Of hydrazine

The base strength of hydrazine is, however, lower than that of ammonia. As might be expected, hydrazine is readily soluble in water from which the hydrate N2H4.H2O can be crystallised. 

H—N—N=N. It is prepared by the oxidation of hydrazine in strongly acid solution the oxidising agent used is usually nitrous acid (i.e. sodium nitrite is added to the acid solution of hydrazine) ... 

Dissolve 10 g. of chloro- 2,4-dinitrobenzenet in 50 ml. of dioxan in a 250 ml. conical flask. Dilute 8 ml. of hydrazine hydrate with an equal volume of water and add this slowly with shaking to the dioxan solution, keeping the temperature between zo " and 25°. Heat under reflux for 10 minutes to complete the reaction and then add 5 ml. of ethanol and heat again for 5 minutes. Cool and filter oflF the orange 2,4-dinitrophenylhydra-zine. Recrystallise the dry product from ethyl acetate m.p. 200° (decomp.). Yield, 7 g. 

Procedure for Bromine and Iodine Estimations. Again cover the beaker as before, but before adding the nitric acid add i g. of hydrazine sulphate and heat the solution on the water-bath until evolution of gas ceases. To ensure complete decomposition of an iodate, however, the heating should be continued for i hour. 

Place 1 0 ml. of hydrazine hydrate (CAUTION corrosive chemical) in a test-tube fitted with a short refiux condenser. Add 10 g. of the methyl or ethyl ester dropwise (or portionwise) and heat the mixture gently under refiux for 15 minutes. Then add just enough absolute ethanol through the condenser to produce a clear solution, refiux for a further 2-3 hours, distil oflF the ethyl alcohol, and cool. Filter oflF the crystals of the acid hydrazide, and recrystallise from ethanol, dilute ethanol or from water. 

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. 

Dissolve 65 g. of hydrazine sulphate in 400 ml. of 2 5. V sodium liyd i oxide solution contained in a 1-htre three-necked flask, equipped with a thermometer, mechanical stirrer and dropping funnel. Immerse the flask in an ice bath and when the temperature reaches 15° (some sodium sulphate... 

Benzil monohydrazone. Method 1. Boil a mixture of 26 g. of hydrazine sulphate, 55 g. of crystallised sodium acetate and 125 ml. of water for 5 minutes, cool to about 50°, and add 115 ml. of methyl alcohol. Filter off the precipitated sodium sulphate and wash with a little alcohol. Dissolve 25 g. of benzil (Section IV,126) in 40 ml. of hot methyl alcohol and add the above hydrazine solution, heated to 60°. Most of the benzil hydrazone separates immediately, but reflux for 30 minutes in order to increase the yield. Allow to cool, filter the hydrazone and wash it with a httle ether to remove the yellow colour. The yield is 25 g., m.p. 149-151° (decomp.). 

Method 2. Drop 10 g. of hydrazine hydrate (85 per cent, aqueous solution see Section 11,49,Id) into a hot solution of 35 g. of benzil (Section IV,126) in 70 ml. of alcohol with stirring. When about three-fourths of the hydrazine hydrate has been introduced, the product begins to separate. After all the reagent has been added, heat the solution under reflux for 5 minutes, cool to 0°, filter at the pump, and wash twice with 20 ml. portions of alcohol. The yield of benzil monohydrazone, m.p. 149-151° (decomp.), is almost quantitative. 

N-(2-Thiazolyl)cyanamide may be converted into guanidino derivatives by the action of hydrazines (487). /V-Aryl-N -(4-aryl-2-thiazolybguanidines... 

This set of compounds is the most thoroughly studied among derivatives of 2-aminothiazole, thanks to the Beyer group. Heterocychzation methods are most commonly used for their preparation (see Chapter II and Refs. 37, 341, and 513-520). Reaction of 2-diazothiazoles (277) with organometallics provides another synthetic method (Scheme 1711 (521). 2-Hydrazinothiazoles may also be obtained by the action of hydrazine on 2-bromothiazoles (388) or on 2-mercaptothiazoles (522). 

Acetyl-3-mercaptopropanol reacts with acetaldehyde in the presence of hydrazine hydrate to yield 2,4-dimethyl-5-(/3-hydroxyethyl)thiazole (10), R, = Rj = Me, R3 = CH2CH2OH (556). 

Thus esters were converted to hydrazides with an excess of hydrazine hydrate in alcohol with a yield of 84% (66). 

Heating diethyl 2-phenyl-4,5-thiazoledicarboxylate (16) in alcohol with an excess of hydrazine hydrate gave a mixture of cyclohydrazide (17) and the open-chain 2-phenyl-4,5-thiazoledicarboxylic dihydrazide (18) (Scheme 11) (5). The relative amounts of these two products depended on... 

The first large-scale use of hydrazine was as fuel for the rocket-powered German ME-163 fighter plane during World War II. Production in the United States began in 1953 at the Lake Charles, Louisiana plant of the Olin Corp., a facility then having a capacity of 2040 metric tons. In 1992 world capacity was about 44,100 metric tons N2H4. 

The many advantageous properties of hydrazine ensure continued commercial utility. Hydrazine is available in anhydrous form as well as aqueous solutions, typically 35, 51.2, 54.4, and 64 wt % N2H4 (54.7, 80, 85, and 100% hydrazine hydrate). 

The freezing point diagram for the hydrazine—water system (Eig. 1) shows two low melting eutectics and a compound at 64 wt % hydrazine having a melting point of —51.6°C. The latter corresponds to hydrazine hydrate [7803-57-8] which has a 1 1 molar ratio of hydrazine to water. The anomalous behavior of certain physical properties such as viscosity and density at the hydrate composition indicates that the hydrate exists both in the Hquid as well as in the soHd phase. In the vapor phase, hydrazine hydrate partially dissociates. 

Hydrazine forms a high (120.5°C) boiling azeotrope with water that has a composition of 58.5 mol % (71.48 wt %) N2H4 at 102.6 kPa (1.02 atm) pressure. This comphcates the separation of hydrazine from water in the manufacturing process because it necessitates the removal of a large amount of water in order to approach the azeotropic composition. 

The explosive limits of hydrazine in air are 4.7—100 vol %, the upper limit (100 vol %) indicating that hydrazine vapor is self-explosive. Decomposition can be touched off by catalytic surfaces. The presence of inert gases significantly raises the lower explosive limit (10) (Table 2). 

Table 2. Lower Explosive Limits of Hydrazine in Other Gases...

Hydrazine as Nucleophile. Reaction of hydrazine and carbon dioxide or carbon disulfide gives, respectively, hydrazinecarboxyhc acid [471-31-8], NH2NHCOOH, and hydrazinecarbodithioic acid [471-32-9], NH2NHCSSH, in the form of the hydrazinium salts. These compounds are useful starting materials for further synthesis. For example, if carbon disulfide reacts with hydrazine in basic medium with an alkyl haUde, an alkyl dithiocarbazate ester is obtained in a one-step reaction ... 

A large excess of hydiazine oi bulky alkyl groups favor monosubstitution. For example, a 60—70% yield of monoisopropylbydrazine [2257-52-7J is achieved by reaction of isopropyl bromide and a fivefold excess of hydrazine (56). 

Branched-chain alkenes react with hydrazine under acidic conditions to give the corresponding alkyl hydrazine. For example, isobutylene bubbled through an aqueous solution of hydrazine and HCl gives /-butyUiydrazine in reasonably good yields (64). 

A process for heating alkyldithiocarbamate salts (31) in the presence of hydrazine hydrate to produce 4-alhylthiosernicarbazides (32) has been described... 

Heterocyclics. One of the most characteristic and useful properties of hydrazine and its derivatives is the ability to form heterocycHc compounds. Numerous pharmaceuticals, pesticides, explosives, and dyes are based on these rings. A review of the appHcation of hydrazine in the synthesis of heterocychcs is available (91). For further information in the field of heterocycHc chemistry, see the General References. 

This reaction is slow and requires elevated temperatures of 120—150°C under pressure. The kinetics (93,94) and mechanism (95,96) of these reactions have been studied. An undesirable competing reaction is the further oxidation of hydrazine by chloramine ... 

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