Aromatic nitro compounds These are the substitution products of aromatic hydrocarbons like benzene.

One or more hydrogen atoms of the aromatic ring are replaced by nitro group.

Nitro benzene Nitro benzene, the simplest of aromatic nitro compounds, is called ‘oil of mirbane’. Preparation of nitro benzene It is prepared by the action of a mixture of con. HNO 3 and con. H2SO4 (nitrating mixture) on benzene maintaining the temperature below 333 K.

Sulphuric acid generates the electrophile –NO2+, nitronium ion-from nitric acid. The formation of nitro benzene from benzene is an example of aromatic electrophilic substitution reaction.

Reduction of nitrobenzene Depending on the nature of the reducing agent and pH of the reducing medium reduction proceeds to different extents and hence different products are formed.

(a) Strongly acidic medium When reduced with tin and hydrochloric acid, aromatic nitro compounds are converted to aryl amines.

(b) Neutral medium When reduced with a neutral, reducing agents like zinc dust and aqueous ammonium chloride, aromatic nitro compounds form aryl hydroxylamines.

(c) Alkaline medium In alkaline medium, Nitro benzene on reduction forms the intermediate products nitrosobenzene (C6H5NO) and phenyl hydroxylamine (C6H5NHOH). These undergo bimolecular condensation reaction. According to the appropriate reducing agent in alkaline medium different products are obtained.

(d) Catalytic reduction Lithium aluminium hydride is a powerful hydride ion donor. So it reduces nitro benzene to Aniline. This reduction can also be carried out by H2/Ni.

(e) Electrolytic Reduction

Vaporized nitro benzene with hydrogen is passed over copper supported on silica at 543 K and aniline is obtained (Manufacturing method). because of intermolecular hydrogen bonding. phenyl hydroxylamine is first produced which rearranges to give p-amino phenol. Preparation: 1. H 2SO4 NHOH Rearrangement HO NH 2 Aromatic amino compounds Amines containing phenyl group are known as aromatic amines. It has higher boiling point than benzene. (i) Amines in which the amino group is directly attached to the benzene ring. This liquid turns brown on exposure to air due to oxidation. . NO 2 Electrolytic reduction Conc. sparingly soluble in water but soluble in organic solvents. These aromatic amines are of two types. NH 2 NH 2 CH 3 Aniline o-Toluidine (ii) Amines in which the amino group is attached to the side chain of benzene ring.When nitro benzene is reduced electrolytically in presence of concentrated sulphuric acid. By the catalytic reduction of nitro benzene. NH 2 Benzyl amine Aniline A colorless oily liquid.

By the chemical reduction of nitrobenzene Under strongly acidic condition such as Sn/HCl or with Hydride donors like LiAlH4. Cl NH 2 2 NH3 CuCl 2 + + NH 4Cl 4. however. By Hoffmann reaction: Using benzamide. the electron pair is localized on the N atom. the lone pair of electrons on the nitrogen atom is involved in resonance and is not easily available for donation to protons. the amide is converted into primary amine containing one carbon less than that of amide. 3. we must look at the availability of the non-bonded electron pair on N. aniline is prepared. HCl is used for the large scale preparation of aniline. By the ammonolysis of chloro benzene Ammonolysis of chloro benzene at high temperature and pressure in presence of copper salts. When an amide (here benzamide) is treated with bromine and alkali. With CH3CH2NH2. [To compare the basicity of an alkylamine (CH3CH2NH2) and an arylamine (C6H5NH2. aniline). With an arylamine. Because of positive charge on nitrogen protonation becomes difficult.NO 2 H2 / Cu / SiO 543 K 2 NH 2 2. This is because. NO 2 Sn / HCl NH 2 Reduction with Fe / con. . CONH 2 NH 2 Br 2 KOH + + CO 2 Basic nature of Aniline Aniline is less basic than aliphatic amines.

(c) With Benzoyl chloride in the presence of sodium hydroxide. [2] Substitution of nitrogen (a) Alkylation with alkyl halides it forms 20. [3] Formation of Schiffs base Aniline (a primary amine) reacts with aldehydes to form aldimines or Schiff’s base.] Reactions of Aniline [1] Salt formation These form crystalline salts with strong mineral acids such as HCl or H2SO4. . (b) Aniline reacts with acetyl chloride and acetic anhydride to form corresponding amides called anilides. 30 amines and finally quaternary ammonium salt. Arylamines are less basic than alkylamines because the electron pair on N is delocalized.the electron pair is delocalized on the benzene ring (see the resonance structures above). and makes C 6H5NH2 less basic than CH3CH2NH2. benzanilide is formed (Schotten-Baumann reaction). This decreases the electron density on N.

NH 2 K2Cr 2O7 / H + O O (p-Benzoquinone) [7] Reaction with Carbonyl chloride Carbonyl chloride form diphenyl urea with aniline.R NH 2 O N H C H R + (Aldimine or Schiff’s base) [4] Reaction with nitrous acid A cold solution of sodium nitrite reacts with aniline dissolved in hydrochloric acid. C6H5NH2 + HNO2  C6H5N2Cl [5] Carbylamine reaction Aniline reacts with chloroform and alcoholic KOH to give an offensive smelling liquid. This reaction is known as ‘diazotization’. p-amino benzene sulphonic acid is formed.4. a clear solution is obtained.6-tribromoaniline. O NH 2 + COCl 2 HN NH [8] Electrophilic substitution reaction (a) Sulphonation Heating with fuming sulphuric acid. which is 2. phenyl isocyanide. This solution contains ‘benzene diazonium chloride’. NH 2 + H SO 2 4 353 K HO 3S NH 2 (b) Halogenation Aniline decolorizes bromine water with the formation of white precipitate. . [6] Oxidation Aromatic amines are readily oxidised by dichromate and sulphuric acid to p-benzoquinone.

Uses of aniline 1. [O] NH 2 NO 2 p-nitro aniline is prepared in the following three stages.NH 2 Br NH 2 Br + 3 Br 2 / H 2O + 3HBr Br (c) Nitration Nitration is accompanied by oxidation. making the arylamine less basic than aniline. making the arylamine more basic than aniline. For preparing dyes and dye intermediates. D= NH2 OH OR NHCOR R . Whereas. Electron-donor groups add electron density to the benzene ring. For the manufacture of anti oxidants in rubber industry. 3. For preparing drugs (e. 4.) sulpha drugs. Effect of substituents on the basicity of aryl amines Substituted anilines are more or less basic than aniline depending on the nature of the substituent.. For making isocyanates required for polyurethane plastics. electron-withdrawing groups remove electron density from the benzene ring.g. 2.

Only diazonium [ArN2+ BF4–] fluro borate can be dried without decomposition. HSO4¯. Structure: The electronic structure Resonance stabilized diazonium ion is further stabilized by the involvement of the benzene ring. Properties: Colorless crystalline solids turning brown on exposure to air. . characterized by the presence of the functional group –N+≡N (diazonium ion) directly bonded to an aryl group (–Ar). C6H5NH2 + HNO2  C6H5N2Cl This is stable only under ice cold condition.. Br¯.N+≡N forms salts with anions such as Cl¯. Nitrous acid is formed by mixing aqueous solutions of sodium nitrite and mineral acid like HCl or H2SO4.W= CHO COR COOR COOH CN NO2 SO3H NR3+ Preparation and synthetic applications of benzene diazonium chloride Aryl diazonium salts form an important class of compounds. NO2¯. These are collectively called aryl diazonium salts. in benzene diazonium ion. The aryl diazonium ion Ar. soluble in water and alcohol and insoluble in ether. Preparation Benzene diazonium chloride is prepared by the action of nitrous acid on aniline at 273 – 278 K. BF4¯ etc. In the dry condition it is quite unstable and decomposes rapidly.

very useful compounds can be prepared from them. halogenated benzene is formed. Cu2I2 C6H5N2Cl + NaNO2 C6H5NO2 [5] Sand Meyer Reaction When aqueous solution of diazonium chloride is warmed with Cu 2Cl2 or Cu2Br2 in halogen acid. . in presence of cuprous salts catalyst. C6H5N2Cl + CH 3OH C6H5OCH 3 + N2 Anisole (Aromatic ether) + HCl C6H5N2Cl + CH 3COOH C6H5OCOCH 3 Phenyl acetate (Ester) + N2 + HCl [3] Replacement by Iodine Aqueous solution of diazonium salt reacts with potassium iodide solution to form Iodobenzene. C6H5N2Cl + H2O C6H5OH + N2 + HCl Similarly –N2Cl can be replaced by alkoxy group by warming with alcohol or by acyloxy group by boiling with carboxylic acids. C6H5N2Cl H3PO4 Cu 2Cl 2 C6H6 + N2 + HCl [2] Replacement by –OH or –OR (alkoxy) or –OCOR (acyloxy) group When the aqueous solution is boiled.Chemical properties They are highly reactive compounds. [1] Reduction to arenes Benzene diazonium chloride is reduced to benzene when treated with Hypophosphorous acid. phenol is obtained. C6H5N2Cl + KI  C6H5I + KCl + N2 [4] Replacement by Nitro group : Diazonium salt when treated with sodium nitrite in the presence of cuprous salt as a catalyst forms nitro compounds.

[8] Replacement by an aryl group: (Gomberg Bachmann Reaction) Decomposition of diazonium salts in presence of sodium hydroxide and benzene. thousands of azo dyes have been synthesised by this procedure. C6H5N2Cl + HCl Cu C6H5Cl + N2 [7] Replacement by cyanide group The diazonium salt solution when treated with cuprous cyanide /potassium cyanide mixture. –NR2 etc. phenyl cyanide is formed. This reaction is known as ‘Gomberg’ or ‘Gomberg Bachmann’ reaction. [9] Reduction Diazonium chloride is reduced to phenyl hydrazine on treatment with SnCl2/HCl or Zn/HCl or NaHSO3. –NHR. the corresponding halobenzene is obtained. also gives phenyl cyanide. coupling usually occurs at para position. .C6H5N2Cl + HCl Cu 2Cl 2 C6H5Cl C6H5N2Cl + HBr Cu 2Br 2 C6H5Br [6] Gattermann reaction When the diazonium chloride solution is warmed with copper powder and the hydrogen halide. –OR. results in the formation of Biphenyl. C6H5N2Cl + KCN Cu2(CN) 2 C6H5CN + N2 + KCl Treatment of diazonium chloride with KCN solution in presence of copper. –NH2. ArN=N Ar’ This reaction is known as Coupling reaction since all these compounds are intensely coloured and used as dyes. [10] Diazonium coupling reaction Diazonium salt reacts with aromatic amine and phenols to give azo compounds of the general formula. The aromatic compound with which it couples should have any one of the groups like –OH.

amines etc. 3) Very useful in the manufacture of azo dyes.. The simplest members are phenol [C6H5OH] and cresols [CH3–C6H4–OH]. PHENOLS These form a class of compounds in which one or more hydrogen atom of the benzene nucleus are replaced by hydroxyl group. Aqueous . cyanides etc.Uses of diazonium salts 1) It is a very valuable intermediate in the preparation of a lot of compounds like phenols. It forms colorless needles (m. Phenol [C6H5OH] Phenol itself was formerly known as carbolic acid. halides. 2) Valuable laboratory reagents like phenyl hydrazine can be prepared. 41°C). 3) Diazo coupling reaction takes place in ice cold condition. Coupling reaction Example: coupling reactions involving diazonium compound The coupling reactions involves 1) Formation of diazonium ion C6H5N2+ (an electrophile) 2) Electrophilic substitution on electron rich aromatic compounds like phenols. has a characteristic odor.p. and is somewhat soluble in water. at para-position.

but its main use is for the preparation of polymers (phenolic resins). H 2O H2O C6H5OH + Na 2CO 3 [4] Crude phenol (of step 3) is subjected to fractional distillation. [3] Filtrate of step 2 is treated with aqueous NaOH when phenols dissolve as phenoxides. [1] Middle oil is washed with H2SO4. It dissolves basic impurities like pyridine (base). [2] Excessive cooling separates naphthalene (a low melting solid). Resonance in phenolate ion Consequence of this Resonance (a) Phenols are stronger acid than alcohols (because the RO–-alkoxide ions are not stabilized by resonance). the phenolate ion is more stabilized by resonance than phenol itself. Phenolic compounds are isolated in following steps. . Acidic nature of phenols Factors that enhance the stability of the anion of acid and that increase the ease of release of proton enhance the strength of an acid. Isolation of phenol from middle oil Middle oil of coal-tar distillation has naphthalene and phenolic compounds. Thus in the case of phenol. Carbon dioxide is then blown through the solution to liberate phenols.solutions of it (or its methyl-substituted derivatives) are applied as disinfectants. C6H5OH + NaOH C6H5ONa + CO 2.

g. especially in presence of a base.. (c) Ortho and para positions are more electron dense. [3] Etherification . Electron donating substituents like –NH2. The reaction of phenols with benzoyl chloride in presence of sodium hydroxide to form benzoates is known as Schotten-Baumann reaction. The acid strength of phenols depends on the nature of the substituent present in the benzene ring. [2] Esterification The hydrogen of the –OH group of phenol can be replaced by acyl group forming esters. Direct esterification of phenol using carboxylic acid in presence of dehydrating agent like con.(b) The electron density is increased in the benzene ring and hence the benzene ring is activated towards electrophilic substitution reaction.groups decrease the acid strength.) strength of phenol varies in the order. CH3. (d) Oxygen is strongly bound to the nucleus hence it is not easily removed. cyano groups increase the acid strength. and the electrophilic substitution takes place at ortho and para positions. Acid chlorides and acid anhydrides react with phenols giving esters more easily. Reactions of Phenol [1] Reaction with zinc dust Phenols on distillation with zinc dust give aromatic hydrocarbons. Electron withdrawng groups like -Nitro. sulphuric acid forms phenol esters but the reaction does not go to completion. (e.

Br OH Br 2 H2O Br OH Br 2.Phenols react with alkyl halides or alkyl sulphates in presence of alkali to form phenolic ethers. 6-tribromo phenol . substituting the hydrogen at ortho and para positions.6-tribromo phenol. however on reaction with PCl 5 it gives chloro benzene C6H5OH + PCl5  C6H5Cl + POCl3 + HCl [5] Reaction with Ammonia When heated with NH3 under pressure in presence of catalysts like anhydrous zinc chloride or calcium chloride. [4] Reaction with phosphorous halide The oxygen of the hydroxyl group in phenol is strongly bound to the benzene ring hence it cannot be easily replaced. The white precipitate consists of 2. This reaction is known as Williamson’s synthesis. Aryl halides do not react with phenols. This alkylation of phenol is a nucleophilic substitution reaction. 4.4. hydroxyl groups of phenols are replaced by amino groups. [6] Halogenation Halogens directly react with phenols. When phenol is treated with bromine water the colour of bromine disappears with the formation of white precipitate.

Mono bromo derivative can be prepared at lower temperature and in the presence of non polar solvents like CCl4 and CS2.gives picric acid. H2SO4 acid and con. OH + HNO 2 HO NO p-nitroso phenol .con. a mixture of ortho and para nitro phenols are formed. [8] Sulphonation It forms a mixture of ortho and para phenol sulphonic acid on reaction with con. [7] Nitration Reaction with nitrating mixture . Nitric acid mixture . H2SO4. [9] Nitrosation It reacts with nitrous acid (a mixture of sodium nitrite and sulphuric acid) to give pnitroso phenol. With dilute nitric acid.

hydroxy benzoic acid is formed. ONa OH COONa CO 2 400 K. a formyl group –CHO is introduced at the ortho or para position to –OH group. which is characteristic of phenol.[10] Coupling with diazonium chloride Phenol couples with benzene diazonium chloride in alkaline medium to form p-hydroxy azobenzene. This is decomposed by dilute hydrochloric acid to salicylic acid. OH CCl 4 NaOH COOH Ortho(Hydroxy benzoic acid) HOOC ParaOH OH + [13] Lederer-Manasse reaction Phenols condense with aqueous formaldehyde in acid or alkaline solution to yield hydroxybenzyl alcohols. [11] Kolbe Schmidt or Kolbe’s reaction When sodium phenoxide is heated with carbon dioxide at 400 K under pressure. sodium salicylate is formed. OH CHCl 3 NaOH CHO Ortho(Hydroxy benzaldehyde) OHC ParaOH OH + Similarly with CCl4 and NaOH. This is called ‘Lederer-Manasse reaction’. This is also called dye test. 4-7 atm HCl OH COOH [12] Riemer-Tiemann reaction When phenol is refluxed with chloroform and sodium hydroxide. .

OH + [H] Ni catalyst OH 443 K Cyclohexanol [17] Houben Hoesch reaction The synthesis of phenolic ketones involves the condensation in diethyl ether of phenols or their ethers with nitriles.Polymeric structures are very easily formed. . O O OH O O + 2 O Phenolphthalein [15] Oxidation Phenol undergoes oxidation to quinone on treatment with chromyl chloride (CrO2Cl2). three dimensional polymers called ‘Bakelite’ are formed. [14] Phthalein fusion Phenols are heated with phthalic anhydride and con. The reaction is carried out in the presence of anhydrous zinc chloride or aluminium chloride and hydrogen chloride. OH + [O] CrO2Cl 2 O O p-Benzoquinone [16] Catalytic hydrogenation Phenol on hydrogenation in presence of nickel forms cyclohexanol. This can be tested by the formation of pink color when it is treated with sodium hydroxide. The resulting ketimine is hydrolysed. H2SO4 to give Phenolphthalein. In presence of excess of formaldehyde.

According to this theory. 3. .Mechanism Dyes and dyeing Dyes are colored compounds used in imparting color to textiles. yarn. a) An organic compound appears coloured due to the presence of certain unsaturated groups (the groups with multiple bonds) in it. It should have a suitable color. food stuffs etc. Natural dyes are extracted from natural substances such as plants. It should be resistant to the action of water.fiber. Color and Structure of Dyes The relationship between the colour of a substance and its structure was explained by a German scientist Otto Witt (1876) through the chromophore and auxochrome theory. animals. Such groups with multiple bonds are called chromophores. There are two major types of dyes . dilute acids and alkalies (all detergents and washing soaps are alkaline in nature). Dyeing can be done at any stage of the manufacturing of textile. A dye should have the following characteristics. 1. or minerals. It should be fast to light. Synthetic dyes are made in a laboratory. 2. Some typical chromophores are. 4. The process of application of a color producing agents to a material. It should be able to fix itself or be capable of being fixed to the fabric. fabric or a finished textile product. usually fibrous or film is known as dyeing.natural and synthetic dyes.

arylcarbonium ion (including triphenylmethines). sulfur. Such supporting groups are called auxochromes.b) The compounds containing the chromophore group is called chromogen. For example. belong to the azo (NN). The color intensity increases with the number of chromophores or the degree of conjugation. and having been studied more than any other class. Auxochromes may be acidic (phenolic) or basic. but deepen the color of the chromogen. In the chemical classification method. accounting for over 50% of all commercial dyes. carbonyl (C=O) (including anthraquinones). but the compound CH3 – (CH=CH)6 – CH3 is yellow in color. Azo dyes contain . Azo dyes The azo dyes are by far the most important class. ethene (CH2=CH2) is colorless. phthalocyanine. in the compound p-hydroxyazobenzene (a bright red dye). For example. –NHR. c) The presence of certain groups which are not chromophores themselves. polymethine andnitro chemical classes. in roughly decreasing order of importance. Some important auxochromes are –OH. –NR2. Classification of Dyes According to Chemical structure Dyes may be classified according to chemical structure or by their usage or application method. The most important organic dyes and pigments. –NH2. colorants are grouped according to certain common chemical structural features.

but more usually both are aromatic. three (trisazo). and leather and to dye cotton that has been mordanted with tannin. . is also used for dyeing paper. Triphenyl methane dyes Triphenylmethane dyes are a group of extremely brilliant and intensely colored synthetic organic dyes having molecular structures based on the hydrocarbon triphenylmethane. or. Examples of azo dyes are Congo red: It was the first known ‘direct dye’ (direct dyes are molecules that adhere to the fabric molecules without help from other chemicals) especially suitable for dyeing cotton (by simple immersion of the fabric in a hot aqueous bath of the dye). wool. Some typical examples are. They exist in the trans form. NH 2 N N NaO3S N N SO3Na H2N Congo Red Bismark brown: It is a diazo dye. jute. Malachite green: Malachite green is used as a direct dye for silk. the dye occurs as lustrous green crystals soluble in water and in alcohol. four (tetrakisazo) or more (polyazo) azo groups. Azo dyes are made by diazotization of a primary aromatic amine followed by coupling of the resultant diazonium salt with an electron-rich nucleophile.at least one azo group (NN) but can contain two (disazo). more rarely. of which at least one. Prepared from benzaldehyde and dimethylaniline. The azo group is attached to two groups.

Rosaniline (Fuchsine or rosaniline hydrochloride) H2N + NH 2 Cl NH 2 .

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