Sodium amalgam amide

Sodium, with l-bromo-3-chloro-cyclobutane to give bicyclo [l.l.O]butane, 51, 55 Sodium amalgam, 50, 50, 51 Sodium amide, with 2,4-pentane-dione and diphenyliodonium chloride to give l-phenyl-2, 4-pentanedione, 51, 128 Sodium azide, 50, 107 with mixed carboxylic-carbonic anhydrides, 51, 49 Sodium borohydride, reduction of erythro-3-methanesulfony-loxy-2-butyl cyclobutanecar-boxylate, 51, 12 reduction of 2-(1-phenylcyclo-pentyl)-4,4,6-trimethyl-5,6-dihydro-1,3(4H)-oxazine to 2-(1-phenylcyclopentyl)-4,4, 6-trimethyltetrahydro-l,3-oxazine, 51, 25 Sodium cyanoborohydride, used... 

Sodium amide has been prepared by the action of gaseous 2 or liquid3 ammonia on sodium, by the action of ammonia on alloys of sodium,4 and by the electrolysis of a solution of sodium cyanide 5 in liquid ammonia with a sodium amalgam electrode. A summary of the chemistry of alkali amides is given by Bergstrom and Fernelius.1... 

Sodium and sodium amalgam may be used for reduction of amides but the yields of amines are generally very low. Primary aromatic amides (benz-amides) were reduced at the carbonyl function with 3.3 equivalents of sodium in liquid ammonia and ethanol while in tert-butyl alcohol reduction took place in the aromatic ring giving 1,4-dihydrobenzamides [984. ... 

F. W. Bergstrom obtained potassium stannous amide, Sn(NH2)2.KNH2, or SnNK(NH3)2, or K[Sn(NH2)3], as a white solid, very soluble in liquid ammonia, by the action of mercury on the product of the reaction of tin with potassium amide by the action of the amide on an excess of tin amalgam or by the action of potassium amide on stannous chloride. The corresponding sodium stannous amide, Sn(NH2)2.NaNH2, or SnNaN(NH3)2, or Na[Sn(NH3)2], was obtained in a similar way. 

Silicon, higher chlorides of, 42 Silicon tetrabromide, 38, 40 Silicon tetrachloride, 44 Silicopropane, octachloro, 44 Silicotungstic acid, 129 analysis, 131 ether complex, 131 Silver, metallic, 4 Silver chloride, reduction of, 3 Silver cyanamide, 98 Silver residues, purification of, 2 Sodium amalgam, 10 Sodium amide, 74 Sodium azide, purification of, 79 Sodium azidodithiocarbonate, 82 Sodium butoxide, 88 Sodium hypochlorite (solution), 90 Sodium iodate, 168 Sodium metaperiodate, 170 Sodium paraperiodate, chlorine method, 169 persulfate method, 170 Strontium amalgam, 11 Sulfur hexafluoride, 121 Sulfuryl chloride, 114... 

Sodium aluminum chloride, 435 Sodium amalgam, 310, 416-417 Sodium amide-Sodium r-butoxide, 417-418 Sodium azide-Triphenylphosphine, 418 Sodium bis(2-methoxyethoxy)aluminum hydride, 166,418-420 Sodium borohydiidc, 323,420-421 Sodium borohydride-Alumina, 421 Sodium borohydride-Bis(2,4-pentane-dionato)copper(ll), 421 Sodium borohydride-Cerium(Ill) chloride,... 

Keck and co-workers have shown that this Diels-Alder reaction offers promise for the synthesis of certain alkaloids and other nitrogen-containing products since the adducts are selectively cleaved to hydroxy amides by aluminum or sodium amalgam. 

Under certain conditions the reduction of amides leads to primary alcohols (cf. method 428). Thus, phenylethylacetamide is reduced by sodium and absolute ethanol to 2-phenyl-1-butanol (75%). a-Naphthylacetamide is reduced by sodium amalgam and hydrochloric acid to a-naphthylcarbinol (63%). Trifluoroethanol is obtained by catalytic hydrogenation of tri-fluoroacetamide over a platinum catalyst. Hydrogenation of the corresponding ester over copper-chromium oxide failed. ... 

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