Hydrazine salts

Hydrazine—borane compounds are made by the reaction of sodium borohydride and a hydrazine salt in THF (23,24). The mono-(N2H4 BH ) and di-(N2H4 2BH2) adducts are obtained, depending on the reaction conditions. These compounds have been suggested as rocket fuels (25) and for chemical deposition of nickel—boron alloys on nonmetallic surfaces (see Metallic COATINGS) (26). 

Reaction of 4-amino-l-azabutadienes (45) with various hydrazine salts at 60°C leads to the expected pyrazoles (46) without isolation of the hydrazone intermediate (eq. 8) (39). 

Most of these compounds, for instance pyrazole itself, are today commercially available, so there is only a minor interest in detailing the experimental procedures used. The best way to prepare pyrazole is the Protopopova method (Section 4.04.3.3.2) and a modification using hydrazine hydrate instead of a hydrazine salt has recently been patented (80GEP2922591). 

Triazole has been prepared by the oxidation of substituted 1,2,4-triazoles, by the treatment of urazole with phosphorus pentasulfide, by heating equimolar quantities of formyl-hydrazine and formamide, by removal of the amino function of 4-amino-l,2,4-triazole, by oxidation of l,2,4-triazole-3(5)-thiol with hydrogen peroxide, by decarboxylation of 1,2,4-triazole-3(5)-carboxylic acid, by heating hydrazine salts with form-amide,by rapidly distilling hydrazine hydrate mixed with two molar equivalents of formamide, i by heating N,N -diformyl-hydrazine with excess ammonia in an autoclave at 200° for 24 hours, and by the reaction of 1,3,5-triazine and hydrazine monohydrochloride. ... 

The reaction is generally performed between 0 and 100 °C with the majority of the reactions being mn at reflux. Polar protic solvents such as methanol, ethanol, isopropanol, and water are commonly used as solvents. Addition of acid or use of acetic acid as solvent generally helps push sluggish reactions. The use of P-ketoesters as the dicarbonyl partner occasionally requires added base for cyclization to occur to form the pyrazolone. When using alkyl hydrazine salts, base may be required to deprotonate the hydrazine for the reaction to take place. 

Impact sensitivity. PA app 10—11 inches (18.3mg sample) vs 8 for RDX, hydrazine salt 15 inches (1 lmg sample) BM app 14— 2lcm vs 70—100+ for RDX and 100+ for TNT, hydrazine salt 92cm (Ref 13), also in this Ref are listed the impact sensy of 8 samples of MEDINA coated with wax (15—31cm)... 

Hydrazine Salt. Fine yellow crysts, mp 123° with decompn (Ref 25). It is prepd by the addn of hydrazine hydrate to TNMe in w (Ref 25), or by the addn of anhyd hydrazine to TNMe in iso-Pr ale (Ref 48). The cryst structure and X-ray diffraction pattern of the pure salt are given in Ref 45. Impact sensy (2.5kg wt), the 50% expln height was found to be 10cm (Ref 25). It is stable to 100° (Ref 48). It is claimed as an ingredient in a thixotropic propint formulation (Ref 41)... 

Iron can be controlled with certain complexing agents, in particular glucono-5-lactone, citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylene diaminetriacetic acid, hydroxyethyliminodiacetic acid, and the salts from the aforementioned compounds. These compounds must be added together with nitrogen-containing compounds such as hydroxylamine salts or hydrazine salts [486,643,1815]. 

For analysis, a silver-containing solution was made alkaline with 25% sodium hydroxide solution and filtered, then the precipitate was washed with ammonium hydroxide to redissolve the silver. Hydrazine (as sulfate) was added to precipitate the silver, and when the mixture was heated, an explosion occurred. This could have been caused by precipitation of explosive silver nitride, rapid catalytic decomposition by silver compounds of the hydrazine salt, and/or ignition of the hydrogen evolved. 

Hydrazine salts have been prepared by the action of hypochlorites on ammonia1 or urea 2 by the hydrolysis of salts of sulfohydrazimethylene disulfonic acid 3 by the hydrolysis of triazoacetic acid 4 by the reduction of diazoacetic ester 5 by the reduction of nitroguanidine followed by hydrolysis 6 by the reduction of the nitroso derivatives of hexamethylene tetramine 7 by the reduction of nitrates or nitrites with zinc in neutral solution 8 by the action of sodium bisulfite on hyponitrous acid... 

This multi-step, one-pot process was taken further by integration of a third supported reagent for the sequential preparation of 3,5-diphenylpyrazole (Scheme 2.17). Following the previously established procedure, acetophenone was deprotonated and acylated to afford the 1,3-dicarbonyl species. This intermediate was easily separated from the spent polymers by filtration and passed without isolation into a suspension of the resin bound hydrazine salt (9), affording the desired pyrazole in 91% yield. In a subsequent publication, the authors reported that the depleted polymeric reagents from the first step of the conversion (i.e. (7) and (8)) were recovered and separated via a selective flotation procedure, enabhng them to... 

Hydrazine or hydrazine salts are carcinogenic in mice after oral administration (pulmonary adenocarcinoma hepatocarcinoma) or intraperitoneal injection (pulmonary carcinoma) and in rats after oral administration (pulmonary adenocarcinoma). Hydrazine induced a significantly greater incidence of nasal tumors, primarily benign, in rats and in hamsters after 1 year of intermittent inhalation exposure at levels up to 5.0ppm. ... 

The magnitude of K value for this self-ionization is in the order of which is greater than that for anhydrous ammonia ionizing to ammonium (NR4+) and amide (NH2 ) ions (K 10-33). Anhydrous hydrazine thus forms salts with hahde and other anions of the composition N2H5 X which are acids. Similarly, metallic hydrazides, M N2H3, are bases in anhydrous hydrazine. Most hydrazine salts are unstable and are sensitive to heat and... 

Hydrazine (or Hydrazonium)-N,N -dicarbonic Acid Diazide. See under HYDRAZINE SALTS OF ORGANIC ACIDS... 

Hydrazine salt of the above compound, mp 186-93° explodes violently on heating... 

Hydrazine salt of 4-nitro-6 chlor-1 -hydroxy-1, 2,3-benzotriazole, orange-yellow amorphous solid very powerful explosive... 

Hydrazine Salt, C2H3N304.N2H4 brick-red pdr, mp 95°(dec), puffs off at higher temp sol in w hot ale si sol in cold ale insol in eth chlf dissolves in acet with decompn (Ref 2, p 2750)... 

Hydrazine reacts with phenol diazonium salts to give products presumed to be the hydrazine salts of a Tetrazenepbenol. Hydrazine dissolved in water is added to an alc-water... 

Impurities present in tech NaN, may be subdivided into w-insol, such as carbonates and oxides of heavy metals and w-sol, such as carbonates of Na Ca, various nitrates and chlorides, hydrazine salts and ammonium salts... 

Sulphur dioxide, when slowly passed into a cooled alcoholic solution of hydrazine, yields the hydrazine salt of hydrazine disulphinic acid, N2H2(S02.N2Hs)2.° When the gas is passed into an aqueous solution of hydrazine hydrate, hydrazine pyrosulphite, (N2H4)2. H2S205, is formed, which, on neutralisation with hydrazine hydrate, yields hydrazine sulphite, (N2H4)2.H2S03. ... 

Of the various methods of estimation which are based on the use of hydrazine salts as reducing agents the following appears to be one of the most satisfactory 8 The tellurium, present either as a derivative of the dioxide or as a tellurate, is dissolved in hydrochloric acid and boiled. Sulphurous acid and hydrazine hydrochloride are added, and on continued boiling the tellurium is precipitated as such and may be collected,... 

Hydrazine in the presence of sulphuric acid reduces arsenic acid to a slight extent to arsine, which is subsequently oxidised to arsenic the reaction does not take place if a considerable concentration of hydrochloric acid is present.4 Arsenites, in the absence of arsenates, are not reduced by hydrazine. An aqueous solution of arsenic acid is reduced to the trioxide by hydrazine salts only after prolonged boiling.5... 

Nitrocyanoacetic Acid Methyl Ester, NC.CH(N02) C02CH3 mw 144.09, N 19.44% lustrous ndls + HzO, mp 76° readily sol in w MeOH diffc sol in eth was obtd by oxidn of isonitrosocyano-acetic acid methyl ester with KMn04 soln. Its Hydrazine salt, C4H4N204 + H2N.NH2, crysts (from MeOH), melts at 168° and its Potassium salt, NC.C( N02K).C02.CH3, lusturous lfts, decomp at 264-66°... 

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