Oxygenated terpenoids

Most essential oils are complex mixtures of terpenic and sesquiterpenic hydrocarbons and their oxygenated terpenoid and sesquiterpenoid derivatives (alcohols, aldehydes, ketones, esters, and occasionally carboxylic acids), as well as aromatic (benzenoid) compounds such as phenols, phenolic ethers, and aromatic esters. So-called terpeneless and sesquiterpeneless essential oils are commonly used in the avor industry. Many terpenes are bitter in taste, and many, particularly the terpenic hydrocarbons, are poorly soluble or even completely insoluble in water-ethanol mixtures. Since the hydrocarbons rarely contribute aitything of importance to their avoring properties, their removal is a commercial necessity. They are removed by the so called washing process, a method used mostly for the treatment of citrus oils. This process takes advantage of the different polarities of individual essential oil constituents. The essential oil is added to a carefully selected solvent (usually a water-ethanol solution) and the mixture partitioned by prolonged stirring. This removes some of the more polar oil constituents into the water-ethanol phase (e.g., the solvent phase). Since... 

Citrus oils are characterized by having a high percentage of terpenoid hydrocarbons and a relatively low content of oxygenated terpenoid compounds that are mainly responsible for their aromatic profiles (Table 8.13). 

Oxygenated terpenoids from a Formosan soft coral Sinularia gibberosa.J. Nat. Prod., 68,1208-1212. 

Open-chain 1,5-polyenes (e.g. squalene) and some oxygenated derivatives are the biochemical precursors of cyclic terpenoids (e.g. steroids, carotenoids). The enzymic cyclization of squalene 2,3-oxide, which has one chiral carbon atom, to produce lanosterol introduces seven chiral centres in one totally stereoselective reaction. As a result, organic chemists have tried to ascertain, whether squalene or related olefinic systems could be induced to undergo similar stereoselective cyclizations in the absence of enzymes (W.S. Johnson, 1968, 1976). 

Chemically, plant essential oils consist largely of mixtures of compounds known as terpenoids —small organic molecules with an immense diversity of structure. More than 35,000 different terpenoids are known. Some are open-chain molecules, and others contain rings some are hydrocarbons, and others contain oxygen. Hydrocarbon terpenoids, in particular, are known as terpenes, and all contain double bonds. For example ... 

Phenazines — These are dibenzopyrazine derivatives with fnnctional groups (hydroxy-, carboxy-) at C, and Cg and an oxygen or methyl gronp at Nj and N,o. There are also more complex structures, substituted phenazines, terpenoidal, and carbohydrate-containing phenazines and phenazines derived from saphenic acid. ... 

The terpenes are simple lipids whose base unit is isoprene. Oxygen-containing ter-penes are called terpenoids, and terpenes with hydroxyl groups are called terpenols. Terpenes are further classified based on the number of isoprene imits in the molecule as shown in Table 22.6. Examples of terpene molecular structures are presented in Figure 22.18. 

Carotenoids are lipid-soluble terpenoids derived from the isoprenoid pathway and are located in hydrophobic areas of cells. All have a 40-carbon isoprene backbone with a variety of ring structures at one or both ends (Fig. 8.2) [25]. The carbon skeleton is derived from five-carbon isoprenoid groups and contains alternating conjugated double bonds. There are two kinds of carotenoids (Fig. 8.2) carotenes composed of carbon and hydrogen and xanthophylls composed of carbon, hydrogen, and oxygen. 

Streibl M, Herout V, Terpenoids-especially oxygenated mono-, sesqui-, di-, and triterpenoids, in Eglinton G, Murphy MTJ (eds.). Organic Geochemistry Methods and Results, Springer-Verlag, Berlin, pp. 401—424, 1969. 

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