The Role of Methoxy Group in the Nazarov Cyclization of 1,5-bis-(2-Methoxyphenyl)-1,4-Pentadien-3-one in the Gas Phase and Condensed Phase

ESI-protonated 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one (1) undergoes a gas-phase Nazarov cyclization and dissociates via expulsions of ketene and anisole. The dissociations of the [M + D]⁺ ions are accompanied by limited HD scrambling that supports the proposed cyclization. Solution cyclization of 1 was effected to yield the cyclic ketone, 2,3-bis-(2-methoxyphenyl)-cyclopent-2-ene-1-one, (2) on a time scale that is significantly shorter than the time for cyclization of dibenzalacetone. The dissociation characteristics of the ESI-generated [M + H]⁺ ion of the synthetic cyclic ketone closely resemble those of 1, suggesting that gas-phase and solution cyclization products are the same. Additional mechanistic studies by density functional theory (DFT) methods of the gas-phase reaction reveals that the initial cyclization is followed by two sequential 1,2-aryl migrations that account for the observed structure of the cyclic product in the gas phase and solution. Furthermore, the DFT calculations show that the methoxy group serves as a catalyst for the proton migrations necessary for both cyclization and fragmentation after aryl migration. An isomer formed by moving the 2-methoxy to the 4-position requires relatively higher collision energy for the elimination of anisole, as is consistent with DFT calculations. Replacement of the 2-methoxy group with an OH shows that the cyclization followed by aryl migration and elimination of phenol occurs from the [M + H]⁺ ion at low energy similar to that for 1.

The synthesis and crystal structure of 2,6,9‐trimethyl‐4,8‐dinitro‐2,6,9‐triazabicyclo[3.3.1]nona‐3,7‐diene

The first preparation of title compound 1 is accomplished. Its heterocyclic structure was characterized spectroscopically and by X‐ray structure analysis.     

A characterization of nonreflexive banach spaces

D. P. Mil'man and V. D. Mil'man considered sequences of decreasing nonempty closed bounded convex sets with empty intersection to obtain characteristics of non-reflexivity. They showed that in every nonreflexive space there is such a sequence which is ω-separated. We show that in every nonreflexive space there is also always such a sequence which is not ω-separated     

Prediction of peptides retention behavior in reversed-phase liquid chromatography based on their hydrophobicity

Hydrophobicity is an important physicochemical property of peptides and proteins. It is responsible for their conformational changes, stability, as well as various chemical intramolecular and intermolecular interactions. Enormous efforts have been invested to study the extent of hydrophobicity and how it could influence various biological processes, in addition to its crucial role in the separation and purification endeavor as well. Here, we have reviewed various studies that were carried out to determine the hydrophobicity starting from (i) simple amino acids solubility behavior, (ii) experimental approach that was undertaken in the reversed-phase liquid chromatography mode, and ending with (iii) some examples of more advanced computational and machine learning models.     

A facile and practical one-pot ‘catch and release’ synthesis of substituted guanidines

A ‘catch and release’ two-step one-pot protocol has been developed for the facile and practical synthesis of substituted guanidines from thioureas and various amines utilizing readily available brominated polystyrene resin.     

Metastable states in homogeneous Ising models

Metastable states of homogeneous 2D and 3D Ising models are studied under free boundary conditions. The states are defined in terms of weak and strict local minima of the total interaction energy. The morphology of these minima is characterized locally and globally on square and cubic grids. Furthermore, in the 2D case, transition from any spin configuration that is not a strict minimum to a strict minimum is possible via non-energy-increasing single flips.