Dimethylamines formamides

Dimeihylamine, C2H7N, (CH3)2NH. Colourless, inflammable liquid with an ammoniacal odour, mp -96" C, b.p. 7°C. Occurs naturally in herring brine. Prepared in the laboratory by treating nitrosodimetbyl-aniline with a hot solution of sodium hydroxide. Dimethylamine is largely used in the manufacture of other chemicals. These include the solvents dimethylacetamide and dimethyl-formamide, the rocket propellant unsym-metrical dimethylhydrazine, surface-active agents, herbicides, fungicides and rubber accelerators. 

In the case of l-dimethylaminobut-l-en-3-yne no 4-methylpyrimidine was isolated because its boiling point is close to that of a side product, dimethylfor-mamide. The latter results from transamination of formamide by dimethylamine in the course of cyclization. The pyrimidines 156 were isolated and characterized as picrates (70ZOR1528). For easier isolation of pure 4-methylpyiimidine... 

Three alternative mechanisms have been mentioned in the literature. Reduction of C02 to CO followed by carbonylation of dimethylamine was ruled out by Haynes et al. [3] for RhCl(PPh3)3 because no carbonyl complexes were detected. Aminolysis of formate complexes (Eq. (14)) was proposed by Kudo et al. [69], but strong evidence has not been obtained. Finally, C02 is known to react with the amine to produce a carbamate salt (Eq. (15)), and it is possible that the pathway to the formamide is by hydrogenation of the carbamate rather than of the C02. 

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. 

Mix 0.25M substituted benzaldehyde, 0.3M nitroethane, 50 ml dry toluene and 5 ml n-butylamine (or other amine), and reflux 3 hours with a Dean-Stark trap (or prepare the nitro-propene as described elsewhere here). Add 50 g iron powder and 1 g FeCl3 optional) and reflux while adding 90 ml concentrated HCI over 3 hours. Reflux 1 hour more, add 2 liters of water and extract 3 times with ether, then dry and evaporate in vacuum (or steam distill until about 3.5 liters of distillate is obtained extract the distillate 3 times with toluene wash the toluene layers with 7 g NaHS03 in 225 ml of water, then 3 times with water and dry, evaporate in vacuum) to get the ketone. Mix 0.13M ketone, 28 g formamide (or dimethyl-formamide if the N.N-dimethylamine is desired) and 3 ml formic acid and heat at 160°. Add 3 more ml formic acid and heat 16 hours at 170-180° adding formic acid from time to time to keep the pH acid. Distill off the water formed (about 16 ml), cool and extract with 3X70 ml benzene. Distill off the benzene and reflux the residue 7 hours with 30 ml concentrated HCI. Chill, basify with 10% NaOH and extract with 3X70 ml ether. Dry and evaporate the ether in... 

An example of the use of DMF as CO source in the Pd-catalyzed aminocarbonylation with microwave irradiation is shown in Scheme 28. Thus, n-bromotoluene was reacted with benzylamine (4 equiv.) in the presence of Pd-dppf catalyst, imidazole, KOBu, and DMF (17equiv.) with microwave irradiation for 20min to give amide 196 in 94% yield (Scheme 28). A proposed mechanism (Scheme 28) has a close similarity to that of the aminocarbonylation of aryl bromide with formamide (see Scheme 22). However, in this process, a large excess (4 equiv.) of benzylamine was used to suppress a possible reaction involving dimethylamine generated in situ from DMF under reaction conditions. 

Metal-Nitrogen Compounds The cobalt catalyzed reaction of primary and secondary amines with carbon monoxide leads to the formation of formamide derivatives. Dimethylamine, for example, gives iV,i T-dimethvlformamide in 60% yield (90, 91). Very likely cobalt-nitrogen compounds are intermediates which undergo a CO insertion and then reduction. The following mechanism has been suggested for the reaction (90). 

A, A-Dimethyl formamide (DMF) [68-12-2] M 73.1, b 76 /39mm, 153 /760mm, d 0.948, 1.4269. Decomposes slightly at its normal boiling point to give small amounts of dimethylamine and... 

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... 

The electrochemical reduction of CO2 in the presence of dimethylamine and [Ru(bipy)2(CO)2] as the catalyst in anhydrous acetonitrile gives dimethylform-amide and formate. Ruthenium carbamoyl complexes are likely intermediates, and the formation of [(bipy)2Ru(CO)(CONMe2)] was confirmed by FT-IR and H Dimethyl formamides are also formed if CO2 is reduced by H2 in the presence of dimethylamine. The catalysts employed were [RuH(Cl)(CO)L3], [RUCI2L3], [OsH(C1)L3], [Os(H)2C1(CO)L3], [IrCl(CO)L2], [Pt2(dppm)3],... 

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... 

Chlorobenzene o-Cresol Cyanuric chloride Dibromodifluoromethane Dibutylamine p-Dichlorobenzene Dimethylamine Dimethylethanolamine Dimethyl formamide 2,6-Dinitrotoluene... 

Dimethylamine Dimethyl formamide Dimethylolpropionic acid 2,2-Dimethylpropanol Diphenylamine Ethylene chlorohydrin Hydrogen cyanide Hydroquinone monomethyl ether Isoquinoline Methyl isocyanate Nonanoic acid Phenolsulfonic acid Phosphorus oxychloride Pyrrole Quinaldine Sodium nitrate Stannic chloride Strontium salicylate Thioglycolic acid o-Xylene 2,3-Xylenol 2,3-Xylidine pharmaceutical mfg., orals Candelilla (Euphorbia cerifera) wax Cholecalciferol Ergocalciferol pharmaceutical mfg., parenterals Cholecalciferol Ergocalciferol pharmaceutical processing Chlorotrifluoromethane pharmaceutical prods. 

Absorption of CO in organic medium containing cuprous aluminium complexes in methanol to produce acetic acid or metyl formate in dimethylamine to make dimethyl formamide... 

Figure 11.15 (a) First mechanism proposed for formation of NDMA by chlorination of water via reaction of chloramines with a dimethylamine to form chlorodimethylamine (CDMA) and thence unsynunetrical dimethylhydrazine (UDMH). (b) Further reactions of UDMH with chloramines to form NDMA plus other identifiable reaction products dimethyldiazene (DMD), tetram-ethyltetrazene (TMT), dimethylcyanamide (DMC), dimethyl-formamide (DMF), formaldehyde dimethylhydrazone (FDMH), formaldehyde monomethylhydrazone (FMMH). Reproduced from Mitch, Env. Sci. TechnoL 36, 588 (2002), copyright (2002) with permission of the American Chemical Society. 

Formic acid/formaldehyde Dimethylamines from formamides... 

There are also other reducing agents, which are not commonly used in practice among them, a few are hydroxylamine [92,114,166], tannins [107,167,168], EDTA [102,153,169,170], formamide [171], tartrate [15,172], hydroquinone [173], o-anisidine [174], dimethylamine borane [114], and... 

Dimethylformamide azine refluxed 5 hrs. with excess n-butylamine and some p-toluenesulfonic acid in benzene with evolution of dimethylamine 4-n-butyl-1,2,4-triazole. Y 80%. F. e. and other N,N-disubst. formamide azines from sec. amines s. R. K. Bartlett and I. R. Humphrey, Soc. (C) 1967, 1664. 

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