Formate, methyl

The slow combustion [93] is measurable at 380 °C, but there is no low temperature mechanism, nor have cool flames been observed [45]. At 560 °C, in a flow system, mixtures of air and methyl formate ignite with explosive violence [47(a)]. The preflame reaction produces methane and methanol. 

---

Most are very sparingly soluble in water note however that methyl formate, methyl oxalate, methyl succinate, methyl and ethyl tartrate, methyl and ethyl citrate are soluble in water. 

Methyl formate. Ethyl formate Methyl acetate Iso-propyl formate Ethyl acetate Methyl propionate "-Propyl formate Iso-propyl acetate Methyl iso-butyrate Iso-butyl formate. Ethyl propionate M-Propyl acetate. Methyl butyrate. ... 

The distillate weighs about 110 g. and contains methyl formate and methylal. If it is placed in a flask provided with a reflux condenser and a solution of 25 g. of sodium hydroxide in 40 ml. of water is added, the methyl formate is liydrolysed to sodium formate and the methylal separates on the surface. The latter may be removed, dried with anhydrous calcium chloride and distilled about 30 g. of methylal, b.p. 37-42°, are obtained. If the aqueous layer is evaporated to diyness, about 25 g. of sodium formate are isolated. 

The conventional electrochemical reduction of carbon dioxide tends to give formic acid as the major product, which can be obtained with a 90% current efficiency using, for example, indium, tin, or mercury cathodes. Being able to convert CO2 initially to formates or formaldehyde is in itself significant. In our direct oxidation liquid feed fuel cell, varied oxygenates such as formaldehyde, formic acid and methyl formate, dimethoxymethane, trimethoxymethane, trioxane, and dimethyl carbonate are all useful fuels. At the same time, they can also be readily reduced further to methyl alcohol by varied chemical or enzymatic processes. 

The Pd-catalyzed reductive carbonylation of methyl acetate with CO and H2 affords acetaldehyde. The net reaction is the formation of acetaldehyde from MeOH, CO, and H2P4]. Methyl formate (109) is converted into AcOH under CO pressure in the presence of Lil and Pd(OAc)2[95],... 

C2F12C12F2 (1,2-dichloro-l, 2-difluoroethane) symmetry elements, 83 CF13C3CN (methyl cyanoacetylene) interstellar, 120 2142X4 (s-tetrazine) fl S3 — X Ag transition, 3971F F1COOCF13 (methyl formate) interstellar, 120... 

The fermentative fixing of CO2 and water to acetic acid by a species of acetobacterium has been patented acetyl coen2yme A is the primary reduction product (62). Different species of clostridia have also been used. Pseudomonads (63) have been patented for the fermentation of certain compounds and their derivatives, eg, methyl formate. These methods have been reviewed (64). The manufacture of acetic acid from CO2 and its dewatering and refining to glacial acid has been discussed (65,66). 

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). 

Formaldehyde is readily reduced to methanol by hydrogen over many metal and metal oxide catalysts. It is oxidized to formic acid or carbon dioxide and water. The Cannizzaro reaction gives formic acid and methanol. Similarly, a vapor-phase Tischenko reaction is catalyzed by copper (34) and boric acid (38) to produce methyl formate ... 

Between 50 and 60% of the formaldehyde is formed by the exothermic reaction (eq. 23) and the remainder by endothermic reaction (eq. 24) with the net result of a reaction exotherm. Carbon monoxide and dioxide, methyl formate, and formic acid are by-products. In addition, there are also physical losses, hquid-phase reactions, and small quantities of methanol in the product, resulting in an overall plant yield of 86—90% (based on methanol). 

Formic acid is currently produced iadustriaHy by three main processes (/) acidolysis of formate salts, which are ia turn by-products of other processes (2) as a coproduct with acetic acid ia the Hquid-phase oxidation of hydrocarbons or (3) carbonylation of methanol to methyl formate, followed either by direct hydrolysis of the ester or by the iatermediacy of formamide. 

The carbonylation of methanol [67-56-1] to methyl formate ia the presence of basic catalysts has been practiced iadustriaHy for many years. Ia older processes for formic acid utili2ing this reactioa, the methyl formate [107-31-3] reacts with ammonia to give formamide [75-12-7] which is hydroly2ed to formic acid ia the preseace of sulfuric acid ... 

Coproductioa of ammonium sulfate is a disadvantage of the formamide route, and it has largely been supplanted by processes based on the direct hydrolysis of methyl formate. If the methanol is recycled to the carbonylation step the stoichiometry corresponds to the production of formic acid by hydration of carbon monoxide, a reaction which is too thermodynamicaHy unfavorable to be carried out directly on an iadustrial scale. 

Other potential processes for production of formic acid that have been patented but not yet commerciali2ed include Hquid-phase oxidation (31) of methanol to methyl formate, and hydrogenation of carbon dioxide (32). The catalytic dehydrogenation of methanol to methyl formate (33) has not yet been adapted for formic acid production. 

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. 

Even though form amide was synthesized as early as 1863 by W. A. Hoffmann from ethyl formate [109-94-4] and ammonia, it only became accessible on a large scale, and thus iadustrially important, after development of high pressure production technology. In the 1990s, form amide is mainly manufactured either by direct synthesis from carbon monoxide and ammonia, or more importandy ia a two-stage process by reaction of methyl formate (from carbon monoxide and methanol) with ammonia. 

However, BASF developed a two-step process (25). After methyl formate [107-31-3] became available in satisfactory yields at high pressure and low temperatures, its conversion to formamide by reaction with ammonia gave a product of improved quaUty and yield in comparison with the earlier direct synthesis. 

Two-Step Process. The significant advantage of the two-step process is that it only requkes commercial-grade methyl formate and ammonia. Thus the cmde product leaving the reactor comprises, in addition to excess starting materials, only low boiling substances, which are easily separated off by distillation. The formamide obtained is of sufficient purity to meet all quaUty requkements without recourse to the costiy overhead distillation that is necessary after the dkect synthesis from carbon monoxide and ammonia. 

The methanol carbonylation is performed ia the presence of a basic catalyst such as sodium methoxide and the product isolated by distillation. In one continuous commercial process (6) the methyl formate and dimethylamine react at 350 kPa (3.46 atm) and from 110 to 120°C to effect a conversion of about 90%. The reaction mixture is then fed to a reactor—stripper operating at about 275 kPa (2.7 atm), where the reaction is completed and DMF and methanol are separated from the lighter by-products. The cmde material is then purified ia a separate distillation column operating at atmospheric pressure. 

A second process is the direct carbonylation of dimethylamine [124-40-3] ia the presence of a basic catalyst or a transition metal. This carbonylation is often mn ia the presence of methanol ia order to help solubilize the catalyst (7), and presumably proceeds through methyl formate as an iatermediate. 

Another method of preparation involving methyl formate has been reported whereia the formate reacts with ammonia and methanol ia the presence of ammonium chloride at 255°C and 2.9 MPa (28.6 atm) (15). In this case, monomethylformamide is present ia considerable quantities as a by-product. 

One report (13) describes the procedure for spinning dry asymmetric ceUulose acetate fiber with a bore skin. Such fibers are spun in a modified dry-spinning process in which a volatile Uquid (methyl formate) is used as the ceUulose acetate solvent. The bore coagulating Uquid is isopropyl alcohol, which is subsequentiy removed. The advantages of these dry fibers over most ceUulose acetate membranes are that they can be stored dry, they are wet-dry reversible, they can be sterilized and packed dry, and they are ready for use without removal of preservatives. 

---