Formamides

DMF, Me2NC(0)H. Dimethyl formamide. DMSO, Mc2SO. Dimethyl sulphoxide. 

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. 

Vilsmeier reagent The reagent obtained from POCI3 mixed with either N,N-dimethyl-formamide or N-methylformanilide. Used for introducing the methanoyl (formyl) (-CHO) group into activated aromatic substrates. 

Fig. X-12. Advancing and receding contact angles of various liquids [water (circles), Gly = glycerol (squares), Form = formamide (diamonds), EG = ethylene glycol (circles), BN = abromonapthalene (squares), BCH = bicyclohexyl (diamond), HD = hexadecane (circles)] on monolayers of HS(CH2)i60R having a range of R groups adsorbed on gold and silver (open and filled symbols respectively). (From Ref. 171.)...

Momany F A 1978 Determination of partial atomic charges from ab initio molecular electrostatic potentials. Application to formamide, methanol and formic acid J. Phys. Chem. 82 592... 

Fig. 2.10 Isometric projection of the electron density around formamide.

R F W Bader s theory of atoms in molecules [Bader 1985] provides an alternative way to partition the electrons between the atoms in a molecule. Bader s theory has been applied to many different problems, but for the purposes of our present discussion we will concentrate on its use in partitioning electron density. The Bader approach is based upon the concept of a gradient vector path, which is a cuiwe around the molecule such that it is always perpendicular to the electron density contours. A set of gradient paths is drawn in Figure 2.14 for formamide. As can be seen, some of the gradient paths terminate at the atomic nuclei. Other gradient paths are attracted to points (called critical points) that are... 

Gradient vector paths around formamide. The paths terminate at atoms or at bond critical points (indicated by squares). 

Volumen and Hydratationswarme der lonen. Zeitschrift filr Physik 1 45-48. aan C M and K B Wiberg 1990. Determining Atom-Centred Monopoles from Molecular Electro-itic Potentials. The Need for High Sampling Density in Formamide Conformational Analysis. imal of Computational Chemistry 11 361-373. 

HC0N(CH3)2, also possess exceptional solvent properties. The alkyl-glycols, dioxan and dimethyl-formamide should be used with caution, however, as their hot vapours are poisonous. 

B) Formamide, acetamide, oxamide, urea, benzamide, salicylamide thiourea. 

Ethyl oxalate is the only liquid ester which gives this rapid separation of the amide, which is therefore characteristic. Methyl and ethyl formate react rapidly with ammonia, but the soluble formamide does not separate methyl succinate gives crystalline succinamide after about I hour s standing, other esters only after a much longer time. The solid esters, other than methyl oxalate, are either soluble in water and remain so when treated with ammonia, or alternatively are insoluble in water and hence clearly not methyl oxalate. 

B) Amides. All colourless solids except formamide, HCONIL, a... 

Note that some N-alkyl-formamides such as dimethylformamide, are also liquid,... 

Boil 1 ml. of formamide in a test-tube and note that ammonia is freely evolved. Carbon monoxide is also produced, but cannot usually be ignited in the presence of the ammonia. 

Formamide. Commercial formamide may contain excess of formic acid. It is purified by passing ammonia gas into the mixture until a slight alkaline reaction is obtained. The ammonium formate thus formed is precipitated by the addition of acetone the filtrate, after drying over anhydrous magnesium sulphate, is distilled under reduced pressure. Pure formamide has b.p. IO571I mm. 

The conversion of an aldehyde or ketone into the corresponding amine by heating with ammonium formate or with formamide and formic acid at about... 

The desired pyridylamine was obtained in 69 % overall yield by monomethylation of 2-(aminomethyl)pyridine following a literature procedure (Scheme 4.14). First amine 4.48 was converted into formamide 4.49, through reaction with the in situ prepared mixed anhydride of acetic acid and formic acid. Reduction of 4.49 with borane dimethyl sulfide complex produced diamine 4.50. This compound could be used successfully in the Mannich reaction with 4.39, affording crude 4.51 in 92 % yield (Scheme 4.15). Analogous to 4.44, 4.51 also coordinates to copper(II) in water, as indicated by a shift of the UV-absorption maximum from 296 nm to 308 nm. 

The Leuckart reaction was originally conceived using a chemical called ammonium formate (HCOONH4) which is very similar to formamide (HCONH2) [30]. It is pretty much believed that this molecule donates its ammonium part to the P2P and then the formate part turns into formic acid (HCOOH) which then acts to reduce the intermediate into its stable formyl derivative (don t ask). 

Since the formamide reaction solution is going to be a lot cleaner than the tarry mess of the original recipe, the chemist has yet another option to explore. Instead of hydrolyzing in the reaction pot, the chemist can add SOOmL of clean dHjO and stir just like in the crappy original method except that this time the chemist is going to look for a heavy oil layer that will settle at the bottom. The up-... 

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