Haloalkanes and Haloarenes \ Previous Years’ CBSE Board Questions / 6.1 Classification | a 1. Which one of the following halides contains | Ca2—X bond? {a) Ally! halide (b) Alkyl halide | (©) Benzyl halide (4) Vinyl halide | (erm), 2021-22)(%) | = 8 3 4 nat ne anexample of a benzylic halide? 6.2 Nomenclature 7. Write the structure of 3-bromo-2-methylprop- 4-ene. (Deihi 2017)(0) 8. Draw thestructure of 2-bromopentane, (Delhi 2014C) 9%. Write the IUPAC names of the following compounds : (i) CHy==CHCH,8r fi) (Cely,cc (3: 10. Give the IUPAC names of the following compounds : () CHy—CH—CH—CHy (A\2014C) Br -d, (ii) CH,=CH—CH,—Ch (Al 2015C)(Hp) | | LL. The synthesis of alky! flouride is best obtained from (a) Free radicals (b) Swarts reaction (€) Sandmeyer reaction (d) Finkelstein reaction. (2023) ‘Which of the following isomer of pentane (CsH,:) will give three isomeric monochlorides.on photochemical chlorination? (a) aay (b) CHyCH{CH3CH,CHy b I—CH.—CHs (d)_Allof the above. (Term 1, 2021-22) in} the following? iodobutane —(NCERT, 1/3, 2020)(ii} chloride method is preferred for alkyl chloride from alcohols. (1/3, A12019)(U)| ‘Write equation for preparation of 1-iodobutane from 1-chlorobutane, (1/3, 412019) How do you convert : Propene to 1-iodopropane? (1/3, Al 2016) ‘Write the major product in the following : Ky mae ON (1/3, Al 2016) ‘Write the structure of the major product in the following reaction: rae a (1/3, 412015) SS 19. Draw the structure of major monohalo product in ‘each of the following reactions : 0 Coe (ii) (NCERT) CH) — CH=CH, + HBr Peso, (Deihi 2014) | 20. Write the mechanism of the following reaction: CH,CH,OH > CH,CH,Br+H,0 (Al 2014)6.5 Preparation of Haloarenes 0 ‘21. The species that attacks benzene in followings a | 30 +a, “> | (cr (HAI, @) AIC, a) cr ¥ : (2023) 6.6 Physical Properties MO 22. Which of the following has highest boiling point? * (@) C.H.—F (b) C.H,—Cl | (0 C,H,—Br (dé) CzHs—1 (Term |, 2021-22) 29. Assertion A): Boiling points of alky| halides decrease — in the order R-I > R-Br > R-Cl > R-F. | 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 explanation of A. Ais true but R is false. Ais false but Ris true. prachlerabeacine he higher &aiéeg pink. than that of ortho or meta isomer. (1/3, 12019) | Explain the following : ‘Alkyl halides, though polar, are immiscible with — water, (NCERT, 1/2,A12017C, 1/3, Foreign 2015) | . Explain why the dipole moment of chlorobenzene is. | lower than that of cyclohexyl chloride. (NCERT, 1/3, Delhi 2016) | ie Give reason : n-Butyl bromide has higher boil i. point than t-butyl bromide. (1/3, Delhi 2015) 6.7 Chemical Reactions 27. Wt | | | 28. Which of the following molecules has a chiral centre: | correctly labelled with an asterisk(*)? | (a) CH,C’HBrCH, | (b) CH,CHCICH, Br | (@) HOCH,C'H(OH)CH,OH | (d) CH;C’Br,CH, | 29. Consider the following compounds Cra Conn y< mn | the correct order of reactivity towards Sy2 reaction (@) ttle tt (b) Hott t (@ Wot d) >to (Term |, 2021-22) In the reaction, O-2- atthe toy ‘compound 'Y' is © )-omesr (a) ©-on ao) @O<) (Term 1, 2021-22) (is) . Enantiomers differ only in (a) boiling point (b) rotation of polarised light (©) melting point (d) solubility. (Term 1,2021-22)(#) Assertion (A) : Chlorobenzene is less reactive towards nucleophilic substitution R are true and R is the correct of A. R are true and R is not the correct explanation of A. (c) Aistrue but Ris false, (@) Aisfalse but Ris true, ‘The reaction given below: ci CH or sana crc OF +2NaCl is called (a) Wurtz reaction (c) Fitting reaction (Term |, 2021-22) (b) Wurte-Fitting reaction (4) None of the above (20210) . Racemisation occurs in (a) Sy2reaction (b) SyLreaction (c) neither 5,2 norSy1 reaction (d) S,2reactionas well as 5,1 reaction. (2020)(7) ‘The conversion of an alkyl halide into an aleohol by ‘aqueous NaOH is classified as (a) adehydrohalogenation reaction (b) asubstitution reaction (c) anadditionreaction (4) dehydration reaction (2020)(0) Out of the following, the one which is most reactive towards nucleophilic substitution reaction is (a) CH;=CH—CI (b) CcHs—Cl () CH,CH=CH—Cl (d) CHy-CH,-CH,-Cl (20200)HEE 1 mark) Read the passage given below and answer the following questions (Q. No.37 to 41): The substitution reaction of alkyl halide mainly occurs by Syl or S,2 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. The rate of Sy1 reactions are _ governed by the stability of carbocation whereas for S.2 _ reactionssteric factor isthe deciding factor. If the starting material is a chiral compound, we may end up with an inverted product or racemic mixture depending upon _ tthe 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. tes 37. Predict the stereochemistry of the product formed if | “~~ anopticallyactivealkylhalideundergoes substitution _ 52. fr BrandCH,—C—CH, Br CH .—CH,— (Dethi 2015) 1. Which would undergo S,1 reaction faster in the following pair : ing pai os CH;—CH,— Br and CH,—C—CH, (2015) | Which would undergo S,2 reaction faster in the following pair and why? CHs—CH,—Br and CHs—CH,—1__ (Foreign 2015) Identify the chiral molecule in the following pair: GY (a12014) Which compound in each of the following pairs will react faster in5,.2 reaction: reaction by $1 mechanism. ()) CH3Br or CHa! Gi) Voevatouien a 38, Name the instrument used for measuring the angle by which the plane polarised light is rotated. ETH 2 maris 99. Predict the major product formed when | 54. (a) CHy —CH—CHy—POh 5.4, ACN 7 2-bromopentane reacts with alcoholic KOH. Bi 40. Give one use of CHly ee 7 41. Write the structures of the products formed when | (b) CH,CH,CH,CI+ KOH S81, 14 Hee ‘s za anisole is treated with HI. (2020) | 55 Why wre: tok ‘vosdtleas & ~ outot()—crictand cit, which wil i react faster in Sy1 reaction with OH"?(One word, 2020) |. Why is t-butyl bromide more reactive towards Sy1 reaction as compared ton-butyi bromide? (2019) |. Out of chlorobenzene and cyclohexyl chloride, which one is more reactive towards nucleophilic | substitution reaction and why ? (201! Which alkyl halide from the following, expect to react more rapidly by an Sy2_ CH, I 45. CHy— CH, — CH —BrorCHy— CH; - Out of chlorobenzene and benzyl chloride, which one | gets easily hydrolysed by aqueous NaOH and why? (2018)(in) | 47. Onto H, —GI= CH= Chand Hy Chace —el Which; mimorms eascive| CHa towards Sy1 reaction and why? (Delhi 2016) | Write the structure of an isomer of compound CiHo8r which is most reactive towards Sy1 reaction. _ (12016) | Which would undergo Su2 reaction faster in the | following pair and why? 1 49. ‘nucleophilic substitution reaction? Give two reasons. (2023} |. In the following pairs of halogen compounds. would undergo S,2 reaction faster? Given reason in support of your answer. (2021C) following Sy1 reaction. NaOH T(CH,),C—OH+NaBr (2/3, 2020) Give reasons: () Racemie mixture is optically inactive. (ii) The presence of nitro group (—NO,) at o/p positions increases the reactivity of haloarenes towards nucleophilic substitution reactions. (A12019, 2/3, Delhi 2015) Give reasons : () C—Cl bond length in chlorobenzene is shorter than C—Cl bond length in CHy—Cl. (ii) Sy1 reactions are accompanied by racemization inoptically active alky! halides, (2/3, Delhi 2016) (i) How do you convert? () Chlorobenzene to Biphery (ii) 2-Bromobutaneto but-2-ene (2/3, Al2016)64. (i) Why is butan-1-ol optically inactive but butan-2-ol is optically active? (i) Although chlorine is an electron withdrawing group, yet it is ortho-, para-directing in electrophilic aromatic substitution reactions. Why? (2/3, Foreign 2015) | 62. (i) Which alkyl halide from the following pair is chiral and undergoes faster S,,2 reaction? i o ~ i) Outer ad 5,2, which reaction occurs wth (a) inversion of | (2/3, Dethi 2014)(in) | im, (b) racemisation? 63. (i) Which alkyl halide from the following pairs would you expect toreact more rapidlybyanS,2 mechanism and why? | CASE E hte —cH,—CH,—CH,— ’ (i) Racemisation occurs inS,1 reactions. Why? | (Foreign 2014)(in) 64, What are ambident nucleophiles? Explain with an example. (2/3,A120140)(8) | 65. Write main product formed when (a) Methy! chloride is treated with Nal/Acetone. {b) 2,4,6+trinitrochlorobenzene is subjected to hydrolysis. {€)_mButyl chloride is treated with alcoholic KOH. (2023) | 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. (2020) | 67. (a) Define the following terms : (i) Enantiomers ii) Racemic mixture | (b) Why is chlorobenzene resistant to nucleophilic _ ‘substitution reaction ? (2019) ‘Out of (CH,),C — Br and (CH,),C —1, which one | is more reactive towards S,,1 and why? (ii) Write the product formed when p-nitro- chlorobenzene is heated with aqueous NaOH at 443 K followed by acidification. (il) Why dextro and isomers of | distillation? (Dethi 2019) | is a single step reaction. For any haloalkane which mechanism is followed : Influences of solvent polarity : In Sy1 reaction, the polarity of the system increases from the reactant to the transition state, because a polar solvent has ‘on the CaM se ‘state than the ns reducing activation energy and accelerating the reaction, InS,,2 reaction, the polarity ST containing 40% water is tice bsolute ethanol. Hence, the level has influence on both $1 and tertiary haloalkane is based on 5,1 mechanism in solvents with a strong polarity (for example ethanol containing water) Answer the following questions. (a) Why racemisation occurs in $y? reactive towards Sy2 reaction? @ CH,CH,—I or CH,CH,—Cl ) (a or Ona oR (c)_ Arrange the following in the increasing order of their reactivity towards Sy! reactions: () 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane (ii) 1-Bromo-3-methylbutane, 2-Bromo-2 ‘methylbutane, 2-Bromo-3-methylbutane (2023) butan-2-ol are difficult to seperate by fractional | 5 Wsior product formed in the following reaction CH, UE 4 mars The following questions are case-based questions. Read the case carefully and answer the questions that follow: 69. Nucleophilic Substitution Nucleophilic substitution reaction of haloalkane can be conducted according to both Sy1 and Sy2 mechanisms. Sy1 is a two step reaction while Sy2 cH,—t-Br+Nsoct,—> Hy ‘Hy Hy () He—¢—ONe (b) CHe-F—-OCHy cH, CH,aie Hy Hy | () CHy-C—O—C—CH, (d) CHy—-C= Hs (erm 1,2021-22)\fa) | om [1 mark) 71. Write the major product(s) of the following reaction: a Cone. H,80, O * (1/3, 2020) 72, Out of 2-bromopentane, 2-bromo-2-methylbutane, and 1-bromopentane, which compound is most reactive towards elimination reaction and why? (173, 412019) m2 73. Write the major product(s) in the following : 0 se FH ota 1 (i) CHy»—CH,—Br (2/3,A12016) 74. Write the structure of the major product in each of the following reactions : W CH,—CH,—CH,—CH —CH+ KOH tenet, i) J cn, SeutAch, A201 ‘Write chemical equations when (i) ethyl chloride is treated with (ii) chlorobenzene is treated with presence of anhydrous AlCl. 2014) 7. Write chemical equations when (i) methyl chloride is treated with AgNOs. (ii) bromobenzene is treated with CH,CI in the presence of anhydrous AICI, (Foreign 2014) HE 3 77. (i) Write the structure of major alkene formed by frelimination of 2. 2, 3-trimethy|-3-bromopentane: with sodium ethoxide in ethanol. (i) Which one of the compounds in the following pairs is chiral? Nera: TL (iil) Identity (A) and (B) in the following : wee, Metsevetmer sg) (2020) (ia) Identity A,B, C.D, E and Fin the following : pce atts a 7 ster Hy =CH =CH, = c F (2020) (Kn) |. Among all the isomers of molecular formula CaHBr, identity (a) the one isomer which is optically active. {b) the one isomer which is highly reactive towards 5y2. (c) the Write the structure of the product when, chlorobenzene is treated with methyl in the presence of sodium metal and dry ether, (€) Write the structure of the alkene by dehydrohalogenation of + I-bromo-1- methyicyclohexane 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 $2 reaction. (i), Write the compound whichis optically active, (ii) Write the compound which is most reactive towards fi-elimination reaction. (Dethi2017)(i1) 64 Methods of Preparation of Haloalkanes MO 1. Major product obtained on reaction of ‘S-phenylpropene with HBr in presence of organic peroxide is (a) 3+phenyl-1-bromopropane (b) 1-phenyl-3-bromopropane (€) 1-phenyl-2-bromopropane (d) S-phenyl-2-bromopropane. (Term , 2021-22) Alkenes decolourise bromine water in presence of CCl, due to formation of (a) allyl bromide (b) vinyl bromide (c)_bromoform (d) vicinal dibromide. (Term |, 2021-22)