Acetic formic anhydride alkylation reactions

The hydroxyquinoline (39-2) provides the starting material for a quinolone that incorporates a hydrazine function. Reaction of (39-2) with 2,4-dintrophenyl O-hydroxylamine ether (41-1) in the presence of potassium carbonate leads to a scission of the weak N-O hydroxylamine bond by the transient anion from the quinolone the excellent leaving character of 2,4-dinitrophenoxide adds the driving force for the overall reaction, resulting in alkylation on nitrogen to form the hydrazine (41-2). The primary amine is then converted to the formamide (41-3) by reaction with the mixed acetic-formic anhydride. Alkylation of that intermediate with methyl iodide followed by removal of the formamide affords the monomethylated derivative (41-4). Chlorine at the 7 position is then displaced by A-methylpiperazine and the product saponified. There is thus obtained amifloxacin (41-6) [48]. 

Formylation of amines and alcohols. Behai,8 discoverer of the reagent, found that it reacts unidirectionally with simple alcohols to produce alkyl formates free from acetates. Hurd et al. J found that acetic-formic anhydride (prepared from formic acid and ketene) reacts quantitatively with aniline to give formanilide. Another study10 established that acetic-formic anhydride mixes endothermally with 2-nitro-2-methyl-l-propanol, exothermally with 2-nitro-2-methyl-l,3-propanediol, and displays no appreciable temperature effect with either 2-nitro-l-butanol or tris-(hydroxymethyl)-nitromethane. Formic esters are favored by avoiding a high reaction temperature and by not using sulfuric acid as catalyst. The mixed anhydride has been used for the preparation of formyl fluoride.11... 

An efficient one-pot procedure for the iV-monomethylation of primary amines has been reported the method involves formylation with acetic formic anhydride followed by borane methyl sulphide reduction. The reaction sequence is applicable to even very weakly basic and sterically hindered amines, and the products are uncontaminated by over-alkylation. In addition, the transition-metal-catalysed j V-monoalkylation of amines by alcohols has been previously reported (c/. Vol. 6, p. 198) as a method to overcome problems associated with over-alkylation. A similar procedure for the preparation of unsymmetrical secondary (and tertiary) amines utilises a ruthenium catalyst, and is particularly suitable for the synthesis of cyclic amines. ... 

Pimentel et al. (2010) studied the OH-radical-initiated oxidation of isopropyl formate in the presence of NOx and reported the following products (molar yields) acetic formic anhydride (43%), acetone (43%), and HCOOH (15-20%). From the observed formation of CH2O in the chlorine-atom-initiated oxidation of iso-propyl formate, Pimentel et al. (2010) deduced that the fate of 0CH2(CH3)CH0C(0)H alkoxy radicals is decomposition (rather than reaction with O2). The resulting alkyl radical (CH3)CH0C(0)H is converted into the alkoxy radical 0(CH3)CH0C(0)H which then decomposes via... 

Paint and varnish manufacturing Resin manufacturing closed reaction vessel Varnish cooldng-open or closed vessels Solvent thinning Acrolein, other aldehydes and fatty acids (odors), phthalic anhydride (sublimed) Ketones, fatty acids, formic acids, acetic acid, glycerine, acrolein, other aldehydes, phenols and terpenes from tall oils, hydrogen sulfide, alkyl sulfide, butyl mercaptan, and thiofen (odors) Olefins, branched-chain aromatics and ketones (odors), solvents Exhaust systems with scrubbers and fume burners Exhaust system with scrubbers and fume burners close-fitting hoods required for open kettles Exhaust system with fume burners... 

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