When nopol (2-pinene-methanol) (1) was oxidized with activated manganese dioxide, 10-formy1-2-pinene (3) was obtained. Homoperillyl alcohol (2) is derived from (1) when (1) was thermally isomerized with the catalyst systems composed of copper and zinc, at 240±5°C under a reduced pressure. In a similar fashion, homoperillylaldehyde (4) was also obtained when the dehydrogenation of (2) was carried out. Compounds (2), (3) and (4) have a mild hydroxycitronellal and ionone-like odor, and the esters of (2) have a mild linallylacetate-like odor ; conceivably these can be used as a stable perfume. Aldehyde (4) was found to give a very sweet oxime, soluble in dil. ethanol.
Treatment of 7-isopropylidene- (1a) and 7-diphenylmethylene- (1b) -2, 3-bis (methoxycarbonyl) norbornadiene with tosyl azide in benzene at 5060°C for 3 days afforded the corresponding N-tosyl-6, 7-bis (methoxycarbonyl) -3-azatricyclo [3.2.1.02.4-exo] oct-6-enes (7a, b) in 35 and 25 % yields, respectively. Similar treatment of 1a, b with ethoxycarbonyl azide gave 1-ethoxycarbonyl-1, 2, 3-triazole (9) and a mixture of (9) and 2, 3-bis (methoxycarbonyl) -6, 6-dimethylfulvene (8), respectively, which might be produced by a retro Diels-Alder mechanism.
From myrtenol (6, 6-dimethyl-bicyclo [3, 1, 1] -2-heptane- 2-methanol) (7) as a starting material, 1-apocamphane-carboxylic acid (6) was synthesized. When the acetate (8) of (7) was chlorinated in ethylene dichloride with dried hydrogen chloride, 2-chloro-apocamphane-methylacetate (9) was obtained. (6) was obtained by the chromic acid anhydride oxidation of 1-apocamphane-methanol (11), which was obtained from dechlorination of the product of saponificaticn of (9) [i.e., 2-chloroapocamphane-methanol (10)] Ester of (6), which is derived from saturated lower alcohol, has a mild woodlike odor.