BY JAllKS M. PETRIE. 435 



in wbieh 3.3 gms. dissolved, etiier dissolved 1 gm., and the remainder was soluble 

 in aleoliol only. These residues appeared to he complex mixtures of acids, and 

 were not further examined. (3) The sodium hydroxide extract contained much 

 chlorophyll. When acidiHed and shaken out with ether 0.2 gm. of substance 

 ■was obtained. (4) The water extract after caustic soda treatment yielded to 

 petroleum spirit 6.6 gms. of a white fatty substance, which was filtered and 

 waslied with cold alcoliol. On recrystallisation a number of times from petro- 

 leum s])irit, it showed a melting point of 47.5° ('., and solidified at 46° ('. The 

 solution of this substance possessed an acid reaction. 



0.155 gm. required 4.85 ccs. of decinormal alkali to neutralise it to phenol- 

 phtlialein. This gives for a monobasic acid, the molecular weight of 320. The 

 iodine-value by Hubl's method was determined: — 



(1). 0.1097 gm. absorbed 0.058 gm. of iodine=52.9 % 

 (2). 0.1012 „ 0.054 " „ =53.1 



The iodine-value eorresppnds to 59 % of oleic acid, and leaves 41 % with a mole- 

 cular weight approximating 374, as probably one of the higher homologues of 

 stearic acid. 



Isolation of Phytoaterol. 



The ethereal solution which remained from the last section, after extraction 

 with alkalis and water, was distilled off. This residue consisted of a mixture of 

 fats and oils, with cei-tain unsaponifiable substances, and weighed 10 gms. It 

 was hydrolysed by boiling for 6 hours with an alcoholic solution of potassium 

 hydroxide, and the products of saponification brought into aqueous solution by 

 heating on the water-bath. In this way there were separated a black insoluble 

 unsaponified portion, and a strongly alkaline aqueous solution . The whole was 

 cooled and agitated with ether many times until notliing further was brought out 

 in solution . 



The unsaponified portion. — The ethereal solution, dark l)rown in colour, con- 

 tained 0.5 gm. of solid, and was distilled off leaving a residue of impure, much 

 discoloured crystals. The latter were dissolved in alcohol and digested with 

 animal charcoal. They were then obtained in a fairly pure condition, and were 

 redissolved and recrystallised twice from dilute alcohol. 



The crystals were pure white witli glistening surfaces, but under the nucro- 

 scope appeared of two kinds — a few broad rectangular flakes with dome ends, 

 and the greater portion consisting of lath-shaped forms with pointed ends. 



The broad flaky crystals presented the appearance of cholesterol, with low 

 refractive index, and with the characteristic bites out of the sides. 



The lath-shaped forms resembled some phytosterol crystals. 



The crystals were exceedingly soluble in chloroform, and the following 

 specific tests were applied : — 



Salkowski's reaction — A chlorufurm solution and concentrated sulphuric 

 acid were mixed, when the former assumed a blood-red colour and the acid a deep- 

 green fluorescence; the red solution when removed and evaporated slowly changed 

 colour, through purple, violet, blue and finally colourless ; on again adding sul- 

 phuric acid the original crimson colour was restored . 



Liehermann's reaction — acetic anhydride and a drop of sulphuric acid added 

 to a chloroform solution gave a rich rose-red colour. 



Iodine and sulphuric acid gave a violet colour, changing to blue and green . 



Schiff's reagent gave a reddish violet residue. 



