370 



otherwise liquefied mass. These crystals were shown to be terpin hydrate, and 

 had evidently been formed by the action of the phosphoric acid on the terpineol. 



When the crude oil of E. Anstraliana was determined quantitatively for 

 cineol, and the cake of cineol-phosphate decomposed in the ordinary way, crystals 

 often occurred in the separated cineol. They were sometimes present in such 

 quantity as to render the junction of the liquids indistinct and correct reading 

 difficult. These crystals were also found to be terpin hydrate, and had evidently 

 been formed by the action of the phosphoric acid on the terpinol. Not being 

 soluble in the petroleum ether, the crystals remained with the cineol phosphate. 



H. J. Prins (Chem. Weekblad, 1917, 14, pp. 630-631) has shown that a good 

 yield of terpin hydrate can be obtained by agitating terpineol with 80 per cent, 

 phosphoric acid at 30 C. 



This reaction with the oils of E. Australiana and E. phellandra is apparently 

 one distinguishing feature between them and other Eucalyptus oils on the market, 

 while the presence of the phellandrene distinguishes the oil of the latter species 

 from that of the former. 



(a) TERPINEOL FROM THE OIL OF E. AUSTRALIANA. 



This was isolated from the " second hour " oil of E. Australiana, 

 distilled for us by Mr. Gough, of Youri, New South Wales, in November, 1919. 

 The crude oil had the following characters : Specific gravity at 15 C. = 0-9081 ; 

 rotation a D 2-0 C. ; refractive index at 20 ; 1-4704, and was soluble in ij 

 volumes 70 per cent, alcohol. The saponification number for the esters, by 

 heating i hours, was 5-2; after acetylation it was 76-9 by heating, and 24-5 

 in the cold with two hours' contact. The cineol was determined by both the 

 resorcinol and the rapid phosphoric acid methods in the portion boiling below 

 190 ; when calculated for the original oil the result was 42 per cent, by resorcinol, 

 and 25 per cent, by phosphoric acid. 



4,000 c.c. of the oil were then distilled, when 65 per cent, came over 

 below 190 C. This fraction and the portion boiling above 190 gave the following 

 results : 



Below 190 C. 



Above 190 C. 



Specific gravity at 15 C. 



Rotation a ... 



Refractive index at 20 C. ... 



Solubility in 70 per cent, alcohol ... 



Cineol by phosphoric acid ... 



Cineol by resorcinol ... 



Saponification number (hot i J hours) 



After acetylation, saponification number in cold, 2 hours' 



0-8997 



contact 



hot, i hours 



if volumes. 

 38 per cent. 

 65 per cent. 



2-7 



13-3 

 41-8 



0-9260 



1-4770 

 i volume. 



9-6 



33'9 

 132-7 



By repeated fractionation of the portion boiling above 190 C. at 10 

 millimetres pressure, the following fractions were finally obtained (temperatures 

 uncorrected) : 



Boiling between 63 and 99 C., amount was 584 c.c. 



100 and 101 C., ,, ,, 300 c.c. 



,, 101 and 110 C., ,, 130 c.c. 



