250 Wülstättcr's Researches on Chlorophyll [Jan. 



son they may be prepared from a mixtiire of these two components. 

 Chlorophylline {a-\-h) is suitable for the preparation of pyrro- 

 phylline, while phylloph3^11ine may be obtained from isochlorophylline 

 {a -\-b). Twenty gm. of crude potassinm chlorophylline salt, dis- 

 solved in 400 c.c. of 35 percent methyl alcoholic potash sol., are 

 heated in a silver beaker slowly to 130°, the temperature held two 

 honrs between 130°-! 35°, then raised diiring the course of an hour 

 to 170°, held for two hours between i70°-i8o°, then raised to 190° 

 during an hour and a half, and finally held about 200° for one hour. 

 The cold mass is diluted with two vol. of water, which precipitates 

 the potassium salt as violet crystalline flakes. The product is fil- 

 tered off, rubbed into a paste with alcohol and ether, and poured 

 into 5 liters of ether. Shaken with 20 gm. of monosodium phos- 

 phate crystals, the greater part of the pyrrophylline goes into the 

 ether. This Solution is washed with dilute sodium phosphate sol. 

 and water, then extracted with 0.03 percent ammonia which re- 

 moves all rhodophylline. The Solution is then conc. to 50 c.c, 

 poured into i liter of petroleum ether and allowed to stand several 

 days at 0°, when the phylline precipitates as a violet red powder; 

 yield, 8.5 gm. 



Phyllophylline is obtained in nearly the same manner, in a yield 

 of 70 percent, as the calcium salt. The free substance is quite un- 

 stable and easily loses its magnesium. The Compound is also pre- 

 pared from pheophytin {a-\-h) by the action of methyl alcoholic 

 potash sol. containing magnesium oxide, by heating for eight hours 

 up to 205° and then three hours at this temperature. The yield 

 from 20 gm. was 6.y gm. of the calcium salt. 



The corresponding porphyrines may be obtained by shaking the 

 phyllines with acetic or hydrochloric acid. They may also be pre- 

 pared from the magnesium- free derivatives of Chlorophyll by heat- 

 ing with methyl alcoholic potash sol. Phytochlorine e gives phyllo- 

 porphyrine when heated several hours at 140°-! 50°. The less basic 

 chlorines give pyrroporphyrine when heated to 220-230°. The reac- 

 tion in the b series is best carried out in the presence of pyridine. 



The principal properties and a comparison of the various deriva- 

 tives in this group are shown in the table on page 251. 



The use of methyl alcoholic potash sol. readily gives a mono- 

 carboxylic acid. If an attempt is made to heat the reaction-mixture 



