

186.40 C14H17+

131.45 C10H11+

19
CONCLUSION

20
5. CONCLUSION:

IR spectra of tert-butyl dehydroabietamide (10) and 2-methyl cyclohexyl dehydroabietamide (11)

showed signal for secondary amide between the ranges of 3300-3500 cm-1 and one signal in the
range of 1540-1870 cm-1 indicating presence of C=O (carbonyl) group.

21
REFERENCES

22
 6. REFERENCES:

1. Resins, natural.
Ullman’s encyclopedia, Page no.335 vol-31.
2. The isolation of dehydroabietic acid from disproportionated rosin.
Noah j. Halbrook, and Lawrence.
J. Org. Chem., 1966, 31(12), 4246-4247.
3. Abietamide derivatives, their production and use.
Murai et al.
US Patent: 4210671(July 1, 1980)
4. Derivatives of Dehydroabietic Acid.
Yolanda T. Pratt.
J. Am. Chem. Soc., 1951, 73 (8), 3803-3807.
5. US Patent: 2580496, Jan.01, 1952.
6. J. Am. Chem. Soc.,1935, 56, p.1934.
7. The preparation of dehydroabietane-1-amine.
Richard F. Stockel

Canadian Journal of Chemistry, Volume 41(1963), 834.

8. The chemistry of resin acids.
Harold H. Zeiss.
Chem. Rev., 1948, 42 (1), 163-187.
9. Influence of Reaction Conditions on the Dimerization of Abietic Acid and Rosin.
R. G. Sinclair, D. A. Berry, W. H. Schuller, and R. V. Lawrence.
Ind. Eng. Chem. Prod. Res. Dev., 1970, 9 (1), 60-65.
10. Inhibition of Rosin Crystallization.
George joseph kutsek.
US Patent: 6939944B2, Sep. 6, 2005.

23

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