Methylamines formamides

Methoxypropyl formamide Methylamine N-Methylaniline Methyl behenate o-Methylbenzyl alcohol 2-Methyl-1-butanol Methyl caproate Methylcyclohexanol acetate N-Methylcyclohexylamine N-Methylethanolamine Methylhydrazine Methyl-(S)-lactate 3-Methylpentane Methyl phthalyl ethyl glycolate 1-Methylpiperidine 2-Methylpropanal Mixed terpenes Naphtha, heavy aliphatic Naphtha, heavy alkylate Naphtha, heavy aromatic Naphtha, hydrodesulfurized heavy Naphtha, hydrotreated heavy Naphtha, hydrotreated light Naphthalene Naphtha, light aliphatic Naphtha, light alkylate Naphtha, solvent-refined light Naphthenic acid Naphthol spirits Neoheptane... 

Examine the geometry of formamide. Is the CN bond shorter than expected for a normal single bond (in methylamine), and closer to that expected for a full double bond (in methyleneimine) Is the CO bond longer than that expected in a carbonyl compound (in formaldehyde), perhaps closer to that appropriate for a single bond (in methanol) Also, compare the electrostatic potential map for formamide with those of formaldehyde and methylamine. Is the CO bond in formamide more or less polar than that in formaldehyde Is the CN bond in formamide more or less polar than that in methylamine Draw whatever Lewis structures are needed to properly describe the geometry and charge distribution of formamide. 

Preparation of formamides from COz and a non-tertiary amine by homogeneous hydrogenation has been well studied and is extremely efficient (Eq. (12)). Essentially complete conversions and complete selectivity can be obtained (Table 17.3). This process seems more likely to be industrialized than the syntheses of formic acid or formate esters by C02 hydrogenation. The selectivity is excellent, in contrast to the case for alkyl formates, because the amine base which would stabilize the formic acid is used up in the synthesis of the formamide consequently little or no formic acid contaminates the product. The only byproducts that are likely to crop up in industrial application are the methylamines by overreduction of the formamide. This has been observed [96], but not with such high conversion that it could constitute a synthetic route to methylamines. 

Group contribution method of Andersen, Beyer, and Watson [51,52] In this method, a given compound is constructed from abase group (methane, cyclopentane, benzene, naphthalene, methylamine, dimethylamine, trimethylamine, or formamide) with known enthalpies of formation, which is then modified by appropriate substitutions to yield the desired molecule. 

Aside from the N-compounds listed above, a number of low-molecular-weight N compounds were also identified. [17] These included ammonia, hydrogen cyanide, dinitrogen (N2), nitric oxide (NO), methylamine, nitrous oxide (N20), formamide, acetamide, and N, N-dimethylmethanamine. 

EXTENSIONS AND COMMENTARY N-Methyltryptamine (monomethyltryptamine, NMT) is an alkaloid that has been found in the bark, shoots and leaves of several species of Virola, Acacia and Mimosa. However, the major snuffs associated with these plant have been shown to also contain 5-MeO-DMT and are discussed there. NMT has been synthesized in a number of ways. One can react 3-(2-bromoethyl)indole with methylamine. NMT can be isolated as the benzoyl derivative from the methylation of tryptamine with methyl iodide followed by reaction with benzoyl chloride, with the hydrolysis of this amide with alcoholic KOH. It can also be synthesized from indole with oxalyl chloride, with the resulting glyoxyl chloride reacting with methylamine in ether to give indol-3-yl N-methylglyoxalylamide (mp 223-224 °C from IPA) which is obtained in a 68% yield, which is reduced to NMT to give the amine hydrochloride (mp 175-177 °C from ) in a 75% yield. The most simple and direct synthesis is the formamide reduction given above. 

The reaction of methylamine with o-chloromethylphenyl 2-chloroethyl ether gives (371). o-(2-Chloroethoxy)acetophenone reacts with amines to give (372) (63HCA1696) and the analogous benzophenones react with formamide to give analogues of (371) with a 5-phenyl substituent (69JPS1460). 

In an initial step, 2-chloroacetic acid ethyl ester is reacted with formamide to give 5-methylimidazole-4-carboxylic acid ethyl ester. Then sodium in ammonia is used to convert that to 4-hydroxymethyl-5-methylimidazole-hydrochloride. Cysteamine HCI (HSCH2CH2NH2-HCI) is then reacted to give 4-(2-aminomethyl)-thiomethyl-5-methyl-imidazole dihydrochloride. Then N-cyanamido-5,5-dimethyl-dithio-carbonate (from cyanamid, KOH, CS2 and ((CH3)2S04) is reacted to give a further intermediate which is finally reacted with methylamine to give cimetidine. 

The three methylamines are important intermediates for the manufacture of solvents, insecticides, herbicides, pharmaceuticals, and detergents. DMA is the most important due to its use in the manufacture of N,N-dimethyl-formamide and N,N-dimethylacetamide, which find wide application as solvents.46116... 

In the case of volatile amines, such as ammonia, methylamine, and dimethylamine, an autoclave must be used to permit reactions at higher temperatures alternatively, silylated amines are applied (Section 1V,D). Instead of these low-boiling and volatile amines, their corresponding acetates (cf. 128 129 141 142), formamides or phosphoroamidates... 

Racemic 2-aminobutan-l-ol (1) is a cheap chemical which can be easily resolved into both its enantiomers on an industrial scale. The asymmetric synthesis of chiral amines from hydrazines derived from (7 )-(—)-2-aminobutan-l-ol [(R)-(—)-l], using the general strategy disclosed in early works, is summarized here. The title hydrazine (4) is prepared as follows (eq 1). Treatment of the amino alcohol [(7 )-(—)-l] with excess ethyl formate followed by LAH reduction of the intermediate formamide gives the N-methylamine [(7 )-(—)-2]. IV-Nitrosation of the latter afforded (R)-(+)-3 which is next reduced to the hydrazine [( )-(—)-4] by means of LAH. Being unstable, the hydrazine (4) must be used immediately without purification. 

A few other A-substituted imines have occasionally been reduced to amine derivatives. Thus, A(-nitro imines (nitrimines) are reduced by NaBH4/dioxane %tOH/AcOH to A -nitroamines (Table 16, entry 14), and nitronate salts are reduced by BH3/THF to hydroxylamines (entry 15) via oximes. Isocyanates are reduced by LiBHEts, LiAlH(OBu )3 (at low temperature), or PhsSnH to formamides, which may be hydrolyzed in acidic workup to amines,while reduction with LAH affords A/-methylamines. ... 

There is a way around the hasslesome purification procedure that will allow the underground chemist to use the ethyl nitrite he has made quickly and easily. The way to do this is to bubble the vapors of the ethyl nitrite into the reaction mixture. This method avoids the unpleasant and possibly dangerous procedure with the sep funnel and subsequent distillation. See Figure 8 back in Chapter 4 on N-methyl formamide. If in that figure, the methylamine containing flask instead contained the ethyl nitrite reaction mixture, and the formic acid containing flask instead had the allylbenzene and palladium chloride in alcohol needed for phenylacetone production, then one could easily picture how to get the ethyl nitrite vapors to directly bubble into the phenylacetone production mix without any need to manipulate the nitrite directly. 

The formation of smaller eompounds sueh as methylamine, formamide, NMF, N-methyl-4-aminobutanoie aeid (in ESI-MS seans), and butanoie aeid (in ESI-MS scans) was also observed (Tables 1 and 2). 

Fluridone is accessible in two ways. l-(3-Trifluormethylphenyl)-3-phenyl-2-propanone (50) is reacted with ethyl formate in the presence of a base to yield the diformyl derivative 51, which is cydized with methylamine to the final product. Alternatively, 50 is condensed with formamidine acetate in the presence of formamide to the 4(lH)-pyridone intermediate 52 and then methylated to give fluridone [34]. 

NaBH4 added portionwise with ice-cooling below 18° during 20 min. to 1,3-dinitrobenzene in formamide-methanol, after additional 15-30 min. treated with methylamine, formaldehyde, and acetic acid -> l,5-dinitro-3-methyl-3-azabicyclo-[3.3.1]non-6-ene. Y 80%. F. e. s. T. Severin, J. Loske, and D. Scheel, B. 102, 3909 (1969). 

Metham potassium. See Potassium N-methyldithiocarbamate Metham sodium. See Metam-sodium Methanal. See Formaldehyde Methanamide. See Formamide Methanamine. See Methylamine, aqueous solutions Methylamine Methanamine, N-methyl-. See Dimethylamine Methanamine, N-methyl-, compd. with borane (1 1). See Dimethylamine borane Methanamine, N-methyl-N-nitroso-. See N-Nitrosodimethylamine Methanamine, N-methyl-, polymer with (chloromethyl) oxirane. See Dimethylamine/epichlorohydrin copolymer Methanaminium, 1-carboxy-N,N,N-trimethyl-, chloride. See Betaine hydrochloride Methanaminium, N-(4-((2-chlorophenyl) (4-(dimethylamino) phenyl) methylene)-2,5-cyclohexadien-1-ylidene)-N-methyl-, chloride. See Basic blue 1... 

At least two reaction pathways may be postulated for the formation of INMF. The first (Scheme B, path a) involves initial reaction of CO with ammonia to give formamide, followed by methylation with Me-Ru generated via ruthenium-catalyzed CO hydrogenation. An alternative pathway would proceed via initial formation of methanol from CO/H2, to be followed by the production of methylamines and subsequent carbonylation (path b). 

Benzyl alcohol allowed to react with NaH in ether containing a little dimethyl-formamide, the resulting mixture added to a slight excess of ethereal tosyl chloride, finally treated with ethereal methylamine benzylmethylamine. Y 72%. F. e. s. W. K. Anderson and T. Veysoglu, Synthesis 1974, 665. 

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