Preparation of Hydrazine Hydrate

Preparation of Hydrazine Hydrate. Assemble an apparatus as shown in Fig. 85a. Grind 30 g of solid potassium hydroxide into a powder in a porcelain mortar wear eye protection ). Add 30 g of hydrazine sulphate to the powder and thoroughly mix the reactants. 

Put the mixture into a copper retort. Close the latter with an asbestos stopper and connect it to a cooler. 

Slowly heat the reaction mixture in a sand bath to 120-125 °C. Do not permit overheating The temperature oj the bath must not exceed 130 °C.) At what temperature does hydrazine hydrate boil Discard the fraction boiling up to 110 °C. Collect the hydrazine hydrate in a preliminarily weighed receiver connected to a cooler via ground-glass joints. Weigh the receiver with the preparation. Calculate the yield. Write the equation of the reaction. 

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The modified procedure involves refluxing the N-substituted phthaUmide in alcohol with an equivalent quantity of hydrazine hydrate, followed by removal of the alcohol and heating the residue with hydrochloric acid on a steam bath the phthalyl hydtazide produced is filtered off, leaving the amine hydrochloride in solution. The Gabriel synthesis has been employed in the preparation of a wide variety of amino compounds, including aliphatic amines and amino acids it provides an unequivocal synthesis of a pure primary amine. 

Indazoles can also be prepared by the [CCC + NN] method. For instance indazolones have been obtained rather simply by the action of hydrazine hydrate on 2-halobenzoic esters (78S633). 

Phenylsemicarbazide has been obtained by the action of hydrazine hydrate on diphenylurea, phenylurethane,i phenyl isocyanate, or the potassium salt of dibenzohydroxamic acid. For its preparation, Curtius method of treating phenylurea with hydrazine liydratc is better Ilian either the older method of... 

Hydrazine Diperchlorate (Hydrazinium Diperchlorate in Gmelin it is called Hydrazonium Hydroperchlorate, HDP). N2H4.2HCIO4, mw 232.97, OB +34.3% white crysts, mp 191°, d 2.21 g/cc (Ref 4) CA Registry No 13812-39-0 Preparation. HDP was first prepd by the interaction of equimolar amts of aq Ba perchlorate and hydrazine sulfate, the pptd Ba sulfate filtered off, and the filtrate evapd on a w bath until crystn occurs (Ref 2). It has also been prepd by the interaction of 2 moles of aq perchloric ac and 1 mole of hydrazine hydrate followed by evapn of the w or its azeotropic removal by distn with trichloroethylene (Ref 6), or by sweeping hydrazine vapors into 70% perchloric ac with dry N (Ref 7)... 

Suhtnicion nickel powders luive been synthesized successfully from aqueous NiCh at various tempmatuTKi and times with ethanol-water solvent by using the conventional and ultrasonic chemical reduction method. The reductive condition was prepared by flie dissolution of hydrazine hydrate into basic solution. The samples synthesized in various conditions weae claractsiz by the m ins of an X-ray diffractometry (XRD), a scanning electron microscopy (SEM), a thermo-gravimetry (TG) and an X-ray photoelectron spectroscopy (XPS). It was found that the samples obtained by the ultrasonic method were more smoothly spherical in shape, smaller in size and narrower in particle size distribution, compared to the conventional one. 

The exothermicity and violence of the reaction of hydrazine hydrate with 1-chloro-2,4-dinitrophenol caused destruction of the reactor in which the reaction was carried out. This reaction is of the same kind as the previous one (2,4-dinitrophenylhydrazine preparation). 

Diaminobiuret has been prepared only from N-tricarboxylic ester and hydrazine hydrate.1 Ethyl hydrazinecarboxylate has been prepared by reduction of nitrourethan electrolytically2 or with zinc dust and acetic acid,3 and by the action of hydrazine hydrate on diethyl carbonate,4 6 ethyl chlorocarbonate,6 and N-tricarboxylic ester.1... 

Phenylhydrazine has been prepared by the reduction of benzene diazonium salts with sulfites 1 by the reduction of benzene diazonium chloride with stannous chloride 2 by the reduction of benzene diazonium hydrate with zinc or sulfur dioxide 3 by the reduction of sodium benzene diazotate with sodium stannite 4 by the reduction of diazoamino benzene 5 by the reduction of nitrosophenyl hydroxylamine or its methyl ether 6 and by the action of hydrazine hydrate on phenol.7... 

Benzotellurepine has been prepared by the addition of Na2Te to o-diethynylbenzene in the presence of hydrazine hydrate, under PTC conditions. The compound is quite unstable but is converted into the more stable dihalides by treatment with SOjClj or Br2- The dihalides regenerate the tellurepine by reduction with NajS. ... 

Preparation of Hydrazine. Assemble an apparatus as shown in Fig. 85b. Put an amount of potassium hydroxide into a two-neck flask provided with a reflux condenser such that there is a 2-3-mm layer of hydrazine hydrate over it. Cool the flask in a bath with ice and transfer the previously prepared hydrazine hydrate into it wear eye protection ). Pass a stream of dry nitrogen through the reaction mixture. Carefully heat the flask until the alkali dissolves completely, then cool the flask to room temperature, and, without stopping the nitrogen stream, replace the reflux condenser with a dephlegmator. Assemble an apparatus for fractional distillation (see Fig. 20) and distil off the anhydrous hydrazine in a nitrogen stream at 112-114 °C. 

With selenium sols prepared by means of hydrazine hydrate at the ordinary temperature, by pouring into a large volume of water it has been shown that the stability of the colloid depends mainly on the degree of dispersion. An optimum concentration of electrolyte is necessary for the stability of the hydrosols. In the absence of electrolytes the system is quite unstable towards freezing. 

T. Curtius and H. Schulz prepared hydrazine difluoride, N2H6F2, by adding hydrofluoric acid to an alcoholic soln. of hydrazine hydrate and also by evaporating an aq. soln. of the base neutralized with hydrofluoric acid. 

T. Cuitius prepared hydrazoic acid by the action of the red gases evolved from a mixture of nitric acid and arsenic trioxide upon a dil. ice-cold soln. of hydrazine hydrate and A. Sabaneeff and E. Dengin obtained a 10-12 per cent, yield of hydrazoic acid by heating hydrazine sulphate with nitric acid (sp. gr. 1 3). The formation of hydrazoic acid by heating various hydrazine salts (q.v.) was studied by J. W. Turrentine. 

Salts of semicarbazide have been prepared by the action of potassium cyanate on hydrazine sulfate 1 by the action of hydrazine hydrate on urea 2 by heating hydrazine ammonium carbonate 3 bv the reduction of nitrourea with zinc dust and hydrover. 27, 31 (1894). 

Heating 9-hydroxy-2-methyl-8-nitro-4//-pyrido[ 1,2-a]pyrimidin-4-one 326 in dimethylformamide in the presence of hydrazine hydrate and Raney nickel at 50°C afforded 8-amino derivative 327 (92KGS1660). 8-Amino derivative 327 was also prepared from 8-phenylazo derivative 328. 

Preparation of l-Cyclopropylmethyl-5-Phenyl-7-Chloro-lH-l,4-Benzodiazepine-2(3H)-one To a solution of 39.5 g (0.0845 mol) of 2-(N-phthalimidoacetyl-N-cyclopropylmethyl)amino5-chlorobenzophenone in a mixture of 423 ml of chloroform and 423 ml of ethanol is added 9.52 g (0.1903 mol) of hydrazine hydrate and 9.52 ml of water. This solution is allowed to stand at room temperature. In 3 hours a precipitate begins to form in the solution. After standing 16 to 24 hours a voluminous pulpy white precipitate forms. The solvents are removed under vacuum while keeping the temperature under 40°C and the residue is partitioned between dilute ammonia water and ether. 

Preparation from Hydrazine Hydrate. Hydrazine hydrate may be substituted for hydrazine sulfate in the preparation of biurea. In this case it is necessary to supply enough additional acetic acid to compensate for the absence of sulfuric acid. Thus, 29 g. of 85% hydrazine hydrate (0.5 mol) and 90 g. of glacial acetic acid (1.5 mol) are dissolved in 500 ml. of water. Eighty-nine grams of potas-... 

This compound is prepared by reacting and mole of guanidine dinitrate with 3 moles of hydrazine hydrate at 100 °C = 212 °F for four hours. The reaction is accompanied by the liberation of ammonia. 

The fused pyrrole ring system (204) has been obtained by the reaction of 17/3-hydroxy-17-methylandrosta-l,4-dien-3-one with tosylmethyl isocyanide in the presence of sodium hydride in DMSO,92 and 17/3-hydroxy-17-methyl-7-oxa-5o -androstano-[3,2-c]- (205) or -[2,3-d]-isoxazoles (206 X = O) have been prepared by treating 7-oxa-2-(hydroxymethylene)-17/3 -hydroxy-17-methyl-5 a -androstan-3-one with hydroxylamine hydrochloride.93 In the presence of pyridine, the isox-azole (206 X = O) is formed, but when the reaction is catalysed by sodium acetate in acetic acid the isomeric steroid (205) results. Cycloaddition of hydrazine hydrate to the same 2-hydroxymethylene-7-oxa-steroid results in the [3,2-c]pyrazole (206 X = NH). A similar addition is encountered in the reactions between 3/3-hydroxy-16-(hydroxymethylene)-5a-androstan-17-one and the substituted hydrazines RNHNH2 (R = H, o-COC6H4NH2, or p-COQHUNH ,) when the corresponding [17,16-c]pyrazoles (207) are formed after cyclization of the intermediate hydrazones.94... 

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