THE MUTUAL INFLUENCE OF HYDROXYL AND CARBOXYL AND 

 SOME RELATED GROUPS IN THE ORTHO POSITION 



A STUDY OF THE ABSORPTION SPECTRA OF PHENOL, O-CRESOL, O-HYDROXY- 



BENZYL ALCOHOL, SALICYLIC ACID AND ITS METHYL ESTER, METHYL 



ETHER OF SALICYLIC ACID AND ITS METHYL ESTER, BENZYL 



ALCOHOL, BENZYL ACETATE, BENZYL METHYL ETHER, 



BENZYL CHLORIDE, AND METHYL BENZOATE 



, By H. D. Gibbs * and D. S. Pratt 



(From the Laboratory of Organic Chemistry, Bureau of Science, 

 Manila, P. I.) 



Five text figures 



The following investigation was undertaken with the view of 

 throwing some light upon the behavior of the compounds which 

 exist in solution during the saponification of methyl salicylate 

 described in the previous paper. 2 



If it be true that the strengths of carboxylic acids are de- 

 termined by the reactivity of the carboxylic >C=0 group, it 

 should be possible to compare spectroscopically certain analogous 

 acids which show ultra-violet absorption bands. Baly and 

 Schaef er 3 state : 



There are thus two influences at work which determine the affinity of the 

 carbonyl group in carboxylic acids, namely, (1) the nature of the adjacent 

 carbon atom, and (2) the condition of the hydroxylic oxygen. 



It is to be expected that these influences would change the 

 relative position and persistence of ultra-violet absorption bands, 

 and that a study of a series of closely related compounds in 

 which they are varied, both collectively and separately, would 

 result in a clearer understanding of the chemical and physical 

 behavior of the compounds in solution. 



The astonishingly great difference between the saponification 

 rates of methyl salicylate and its sodium salt (6.63 and 0.161, 

 respectively) must be due to a decreased activity of the carbonyl 

 which in this case is attributed to a change in the equilibrium 

 of forces between this group and the hydroxyl group in the 

 ortho position. 



1 Associate professor of chemistry, University of the Philippines. 



2 Gibbs, Williams, and Galajikian, This Journal, Sec. A (1913), 8, 1. 

 3 Journ. Chem. Soc. London (1908), 93, 1814. 



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