70 Report of Schimmel § Co. 1922. 



Fractions of the b. p. 86.5 to 91.5° and the sp. gr. 0.9403 and 0.9363 showed the 

 characteristic smell of terpinenol reminding slightly of terpineol. Since they contained 

 additionally a small amount of borneol which could not be removed by freezing-out 

 the presence of terpinenol, an alcoholic connected structurally with terpinene and 

 therefore often found in oils containing this terpene, had to be proved by oxidizing 

 it, by means of cold 1 per cent, permanganate solution,' to the glycerol Ci H 2 o0 3 . The 

 neutral product obtained hereby (b. p. 160 to 165° [9 mm.]) solidified soon when 

 triturated with chloroform and ether. Whereas, however, Wallach 1 ) found the m. p. 

 of the glycerol from terpinenol-4 to be 114 to 116° (glycerol from terpinenol-1, m. p. 

 120 to 121°), the glycerol obtained by us melted already below 100°, thus proving 

 that the body was not uniform. Only after repeated fractional crystallization it was 

 possible to isolate small amounts of the body with the m. p. Ill to 113°. When 

 heated with dilute hydrochloric acid in a current of steam it yielded, in addition to 

 cymene, carvenone; semicarbazone, m. p. ; 201 to 202°. The sublimate of the glycerol 

 melted at 128 to 129°. A somewhat larger amount of the glycerol was prepared and 

 transformed, by oxidation with alkaline potassium permanganate, into the «,a'-dihydroxy- 

 «-methyl-«-isopropyl adipic acids of the m. p. 205 to 206° and 188 to 189°. Although 

 we did not succeed in separating the resulting mixture of the active and the inactive 

 acid (m. p. 195 to -200°) into the separate acids with the correct melting point, it was 

 possible to isolate, from the mixture of bilactones obtained by heating the acid mixture 

 to 200° (m. p. 65 to 71°), the bilactone, m. p. 70 to 72°, corresponding to the acid 

 m. p. 188 to 189°, by resorting to fractional crystallization. This bilactone easily 

 passed over, on heating with caustic potash, into the acid m. p. 187 to 188°. 



A further proof for the presence of terpinenol-^ in the fraction mentioned above 

 was furnished by the formation of terpinene dihydrochloride, m. p. 51 to 52° when the 

 solution in glacial acetic acid was saturated with hydrogen chloride gas. However, 

 we were unsuccessful in attempting to prove the presence in the terpinenol-containing 

 fraction of «-terpineol, which would account for the unsharp melting point of the glycerol 

 C10H.20O3 owing to a possible admixture of the glycerol of «-terpineol (m. p. about 121°). 

 It may, therefore, be taken for granted that the incorrect melting point of the neutral 

 oxidation-product may be ascribed to the low content of borneol in the terpinenol fractions. 



Small amounts of geraniol were found to be present in fractions boiling between 

 91.5 and 102° (7 mm.); d 16 o 0.9259; faint odour of geraniol. On treatment of the 

 solution in benzene with phthalic anhydride and subsequent saponification of the 

 resulting solution of the ester-salt, an oil, b. p. 225 to 231°, with a pronounced odour 

 of geraniol was formed. It yielded a diphenylurethane, m. p. 82°; on oxidation with 

 bichromate solution, citral was the result. 



The high-boiling fractions (b. p. 102 to 106° [7 mm.]; d 15 o 0.9326 to 0.9386) were 

 not entirely free from thymol. After the phenol had been removed and the liquid 

 distilled over sodium, a sub-fraction showed the following properties: — b. p. 259 to 

 264°; diso 0.9105; « D -f7°54'. On heating with glacial acetic and sulphuric acids, 

 followed by steam-distillation, caryophyllene alcohol, m. p. 94 to 95° was formed, so 

 that the presence of caryophyllene in the sesquiterpene fraction was rendered probable. 

 In addition, small amounts of a second sesquiterpene and possibly also of a sesqui- 

 terpene alcohol seemed to be present in this Spanish oil. 



Hence, the following bodies, besides thymol, have been proved to be important 

 constituents of the oil in question: — a new terpene, b. p. 155°, camphene, /-terpinene, 



L ) Liehig's Annalen 350 (1906), 169. 



