Alcohol Ether & Phenol, Halogen Derivatives, Benzene & Toluene

Chapter
Alcohol Ether & Phenol, Halogen

Derivatives, Benzene & Toluene
E xercise # 1
Q.1 Which of the following statements is untrue :
[1] A primary alcohol has CH2OH group
[2] A secondary alcohol has two carbon atoms
[3] A tertiary alcohol has a minimum of four carbon atoms
[4] A primary alcohol with a branched chain has a minimum of four carbon atoms
Q.2 Which of the following is not a dihydric alcohol :
[1] Trimethylene glycol [2] Ethylene glycol [3] Glycerine [4] Glycol
Q.3 Which of the following compounds does not contain at least two primary carbon atoms and two primary
alcoholic groups :
[1] Glycerol [2] Glycol [3] Trimethylene glycol [4] Methyl glycol
Q.4 Which of the following reactions does not lead to formation of an alkanol :
dil. / H2SO4
[1] RCOOR’ + KOH [2] R2O + H2O  

Na  ethanal
[3] RCOR’ + 2H   [4] (RCO)2O + H2O
Q.5 Which of the following reducing agents reduces carboxylic acids to alkanols :
[1] Sodium and ethanol [2] Sodium and n–butyl alcohol
[3] Lithium aluminium hydride [4] Magnesium amalgam and conc. HCl
Q.6 Which of the following enzymes is not present in yeast :
[1] Maltase [2] Zymase [3] Invertase [4] Diastase
Q.7 The enzyme diastase is present in :
[1] Wash [2] Wort [3] Malt [4] Yeast
Q.8 Starch is converted into sugar by the enzyme :
[1] Maltase [2] Zymase [3] Maltose [4] Diastase
Q.9 Which enzyme converts glucose into ethanol :
[1] Invertase [2] Zymase [3] Maltse [4] Diastase
Q.10 Maltose (a disaccharide) is converted into the monosaccharide by the enzyme :
[1] Invertase [2] Maltase [3] Zymase [4] Diastase
Q.11 Which enzyme converts canesugar into a mixture of glucose and fructose :
[1] Zymase [2] Invertase [3] Maltase [4] Diastase
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SARWAR CLASSES Alcohol Ether & Phenol, Halogen Derivatives, Benzene & Toluene
Q.12 Which of the following statements is false :

[1] Industrial alcohol is rectified spirit
[2] Industrial methylated spirit contains 95% ethanol and 5% methanol
[3] Mineralised methylated spirit contains 90% rectified spirit, 9% methanol and 1% petroleum oil
[4] Alcohol can be dried over calcium chloride
Q.13 Ethanol cannot be denatured by adding :
[1] Pyridine [2] Caoutchoucine [3] Methanol [4] Methanal
Q.14 Methanol is not prepared by :
[1] Destructive distillation of wood [2] Catalytic hydrogenation of carbon monoxide
[3] Catalytic oxidation of methane [4] Hydroboration–oxidation of ethylene
Q.15 Pyroligneous acid contains :
[1] Acetic acid, acetone and ethanol [2] Formic acid, acetone and methanol
[3] Methanol, acetic acid and acetone [4] Formic acid, ethanol and acetone
Q.16 Methanol reacts with calcium chloride to form an alcoholate of the structure :
[1] CaCl2.2CH3OH [2] CaCl2.4CH3OH [3] CaCl2.3CH3OH [4] CaCl2.CH3OH
Q.17 Methanol is not used as :
[1] Solvent [2] An antifreeze [3] Heart stimulant [4] Motor fuel
Q.18 Which of the following statements is incorrect :
[1] The catalyst used in the hydrogenation of carbon monoxide is a mixture of oxides of copper, zinc
and chromium
[2] Synthesis gas is a mixture of CO and hydrogen in the ratio 1 : 3 by volume
[3] Methanol forms an azeotrope with acetone and also with water
[4] Methanol vapours form an expolsive mixture with air or oxygen when ignited
Q.19 Which of the following reactions of alkanols does not involve C–O bond breaking :
[1] CH3CH2OH + SOCl2 [2] CH3CH(OH)CH3 + PBr3
[3] CH3CH2OH + CH3COOH [4] ROX + HX
Q.20 Which of the following compounds does not have an ester linkage :
[1] Ethyl acid sulphate [2] Diethyl hydrogen phosphate
[3] Ethyl acetate [4] CH3CO–O–CO–CH3
Q.21 Which of the following is a correct statement :
[1] An alcohol is a stronger acid than water
[2] An alkoxide ion is a stronger base than hydroxide ion
[3] Amide ion is a weaker base than alkoxide ion
[4] Ammonia is a stronger acid than an alcohol
Q.22 Which of the following is least soluble in water :
[1] CH3OH [2] CH3CH2OH [3] CH3CH2CH2OH [4] CH3CH2CH2CH2OH
LGF, Venus Tower, Opp. Jamia Urdu, Medical Road Aligarh. 9219418880, 9997394458
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Q.23 Which of the isomers of n–butyl alcohol exhibit optical isomerism :

[1] Butyl alcohol [2] Sec. Butyl alcohol
[3] 2–Methyl–1–propanol [4] 2–Methyl–2–Propanol
Q.24 Alcohols are reduced by red phosphorus and hydroiodic acid into :
[1] Aldehydes [2] Alkoxyalkanes [3] Alkanes [4] Anhydrides
Q.25 Which of the following alcohols does not give an aldehyde on oxidation :
[1] Benzyl alcohol [2] Sec. butyl alcohol [3] Allyl alcohol [4] Crotyl alcohol
Q.26 Which of the following alcohols gives a red colour in victor Meyer test :
[1] n–Propyl alcohol [2] Isoproyl alcohol [3] (CH3)3C–OH [4] Sec. Butyl alcohol
Q.27 Methanol can be distinguished from ethanol by the following except :
[1] Reaction with iodine and alkali [2] Reaction with salicylic acid and H2SO 4
[3] Reaction with Lucas reagent [4] Boiling point
Q.28 Methanol on heating with salicylic acid and a few drops of conc. H2SO 4 gives the smell of :
[1] Bitter almonds [2] Oil of wintergreen [3] Rotten eggs [4] Mustard oil
Q.29 Which of the following alcohols gives iodoform reactions :
[1] n–propyl alcohol [2] Isobutyl alcohol [3] sec. Butyl alcohol [4] n–Butyl alcohol
Q.30 The compounds A, B and C in the reaction sequence :
diastase maltase zymase

A   B  C  C2H5OH + CO2 are :
[1] Starch, sucrose, fructose [2] Starch, sucrose, glucsoe

[3] Sratch, maltose, glucose [4] Starch, surcose, maltose
Q.31 Methanol on heating with hot copper gives the smell of :
[1] Oil of bitter almonds [2] Oil of mirbane [3] Formalin [4] Vinegar
Q.32 Addition of borane to 1–butene followed by oxidative alkaline hydrolysis gives :
[1] n–butyl alcohol [2] sec. butyl alcohol [3] isobutyl alcohol [4] ter. butyl alcohol
Q.33 The compound A, B and C in the reaction sequence :
PBr3 alc. KOH Br2

CH3–CH2OH   A   B   C are given by the set :
[1] Ethyl bromide, CH3CH2OH, CH3CHBr2 [2] C2H5Br, CHCH, CH2=CHBr

[3] C2H5Br, CH2=CH2, CH2Br–CH2Br [4] C2H5Br, CH3CH2OH, BrCH2–CH2Br
Q.34 Alcohol are stronger acids than alkanes. This is clear from the reaction :
[1] 2ROH + 2Na 2RO –Na+ + H2 [2] ROH + R’MgX R’H + RO–MgX
[3] ROH + R’COOH R’COOR + H2O [4] ROH + R’COCl R’COOR + H2O
Q.35 The main product obtained by heating ethanol with concentrated sulphuric acid at 140ºC is :
[1] Ethylene [2] Ethyl hydrogen sulphate
[3] Ethoxyethene [4] Ethoxyethane
Q.36 The oxidation of a secondary alkanol with Cr(VI) leads to the formation of :
[1] An alkanone and Cr (II) [2] A ketone and Cr (III)
[3] An alkanal and Cr (III) [4] A ketone and Cr (II)
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Q.37 Polyhydroxy alcohols have higher boiling point than monohydric alcohols because :
[1] The former have more than one OH group
[2] The former have higher moelcular weights
[3] The former provide more than one site per moelcule for hydrogen bonding
[4] The latter are more volatile
Q.38 The “notorious” alcohol deposited on the walls of arteries and the chie constituent of gallstones is :
[1] Ethanol [2] Cholesterol [3] Glycol [4] Glycerol
Q.39 The molecular formula C7H8O represents the following except :
[1] A mixed aliphatic ether [2] Phenolic compounds
[3] A cycloalkanol [4] An aralkanol
Q.40 Most phenolic compounds are insoluble in water but phenol is slightly soluble. This is due to :
[1] the presence of a hydroxy group [2] Hydrogen bonding with water molecules
[3] Its low melting point [4] High boiling point
Q.41 Which of the following compounds shows intramolecular hydrogen bonding :
[1] p–Nitrophenol [2] Ethanol [3] o–Nitrophenol [4] Methanamine
Q.42 Which of the following reactions will not lead to a phenol :
Fuse Boil
[1] C6H5SO 3Na + NaOH   [2] C6H5N2Cl + H2O  
NaOH
OH
Heat
[3] C6H5ONa + RX 
Heat
 [4] + NaOH(CaO)  
COONa
Q.43 Phenol is commercially prepared by :

[1] Decarboxylation of sodium salicylate
[2] Distilling diazonium sulphate solution
[3] Cumene–phenol process
[4] Fusion of sodium benzene sulphonate with solid caustic soda
O2 Aq. H3 O 
Q.44 The compounds A, B and C in the reaction sequence cumene   A    B + C are given
by the set :
[1] Cumene oxide, phenol, CH3CHO [2] Cumene hydroperoxide, Catechol, CH3CHO
[3] Cumene hydroperoxide, Phenol CH3COCH3 [4] Cumene oxide, Phenol, CH3COCH3
Q.45 Sodium phenate reacts with acetyle chloride to form :
[1] Methyl benzoate [2] Acetyl phenol [3] Phenyl acetate [4] Chlorobenzene
Q.46 Phenol undergoes electrophilic substitution reactions more readily than all benzene derivatives because
of :
[1] Slightly water solubility of phenol
[2] Acidic nature of phenol
[3] Strongly electron–releasing nature of phenoxide ion
[4] Low melting point of phenol
5
K 2 S2 O8
Q.47 The reaction, Phenol 
NaOH
Quinol, is called :
[1] Lederer–Manasse reaction [2] Reimer–Tiemann reaction

[3] Elbs persulphate oxidation [4] Kolbe’s reaction
Q.48 Phenol when refluxed with CHCl3 and alkali at 60ºC gives :
[1] Benzaldehyde [2] Benzoic acid [3] Salicylic acid [4] Salicyladehyde
Q.49 Phenol can be distinguished from ethanol by reactions with the following except :
[1] Iodine and alkali [2] Ferric chloride [3] Acetyl chloride [4] Bromine
Q.50 Reimer–Tiemann formylation reaction involves addition of :
[1] Chloroform on phenoxide ion [2] Trichloromethyl carbanion on phenoxide ion
[3] Dichlorocarbene on phenoxide ion [4] Hydroxide ion on phenol
Q.51 Phenol on treatment with methyl chloride in the presence of anhydrous AlCl 3 gives chiefly :
[1] o–cersol [2] m–cersol [3] anisole [4] p–cersol
Q.52 Phenol reacts with aqueous solution of bromine to give :
[1] Tribromobenzene [2] Trinitorphenol
[3] 2,4,6–tribromophenol [4] A mixture of ortho bromophenol and para
bromophenol
Q.53 Which of the following is the correct stabiltiy order :
– –
[1] OH > O [2] OH > O
– –
[3] O > OH [4] O > OH
Q.54 Which of the following reactions leads to an ether formation :

Aq. NaOH Aq. NaOH
[1] p–cersol + p–nitrobenzyl bromide 
 [2] Phenol + chloroacetic acid 

OH –
[3] Phenol + benzoyl chloride   [4] Phenol + benzenesulphonyl chloride
Q.55 Phenol on heating with conc. sulphuric acid at 110ºC gives mainly :
[1] Benzenesulphonic acid [2] p–phenolsulphonic acid
[3] o–phenolsulphonic acid [4] m–phenolsulphonic acid
Q.56 Heating of a phenol with sodium nitrite and a few drops of H2SO 4 gives a dark colour. This reaction
mixture turns blue on addition of alkali. This reaction is called :
[1] Lederer–Manasse reaction [2] Lucas test
[3] Liebermann nitroso reaction [4] Lossen rearrangement
Q.57 A water insoluble aromatic compound dissolves in sodium hydroxide but not in aqueous NaHCO3. It is
likely to be :
[1] C6H5COOH [2] C6H5COCH3 [3] C6H5OH [4] C6H5NH2
Q.58 The reaction of phenol with chloroform and alkali is known as :
[1] Carboxylation of phenol [2] Diazotisation of phenol
[3] Nitrosation of phenol [4] Formylation of phenol
Q.59 Phenol on heating with phthalic anhydride and sulphuric acid gives :
[1] Phenetole [2] Phenolphthalein [3] Phenanthrene [4] Pseudonitrole
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Q.60 Anisole is obtained from phenol by reaction with :

[1] NaOH + CHCl 3 [2] NaOH + CH3I [3] NaOH + C2H5I [4] NaOH + CO 2
Q.61 Phenol on treatement with aqueous solution of ferric chloride gives :
[1] Red colour [2] Violet colour [3] Blue colour [4] Orange colour
Q.62 Phenol is not used in the manufacture of :
[1] Phenolic resins [2] Dyes and herbicides
[3] Petrol subtitutes [4] Expolsives and wood preservatives
Q.63 Which of the following is not a correct statement :
[1] Phenol is a much weaker acid than benzoic acid
[2] The reaction of ferric chloride with phenol to give violet colour is characteristic of –C=C– group
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[3] Phenol is a stronger acid than ethanol but weaker than benzyl alcohol OH
[4] Picric acid does not contain a –COOH group

Q.64 Select the incrorrect statement :
[1] Phenoxide ion is stabilized more than phenol
[2] Cyclohexanol is a stronger acid than phenol
[3] Phenol on refluxing with conc. HBr does not give bromobenzene
[4] Cyclohexanol on heating with HBr forms bromocyclohexane
Q.65 The widely used pain reliever aspirin is prepared by :
[1] Treating phenol with Ac2O [2] Reacting salicylic acid with methanol
[3] Reacting salicylic acid with acetic anhydride [4] Reacting phenol with sulphuric acid
Q.66 Ethers are more volatile than alcohols containing same number of carbon atoms. This is because :
[1] Ethers are polar compounds [2] Ethers do not exhibit hydrogen bonding
[3] Ethers are immiscible with water [4] Ethers are miscible with water
Q.67 Ethanol when heated with concentrated sulphuric acid gives all of the following compounds except :
[1] C2H5–O–SO2OH [2] C2H5–O–C2H5 [3] CH2=CH2 [4] CHCH
Q.68 The preparation of ethers from alcohols by using sulphuric acid is called :
[1] Williamson’s ether synthesis [2] Williamson’s continuous etherification process
[3] Ziesel’s method [4] Zerewitinoff method
Q.69 Ether is used as :
[1] An antiseptic and a solvent
[2] An anaesthetic and a solvent
[3] A fire extinguisher under the trade name pyrene
[4] A dry cleaning solvent
Q.70 Ether reacts wtih air to form :
[1] Acetic anhydride [2] Ether hydroperoxide [3] An ester [4] Alkanol
Q.71 Ether bottles should not be kept open in air because :
[1] Ether is an anaesthetic [2] Ether forms an explosive peroxide
[3] Ether is costly [4] Ether gets oxidised to ethanol
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Q.72 The reaction of HI on ethers is important because it is used for estimation of :

[1] Alcoholic groups in natural compounds [2] Ether groups in natural compounds
[3] Amino groups in natural compounds [4] Carbonyl groups in natural compounds
Q.73 The decomposition of ethers by HI or HBr is called :
[1] Zerewitinoff’s reaction [2] Ziesel’s method
[3] Williamson’s method [4] Hell–volhard–Zelinsky reaction
Q.74 The simplest cyclic ether is :
[1] Furane [2] Tetrahydrofuran [3] Anisole [4] Ethylene oxide
Q.75 Ethers are not prepared by :
[1] Expoxidation
[2] Reaction of a sodium alkoxide with an alkylhalide
[3] Heating a silver carboxylate with alkyl halide
[4] Williamson’s continuous etherification process
Q.76 Which of the following ethers has highest boiling points is :
[1] Ethyl ether [2] Vinyl ether [3] Phenyl ether [4] Tetrahydrofuran
Q.77 The Williamson synthesis involves :
[1] A nucleophilic addition [2] An electrophilic substitution
[3] SN2 displacement [4] SN1 displacement
Q.78 Which of the following statements is untrue :
[1] Anisole on treatent with HI forms phenol and CH3I
[2] 2–Ethoxypropane on heating with HBr forms isopropyl bromide and ethyl bromide
[3] Air ether–vapour mixtures are used as anaesthetic
[4] Air ether–vapour mixtures detonate violently
Q.79 Ethoxyethane on reaction with ethanoyl chloride in presence of anhydrous AlCl3 gives :
[1] Ethyl methyl ketone [2] Ethyl acetate
[3] Ethyl methanoate [4] Diethyl ketone
Q.80 Which of the following reactions does not lead to formation of ethanol :
Na  ethanol LiAlH4
[1] CH3COOC2H5   [2] CH3COOH  
dil. H2SO4  heat

[3] CH2=CH2 + CO + H2 [4] Diethyl ether  
Answer Key
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 2 3 4 4 3 4 3 4 2 2 2 4 4 4 3 2 3 3 3 4
Qus. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 2 4 2 3 2 1 3 2 3 3 3 1 3 2 4 2 3 2 3 2
Qus. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Ans. 3 3 3 3 3 3 3 4 3 3 4 3 3 1 2 3 3 4 2 2
Qus. 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80
Ans. 2 3 3 2 3 2 4 2 2 2 2 2 2 4 3 3 3 3 2 3
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E xercise # 2
Q.1 Glycerol reacts with nitric acid to form an explosive compound called nitroglycerine having the structure
:
[1] CH2OH [2] CH2OH [3] CH2–O–NO2 [4] CH2–O–NO2

| | | |
CHOH CH–O–NO2 CH–O–NO2 CH–O–NO2
| | | |
CH2–O–NO2 CH2OH CH2–O–NO2 CH2OH
Q.2 Crotyl alcohol has the structure :

[1] CH2=CH–CH2OH [2] CH2=CH(OH)–CH3
[3] CH3–CH=CH–CH2–OH [4] CH(OH)=CH–CH3
Q.3 The missing structures A and B in the reaction sequence :
Al O (i) O3
2 3
R–CH2–CH2OH 
350ºC
R–CH=CH2 
(ii) Zn. H O

 RCHO + A
3
Reduce
B
are given by the set :
[1] CH3OH, RCOOH [2] Methanal, RCH2OH [3] Ethanal, RCOOH [4] Methanal, RCHOHR’
Q.4 The missing structures A and B in the reaction sequence :
B2H6 H2 O2  NaOH
CH3–CH=CH2   A   B are given by the set :
[1] CH3–CH2–CH2–BH2, CH3–CH2–CH2OH [2] (CH3CHCH)2BH, CH3–CH2–CH2OH
[3] (CH3)2CH–CH2–BH2, CH3–CH(OH)–CH [4] (CH3–CH2–CH2)3 B, CH3–CH2–CH2OH
Q.5 Which of the following reactions is an example of hydrogenolysis :
Dil. H2 SO4 Na 
[1] C2H5–O–C2H5   C2H5OH [2] CH3COOC2H5 
C2H5 OH C2H5OH

LiAlH4 2H
[3] CH3COOH   C2H5OH [4] CH3CHO   C2H5OH
Q.6 The compounds A, B and C in the reaction sequence :
(i) CH3CHO
HBr Mg (ii) H3O
CH3CH2OH   A    B   C are given by the set :
[1] CH3CH2Br, CH3CH2MgBr, (CH3)3C–OH

[2] CH3CH2Br, (CH3CH2)2Mg, (CH3)2CHCH2OH
[3] CH3CH2Br, CH3CH2MgBr, CH3CH(OH)CH2CH3
[4] CH3CHBr2, CH3CH(MgBr)2, CH3CH(OH)CH3
Q.7 A primary alcohol on oxidation :
[1] Loses only one –hydrogen [2] Loses no –hydrogen
[3] Can lose both –hydrogens [4] Can lose one –hydrogen or both –hydrogen atoms
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Q.8 which of the following is not a common oxidant for alkanols :

[1] Heptavalent manganese [2] Hexavalent chromium
[3] Tetravalant manganese [4] Chromium trioxide in acetic acid
Q.9 In the industrial preparation of ethanol from starch by fermentation processes, a small amount of inferior
liquor called “fusel oil” is obtained, This is chemically a mixture of :
[1] Propyl alcohol, isobutyl alcohol active amyl alcohol and excess of isopentyl alcohol
[2] Propyl alcohol, ispropyl alcohol and isopentyl alcohol
[3] Methanol, ethanol and 1–propanol
[4] Methanal + ethanal + propanal
Q.10 Which of the following statements is not true :
[1] Pure phenol is a colourless crystalline solid [2] Phenol has a low melting point
[3] Phenol has a very low boiling point [4] Phenol turns pink on exposure to air
Q.11 Select the wrong statement :
[1] Ka of phenol is of the order of 10–10 [2] Phenol is stronger acid than CH3COOH
[3] Acetic acid is stronger acid than C6H5OH [4] Sodium phenate is soluble in water
Q.12 The reaction
OH
120ºC +
O Na+ + CO 2 
7 atmospheres
 COO Na
is called :
[1] Elbs persulphate oxidation [2] Kolbe reaction
[3] Reimer–Tiemann reaction [4] Lederer–Manasse reaction
Q.13 Sodium phenate on heating with CO2 under presssure gives mainly :
[1] o–hydroxybenzaldehyde [2] o–hydroxybenzyl alcohol
[3] o–hydroxybenzoic aicd [4] o–hydroxyphenol
Q.14 Nitration of phenol with conc. nitric acid gives :
[1] o–nitrophenol [2] m–nitrophenol [3] p–nitrophenol [4] 2,4,6–trinitrophenol
Q.15 Phenol reacts with benzenediazonium chloride solution to from a compound of the structure :
[1] HO N=N Cl [2] N=N OH
[3] N–N [4] N=N Cl

| |
OH Cl
Q.16 Which of the following sets of groups activates the ortho and para positios in electrophilic aromatic
substitutions
O
[1] –OH, –NO2, –CHO [2] –NH2, –NO2, –C–O–H
[3] –OH, O –, –OR [4] –OR, –CN, –Cl
Q.17 Deoxygenation of phenol can be achieved by distillation with :
[1] Raney nickel [2] Lithium aluminium hydride
[3] Sodium borohydride [4] Zinc dust
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Q.18 Phenol and benzoic acid are distinguished by :

[1] Lucas reagent [2] Victor Meyer test
[3] Caustic soda [4] Sodium bicarbonate
Q.19 Phenol is distinguished from ethanol by the reaction with :
[1] Red litmus [2] Aqueous ferric chloride
[3] Alkaline –naphthol [4] Sodium bicarbonate solution
NaNO
2 H2 O NaOH
Q.20 Phenol 
conc. H2SO4
 Green product   red product   Blue product :
this reaction is associated with the name of :

[1] Gattermann [2] Hofmann [3] Liebermann [4] Reimer–Tiemann
Q.21 The sulphur analogue of phenol is not called :
[1] Phenyl mercaptan [2] thiophenol
[3] Phenyl hydrogen sulphide [4] Benzenethiol
Q.22 Which of the following is not correctly matched :
[1] Phenol + CHCl 3 + NaOH Heat — Salicylaldehyde
 
Heat
[2] Phenol + Phthalic anhydride 
H2SO4
 — Phenetole
[3] Phenol Br2 water — Tribromophenol

 
Heat, Pr essure
[4] Sodium phenate + CO 2  — Salicylic acid
Q.23 In the reaction sequence :
NaOH CH3I HI
SO 3Na 
350ºC
 A   B   C+D
A, B, C and D are given by the set :

[1] Sodium phenate, anisole, C6H5I, CH3OH [2] Sodium phenate, phenetole, C2H5I, C6H5OH
[3] Sodium phenate, anisole, C6H5OH, CH3I [4] Sodium phenate, phenetole, C6H5I, C2H5OH
Q.24 Anisole does not react with HI to from C6H5I and CH3OH because :
[1] C6H5 is less stable [2] C6H5I has high molecular weight
[3] Aromatic carbon–oxygen bond is stronger [4] CH3OH is more volatile than CH3I
Q.25 Which of the following is a schotten–baumann reaction :
[1] C6H5OH + CH3COCl  C6H5OCOCH3 + HCl
[2] C6H5OH + C6H5COCl  C6H5COOC6H5 + HCl
[3] 3C6H5OH + PCl 5 + H2O  (C6H5)3PO4 + 5HCl
[4] C6H5OH + (CH3CO)2O  C6H5OCOCH3 + CH3COOH
Q.26 The methoxy groups in natural compounds are estimated by reaction with :
[1] H2SO 4 [2] HF [3] HI [4] BF 3
HBr C2H5 ONa
Q.27 In the reaction sequence A   B   Ethoxyethane A and B are :
[1] C2H6, C2H5Br [2] CH4, CH3Br [3] CH2=CH2, C2H5Br [4] CHCH, CH2=CH–Br
11
Q.28 Oxonium salt of ether has the structure :
+ +
[1] C2H5–O–CH–O –H [2] CH3–CH2–O –CH2–CH3
| | |
CH3 H H
+
[3] (C2H5)2O  O [4] CH3–CH2–O–CH2–CH2–O–O –H
|
H
Q.29 In the Williamson synthesis of ethers given by the general equation :

R–X + R’ONa R–O–R’ the yield from R–X follows the sequence :
[1] CH3 > 1º > 2º > 3º [2] CH3 < 1º < 2º < 3º
[4] CH3 < 1º < 2º > 3º [4] CH3 > 1º < 2º < 3º
Q.30 On Boiling with conc. HBr ethyl phenyl ether yields :
[1] Phenol and ethyl bromide [2] Bromobenzene and ethanol
[3] Phenol and ethane [4] Bromobenzene and ethane
Q.31 Which enzyme is used in the reaction :
C6H12O 6 2C2H5OH + 2CO 2
[1] Zymase [2] Invertase [3] Diastase [4] Maltase
Q.32 Which of the following property is not shown by C2H5–O–C2H5
[a] Iodoform test [2] Reaction with CH3–COCl
[3] Action of HI [4] Action of AgNO 3
Correct answer is :
[1] b, c [2] a, d [3] a, b & c [4] c, d
300ºC
Q.33 The product of the reaction CH3CH2OH + Cu   is :
[1] C6H6 [2] CH3COCH3 [3] CH3CHO [4] CH3COOH
673 K, 300 atm

Q.34 Reaction : CO + H2 (water gas) + H2 
Cr2O3 – ZnO
?
may be used for manufacture of :

[1] HCHO [2] HCOOH [3] CH3OH [4] C2H5OH
Q.35 When ethanol vapours are passed through heated alumina (250ºC). The compound formed is :
[1] CH2=CH2 [2] CH2———CH2
O
[3] CH3–CH2–O–CH2CH3 [4] CH3–CH=CH2

Q.36 When the vapours of alcohol is passed over copper or zinc oxide then the following compound has no
chances to be formed :
[1] Alkanal [2] Alkyne [3] Alkene [4] Alkanone
Q.37 For industrial method to produce methanol we choose :
[1] CO + H2 [2] CH4 + H2O [3] HCHO + H2 [4] None
12
Q.38 –OH group of ethyl alcohol is neutral whereas acetic acid is acidic because :
[1] Ethyl alcohol molecule undergoes association
[2] Ethyl alcohol is covalent compound
[3] Acetic acid is an electrovalent compound [4] In acetic acid OH group is attached to electronegative
carbonyl group
Q.39 Lucas reagent is :
[1] Conc. HCl and anhydrous ZnCl2 [2] Conc. HCl and hydrous ZnCl2
[3] Conc. HNO3 and hydrous ZnCl 2 [4] Conc. HNO3 and anhydrous ZnCl 2
Q.40 Isopropyl alcohol is heated at 300ºC in presence of Cu catalyst to give :
[1] Acetone [2] Dimethyl ether [3] Acetaldehyde [4] Ethane
Q.41 Which statement is incorrect for C2H5OC2H5 is :
[1] It is an extracting solvent [2] It is an anaesthetic
[3] It is more reactive than alcohol [4] It shows dipole moment
Q.42 C2H5–O–C2H5 with cold HI forms :
[1] Only C2H5OH [2] Only C2H5I [3] Both the above [4] None of the above
Q.43 When ethanol is refluxed with conc. H2SO 4 at 150–170ºC the resulting compound is :
[1] Ethylene [2] Ethyl hydrogen sulphate
[3] Diethyl ether [4] Acetaldehyde
Q.44 The high boiling point of ethanol (78.2ºC) compared to dimethyl ether (–23.6ºC) though both having the
same molecular formula C2H6O is due to :
[1] Hydrogen bonding [2] Ionic bonding
[3] Co–ordinate Co–valent bonding [4] Resonance
Q.45 With which of the following compounds the grignard reagent should be treated in order to produce
secondary alcohol :
[1] CH3COCH3 [2] CH3CHO [3] CO 2 [4] HCHO
Q.46 C2H5OH can be differentiated from CH3OH by :
[1] Reaction with HCl [2] Reaction with NH3
[3] By iodoform test [4] By solubility in water
Q.47 The reaction between an alcohol and an acid is called :
[1] Esterification [2] Sponification [3] Hydrolysis [4] Hydrogenation
Q.48 How does alcohol react to litmus :
[1] Colour changes from red to blue [2] Colour changes from blue to red
[3] Colour is not effected [4] Not possible to predict
Q.49 When wine is put in air it becomes sour due to :
[1] Oxidation of C2H5OH [2] Reduction of C2H5OH
[3] Formation of C2H5NH2 [4] Dissolution of CO 2
13
Q.50 Absolute alcohol can not be obtained by simple fractional distillation because :
[1] Pure C2H5OH is unstable
[2] C2H5OH forms H–bonding with water
[3] Boiling point of C2H5OH is very close to that of water
[4] Constant boiling azeotropic mixture is formed with water
Q.51 When vapours of an alcohol are passed over hot reduced copper, alcohol is converted into alkene, the
alcohol is :
[1] Tertiary [2] Primary [3] Secondary [4] None
Q.52 Absolute alcohol is prepared from rectified spirit by :
[1] Steam distillation [2] Azeotropic distillation
[3] Simple distillation [4] Fractional distillation
Q.53 When glycerol is heated with KHSO 4, which is formed :
[1] Glyceric acid [2] Acrolein [3] glyceraldehyde [4] Dihydroxy acetone
Q.54 Ethylene glycol on oxidation with periodic acid give :
[1] Glyoxal [2] Oxalic acid [3] Formaldehyde [4] Glycolic acid
Q.55 23 gms of sodium of reaction with methyl alcohol gives :
[1] Half mole of H2 [2] One mole of H2 [3] One mole of O 2 [4] none
Q.56 Diethyl ether is prepared by passing ethyl alcohol vapours over a catalyst under high pressure and
temperature. The catalyst is :
[1] SiO 2 [2] CuO [3] Al 2O 3 [4] Ag2O
Q.57 Phenol is :
[1] A base weaker than ammonia [2] An acid stronger than carbonic acid
[3] An acid weaker than carbonic acid [4] A Neutral compound
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 3 3 2 4 2 3 4 3 1 3 2 2 3 4 2 3 4 4 2 3
Qus. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 3 2 3 3 2 3 3 2 1 1 1 2 3 3 3 2 1 4 1 1
Qus. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57
Ans. 3 3 1 1 2 3 1 3 1 4 1 2 2 3 1 3 3
E xercise # 3
Q.1 Tonics in general contain : [MNR 1995]
[1] Ether [2] Methanol [3] Ethanol [4] Rectified spirit
Q.2 Which will dehydrate easily : [Roorkee 1995]
[1] 3–methyl–2–butanol [2] Ethyl alcohol
[3] 2–methyl propane–2–ol [4] 2–methyl butanol–2
Q.3 Which of the following reacts with phenol to give salicylaldehyde after hydrolysis :[MP PMT 1995]
[1] Dichloromethane [2] Trichloromethane [3] Methyl chloride [4] None of these
Q.4 Which of the following is most soluble in water : [MP PMT 1995]
[1] Normal butyl alcohol [2] Isobutyl alcohol
[3] Tertiary butyl alcohol [4] Secondary butyl alcohol
Q.5 Ethyl alcohol exhibits acidic character on reacting with : [MP PMT 1995]
[1] Acetic acid [2] Sodium metal [3] Hydrogen iodide [4] Acidic potassium
dichromate
Q.6 Phenol is obtained by heating aqueous solution of : [MP PMT 1995]
[1] Aniline [2] Benzene diazonium chloride
[3] Benzoic acid [4] None of these
Q.7 For phenol, which of the following statements is correct : [MP PMT 1995]
[1] It is insoluble in water
[2] It has lower melting point compared to aromatic hydrocarbons of comparable molecular weight
[3] It has higher boiling point than toluene
[4] It does not show acidic property
Q.8 Conversion of glucose into ethyl alcohol is made by : [MP PMT 1995]
[1] Acid [2] Enzyme [3] Hydroxylamine [4] Phenyl hydrazine
Q.9 The reaction of C2H5OH with H2SO 4 does not give : [MP PMT 1996]
[1] Ethylene [2] Diethyl ether [3] Acetylene [4] Ethyl hydrogen sulphate
Q.10 The final product obtained by distilling ethyl alcohol with the excess of chlorine and Ca(OH) 2 is :
[MP PET 1996]
[1] CH3CHO [2] CCl3CHO [3] CHCl 3 [4] (CH3)2O
Q.11 Methyl alcohol (methanol), ethyl alcohol (ethanol) and acetone (propanone) were treated with iodine
and sodium hydroxide solutions. Which substances will give iodoform test :
[1] Only ethyl alcohol [2] Only methyl alcohol and ethyl alcohol
[3] Only ethyl alcohol and acetone [4] Only acetone
15
Q.12 The following reaction : [MP PET 1997]
OH OH
Anhydrous
+ HCl + HCN 
ZnCl2

CHO
is known as :
[1] Perkin reaction [2] Gattermann reaction [3] Kolbe reaction [4] Gattermann–Koch reacton
Q.13 The alcohol which does not give a stable compound on dehydration is : [MP PET 11997]
[1] Ethyl alcohol [2] Methyl alcohol [3] n–propyl alcohol [4] n–butyl alcohol
Q.14 Phenol reacts with CHCl 3 and NaOH (at 340 K) to give : [MP PMT 1997, CBSE 2002]
[1] o–chlorophenol [2] Salicylaldehyde [3] Benzaldehyde [4] Chlorobenzene
Q.15 What amount of bromine will be required to convert 2g of phenol into 2,4,6–tribromophenol :
[MP PMT/PET 1998]
[1] 4.00 [2] 6.00 [3] 10.22 [4] 20.44
Q.16 Carbolic acid is : [MP PET/PMT 1998]
[1] Phenol [2] Phenyl benzoate [3] Pheny lacetate [4] Salol
Q.17 The reagent used for the dehydration of an alcohol is : [MP PET/PMT 1998]
[1] Phosphorus pentachloride [2] Calcium chloride
[3] Aluminium oxide [4] Sodium chloride
Q.18 Which of the following reacts first with lucas reagent : [MP PMT 1999]
[1] C3H7OH [2] (CH3)2CHOH [3] (CH3)3COH [4] C6H5OH
Q.19 Which of the following is not true in case of reaction with heated copper at 300ºC : [CPMT 1999]
[1] Phenol  Benzyl alcohol [2] Primary alcohol  Aldehyde
[3] Secondary alcohol  Ketone [4] Tertiary alcohol  Olefin
Q.20 The correct order of boiling point for primary (1º), secondary (2º) and tertiary (3º) alcohol is :
[CPMT 1999 ; Raj PMT 2002]
[1] 1º > 2º > 3º [2] 3º > 2º > 1º [3] 2º > 1º > 3º [4] 2º > 3º > 1º
Q.21 Which of the following is the most suitable method for removing the traces of water from ethanol :
[CPMT 1999]
[1] Heating with Na metal [2] Passing dry HCl through it
[3] Distilling it [4] Reacting with Mg
Q.22 A compound A on oxidation gave acetaldehyde, then again on oxidation gave acid. After first oxidation it
was reacted with ammoniacal AgNO3, then silver mirror was produced. A is likely to be [Delhi PMT 1996]
[1] Primary alcohol [2] Tertiary alcohol [3] Acetaldehyde [4] Acetone
Q.23 Maltose on hydrolysis gives : [BHU 1996]
[1] Mannose + glucose [2] Galactose + glucose
[3] Glucose [4] Mannose + fructose
Q.24 With oxalic acid, glycerol at 260ºC gives : [BHU 1996]
[1] Allyl alcohol [2] Glyceryl mono–oxalate
[3] Formic acid [4] Glyceraldehyde
Q.25 Phenol is used in the manufacture of : [AIIMS 1996]
[1] Bakelite [2] Polystyrene [3] Nylon [4] PVC
16
Q.26 Assertion : A triester of glycerol and plamitic acid on boiling with aqueous NaOH gives a solid cake
having soapy touch :
Reason : Free glycerol is liberated which is a greasy solid : [AIIMS 1996]
[1] Both assertion and reason are true statements and reason is the correct explanation of assertion
[2] Both assertion and reason are true statements and reson is not the correct explanation of assertion
[3] Assertion is true but reason is a false statement
[4] Both asseration and reason are false statement
Q.27 Which of the following reaction shows industrial method of preparation of CH3OH :[CPMT 1996]
Catalyst
[1] CO + H2 
300ºC
 [2] CH3Cl + H2O [3] CH3NH2 + HNO 2 [4] CH3Br + aq. KOH
Q.28 The alcohol that produces turbidity immediately with ZnCl 2 + conc. HCl at room temperature :
[EAMCET 1997]
[1] 1–hydroxybutane [2] 2–hydroxybutane
[3] 2–hydroxy–2–methylpropane [4] 1–hydroxy–2–methylpropane
Q.29 Which of the following explains the viscous nature of glycerol : [JIPMET 1997]
[1] Covalent bonds [2] Hydrogen bond [3] Vander Wall’s forces[4] Ionic forces
Q.30 Which of the following statments is correct : [BHU 1997]
[1] Phenol is less acidic than ethyl alcohol [2] Phenol is more acidic than ethyl alcohol
[3] Phenol is more acidic than carboxylic acid [4] Phenol is more acidic than carboxylic acid
Q.31 Which gas is eliminated in fermentation : [RPMT 1997]
[1] O 2 [2] CO 2 [3] N2 [4] H2
Q.32 When phenol reacts with CHCl 3 and KOH, the product obtined would be : [RPMT 1997]
[1] Salicylaldehyde [2] p–hydroxy benzaldehyde
[3] Both (a) and (b) [4] Chloretone
Q.33 Absolute alcohol is : [RPMT 1997]
[1] 100% pure ethanol [2] 95% alcohol + 5% H2O
[3] Ethanol + water + phenol [4] 95% ethanol + 5% methanol
Q.34 The reaction of CH3CH = CH OH with HBr gives : [IIT 1998]
[1] CH3–CHBrCH2 OH [2] CH3CH2CHBr OH
[3] CH3CHBrCH2 Br [4] CH3CH2CHBr Br
Q.35 Benzenediazonium chloride on reaction with phenol in weakly basic medium gives : [IIT 1998]
[1] Diphenyl ether [2] p–hydroxyazobenzene
[3] Chlorobenzene [4] Benzene
17
Q.36 The most suitable method for the separation of a 1 : 1 mixture of ortho and para nitrophenols is :
[CBSE 1994, 99, CPMT 1997]
[1] Distillation [2] Sublimation [3] Crystallization [4] Chromatography
Q.37 R–OH + HX  R–X + H2O
In the above reaction, the reactivity of different alcohols is : [CPMT 1997]
[1] Tertiary > Secondary > Primary [2] Tertiary < Secondary < Primary
[3] Tertiary < Secondary > Primary [4] Secondary < Primary < Tertiary
Q.38 The boiling point of glycerol is more than propanol because of : [CPMT 1997, 2002]
[1] Hydrogen bonding [2] Hybridisation [3] Resonance [4] All the above
Q.39 Which statement is not correct about alcohol : [AFMC 1997]
[1] Alcohol is lighter than water
[2] Alcohol evaporates quickly
[3] Alcohol of less no. of carbon atoms is less soluble in water than alcohol of high no. of carbon atoms
[4] All of these
Q.40 An organic compound A reacts with sodium metal and forms B, On heating with conc. H2SO 4. A gives
diethyl ether A and B are : [AFMC 1998]
[1] C2H5OH and C2H5ONa [2] C3H7OH and CH3ONa
[3] CH3OH and CH3ONa [4] C4H9OH and C4H9ONa
Q.41 The reaction of aromatic acyl chloride and phenol in the presence of a base NaOH or pyridine is called:
[AFMC 1998]
[1] Kolbe’s reaction [2] Perkin’s reaction
[3] Sandmayer’s reaction [4] Schotten–Baumann reaction
Q.42 In the Liebermann’s nitroso reaction, sequential changes in the colour of phenol occurs as :
[AFMC 1998; BHU 1999]
[1] Brown or red  green  red  deep blue [2] Red  deep blue  green
[3] Red  green  white [4] White  red  green
Q.43 Which one of the following reactions does not yield an alkyl halide : [EAMCET 1998]
[1] Diethyl ether + Cl 2 [2] Diethyl ether + HI
Re duction SO2Cl2
[3] Diethyl ether and PCl 5 [4] Diethyl ether   X  
Q.44 The reaction between an alcohol and an acid with the elimination of water molecule is called :
[MH CET 1999]
[1] Esterification [2] Saponification [3] Etherification [4] Elimination
Q.45 3–pentanol is a : [Raj PET 2002]
[1] Primary alcohol [2] Secondary alcohol [3] Tertiary alcohol [4] None of these
Q.46 Which of most acidic : [Raj PET 1999]
[1] H2O [2] C2H5OH [3] CH3OCH3 [4] C6H5OH
18
Q.47 The compound X in the reaction :
ONa OH
390ºC HCl
+ CO 2 
 X 
 is : [Roorkee 1999]
COOH
COONa ONa ONa OCOONa

[1] [2] [3] [4]
COONa COOH
Q.48 Condensation of phenol and phthalic anhydride gives : [Raj PMT 1999]
[1] Methyl orange [2] Phenol red [3] Salicylic acid [4] Phenolphthalein
Q.49 The role of conc. H2SO 4 in the esterification process is : [Raj PMT 1999]
[1] Catalyst [2] Dehydrating agent [3] Hydrolysing agent [4] Dehydrating agent and
catalyst
Q.50 Methanol and ethanol are distingusihed by the : [MP PET 1999]
[1] Action of HCl [2] Iodoform test [3] Solubility in water [4] Sodium
Q.51 When 2–ethylanthraquinol dissolved in a mixture of benzene and cyclohexanol is oxidised, the product
is [JIPMER 1999]
[1] Ethanol [2] Hydrogen peroxide [3] Anthracene [4] None of these
Q.52 Phenol is heated with phthalic anhydride in the presence of concentrated H 2SO 4. The product gives
pink colour with alkali. The product is : [Karnataka CET (Med.) 2000]
[1] Bakelite [2] Fluorescein [3] Salicylic acid [4] Phenolphthalein
Cu 2 3 Al O
Q.53 A 

 CH3CH2OH 

B. A and B respectively are. [Rajasthan (Engg./Med.) 2000]
[1] Alkene, alkanal [2] Alkyne, alkanal [3] Alkanal, alkene [4] Alkene, alkyne
Q.54 The alcohol manufactured from water gas is : [AFMC 2000]
[1] Ethanol [2] Butanol [3] Methanol [4] Isobutanol
Q.55 Which of the following does not form phenol or phenoxide : [AFMC 2000]
[1] C6H5Cl [2] C6H5COOH [3] C6H5N2Cl [4] C6H5SO3Na
Q.56 Which of the following differentiate between C2H5OH and CH3OH : [BHU 2000]
[1] HCl [2] NH3 [3] H2O [4] I2 + KOH
Q.57 Action of nitrous acid with ethylamine produces : [BHU 2000]
[1] Ethane [2] Ammonia [3] Ethyl alcohol [4] Nitroethane
Q.58 An unknown compound ‘D’, first oxidised to aldehyde and then acetic acid by a dilute solution of
K2Cr2O7 and H2SO 4. The unknown compound ‘D’ is : [BHU 2000]
[1] CH3CHO [2] CH3CH2OH [3] CH3CH2CH2OH [4] CH3CH2CH3
Q.59 Carbinol is : [Raj PMT 2000]
[1] C2H5OH [2] CH3OH
[3] (CH3)2CHOH [4] CH3CH2CH(OH)CH3
19
Q.60 From which of the following tertiary butyl alcohol is obtained by the aciton of methyl magnesium iodide:
[MP PET 2000]
[1] HCHO [2] CH3CHO [3] CH3COCH3 [4] CO2
600º C
Q.61 Reaction : CH3OH + O2 
Ag
 product
The product is : [RPET 2000]

[1] CH2=C=O [2] H2C=O [3] C2H4 [4] C2H2
Jone ' s
Q.62 CH3–CH=CH–CH(OH)–CH3 
reagent
 X,
Product X is : [RPET 2000]

[1] CH3CH2CH2CH(OH)CH3 [2] CH3CH=CHCOCH3
[3] Both the above [4] CH3CH2CH2COCH3
Q.63 Methyl alcohol is toxic. The reason assigned is : [RPET 2000]
[1] It stops respiratory track [2] It reacts with nitrogen and forms CN– in the lungs
[3] It increases CO 2 content in the blood [4] It is a reduction product of formaldehyde
Q.64 Assertion (A) : Phenol is more reactive than benzene towards electrophilic substitution reaction.
Reason (R) : In the case of phenol, the intermediate carbocation is more resonance stabilized
[IIT 2000]
[1] Both A and R are true and R is a correct explanation of A
[2] Both A and R are true but R is not a correct explanation of A
[3] A is true but R is false
[4] Both A and R are false
Q.65 When phenol is reacted with CHCl 3 and NaOH followed by acidification, salicyldehyde is obtained.
Which of the following species are involved in the above mentioned reaction as inter mediate :
O O O
H CHCl2 H
[1] CCl3 [2] [3] CHCl [4] All of these
|
OH
Q.66 Which of the following compound dehydrates most easily : [BHU 2002]
[1] R3COH [2] R2CHOH [3] CH3CH2OH [4] CH3CH2CH2OH
Q.67 The reaction of ethylene glycol with PI3 gives : [MP PMT 2000]
[1] ICH2CH2I [2] CH2=CH2 [3] CH2=CHI [4] ICH=CHI
Q.68 The reaction of Lucas reagent is fast with : [MP PMT 2000]
[1] (CH3)3COH [2] (CH3)2CHOH [3] CH3(CH2)2OH [4] CH3CH2OH
Q.69 Which one of the following will most readily be dehydrated in acidic condtion : [IIT Scr. 2000]
O O
O OH OH
| |
[1] [2] [3] [4]
OH OH
20
Q.70 Acetone on treatement with CH3–Mg–I and on further hydrolysis gives : [UPSEAT 2000]
[1] Isopropyl alcohol [2] Primary alcohol [3] Acetic acid [4] 2–methyl –2–propanol
Q.71 When phenol reacts with ammonia in presence of ZnCl 2 at 300ºC, it gives : [AFMC 2001]
[1] Primary amine [2] Secondary amine [3] Tertiary amine [4] Both (2) and (3)
Q.72 Maltose, on hydrolysis, gives : [CPMT 2001]
[1] Glucose [2] Fructose [3] Maltose [4] Mannose
Q.73 With excess bromine, phenol reacts to form : [BHU 2001]
OH OH
OH | |
| Br Br Br
[1] [2] [3] [4] Mixture of (1) and (2)
| |
Br Br
Q.74 The compound that will react most readily with NaOH to form methanol is : [IIT Scr. 2001]
[1] (CH3)4N+I– [2] CH3OCH3 [3] (CH3)3S+I– [4] (CH3)3Cl
Q.75 When ethyl alcohol (C2H5OH) reacts with thionyl chloride, in the presence of pyridine, the product
obtained is : [AIIMS 2001]
[1] CH3CH2Cl + HCl [2] C2H5Cl + HCl + SO 2
[3] CH3CH2Cl + H2O + SO 2 [4] CH3CH2Cl + Cl2 + SO 2

Q.76 Oil + NaOH(aq)   Glycerol + Soap
Above reaction is called : [UPSEAT 2001]

[1] Saponification [2] Esterification [3] Hydrogenation [4] None of these
Q.77 Assertion (A) : Phenol is a weak acid than ethanol
Reason (R) : Groups with + M effect and –I effect decrease acidity at p–position [AIIMS 2002]
[1] Both A and R are true and the R is a correct explanation of A
[2] Both A and R are ture but R is not a correct explanation of A
[3] A is true but the R is false
[4] Both A and R are false
Q.78 Which of the following product is formed, when ether is exposed to air : [AIIMS 2000]
[1] Oxide [2] Alkanes [3] Alkenes [4] Peroxide of diethyl ether
Q.79 Electrophilic subsitution reaction in phenol take place at : [Raj PMT 2002]
[a] p–position [2] m–position [3] o–position [4] o– and p– position
Q.80 In the sequence of the following reactions
HI KCN reduction HNO3

CH3OH  CH3I   CH3CN   X  Y
X and Y are respectively : [MP PMT 2002]

[1] CH3CH2NH2 and CH3CH2OH [2] CH3CH2NH2 and CH3COOH
[3] CH3CH2OH and CH3CHO [4] CH3OCH3 and CH3CHO
21
H2O
Q.81 The reaction : (CH3)3C–Br   (CH3)3–C–OH [AIEEE 2002]
[1] Elimination reaction [2] Substitution reaction

[3] Free radical reaction [4] Displacement reaction
Pyridine
Q.82 The reaction : C2H5OH + SOCl 2   C2H5Cl + SO 2 + HCl [AIIMS 2002]
is known as :
[1] Kharasch effect [2] Darzen’s procedure
[3] Williamson’s synthesis [4] Hunsdieker synthesis reaction
Q.83 Glucose  ethyl alcohol in this reaction enzyme is : [Raj PMT 2002]
[1] Zymase [2] Invertase [3] Maltase [4] Diastase
Q.84 During dehydration of alcohols to alkenes by heating with conc. H2SO 4 the initiation step is :
[AIEEE 2003]
[1] Protonation of alcohol molecule [2] Formation of carbocation
[3] Elimination of water [4] Formation of an ester
OH
|
O C2H5–
Q.85 + C2H5I 
Anhydrous (C H OH)
 [IIT Scr. 2003]
2 5
[1] C6H5OC2H5 [2] C2H5OC2H5 [3] C6H5OC6H5 [4] C6H5I

Q.86 Propan–1–ol can be prepared from propene by : [AIIMS 2003]
[1] H2O / H2SO4 [2] Hg(OAc)2 / H2O followed by NaBH4
[3] B2H6 followed by H2O 2 [4] CH3CO 2H / H2SO 4
Q.87 Cresol has : [CPMT 2003]
[1] Alcoholic – OH [2] Phenolic – OH [3] – COOH [4] –CHO
Q.88 Phenol and benzoic acid is distinguished by : [BHU 2003]
[1] NaOH [2] NaHCO3 [3] Na2CO 3 [4] H2SO 4
Q.89 Which compound has the highest boiling point : [MP PET 2003]
[1] Acetone [2] Diethyl ether [3] Methanol [4] Ethanol
Q.90 When phenol is heated with phthalic anhydride in concentrated sulphuric acid and the hot reaction
mixture is poured into a dilute solution of sodium hydroxide, the product formed is : [MP PET 2003]
[1] Alizarin [2] Methyl orange [3] Fluorescein [4] Phenolpthalein
Q.91 4–chloro–3, 5–dimethyl phenol is called : [Karanataka CET 2003]
[1] Chloramphenicol [2] Paracetamol [3] Barbital [4] Dettol
NaOH
Q.92 CH2=CH2 + B2H6 
H2SO4
 Product, Product is :
[1] CH3CH2CHO [2] CH3CH2OH [3] CH3CHO [4] None of the above
22
Q.93 A + CCl 4 + KOH  Salicylic acid

‘A’ in above reaction is : [Raj PMT 2003]
OH NO2 CHO
| | |
[1] [2] [3] [4]
Q.94 Alcohol which gives red colour with Victor Meyer test is : [Raj PMT 2003]
[1] C2H5OH [2] CH3–CH(OH)–CH3 [3] C(CH3)3OH [4] None of the above
Q.95 The product ‘A’ in the following reaction is :
H2C———CH2 RMgI
 A [MP PMT 2003]
O
R
[1] RCHOHR [2] RCHOH . CH3 [3] RCH2 . CH2OH [4] CHCH2OH
R
Alkali
Q.96 In the reaction Ar–OH + RX  A A is : [MP PET 1994]
[1] An aldehyde [2] An aryl chloride [3] An ether [4] A ketone

Q.97 When a mixture of ethanol and methanol is heated in the presence of concentrated H2SO4, the resulting
organic product or products is / are : [Manipal MEE 1995]
[1] CH3OC2H5 [2] CH3OCH3 and C2H5OC2H5
[3] CH3OC2H5 and CH3OCH3 [4] CH3OC2H5, CH3OCH3 and C2H5OC2H5
Q.98 In Williamson’s synthesis, ethoxyethane is prepared by : [MP PMT 1995]
[1] Passing ethanol over heated alumina [2] Sodium ethoxide with ethyl bromide
[3] Ethyl alcohol with sulphuric acid [4] Ethyl iodide and dry silver oxide
Q.99 Dimethyl ether when heated with excess HI gives : [CPMT 1996]
[1] CH3I and CH3OH [2] CH3I and H2O
[3] C2H6 + CH3I and CH3OH [4] CH3I and HCHO
Q.100 Methyl–terbutyl ether on heating with HI of one molar concentration gives : [MP PET 1997]
[1] CH3I + (CH3)3COH [2] CH3OH + (CH3)3Cl
[3] CH3I + (CH3)3Cl [4] None of the above
Q.101 The reaction of CH3MgI with acetone and hydrolysis of the resulting product gives :[MP PMT 1999]
[1] CH3CH2CH2OH [2] CH3CH2CH2CH2OH [3] (CH3)2CHOH [4] (CH3)3COH
Q.102 The ether O–CH2 when treated with HI produces : [IIT 1999]
[1] CH2I [2] CH2OH [3] I [4] None of these
Q.103 Ethyl chloride is converted into diethyl ether by : [CBSE 1999]

[1] Wurtz synthesis [2] Grignard reaction [3] Perkin’s reaction [4] Williamson’s synthesis
23
Q.104 Which of the following compounds will react with NaHCO 3 solution to give sodium salt and carbon
dioxide : [CBSE 1999]
[1] Phenol [2] n–hexanol [3] Acetic acid [4] Both (1) and (2)
Q.105 Heating mixture of ethyl alcohol and acetic acid in presence of conc. H2SO4 produces a fruity smelling
compound. This reaction is called : [AIIMS 1996]
[1] Neutralisation [2] Ester hydrolysis [3] Esterification [4] Williamson’s synthesis
Q.106 When ether is reacted with O 2. It undergoes explosion due to : [CPMT 1996]
[1] Peroxide [2] Acid [3] Ketone [4] TNT
Q.107 Which of the following is obtained when C2H5OC2H5 is heated with conc. H2SO 4 :[CPMT 1996]
[1] CH2=CH2 [2] C2H5OH [3] C2H5SO4H [4] CH3CH2CH2CH3
Q.108 In which of the following reaction, phenol or sodium phenoxide is not formed : [CPMT 1996]
[1] C6H5N2Cl + alc. KOH [2] C6H5OCl + NaOH
H2O
[3] C6H5N2Cl + aq. NaOH [4] C6H5NNCl 


Q.109 The oxidation product of 2–proponol with hot conc. HNO 3 is : [JIPMER 1997]
[1] Ethanoic acid [2] Propanone [3] Propanal [4] None of these
Q.110 Isopropyl alcohol on oxidation gives : [RPMT 1997]
[1] Acetone [2] Acetaldehyde [3] Ether [4] Ethylene
Q.111 Highest boiling point is of : [RPMT 1997]
[1] Ethanol [2] Ether [3] Alkane [4] Aldehyde
Q.112 The compound which does not react with sodium is : [CBSE 1994]
[1] C2H5OH [2] CH3–O–CH3 [3] CH3COOH [4] CH3–CHOH–CH3
Q.113 R–CH2–CH2OH can be converted into RCH2CH2COOH. The correct sequence of the reagents is
[AIIMS 1997]
[1] PBr3, KCN, H3O + [2] PBr3, KCN, H2 [3] HCN, PBr3, H + [4] KCN, H+
Q.114 Phenylmethanol can be prepared by reducing the benzaldehyde with : [CBSE 1997]
[1] CH3Br [2] Zn and HCl [3] CH3Br and Na [4] CH3I and Mg
Q.115 When anisole is heated with HI, the product is : [CET Pune 1998]
[1] Phenyl iodide and methyl idodie [2] Phenol and methanol
[3] Phenyl iodide and methanol [4] Methyl iodide and phenol
Q.116 The ether that undergoes electrophilic substitution reaction is : [JIPMER 2001]
[a] CH3OC2H5 [2] C6H5OCH3 [3] CH3OCH3 [4] C2H5OC2H5
Q.117 When ether is exposed in air for sometime an explosive substance produced is : [RPMT 2002]
[1] Peroxide [2] TNT [3] Oxide [4] Superoxide
Q.118 Ether which is liquid at room temperature is : [BVP 2002]
[1] C2H5OCH3 [2] CH3OCH3 [3] C2H5OC2H5 [4] None of these
Q.119 In the following reaction [MP PMT 2002]
Re d P  HI
C2H5OC2H5 + 4[H]   2X + H2O, X is :
[1] Ethane [2] Ethylene [3] Butane [4] Propane
Q.120 An ether is more volatile than an alcohol having the same molecular formula. This is due to :
[AIEEE 2003]
[1] Dipolar character of ethers [2] Alcohols having resonance structures
[3] Inter–molecular hydrogen bonding in ethers [4] Inter–molecular hydrogen bonding in alcohols
24
Q.121 Among the following compounds which can be dehydrated very easily is : [AIEEE 2004]
[1] CH3CH2CH(CH3)CH2CH2OH [2] CH3CH2CH2CH(OH)CH3
CH3
|
[3] CH3CH2 C CH2CH3 [4] CH3CH2CH2CH2CH2OH
|
OH
Q.122 Choose the correct molecular formula of the following molecules : [VITEEE 2005]
(i) Propanone (ii) Propanal and (iii) n-propanol
[1] CH3COCH3, CH3CH2CH2OH and CH3CH2CHO[2] CH3CH2CH2OH, CH3COCH3 and CH3CH2CHO
[3] CH3CH2CHO, CH3COCH3 and CH3CH2CH2OH[4] CH3COCH3, CH3CH2CHO and CH3CH2CH2OH


H
Q.123 The following reaction is an example RCOOR’ + R”OH  RCOOR” + R’OH [VITEEE 2005]
[1] Esterification [2] Saponification [3] Hydrolysis [4] Transesterification
Q.124 An organic compound, C3H6O does not give a precipitate with 2,4-dinitrophenyl hydrazine reagent and
does not react with metallic sodium. It could be [VITEEE 2005]
[1] CH3 — CH2 — CHO [2] CH3 — CO — CH3 [3] CH2 = CH — CH2OH [4] CH2 = CH — O — CH3
Q.125 The best reagent to convert pent-3-en-2-ol into pent-3-in-2-one is [AIEEE 2005]
[1] Acidic dichromate [2] Acidic permanganate
[3] Pyridinium chloro-chromate [4] Chromic anhydride in glacial acetic acid
Q.126 Acid catalyzed hydration of alkenes except ethene leads to the formation of [AIEEE 2005]
[1] Primary alcohol [2] Secondary or tertiary alcohol
[3] Mixture of primary and secondary alcohols [4] Mixture of secondary and tertiatry alcohols
Q.127 Methylphenyl ether can be obtained by reacting [J & K 2005]
[1] Phenolate ions ane methyl iodide [2] Methoxide ions and bromobenzene
[3] Methanol and phenol [4] Bromo benzene and methyl bromide
Q.128 The best method to prepare cyclohexene from cyclohexanol is by using - [IIT 2005]
Conc. HCl + ZnCl2 [2] Conc. H3PO 4 [3] HBr [4] Conc. HCl
Q.129 Which of the following compound is most acidic ? [BCECE 2005]
[1] CH4 [2] C2H6 [3] CH  CH [4] C2H5OH
Q.130 Which of the following reaction is correctly represented - [Orissa JEE 2005]
CH3 OCH3 CH3 OH CH3 OCH3 CH3 Br
[1] + HBr +CH3Br[2] + HBr  + CH3OH
CH3 OCH3 Br OCH3 CH3 OCH3 H OCH3

[3] + HBr + CH4[4] + HBr  + CH3Br
Q.131 Tertiary butyl alcohol gives tertiary butyl chloride on treatment with - [Orissa JEE 2005]
[1] Conc. HCl/anhydrous ZnCl2 [2] KCN
[3] NaOCl [4] Cl 2
Q.132 HO + N+2Cl- 
base
 [DPMT 2005]
[1] N=N OH [2] O
[3] [4] OH
Q.133 The general moleculat formula, which represents the homologous series of alkanols is -
[CPMT 2006]
[1] CnH2nO [2] CnH2n+1O [3] CnH2n+2O [4] CnH2nO 2
Q.134 Among the following the one that gives positive iodoform test upon reaction with I2 abnd NaOH is -
[AIEEE 2006]
CH3
[1] C6H5CH2CH2OH [2] | [3] PhCHOHCH3 [4] CH3CH2CH(OH)CH2CH3
CH3  CHCH2OH
25
Q.135 In the following sequence of reactions, [ AI E E E
2007]
P I 2 A
CH3CH2OH  Mg B HCHO C H 2O D
    
Ether
the compound ‘D’ is :

[1] n-propyl alcohol [2] propanal [3] butanal [4] n-butyl alcohol
Answer Key
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 3 4 2 3 2 2 3 2 3 3 3 2 2 2 3 1 3 3 1 1
Qus. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 4 1 3 1 1 3 1 3 2 2 2 3 1 2 2 1 1 1 3 1
Qus. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Ans. 4 1 1 1 2 4 2 4 4 2 1 4 3 3 2 4 3 2 2 3
Qus. 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80
Ans. 2 2 2 1 2 1 2 1 1 4 1 1 3 1 2 1 4 4 4 1
Qus. 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100
Ans. 2 2 1 1 1 3 2 2 4 4 4 2 1 1 3 3 4 2 2 1
Qus. 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120
Ans. 4 1 4 3 3 1 3 2 2 1 1 2 1 2 4 2 1 3 1 4
Qus. 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135
Ans. 3 4 4 4 3 2 1 2 4 1 1 1 3 3 1
26
Halogen Derivatives of Alkanes

1. HALOGEN DERIVATIVES OF ALKANES
 Halogen derivatives of alkanes are formed by subsitution of one or more hydrogen atoms of an
alkane by halogen (F, Cl, Br or I).
–H
R–H R–X
Alkane +X Haloalkane
(Halogen atom is normally represented by X)

 Halogen derivatives of Alkanes are divided into mono di, tri, etc. Substitution products according to
the number of halogen atoms in the molecule.
1.1 MONOHALO ALKANES
(i) These are halogen derivatives of alkanes having general formula CnH2n + 1X. where X = F, Cl, Br and I.
(ii) Monohalo alkanes are of three types :
(a) Primary alkyl halides in which halo group is present on primary carbon atom, i.e. R – CH2 – X
(b) Secondary alkyl halides in which halo group is present on secondary carbon atom, i.e. R  CH  R
|
X
X
|
(c) Tertiary alkayl halides in which halo group is present on tertiary carbon atom, i.e. R  C  R
|
R
 Methods of Preparation of Alkyl Halide
(a) By Halogenation of Alkanes

Halogenation of alkanes takes place by free radical mechanism.
h
R–H + X–X   R–X + H–X
Peroxide
R–H + Cl–SO2–Cl   R–Cl + SO2 + H–Cl
(b) By Hydrohalogenation of Alkenes
Alkyl halides are formed by addition of hydrogen halide on alkenes according to Markownikoff’s rule.
R–CH=CH2 + H–X
Peroxide
R–CH=CH2 + H–Br   R–CH2–CH2–Br
(c) By halogen exchange in alkyl Halides :
(i) By Silver Halide :
This reaction is called Swart reaction.
Ethylene glycol
R – I + Ag–F     R – F + Ag – I
27
(ii) By Sodium or Potassium Halide :
This reaction is called Finkelstein reaction.
Acetone
R – Cl + KI   R – I + KCl
(d) From Alkanols
(i) By Conc. HCl :
This is called Grove’s method.
Anhyd . ZnCl2
R–OH + H–Cl     R–Cl + H–OH
(ii) By Red Phosphorus and Bromine :
2P + 3Br2 2PBr3
3R–OH + PBr3 3R–Br + H3PO3
(iii) By Red Phosphorus and Iodine :
2P + 3I2 2PI3
3R–OH + PI3 3R–I + H3PO3
(iv) By Phosphorus pentachloride :
R–OH + PCl5 R–Cl + POCl3 + HCl
(v) By Phosphorus trichloride :
3R–OH + PCl3 3R–Cl + H3PO3

(vi) By Thionyl chloride :
R–OH + SOCl2 R–Cl + SO2 + HCl
The above reaction is performed in the presence of pyridine. Called Darzens reaction.
(vii) From KBr and Conc. H3SO4 :
2R–OH + H2SO4 + 2KBr 2R–Br + K2SO4 + 2H2O
(viii) From KI and H3PO4 :
2R–OH + H3PO4 + 2KI 2R–I + K2HPO4 + 2H2O
(e). From Alkanoic Acids :
CCl4
R–COOAg + Br–Br   R–Br + CO2 + AgBr
It is called Hunsdiecker reaction.
(f). From Alkylamines :
Alkyl chlorides are formed by the reaction of Tilden’s reagent or Nitrosyl chloride (NOCl) on
alkylamines.
R–N H2 R + N + H2O
|
+ Cl–N=O Cl N
28
 Physical Properties
(i) CH3F, CH3Cl, CH3Br, C2H5F and C2H5Cl are found in gaseous state at room temperature.
(ii) Alkyl halides are normally sweet-smelling gases and liquids, whereas odourless in solid state.
(iii) All alkyl halides are insoluble in water.

(iv) Boiling points of alkyl halides change in the following order.
(a) On having same alkyl group
R–I > R–Br > R–Cl > R–F
(b) On having same halogen atom
CH3 CH3
| |
CH3–CH2–CH2–CH2–X > CH3–CH–CH2–X > CH3–CH2–CH–X > (CH3)3C–X
Primary unbranched Primary branched Secondary Tertiary
 REACTIONS
1. Nucleophilic substitution reaction [SN] :
 –
Bond polarity : R — X [–I effect]
Order of dipole moment [CH3X] :
CH3–Cl [1.86D] > CH3–Br [1.7D] > CH3–I [1.64D]
 
R—X + Nu  R—Nu + X
In this reaction reactivity order is as follows :
R – I > R – Br > R – Cl > R – F
29
 R—X REACTION
Reagent Product
Na/dry ether R–R
KOH (aq.) ROH
Ag2O (moist) ROH
NaI RI
NaOR ROR
R’COOAg R’COOR
Ag2O (dry) ROR
KCN RCN
AgCN 
RN C
R’C CNa R’C CR
KNO2 RONO
AgNO2 RNO2
Na2SO3 RSO3Na
NaSR’ RSR’
Na2S R2S
KSH RSH
NH3 RNH2
RNH2 R2NH
R2NH R3N
R3N R4N+X–
2. Elimination Reaction
Dehydrohalogenation : Alkyl halides give elimination reaction in the presence of strong base such as
 
alc. KOH/, alc. NaOH/, R O N a /Ethanol, ‘ NaH/, NaNH2/
X
|
Base 
R  CH2  CH  R   R  CH  CH  R
3. Oxidation reaction
(i) Only primary and secondary alkyl halides undergo oxidation. Tertiary alkyl halide does not undergo oxida-
tion.
(ii) Primary alkyl halides give aldehyde where as secondary alkyl halides give ketone in this reaction.
(iii) Oxidising agent is either :
(a) Dimethyl sulphoxide or
(b) Reaction with (CH2)6N4 followed by hydrolysis.
(iv) Reactivity number of hydrogens.
30
O
||
DMSO or
R – CH2 – X    R  C  H
(i ) ( CH2 )6 N4
( ii) H2O H
X O
| ||
DMSO or
R  CH  R    R  C  R
(i ) ( CH2 )6 N4
( ii) H2O H
O
||
( CH2 )6 N4
C6H5CH2 – X    C 6H5  C  H
H2O H
Note : (1) Oxidation of Benzyl halides by (CH2)6N4 is known as sommelet aldehyde synthesis.
(2) Oxidation of alkyl halide with DMSO is known as swern oxidation.
4. Coupling Reactions
(A) By Wutrz Reaction : An alkane having even number of carbon atoms. This is called Wurtz synthesis or
Wurtz Reaction.
Dry ether
R–X + 2Na + X–R    R–R + 2NaX
Alkane having odd number of carbon atoms can be obtained by mixed Wurtz synthesis.
Dry ether
R–X + X–R’  Na
 R–R + R–R’ + R’–R’
CH3–CH3
CH3–I Dry ether
    + CH3–CH2CH3
+ CH3CH2–I Na
+ CH3–CH2–CH2CH3
(B) By Wurtz-Fitting Reaction
Dry ether
R–I + 2Na + I–Ar    R–Ar + 2Nal
Dry ether
CH3–I + 2Na + I–C6H5    CH3–C6H5 + 2NaI
5. Reaction with Metals
Synthesis of Grignard’s Reagents

Dry ether
R–X + Mg    R–MgX
Synthesis of Frankland’s Reagents
Dry ether
2R–X + 2Zn    R–Zn–R + ZnX2
Synthesis of Tetraalkyllead
4R–X + 4Pb/Na R4Pb + 4NaCl + 3Pb
Tetraethyllead and tetramethyllead are high quality antiknock compounds.
31
 Uses of Alkyl Halides

(i) Alkyl halides are used as weak refrigerants, but more suitable freons are now being used in place of
alkyl halides.
(ii) Synthesis of detergents is carried out from alkyl halides by Strecker’s reaction.
(iii) Synthesis of antiknock compounds.
(iv) Allkyl halides, especially alkyl bromides and alkyl iodides are used for the synthesis of other organic
compounds of almost all classes, in laboratory and in industry.
(v) Alkyl halides are generally used as starting substances for the manufacture of alcohols, ethers and
esters.
(vii) Synthesis of important organometallic compounds, like Grignard’s reagents. Frankland’s reagents, etc., is
carried out from alkyl halides.
1.2 HALOBENZENE
1. Chlorobenzene, C6H5Cl
1.1 Methods of Preparation :
[1] Chlorination of Benzene :
Chlorobenzene is obtained on reacting benzene with chlorine in the presene of a halogen carrier. Lewis
acids (AlCl3, FeBr3, BF3, etc) some elements (iron powder, iodine, etc.) or some tertiary amine bases
(pyridine) can be used as halogen carriers.
H Cl
| |

+ Cl2  + HCl
Bromobenzene is obtained if bromine is used in place of chlorine in the above reaction.

[2] Dehydroxylative Chlorination of Phenol :
Chlorobenzene is formed on reacting phenol with phosphorus pentachloride. Yields of chlorobenzene are
low due to formation of triphenyl phosphate (C6H5)3PO4 as the major product.
OH Cl
| |
+ PCl5 + POCl3 + HCl
OH Cl O
OH Cl P=O O P=O + 3HCl
OH Cl O
(C6H5)3PO4 or
Triphenyl phosphate
[3] Deaminative Chlorination of Aniline :

Chlorobenzene can be obtained by Sandmeyer’s reaction (Cuprous chloride, in the presence of Cu2Cl2) or
Gatermann reaction (in the presence of copper powder) of the benzenediazonium chloride salt obtained by
32
diazotisation (reaction of aqueous NaNO2 and aqueous HCl at 0º C) of aniline.
NH2 N2Cl Cl
| | |
NaNO
2 HCl. Cu Cl
2 2
  
HCl 0º or HCl. Cu powder
N2Cl I
| |
+ KI + N2 + KCl
For the synthesis of flurobenzene, benzenediazonium fluoroborate is heated. This is called Balz–Schiemann
reaction.

N2Cl 
| N2BF4 F
| |

+ HBF4 
  
–HCl –N , –BF
2 3
[4] Decarboxylation of Chlorobenzoic Acids :

Dry distillation of o–, m– or p–chlorobenzoic acid with soda lime gives chlorobenzene by decarboxylation.
Cl Cl
| |
Soda lime
COOH 
[5] Dehydroxylation of Chlorophenols :

On dry distillation of o–, m– or p–chlorophenol with zinc dust, chlorobenzene is obtained by
dehydroxylation.
Cl Cl
| |
Zinc dust
OH


or HCl.Dry distillation
[6] Decarboxylative Bromination of Benzoic Acid :

For the preparation of bromobenzene, silver salt of benzoic acid is heated with bromine in CCl4 solution.
This is called Borodine–Hunsdiecker reaction.
COOAg Br
| |
CCl4
+ Br2 


 + CO2 + AgBr
Flurobenzene, chlorobenzene and iodobenzene cannot be prepared by the above method.

[7] Raschig Process :
Manufacture of chlorobenzene on large scale is carried out by Raschig process. In this method. the
mixture of benzene vapour. HCl gas and the oxygen (air) is passed over heated copper-iron catalyst or
CuCl2 catalyst with pressure at 250ºC.
H Cl
| |
Pr essure 250º
+ O2 + HCl 
Cu / Fe or CuCl

 + H2O
2
33
1.2 Physical Properties :

Chlorobenzene is a colourless, volatile, inflammable, liquid (boiling point = 132º) having faint smell resembling
almonds. It is a little bit poisonous (less than benzene), insoluble in water and soluble in organic solvents.
1.3 Reactions :
[A] Reactions due to chlorine atom.
[B] Reactions due to Benzene ring.
1.3.1 Reactions Due to Chlorine Atom :
Reactivity of chlorobenzene towards nucleophilic substitution reactions is very less. This is mainly due to
(i) Greater ‘pi’ electron density on ring carbons which repels the attacking nucleophile.
(ii) Chlorine bearing carbon of chlorobenzene is sp2 hybridised and hence the polarity of C — Cl bond in
chlorobenzene is less than that of C — Cl bond in ethyl chloride.
The reactivity of chlorobenzene increases when – M or – I effect causing groups are bonded at ortho or para
positions of chlorobenzene. These groups decrease pi electron density on the ring and then nucleophile
can attack easily on chloro benzene.
Cl
Cl
NO2
Thus is more reactive than towards nucleophilic substitution.
Nucleophilic substitution in chlorobenzene takes place by elimination-addition mechanism. In this reaction

Benzyne is formed as an intermediate.
Cl
H H KNH2
+ KCl + NH3
H H
H Benzyne
NH2
+ NH3
Aniline
1. Reduction or Dechlorination :
Benzene is formed on reduction of chlorobenzene by nickel-aluminium alloy in the presence of small
amounts of a base.
Cl H
| |
Ni / Al
+ H2   + HCl
2. Dechlorinative Amination :
On heating with ammonia in the presence of cuprous oxide, aniline is formed.
Cl NH2
| |

2 + NH3 + Cu2O  2 + H2O + Cu2Cl2
34
3. Dechlorinative Hydroxylation :
[a] By Dow process : Phenol is formed on heating chlorobenzene with caustic soda (NaOH) or wasing
soda (Na2CO3) solution at a high temperature (300º) under pressure in the presence of a copper salt. This
method is used for the manufacture of phenol on large scale and is known as Dow process.
Cl OH
| |
300º
+ NaOH 
Pr essure
 + NaCl
[b] By steam : On passing a mixture of chlorobenzene and steam through heated silica at 500º, phenol is
formed.
Cl OH
| |
500º
+ H2O 
SiO

 + HCl
2
4. With Magnesium Metal :

In order to obtain high yields of phenylmagnesium halide, iodobenzene (or bromobenzene) is reacted with
magnesium in dry and pure ether. Flurobenzene and chlorobenzene react very slowly. Therfore, they are
practically not suitable for preparing a Grignard’s reagent.
Br MgBr
| |
Dry and pure ether
+ Mg  
1.3.2 Reactions Due to Benzene Ring :

[i] Electrophilic Substitution or SE Reactions :
Due to strong negative inductive effect (–I) of chloro substituent of chlorobezene, it decreases electron
density in benzene ring. As a result, the attacking electrophile is very weakly attracted by the benzene
ring. Therefore, its electrophilic substitution occurs with slow rate as compared to unsubstitued benzene.
Thus, chloro substituent deactivates the benzene ring. Due to the presence of nonbonded electron pair on
chlorine. It is o– and p–directing by positive mesomeric (+ M) effect. Thus chlorine atom directly bonded to
benzene ring gives mainly o– and p– SE products on electrophilic substitution.
5. Halogenation :
Cl Cl Cl
| | |
Cl
Iron powder. 
+ Cl2 HCl
 +
o–Dichlorobenzene |
Cl
p–Dichlorobenzene
6. Sulphonation :
Cl
Cl Cl |
| |
Conc. H SO .  SO3H
2 4
 
–H2O +
SO3H
o– and p–chlorobenzensulphonic acids
35
7. Nitration :
Cl Cl Cl
| | |
Conc. HNO3  NO2
Conc.H2SO4 , 
  +
–H2O
|
NO2
[ii] Condensation Reaction :
8. Bimolecular Condensation wtih Chloral :

On heating mixture of chlorobenzene and chloral hydrate in the presence of small amount of concentrated
sulphuric acid, p, p’–dichlorodiphenyltrichloroethane, whose abbreviated name is D.D.T. It is a strong
germicide and its IUPAC name is 1,1,1–trichloro–2,2–bis(4-chlorophenyl) ethane.
Cl
Cl H
H SO
2 4 CH–CCl3
+ O=CH–CCl3 
H O 2
Cl
Cl H
D.D.T
In the above reaction o, p’–dichloro isomer is also formed in minor amount (about 25%) as a by–product.
Cl
Cl H
H SO
2 4 CH–CCl3
+ O=CH–CCl3 
–H2O
H
Cl
Cl o,p'–Dichlorodiphenyltrichloroethane
1.4 Uses :
[1] In the manufacutre of strong germicide, D.D.T.
[2] In the manufacture of many medicines and compounds (phenol, aniline, alkylbenzenes, dichlorobenzenes,
phenylmagnesium halides, etc.) and as intermediate in several reactions.
[3] As a solvent.
2. Benzyl chloride [C6H5CH2Cl]

2.1 Preparation :
u.v. light
C6H5 – CH3 + Cl2 boil
C6H5 – CH2OH + PCl5 C6H5CH2Cl

ZnCl2
C6H5 –CH2OH + HCl 60º
36
2.2 Chemical Properties :
aq. NaOH
CH3CH2OH (Benzyl alcohol)
alc. NH3
C6H5CH2NH2 (Benzyl amine)
alc. KCN
C6H5CH2CN (Benzyl cyanide)
CH3COOAg
C6H5— CH2 — OOC — CH3 (Benzyl acetate)
alc. AgNO3
C6H5–CH2Cl AgCl (white precipitate)
Na
C6H5CH2–CH2C6H5 (Dibenzyl)
Na + – Cl
C6H5–CH2–C6H5 (Diphenylmethane)
[O]
C6H5COOH
[H]
C6H5CH3
Mg + ether
C6H5CH2MgCl (Benzyl magnesium chloride)
2.3 Uses :
 Chlorobenzene is used in the manufacture of phenols, aniline.
 Chlorobenzene is used as a solvent.
 In the manufacture of DDT, used as an insecticide.
 Benzyl chloride is used for the introduction of benzyl group in organic compounds.
 As a starting material in the manufacture of benzyl alcohol, benzylamine and benzaldehyde.
1.3 DIHALOALKANES
Dihalides are classified as :
(a) Gem dihalides (b) Vicinal dihalides (c) dihalides
(a) Gem dihalides : Dihalides having two halo groups on same carbon atom is known as gem dihalide
eg. R – CH2 – CHX2 Terminal gem dihalide
X
|
R CR Non-terminal gem dihalide
|
X
(b) Vicinal dihalides : Vichinal dihalides contains two halogen atoms on adjacent carbon atom. i.e vicinal posi-
tion.
X X
| |
eg. R  CH  CH  R vicinal positions
37
(c) dihalides : They have two halogens on first and last carbon atoms.
CH2 — Br
eg. (CH2)n
CH2 — Br
 General Methods of Preparation :
1. By halogenation of Alkenes :
vic-Dihalides are formed by electrophilic addition of halogens on alkenes.
CH2=CH2 + Br2 Br–CH2–CH2 –Br

Ethylene dibromide
2. By Hydrohalogenation of Alkynes :
gem-Dihalides are formed by electrophilic addition of halogen acids on alkynes.
HCl HCl
HCCH  CH2=CHCl  CH3–CHCl2
Vinyl Chloride Ethylidene dichloride
vic-Dibromide is formed by addition of HBr in the presence of a peroxide.
HBr HBr
R–C  CH  R–CH = CHBr 
Peroxide  R–CH–CH2
Peroxide
| |
Br Br
3. By the Action of Halogen Acids on Glycols :
Anhyd
CH2–CH2 + 2HCl   CH2–CH2 + 2H2O
ZnCl2
| | | |
OH OH Cl Cl
CH2–CH2 + 2PCl5 CH2–CH2 + 2POCl3 + 2HCl

| | | |
OH OH Cl Cl
4. By Hunsdiecker Reaction of Dicarboxylic acids :
4 CCl
CH3–CH–COOAg + Br2   CH3–CH–Br + 2CO2 + 2AgBr
| |
COOAg Br
Silver methylmalonate Ethylidene dibromide
CH2–COOAg CCl4
CH2–Br
| + Br2   | + 2CO2 + 2AgBr
CH2–COOAg CH2–Br
Silver succinate Ethylene dibromide
5. By Reaction of PCl5 on Carbonyl Compounds : Gem dichlorides are obtained.

R–CH=O + PCl5 R–CHCl2 + POCl3
R–CO–R + PCl5 R–CCl2–R + POCl3
38
 Physical Properties of Dihaloalkanes

(i) They all are colourless
(ii) CH2F2 is a gas at room temperature.
(iii) They are heavier than water, insoluble in water and soluble in nonpolar solvents.
(iv) Reactivity of alkyl halide
CH3Cl > CH2Cl2 > CHCl3 > CCl4
(v) Reactivity of vic-dihaloalkanes is more than that of gem-dihaloalkanes.
CH2Br–CH2Br > CH3CHBr2
 Reactions
1. Reduction : Both on reduction form alkanes.
Pd catalyst
CH2Cl–CH2Cl + 2H2    CH3–CH3 + 2HCl
2. Hydrolysis
H O
 [CH3CH(OH)2] 2 CH3CHO
Aq. KOH
CH3CHCl2 
Ethylidene dichloride Acetaldehyde
Aq. KOH
Cl–CH2–CH2–Cl   HO–CH2–CH2–OH
Ethylene dichloride Ethylene glycol
3. Dehydrohalogenation : Both on dehydrohalogention form alkynes containing same number of carbon.
H Cl H Cl
| | | |
Alc. KOH NaNH2
H–C–C–H –HCl
  H–C=C–H   H–CC–H
–HCl
| |
H Cl Vinyl chloride Acetylene
Ethylidene dichloride
4. Reaction with Zn : Vicinal dihalides on reaction with zinc metal form alkenes containing same number
of carbons.

CH 2 — C H 2  Zn    C H 2  CH 2  ZnC l2
| |
Cl Cl
1, 2  D ich loroe than e E the ne
Geminal dihalides on reaction with zinc metal form alkene containing double the number of carbon atoms.
Cl
Cl
| |

CH3 — C — H + 2Zn + H  C  CH3  CH3  CH  CH  CH3  2ZnCl2
| |
Cl
Cl
But  2  ene
1,1 - Dichloroethane
 Uses of Dihaloalkanes
39
1. As solvents for non-polar compounds.

2. As fumigants for grains and fruits.
3. Ethylene dibromide is used to remove lead from gasoline containing tetraethyllead.
1.4 TRIHALOALKANES : HALOFORM : CHX3
 Preparation of Haloform
 The following compound give haloform reaction.

 Acetaldehyde, all methyl ketones, acetone, ethylalcohol, all 2-alkanols etc.
When the following compounds are heated with alkali and halogen haloform is obtained.
or H
CH3—C— R CH3 CO — group
O alkyl group
or
H
CH3—CH— R CH3 CH(OH) — group
OH alkyl group
Acetone (CH3–CO–CH3)
Butanone (CH3–CO–CH2–CH3)
2-Pentanone (CH3–CO–CH2–CH2–CH3)
3-Methylbutanone {CH3–CO–CH(CH3)2}
 Haloform Reaction
C 2H5 OH  4 X 2  6NaOH  CHX3  5NaX  5H2 O  HCOONa
CH3 COCH3  3 X 2  4NaOH  CHX3  3NaX  CH3 COONa  3H2O
(i) Chloroform : CHCl3
 Preparation of Chloroform
1. Laboratory Methods – Chloroform Reaction
On heating ethyl alcohol with bleaching powder, the reaction occurs in the followings steps :
(i) CaOCl2 + H2O  Ca(OH)2 + 2Cl
(ii) CH3CH2OH + 2Cl  CH3CHO + 2HCl
(iii) CH3CHO + 6Cl  CCl3 CHO + 3HCl

Chloral
(iv) 2CCl3CHO + Ca(OH)2  2CHCl3 + (HCOO)2Ca
40
2. Industrial Methods :
(i) By Chlorination of Methane :
400 – 500 º
CH4 + 3Cl2    CHCl3 + 3HCl
(ii) By Reduction of Carbon tetrachloride :

2CCl4 + 2Fe + 2H2O 2CHCl3 + FeCl2 + Fe(OH)2
3. Methods of Preparation of Pure Chloroform :
CCl3CHO.H2O + NaOH CHCl3 + HCOONa + H2O

Chloral hydrate
 Physical Properties
Chloroform is a colourless sweet-smelling volatile and noninflammable liquid, which is immiscible with
water and heavier than water. It is miscible with organic liquids, like alcohol, ether, etc., and is a very good
solvent for non-polar compounds. Its boiling point is 61º.
 Reaction
A. Due to Breaking of Carbon-Hydrogen Bond.

(i) By Heterolysis (In the presence of caustic alkali)
(ii) By Homolysis (At high temperature)
B. Due to Breaking of Carbon-Chlorine Bond
(i) In the presence of a Lewis acid (Heterolysis)
Cl Cl
| |+ –
H– C – Cl H – C + :Cl
| |
Cl Cl
(ii) At high temperature (Homolysis)
 
HCCl2 — Cl HCCl2 + Cl
1. Oxidation :
Chloroform undergoes oxidation to form carbonyl chloride (phosgene) by oxygen on keeping it in contact
with air in the presence of light
h
Cl3C–H + O=O   [Cl3 C–O–O–H]
A peroxide
Cl3C–O–O–H + Cl3C–H [2Cl3C–O–H]
Cl3C–O–H Cl2C=O + HCl

Phosgene
Phosgene (COCl2) is a highly poisonous compound. This is the reason why the sample of chloroform
exposed to air and light is not used as an anaesthetic.
41
2. Reduction :
Zn  HCl
CHCl3 + 2H   CH2Cl2 + HCl
Fe  steam
CHCl3 + 6H    CH4 + 3HCl
3. Chlorination :
h
CHCl3 + Cl2   CCl4 + HCl
4. Dechlorination :
300 º
CHCl3 + 6AgCl + Cl3CH   CHCH + 6AgCl
5. Nitration :

Cl3C–H + HO–NO2  Cl3C–NO2 (chloropicrin) + H2O
6. Addition on Acetone :
CH3 CH3
| |
Cl3C + C–CH3 Cl3C–C–CH3
| |
H O OH
Chloretone
7. Addition on Acetylene dichloride :
Cl–CH=CH–Cl Cl–CH–CH–Cl
| |
H CCl3
+ H–CCl3
1,1,1,2,3–pentachloropropane
8. With Antimony trifluoride :

2CHCl3 + 2SbF3 CF2=CF2 + 2SbCl3 + 2HF
9. Hofmann Carbylamine Reaction :
CHCl3 + KOH :CCl2 + KCl + H2O
dichloro carbene
R–NH2 + :CCl2 + 2KOH R–NC + 2KCl + 2H2O
It is called isocyanide test.
10. Friedel-Crafts Reaction :
[I] [II] [III]

CHCl3 C6H6 C6H6
C6H6  
 C6H5CHCl 2   (C6H5)2CHCl 
–HCl
 (C6H5)3CH
–HCl
–HCl
11. Reimer-Tiemann Formylation
CHCl3 + KOH :CCl2 + KCl + H2O
OH OH
C6H5OH + :CCl2 C6H4 2KOH
  C6H4
2KCl
CHCl2 H2O
CHO
42
12. Freons : Polychlorofluoro derivatives of alkanes are called chlorofluorocarbons (C.F.C.) or Freons.
 Test of Purity of Chloroform
Pure Chloroform does not give any ppt. with AgNO3 solution.
2CHCl3 + O2 2COCl2 + 2HCl
HCl + AgNO3 AgCl (White ppt.) + HNO3
 Uses
1. As an anaesthetic
2. As a solvent for fat, oil and non-polar substances
3. As an antiseptic
4. In the manufacture of a hypnotic drug named chloretone
5. In the manufacture of a war gas named chloropicrin
6. In the manufacture of triphenylmethane dyes
7. In the manufacture of a polymer named teflon
(ii) Iodoform CHI3
Iodoform Reaction
A yellow precipitate of CHI3 is obtained on mixing saturated solution of sodium carbonate in the compound
that gives haloform reaction, and heating the solution with adding iodine pinch by pinch. This reaction is
called iodoform test.
Na2CO3 is a strong base due to hydrolysis of CO32– ion.
CO32– + H2O HCO3– + OH–
2OH– + I2 I– + IO– + H2O
R R
| |
CH3–CHOH + NaOI CH3–C=O + NaI + H2O
2-Hydroxy 2º alcohol
R R
| |
CH3–C=O + 3NaOI Cl3–C=O + 3NaOH
A methyl ketone Triiodo derivative
R R
| |
Cl3–C=O + NaOH CHI3 + COONa
43
1.5 Tetrahaloalkane
Carbont et r ac hloride, Tet r achlor omet hane, CCl 4
 PREPARATION :
1. By Chlorination of Methane :
250  400 º
CH4 + 4Cl2    CCl4 + 4HCl
2. By Chlorination of Chloroform :
CHCl3 + Cl2 CCl4 + HCl
3. By Chlorination of Carbon disulphide :
CS2 + 3Cl2 CCl4 + S2Cl2 (Sulphur monochloride)
S2Cl2 + CS2 CCl4 + 6S
 Reactions
500 º
1. Oxidation : CCl4 + H2O   COCl2 + 2HCl
Fe  H2O
2. Reduction : CCl4 + H2   CHCl3 + HCl
2KOH 2KOH 2KOH

3. Alkaline Hydrolysis : Cl2CCl2   [Cl2C=O] 
– 2KCl
 [(HO)2CO] –
– 2KCl

 K2CO3
2H2O
4. Dechlorinative Fluorination :
CCl4 + HF CFCl3 + HCl

Freon-11
CCl4 + 2HF CF2Cl2 + 2HCl

Freon-12
5. Reimer-Tiemann Carboxylation :
When phenol is heated with carbon tetrachloride and KOH, then salicylic acid (o-hydroxybenzoic acid) is
obtained. C6H5OH + CCl4 + KOH (OH)C6H4(COOH) (salicylic acid)
6. Friedel-Crafts Reaction :
AlCl3
C6H5–H + Cl –CCl3   C6H5–CCl3 + HCl
Benzotrichloride
(Benzylidyne chloride)
 Uses
1. As an industrial solvent for fats, oils, waxes, gums, resins, rubbers, etc.
2. As a laboratory solvent and reagent
3. In dry cleaning
44
4. As fire extinguisher under the commercial name, ‘Pyrene’.
5. In the manufacture of refrigerants, like Freon-11 and Freon-12
6. As a fumigant, anthelmintic and insecticide.
1.6 Freons (Polychlorofluoro Alkane)
SbCl4F
(i) CCl4 + HF   CCl3F + HCl
Freon-11
SbCl4F
(ii) Freon–11 + HF   CCl2F2 + HCl
Freon-12
SbCl4F
(iii) C2Cl6 + 2HF   C2Cl4F2 + 2HCl
Freon-112
Bromine-containing compounds are popularly used to extinguish fires and are called Halons
e.g.
CBrClF2 Bromochloro difluoromethane Halon – 1211
CBrF3 Bromotrifluoro Methane Halon – 1301
 Uses
1. As refrigerants in refrigerators, air conditioners, cold storages, etc.
2. As inert solvents.
3. As aerosol propellants
45
Solved Example
Ex.1 For the preparation of 2–propanol, methyl magnesium chloride will react with the following reagent
[1] Oxirane [2] Ethanal [3] Methanal [4] Propanal
Sol. [2] Alkyl magnesium halides on reacting with aldehydes other than formaldehyde give secondary alcohol.
R R
| |
H2O
RMgX + R’ – CHO  R’– CH–OMgX   R’ – CH–OH
Methyl magnesium chloride will react with CH3CHO (Ethanal)
Ex.2 In Zerewittnoff’s method Grignard’s reagent reacts with the following
[1] A primary amine [2] a primary alcohol
[3] Acetylene [4] All of above
Sol. [4] In Zerewitinoff method, Grignard’s reagent reacts with the compounds containing active H–atom because
it is a method to estimate active H–atom in compounds.
Ex.3 The compound formed by reaction of 1,1–dichloropropane with Zn can also be prepared by the following
reaction
[1] 3, 4–Dibromohexane with zinc [2] 3–Bromohexane with alcoholic KOH
[3] both of the above [4] None of above
Sol. [3] 1,1–Dichloro propane on reacting with Zn gives 3-hexene
CH3CH2CHCl2 + Zn + Cl2CHCH2CH3  CH3–CH2–CH = CH–CH2–CH3
3–Hexene
Choice [1] and [2] also give 3–hexene
CH3—CH2—CH—CH—CH2CH3+ Zn CH3CH2–CH=CH–CH2CH3
| |
Br Br
CH3—CH2—CH—CH2—CH2 CH3 + alc. KOH

|
Br
CH3CH2–CH=CH–CH2CH3 + KBr + H2O
Ex.4 Which of the following compounds gives iodoform with I2 + NaOH
[1] CH3CH2OH [2] CH3CH2CH2OH [3] CH3OH [4] CH3COOH
46
Sol. [1] The compounds having following types of structure
CH3—C—R or CH3—CH—R
|| |
O OH
(R=H or alkyl) give iodoform with I2 + NaOH
Ex.5 Identify Z in the following reaction sequence
alc. KOH
C2H5I  Br2 KCN
 X   Y  Z
[1] Br–CH2–CH2–CN [2] CH3CH2–CN
[3] CN–CH2–CH2–CN [4] BrCH = CHCN
alc.KOH
Sol. [3] C2H5I  Br2 2KCN
 CH2=CH2   CH2—CH2   CH2—CH2
| | | |
Br Br CN CN
Ex.6 The following compound is obtained when CH3CH2CHBr2 is boiled with aqueous caustic potash -
[1] CH3–CCH [2] CH3–CH=CHBr [3] CH3CH2CHO [4] None of these
OH
Aqueous KOH
Sol. [3] CH3–CH2CHBr2   CH3CH2CH   CH3CH2CHO
 H O2
OH
Ex.7 Which of the following properties is not common for ethylene chloride and ethylidene chloride
[1] Both are dihalogen derivatives [2] Both are positional isomers
[3] Both give same product on reacting with alcoholic caustic potash
[4] Both react with aqueous caustic potash and given the same product
Sol. [4] Both react with aqueous Caustic potash and give different products
Aqueous KOH
CH2—CH2   CH2—CH2
| | | |
Cl Cl OH OH
Ethylene glycol
Aqueous KOH
CH3CHCl2   CH3CH(OH)2 
H2O
 CH3CHO
Acetaldehyde
Ex.8 A primary amine is formed when Grignard reagent reacts with the following compound.
[1] Ammonia [2] Methylamine [3] Chloramine [4] Acetonitrile
Sol. [3] RMgCl + ClNH2  RNH2 + MgCl2
47
Ex.9 In the preparation of Grignard reagent iodine crystal is used as
[1] It catalyses the reaction [2] It exchanges with alkyl halide
[3] It inhibits the reaction [4] None of the above
Sol. [1] Iodine crystal catalyses the reaction
Q.10 With which of the following functional group Grignard reagent gives substituion reaction
[1] >C=O [2] –CHO [3] –CCH [4] >C=S
Sol. [3] –CCH+RMgX  RH + –CCMgX
Q.11 Which of the following pair will be ideal in the formation of
C2H5
|
CH3— C —OH
|
C2H5
[1] CH3– C –C2H5, C2H5MgBr [2] C2H5– C –C2H5, CH3MgBr

|| ||
O O
[3] CH3COOC2H5, 2C2H5MgBr [4] All the above
Sol. [4] All the pairs given in [1] , [2] and [3] are suitable for the synthesis of tertiary alcohol.

H / H2O
Ex.12 CH3Li + CH2—CH2    A
O

H / H2O
CH3MgI + CH2—CH2   B
O
The false statement about the product A and B is
[1] Both are primary alcohols
[2] Both do not turn blue litmus to red
[3] The isomer of A and B is symmetrical ether
[4] Both have the same boiling points
Sol. [3] A and B are nothing but n-propyl alcohol. Its isomer is an unsymmetrical ether [CH3OCH2CH3]
48
E xercise # 1
Q.1 Which of the following is a colourless gas :
[1] Freons [2] Chloroform [3] Iodoform [4] Ethanol
Q.2 Two monochloro derivatives are possible for which of the following :
[1] Ethane [2] n-Butane [3] Isopentane [4] Benzene
Q.3 The following compound is formed by the reaction of chloroform with Conc. HNO3 :
[1] CHCl2NO2 [2] CCl3NO2 [3] CHCl2HNO3 [4] None of these
Q.4 Which of the following is a freon ?
[1] CCl4 [2] CCl2F2 [3] CF4 [4] CF2Br2
Q.5 The sample of chloroform used as anaesthetic is tested by :
[1] Fehling solution [2] Ammoniacal Cu2Cl2
[3] AgNO3 solution [4] Boiling with KOH and then adding AgNO3 solution
Q.6 Phosgene is :
[1] PH3 [2] POCl3 [3] CS2 [4] COCl2
Q.7 Grignard reagent is prepared by the following reaction :
[1] Magnesium and alkane [2] Magnesium and aromatic hydrocarbon
[3] Magnesium and alkyl halide [4] Zinc and alkyl halide
Q.8 The compound used as fire extinguisher is :
[1] Ammonia [2] Chloroform [3] Carbon disulphide [4] Carbon tetrachloride
ZnX 2
Q.9 In the reaction C2H5OH + HX   C2H5X, the order of the reactivity of HX is :
[1] HBr > HI > HCl [2] HI > HCl > HBr [3] HI > HBr > HCl [4] HCl > HBr > HI
Q.10 What is the correct order of reactivity of the following alkyl halides if the halogen atom is same ?
[1] (1º) > (2º) > (3º) [2] (3º) > (1º) > (2º) [3] (3º) > (2º) > (1º) [4] (1º) > (3º) > (2º)
Q.11 The main product of the reaction of propane with chlorine at 25ºC in the presence of sunlight is :
[1] 1-Choropropane [2] 2-Chloropropane [3] Chloroethane [4] Chloromethane
Q.12 Which of the following compounds is used as refrigerant ?
[1] Acetone [2] CCl4 [3] CF4 [4] CCl2F2
Q.13 Which of the following will give iodoform test ?
[1] 3-Pentanone [2] Formaldehyde [3] Butanone [4] Benzyl alcohol
Q.14 Carbon tetrachloride is used as fire extinguisher under the name :
[1] Pyrene [2] Phosgene [3] Phosphine [4] None of these
Q.15 Compounds A, B and C in the following reaction sequence are :

AgCN H3 O
C2H5Br   A   B + C
[1] C2H5CN, C2H5COOH, NH3 [2] C2H5NC, C2H5NH2, HCOOH

[3] C2H5NC, C2H5NHCH3, HCOOH [4] None of these
49
Q.16 Which of the following is a solid at room temperature :

[1] Methyl chloride [2] Chloroform [3] Iodoform [4] Bromoform
Q.17 Which of the following samples of chloroform will give white precipitate with silver nitrate ?
[1] Pure chloroform [2] Chloroform exposed to air
[3] Both of the above [4] None of the above
Q.18 Which of the following is boiled with ethyl chloride for the preparation of ethyl alcohol ?
[1] Alcoholic KOH [2] Aqueous KOH [3] H2O [4] H2O2
Q.19 The product of the reaction of ethyl bromide with silver nitrite is :
[1] Nitroethane [2] Nitroethane and ethyl nitrite
[3] Ethyl nitrite [4] Ethane
Q.20 The compound X in the reaction X + Zn  3-Hexene, is :
[1] 3, 4-Dichlorohexane [2] 1, 1-Dichloropropane [3] Both of the above [4] None of the above
Q.21 The following is obtained by heating iodoform with Ag powder :
[1] Acetylene [2] Ethylene [3] Methane [4] Ethane
Q.22 The most inert compound is
[1] Iodoform [2] Dichloromethane [3] Dichlorodifluoro [4] Chloroform
Q.23 The following is not obtained by the hydrolysis of a gem dihalide ?
[1] A 1, 2-Diol [2] An aldehyde [3] A ketone [4] None of these
Q.24 1% pure alcohol is added to the chloroform used in hospitals because :
[1] It stops the oxidation of chloroform
[2] The poisonous gas phosgene is not formed
[3] Phosgene is formed but ethyl alcohol converts it into diethyl carbonate
[4] It is helpful in producing unconsciousness
Q.25 What is false for alkyl halides ?
[1] These are completely soluble in water [2] These give nucleophilic substitution reactions
[3] These are insoluble in water [4] These are soluble in organic solvents
Q.26 The reactivity of alkyl halides depends upon :
[1] the nature of halogen atom [2] the nature of alkyl group
[3] both of the above [4] None of these
Q.27 Hunsdicker reaction is an example of :
[1] Decarboxylation [2] Debromination
[3] Decarboxylation and bromination [4] Bromination
Q.28 C4H9Br can represent :
[1] A 3º bromoalkane [2] A 2º bromoalkane [3] A 1º bromoalkane [4] All of the above
Q.29 The reason to keep chloroform in the dark brown coloured bottle is :
[1] To stop its oxidation [2] To stop its decomposition
[3] To stop the formation of carbon tetrachloride from it [4] To stop its hydrolysis
Q.30 Which of the following metals is used in Wurtz synthesis :
[1] Ba [2] Al [3] Na [4] Fe
50
Q.31 CCl4 does not give a precipitate with AgNO3 . Its reason is :
[1] The formation of a complex [2] The evolution of Cl2 gas
[3] Chloride ion is not formed [4] AgNO3 does not give Ag ions
Q.32 In carbylamine test, alcoholic KOH is heated with :
[1] Chloroform and silver powder [2] Trihalomethane and a primary amine
[3] Alkyl halide and a primary amine [4] Alkyl cyanide and a primary amine
Q.33 At room temperature, iodoform is :
[1] A colourless liquid [2] A violet coloured gas [3] A yellow solid [4] A grey liquid
Q.34 In the Darzen’s process for the preparation of alkyl chlorides, alcohol react with :
[1] Thionyl chloride in pyridine [2] Sulphuryl chloride in pyridine
[3] HCl + anhy. ZnCl2 [4] None of the above
Q.35 The final product (Y) of the following reaction is :
Br2 Pd / H2
C2H4  X    Y
[1] CH3CH2Br [2] CH3–CH3 [3] C2H2 [4] C2H4Br2
Q.36 The reaction of bleaching powder with ethanol is :
[1] Hydrolysis [2] Oxidation [3] Halogenation [4] All of the above
–
OBr
Q.37 A   CHBr3
The compound is :
[1] Isopropyl alcohol [2] Isobutyl alcohol [3] Neopentyl alcohol [4] n-Butanol
Q.38 The following reagent is required for the conversion of a primary amine into a primary alkyl halide :
[1] SOCl2/Pyridine [2] Luca’s reagent [3] Tilden’s reagent [4] PCl5
Q.39 The product of the reaction of ethyne with hydrochloric acid can also be prepared by the following reaction
[1] Ethanal with PCl5 [2] Ethene with Cl2 [3] Ethyl chloride with Cl2 [4] None of these
Q.40 Strecker’s reaction is :
[1] ROH + SOCl2  [2] 2RBr + 2Zn  [3] RCl + Na2SO3  [4] ROH + PCl5 
Q.41 Which will react with aqueous KOH with difficulty ?
[1] Allyl chloride [2] Vinyl chloride [3] Chlorobenzene [4] [2] and [3] Both
Q.42 Which of the following compounds is used as methylating agent ?
[1] C2H5Cl [2] C2H5Br [3] C2H5I [4] CH3I
Q.43 The following reagent is used in the preparation of an unsaturated compound from chloroform :
[1] Zn + H2O [2] Fe + H2O [3] Zn [4] Ag powder
Q.44 The halogen derivative used as an antiseptic is :
[1] CHCl3 [2] CHBr3 [3] CCl4 [4] CHI3
Q.45 Which of the following reagents is used to step up the C-chain in alkyl halides :
[1] HCN [2] KCN [3] NH4CN [4] AgCN
Q.46 The following group is replaced by a halogen atom :
[1] Hydroxyl group (–OH)[2] Aldehyde (–CHO) [3] Nitro (NO2) [4] Ketone (> C=O)
Q.47 CCl4 is insoluble in water because :
[1] Water is polar [2] CCl4 is nonpolar [3] Water and CCl4 are polar [4] None of the above
51
Q.48 The compound formed by the reaction of ethyl chloride with sodium-lead alloy is :
[1] Tetraethyl lead [2] Sodium ethoxide [3] Ethyl sodium [4] No reaction
Q.49 Which of the following reagents reduces alkyl halide by hydride ion ?
[1] Na/C2H5OH [2] NaBH4 [3] Pd/H2 [4] Zn–Cu/C2H5OH
Q.50 The compound with highest boiling point is :
[1] C2H5I [2] C2H5Br [3] C2H5Cl [4] C3H7Cl
Q.51 The following alkane is not obtained by the reaction of ethyl iodide with propyl iodide and sodium metal in
the presence of dry ether
[1] Propane [2] Butane [3] Pentane [4] Hexane
Q.52 The reaction of methane with iodine is carried out in the presence of HIO3 because HIO3
[1] Gives iodine in the iodination of methane [2] Oxidises HI formed in the reaction
[3] Reduces HI formed in the reaction [4] Changes the I2 molecule into I atoms.
Q.53 The following compound is obtained when a mixture of carbon tetra chloride vapours and water vapours is
heated at 500°C
[1] Carbon dioxide [2] Phosgene gas [3] Phosphine gas [4] Phosphoryl chloride
Q.54 The following compound is formed when the product of the reaction of chloroform with 1-butene is heated
with aqueous caustic soda
[1] Butanoic acid [2] 2-Methyl butanoic acid
[3] 1,1,1–Trichloro-2-methyl butane [4] Reaction does not take place
Q.55 The product of the reaction of ethyl iodide with Zn-Cu couple/alcohol can also be prepared by the following
reaction
[1] By the hydrolysis of the product obtained from the reaction of ethyl iodide with Mg in dry ether.
[2] Reaction of iodomethane with Na in dry ether
[3] By the reduction of ethyl alcohol with red P + HI
[4] All of the above
Q.56 The following compound is obtained on heating 2,2–dichloropropane with aqueous KOH
[1] 2,2–Propandiol [2] 1,2–Propandiol [3] Propanone [4] Propanal
Q.57 The product of which of the following reactions is not a vicinal dihalide
[1] Reaction of ethylene glycol with P +Br2
[2] Reaction of HCl with ethyne
[3] Reaction of HBr with ethyne in the presence of peroxide
[4] Reaction of Cl2 with propene
Q.58 Ethylene chloride and ethylidene chloride are positional isomers. Which of the following statement is not
applicable on both
[1] both are dihalogen derivatives
[2] Both form the same product with aqueous potash
[3] Both form the same product with alcoholic potash
[4] Both give Beilestein test
Q.59 Which of the following chlorides hydrolyses most easily
[1] CH3CH2CH2Cl [2] CH2=CH–Cl [3] CH2=CH–CH2Cl [4] (CH3)2CHCH2Cl
52
Q.60 A dihalogen derivative (A) with three C-atoms gives a hydrocarbon (B) on reacting with alco. KOH. (B) gives a
white precipitate with Tollen’s reagent. (A) on heating with aqueous KOH gives a ketone. Compound (A) is
[1] 1,1–Dihoalo propane [2] 1,2–Dihalopropane [3] 2,2–Dihalopropane [4] 1,3–Dihalopropane
Q.61 A five C-atom hydrocarbon is formed by the reduction of a chloroderivative (A) of an alkane with Zn-Cu
couple. (A) is dissolved in dry ether and then treated with metallic sodium to give 2,2,5, 5–tetramethyl
hexane. The IUPAC name of compound (A) is
[1] Neopentyl chloride [2] 1–chloro-2,2-dimethyl propane
[3] 1-chloro-3-methyl butane [4] 2-chloro-3-methylbutane
Q.62 The unsaturated hydrocarbon obtained by the reaction of a dihalogen derivative with alcoholic potash gives
a red precipitate with ammonical cuprous chloride. The dihalogen derivative gives propanal on heating with
aqueous potash. The dihalogen derivative is -
[1] 1,1–Dichloropropane [2] 1,2–Dichloropropane [3] 2,2–Dichloropropane [4] 1,4–Dichloropropane
Q.63 The following reaction is used in the Darzen’s process for the preparation of alkyl chloride
[1] Alcohol with nitrosyl chloride [2] Alcohol with thionyl chloride in the presence of pyri-
dine
[3] Alcohol with HCl in the presence of anhy. ZnCl2 [4] None of these
Q.64 3.94 g of iodoform is heated with Ag powder. What will be the volume of the gas obtained at NTP
[1] 224 ml. [2] 112 ml [3] 22400 ml. [4] 2240 ml
Q.65 The following is formed by the reaction of chloroform with 1,2-dichloro ethene
[1] Chloral [2] D.D.T. [3] Chloretone [ 4 ] 1 , 1 , 1 , 2 , 3 -
pentachloropropane
Q.66 The product of the reaction of ethyl bromide with dry silver oxide in ethanol is the functional isomer of
[1] A primary alcohol [2] A secondary alcohol [3] A tertiary alcohol [4] All of the above
Q.67 The compound (A) in the following reaction sequence is
PCl5
(A)  Alco. KOH
(B)  H2 / Ni
 (C)   Propane
[1] Chloroethane [2] Ethanol [3] 1,2-Dichloroethane [4] Propan-2-ol

Q.68 The false statement about the freons is
[1] these are high boiling point liquids [2] these are non inflammable and flameless liquids
[3] these are nonpoisonous and inert [4] these are used as refrigerants
Q.69 Alkyl halides are insoluble in water althought they are polar. Its reason is
[1] They are unable to form hydrogen bonds with water [2] They are able to form hydrogen bonds with water
[3] Their density is higher than water [4] Their density is less than water
Q.70 Which of the following is a false statement
[1] The product of the reaction of ethyl iodide with silver cyanide is ethyl isocyanide
[2] The formation of ether from the reaction of methyl iodide with dry Ag2O is called Williamson’s synthesis
[3] The test of chloroform is possible with Hofmann carbylamine reaction
[4] Iodoform gives violet vapours on heating
Q.71 Ethylene chloride and ethylidene chloride are
[1] Functional isomers [2] Chain isomers [3] Metamers [4] Position isomers
53
Q.72 An alkyl isocyanide can be prepared by the following reaction

[1] By heating an amide with P2O5
[2] By heating an alcohol with NH3 in the presence of anhy. ZnCl2
[3] By the reaction of an alkyl halide with AgCN
[4] By the reaction of an alkyl halidewith KCN
Q.73 In the laboratory, chloroform is prepared by the following method
[1] By oxidation of alcohol with bleaching powder
[2] By reduction of carbon tetrachloride with Fe + H2O
[3] By oxidation of carbon tertrachloride with bleaching powder
[4] None of the above
Q.74 A and B in the following reactions are respectively
Zn H2O
(i) CHCl3  Zn HCl
A (ii) CHCl3  B
[1] CH2Cl2 and CH4 [2] CH4 and CH2Cl2 [3] CCl3CHO and CH4 [4] CCl3CHO and CH2Cl2
Q.75 The product obtained by the reaction of silver propanoate with bromine in carbon tetrachloride solution is
[1] Bromoethane [2] Silver-3-bromopropanoate
[3] Ethanoyl bromide [4] None of the above
Q.76 Which of the following plastics is a last product of the reaction
HF
CFCl3 
SbF3

 X 
800C Polymerisation
 Y   Plastic
[1] Backellite [2] Teflon [3] Polyethene [4] None of the above
Q.77 Benzene can be converted to isopropyl benzene (Cumene) by the following reagent
[1] CH3CH2CH2Cl + Anhy. AlCl3 [2] CH3–CH = CH2 + Anhy. AlCl3
[3] Both of the above [4] None of the above
Q.78 The adduct of a compound (A) with isopropyl magnesium halide on hydrolysis gives a tertiary alcohol. The
compound (A) is
[1] An ester [2] A secondary alcohol [3] A primary alcohol [4] An aldehyde
Q.79 A salt solution reacts with some drops of chloroform and the mixture is shaken with chlorine water. The
chloroform layer becomes violet. Salt solution contains
[1] NO2– ion [2] NO3– ion [3] Br– ion [4] I– ion
Q.80 The product obtained by the hydrolysis of the adduct formed by the reaction of ethyl magnesium iodide with
methanal can also be prepared by the following reaction
[1] Reduction of ethanal with Na/C2H5OH [2] 1-Bromopropane with aqueous KOH
[3] Iodoethane with alco. KOH [4] 1-Bromopropane with alco. KOH
54
Answer Key
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 1 2 2 2 3 4 3 4 3 3 2 4 3 1 2 3 2 2 1 3
Qus. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 1 3 1 3 1 3 3 4 1 3 3 2 3 1 2 4 1 3 1 3
Qus. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Ans. 4 4 4 4 2 1 2 1 2 1 1 2 2 2 4 3 2 2 3 3
Qus. 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80
Ans. 2 1 2 2 4 4 4 1 1 2 4 3 1 2 1 2 3 1 4 2
55
E xercise # 2
Q.1 An organic compound contains about 7.7% carbon. Its acidic sodium extract gives a white precipitate with
AgNO3. This precipitate is soluble in the excess of ammonia. The compound is
[1] CHCl3 [2] CHBr3 [3] CHI3 [4] CCl4
Q.2 Match the following and pick up the correct answer
Compound Use
A CHCl3 (i) Refrigerant
B CCl4 (ii) Fire extinguisher
C CF2Cl2 (iii) Anaesthetic
The correct answer is
[1] A–(i), B–(ii), C–(iii) [2] A–(iii), B–(ii), C–(i) [3] A–(iii), B–(i), C–(ii) [4] None of the above
Q.3 Ethylidene bromide can be prepared by the following reaction
[1] Acetone with PBr3 [2] Acetone with PBr5 [3] Ethene with HBr [4] Ethyne with HBr
Q.4 A compound (A) is formed by the reaction of ethylene with bromine which on reacting with aqueous KOH
gives a compound (B). The compound (B) can also be prepared by the reaction of ethylene with the
following
[1] Baeyer’s reagent
[2] Oxygen in the pesence of silver catalyst and then acidic hydrolysis
[3] performic acid and the product undergoes acidic hyrolysis
[4] All of the above
Q.5 The product of the reaction of methyl magnesium bromide with methanol can also be prepared by the
following reaction
[1] Reduction of methyl bromide [2] Decarboxylation of sodium ethanoate
[3] Reduction of methyl alcohol [4] All of the above
Q.6 The product of the reaction of sodium acetylide with alkyl halide is
[1] A terminal alkyne [2] A terminal alkene [3] A non terminal alkyne[4] [1] and [3] both
Q.7 Carbon tetrachloride can be prepared by the following reaction
[1] CS2 with Cl2 in the presence of I2 [2] CS2 with S2Cl2 in the presence of I2
[3] CHCl3 with Cl2 in the presence of I2 [4] All of the above
Q.8 The adduct of which of the following compounds with Grignard’s reagent does not form a primary alcohol on
hydrolysis
[1] O2 [2] Oxirane [3] Methanal [4] Ethanal
Q.9 For the preparation of -butylene from methyl magnesium chloride, it will be reacted with
[1] Propene [2] Propyl chloride [3] 3–Chloro propene [4] 2–Chloro propene
Q.10 The vapour density of an organic compound is 23.0. It contains 52.17% C and 13% H. It gives iodoform
test. The compound is
[1] Ethanol [2] dimethyl ether [3] Acetone [4] Methanol
56
Q.11 Identify Z in the following reaction
Na / C2H5OH HNO2 
CH3CN  KMnO4 , H
 X   Y  Z
[1] CH3CHO [2] CH3CONH2 [3] CH3COOH [4] CH3CH2NHOH

Q.12 Which of the following is a correct statement
[1] C2H5Br reacts with alcoholic KOH to give C2H5OH
[2] Reaction of C2H5Br with metallic Na gives ethane
[3] C2H5 Br reacts with sodium ethoxide to give ether
[4] C2H5Br reacts with AgCN to give ethyl cyanide
Q.13 The product of the reaction of chloromethane with sodium sulphide is
[1] Dimethyl sulphide [2] Methan thiol
[3] Mixture of both the above [4] None of the above
Q.14 The compound with highest boiling point is -
[1] Ethylene bromide [2] Ethylene chloride [3] Ethylidene bromide [4] Ethylidene chloride
Q.15 The main product obtained by the electrolysis of the aqueous ethanolic solution of potassium bromide and
sodium carbonate, is
[1] Ethyl bromide [2] Bromoform [3] Ethylene bromide [4] Ethylidene bromide
Q.16 Which of the following is Swart’s reaction

[1] C2H5Cl + AgF   C2H5F + AgCl [2] 2C2H5Br + 2Zn  (C2H5)2Zn + ZnBr2
[3] 2CHCl3 + 6Ag  CH  CH + 6AgCl [4] C2H5Br + NaI  C2H5I + NaBr

Q.17 The chloroform exposed to air and sunlight gives white precipitate with AgNO3 solution because it contains
[1] Phosgene [2] Hydrogen chloride [3] Chlorine [4] Mixture of all the above
Q.18 The following type of compounds are obtained by the reaction of a carboxylic acid with lead tetra acetate
and lithium chloride in benzene
[1] Alkyl halides [2] Acid chlorides [3] CO2 + H2O [4] None of the above
HALOBENZENE
Q.19 Which of the following reactions is more suitable than the remaining three for obtaining iodobenzene ?
[1] N2Cl + KI [2] N2Cl + HI
[3] OH + HI [4] Cl + NaI
Q.20 The reaction of chlorobenzene with which of the following reagents is not an example of electrophilic
substitution reaction ?
[1] Cl 2 + Fe powder [2] Conc. H2SO 4
[3] Conc. HNO 3 + Conc. H2SO 4 [4] CCl3CHO + Conc. H2SO 4
Q.21 At the time of preparation of chlorobenzene from benzne, which of the following can be used as a
halogen carrier ?
[1] A lewis acid [2] Elements like iron, iodine etc
[3] A tertiary amine base [4] All of the above
57
Q.22 Which of the following can be obtained by Balz–Schiemann reaction ?

[1] Fluorobenzene [2] Chlororbenzene [3] Bromobenzene [4] Iodobenzene
Q.23 Which of the following reactions can be used to obtain chlorobenzene from benzenediazonium chloride ?
[A] Sandmeyer reaction [2] Balz–Schemann reaction
[C] Rashing process [4] Gattermann reaction
[1] A and B [2] A, B and C [3] A, C and D [4] C and D
Q.24 Which of the following catalysts is used in the preparation of chlorobenzene by Gattermann reaction ?
[1] CuSO 4 [2] CuCl 2 [3] Cu2Cl 2 [4] Cu
Q.25 Which of the following catalysts is used in the preparation of chlorobenzene by Sandmeyer’s reaction ?
[1] CuCl 2 [2] Cu2Cl 2 [3] CuSO 4 [4] Cu
Q.26 Which of the following compounds is obtained by Borodine–Hunsdiecker reaction of silver benzoate ?
[1] Fluorobenzene [2] Chlorobenzene [3] Bromobenzene [4] Iodobenzene
Q.27 Which of the following reagents is used for obtaining chlorobenzne from p–chlorophenol ?
[1] Zinc dust [2] Soda lime [3] Sodamide [4] Copper powder
Q.28 All of the following properties are exhibited by chlorobenzene, except :
[1] Almond-like faint smell [2] Volatility
[3] Influammability [4] Nonpoisonous nature
Q.29 In Dow process, chlorobenzene is reacted with which of the following reagents ?
[A] O2 + HCl [B] NaOH [C] H2O [4] Na2CO 3
[1] A and C [2] A and D [3] B and C [4] B and D
Q.30 Condensation of chlorobenzene and chloral hydrate is carried out in the presence of concentrated
sulphuric acid for obtaining ?
[1] D.D.T. [2] Chloropicrin [3] B.H.C [4] Dichlorodiphenylethane
Q.31 The best method for the preparation of chlorobenzene is :
[1] FeCl3
+ Cl 2  –Cl [2] –OH + PCl 5  –Cl + POCl 3 + HCl

[3] hv
+ Cl 2  –Cl [4] hv
–OH + Cl 2  –Cl
 
Q.32 Highest yield of chlorobenzene is obtained in the reaction :
2 Cl 2 Cl
[1] C6H6 
FeCl
 PCl5
[2] Phenol  [3] C6H6 
h
 [4] All the above
3
Q.33 Chlorobenzene is :
[1] Nearly as reactive as methyl chloride [2] More reactive than ethyl bromide
[3] Less reactive than benzyl chloride [4] More reactive than isopropyl chloride
58
Answer Key
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 4 2 4 4 4 1 4 4 3 1 3 3 1 1 2 1 2 1 1 4
Qus. 21 22 23 24 25 26 27 28 29 30 31 32 33
Ans. 4 1 3 4 2 3 1 4 4 1 1 1 3
59
E xercise # 3
Q.1 H2O
In the reaction C2H5MgBr + H2C—CH2  A A is - [MP PET 1994, CBSE –1998]
O
[1] C2H5CH2CHO [2] C2H5CH2CH2OH [3] C2H5CH2OH [4] C2H5CHO
Q.2 Which one will give positive iodoform test [Roorkee- 1995]
[1] CH3 – CH2 – OH [2] CH3 – COO – CH3
[4] CH3 – CH2 – CO – CH2 – CH3 [4] CH3 – CH – CO – CH2 – CH3

|
CH3
Q.3 War gas is formed from [BHU- 1995]

[1] PH3 [2] C2H2 [3] Zinc phosphate [4] Chloropicrin
Q.4 C2H5Cl + KCN  X 

Hydrolysis
 Y, ‘X’ and ‘Y’ are [MP PET- 1995]
[1] C2H6 and C2H5CN [2] C2H5CN and C2H6

[3] C2H5CN and C2H5CH2NH2 [4] C2H5CN and C2H5COOH
Q.5 Iodoform is formed on warming I2 and NaOH with [MP PET- 1995]
[1] C2H5OH [2] CH3OH [3] HCOOH [4] C6H6
Q.6 Carbon-halogen bond is strongest among the following [MP PMT- 1995]
[1] CH3Cl [2] CH3Br [3] CH3F [4] CH3I
Q.7 A compound A has a molecular formula C2Cl3OH. It reduces Fehling solution and on oxidation gives a
monocarboxylic acid (B). A is obtained by action of chlorine on ethyl alcohol. A is [MP PET 1997]
[1] Chloral [2] CHCl3 [3] CH3Cl [4] Chloroacetic acid
Q.8 For a given alkyl group the densities of the halides follow the order [MP PMT-1997]
[1] RI < RBr < RCl [2] RI < RCl < RBr [3] RBr < RI < RCl [4] RCl < RBr < RI
Q.9 AgNO3 does not give precipitate with chloroform because [MP PET-1999]
[1] CHCl3 is inosluble in water [2] CHCl3 does not ionise in water
[3] CHCl3 is an organic compound [4] AgNO3 is insoluble in CHCl3
Q.10 Which of the following alkyl halides is used as a methylating agent [MP PET- 1999]
[1] C2H5Cl [2] C2H5Br [3] C2H5l [4] CH3l
Q.11 In which one of the following conversions phosphorus pentachloride is used as a reagent [EAMCET-1997]
[1] H2C = CH2  CH3CH2Cl [2] HC  CH  CH2 = CHCl
[3] CH3CH2OH  CH3CH2Cl [4] None of these
Q.12 An organic halide is shaken with aqueous NaOH followed by the addition of dil. HNO3 and silver nitrate
solution gave white ppt. The substance can be [JIRMER 1997]
[1] C6H4(CH3)Br [2] C6H5CH2Cl [3] C6H5Cl [4] None of these
60
Q.13 In which alkyl halide. SN2 mechanism is favoured maximum [RPMT 1997]
[1] CH3Cl [2] CH3CH2Cl [3] (CH3)2CHCl [4] (CH3)3C–Cl
Q.14 Reaction of t-butyl bromide with sodium methoxide produces [CPMT 1997]
[1] Isobutane [2] Isobutylene [3] Sodium t-butoxide [4] t-butyl methyl ether
Q.15 When alkyl halides are heated with dry Ag2O, it gives [CBSE 1998]
[1] Ester [2] Ether [3] Ketone [4] AgCl + hydrocarbon
Q.16 DDT is prepared by reacting chlorobenzene with [BHU 1998]
[1] CCl4 [2] CCl3 – CHO [3] CHCl3 [4] Ethane
Q.17 Light
C3H8 + Cl2  C3H7Cl + HCl is an exmple of which of the following types of reactions
[CPMT 1999]
[1] Substitution [2] Elimination [3] Addition [4] Rearrangement
Q.18 Compound A reacts with PCl5 to give B which on treatment with KCN followed by hydrolysis gave propionic
acid. What is A and B respectively [EAMCET 1998]
[1] C3H8 and C3H7Cl [2] C2H6 and C2H5Cl [3] C2H5Cl and C2H5Cl [4] C2H5OH and C2H5Cl
Q.19 Which of the following would be produced when acetylene reacts with HCl [MH CET 1999]
[1] CH3CH2Cl [2] CH3CHCl2 [3] CHCl = CHCl [4] CH2 = CHCl
Q.20 An alkyl bromide (X) reacts with Na to form 4,5-diethyloctane. Compound X is [Roorkee 1999]
[1] CH3(CH2)3Br [2] CH3(CH2)5Br
[3] CH3(CH2)3CH.Br.CH3 [4] CH3(CH2)2CH.Br.CH2CH3
Q.21 False statement is [RPET 1999]
[1] Chloroform is heavier than water [2] CCl4 is non-inflammable
[3] Vinyl chloride is more reactive than allyl chloride[4] Br– is a weak nucleophile as compared to I–
Q.22 Statement “Ozone in atmosphere is decreased by chloro-fluoro-carbon (Cl2F2C)” [RPET 1999]
[1] Is true [2] Is false
[3] Only in presence of CO2 [4] Only in adsence of CO2
Q.23 Number of –bonds present in B.H.C. (Benzene hexachloride) are [RPMT 1999]
[1] 6 [2] Zero [3] 3 [4] 12
Q.24 Which of the following are correct statements about C2H5Br [Roorkee 1999]
[1] It reacts with metallic Na to give ethane
[2] It gives nitroethane on heating with aqueous ethanolic solution of AgNO2
[3] It gives C2H5OH on boiling with alcoholic potash
[4] None of these
Q.25 The use of the product obtained as a result of reaction between acetone and chloroform is
[RPMT 1999]
[1] Hypnotic [2] antiseptic [3] Germicidal [4] Anaesthetic
Q.26 Chloroform with zinc dust in water gives [UPSEAT 2000]
[1] CH4 [2] Chloropicrin [3] CCl4 [4] CH2Cl2
Q.27 When ethyl iodide is heated with silver nitrate, the product obtained is [CPMT 2000]
[1] C2H5Ag [2] Ag–O–NO2 [3] C2H5O–NO2 [4] C2H5I–NO2
61
Q.28 Gem-dibromide is [RPMT 2000]

[1] CH3CH(Br)OH(Br)CH3 [2] CH3CBr2CH3 [3] CH2(Br)CH2CH2(Br) [4] CH2BrCH2Br
Q.29 The correct order of C–X bond polarity is [RPMT 2000]
[1] CH3Br > CH3Cl > CH3I [2] CH3I > CH3Br > CH3Cl
[3] CH3Cl > CH3Br > CH3I [4] CH3Cl > CH3I > CH3Br
Q.30 The product of the reaction CH2 = CH – CCl3 + HBr is [RPET 2000]
[1] CH3 –CH(Br) – CCl3 [2] CH2(Br)–CH2–CCl3
[3] BrCH2 –CHCl – CHCl2 [4] CH3 – CH2 – CCl3
Q.31 R–X + NaOH  ROH + NaX, The above reaction is classified as [RPET 2000]
[1] Nucleophilic substitution [2] Electrophilic substitution

[3] Reduction [4] Oxidation
Q.32 Decreasing order of reactivity of HX in the reaction ROH + HX  RX + H2O [RPET 2000]
[1] HI > HBr > HCl > HF [2] HBr > HCl > HI > HF [3] HCl > HBr > HI > HF [4] HF > HBr > HCl > HI
Q.33 CFxCly [where x + y = 4]. These compounds are not used as refrigerants because [RPET 2000]
[1] These are fluoro carbons [2] These are difficult to synthesis
[3] They deplete ozone layer [4] None of the these
Q.34 CHCl3 and HF lead to the formation of a compound of fluorine of molecular weight 70. The compound is
[RPET 2000]
[1] Fluoroform [2] Fluorine monoxide [3] Fluorine dioxide [4] Fluromethanol
Q.35 When methyl bromide is heated with Na it gives [MP PMT 2000]
[1] CH4 [2] C2H6 [3] C2H4 [4] CH3OH
Q.36 The order of reactivities of the following alkyl halides for a SN2 reaction is [IIT Screening 2000]
[1] RF > RCl > RBr > RI [2] RF > RBr > RCl > RI [3] RCl > RBr > RF > RI [4] RI > RBr > RCl > RF
Q.37 Preparation of alkyl halides in laboratory is least preferred by [Delhi PMT 2000]
[1] Treatment of alcohols [2] Addition of hydrogen halides to alkenes
[3] Halide exchange [4] Direct halogenation of alkanes
Q.38 Which of the following organic compounds will give a mixture of 1–chlorobutane and 2–chlorobutane on
addition of HCl [CPMT 2001]
CH3 H
| |
[1] CH3 – CH –CH = CH2 [2] HC  C – C =CH2 [3] CH2 = CH – CH = CH2 [4] CH2=CH–CH2–CH3
Q.39 When CH3CH2CHCl2 is treated with NaNH2 the product formed is [CBSE 2002]
NH2 NH2
[1] CH3–CH=CH2 [2] CH3–CCH [3] CH3CH2CH [4] CH3CH2CH
Cl NH2
Q.40 Why is chloroform put into dark coloured bottles [MP PET 2002]
[1] To prevent evaporation [2] To prevent from moisture
[3] To prevent it from oxidation to form phosgene [4] To prevent its reaction with glass
Q.41 Which of the following is Teflon [RPMT 2002]
[1] [–CF2–CF2–]n [2] CF2=CF2 [3] CF  CF [4] None of these
62
Q.42 AgNO3 does not give precipitate with CHCl3 because [CPMT 2002]
[1] CHCl3 does not ionise in water [2] AgNO3 does not reacts with CHCl3
[3] CHCl3 is chemically inert [3] None of these
Q.43 What is the main product of the reaction between 2-methyl propene with HBr [RPMT 2002]
[1] 1-bromo butane [2] 1-bromo-2 methyl propane
[3] 2-bromo butane [4] 2–bromo-2 methyl propane
Q.44 Among the following, the molecule with the highest dipole moment is [IIT Screening 2003]
[1] CH3Cl [2] CH2Cl2 [3] CHCl3 [4] CCl4
Q.45 At higher temperature, iodoform reaction is given by [AIIMS 2003]
[1] CH3CO2CH3 [2] CH3CO2C2H5 [3] C6H5CO2CH3 [4] CH3CO2C6H5
Q.46 Iodoform test is not given by [CPMT 2003]
[1] 2–pentanone [2] 3–pentanone [3] Ethanol [4] None of these
Q.47 Which of the following reactions leads to the formation of chloetone [RPMT 2003]
[1] CHCl3 + CH3COCH3 [2] CCl4 + Acetone [3] CHCl3 + KOH [4] CHCl3 + HNO3
Q.48 CH3–CH2–CH2Br + KOH(alc.)  Product , Product in above reaction is [RPMT 2003]
[1] CH3–CH=CH2 [2] CH3–CH2–CH3 [3] [1] and [2] both [4] None of these
Q.49 1,2 di-bromo cyclohexane on dehydro halogenation gives [UPSEAT 2003]
[1] [2] [3] [4] None of these
Q.50 Wurtz reaction of methyl iodide yields an organic compound X. Which one of the following reactions also
yields X . [EAMCET 2003]
dryether
[1] C2H5Cl + Mg  [2] C2H5Cl + LiAlH4 

Ag powder
[3] C2H5Cl + C2H5ONa  [4] CHCl3 


Q.51 Acetyl bromide reacts with excess of CH3MgI followed by treatment with a saturated solution of NH4Cl
gives [AIEEE 2004]
[1] Acetyl iodide [2] Acetamide [3] 2–methyl–2–propanol [4] Acetone
Q.52 Using anhydrous AlCl3 as catalyst, which one of the following reactions produced ethylbenzene (PhEt)
[1] CH3 – CH = CH2 + C6H6 [2] H2C = CH2 + C6H6
[3] H3C – CH3 + C6H6 [4] H3C – CH2OH + C6H6
[CPMT pre. 2004]
Q.53 Which of the following is responsible for depletion of the ozone layer in the upper strata of the atmosphere
[CPMT pre. 2004]
[1] Ferrocene [2] Fullerences [3] Freons [4] Polyhalogens
Q.54 Which of the following is least reactive in a nucleophilic substitution reaction [CPMT pre. 2004]
[1] CH2 = CHCl [2] CH3CH2Cl [3] CH2 = CHCH2Cl [4] (CH3)3C – Cl
Q.55 Chloropicrin is obtained by the reaction of ? [CPMT pre. 2004]
[1] nitric acid on chlorobenzene [2] chlorine on picric acid
[3] nitric acid on chloroform [4] steam on carbon tetrachloride
63
Q.56 Which of the following will not form a yellow precipitate on heating with an alkaline solution of iodine
[CPMT pre. 2004]
[1] CH3CH2CH(OH)CH3 [2] CH3OH [3] CH3CH2OH [4] CH3CH(OH)CH3
Q.57 When benzene is treated with acetyl chloride in presence of AlCl3 gives [RPMT 2004]
[1] C2H5Cl [2] C6H5COCH3 [3] CH3COCH3 [4] C6H5Cl
Q.58 Product formed when C2H5 is reacted with ammonical Cu2Cl2 is
[RPMT 2004]
[1] C2H4 [2] CCl2 [3] CCl2H2 [4] C2Cu2
Q.59 Westrosol is [RPMT 2004]
[1] Ethylene dichloride [2] Acetylene tetrachloride [3] Acetylene dichloride [4] Trichloro ethene
Q.60 When acetylene is treated with aresenic trichloride gives [RPMT 2004]
[1] Lewisite [2] Bakelite [3] Glucoside [4] Boxite
Q.61 Chloroform is tested before anaesthetic use with [RPMT 2004]
[1] Fehling solution [2] heating with AgNO3 and then heated with KOH
[3] Ammonical Cu2Cl2 [4] AgNO3
Q.62 Which of the following will give iodoform test [RPMT 2004]
H CH3
[1] CH3 — C — OH [2] CH3OH [3] CH3CH2CH2OH [4] H3C — C — OH
H CH3
OH
CCl4 / NaOH
Q.63     X, ' X' is [RPMT 2004]
[1] Salicylic acid [2] Ferric acid [3] Sodium benzoate [4] Salicyl aldehyde
Q.64 The compound formed on heating chlorobenzene with chloral in the presence of concentrated sulphuric
acid is
[AIEEE 2004]
[1] Freon [2] DDT [3] Gammexene [4] Hexachloroethane
Q.65 Among the following the most reactive towards alcoholic KOH is
[AIIMS 2004]
[1] CH2 = CHBr [2] CH3COCH2CH2Br [3] CH3CH2Br [4] CH3CH2CH2Br
Q.66 Among the following, the one which reacts most readily with ethanol is [AIIMS 2004]
[1] p–nitrobenzyl bromide [2] p–chlorobenzyl bromide
[3] p–methoxybenzyl bromide [4] p–methylbenzyl bromide
64
Cl
Q.67 with 2 equiv. of Na in ether will yield [JEE (SCR) 2005]

Br
Cl
[1] [2] [3] [4]
Br
Q.68 Which one of the following functional groups can be identified by iodoform test
[VITEEE 2005]
[1] –COCH3 [2] – COOH [3] –CH2OH [4] –CH2–O–CH2–
Q.69 Which of the following undergoes nucleophilic substitution exclusively by SN1 mechanism
[CPMT 2005]
[1] Benzyl chloride [2] Isopropylchloride [3] Chlorobenzene [4] Ethyl chloride
Q.70 Identify X and Y in the following sequence
X
C2H5Br  Y
product  C3H7NH2 [Orissa JEE 2005]
[1] X = KCN, Y = LiAlH4 [2] X = KCN, Y = H3O +

[3] X = CH3Cl, Y = AlCl 3/HCl [4] X = CH3NH2, Y = HNO 2
Q.71 One of the following that cannot undergo dehydrohalogenation is - [J & K 2005]
[1] Iso-propyl bromide [2] Ethanol [3] Ethyl bromide [4] None of these
Q.72 The major product obtained on treatment of CH3CH2CHFCH3 with CH3O–/ CH3OH is [AIIMS 2005]
[1] CH3CH2CH(OCH3)CH3 [2] CH3CH=CHCH3
[3] CH3CH2CH=CH2 [4] CH3CH2CH2CH2OCH3
Q.73 Which of the following is liquid at room temperature - [AFMC 2005]
[1] CH3I [2] CH3Br [3] C2H5Cl [4] CH3F
Q.74 Which of the following haloalkanes is most reactive - [KCET 2005]
[1] 1-chloropropane [2] 1-bromopropane [3] 2-chloropropane [4] 2-bromopropane
HALOBENZENE
Q.75 C6H5Cl prepared by aniline with :
[IIT 1984]
[1] HCl [2] Cu2Cl 2
[3] Cl 2 in presnece of anhydrous AlCl 3 [4] HNO2 and then heated with Cu2Cl 2
Q.76 An important insecticide is obtained by the action of chloral on chlorobenzene. It is :
[KCET 1989]
[1] BHC [2] Gammexene [3] DDT [4] Lindane
Q.77 C6H5CH2Cl + KCN (aq.)  X+ Y
Compounds X and Y are : [BHU 1979]
[1] C6H6 + KCl [2] C6H5CH2CN + KCl [3] C6H5CH3 + KCl [4] None of these
65
Q.78 Chlorobenzene is :
[1] Less reactive than benzyl chloride [2] More reactive than ethyl bromide
[3] Nearly as reactive as methyl chloride [4] More reactive than ispropyl chloride
Q.79 What is the decreasing order of reactivity amongest the following compounds towards aromatic
electrophilic substitution : [IIT 1995]
I. Chlorobenzne II. Benzene III. Anilinium chloride IV. Toluene
[1] I > II > III > IV [2] IV > II > I > III [3] II > I > III > IV [4] III > I > II > IV
Q.80 The commercial uses of DDT and benzene hexachloride are :
[1] DDT is a herbicide, benzene hexachloride is a fungicide
[2] Both are insecticides
[3] Both are herbicides
[4] DDT is a fungicide and benzene hexachloride is a herbicide
Q.81 DDT can be prepared by reacting chlorobenzene (in the presnece of conc. H 2SO 4) with :
[1] Cl2 in ultraviolet light [2] Chloroform
[3] Trichloroacetone [4] Chloral hydrate
200– 250ºC
Q.82 Following equation illustrates : C 6 H 5 Cl + 2NaOH 
200 atm
 C H ONa + NaCl + H O
6 5 2
[Bihar CEE 1995]

[1] Dow’s process [2] Kolbe’s process
[3] Carbylamine test [4] Haloform reaction
Q.83 Replacement of Cl of chlorobenzene to give phenol requires drastic condition but chlorine of
2,4–dinitrochlorobenzene is readlly replaced because : [CBSE 1997]
[1] NO 2 make ring electron rich at ortho and para
[2] NO2 withdraw e– from meta position
[3] NO 2 donates e– at meta position
[4] NO2 withdraws e– from ortho/para position
Q.84 The chlorobenzene is generally obtained from a corresponding diazonium salt by reacting it with :
[MP PMT 2000]
[1] Cu2Cl 2 [2] CuSO 4 [3] Cu [4] Cu(NH3)42+
Q.85 The reaction between chlorobenzene and chloral in the presence of concentrated sulphuric acid produces
[Pb. PMT 2001]
[1] Gammexane [2] pp–dichloro diphenyl trichloro ethane
[3] Chloropicrin [4] Benzene hexachloride
Q.86 Aryl halide is less reactive than alkyl halide towards nuclophilic substitution because :
[Rajasthan PMT 2002]
[1] Less stable carbonium ion
[2] Due to large C–Cl bond energy
[3] Inductive effect
[4] Resonance stabilization and sp2 hybridisation of C attached to halide
66
Q.87 Bottles containing C6H5I and C6H5CH2I lost their original labels. They were labelled A and B for testing.
A and B were separately taken in test tubes and boiled with NaOH solution. The end solution in each
tube was made acidic with dilute HNO 3 and then some AgNO 3 solution was added. Substance B give
a yellow precipitate. Which one of the following statements is true for this experiment [AIEEE 2003]
[1] A was C6H5I [2] A was C6H5CH2I
[3] B was C6H5I [4] Addiotion of HNO 3 was unnecesary

Q.88 The compound formed on heating chlorobenzene with chloroal in the presence of conc. H2SO 4 is :
[AIEEE 2004]
[1] Hexachloroethane [2] D.D.T. [3] Freon [4] Gammaxene
CH2
Q.89 What will be the product in the following reaction NBS [BHU 2005]

Br CH3
CH3
[1] [2]
Br
CH3
CH3Br
[3] [4]
Br
CCl3
Q.90 1 eqv . of Br / Fe
2
     A. Compound A is - [Orissa JEE 2005]
CCl3 CCl3
Br
[1] [2]
Br
CCl3
CCl3
[3] [4]
Br Br Br
Q.91 When phenyl magnesium bromide reacts with t-butanol, the product would be - [IIT 2005]
[1] Benzene [2] Phenol [3] t-butyl benzene [4] t-butyl phenyl ether
Q.92 Analyse the following reaction and identify the nature of A and B [Karala CET 2005]
HBr HBr
B hv
  A
Br
[1] Both A and B are [2] Both A and B are
Br
Br Br
[3] A is & B is [4] A is & B is
Br Br
67
Answer Key
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 2 1 2 4 1 3 1 4 2 4 3 2 1 2 2 2 1 4 2 4
Qus. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 3 1 2 2 1 1 3 2 3 2 1 1 3 1 2 4 4 4 2 3
Qus. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Ans. 1 1 4 3 4 2 1 1 1 2 3 2 3 1 3 2 2 4 4 1
Qus. 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80
Ans. 4 1 1 2 2 3 4 1 2 1 2 2 1 4 4 3 2 1 2 4
Qus. 81 82 83 84 85 86 87 88 89 90 91 92
Ans. 4 1 4 1 2 4 1 2 1 1 1 3
68
Benzene
1. Aromatic Compounds : Main Source
Bituminous coal when subjected to destructive distillation in the absence of air [1000º–1200ºC] the chief
constituent obtained is coal tar.
Fractional distillation of coal tar : Different fractions are :
Fraction Temperature Main constituents
(a) Light oil 80 – 170ºC Benzene, toluene, xylene etc.

(b) Middle oil 170º – 230ºC Naphthalene,
(carbolic oil) Phenol etc.
(c) Heavy oil 230º 270ºC Cresols, naphthalene
(d) Green oil 270º – 360ºC Anthracene
(e) Pitch Residue Carbon
2. Characteristic of Aromatic Compounds

[i] Aromatic compounds contain high percentage of carbon. They burn with smoky flame,
[ii] Aromatic compounds have the cyclic system and contain (4n + 2) electrons [Huckel rule].
Where n = 0, 1, 2, 3, .............
Dipropylcyclopropenium n=0 2–electron
perchlorate
Benzene, pyridine, pyrrole, n=1 6–electron
Furan, thiophen etc.
Napthalene n=2 10–electron
Anthracene n=3 14–electron
Some Formulae of Benzene :
[a] Ladenberg’s prism formula : [b] Claus-diagonal formula :
[c] Dewar’s parallel formula :
[d] Armstrong and Baeyer’s centric formula :
[e] Thiele’s formula :
Criteria for aromaticity :

Aromaticity means :
– Unusual stability :
Aromatic compounds are hightly stable, as they have low heat of hydrogenation and low heat of combustion.
– Substitution reaction :
Aromatic compounds although contain double bond but give electrophilic substitution reaction (nitration,
halogenation, sulphonation etc.)
– Resistant to oxidation :
69
Aromatic compounds are stable. Benzene ring is not affected by aq. KMnO4, HNO3 etc.
Criteria : Mainly aromaticity is due to
[i] Resonance energy
[ii] Huckel rule
[iii] Cyclic clouds of delocalised -electrons
3. Few Groups
C6H5 – [Phenyl] C6H5CH2 – [Benzyl]
C6H5CH < [Benzal] or [Benzylidene] C6H5C  [Benzo] or [Benzylidyne]
CH3 – C6H4 – [o, m, p – Tolyl]
Few Compounds :
 = C6H5 — or
Hydrocarbons :
 – CH3 – C2H5 – CH(CH3)2
Toluene Ethyl benzene Isopropyl benzene
– C(CH3)3  – CH = CH2
t–Butyl benzene Vinyl benzene (Styrene)
CH3
|
CH3
(o-xylene)
1,2-[ortho]
CH3
|
|
CH3
1,4-(para)
CH3
|
H3C CH3
1,3,5-Trimethyl benzene
[Mesitylene]
70
4. Benzene
[i] Discoverer : Michael Faraday
[ii] C–hybridisation : sp2
[iii] Geometry – Hexagonal
[iv] Bond angle : 120º
[v] C–C Bond length : 1.39Å
[vi] C–H Bond length : 1.09 Å
[vii] Resonance in bezene :
[ix] Number of angles of 120º : 18

[x] Localized and delocalized –orbital
Localized –orbital Localized –orbital
2 3 2 3
1 4 1 4
6 5
6
5
Obviously, each orbital formed in the partial overlapping is attracted by two carbon nucleus hence less
stable.
Delocalized p-orbital :
4.1 Methods of Preparation of Benzene :

[1] Isolation From ‘Light Oil Fraction – Industrial method :
In ‘light oil’, at least 60–65% benzene is present. Alkaline impurities (aniline, pyridine, quinolene, etc.) are
removed by washing ‘light oil’ with cold and conc. H2SO4. The acidic impurities are removed by washing
with dilute NaOH solution. After that, NaOH is removed by washing with water. Three fractions are obtained
at different temperature ranges by fractional distillation of the neutral sample of oil.
71
[i] 90% Benzol (90’s benzol). 80–110º
[ii] 50% Benzol (50’s benzol). 110–140º [iii] Solvent naphtha – 140º–170º
The 90% benzol contains about 70% benzene 24% toluene and remaining xylenes. Fractional distillation
gives benzene at 80º, toluene at 110º and a mixture of all the three xylenes at 137–145º. Crystals are
formed on cooling benzene from which pure benzene can be obtained by melting the crystals.
[2] Decarboxylation of Sodium Benzoate – Laboratory Method :
Benzene is formed on dry distillation of sodium benzoate with soda lime.
Dry distillation
C6H5COONa + NaOH   C6H6 + Na2CO3
[3] Reduction of Phenol :
Dry distillation
C6H5OH + Zn   C6H6 + ZnO
[4] Reduction of Phenol – Fisher Mehod :
MoO3
C6H5OH + H2   C6H6 + H2O
[5] Hydrolysis of Benzene sulphonic Acid :

C6H5SO3H + H2O (steam)   
dil.H C l
 C H + H SO
6 6 2 4
[6] Reduction of Benzenediazonium Chloride :
C6H5N2Cl + C2H5OH C6H6 + CH3CHO + N2 + HCl
Hypophoshorus acid (H3PO2) or sodium stannite (SnCl2 + NaOH) or formic acid can also be used for
reduction in place of ethanol.
C6H5N2Cl + H3PO2 + H2O C6H6 + H3PO3 + N2 + HCl
SnCl2
C6H5N2Cl + 2H 
NaOH
 C6H6 + N2 + HCl
C6H5N2Cl + HCOOH C6H6 + CO2 + N2 + HCl

[7] Hydrolysis of Phenylmagnesium bromide :
C6H5MgBr + H2O C6H6 + Mg(OH)Br
[8] Reduction of Chlorobenzene :
Ni / Al
C6H5Cl + NaOH + 2H 
 C6H6 + NaCl + H2O
[9] Trimerisation of Acetylene :
Ni(CO)4 (C6H5 )3 P
3C2H2   C6H6
In benzene
[10] Hydroforming of n–Hexane :
Heavy metal oxides
CH3(CH2)4CH3   C6H6 + 4H2
500º
Benzene is a colourless liquid (boiling point, 80º), having a characteristic smell. It forms a colourless
crystaline solid (melting point, 5.4º) on cooling. It burns with smoky or sooty flame. It is lighter than water
(relative density, 0.8790) and is immiscible with water. Being nonpolar in nature. It is miscible with many
organic solvents, like alcohol ether, acetone, acetic acid, carbon tetrachloride, carbon disulphide, etc.
4.3 Reaction :
Benzene is a compound having very low reactivity, because it remains unaffected by many common reagents,
like HCl, KOH, NaOH, KMnO4, K2Cr2O7, etc.
Benzene shows the following types of reactions :
[a] Addition
[b] Electrophilic substitution
[c] Oxidation
[d] Pyrolysis
[e] Pi complex formation
4.3.1 Addition Reaction :
1. Hydrogenation
[i] Catalytic Hydrogenation :
72
2 3H

Ni / Pt / Pd
[ii] Reduction with HI

Benzene on heating with conc. HI at 250º undergoes complete reduction to form cyclohexane.
CH3
12HI, 250º
 +
–6 I2
Methylcyclopentane
[iii] Birch Reduction :

When benzene in ethanol solution is reacted with sodium and liquefied ammonia, then 1,4–cyclohexadiene
is formed. This partial reduction of benzene (dihydrogenation) is called Birch reduction or Birch reaction.
Na  liquefied NH
3

in C2H5OH
2. Halogenation :
hv
+ 3Cl2 

Benzene hexachloride is also known by many other names e.g., B.H.C., gammaxene, gammane,
lindane 666 (triple six) and 1,2,3,4,5,6–hexachlorocyclohexane. It was found that the  isomer is a very
strong insecticide and pesticide, hence the names gammaxene and gammane.
3. Ozonolysis :
+ 3O3
C6H6O9 + 3H2O 3 + 3H2O2
3H2O2 + 3Zn 3ZnO + 3H2O

4.3.2 Electrophilic Subsitution :
A continuous  cloud is spread above and below the benzene ring. Due to this, an electrophile is attracted
towards the benzene ring. This electrophile removes proton (the weaker electrophile) and take its place in
order to gain greater stability and forms an electrophilic substitution product or SE product. This
process is called aromatic electrophilic substitution.
Nonaromatic intermediate carbocation formed in an aromatic electrophilic substitution reaction is known

as Wheland intermediate.
73
Mechanism of Aromatic SE reaction :
H
H E
H H H + H
+ E+
Slow
H H H H
H H
Cyclic Secondary carbocation
Cyclic secondary carboncation formed is satibilised by resonance.
H E H E H E
H + H H H H + H
H H H + H H H
H H H
E
H E
H + H +
—H
Fast
H H
H
This is called as SE2 mechanism i.e.; substitution electrophilic bimolecular reaction.
4. Halogenation :
Cl–Cl + AlCl3
5. Nitration :
NO2 NO2 NO2

| | |
  
NO2 NO2 NO2
<60º >60º Fummg H2SO4
 
–H Nitrobenzene –H O2N 100º O2N NO2
m-Dinitrobenzene  1,2,3-Trinitrobenzene (TNB)
–H
6. Sulphonation :
H2SO4 SO3 + H2O
(Conc.)
– 
H SO3 + H SO3H
| | |
+ SO3
80º
Benzenesulphonic acid
74
7. Friedel–Crafts Reaction :
Friedel–Crafts reaction involves replacement of hydrogen atom of an aromatic ring by a carbocation
species obtained from a compound in the presence of anhydrous aluminium chloride. Fridel–Crafts reaction
is always carried out in nitrobenzene (boiling point. 211º) medium and in the presence of anhydrous AlCl3.
[i] Friedel-Crafts Alkylation :
Anhyd. AlCl
3  C H – CH  HCl
C6H6  CH3 – Cl  6 5 3
Methyl chloride Toluene
Anhyd. AlCl
3  C H – C H  HCl
C6H6  C2H5 – Cl  6 5 2 5
Ethylbenzene
Anhyd. AlCl3
C6H6  CH3 CH2 CH2 – Cl   C6H5 – CH(CH3 )2  C6H6 – CH2 CH2 CH3
nPr opyl chloride Cumene (67%) nPr opylbenzene (33%)
A mixture of cumene and n–propylbenzene is also obtained on taking propylene in place of n–propyl
chloride in the above reaction.
Anhyd.
2C6H6 + CH2Cl2 
AlCl
 C6H5 – CH2 – C6H5  2HCl
3 Diphenylmethane
Anhyd.
3C6H6 + CHCl3 
AlCl
 (C6H5 )3 CH + 3HCl
3
Triphenylmethane
Anhyd.
3C6H6 + CCl4 
AlCl3
 (C H ) C – Cl + 3HCl
6 5 3
Trityl chloride
[ii] Friedel–Crafts Acylation :
[a] Acetylation :
Anhyd. AlCl3
C6H6 + ClCOCH3   C6H5 COCH3 + HCl
Acetyl chloride Acetophenone
Anhyd. AlCl3
C6H6 + (CH3 CO)2 O   C6H5 COCH3 + CH3COOH
Acetic anhydride Acetophenone
[b] Benzoylation :
Anhyd. AlCl3
C6H6 + ClCO C 6 H 5   C 6 H5 COC 6 H5 + HCl
Be nzoyl chlo rid e benzophenone
Anhyd. AlCl3
2C 6 H6 + ClC O C l   C 6 H5 CO C 6 H5 + 2HCl
Benzene Phosgene Be nzop hen one
(Excess)
[iii] Formylation, or Gattermann–Koch Aldehyde Synthesis :


HCl  CO [H – CO – Cl]

3 A n h yd. A lC l
C 6H6  H – C O – C l        C 6H5 C H O  H C l
F o rm yl ch lo rid e B e n za ld e h yd e
The above conversions can be carried out by taking many other compounds in place of anhydrous AlCl3,
e.g., FeCl3, FeBr3, SnCl2, ZnCl2, BF3, etc.
8. Deuteration :
By using deuterosulphuric acid a hydrogen atom of benzene can be substituted by deuterium.
 
C 6 H5 – H  D 2 S O 4   C 6H5 – D  HDSO4
D euteroben ze ne
9. Mercuration :
Benzene on heating with mercuric acetate forms Acetoxymercuribenzene.
CH3COO
Hg + H–C6H5 CH3COOH +
CH3COO CH3 COOHg–C6H5
Phenylmercuric acetate
(Acetoxymercuribenzene)
75
4.3.3 Oxidation :
10. Catalytic Air Oxidation :
Oxidation of benzene by air in the presence of vanadium pentaoxide can be carried out as follows :
[i] At 300º – Phenol is obtained as the major product
H OH
| |
V2O5
+ [O]  
300º
Phenol
[ii] At 450º – Maleic anhydride is obtained as the major product.
V O
2 5
+ 9[O]  O + 2CO2 + 2H2O
450º
O
Maleic anhydride
11. Silver Oxide Oxidation :

Mainly p-benzoquinone is formed when oxidation of benzene is carried out by silver oxide and HNO3.
O
||
Ag O
2 
+ 3[O]  + H2O
HNO3
||
O
p-Benzoquinone
12. Combustion :
2C6H6  15O2 12CO2  6H2 O
4.3.4 Catalytic Pyrolysis :
When the vapours of benzene are passed through red-hot copper or iron tube at 600º biphenyl is formed.
C6H5–H + H–C6H5 C6H5–C6H5 + H2
4.3.5  Complex Formation :
A complex is obtained on heating benzene and chromic chloride with anhydrous AlCl3 and Al2O3 at 180º,
which on reduction forms dibenzenechromium (C6H5)2Cr.
AlCl  Θ
3 
2C6H6 + CrCl3 
Al 2O3
(C6H6 )2 Cr AlCl4 
Reduction
 Cr
A complex
Dibenzenechromium
Dibenzenechromium is an organometallic compound.

Dibenzenechromium is a charge transfer complex or a –complex or a sandwich compound. In this,
electron charge of  clouds of two benzene rings is attracted towards the d–orbital of chromium atom. Here
benzene behaves as a  base.
4.4 Uses of Benzene :
[1] As an industrial solvent.
[2] In dry cleaning.
[3] As a constituent of power alcohol.
[4] In the manufacture of an insecticide and pesticide.
[5] In the manufacture of an explosive.
[6] In the manufacture of dyes.
[7] In the manufacture of medicines.
[8] In the manufacture of perfumes.
[9] In the synthesis of many aromatic compounds.
[10] As a fuel.
76
5. Directive influence of substituent
(i) Directive influence of substituent ‘S’
–S (Compound)
[i] S–Activates the benzene ring (Pumps in the electron density)
[ii] S–Exerts + M or + R effect
[iii] S–Either negatively charged or contains lone pair of electrons.
Examples :
 2E


 +
– 2H
Supposing S = NH2
Lone pair of electrons present on the N–atom interact with delocalised p-orbital of benzene ring and increases
the electron density at ortho and para positions. Obviously the electrophile attacks at o and p positions.
Decreasing order of o–, p-directing strength :

–O– > –NH2 > – NHR > – NR2 > –OH > –OR ; –NHCO > –COOR > –R > Ar > –X
When an electrophilie attacks at ortho and para positions of Toluene, the cyclic secondary carbocation
formed is especially stable when compared with the carbocation formed by attack of electrophilie at meta
position.
CH3 CH3 CH3
+ H H
Y +
Y Y
ortho +
(More Stable)
CH3 CH3 CH3
Y+ +
para (+)
H Y H Y
(More Stable)
CH3 CH3 CH3
Y+ +
H H etc.
meta
Y Y
+
77
In Toluene thus attack of electrophilie takes place faster at ortho and para positions when compound with
attack at meta position.
(ii) Directive influence of substituent ‘G’
–G (compound)
G–(m-directing)
[i] G–Deactivates the ring [withdraws electron density]
[ii] G–Exerts –M or –R effect
[iii] G–Either positively charged or electron attracting character.
Examples : , –NO2, –CN, –SO2OH, –CHO, –COOR etc.
E



H
–NO2, withdraws electron density from the benzene ring and makes the ortho and para positions as
electron deficient centres. Obviously electrophile attacks at m-position, since it possesses a relatively
high electron density.
– –
O O O O O O
N N N
+
etc.
+
Decreasing order of m-directing strength :
> –NO2 > –CN > –SO2OH > –CHO > –COR > –COOH > –COOR > –CONH2 > –NH3
When an electrophilie attacks at meta position of nitrobenzene, the cyclic secondary carbocation formed
is more stable than the carbocation formed by attack of electrophilie at ortho and para position of
nitrobenzene.
O O O O
+ +
N N
H
+
Y+
Y
ortho
(highly unstable)
O O O O O O
+ + +
N N N
+
Y+
para +
H Y H Y
(highly unstable)
78
O O O O O O O O
+ + + +
N N N N
Y+ + +
H H H
meta
Y Y Y
+
6. Toluene, C6H5CH3
6.1 Methods of Preparation
1. From ‘Light Oil’ Fraction – Industrial Method :
Toluene fraction can be collected by distillation at 110º after separation of benzene from 90% benzol.
2. By Hydroforming of n–Heptane :
Heavy metal CH3

oxides
CH3(CH2)5CH3  + 4H2

500º
3. By Friedel–Crafts Methylation of Benzene :
AlCl3
C6H5–H + Cl–CH3   C6H5–CH3 + H–Cl
4. By Wurtz–Fitting Reaction :
2Na. Ether
C6H5–I + I–CH3 
 C6H5–CH3
–2NaI
5. By Dehydroxylation of Cresols :
Dry distillation
CH3 – C6H4 – OH  Zn   CH3–C6H5 + ZnO
Cresol (o, m or p)
6. By Decarboxylation of Toluic Acids :
CaO
CH 3 – C6H4 – COONa  NaOH 
Dry distillation
 CH –C H + Na CO
3 6 5 2 3
Sodium toluate
(o, m or p)
7. By Hydrolysis of Toluene Sulphonic Acids :

CH3 – C6H4 – SO3H  HOH  CH –C H + H SO
Conc. acid 3 6 5 2 4
Toluene sulphonic acids
(o, m or p)
8. By Reduction of Benzyl Chloride :

C6H5–CH2Cl + 2H C6H5–CH3 + HCl
9. By Reduction of Toluenediazonium Chlorides :
CH3 – C6H4 – N2Cl  2H C6H5–CH3 + N2 + HCl

Toluenediazonium chlorides
(o, m or p)
Ethanol, hypophoshorous acid (H3PO2), sodium stannite (SnCl2 + NaOH) or formic acid can be used as
the reducing agents.
79

Toluene is a colourless liquid (boiling point 111º). It has benzene–like smell. It is lighter than water and
immiscible with water. It is miscible with organic solvents, like alcohol, ether, benzene, etc. It also burns
like benzene with smoky and sooty flame.
6.3 Reactions :
The following three types of reactions are shown by Toluene :
[A] Reactions due to benzene nucleus.
[B] Reactions due to methyl side chain.
[C] Reactions due to whole molecule (Combustion)
6.3.1 Reactions Due to Benzene Nucleus :

1. Catalytic Hydrogenation :
Ni / Pt CH3
CH3 + 3H2  

Methylecyclohexane
2. Nitration :
CH3 CH3
CH3 | | CH3
| NO2 |
H SO H SO NO2 H SO
2
4 2
4 2
4
HNO3 + HNO3 HNO3
o–Nitrotoluene
NO2
NO2
p–Nitrotoluene 2,4–Dinitrotoluene
CH3
|
O2N NO2
NO2
2,4,6–Trinitro toluene (TNT)
3. Sulphonation :
CH3 CH 3 CH3
| | SO2OH |
Conc.
H2 SO4
 +
o-Toluene sulphonic |
acid SO2OH
p-Toluene sulphonic
acid
4. Alkylation :
CH3 CH3 CH3

| | |
CH3
FeBr
3
 +

|
o-Xylene CH3
p-Xylene
80
5. Free Radical Nuclear Additive Chlorination :
hv
C6H5CH3 + 3Cl2   C6H5 CH3 Cl6
Toluene hexachloride
6. Nuclear Electrophilic Substitutive Chlorination :
CH3 CH3 CH3

| | |
Cl
FeBr
3
 +
Cl2
o-Chlorotoluene |
Cl
p-Chlorotoluene
6.3.2 Reactions Due to Methyl Side Chain :

7. Free Radical Side Chain Substiutive Chlorination :
2  Cl Cl2 Cl2
C6H5–CH3  C6H5 – CH2 Cl   C6H5 – CHCl2   C6H5 – CCl3
110º 110º 110º
Benzyl chloride Benzal chloride Benzotrichloride
8. Oxidation :
Benzoic acid is obtained on oxidation of toluene by alkaline permanganate or acidified dichromate or
dilute nitric acid.
C6H5–CH3 _ 3[O] C6H5–COOH + H2O
If more than one side chain is present, then the same number of COOH groups will be formed for example,
phthalic acid is formed from o-xylene.
CH3 COOH
3[O]


–H2O
CH3 COOH
o-Xylene Phthalic acid
9. Etard’s Reaction :
A complex is formed by the reaction of toluene and chromyl chloride in carbon tetrachloride solution. This
complex gives benzaldehyde on hydrolysis.
C6H5–CH3 + 2CrO2Cl2 [C6H5–CH(OCrCl2OH)2]
HOH
[C6H5–CH(OCrCl2OH)2]  C6H5–CH=O
6.3.3 Reaction due to Whole Molecule :

10. Combustion :
C6H5–CH3 + 9O2 7CO2 + 4H2O
6.4 Uses :
[1] As a constituent of aviation gasoline.
[2] As a solvent.
[3] In the manufacutre of explosive.
[4] In the manufacture of dyes.
[5] In the manufacture of medicines.
[6] In the manufacture of perfumes.
[7] In the synthesis of many aromatic compounds.
81
Solved Example
Ex.1 Which of the following is not correctly matched :
[1] Hydrolysis of phenyl magnesium iodide – benzene
[2] –Isomer of BHC – lindane
[3] (2n + 4) Rule – aromaticity
[4] Trimerisation of propyne – mesitylene
Ans. [3]
Sol. The Huckel rule to account for aromaticity is closed ring of (4n + 2) electrons.
Ex.2 The resonance of the –electron cloud in the benzene ring was confirmed after ozonolysis of :
[1] Benzene [2] Toluene [3] o–Xylene [4] None of these
Ans. [3]
Sol. Benzene is an aromatic hydrocarbon having carbon atom in sp2 hybridized and, one p-orbital of carbon
remains unhybridized, which overlaps colaterally to form a continous –electron cloud both above and
below the plane of the benzene ring. There are two resonating structure of benzene.
Ex.3 Ozonolysis of benzene yields :

[1] Glyoxal [2] Glycerine [3] Glycol [4] Glycerol
Ans. [1]
Sol. Ozonolysis of benzene yields glyoxal. Benzene adds three molecules of ozone and forms benzene
triozonide which on decomposition with water gives three molecules of glyoxal.
C6H6  3O3 C6H6 O9

benzene ozone benzene triozonide
C6H6O9 H–C=O
H2O |
  3
H–C=O
benzene trizonide Glyoxal
Ex.4 Which of the following will show aromatic character :
I II III IV
[1] I, II and III [2] II and III [3] II and IV [4] All the four
Ans. [3]
82
Sol. Benzene has 6 electrons (2 from each double bond) present in cyclic continous form.
benzene furan
Furan also has 6 electrons present in continous cyclic cloud, note that the unused pair of electrons
present in p–orbitals is involved in overlapping forming sextet.
Ex.5 Benzene undergoes subsitution reaction more easily than addition because :
[1] It has cyclic structure [2] It has three double bonds
[3] It has six hydrogen atoms [4] Of resonance
Ans. [4]
Sol. If there were no resonance in benzne,  electrons would have not been delocalised and hence easily
available to undergo addition reactions as in ethylene. Further the subtituted benzene is stable due to
resonance.
Ex.6 Which of the following reagents and conditions convert benzene to chloro–benzene :
[1] Cl 2, sunlight, heat [2] HCl, heat [3] HCl, sunlight, heat [4] Cl 2, AlCl 3, cold
Ans. [4]
Sol. Chlorination of benzene is carried out by chlorine in presence of halogen carrier like AlCl 3.
Ex.7 Which of the following structures correspond to the product expected, when excess of C6H6 reacts with
CH2Cl 2 in presence of anhydrous AlCl3 :
[1] CH [2] CHCl2

|
Cl
Cl
|
[3] C [4] CH2
|
Cl
Ans. [4]
Sol. The reaction takes place as follows :
CH2
+ ClCH2Cl +
Ex.8 Benzene reacts with n-propyl chloride in the presence of anhydrous AlCl 3 to give predominantly :
[1] n–Propylbenzene [2] Isopropylbenzene
[3] 3–Propyl–1–chlorobenzene [4] No reaction
Ans. [2]

Sol. Propyl carbonium ion, CH3CH2 CH2 is primary carbonium ion, it rearranges to the more stable secondary

carbonium ion CH3 CHCH3, which then reacts to form isopropylbenzene.
83
 
CH3–CH–CH2 CH3–CH–CH3
|
H
propyl carbonium ion (1º) isopropyl carbonium ion (2º)
Ex.9 Which of the following reactions of benzene does not account for the three ‘C = C’ bonds in the molecule–
3 FeBr
[a] Benzene + Br2 
conc. H SO
 bromobenzene + HBr
2 4
[b] Benzene + HNO 3  nitrobenzene + H2O

[c] Benzene + 3O 3  Triozonide
Ni
[d] Benzne + 3H2  cyclohexane
[1] a, c [2] b, d [3] b, c, d [4] a, b
Ans. [4]
Sol. a and b are the electrophilic subsitution reactions and do not account for the C = C bond reaction.
Ex.10 The function of anhydrous aluminium chloride in the Friedel–Craft’s reaction is :
[1] Absorb water [2] To absorb hydrochloric acid
[3] To produce an electrophile [4] To produce nucleophile
Ans. [3]

Sol. AlCl 3 + CH3Cl  AICl 4– + CH3
electrophile
CH3

CH
3

toluene
Q.11 In which of the following reaction t–butylbenzene is formed :
BF3 .HF
[1] Benzene + t–butyl chloride, AlCl 3 [2] Benzene + (CH3)2C = CH2  
H2SO4
[2] Benzene + t–butyl alcohol   [4] All of these
Ans. [4]
CH3
|
CH3–C–CH3
CH3 |
| AlCl3
Sol. + CH3–C–Cl   + HCl
|
CH3
CH3
|
CH3–C–CH3
CH3 |
BF .HF
3
+ C = CH2 
CH3
CH3
|
CH3–C–CH3
CH3 |
| H2 SO4
+ CH3–C–OH 
 + H2O
|
CH3
Ex.12 The order of reactivity of :
–CH3 (I), –CH2–CH3 (II), –CH(CH3)2 (III) and –C(CH3)3 (IV)
Where  = C6H5
[1] I > II > III > IV [2] IV > III > II > I [3] II > I > III > IV [4] III > II > I > IV
Ans. [1]
84
Sol. More are the number of –hydrogen present in the alkyl group attached to the benzene ring more
pronounced will be the hyperconjugation and the benzene ring will be more electron rich and easily be
attacked by an electrophile. –hydrogen in –CH3, –CH2 –CH3, –CH(CH3)2 and –C(CH3)3 respectively
are three, two one and zero.
Light
Ex.13 Ethylbenzene + Cl 2   (main) compound is :
[1] o– & p– Chloroethylbenzene [2] 1–Chloroethylbenzene

[3] 2–Chloroethylbenzene [4] m–Chloroethylbenzene
Ans. [2]
Cl
|
C2H5 CH–CH3
| |
Sol. Light
+ Cl 2 
1-chloroethylbenzene
Ex.14 Which of the following triad of group activates the benzene ring and directs the electrophille to o– and
p–position for substitution :
[1] –NO2, –CHO, –COOH [2] –OH, –O –, –CH3
[3] –OH, –SO2OH, –NO2 [4] –NH2, –CHO, –SO2OH
Ans. [2]
Sol. Groups given in [2] activate the benzene ring and directs the electrophile towards o– and p– positions
for substitutuion.
CrO2 Cl2 H2O

Ex.15 –CH3  A  B
The functional group present in B and name of the reaction would be :

[1] –CHO, Gattermann aldehyde synthesis [2] –CHO, Etard reaction
[3] –COCH3, Friedel Crafts reaction [4] –CHO, Oxo reaction
Ans. [2]
Sol. The compound ‘B’ is benzaldehyde and the reaction is called Etard reaction.
Ex.16 Formation of which of the following compound confirms the unsaturation character of benzene :
[1] Cyclohexane [2] Gammexane [3] Triozonide [4] All the above
Ans. [4]
Sol. Formation of all the three compounds are the result of addition reaction. Hence confirm the unsaturation
nature of benzene.
Ex.17 The possible isomers of C7H7Cl will be :
[1] 5 [2] 4 [3] 3 [4] 2
Ans. [2]
Sol. There are four isomers o,m & p–chlorotoluenes and benzyl chloride.
Ex.18 Toluene may be prepared by :
[1] Toluic acid [2] Cresol
[3] Toluene sulphonic acid [4] All the above
85
Ans. [4]
Sol. Toluene may be prepared by all the above compounds descrbied earlier.
Ex.19 Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH gives
:
[1] o–Cresol [2] p–Cresol
[3] 2,4–Dihydroxy toluene [4] Benzoic acid
Ans. [4]
2 Cl Cl2 Cl2
Sol. C6H5CH3 
hv
C6H5CH2Cl   C6H5CHCl2   C6H5CCl3
NaOH NaOH NaOH
C6H5CH2OH C6H5CHO C H
6 5COOH
Ex.20 Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with :
[1] SO2Cl 2 [2] SOCl 2 [3] S2Cl 2 [4] NaOCl
Ans. [1]
CH3 Cl or CH2Cl
2

Sol. SO2Cl2
86
E xercise # 1
Q.1 Which one of the following halide is most unlikely to yield product when react with benzene in presence
of anhydrous aluminium chloride :
[1] CCl4 [2] CH3CH2Cl [3] C6H5Cl [4] CH3CHClCH3
Q.2 Which one of the folloiwng is benzo radical :
[1] C6H5– [2] C6H4 < [3] C6H5CH2– [4] C6H5–C

Q.3 Benzene + anhydrous AlCl3 + Carbonyl chloride A.
Benzene + anhydrous AlCl3 + Chloroformamide B.
Product A and B are :
[1] Benzoyl chloride, benzamide [2] Benzylchloride, Benzylaminoformate
[3] Benzylchloride, Benzamide [4] Benzoyl chloride, Benzylaminoformate
H3O 
Q.4 Benzene + Conc. H2SO 4 
I
 ArSO3H 
II
 ArH + H2SO4. In the above sequence, the II reaction

is known as :
[1] Sulphonation [2] Elimination [3] Protonolysis [4] Dehydrosulphonation
Q.5 Dibenzene chromium is a :
[1] Sandwich compound [2] Complex
[3] Both the above [4] None of the above
Q.6 Reaction of benzene with n–propyl bromide in presence of FeBr 3, the chief product is :
[1] n–propyl benzene [2] Isopropyl benzene [3] Both the above [4] None of the above
Q.7 Ethyl benzene is obtained from benzene and ethyl bromide in presence of :
[1] Vacant orbital acid [2] Lewis base [3] Selenium dioxide [4] Bromine water
Q.8 The ultimate product in the reaction :
AlCl3
Benzene + CCl 4  ? is :
[1] Benzal trichloride [2] Tetraphenyl methane

[3] Triphenyl chloromethane [4] Benzyl chloride
Q.9 When acetyl chloride and anhydrous aluminium chloride are used in Friedel Crafts reaction, the
electrophile is :
[1] Cl + [2] CH3CO+ [3] CH3+ [4] AlCl 3+
3 CH COCl Zn–Hg
Q.10 C6H6 
AlCl
 A 
HCl
B:
3
The end product in the above sequence is :

[1] Toluene [2] Ethyl benzene [3] Both the above [4] None
Q.11 Benzene diazonium chloride does not give benzene when treated with the following reagent :
[1] H3PO 2 [2] C2H5OH [3] SnCl 2 + NaOH [4] H2O
Q.12 For the centric formula of benzene credit goes to :
[1] Dewar [2] Kekule [3] Ladenburg [4] Armstrong and Baeyer’s
87
Q.13 Which of the following compound is called cumene :

[1] Vinyl benzene [2] Ethyl benzene [3] Isopropyl benzene [4] t–Butyl benzene
air, V2O5 air, V O

2 5
Q.14 A 
450º C
 
300º C B
The compounds A and B are respectively :

[1] Maleic anhydride and phenol [2] Maleic acid and p–benzoquinone
[3] Carbon dioxide and carbon monoxide [4] Benzoic acid and perbenzoic acid
AlCl3
Q.15 C6H6 + A  C6H5CONH2
A in the above reaction is :
[1] NH2CONH2 [2] ClCONH2 [3] CH3CONH2 [4] CH2(Cl)CONH2
Q.16 Aromatic hydrocarbons can be obtained from naptha by :
[1] Catalytic cracking [2] Catalytic reforming [3] Refining [4] Destructive distillation
Q.17 The true statement for benzene is :
[1] It is heavier than water [2] It is lighter than water
[3] It is soluble in water [4] It’s structure is non–planar
Q.18 [a] C6H6 + reagent – I  C6H5CHO ; [b] C6H6 + reagent – II  C6H5CHO
Reaction [a] is Gattermann synthesis while reaction [b] is Gattermann Koch synthesis. The reagents
related to [a] and [b] are respectively :
[1] [a] CO + HCl + AlCl 3 [b] CO + HCN + AlCl 3
[2] [a] HCN + HCl + AlCl 3 [b] CO + HCl + AlCl 3
[3] [a] CO 2 + AlCl 3 [b] ClCONH2 + AlCl3
[4] [a] HCHO + HCl + ZnCl 2 [b] CO + HCl + AlCl 3
Q.19 Which statement is wrong :
[1] In the chlorination of benzene by [FeCl 3 + Cl 2] chloronium ion is formed
[2] Solution of bromine in CCl 4 is not decolourised by benzene
[3] Chiefly phenol and napthalene are the constituents of light oil
[4] In sulphonation benzene reacts with hot and conc. H2SO 4
Q.20 Direct iodination of benzene is not possible because :
[1] Iodine is an oxidising agent [2] The product C6H5I is reduced to C6H6 by HI
[3] HI is an unstable compound [4] Ring is deactivated
HF
Q.21 Benzene + propene   Cumene.
Here the function of HF is :
[1] Proton donor [2] Solvent [3] Both the above [4] None
Q.22 It has been imagined that :
[I] A 22–membered, ring (12–double bond) and (II) A 30–membered ring (15–double bond) can be easily
prepared. Point which system is aromatic and which one is non–aromatic :
[1] (I) Aromatic (II) non–aromatic [2] (I) Non–aromatic (II) aromatic
[3] (I) and (II) aromatic [4] (I) and (II) non–aromatic
Q.23 Presence of unstauration in benzene is confirmed by the formation of this compound :
[a] Toluene [b] Cyclohexene [c] Tri–ozonide [d] Dibenzene chromium
[e] Gammexane
88
Correct answer is :
[1] a, c, b [2] b, c, e [3] c, d, e [4] a, c, d
Q.24 Compounds with aromatic characteristics are :
[a] Gammexane [b] Hexachlorobenzene
[c] Benzene triozonide [d] Cyclohexylamine
[e] N–Phenylacetamide
The correct code is :
[1] b, e [2] a, c, d [3] c, d [4] a, d
Q.25 Benzene was discovered by :
[1] Ramsay [2] Dalton [3] Faraday [4] Priestley
COCH2CH3 CH2CH2CH3
step–1 step–2
Q.26 
 

The correct set of reagents used in step–1 and step–2 are :

Step–1 Step–2
[1] AlCl3 and CH3COCl Pd/BaSO4
[2] AlCl3 and (CH3CO)2O Zn–Cu/H2O
[3] ZnCl2 and CH3COCl Zn–Hg/HCl
[4] AlCl3 and CH3CH2COCl Zn–Hg/HCl
Q.27 Benzene in presence of u.v. light reacts with chlorine to form :
[1] Benzenehexachloride [2] Benzyl chloride
[3] 1,3,5–Trichlorobenzene [4] Chlrobenzene
Q.28 Aromatic compounds undergo most readily :
[1] Nucleophilic substitution [2] Electrophilic substitution
[3] Nucleophilic addition [4] Electrophilic addition
Q.29 Which of the following is formed on reacting benzene with fuming sulphuric acid at 80ºC ?
[1] Phenolsulphonic acid [2] Benzenesulphonic acid
[3] m–Disulphonic acid [4] Benzenedisulphonic acid
Q.30 Which of the following compounds would have slower rate of electrophilic bromination than benzene :
NO2 CH3 OH NH2

| | | |
[1] [2] [3] [4]
Q.31 Catalytic hydrogenation of benzene gives :

[1] Toluene [2] Xylene [3] Cyclohexane [4] Benzoic acid
Q.32 Among the following statement on the nitration of aromatic compounds, the false one is :
[1] The rate of nitration of benzene is almost the same as that of hexadeutero benzene
[2] The rate of nitration of toluene is greater than that of hexadeuterobenzene
[3] The rate of nitration of benzene is greater than that of hexadeutrero benzene
[4] Nitration is an electrophilic substitution reaction
Q.33 Sulphonation of benzene differs from most of the other electrophilic substitution reactions in that the
reaction
[1] Is reversible [2] Requires the presence of a Lewis acid catalyst
[3] Takes place with expolsive violence [4] Requires elevated temperature
89
Q.34 Benzene reacts with a mixture of HNO3 and H2SO 4 followed by addition of Cl2/FeCl3 to form :
[1] 3–Chloro–1–nitrobenzene [2] 2–Chloro–1–nitrobenzne
[3] 4–Chloro–1–nitrobenzene [4] 2–and 4–chloro–1–nitrobenzene
Q.35 The reason for the equal C–C bond lengths in benzene is :
[1] sp2 hybridisation state of C–atoms and delocalisation of –electrons
[2] sp2 hybridisation state of C–atom and localisation of –electrons
[3] sp3 hybridisation sate of C–atoms and resonance
[4] None of these
Q.36 Which of the following is a correct statement about benzene ?
[1] All the C–C bond lengths are not equal
[2] All the bond angles are not equal
[3] All the C–atoms are not in sp2 hybridisation state
[4] Three C–C bond lengths are not different than other three C–C bond lengths
Q.37 C–C bond length in benzene is :
[1] 1.54 Å [2] 1.40 Å [3] 1.36 Å [4] 1.20 Å
Q.38 Which of the following reactions is not an example of electrophilic substitution ?
[1] C6H6 + +NO2  C6H5NO2 + H+ AlCl3
[2] C6H6 + CH3Cl  C6H5–CH3 + HCl
OH
|
Anhy.
UV light
[3] C6H6 + Cl2   C6H6Cl 6 [4] C6H5OH + CO + HCl 
AlCl3


|
CHO
Q.39 Which of the following does not react with benzene in the presence of anhy. AlCl 3 ?
[1] C6H5Cl [2] CH3CH2Cl [3] CH3–CH(Cl)–CH3 [4] CCl4
Q.40 The product of the reaction of benzene with ozone on hydrolysis gives :
[1] Ethane dial [2] Methanoic acid [3] Methyl glyoxal [4] None of these
Q.41 The intermediate formed in the reaction of benzene with an electrophile is :
[1] Whiland intermediate [2] –complex
[3] Cyclic secondary cation [4] All of the above
Q.42 The compounds obtained by the reduction of benzene with Na/C2H5OH and liquid ammonia is :
[1] Cyclohexane [2] Cyclohexa–1, 4–diene
[3] Cyclohexane + methyl cyclopentane [4] All of the above
Q.43 Cl2
X  Hydrolysis
 Benzotrichloride   Y. X and Y respectively are :
[1] Benzene, Benzaldehyde [2] toluene, Benzaldehyde
[3] Toluene, Benzoic acid [4] Benzene, Benzoic acid
Q.44 Fumin g sulphuric acid

C6H6  NaOH Zn dust
 (A)   (B)  (C)
In the above reaction compound (C) is :
[1] Phenol [2] Benzene
[3] Benzene sulphonic acid [4] None of these
Q.45 Benzene is reduced with HI at 250ºC to from :
[1] Methyl cyclopentane [2] Cyclohexane
[3] A mixture of both of the above [4] None of the above
90
Q.46 Benzene reacts with chlorine in the presence of iron. The product is :
[1] Benzene hexachloride [2] Chlorobenzene
[3] Benzyl chloride [4] Benzoyl chloride
Q.47 Which of the following groups deactivates benzene nucleus ?
[1] –CH3 [2] –CCl 3 [3] –OH [4] –NH2
Q.48 When benzene is heated with mercuric acetate at 110ºC, the product obtained is :
[1] Phenyl mercuric acetate [2] Phenyl mercury
[3] Phenyl acetate [4] A mixture of all of the above
Q.49 Benzene can not be prepared by the following reaction :
[1] Benzenediazonium chloride + Phosphrous acid
[2] Phenyl magnesium bromide + water
[3] Benzene sulphonic acid + dil. H2SO 4
[4] Benzendiazonium chloride + water
HCl  HCN 3CH CHO

Q.50 C6H6 
Anhy. AlCl3
 (A) 
Base
 (B) Compound (B) in above reaction sequence is :
[1] Cinnamaldehyde [2] Salicylaldehyde [3] Phenylacetaldehyde [4] Phenyl acetic acid
Answer Key
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 3 4 1 3 3 2 1 3 2 2 4 4 3 1 2 2 2 2 3 2
Qus. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 3 2 2 1 3 4 1 2 2 1 3 3 1 1 1 4 2 3 1 1
Qus. 41 42 43 44 45 46 47 48 49 50
Ans. 4 2 3 2 3 2 2 1 4 1
91
E xercise # 2
Q.1 The correct structure of benzene was suggested by :
[1] Faraday [2] Devy [3] Kekule [4] Wohler
Q.2 A mixture of benzene and benzoic acid is separated by the following reagent :
[1] Toluene [2] NaHCO3 [3] HCl [4] Diethyl ether
Q.3 Which of the following is not a correct statement ?
[1] SO3 is the active electrophile in the sulphonation of benzene
[2] Nitronium ion is the active electrophile in the nitration of benzene
[3] Bromide ion is the active electrophile in the bromination of benzene
[4] Alkyl carbocation is the active electrophile in the alkylation of benzene
?
Q.4 Benzene 
100º
 1,3,5–Trinitrobenzene
The reagent in this case is :

[1] Conc. HNO 3 [2] dil HNO 3
[3] Nitrogen dioxide dissolved in conc. HNO3 [4] Acetyl nitrate

H , Ag , HOCl
Q.5 The product of the reaction : Benzene   ? is :
OH
[1] C6H5Cl, H2O [2] C6H4 , H2O [3] C6H5OH, AgCl [4] None of the above
Cl(p)
Q.6 Identify the correct products A and B in the sequence :

NO
2 SnCl2 / HCl 2 NaNO / HCl
C6H6  A   B 
0ºC


[1] Nitrobenzene, Nitrosobenzene [2] Nitrobenzene, phenylhydroxylamine

[3] Nitrobenzene, benzene diazonium chloride [4] Nitrobenzene, phenol
Q.7 Benzene vapour mixed with air passed over vanadium pentaoxide, the product is :
[1] Dicarboxylic acid [2] Anhydride of monocarboxylic acid
[3] Anhydride of unsaturated dicarboxylic acid [4] Anhydride of unsaturated monocarboxylic acid
Q.8 Ozonolysis, of benzene and subsequent hydrolysis gives :
[1] Glycol [2] Glycolic acid [3] Glycine [4] Glyoxal
Q.9 Wrong statement for benzene is :
[1] Stable to permanganate [2] Gives substitution reaction
[3] Does not form sandwich compound [4] Unreactive to H2SO 4 at 0ºC
Q.10 Choose the pair, where members differ in molecular formula :
[1] Lindane and triple six [2] Glycine and aminoacetic acid
[3] Aniline and oil of mirbane [4] Urotropine and aminoform
92
Q.11 Benzene and cyclohexene can be distinguished by :

[1] Br2 water solution [2] H2 gas + Ni
[3] Cl 2 in dark , cold, Fe [4] None of these
Q.12 Which of the following reactions is not shown by benzene :
[1] Addition [2] Oxidation
[3] Side chain substitution [4] Complex formation
Q.13 Choose the wrong statement
[1] The dipole moment of benzene is zero .
[2] The properties of benzene resembles with alkene.
[3] C–C(six) bonds in benzene are of equal length
[4] Benzene is a planar molecule with bond angle of 120º
Q.14 The source of benzene is :
[1] Coaltar [2] Gasoline [3] Raschig process [4] None
Q.15 Which of the following saturated group deactivate the benzene ring :
[1] –CH=CH2 [2] –NO2 [3] –CCl 3 [4] –OH
Q.16 Reduction of benzene in alcohol by [Sodium + liquid ammonia] is called
[1] Clemeon reduction [2] Wolf-Kishner reduction
[3] Birch reduction [4] Mendius reaction
Q.17 Cumene or isopropyl benzene is formed in the reaction :
AlCl3
[1] C6H6 + CH2 = CH–CH3  AlCl3
[2] C6H6+CH3–CH2–CH2Cl 
 
[3] Both the above [4] None of the above

Q.18 Acetylene  benzene  cyclohexane. In the above sequence the hybridised carbon changes as :
sp  sp2  sp3
In this change, the angle of hybridised orbitals :
[1] Remains unaltered [2] Increases continuously
[3] Decreases continuously [4] First increases then decreases
Q.19 BHC contains predominantly its following isomer :
[1]  [2]  [3]  [4] 
Q.20 Which of the following group is divalent :
[1] Benzoyl [2] Benzyl [3] Benzal [4] p-Tolyl
Q.21 C–C Bond length in benzene is .......... then [CC] and [C=C] bond length but ...... than [C–C] bond
length in alkane.
[1] Greater, smaller [2] Smaller, smaller [3] Smaller, greater [4] Greater, greater
Q.22 Benzene with ethanol
[1] Is insoluble [2] Forms azeortropic mixture
[3] Forms ternary mixture [4] None of the above
Q.23 Toluene reacts with chlorine in presence of ferric chloride to give :
[1] Benzyl chloride [2] Benzal chloride [3] Benzotrichloride [4] o and p chlorotoluene
93
Q.24 A hydrocarbon contains 10.5 gm carbon per gm of hydrogen. Its empirical formula would be :
[1] C6H6 [2] C7H8 [4] C6H7 [[4] C6H8
Q.25 Chlorination of toluene would lead to the formation of :
[1] o–Chlorotoluene [2] p–Chlorotoluene
[3] o– and p– Chlorotoluene [4] m–Chlorotoluene
Q.26 The main product formed by the reaction of toluene with chlorine in the presence of ferric chloride is :
[1] Benzoyl chloride [2] Benzyl chloride [3] Benzotrichloride [4] o– and p–chlorotoluene
Q.27 Toluene is used in the preparation of :
[1] Saccharin [2] T.N.T [3] Chloramine–T [4] All of the above
Q.28 The product obtained by the chlorination of toluene in the presence of light and heat is hydrolysed with
aqu. NaOH to form :
[1] o–Cresol [2] p–Cresol
[3] 2,4–Dihydroxy toluene [4] Benzoic acid
Answer Key
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 3 2 3 3 1 3 3 4 3 3 1 3 2 1 3 3 3 3 3 3
Qus. 21 22 23 24 25 26 27 28
Ans. 1 2 4 2 3 4 4 4
94
E xercise # 3
Q.1 Aromactic compounds burn with sooty flame because : [BIT 1991]
[1] They have a ring structure of carbon atoms
[2] They have a relatively hight percentage of hydrogen
[3] They have a relatively high percentage of carbon
[4] They resist reaction with oxygen of air
Q.2 Select the true statment about bezene from amongst the following : [CBSE 1992]
[1] Because of unsaturation benzene easily undergoes addition reactions
[2] There are two types of C–C bonds in bezene molecule
[3] There is a cyclic delocalisation of  electrons in benzene
[4] Monosubstitution of benzene group gives three isomeric substances
Q.3 The function of anhydrous AlCl3 in the Friedel–Craft’s reaction is to : [MLNR 1986]
[1] Absorb water [2] Absorb HCl
[3] To produce electrophile [4] To produce nucleophile
Q.4 Benzene reacts with CH3COCl in the presence of AlCl 3 to give : [CBSE 1991]
[1] C6H5Cl [2] C6H5COCl [3] C6H5CH3 [4] C6H5COCH3
Q.5 Which of the following catalysts is used for preparing toluene by reacting benzene with methyl chloride:
[CPMT 1985]
[1] Ni [2] Anhydrous AlCl 3 [3] Pd [4] Pt
Q.6 The attacking (electrophilic) species in sulphonation of benzene is :[RPMT 1997 ; CPMT 1999, 2002]
[1] SO 2 [2] SO 3 [3] SO 42– [4] HSO3–
Q.7 Benzene vapour mixed with air when passed over V2O 5 catalyst at 775K gives :
[AFMC 1991; CPMT 2001; MP PMT 2003]
[1]Glyoxal [2] Oxalic acid [3] Maleic anhydride [4] Fumaric acid
Q.8 Attacking or reactive or electrophilic species in nitration of benzene is or In the nitration of benzene with
concentrated H2SO 4 + HNO 3, the attack on ring is made by :
[CBSE 1994; MP PET 1996; PMT 1998; BHU 2001]
[1] NO 2– [2] NO2+ [3] NO 3– [4] NO 2
Q.9 Which of the following reactions takes place when a mixture of concentrated HNO3 and H2SO 4 reacts
on benzene at 350 K : [CPMT 1985]
[1] Sulphonation [2] Nitration [3] Hydrogenation [4] Dehydration
Q.10 Chemical name of the inseciticide gammexene is :
[CPMT 1981; MP PET 1995; MP PMT 1996; CBSE 1999; MP PET 1999]
[1] DDT [2] Benzene hexachloride
[2] Chloral [4] Hexachloroethane

Q.11 The number of  and  bonds in a molecule of benzene is :
[MP PMT/PET 1988; BHU 1995; CPMT 1997]
[1] 6 and 3 [2] 9 and 3 [3] 12 and 3 [4] 6 and 6
95
Q.12 The bond order of individual carbon–carbon bonds in benzene is : [IIT 1981; MP PET 2000]
[1] One [2] Two [3] Between one and two[4] One and two, alternately
Q.13 The centric structure of benzene was proposed by : [CPMT 1982, 83, 89]
[1] Dewar [2] Ladenberg [3] Kekule [4] Armstrong and Baeyer
Q.14 The product formed when acetylene is passed through red hot tube is :
[BHU 1989; Rajasthan PMT 2003]
[1] Benzene [2] Cyclohexane [3] Neoprene [4] Ethane
Q.15 Which of the following structures correspond to the product expected, when excess of C6H6 reacts with
CH2Cl 2 in presence of anhydrous AlCl3 : [CBSE 1989]
[1] CH [2] CHCl2

|
Cl
Cl
|
[3] C [4] CH2
|
Cl
Q.16 Methyl group attached to benzene can be oxidised to carboxyl group by reacting with :
[Karnataka CET 1993]
[1] Fe2O 3 [2] AgNO 3 [3] KMnO 4 [4] Cr2O 3
Q.17 Benzene is prepared in laboratory from which one of the following compounds [CPMT 1996]
[1] C6H5N2Cl [2] C6H5OH [3] C6H5COONa [4] C6H5SO3H
Q.18 Catalytic hydrogenation of benzene gives : [AIIMS 1996]
[1] Xylene [2] Cyclohexane [3] Benzoic acid [4] Toluene
Q.19 Benzene is obtained from : [CPMT 1996]
[1] Coaltar [2] Plant [3] Animal [4] Charcoal
Q.20 Nitrobenzene can be prepared from benzene by using a mixture of conc. HNO3 and conc. H2SO4. In the
nitrating mixture, HNO 3 acts as a : [IIT 1997]
[1] Base [2] Acid [3] Reducing agent [4] Catalyst
Q.21 Among the following statements on the nitration of aromatic compounds, the false one is :[IIT 1997]
[1] The rate of nitration of benzene is almost the same as that of hexadeuterobenzene
[2] The rate of nitration of toluene is greater than that of benzene
[3] The rate of nitration of benzene is greater than that of hexadeuterobenzene
[4] Nitration is an electrophilic substitution reaction
Q.22 After ozonolysis of benzene (not hydrolysis), the product is : [Rajasthan PMT 1997; CPMT 1997]
[1] Benzene triozonide [2] Glyoxal [3] Ethanediol [4] All of these
Q.23 Which one of these is not compatible with arenes : [CBSE 1998]
[1] Greater stability [2] Delocalisation of –electrons
[3] Electrophilic additions [4] Resonance
Q.24 Benzene is the polymer of : [RPET 1999; Bihar MEE 1999]
[1] Methane [2] Ethane [3] Ethylene [4] Ethyne
HNO
3  2  Cl
Q.25 C6H6 
H2SO4 X 
FeCl3 Y In the above sequence Y is : [AIIMS 1999]
[1] 1–nitrochloro benzene [2] 3–nitrochlorobenzene
[3] 4–nitrochlorobenzene [4] 1,2–nitrochlorobenzene
Q.26 If benzene reacts with Cl2 in presence of ultra violet light then which of the following is formed :
[AIIMS 1999]
[1] C6Cl 6 [2] CCl4 [3] C6H5Cl [4] C6H6Cl 6
Q.27 Nitration of benzene is a : [RPMT 1999]
[1] Electrophilic displacement [2] Electrophilic addition
[3] Nucleophilic addition [4] Nucleophilic displacement
96
Q.28 Benzene can be obtained in the reaction : [RPET 2000]
[1] Ethene + 1, 3–butadiene [2] Trimerisation of ethyne
[3] Reduction of PhCHO [4] All of these
Q.29 Thiophene and benzene are separated by : [RPET 2000]
[1] Sulphonation of thiophene [2] Sulphonation of benzene
[3] Nitration of thiophene [4] Nitration of benzene
Q.30 In chlorination of benzene, the reactive species is : [MP PET 2000]
[1] Cl + [2] Cl – [3] Cl 2 [4] Cl 2–
Q.31 C6H6 + 3Cl 2  C6H6Cl 6. This reaction takes place when : [MP PET 2002]
[1] Chlorine is bubbled through benzene [2] When the mixture is kept in dark
[3] Chlorine (aq.) is shaken with benzene [4] When the mixture is exposed to sunlight
Q.32 The compound ‘A’ when treated with HNO 3 (in presence of H2SO 4) gives compound ‘B’ which is then
reduced with Sn and HCl to aniline. The compound ‘A’ is : [MP PET 2002]
[1] Toluene [2] Benzene [3] Ethane [4] Acetamide
Q.33 Three fused benzene rings are found in : [Kerala (Engg.) 2002]
[1] Naphthalene [2] Anthracene [3] Phenanthroline [4] Triphenyl methane
Q.34 Benzene is obtained by : [Delhi PMT 2002]
[1] Substitution of three acetylene molecules [2] Addition of three C2H2 molecules
[3] Polymensation three C2H5 molecules [4] Condensation of three C2H5 molecules
Q.35 Benzene can react with : [UPSEAT 2003]
[1] Br2 water [2] HNO3 [3] H2O [4] CH3OH
Q.36 Benzene hexachloride is used as : [MP PMT 1994; Karnataka CET 1999]
[1] Dye [2] Antimalerial drug [3] Antibiotic [4] Insecticide
Q.37 Benzene reacts with Cl 2 to form Benzene hexachloride in presence of : [MP PET 1999]
[1] Nickel [2] AlCl 3 [3] Bright sunlight [4] Zn
Q.38 C6H6Cl 6, on treatement with alcoholic KOH, yields :
[AFMC 2000]
[1] C6H6 [2] C6H3Cl 3 [3] (C6H6)OH [4] C6H6Cl 4
Q.39 When chlorine is passed through warm benzene in presence of the sunlight the product obtained is :
[Karnataka CET 2003]
[1] Benzotrichloride [2] Chlorobenzene [3] Gammexane [4] DDT
Hg / H 2 
Q.40 Ph–CC–CH3   [A]. [A] is : [IIT– 2002]
O OH
[1] Ph [2] Ph [3] Ph [4] Ph
O OH
H3C H3C H3C H3C
Q.41 What is the end product which is obtained on the nitration of toluene : [MP PMT/PET
1988]
[1] o–nitrotoluene [2] p–nitrotoluene [3] 2,4–dinitrotoluene [4] 2,4,6–trinitrotoluene
Q.42 The reaction of toluene with chlorine in presence of ferric chloride gives predominantly
[IIT1986; DCE 2000]
[1] Benzoyl chloride [2] m–chlorotoluene [3] Benzyl chloride [4] o– and p–chlorotoluenes
Q.43 Nitration of toluene takes place at : [NCERT 1990]
[1] o–position [2] m–position [3] p–position [4] Both o– and p–positions
Q.44 The compound formed as a result of potassium permanganate oxidation of ethylbenzene is :
[MP PMT/PMT 1998]
[1] Benzoic acid [2] Benzyl alcohol [3] Benzophenone [4] Acetophenone
Q.45 Toluene can be oxidised to benzoic acid by : [AIIMS 1999]
[1] KMnO 4 [2] K2Cr2O 7 [3] H2SO 4 [4] Both [1] and [2]
Q.46 In presence of light toluene on reaction with chlorine gives : [RPET 1999]
[1] Benzoyl chloride [2] Ortho Chlorotoluene [3] Para chloro toluene [4] Benzyl chloride
97
Q.47 Xylenes on oxidation with acidic KMnO4 gives : [JIPMER 2000]

[1] Terphthalic acid [2] Phthalic acid [3] Isophthalic acid [4] All of these
Q.48 The compound ‘A’ having formulae C8H10 (aromatic) which gives 1 mononitro substitute and 3
nitrosubstitute compound is : [Delhi PMT 2002]
[1] m–Xylene [2] p–Xylene [3] o–Xylene [4] Ethyl benzene
Q.49 Which one of the following is a free-radical substitution reaction : [CBSE 2003]
CH3 CH2Cl
boiling
[1] CH3CHO + HCN  CH3CH(OH)CN [2] + Cl 2 

CH3 CH2Cl CH2NO3

anh. AlCl3
+ CH3Cl 
[3]  [4] + AgNO 2 
Q.50 Chlorination of toluene in the presence of light and heat followed by treatement with aqueous NaOH
gives [IIT 1990]
[1] o–cresol [2] p–cresol [3] 2,4–dihydroxy toluene[4] Benzyl alcohol
Q.51 Toluene reacts with chlorine in the presence of light to give : [MH CET 1999; 2002]
[1] Benzyl chloride [2] Benzoyl chloride [3] p–chloro toluene [4] o–chloro toluene
Q.52 Oxidation of toluene by a strong oxidizing agent gives [VITEEE-2005]
[1] Phenol [2] Benzaldehyde [3] Benzoic acid [4] Benzophenone
Q.53 Which of following having delocalised electron [BCECE 2005]
[1] Benzene [2] Cyclohexane [3] CH4 [4] C2H6
Q.54 Pyridine is less basic than triethylamine because - [AIIMS 2005]
[1] Pyridine has aromatic character [2] Nitrogen in pyridine is sp2 hybridized
[3] Pyridine is a cyclic system [4] In pyridine,lone pair of nitrogen is delocalized
Q.55 When toluene is treated with KMnO4, what is produced [AFMC 2005]
[1] Benzene [2] Chlorobenzene [3] Benzaldehyde [4] Benzoic acid
OH
( i) O2 heat
Q.56 AlCl3
+ CH3–CH2CH2–Cl   [P]    
(ii) H3 O , heat [Q] + [IIT 2006]
CH3
H3C CH3
OHC OHC
[1] CH3 [2]
CHO
CH3
H3C CH3
O O
[3] H3C [4] H3C
CH3 CH3
Q.57 The reaction of toluene with Cl2 in presence of FeCl3 gives predominantly : [AIEEE 2007]
[1] bonzoyl chloride [2] benzyl chloride [3] o-and p-chlorotoluene[4] m-chlorotoluene
Q.58 The compound formed as a result of oxidation of ethyl benzene by KMnO4 is - [AIEEE 2007]
[1] benzophenone [2] acetophenone [3] benzoic acid [4] benzyl alcohol
98
Answer Key
Qus. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Ans. 3 3 3 4 2 2 2 2 2 2 3 3 4 1 4 3 3 2 1 1
Qus. 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
Ans. 3 1 3 4 2 4 1 2 2 1 4 2 2 2 2 4 3 2 3 2
Qus. 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58
Ans. 2 4 4 1 4 4 4 2 2 4 1 2 1 4 4 3 3 3

Alcohol Ether &amp; Phenol, Halogen Derivatives, Benzene &amp; Toluene

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Chapter

Alcohol Ether & Phenol, Halogen

Q.12 Which of the following statements is false :

Q.23 Which of the isomers of n–butyl alcohol exhibit optical isomerism :

diastase maltase zymase

[1] Starch, sucrose, fructose [2] Starch, sucrose, glucsoe

PBr3 alc. KOH Br2

[1] Ethyl bromide, CH3CH2OH, CH3CHBr2 [2] C2H5Br, CHCH, CH2=CHBr

Q.43 Phenol is commercially prepared by :

[1] Lederer–Manasse reaction [2] Reimer–Tiemann reaction

Q.54 Which of the following reactions leads to an ether formation :

Q.60 Anisole is obtained from phenol by reaction with :

[4] Picric acid does not contain a –COOH group

Q.72 The reaction of HI on ethers is important because it is used for estimation of :

dil. H2SO4  heat

[1] CH2OH [2] CH2OH [3] CH2–O–NO2 [4] CH2–O–NO2

Q.2 Crotyl alcohol has the structure :

[1] CH3–CH2–CH2–BH2, CH3–CH2–CH2OH [2] (CH3CHCH)2BH, CH3–CH2–CH2OH

[3] (CH3)2CH–CH2–BH2, CH3–CH(OH)–CH [4] (CH3–CH2–CH2)3 B, CH3–CH2–CH2OH

Q.5 Which of the following reactions is an example of hydrogenolysis :

Q.6 The compounds A, B and C in the reaction sequence :

[1] CH3CH2Br, CH3CH2MgBr, (CH3)3C–OH

Q.8 which of the following is not a common oxidant for alkanols :

[1] HO N=N Cl [2] N=N OH

[3] N–N [4] N=N Cl

Q.18 Phenol and benzoic acid are distinguished by :

this reaction is associated with the name of :

[3] Phenol Br2 water — Tribromophenol

A, B, C and D are given by the set :

Q.28 Oxonium salt of ether has the structure :

Q.29 In the Williamson synthesis of ethers given by the general equation :

[1] C6H6 [2] CH3COCH3 [3] CH3CHO [4] CH3COOH

673 K, 300 atm

may be used for manufacture of :

[3] CH3–CH2–O–CH2CH3 [4] CH3–CH=CH2

Q.53 When glycerol is heated with KHSO 4, which is formed :

Q.54 Ethylene glycol on oxidation with periodic acid give :

Q.55 23 gms of sodium of reaction with methyl alcohol gives :

[1] SiO 2 [2] CuO [3] Al 2O 3 [4] Ag2O

[3] An acid weaker than carbonic acid [4] A Neutral compound

Q.12 The following reaction : [MP PET 1997]

Q.34 The reaction of CH3CH = CH OH with HBr gives : [IIT 1998]

[1] CH3–CHBrCH2 OH [2] CH3CH2CHBr OH

[3] CH3CHBrCH2 Br [4] CH3CH2CHBr Br

Q.47 The compound X in the reaction :

COONa ONa ONa OCOONa

The product is : [RPET 2000]

Product X is : [RPET 2000]

Above reaction is called : [UPSEAT 2001]

HI KCN reduction HNO3

X and Y are respectively : [MP PMT 2002]

[1] Elimination reaction [2] Substitution reaction

[1] C6H5OC2H5 [2] C2H5OC2H5 [3] C6H5OC6H5 [4] C6H5I

Q.93 A + CCl 4 + KOH  Salicylic acid

[1] An aldehyde [2] An aryl chloride [3] An ether [4] A ketone

[1] CH2I [2] CH2OH [3] I [4] None of these

Q.103 Ethyl chloride is converted into diethyl ether by : [CBSE 1999]

[3] CH3CH2CHO, CH3COCH3 and CH3CH2CH2OH[4] CH3COCH3, CH3CH2CHO and CH3CH2CH2OH

CH3 OCH3 Br OCH3 CH3 OCH3 H OCH3

[1] N=N OH [2] O

the compound ‘D’ is :

Halogen Derivatives of Alkanes

(Halogen atom is normally represented by X)

(a) By Halogenation of Alkanes

Alcohol Ether & Phenol, Halogen Derivatives, Benzene & Toluene

Alcohol Ether & Phenol, Halogen Derivatives, Benzene & Toluene