Geranyl acetate hydrogenation

Geranyl acetate (a diene) takes up 2 moles of hydrogen unselectively in 48 hours to give the saturated acetate, 3,7-dimethyloctyl acetate, bp 109-110712 mm, 1.4261. (Geraniol itself has an allylic hydroxyl and appears to suffer decarbonylation under these reaction conditions.)... 

Synthesis from (3-Pinene. Pyrolysis of /3-pinene yields myrcene, which is converted into a mixture of predominantly geranyl, neryl, and linalyl chloride by addition of hydrogen chloride in the presence of small amounts of catalyst, e.g., copper(I) chloride and an organic quaternary ammonium salt [29]. After removal of the catalyst, the mixture is reacted with sodium acetate in the presence of a nitrogen base (e.g., triethylamine) and converted to geranyl acetate, neryl acetate, and a small amount of linalyl acetate [30]. 

The radical cations of diene systems in cyclic molecules are also capable of reaction as demonstrated by Demnth, Roth and their coworkers. They have studied the influence of phase on the photochemical reactivity of some naturally occurring dienes. Thns the irradiation of the diene 10 in homogeneous solution (acetonitrile/water) in the presence of an electron-accepting sensitizer such as cyanonaphthalene (CN) or DCB brings about fraws,cw-isomerization only. However, when the electron transfer reaction is carried out in the presence of sodinm dodecyl sulphate, transannular hydrogen abstraction reactions yield the two prodncts 11 and 12. Similar reactivity is observed with frans-geranyl acetate 13 and all-trawi-famesyl acetate 14. The authors report that these cyclizations are the flrst examples of biomimetic processes brought about under SET conditions. 

Synthesis from (3-Pinene. For a description of this route, see under Geraniol. Addition of hydrogen chloride to myrcene (obtained from /3-pinene) results in a mixture of geranyl, neryl, and linalyl chlorides. Reaction of this mixture with acetic acid-sodium acetate in the presence of copper(I) chloride gives linalyl acetate in 75-80% yield [37]. Linalool is obtained after saponification. 

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