Nitrogen -2 Hydrazine

Phj/skai deanfipthn Fuming, colorless liquid smells like ammonia 

History /ap ication note Isolated in 1890 by T. Curliu good reducing agent methyl derivatives used as rocket fuels 

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HMX, Octagen, Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazine under Secondary Aliphatic Amines HxCDF Hexachlorodibenzofurans under Dioxin and Related Compounds Hydrazine under Ions with Nitrogen Hydrazine Derivatives... 

Nitrogen, phosphorus and arsenic form more than one hydride. Nitrogen forms several but of these only ammonia, NHj, hydrazine, N2H4 and hydrogen azide N3H (and the ammonia derivative hydroxylamine) will be considered. Phosphorus and arsenic form the hydrides diphosphane P2H4 and diarsane AS2H4 respectively, but both of these hydrides are very unstable. 

Pure hydrazine is a colourless liquid, melting point 275 K, and boiling point 387 K. It is surprisingly stable for an endothermic compound = -i- 50.6 kJ mol ). Each nitrogen atom has a lone pair of electrons and either one or both nitrogen atoms are able to accept protons to give and the less stable... 

In aqueous solution hydrazine can behave either as an oxidising or reducing agent. Powerful reducing agents such as zinc reduce hydrazine to ammonia, while chlorine oxidises it to give nitrogen. 

The problem of the synthesis of highly substituted olefins from ketones according to this principle was solved by D.H.R. Barton. The ketones are first connected to azines by hydrazine and secondly treated with hydrogen sulfide to yield 1,3,4-thiadiazolidines. In this heterocycle the substituents of the prospective olefin are too far from each other to produce problems. Mild oxidation of the hydrazine nitrogens produces d -l,3,4-thiadiazolines. The decisive step of carbon-carbon bond formation is achieved in a thermal reaction a nitrogen molecule is cleaved off and the biradical formed recombines immediately since its two reactive centers are hold together by the sulfur atom. The thiirane (episulfide) can be finally desulfurized by phosphines or phosphites, and the desired olefin is formed. With very large substituents the 1,3,4-thiadiazolidines do not form with hydrazine. In such cases, however, direct thiadiazoline formation from thiones and diazo compounds is often possible, or a thermal reaction between alkylideneazinophosphoranes and thiones may be successful (D.H.R. Barton, 1972, 1974, 1975). 

Low-valent nitrogen and phosphorus compounds are used to remove hetero atoms from organic compounds. Important examples are the Wolff-Kishner type reduction of ketones to hydrocarbons (R.L. Augustine, 1968 D. Todd, 1948 R.O. Hutchins, 1973B) and Barton s olefin synthesis (p. 35) both using hydrazine derivatives. 

The principal reactions of this class of compounds are summarized in Scheme 172. In most of these reactions the reactive nucleophilic center is the terminal NHj group, although the other exocyclic nitrogen may also be involved, as shown by acetylation, which yields 284 and 285. However, the structure of compound 281 is not the one proposed in a recent report (1582) that attributes the attack to the other exocyclic nitrogen. The formation of osazones (287) from sugars, 2-hydrazinothiazoles, and hydrazine has been reported (525, 531). 

Volatile hydrides, except those of Periodic Group VII and of oxygen and nitrogen, are named by citing the root name of the element (penultimate consonant and Latin affixes. Sec. 3.1.2.2) followed by the suffix -ane. Exceptions are water, ammonia, hydrazine, phosphine, arsine, stibine, and bismuthine. 

Reductions. Hydrazine is a very strong reducing agent. In the presence of oxygen and peroxides, it yields primarily nitrogen and water with more or less ammonia and hydrazoic acid [7782-79-8]. Based on standard electrode potentials, hydrazine in alkaline solution is a stronger reductant than sulfite but weaker than hypophosphite in acid solution, it falls between and Ti ( 7). 

Urea Process. In a further modification of the fundamental Raschig process, urea (qv) can be used in place of ammonia as the nitrogen source (114—116). This process has been operated commercially. Its principal advantage is low investment because the equipment is relatively simple. For low production levels, this process could be the most economical one. With the rapid growth in hydrazine production and increasing plant size, the urea process has lost importance, although it is reportedly being used, for example, in the People s RepubHc of China (PRC). 

Materials of Construction. In choosing the proper materials of constmction for storing and using hydrazine, it is necessary to consider both the effects of the material on the stabiUty and quaUty of the hydrazine as well as the effect of the hydrazine on the material of constmction. Hydrazine is thermally stable, storable for years without adverse effects either to the product or the storage container provided the recommended materials are used, all systems are clean, and an inert gas, ie, nitrogen, is maintained over the system at all times. Table 10 is a brief listing of materials compatibiUty (125). 

Agricultural Uses. Pesticides represent the second largest commercial market for hydrazine. Hundreds of hydrazine derivatives have been patented for a wide range of agricultural appHcations. Table 13 presents a sampling of the 50—60 that are commercially available or developmental products. These compounds are made from hydrazine, MMH, and UDMH and are for the most part heterocycHc nitrogen compounds (see Insect control technology). 

Aluminum chloride [7446-70-0] is a useful catalyst in the reaction of aromatic amines with ethyleneknine (76). SoHd catalysts promote the reaction of ethyleneknine with ammonia in the gas phase to give ethylenediamine (77). Not only ammonia and amines, but also hydrazine [302-01-2] (78), hydrazoic acid [7782-79-8] (79—82), alkyl azidoformates (83), and acid amides, eg, sulfonamides (84) or 2,4-dioxopyrimidines (85), have been used as ring-opening reagents for ethyleneknine with nitrogen being the nucleophilic center (1). The 2-oxopiperazine skeleton has been synthesized from a-amino acid esters and ethyleneknine (86—89). 

Group 15 (VA) Perchlorates. Nitrogen perchlorates have been used as oxidizers in rocket propellants. Hydrazine perchlorate [13762-80-6] NH2NH2CIO4, and hydrazine diperchlorate, CIO4NH2NH2CIO4, have been investigated as oxidizers for propellant systems (60). Anhydrous salts can be... 

Cross-linked PVP can also be obtained by cross-linking the preformed polymer chemically (with persulfates, hydrazine, or peroxides) or with actinic radiation (63). This approach requires a source of free radicals capable of hydrogen abstraction from one or another of the labile hydrogens attached alpha to the pyrrohdone carbonyl or lactam nitrogen. The subsequently formed PVP radical can combine with another such radical to form a cross-link or undergo side reactions such as scission or cyclization (64,65), thus ... 

Nitrite can be deterrnined by reaction with sulfanilamide to form the diazo compound, which couples with /V-(1-naphthyl)ethylenediamine dihydrochloride to form an intensely colored red azo dye. Nitrate can be deterrnined in a similar manner after reduction to nitrite. Suitable reducing agents are cadmium filings or hydrazine. This method is useful at a nitrogen concentration of 10 -lO " M. 

Ammonia, hydrazine, nitrites, and azides ate oxidized by bromine. Nitrogen is often a product of such reactions. 

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