Nitration general

Most nitrations are highly exothermic and hence release a lot of reaction heat for most experimental protocols [37, 94]. This high exofhermidty may even lead to explosions [37, 38]. Nitration agents frequently display acid corrosion [37]. For these reasons, nitrations generally are regarded as being hazardous [37, 38]. 

The chlorides, bromides, iodides, and cyanides are generally vigorously attacked by fluorine in the cold sulphides, nitrides, and phosphides are attacked in the cold or may be when warmed a little the oxides of the alkalies and alkaline earths are vigorously attacked with incandescence the other oxides usually require to be warmed. The sulphates usually require warming the nitrates generally resist attack even when warmed. The phosphates are more easily attacked than the sulphates. The carbonates of sodium, lithium, calcium, and lead are decomposed at ordinary temp, with incandescence, but potassium carbonate is not decomposed even at a dull red heat. Fluorine does not act on sodium bofate. Most of these reactions have been qualitatively studied by H. Moissan,15 and described in his monograph, Lefluor et ses composes (Paris, 1900). 

If compressed air stirring is used, attention should be paid to the purity of air. Usually the air coming from the compressor contains a certain amount of lubricating oil. If this oil were to enter the nitrator it would react with the mixed acid and produce a dangerous rise in temperature. Thus the air must be purified before entering the nitrator. Generally a filter filled with coke or pumice is used. 

Nitrates generally bidentate in these. bTh salt analogous. c crypt = ligand (55). dL = ligand (56). 

Nitration of phenols. Phenols can be nitrated in a two-phase system (ether-water) by NaN03(l equiv.) and HC1 (excess) in the presence of a catalytic amount of several rare earth nitrates in yields generally > 80%. The o/p ratio can be controlled to some extent by change in the acidity, but ort/io-nitration generally predominates. Aromatic hydrocarbons are not nitrated under these conditions. 

The ionic nitrates generally melt to liquids which are stable to various degrees above their melting points. These liquids can be distilled under reduced pressure.11 The covalent nitrates are generally not stable as liquids. When heated, they first sublime, frequently giving molecular vapors, and then decompose. The cation influences the stability of the anion through its ability to distort its structure in the same manner as for carbonates and sulfates, as discussed in Chapters 2 and 4. 

PPA = polyphosphoric acid al = alkylation ac = acylation chlor = chlorination iso = isomerization halo = halogenation cycl = cyclization poly = polymerization for = formylation dehydr = dehydration nitr - nitration general = active in most Friedel-Crafts reactions deal = dealkylation rearr = rearrangement. 

Nitrates generally bidentate in these. Th salt analogous. 

The sulphuric acid used does not take part in the reaction, but its presence is absolutely essential to combine with the water set free, and thus to prevent the weakening of the nitric acid. The acid mixture used at Waltham Abbey consists of 3 parts by weight of sulphuric acid of 1.84 specific gravity, and 1 part of nitric acid of 1.52 specific gravity. The same mixture is also used at Stowmarket (the New Explosive Company s Works). The use of weaker acids results in the formation of collodion- cotton and the lower nitrates generally. 

Benkeser [145], Speier [146], and Eabom [147] have shown that intact ring nitration generally predominates and protodesilylation plays a signi-hcant role under the reaction conditions. 

Originally, general methods of separation were based on small differences in the solubilities of their salts, for examples the nitrates, and a laborious series of fractional crystallisations had to be carried out to obtain the pure salts. In a few cases, individual lanthanides could be separated because they yielded oxidation states other than three. Thus the commonest lanthanide, cerium, exhibits oxidation states of h-3 and -t-4 hence oxidation of a mixture of lanthanide salts in alkaline solution with chlorine yields the soluble chlorates(I) of all the -1-3 lanthanides (which are not oxidised) but gives a precipitate of cerium(IV) hydroxide, Ce(OH)4, since this is too weak a base to form a chlorate(I). In some cases also, preferential reduction to the metal by sodium amalgam could be used to separate out individual lanthanides. 

Note cautiously the characteristic odour of acetaldehyde which this solution possesses. Then with the solution carry out the following general tests for aldehydes described on p. 341 Test No. I (SchiflF s reagent). No. 3 (Action of sodium hydroxide). No. 4 (Reduction of ammoniacal silver nitrate). Finally perform the two special tests for acetaldehyde given on p. 344 (Nitroprusside test and the Iodoform reaction). 

Oxidation, (a) Ammoniacal silver nitrate. To a few ml. of ammoniacal AgNOj (preparation, p. 525), add a few drops of cold aqueous benzo quinone solution a silver mirror or (more generally) a dark precipitate of metallic silver is formed in the cold. 

D) No general reaction can be cited for the preparation of crystalline derivatives of Class (iii). Triphenylamine, when nitrated in acetic acid with fuming nitric acid, gives tri-/>-nitrophenylamine, m.p. 280°. The presence of substituents in the phenyl groups may however complicate or invalidate nitration. 

Since the silver salts of the carboxylic acids are usually soluble in dilute nitric acid, they must be prepared by treating an aqueous solution of a neutral salt of the acid (and not the free acid itself) with silver nitrate solution. It is not practicable to attempt to neutralise the acid with sodium or potassium hydroxide solution, because the least excess of alkali would subsequently cause the white silver salt to be contaminated with brown silver oxide. The general method used therefore to obtain a neutral solution j to dissolve the acid in a small excess of ammonia solution, and then to boil the solution until all free... 

In practice superheated steam is generally employed for substances with a low vapour pressure (< 5-1 mm.) at 100°. Thus in the recovery of the products of nitration or aromatic compounds, the ortho derivative e.g., o-nitrophenol) can be removed by ordinary steam distillation the... 

Nitro derivatives. No general experimental details for the preparation of nitro derivatives can be given, as the ease of nitration and the product formed frequently depend upon the exact experimental conditions. Moreover, some organic compounds react violently so that nitrations should always be conducted on a small scale. The derivatives already described are usually more satisfactory for this reason the nitro derivatives have been omitted from Table IV,9. 

Nitration products. Although no general method of nitration can be given, the following procedure is wddely applicable. 

Aromatic aldehydes react with the dimedone reagent (Section 111,70,2). All aromatic aldehydes (i) reduce ammoniacal silver nitrate solution and (ii) restore the colour of SchifiF s reagent many react with sodium bisulphite solution. They do not, in general, reduce Fehling s solution or Benedict s solution. Unlike aliphatic aldehydes, they usually undergo the Cannizzaro reaction (see Section IV,123) under the influence of sodium hydroxide solution. For full experimental details of the above tests, see under Ali-phalic Aldehydes, Section 111,70. They are easily oxidised by dilute alkaline permanganate solution at the ordinary temperature after removal of the manganese dioxide by sulphur dioxide or by sodium bisulphite, the acid can be obtained by acidification of the solution. 

Nitro compounds and their reduction products. Tertiary nitro compounds (these are generally aromatic) are reduced by zinc and ammonium chloride solution to the corresponding hydroxylamines, which may be detected by their reducing action upon an ammoniacal solution of silver nitrate or Tollen s reagent ... 

Nitration is important for two reasons firstly, because it is the most general process for the preparation of aromatic nitro compounds secondly, because of the part which it has played in the development of theoretical organic chemistry. It is of interest because of its own characteristics as an electrophilic substitution. 

Nitronium salts in solution in inert organie solvents have been used in reeent years to nitrate a wide range of aromatic compounds. Yields are generally good, but in preparative work the method is advantageous only in speeial cases, notably where the aromatie contains a hydrolysable substituent ( 4.4). 

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