6- Hydroxy-camphene

Adiwidaja, G., Meyer, B., and Thiem, ]., Synthesis and crystal structure of endo-2-dimethylphosphono-exo-2-hydroxy-(-)camphene for the determination of 3J(CCCP) vicinal coupling constants, Z. Naturforsch. Teil B, 34B, 1547, 1979. 

Further experiments of this type by Renwick et al. (396) established that D. brevicomis and D. frontalis oxidize camphene (619) to 6-hydroxy-camphene (camphenol, 620). Both sexes of D. brevicomis transformed myrcene into 2-methyl-6-methylene-2,7-octadien-l-ol (myrcenol, 621), whereas ipsdienol was a major product in males only. 

Ordinary commercial camphor is (-i-)-cam phor, from the wood of the camphor tree. Cinnamonum camphora. Camphor is of great technical importance, being used in the manufacture of celluloid and explosives, and for medical purposes, /t is manufactured from pinene through bornyl chloride to camphene, which is either directly oxidized to camphor or is hydrated to isoborneol, which is then oxidized to camphor. A large number of camphor derivatives have been prepared, including halogen, nitro and hydroxy derivatives and sulphonic acids. 

The reaction of linalool with boron trifluoride etherate has been re-examined no pinenes or camphene were obtained.146 Dehydrolinalool reacts with methyl iso-propenyl ether under acidic conditions by Claisen rearrangement to give the allene (58).147 Further papers in this section include reaction of monoterpenoid alcohols with paraformaldehyde-acetic anhydride-sodium acetate,148 rearrangement of the alcohol (47 X = OH) to the oxabicycloheptane (59) and the ketone (60),149 and the rearrangement of a typical monoterpenoid vicinal hydroxy-ester to an epoxide.150... 

The deamination of the bornylamines by various methods has been examined including the use of nitrous acid in acetic acid. ° Whereas ring-opened compounds are obtained to some extent from endo-bornylamine, practically none are obtained from the exo-isomer. This work should be taken in conjunction with an earlier paper dealing with the same reaction in water, conditions which lead to less camphene and more hydroxylated compounds with both endo- and exo-bornylamines. It is claimed that the camphor obtained in the deamination of 2-exo-hydroxy-3-exo-aminobornane with nitrous acid is formed via a 2,3-endo-endo hydrogen shift. 

Rowachol has been shown to inhibit hepatic cholesterol synthesis mediated by a decreased hepatic 5-3-hydroxy-3-methylgutaryl-CoA reductase activity (Middleton and Hui, 1982) the components mostly responsible for this activity were menthol and 1,8-cineole, with pinene and camphene having no signi cant effect (Clegg et ah, 1980). A reduction in cholesterol crystal formation in the bile of gallstone patients has been demonstrated in a small trial using Rowachol (von Bergmann, 1987). 

Camphene has been hydroformylated under varying conditions (Scheme 6.12). In the first studies, it was treated at a syngas pressure of 3000 psi (about 207 bar) in the presence of an unmodified Co catalyst [82]. The protocol was conducted in a 60 g scale and gave 65% of the diastereomeric aldehydes that showed a note of borneol and camphor. The position of the carbonyl group was clarified chemically by conversion into the corresponding carboxylic acid, ester, hydroxy, or bromo derivatives. 

The reduction of a number of sultones in the bornyl and camphene series with lithium aluminium hydride can lead to a variety of products, depending on the reaction conditions. Thus 10-isobornyl sultone, when reduced in ether at room temperature, gives the corresponding sultine in 70% yield, whereas reduction in refluxing THF afforded l-mercaptomethyl-2-exo-hydroxy-7,7-dimethyl-bicyclo-[2,2,1 ]heptane. The propargylic sulphite (106), when heated to 180 °C, gave sultone (107) in 22% yield its structure was proved by A"-ray studies. The... 

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