Pinenes fenchone from

Fenchane derivatives occur as fenchones and fenchols in several ethereal oils. Oil of fennel, obtained from the dried fruit of Foeniculum vulgare (Umbelliferae), contains up to 20 % (+)-fenchone, and is associated with limonene, phellandrene and a-pinene. (-)-Fenchone is isolated from the tree of life Thuja occidentalis (Cu-pressaceae), which is cultivated as hedges. The dextrorotatory enantiomer of a-fenchol with an endo OH, requested in perfumery, as well as its stereoisomers are found in fresh lemon juice, in oil of turpentine obtained from Pinus palustris (Pina-ceae), in ethereal oils originating from the Lawson white cedar Chamaecyparis lawsoniana (Cupressaceae) and other plant families such as Ferula, Juniperus, and Clausena species... 

In summary, Foeniculum is stated to have three species, F. vulgare (fennel), F. azoricum Mill. (Florence fennel) and F. dulce (sweet fennel). Fennel is widely cultivated, both in its native habitat and elsewhere, for its edible, strongly flavoured leaves and seeds. The flavour is similar to, but milder than, that of anise and star anise. Anethole and fenchone are the major constituents of the solvent extract of seed phenols, free fatty acids, carbohydrates, proteins, vitamins and minerals have been reported in varying proportions. In the mature fruit, up to 95% of the essential oil is located in the fruit, greater amounts being found in the fully ripe fruit. Approximately 45 constituents have been determined from fennel seed oil, the main constituents being frans-anethole, fenchone, estragol (methyl chavicol), limonene, camphene, a-pinene and other monoterpenes, fenchyl alcohol and... 

Fig. II Selected experimental and calculated results for the temperature dependence of the optical rotation at 365 nm. Top-. Fenchone. Center a-Pinene. Bottom Camphene. Data to prepare the plots were taken from [125] (experimental data were from Wiberg et al., J. Phys. Chem. A (2005), 109 3405)...

Camphene is a solid terpene. The dextro variety d-camphene is found in camphor, ginger and spike oils, and the levo variety, 1-camphene is in citrondla and valerian oil and in French and American turpentine. Bornylene does not occur in nature but has been prepared from the alcohol corresponding to it known as Borneol or Borneo camphor. This, as previously stated, may be prepared from pinene so that Bornylene itself may be made from pinene. Fenchene, also, is not found in nature but is obtained by reduction of fenchone a terpene ketone found in fennel oil and in Thuja oil. 

Oil of Cedar Leaf. Cedar leaf oil. Obtained by steam distillation from the fresh leaves of Thuja occidentalis L, Cupressaceae. Although this oil is known commercially as cedar leaf oil, the tree from whose leaves it is obtained is not a true cedar it is a coniferous tree popularly known as "arbor vitae, sometimes erroneously called white cedar. Habit. Canada and Northern U.S. Constit. o-pinene, d-ikujone, a -fenchone. 

Oil of Fennel. Volatile oil from the dried fruit of Foeniculum vulgare Mill., Umbelliferae. Also from the sweet fennel plant (var. duke). Constit 50-60% anethole, —20% fenchone, pinene, limonene. dipentene, phellandrene. 

Oil of White Cedar. Oil of arbor vitae oil of thuja. Volatile oil from leaves of Thuja occidental is L,., Cupress. aceae. Constit. d-Thujone, f-fenchone, d-pinene. 

The reference standards of different monoterpenes, sesquiterpenes, and alkanes were obtained from Aldrich Chemical Co., Inc. (Milwaukee, WI, USA), Fluka Chemical Corporation (New York, NY, USA), Roth Co. Chemische Fabrik (Karlsruhe, Germany), Sigma Chemical Co. (St. Louis, MO, USA) and Varian Associated (Houston, TX, USA). These reference standards include tricyclene, a-pinene, sabinene, a-phellandrene, 1-decene, limonene, fenchone, a-terpineol, a-terpinolene, c/s-verbenol, cis- and trans-carveol, cA-dihydrocarveol, a-longipinene, a-cedrene, (-)-isolongifolol, a-humulene, valencene, cuparene, myristyl alcohol, citronellyl acetate, neryl acetate, geranyl acetate, camphene, alloaromadendrene, -eicosane, and n-heneicosane. Solutions were prepared in methanol at concentrations of 10 mg/mL. For GC/MS analysis each standard solution was diluted by mixing 0.1 mL of the standard solution with 0.9 mL of methanol. 

FIGURE 14.162 Relationship of the metabolism of (-)-f5-pinene ( ), (+)-fenchol (11 ) and (-)-fenchone (12 ) by Aspergillus niger TBUYN-2. (Modified from Noma, Y. and Y. Asakawa, 2005a. Book of Abstracts of the 36th ISEO, p. 32.)... 

The bulk of the oil boiled between 190 and 220. The following ter-penes were identified in the oil o-pinene, y8-pinene, 1-limonene, dipen-tene, and X-terpinene. A considerable amount of a-terpinene was found (this had previously been identified by Teeple), as well as borneol and methyl-chavicol. Fenchyl alcohol was also found as a constituent of the oil, and traces of camphor and cineol. The presence of fenchyl alcohol is of particular interest as it occurs in the inactive variety. It is well known that this body results from the reduction of fenchone, but it has never before been discovered as a natural constituent of an essential oil The table below shows the character of the fenchyl alcohol occurring in this oil and of those prepared by the reduction of active and inactive fenchone. 

Fenchone (254) occurs in a number of essential oils, such as cedar leaf and lavender, and the (—)-isomer is particularly important in fennel. Synthetic material is made from pinene. Addition of carboxylic acids to a-pinene gives the corresponding esters of fenchol. These esters can be hydrolyzed to fenchol, which is then oxidized to fenchone. It is used mainly in reconstitution of fennel oils. 

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