Benzoxazine Formation Mechanism Evaluation by Direct Observation of Reaction Intermediates.

Benzoxazine formation is a fundamental step in the preparation of polybenzoxazine resins, and a detailed description of the mechanism governing the formation of benzoxazine and side products is vital for improving the properties and performance of these resins. Determination of the nature and properties of reaction intermediates is not trivial. Therefore, a Mannich-type condensation of aniline, formaldehyde, and phenol was evaluated as a potential method to form benzoxazine. Coupling positive mode electrospray ionization mass spectrometry (ESI(+)-MS) with infrared multiple photon dissociation (IRMPD) spectroscopy allowed unambiguous determination of an iminium-based mechanism and the direct observation of iminium intermediates. The benzoxazine formation mechanism was indirectly confirmed by the observation of side products that are relevant to the polymerization step, and directly confirmed by the identification of four distinct reaction intermediates that were completely characterized by IRMPD spectroscopy. The benzoxazine monomer was also shown to undergo isomerization under standard ESI-MS analysis conditions, suggesting the presence of a mixture of three isomers during their usual ESI-MS analysis.

Evaluation of Common Theoretical Methods for Predicting Infrared Multiphotonic Dissociation Vibrational Spectra of Intramolecular Hydrogen-Bonded Ions.

Infrared photodissociation analyses are supported by theoretical calculations that allow a trustworthy interpretation of experimental spectra of gaseous ions. B3LYP calculations are the most prominent method used to model IR spectra, as detailed in our bibliographic survey. However, this and other commonly used methods are known to provide inaccurate energy values and geometries, especially when it comes to long-range interactions, such as intramolecular H-bonds, which show increased anharmonicity. Therefore, we evaluated some of the most commonly used density functional theory methods (B3LYP, CAM-B3LYP, and M06-2X) and basis sets (6-31+G(d,p), 6-311++G(d,p), 6-311++G(3df,2pd), aug-cc-pVDZ, and aug-cc-pVTZ), including anharmonicity and dispersion corrections. The results were compared to MP2 calculations and to experimental high-frequency (2000-4000 cm-1) IR multiphotonic dissociation (IRMPD) spectra of two protonated model molecules containing intramolecular hydrogen bonds: biotin and tryptophan. M06-2X/6-31+G(d,p) was shown to be the most cost-effective level of theory, whereas CAM-B3LYP was the most efficient method to describe the van der Waals interactions. The use of the dispersion correction D3, proposed by Grimme, improved the description of O-H vibrations involved in H-bonding but worsened the description of N-H stretches. Anharmonic calculations were shown to be extremely expensive when compared to other approaches. The efficiencies of well-established scaling factors (SFs) in opposition to sample-dependent SFs were also discussed and the use of fitted SFs were shown to be the most cost-effective approach to predict IRMPD spectra. M06-2X/6-31+G(d,p) and CAM-B3LYP/aug-cc-pVDZ were also tested against the fingerprint region. Our results suggest that these methods can also be used for analysis in this lower frequency range and should be regarded as the methods of choice for cost-effective IRMPD simulations rather than the ubiquitous B3LYP method, especially when further molecular properties are needed.