P-Caryophyllene epoxide

Group 32 shows various epoxides like p-caryophyllene epoxide (Flavis 16.043). 

P-Caryophyllene alcohol acetate. See Caryophyllene alcohol acetate Caryophyllene epoxide p-Caryophyllene epoxide. See P-Caryophyllene oxide P-Caryophyllene oxide CAS 1139-30-6 EINECS/ELINCS 214-519-7 Synonyms Caryophyllene epoxide p-Caryophyllene epoxide Epoxycaryophyllene (-... 

FIGURE 20.133 Biotransformation of (-)-P-caryophyllene epoxide (453) by various fungi. 

Hashizume, T., and I. Sakata Constituents of Japanese Peppermint Oil. II. Isolation and Identification of ( —)-p-Caryophyllene Epoxide from Okako No. 6 . Agric. Biol. Chem. 34, 638 (1970). 

Finally, p-caryophyllene was also subjected to the MTO-catalyzed oxidation. Here, the biphasic system with CH2C12 as the solvent is very effective, with full conversion and selectivity for the internal epoxide after only 1 h of reaction time and a very low catalyst amount of 0.1 mol%, using a 10 1 mixture of 3-methylpyrazole and 1-methylimidazole as nitrogen base [55],... 

SYNS CARYOPHYLLENE EPOXIDE CARYOPHYLLENE OXIDE (-)-CARYOPHYLLENE OXIDE P-CARYOPHYLLENE OXIDE EPOXY-CARYOPHYLLENE (-)-EPOXYDIHYDROCARY-OPHYLLENE 5-OXATRICYCLO(8.2.0.0 > DODECANE, 4,12,12-TRIMETHYL-9-METHYLENE-, (1R,4R,6R,10S)- 4.11.11-TRIMETHYL-8-METHYLENE-50XATRI-CYCL0-(8.2.0.0(4,6))DODECANE... 

Croton sylvaticus Hochst. The essential oil of semi-dried C. sylvaticus leaves (0.14%) contained mainly the sesquiterpenes p-caryophyllene oxide (35%) and a-humulen-1,2-epoxide (12%) (56). The aqueous extract of the stem bark of C. sylvaticus reduced exploratory activity, prolonged ether anesthesia, relaxed the muscles and had analgesic effects on mice (5 7). The plant is used for treatment of swellings caused by kwashiorkor, for tuberculosis and as a purgative (35). 

Euphorbiaceae Croton sylvaticus Hoscht. Leaves SD 0.14 P-caryophyllene oxide, a-humulen-1,2-epoxide 56... 

Fermentation of (-)-p-caryophyllene (451) with D. gossypina afforded 14 different metabolites (453-457j), among which 14-hydroxy-5,6-epoxide (454) and the corresponding acid (455) were the major metabolites. Compound 457j is structurally very rare and found in Poronia punctata. The main reaction path is epoxidation at C5, C6 as mentioned earlier and selective hydroxylation at C4 (Abraham et ah, 1990) (Figure 20.132). 

Fermentation of (-)-P-caryophyllene (451) with Diplodia grossypina afforded 14 different metabolites (453-457J), among which 14-hydroxy-5,6-epoxide (454) and the corresponding acid... 

Roots of Echinacea purpurea contain up to 0.2% essential oil [4, 14,15, 21, 67, 69, 74]. According to Becker [75] and Martin [76] it is composed of 2.1% caryophyl-lene, 0.6% humulene and 1.3% caryophyllene epoxide. Heinzer et al. [14] have analyzed the essential oil by gas chromatography-mass spectrometry (GC-MS) and found compounds of the type dodeca-2,4- dien-l-yl-isovalerate, as well as palmitic and linolenic acid, vanillin, p-hydroxycinnamic acid methyl ester and germacrene D, which had already been reported by Bohlmann and Hoffmann [27] for the aerial parts of the plant. Nevertheless, . purpurea roots are not a typical essential oil drug, and therefore analysis of the essential oil has not been used often for standardization purposes of phytopreparations. However, gas chromatography of the essential oil can be used for the discrimination of the species (see Fig. 1) [14]. 

The primary aromatic substances in beer are derived from raw materials (barley or hops) that confer the beer s typical odour and taste. Bitter acids of hops have a bitter taste (see Section 8.3.5.1.3), but hop cones also contain 0.3-1% m/m of terpenoids (60-80% of hop essential oil), which have a considerable influence on the smell of beer. The main components of aromatic hop oils are sesquiterpenic hydrocarbons in which a-humulene, P-caryophyllene and famesene dominate. The major monoter-penic hydrocarbon is myrcene. For example, the essential oil content of fine aromatic varieties, such as Saaz, is 0.8% m/m, of which 23% is myrcene, 20.5% a-humulene, 14% famesene 6% and P-caryophyUene. Significant components of the hop aroma in beer are mainly isomeric terpenoid monoepoxides resulting from autoxidation and diepoxides of a-humulene and fS-caryophyUene, but also other terpenoids. Important components of hops odour are also various alcohols (such as geraniol and hnalool), esters (ethyl 2-methylpropanoate, methyl 2-methylbutanoate, propyl 2-methylbutanoate and esters of terpenic alcohols, such as geranyl isobutanoate), hydrocarbons, aldehydes and ketones formed by oxidation of fatty acids, such as (3E,5Z)-undeca-l,3,5-triene, (Z)-hex-3-enal, nonanal, (Z)-octa-l,5-dien-3-one, their epoxides, such as ( )-4,5-epoxydec-2-enal and sulfur compounds. Other important components of hops are so-called polyphenols (condensed tannins) that influence the beer s taste and have antioxidant effects. Less important compounds are waxes and other hpids. Hop products, such as powder, pellets and extracts (by extraction with carbon... 

Essential oil components common to the aerial parts of E. pallida, E. purpurea, and E. angustifolia include bomeol, bornylace-tate, pentadeca-8-en-2-one, germacrene D, caryophyllene, caryophyllene epoxide, and palmitic acid. According to another report, the aerial parts contain P-myrcene, a- and P-pinene, limonene, camphene, tran -ocimene, 3-hexen-l-ol, and 2-methyl-4-pentenal. The same report lists dimethyl sulfide, 2- and 3-methylbutanal, 2-propanal, 2-methylpropa-nal, acetaldehyde, camphene, and limonene as the main volatile constituents of the roots, in addition to a-phellandrene that is present only in E. purpurea and E. angustifolia roots. ... 

Naya and Kotake, in an examination of Japanese hop oil, have isolated three humulane-type compounds, viz., humuladienone (161, R = Me), humulenone II (161,R = =CH2), and humulol (162), in addition to the tricyclic diol (163, R = OH), m.p. 207 °C. This diol has already been prepared in two different ways (a) Sutherland et treated humulene (164) with AT-bromosuccini-mide in aqueous acetone and converted the resultant bromohydrin (163, R = Br) to the diol (163, R = OH), m.p. 205—206 °C, by hydrolysis, (b) McKervey and Wright obtained the same diol, m.p. 201—203 °C, by acid-catalysed (20% sulphuric acid) rearrangement of humulene 1,2-epoxide (165), a known natural product. On the basis of these findings and the fact that both caryophyllene (166) and humulene can be derived from the above bromohydrin by two in vitro steps, McKervey and Wright postulated that humulene 1,2-epoxide may be involved in the biosynthesis of the tricyclic diol and caryophyllene. This postulate does not, however, readily accommodate the observed rotations of the relevant... 

Alcohol 2.1 is the only example of this class, and was isolated from Lactarius camphoratus (79) which belongs to Section Olentes (2). The compound is presumably the product of 1-9 cyclization of a humulene precursor. The structure and absolute configuration of this new caryophyllene oxide (2.1) was determined by a combination of spectral data and a single-crystal X-ray analysis of the p-bromobenzoate derivative 2.3. The NMR spectrum of 2.1 exhibited only two methyl signals, one of them at 51.20, together with one-proton doublet of doublets centred at 52.93, strongly suggesting the presence of the 4,5-epoxide. The C-12 methylene protons were shifted downfield (5 3.84) in the 220 MHz NMR spectrum of the acetyl derivative (2.2). Moreover,... 

Caryophyllane-2,6-a- and -P-oxides have been prepared from (— )-isocaryophyll-ene. Intramolecular epoxide opening has been studied for seven diols prepared by oxidation of the exocyclic double-bond of caryophyllene and isocaryophyllene epoxides. ... 

An example of terpenic 1,2-epoxides is -caryophyllene oxide, also known as (-)-epoxycaryophyllene (8-31), which occurs in many essential oils. An example of terpenic 1,4-epoxides is the so-called (-l-)-dill ether, (3J ,4S,8S)-3,9-epoxy-p-menth-l-ene (8-31), which is a typical component of the essential oil of caraway (30%) and dill. An example of unsaturated 1,4-epoxides is (-l-)-menthofuran (8-31), the metabolite of ketone (-l-)-pulegone. Both compounds are components of peppermint oil (see Table 8.32, later) and are hepatotoxic. Monoterpenoid compound (- -)-l,8-cineole (also known as limonene oxide, eucalyptol or 1,8-epoxy-p-menthane 8-31) is an example of more complex structures. It is present in essential oils of many types of spices, and higher quantities are found in the essential oil of trees of the genus Eucalyptus (Myrtaceae). Trivial and systematic names of selected ethers are given in Table 8.8. 

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