Formic acid: esterification

Other mechanisms for the synthesis of alkylformates, not via formic acid esterification, are possible. Hydrogenation of C02 to CO, followed by catalytic car-bonylation of alcohol, would produce alkyl formate. This mechanism seems more likely for the anionic metal carbonyls because they are known catalysts for alcohol carbonylation. However, Darensbourg and colleagues [64, 74, 85] showed... 

Formic acid exhibits many of the typical chemical properties of the aHphatic carboxyHc acids, eg, esterification and amidation, but, as is common for the first member of an homologous series, there are distinctive differences in properties between formic acid and its higher homologues. The smaller inductive effect of hydrogen in comparison to an alkyl group leads, for example, to formic acid = 3.74) being a considerably stronger acid than acetic acid... 

Formic acid forms esters with primary, secondary, and tertiary alcohols. The high acidity of formic acid makes use of the usual mineral acid catalysts unnecessary in simple esterifications (17). Formic acid reacts with most amines to form formylamino compounds. With certain diamines imida2ole formation occurs, a reaction that has synthetic utiHty (18) ... 

Reaction of 1-pentanol with propionic acid provides 1-pentyl propionate [624-54-4] a new coatings solvent for automotive refinish and OEM paints, apphances, and for higher-solids systems (37). The esterification of 1-pentanol with formic acid to 1-pentyl formate [638-49-3] is conducted by concomitant removal of by-product water by a2eotropic distillation with diethyl ether (38). 

Consider the esterification of ethyl alcohol with formic acid to give ethyl formate (and water) in a mixed alcohol-water solvent, such that the alcohol and water are present in large excess. Assume that this is pseudo-first-order in both esterification (forward) and hydrolysis (reverse) directions ... 

The gas-phase esterification reaction has not been observed with formic acid. The reason for this behaviour has been explained on the basis of the proton affinities of the acid and alcohols as indicated in (73) and (74). Thus,... 

The methyl ester has also been obtained by esterification of cyclopentanecarboxylic acid.8 The acid, in turn, has been prepared by the Favorskii rearrangement,6 7 9-11 by the reaction of cyclopentyl Grignard reagent with carbon dioxide,12 by the carbonylation of cyclopentyl alcohol with nickel carbonyl13 or with formic acid in the presence of sulfuric acid,14 and by the hydrogenation of cyclopentene-1-carboxylic acid prepared from ethyl cyclopentanone-2-carboxylate 15 or from cyclopentanone cyanohydrin.16... 

Carbonyl)chlorohydridotris(triphenylphosphine)ruthenium(II) was used as a catalyst in the transfer hydrogenation of benzaldehyde with formic acid as a hydrogen source. Under these conditions, the reduction ofbenzaldehyde to benzyl alcohol is accompanied by esterification of the alcohol with the excess of formic acid to provide benzyl formate (Scheme 4.16). In this microwave-assisted reaction, the catalyst displayed improved turnover rates compared to the thermal reaction (280 vs. 6700 turnovers/h), thus leading to shorter reaction times36. 

Low Molecular Weight Acids. The method devised for analyzing free fatty acids will resolve Ci to CB acids as shown in Figure 1, except for formic and propionic acids which are poorly resolved under the conditions used. Propionic acid, however, has been shown to be absent in all mixtures of oxidation products, and thus it presents no problem in this study. Acetophenone, shown in the chromatogram, was a convenient and reliable internal standard for this technique. Detection by thermal conductivity was selected because the flame ionization detector is insensitive to formic acid and, as noted, the high volatility of methyl formate and acetate precludes their quantitative determination by reasonably simple esterification procedures. 

Esters of formic acid (Expt 5.143) are most simply prepared from the alcohol and an excess of formic acid, which, being a comparatively strong acid, does not require the use of added mineral acid to catalyse the esterification reaction. Sulphuric acid in any case should not be added since it causes the decomposition of formic acid to carbon monoxide. 

A-7. Draw the structure of the tetrahedral intermediate in the esterification of formic acid with 1-butanol. 

Changes in the amount of solvent will not affect the equilibrium in any system where the number of dissolved particles of reactants is the same as the dissolved particles of products. For example, the esterification of methyl alcohol with formic acid in an inert solvent, as below, does not respond to concentration changes. Note that, if the solvent is not water, then H2O must be in the K expression. 

Dimethylformamide was suggested for the GC detection of microgram amounts of formic acid [182]. After esterification of acids with diazomethane the sample was treated with a dimethylamine—water mixture (1 2). Dimethylformamide was thus produced from formic acid ester, while other acids present were analysed as methyl esters. 

The formylation method is based on the determination of the ratio of the extent of esterification of cellulose by formic acid after a given time interval to that of soluble starch for the same... 

This product comes from the esterification reaction of formic acid with methanol according to the following reaction ... 

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