Haloalkanes and Haloarenes LCL Previous Years’ CBSE Board Questions Daa 6.1 Classification Erm 1. Which one of the following halides contains — Cye—Xbond? (a) Ally halide (¢) Benzyl halide (b) Alkyl halide (6) Vinyl halide allylic halide? vinylichalide? (ai2017) CHCl, CH.CH.CI | 4 onto CF ans CT HA hich is ‘an example of a benzylic halide? (ai2017)(0) 6.2 Nomenclature Devs teeny | € 5. Write the IUPAC name of CHsCH—=CH—G—CHy Br (412019, Deihi 2013) 6. Write the structure of 1-bromo-4-chlorobut-2-ene. (Delhi 2017) | 7. Write the structure of 3-bromo-2-methylprop: 1-ene. (Dethi2017)(1) | 8. Drawthe structure of 2-bromopentane. (Dethi 2014C) _ (marks) 9. Write the IUPAC names ofthe following compounds : () CH,=CHCH,8r | i) (CCl),CC1 (ai2014c) ‘marks 110. Give the IUPAC names of the following compounds : () CHy—CH—CH,—CHy r Co) a. or (ii) CH»=CH—CH,—Cl (012015¢)(0) | (Term |, 2021-22) ip) | 1 | x 2 ont of Cand OY. which an cme of | (ai2017)_ eee | 6.4 Methods of Preparation of Haloalkanes a | 11. The synthesis of alkyl flouride is best obtained from (a) Free radicals (b) Swarts reaction (€) Sandmeyer reaction (d) Finkelstein reaction. (2023) 12. Which of the following isomer of pentane (CsH:) will sive three isomeric monochlorides on photochemical chlorination? {b) CH3CH,CH;CH,CH3, (©) CHy-CH—CH,—CH (6) Allofthe above, (Term |, 2021-22) (ia) MEM (mar) 13. How ean you convert the following? But-1-ene to 1-iodobutane _(NCERT, 1/3, 2020) (ha) 14. Give reason for the following: Thionyl chloride method is preferred for preparing | alkyl chloride from alcohols. (13, 412019)(0) 15. Write equation for preparation of 1-iodobutane from 1-chlorobutane. (173,412019) 16. Howdo you convert: Propene to 1-iodopropane? (173,412016) | 17. Write the major product in the following : ‘CH, —CHy, Sor, ON (1/3, 12016) 18. Write the structure of the major product in the following reaction: Cy CH= C—CHye Hr—> nt (1/3,A12015) MMMM omar) | 19. Draw the structure of major monohalo product in each of the following reactions: @ (on 2 (i) Orono =CH, + HBr Perone, (Delhi 2014) | 20. Write the mechanism of the following reaction: CH;CH,OH“®" > CH,CH,Br+H,0 —(Al2014) (NCERT) © semned ith nt Seamer6.5 Preparation of Haloarenes 21. The species that attacks benzene in followingis - Oa= fa) cr 2 AIC, = (c) AICI, = (d) CI* (2023) 6.46 Physical Properties 22. Which of the following has highest ing point? fa) CHs—F (b) CHs— (0) CHs— (6) GHs—! (Term |, 2021-22) | 23. in the order Rel > ReBr > R-Cl > RF. Reason (R) : van der Waals’ forces decrease with increase in the size of halogen atom. (a) Both A and R are true and R is the correct explanation of A. (b) Both A and R are true and R is not the correct explanation of A. (c) Aistrue but Ris false. (A) Aisfalse but Ris true. EE 1 mary 24. Give reason for the following : Assertion (A) :Boiling pointsof alkylhalides decrease _ 31. | a2 (2020) | p-dichlorobenzene has higher melting point than | that of ortho or meta isomer. Explain the following : (1/3, 12019) 2s. Alkyl halides, though polar, are immiscible with | water. (NCERT, 1/2, Al2017C, 1/3, Foreign 2015) 26. lower than that of cyclohexyl chloride. Explain why the dipole moment of chlorobenzene is _ (NCERT, 1/3, Delhi 2016) 27. Give reason : r-Butyl bromide has higher point than t-butyl bromide. (1/3, Delhi 2015) 6.7 Chemical Reactions | 35. MO 28. Which of the following molecules has a chiral centre correctly labelled with an asterisk(")? (a) CH,C'HBrCHy, (b) CH,C'HCICH,Br (9) HOCH,C'H(OH)CH,OH (d) CHsC’Br,CH, 29. Consider the following compounds On Ore (2023) | the correct order of reactivity towards S2 reaction (a) toto (b) > t>t (2 Werm (@) M>ton (Term , 2021-22) In the reaction, Optra tor compound "is © Crowes @ ()-on © 90 (Term 1, 2021-22)(n) Enantiomers differ only in {a) boiling point (0) rotation of polarised light (€)_ melting point (@) solubility. (Term 1,2021-22)(8)) Assertion (A) : Chlorobenzene is less reactive towards nucleophilic substitution reaction. Reason (R) : Nitro group in chlorobenzene increases its reactivity towards nucleophilic substitution reaction. (a) Both A and R are true and R is the correct explanation of A. (b) Both A and R are true and R is not the correct ‘explanation of A. (c) Aistrue but Ris false. (d) Aisfalse butRistrue. (Term, 2021-22)(U) (a) Wurtz reaction (©) Fitting reaction Racemisation occurs in (a) Sy2 reaction (b) Sy reaction (0) neither 5,2 nor Sy reaction (d) Sy2reaction as well as S,.1 reaction. (2020)(f) ‘The conversion of an alkyl halide into an alcohol by ‘aqueous NaOH is classified as {a) adehydrohalogenation reaction (b) a substitution reaction (©) anaddition reaction (@) adehydration reaction (2020)(0) ). Out of the following, the one which is most reactive towards nucleophilic substitution reaction is (a) CH; =CH—CI (b) CoHs—Cl (0) CH;CH=CH—CL (d) CH,-CH,-CH,-Cl (2020¢) © semned ith nt SeamerEE (1 mark Read the passage given below and answer the following questions (Q. No. 37 to The substitution reaction of alkyl halide mainly occurs by Sy1 or Sy2 mechanism. Whatever mechanism alkyl halides follow for the substitution reaction to occur, the _ polarity of the carbon halogen bond is responsible for these substitution reactions. Therate of Sy1reactionsare governed by the stability of carbocation whereas for Sy2__ reactions steric factor is the deciding factor. Ifthe st material is a chiral compound, we may end up with an inverted product or racemic mixture depending upon the type of mechanism followed by alkyl halide. Cleavage of ethers with HI is also governed by steric factor and stability of carbocation, which indicates that in organic chemistry, these two major factors help us in deciding the kind of product formed. 37. Predict the stereochemistry of the product formed if anoptically active alky| halide undergoes substitution reaction by S,1 mechanism. 38. Name the instrument used for measuring the angle by which the plane polarised light is rotated. Predict the major product formed when 2sbromopentane reacts with alcoholic KOH. 40. Give one use of CHI, 3 41. Write the structures of the products formed when _ anisole is treated with HI. (2020) 42. ower )-ciycians cr, ch hich react faster in $,,1 reaction with OH"? (One word, 2020) 43, Why is t-butyl bromide more reactive towards S,.1 reaction as compared ton-butyl bromide ? 44, Out of chlorobenzene and cyclohexyl chloride, which one is more reactive towards nucleophilic ‘substitution reaction and why ? (2019) 45. Which alkyl halide from the following pair would you ‘expect to react more rapidly by an Sy2 mechanism? CH, (CHy— CH, — ot — BrorCH;—C—Br CHs 46. Out of chlorobenzene and benzyl chloride, which one sets easily hydrolysed by aqueous NaOH and why? (2018) (fim) | 47. OutofCH,—CH—CH,—Cland Hy Hy CH= CH—=CL which is more reactive CH towards Sy1 reaction and why? 48. Write the structure of an isomer of compound C.HyBr which is most reactive towards Sy reaction. (a12016) 19. Which would undergo Sy2 reaction faster in the following pair and why? (2019) © Hs (A12019)(i0) | (Deihi 2016) p CHs—CHa— Brand cHs—¢—CHy Br (Dethi 2015) | 90. Which would undergo Sy1 reaction faster in the following pair: fr CHy—CH,—BrandcH,—¢—cH, br (412015) 51. Which would undergo 5,2 reaction faster in the following pair and why? (CHy—CH,—BrandCHs—CH;—1 (Foreign 2015) | 52. Identify the chiral molecule in the following pair: Ee ges (a12014) 53. Which halogen compound in each of the following pairs willreact fasterinS,2 reaction: (0 CHBror CH! (i). (CH,)sCClor CHCl (Al 2014, Delhi 2014C) MBM emerts) 54. (a) CH —CH—CHy Ae yg AEN on (b) CH,CH,CH,Cl+ KOH S24, 4 HBr (2023) | 55. Why haloarenes are not reactive towards nucleophilic substitution reaction? Give tworeasons. (2023) | 56. In the following pairs of halogen compounds, which would undergo $2 reaction faster? Given reason in support of your answer. ant A tis (i cHy—¢—c1 ,cH,—cH,—c1 Hy 57. Write the mechanism ofthe following Sy reaction. (CH3)3C—Br 24 (CH,),C—OH + NaBr (2/3, 2020) (2021¢) 58. Givereasons: (i) Racemic mixture is optically inactive. (il) The presence of nitro group (—NO,) at o/p positions increases the reactivity of haloarenes towards nucleophilic substitution reactions. (Al 2019, 2/3, Delhi 2015) 59. Give reasons: (i) C—Cl bond length in chlorobenzene is shorter than C—Cl bond length in CH—Cl. (i) Sy reactions are accompanied by racemization in optically active alkyl halides. (2/3, Delhi 2016) (ip) 60. Howdo you convert? (i) Chlorobenzene to Biphenyl (i) 2-Bromobutane to but-2-ene (2/3,A12016) © semned ith nt Seamer61. (i) Whyis butan-1-ol optically inactive but butan-2-1 is optically active? (ii) Although chlorine is an electron withdrawing group, yet it is ortho, para-directing in ‘electrophilic aromatic substitution reactions. ‘Why? (2/3, Foreign 2015) ‘Which alkyl halide from the following pair is chiral and undergoes faster S,2reaction? a~s, 0 YO - Br ‘Out of 5,1 and $,2, which reaction occurs with (@) inversion of configuration (0) racemisation? (2/3, Dethi2014)2) ‘Which alkyl halide from the following. pairs ‘would youexpect to react more rapidly by anS,.2 mechanism and why? CH=CH GHC Br 62. (i) Gi) 63. (i) ‘CH, —CH,—CH,—CH,—Br (i) Racemisation occurs in Sy reactions. Why? (Foreign 2014) (An) 64, What are ambident nucleophiles? Explain with an ‘example. (2/3,A12014C)(R) HET (3 marks) 65. Write main product formed when (a) Methyl chloride is treated with Nal/Acetone. (b) 24,6trinitrochlorobenzene is subjected to hydrolysis. (€)_m-Buty| chlorideis treated with alcoholic KOH, (2023) 66. Give reasons: (a) Grignard reagent should be prepared under anhydrous conditions, (b) Alkyl halides are “immiscible with water although they are polar, and (© Chloroform is stored in dark coloured bottles | filled up to the brim. (20200) | (a) Define the following terms | () Enantiomers (i) Racemic mixture (b) Why is chlorobenzene resistant to nucleophil substitution reaction ? (2019) () Outof (CH,)C — Br and (CH,),C — 1, which one is more reactive towards Sy1.and why? | (i) Write the product formed when p-nitro~ chlorobenzene is heated with aqueous NaOH at | 443K followed by acidification. (ii) Why dextro and laevorrotatory isomers of butan-2-ol are difficult to separate by fractional lation? (Delhi 2019) BE mais) ‘The following questions are case-based questions. Read the case carefully and answer the questions that follow: 69. ‘Nucleophilic Substitution Nucleophitic substitution reaction of haloalkane | ‘can be conducted according to both Sy1 and Sy2 mechanisms, Sy is a two step reaction while Sy2 | 67. is a single step reaction. For any haloalkane which ‘mechanism is followed depends on factors such as structure of haloalkane, properties of leaving group, ‘nucleophilic reagent and solvent. Influences of solvent polarity : In Swi reaction, the polarity of the system increases from the reactant to the transition state, because a polar solvent has a greater effect on the transition state than the reactant, thereby reducing activation energy and accelerating the reaction, InSy2 reaction, the polarity of the system generally does not change from the reactant to the transition state and only charge dispersion occurs. At this time, polar solvent has a ‘great stabilizing effect on Nu” than the transition state, thereby increasing the activation energy ‘and slow down the reaction rate. For example, the decomposition rate (Sy1) of tertiary chlorobutane at 25°C in water (dielectric constant 79) is 300000 times faster than in ethanol (dielectric constant 24). The reaction rate (Sy2) of 2-Bromopropane ‘and NaOH in ethanol containing 40% water is twice slower than in absolute ethanol. Hence, the level of solvent polarity has influence on both Sy1 and ‘Sy2 reaction, but with different results. Generally ‘speaking weak polar solvent is favourable for Sy2 reaction, while strong polar solvent is favourable for ‘Sy. Generally speaking the substitution reaction of tertiary haloalkane is based on S,1 mechanism in solvents with a strong polarity (for example ethanol containing water) ‘Answer the following questions. (a) Why racemisation occurs in S12 {b) Why isethanol less polar than water? ing in each pair is more reactive towards Sy2 reaction? () CHyCH,—lor CHsCH,—CI {€)_ Arrange the following in the increasing order of their reactivity towards Sy1 reactions: ()) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane (ii) 1-Bromo-3-methylbutane, 2-Bromo-2 ‘methylbutane, 2-Bromo-3-methylbutane (2023) tals, E 70. Major product formed in the following reaction cH, cH,—d-er+naocH,—> by, ‘cs Hs (a Hyc-€-oNa—) CH—C-0CH bs, bn, © semned ith nt SeamerGs CH Gis i) oi eof cn, (d) CH;—C=CH, Hy CHy (erm ,2021-22)(fi) BES man) 7.1L. Write the major product(s) ofthe following reaction: c one. 4,50, O = (1/3, 2020) 72. Out of 2-bromopentane, 2bromo-2ethybutane | -bromopentane, which compound. is reactive towards elimination reaction and why? (1/3, Al 2019)» EET 2 mars) | 73. Write the major product(s) inthe following : | @ 20 PO ayate? (i) CHy—CH,—Br “5 (2/3,412016) | 74. Write the structure of the major product in each of the following reactions : (i) CHy—CH,—CH,—CH—CH,+KOH Ettanel, Br © | a O +cH,ci ACh, 75. Write chemical equations when (i) ethyl chlorides treated with aqueous KOH. (il) chlorobenzene is treated with CH,COCI in presence of anhydrous AICl, (Foreign 2014) _ 76. Write chemical equations when i (i) methyl chloride is treated with AgNO;. | (2/3, 412015) (ii) bromobenzene is treated with CH,CI in the | gi. presence of anhydrous AlCl. (Foreign 2014) _ HEY (3 marks) ——— 77. (i) Write the structure of major alkene formed by f-elimination of 2, 2, 3-trimethy-3-bromopentane ‘with sodium ethoxide in ethanol. (i) Which one of the compounds in the following pairsis chiral? i Br Br Aw (i) Kdentity (A) and (B) in the following: 8 wcities y (2020) a) Identity A,B, C,D, E and Fin the following : et® p at#5a whips accratcficon [Natirether Hy CH CH € Cs Juocss, e (2020) i) ‘Among all the isomers of molecular formula C.HyBr, identity (a) the one isomer which is optically active. (b) theone isomer which ishighly reactive towards S,2. (€) the two isomers which give same product on dehydrohalogenation with alcoholic KOH. (2019) (a). Identify the chiral molecule in the following pair: tae w i) (b) Write the structure of the product when chlorobenzene is treated with methyl chloride in the presence of sodium metal and dry ether. (C) Write the structure of the alkene formed by dehydrohalogenation of — 1-bromo-1- methylcyclohexane with alcoholic KOH. (2018) Following compounds are given to you: 2-Bromopentane, 2-Bromo-2-methylbutane, 1-Bromopentane (i) Write the compound which is most reactive towards S,2 reaction. (ii), Write the compound which is optically active. Write the compound which is most reactive towards f-elimination reaction. (Dehi 2017)(U)) CBSE Sample Questions 6.4 Methods of Preparation of | Haloalkanes Mm 1. Major product obtained on reaction of 3-phenylpropene with HBr in presence of organic peroxide is (a) S-pheny!-1-bromopropane (b) 1-phenyl-3-bromopropane (©) 1-phenyl-2-bromopropane (d) 3-phenyl-2-bromopropane. (Term, 2021-22) Alkenes decolourise bromine water in presence of CCl, due to formation of {a) ally! bromide (b) vinyl bromide (©) bromoform (4) vicinal dibromide. (Term |, 2021-22) © semned ith nt Seamer6.5 Preparation of Haloarenes MRM 3. The reaction of toluene with Cl, in presence of FeCl, ives ‘X while the reaction of toluene with Clin presence of light gives Y: Thus X’and"Y’ are (a) X= benzyl chloride, Y = o- and p-chlorotoluene {b) X= m-chlorotoluene, Y= p-chlorotoluene (c) X=0-andp-chlorotoluene, Y=trichloromethylbenzene (d) X= benzyl chloride, Y= m-chlorotoluene. (Term , 2021-22) 6.6 Physical Properties | 4. Which of the following isomers has the highest melting point? {a) 1,2-Dichlorobenzene (b) 1.3-Dichlorobenzene (©) 1.4-Dichlorobenzene (¢) Allisomers have same melting points. (Term |, 2021-22) 6.7 Chemical Properties | c= | 5. Which one of the following compounds is more reactive towards Sy! reaction? (a) CHy==CHCH,8r (0) C.H,CH.Br (0) CAHsCH (C,Hg8r (a) C.HsCHICHS) Br (2022-23) 6. Which of the followingis a correct statement for C3H,B? (a) Itreacts with metallic Na to give ethane. {(b) It gives nitroethane on heating with aqueous solution of AgNO}. {€) It gives C:HsOH on boiling with alcoholic potash. (a) It forms diethylthicether on heating with alcoholic KSH. (erm |, 2021-22) 7. Which reagents are required for one step conversion of chlorobenzene to toluene? (a) CH:CVAICl, (b) CH,CI.Na, dry ether (©) CH,Cl/Fe dark (4) NaNO,/HCI/0-5*C 8. Complete the following analogy: Same molecular formula but different structures : ‘A: Non superimposable mirror images: B (a) A; Isomers, B; Enantiomers {b) A:Enantiomers, B: Racemic mixture (c) A:Stereoisomers, B:Retention (d) A: Isomers, B: Stereoisomers (2020-21) (Ferm, 2021-22) | 9% Identify A,B, Cand D: kon ce Helen, « des noH 5 (a) A=CjH« B= CzHsOH,C =CHsNC,D=CHsCN (0) A= GoH:OH, B= CHa. C=CaHSCN,D=CHsNC (©) A= Gas, B = CaHsOH, C= C2HsCN, D= CoHsNC (d) A=C,H.OH,B=C,H,,C=C,H,NC,D=C,H,CN (2020-21) Ss) 10, Give reason for the following: (a) During the electrophilic substitution reaction of haloarenes, para-substituted derivative is the major product. (b) The product formed during Sy1 reaction is a racemic mixture. oR (a) Name the suitable alcohol and reagent, from which 2-chloro-2-methyl propane can be prepared. (b) Out of the chloromethane and fluoromethane, ‘hich one has higher dipole moment and why? (2022-23) LL. The followinghaloalkanes are hydrolysedin presence of aq. KOH: (i) 2-Chlorobutane (ii) 2-Chloro-2-methylpropane Which of the above is most likely to give a racemic ‘mixture? Justify your answer. (2020-21) | 12. With the help of resonating structures explain the effect of presence of nitro group at ortho-position in chlorobenzene. ‘oR Carry out the following conversions in not more than 2steps: (Aniline to chlorobenzene i) 2-Bromopropane to 1-bromopropane (2020-21) | EY mans) 19. (a) Identify the major product formed when 2cyclohexylchloroethane undergoes. a dehydrohalogenation reaction. Name the reagent which is used to carry out the reaction. (0) Why are haloalkanes more reactive towards nucleophilic substitution reactions than haloarenes and vinylic halides? oR (a) Name the possible alkenes which will yield 4-chloro-1-methylcyclohexane on their reaction with HCL Write the reactions involved, (0) Allyl chloride is hydrolysed more readily than n-propyl chloride. Why? (2022-23) © semned ith nt Seamer