Tricyclene derivatives

Tricyclenes. Benzenesulfenyl chloride reacts with 5-methylene-2-norbomene (1) to form the tricyclene derivative 2. This reaction was used to synthesize tricyclo-efca-santalol (3)1 and cyclosativene (4).2... 

Camphene is found in higher concentrations in the essential oils of common coniferous trees, for example, Abies alba or Tetraclinis articulata, in the rhizome of Zingiber officinale as well as in S. officinalis and R. officinalis (Bornscheuer et al 2014). There is only one publication on various biotransformation products in the urine of rabbits after its oral administration. As shown in Figure 9.2, camphene is metabolized into two diastereomeric glycols (camphene-2,10-glycols). Their formation obviously involves two isomeric epoxide intermediates, which are hydrated by epoxide hydrolase. The monohydroxylated camphene and tricyclene derivatives were apparently formed through the nonclassical cation intermediate (Ishida et al., 1979). So far, there are no studies available about the biotransformation of camphene in humans. 

Photolysis of a benzene solution of chloranil and N gave rise to the norbornene analogues of 7,8, and 10 and the tricyclene derivative 9. By contrast, in acetonitrile solution, formation of only small amounts of type 8 and 9 adducts was detected/ The photoreaction of chloranil and Q gave rise to the type 7 adduct as the sole product. Irradiation of Q in acetone or methanol solution under Rose Bengal-sensitized (RB) conditions generated about 70% of N and adducts 11 and 12. ... 

The C-NMR of nortricyclene, 2, has been referred to, and Lippmaa reported on a number of derivatives the C-NMR spectrum of quadricyclene, 65, was assigned. The effect of 4-substituents inter alia on the cyclopropyl carbons C(2) and C(6) of 4-substituted tricyclenes (66) showed that there was an essentially linear dependence between SC(2) and... 

Table 1 lists the experimental conditions for the electrochemical formation of a cyclopropyl ring from a variety of 1,3-dihaloalkanes, mostly from dibromoalkyl derivatives. A free cyclopropyl ring as well as a spiro derivative (entry 6), bicyclobutanes (entries 8-10) and other fused and highly strained systems such as tricyclene (entry 11) and a propellane derivative (entries 12,13) were obtained. In addition, Carroll and Peters have found evidence for the intermediacy of [2.2.1 ]propellane upon reducing 1,4-dihalonorbor-nanes electrochemically at a low temperature, although attempts to isolate it were unsuccessful. The intramolecular electrochemical reduction of a dihalo-substituted tricyclic compound leads to cyclization with formation of a tetracyclic derivative in which... 

New routes to camphenilone and dehydrocamphene derivatives using alkenes614 or allenic esters as dienophiles in Diels-Alder reactions515 have been developed. Lewis acid-catalysed coupling of a,0-unsaturated methyl ketones with cyclo-pentadiene favoured exo-products except when TiCl4 was used,516 and led to isocamphanes that were spasmolytics.517 The tricyclene (214) could be converted... 

Several 7,7-dimethylnorbomane derivatives are now more readily accessible from camphenilone (227). The stages of the synthesis as far as the hydrocarbon mixture are as shown in Scheme 8, but the main difficulty is the separation of apobomene (228) from the tricyclene hydrocarbon (229) they are not separated... 

The reaction system discussed above was applied to optically pure a-pinene, (3-pinene, tricyclene, and nopol. 4-Cyanophenyl and/or methoxy substituted derivatives in optically pure or racemic mixture forms were isolated as products. Nucleophile-assisted cleavage of the radical cation has been proposed... 

Similarly solvolysis of bornyl derivatives and deamination of bornyl amine produce tricyclene is low yield 98,185,186). As in the deamination of isobutylamine, the yield of 1,3-hydrogen elimination increases when the carbonium ion is generated in a non-polar solvent (diglyme), in this case from the tosylhydrazone 187). That the formation of tricyclene... 

---