The development of transition metal-based heterogeneous catalysts for economical and efficient synthesis of secondary imines remains both desirable and challenging. Herein, for the first time, we present two kinds of Rh nanoparticle anchored uniform spherical COF heterogeneous catalysts with well-defined crystalline structures for the effective one-pot tandem reductive amination of aldehydes on a gram scale. This reaction is carried out using ammonia as a nitrogen source and hydrogen gas as the source of hydrogen, which is not only an atom-economical but also an environmentally friendly process for the selective production of secondary imines. In particular, in the presence of the betterdesigned Rh nanoparticles anchored COF2 catalyst, the starting material aldehydes could be fully converted (99% conversion), and 95% selectivity of N-benzylidene(phenyl)methanamine is obtained under mild reaction conditions (2 MPa of H 2 and 90 °C). Additionally, the Rh/COF2 catalyst is also applied to a variety of substituted aromatic aldehyde compounds, manifesting good yields in corresponding secondary imines. This work not only expands the COF family but also offers economical and effective access to acquire various aromatic amine targets, especially secondary imines.
Neutral starch microspheres (NSMs) were synthesized by an inverse microemulsion technology with epichlorohydrin as a crosslinker and soluble starch as starting material. Anionic starch microspheres (ASMs) were prepared from NSMs by the secondary polymerization with chloroacetic acid as the anionic etherifying agent. Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and laser diffraction particle size analyzer were used to characterize the anionic starch microspheres. The results showed that structure of the microspheres was compact and the hardness of microspheres was great, and the average diameter of the product was about 75 µm. The anionic starch microspheres (ASMs) were used to adsorb methylene blue (MB) from aqueous solution. Effects of adsorption time, initial concentration of MB, and temperature on the adsorption of MB onto ASMs were studied, and the equilibrium and kinetics of the adsorption process were further investigated. It shows that ASMs can effectively remove MB from the solution. The adsorption equilibrium data correlates well with the Langmuir isotherm model compared with Frendlich isotherem model. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-order kinetic model provided a better correlation of the experimental data in comparison with the pseudo-first-order model. Temperature variations did not significantly affect the adsorption of MB onto ASMs.
The reaction of hydrazides with triphosgene in the presence of triethylamine is a facile method to construct various oxadiazolones. Utilizing this reaction, a new class of colorimetric and fluorogenic phosgene chemosensors were developed with the BODIPY as fluorophore, five BODIPYbased hydrazides, which exhibited highly effective reactions with phosgene. The mechanism was updated. Finally, the test paper with a hydrazide was fabricated for facile, selective, and visual detection of phosgene gas.
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