Mixtures of nitric and sulfuric acids

The overall reactivity of the 4- and 5-positions compared to benzene has been determined by competitive methods, and the results agreed with kinetic constants established by nitration of the same thiazoles in sulfuric acid at very low concentrations (242). In fact, nitration of alkylthiazoles in a mixture of nitric and sulfuric acid at 100°C for 4 hr gives nitro compounds in preparative yield, though some alkylthiazoles are oxidized. Results of competitive nitrations are summarized in Table III-43 (241, 243). For 2-alkylthiazoles, reactivities were too low to be measured accurately. 

An other example is the oxidation of 4-(hydroxymethyl)thiazole with a mixture of nitric and sulfuric acids at -5°C (24, 27). 

Nitration Phenols are nitrated on treatment with a dilute solution of nitric acid in either water or acetic acid It IS not necessary to use mixtures of nitric and sulfuric acids because of the high reactivity of phe nols... 

The practical problems He ia the separatioa of the chlorine from the hydrogea chloride and nitrous gases. The dilute nitric acid must be reconcentrated and corrosion problems are severe. Suggested improvements iaclude oxidation of concentrated solutions of chlorides, eg, LiCl, by nitrates, followed by separation of chlorine from nitrosyl chloride by distillation at 135°C, or oxidation by a mixture of nitric and sulfuric acids, separating the... 

Cellulose nitrate (pyroxylin) [9004-70-0], made from cellulose and a mixture of nitric and sulfuric acids, is called gun cotton and is used in explosives. Nitrates of lower DS find some appHcation in coatings and adhesives. 

Nitrobenzotrichloride is also obtained in high yield with no significant hydrolysis when nitration with a mixture of nitric and sulfuric acids is carried out below 30°C (31). 2,4-Dihydroxybenzophenone [131 -56-6] is formed in 90% yield by the uncatalyzed reaction of benzotrichloride with resorcinol in hydroxyHc solvents (32) or in benzene containing methanol or ethanol (33). Benzophenone derivatives are formed from a variety of aromatic compounds by reaction with benzotrichloride in aqueous or alcohoHc hydrofluoric acid (34). 

MO calculations of the cinnoline ring system show that the relative order of reactivities for electrophilic substitution is 5=8>6 = 7>3 4. This is confirmed experimentally, as nitration of cinnoline with a mixture of nitric and sulfuric acids affords 5-nitrocinnoline (33%) and 8-nitrocinnoline (28%). Similarly, 4-methylcinnoline gives a mixture of 4-methyl-8-nitrocinnoline (28%) and 4-methyl-5-nitrocinnoline (13%). 

Nitration of toluene by mixture of nitric and sulfuric acids produces an explosive material known as TNT (trinitrotoluene). The overall reaction can be shown as... 

Nitration Chemical reaction of a substance in which the nitro group (-N02) is introduced into the molecule often accomplished under highly reactive conditions using mixtures of nitric and sulfuric acids at high temperatures. Byproducts of the reaction may have explosive properties if reaction control is lost, may lead to vigorous and strongly exothermic runaway reactions due to oxidation of the reactants. 

More recently, microwave chemistry has also been used to achieve covalent functionalization. In particular, these treatments can functionalize CNTs with sulfonated and carboxylic groups using a mixture of nitric and sulfuric acid under microwave radiation for 3 min, thus resulting in highly dispersible CNTs in ethanol and water... 

Unknown compound D, which has the formula CjqHjq, readily decolorizes a bromine in Ccirbon tetrachloride solution. When D is allowed to react with hydrogen and a catalyst, E is obtained. The M for E has an m/e value of 134. When E is heated with a mixture of nitric and sulfuric acid, only one product is produced. That compound has an M of 179. Heating either D or in hot chromic acid produces a solid F, CgHgO, whose melting point is in excess of 300 degrees Celsius. Give structures for D, E, and F. 

The reaction of compound D or E with a mixture of nitric and sulfuric acid nitrates the ring. The odd M indicates an odd number of nitrogen atoms and the mass increase (179 - 134 = 45) indicates the product is mononitro. 

Heterogeneous fluid-fluid reactions are made to take place for one of three reasons. First, the product of reaction may be a desired material. Such reactions are numerous and can be found in practically all areas of the chemical industry where organic syntheses are employed. An example of liquid-liquid reactions is the nitration of organics with a mixture of nitric and sulfuric acids to form materials such as nitroglycerin. The chlorination of liquid benzene and other hydrocarbons with gaseous chlorine is an example of gas-liquid reactions. In the inorganic field we have the manufacture of sodium amide, a solid, from gaseous ammonia and liquid sodium ... 

Mixed Nitrating Acids a mixture of nitric and sulfuric acid in various ratios and adjusted to the desired DVS values (dehydrating value of sulfuric acid)... 

Two open-vessel wet digestion methods using mixtures of nitric and sulfuric acids and H2O2 were developed and optimised to determine metals in plants... 

C-Nitration Picric acid TNT HNS Mixture of nitric and sulfuric acids Mixture of nitric and sulfuric acids Mixture of nitric and sulfuric acids... 

N-Nitration Tetryl RDX HMX Mixture of nitric and sulfuric acids Nitric acid and ammonium nitrate Nitric acid and ammonium nitrate... 

The W-process is based on the condensation of potassium amido-sulfonate with formaldehyde, and the nitration of the condensation product as shown in Reaction 7.13 (overleaf). Potassium amidosulfon-ate and formaldehyde are reacted together to produce potassium methyleneamidosulfonate. This product is nitrated to RDX by a mixture of nitric and sulfuric acids. 

In 1845, as vulcanized rubber was becoming popular, the Swiss chemistry professor Christian Schobein wiped up a spilled mixture of nitric and sulfuric acids with a cotton rag that he then hung up to dry. Within a few minutes, the rag burst into flames and then vanished, leaving only a tiny bit of ash. Schobein had discovered nitrocellulose, in which most of the hydroxyl groups in cellulose are... 

Nitromethylbenzene-2,6-D2 is nitrated by a mixture of nitric and sulfuric acids at the same rate as ordinary 4-nitromethylbenzene under conditions in which the rate of nitration v is given by v = k[nitromethylbenzene] [N02 ]. (Review Section 15-6B.)... 

Amino-3-nitrotoluene has been prepared by the nitration of oxalotoluide 4 and by the nitration of o-acetotoluide in acetic acid with fuming nitric acid 6 or with a mixture of nitric and sulfuric acid.3... 

Data have been presented on the kinetics of nitration of acetanilide in mixtures of nitric and sulfuric acids.29 A review discusses the several mechanisms operative in the nitration of phenol including /> / -sclective nitrosation-oxidation and mechanisms involving phenoxy radical-nitrogen dioxide reaction yielding a 55 45 ortho para nitration ratio.30 The kinetics of mononitration of biphenyl-2-carboxylic acid have been investigated in several solvents. The maximum ortho para product ratio of 8.4 is observed in tetrachloromethane.31 Nitration products were not formed in the presence of dioxane.31,32 Quantum-chemical AMI calculations were performed and the predominant formation of the ortho-nitro product is accounted for by stabilization of the cr-complex by the carboxyl group.33... 

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