— 176 — 



ferred that the substance consisted partly of oxygenated bodies, partly 

 of chloro-cymene and partly of dichloride. The preparations which had 

 been purified by steam distillation, when fractionated, were all found to 

 contain oxygen, even when an excess of phosphorus pentachloride was used. 

 It is therefore probable that the product of conversion consists of 

 a mixture of monochloride and dichloride, the latter being again con- 

 verted into carvenone during the distillation. In every experiment 

 some parts were obtained which were lighter than water and others 

 which were heavier. These results were specially confirmed by the 

 analysis of the fractions boiling between 95 at ioo° at 10 mm. in 

 each experiment. The sp. gr. of pure monochloro terpinene there- 

 fore does not appear to be much higher than 1. Proof that the 

 monochloride which is formed by the method described belongs to 

 the terpinene series was afforded by oxidation into a, a'-dihydroxymethyl- 

 zlrapropyladipic acid, which acid was also obtained liberally from the 

 hydrocarbon obtainable by the reduction of the chloride with sodium 

 in alcoholic solution. 



G. G. Henderson and W. Cameron have investigated the action of 

 chromyl chloride on terpinene 1 ). While in the reciprocal action between 

 chromylchloride and pinene 2 ), camphene, or limonene additive pro- 

 ducts are the first to be formed, which only yield ketone- or aldehyde- 

 like bodies when treated further, there results from terpinene a brown 

 oil, almost entirely volatile with steam, from which, with bisulphite, 

 a-p-toluylpropylic aldehyde, C 10 H 12 O, (b. p. 222 at 760 mm.; 

 d^o 0,984; n D 1,51436; mol. refr. 45,3; semicarbazone, m. p. 155 ) 

 was isolated. After elimination of the aldehyde, p-toluyl-methyl ketone 

 (b. p. 109° at 14 mm., m. p. of the semicarbazone 204 to 205 ), cymene, 

 and a ketone C 9 H 12 O which was not definitely identified, were shown 

 to be present. As a-p-toluyl-propyl aldehyde and p-toluyl-methyl- 

 ketone are cymene derivatives, the authors assume that terpinene is first 

 oxidised by chromyl chloride into cymene, and that from the latter 

 the aldehyde and the ketone are formed. These observations also 

 throw a new light upon the results of the authors' earlier investigations 

 into the action of chromyl chloride on limonene 3 ). For it was shown 

 that the products then obtained are identical with a-p-toluyl propylic 

 aldehyde and p-toluyl-methyl ketone, and as a result the formula 

 C 10 H 14 O, which was given for the aldehyde at the time, must be 

 replaced by C 10 H 12 O, with which the analytical values of the semicar- 

 bazone too agree better. 



x ) Journ. Chem. Sr>c. 95 (1909), 969. 



2 ) Report April 1900, 55; October 1903, 85; April 1904, 108, April 1908, 

 180; November 1908, 171. 



3 ) Comp. Report April 1908, 180. 



