Preparation of 5‐Substituted‐1H‐Tetrazoles Catalyzed by MOFs via Two Strategies: Direct Condensation of Aryl Nitriles with Sodium Azide, and Tri‐Component Reaction Method

Abstract

Various 5‐substituted‐1H‐tetrazoles were synthesized via two strategies; direct [3+2] cycloaddition of substituted aryl nitriles with sodium azide, and tri‐component reaction of aldehydes, hydroxylamine hydrochloride with sodium azide in dimethylformamide (DMF) by applying M2(BDC)2(DABCO) [M: Cu, Co and Ni, BDC=1, 4‐benzenedicarboxylic acid, and DABCO= 1,4‐diazabicyclo[2.2.2]octane] as heterogeneous catalyst. Short reaction time, high yield, totally straightforward procedure and easy work‐up, as well as preparing tetrazole derivatives via relatively cheap and easily available aldehydes (in three‐component method) are some beneficial features of mentioned methodologies. It was found that among three studied transition metals, copper has a unique advantage over other metals in formation of the desired product.

Synthesis of (E)-2-(1H-tetrazole-5-yl)-3-phenylacrylenenitrile derivatives catalyzed by new ZnO nanoparticles embedded in a thermally stable magnetic periodic mesoporous organosilica under green conditions

“…One of the advantages of this strategy is the use of available, easy and inexpensive basic compounds, namely aldehydes and sodium azide along with relatively expensive nitriles, which has made these reactions economically viable and easy to do on an industrial scale 56 – 60 . Among different catalytic systems for benzylidenemalononitrile derivatives, which are generally prepared by condensation of aldehydes and molononitrile, Fe 3 O 4 @BNPs-CPTMS-Chitosan-Pd(0) 61 , Cu(II) immobilized on Fe 3 O 4 @HNTs–tetrazole nanocomposite 62 , secondary amine/Cu(II) bifunctional magnetic nanoparticles 63 , Fe 3 O 4 magnetic nanoparticles under microwave irradiation 64 , NiO 2 nanoparticles 65 , silica molybdic acid 66 and Cu 2 (BDC) 2 (DABCO) metal–organic framework 67 could be mentioned. In spite of their merits, there are some disadvantages to the most of previously reported protocols for the synthesis of tetrazoles.…”

Fe3O4 ‐PTh‐SO3H: A Retrievable Solid‐acid Nanocatalyst for the Green Synthesis of Imidazole and Tetrazole Derivatives

“…Therefore, many methods have been reported to produce them [53,54] . For this purpose, many homogeneous and heterogeneous catalysts have been applied such as Fe 3 O 4 @L‐lysine‐Pd(0), [55] Fe 3 O 4 @SiO 2 ‐TCT‐PVA−Cu(II), [56] PtNPs@VC, [57] FeTSPP, [58] Boehmite@SiO 2 @Tris‐Cu(I), [59] SiO 2 ‐H 3 BO 3 , [29] Cu‐MCM‐41, [60] and Cu 2 (BDC) 2 (DABCO) [61] …”

“…[53,54] For this purpose, many homogeneous and heterogeneous catalysts have been applied such as Fe 3 O 4 @L-lysine-Pd(0), [55] Fe 3 O 4 @SiO 2 -TCT-PVAÀ Cu(II), [56] PtNPs@VC, [57] FeTSPP, [58] Boehmite@SiO 2 @Tris-Cu(I), [59] SiO 2 -H 3 BO 3 , [29] Cu-MCM-41, [60] and Cu 2 (BDC) 2 (DABCO). [61] Following our previous study on the synthesis and applications of heterogeneous catalysts, [62,63] we applied PTh to coat Fe 3 O 4 nanoparticles (MNPs) to produce a nanocomposite Fe 3 O 4 -PTh, followed by sulfonation to synthesize Fe 3 O 4 -PTh-SO 3 H as a solid acid nanocatalyst. Using PTh as a polymer coating on the surface of Fe 3 O 4 NPs reduced the agglomeration of MNPs.…”

Enhanced catalysis through structurally modified hybrid 2-D boron nitride nanosheets comprising of complexed 2-hydroxy-4-methoxybenzophenone motif

“…Thereafter, a plethora of homogeneous catalysts like bronsted acids, lewis acids, AlCl 3 , CdCl 2 , Fe(OAc) 2 , copper (I) chloride, etc. as well as a few heterogeneous catalytic systems have been reported for their synthesis in literature 35 – 38 . However, commercial utilization of aforementioned protocols is hindered due to innate shortcomings such as use of expensive metal salts, toxic solvents, prolonged reaction time, unsatisfactory yield, difficulty in separation and recovery of the catalyst 39 – 44 .…”