Hydrazine, anhydrous, preparation

Hydrazine is prepared, anhydrous and in good yield, by glow discharge electrolysis of liquid ammonia a platinum cathode is immersed in liquid and a platinum wire anode is mounted just... 

MMHa.nd UDMH. MonomethyUiydrazine and yyz -dimethylhydrazine are manufactured by Olin Corp. using the same Raschig process and equipment employed for anhydrous hydrazine. Chloramine, prepared as described above, reacts with methylamine or dimethylamine instead of with... 

Hunsdiecker reaction, modified for preparation of 1-bromo-3-chlorocyclobutan9, 51, 106 Hydrazine, anhydrous, 50, 3, 4, 6... 

B. Acetone, hydrazone. Anhydrous hydrazine is prepared by heating under reflux 100% hydrazine hydrate with an equal weight of sodium hydroxide pellets for 2 hours, followed by distillation in a slow stream of nitrogen introduced through a capillary leak. (Caution Distillation in air can lead to explosion.) The distillate boils at 114-116° and the yield is 95-97% (Note 6). 

Hydrazine, H2N—NH2, is the simplest diamine. Free hydrazine never has been detected in nature on earth although many hydrazine derivatives have been found. Anhydrous hydrazine was prepared first by Lobry de Bruyn in 1894, In 1938, Fairmont Chemicals began the first production of hydrazine in the United States the quantity produced was small, and the product was mainly for captive use in boiler feedwater treatment. In World War II, hydrazine became important to Germany as a component of missile fuel. In 1954, Olin Chemicals built the first U.S. commercial N2H4 plant, of about 4 million Ib/year capacity. Hydrazine mainly is consumed as a high energy rocket fuel, an oxygen... 

The independent preparation of potassium phthabmide (from a solution of phthalimide in absolute ethanol and potassium hydroxide in 75 per cent, ethanol) may be avoided in many cases by boiling phthalimide with the halide in the presence of anhydrous potassium carbonate. The N-substituted phthalimide (I) is frequently cleav with difficulty this is often facilitated by reaction with hydrazine hydrate to give an intermediate product, which is easily decomposed by hydrochloric acid to 3deld the insoluble hydrazide of phthaUc acid (II) and the primary amine (III) ... 

Girard s reagent P , C5H5NCH2C0NHNH2 C1. In a 1-htre threenecked flask, equipped as in the previous preparation, place 200 ml. of absolute ethyl alcohol, 63 g. (64 -5 ml.) of pure anhydrous pyridine and 98 - 5 g. (84 5 ml.) of ethyl chloroacetate. Heat the mixture under reflux for 2-3 hours until the formation of the quaternary salt is complete acidify a small test-portion with dilute sulphuric acid it should dissolve completely and no odour of ethyl chloroacetate should be apparent. Cool the mixture in ice and salt. Replace the thermometer by a dropping funnel, and add a solution of 40 g. of 100 per cent, hydrazine hydrate in 60 ml. of absolute ethanol all at once. A vigorous exothermic reaction soon develops and is accompanied by vigorous effervescence. The pro duct separates almost immediately. When cold, filter with suction, wash... 

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) ... 

The beads prepared above (11.58 g.) are suspended in 175 ml. of boiling absolute ethanol, and 0.94 g. (0.0159 mole) of aqueous 85% hydrazine monohydrate is added with stirring. The resulting mixture is refluxed for 10 hours, after which the polymer is collected by filtration and washed with 150-ml. portions of ethanol, aqueous 0.2A sodium hydroxide, distilled water, and anhydrous methanol. After vacuum drying at 60° for four hours, the yield of polymeric benzylamine is 10.38 g. 

Hydrazine is an endothermic compound and the vapour is exceptionally hazardous in that once it is ignited, it will continue to bum by exothermic decomposition in complete absence of air or other oxidant [1]. Distillation of anhydrous hydrazine (prepared by dehydrating hydrazine hydrate with solid sodium... 

By conventional procedures, 106 gm of benzaldehyde reacts in 600 ml of ether with 66 gm of anhydrous hydrazine to give benzalhydrazone which is directly oxidized in anhydrous ether with 300 gm of mercuric oxide to phenyl-diazomethane.) (See Volume I, Chapter 15, p. 398, for oxidation of hydrazones, p. 390 for an alternative preparation of phenyldiazomethane.)... 

The azines represent another class of organic compounds which, in principle, should be reducible to azo compounds. The method is attractive since, with the availability of anhydrous hydrazine, azines are readily prepared from a wide variety of ketones and aldehydes. Evidently, introduction of 1 gram-molecule of hydrogen into an azine molecule has only recently been accomplished (see Section 6, Procedure 8) [73], Two preparations involving the 1,4-addition of chlorine to an azine system have been carried out and are illustrated here. 

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. 

Pour 2-3 ml of hydrazine on a watch glass and ignite it. The hydrazine should burn with a violet flame. If the sample of the obtained preparation does not ignite, freeze out the anhydrous hydrazine. To do this, put the receiver into a bath with ice. Pour the liquid off the precipitated crystals (what is the composition of the liquid and the crystals ), melt the crystals again, and repeat the operation. 

The 4-aminopyrimidines 367 and 368 were prepared by the reaction of the benzylidene malononitriles with thiourea or S-methylisothiourea, respectively. Nucleophilic substitution at the 2-position of 368 with hydrazine gave the 2-hydrazino derivative 369, whose treatment with carbon disulfide yielded the triazolopyrimidine 373 rather than its isomeric compound [83ZN(B)1686]. Heating 369 with benzoyl chloride in anhydrous dioxane,... 

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