SUNLIGHT UPON METHYL ALCOHOL. d 59 
Il. THE OXIDATION OF METHYL ALCOHOL UNDER THE INFLUENCE 
OF A, SUNLIGHT, AND, B, HYDROGEN PEROXIDE. 
INTRODUCTION. 
During the study of the hydrolysis of methyl salicylate,’ it 
was noted that this ester was quite prone to turn yellow when 
exposed to the sunlight. The isolation of the compounds formed 
prove to be quite difficult and necessitated a preliminary inves- 
tigation of the products of hydrolysis. Formaldehyde was 
usually found in the reacting mixture when the hydrolysis was 
_ carried on in the sunlight, especially in the presence of acids, 
and since this compound could only result from the oxidation of 
methyl alcohol which, according to the available literature, was 
impossible, the first phase of the investigation concerned itself 
with this problem. 
A. THE OXIDATION OF METHYL ALCOHOL IN THE PRESENCE OF OXYGEN AND 
SUNLIGHT. 
While methyl and ethyl alcohols have been oxidized to the cor- 
responding aldehydes by the influence of sunlight in the presence 
of other reacting substances or catalyzers, no aldehydes have 
been detected, previous to this work, when the sunlight acted 
in the presence of oxygen and water alone. 
From the general behavior of the alcohols it is to be expected 
that a reaction will take place with oxygen, the governing con- 
ditions being temperature and intensity of the light. 
Nef* has found that formaldehyde and acetaldehyde are among the 
products formed by the dissociation of methyl and ethyl alcohols under 
the influence of heat at about 600°. Methyl alcohol dissociates and the 
products unite in view of the methylene hypothesis, according to the ex- 
pressions 
CH.OH = CH.< + H.0 = H.C:0 +H. = C:0 + 2H.. 
CH) om = CH. T=) 
He points out’ that the dissociation temperature of compounds may be 
lowered very much through the influence of agents such as light, the silent 
electric discharge, powdered metals, water, alkalies, or acids. 
"Part I. The separation of salicylic acid from methyl-salicylate and the 
hydrolysis of the ester. This Journal, Sec. A (1908), 3, 101; and Journ. 
Am. Chem. Soc. (1908), 30, 1465; Part II, Solubility in water at 30°. 
This Journal, Sec. A (1908), 3, 357; Part III. The coloration of methyl- 
salicylate and some allied compounds in the sunlight, by H. D. Gibbs, R. R. 
Williams, and D. S. Pratt. See the following article, page 79; Part IV. 
The saponification of methylsalicylate and methyl benzoate, by H. D. Gibbs 
and R. R. Williams. In press. 
*Ann. d. Chem. (Liebig) (1901), 318, 195. 
*“Ibid., (1897), 298, 202. 
