Mercuric compounds with nitrogen

The mechanism of oxynitration is generally accepted to involve the formation of phenyl mercuric nitrate which reacts with nitrogen oxides in the nitric acid to form a nitroso compound and then a diazonium salt the latter forms a phenol under the aqueous conditions which is then further nitrated. The use of more concentrated nitric acid favours a process of mercuration-nitration and suppresses the formation of phenols. ... 

It becomes a problem in semantics to set a time limit for "development within which a process can be considered "spontaneous or "instantaneous . These two words seem to apply well to such extremely sensitive compounds as Nitrogen Triodide and Cupric Azide, which explode at the slightest touch when dry and, in addition, explode at a fairly low temperature. Attempts to correlate initiation in such cases with the attainment of a certain temperature seem unrealistic, especially in view of differences between relative sensitivity of different compounds to mechanical and thermal influences. For example, Mercuric Azide is so sensitive to impact that it explodes even under water, hut its heat sensitiveness is about the same as that for Cadmium Azide, which has been reported not to explode by percussion (Ref 5) Information about susceptibility of different explosives to spontaneous detonation is highly important from the viewpoint of safety. In Refs which follow are listed examples of spontaneous detonations of substances, some of them previously considered safe in this respect... 

Ruff and Geisel 3 assume that the compound of nitrogen sulphide with ammonia dissociates in anhydrous ammonia solution forming (A), N S NHa, and (b), S S(NH)a, of which the former yields an insoluble mercuric salt, N S NHg, and the latter an insoluble lead salt,... 

For the preparation of chlorides or bromides, the diazonium salt is decomposed with a solution of cuprous chloride or bromide in the corresponding halogen acid (Sandmeyer reaction). It is possible to prepare the aryl bromide from the diazonium chloride or sulfate. A variation Involves the use of copper powder and a mineral acid for the decomposition step (Gattermann reaction). Both procedures are illustrated by the syntheses of the isomeric bromotoluenes and chlorotoluenes. The usual conditions of the Sandmeyer reaction fail in the preparation of the chloro- and bromo-phenanthrenes. However, these compounds can be successfully obtained by the interaction of the diazonium compound with mercuric and potassium halides (Schwechten procedure). Another procedure for formation of aryl bromides involves treatment of the amine hydrobromide with nitrogen trioxide in the presence of excess 40% hydro-bromic acid. The Intermediate diazonium perbromide is then decomposed by heat. ... 

One method for the preparation of diphenylacetylene involves oxidation of benzil dihydrazone with mercuric oxide the intermediate diazo compound loses nitrogen as formed to give the hydrocarbon ... 

Mercury-nitrogen compounds. By the interaction of mercuric salts with ammonia in aqueous solution a number of compounds can be obtained, depending on the conditions. They include ... 

It is important to preserve samples of waste water, particularly for determining cyanide, phenol, organic compounds and nitrogen compounds, etc. (e.g. with chloroform, by alkalization or with mercuric chloride) (see 1.7). 

The compounds of the amides with bivalentmercuryarecharacteristic. In them the metal is united to the nitrogen and is not in ionic combination, as in a salt. They are formed by the action of mercuric oxide, e.g. 

Fire or explosion hazard may arise from the foUowing ammonia reactions Reaction with halogens produces nitrogen trihahdes which explode on heating its mixture with fluorine bursts into flame reacts with gold, silver, or mercury to form unstable fulminate-type shock-sensitive compounds similarly, shock-sensitive nitrides are formed when ammonia reacts with sulfur or certain metal chlorides, such as mercuric, or silver chloride liquid ammonia reacts violently with alkah metal chlorates and ferricyanides. 

Among the oxidative procedures for preparing azo compounds are oxidation of aromatic amines with activated manganese dioxide oxidation of fluorinated aromatic amines with sodium hypochlorite oxidation of aromatic amines with peracids in the presence of cupric ions oxidation of hindered aliphatic amines with iodine pentafluoride oxidation of both aromatic and aliphatic hydrazine derivatives with a variety of reagents such as hydrogen peroxide, halogens or hypochlorites, mercuric oxide, A-bromosuccinimide, nitric acid, and oxides of nitrogen. 

Although three early papers briefly discussed reactions between methylcobalamin and mercury compounds (30-32), the most systematic investigation has come from Wood and co-workers (33). They proposed the mechanism shown in Fig. 1, with values for the various rate constants presented in Table I. Species 2 and 3, in which the benzimidazole nitrogen no longer bonds to the cobalt atom, are termed base-off compounds, whereas 1 is base-on methylcobalamin and 4 is aquocob(III)alamin, the usual product of aqueous transmethylation by 1. Each one of these species has a unique ultraviolet-visible spectrum, which allows quantitative studies by spectrophotometric techniques to be made (28, 32, 33). The mercuric acetate-1 exchange is so rapid that it must be studied using stopped-flow kinetic techniques (33). 

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