Identification of 15-Hydroperoxyabietic Acid as a Contact Allergen in Portuguese Colophony

Abstract

15-Hydroperoxyabietic acid (15-HPA) has been isolated from Portuguese colophony of the gum rosin type and identified as its methyl ester. The structure of the compound was elucidated using UV, IR, NMR and mass spectrometry. 15-HPA methyl ester was found to be an elicitor when tested in colophony-sensitized guinea-pigs. The sensitizing capacity was verified in the same species and 15-HPA methyl ester was considered to be a strong allergen. The eliciting potential was also verified in patients with known allergy to colophony. The Portuguese gum rosin investigated contained approximately 1% of 15-HPA. Based on its allergenicity and the amounts isolated, we conclude that 15-HPA is a main contact allergen in Portuguese gum rosin.

Colophony allergy: a review

“…Results from guinea pig sensitization studies may not reflect human responses. Compounds such as 15-hydroperoxyabietic acid are unstable (44), and some such as 15-hydroperoxydehydroabietic acid are present at such low concentration in colophony that their relevance may be doubtful (45). These oxidized resin acids from modified and unmodified colophony have been esterified and extracted for patch testing.…”

Lichen extracts as raw materials in perfumery. Part 2: treemoss

“…However, it rapidly autoxidizes to the hydroperoxide 86, which is identified as a major allergen in colophony. [38] Other oxidized species derived from dehydroabietic acid (DHA) 87, such as 15-hydroperoxy-dehydroabietic acid 88 and 7-oxodehydroabietic acid (7-ODHA) 89, are also sensitizers ( Figure 7). In particular, a haptenation mechanism involving 89 has been proposed, which may account for the allergic contact dermatitis (ACD) observed from exposure to resin acids.…”

Abietic acid [MAK Value Documentation, 2013]

“…1985) Purity/impurities commercially available abietic acid has a purity of 85% to 90% (no other details; Karlberg 1989) or 74% with 13.6% isopimaric acid and 7.5% dehydroabietic acid (Karlberg et al 1985); abietic acid and dehydroabietic acid [1740-19-8] can contain oxidation products, e.g. 13,14--epoxides, 13,14--epoxides, 7-oxo-or 15-hydroperoxy compounds (see Figure 2; Karlberg and Gäfvert 1996;Karlberg et al 1988 a, b) Production abietic acid is acomponent of raw tall oil (mixture of resin acids, terpenes and fatty acids) and one of the main components of rosin (colophony). Tall oil is the term for the most important by-product occurring in the production of cellulose according to the sulfate process via decomposition of woods rich in resin.…”

“…Under the influence of light, heat and oxygen they form oxidation products such as hydroperoxides, peroxides, epoxides and ketones, which apparently occur or are formed regularly in preparations containing abietic acid-or dehydroabietic acidic. Important allergens such as 15-hydroperoxyabietic acid (Karlberg and Gäfvert 1996;Karlberg et al 1988 a, b), 13,14--epoxyabietic acid ), 7-oxodehydroabietic acid (Sadhra et al 1996(Sadhra et al , 1997, 15-hydroperoxydehydroabietic acid (Shao et al 1995) and dehydroabietic acid peroxides (Gäfvert et al 1992) occur among these oxidation products (see also Section 5.4.1; Figure 2; Gäfvert 1994;Gäfvert et al 1992;Hausen et al 1989Hausen et al , 1993Karlberg 1988Karlberg , 1991Karlberg and Gäfvert 1996;Karlberg et al 1988 c;Khan and Saeed 1994). No allergenic effect for the pimaric acid type of resin acids (Figure 1) was found (Ehrin and Karlberg 1990).…”