Catalytic methoxycarbonylation of 1,6-hexanediamine with dimethyl carbonate to dimethylhexane-1,6-dicarbamate using Bi(NO3)3

Highly selective methoxycarbonylation of aliphatic diamines with methyl phenyl carbonate to the corresponding methyl N-alkyl dicarbamates

“…Therefore, DMC is usually used as the dialkyl carbonate in Reaction 7, reacting with alkylamines in the presence of metal salts (Lewis acid catalysts [3,4]) such as AlCl 3 and FeCl 3 , or base catalysts such as CH 3 ONa [5]. We also have reported that various metal salts, including Pb(OAc) 2 [6] and Bi(NO 3 ) 3 [7], homogeneously catalyze the reactions of aliphatic or aromatic amines, such as 1,6-hexanediamine (HDA), with www.elsevier.com/locate/apcata Applied Catalysis A: General 289 (2005) 174-178 DMC to produce the corresponding methyl N-alkyl carbamates. Therefore, the synthetic method expressed by Reaction 7 would be a desirable route if the rate of Nalkylcarbamate formation can be increased.…”

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

“…The typical aliphatic diamine, 1,6-hexanediamine (HDA) could be selected as the model substrate to illuminate this protocol as shown in Table 1, and good results were obtained over the following catalysts, such as MgO/ZrO 2 , [14] Zn/SiO 2 , [15] Bi(NO 3 ) 3 , [16] Sc(OTf) 3 , [17] AlSBA-15, [18] Mn(OAc) 2 , [19] ZnAlPO 4 , [20] MIm(CH 2 ) 4 SO 3 HtfO IL, [21] CH 3 COONa [22] and NaOCH 3 . [23] In this process, the reaction could proceed at very mild conditions (≤80 ℃), and 50%-98% yield of dimethylhexane-1,6-dicarbamate (MHDC) could be obtained.…”

“…However, some reaction solvents (such as CH 3 OH), long reaction time, relatively high temperature, high molar ratios of DMC to HDA or separation problems of homogeneous catalysts are reported in most of these studies. [14][15][16][17][18][19][20][21][22][23] In our recent work, a new catalyst based on alkali metal salt of 3-amino-1,2,4-triazole potassium (KATriz) was developed, which was prepared by simple neutralization of equimolar 3-amino-1,2,4-triazole and KOH. The results showed that KATriz could efficiently improve the MHDC synthesis from HDA and DMC at ambient temperature (100% HDA conversion with ca.…”

Research Progress on Application of Organic Diamines and Their Derivatives

“…The carbamatesare synthesized from diamines and DMC. It was reported [29] that dimethylhexane-1,6-dicarbamate could be synthesized from 1,6-hexanediamine with dimethyl carbonate. This reaction was catalyzed by Bi(NO 3 ) 3 in a yield of 84 % at 353K in 18 h (see Scheme 4).…”