256 

 (c) Chemistry of the Leaf Oil. 



The material for this investigation was forwarded to us by the Government 

 of Western Austraha, and was received the 26th June, 1903. As there were 

 numerous fruits upon the branchlets, it was thought desirable to distil them 

 separately, and none was left upon the branchlets, so that this oil was distilled 

 entirely from the leaves and terminal branchlets. The distillation was continued 

 for seven hours, and 354 lb. of material gave 31 oz. of oil, equal to 0-547 P^^ cent. 

 The crude oil was of a light amber colour and had a slight "pine-needle oil " odour, 

 but inclining more to that of turpentine, and was but little soluble in alcohol. 

 Over go per cent, of the oil consisted of dextro-rotatory pinene, and this had a 

 very high specific rotation. The amount of esters was very small, and this was 

 found to consist of the esters of borneol and geraniol, most probably in combination 

 wdth acetic acid alone, as the indications for that acid were most marked. Limonene 

 and dipentene do occur, but only in very small amounts, because in one distillation 

 less than 2 per cent, was obtained distilling between 173° and 200° C. The presence 

 of dextro-rotatory limonene was indicated by the specific gravity and rotations 

 of the two larger fractions, and by the slightly less rotation of the pinene fraction. 



The specific gravity of the crude oil at jj° C. =0-8591; rotation Ad = 

 + 42-2°; refractive index at ig° C. = 1-4739. The saponification number (mean 

 of three determinations) was 5-29, equal to 1-85 per cent, of ester as bornyl and 

 geranyl acetates.. In the cold, with two hours' contact, the saponification number 

 was 3-71, equal to 1-3 per cent, of ester, thus indicating the presence of geranyl- 

 acetate. 



On redistilling, practically nothing came over below 155° C. Between 155° 

 and 160°, 75 per cent distilled; between 160° and 165°, 11 percent.; between 165° 

 and 200°, 6 per cent. ; between 200° and 250°, 3 per cent. Although separated 

 into the above fractions, yet only about i per cent, was obtained between 180° 

 and 230° C. 



The specific gravity of the first fraction at \{-° C. = 0-8551 ; of the second, 

 0-856; of the third, 0-8565; of the fourth, o-gogg. The rotation of the first 

 fraction a^ = + 43-6; of the second, -|- 47-2°; of the third, -|- 52-8°. This 

 indicates that the predominant limonene is the dextro-rotatory form. The ester 

 in the fourth fraction was determined, the saponification number being 69-78, 

 equal to 24-4 per cent. Both borneol and geraniol were present as mixed esters, 

 thus being in agreement in this respect wit-h most species of Callitris. 



To prepare the pinene, 100 c.c. of the oil boiling below 160° was again distilled, 

 and 51 c.c. obtained between 155-156° C. This had a specific gravity at 15° C. 

 = o-857g; rotation a^ = + 42-7°, or specific rotation [aj^ = -|- 49-77; refractive 

 index, 1-4714 at 24° C. The nitrosochloride, which melted at 108° C, and the 

 nitrosopinene melting at 132° C. were prepared, thus giving results conforming 



