Sesquiterpene

Although the term terpene once referred only to hydrocarbons current usage includes functionally substituted derivatives as well grouped together under the general term isoprenoids Figure 26 6 (page 1086) presents the structural formulas for a number of representative examples The isoprene units m some of these are relatively easy to identify The three isoprene units m the sesquiterpene farnesol, for example are mdi cated as follows m color They are joined m a head to tail fashion... 

The trimer famesyl pyrophosphate (35), in addition to serving as a pregenitor of steroids via squalene (114), is also the pregenitor of the compounds known as sesquiterpenes. It has been suggested that famesyl pyrophosphate (88) similarly serves as the carbon backbone of alkaloids such as deoxynuphatidine (120) ftom Nupharjapomcum (Nymphaceae) (water hhes) and dendrobine (121) Dendrobium nobikl indl. (Orchidaceae) (Table 11). 

The latter is the source of the Chinese dmg Chin-Shih-Hu. Compared to the other families of bases discussed eadier, the numbers of alkaloids supposedly derived from famesyl pyrophosphate or a close relative is small. However, given the wide variety of plant families containing sesquiterpenes, it is most likely that the numbers of compounds to be found will dramatically increase. 

It has been found that the flavor of fmit can be increased by a process called precursor atmosphere (PA) (77). When apples were stored in a controlled atmosphere containing butyl alcohol [71-36-3] the butyl alcohol levels increase by a factor of two, and the polar products, butyl ester, and some sesquiterpene products increase significantly. The process offers the possibiUty of compensating for loss of flavor in fmit handling and processing due to improper transportation conditions or excessive heat. 

Intramolecular Friedel-Crafts acylations of olefins also give cycHc a,P-unsaturated cycHc ketones. Cyclopropane fused bicyclo[5.3.0]octenones, thus obtained, were used in the preparation of the marine sesquiterpenes, africanol [53823-07-7] and dactjlol [58542-75-9] (174). 

Amyris Oil. Obtained by steam distillation of the wood of y m hakamijera L., the so-called West Indian sandalwood which is indigenous to northern South America, Central America, and the West Indies, amyris oil [8015-65-4] is a pale yellow to brownish yellow viscous oil with a slightly oily-sweet and occasionally peppery balsamic woody note. It finds use as a blender and fixative for soap fragrances. The volatile constituents, which are primarily hydrocarbon and oxygenated sesquiterpenes, are shown in Table 22 and Figure 5 (63). 

Cyclic sesquiterpenes having the cedrene skeleton have also been isolated. When R = COOH, this stmcture (11) has been named sheUoflc acid. 

Terpenes are characterized as being made up of units of isoprene in a head-to-tail orientation. This isoprene concept, invented to aid in the stmcture deterrnination of terpenes found in natural products, was especially useful for elucidation of stmctures of more complex sesquiterpenes, diterpenes, and polyterpenes. The hydrocarbon, myrcene, and the terpene alcohol, a-terpineol, can be considered as being made up of two isoprene units in such a head-to-tail orientation (1). 

The majority of the turpentine comes from the southeastern United States, which consists of 60—70% a-pinene, 20—25% P-pinene, and 6—12% other components. Because there is variation in components from different species of the pine tree as well as variation from the many paper pulp mills, there is obviously variation in the analysis of sulfate turpentines. Some of the other components consist of -menthadienes, alcohols, ethers such as anethole [104-46-1] and methylchavicol [104-67-0] and the sesquiterpene hydrocarbon, P-caryophyUene [87-44-5]. 

Turpentine from the western United States is different from that of the southern states in that it contains 3-carene ranging from 12—43%, depending on the species of pine tree. Indian turpentine also contains about 60% 3-carene and about 15% of the sesquiterpene longifolene. Turpentine from Sweden, Finland, CIS, and Austria all contain 3-carene however, a- and P-pinene are commercially the most important components of the turpentines. 

Sesquiterpenes are formed by the head-to-tad arrangement of three isoprene units (15 carbon atoms) there are, however, many exceptions to the rule. Because of the complexity and diversity of the substances produced in nature, it is not surprising that there are many examples of skeletal rearrangements, migrations of methyl groups, and even loss of carbon atoms to produce norsesquiterpenoids. 

Important commercial sesquiterpenes mosdy come from essential oils, for example, cedrene and cedrol from cedarwood oil. Many sesquiterpene hydrocarbons and alcohols are important in perfumery as well as being raw materials for synthesis of new fragrance materials. There are probably over 3000 sesquiterpenes that have been isolated and identified in nature. 

The sesquiterpenes found in essential oils have low volatilities compared with monoterpenes and so are isolated mainly by steam distillation or extraction, but some are also isolated by distillation or crystallization. Most of the sesquiterpene alcohols are heavy viscous Hquids and many crystallize when they are of high enough purity. Sesquiterpene alcohols are important in perfume bases for their odor value and their fixative properties as well. They are valuable as carriers of woody, balsamic, or heavy oriental perfume notes. 

Gedrene and Gedrol. Cedarwood oil is one of the essential oils whose production is large and provides a source for synthesizing a number of derivatives. Gedrene (91) and thujopsene (92) are the two main sesquiterpene hydrocarbons found in the oil, along with a number of minor components (187). Gedrol [77-53-2] (93) is the main alcohol component of the oil. 

Patchouli alcohol. Patchouli oil comes from Pogostemonpatchouli and the main constituent is patchouli alcohol [5986-55-0] (105) or patchoulol. Another component of the essential oil is norpatchoulenol (106), a norsesquiterpene derivative as a minor (3—5%) constituent, important ia determining the overall odor of the essential oil (197). The price of patchouli oil ia 1995 was 20.90/kg from Indonesia (69). Alarge proportion of the oil (40—60%) is comprised of sesquiterpene hydrocarbons that do not have much odor value. World production of the oil was at about 750 t ia 1984. It is valuable ia perfumery bases because of its characteristic woody, herbaceous odor (198). 

Guaiol and Bulnesol. The main constituents of guaicwood oil are the sesquiterpene alcohols guaiol [489-86-1] (107) and bulnesol (108). When the alcohols are dehydrated with acid, many of the hydrocarbons formed are also found ia patchouli oil. 

Essential Oils. Volatile oils from plants are referred to as essential oils. The oils can be obtained through steam distillation, solvent extraction, or separation of the oils from pressed fmit. They consist of oxygenated compounds, terpenes, and sesquiterpenes. The primary flavor components of essential oils are oxygenated compounds. Terpenes contain some flavors but are often removed from the essential oil because they are easily oxidized (causiag off-flavors or odors) and are iasoluble. Essential oils are prepared from fmits, herbs, roots, and spices. 

Heating or irradiating alkenes in the presence of sulfur gives relatively low yields of thiiranes. For example, a mixture of sulfur and norbornadiene in pyridine-DMF-NHa at 110 °C gave a 19% yield of the monoepisulfide of norbornadiene as compared with a 78% yield by the method of Scheme 120 (79JCS(Pi)228). Often 1,2,3-trithiolanes are formed instead of thiiranes. The sesquiterpene episulfides in the essential oil of hops were prepared conveniently by irradiation of the terpene and sulfur in cyclohexane (Scheme 135) (80JCS(Pl)3li). Phenyl, methyl or allyl isothiocyanate may be used as a source of sulfur atoms instead of elemental sulfur. 

Sponge sesquiterpenes H NMR, 4, 560 Squalene synthesis, 1, 469 Squalene oxide occurrence, 7, 119 Squamalone... 

The roots contain essential oil with mono- and sesquiterpenes (valcrcnic acids). 

Sesquiterpenes and flavonoids (flavones, flavanones, flavanes) are two elasses of natural substan-ees which occur frequently in plants and whieh have 15 C atoms in their framework. The nine... 

In the //broadband decoupled C NMR spectrum, 15 carbon signals can be identified, in agreement with the molecular formula which indicates a sesquiterpene. The DEPT experiments show that the compound contains four quaternary C atoms, three CH units, seven CH units and a CH3... 

Table 47.2. Assembly of the partial structures A-E to form the decalin framework F of the sesquiterpene...

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