Anise constituents

CioHi O. White leaflets, with a strong smell and sweet taste, m.p. 22 C, b.p. 235 C. The chief constituent of anise and fennel oils and other essential oils, from which it is manufactured. It can also be prepared from anisole (meihoxybenzene). It is widely used for flavouring pharmaceuticals and dentifrices, and in perfumery. 

Anisic aldehyde, CgHgOj, is a methyl ether of para-oxy-benzaldehyde, which is found to a small extent in the oils of fennel and aniseed. It is manufactured on an extensive scale artificially, and is the basis of all the perfumes of the hawthorn or May blossom type. It is known commercially as aubepine . A certain amount of anisic aldehyde is obtained as a by-product in the manufacture of coumarin, but the greater- part of it is obtained by very careful oxidation of anethol, the characteristic constituent of aniseed oil, which has the constitution—... 

Estragol, or methyl-chavicol, Cj(,H,.,0, is a constituent of tarragon, anise-bark, bay, fennel, and other essential oils. It is a strongly odorous liquid having the following characters —... 

Anethole, C H O, a major constituent of the oil of anise, has the lH NMR spectrum shown. On oxidation with Na2Cr207, anethole yields p-methoxy-benzoic acid. What is the structure of anethole Assign all peaks in the NMR spectrum, and account for the observed splitting patterns. 

Parthenin (19) has at a concentration of 50 ppm no effect on the germination of the bean Phaseolus vulgaris but inhibits the development of radicles and hypocotyls (41). Similar effects were observed by Kanchan for Parthenlum hysteropherus and Eleusine coracana coleoptiles (42) and it was shown that besides parthenin (19), caffeic acid, vanillic acid, ferulic acid, chlorogenic acid an3 anisic acid were major constituents in P. hysteropherus (43). 

A recent survey about essential oils and their pure constituents used to control Varroa jacobsoni, contained three interesting tables that reported the toxicity of essential oils for V. jacobsoni and Apis mellifera after 24, 48 and 72 hours in a topical application and in an evaporation test, and the effects of essential oils on behavior and reproduction of V jacobsoni and on the bee brood [63]. The most interesting oils were those of cinnamon and clove, with 100% mite mortality after 24 h and no significant toxicity on honey bees. Furthermore, clove essential oil produced small brood mortality, and it was an inhibitor of mite reproduction. Other effective oils were anise, fennel, lavender, rosemary and wintergreen, which killed 100% mites after 48-72 hours. On the contrary, the oils obtained from garlic, onion, oregano and thyme, were found to be very toxic for honey bees. Among pure constituents, camphor, linalool, linalyl acetate and pinene resulted small brood mortality and inhibited mite reproduction. 

Brandy or alcohol extracts of spices and herbs may be used for flavoring vermouth (Rizzo, 1957). Spices like anola, and ginger are known to possess medicinal properties, as well as antimicrobial activities (Joshi and John, 2002). The precise details of extraction differ among manufactures. The more important botanical constituents include coriander, cloves, chamomile, dittany of Crete, orris, and quassia. Additional flavorant may include allspice, angelica, anise, bitter almond, cinchona, coriander, juniper, nutmeg, orange peel, and rhubarb. 

It is made by the oxidation of anethole (the chief constituent of anise, star anise, and fennel oils). 

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... 

About 170 other volatile constituents, mostly present at below lppm levels, have been reported in vanilla by Klimes and Lamparsky (1976). Besides vanillin (85% of total volatiles), other important aroma components are glucovanillin, anisic acid, aldehyde, p-hydroxybenzoic acid, p-hydroxy-benzaldehyde (up to 9%), vanillic acid, p-... 

The seeds contain some volatile oil, resin and a large amount of fixed oil (Meisner, 1818). The fruit (without the seeds) contains volatile oil, resin, fat, tannin, pectin and mucilage. The volatile oil (oil of star-anise) amounts to about 4-5% and is almost identical with oil of anise (from P. anisum, LinnS). Star-anise oil from Chinese fruit has a specific gravity at 15°C (59°F) of 0.980-0.990 and its known constituents are anethol, phel-landrene, safrol and hydro-quinone-ethyl-ether (Fliickiger, 1879). Poisonous sikimin has been detected in the fruit (Eykmann, 1881), while Schlegel (1885) found a crystalline principle of a pronounced odour of musk. He also found saponin in the watery extract. 

The essential oil from star anise fruits traditionally is extracted by steam distillation. This process is not expensive but can induce thermal degradation, hydrolysis and water solubilization of some fragrance constituents (Reverchon, 1997). 

Singh, G., Maurya, S., deLampasona, M.P. and Catalan, C. (2006) Chemical constituents, antimicrobial investigations and antioxidative potential of volatile oil and acetone extract of star anise fruits. Journal of the Science of Food and Agriculture 86(1), 111-121. 

Essential oil from anise shows potent fumigant activity against the larvae of Lycoriella ingenue (Dufour). /rans-Anelhole, the chief constituent of the anise oil, was toxic with an LC50 value of 0.20jxl/1 (Park etal., 2006). Essential oils extracted from the seeds of anise exhibit significant repel-lency against the adult females of the mosquito, C. pipiens (Erler et al., 2006). 

De Maack, F., Frunet, D., Malnati, J.C. and Estienne, J. (1982) Study of minor constituents in anethole samples obtained from anise oil. I. Study of the origin of an anethole by the identification of sesquiterpenes. Ann Falsif Expert Chim Toxicology 75, 357-367 (quoted from Ross, I.A., 2001). 

Ishikawa, T., Fujimatu, E. and Kitajima, J. (2002) Water-soluble constituents of anise new glucosides of anethole glycol and its related compounds. Chemical and Pharmacological Bulletin 50(11), 1460-1466. 

Food systems are often not composed of one type of constituent but of a mixture thereof Usually one does not operate at conditions where all constituents mix homogeneously, and even if that were the case, the formulation window turns out to be rather narrow (e.g., the case of Fastis, an anise-holding drink (Grillo 2003)). In most cases one finds that demixing occurs, leading to a situation of each constituent forming its own phase separated from the other phases by a so-called interface. 

Ethers.—Ethers are also constituents of essential oils either as simple ethers or as mixed ether-alcohol or ether-aldehyde compounds. Examples of such oils are oil of anise containing anis aldehyde and anethole (p. 661), and oil of clove which contains eugenole (p. 623). 

Anise is a herbaceous annual cultivated extensively in Europe. The essential oil is obtained by steam distillation of dried fruits (seeds). The distillate is a clear-to-pale yellowish oil. It solidifies at low temperatures and has a characteristic sweet licorice-like odor and flavor. Its main constituents include anethol (approximately 90%), methylchavicol, p-methoxyphe-nylacetone, and acetic aldehyde. Anise oil is used frequently at concentrations of up to approximately 3000 ppm in liquid preparations. 

Anethol, which has a boiling point of about 235° C. has heretofore been recognized as a constituent of oil of anise and has been derived from anise seed, being used principally as a flavoring. However, anethol has not heretofore been recognized as a constituent of pine oil. 

In order to verify further these results the same investigations were carried out with anise seeds from Turkey and star anise from China which both contain trans-moihol as the main constituent. The formation of aldehyde during steam distillation was less pronounced compared to the fennel oils, although a 1.6-2.6 times higher content of anise aldehyde was detected in the steam distillates compared to the C02-extracts. The cA-anethol content was increased by 50% for the distillates, which confirms the results found for the fennel oils. 

Composition The ISO standard for aniseed [15] specifies the E-anethole content as 87-94%. Z-anethole (the more toxic isomer and transformation product of E-anethole when exposed to UV light [16]) is limited to 0.4%. The typical constituent of aniseed oil, pseudoisoeugenyl 2-methylbutyrate ]17] can occur up to 2%. Eor further confirmation of its natural origin by chirality GC, see ] 18]. Further constituents are methyl chavicol (up to 3%), gamma-himachalene (up to 5%), anisic aldehyde (up to 1.4%) and e.g. small amounts of monoterpenes. 

Composition According to ISO [19], the oil contains 86-95% E-anethole, up to 1.0% Z-anethole and up to 6.0% methyl chavicol. Eoeniculin can occur up to 3.0%, anisic aldehyde is limited to 0.5%. Further constituents are monoterpenes like a-pinene, a-phellandrene, limonene, linalool and a-terpineol. Besides P-caryophyllene, two further sesquiterpenes are typical trace components for Chinese star anise oil, namely E-and Z-a-bergamotene. 

Composition E-anethole (bitter fennel 55-75%, sweet fennel 80-95%), fenchone (bitter fennel 12-25%, sweet fennel below 1%), methyl chavicol (2-6%), limonene, a-pinene, a-phellandrene, cis-anethole and anisic aldehyde. For further constituents see [99,100]. Ravid et al. ]101] employed chirality GC to prove that enantiomerically pure (-i-)-fenchone is present in fennel oil. 

Tahiti vanilla (V. tahitensis Moore), which possess a different aroma, is considered as less valuable and can be distinguished from V. planifolia because of its constituents p-anisic acid and p-anisaldehyde [295[. The smaller vanillons (Vanilla pompona Schiede) are practically not available anymore. 

This lactone has an odor reminiscent of coconut it is one of the flavor constituents of fruits, distilled beverages and wine. The sensory properties, mentioned by Dufosse et al. (1994) are strongly coconut, fatty, anise, liquorice, fruity, almond. Mosandl and Gunther (1989) described the odor as strong, sweet, soft-coconut with fatty-milky aspects for the (R)-enantiomer and fatty moldy, with a weak coconut note for the (S), less intense than the (R). The flavor of the (7 )-lactone is herbal, coumarinic, coconut and of the (5) coconut, creamy, dairy, mouthfeel (Chemisis, 1993). The threshold is supposed to be very low (estimated at 30ppb in wine by Nakamura et al., 1988). 

Fig. 3A, B The major constituent of the essential oils 1-6 is detectable VS reagent as a red-violet to brown-violet zone at R, 0.9-0.95. In the essentia] oil of anise (1), staranise (2), bitter fennel (3) or. sweet fennel (4) it is anethole (Tl) with smaO amounts of the isomer methylchavicol, while basil (5) has predominantly methylchavicol which has the same R, value as anethole. The prominent zone of sassafras oil (6) is safrole (T2). Anethole (Tl) and safrole (T2) can be separated in the solvent toluene (see Fig. 4C), where safrole then shows a higher R, value.

Our own work on structure-activity relationships of convulsant sesquiterpene lactones was initiated after isolation of a variety of seco-prczizaanc type compounds from Illicium floridanum and I. parviflorum, both endemic to the southern United States [157, 179-181]. A study on the in-vivo toxicity of several of these compounds [182] showed that anisatin, major constituent in leaves and fruits of I. floridanum (as in those of other previously studied toxic Illicium (=star anise) species, review see [3]), was apparently the only derivative in the tested series which was toxic to mammals, although further compounds, such as pseudoanisatin (PSA, structure 4 in Fig. (27)) were accumulated in the plant in similarly high amounts [179, 180]. In the light of reports that indicated an identical mechanism of action and -possibly- the existence of a common binding site for anisatin and picrotoxinin [156-161] the question arose which structural features in these compounds were similar enough to warrant an identical mode of molecular recognition at the channel protein. 

The fruits of the Illicium species are distinctive star-shaped follicles which emit a characteristic refreshing flavor. The fruits of I. vernum Hook, in particular, are the source of the only economically important product derived from the genus Chinese star anise, which is widely used as a spice for flavoring food and beverages. Hence, essential oils have been the primary subject of chemical research on Illicium species and the presence of volatile phenols have been reported as constituents of various parts of all Illicium studied so far. On the other hand, the fruits of /. anisatum, Japanese star anise, have been known to be very toxic for several centuries. Many researchers had been involved in the attempt to isolate the toxic substance since the middle of the 19th century. In 1952, Lane et al. succeeded in the isolation of the 0 pure toxic principle named anisatin (1) [4]... 

Synonyms Hydroquinone monoethyl ether Uses Stabilizer in butyl acrylate monomer inhibitor in paper/paperboard in contact with aq./fatty foods in food-pkg. adhesives trace constituent in anise... 

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