Caryophyllenic acid

Carvomenthol, T5 Carvomenthone, T5 Carvone, T5 cw-carvotanacetol, T1 Carvotanacetone, T1 Caryophyllene, T6 tranj-caryophyllenic acid, T6 Cascarillin, T39 Cassaic acid, T39 Cassaine, T39 Cassine, K30 Castoramine, K7 ... 

Fig. 1 Sketch of the chromatographic separation of a mixture (G) of cholesterol (1), stearic acid (2), tripalmitin (3) and caryophyllene (4).

By using pyridine to split off the hydrochloric acid, Semmler and Mayer obtained a caryophyllene substantially identical with that obtained by Schimmel, but of optical rotation - 57°, indicating that Schimmel s body was a mixture of the two compounds. Semmler and Mayer give the following formulae for the caryophyllenes indicated by the above, together with that of the hydrochloride, to indicate the transpositions which occur —... 

Caryophyllene dihydrochloride, Cj5H24.2HCl, may be obtained by saturating a quite dry ethereal solution of the sesquiterpene with dry hydrochloric acid gas, and exposing the mixture to very intense cold. It melts at 69° to 70°. 

Caryophyllene nitrosochloride, (CjgHgJjN OoCL, is obtained when a mixture of the sesquiterpene, alcohol, ethyl acetate, and ethyl nitrite is cooled in a freezing mixture, and then treated with a saturated solution of hydrochloric acid in alcohol. The reaction mass is allowed to stand on ice for an hour and is then exposed to sunlight. Thus prepared it melts at about 158° to 163°, and can be separated into two compounds, one being that of a-caryophyllene and the other that of yS-caryophyllene Deussen s sesquiterpenes of natural caryophyllene from clove oil), a-caryophyllene nitrosochloride melts at 177", and /3-caryophyllene nitrosochloride at 159°. They can be separated by fractional crystallisation. The corresponding a-nitrolbenzylamine melts at 126° to 128°, and the /3-nitrolbenzylamine at 172° to 173°. The bimolecular formula given above is probable but not certain. 

Nitroso-caryophyllene, CjgHjgNO, is prepared by splitting off hydrochloric acid from the corresponding nitrosochloride, by means of sodium methylate. a-Nitrosocaryophyllene melts at 116° and is optically inactive (as is the a-nitrosochloride), and yS-nitrosocarj-ophyllene melts at 120° to 121° and has a specific rotation -H 61-77° (as against — 98 07°for the /3-nitrosochloride). 

Caryophyllene nitrosite is an interesting compound. It has the formula CJ5H24N2O3, and was first produced by Schreiner and Kremers. It is form by treating a mixture of equal volumes of the sesquiterpene and petroleum ether with a concentrated solution of sodium nitrite and glacial acetic acid. It crystallises in fine blue needles when re-crvstallised from alcohol it melts at 115° and has a specific rotation -h 103°. 

From the mother liquors of the preparation of the nitrosite from caryophyllene, a sesquiterpene is obtained, which may be the product of inversion by acids, or may be naturally present. It has the following characters —... 

Strategies based on reconnections which have been applied succesfully to sesquiterpenes, such as caryophyllene, isocaryophyllene and hirsutic acid, as well as to Cecropia juvenile hormone. 

By using betulin as substrate, some mechanistic studies were performed and it was demonstrated that these reactions are catalyzed by Brpnsted acid species generated in situ from the hydrolysis of Bi(0Tf)3-.vH20. This process was also applied to other terpenic compounds. The sesquiterpene ( )-caryophyllene oxide originated clov-2-en-9a-ol by a cariophyllene-clovane rearrangement (Scheme 41) whereas 3-oxo- l 8a-olean-28- l 3(3-olide was obtained from oleanonic acid (Scheme 42). With this triterpene derivative, only 28,13(3-lactonization occurred, with inversion of the configuration of the stereocenter at C18 [133],... 

Approximately 230 volatile compounds have been identified in raspberry fruit [35]. The aroma of raspberries is composed of a mixture of ketones and aldehydes (27%) and terpenoids (30%), alcohols (23%), esters (13%) and furanones (5%). The raspberry ketone (Fig. 7.5) along with a-ionone and jS-ionone have been found to be the primary character-impact compounds in raspberries. Other compounds such as benzyl alcohol, (Z)-3-hexen-l-ol, acetic acid, linalool, geraniol, a-pinene, jS-pinene, a-phellandrene, jS-phellandrene and jS-caryophyllene contribute to the overall aroma of mature red raspberries [101-105]. The most important character-impact compounds of raspberries are summarised in Table 7.3. 

Daucus carota L. subsp. sative Hoffm. Nan He Chi (Carrot) (whole plant) Carotenes, lycopene, phytofluere, umbelliferone, alpha-pinene, camphene, myrcene, daucol, alpha-phellandrene, bisabolene, luteolin-7-glucoside, daucine, pyrrolidine, geraniol, citronellol, carotol, citral, caryophyllene, p-cymene, asarone, daucosterol, petroselinic acid.48 For chronic dysentery, worms, carminative, diuretic, emmenagogue, lower blood sugar, prevent cancer, diabetes, dyspepsia and gout. 

Lindera glauca (Sieb. et Zucc.) Blume Bai Ye Diao Zhang (fruit) Essential oils, cineole, limonene, caryophyllene, bornylautate, fatty acids, camphene, beta-pinene.55 Carminative properties, treat arthritis joint pain. 

China Valeriana altemifolia Bunge. V. amurensis R Smira. ex Kom. V. fauriei Briq. V.fauriei Briq. var. dasycarpa V. subbipinnatifolia A. Baranow Bomyl isovalerate, isovaleric acid, bomeol, camphene, pinene, d-terpineol, 1-limonene, pyrryl-a-methyl ketone, alpha-fenchene, myrcene, phellandrene, 1-caryophyllene, erpinene, terpinolene, eremophilene, selinene, cadinene, valerianol, valerenone, myrtenol, bisabolene, chatinine, caffeic acid.48 Antispasmodic, aphrodisiac, emmenagogue, stimulant, sudorific, backache, cramps, influenza, nausea, numbness. 

Caryophyllene. (-)-Caryophyllene can be isolated from Indian turpentine and has been used to prepare a number of woody aroma products. The epoxides are produced by reaction with peracids. Acetylation of caryophyllene also gives a useful methyl ketone (180) (Fig. 8). Acid-catalyzed rearrangement of caryophyllene in the presence of acetic acid gives a mixture of esters, which are related to caryolan-l-ol and clovan-2-ol (181). 

By enrichment culture technique, a bacterium was isolated from local sewage sludge, utilising caryophyllene as the sole source of carbon and energy [103]. Fermentation of / -pinene by this culture in a mineral salt medium (Seuberf s medium) at 30°C with agitation and aeration for four days yielded a few neutral and acidic transformation products. The metabolites isolated and identified were camphor (2), bomeol (1),... 

Eugenol (80-90%), acetyleugenol (2-3%), caryophyllene, furfural, methyl amyl ketone, salicylic acid (small quantity) Clove stem oil, cedarwood, copaiba or gurjun oil, phenol, oil of turpentine. Chief test estimation of eugenol... 

The common theme so far in our correlation experiments has been to allow spins to evolve during q under the influence of directly coupled nuclear spins. We have seen the power of COSY, HMQC, HMBC, and INADEQUATE to provide us with detailed structural information for ipsenol, caryophyllene oxide, and lactose. In this section, we will develop another method for showing correlations and apply it to molecules with distinct, isolated proton spin systems such as carbohydrates, peptides, and nucleic acids. 

Eugenol, the primary component of clove s volatile oils, functions as an antiinflammatory substance. In animal studies, the addition of clove extract to diets already high in anti-inflammatory components (like cod liver oil, with its high co-3 fatty acid content) brings a synergistic effect. In some studies, it further reduces inflammatory symptoms by another 15-30%. Clove also contains a variety of flavonoids, including kaempferol and rhamnetin, which also contribute to clove s anti-inflammatory and antioxidant properties. Another constituent of clove oil, /J-caryophyllene, also contributes to the anti-inflammatory activity (Ghelardini et al., 2001). 

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