Limonene Chemical

The major monoterpene hydrocarbons present in pepper oil are a- and (3-pinenes, sabinene and limonene. Chemical structures of major aroma compounds are illustrated in Fig. 2.1. 

Uses ndReactions. Some of the principal uses for P-pinene are for manufacturing terpene resins and for thermal isomerization (pyrolysis) to myrcene. The resins are made by Lewis acid (usuaUy AlCl ) polymerization of P-pinene, either as a homopolymer or as a copolymer with other terpenes such as limonene. P-Pinene polymerizes much easier than a-pinene and the resins are usehil in pressure-sensitive adhesives, hot-melt adhesives and coatings, and elastomeric sealants. One of the first syntheses of a new fragrance chemical from turpentine sources used formaldehyde with P-pinene in a Prins reaction to produce the alcohol, Nopol (26) (59). 

D-limonene (Florida Chemicals). A compound of optically active terpene (CioHie) derived as an extract from orange and lemon oils limited data shows veiy low viscosity at low temperatures—only one centipoise at —50°C natural substance having questionable stabihty, Theiminol D-12 (Mon.santo). A synthetic hydrocarbon clear liquid ... 

Chemical Designations - Synonyms Limonene para-Mentha-1,8-diene Phellandrene Terpinene delta-1,8-Terpodiene Chemcal Formula CjoH]j. 

The weight of chemical evidence is strongly in favour of dipentene, being actually i-limonene, that is, merely the racemic form of the active limonenes. Semmler has suggested, however, that a slight difference may exist between the constitutions of these terpenes. ... 

In order to expand the chemical sampling of this species to its entire range and to investigate xylem terpenoids in detail, Zavarin et al. (1990) collected wood samples from 191 trees from 20 areas, isolated the monoterpene fractions, and subjected them to GLC analysis. The major component was identified as a-pinene, with P-pinene, 3-carene, and limonene as lesser, but stiU important, components. Minor... 

The third paper in this set Zavarin and Snajberk (1976) described their efforts to detect chemical races within big cone Douglas fir. Analysis of the cortical monoterpenoid fraction of 33 trees revealed that the major component was a-pinene, with P-pinene, 3-carene, and limonene present in lesser amounts. The monoterpene profiles of different populations varied somewhat from each other, but the overall profile of big cone Douglas fir was clearly different from that of Douglas fir. There was no evidence for gene flow between the southernmost population of Douglas fir at Lompoc and the closest population of big cone Douglas fir at Figueroa, sites separated by only 34 km. 

The first observation is the similarity between the chemical compositions of both the Boswellia carteri and Boswellia sacra. For these three olibanum samples, a-pinene (2), (3-myrcene (8) and limonene (14) are the predominant monoterpenes. p-Caryophyllene (73) is the major sesquiterpene besides a-copaene (65), a-humulene (also called a-caryophyllene) (78) and caryophyllene oxide (95). The characteristic olibanum compounds isoincensole and isoincensole acetate (128) together with cembrene A (120) are the main diterpenes. 

Synonym d-p-mentha-l,8,-diene, (R)-(+)-p-mentha-l,8-diene, (+)-l-methyl-4-(l-methylethenyl)cyclohexene, p-mentha-1,8-diene, carvene, cinene, citrene, cajeputene, kautschin Chemical Name dextro-limonene, (R)-(+)-limonene CAS Registry No 5989-27-5 Molecular Formula C10H16 Molecular Weight 136.234 Melting Point (°C) ... 

A quite different limonene conversion is the dehydrogenation into p-cymene, thus giving a green aromatic. Pd-catalysts give yields of >95% [18]. p-Cymene can be oxidized to the hydroperoxide, which can be rearranged to p-cresol, a valuable chemical. 

Another illustration of the use of such a biocatalytic approach was the synthesis of either enantiomer of a-bisabolol, one of these stereoisomers (out of four) which is of industrial value for the cosmetic industry. This approach was based on the diastereoselective hydrolysis of a mixture of oxirane-diastereoiso-mers obtained from (R)- or (S)-limonene [68]. Thus,starting from (S)-hmonene, the biohydrolysis of the mixture of (4S,81 S)-epoxides led to unreacted (4S,8S)-epoxide and (4S,8i )-diol. The former showed a diastereomeric purity (> 95%) and was chemically transformed into (4S,8S)-a-bisabolol. The formed diol... 

In the search for environmentally benign chemicals that might deter birds such as starlings, crows, or pigeons from roosting en masse, spices and herbs such as rosemary, cumin, and thyme look promising. In some experiments, the birds feet were immersed in oil extracts of the spices. Starlings also avoided perches treated with starch mixes of (R)-limonene, (S)-limonene, (3-pinene, or methiocarb. The first three occur in rosemaiy, cumin, and thyme (Clark, 1997). 

Terpenes are polymers of the 5-carbon compound isoprene (Figure 1.12) and, as such, generally display properties similar to those of hydrocarbons. Terpenoids are substituted terpenes (i.e. contain additional chemical groups, such as an alcohol, phenols, aldehydes, ketones, etc.). Only a few such substances could be regarded as true drugs. Terpenes, such as limonene, menthol and camphor, form components of various essential oils with pseudo-pharmaceutical uses. A number of these molecules, however, exhibit anti-tumour activity, of which taxol is by far the most important. 

Figure 5.7. There are many examples now known of the synthesis of NPs via matrix pathways (see also Figure 9.3). However, a nice example of the benefit of such flexibility was revealed when a mutant of spearmint that had smelled more like peppermint was studied.A comparison of the terpenes in both plants revealed that the single gene mutation had not resulted in a single chemical change but multiple changes, in the mutant plant, a hydroxyl group was added to the 3-position of the cyclohexene ring of limonene while the wild-type hydroxylated the 6-position. Some of the other wild-type tailoring enzymes in the mutant did not discriminate fully between the 3- and 6-hydroxylated products so a new family of NPs were produced which gave the mutant plant an odour of peppermint.

The main renewable resource for L-carvone is spearmint oil (Mentha spicata), which contains up to 75% of this flavour chemical. There also exists a synthetic process for the manufacturing of L-carvone, which is based on (-t)-limonene, which is available as a by-product of the citrus juice industry as a major component of orange peel oil (Scheme 13.4). The synthesis was developed in the nineteenth century and starts with the reaction of (-t)-limonene and nitrosyl chloride, which ensures the asymmetry of the ring. Treatment with base of the nitrosyl chloride adduct results in elimination of hydrogen chloride and rearrangement of the nitrosyl function to an oxime. Acid treatment of the oxime finally results in l-carvone. 

Scheme 13.4 Chemical synthesis of l-carvone from (+)-limonene...

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