Interaction of polynitro-compounds with aromatic hydrocarbons and bases. Part. XII. Complexes of N-alkylated anilines with s-trinitrobenzene and s-trinitrotoluene

Abstract

Interaction of Polynitro-compounds, etc. Part X I I .

Charge transfer adducts of binuclear rare earth 3,5-dinitrobenzoates with N,N-dimethylaniline and toluene

“…5a demonstrates the spectra of solutions of europium compounds 1 and 6 in THF (10 - hence the CT is weaker, the ΔH f of complex formation is -3.2 kcal/mol, λ max ~ 400 nm; in the second case, a stronger complex is formed, ΔH f = -7.9 kcal/mol, λ max ~ 620 nm (solutions of the compounds in heptane were studied) [19]. The aniline-TNB complex has a λ max value close to that found for the solution of complex 1 (CT band λ max = 390 nm in cyclohexane [17]); apparently, the degree of CT in the DMA-DNBZ complex in solution is a little smaller than that in the aniline-TNB complex.…”

“…An absorption band of this kind characterizes a complex as a whole rather than one of its components. The absorption maximum of this band for the DMA-TNB complex is λ max = 475 nm in cyclohexane and 469 nm in dioxane [17].…”

n–π Electron donor–acceptor complexes. I. Aliphatic amines with benzonitrile

“…There is little correlation between the pK, values of amines and their respective K values with benzonitrile (Table 1); this is hardly surprising, as the pKa value is a measure of the Bronsted basicity, while the K is presumably a measure of the Lewis basicity of alkyl amines (32). It has been found that the electron donor strength of R3N > R,NH > RNH, predicted from the inductive effect of alkyl groups is expected to change when bulky substituent groups exert steric hindrance in the case of complex formation (33, 34).…”

“…It is evident, as is shown in Table 1, that this is so. Assuming that is not drastically different for different amines (32), the increase in &AD at 300 nm reflects the shift in hma, with the order R3N > R2NH > RNH,, as is observed for the cited n-n complexes (6) -Work is in progress to assess these conclusions from further thermodynamic data such as AH and AS measurements. Stronger n-acceptors such as nitro-substituted benzenes will be chosen in order to avoid some of the experimental difficulties found for the benzonitrile systems.…”

Reactivity constants in copolymerization

“…4. 5 Therefore, it might be concluded that tlie mode of the deconiposition of Bzz02 with dialkylanilines is similar to that of the occurrelice of basicity (pK,) of these substituted anilincs.The driving force of the latter reaction is an affinity of proton to the lone pair of the nitrogen atom of these anilines. This conclusion is in accordance with our interpretation on the decomposition mode of Bz202 in the presence of di-n-alkylaniline, whose intermediate is (III) …”