PereRol Haloalkanes and Haloarenes aes HY JEE | UTJEE | WT IEE | JEE Advanced | JEE Advanced | JEE Advanced | JEE Advanced | JEE Advanced row | 2011 | 202 | 2013 a0 ois am16 2017 Paper_[ Paper | Paper | Paper Paper Paper Paper Paper “Topic tee etat: (ote fs [eto [ete Clasieation Nomen Natur of CX Bond Methods of Preparation 7 Pyscal Properties 1 Casnial Reactions 1 qi Poshalogen Compounds r v CUE 1. Benzyl elloride (C,HCH,CD can be prepared from tol- | 4. The order of reactivities of the following ally! halides uene by chlorination with: fora SN, reaction is: (a) soc, (8) soct, (A) RF> RCL> RBr> RE oa (D) Naocl (B)_RF>RBr> RCI> RE (ITT JEE. 1998) (©) RCL> RBr> RF> RI 2. Assertion: Addition of Bro -butene gives two optical (D) I> RBE> RCI> RE isomers. AULT JEE 2000) Reason: The product comtains one asymmetric carbon, (A) If both assertion and reason are correct, and rea- som is the correct explanation of the assertion, (B) Ifboth assertion and reason are correct, but reason is mot the correct explanation of the assertion, 5. Assertion: |-Butene on reaction with HBr in the pres- cence of a peroxide produces I-bromobutane Reasor (A) If both assertion and reason are correct, and rea- son is the correct explanation of the assertion, involves the formation of primary radical. (©) assertion is correet but reason is incorrect (B)_Ifboth assertion and reason are correct, but reason (D)_IFassertion i incartect but reason is correct. QO is not the correct explanation of the assertion. VT JEE 1998) (C) Lf assertion is correct, but reason is incorreet. <3: Tolnene,. when tied with: Br,/Be, elves p-bromecalu (D) IFassertion is incorrect, but reason is correct lene as the major product because the CH, group: (ITJEE 2000) (A) is pant ditecting. (B) is meta directing (C) activates the ring by hyper conjugation. (D) deactivates the ring. 6. Assertion: Addition of bromine to wans-e-bucene yields meso-2,3-dibromobutane. romine addition to an alkene is an electro- Philie addition, IT JEE 1999)(A) IP both assertion and reason are correct, and rea- som is the correct explanation of the assertion, (B) 1Pboth assertion and reason are correct, but reason is not the correct explanation of the assertion, (©) assertion is correct, but reason is incorrect (D) IFassertion is ineorreet, but reason is correct, 1 JEE 2001) IWientify the set of reagents/reaetion conditions X and Y in the following set of transformations CH, — CH, — CH, > product Scr, GH er (A) X= dilute aqueous NaOH, 20°C: ¥ acid, 20 °C. Be‘acetic (B)_X = concentrated aleoholic NaOH; 80 °C: ¥ HBr/acetie avid, 20°C (©) X= dilute aqueous NaQH, 20°C; ¥ = Br /CHCL,, (D)_ X=concentrated aleoholic NaOH, 80°C; Y cute, °C. (UT JEE Screening 2002) Among the following, the molecule with the highest pole moment is (a) CHCl © cul, (8) CHO, (D) ccl, (UT SEE Sere 18 2003) ‘The major product formed in the following reaction is i ‘ “ayn a ne, ul N 7 cH, 5 @) HK. Ho N (©) Hee. OI Cy Cy Br Ho N (D) He. chs ee Br (ITT JEE Sereening 2004) 10, 7-Bromo-1,3,5-eyetoheptatriene exists as ionic species n aqueous solution while 5-bromo-1,3 cyclopentadiene does not ionise even in the presence of Ag (aq). Explain. (IIT JEE Main 2004) 11, Inthe following reaton sequence identity A 10D. a ew ene Hot, 9 200, “ow 4 Sagres > 8 EO SP (UT SEE Main 2004) 12, What is the product formed when I-bromo-3-chlorocy- clobutane reacts with two equivalents of metalic sociurn in presence of ether? a a) ® 8 © ) (IT SEE Sereening 2005) 13. When phenyl magnesium bromide reacts with ert butanol, the product formed is (A) benzene, (B) phenol (C) tert-butyl benzene. (D) tert-butyl phenyl ether (IT JEE Sereening 2005) 14, Give reasons: @ o HE er (CHs cruomiay ASIN ite solutionC CO. 4 NOz «) aT Ly | SH PaiC| 3 mole of He ( (~ )) stores A eater J ~ (IT JEE Main 2005) 15, Inthe fllowing reaction sequence err (Brown tunes and 8 a get, Co €iIntermaciate) > b (Espiosive product Identify A, B, C, and D. Also write chemical equations: for conversion of A to Band A to C. (IT JEE Main 2005) 16, cH Hye SEES M Gsomeric C:Hy0! = m isomeric cH, preduts produ) What are N and M? (A) 66 (B) 64 © 44 (D) 33 (UT SEE 2006) 17. The reagent(s) forthe following conversion: BN Ay to ivare (A) alcoholic KOHL (B) alcoholic KOH following by NaNI, (C) aqueous KOH followed by NaNH, (D) VZn'CH,0#, (IIT SEE 2007 Paper-1) 18, Statement-t: Bromobenzene upon reaction with Br,/Fe ives 1,4-dibromobenzene as the major product and Statement-2: In bromobenzene, the inductive effect of the bromo group is more dominant than the mesomerie effect in directing the incoming electrophile. (A) StatementI is True, Statement-2 is True; Siate- ment-2 is correct explanation for Statement-1. (B) Statement is True, Statement-2 is True; State- ment-2 is not a correct explanation for Siate- ment (©) Statement-1 is True, Statement-2 is False. (D) Statement1 is False, Statement-2 is True. (IIT SEE 2008 Paper-1) 19, The major product of the following reaction is Mo. 8 F Pst towne No, Ma. SPH Me seh F F w ff B ZMeer Me. ,SPh © o No; No; IFT JEE 2008 Paper-1) 20, The synthesis of 3-oetyne is achieved by adding a bro- roalkane into a mixture of sodium amide and an alkyne. The bromoalkane and alkyne, respectively, are (A) BICHCH, CH,CH,CH, and CH, CHC (B) BICHI, CH, Cll, and CH, CH, CH,C= CU. (©) BOCH, CH,CH,CH, CH, and CH, C= CH. (D) BICH, CH, CH,CH, and CH,CHLC= CHL IT SEE. 2019 Paper-1) H. 21, KI in acetone undergoes S,2 reaction with each of P, Q, Rand S. The rates of the reuction vary as wo SS a ie—01 > a ( 2 , ° A é (A) P>Q>R>S. (B S>P>R>Q (©) PoR>O>8 (D) R>P>S>Q (GEE Advanced 2013 Papert) 22, The reactivity of compound Z with diferent halogens ander appropiate contitiens is given below Pa Cue Pho olaserved pattern of electrophilic substitution can be explained by (A) the steric effect of the halogen. (B) the steric effect ofthe tert-butyl group. (©) the electronic effect of the phenolic group. (D) the electronic effect ofthe Jert-butyl group. (IRE Advanced 2014 Paper-1) Mono-ralo eubetutes devatve when X= Dial substivtod dorvatve when X,= Bip Tishala substituted dervatve when X= Cle 23. In the following reaction, the major product is cat ei ow oo omy we & B® © ) NS ts Hye Ae a os on we Ne, (IEE Advanced 2015 Paper-1) 24, Compounds) that on hydrogenation produce(s) opti- cally inactive compounds) is(are) te 90! 8 eNom B) Och @B) Ne SH © om, ®) tue (GEE Advanced 2015 Paper-1) 25. In the following monobromination reaction, the number of possible chiral products is CHCHCHy 10m fe = 0G CH (1.0 moley (Enantiomercaly pure) (IEE Advanced 2016 Paper-1)ANSWER KEY LO 2A 3A) 4.0) 12D) 1A) 16 (B) 1B) BC) 23. (D) 24. (B),(D) 25.5 50) 19.) 6. (B) 20. (D) 7. (B) 21. (B) BA) 9B) 22. (A), (B).(C) ANSWERS WITH EXPLANATIONS. 1. Topie: Methods of Preparation Bonzy! chloride can be prepared ftom toluene by chlo- ination with Cl, Hs cH.cl +H! Answer (C) 2. Topie: Methods of Preparation Assertion is correct that Addition of Br, to L-butene ives two optical isomers. Reason is correct that the product contains one asym- metric carbon, And reason is correct explanation of the Answer (A) 3. Topic: Methods of Preparation Toluene, when treated with Br/Fe gives p-bromotoulene as a major product because the CI, group is para ditect= ing and deactivates the ring, hs hy Answer (A), (D) 4. Topic: Nature of C—X Bond SN, reaction depends on steric hindrance, The order of reactivity inereases down the halogen group Therefore, onder of reetivity ofthe alkyl halides for SN, reaction is: RI > RBr> RCI> RF. Answer (D) 5. Topic: Methods of Preparation 1 -Butene on reaction with HBr in presence of a peroxide produces I-bromobutone, 6. h (tty — CH, — CH, — Br Therefore, assertion in correet It involves the formation of primary radical reason is incorrect. I involves formation of secondary radicals. Answer (C) ‘Topic: Methods of Preparation Addition of bromine to trans-2-butene yields meso-2, 3-dibromobutane. This assertion is correc. Bromine addition to an alkene is an electrophilic adui- tion. The reason is correct, But this is not correct expla nation ofthe assertion, Answer (B) ‘Topic: Chemical Reactions The given reaction sequence depicts dehydrobromina- tion of I-bromopropane by strong base to form [-pro- pene followed by Markonixov addition of HBr to give 2-bromopropane, The reactions, along with reactants tnd reaction conditions are as Follows: SCAPIES Cis — CH= Cte Procuct oH —EH— Br Answer (B) Nature of CX Bond CH, molecule is symmetrical, so it has zero dipole moment. Replacement of one of the H-atom by one CY atom increases the dipole moment. The increase in dipole moment is more than the expected value because the bond dipole moment of C-H bond and C-CI bond tre in the same direction and so strengthen each another, Replacement of another I-atom of Cl increases the bond angle due :o lone pair lone pair repulsion between two Cl atoms, thereby reducing the dipole moment of the molecule, Replacement with the thitd Cl atom furs ther increases the bond angle and reduces the dipolemoment, When the fourth Cl atom is introduced, the riolecule (CCL) again becomes symmetrical and dipole ‘moment reduees to zero, So, CH,CI will have the ma ‘mum dipole moment. Answer (A) 9. Topic: Chemical Reactions The given reaction is an example of electrophilic sub- stitution action (bromination) on substituted aromatic ring. The reaction occurs usually at the electron density rich ortho- and para-positions, The ring to which the KH group of the substivuent is attached, has inereased electron density due to resonance (+M) effect, so under- oes substitution, Since the ortho-position is occupied; bromine substitution takes place atthe para-position. Ho nyo Hey A AL cH paar, HOV AN cls Af 2 Br Answer (B) 10, Topic: Chemical Reactions The intermediate carbocation formed on ionisation of F-bromo-13S-cyeloheptattiene is an aomatic co pound (6 peelectrons, so Iluckel’s rule, An + 2is obeyed) and hence highly stable o=6 ‘Aromatic fon (ight stable) The carbocation formed from S-bromo-1,3-cyelopenta- iene will be anti-aromatic and hence high unstable, so it does not undergo ionisation, even in the presence of Ag(aq) ions. AA ‘Antvaromati ion ‘highly unstable) 11, Topic: Chemi The reuetion sequen: 11 Reactions Sed Oo on™ _socwcraie Co D 2 13, enero ‘CH, ae c ‘Topic: Polyhalogen Compounds (On reaction with two equivalents of sodium in presence of ether, I-bromo-3-chlorocyelobutane undergoes intra- ‘molecular Wurtz reaction Br 4+ NaBr + Nac or Answer (D) “Topic: Chemical Reactions Phenyl magnesium bromide reacts with feri-butanol to form benzene. The mechanism as shown below: Hy i: cy, 1 nyt by" ten I Oo Se I Answer (A)14, Topic: Chemical Reactions (a) In reaction (i), tertiary alkyl halide undergoes nucle- phic substittion by S,1 mechanism and reaction mixture is acidic du to presence of hydrogen ions. os os mf SEM my 06a tr bu by In reaction (i, the phenyl halide is relatively unte- active towarcs nuclenphilic substitution both by 1 and $,2 mechanism. The presence of eleiron-eles- ing allyl group onthe benzene ring further decreases thVe reactiviny cH, — HCH “6 In reaction (i), the aryl halide can undergo mucleo- philic substitution reaction due to the presence of strong electron withdrawing groups at ortho- and ara positions. Nog CH ES No reaction icy In reaction (i), there is no mesomeric effect of the nitro group on ortho and para position is observed, ong c In reaction (i), due to +M effect of -NO group, NO sgroup is electron donating and artho-, pura- ditect ing in electrophilic aromatic substitution reaction {In reaction (ii), due to -M effect of NO,, NO, group as electron withdrawing and meta-directing in elec- twophilic aromatie substitution reaction (@) In the given reduction reaction, if the eeniral ring is reduced, three Foursmembered anti-aromatic rings can be stabilised. On the other hand, ifthe terminal ring is reduced, then only one anti-aromatie ring ean be stabilised 18, Topic: Chemical Reactions ‘The overall reaction sequences are 2H,SO,+ 2NaBr—+ MnO, + Br, +Na,SO, * sein +MnSO, +2H,0 H,$0,+ HINO, > HSO, +NO,+H,0 * c on. ots Ne NOs +303, +o No, TAT) 16. Topic: Chemical Reactions “The possible isomeric products (N) formed from the reaction are one Gs i e “ ee te kg - oy ne He ‘5 chs ctestatn TEST Petes wn am % ie wed oneay ned ocne & Thus, a total of 2+ 2+ 1 + 1=6 isomer Since d, Fisomers cannot be separated on fractional Ullation, so the isomers (M) are four: onl HE—C— CHG + HE —CH— Ch chy formed, GH: 9 lee HaC—C—CH.CH, 4 Answer (B) 17. Topic: Chemical Reactions ‘The conversion reactions are as follows: ne itHence, the requited reagems are alcoholic KOH fol- lowed by NeNII, Answer (B) 18, Topi In bromobenzene, it is the mesomeric effet which reels the incoming electrophile, themical Reae' wr we AL sn, Ry Oe i ‘astra erzane 1.4-cibroma benzene: (Major product Answer (C) 19, Topic: Polyhalogen Compounds The nucleophilic substitution will preferably take place oon alky! halides than on aryl halides. The reaction pro- ceeds by 5,2 mechanism (polar aprotic solvent DME) nd results in inversion of configuration of the product @sPh iS ie no, Answer (A) themical Reactions mat ~ orig” 20, Topi The reaction for formation of T-octyne is CH, CH, ~C= Ch $CH, ~CH, <= CNet cH, -CHH cH, [Br Nal] C= C-CH, ~CH, + CH,CH,CH,CH.C= —CH,CH, + Nabe Answer (D) 21, Topic: The relative reactivities towards S,2 reaction $ > P >R >a themical Reactions Answer (B) 22, Topic: Polyhalogen Compounds + ltBuhy) tor on ‘ Ss i £8 4 C(CHaly on on cok a Ka + Gp(Leastbyy) —> (7 Scictye ‘C(CHa)» & & Answer (A),(B).(C) 23. Topic: Methods of Preparation 1 A-addition is the major product as itis the result ofthe formation of a stable allylic carbocation. cH, OH ier ‘i bi Answer (D)_ 24, ‘Topic: Physical Properties a Ha Sel sal el owen a a oe we © oe pica inactive “Answer (B).(D)25, Topic: Polyhalogen Compounds A total of 5 chiral and 2 achiral produets are possible on. ‘monobromination ofthe given compound, (HCH oH, Ch —cH,— cH, 1 re csc al es Hy oH ci eal rset ‘Ohl reduce CCH ~ Chis oy ei poset Os * hil product Gat + uaa Cacrerer —— Veale oH oy onal eect tl pr Gate Answer (8) eto OH Chiral prot