Formamide from methyl formate

Acid Amides can be produced by acylating ammonia with esters, acid anhydrides, or the acids themselves (above 100 °C) an important product is formamide from methyl formate. Alternatively acid amides can be synthesized by reacting acid halides with ammonia. Catalytic hydrogenation converts the acid amides to primary amines. Ammonia and aldehydes or ketones are the basis for different stable products. With formaldehyde hexamethylenetetramine (urotropine) is obtained with acetaldehyde, ammono acetaldehyde with benzaldehyde, hydrobenzamide with ethylene and propylene oxides, aqueous ammonia reacts to form ethanol- or propanolamine. 

Formamide chemistry. Production of formamide from methyl formate is accomplished by reacting anhydrous ammonia with methyl formate at 65°C (150 F) and 13 bars (190 psig). 

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. 

In Ihe 1990s. formamide is mainly manufactured cither by direct synthesis from carbon monoxide and ammonia, or more importantly in a two-stage process by reaction of methyl formate (front carbon monoxide and methanol) with ammonia. 

Fig. 7. Direction and magnitude of the total dipole moment in methyl formate (Curl, 1959) and in formamide (Kurland and Wilson, 1957) (from Poland and Scheraga, 1967).

BASF has obtained European patent 1,110,913, which describes HCN production from gaseous formamide in a fluidized bed. Elements of the commercialized formamide process are included in a methyl methacrylate process that Mitsubishi Gas Chemical started up in 1997. The formamide is obtained by reacting hydroxyisobutyramide with methyl formate. Therefore the external requirements for HCN are reduced to the replacement of... 

Formic acid can be derived from acidolysis of formamide, such as the reaction of sulfuric acid with formamide. The manufacture of formamide, however, is produced by ammoniation methyl formate [16J ... 

Commercialization of the carbonylation technology for producing methyl formate and hydrolysis to formic acid with the flexibility to manufacture formamide simultaneously from the same intermediate was fortuitous. It addressed the problem of reduced formic acid supply and the changes taking place in the markets for formic acid and formamide. In... 

Methyl formate is the product from the esterification reaction of methanol and formic acid. The solvent is readily hydrolyzed in water, a reaction which is accelerated by alkaline conditions. The solvent is used in the manufacture of formamide and N,N-dimethylformamide as well as a reactive intermediate in organic synthesis. Methyl formate is used in special coating formulations for quick drying films. The solvent is useful in spray applications because of its high vapor pressure, low viscosity, and low surface tension which enables quick release of entrapped air and a blemish free film. Methyl formate is used as a component in certain blowing agents to produce synthetic rubber foams. 

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-... 

To avoid any complications caused by the intermolecular association, Goodman (78) reinvestigated the optical rotation of the peptides in dimethyl formamide, since in this medium the specific rotation is independent of concentration. From the latter study it was concluded that at 25° C the spontaneous helix formation of poly-y-methyl-L-glutamate in dimethyl formamide is occurring at the critical range of 7—9 units. Extension of these studies (73 b, 79) led to a better understanding of temperature and solvent effects upon the helix-coil transition of oligomeric polypeptides. 

First, 1 2 metal complexes of (mainly mono-) azo dyes, without sulfonic or carboxylic acid groups, and trivalent metals (see Section 3.11). The metals are preferably chromium and cobalt nickel, manganese, iron, or aluminum are of lesser importance. Diazo components are mainly chloro- and nitroaminophenols or amino-phenol sulfonamides coupling components are (3-naphthol, resorcinol, and 1-phe-nyl-3-methyl-5-pyrazolone. Formation of a complex from an azo dye and a metal salt generally takes place in the presence of organic solvents, such as alcohols, pyridine, or formamide. An example is C.I. Solvent Red 8, 12715 [33270-70-1] (1). 

Umbellamine possesses a phenolic hydroxy-group (bathochromic shift of the long wavelength u.v. maximum from 295 to 309 nm in alkali formation of an 0-acetyl derivative and a methyl ether (236) with diazomethane in dimethyl formamide-ether), which must be in the unknown component. This half of umbellamine (235) appears from i.r. and n.m.r. evidence, and the formation of only an 0-acetyl derivative, to be an N-methylindoline. 

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... 

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