Patchouli acetate

Acetates, benzoates, tosylates, and mesylates exhibit analogous [l,2,3]-eliminations upon (gas phase) pyrolysis. Thus, Patchouli-acetate (104) reacts to 105 and 106 (52%, and 46%, resp.)65) and 57 yields 107 (low conversion) with migration of phenyl40). In the pyrolysis of bomyl benzoate (108) mainly (54 %) camphene (109)66) is formed, the atisine-derivative 110 (a or P) yields stereospecifically 111 (ot-epimer, 90 %) or 112 (P-epimer, 95 %)67), and the adamantane mesylate (113) yields the alkene 114 (38 %)68). 

Patchouli acetate (431) was also treated in the same medium to give 426 and 429 (Matsui and Miyazawa, 2000). 5-Hydroxy a patchoulene (432) was incubated with G. cingulata to afford la-hydroxy derivative (426) (Miyazawa et al., 1998b). 

The Prins reaction with formaldehyde, acetic acid, acetic anhydride, and camphene gives the useful alcohol, 8-acetoxymethyl camphene, which has a patchouli-like odor (83). Oxidation of the alcohol to the corresponding aldehyde also gives a useful iatermediate compound, which is used to synthesize the sandalwood compound dihydo- P-santalol. 

In detergent perfumes, the stabiUty of vanillin is not always certain. It depends on the association made with other raw materials, eg, with patchouli, frankincense, cloves, most of the animal notes, and such chemicals as amyl saUcylate, methyl ionones, heflotropin, gamma undecalactone, linalool, methyl anthrarulate, benzyl acetate, phenyl ethyl alcohol, cedar wood derivatives, oak mosses, coumarin, benzoin. Pern balsam, and cistus derivatives. In some cases, these mixtures can cause discoloration effects. 

The mellis accord, which makes up an important part of the fragrance here incorporates amyl salicylate in addition to benzyl salicylate, with the patchouli and woody aspect being accentuated, using cedryl acetate rather than the more traditional products derived from vetiver. Vertofix had yet to be discovered. The dominant spices, in combination with eugenol, are clove and cinnamon. 

Although we have described the perfumes in this family as being based on Hedione, in Coriandre the material used is Magnolione, a closely related material with a very similar though rather more jasminic olfactory character. This makes up some 20% of the formula with 10% of patchouli. Methyl ionone, vetiveryl acetate, cedryl acetate, Vertofix, and sandalwood make up the woody aspect of the fragrance, with a small amount of Galaxolide as the musk. 

Apart from the materials already mentioned the top note contains a simple mixture of bergamot and orange. The middle note is dominated by a traditional jasmin base, with muguet (hydroxycitronellal 10%), and rose. At the heart of the perfume is the classical chypre accord between vetiveryl acetate (10%), methyl ionone, oakmoss, aldehyde C14, coumarin, sandalwood, patchouli, musk ketone, and amber. The amber note can be reproduced by the simple but effective combination of labdanum, olibanum, and vanilla. Small amounts of other animalic notes such as civet may also be used. 

The typical chypre base note contains patchouli (6%), methyl ionone (the beta form was used in Aramis), vetiveryl acetate, cedryl acetate, oakmoss, and animalic notes. It is interesting also to find aldehyde Cl 8 being used in a similar way to that of aldehyde C14 in many of the earlier chypres. An important part of the amber character comes from the use of Dynamone, a speciality material derived from cistus, difficult to use, but of great diffusion and persistence. 

In Casmir the same technique is used but in an oriental context. The formula is constructed around large amounts of Hedione (20%), Galaxolide and ethylene brassylate, a combination of Iso E super and Vertofix, and vanillin (14%), which together make up some 80% of the formula. In deference to the oriental character linalool and linalyl acetate are present to provide a top note with traces of rose, vetiver, and patchouli, in the background. A strong fruity note, characteristic of many modem American perfumes, is also included. 

Thomas and Ozainne have published the full details of the reaction of patchouli alcohol (635) with lead tetra-acetate which produces the bicyclic ketone (637) as a major product. This ketone is the source of a number of interesting rearrangements as outlined in Scheme 82. What is particularly intriguing about... 

A useful synthesis (ref.ll)of patchouli alcohol, an important fragrant constituent of patchouli oil, from (+)-camphor, that onetime important natural product which was employed as a plasticiser for nitrocellulose (itself a semi-synthetic polymer), was complicated by structural revision of the sesquiterpene alcohol. Dihydrocarvone (14) obtained by saturation of the ring double bond in carvone, a major constituent of oil of spearmint has been employed for two very different sesquiterpenes, the ketone campherenone (15) and the alcohol, occidentalol (16). In the first case an enol acetate was converted to a bicyclic intermediate by earlier established methodology and the route emulated a plausible biogenetic sequence giving racemic campherenone (ref.12) as shown. Any chirality in (14) is apparently lost. 

Phytochemistry Needles and young branches contain vitamin C, essential oil (with up to 40 components such as camphene, myrcene, bomyl acetate, and others), flavonoids, and microelements (iron, manganese, chromium, aluminium and copper Bykov 1950). Thirty-eight diterpenoids have been identified in the oleoresin (Raldugin et al. 1991). Sesquiterpenoids, diterpenoids, triterpenoids, steroids, and tocopherol were isolated from needles and twigs. Dehydroabietol, patchouli alcohol, guaiol, P-sitosterol, and campesterol were the main components of the unsaponifiable matter (Zhou 2001). 

In leaves extracts, the main constituents included Salicylic acid (14.466%), Ethanol,(2-(3,4-dihydroxyphenyl)-(13.254%), Catechol Monoethyl Ether (7.577%), Benzeneacetic acid, a-hydroxy-, methyl ester (6.151%), Patchouli alcohol (5.130%), 5-Methyl-2,4-diisopropylphenol (3.316%), 4-Hydroxyphenylethanol (2.799%), Hexanoic acid,6-iodo-(2.730%), 1-Phenylethanol (2.351%), Benzeneacetic acid (2.164%), Methylbenzene (1.570%), Octacosane (1.517%), n-Pentadecanoic acid (1.504%), 9-Methyl-Z-lO-tetradecen-l-ol acetate (1.457%), 1-Hexacosene (1.359%), j -Hydroxybenzoic acid (1.001%). 

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