HALO ALKAES & HALO ARENES

II Intext Questions

10.4 Write the products of the following reactions:

10.5 Draw the structures of major monohalo products in each of the following
reactions:

.10.9 Identify A, B, C, D, E, R and R1 in the following:

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III EXERCISE QUESTIONS

10.14 Write the structure of the major organic product in each of the following reactions:

10.10 Predict all the alkenes that would be formed by dehydrohalogenation of the
following halides with sodium ethoxide in ethanol and identify the major alkene:
a) 1-Bromo-1-methylcyclohexane
b) 2-Chloro-2-methylbutane
c) 2,2,3-Trimethyl-3-bromopentane.

10.11 How will you bring about the following conversions?

(i) Ethanol to but-1-yne
(ii) Ethane to bromoethene
(iii) Propene to1-nitropropane
(iv) Toluene to benzyl alcohol
(v) Propene to propyne
(vi) Ethanol to ethyl fluoride
(vii) Bromomethane to propanone
(viii) But-1-ene to but-2-ene
(ix) 1-Chlorobutane to n-octane
(x) Benzene to biphenyl.

10.19 How the following conversions can be carried out?

(i) Propene to propan-1-ol
(ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane
(iv) Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile
(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3, 4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi) Ethyl chloride to propanoic acid
(xii) But-1-ene to n-butyliodide
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 (xiii) 2-Chloropropane to 1-propanol
(xiv) Isopropyl alcohol to iodoform
(xv) Chlorobenzene to p-nitrophenol
(xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane
(xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx) Aniline to phenylisocyanide

10.22 What happens when

(i) n-butyl chloride is treated with alcoholic KOH,
(ii) bromobenzene is treated with Mg in the presence of dry ether,
(iii) chlorobenzene is subjected to hydrolysis,
(iv) ethyl chloride is treated with aqueous KOH,
(v) methyl bromide is treated with sodium in the presence of dry ether,
(vi) methyl chloride is treated with KCN?

10.21 Primary alkyl halide C4H9Br (a) reacted with alcoholic KOH to give compound (b).
Compound (b) is reacted with HBr to give (c) which is an isomer of (a). When
(a) is reacted with sodium metal it gives compound (d), C8H18 which is different
from the compound formed when n-butyl bromide is reacted with sodium.
Give the structural formula of (a) and write the equations for all the reactions.

ALCOHOLS , PHENOLS AND ETHERS

I EXAMPLE QUESTION:

11.6 The following is not an appropriate reaction for the preparation of

t-butyl ethyl ether.

(i) What would be the major product of this reaction ?

(ii) Write a suitable reaction for the preparation of t-butylethyl ether.

11.7 Give the major products that are formed by heating each of the following
ethers with HI.

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11.5 Write the structures of the major products expected from the following
reactions:

(a) Mononitration of 3-methylphenol

(b) Dinitration of 3-methylphenol
(c) Mononitration of phenyl methanoate

II INTEXT QUESTIONS

11.12 Predict the products of the following reactions:

11.4 Show how are the following alcohols prepared by the reaction of a suitable
Grignard reagent on methanal ?

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11.5 Write structures of the products of the following reactions

11.6 Give structures of the products you would expect when each of the
following alcohol reacts with (a) HCl –ZnCl2 (b) HBr and (c) SOCl2.
(i) Butan-1-ol (ii) 2-Methylbutan-2-ol

11.7 Predict the major product of acid catalysed dehydration of

(i) 1-methylcyclohexanol and (ii) butan-1-ol

11.9 Write the equations involved in the following reactions:

(i) Reimer - Tiemann reaction (ii) Kolbe’s reaction

11.10 Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane

starting from ethanol and 3-methylpentan-2-ol.

III EXERCISE QUESTIONS .

11.32 Show how would you synthesise the following alcohols from appropriate
alkenes?

11.6 What is meant by hydroboration-oxidation reaction? Illustrate it with an example.

11.9 Give the equations of reactions for the preparation of phenol from cumene.

11.10 Write chemical reaction for the preparation of phenol from chlorobenzene.
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11.12 You are given benzene, conc. H2SO4 and NaOH Write the equations for the
preparation of phenol using these reagents.

11.13 Show how will you synthesise:

(i) 1-phenylethanol from a suitable alkene.
(ii) cyclohexylmethanol using an alkyl halide by an SN2 reaction.
(iii) pentan-1-ol using a suitable alkyl halide?

11.17 Give equations of the following reactions:

(i) Oxidation of propan-1-ol with alkaline KMnO4 solution.
(ii) Bromine in CS2 with phenol.
(iii) Dilute HNO3 with phenol.
(iv) Treating phenol wih chloroform in presence of aqueous NaOH.

11.18 Explain the following with an example.

(i) Kolbe’s reaction.
(ii) Reimer-Tiemann reaction.
(iii) Williamson ether synthesis.
(iv) Unsymmetrical ether.

11.20 How are the following conversions carried out?

(i) Propene → Propan-2-ol.
(ii) Benzyl chloride → Benzyl alcohol.
(iii) Ethyl magnesium chloride → Propan-1-ol.
(iv) Methyl magnesium bromide → 2-Methylpropan-2-ol.

11.21 Name the reagents used in the following reactions:

(i) Oxidation of a primary alcohol to carboxylic acid.
(ii) Oxidation of a primary alcohol to aldehyde.
(iii) Bromination of phenol to 2,4,6-tribromophenol.
(iv) Benzyl alcohol to benzoic acid.
(v) Dehydration of propan-2-ol to propene.
(vi) Butan-2-one to butan-2-ol.

11.24 Write the names of reagents and equations for the preparation of the following
ethers by Williamson’s synthesis:
(i) 1-Propoxypropane (ii) Ethoxybenzene
(iii) 2-Methoxy-2-methylpropane (iv) 1-Methoxyethane

11.25 Illustrate with examples the limitations of Williamson synthesis for the
preparation of certain types of ethers.

11.28 Write the equation of the reaction of hydrogen iodide with:

(i) 1-propoxypropane (ii) methoxybenzene
(iii) benzyl ethyl ether.

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11.31 Write equations of the following reactions:
(i) Friedel-Crafts reaction – alkylation of anisole.
(ii) Nitration of anisole.
(iii) Bromination of anisole in ethanoic acid medium.
(iv) Friedel-Craft’s acetylation of anisole.

ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

I INTEXT QUESTIONS

12.2 Write the structures of products of the following reactions;

12.5. Predict the products of the following reactions

12.7 Show how each of the following compounds can be converted to benzoic acid.
(i) Ethylbenzene
(ii) Acetophenone
(iii) Bromobenzene
(iv) Phenylethene (Styrene)

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EXAMPLE QUESTIONS:

12.1 Give names of the reagents to bring about the following transformations:
(i) Hexan-1-ol to hexanal
(ii) Cyclohexanol to cyclohexanone
(iii) p-Fluorotoluene to p-fluorobenzaldehyde
(iv) Ethanenitrile to ethanal
(v) Allyl alcohol to propenal
(vi) But-2-ene to ethanol

12.5 Write chemical reactions to affect the following transformations:

(i) Butan-1-ol to butanoic acid
(ii) Benzyl alcohol to phenylethanoic acid
(iii) 3-Nitrobromobenzene to 3-nitrobenzoic acid
(iv) 4-Methylacetophenone to benzene-1,4-dicarboxylic acid
(v) Cyclohexene to hexane-1,6-dioic acid
(vi) Butanal to butanoic acid.

12.4 An organic compound (A) with molecular formula C8H8O forms an orange-red precipitate
with - 2,4-DNP reagent and gives yellow precipitate on heating with iodine in the presence
of sodium hydroxide. It neither reduces Tollens’ or Fehlings’ reagent, nor does it decolourise
bromine water or Baeyer’s reagent. On drastic oxidation with chromic acid, it gives a
carboxylic acid (B) having molecular formula C7H6O2. Identify the compounds (A) and (B) and
explain the reactions involved.

EXERCISE QUESTIONS

12.17 Complete each synthesis by giving missing starting material, reagent or products

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13.9 Give the structures of A, B and C in the following reactions:

12.6 Predict the products formed when cyclohexanecarbaldehyde reacts with

following reagents.
(i)PhMgBr and then H3O+
(ii) Tollens’ reagent
(iii) Semicarbazide and weak acid
(iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid

12.7 Which of the following compounds would undergo aldol condensation, which the
Cannizzaro reaction and which neither? Write the structures of the expected products of aldol
condensation and Cannizzaro reaction.
(i) Methanal
(ii) 2-Methylpentanal
(iii) Benzaldehyde
(iv) Benzophenone
(v) Cyclohexanone
(vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde
(viii) Butan-1-ol
(ix) 2,2-Dimethylbutanal

12.8 How will you convert ethanal into the following compounds?
(i) Butane-1,3-diol
(ii) But-2-enal
(iii) But-2-enoic acid

12.14 How will you prepare the following compounds from benzene? You may use any
inorganic reagent and any organic reagent having not more than one carbon atom
(i) Methyl benzoate
(ii) m-Nitrobenzoic acid
(iii) p-Nitrobenzoic acid
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 (iv) Phenylacetic acid
(v) p-Nitrobenzaldehyde.

12.15 How will you bring about the following conversions in not more than two steps?
(i) Propanone to Propene
(ii) Benzoic acid → Benzaldehyde
(iii) Ethanol → 3-Hydroxybutanal
(iv) Benzene → m-Nitroacetophenone
(v) Benzaldehyde → Benzophenone
(vi) Bromobenzene →1-Phenylethanol
(vii) Benzaldehyde → 3-Phenylpropan-1-ol
(viii) Benazaldehyde → α-Hydroxyphenylacetic acid
(ix) Benzoic acid → m- Nitrobenzyl alcohol

12.16 Describe the following:

(i) Acetylation
(ii) Cannizzaro reaction
(iii) Cross aldol condensation

(iv) Decarboxylation

12.9 Write structural formulas and names of four possible aldol condensation products from
propanal and butanal. In each case, indicate which aldehyde acts as nucleophile and which as
electrophile.

12.10 An organic compound with the molecular formula C9H10O forms 2,4-DNP derivative,
reduces Tollens’ reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1,2-
benzenedicarboxylic acid. Identify the compound.

12.11 An organic compound (A) (molecular formula C8H16O2) was hydrolysed with dilute
sulphuric acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic
acid produced (B). (C) on dehydration gives but-1-ene.Write equations for the reactions
involved.

12.19 An organic compound contains 69.77% carbon, 11.63% hydrogen and rest oxygen. The
molecular mass of the compound is 86. It does not reduce Tollens’ reagent but forms an -
addition compound with sodium hydrogensulphite and give positive iodoform test. On -
vigorous oxidation it gives ethanoic and propanoic acid. Write the possible structure of -
the compound.

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 AMINES

III EXERCISE QUESTIONS

13.11 Complete the following reactions:

13.5 How will you convert:

(i) Ethanoic acid into methanamine
(ii) Hexa nenitrile into 1-aminopentane
(iii) Methanol to ethanoic acid
(iv) Ethanamine into methanamine
(v) Ethanoic acid into propanoic acid
(vi) Methanamine into ethanamine
(vii) Nitromethane into dimethylamine
(viii) Propanoic acid into ethanoic acid?

13.7 Write short notes on the following:

(i) Carbylamine reaction
(ii) Diazotisation
(iii) Hofmann’s bromamide reaction
(iv) Coupling reaction
(v) Ammonolysis
(vi) Acetylation
(vii) Gabriel phthalimide synthesis.

13.8 Accomplish the following conversions:

(i) Nitrobenzene to benzoic acid
(ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline
(iv) Aniline to 2,4,6-tribromofluorobenzene
(v) Benzyl chloride to 2-phenylethanamine
(vi) Chlorobenzene to p-chloroaniline
(vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(ix) Aniline to benzyl alcohol

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13.6 Describe a method for the identification of primary, secondary and tertiary amines.
Also write chemical equations of the reactions involved.

13.13 Write the reactions of

(i) aromatic and
(ii) aliphatic primary amines with nitrousacid.

13.10 An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms compound ‘B’ which
on heating with Br2 and KOH forms a compound ‘C’ of molecular formula C6H7N. Write the structures and
IUPAC names of compounds A, B and C.

I EXAMPLE QUESTIONS

13.1 Write chemical equations for the following reactions:

(i) Reaction of ethanolic NH3 with C2H5Cl.
(ii) Ammonolysis of benzyl chloride and reaction of amine so formed
with two moles of CH3Cl.

13.2 Write chemical equations for the following conversions:

(i) CH3–CH2–Cl into CH3–CH2–CH2–NH2
(ii) C6H5–CH2–Cl into C6H5–CH2–CH2–NH2

13.3 Write structures and IUPAC names of

(i) the amide which gives propanamine by Hoffmann bromamide
reaction.
(ii) the amine produced by the Hoffmann degradation of benzamide.

13.5 How will you convert 4-nitrotoluene to 2-bromobenzoic acid ?

II INTEXT QUESTIONS

13.3 How will you convert

(i) Benzene into aniline (ii) Benzene into N, N-dimethylaniline
(iii) Cl–(CH2)4–Cl into hexan-1,6-diamine?

13.5 Complete the following acid-base reactions and name the products:
(i) CH3CH2CH2NH2 + HCl 
(ii) (C2H5)3N + HCl 

13.6 Write reactions of the final alkylation product of aniline with excess of methyl
iodide in the presence of sodium carbonate solution.

13.7 Write chemical reaction of aniline with benzoyl chloride and write the name of
the product obtained.

13.8 Write structures of different isomers corresponding to the molecular formula,

C3H9N. Write IUPAC names of the isomers which will liberate nitrogen gas on
treatment with nitrous acid.

13.9 Convert
(i) 3-Methylaniline into 3-nitrotoluene. (ii) Aniline into 1,3,5 - tribromobenzene

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