Dual Utility of Heterogeneous Catalyst ZSM‐5 for C–C Cleavage Leading to Nitriles, and for the Synthesis of Hydrazides

Abstract

A unique reactivity of zeolite based heterogeneous catalyst (ZSM‐5) is disclosed. ZSM‐5 in combination with NaNO2 resulted in direct access to nitriles by C−C cleavage of acetone derivatives at more substituted carbon. This cyanide free nitrile synthesis could be promising where one or more cyano‐labile electrophiles are present. Further, the catalyst has been successfully utilized for the synthesis of hydrazides from nitriles. Wide scope with high chemical yields have been achieved. Moreover, ZSM‐5 was recycled and reused several times without significant loss in its activity.

Synthesis of Acyl Hydrazides and Hydrazones from Activated Amides

“…The crude product was purified by silica gel column chromatography (CH 2 Cl 2 /MeOH) to afford the product. 9 According to the general procedure, 1-benzoylpyrrolidin-2-one (189 mg, 1.0 mmol) gave 2a (125.2 mg, 0.92 mmol, 92% yield, white solid) after column chromatography (CH 2 Cl 2 /MeOH, 19:1); mp 113-114 °C. FTIR (neat): 1651, 3310 cm -1 .…”

“…MS (EI): m/z = 150.08 (M + ). 9 According to the general procedure, 1-(4-methylbenzoyl)pyrrolidin-2-one (203 mg, 1.0 mmol) gave 2d (122 mg, 0.81 mmol, 81% yield, light yellow solid) after column chromatography (CH 2 Cl 2 /MeOH, 19:1); mp 115-116 °C. FTIR (neat): 1658, 3480 cm -1 .…”

“…The crude product was purified by silica gel column chromatography (CH 2 Cl 2 /MeOH) to afford the product. 9 According to the general procedure, 1-benzoylpyrrolidin-2-one (189 mg, 1.0 mmol) gave 2a (125. 9 According to the general procedure, 1-(4-methylbenzoyl)pyrrolidin-2-one (203 mg, 1.0 mmol) gave 2d (122 mg, 0.81 mmol, 81% yield, light yellow solid) after column chromatography (CH 2 Cl 2 /MeOH, 19:1); mp 115-116 °C.…”

“…9 According to the general procedure, 1-benzoylpyrrolidin-2-one (189 mg, 1.0 mmol) gave 2a (125. 9 According to the general procedure, 1-(4-methylbenzoyl)pyrrolidin-2-one (203 mg, 1.0 mmol) gave 2d (122 mg, 0.81 mmol, 81% yield, light yellow solid) after column chromatography (CH 2 Cl 2 /MeOH, 19:1); mp 115-116 °C. 7 According to the general procedure, 1-(4-(tert-butyl)benzoyl)pyrrolidin-2-one (245 mg, 1.0 mmol) gave 2e (173 mg, 0.90 mmol, 90% yield, white solid) after column chromatography (CH 2 Cl 2 /MeOH, 19:1); mp 124-125 °C.…”

Synthesis of Acyl Hydrazides from Carboxamides and Hydrazine Hydrate Under Metal‐Free Conditions at Room Temperature

“…Additional references cited within the Supporting Information. [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45] Table 6. Transamidation of different N-tosyl α-ketoamides with benzylamine.…”