4oo 



The material of E. Perriniana from which the oil was distilled, was 

 collected in September at Tingiringi Mountain, a locality in South-eastern 

 New South Wales. The crude oil was rich in cineol, but phellandrene was 

 not detected at this time of the year. The general characters agreed with 

 those of the oil distilled from material of the same species collected at 

 Strickland, in Tasmania. 



The abnormally low refractive index of the lower boiling fractions led to 

 the identification of this ester, because a refractive index, 1-4519 at 20 in 

 ordinary fractions, had not previously been detected in Eucalyptus oils. The 

 first notification ol this ester was published by one of us in the Proc. Roy. 

 Soc., N.S.W., December, 1914. 



EXPERIMENTAL. 



The Acid. The crude oil (200 c.c.) of E. Perriniana was distilled, and 

 the portion which came over below 190 C. boiled with aqueous potash under a 

 reflex condenser for some hours. The aqueous portion was separated and 

 distilled, but nothing came over below the boiling point of water, so that 

 methyl, ethyl, and propyl alcohols were absent. The remainder was evaporated 

 to dryness and the potassium salt decomposed by sulphuric acid and distilled 

 until all the volatile acids had come over. The distillate had an odour of 

 butyric acid strongly marked. The free acid was exactly neutralised with 

 barium hydrate solution, evaporated to dryness and heated, in the air-bath to 

 105 C. A molecular weight determination with the thus prepared barium salt 

 gave the following : 



0-3592 gram, gave 0-2668 gram. BaSO 4 = 74-28 per cent. 



Barium butyrate forms, theoretically, 74-91 per cent. BaSO 4 , so that 

 butyric was probably the only volatile acid present. The odour and other 

 indications suggested the normal form for this acid, and the ethyl ester 

 prepared with it gave the characteristic pineapple odour. To decide the 

 point the calcium salt was prepared by decomposing the remainder of the 

 barium salt with sulphuric acid, distilling over the volatile acid, exactly 

 neutralising with freshly prepared and filtered lime water, using a trace of 

 phenolphthalein as indicator, and evaporating to a small bulk on the water 

 bath until a portion of the solid salt separated; this dissolved again, however, 

 when the liquid cooled. The solution was transferred to a test-tube and again 

 heated, when the precipitate again formed, but dissolved on cooling. This 

 peculiarity of the calcium salt indicates that the acid of this ester is normal 

 butyric. 



The Alcohol. The oil after saponification, was separated and distilled, 

 when about 2 per cent, came over telow 150 C. A trace of cineol was present 

 and most probably a trace of pinene also. This portion was carefully oxidised 

 with K 2 Cr 2 O 7 + H 2 SO 4 , heated to boiling, and allowed to stand for 24 

 hours. A volatile acid with the odour of butyric was readily detected. This 

 was distilled over, exactly neutralised with barium hydrate solution, and 

 evaporated to dryness and heated in the air oven. The barium salt thus 

 obtained was identical in odour and gave reactions similar to that from the acid 

 of the ester. Although the amount of the available salt was but small, yet, 

 there was sufficient to enable a quantitative determination for molecular weight 

 to be made. 



0-0354 gram, gave 0-0264 gram. BaSO 4 = 74-58 per cent. 

 Barium butyrate gives 74-91 per cent. BaSO 4 . 



As the ester is thus shown to be butyl-butyrate it might be assumed that 

 both the alcohol and the acid are identical in form,. Sufficient acid from 



