Photoluminescent materials, that are now ubiquitous in our everyday life, have particularly attracted the attention of the scientific community these past few years due to potential important applications such as in bioimaging, sensing, or optoelectronics. In this context, relatively few different families of molecules have been reported to exhibit fluorescence in the aggregated or solid-state through the excited-state intramolecular proton transfer (ESIPT) photochemical process. The preparation and subsequent determination of photochemical properties of an underexplored family of 1,5-benzodiazepin-2-one derivatives are reported. From these data and X-ray diffraction analysis study, it emerged that photoluminescence (in the range 520-655 nm) was mostly attributed to ESIPT. The photoluminescent potential of 1,5-benzodiazepin-2-ones, their facile access, and functionalization were demonstrated through the preparation of two fluorogenic probes for the selective detection of biothiols.
Abstract:The CuI-or Ag 2 CO 3 -catalyzed [3+2] cycloaddition of propargyl-substituted dihydroisoindolin-1-one (3) with arylnitrile oxides 1a-d (Ar = Ph, p-MeC 6 H 4 , p-MeOC 6 H 4 , p-ClC 6 H 4 ) produces in good yields novel 3,5-disubstituted isoxazoles 4 of the ethyl-2-benzyl-3-oxo-1-((3-arylisoxazol-5yl)methyl)-2,3-dihydro-1H-isoindole-1-carboxylate type. With aryl azides 2a-d (Ar = Ph, p-MeC 6 H 4 , p-OMeC 6 H 4 , p-ClC 6 H 4 ), a series of 1,4-disubstituted 1,2,3-triazoles 6 (ethyl-2-benzyl-3-oxo-1-((1-aryl-1H-1,2,3-triazol-4-yl)methyl)-2,3-dihydro-1H-isoindole-1-carboxylates) was obtained. The reactions proceed in a regioselective manner affording exclusively racemic adducts 4 and 6. Compared to the uncatalyzed cycloaddition, the yields are significantly improved in the presence of CuI as catalyst, without alteration of the selectivity. The regio-and stereochemistry of the cycloadducts has been corroborated by an X-ray diffraction study of 4a, and in the case of 6a by XH-correlation and HMBC spectra.
The present work arose out of a desire to fundamentally understand the molecular geometry, weak interactions, electron density delocalization, and chemical reactivity features of 1,5‐benzodiazepines‐containing family. Herein, a complete X‐ray crystallographic study, supported by trustworthy sets of computational approaches, has been reported for two organic crystals. Quantifying intramolecular and intermolecular interactions by Hirshfeld‐Becke surfaces analysis conjointly with noncovalent interaction‐reduced density gradient topological study revealed that supramolecular assemblies are stabilized by N‐H
…O (inter) and O‐H
…N (intra) hydrogen bonds, Cg
…Cg (π
…π) and C‐H(O)
…π intercontacts, as well as Van der Waals interactions and steric effects. The long‐range‐corrected functional wB97XD, which uses Grimme's D2 dispersion model, seems to be just right for our systems. The quantum theory of atoms in molecules analysis confirms that both significant O1‐H1…N1 and N2‐H2A…O2 H‐bonds are weak and electrostatic in nature. Furthermore, global reactivity indices computed via the conceptual density functional theory framework allows these molecules to be classified as moderate electrophiles and marginal nucleophiles. The active sites favorable for nucleophilic/electrophilic attacks were also predicted based on local Parr functions. Finally, a comparative evaluation on the aromaticity character and π‐π stacking ability has been done for different (pseudo) rings.
A novel and practical synthesis of 3-benzoylquinoxalin-2(1H)-ones from benzodiazepin-2-ones in two steps from commercially available starting materials is reported. The reaction was achieved in the presence of N-bromosuccinimide in DMSO which served both as a solvent and an oxidant. Significantly, the yet unknown ketone to alcohol fluorescence turn-on of benzoylquinoxalinones was unveiled through the preparation of a fluorescently labelled cholesterol conjugate.
A series of novel O-triazolyl-1,5-benzodiazepin-2-ones 6aeo and O-isoxazolyl-1,5benzodiazepin-2-ones 7aeo was synthesized via a Cu(I)-catalyzed 1,3-dipolar alkyne eazide coupling reaction of N-substituted-1,5-benzodiazepineealkyne derivatives 3aec with various aromatic azides 4aee and nitrile oxides 5aee, respectively. The chemical structures of synthesized compounds were determined using 1 H NMR, 13 C NMR, heteronuclear multiple bond correlation (HMBC), high-resolution mass spectra, as well as elemental analysis and was further confirmed by an X-ray diffraction analysis for compound 7d.
International audienceA new family of fluorescent 1,5-benzodiazepin-2-one (HBD) borate complexes was prepared in good yields, and fully characterized by means of MS, NMR and IR spectroscopy, as well as X-ray crystal structure analysis for compound 13. Unlike their uncomplexed congeners, most of these cyclic boranils were emissive both in solution and the solid state, with maxima in the range of 426–596 nm. A systematic study of substituent effects revealed that the presence of a halogen atom specifically at position 8 of the fused-aromatic ring system led to an increase in fluorescence intensity in solution while electron rich substituents tended to extinguish the photoluminescence. Finally, a proof-of-concept study highlighted that the amide moiety of the benzodiazepinone framework could be functionalized with a chemical handle useful for subsequent specific modifications
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.