Methylamine nitrile reduction

Hydroxy-3-methoxy-B-nitrostyrene. A mixture of methylamine hydrochloride (7 g, see precursor section for synthesis) and 10 g of sodium carbonate in 100 ml of methanol is stirred well, filtered, and added to a solution of 219 g of vanillin and 85 ml of nitromethane in 600 ml of ethanol. Keep this solution in the dark at room temp for 71 hours to make the nitrostyrene crystallize out. Filter and wash with cold methanol. Yield 225 grams, nip 166-168°. This and the other two nitriles are reduced by the method listed in the reduction section, JACS, 72, 2781. This reduction can be used to reduce many of the nitro type compounds. 

Treatment of [RuC1(NH3)5]2+ with Ag(02CCF3), followed by zinc amalgam reduction and addition of amine yields [Ru(L)(NH3)5]2+ (L = cyclohexylamine, benzylamine, methylamine).192 Oxidation of these complexes with Br2 produces the corresponding ruthenium(TII) species [Ru(L)(NH3)5]3+.192 Subsequent oxidation of the amine ligand can readily occur to give imine and nitrile products, explaining the relatively few complexes of this type that have been isolated (see Section 45.4.2). 

At a time when the only practicable methods for the preparation of nitrometliane were tlie interaction of metliyl iodide with silver nitrile and the Kolbe reacUon from chloracetic acid, the explosive was far too expensive to merit consideration. Tlie present cheap and large scale production of nitrometliane by the vapor-phase nitration of methane and of ethane has altered the situation profoundly. Trimethylolnitromethane tnnitrate is an explosive which can now be produced from coke, air, and natural gas. Nitro-methane too has other interest for the manufacturer of explosives. It may be used as a component of liquid explosives, and it yields on reduction methylamine which is needed for the preparation of tetryl. 

Most pyrimidine carbonitriles show normal nitrile chemistry reductive reactions to methylamines by metal hydrides, hydrolytic reactions, reduction to aldehydes and formation of ketones with Grignard reagents. However, in highly electron-deficient pyrimidines, competition may arise between addition to an electrophilic substituent and the electrophilic pyrimidine ring. In the 5-cyano derivative (426), specific attack of organometallics is in the 4-position, with formation of the dihydro derivatives (427) instead of a ketone <83ACS(B)6I3>. 

Nitriles are inert toward NaBH3CN even under strongly acidic conditions. However, methylation with Me2Br+SbF6 and subsequent reduction with NaBH3CN affords the corresponding methylamine (eq 24). ... 

Diamines were also prepared via Michael addition reaction of bis(trimethylsilyl)methylamine with acrylonitrile followed by reduction of the nitrile group with lithium aluminum hydride (eq 22).i ... 

Other starting materials to make f, aside from nitriles, are fatty alcohols. F. are obtained by reductive alkylation of ammonia or methylamine with fatty alcohols at 90-190 °C under low hydrogen pressure in the presence of Raney nickel. If water is removed continuously from the reaction mixture, only secondary or tertiary amines are obtained. This reaction is mainly used when starting from synthetic fatty alcohols and focuses on the manufacture of textile softeners. It is, however, also used for making medium-chain (Cg-Cio) trialkylamines... 

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