Methyl formamide, oxidation

Dimethylformamide is also a suitable solvent [50], it has, however, the disadvantage of being oxidized at fairly low potentials to A-acyloxy-iV-methyl formamide [51]. The influence of the composition of the ternary system water/methanol/dimethyl-formamide on the material and current yield has been systematically studied in the electrolysis of co-acetoxy or -acetamido substituted carboxylates [32]. Acetonitrile can also be used, when some water is.added [52]. The influence of various solvents on the ratio of Kolbe to non-Kolbe products is shown in Table 1 [53]. 

The reaction is highly influenced by the solvent therefore among others NMP, DMF, dioxane, methyl formamide, dimethyl acetamide and tetramethyl urea were tested. The best results were achieved in DMF and tetramethyl urea. Using these solvents and PdCl2/CuCl or RhCl3/FeCl3 [27] as catalysts, oxidations of 10-undecenoic acid methylester, 9-decenoic acid methylester and 13-tetradecenoic acid methylester were carried out on a preparative scale (Table 2). 

C7H7CIO2S Combustible liquid (flash point 204°F/96°C oc). Reacts with moisture in air, forming/r-toluenesulfonic acid and hydrogen chloride fumes. Reacts with water, steam, forming hydrochloric acid and p-toluenesulfonic acid fumes. Violent reaction with strong bases, strong oxidizers, dimethyl sulfoxide, methyl formamide. Aqueous solution incompatible with sulfuric acid, caustics, ammonia, aliphatic amines, alkanolamines, isocyanates, alkylene oxides, epichlorohydrin. Increases the explosive sensitivity of nitromethane. 

BENZENE SULFOCHLORIDE (98-09-9) Combustible liquid (flash point 266°F/130°C). Contact with water, steam, or water solutions forms hydrochloric, chlorosul-fonic, and benzenesulfonic acids. Aqueous solutions of this chemical are strong acids and react violently with bases. Violent reaction with strong oxidizers, dimethyl sulfoxide, and methyl formamide. Incompatible with ammonia, aliphatic amines, alkylene oxides, epichlorohydrin, isocyanates, water solutions. Attacks metals in the presence of moisture. 

The reaction of monomethylamine with carbon monoxide and subsequent oxidation of methyl formamide is illustrated in Eqs. (8) and (9) ... 

A solution of 1,3,5-trinitrobenzene in N-methylformamide was subjected to electrolysis at —0.70 V (Path A, Scheme 18). The controlled-potential electrolysis was stopped after a passage of one electron per each molecule. The formed anion-radical species of 1,3,5-trinitrobenzene were allowed to react with N-methyl-formamide. Under the used experimental conditions the o -complexes were the only species present in the reaction mixtures. Exhaustive oxidative controlled-potential electrolysis at 1.30 V gave A-methyl-iV-(2,4,6-trinitrophenyl)formamide (Sn product) in good yield (80%). Without a preliminary reductive electrolysis (Path B, Scheme 18), the same type of o -complexes proved to be formed, and after exhaustive oxidative controlled-potential electrolysis at 1.30 V, A-methyl-iV-(2,4,6-trinitrophenyl)formamide (Sn product) was obtained in 20% yield. 

The hydrolyzed oxidant AgOH" is the active species in reaction " with AT-methyl formamide derivatives in strong HCIO4 media. Initial reaction involves C-N bond scission [equation (17)] with formation of a metal-bound C-centered radical which is further oxidized to give CO2. 

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. 

Tertiary Af-alkyl-Al,(V-bis(2-fluoro-2,2-dinitroethyl)atnines containing 77-methylene or A -methyl groups are oxidized by chromium trioxide in acetic acid to Af,Al-bis(2-fluoro-2,2-dimtroethyl)formamides [ 5] (equation 82)... 

Benzenediamine (199) and C-(2-chloro-2-phenylacetyl)formamide (200) gave 3-phenyl-3,4-dihydro-2-quinoxalinecarboxamide (201), formulated as its 1,4-dihydro tautomer (EtOH, reflux, 6 h 56%) in contrast, the same substrate (199) with methyl C-(2-chloro-2-phenylacetyl)formate cyanohydrin (202) gave methyl 3-phenyl-2-quinoxalinecarboxylate (203), presumably by aerial oxidation of a dihydro precursor (MeCN, reflux, 12 h 7%). ... 

Spirothiopyrans 45b including a benzopyrylium ring have been prepared in one step by condensation of 2-aminovinyl-3-formyl chromone-4-thione 47 with 1,2,3,3-tetramethylindolinium salts in ethanol (Scheme 25).90 The precursor 47 is prepared from 3-carboxymethylene-2-methyl-chromone-4-thione 48. First, oxidation of 48 with pyridinium dichromate in CH2C12, and then condensation with dimethyl formamide dimethyl acetal in benzene gave compound 47. 

Tetraphenylporphin (H2TPP) was prepared from pyrrole and benzaldehyde (25). The tetraphenylchlorin contamination was oxidized by use of 2,3-dichloro-5,6-dicyano-p-benzoquinone (26). Octaethylporphin (H2-OEP)was prepared by the method of Paine et al.(27) from 3,4-diethyl-2-ethoxy-carbony1-5-methyl-pyrrole (28). Zinc(II)-tetraphenylporphin (ZnTPP) was prepared by refluxing H2TPP and zinc acetate in dimethyl-formamide (29). ZnTPP was dissolved at a concentration of 10 -10 ... 

A phosgene-free synthesis of alkylisocyanates makes use of the indirect electrochemical oxidation in the alpha-position to nitrogen of formamides. Bromide in methanol solution acts as the redox catalyst, which, presumably, is oxidized to the methyl hypobromite [9] ... 

Normally, alcohols can be selectively oxidized with PDC in the presence of tertiary amines.148 Although TV-methyl tertiary amines are transformed into formamides by PDC,149 this reaction is usually slow enough so that selective oxidation of alcohols with PDC can be possible. 

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