With Iron

(a) Li, J.-J., Johnson, D.S., Sliskovic, D.R., and Roth, B.D. (2004) Contemporary Drug Synthesis, John Wiley Sons, Inc., Hoboken, NJ, (b)For Gleevec see Loiseleur, O., Kaufmann, D, Abel, 

Hartwig, J.E (2000) Palladium-catalyzed amina-tion of aryl halides and sulfonates, in Modern Amination Methods (ed A. Ricci), NJ ley-VCH Verlag GmbH. 

Sawant, S.D., Srinivas, M., Aravinda Kumar, K.A., Lakshma Reddy, G., Pal Singh, P., Singh, B., Kumar Sharma, A., Sharma, P.R., and Vishwakarma, R.A. (2013) Tetrahedron Lett, 

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It is prepared by reduction of nitrobenzene with iron and NaOH. It is also prepared by an electrolytic reduction of nitrobenzene. It is widely used for the preparation of benzidine. 

Colourless crystals m.p. 50 C, b.p. 301 C. Basic and forms sparingly soluble salts with mineral acids. Prepared by the reduction of 1-nitronaphthalene with iron and a trace of hydrochloric acid or by the action of ammonia upon l-naphlhol at a high temperature and pressure. 

N-phenylhydroxylamine, PhNHOH and further reduction can give azoxybenzene, azobenzene, hydrazobenzene and aniline. The most important outlet commercially for the nitro-compounds is the complete reduction to the amines for conversion to dyestufTs. This is usually done in one stage with iron and a small amount of hydrochloric acid. 

Ditrophenol, -nitropbenol, C H NOj. Colourless needles m.p. 114 C. Prepared as 2-nitrophenol. Reduction with iron and hydrochloric acid gives 4-aminophenol. 

Prepared by mononilrating toluene, as a 40% constituent of the mixture of isomers. It is reduced to p-toluidine with iron and hydrochloric acid. 

CfiHgNj. Colourless crystals m.p. 63 C, b.p. 2%TC. Turns brown in air. Prepared by a one-stage reduction of m-dinitrobenzene with iron and hydrochloric acid. 

Carbon dioxide (CO2) is a very common contaminant in hydrocarbon fluids, especially in gases and gas condensate, and is a source of corrosion problems. CO2 in the gas phase dissolves in any water present to form carbonic acid (H2CO3) which is highly corrosive. Its reaction with iron creates iron carbonate (FeCOg) ... 

In small numbers, anodes have been made with iron (Fe), aluminium (Al), and titanium (Ti). 

Before this treatment, the cassiterite content of the ore is increased by removing impurities such as clay, by washing and by roasting which drives off oxides of arsenic and sulphur. The crude tin obtained is often contaminated with iron and other metals. It is, therefore, remelted on an inclined hearth the easily fusible tin melts away, leaving behind the less fusible impurities. The molten tin is finally stirred to bring it into intimate contact with air. Any remaining metal impurities are thereby oxidised to form a scum tin dross ) on the surface and this can be skimmed off Very pure tin can be obtained by zone refining. 

By the brown ring test with iron(II) sulphate and cold concentrated sulphuric acid. 

Corrosion problems are particularly important when two metals are in contact. The more reactive metal becomes the cathode of the cell and goes into solution when the cell is activated by an electrolyte. A typical cell is shown in Figure 13.7. When the metal in contact with iron is more reactive than iron itself, the iron is protected from corrosion. This is important when mechanical strength... 

The azoxybenzene in turn, when heated with iron filings, readily undergoes C4HjNO NC,Hs + Fe = C.HjNtNC.Hs + FeO further reduction to azobenzene. 

Reduction of aldehydes with iron and glacial acetic acid, for example ... 

Method B. Reduction with iron and hydrochloric acid. Place 40 ml. of water and 30 g. of grease-free iron filings (1) in a 750 or 1,000-ml. round-bottomed flask, and 25 g. (21 ml.) of nitrobenzene in a small beaker or conical flask. W arm the former on a water bnth at about 60°. Add... 

In a 500 ml. bolt-head flask, provided with a mechanical stirrer, place 70 ml. of oleum (20 per cent. SO3) and heat it in an oil bath to 70°. By means of a separatory funnel, supported so that the stem is just above the surface of the acid, introduce 41 g. (34 ml.) of nitrobenzene slowly and at such a rate that the temperature of the well-stirred mixture does not rise above 100-105°. When all the nitrobenzene has been introduced, continue the heating at 110-115° for 30 minutes. Remove a test portion and add it to the excess of water. If the odour of nitrobenzene is still apparent, add a further 10 ml. of fuming sulphuric acid, and heat at 110-115° for 15 minutes the reaction mixture should then be free from nitrobenzene. Allow the mixture to cool and pour it with good mechanical stirring on to 200 g. of finely-crushed ice contained in a beaker. AU the nitrobenzenesulphonic acid passes into solution if a little sulphone is present, remove this by filtration. Stir the solution mechanically and add 70 g. of sodium chloride in small portions the sodium salt of m-nitro-benzenesulphonic acid separates as a pasty mass. Continue the stirring for about 30 minutes, allow to stand overnight, filter and press the cake well. The latter will retain sufficient acid to render unnecessary the addition of acid in the subsequent reduction with iron. Spread upon filter paper to dry partially. 

Compounds containing two primary amino groups attached to a benzene ring can be prepared by the reduction of dinitro compounds and of nitroanilines, usually with tin or stannous chloride and hydrochloric acid or with iron and very dilute hydrochloric acid. / ara-diamines may also be obtained by the reduction of aromatic amino-azo compounds (e.g., p-aminodimethylanihne from methyl orange, see Section IV,78). p-Phenylenediamine may also be prepared from p-nitroacetanilide reduction with iron and acid yields p-amino-acetaniUde,.which may be hydrolysed to the diamine. 

It is alloyed with iron, nickel and other metals to make Alnico, an alloy of unusual magnetic strength with many important uses. Stellite alloys, containing cobalt, chromium, and tungsten, are used for high-speed, heavy-duty, high temperature cutting tools, and for dies. 

Hafnium has been successfully alloyed with iron, titanium, niobium, tantalum, and other metals. Hafnium carbide is the most refractory binary composition known, and the nitride is the most refractory of all known metal nitrides (m.p. 3310C). At 700 degrees C hafnium rapidly absorbs hydrogen to form the composition HfHl.86. 

Complexation of bromine with iron(III) bromide makes bromine more elec trophilic and it attacks benzene to give a cyclohexadienyl intermediate as shown m step 1 of the mechanism (Figure 12 6) In step 2 as m nitration and sulfonation loss of a proton from the cyclohexadienyl cation is rapid and gives the product of electrophilic aromatic substitution... 

Titrate the permanganate formed with iron(ll) as under iron(ll) Mn/5 = 10.9876... 

Atoms of mercury cling together to form the familiar liquid, atoms of iron hold together to form the solid metal, and atoms of hydrogen and oxygen combine to form molecules that hold together as water. All matter is composed of atoms, sometimes aU of one sort (as with iron), and sometimes a combination of atoms (as with rust, which is a combination of atoms of the element iron and atoms of the element oxygen). 

Textile dyes were, until the nineteenth century invention of aniline dyes, derived from biological sources plants or animals, eg, insects or, as in the case of the highly prized classical dyestuff Tyrian purple, a shellfish. Some of these natural dyes are so-caUed vat dyes, eg, indigo and Tyrian purple, in which a chemical modification after binding to the fiber results in the intended color. Some others are direct dyes, eg, walnut sheU and safflower, that can be apphed directly to the fiber. The majority, however, are mordant dyes a metal salt precipitated onto the fiber facUitates the binding of the dyestuff Aluminum, iron, and tin salts ate the most common historical mordants. The color of the dyed textile depends on the mordant used for example, cochineal is crimson when mordanted with aluminum, purple with iron, and scarlet with tin (see Dyes AND DYE INTERMEDIATES). 

Methanol can be converted to a dye after oxidation to formaldehyde and subsequent reaction with chromatropic acid [148-25-4]. The dye formed can be deterruined photometrically. However, gc methods are more convenient. Ammonium formate [540-69-2] is converted thermally to formic acid and ammonia. The latter is trapped by formaldehyde, which makes it possible to titrate the residual acid by conventional methods. The water content can be determined by standard Kad Eischer titration. In order to determine iron, it has to be reduced to the iron(II) form and converted to its bipyridyl complex. This compound is red and can be determined photometrically. Contamination with iron and impurities with polymeric hydrocyanic acid are mainly responsible for the color number of the merchandized formamide (<20 APHA). Hydrocyanic acid is detected by converting it to a blue dye that is analyzed and deterruined photometrically. 

The copper-chelating abihty of sahcylaldoxime has been used to remove copper from brine in a seawater desalination plant effluent. A carbon—sorbate bed produced by sorption of the oxime on carbon proved to be extremely effective in the continuous process (99). In another apphcation, the chelating abihty of sahcylaldoxime with iron and copper was used to stabilize bleaching powders containing inorganic peroxide salts (100). 

Minerals. Iron-bearing minerals are numerous and are present in most soils and rocks. However only a few minerals are important sources of iron and thus called ores. Table 2 shows the principle iron-bearing minerals. Hematite is the most plentiful iron mineral mined, followed by magnetite, goethite, siderite, ilmenite, and pyrite. Siderite is unimportant in the United States, but is an important source of iron in Europe. Tlmenite is normally mined for titania with iron as a by-product. Pyrite is roasted to recover sulfur in the form of sulfur dioxide, leaving iron oxide as a by-product. 

Hexa.cya.no Complexes. Ferrocyanide [13408-63 ] (hexakiscyanoferrate-(4—)), (Fe(CN) ) , is formed by reaction of iron(II) salts with excess aqueous cyanide. The reaction results in the release of 360 kJ/mol (86 kcal/mol) of heat. The thermodynamic stabiUty of the anion accounts for the success of the original method of synthesis, fusing nitrogenous animal residues (blood, horn, hides, etc) with iron and potassium carbonate. Chemical or electrolytic oxidation of the complex ion affords ferricyanide [13408-62-3] (hexakiscyanoferrate(3—)), [Fe(CN)g] , which has a formation constant that is larger by a factor of 10. However, hexakiscyanoferrate(3—) caimot be prepared by direct reaction of iron(III) and cyanide because significant amounts of iron(III) hydroxide also form. Hexacyanoferrate(4—) is quite inert and is nontoxic. In contrast, hexacyanoferrate(3—) is toxic because it is more labile and cyanide dissociates readily. Both complexes Hberate HCN upon addition of acids. 

Dicalcium hexakiscyanoferrate [13821 -08 ] Ca2[Fe(CN)g], is formed as yellow crystals by reaction of Hquid or gaseous HCN with iron(II) chloride in water containing Ca(OH)2 or CaCO and having pH > 8. It is used to prevent caking of other substance and serves as a useful starting material in the preparation of other [Fe(CN)g] salts. Examples of mixed salts include calcium dicesium hexakiscyanoferrate [15415-35-7] CaCs2[Fe(CN)g], and calcium dipotassium hexakiscyanoferrate [20219-00-5] CaK2[Fe(CN)g]. 

In analogy to the situation for bipyridine, the blue tris(l,10-phenanthroline)iron(3+) ion [1347949-7], [Fe(phen)2], must be obtained by oxidation of the corresponding iron(II) ion. [Fe(phen)2] has an absorption maximum at 590 nm, an absorptivity of 600 (Mem), and a formation constant of 10 . In solutions of pH > 4, this species is reduced to the iron(II) complex. The reduction is instantaneous in alkaline solution. At pH < 2, protons compete with iron(III) for the phenanthroline nitrogens and coordination is incomplete. [Fe(phen)2] is used most often in solution as an oxidant, but the trichloride [40273-22-1] and the triperchlorate monohydrate [20774-81-6] salts have been prepared. 

PefractoTy lime is synonymous with dead-burned dolomite, an unreactive dolomitic quicklime, stabilized with iron oxides, that is used primarily for lining refractories of steel furnaces, particularly open hearths. 

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