A New Route to Lactam Precursors from Cycloalkanes: Direct Production of Nitrosocycloalkanes or Cycloalkanone Oximes by Using tert‐Butyl Nitrite and N‐Hydroxyphthalimide

Abstract

Clean and selective: Nitrosation and oximation of cycloalkanes was achieved by treating them with tBuONO under Ar in the presence of a catalytic amount of N‐hydroxyphthalimide (see scheme). The novel, clean nitrosation procedure uses halogen‐free, relatively mild reaction conditions and results in good product selectivity (almost no organic byproducts) and high recovery of the catalyst.

Liquid-phase oxidation of toluene by molecular oxygen over copper manganese oxides

“…[1] For example, selective catalytic oxidation of methylbenzenes to corresponding alcohols, aldehydes and carboxylic acid by molecular oxygen is of great economic and industrial importance [1,2]. For instance, industrial grade benzoic acid is used as a chemical intermediate and as a diverting agent in crude-oil recovery applications, in addition, the oxidation of toluene to benzoic acid with O 2 is a key step for synthesizing e-caprolactamin in Snia-Viscosa process [3,4]. Presently, the principal industrial production of benzoic acid via oxidation of toluene employ homogeneous cobalt catalysts in an air pressurized aqueous acetic acid mixture in the presence of Mn ions and bromide promoters [5].…”

Liquid-phase oxidation of toluene by molecular oxygen over copper manganese oxides

“…For example, selective catalytic oxidation of methylbenzenes to corresponding alcohols, aldehydes and carboxylic acid by molecular oxygen is of great economic and industrial importance [1,2]. For instance, industrial grade benzoic acid is used as a chemical intermediate and as a diverting agent in crude-oil recovery applications, in addition, the oxidation of toluene to benzoic acid with O 2 is a key step for synthesizing e-caprolactamin in Snia-Viscosa process [3,4]. Presently, the principal industrial production of benzoic acid via oxidation of toluene employ homogeneous cobalt catalysts in an air pressurized aqueous acetic acid mixture in the presence of Mn ions and bromide promoters [5].…”

New Strategies for Sulfate-Free Synthesis of Lactams from Cycloalkanes Using NHPI as a Key Catalyst

“…This shows that the concomitant generation of NO and PINO from tBuONO and NHPI is important to obtain 2e. 8 As the nitrosation of le with t-BuONO in the presence of NHPI was considerably affected by the initial pressure, the nitrosation of la and le was examined under varying Ar pressures (Figure 1 (a) and (b)) by freezing the reaction mixture and degassed in vacuo.…”