Pine oleoresin

Pine oleoresin [1 kg. containing 260 g. (0.86 mole) of levo-pimaric acid] (Notes 1 and 2) is dissolved in 2 1. of acetone in a 4-1. beaker. A solution of 200 g. (2.2 moles) of 2-amino-2-methyl-1-propanol (Note 3) in 200 ml. of acetone is added as rapidly as possible with stirring. The pasty precipitate which forms almost immediately is collected by suction filtration and is pressed as dry as possible using a rubber dam (Note 4). The crude moist precipitate is returned to a 2-1. beaker and is dissolved in the minimum volume ( 1 1.) of boiling methanol. The methanolic solution is cooled to 5° in a refrigerator and stirred occasionally to expedite crystallization. When the crystallization is completed, the solid is collected by suction filtration. The precipitate is redissolved in a minimum volume of boiling methanol ( l 1.) (Note 5), the solution concentrated to two-thirds its original volume (Note 6), cooled to 5°, and the amine salt allowed to... 

In pine oleoresin, many resin acids occur. This procedure illustrates how, by the use of a specific amine, it is possible to get a specific precipitation of one resin acid from a mixture of acids. 

The diterpene acid, abietic acid, is a major constituent of rosin, which is obtained as a nonvolatile residue in the manufacture of turpentine by steam distillation of pine oleoresin or shredded pine stumps. Abietic acid is used extensively in varnishes and as its sodium salt in laundry soaps. 

About 50% of spruce oleoresin consists of resin acids, 20-30% are volatile monoterpenes, and the remainder, terpenoids and fatty acid esters. Pine oleoresin contains a higher percentage of resin acids, about 70-80%, than spruce oleoresin. 

The oleoresin present in the resin canals of certain conifers, especially pine, is secreted as a viscous fluid when the tree is wounded. Pine oleoresin contains about 25% volatile components known as "volatile oil" (or turpentine) the nonvolatile residue consists mainly of resin acids. 

Loeblich and Lawrence1 describe a method for isolating neoabietic acid from pine oleoresin or rosin in 8-12% yield by recrystallization of the 2-amino-2-methyl-1,3-propanediol salt. 

The only method previously available for the isolation of palustric acid was by partition chromatography. The net method is based upon the precipitation of the 2,6-dimethylpiperidine salt of the resin acids from an acetone solution of pine oleoresin or rosin followed by selective crystallization of the salt from 1 1 methanol-acetone. The yield of pure palustric acid from slash gum rosin was 4%. A 10-g. portion of the amine salt was converted into the free acid by dissolving it in 350 ml. of 95% ethanol and adding, with stirring, 100 ml. of 3 Al cold H3POt Ice-water was added to the point of cloudiness and the precipitated acid was washed with water and crystallized from hot 95% ethanol. 

Lawrence et al. "> describe a method for isolation of isodextropimaric acid from the complex mixture of resin acids present in pine oleoresin and gum rosin by precipitation of the piperidine salt from //-heptane solution, followed by selective recrystallization from ethanol. 

Cembranoids, a macrocylic class of diterpene hydrocarbon were first isolated from pine oleoresins [156, 157] and the tobacco plant [158]. Since then, the structures of circa 300 naturally occurring cembranoids have been elucidated and a comprehensive compilation of these diterpenes published through 1990 has been published [159]. Known cembranoids include both hydrocarbons and oxygen-containing compounds such as epoxy, oxo, hydroxy, and lactone functions. Most congeners are polyoxygenated. 

Levopimaric Acid. UR)-l,2,3,4,4a,4b-abietadienoic acid i-pimaric acid 0-pimaric acid /-sapietic acid. C HjjOj mol wt 302.44. C 79.42%, H [0.00%. O [0.58%. Isolation from American pine oleoresin Palkin, Harris, J. Am. Chem. Soc. 55, 3677 (1933) from French galipot, from Pinos maritima Ruzicka, Bacon, Heh. Chim. Acta 20, 1542 (1937) from Pittas paiustris Harris, Sanderson, J. Am. Chem. Soc. 70, 334, 3671 (1948). Structure Ruzicka, Kaufmann, Helv. 

COYNE, J.F., LOTT, L.H., Toxicity of substances in pine oleoresin to southern pine beetles, J. Georg. Entomol. Soc., 1961,11, 301-305. 

Fractionation of pine oleoresin or turpentine yields pine oil (8002-09-3), mostly secondary and tertiary terpene alcohols, at 93 C to 107°C. Pine oil is used as a disinfectant, insecticide, and odorant,... 

Southern pine beetles, Dendroctonua frontalis, were assayed for susceptibility to 16 terpenoids from pine oleoresin (15). The LDcq of d-limonene was 0.47 pg/insect, while i-limonene was slightly less toxic (0.55 /lig/insect), as was myrcene (0.62 /jg/insect). The most toxic chemical tested was limonene dioxide (0.24 /ig/insect), indicating that oxidation of limonene may be an activation process (15). 

Gum thus n. Botanically, the oleoresin from trees of Boswellia species native to Arabia and Somaliland. As applied to the naval stores industry, the term refers to the crystallized pine oleoresin or scarpe collected from scarified faces of trees being worked for turpentine. Langenheim JH (2003) Plant resins chemistry, evolution ecology and ethnobotany. Timber Press, Portland,... 

Venice turpentine n. Same as larch turpentine, the oleoresin of the European larch tree (Larix europea or Larix deciduas). The term is also now used widely to describe the clear yellow liquid portion of pine oleoresin, or a synthetic product of similar composition made by dissolving rosin in a terpene solvent. 

Sex pheromone of Dendroctonus brevicomis sequestered from pine oleoresin together with two bicyclic ketals synthesized by the beetle... 

Monoterpenes Terpene mixture of pines (Pinus ponderata) (D 6.1.1) Attracting the Western pine beetle (Dendroctonus hrevicomis). The female beetles attract males by sequestering myrcene, av constituent of pine oleoresin (E 4)... 

Industrial Applications of Terpenes Obtained from Pine Oleoresin. 4047... 

Pine oleoresin is an abundant source of useful terpenes. It has two major fractions turpentine, which is the volatile fraction, and rosin, which is the solid fraction. A key element of tree defense, oleoresin is an important nonwood forestry product because of the various conventional and potential uses of its terpenes. Oleoresin derivatives can be used by different industries, including pharmaceutical, cosmetic, and food industries, as well as by the chemical industry in the manufacturing of various products, such as paint, varnishes, adhesives, insecticides, and disinfectants. Biotic and abiotic factors that affect oleoresin production can be used to improve yields by promoting specific... 

Pine oleoresin applications Pine oleoresin biosynthesis methods Terpenes Wounding defense response... 

Pine oleoresin is probably one of the oldest natural products used in large scale by humans. In ancient times, oleoresin was used for lighting, to seal, and preserve wooden ships [1] and as sealant of Greek urns in religious ceremonies [2]. Presently, pine oleoresin has been widely applied as feedstock for chemical industries to produce several types of by-products, such as cleaners, insecticides, solvents, paper sizing, paint, printer ink, pharmaceuticals, cosmetics, aroma and flavor compounds, food additives, among others [3-5]. 

Trade parameters of by-products of pine oleoresins are also cmcial when choosing the species to be tapped. For example, pinenes are the most versatile and widely used compounds of turpentine purchased by the chemical industry to produce mainly pine oil and food additives [3, 43-51]. Alpha-pinene is often the most abundant... 

Mechanical Wounding Methods and Physiological Treatments Used to Improve Pine Oleoresin Yields... 

Different t)q)es of industries can make use of oleoresins from pines pharmaceutical and perfume industries, food additives, and other chemical industries (household cleaning products, paints, inks, varnishes, rubber, insecticides, aromatherapy). These various uses are due to their pleasant fragrance [140,141], antimicrobial activity, among various other physical and biological properties. Examples of different terpenes obtained from pine oleoresin and their importance in distinct industrial segments are listed in Table 136.4. 

There is a large-scale industry involved in producing gum rosin. In 2005, for example, China produced 700,000 t of tall oil resin (TOR) derived from tapping oleoresin of pine trees [168]. Rosin is a highly valued derivative of pine oleoresin. 

Acknowledgments Research on pine oleoresin in the senira- author laboratory (AGFN) is... 

McReynoIds RD (1971) Heritability and seasonal changes in viscosity of slash pine oleoresin. USDA Forest Service Research Note SE-155, Southeastern Forest Experiment Station, Asheville, North Carolina... 

Davis BL, Heck EE (1943) L-Ptmaric acid content of Longleaf and Slash Pine oleoresins. Ind Eng Chem 35(2) 171-172... 

Smith R H 1964 The monoterpenes of lodgepole pine oleoresin. Phytochemistry 3 259-262... 

Gibbs J N 1972 Tolerance of Fomes annosus isolates to pine oleoresins and pinosylvins. Eur J For Pathol 12 147-151... 

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