J. N. Spencer

Hydrogen bonding by alcohols and amines

The pure base calorimetric method has been used to determine the enthalpies of hydrogen bond complex formation between aliphatic amines and alcohols. The enthalpies of complexation for the series methanol-n-butanol bonding with triethylamine increase with decreasing alkyl chain length in accordance with the electron donating properties of alkyl groups. Unexpectedly, the enthalpies for the complexes of n-butanol with tributylamine, tripropylamine, and triethylamine increase with decreasing alkyl chain length.Primary and secondary amines form hydrogen bonded complexes with n-butanol in which the amine protons form an NH···O bond with the alcohol and the alcohol hydroxyl proton donates a proton to the amine nitrogen. The difference in enthalpy of complex formation between tertiary amines and secondary amines is largely accounted for by the involvement of the amine proton of the secondary amine. Primary amines, like secondary amines, donate only one proton to the complex with n-butanol but have a larger complex enthalpy than secondary amines probably because of steric hindrance and differences in basicity.

Solvent effects on hydrogen bond formation

Enthalpies of solution have been used to calculate transfer enthalpies for phenol, pyridine, and DMSO between the solvent cyclohexane and the solvents CCl4, benzene, and CHCl3. By use of model compounds, enthalpies due to interactions with phenol, pyridine, and DMSO have been determined. These enthalpies are used to calculate the effect of solvation relative to cyclohexane on hydrogen bonded complexes in CCl4 and benzene solvents. Correlations with enthalpies due to interactions and frequency shifts for the hydroxyl stretch in these solvents have also been made.

Hydrophobic hydration of thymine

The solubilities of adenine in water, thymine in methanol, and uracil in methanol were determined over the temperature range 15–40°C. From these and previously reported data the thermodynamic functions for the transfer of the solute from water to methanol were calculated. The differences in transfer functions for uracil and thymine are due to hydrophobic hydration of the methyl group of thymine.

Amide interactions in chlorinated solvents

Enthalpies of solution and of transfer of amides for the solvents chloroform (CHCl3), methylenechloride (CH2Cl2), carbontetrachloride (CCl4), cyclohexane (C6H12), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and ethylacetate (EtOAc) have been used to isolate and quantify the solvation interactions of amides in chlorinated solvents. Specific interactions at the aminde carbonyl and N−H groups have been identified. An analysis of the transfer enthalpies of pyrrole and methylpyrrole from cyclohexane to the chlorinated solvents shows that specific interactions between the pyrroles and these solvents are similar in nature. A means of calculating differences in the transfers of different solutes between the same solvent pair is given.

Linear free energy relations and solvent effects for complexes ofm-cresol and various bases

The enthalpies, entropies, and equilibrium constants for the hydrogen bonded complexes of m-cresol with ten bases in cyclohexane solvent have been determined by calorimetric and spectroscopic methods. The logarithm of the equilibrium constant correlates well with the dipole moment of the base and the solvatochromic parameter β which measures the electron donating ability of the base. The enthalpy and entropy data show that the dipole term does not enter into the log K correlation as a consequence of electrostatic interactions between acid and base in the complex. The free base-solvent interaction, which appears to be dipolar in origin, reduces the entropy of the free base and hence contributes to a favorable entropy change for complex formation. The present data are compared to previously reported data obtained in CCl4 solvent. Solvent effects on the thermodynamic parameters in CCl4 and cyclohexane appear to be related to dipolar interactions by m-cresol and the bases with the two solvents.

Solvent effects on the thermodynamics of the formation of hydrogen bonded complexes ofm-cresol III

Thermodynamic parameters for the hydrogen bonded complexes of m-cresol with various bases in the solvent benzene have been determined from calorimetric and spectroscopic data. These data were analyzed by linear solvation energy relationships. When combined with data previously determined for the same complexes in CCl4 and cyclohexane solvents, it is shown that solvent effects on the thermodynamics of hydrogen bond formation are due to solvation of the free m-cresol and base through dipolar and perhaps donor-acceptor interactions.