Terpene acid

Although a small amount of acyclic terpene acids such as geranic acid and citronel-lic acid occurs in many essential oils, often as esters, they are rarely used in perfume and flavor compositions. Methyl geranate is an intermediate in a-damascone synthesis and is sometimes needed in the reconstitution of essential oils. 

Tall oil, derived from the Swedish tallolja meaning pine oil, is recovered from the black liquor of softwood pulping. It is taken out at an intermediate stage of the multiple-effect evaporation when the liquor contains about 30% total solids, after it is allowed to stand [21]. The soaps (sodium salts of fatty acids present) are insoluble, cream to the top of the vessel, and are skimmed off. The residual black liquor is returned to the evaporators to continue chemical recovery. The soap yield, which can range from 10 to 200 kg/tonne of pulp (or even higher for pine), is then acidified and the free fatty acids and resin acids obtained are separated by distillation. The fatty acids recovered consist mainly of oleic and linoleic acids and are employed in soap manufacture and as the drying oil components of paints and varnishes [22] (Chap. 19). Resin acids consist of terpene acids such as abietic acid and its positional and reductive variants, and are mainly employed in paper sizing. 

Sharma, M.L., A. Kaul, A. Khajuria, S. Singh, and G.B. Singh. 1996. Immunomodulatory activity of bosweUic acids (jjentacycUc tii-terpene acids) from Boswellia serrata. Phytother. Res.l0(2) 107-112. 

Composition S. balsam consists of up to ca. 50% tri-terpene acids, and more than 45% of cinnamyl cinna-mate (see cinnamic acid) and 3-phenylpropyl cinna-mate (a) (CigHigOj, Mr 266.34), together with small amounts of more volatile compounds such as cinna-myl alcohol and hydrocinnamyl alcohol. The typical odor notes of S. are determined mainly by the trace content of styrene (b) (CgH, Mr 104.15). 

Many terpenes contain additional functional groups, especially carboxyl groups and hydroxyl groups. A terpene aldehyde, a terpene alcohol, a terpene ketone, and a terpene acid are shown next. 

The most representative naturally-occurring polyester is shellac , a resin secreted by female lac bugs in India and Thailand. Shellac is a complex mixture of monoesters and polyesters, whose backbone is mainly formed of terpenic acids, aleuritic acid and several minor fatty acids (Wang et al., 1999). This is therefore a non-homogeneous material from a chemical point of view, because it contains isolated and conjugated double bonds, and aldehydic and primary alcoholic groups, that make shellac a polyfunctional resin (Fig. 1.1). 

Shellac main components (a) aleuritic acid and (b) terpenic acids (R = COOH, CH2OH, CHO, R = CH3, CH2OH). 

Pine oil Mixing terpene alcohol and terpenes Acid value 1-2 CM3terpene alcohol 50-75 % CyMch terpene alcohol 50 60 % Oxidation product of dialkylphosphorodithioic acid 1-10 % solution... 

Shellac, a resin, is the most representative material in the naturally occurring polyesters category. It is a mixture of monoesters and polyesters (secreted by female lac bug), with a backbone mainly consisting of aleuritic acid, terpenic acids, and minor fatty acids (Wang, 1999). This resin is used as a food additive and also as a pharmaceutical glaze. It also serves as coating material for tablets and capsules, particularly in time-released or delayed-action pills, because it stops the piU from breaking down in the stomach. 

Kalogeropoulos N, Chiou A, Mylona A, loaimou MS, Andrikopoulos NK (2007) Recovery and distribution of natural antioxidants (a-tocopherol, polyphenols and terpenic acids) after pan-frying of Mediterranean finfish in virgin olive oil. Food Chem 100 509-517 Cacace JE, Mazza G (2003) Mass transfer process during extraction of phenolic compounds from milled berries. J Food Eng 59 379-389... 

Due to its high content of hoswellic acid, olibanum has been demonstrated to have antioxidant properties on seed oils (cottonseed and sunflower) 0.1% olibanum has activity comparable to 0.02% butylated hydroxyani-sole (BHA). The water-soluble extract inhibits NO production in rat macrophages resulting in both hepato- and renal protection. The hexane extract has also been reported to possess hepatoprotective activity. Olibanum has been reported to possess anticancer and cancer chemopreventive effects in different conditions. As snch, it was successfiil in reversing breast cancer brain metastases in a patient who was not responsive to standard therapy. Acetyl bosweUic acids induce mahgnant cell apoptosis through caspase activation. Terpene acids of... 

Other nonphenolic compounds have also been extracted from olive leaves such is the case with terpenic acids including oleanolic, ursolic, and maslinic acids, which were extracted by Albi et al. [259]. Both maceration and Soxhlet extraction using hexane as extractant were used to remove terpenic dialcohols, triglycerides, a-tocopherol, ester waxes, squalene, and (3-carotene, among other substances [260]. The extraction efficiency was similar, the differences between the two methods never exceeding 5%. 

Albi, T., Guinda, A., and Lanzon, A., Procedure for isolation and determination of terpenic acids from the olive leaf (Olea europaea), Grasas Aceites, 52, 275, 2001. Guinda, A. et al., Aislamiento y cuantificacion de los componentes de la hoja del olivo Extracto de hexano, Grasas Aceites, 53, 419, 2002. 

Hudlicky T, Short RP (1982) Terpenic Acids by Cyclopentane Annulation of Exocyclic Dienes. Synthesis of Triquinane Portion of Retigeranic Acid. J Org Chem 47 1522... 

FAMEs), terpenes, acids, amines, solvents Minimum temperature 40°C Maximum temperature 280 °C... 

The presence of oleanolic acid (a triterpenic acid, of the a-amyrin series), as a consistent component of the olive fruit and of its oil, has long been known (Canzoneri, 1906 Parisi and De Vito, 1931 Scurti and Tomasi, 1912). More recent is the identification of maslinic (Cag-lioti, 1961) and crategolic (Vioque et al., 1961) acids. The presence has yet to be confirmed in vegetable oils —in particular, olive oil— of other terpenic acids such as ursolic and betulinic (Mazuelos Vela, 1964 Thiers et al., 1959) these acids are very probably in free form in the oil. 

An optically active, secondary terpene alcohol. ( —)-Piperilol is found in various eucalyptus oils and (-l-) piperitol in the oil from a species of Andropogon. A somewhat viscous oil of pleasant smell. It yields piperitone on oxidation with chromic acid. 

Strategy Problem 6 A labelled compound for biosynthetic studies. Mevaloitic acid (TM 418) is an intermediate in the biosynthesis of terpenes and steroids (Tedder, volume 4, p.217 ff). To study exactly what happens to each carbon atom during its transformation into, say, hmonene (418A), we need separate samples of mevalonic acid labelled with in each carbon atom in the molecule. This turns our normal strategy on its head since we must now look for one carbon discoimections. You can use reagents like Na CN, and... 

Bromomethyl)- or (hydroxymethyl)cycIopropane derivatives undergo acid-catalyzed homoallyiic rearrangements to yield trans-olefins (J.P. McCormick, 1975 S.F. Brady, 1968 M. Julia, 1974). This rearrangement is the basis of Julia s terpene synthesis (see. p. 70). 

The enzyme catalyzed reactions that lead to geraniol and farnesol (as their pyrophosphate esters) are mechanistically related to the acid catalyzed dimerization of alkenes discussed m Section 6 21 The reaction of an allylic pyrophosphate or a carbo cation with a source of rr electrons is a recurring theme m terpene biosynthesis and is invoked to explain the origin of more complicated structural types Consider for exam pie the formation of cyclic monoterpenes Neryl pyrophosphate formed by an enzyme catalyzed isomerization of the E double bond m geranyl pyrophosphate has the proper geometry to form a six membered ring via intramolecular attack of the double bond on the allylic pyrophosphate unit... 

Bile acids (Section 26 13) Steroid derivatives biosynthesized in the liver that aid digestion by emulsifying fats Bimolecular (Section 4 8) A process in which two particles re act in the same elementary step Biological isoprene unit (Section 26 8) Isopentenyl pyrophos phate the biological precursor to terpenes and steroids... 

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