Melamine trisulfonic acid-catalyzed N-formylation of amines under solvent-free conditions

Formylation of Amines

“…In a procedure reported by Yang, melaminetrisulfonic acid (MTSA, 7 ) catalyzed formylation with formic acid in solvent-free conditions (Scheme 9) [32]. The amine, two equivalents of formic acid, and 3 mol% 7 were stirred at 60 °C until completion of the reaction (40–90 min).…”

Acidic ionic liquid immobilized on nanoporous Na+-montmorillonite as an efficient and reusable catalyst for the formylation of amines and alcohols

“…Comparison shows that aliphatic amines were reacted faster than aromatic ones (Table 3, entries 11 and 14 versus entry 1). Furthermore, this method was successfully applied for the formylation of aliphatic alcohols with formic acid under mild reaction conditions and the corresponding O-formylated products were obtained in high yields (Table 3, entries [15][16][17][18][19][20][21][22]. It is known that these reactions give the products in longer reaction times than formylation of amines.…”

“…Among various procedures that have been developed and documented for the preparation of formamide derivatives [9,10], the reaction between amines and formic acid is the simplest and most important approach. For this purpose, a variety of catalysts and reagents have been used to facilitate this reaction [11][12][13][14][15][16][17][18]. Although these procedures provide an improvement in the synthesis of these types of compounds, many of them suffer from disadvantages such as long reaction times, harsh reaction conditions, the need for excess amounts of the reagent, thermal instability, by-products formation, use of toxic reagents and non-recoverability of the catalyst.…”

The immobilized NaHSO4·H2O on activated charcoal: a highly efficient promoter system for N-formylation of amines with ethyl formate

“…1 Formamides as important class of amine derivatives have been used widely in the synthesis of pharmaceutically valuable compounds such as fluoroquinolines, 2 1-arylimidazole-5-carboxylates, 3 1-formyl-1,2-dihydroquinolines 4 nitrogen bridged heterocyles, 5 oxazilidones, 6 cancer chemotherapeutic agents, 7 fungicides, 3,8 preparation of isocyanates, 9 foramidines, 10 and nitriles, 11 the Vilsmeier-Haake formylation reaction, 12 allylation 13 and hydrosilylation 14 of carbonyl compounds. Due to wide synthetic and biological applications of formamides, a number of methods and reagents such as Cl3CCHO, 15 CH(OEt)3, 16 NaOEt/CHCl3, 17 HCO2NH4, 18 HCO2NH4/nano Fe3O4/PEG-400, 19 2,2,2-trifluoroethyl formate, 20 phenyl formate, 21 pentafluorophenyl formate, 22 acetic formic anhydride, 23 and KF-Al2O3/CHCl3, 24 formic acid in the presence of HCO2Na, 25 NH2OH•HCl, 26 I2, 27 DCC, 28 EDCI, 29 ZnCl2, 30 In, 31 ZnO, 32 TiO2-P25 (TiO2-SO4 2-) 33 nanoceria, 34 Zr-MCM-41, 35 NiFe2O4@SiO2-PPA, 36 γ-Fe2O3@HAp-SO3H, 37 WO4(SO3H)2, 38 Fe(III)-exchanged sepiolite, 39 2-chloro-4,6-dimethoxy-1,3,5-triazine, 40 melamine trisulfonic acid, 41 thiamine hydrochloride, 42 TBD-based ionic liquids,…”