144 



PROCEEDINGS OF THE AMERICAN ACADEMY. 



In deriving this compound from a substance having Formula II. the 

 atom of oxygen must take up a molecule of sodic methylate, thus pro- 

 ducing the intermediate body of these formulas :* — 



CI 



\ 



O 



\ 



CI 



CH,0 



CI 



CI 

 ONa 



CH,0 



CI 



CI 



0CH3 



Oxide. 



Uemiacetal. 



Intermediate Body. 



and then we must assume that the ONa of this body is converted into the 

 OCH3 of the hemiacetal by sodic methylate, an assumption which cannot 

 be justified by any analogy, so that Formula II. must also be rejected. f 



There remain only Formulas III. and IV., the unsymmetrical struc- 

 ture of which made us at first think them highly improbable ; as a matter 

 of fact, however, both of them explain in a satisfactory manner all the 

 observations. This we will show only with Formula III., since For- 

 mula IV. would behave in a similar manner in every case. 



The conversion of the oxide into chloranilic acid by sodic hydrate 

 would take place in three stages ; first, the addition of one molecule of 

 sodic hydrate to the atom of oxygen, thus : — 



O 



\./ 



OCOC.H 



6 ^^5 



NaO OCOCsHg 



O 



CI 



CI 



0CH3 



HO- 



CI 



CI 

 OCH3 



HO 

 CI 



CI 

 OH 



CH3O OCOCeHg 



Oxide. 



CH3O OCOCgHj 



Intermediate Product. 



o 



Chloranilic Aoid. 



second, the saponification of the acetal groi^ps to the quinone ; and third, 

 the saponification of the methoxy group to a hydroxyl.$ 



* In these formulas tlie radicals in the quinone positions have been left out for 

 the sake of simplicity. They offer no difficulties, as will be shown later. 



t It is perhaps worth while to state that the conversion of the hypothetical 

 intermediate body into the hemiacetal could be brought about by splitting off sodic 

 benzoate, thus forming a new oxide, which afterward might react with the sodic 

 methylate; but, as this new oxide must have the conformation of either Formula 

 III. or IV., it does not seem worth while to bring this strained hypothesis forward 

 as a support for Formula II. 



J That such methoxy groiips on a quinone ring are saponified by sodic hydrate 

 has been shown by the experiments of H. S. Grindley and one of us. (These Pro- 

 ceedings, XXX. 433.) In this respect they resemble those in picric ether or trinitro- 

 phloroglucine ether much more than those in anisol. 



