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0031-9422(94)00762-4
Abstract--A new hydroperoxide, 15-hydroperoxydehydroabietic acid (15-HPDA), with contact allergenic properties
has been detected in rosin obtained from Pinus species. Detection was facilitated using a synthetic preparation of 15HPDA for reference purposes. The synthesis and the detection (HPLC and GC) of 15-HPDA in rosin are described.
The allergenic activity of 15-HPDA was studied in an experimental sensitization test on guinea-pigs.
INTRODUCTION
In our research on naturally occurring allergenic substances we have especially studied the allergenic activity
of compounds found in colophony (gum rosin), the
distillation residue of oleoresin from Pinus palustris Mill.
and other Pinus species [1, 2]. Colophony is among the 10
most common causes of delayed hypersensitivity [3-5].
Gum rosin and tall oil rosin, a by-product in the pulp
industry, are used almost interchangeably in technical
products and world production is about one million tons
a year. Colophony is a complex mixture of diterpene resin
acids (85-90%), diterpene alcohols, aldehydes and hydrocarbons. The major resin acids are abietic acid (1) and
dehydroabietic acid (3) [6]. In particular, abietic acid is
easily oxidized by atmospheric oxygen. In nature the
oxidation gives an antimicrobial effect to the exudate
when this comes in contact with air owing to wounding of
the tree. The tree is then protected from microbes until
healed.
In previous studies we have isolated oxidation products of abietic acid and dehydroabietic acid and identified them as contact allergens [7-10]. 15-Hydroperoxyabietic acid (15-HPA) (2) in gum rosin and tall oil rosin
has been identified as a major contact allergen among the
oxidation products [7]. However, the corresponding
hydroperoxide of dehydroabietic acid (15-HPDA) (4) has
not been previously identified. Since didehydroabietic
acid peroxide (DeA-OO-DeA) (5) is another of the identified allergenic compounds [10], it is reasonable to assume
that 15-HPDA could be an intermediate in the formation
of this peroxide. Owing to the structural similarity between 15-HPDA and the earlier identified 15-HPA it is
probable that 15-HPDA could be a contact allergen with
853
854
COOCH 3
1 RI=R2=H,
l a RI=H, R2=CH3
3a
2 RI=OOH, R2-H,
2a R1-OOH, R2=CH3
~ Hg(OAc)2
~ H2SO4
4~*COOCH3
COOCH 3
7
4a
3 RI=R2=H,
3a RI=H, R2=CH3
4 RI=OOH, R2=H,
4a RI=OOH, R2=CH3
I~HPDA
J
2.~o
6.~o
10.00
14.()0
18.00
22.00 (min)
Fig. 1. HPLC-chromatogram of tall oil rosin. Peak eluting at 18.9 was identified as 15-HPDA with MS (first
eluting peak in the magnified section). For HPLC conditions, see Experimental.
Challenge material
Conc. (%)
15-HPDA
15-HPDA
Gum rosin
Vehicle control (pet.)
5
1
10
855
Exposed group
(n = 15)*
Control group
(n = 15)
Positive
reactions
P(exp/co)
Positive
reactions
14
13
2
1
< 0.001
< 0.001
NSt
NS
0
0
0
0
856
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