Experimental and Theoretical Investigation of the Reaction of Secondary Amines with Maleic Anhydride

Abstract

The reaction of secondary amines, namely 1-methylpiperazine, pyrrolidine, morpholine, 2-methylpiperidine, and diethylamine, with maleic anhydride has been investigated experimentally and theoretically at the DFT level. Under kinetic control, i.e. at −78°C or −15°C, amines add across the C=O functionality exclusively and the initially formed addition products isomerize to the corresponding N-substituted maleimic acid derivatives. In contrast to the acyclic α,β-unsaturated carbonyl compounds, amine does not add across the C=C functionality in maleic anhydride even under thermodynamic control. This behaviour of maleic anhydride can be rationalized on the basis of the local condensed Fukui functions, which reveal that the carbonyl carbon atoms in maleic anhydride are much harder than in an acyclic α,β-unsaturated carbonyl compound, such as acrolein. This prompts the amines to attack the carbonyl group in maleic anhydride exclusively.

Byproduct‐Free Synthesis, Characterization, and Reactivity of 1, 2‐Diaminosiloxane Monolayers on Silicon/Silicon Dioxide

“…For succinic anhydride, nucleophilic attack by the amine on the carbonyl group is expected to form the corresponding succinamide. For maleic anhydride, however, the amine can alternatively add across the alkene in a Michael fashion . In this case, rinsing the surface would be expected to result in hydrolysis of the anhydride portion of the Michael adduct to produce carboxylic acids.…”

“…For maleic anhydride, however, the amine can alternatively add across the alkene in a Michael fashion. [24][25][26][27][28] In this case, rinsing the surface would be expected to result in hydrolysis of the anhydride portion of the Michael adduct to produce carboxylic acids. These anhydrdes were allowed to react in separate experiments with freshly prepared monolayers ( Figure 6).…”

Stretchable anisotropic conductive film (S-ACF) for electrical interfacing in high-resolution stretchable circuits

“…3B). The reactions are well known from various previous studies (62)(63)(64)(65)(66). The reaction process between SEBS-MA and the amine group of APTES, which is the ring-opening amide reaction, is illustrated in Fig.…”

Synergy between Experimental and Theoretical Results of Some Reactions of Annelated 1,3-Azaphospholes

“…The chemical reactivity at a particular molecular site could be rationalized using a quantitative descriptor, the Fukui function (f(r)). We recently used Fukui function to rationalize 1,2- versus 1,4-addition of amines to maleic anhydride [ 46 ]. The difference in the behavior of indolizine and 2-phosphaindolizine towards electrophilic reagents can be rationalized on the basis of the Fukui functions calculated at the B3LYP/6-31+G* level ( Figure 4 ) [ 47 ].…”