Alkyl nitrite reoxidant

Based on their alkyl nitrite technology, Ube developed their own new proeess for the manufacture of dialkyl oxalates by oxidative carbonylation of alcohols. This process is a two-step reaction, in which alkyl nitrite acts as an reoxidant for the palladium catalyst system, similarly to the situation in the preparation of dialkyl carbonates mentioned above. The published patent literature does not make it possible to give exact details about the Ube industrial plant in Yamaguchi, Japan, which has produced several thousands tons of dibutyl oxalate annually since 1978. The first step of the manufacturing process for dialkyl oxalates is the preparation of the gaseous alkyl nitrite from NO, oxygen, and... 

Oxidative Carbonylation of Alcohols. Oxalates and carbonates are formed by the oxidative carbonylation of alcohols. The reaction can be made catal3dic by using PdCl2 and CUCI2 under oxygen in the alcohol. Either oxalate or carbonate is obtained chemoselectively under different conditions (eq 33). Alkyl oxalates are produced commercially using alkyl nitrites as reoxidants (eq 34). ... 

---