viii, a, i Gibbs, Williams, Galajikian: Methyl Salicylate IV 3 



ester. The formation of the colored compound has a very slight 

 effect on the rate of saponification even in the light. 



The third reaction, that of the formation of a salt of the ester, 

 has been studied 8 and is responsible for some of the most in- 

 teresting derivatives of this substance. It has been of special 

 interest historically because of the analogy of these salts to 

 those of acetoacetic ether. The same reactivity of the phenol 

 group is exhibited by the free acid 9 and its salts as well as by the 

 ester. Therefore, the rate of saponification of the ester is also 

 affected by the formation of basic salicylates C 6 H 4 (OM) 

 COOM. 



Lastly must be taken into account the limited solubility of 

 methyl salicylate which renders the system nonhomogeneous 

 during saponification unless carried out with low concentrations. 

 Saponification in nonhomogeneous systems has been studied by 

 Kremann 10 in the case of ethyl benzoate. 



The saponification of methyl salicylate with sodium hy- 

 droxide has been carefully investigated by Goldschmidt and 

 Scholz in one of their series of papers. 11 However, it was seen 

 that the problem could be attacked from a different standpoint 

 and some corrections made in their formula as applied to methyl 

 salicylate. The work of Goldschmidt and Scholz will be taken 

 up again in the discussion of our own results. 



I. CARBON DIOXIDE FORMATION 



An experiment was first carried out to determine if carbon 

 dioxide was formed from methyl salicylate at low temperature, 

 and, if so, under what conditions and to what extent. 



•Graebe, Ann. Phar. (1866), 139, 134; Schreiner, Ann. d. Chem. (1879), 

 197, 19; Freer, Am. Chem. Journ. (1892), 14, 411; Nicola, Chem. Cen- 

 tralbl. (1907), 2, 49. 



"Piria, Ann. d. Chem. (1855), 93, 262; Lajoux et Grandval, Compt. 

 rend. Acad. sci. (1893), 117, 44; Adam, Bull. Soc. chim. (1894), 11, 204; 

 Kellas, Zeitschr. f. physik. Chem. (1897), 24, 220; Imbert et Astruc, 

 Compt. rend. Acad. sci. (1900), 130, 35; Buroni, Gazz. chim. ital. (1902), 

 32, 311; Ley und Erler, Zeitschr. f. elek. Chem. (1907), 13, 797; de 

 Coninck, Compt. rend. Acad. sci. (1907), 144, 757, 1118; Goldschmidt 

 und Scholz, Ber. d. deutschen chem. Ges. (1907) 40, 624; Kailan, Monatsh. 

 f. Chem. (1907), 28, 115; Thiil und Roemer, Zeitschr. f. physik. Chem. 

 (1908), 63, 711. 



10 Monatsh. f. Chem. (1905), 26, 315. See also Reicher, Ann. d. Chem. 

 (1885), 228, 285. 



11 Ber. d. deutschen chem. Ges. (1907), 40, 636. See also Kellas, Zeitschr. 

 f. phys. Chem. (1909), 66, 81; (1909), 67, 257; and Finlay and Turner, 

 Journ. Chem. Soc. (1905), 87, 747. 



