Hydrazine sodium amide

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) ... 

Each year, about half the 3 X 108 kg of hydrogen used in industry is converted into ammonia by the Haber process (Section 9.12). Through the reactions of ammonia, hydrogen finds its way into numerous other important nitrogen compounds such as hydrazine and sodium amide (see Section 15.2). 

Sodium amide is a dehydrating agent. It is used in preparing sodium cyanide and hydrazine, and in many organic synthetic reactions such as Claisen condensations, alkylations of ketones and nitriles, and in ammonoly-sis reactions. 

Iron cyclopentadienyl complexes of 3-(2-chlorophenyl)propanones are cyclized with hydrazine into 1,4-dihydrocinnoline complexes, demetalated with sodium amide to give 3- or 3,4-disubstituted cinnolines (70-80%) (Scheme 29) (88JHC1107). 

All technical processes for the synthesis of hydrazine yield either hydrazine in aqueous solution or hydrazine hydrate. Most applications can use hydrazine hydrate, but for some applications, for example, rocket propulsion, anhydrous hydrazine is necessary. The water can be removed by a chemical reaction followed by distillation or by azeotropic distillation with an auxiliary fluid. As water binding chemicals, calcium carbide, sodium hydroxide, calcium oxide, calcium hydride, barium oxide, barium hydroxide, and barium pemitride Ba3N4 have been used. The use of sodium or calcium metal and sodium amide is best avoided because of the formation of explosive hydrazides. Starting from hydrazine hydrate (64% hydrazine), sodium hydroxide is generally used... 

Hydrazine only acts as a base with very strong bases, for example, sodium amide or sodium hydride. 

For the synthesis of sodium azide, precursors with two nitrogen atoms, hydrazine N2H4 and N2O, are used. In the technical process, sodium azide is obtained from dry N2O, which is passed dnough a sodium amide melt. 

With alkylamines, the primary reaction products are aminophosphonium salts, [Ph3PNHR]+Br , which need to be dehydrobrominated with ammonia or sodium amide. In a similar marmer, dichlorotriphenylphosphorane reacts with hydrazine dihydrochloride, at 180-220 °C, to form a bis(phosphorane)diimine after treatment with a strong base (hquid ammonia or potassium teri-butoxide), equation (3). ... 

Liquid ammonia as solvent sodium amide ammonium amalgam hydrazine hydroxylamine. 

Another blowing agent which has become important of late is sodium azide, which in addition to being synthesized from sodium amide and chloramine can also be produced from methyl nitrite and hydrazine hydrate. Sodium azide is utilized in the airbags installed in motor vehicles. 

Sodium hydrazide, R NNIdNa. Mol. wt. 54.04. The reagent is a crystalline yellow solid which explodes at temperatures above 70° or in the presence of oxygen. It is prepared by reaction of sodium amide with anhydrous hydrazine under nitrogen at 0°, for most purposes as a suspension in ether, diisopropyl ether, benzene, or a mixture of these solvents. ... 

Derivation Reaction of hydrazine and nitrous acid, or of nitrous oxide and sodium amide (with heat). 

NH2NH2-2HC1 Hydrazine dihydrochloride, 1 92 NH2NH2C2H3N302 Hydrazine urazolate, 5 53, 54 [NH2NH3JHS04 Hydrazonium hydrogen sulfate, 1 90, 92 NH2N02 Nitramide, 1 68, 72 NH2Na Sodium amide, 1 74, 2 80, 128... 

Sodium amide/hydrazine Reductions with sodium hydrazide/hydrazine NaNH IHsN NH ... 

A soln. of anhydrous 1-methyl-1-phenylhydrazine in triethylamine added during 0.5 hr. to stirred triphenylphosphine dibromide in dry benzene, and stirring continued an additional hr. N -methyl-N -phenylhydrazinotriphenylphospho-nium bromide (Y 87.3%) stirred with sodium amide in liq. NH3 under anhydrous conditions N -methyl-N -phenyltriphenylphosphine aminoimine (Y 90.1%) refluxed 2 hrs. with methyl iodide N,N -dimethyl-N -phenyltriphenylphospho-nium iodide (Y 95.5%) refluxed 2 hrs. with ale. 2%-KOH 1,2-dimethyl-1-phenylhydrazine (Y 88.0%).—This is a new and convenient method for the prepn. of 1,1,2-trisubst. hydrazines. F. e. s. H. Zimmer and G. Singh, J. Org. Ghem. 29, 1579 (1964). 

Hydrazine deacylates amides (Gabriel amine synthesis) via the Ing-Manske protoeol. This procedure has its limitations, as shown in the synthesis of penicillins and cephalosporins where it was observed that hydrazine reacts with the azetidinone ring. In this case. Sodium Suffide was used. ... 

Addition of nucleophiles to the cyano group of cyanothiadiazole under basic conditions takes place with unusual ease <88AG(E)434,94ACS372). Hydrolysis to the amide, for example, can be effected at 0°C in the presence of a catalytic amount of sodium hydroxide or basic ion-exchange resin. At reflux temperature, hydrazine and monosubstituted hydrazines convert 3,4-dicyano-l,2,5-thia-diazole into the l,2,5-thiadiazole[3,4-. The base-catalyzed addition of acetone to cyanothiadiazole forms an enamino ketone, used as a key intermediate for the synthesis of a number of heterocyclic ring systems, e.g. isothiazole, isoxazole, pyrazole, pyrimidine, and thiazole <77H(6)1985>. 

The bicyclic meso-ionic 3-oxo-l,2,4-triazolo[4,5-a]pyridines (206) have been prepared by the following methods (i) the reaction of the hydrazines (207, X = H) with phosgene, (ii) heating the amide (207, X = CONH2) or the carbamate (207, X = COjEt), and (iii) alkylation or acylation of 3-oxo-l,2,4-triazolo[4,5-a]pyridine (208). The isomeric meso-ionic 2-oxo-l,3,4-triazolo[4,5-a]pyridines (209) are formed from the carbamoyl chlorides (210) and sodium azide. ... 

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