KESULTS OF EXAMINATIONS. 13 



nit (M! very reluctantly from the mother liquor. The nitrosochlorido, 

 after several precipitations from chloroform with methyl alcohol, 

 melted at 103; the melting point of its nitrolpiperidme was 118. 

 These results prove the presence of Z--pinene. 



}-pinene. The fractions boiling between 168.2 and 172.4 were 

 redistilled several tunes and about 60 per cent (based on the 

 original 500 grams) boiled between 165 and 170. After seven 

 fractionations, the final one made over metallic sodium, 200 grams 

 were obtained having the following properties: Boiling point, 166.6 

 to 167.6; specific gravity, 0.8670; index of refraction, 1.4762; spe- 

 cific rotation, [a] D = 15.33. This fraction was then examined for 

 /?-pinene by Wallach's 1 method, which is as follows: The volatile 

 oil was emulsified with 500 c. c. of water and oxidized with 467 grams 

 of potassium permanganate and 100 grams of caustic soda in 5.5 

 liters of water with careful cooling. The resulting liquor was dis- 

 tilled with steam and 137 grams of oil recovered. After filtration 

 from the manganese sludge and evaporation to two liters, a stream 

 of carbon dioxide being continuously passed through the solution, 

 a copious precipitate of crystalline sodium nopinate was obtained. 

 After being washed with water and then dried the crude sodium 

 nopinate amounted to 13.8 grams. This gives a yield of 21.9 per 

 cent of the sodium salt based on 63 grams of oxidized oil. The yield 

 is comparatively high and shows the purity of the /?-pinene frac- 

 tion. The nopinic acid was liberated with dilute sulphuric acid. 

 After two crystaUizations from water it melted at 126. 



Limonene. The fractions of the original oil boiling above 172.4 

 and the residues boiling above 170 obtained from the fractionation 

 of the /?-pinene fraction were examined for limonene. By repeated 

 distillation two 1-rotatory fractions were obtained, as follows: (1) 

 Boiling point, 174 to 175.7; specific gravity, 0.8621 at 15 C.; (2) 

 boiling point, 175.7 to 178.6; specific gravity, 0.8608 at 15 C. 

 Fraction 1 when dissolved in glacial acetic acid and treated with a 

 solution of bromine in acetic acid gave a tetrabromide after a small 

 amount of water had been added. The crystalline tetrabromide 

 melted at 104 after several . crystallizations from ethylacetate. 

 Fraction 2 was redistilled over sodium, diluted with ether, and treated 

 with dry hydrogen chloride. A dihydrochloride was obtained 

 which melted at 50 C. The results show the presence of Z-limonene. 



EXAMINATION OF THE ROSIN. 



A "water white" sample of the rosin had the following properties: 

 Specific gravity, 1.068; acid number, 148.8; saponification number, 



i Annalen, p. 228, vol. 356, 1907. 



