— 185 — 



on caryophyllene dihydrochloride, quite a number of different investigators 

 have made research into the subject of the action of hydrochloric acid 

 upon this oil. Blanchet gives the m. p. of the hydrochloride at 77°, 

 Soubeiran and Capitaine, on the other hand, at 54°. Later investigators, 

 including Brix 1 ) and Umney 2 ), have failed to obtain a solid hydrochloride. 

 The oil examined by us (150 g) possessed the constants: d 150 0,9036, 

 « D — 9° 58'. It was split up by fractionation into three approximately 

 equal parts: 



I. B. p. 113 to 115° (6mm.), d 15 o 0,8989, « D — 8°7 f 

 II. B. p. 115 to 119° (6 mm.), d 15 o 0,8960, « D — 10° 1' 

 III. B. p. 119 to 133° (6 mm.), d 15 o 0,8968, « D — 11° 58' 

 after which the hydrochlorides were prepared by the familiar method of 

 passing hydrochloric acid into the well-cooled ethereal solution. Only 

 from the last fraction a solid hydrochloride could be obtained without 

 special trouble. In the case of the other two fractions we were compelled 

 to cool down considerably the residue for some time and to spread the 

 oily mass, which was studded with crystals, upon porous tiles. The 

 melting points of the various hydrochlorides ranged from 60 to 90° and 

 were therefore not very different from those of Blanchet or of Soubeiran 

 and Capitaine. The separation, however, was very easily accomplished 

 by fractional crystallisation. The principal portion crystallised out in 

 minute needles, melted at 113 to 115°, ([<*] D — 34° 28' in a 2,5°/o chloro- 

 form solution), and suffered no depression of melting point when mixed 

 with 1-cadinene dihydrochloride. The hydrochloride melting at 65 to 70° 

 (Md + 18° 35' in a 2,1% chloroform solution), of which a smaller quantity 

 was obtained, was identical with caryophyllene dihydrochloride. The yield 

 of cadinene dihydrochloride was about 4 to 5°/o, of caryophyllene dihydro- 

 chloride about 0,5°/o. It follows from this that, in addition to the inactive 

 caryophyllene first detected by Wallach, and identified as ^-caryophyllene 

 by Deussen and Hahn, and in addition also to 1-cadinene, /^-caryophyllene 

 is present in the oil. In contradistinction to the /^-caryophyllene of oil of 

 clove stalks, however, /^-caryophyllene occurs in copaiva balsam oil in 

 small quantities only. The increase in optical rotation coupled with a rise 

 in the boiling point which has been noticed by Deussen is mainly due 

 to 1-cadinene. Of course the above does not exclude the possibility of 

 the occurrence in copaiva balsam oil of other sesquiterpene hydrocarbons 

 besides the foregoing. 



A continuation has now appeared of Haarmann's 3 ) paper on caryophyllene 

 which we discussed in our last October Report 4 ). In this continuation the 



*) Monatsh. f. Chem. 2 (1882), 507. 



2 ) Pharmaceutical Journal III. 24 (1893), 215. 



3 ) Berl. Berichte 43 (1910), 1505. 



*) Berl. Berichte 42 (1909) 1062; Report October 1909, 177. 



