Alkoxycarbonylation of Industrially Relevant Anilines Using Zn₄O(O₂CCH₃)₆ as Catalyst

Abstract

An efficient procedure is presented for the alkoxycarbonylation of industrially important amines using environmentally friendly alkyl carbonates as reagents and Zn4O(OAc)6 as catalyst. Aromatic amines in particular (thirteen examples) consistently give high yields (up to 98%), regardless of the electronic properties of the substituents or the ring substitution pattern.

Methyl N-phenyl carbamate synthesis over Zn/Al/Ce mixed oxide derived from hydrotalcite-like precursors

“…So far, various metal salts including Zn, 11,[19][20][21][22] Pb, 8,11 Sn, 23 Na, 24 etc. had been successfully employed as homogeneous catalysts for the synthesis of MPC and other carbamates.…”

One‐Pot Preparation of Methyl N‐Phenyl Carbamate and Zn(OAc)2/SiO2 Catalyst with Enhanced Stability

“…And the diffraction peaks appearing at 2θ values of 13.2°, 33.4°, 59.4° can be assigned to the (002), (100) and (110) reflection of Zn 5 (OH) 8 (OAc) 2 ⋅2H 2 O . The formation of Zn 4 O(OAc) 6 is due to the reaction of Zn(OAc) 2 and DMC, and Zn 4 O(OAc) 6 exhibits better catalytic performance in the reaction between aniline and DMC . The reaction between Zn 4 O(OAc) 6 and methanol caused the formation of Zn 5 (OH) 8 (OAc) 2 ⋅2H 2 O.…”

Important Green Chemistry and Catalysis: Non‐phosgene Syntheses of Isocyanates – Thermal Cracking Way

“…Besides, aromatic amine substrates consistently gave high yields (up to 98%) with DMC or DEC using Zn 4 O(OAc) 6 as a catalyst, regardless of the electronic properties of the substituents or the ring substitution pattern. [32] The general mechanism for the methoxycarbonylation between DMC and diamines was proposed for the basic catalytic system (Scheme 3). First, anion acted as a nucleophile taking a hydrogen proton from amino in diamines to generate the nitranion.…”