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Chemistry · Textbook solutions

Haloalkanes and Haloarenes

Every solved example, exercise, and miscellaneous question — in the order the textbook teaches them. · 40 questions

Worked Examples

9 q

Solved Examples

Worked · 9
  1. Eg 6.1
    Draw the structures of all the eight structural isomers that have the molecular formula C5H11Br\text{C}_5\text{H}_{11}\text{Br}. Name each isomer according to IUPAC system and classify them as primary, secondary or tertiary bromide.
  2. Eg 6.2
    Write IUPAC names of the following: (i) CH3CH=CHCH(Br)CH3\text{CH}_3\text{CH}=\text{CH}\text{CH}(\text{Br})\text{CH}_3 (ii) CH2=C(CH3)CH(Br)CH3\text{CH}_2=\text{C}(\text{CH}_3)\text{CH}(\text{Br})\text{CH}_3 (iii) CH3CH=C(CH3)CH(Br)CH3\text{CH}_3\text{CH}=\text{C}(\text{CH}_3)\text{CH}(\text{Br})\text{CH}_3 (iv) CH3CH=C(CH3)CH2Br\text{CH}_3\text{CH}=\text{C}(\text{CH}_3)\text{CH}_2\text{Br} (v) CH3CH=CHCH2Br\text{CH}_3\text{CH}=\text{CH}\text{CH}_2\text{Br} (vi) CH2=C(CH3)CH2Br\text{CH}_2=\text{C}(\text{CH}_3)\text{CH}_2\text{Br}
  3. Eg 6.3
    Identify all the possible monochloro structural isomers expected to be formed on free radical monochlorination of (CH3)2CHCH2CH3(\text{CH}_3)_2\text{CHCH}_2\text{CH}_3.
  4. Eg 6.4
    Write the products of the following reactions: (i) C6H5CH=CH2+HBr\text{C}_6\text{H}_5\text{CH}=\text{CH}_2 + \text{HBr} \rightarrow (ii) CH3CH2CH=CH2+HCl\text{CH}_3-\text{CH}_2-\text{CH}=\text{CH}_2 + \text{HCl} \rightarrow (iii) C6H5CH2CH=CH2+HBrPeroxide\text{C}_6\text{H}_5\text{CH}_2-\text{CH}=\text{CH}_2 + \text{HBr} \xrightarrow{\text{Peroxide}}
  5. Eg 6.5
    Haloalkanes react with KCN to form alkyl cyanides as main product while AgCN forms isocyanides as the chief product. Explain.
  6. Eg 6.6
    In the following pairs of halogen compounds, which would undergo SN2\text{S}_\text{N}2 reaction faster? (i) C6H11CH2Cl\text{C}_6\text{H}_{11}\text{CH}_2\text{Cl} (chloromethylcyclohexane) and C6H11Cl\text{C}_6\text{H}_{11}\text{Cl} (chlorocyclohexane) (ii) CH3CH2CH2CH2I\text{CH}_3\text{CH}_2\text{CH}_2\text{CH}_2\text{I} (1-iodobutane) and CH3CH2CH2CH2Cl\text{CH}_3\text{CH}_2\text{CH}_2\text{CH}_2\text{Cl} (1-chlorobutane)
  7. Eg 6.7
    Predict the order of reactivity of the following compounds in SN1\text{S}_\text{N}1 and SN2\text{S}_\text{N}2 reactions: (i) The four isomeric bromobutanes (ii) C6H5CH2Br\text{C}_6\text{H}_5\text{CH}_2\text{Br}, C6H5CH(C6H5)Br\text{C}_6\text{H}_5\text{CH}(\text{C}_6\text{H}_5)\text{Br}, C6H5CH(CH3)Br\text{C}_6\text{H}_5\text{CH}(\text{CH}_3)\text{Br}, C6H5C(CH3)(C6H5)Br\text{C}_6\text{H}_5\text{C}(\text{CH}_3)(\text{C}_6\text{H}_5)\text{Br}
  8. Eg 6.8
    Identify chiral and achiral molecules in each of the following pair of compounds. (Wedge and Dash representations according to Class XI. (i) (i) CH3CH(Br)OH\text{CH}_3\text{CH}(\text{Br})\text{OH} (ii) CH3CHBr2\text{CH}_3\text{CHBr}_2 (ii) (i) CH3CH(OH)CH2CH2CH3\text{CH}_3\text{CH}(\text{OH})\text{CH}_2\text{CH}_2\text{CH}_3 (pentan-2-ol) (ii) CH3CH2CH(OH)CH2CH3\text{CH}_3\text{CH}_2\text{CH}(\text{OH})\text{CH}_2\text{CH}_3 (pentan-3-ol) (iii) (i) CH3CH(Br)CH2CH3\text{CH}_3\text{CH}(\text{Br})\text{CH}_2\text{CH}_3 (ii) CH3CH2CH2CH2Br\text{CH}_3\text{CH}_2\text{CH}_2\text{CH}_2\text{Br}
  9. Eg 6.9
    Although chlorine is an electron withdrawing group, yet it is ortho-, para- directing in electrophilic aromatic substitution reactions. Why?

Intext Questions

9 q
  1. Intext 6.1
    Write structures of the following compounds: (i) 2-Chloro-3-methylpentane (ii) 1-Chloro-4-ethylcyclohexane (iii) 4-tert. Butyl-3-iodoheptane (iv) 1,4-Dibromobut-2-ene (v) 1-Bromo-4-sec. butyl-2-methylbenzene.
  2. Intext 6.2
    Why is sulphuric acid not used during the reaction of alcohols with KI?
  3. Intext 6.3
    Write structures of different dihalogen derivatives of propane.
  4. Intext 6.4
    Among the isomeric alkanes of molecular formula C5H12\text{C}_5\text{H}_{12}, identify the one that on photochemical chlorination yields (i) A single monochloride. (ii) Three isomeric monochlorides. (iii) Four isomeric monochlorides.
  5. Intext 6.5
    Draw the structures of major monohalo products in each of the following reactions: (i) cyclohexanol + SOCl2+\ \text{SOCl}_2 \rightarrow (ii) 1-ethyl-4-nitrobenzene Br2, heat or UV light\xrightarrow{\text{Br}_2,\ \text{heat or UV light}} (iii) 4-(hydroxymethyl)phenol + HClheat+\ \text{HCl} \xrightarrow{\text{heat}} (iv) 1-methylcyclohex-1-ene + HI+\ \text{HI} \rightarrow (v) CH3CH2Br+NaI\text{CH}_3\text{CH}_2\text{Br} + \text{NaI} \rightarrow (vi) cyclohexene + Br2heat, UV light+\ \text{Br}_2 \xrightarrow{\text{heat, UV light}}
  6. Intext 6.6
    Arrange each set of compounds in order of increasing boiling points. (i) Bromomethane, Bromoform, Chloromethane, Dibromomethane. (ii) 1-Chloropropane, Isopropyl chloride, 1-Chlorobutane.
  7. Intext 6.7
    Which alkyl halide from the following pairs would you expect to react more rapidly by an SN2\text{S}_\text{N}2 mechanism? Explain your answer. (i) CH3CH2CH2CH2Br\text{CH}_3\text{CH}_2\text{CH}_2\text{CH}_2\text{Br} or CH3CH2CH(Br)CH3\text{CH}_3\text{CH}_2\text{CH}(\text{Br})\text{CH}_3 (ii) CH3CH2CH(Br)CH3\text{CH}_3\text{CH}_2\text{CH}(\text{Br})\text{CH}_3 or (CH3)3CBr(\text{CH}_3)_3\text{CBr} (iii) CH3CH(CH3)CH2CH2Br\text{CH}_3\text{CH}(\text{CH}_3)\text{CH}_2\text{CH}_2\text{Br} or CH3CH2CH(CH3)CH2Br\text{CH}_3\text{CH}_2\text{CH}(\text{CH}_3)\text{CH}_2\text{Br}
  8. Intext 6.8
    In the following pairs of halogen compounds, which compound undergoes faster SN1\text{S}_\text{N}1 reaction? (i) (CH3)3CCl(\text{CH}_3)_3\text{CCl} (2-chloro-2-methylpropane) and CH3CH2CH(Cl)CH2CH3\text{CH}_3\text{CH}_2\text{CH}(\text{Cl})\text{CH}_2\text{CH}_3 (3-chloropentane) (ii) CH3CH2CH2CH2CH2CH(Cl)CH3\text{CH}_3\text{CH}_2\text{CH}_2\text{CH}_2\text{CH}_2\text{CH}(\text{Cl})\text{CH}_3 (2-chloroheptane) and CH3CH2CH2CH2CH2CH2Cl\text{CH}_3\text{CH}_2\text{CH}_2\text{CH}_2\text{CH}_2\text{CH}_2\text{Cl} (1-chlorohexane)
  9. Intext 6.9
    Identify A, B, C, D, E, R and R1\text{R}^1 in the following: C6H11Br\text{C}_6\text{H}_{11}\text{Br} (bromocyclohexane) + Mgdry etherAH2OB+\ \text{Mg} \xrightarrow{\text{dry ether}} \text{A} \xrightarrow{\text{H}_2\text{O}} \text{B} RBr+Mgdry etherCD2OCH3CH(D)CH3\text{R}-\text{Br} + \text{Mg} \xrightarrow{\text{dry ether}} \text{C} \xrightarrow{\text{D}_2\text{O}} \text{CH}_3\text{CH}(\text{D})\text{CH}_3 CH3C(CH3)2C(CH3)2CH3\text{CH}_3\text{C}(\text{CH}_3)_2\text{C}(\text{CH}_3)_2\text{CH}_3 (2,2,3,3-tetramethylbutane) Na/etherR1XMgDH2OE\xleftarrow{\text{Na/ether}} \text{R}^1-\text{X} \xrightarrow{\text{Mg}} \text{D} \xrightarrow{\text{H}_2\text{O}} \text{E}

Exercises

22 q
  1. Ex 6.1
    Name the following halides according to IUPAC system and classify them as alkyl, allyl, benzyl (primary, secondary, tertiary), vinyl or aryl halides: (i) (CH3)2CHCH(Cl)CH3(\text{CH}_3)_2\text{CHCH}(\text{Cl})\text{CH}_3 (ii) CH3CH2CH(CH3)CH(C2H5)Cl\text{CH}_3\text{CH}_2\text{CH}(\text{CH}_3)\text{CH}(\text{C}_2\text{H}_5)\text{Cl} (iii) CH3CH2C(CH3)2CH2I\text{CH}_3\text{CH}_2\text{C}(\text{CH}_3)_2\text{CH}_2\text{I} (iv) (CH3)3CCH2CH(Br)C6H5(\text{CH}_3)_3\text{CCH}_2\text{CH}(\text{Br})\text{C}_6\text{H}_5 (v) CH3CH(CH3)CH(Br)CH3\text{CH}_3\text{CH}(\text{CH}_3)\text{CH}(\text{Br})\text{CH}_3 (vi) CH3C(C2H5)2CH2Br\text{CH}_3\text{C}(\text{C}_2\text{H}_5)_2\text{CH}_2\text{Br} (vii) CH3C(Cl)(C2H5)CH2CH3\text{CH}_3\text{C}(\text{Cl})(\text{C}_2\text{H}_5)\text{CH}_2\text{CH}_3 (viii) CH3CH=C(Cl)CH2CH(CH3)2\text{CH}_3\text{CH}=\text{C}(\text{Cl})\text{CH}_2\text{CH}(\text{CH}_3)_2 (ix) CH3CH=CHC(Br)(CH3)2\text{CH}_3\text{CH}=\text{CHC}(\text{Br})(\text{CH}_3)_2 (x) p-ClC6H4CH2CH(CH3)2p\text{-ClC}_6\text{H}_4\text{CH}_2\text{CH}(\text{CH}_3)_2 (xi) m-ClCH2C6H4CH2C(CH3)3m\text{-ClCH}_2\text{C}_6\text{H}_4\text{CH}_2\text{C}(\text{CH}_3)_3 (xii) o-Br-C6H4CH(CH3)CH2CH3o\text{-Br-C}_6\text{H}_4\text{CH}(\text{CH}_3)\text{CH}_2\text{CH}_3
  2. Ex 6.2
    Give the IUPAC names of the following compounds: (i) CH3CH(Cl)CH(Br)CH3\text{CH}_3\text{CH}(\text{Cl})\text{CH}(\text{Br})\text{CH}_3 (ii) CHF2CBrClF\text{CHF}_2\text{CBrClF} (iii) ClCH2CCCH2Br\text{ClCH}_2\text{C}\equiv\text{CCH}_2\text{Br} (iv) (CCl3)3CCl(\text{CCl}_3)_3\text{CCl} (v) CH3C(p-ClC6H4)2CH(Br)CH3\text{CH}_3\text{C}(p\text{-ClC}_6\text{H}_4)_2\text{CH}(\text{Br})\text{CH}_3 (vi) (CH3)3CCH=CClC6H4I-p(\text{CH}_3)_3\text{CCH}=\text{CClC}_6\text{H}_4\text{I-}p
  3. Ex 6.3
    Write the structures of the following organic halogen compounds. (i) 2-Chloro-3-methylpentane (ii) pp-Bromochlorobenzene (iii) 1-Chloro-4-ethylcyclohexane (iv) 2-(2-Chlorophenyl)-1-iodooctane (v) 2-Bromobutane (vi) 4-tert-Butyl-3-iodoheptane (vii) 1-Bromo-4-sec-butyl-2-methylbenzene (viii) 1,4-Dibromobut-2-ene
  4. Ex 6.4
    Which one of the following has the highest dipole moment? (i) CH2Cl2\text{CH}_2\text{Cl}_2 (ii) CHCl3\text{CHCl}_3 (iii) CCl4\text{CCl}_4
  5. Ex 6.5
    A hydrocarbon C5H10\text{C}_5\text{H}_{10} does not react with chlorine in dark but gives a single monochloro compound C5H9Cl\text{C}_5\text{H}_9\text{Cl} in bright sunlight. Identify the hydrocarbon.
  6. Ex 6.6
    Write the isomers of the compound having formula C4H9Br\text{C}_4\text{H}_9\text{Br}.
  7. Ex 6.7
    Write the equations for the preparation of 1-iodobutane from (i) 1-butanol (ii) 1-chlorobutane (iii) but-1-ene.
  8. Ex 6.8
    What are ambident nucleophiles? Explain with an example.
  9. Ex 6.9
    Which compound in each of the following pairs will react faster in SN2\text{S}_\text{N}2 reaction with OH^{-}\text{OH}? (i) CH3Br\text{CH}_3\text{Br} or CH3I\text{CH}_3\text{I} (ii) (CH3)3CCl(\text{CH}_3)_3\text{CCl} or CH3Cl\text{CH}_3\text{Cl}
  10. Ex 6.10
    Predict all the alkenes that would be formed by dehydrohalogenation of the following halides with sodium ethoxide in ethanol and identify the major alkene: (i) 1-Bromo-1-methylcyclohexane (ii) 2-Chloro-2-methylbutane (iii) 2,2,3-Trimethyl-3-bromopentane.
  11. Ex 6.11
    How will you bring about the following conversions? (i) Ethanol to but-1-yne (ii) Ethane to bromoethene (iii) Propene to 1-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.
  12. Ex 6.12
    Explain why (i) the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride? (ii) alkyl halides, though polar, are immiscible with water? (iii) Grignard reagents should be prepared under anhydrous conditions?
  13. Ex 6.13
    Give the uses of freon 12, DDT, carbon tetrachloride and iodoform.
  14. Ex 6.14
    Write the structure of the major organic product in each of the following reactions: (i) CH3CH2CH2Cl+NaIheatacetone\text{CH}_3\text{CH}_2\text{CH}_2\text{Cl} + \text{NaI} \xrightarrow[\text{heat}]{\text{acetone}} (ii) (CH3)3CBr+KOHheatethanol(\text{CH}_3)_3\text{CBr} + \text{KOH} \xrightarrow[\text{heat}]{\text{ethanol}} (iii) CH3CH(Br)CH2CH3+NaOHwater\text{CH}_3\text{CH}(\text{Br})\text{CH}_2\text{CH}_3 + \text{NaOH} \xrightarrow{\text{water}} (iv) CH3CH2Br+KCNaq. ethanol\text{CH}_3\text{CH}_2\text{Br} + \text{KCN} \xrightarrow{\text{aq. ethanol}} (v) C6H5ONa+C2H5Cl\text{C}_6\text{H}_5\text{ONa} + \text{C}_2\text{H}_5\text{Cl} \rightarrow (vi) CH3CH2CH2OH+SOCl2\text{CH}_3\text{CH}_2\text{CH}_2\text{OH} + \text{SOCl}_2 \rightarrow (vii) CH3CH2CH=CH2+HBrperoxide\text{CH}_3\text{CH}_2\text{CH}=\text{CH}_2 + \text{HBr} \xrightarrow{\text{peroxide}} (viii) CH3CH=C(CH3)2+HBr\text{CH}_3\text{CH}=\text{C}(\text{CH}_3)_2 + \text{HBr} \rightarrow
  15. Ex 6.15
    Write the mechanism of the following reaction: nBuBr+KCNEtOH-H2OnBuCN\text{nBuBr} + \text{KCN} \xrightarrow{\text{EtOH-H}_2\text{O}} \text{nBuCN}
  16. Ex 6.16
    Arrange the compounds of each set in order of reactivity towards SN2\text{S}_\text{N}2 displacement: (i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane (ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane (iii) 1-Bromobutane, 1-Bromo-2,2-dimethylpropane, 1-Bromo-2-methylbutane, 1-Bromo-3-methylbutane.
  17. Ex 6.17
    Out of C6H5CH2Cl\text{C}_6\text{H}_5\text{CH}_2\text{Cl} and C6H5CHClC6H5\text{C}_6\text{H}_5\text{CHClC}_6\text{H}_5, which is more easily hydrolysed by aqueous KOH.
  18. Ex 6.18
    pp-Dichlorobenzene has higher m.p. than those of oo- and mm-isomers. Discuss.
  19. Ex 6.19
    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 (xiii) 2-Chloropropane to 1-propanol (xiv) Isopropyl alcohol to iodoform (xv) Chlorobenzene to pp-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
  20. Ex 6.20
    The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in the presence of alcoholic KOH, alkenes are major products. Explain.
  21. Ex 6.21
    Primary alkyl halide C4H9Br\text{C}_4\text{H}_9\text{Br} (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\text{C}_8\text{H}_{18} 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.
  22. Ex 6.22
    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?