Nitric anhydride

Salpetersaure. /. nitric acid, -anhydrid, n. nitric anhydride, (di)nitrogen pentoxide, nitrogen(V) oxide, -ather, m. nitric ether (ethyl nitrate), -bad, n. nitric acid bath, -dampf, m. nitric acid vapor or fume. 

When olefin hydrocarbons react with nitrogen dioxide or nitrous and nitric anhydride, they are added to a double bond. .. 

Synonyms dinitrogen pentoxide nitric anhydride nitric acid anhydride. Uses... 

The synthesis of 3-nitro-l-substituted uracil derivatives 30 can readily be performed with trifluoroacetic nitric anhydride, and this procedure is used in nucleoside chemistry to convert the uracil 3-nitrogen to a good leaving group <1995JA3665, 1997JOC1547, 20020L1827>. 

The related pyrido[3,4- ]-l,2,3>4-tetrazine 2,4-dioxide 11 was accessed using a similar sequence of reactions, starting with the hydroxylamine 172 as shown in Scheme 30. The key differences are that the 4-amino derivative 175 was accessed through displacement of an ethoxy group from the intermediate 174 rather than by the chlorine displacement used above, and that ring closure this time could only be achieved with nitronium tetrafluoroborate. Nitric anhydride, in contrast to the reaction shown in Scheme 29, gave no product <2004RCB2577>. 

The nomenclature for this homologous series is somewhat confused. The term PANs has been used historically to denote peroxyacyl nitrates, and this terminology continues to be used extensively in the literature, despite the lack of adherence to traditional IUPAC rules of nomenclature. Because the PANs can be considered to be mixed anhydrides of carboxylic acids and nitric acid, another suggestion (Roberts, 1990) has been peroxyacetic nitric anhydride for CH,C(0)00NO2 and peroxy carboxylic nitric anhydrides for the whole class of compounds. Although it does not follow the IUPAC rules, it would be consistent with the widespread use of the name PAN but also reflect the structure more accurately. Table 6.20 shows the structures and commonly used names of some PANs that have been observed in the atmosphere and/or in laboratory studies. 

Peroxyacetyl nitrate (peroxyacetic nitric anhydride) PAN O II ch,coono2... 

Two atonu of nitrogen and fire atonu of oxygen form nitric anhydride. 

If the iodine be in large enough excess, the reaction proceeds until the nitric acid is so dil. by the production of water in the reaction, that it has no further action on the iodine even though the acid is cone, enough to keep the iodic acid sparingly soluble and to hold considerable quantities of iodine in soln. The yield of iodic acid by the action of nitric acid on iodine is not very great—about 4 per cent. a much greater yield—about 40 per cent.—is obtained by the action of nitric anhydride... 

In some more complex cases, secondary amines can be nitrated with nitrating mixtures. Diethanolnitramine dinitrate (DINA), for example, can be prepared by the action on diethanolamine of a mixture of nitric acid, nitric anhydride and zinc chloride (this is dealt with in more detail on p. 10). 

In method 5, as in method 1, nitrolysis of hexamethylenetetramine occurs, the alcohol groups so produced being esterified with acetic anhydride and not with nitric anhydride as in method 1. The most important by-product formed to the extent of nearly 10% by method 5 is octogen (XI). It is produced as outlined above, as a result of hexamine nitrolysis (p. 90). 

The possibility of attaining a nitrogen content of 14.0% by nitrating with the help of nitric anhydride was indicated by Hoitsema [1]. His experiments have since been repeated and modified by many workers, as shown in the chapter on nitrating cellulose with nitric anhydride. 

Dalmon [72] reacted the fibre of Chinese nettle (ramie) with nitric anhydride in a stream of dry air. Nitrocellulose containing as much as 14.12% N, i.e. cellulose trinitrate (within the limits of analytical error), was obtained. T. Urban-ski and Janiszewski [56] obtained a nitrogen content of 13.90-13.95% on repeating these experiments with cotton (linters) at 25°C. 

It has been demonstrated (T. Urbanski and Janiszewski [47]) that it is possible to nitrate starch by means of nitric anhydride vapour in a stream of air or with... 

Nevertheless these experiments have helped to clarify the chemical character of lignin. From this point of view the researches of Freudenberg et al. [65], who acted on lignin with nitrogen dioxide or with nitric anhydride are also of importance. 

Packed column technology has been used in airborne gas chromatographs for the separation and quantitation of sulfur species (46, 47) and peroxyacetic nitric anhydride (48). The combination of sample preconcentration and sensitive detectors has yielded detection limits that are superior to corresponding continuous sensors. For S02, a detection limit of 25 pptrv was claimed, and for peroxyacetic nitric anhydride the detection limit was roughly 60 pptrv for an 50-cm3 air sample. Analysis times for samples were on the order of 10 min. 

Nitric anhydride, 3 78 Nitric oxide [see Nitrogen (II) oxide] Nitrido compounds with osmium, 6 204... 

At high concentrations (mixtures with a low water content) Sapozhnikov found certain anomalies in the vapour pressure of HN03 and in its electric conductivity. He ascribed them to the formation of nitric anhydride N205. Thus the equation will be ... 

Sapozhnikov5s view was partly confirmed by Walden [17], Halban and Eisen-brand found [18] that the absorption spectrum of pure nitric acid in the ultraviolet differed completely from its spectrum when in solution in anhydrous sulphuric acid. The authors explained this observation by assuming the existence of the nitric anhydride or the mixed nitric-sulphuric anhydride. This assumption seemed to be all the more probable as in some earlier papers the idea had already been expressed that N205 might exist in concentrated nitric acid. Thus in 1898... 

According to Titov s paper of 1941 nitric anhydride dissociates into the nitronium Mid nitrate ions ... 

Ingold and his co-workers regarded nitric anhydride as nitronium nitrate (N02)+(N03) (see also eqn. 24). They obtained nitronium di- and trisulphates by treating nitric anhydride with S03 ... 

Further investigations of Chedin [60a-62] and of Susz, Briner and Favarger [63] have shown that a solution of nitric anhydride (N205) in nitric acid produces both 1050 and 1400 cm"1 lines. From this the assumption has been advanced that the two lines indicate the presence of N205 in mixtures of nitric and sulphuric acids. Thus it seemed that Sapozhnikov s theory (p, 10) had been confirmed. However, further investigations have shown that this interpretation of the results is not quite right. For Chedin stated that solutions of N205 in carbon tetrachloride, chloroform, nitromethane and phosphorus oxychloride produced the 707, 860, 1033, 1240 and 1335 cm"1 lines (in addition to the solvent line), while there were... 

On the grounds of Walden s observations (in his ciyometric studies), that nitric anhydride exists in POCl3 solution in a non-associated form, Mid that according to Russ Mid Pokomy [64] it is associated when in solid form, Chedin has come to a conclusion that the Raman 1050 and 1400 cm 1 lines correspond to associated N205, while the 707, 860, 1033, 1240, and 1335 cm"1 lines correspond to the non-associated, monomolecular form of N2Os. Consequently N2Os in nitric acid or in nitric and sulphuric acids solution would appear to exist in mi associated form. 

Nitric anhydride produces a spectrum composed of the two lines, since it undergoes dissociation according to the eqn. (24) given on p. 15. 

In 1924, Klemenc and Scholler [34] stated that m- xylene-2,6-disulphonic acid is nitrated with nitric anhydride in sulphuric acid twice as rapidly as when it is nitrated with nitric acid in sulphuric acid, the molar concentration being the same. This was illustrated in the following scheme, where the nitrating agent was denoted by X ... 

According to Schaarschmidt [18] the mechanism of nitration with a mixture of nitric and sulphuric acids consists in the formation of nitric anhydride which becomes attached to the aromatic compound. The addition compound is unstable and decomposes, giving a nitro compound and nitric acid. The mechanism of nitration suggested by Schaarschmidt is ... 

By analogy with the chlorination mechanism, in which we assume a chain reaction, Boord also suggests another chain mechanism with repeating links. He assumes that nitric acid undergoes decomposition at a high temperature to form nitric anhydride ... 

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