Formic acid from methyl formate

Formic acid, methyl formate, and CO were detected when photoreduction was performed in Ti silicalite molecular sieve using methanol as electron donor.173 Mechanistic studies with labeled compounds indicated, however, that CO originates from secondary photolysis of formic acid, whereas methyl formate emerges mainly from the Tishchenko reaction of formaldehyde, the initial oxidation product of methanol. 

BASF commissioned a very large carbonylation plant in Ludwigshafen, Germany for the production of formic acid through methyl formate intermediate. Eventually, a market for dimethylformamide (DMF) developed which equaled the previous market for formic acid. The carbonylation process for methyl formate offered the flexibility to produce DMF instead of formic acid. BASF announced that the capacity of the Ludwigshafen formic acid plant will be increased from 100,000 to 180,000 metric tons per year. 

The Leuckart-Wallach reaction is the oldest method of reductive amination of carbonyl compounds. It makes use of formamide, formic acid or ammonium formate at high temperature. The final product is a formamide derivative, which can be converted to an amine by reduction or hydrolysis. The method has been applied to the preparation of 1,2-diamines with a norbornane framework, which are interesting rigid analogues of 1,2-diaminocyclohexanes. As a matter of fact, starting from N-acetyl-2-oxo-l-norbornylamine 222, the diamide 223 was obtained with excellent diastereoselectivity and then converted to the M-methyl-N -ethyl derivative 224 by reduction with borane [ 104] (Scheme 34). On the other hand, when the reac-... 

The mjz = 60 ion current (Fig. 13.7c), which results from methyl formate and hence is indicative of formic acid formation, equally increases in a pronounced step after raising the potential, and then decays slowly with time. (The higher noise in these data is due to the very low concentration of methyl formate species.)... 

Figure 5.6 Alcohols, aldehydes, ketones and acids 15, ethylene glycol 16, vinyl alcohol 17, acetaldehyde 18, formaldehyde 19, glyoxal 20, propionaldehyde 21, propionaldehyde 22, acetone 23, ketene 24, formic acid 25, acetic acid 26, methyl formate. (Reproduced from Guillemin et at. 2004 by permission of Elsevier)...

From Methyl Formate By chlorination of methyl formate, obtained from methyl alcohol and formic acid according to the equation ... 

Several organic species (formaldehyde, formic acid, methanol, methyl-peroxide, etc.) are transferred from the gas to the aqueous-phase and contribute to the atmospheric aqueous-phase reaction system (Graedel and Weschler, 1981). The complex formation by S(IV) and aldehydes has already been discussed. Formaldehyde is very soluble in water because it hydrates to its diol form, methylene glycol ... 

Secondary1005,1031-1033 and tertiary amines1021,1029 1033-1035 are obtained analogously from ketones, by using the amine formate or jV-alkyl- or N,N-dialkyl-formamide in place of ammonia (or ammonium formate) or formamide. In this way iV-methyl- and iV,iV-dimethyl-cyclohexylamine are obtained from cyclohexanone and formic acid by methyl- and dimethyl-formamide, respectively, whereas formamide and formic acid give cyclohexylamine.1033... 

Formic acid is produced in nature (biofuels), commercially, and as a byproduct of commercial synthesis. Renewable, carbon neutral, synthesis processes are also under investigation to form formic acid from CO2 [13]. Reagent grade formic acid requires further purification to remove ppm levels of common substituent impurities, i.e., methyl formate, methanol, and acetic acid [14]. 

Production of methyl formate from methanol also leads to the potential produetion of formic acid from methanol [87]. Formic acid is produced commercially as a side produet of the liquid-phase oxidation of w-butane to acetic acid. It has been suggested, however, that new formie acid capacity will best be obtained by hydrolysis of methyl formate because of raw material costs [87]. The methyl formate could be produeed by either the carbonylation or dehydration of methanol according to the technologies discussed previously. 

The Seientific Design/Bethlehem Steel process for formic acid production is based on the methanol carbonylation route to methyl formate [87,98,99]. The methyl formate is subsequently hydrolyzed and the products separated to yield pure formic acid and methanol The methanol is recycled to the carbonylation reactor, and overall methanol usage is about 2 kg per 100 kg product [99]. The reaction of methyl formate and water to form formic acid is an equilibrium reaction performed at 0.3 MPa and 80°C, with a residence time of about Ih [87]. The overall process stoichiometry yields formic acid from CO and H2q according to the reactions... 

Hydrolysis (Ion exchange resin) formic acid and methanol from methyl formate lactic acid and methanol from methyl lactate... 

Anhydrous, monomeric formaldehyde is not available commercially. The pure, dry gas is relatively stable at 80—100°C but slowly polymerizes at lower temperatures. Traces of polar impurities such as acids, alkahes, and water greatly accelerate the polymerization. When Hquid formaldehyde is warmed to room temperature in a sealed ampul, it polymerizes rapidly with evolution of heat (63 kj /mol or 15.05 kcal/mol). Uncatalyzed decomposition is very slow below 300°C extrapolation of kinetic data (32) to 400°C indicates that the rate of decomposition is ca 0.44%/min at 101 kPa (1 atm). The main products ate CO and H2. Metals such as platinum (33), copper (34), and chromia and alumina (35) also catalyze the formation of methanol, methyl formate, formic acid, carbon dioxide, and methane. Trace levels of formaldehyde found in urban atmospheres are readily photo-oxidized to carbon dioxide the half-life ranges from 35—50 minutes (36). 

World installed capacity for formic acid is around 330,000 t/yr. Around 60% of the production is based on methyl formate. Of the remainder, about 60% comes from Hquid-phase oxidation and 40% from formate salt-based processes. The largest single producer is BASF, which operates a 100,000 t/yr plant at Ludwigshafen in Germany. The only significant U.S. producer of formic acid is Hoechst-Celanese, which operates a butane oxidation process. 

Methyl formate and propylene oxide have close boiling poiats, making separation by distillation difficult. Methyl formate is removed from propylene oxide by hydrolysis with an aqueous base and glycerol, followed by phase separation and distillation (152,153). Methyl formate may be hydrolyzed to methanol and formic acid by contacting the propylene oxide stream with a basic ion-exchange resia. Methanol and formic acid are removed by extractive distillation (154). 

Several examples exist for the conversion of 5-aminothiazoles into the corresponding thiazolopyrimidines. Shaw and Butler report the formation of aminothiazole thiocarboxyamide 27 from the thioamide 26 and carbon disulphide using Cook and Heilbron s procedure. Methylation of 27 gave carboxythioimidate 28 which then reacted with sodium hydroxide to give amino-nitrile 29, and with formic acid and acetic anhydride to give the thiazolopyrimidine 30. 

The common name of an ester consists of two words. The first word (methyl, ethyl,...) is derived from that of the alcohol the second word (formate, acetate,...) is the name of the acid with the -ic suffix replaced by -ate. Thus ethyl formate (Table 22.4) is made from ethyl alcohol and formic acid ... 

Figure 4. (a) Selected residues from the combining site of antibody 5C8 com-plexed to piperidine-A/-oxide hapten 4, as determined by X-ray crystallography.1151 The linker portion of the hapten has been truncated to a methyl for comparison with the theozyme complex, (b) The formate/formic acid theozyme complexed to the model of hapten 4, as optimized through quantum mechanical calculations.161... 

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