432 THE CHEMICAL ESAIIIXATIOX OF MACROZAMIA SPIRALIS, 



was evaporated with sulphuric acid, when the pungent vapours of acetic acid 

 were recognised, and on addition of alcohol, the odour of ethyl acetate was very 

 marked . 



The whole fluid was neutralised with baryta water and evaporated to dry- 

 ness. This left a residue of barium salts of the organic acids weighing 0.93 

 gm., which was converted into barium sulphate. 



0.93 gm. Ba salt yielded 0.847 gm. BaS04=91.1 % 

 Acetic acid requires „ =91.3 

 The barium salt represents 0.54 gm. of acetic acid in the aqueous solution, with 

 a trace of formic acid. 



(2) . The ether extract of the volatile distUlate was agitated successively with 

 ammonium carbonate, sodium carbonate, and sodium hydroxide until nothing, fur- 

 ther was removed in solution by each solvent. These alkaline fluids were then 

 acidulated and extracted with ether, the solvent distilled off, and the residue 

 converted into barium salt by titration with decinormal baryta solution. The 

 latter was decomposed by sulphuric acid, and the barium sulphate weighed. 



The ammonium carbonate extract was too small in amount for analysis, but 

 the sodium carbonate solution gave 0.226 gm. of barium salt. 



0.04G5 gm. Ba salt yielded 0.032 gm. BaSO4=68.80 % 

 Valerianic acid, C4Hn .COOH, requires ., ^68.73 

 By titration the sodium carbonate extract was found to contain 0.3 gm. of 

 valerianic acid. 



The sodium hydroxide extract was neutralised by 0.5 ec. of baryta. It 

 left a small residue on evaporation, which possessed the odour of cresol. 



The ethereal solution remaining after the treatment with alkaline liquids 

 was dried and distilled at a low temperature. There was obtained in this way 

 a pale yellow limpid essential oil weighing 2.15 gms. This oil possessed a 

 strong fi'agrant odour like canq^hor, and when kept in a desiccator over suli>huric 

 acid, it was nearly all lost by evaporation in 3 days. This exceedingly volatile 

 oil left about . 25 gm . of a yellow solid on spontaneous evajioration . 



The volatile constituents in the steam distillate were thus identified: — 



trace of formic acid ('H2O2 



0.54 gm. acetic acid t^2H402 



0.30 gm. valerianic acid . . . . Cr.HioOa 

 2.15 gms. essential oils. 



For comparison with these acids we may mention the historic work of 

 Chevreul on another plant survival from the past, G-inlcgo hihiha, the maiden-hair 

 tree of China and .Japan. This is the sole representative now existing of the 

 very ancient branch constituting the second Order of the Gynmosperms. and 

 has much in common with the cycads. Ciievreul and Becharap* isolated a com- 

 plete series of acids from Ci to Ct, viz., formic, acetic, propionic, butyric, vale- 

 rianic, eaproic and caprylie acids. The second, fourth and sixtli predominated. 

 This result was ot)tained after many trials, and only after extracting a large 

 amount, 30 kilos, was sufficient of the third, fiftli and seventh acids obtained 

 to enable them to l)e identified. It is quite probable that small amounts of the 

 other acids are present in Macrozarma also, but if so they can be recognised only 



•Comptes rendus de I'Acad. des Sciences, 5.3. 1861, 1225; Annales chim. et de phys., i., 

 1864, 288. 



