Diazonium nitrate, formation

The reaction of primary aromatic nitramines with nitrous acid is specific and leads to the formation of diazonium nitrate (Bamberger [23]). According to Stevens [24] this reaction is also a kind of reduction, and presumably may be represented as follows ... 

The reactions involve the initial formation of the nitroso compound which reacts further with the nitrous acid present to yield the diazonium nitrate. The reaction has been shown to involve exactly 3 moles of nitrous acid and the mechanism is probably as follows 16... 

Mechanistically, the reactions of adamantane and ethers with NO are rationally explained by considering the formation of carbocations as transient intermediates (Scheme 6.14). The generation of PINO from NHPI in the presence of NO is confirmed by ESR measurements [170], but the formation of PINO by this method may be due to traces of NO2 contained in the reaction system. On the other hand, Suzuki has suggested the formation of a cationic species via a diazonium nitrate in the nitration of alkenes with N O [ 17 5 ]. The nucleophilic attack of the benzonitrile and water on the adamantyl and benzylic cations would result in the amide and aldehyde, respectively [170]. 

The formation of 3,3, 4,4 -tetrachloroazobenzene, l,3-bis(3,4-dichlorophenyl)triazine and 3,3, 4,4 -tetrachlorobiphenyl from 3,4-dichloroaniline and nitrate by E. coli plausibly involved intermediate chemical formation of the diazonium compound by reaction of the amine with nitrite (Corke et al. 1979) (Figure 2.2g). 

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. ... 

The formation of a diazonium group from the arylamine derivative can be done by treatment with sodium nitrate in HC1 (see protocol in Chapter 9, Section 6.1). 

ANILINE (62-53-3) Combustible liquid (flash point 158°F/70°C). Unless inhibited (usually by methanol), readily able to polymerize. Violent reaction, including the possibility of fire, explosion, and the formation of heat- or shock-sensitive compounds may result from contact with acetic anhydride, benzene diazonium-2-carboxylate, aldehydes, alkalis, benzenamine hydrochloride, boron trichloride, l-bromo-2,5-pyrrolidinedione, chlorosulfonic acid, dibenzoyl peroxide, fluorine nitrate, halogens, hydrogen peroxide, isocyanates, oleum, oxidizers, organic anhydrides, ozone, perchloryl fluoride, perchromates, potassium peroxide, P-propiolactone, sodium peroxide, strong acids, trichloromelamine. Strong reaction with toluene diisocyanate. Reacts with alkaline earth and alkali metals. Attacks some plastics, rubber, and coatings. Incompatible with copper and copper alloys. 

Further, certain substituents, such as the nitro group and halogens, favor formation of the hydrocarbon. For instance, even with very dilute alcohol tribromobenzenediazonium chloride affords tribromobenzene almost exclusively, with only traces of tribromophenol and the nitrated hydrocarbons are similarly obtained in very good yields from nitrated diazonium compounds. 

Mechanistically, their formation can be explained either by rearrangement of the intermediate A -nitroamines in acidic medium or by the direct nitration of 5a. Alternatively, BTDOs are prepared from anilines 39 by diazotization and treatment of diazonium salts 41 with t 7-chloroperbenzoic acid (MCPBA). A third methodology consists of a P4O10- or PCls-promoted ring closure of iV-nitroanilines 40, achieved in the case of 5a and 5h <2000RCB482>. 

A novel method of formation of the triazolop5uidine 1 has been described by Deady and Devine from an aminonaphthyridinone 47 (Scheme 3) (06T2313). When compound 47 in fluoroboiic acid at 0 °C is treated with aqueous sodium nitrate, a diazonium salt 48 is formed. When this salt is suspended in water and treated with 10% sodium hydroxide, it results in a white solid, the triazolopyrido aldehyde 50. A plausible mechanism requires that, reasonably, position 7 in 48 is more electron deficient than position 8 and hydrolysis occurs as shown in Scheme 3. The presumed intermediate 49 is not isolated. 

Preparation and subsequent decomposition of polymers with diazonium salts can also be used to form graft cowlymers. An example is a nitrated polystyrene, reduced to the amine derivative and then diazotized. The decomposition of the diazonium salt results in the formation of radicals ... 

Human antibodies are the proteins called gamma globulin in the serum of the blood. They have molecular mass about 270,000 d. Proteins and polysaccharides foreign to the individual or the species of animals, when injected, may serve as antigens. Also, small molecules may be attached to proteins and injected to induce formation of antibodies with the power of combining specifically with them. For example, if / -amino-benzoic acid, H2NCeH4COOH, is treated with hydrochloric acid and sodium nitrate it forms the diazonium ion N= N—C6H4COOH, which... 

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