Symmetrical Bis-Hydrazone Ligand-Based Binuclear Oxido/Dioxido-Vanadium(IV/V) Complexes: Synthesis, Reactivity, and Catalytic Applications for the Synthesis of Biologically Potent 2-Phenylquinazolin-4-(3H)-ones

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 22, 2025

Symmetrical bis(hydrazone)-based ligands, H4dar(bhz)2 (I), H4dar(fah)2 (II), H4dar(nah)2 (III), and H4dar(inh)2 (IV) obtained from 4,6-diacetylresorcinol (H2dar) different hydrazides [benzoylhydrazide (Hbhz), isonicotinoylhydrazide (Hinh), nicotinoylhydrazide (Hnah), 2-furoylhydrazide (Hfah)], were used to prepare potassium salts of binuclear cis-[VVO2]+ complexes, {K(H2O)2}2[(VVO2)2dar(bhz)2] (1), {K(H2O)2}2[(VVO2)2dar(fah)2] (2), {K(H2O)2}2[(VVO2)2dar(nah)2] (3), {K(H2O)2}2[(VVO2)2dar(inh)2] (4), [VIVO]2+ [{VIVO(MeOH)}2dar(bhz)2] (5), [{VIVO(MeOH)}2dar(fah)2] (6), [{VIVO(MeOH)}2dar(nah)2] (7), [{VIVO(MeOH)}2dar(inh)2] (8). In the presence warm MeOH/DMSO (4:1), 3 changed {K(H2O)2}[(VVO2)2Hdar(nah)2]·DMSO (3a·DMSO). Single crystal XRD studies 1 3a confirm a structure along with distorted square pyramidal geometry each vanadium center where bis{ONO(2-)} ligands coordinate through phenolate-O, azomethine-N, enolate-O atoms unit. While growing crystals 6 in EtOH, part it oxidizes gives [{VVO(OEt)}2dar(fah)2] (9) powdery 6. Complex 9 has octahedral structure. These complexes as catalysts for synthesis biologically important 2-phenylquinazolin-4-(3H)-ones having aryl aldehydes, they all show excellent catalytic performance (up 97% yield) less reaction time low temperature, 70% aqueous TBHP/30% H2O2 greener oxidant. Generally, these perform better than their mononuclear analogues. Spectroscopy, DFT studies, isolated intermediates have helped proposing suitable mechanism reaction.

Язык: Английский

Acceptorless dehydrogenation under neat reaction conditions: Synthesis of 2-aryl/alkyl quinazolinones using supported Ni NPs as catalyst

Synlett, Год журнала: 2024, Номер 35(20), С. 2496 - 2502

Опубликована: Авг. 15, 2024

Abstract We report here a Ni-NPs-catalyzed one-pot synthesis of 2-alkyl/aryl quinazolinone motifs via acceptorless dehydrogenation alcohol, condensation an aldehyde intermediate with 2-aminobenzamide, followed by second the cyclized intermediate. The protocol is atom-economical and require earth-abundant Ni as catalyst. present involves annulation 2-aminobenzamide various types primary alcohols, including aryl/heteroaryl methanol, aliphatic produces high yields desired products under neat conditions. catalyst was synthesized high-temperature pyrolysis strategy, using ZIF-8 sacrificial template. NPs@N-C characterized XPS, HR-TEM, HAADF-STEM, XRD, ICP-MS. stable even in air at room temperature displayed excellent activity dehydrogenative coupling quinazolinones could be recycled five times without appreciable loss its activity.

Язык: Английский