STRUCTURAL EFFECT IN FORKED CONJUGATIVE SYSTEMS——BIFURCATION-TYPE OF FORKED POLYENIC NITRILES,CARBOXYLIC ACIDS AND ESTERS

Abstract

Five homologous series of bifurcate systems of aliphatic and aromatic polyenic cyano and carboxylic compounds have been prepared and studied. The electronic absorption spectra forthe series and the NMR chemical shifts for the methyl-, methylene- and beta-protons havebeen found to conform very well to the rule of homologous linearity. The mass spectra forthe α-cyano polyenic ester series show strong peaks for the fragments of M-COOEt but noneof M-CN, indicating that the CN group seems to be in stronger conjugation with the poly-enic chain than the COOEt group does. In all the forked series studided, a red shift in electronic spectra is brought about upon the introduction of an electron-attractive branching group, just like the case of introducing an electron-repelling substituent. This has been taken as an indication of the predominance of themolecular integrality over the group characteristics. By means of the method of similar triangles between a homologous line for a linearseries and that for the corresponding forked compounds, the equivalent △Ns for a branching group may be calculated with accuracy. Based on the value of this equivalent, the substituentnature of the structural effect of the branching group has been inferred. The electronic absorption maxima for four series of the forked compounds have been cal-culated by means of the extended homologous equation for the corresponding linear compounds.With an appropriate correction for the positional effect of the substituent equivalent, the cal-culated wavelengths agree generally with experimental data within ± 7nm.