2,2,2-Trifluoroethyl Formate:  A Versatile and Selective Reagent for the Formylation of Alcohols, Amines, andN-Hydroxylamines

Abstract

[reaction: see text] Treatment of a variety of alcohols, amines, and N-hydroxylamines with 2,2,2-trifluoroethyl formate gave the corresponding formylated adducts in high yields.

Guanidine derived ionic liquids: catalyst free medium for N-formylation of amines

“…The physical data (mp, IR, NMR) of known compounds were found to be identical with those reported in the literature. [11][12][13][14] Spectra data for selected products: 2b. 1 …”

“…Acetic formic anhydride 6 continues to be the most widely used formylating reagent, but it is sensitive to atmospheric moisture and cannot be stored due to decomposition to acetic acid and carbon monoxide. Many other useful formylation reagents have been reported such as chloral, 7 activated formic acid using DCC 8 or EDCI, 9 activated formic esters, 10 ammonium formate, 11 2,2,2-trifluoroethyl formate 12 and aq. 85%…”

Synthesis of N-Formylation of Amines using Various Ion Exchanged Forms of Zeolite-A as Catalysts

“…The main application of Formamides is to use in the synthesis of Formamidines [7] and in peptide synthesis acts as useful amino protecting group [8]. Various methods have been previously reported in literature for the synthesis of N-Formylation of amines and various catalysts were used for this reaction, such as acetic formic anhydride [9], activated formic acid using Dicyclohexylcarbodiimide [10] or,1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide [11], chloral [12], activated formic esters [13], ammonium formate [14], 2,2,2-trifluoroethyl formate [15], ZnO [16], PEG-400 [17], Formic acid-ZnCl 2 [18], polyvinyl alcohol [19], Na + -montmorillonite [20], Nano Cerium Oxide [21], Natrolite zeolite [22], HCOOH Sodium formate [17], Silica-bonded N-Propyl Sulfamic acid [23], TiCl 3 (OTF) [24], CDMT [25], KF-AL 2 O 3 [26], Formic acid in Toluene [18], Formic acid in polyethylene glycol [17], Natural HEU Zeolite [27] . However above listed methods have some limitations such as long reaction time, formation of undesirable byproducts, hygroscopicity expensive reagents, and thermal instability of the reagents, and high temperature for reaction completion.…”

Formylation and acetylation of alcohols using Amberlyst-15®as a recyclable heterogeneous catalyst

“…O-formylation is the most common process for alcohol group protection. Some of the explored methods showed the potential utility but suffer from drawbacks such as harsh reaction environment, poor yields of the desired product, the formation of side products, and longer reaction time (6). Easily accessible formylating agents such as formic acid are hazardous for reaction and may lead to formation of undesirable products whereas the anhydride and the acid chloride of formic acid are highly unstable at room temperature.…”