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Optical anisotropies of amides and peptides in dioxane

The molar Kerr constants mK, molar refractions mR, and dipole moments μ are reported for the N‐methylacetamides CX3CONHCH3 (X = H, CH3, F. CI, Br) and acetamides CX3CONH2 (X = H, F, Cl, Br). The components of the polarizability tensor α are deduced for N‐methylacetamide and acetamide on the basis of the bond additivity approximation. This α is found to be considerably more anisotropic than was indicated in previous determinations by other methods. The data for N‐methylacetamide were used to calculate mK, μ, and γ2 (anisotropy squared) of N‐acetyl‐N′‐methylglycine amide and N‐acetyl‐N′‐methyl‐alanine amide as functions of the torsional angles (ϕ,Ψ). The statistical mechanical averages of mK, μ, and γ2 were calculated from conformational energies obtained by the methods of Scheraga.