Menthone from /-menthol

Monocyclic and bicyclic oxygenated terpenes include some familiar and interesting substances such as menthone and menthol from peppermint oil, 1,8-cineole from eucalyptus, and ascaridole, which is a naturally occurring peroxide from chenopodium oil ... 

An asymmetric center next to a carbonyl group is not disturbed during the reduction. Thus from (—)-menthone a menthol mixture [71% of (—)-menthol and 29% of neomenthol (cis)] is obtained that can be reoxidized to (—)-menthone 359... 

Menthone and menthol are both Isolated from mint. Explain why menthol Is a solid at room temperature but menthone is a liquid. 

Muckiger and Power isolated two laevo-rotatory terpenes from English peppermint oil, but their purity is doubtful. It is probable that they were mixtures of pinene, phellai rene, and limonene. A dextrorotatory sesquiterpene.(cadinene ) is also psresent, as well as menthone,. and menthol, both in the free state and as acetate and isovalerianate. 

Natural menthol is obtained by freezing the essential oU, eg, Mentha arvensis and the menthol crystals ate separated by centrifuging the supernatant hquid away from the crystals. The supernatant oU is then caUed dementholized cornmint oU. Impurities in the crystals come from the essential oU and usuaUy give a slight peppermint aroma to the crystallized menthol. The cornmint oU, rich in (—)-menthone (- 28%) and (—)-menthol (- 32%), can be further processed to give additional natural menthol. 

The earlier researches of Charabot have shown that the essential oil of the flowers is richer in menthone than the essential oil of the leaves. And it is in spite of a circulation of menthol, a soluble principle, from the leaf to the inflorescence, that this latter organ contains an essential oil particularly rich in menthone. It must therefore be that the menthol is there converted into menthone by oxidation. 

Menthol, Cj Hj OH, is the characteristic alcohol of oil of peppermint, from which it separates in fine crystals on cooling. It also results from the reduction of the corresponding ketone, menthone, Cj HigO, and. also of pulegone, CioHigO. ... 

The most reliable work on the isomeric menthols is that of Pickard and Littlebury.2 Starting from the mixture of alcohols which Brunei had obtained by the reduction of thymol, and which he had described under the name of thymomenthol, they isolated from it about 60 per cent, of isomeric menthols, 30 per cent, of menthones, and several other compounds. They prepared the phthalic acid esters and converted them into their magnesium and zinc salts, which were then fractionally crystallised. 

Werkhoff P, Hopp R, Isolation and gas chromatographic separation of menthol and menthone enantiomers from natural peppermint oils, in Brunke EJ (ed.). Progress in Essential Oil Research, Walter de Gruyter, Berlin, Germany, pp. 529— 549, 1986. 

Figure 15.7 Response of the molecular imprinted polymer quartz crystal microbalance (MIP-QCM) sensor to monoterpene analogues ( ) L-menthol, (A) D-menthol, ( ) citronel-lol, (A) citronellal, and (O) menthone. Reprinted from Percival et al. (2001). Copyright 2001 American Chemical Society.

Menthol from Dementholized Cornmint Oil. Dementholized cornmint oil, from which (-)-menthol has been removed by crystallization and which still contains 40-50% free menthol, can be reused for producing (-)-menthol. The fairly large quantity of (-)-menthone in the oil (30-50%) is hydrogenated to form a mixture of mainly (-)-menthol and (+)-neomenthol the (-)-menthyl esters present (chiefly (-)-menthyl acetate) are saponified. Additional (—)-menthol is then separated from other components by crystallization, distillation, or via the boric acid esters. 

Menthol from (+)-3-Carene. An Indian manufacturing process for (—)-menthol starts from 3-carene, the major component of Indian turpentine oil (55-65%). (+)-3-Carene isomerizes to (+)-2-carene, which can be pyrolyzed to (+)-tra s-2,8-/ -menthadiene. Isomerization of the latter yields (+)-isoterpi-nolene, which is hydrogenated to give >50% (+)-3-/ -menthene. Epoxidation and subsequent rearrangement lead to a menthone isomenthone mixture,... 

Exercise 30-6 Reduction of the ketone group of (—)-menthone, which has its alkyl groups trans to one another, gives two products, known as (—(-menthol and (+)-neomenthol. These two substances differ considerably in their reactions. (+)-Neomenthol undergoes dehydration either in methanoic acid or when treated with phosphorus pentachloride, whereas (—(-menthol gives a methanoate ester with methanoic acid and a chloride with phosphorus pentachloride. What is the relationship between neomenthol and menthol, and why do they behave differently with methanoic acid and phosphorus pentachloride What is the likely structure of the menthene from dehydration of neomenthol (Review Sections 8-8D, 12-3D, and 12-5.)... 

In other systems, a particular structure may be found as a mixture of diastereoisomers. Peppermint (Mentha x piperita Labiatae/Lamiaceae) typically produces (—)-menthol, with smaller amounts of the stereoisomers (+)-neomenthol, (+)-isomenthol, and (+)-neoisomenthol, covering four of the possible eight stereoisomers (Figure 5.16). Oils from various Mentha species also contain significant amounts of ketones, e.g. (—)-menthone, (+)-isomenthone, (—)-piperitone, or (+)-pulegone. The metabolic relationship of... 

There are four diastereomeric menthols according to the relative orientations of the methyl, isopropyl, and hydroxyl groups. They are known as menthol, isomenthol, neomenthol, and neoisomenthol, each of which exists in two enantiomeric forms. The most abundant and readily available is /-menthol, or (/A 2.S, 5iZ)-(-)-menthol (23), whereas other stereoisomers, although available from nature, are more economically produced through chemical derivatizations from menthone, limonene, and a-pinene. Commercial (-)-menthol from natural sources can be as pure as 99% in both chemical and optical purities. Synthetic menthol is currently made by an asymmetric isomerization (see Chapters 12 and 31).34... 

The procedure is commendable for its sinq>licity, reduced toxicity (chromium in all its oxidation states is carcinogenic) and achieves good yields of ketones from alcohol, for example, octan-2-ol is oxidized into octan-2-one (92%), cyclohexanol into cyclohexanone (90%) and menthol into menthone (98%). Pyridinium chromate is also a well-known oxidant for allylic oxidations. As a silica gel supported reagent, this is turned into an efficient alcohol oxidant that will leave acid-labile functions unscathed. Another advantage of the reagent is the long shelf-life of more than a year. These solid-supported oxidants also greatly facilitate pr uct work-up, when compared with their solution counterparts. 

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