Nitration with dilute nitric acid

Konovalov [15] nitrated aliphatic hydrocarbons in sealed tubes at 120-130°C, using dilute nitric acid of concentration 6.5-19%. From normal hydrocarbons he obtained secondary nitro compounds in yields varying from 40% (2-nitro-hexane from hexane) to 49-50% (2-nitrooctane from octane). Aromatic hydrocarbons with an aliphatic substituted group when nitrated under the same conditions gave nitro derivatives with a nitro group in the side chain. For example, ethylbenzene, when nitrated with 12.5% nitric acid at 105-108°C, gives phenyl-nitroethane in 44% yield. The optimum yield is obtained with 13% acid. 

Cycle-polymethylenic hydrocarbons can also be nitrated with dilute nitric acid (e.g. Wichterle [15a]). 

Grundman and Haldenwanger [70] nitrated cyclohexane with nitric acid (34% HN03) at 122°C under 4 atm pressure. Nitrocyclohexane and gem-dinitrocyclo-hexane (I) resulted (m. p. 218°C). 

On the contrary, olefins can readily be nitrated to nitroolefins by means of 12.5% nitric acid as shown by Konovalov [15], 

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A brief account of aromatic substitution may be usefully given here as it will assist the student in predicting the orientation of disubstituted benzene derivatives produced in the different substitution reactions. For the nitration of nitrobenzene the substance must be heated with a mixture of fuming nitric acid and concentrated sulphuric acid the product is largely ni-dinitrobenzene (about 90 per cent.), accompanied by a little o-dinitrobenzene (about 5 per cent.) which is eliminated in the recrystallisation process. On the other hand phenol can be easily nitrated with dilute nitric acid to yield a mixture of ortho and para nitrophenols. It may be said, therefore, that orientation is meta with the... 

Phenol may be nitrated with dilute nitric acid to 3deld a mixture of o- and nitrophenols the 3deld of p-nitrophenol is increased if a mixture of sodium nitiute and dilute sulphuric acid is employed. Upon steam distilling the mixture, the ortho isomer passes over in a substantially pure form the para isomer remains in the distillation flask, and can be readily isolated by extraction with hot 2 per cent, hydrochloric acid. The preparation of m-nitrophenol from wt-nitroaniline by means of the diazo reaction is described in Section IV,70. 

Cerium was the first rare-earth element discovered, and its discovery came in 1803 by Jons Jakob Berzelius in Vienna. Johann Gadohn (1760—1852) also studied some minerals that were different from others known at that time. Because they were different from the common earth elements but were all very similar to each other, he named them rare-earth elements. However, he was unable to separate or identify them. In the 1800s only two rare-earths were known. At that time, they were known as yttria and ceria. Carl Gustav Mosander (1797—1858) and several other scientists attempted to separate the impurities in these two elements. In 1839 Mosander treated cerium nitrate with dilute nitric acid, which yielded a new rare-earth oxide he called lanthanum. Mosander is credited with its discovery. This caused a change in the periodic table because the separation produced two new elements. Mosander s method for separating rare-earths from a common mineral or from each other led other chemists to use... 

Zaraisky. A.P. Kachurin. O.I. Velichko. L.H. TikJionova, I.A. Furin, G.G. Shur, V.B. Vol pin. M.E. Cyclic trimeric perfluoro-o-phenylenemercury as the phase transfer catalyst for nitration with dilute nitric acid. Izv. Akad. Nauk, Ser. Khim. 1994. 547-548. [Russ. Chem. Bull. 1994. 43. 507-508. (Engl. Transl.)]. 

This activation of the benzene ring is also shown in the nitration of phenol. With benzene, we need a mixture of concentrated nitric and sulfuric acids to reflux with benzene at about 55 °C for nitration to take place (see page 385). However, the activated ring in phenol readily undergoes nitration with dilute nitric acid at room temperature ... 

It should be noted that aliphatic compounds (except the paraffins) are usually oxidised by concentrated nitric acid, whereas aromatic compounds (including the hydrocarbons) are usually nitrated by the concentrated acid (in the presence of sulphuric acid) and oxidised by the dilute acid. As an example of the latter, benzaldehyde, CjHsCHO, when treated with concentrated nitric acid gives ffi-nitrobenzaldehyde, N02CgH4CH0, but with dilute nitric acid gives benzoic acid, CgHgCOOH. 

If phenol is treated even with dilute nitric acid at room temperature, nitration readily occurs with the simultaneous formation of the yellow o-nitro-phenol and the white /> nitrophenol. These compounds can be readily... 

It is preferable to use Tollen s ammoniacal silver nitrate reagent, which is prepared as follows Dissolve 3 g. of silver nitrate in 30 ml. of water (solution A) and 3 g. of sodium hydroxide in 30 ml. of water (solution B). When the reagent is requir, mix equal volumes (say, 1 ml.) of solutions A and JB in a clean test-tube, and add dilute ammonia solution drop by drop until the silver oxide is just dissolved. Great care must be taken in the preparation and use of this reagent, which must not be heated. Only a small volume should be prepared just before use, any residue washed down the sink with a large quantity of water, and the test-tubes rinsed with dilute nitric acid. 

Nitrogen and sulphur absent, (i) If only one halogen is present, acidify with dilute nitric acid and add excess of silver nitrate solution. A precipitate indicates the presence of a halogen. Decant the mother liquor and treat the precipitate with dilute aqueous ammonia solution If the precipitate is white and readily soluble in the ammonia solution, chlorine is present if it is pale yellow and difficultly soluble, bromine is present if it is yellow and insoluble, then iodine is indicated. Iodine and bromine should be confirmed by the tests given below. 

Qualitative. The classic method for the quaUtative determination of silver ia solution is precipitation as silver chloride with dilute nitric acid and chloride ion. The silver chloride can be differentiated from lead or mercurous chlorides, which also may precipitate, by the fact that lead chloride is soluble ia hot water but not ia ammonium hydroxide, whereas mercurous chloride turns black ia ammonium hydroxide. Silver chloride dissolves ia ammonium hydroxide because of the formation of soluble silver—ammonia complexes. A number of selective spot tests (24) iaclude reactions with /)-dimethy1amino-henz1idenerhodanine, ceric ammonium nitrate, or bromopyrogaHol red [16574-43-9]. Silver is detected by x-ray fluorescence and arc-emission spectrometry. Two sensitive arc-emission lines for silver occur at 328.1 and 338.3 nm. 

The solution of silver nitrate is acidified with dilute nitric acid, boiled so as to decompose any silver sulphite that might have been formed, and the precipitate filtered, washed, etc. 

The method may be applied to those anions (e.g. chloride, bromide, and iodide) which are completely precipitated by silver and are sparingly soluble in dilute nitric acid. Excess of standard silver nitrate solution is added to the solution containing free nitric acid, and the residual silver nitrate solution is titrated with standard thiocyanate solution. This is sometimes termed the residual process. Anions whose silver salts are slightly soluble in water, but which are soluble in nitric acid, such as phosphate, arsenate, chromate, sulphide, and oxalate, may be precipitated in neutral solution with an excess of standard silver nitrate solution. The precipitate is filtered off, thoroughly washed, dissolved in dilute nitric acid, and the silver titrated with thiocyanate solution. Alternatively, the residual silver nitrate in the filtrate from the precipitation may be determined with thiocyanate solution after acidification with dilute nitric acid. 

Bromides can also be determined by the Volhard method, but as silver bromide is less soluble than silver thiocyanate it is not necessary to filter off the silver bromide (compare chloride). The bromide solution is acidified with dilute nitric acid, an excess of standard 0.1M silver nitrate added, the mixture thoroughly shaken, and the residual silver nitrate determined with standard 0.1 M ammonium or potassium thiocyanate, using ammonium iron(III) sulphate as indicator. 

Iodides can also be determined by this method, and in this case too there is no need to filter off the silver halide, since silver iodide is very much less soluble than silver thiocyanate. In this determination the iodide solution must be very dilute in order to reduce adsorption effects. The dilute iodide solution (ca 300 mL), acidified with dilute nitric acid, is treated very slowly and with vigorous stirring or shaking with standard 0.1 M silver nitrate until the yellow precipitate coagulates and the supernatant liquid appears colourless. Silver nitrate is then present in excess. One millilitre of iron(III) indicator solution is added, and the residual silver nitrate is titrated with standard 0.1M ammonium or potassium thiocyanate. 

Determination of chloride as silver chloride Discussion. The aqueous solution of the chloride is acidified with dilute nitric acid in order to prevent the precipitation of other silver salts, such as the phosphate and carbonate, which might form in neutral solution, and also to produce a more readily filterable precipitate. A slight excess of silver nitrate solution is added, whereupon silver chloride is precipitated ... 

Seif-Test 12.1A Copper reacts with dilute nitric acid to form copper(II) nitrate and the gas nitric oxide, NO. Write the net ionic equation for the reaction. 

Chhatre et al. (1993) have reported that highly selective ort/io-nitration of phenol with dilute nitric acid can be realized by using a microemulsion medium. It seems that in the microemulsion medium, phenol orients in such a way that the phenyl group remains extended towards the side of the organic phase, whereas the hydroxyl group protrudes in the aqueous... 

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