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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
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. NH 2 Benzyl amine Aniline A colorless oily liquid.When nitro benzene is reduced electrolytically in presence of concentrated sulphuric acid. These aromatic amines are of two types. because of intermolecular hydrogen bonding. This liquid turns brown on exposure to air due to oxidation. (i) Amines in which the amino group is directly attached to the benzene ring. phenyl hydroxylamine is first produced which rearranges to give p-amino phenol. 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. sparingly soluble in water but soluble in organic solvents. . NO 2 Electrolytic reduction Conc. Preparation: 1. Vaporized nitro benzene with hydrogen is passed over copper supported on silica at 543 K and aniline is obtained (Manufacturing method). By the catalytic reduction of nitro benzene.
By the ammonolysis of chloro benzene Ammonolysis of chloro benzene at high temperature and pressure in presence of copper salts. the amide is converted into primary amine containing one carbon less than that of amide. NO 2 Sn / HCl NH 2 Reduction with Fe / con.NO 2 H2 / Cu / SiO 543 K 2 NH 2 2. we must look at the availability of the non-bonded electron pair on N. By Hoffmann reaction: Using benzamide. With an arylamine. When an amide (here benzamide) is treated with bromine and alkali. HCl is used for the large scale preparation of aniline. [To compare the basicity of an alkylamine (CH3CH2NH2) and an arylamine (C6H5NH2. 3. . Cl NH 2 2 NH3 CuCl 2 + + NH 4Cl 4. the electron pair is localized on the N atom. With CH3CH2NH2. aniline is prepared. By the chemical reduction of nitrobenzene Under strongly acidic condition such as Sn/HCl or with Hydride donors like LiAlH4. CONH 2 NH 2 Br 2 KOH + + CO 2 Basic nature of Aniline Aniline is less basic than aliphatic amines. the lone pair of electrons on the nitrogen atom is involved in resonance and is not easily available for donation to protons. This is because. however. aniline). Because of positive charge on nitrogen protonation becomes difficult.
the electron pair is delocalized on the benzene ring (see the resonance structures above). Arylamines are less basic than alkylamines because the electron pair on N is delocalized. benzanilide is formed (Schotten-Baumann reaction). and makes C 6H5NH2 less basic than CH3CH2NH2. This decreases the electron density on N. (c) With Benzoyl chloride in the presence of sodium hydroxide. (b) Aniline reacts with acetyl chloride and acetic anhydride to form corresponding amides called anilides.] Reactions of Aniline  Salt formation These form crystalline salts with strong mineral acids such as HCl or H2SO4. 30 amines and finally quaternary ammonium salt.  Formation of Schiffs base Aniline (a primary amine) reacts with aldehydes to form aldimines or Schiff’s base. .  Substitution of nitrogen (a) Alkylation with alkyl halides it forms 20.
6-tribromoaniline. phenyl isocyanide.R NH 2 O N H C H R + (Aldimine or Schiff’s base)  Reaction with nitrous acid A cold solution of sodium nitrite reacts with aniline dissolved in hydrochloric acid. This reaction is known as ‘diazotization’. p-amino benzene sulphonic acid is formed. . which is 2. This solution contains ‘benzene diazonium chloride’. a clear solution is obtained.4. O NH 2 + COCl 2 HN NH  Electrophilic substitution reaction (a) Sulphonation Heating with fuming sulphuric acid. C6H5NH2 + HNO2 C6H5N2Cl  Carbylamine reaction Aniline reacts with chloroform and alcoholic KOH to give an offensive smelling liquid. NH 2 + H SO 2 4 353 K HO 3S NH 2 (b) Halogenation Aniline decolorizes bromine water with the formation of white precipitate.  Oxidation Aromatic amines are readily oxidised by dichromate and sulphuric acid to p-benzoquinone. NH 2 K2Cr 2O7 / H + O O (p-Benzoquinone)  Reaction with Carbonyl chloride Carbonyl chloride form diphenyl urea with aniline.
For preparing dyes and dye intermediates. making the arylamine less basic than aniline. 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. 4.) sulpha drugs..g. 3. For making isocyanates required for polyurethane plastics. 2. For the manufacture of anti oxidants in rubber industry. Electron-donor groups add electron density to the benzene ring. making the arylamine more basic than aniline. electron-withdrawing groups remove electron density from the benzene ring. [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. D= NH2 OH OR NHCOR R . Whereas. For preparing drugs (e. Uses of aniline 1.
NO2¯. Nitrous acid is formed by mixing aqueous solutions of sodium nitrite and mineral acid like HCl or H2SO4. Br¯. Preparation Benzene diazonium chloride is prepared by the action of nitrous acid on aniline at 273 – 278 K. HSO4¯. characterized by the presence of the functional group –N+≡N (diazonium ion) directly bonded to an aryl group (–Ar). These are collectively called aryl diazonium salts. C6H5NH2 + HNO2 C6H5N2Cl This is stable only under ice cold condition.. In the dry condition it is quite unstable and decomposes rapidly. BF4¯ etc. Structure: The electronic structure Resonance stabilized diazonium ion is further stabilized by the involvement of the benzene ring.N+≡N forms salts with anions such as Cl¯. The aryl diazonium ion Ar. .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. Only diazonium [ArN2+ BF4–] fluro borate can be dried without decomposition. Properties: Colorless crystalline solids turning brown on exposure to air. soluble in water and alcohol and insoluble in ether. in benzene diazonium ion.
phenol is obtained. in presence of cuprous salts catalyst. Cu2I2 C6H5N2Cl + NaNO2 C6H5NO2  Sand Meyer Reaction When aqueous solution of diazonium chloride is warmed with Cu 2Cl2 or Cu2Br2 in halogen acid. very useful compounds can be prepared from them. . halogenated benzene is formed.  Reduction to arenes Benzene diazonium chloride is reduced to benzene when treated with Hypophosphorous acid. C6H5N2Cl + CH 3OH C6H5OCH 3 + N2 Anisole (Aromatic ether) + HCl C6H5N2Cl + CH 3COOH C6H5OCOCH 3 Phenyl acetate (Ester) + N2 + HCl  Replacement by Iodine Aqueous solution of diazonium salt reacts with potassium iodide solution to form Iodobenzene.Chemical properties They are highly reactive compounds. 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 + KI C6H5I + KCl + N2  Replacement by Nitro group : Diazonium salt when treated with sodium nitrite in the presence of cuprous salt as a catalyst forms nitro compounds. C6H5N2Cl H3PO4 Cu 2Cl 2 C6H6 + N2 + HCl  Replacement by –OH or –OR (alkoxy) or –OCOR (acyloxy) group When the aqueous solution is boiled.
.  Diazonium coupling reaction Diazonium salt reacts with aromatic amine and phenols to give azo compounds of the general formula.  Reduction Diazonium chloride is reduced to phenyl hydrazine on treatment with SnCl2/HCl or Zn/HCl or NaHSO3. –NH2.  Replacement by an aryl group: (Gomberg Bachmann Reaction) Decomposition of diazonium salts in presence of sodium hydroxide and benzene.C6H5N2Cl + HCl Cu 2Cl 2 C6H5Cl C6H5N2Cl + HBr Cu 2Br 2 C6H5Br  Gattermann reaction When the diazonium chloride solution is warmed with copper powder and the hydrogen halide. ArN=N Ar’ This reaction is known as Coupling reaction since all these compounds are intensely coloured and used as dyes. phenyl cyanide is formed. thousands of azo dyes have been synthesised by this procedure. –NHR. This reaction is known as ‘Gomberg’ or ‘Gomberg Bachmann’ reaction. coupling usually occurs at para position. The aromatic compound with which it couples should have any one of the groups like –OH. the corresponding halobenzene is obtained. results in the formation of Biphenyl. –OR. C6H5N2Cl + HCl Cu C6H5Cl + N2  Replacement by cyanide group The diazonium salt solution when treated with cuprous cyanide /potassium cyanide mixture. C6H5N2Cl + KCN Cu2(CN) 2 C6H5CN + N2 + KCl Treatment of diazonium chloride with KCN solution in presence of copper. also gives phenyl cyanide. –NR2 etc.
and is somewhat soluble in water.. Aqueous .Uses of diazonium salts 1) It is a very valuable intermediate in the preparation of a lot of compounds like phenols. amines etc. 3) Diazo coupling reaction takes place in ice cold condition. halides. The simplest members are phenol [C6H5OH] and cresols [CH3–C6H4–OH].p. 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. cyanides etc. It forms colorless needles (m. 3) Very useful in the manufacture of azo dyes. has a characteristic odor. PHENOLS These form a class of compounds in which one or more hydrogen atom of the benzene nucleus are replaced by hydroxyl group. 2) Valuable laboratory reagents like phenyl hydrazine can be prepared. 41°C). at para-position. Phenol [C6H5OH] Phenol itself was formerly known as carbolic acid.
H 2O H2O C6H5OH + Na 2CO 3  Crude phenol (of step 3) is subjected to fractional distillation. . the phenolate ion is more stabilized by resonance than phenol itself.  Middle oil is washed with H2SO4. Thus in the case of phenol. but its main use is for the preparation of polymers (phenolic resins). Carbon dioxide is then blown through the solution to liberate phenols.  Filtrate of step 2 is treated with aqueous NaOH when phenols dissolve as phenoxides. Isolation of phenol from middle oil Middle oil of coal-tar distillation has naphthalene and phenolic compounds. C6H5OH + NaOH C6H5ONa + CO 2. Phenolic compounds are isolated in following steps.solutions of it (or its methyl-substituted derivatives) are applied as disinfectants.  Excessive cooling separates naphthalene (a low melting solid). It dissolves basic impurities like pyridine (base). 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). 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.
and the electrophilic substitution takes place at ortho and para positions.(b) The electron density is increased in the benzene ring and hence the benzene ring is activated towards electrophilic substitution reaction. Acid chlorides and acid anhydrides react with phenols giving esters more easily. especially in presence of a base.. (c) Ortho and para positions are more electron dense. (d) Oxygen is strongly bound to the nucleus hence it is not easily removed.groups decrease the acid strength. CH3. 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.) strength of phenol varies in the order. The acid strength of phenols depends on the nature of the substituent present in the benzene ring. cyano groups increase the acid strength.  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. Reactions of Phenol  Reaction with zinc dust Phenols on distillation with zinc dust give aromatic hydrocarbons. Electron withdrawng groups like -Nitro. (e. sulphuric acid forms phenol esters but the reaction does not go to completion.g.  Etherification .
4. This reaction is known as Williamson’s synthesis. however on reaction with PCl 5 it gives chloro benzene C6H5OH + PCl5 C6H5Cl + POCl3 + HCl  Reaction with Ammonia When heated with NH3 under pressure in presence of catalysts like anhydrous zinc chloride or calcium chloride. 6-tribromo phenol . Aryl halides do not react with phenols. hydroxyl groups of phenols are replaced by amino groups. This alkylation of phenol is a nucleophilic substitution reaction.6-tribromo phenol. When phenol is treated with bromine water the colour of bromine disappears with the formation of white precipitate. 4. substituting the hydrogen at ortho and para positions.Phenols react with alkyl halides or alkyl sulphates in presence of alkali to form phenolic ethers.  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. Br OH Br 2 H2O Br OH Br 2.  Halogenation Halogens directly react with phenols. The white precipitate consists of 2.
 Nitrosation It reacts with nitrous acid (a mixture of sodium nitrite and sulphuric acid) to give pnitroso phenol.  Sulphonation It forms a mixture of ortho and para phenol sulphonic acid on reaction with con. With dilute nitric acid.Mono bromo derivative can be prepared at lower temperature and in the presence of non polar solvents like CCl4 and CS2. a mixture of ortho and para nitro phenols are formed.gives picric acid. H2SO4.con. Nitric acid mixture . OH + HNO 2 HO NO p-nitroso phenol . H2SO4 acid and con.  Nitration Reaction with nitrating mixture .
which is characteristic of phenol. This is called ‘Lederer-Manasse reaction’. ONa OH COONa CO 2 400 K. a formyl group –CHO is introduced at the ortho or para position to –OH group. sodium salicylate is formed. 4-7 atm HCl OH COOH  Riemer-Tiemann reaction When phenol is refluxed with chloroform and sodium hydroxide. This is decomposed by dilute hydrochloric acid to salicylic acid. OH CCl 4 NaOH COOH Ortho(Hydroxy benzoic acid) HOOC ParaOH OH +  Lederer-Manasse reaction Phenols condense with aqueous formaldehyde in acid or alkaline solution to yield hydroxybenzyl alcohols. hydroxy benzoic acid is formed. This is also called dye test. . Coupling with diazonium chloride Phenol couples with benzene diazonium chloride in alkaline medium to form p-hydroxy azobenzene. OH CHCl 3 NaOH CHO Ortho(Hydroxy benzaldehyde) OHC ParaOH OH + Similarly with CCl4 and NaOH.  Kolbe Schmidt or Kolbe’s reaction When sodium phenoxide is heated with carbon dioxide at 400 K under pressure.
This can be tested by the formation of pink color when it is treated with sodium hydroxide. OH + [O] CrO2Cl 2 O O p-Benzoquinone  Catalytic hydrogenation Phenol on hydrogenation in presence of nickel forms cyclohexanol. In presence of excess of formaldehyde. The resulting ketimine is hydrolysed.  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.Polymeric structures are very easily formed. . OH + [H] Ni catalyst OH 443 K Cyclohexanol  Houben Hoesch reaction The synthesis of phenolic ketones involves the condensation in diethyl ether of phenols or their ethers with nitriles. three dimensional polymers called ‘Bakelite’ are formed. O O OH O O + 2 O Phenolphthalein  Oxidation Phenol undergoes oxidation to quinone on treatment with chromyl chloride (CrO2Cl2). H2SO4 to give Phenolphthalein.
1. There are two major types of dyes . A dye should have the following characteristics. 3. It should be resistant to the action of water. According to this theory. or minerals. 2. animals. food stuffs etc. 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. It should be fast to light. The process of application of a color producing agents to a material. a) An organic compound appears coloured due to the presence of certain unsaturated groups (the groups with multiple bonds) in it. fabric or a finished textile product. Dyeing can be done at any stage of the manufacturing of textile.natural and synthetic dyes. Some typical chromophores are. dilute acids and alkalies (all detergents and washing soaps are alkaline in nature). usually fibrous or film is known as dyeing. Synthetic dyes are made in a laboratory.Mechanism Dyes and dyeing Dyes are colored compounds used in imparting color to textiles. It should have a suitable color. . 4. Such groups with multiple bonds are called chromophores. It should be able to fix itself or be capable of being fixed to the fabric.fiber. Natural dyes are extracted from natural substances such as plants. yarn.
The color intensity increases with the number of chromophores or the degree of conjugation. Classification of Dyes According to Chemical structure Dyes may be classified according to chemical structure or by their usage or application method. phthalocyanine. –NHR. In the chemical classification method. Auxochromes may be acidic (phenolic) or basic. carbonyl (C=O) (including anthraquinones). Some important auxochromes are –OH. arylcarbonium ion (including triphenylmethines). polymethine andnitro chemical classes. –NR2. –NH2. colorants are grouped according to certain common chemical structural features. For example. accounting for over 50% of all commercial dyes.b) The compounds containing the chromophore group is called chromogen. belong to the azo (NN). sulfur. ethene (CH2=CH2) is colorless. For example. The most important organic dyes and pigments. Azo dyes The azo dyes are by far the most important class. in the compound p-hydroxyazobenzene (a bright red dye). Such supporting groups are called auxochromes. Azo dyes contain . and having been studied more than any other class. c) The presence of certain groups which are not chromophores themselves. but the compound CH3 – (CH=CH)6 – CH3 is yellow in color. in roughly decreasing order of importance. but deepen the color of the chromogen.
but more usually both are aromatic. three (trisazo). 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. Malachite green: Malachite green is used as a direct dye for silk. . Some typical examples are. Prepared from benzaldehyde and dimethylaniline. is also used for dyeing paper. jute. of which at least one. more rarely. 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). 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 (NN) but can contain two (disazo). and leather and to dye cotton that has been mordanted with tannin. four (tetrakisazo) or more (polyazo) azo groups. wool. They exist in the trans form. the dye occurs as lustrous green crystals soluble in water and in alcohol. NH 2 N N NaO3S N N SO3Na H2N Congo Red Bismark brown: It is a diazo dye. The azo group is attached to two groups.
Rosaniline (Fuchsine or rosaniline hydrochloride) H2N + NH 2 Cl NH 2 .
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