Sodium hydrazide

Hydrazinium salts, N2H5 X, are acids in anhydrous hydrazine, metallic hydrazides, N2H, are bases. Neutralization in this solvent system involves the hydrazinium and hydrazide ions and is the reverse of equation 7. Metal hydrazides, formally analogous to the metal amides, are prepared from anhydrous hydrazine and the metals as well as from metal amides, alkyls, or hydrides. (The term hydrazide is also used for organic compounds where the carboxyUc acid OH is substituted with a N2H2.) Sodium hydrazide [13598-47-5] is made from sodium or, more safely, from sodium amide (14) ... 

Anhydrous hydrazine and sodium react in ether to form sodium hydrazide, which explodes in contact with air. Hydrazine hydrate and sodium react very exother-mally, generating hydrogen and ammonia. 

Figure 22 Structures of the hexameric sodium hydrazide 317 and the mixed mono- and dianionic complex 318. Hydrogen atoms have been omitted for clarity.

Calcium hydrazide, 3932 Lithium hydrazide, 4496 Sodium hydrazide, 4500 See also V-METAL DERIVATIVES... 

The hydrazination of aza-aromatics, using sodium hydrazide, has been reported, but no detailed mechanism was given (64AG206). On treatment of 3-i -l,2,4,5-tetrazines R = CH3, C2H5, C6H5) with 3 equiv of... 

Bromonaphthalene has been reduced to naphthalene in good yield by hydrogenation over Raney nickel in methanolic potassium hydroxide, by triphenyltin hydride in benzene, by magnesium in isopropyl alcohol, by sodium hydrazide and hydrazine in ether, and by copper(I) acetate in pyridine. ... 

Pyridine reacts with sodium hydrazide in the presence of hydrazine to yield 2-hydrazinopyridine in the absence of free hydrazine a hydrazo compound is formed (Scheme 88) (64AG(E)342). A difference between hydrazination and amination is the formation of 1,4-adducts which cannot be rearomatized even on heating. This is reflected in the behaviour of quinoline, which gives only a 0.5% yield of a -hydrazino product, whereas 4-methylquino-line is hydrazinated in 76% yield (64AG(E)342). Acridine behaves differently with sodium hydrazide/hydrazine, 9,10-dihydroacridine is formed almost quantitatively, but reaction in the absence of hydrazine yields 9-aminoacridine (65%). An even higher yield of 9-amino-acridine is obtained when sodium Af.AC-dimethylhydrazide is used (Scheme 89). Good evidence for intermediacy of (151) comes from the isolation of (152) on hydrolysis of (151). 

Hydrazide is a deriv of Hydrazine (qv) of general formula MHN.NH2, where M means metal. One such compd, Sodium Hydrazide, NaHN.NH2, mw 54.04, N 51.85%, is extremely explosive. It can be prepd by the action of Na on anhydrous hydrazine or from NaNH2 and hydrazine Refs 1) Gmelins Handbuch, 8th ed (1936),... 

Salts of very powerful oxidizing acids (eg chromic or permanganic) are unknown, and are unlikely to exist. Hydrazonium iodate may exist in solution at low temp (Ref 27a). Alkali metals, amides and hydrides react with hydrazine to give the corresponding alkali hydrazide. Sodium hydrazide explodes violently in the presence of 02 or when heated above 100°C—a typical behavior of the alkali hydrazides. For other reactions, see Ref 24 Explosive and Combustion Properties... 

Very little information is available for monomeric sodium amides. Addition of pmdeta to NaN(CH2Ph)(CHMePh) effects its transformation into the monomeric l,3-diphenyl-2-azallyl salts [(pmdeta)NaN(CHPh)2] and (pmdeta) a (CHPh)(C lePh)J. " However, the sodium hydrazide salt [(thf)3NaN(Ph)N(SiMe3)2] crystallizes as monomers featuring... 

Dibromobenzo[6]thiophene and its 6-carboxylic acid undergo bisdehalogenation on treatment with sodium hydrazide and hydrazine 515 and on catalytic reduction in alkaline solution,77 respectively. Bromonitrobenzo[6]thiophenes readily undergo debromination on treatment with copper and quinoline,412 copper bronze and benzoic acid,84 or tin and hydrochloric acid.516... 

Hydrazine attacks indiarubber, and cork and, when boiled in aq. soln.) glass is eroded. Hydrazine hydrate and sodium develop much heat, with the expulsion of hydrogen and ammonia. When the liquid cools, a crystalline substance is formed which is soluble in water and alcohol, and which is thought to be sodium hydrazide hydroxide, N2H5ONa. The aq. soln. gives the reactions for hydrazine. T. Weich-selfelder prepared the derivatives ... 

According to E. Scandola, when hydrazine is added drop by drop to finely granulated sodium suspended in ether, and then heated on a water-bath with a reflux condenser, a white substance is formed which explodes in air. If left in contact with the ether, it loses its explosive property. The white compound does not act on silver nitrate in ammoniacal soln. Its structure is supposed to correspond with sodium triimide or sodium hydrazide ... 

This substance was studied by T. W. B. Welsh, who found that the electrolysis of soln. of sodium hydrazide in anhydrous hydrazine furnishes nitrogen and hydrogen... 

Calcium hydrazide, 3926 Lithium hydrazide, 4491 Sodium hydrazide, 4495 See also A -METAL DERIVATIVES... 

Dinitrochlorobenzene. Strongly exothermic reaction with 2,4-dinitrochlorobenzene.3 Mercuric Oxide. Dropwise addition to mercuric oxide may result in an explosion.2,4 Sodium. Dropwise addition to a suspension of Na in ether and heating forms sodium hydrazide, which explodes in air reacts very exothermally with Na with the liberation of H2 and NH3.5... 

Hydrazine. Mixture with anhydrous hydrazine forms sodium hydrazide, which explodes on contact with air. Mixture with hydrazine hydrate causes strongly exothermic reaction to give H2 and ammonia.15... 

The reaction of sodium alkylamides with pyridine gives 2-amino-pyridine derivatives,301 but this does not appear to have been exploited with substituted pyridines. Similarly, pyridine gives 2-hydrazinopyridine on treatment with sodium hydrazide/hydrazine followed by hydrolysis.301 ... 

Sodium hydrazide, NH2-NHNa.—The hydrazide is produced by the interaction of hydrazine hydrate and sodamide 3... 

Mixtures of 1,3,5- and 1,3,6-cyclooctatriene were obtained by partial reduction of cyclooctatetraene in ways such as protonation of cyclooctatetraene dianion3d-4 and reduction with zinc-alkali.2 5 1,3,6-Cyclooctatriene is the major product in these reductions. However, since 1,3,6-cyclooctatriene isomerizes to 1,3,5-cyclooctatriene on treatment with base, quenching cyclooctatetraene dianion with methanol and subsequent heating affords 1,3,5-cyclooctatriene in an 80% yield.3d Reduction of cyclooctatetraene with sodium hydrazide and hydrazine also produces 1,3,5-cyclooctatriene.6 Therefore, when cyclooctatetraene is available in quantity, these procedures are the methods of choice. 

Styrenes and stilbenes are cleaved by sodium hydrazide in boiling ether, RiCIti-CMej giving MezC—NNH2 (53%) and toluene (74%) after 6 h reflux. A wide variety of alkenes, dienes and aralkenes are also cleaved by diazonium salts (Scheme 97). Yields and reaction rates vary widely. 

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