248 Willstätter's Rcsearches on Chlorophyll [Jan. 



bluish green, in conc. nitric acid, emerald green. Both modifica- 

 tions show strongly acid properties, being completely extracted from 

 etiler by 0.0 1 percent ammonia. It forms a characteristic tri-potas- 

 sium Salt — brown or steel blue prisms ; a cesium salt (complex salt) 

 — steel-bkie prisms : and a trimethyl ester — long, steel-blue prisms, 

 melting at 188-90°, which may be hydrolyzed with alcoholic potash. 



Phytochlorine / has been isolated in a pure State and is isomeric 

 with the anhydrous form o£ phytochlorine e. This is extracted 

 from ether by 1 1 percent hydrochloric acid. 



Phytorhodine g, C34H34O7N4, crystallizes from ether in large 

 six-sided prisms, having a dark red color with metallic luster. It 

 may be extracted from ether with 0.00 1 percent ammonia. Its 

 trimethyl ester forms black, rectangular tables, melting at 207^-2 10°. 



The phyllines and porphyrines.-^ The magnesium complex 

 of the Chlorophyll molecule remains intact when heated with alkali 

 and a series of magnesium-containing carboxylic acids result, hav- 

 ing splendid blue and red colors. These are called phyllines. A 

 second series of acids is obtained by removing the metal with min- 

 eral acids, giving the so-called porphyrines. Isochlorophylline a 

 gives, under these conditions — the dicarboxylic acids : cyanophyl- 

 line, in Solution blue ; and erythrophylline : in Solution red ; the mon- 

 ocarboxylic acid : phyllophylline, in Solution bluish red. Chloro- 

 phylline a gives the dicarboxylic acids : glaucophylline, in Solution 

 blue ; and rhodophylline, bluish red ; and the monocarboxylic acid : 

 pyrrophylline, in Solution bluish red. The h series is decomposed 

 with more difficulty, because it contains an extra oxygen atom, 

 which must be reduced without Splitting off carbon dioxide. This 

 has been accomplished by the use of pyridine. The end products 

 are the same, namely, phyllophylline and pyrrophylline. Of the 

 dicarboxylic acids, only rubiphylline has been isolated in a pure state. 



The first change or decomposition of the chlorophylline mole- 

 cule is brought about by heating with methyl alcoholic potash six 

 and one half hours at 140°, the reaction being smoother if pyridin 

 is added to the reaction mixture. In this the lactam group is broken 

 open and probably the carboxyl group thus formed is split off as 



28 Willstätter and Pfannenstiel: Ann. d. Chem., 358, 267 (1907); Willstätter 

 and Fritzsche: Ihid., 371, 33 (1909). 



