This is the third paper of a series in which the proton-attracting powers of different liquids are compared by a measurement of the perturbation they produce on the OD vibrational band of CHaOD. Data showing the absorption of the OD group of CHaOD in seventy-seven different solvents are given in the present paper, in a table listing positions of the band and shifts from the position of the unperturbed OD absorption band. Ketones, aldehydes, organic and inorganic esters, ethers, nitriles, amines, glycols, amides and a few other types of compounds were studied. Many interesting variations due to differences in structure were detected. With certain exceptions a linear relation was found to exist between the logarithms of the basicity constants of the solvents as measured in water solution and the shifts they cause in the OD band. A close correlation was observed between the effects of these solvents on the OD band of heavy methyl alcohol and their solubilities and heats of mixing with certain other compounds. No correlation was evident between the absorption data and the dielectric constants and dipole moments of the solvents. A relationship was found to exist between the protonacceptor power of a given atom and the electro-negativities of the atoms adjacent to it in the molecule.

phenylhydrazone, N-butyl-N-phenyl-N'a-naphthylurea, and 3-ethyl-2-propylquinoline hydriodide and methiodide. Chicago, Illinois

Forty-two different organic liquids are rated according to their proton-attracting power by comparing the strength of the hydrogen bonds which they form with heavy methyl alcohol. The classes of liquids studied are: aldehydes, ketones, esters, ethers and amines. The amount of perturbation which the different solvents cause in the OD vibrational band of the CH3OD is taken as a measure of the strength of the deuterium bridges formed with the CH3OD. The study is a continuation of a previous work in which twenty-six similar liquids were studied, and the results agree with those of the former study in showing that according to proton-attracting power the different classes are in the order: esters<aldehydes and ketones<ethers <amines. From the study it is possible to observe the effects of unsaturation, substitution, and other structural variations on the electron donor power of the O or N atom to which the OD group forms a bond. It is shown that the strength of the deuterium bonds formed with CH3OD bears a close relation to the basicities of the solvents, to their solubilities for other proton donor solutes, and to their reactivity with other compounds. There appears to be no correlation between the dipole moments of the solvents and the strengths of the bonds formed with the CH3OD.

at 162-164°. 29 The benzyl benzoate fraction boiled at 145-151 °(4 mm.). Benzyl trimethylacetate was obtained mixed with neopentyl benzoate as a fraction boiling at 113-118°( 15 mm.). The amounts of each of the esters in this fraction were determined by saponification and determination of the quantities of the respective alcohols and acids. From the residues of the reaction of this ester a solid, which crystallized from alcohol in fine white needles, was obtained. Analytical data (Table III) indicated that this substance had the molecular formula C11H22O.

Recent solubility and heat of mixing experi-ments8 provide evidence that acetylene and phenylacetylene may act as proton donors in the presence of the organic solvents mentioned previously. We have undertaken the researches reported here to ascertain whether electron-donor solvents such as amines and ethers produce in the acetylenic CH of phenylacetylene perturbations