NATURAL DYES AND COLORING MATTERS. 451 



about 5.0 grams of this body from about 1 kilogram of crude extract obtained 

 from about 8 kilograms of wood. After recrystallizing five times from a mixture 

 of chloroform and alcohol it was obtained in a pure state, melting at 163°. As 

 stated by Cazeneuve and Hugonenq, it is very insoluble in water, cold alcohol 

 and carbon bisulphide, slightly soluble in ether and insoluble in alkalies and 

 acids. These authors " assign the formula C 20 H 16 O 6 to the body. Two combustions 

 of the pure substance isolated by me gave the following results : 



0.1809 gram substance gave 0.4554 gram C0 2 and 0.0763 gram H 2 0; 0.1820 

 gram substance gave 0.4620 gram C0 2 and 0.0775 gram H 2 0. 





Calculated for 



Cl4H 12 04. 



Found (per cent). 

 I. II. 



c= 



68.85 



68.74 69.20 



H= 



4.91 



4.69 4.72 



Two molecular weight determinations by the freezing-point method, using benzol 

 as a solvent, gave the values 260 and 280. The true molecular weight being a 

 multiple of C 7 H O 2 , must be 244, or the value corresponding to the formula 

 C 14 H 12 4 . Judging from the low melting point and the formula advanced by the 

 above authors, the substance obtained by them probably was not pure. 



The second crystalline body, homopterocarpin, occurs in narra in rather 

 large amount. Cazeneuve and Hugonenq 43 describe it as melting at 82°-86° and 

 assign to it the formula C 24 H 24 6 . After crystallizing eight times from hot 

 alcohol I obtained this body in the form of colorless needles melting sharply at 

 86°. Analysis of a carefully purified sample gave the following results: 

 I. 0.1787 gram substance gave 0.0892 gram H 2 and 0.4681 gram CO,. 



II. 0.1921 gram substance gave 0.0975 gram H 2 and 0.5027 gram C0 2 . 



Calculated for Pound (per cent). 



Ci 7 H 16 4 . I. II. 



C= 71.83 71.43 71.36 



H= 5.63 5.54 5.63 



The molecular weight determinations made by the freezing-point method, using 

 benzene as a solvent, gave the values 266 and 272. The molecular weight cal- 

 culated for C 1T H 16 4 is 284. 



The substance is insoluble in hot, concentrated potassium hydroxide and it is 

 very slowly acted upon at 200 degrees. Ten grams of the substance were heated 

 for one and one-half hours at 200 to 210 degrees with 50 grams of potassium 

 hydroxide dissolved in a little water. At the end of this time the mixture was 

 cooled and about 6.0 grams of the unchanged substance recovered. Water was 

 added and the solution acidified and extracted with ether. The crude etherical 

 extract with ferric chloride gave a blue color reaction lasting for several minutes 

 and when tested by fusion with phthalic anhydride gave fluorescein. Therefore 

 resorcinol was present. No other phenolic bodies were detected. 



Distillation with zinc dust gave resorcinol dimethyl ether. Twenty-five grams 

 of the substance yielded 9.5 grams of oil which on distillation gave 4.0 grams 

 boiling from 210 to 230 degrees. This fraction was insoluble in a 10 per cent 

 solution of caustic soda and gave no color reaction with ferric chloride. Treat- 

 ment with hydriodic acid yielded resorcinol which was identified by fusion with 

 phthalic anhydride, as above. 



Phenyl hydrazine and phosphorus pentachloride do not react with homop- 

 terocarpin. All the oxygen appears to be bound as in an ether. 



u Ann. chim. et plwjs., Paris (6) (1889), 17, 113. 

 45 hoc. cit. 



