re 8 oe i ” ot enes ‘ Haloa ” a ¢ Chapter Analysis wart, Last 9 Veni aaa Exai f sen her gies you an analytical picture ofthis chapter 1 Th a ajdt om ean Pm Ma 3 Number of Questions asked in last 3 ye eo, Short Answer Type (3 ma Tong Answer (5 marks) | Value Based Questions (4 marks) | “s- 1n2015, in Delhi st, one question of 1 mark based on Sy2 Reaction ‘on Conversion were asked. * In All India scone question of | mark based on Sy1 Reaction and oni ‘Happens When Type of 3 marks were asked. + 11 2016, only one question of 3] marks based on Nucleophilic © [n2017, one same question in both sets of 3 marks based on $2 R B-elimination Reaction was asked. On the basis of above analysis, it can be said that, it feet cua grin energie oasc alogen derivatives are called peat joalkanes). They have general for \py the replacement of a hydroge Pe : a tam, ene ee sna), aomate halogen derenta po tad aryl halides or haloarenes. Haloalkanes Pe carton an eerie i larenes oats kala 2 nybridised carbon atoms of an aryl Joalkanes and haloarenes can be classified as no, di or polyhalogen compounds depending ‘yhether they contain one, two or more Jogen atoms in the structure. e.C,H,X-Monohaloalkane a Cr onohaloarene x i 2 | Dihaloalkane cat ‘ono halocompounds can be classified according p the hybridisation of the carbon atom to which he halogen is bonded. ompounds containing p° C-bond (a) Alkyl Halides In alkyl halides, the halogen atom is bonded to an alkyl group. They can be further classified as primary, secondary or tertiary. OPIC 1] Introduction, Nome ‘ Nclature and Preparation (b) Allylic Hat ic Halides iene These are the compounds allylic carbon. 'geN atom is bonded 4o an ” ~O (i) enzyle Hate xe Benaylc Halldes Tes ae the compo S rhich the halogen atom is ‘bonded to a 9 hyridised carbon atm nent tan aromatic compound (a) Vinylic Halides ‘These are the compounds in which : in which the i some bonded w se com ae ~ oO (b) Aryl Hialides These are the compounds in which the halogen atom is bonded to sp” hybridised carbon atom of an aromatic ring oe He Nomenclature ‘The common names of alky! halides are derived by naming the alkyl group followed by the halide. ‘Allyl halides are named as halo substituted hydrocarbon in the TUPAC system of nomenclature.Ben © chopterwise CBSE Solved Papers Rx +Hx (where, X =Cl, Br, I) From Alkenes Addition of halogen acids RCH =CH,+HX—> R— CHX— cH, (Markownikoffs addition) RCH = CH, +HX—™# 5 RCH, — CH,—X (Anti-Markownikoffs addition) Addition of halogens H c= + By SCL, arc, —CH,Br vic-dibromide_ 10; Haloalkanes and Haloarenes jc halogenation palkanes are prepared by treating alkyl fide bromide in the presence of a metallic fe such as AgF, Hg F,-CoF, or SbF). This n is known as Swarts reaction, AgF ——> Silver fluoride CHE Fluoromethane + AgBr Silver bromide dine-Hunsdiecker ion tally, bromoalkanes are prepared by the yn known as Borodine-Hunsdiecker reaction. pig ely OAR + Bl ——> CH,Br+ CO, + AgBr stein reaction \dides are often prepared by the reaction of lorides/oromides with Nal in dry acetone. ction is known as Finkelstein reaction. Acetone XNA =Cl Br 1.2 Preparation of Haloarenes Fecly dark let ae Benzene cuxynx a + nyor [where x=, wo a Sandmeyer ie action haha (eee cay ax a br= dlp oH Kea where, x (ii) + PX Phenol Njcr ones i NjBFy nore (| )+ Her, —__, ZF vorobore aed : a — +85 + Nt Fuorberzene ‘This reaction is called Balz-Schiemann reaction and is used to prepare fluoroarenes.260 —— YEARS Paevious EARS TOPIC 1 @1Mark Questions 4. Write the structure of , 4-dinitrochlorobenzene. elhl 2077 x = an which is an 2. ome (> sei is an example of allylic halide? allinaie 2077 3, Write the structure of L-bromo-4-chlorobut-2-ene. Delhi2017 4, Write the structure of 8-bromo-2-methylprop-1-ene. Delhi2017 5. Draw the structure of 2-bromopentane. Delhi 20140 6. Write the IUPAC name of (CH,),CH CH (Cl) CH. oethi 203 7, Write the IUPAC name of Hy —CH— CH,— CH=CH, cl ‘elhi 2013, 8. Write the IUPAC name of CH, I ee ae Delhi 2019 Br 9. Write the IUPAC name of the following compound: CH, | Cty — F—CH— CH, ag CH, Cl BSE Solved Papers : g @ Chapterwise Cl ners Pepe compound: 10. Write the TUPAC name of the fy Aline oe Hy ca 44, Write the IUPAC name of the folloy ‘compound: e ye Mids 12. A hydrocarbon C;H)» gives only one monochlorination product, Identify the hydrocarbon, pelhi 20130 13. Give the IUPAC name of the following compound: Br a CHiy—0— Gr CH panizon 14, What happens when bromine attacks CH, = CH—CH,— C= CH? aT All india 2012 15, Write the IUPAC name of the following compound (CH), CCH,Br. bethi zon 16. Write the IUPAC name of the following compound: CH, =CHCH,Br. 17. Draw the structure of 1,4-dibromobut-2-ene, Delhi gone; All india 20106 18. Draw the structure of 2-(2-bromophenyl) butane. Dethi 2011¢ 19, Draw the structure of 2-(2-chlorophenyl)-1-iodooctane, altindia 20m 20. Draw the structure of the following compound: L-bromo-4-sec-butyl-2-methylbenzene ors; Al ndia 2on1e ‘diazonivun Compete ation CCH CEanes ond Haloarenes xe of the following compound ylpentane yucture of the following the rrophenyl)-2- ip Det and: 9-(4-chloropbe yl)-2-methyl Allndia 2010 beth 2 4 ive the IUPAC name of the following * compound: HC CH a u/s HyC si india 2010; Foreign 2008, 2008 125, Draw the structure of the compound, 4-tert-butyl-3-iodoheptane. all india 20100 26, Write the IUPAC name of the following compound: CH, | HC— §—CHLCl ‘minds zoe CH; 27. Draw the structure of the compound, 1-chloro-4- ethyleyclohexane. All indi 28. Draw the structure of the following compound. 4-bromo-3-methylpent-2-ene. Foreign 2010 29, Write a chemical reaction in which the iodide ion replaces the diazonium group in a diazonium salt, HOTS; All Indio 2008; Delhi 2008 30. Complete the following chemical equation : Peroxide CH,CH,CH = CH, + HBr——> ethi 2008 31, Write the IUPAC name of CICH,C = CCH,Br. allindia 20080 B 261 2 Marks Questions 82. Write the : reaction: "MM of the fallowing (CH,CH,OH —BBr eth 20% sli care, mater of major ‘monoh: thefllowing reasons ® Cone @ €)-ca.—ciones HBpPenée, Alina anna 34. Draw the structures of the following organic halogen compounds = @ p-bromochlorobenzene (i) 1-chloro-4-ethyleyclohexane Allindia 2046 35. Draw the structures of the following organic halogen compounds: () 4-tert-butyl-3-iodoheptane (i) 4-bromo-3-methylpent-2-ene Allindia 20140 36. Write the IUPAC names of the following compounds : (@ CH, = CHCH,Br Gi) (CCh,)gCCL_altindie 0140 37. Complete the following reactions: CH; ® ely ita Gi) CH,CH,CH CH, + HBr —> All india 2009 38. Complete the following reactions @) C,HsN,Cl+ KI—> €) No acC Bs Bry SO, He oan beth 206; Al indo 2008262 @ Chopterwise CBSE Solved Papers + CHEMISTpy (3 Marks Questions 5 oa en ee 38, Give the TUPAC names ofthe allowing ae ff compounds: : @ CH,—¢H— CH, —CH, a @ Br Dou—cr—ar, Br nee tt @ ie 2eblorednetybutme SAY o SS Br : 3a (ii) CH, = CH—CH,—CI 7. Gy tr eta Allindia compartment 2015 4 40. Complete the following reactions pee (As double bond is given preference over halogen) a ocy errs 1 UN on + HBr 1 «o<) a Na (iii) CH,CH,CH —CH, + HBr —> Foreign 207, 2009, A a a @ Explanations 2ehloro-3,3-dimethyibutane 1. The strcture of 24-dinitrochlorobenzene Is a le ‘NO, i e é 10. ce Bs Sci No, o a 2. Inallylic halides, the halogen is bonded to the Need chorea eee sp’ -hybridised carbon atom next to a arbon-carbon double bond. Thus, 1". on, — Gat, — cu—ci, x i ca 2romo-tchloropentane mn Dhaloylober ene ‘Numbering will be done in alphabetically manner is an allylic halide. o ee iS 3. The structure of 1-bromo-4-chlorobut-2-ene is iz Haseaa per ones oh H,C—CH =CH—CH, Pen ae I I rf a Br. io ‘4, The structure of 3-bromo-2-methyl prop-1-ene is HY—C—CH, BrCH,—C =CH, o | CH, o cH,» ylprop-ene cu Br OH 1 cH—CH.— 6— C—Br oot, alkanes ond Haloarenes, x4 aa (vey formed when Br, eed ner, 1 ee eof Bri Used the following —CH,—© a Br Br (ot cn HO nh The—cu—cit,_cxy, 1 -bromo-4-se-bury-2-meihylbenzene 21. genta dh, ty f My 2ehloro-3-metbyipentane 22, “cat, i 2 Hy o © cH, I a 3-(4-chloropheny)-2-methyip . aS i No a iB ‘Br 1 Histemey oe cH, Br as CH 1 2.2-ditnethyl propane mi _ éuCH Bt ; opirene 0% HWA, aH “4 atoms, —Br at C, and G,, double " ae en, andy Br Hye 1,4-dibromobut-2-ene o 4-bromo-3-methylpent -2-ene ee ieshaegla 6 25, ¢ny—Cu,—¢n — 6,0, 1 ace op Ai im a Gc, C—O 4te-butyl-Slodohepiane | cH, pelea 26. H,¢-?0—CHi,C. tu 2.(2-bromophenyl) butane o een cecrreans - ———) Cyclic ‘arrangement of 6C- atoms; ClatC-1 and \ CoH at C4. ane Oa — | -chloro-4-ethyleyelohexane o 2(2 RBr > RCL> RF iy Amongst, someric dichlorobenzene, p-isomer has highest melting point due to For isomeric alkyl halides, boiling point decreases with branching, (i) Alkyl halides are slightly soluble in water because they do not form H-bonds with water. (v) The stability of haloalkanes decreases as the strength of C—X bond decreases, (RF > RBr > RCI > RI) due to increase in size of halogen atom down the group. Alternatively, bond dissociation enthalpy for C—X bond decreases down the group. (vi) C—X_ bond in aryl halides is shorter (due to partial double bond character acquired by C—X bond due to resonance), stronger and less polar than in alkyl halides. (3) Refer to solution 37 (i, (a mised vw | ae OH Pe HOB o (iii) Refer to solution 37 (ii), f m jroPic 2] Properties of Haloalkanes and yaloarenes Including Polyhalagen Compounds 2.2 Chemical Properties Nucleophilic substitution reactions ‘Nucleophilic substitution reactions are of two types S,1 reactions Rate [RX], occurs in two steps: step 1- involving formation of carbocation intermediates, and in step 2, the carbocation thus formed is attached by the nucleophile. Step 1 is slowest and hence, is a rate determining step favoured by polar solvents. During Sy1 reactions, optically active alkyl halides give racemic products. Sylis shown by 3° alkyl halides S,2 reactions Rate «[ RX][O"H] occurs in one step through a transition state, favoured by solvents of low polarity and occurs from back side resulting in. inversion of products. Sy2is shown by 1° alkyl halides.@ chopterwise CBSE Solved Papers y 266 2 mechanisms are as follows + of reactivity in Sy1 and Sw For Sx} 2, 1, CX For Sx2 kyl vactivity of alkyl halides in Sy and Sy2 teactions is RI > RBr> R¢ls pe « Fora given alkyl group, reactivity of l 3 ron eaving group tendency isi >BY >Ch 7E In case of optically active alky! halides, Sy2 mec ‘while, S1 mechanism results in racemisation. hanism results in the inversion of configuration e an a es rophiles have two nucleophilic sites through which they éab atta ef Bias ener 3 pone aaa ross reasive than ary halides towards nucleophilic substitution Teactions iggy we!” to the following reasons i) In haloalkan there is single bond between RX, which needs less bond dissociation ae they are more reactive towards nucleophiles, In haloarenes, theres do Fac aracter between C-—-X bond due to resonance, therefore, has more bond 4iss0Giatiog i) Carbon attached to halogen i sp-hybridised in haloalkane and sp?-hybri sp-hybridised carbon is less s-charact ised in electronegative than sp?-hybridised carbon due to less ter, Thus, C—X bond length is shorter in haloarenes than in haloalkanes.. (iii) This dificult for electron rich nucleophiles to approach electron rich benzene ring in haloarenes. There is no such thing in haloalkane, + The phenyl cation formed as a result of self ionisation in haloarenes is not stabilised by resonance, Thus, it doesn’t undergo 5,1 mechanism. Elimination reactions Haloalkanes having -hydrogen atom undergoes f-elimination when heated with alcoholic solution of KOH, Hydrogen atom from B-position and halogen atom from a-position is eliminated to give unsaturated product. Flow Chart for Some Chemical Properties of Alkyl Halides with ENO, }> R—-0—N=O With AgNO }-+ n—No, With aqueous allali_}-> ROH Wik Nac} RON AT {nat With ACN > RN ¢ Hlimination 1 ,Witvale. KOK | Unsaturated (Major product willbe reaction “["|_oFNaNita,KNH, [ hydrocarbons decided by Saytzeff rule) [Reaction with metals }{With Mg }> RMgx (Grignard reagent) Ware reason {With Na} Alkaneskanes and Halogrenes en 10 267 ic Points About Optical lsomerism roon arom which iS attached to four different monovalent y Mj carbon atom. atoms is called asymm, ha tric or al fomers arc the mirror images of each other and are non anti superimp ) eat nces which rotate the plane Polarised light towards ight are ealeg we sae which rotate the plane polarised light towards left ar clea age (and ho ory (- oduct formed in a reaction has same stereochemistry as that ofr aa ifthe pe : ; ) 1 retention of configuration. actant, this process fg uct formed in a reaction has a stereochemistry o} ahe prod ! of configuration. Many of the alkyl or aryl h }ppOsite to that of reactant, j Ato -actant, it leads to lide compounds can show optical isomerism. 19 tina reaction, 50% inversion and 50% retention occurs, the process i called racemisat the product is called racemic mixture. A racemic mixture is optically inactive as it is amivty i ‘ontaining two enantiomers in equal proportion and have zero optical rotation, a Jectrophilic Substitution Reactions (in Aryl halides) jalogen atom is o-, p-directing in electrophilic substitution reactions since, electron density increases at ‘nd p-positions due to +R-effect. eaction with Metals when aryl halide is heated with alkyl halide in the presence of sodium in dry ether, halogen atom is placed by alkyl group and alkyl arene is formed. This reaction is called Wurtz-Fittig reaction. Teluene hhen aryl halides react with sodium in the presence of dry ether, two aryl groups are joined together :nd diphenyl is formed. This reaction is called Fittig reaction. s Diphenyl268 @ Chapterwise Case , Flow Chart for Some Chemical Properties of Aryl Halides 1. [With metals }> Organometallic compounds ‘Wurtz-Fittig and Fittig reactions (Na/bry ether ) Ullmann reaction (cu) Halogenation ¥5/halogen carrier powerful i 1) CCl is se’ name Pye (i) Freon-12 (| =e PREVI EXAMINA TOPIC 2 Q1Mark ¢ 1. Write the. compound towards §, 2 Out of CH CH —oH Which is » Teaetion 4methane (CH,Cl,) is used as pichlncin aerosols, as paint remover. Di ronee ro higher levels causes nausea, Fost aainess 42% jinalogen derivatives of methane are riled haloforms. jg CHCI, (Chloroform), CHI, (Iodoform, sed as an antiseptic) ¢nloroform is stored in dark coloured i itl as in presence of light, it gets converted into highly poisonous substance, phosgene (COCI,). DDT is 1, 1, 1-trichloro-2, 2-bis (4-chlorophenyl) ethane and is used as a powerful insecticide, ‘v) CCl, is used as a fire extinguisher under the name pyrene. (i) Freon-12 (CF,Cl,) is used as a refrigerant, (” PREVIOUS YEARS’ EXAMINATION QUESTIONS TOPIC 2 @1Mark Questions 1. Write the structure of an isomer of compound C,HyBr which is most reactive towards Sy reaction. allindia 2016 2. Out of CH, ie CH,—Cland CHs CH = Cita CH; which is more reactive towards Sy1 reaction and why? Delhi 2016 269 i Soa Undergo 81 react, inthe following pairy \ **t1O” faster CH —CH,—cH, 5, and hen = Br 4. Which would undergo §, z y 2 reactic in the following pair eee and why? cH, CH; —CH,—Br and en, = ' Ee cHp ‘eth 2015, Foreign 2015, 5. Which would undergo S y2 reaction faster in the following pair and why? CH; —CH,—Br and CH, — CH,—1 Foreign 2015 6. Identify the chiral molecule in the following pair, reactive | rapidly by an Sy 2 mechanism and 0 SAT poe ee ahi 2008 a ee cH,— cH,—cH— cH, 25. Which one in the following pairs i Calero 1 undergoes Sy 1 substitution reaetion faster 6 i) Propene Br and why? Det (i) 2-brome CH,—CH, —CH, —cH, — t ul 1H, — CH, — CH, — Br @ Cs ‘%. Write the m (i) Racemisation occurs in Sy1 reactions, fal Why? foreign 2014 1 ree _ Why? foreign 20 ® 18. Which compound in each of the followin, » Le oh € pairs will react faster towards r iia £ Sy2 reaction with —OH? Why? ee on : 26. Suggest a possible mechanism for the (@ CH,Br or CHI foll i 2 following reaction: ® 20H, (CH, )CClor CH, C1 n- BuBr+ KCN #0H. 1.0, pucn Sethi 20036; lindo 20080 Delhi 2614, ki 2014, Al india 20100; Deie reason for the following of reactivity of haloalkanes +: , (CH) C—CH,Cl Mo follow Sy2 mechanism, ni anism of Sy1 reaction of pelhi 20080 that haloalkanes are more nucleophiles? jy Which one of the following react © aster towards Sy 1 reaction and why? cl HY «eal ® @ Delhi 2008 (3 Marks Questions ‘30, Following compounds are given to you: 2-bromopentane, 2-bromo-2-methylbutane, 1-bromopentane @ Write the compound which is most reactive towards Sy2 reaction. (ii) Write the compound which is optically active. (ii) Write the compound which is most. reactive towards f-elimination reaction, Delhi 2017; All india 2017 31. How do you convert the following? (i) Chlorobenzene to biphenyl. (i) Propene to 1-iodopropane. (ai) 2-bromobutane to but-2-ene. Delhi 2015 32. Write the major product(s) in the following: @ a Ge He Uv agit Bes UV eh, O2N Gi) 20H eg 8s eee cl ip _ and Haloarenes __ chloride, (Gi) Sl reactions are accompanied pgemisation in optically active alkyl halides. Foreign 2015 34. How can the followi con wing aaa 1g conversions be i) Aniline to bromobenzene Gi) Chlorobenzene to 2-chloroacetophenone (aii) Chloroethane to butane altmaia asc 35. What happens when @ chlorobenzene is treated with Cl, FeCl? Gi) ethyl chloride is treated with AgNO,? (Gi) 2-bromopentane is treated with alcoholic KOH? Write the chemical equations in support of your answer. all india 2015 36. Give reasons: (@ n-butyl bromide has higher boiling point than t-butyl bromide. Gi) Racemic mixture is optically inactive. (ii) The presence of nitro group (—NO,) at o/p-positions increases the reactivity of haloarenes towards nucleophilic substitution reactions. Delhi 2018 37. (i) Why are alkyl halides insoluble in water? Gi) Why is butan-1-ol optically inactive but butan-2-ol is optically active? (iii) Although chlorine is a oeee withdrawing group, yetitis ortho, para. directing electrophilic aromatic substitution reactions. ‘Why? Foreign 2015272 @ Chapterwise CBSE Solved Papers 5 38. (i) Draw the structures of major monohalo products in each of the following reactions: Come \ 4 +HBr——> (ii) Which halogen compound in each of the following pairs will react faster towards Sy2 reaction? (a) CH,Br or CHI (©) (CH), — Clor CH, — C1 Delhi 20re 39. (i) Which compound in each of the following pairs will react faster towards Sy2 reaction with —OH group? (@) CH,Br or CHI (b) (CH, )y CCl or CHCl (ii) Write the product(s) of the following reactions. (a) CH,— C1+KCN—>? + CH —Cl Delhi 20140 40. Give reasons for the following @ Ethyl iodide undergoes Sy2 reaction faster than ethyl bromide. Gi) ()2-butanol is optically inactive. (ii) CX bond length in halobenzene is smaller than C—X bond length in CH, —X. allindio 2013 41. Explain the following: () The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride. (i) Alky] halides, though polar, are immiscible with water. (ii) Grignard’s reagents should be prepared under anhydrous conditions, delhi 2013¢ Anbyd AlCl,» , 5 42, Although, chlorine is an electron withdrawing group, Yet it is ortho, para-directing in electrophilic fromatic substitution reactions. Explain, why is it 60? Delhi 2012 43. Answer the following questions: (i) What is meant by chirality of a compound? Give an example. i) Which one of the following Wi ends is moe early hydrolysed by KOH and why? CH,CHCICH,CH, or CH,CH,CH,CH,CI (ii) Which one undergoes Sy2 substitution reaction faster and why? ES All india 20% 44. Answer the following: (@ Haloalkanes easily dissolve in organic solvents. Why? i) What is the racemic mixture? Give an example. (ii) Of the two bromo derivatives, C,H,CH(CH, )Br and (CiHs)CH (C,H) Br, which one is more reactive towards Sy1 substitution reaction and why? Delhi ont 45, Rearrange the compounds of each of the following sets in order of reactivity towards Sy 2 displacement. acon wit (@ 2-bromo-2-methylbutane, mes for Lbromopentane, 2-bromopentane, — ““ (i) 1-bromo-8-methylbutane, Haber 2-bromo-2-methylbutane, Petan th 3-bromo-2-methylbutane, ete a (ii) 1-bromobutane, “tes L-bromo-2, 2-dimethylpropane, sti 1-bromo-2-methylbutane, etna L-bromo-3-methylbutane. SslK Allindia 201 be Seto, “yyfer 10: Haloalkanes and Haloorenes Ip) Write the mechanism of the following HOMO pn BuCN f) Why is the dipole moment of chlorobenzene lower than that of Cyclohexyl chloride? oetn zone Write a chemical test to distinguich between (a) chlorobenzene and benzyl chloride (b) chloroform and carbon tetrachloride G@) Why is methyl chloride hydrolysed more easily than chlorobenzene? D niincie zone State one use of DDT and iodoform. Gi) Which compound in the following couples will react faster towards } 3,2 displacement and why? (2) 1-bromopentane or 2-bromopentane (b) 1-bromo-2-methyl butane or 2-bromo-2-methyl butane Delhi 2010 would you differentiate between ‘and Sx2 mechanism of substitution tions? Give one example of each. the dipole moment of chlorobenzene is lower than that of cyclohexyl | CH,Cl will react faster in Sy2 reaction with —OH? allindia 2010 reasons for the following Joint than those of 0” and m-isomers fi) Haloarenes are less reactive than haloalkanes towards nucleophilic substitution reaction. i) The treatment of alkyl chloride with aqueous KOH leads to the formation of alcohol but in the presence of alcoholic KOH, alkene is the major product. All indie 20096; Delhi 2008, 20080 @ Explanations 1. Tersary (3%) alkyl halides are most reactive ‘towards $41 Teactions followed z and primary (1*) alkyl halides, oo Gligbe as four uomers, CH, —Ci,— cr Pets cs cm, “cate cx, chan, 2bromabtane (tip chi CH, —ck— CHB ese Th (ray al) cH, a ctype cH, 2 trom --meti propane (Grange) ‘As 3° alkyl halides form a morestable 3° carbocation intermediate than secondary and primary alky! halides which form 2" and 1" carbocation, respectively Hence the ome, Hj B (beam -etopans of cH, ‘compound C,HBr is most reactive towards Sy reactions. o 2 Cy CE = Gill unica cH ‘Syl reaction faster because itis a secondary alkyl Halide and forms a secondary carbocation that can stabilise itself more than primary carbocation formed by CHy— CCH, © cH. 3 18. Secondary alkyl halides prefer 1o undergo Sy) reaction than primary alkyl halides because of formation of more stable 2 carbocation. Hence, ou ofthe given pairCH—GH— CH, br would undergo Sy1 reaction faster. o 4. On the basis of steric hindrance, 1° alkyl halides are more reactive than tert-alkyl halides toward Sy2racton. Thus, ya Breall undergo Sy 2reaction faster. Undergo primary bale, less hindered.)274 5. Asi” ion is a better leaving group than Brion. therefore iodides are more reactive than bromides. Therefore, CH,— CH,—1 is more reactive than CH,—CH,—Br towards Su 2 reaction and hence, GH;— CH,—I would undergo Sy 2reaction faster than CHy— CHa ¥%, eT ischial molecule asitcontalns a ‘an asymmetric carbon atom (which is denoted by") 7. When CH,—Br is treated with KCN, methyl cyanide is obtained. cH, Car + Kt oN > Me iam weaiyt Gane CH,—CN + KBr Methyl tassjum Grane bromide It is a nucleophilic substitution reaction. Nucleophile GN~ substitutes Br”. 8. Ethyl chloride undergoes hydrolysis to form etbyl alcohol (through Sy 2nucleophilic substitution). CH + KOH (aq) H0H + KL thy corde Ethanol 9. The reactivity towards Sy1 reaction depends upon the stability of the intermediate carbocation Which an alkyl halide gives on ionisation. Thus, o o 1 iosbein,t BS Sa wat : > cataton aan (more stable) ca onan A oe Sig cone 2 eran te) ‘As 3°carbocations are more stable than a 2 carbocations, therefore, a will react faster than Gin Syl reaction. o 10, 11 can be done by treating the methyl bromide with alcoholic silver cyanide. CH,Br+AgCN—> CH,NC + AgBr o (Ale) Methyl isocyanide 11. Order of reactivity of four isomeric bromobutanes in Syl reaction is (CH,),CBr ee > @ Chapterwise CBSE Solved Papers ; CHEMIsTpy 7 (city ,CHCHBr >CH.CH.CH CH 42. V-bromopentane is a primary aly! sar anne lea eoateraaae Since, primary alkyl halides are stercay hindered therefore, 1-bromopentane rash towards Sy 2reaction. fester 42. ‘The hycirolyss of alkyl halide with a 0 see by Sql mechanism. Further, theres so in Syl depends upon the stability of carbo Since, CH ,CHCICH,CH, forms more stable 3 carbocation on ionisation than CH CH,CH,CH, CL, therefore, CH,CHCL Sydvolaes faster than CH, CH,Ct,ca,@q 8% 14, Hlaloarenes in presence of Lewis aid reac yin lay! halide or acid chloride to give a mixture qt g-and p-haloalkylbenzene (orhaloacybenzeng) a a aan on or ee, ieee a a ° pou Lots (OY te AICI, aaishe tpi ool 15. (i) (a) 7\/ py undergoes faster towarts S EA eo a) (ii) (a) Sp2 reaction occurs (b) SyL reaction proceeds 3K,Haloolkanes and Haloarenes solution 8 Anhydrous 9,000 ae a +O yexe Wy =I cocHy ») in5y2 reactions, reactivity depends upon the tn Ss indrance. CH,CH;—CH, — CH, — Bris srimary alkyl halide while Fe CHy—CH — CH isa secondary alkyl tt. Br hatde, Since, primary alkyl halides are sterically hall findered therefore, CH, CH,CHCH, Br rests faster towards Sy 2reaction. o tn Sql reactions, if the alkyl halide is optically 1m Se dhe product obtained is a racemic mixture: activfjrermediate carbocation formed in slowest Tap being. sp'-bybridised is planar (achiral) soe therefore, the attack of the nucleophile on Pet occur from both the faces (front and back) + requal ease, forming a 50:50 mixture of two eve. the products with opposite configuration. Thus, Sql reaction of optically active alkyl halides dre accompanied by racemisation. €8; cy CH ag po "CH;CH, ‘Planar carbocation (achiral) ban 2-0 un tal (anasto) 275 (0) Lesser he bond desc tomamncsnaanent a” cacenemac tunaagenete ea Seen: ‘action. More the steric hindrance, lesser the | eee (i) CHL will react fa > > Dee aor dco : : a Rees eae Paes Deonamecey ere Sores tnaeemacietene ee eae im 8 JNO, +AgCl es 4 | Race oO cya 5 benzene “Ambident nucleophiles have two nucleophilic ssites through which they can attack, eg nitrite ion isan ambident nucleophile ro-N=o} tran attack through oxygen resulting in the tion of allyl nitrites, Also, it can attack topugh nitrogen resulting inthe formation of nitroalkanes. _pwence reer * tea site o BX+NOg—> BNO, +4 ‘wuoaliene o276 at. bond character whlle in CH fhalobenzene fs shorter than in CH, —%: iets oxidised to phosgene (carbonyl chlor €0Ci,),a poisonous compound. Thus to prevent the formation of phosgene; Chloroform is stored in dark brown botdes filled upto brim, cucl, +40," coc, + Hcl histor” 2 carton cowie tebagen 122, Two reasons for the less reactivity of chlorobenzene towards a nucleophilic substitution reaction are as follows: (i) Resonance Effect The electron pair of chlorine atom is involved in conjugation with the x-electrons of the benzene ring and the following resonating structures are obtained ‘Asa result, electrons of C—Cl bond get localised and a partial double bond ‘character develops in the bond and hence; it becomes difficult for the nucleophile to cleave the C—Cl bond. (i) Increased Electron Density A repulsion is suffered by the nucleophile due to increased clectron density on the benzene ring which prohibits the nucleophile to make a close ‘access for the attack on the molecule, 23, |(0 Steng intermolecular H-bonding ama molecules. o o 1 water | (@ Consider reactive nature of Grignard's reagent | [Ewa water, (i) Tobe miscible with (or soluble in water) water, the solute-water force of attraction must be stronger than the solute-solute and ‘water-water forces of attraction. Alkyl halides are polar molecules and so held together by 4) Due to delocalisation of lone pairs of electrons ofthe x atom over the benzene ring, C— fond in halobenzene acquires some double x, C—X bond isa pure single bond, Therefore, C—2 bond in tn the presence of air and sunlight, chloroform. dipole-dipole interactions, H-bonds exist between the we ‘The new force of attraction ber, halides and water molecules ig forces of attraction already o x os ‘are immiscible with (Or insoluble in) (a) presence of moisture, aig + HOH rinarts ‘een ‘Therefore, Grignard’s reagents o prepared under anhydrous conditions 24. (i) therefore undergoes Sy 2reaction faster Idaving group because of is larger size 25. reaction depends upon the stability ofthe a (0) JR tertiary halide reacts faster than Setondary halide towards Sy1 reactions because of the greater stability of tertiary carbocation interm [For detal, refer to solution 9}. cl Grignard’ reagents are very reactive, Soca escent allyl halidealil age’ Gos St ‘molecules, Hence, alkyl halides (qatar ‘gh wer theyreactto give al Fiat Metomx should. be. a ‘CHCl, i isa primary halide ang therefore, it undergoes Sy 2reaction faster. () Tac ooo ae ‘carbocation formed. So, compere the stabity | locarbocationtomed OS Se P earocation e (more stable} AA cnn iy er 1 carbocation ies stable) a sole reacts faster because of seater stability of secondary carbocation than primary, 26. KCN is a reagent that gives CN™ion as nucleophile in aqueous medium, 0 o (i) AX 7 asiodide ion isabener abe sou sp Core 08 yh to put asreactons a lari sol ai) The nmi and b tinh and fo (ay cor + Theses inv i Formato t4,¢ tack ling ay,Clanes and Haloarenes forms of KCN Its a resonance 2o2Hi08 {Prrowing two contributin scott fo 7 fre rola __5C1,CH.CHCRLEN + ie aetna yon 99, BUCN RB *ambident nucleophile therefore i arog C-atom or Uough N-atom, ‘iis a stronger bond than GA tack occurs through 9 anid pond, therefore o sikyl group is same, the reactivity of cals decided by the halogen present ae sizeof halogen atom, larger isthe cad length, and weaker isthe band. reactive i the alkyl halide {sizeof halogen is FeclR—Br >R—Cl a since, reactivity of Sy2 reactions depends upon sindrance and les sterically hindered reacts faster in $2 reaction. As ge steric hindrance in the case of ‘entyl chloride so, it does not follow ) wh i a ‘Thus, more she order Tas 277 loarenes ae mse mote eae AE mete suonger nd egues iy exo ication entre Inhaloalkancs ‘P-brised intact 5p°-hybridised carbon is less lectronegative than hybridise carbon due less character The ‘C—Xbond in haloalkane eo ‘electrons to halogen. oe (6) 1s atc for eeciron rch nucleophiles to approach electron rich benzene ring in $ duet repulsion while there is no exh hig inhlatianes ® operate « ‘eaction because (I) will form more stable 2° carbocation as compared to NN We vbioh forms carbocation. 80. (i) S2reactions involve the formation of {transition state. Higher the steric hinderance, lesser the stability of transition state and o lower is their reactivity towards S.2 (CH,CH,CHCH,CH,Dr> CH,CHCHETLEH, -bremopenane t cH i iE eopenty chloride o Lee d out in 2 generally carried out i ssl reactions are generally polarprotic solvents (like water, alcohol, acetic - acid, irc), The reaction between fert-butyl >a 0 tomide and hydroxide ion yields tert-butyl he alcohol and follows the first order kinetics fees ce heaps (CH)),CBr + OH” —>(CH,),COH + Br w 6 Ps : il yunds, 2-bromopentane The steps involved are (i) Among the given compat {) Fomation of carbocation intermediate is opal ‘active due to presence of chiral SI * a carbon (*} (Cit) C—Br S10 CH,),C" + BE 5 (carocation) ue 4 (i) Attack of nucleophile on. carbocation forme ie leading to formation of substituted product Hh lj 4 (Hyjc + On, BM (CH),COH (xudeophile) ooH! aio? Bi chopterwise CBSE Solved Papers « (é PHT, | 2 - oS or sentsscatonson (i) 2086 =A ; Ac eur aiferet pes of f ee eeepe tae pk (uy rem enchants mot ace ona a ot batted alkenes he maior mai E sedis 2,3~ dimethyl butane ; oe e i (ul) city, — we, Uheomoethane CHC, Nate, ® Stag oe C snzene to biphenyl . (i) In chlorobenzene, the lone pai of 21 Near 38 Oe cnen Cre ele O”\ tera Prater, elections of the benzene ing. saree a, 2 pee ‘C— Clbond acquires some double bund ciecbanene cinta character while nCH,— Cl bond isarne single bond. Since, bond length of ¢—"'q. Kee single bond is greater than — Cl] patie partial double bond. Therefore, C— €ltong ben {in halobenzene is shorter than that in o cH—d. e (ji) Im chlorobenzene, the Cl-atomnis linked toa @ (1) Propene to 1-lodopropane ye cheese < CH,— CH =CH, + HBr cyclohexyl chloride, the Cl-atom islinked toa ay bia sp°-hybridised carbon atom, Now, fo (ci1.£00), ‘9 -hybridised carbon has more -characer sy, i SUNG Lornireaaas?) Hy CE itis more electronegative, (artes paGen) theres mare decsoacaeee eee ‘electrons of C—Cl bond near the Cl-atom is a less in chlorobenzene than in cyclohexyl CH,— CH,CH,1 + NaBr chloride, Hence, the C—Cl bond of (es Acetone/A chloride is more polar, Le. it has higher dipole (iil) 2-bromobutane to but-2-ene moment, ere pascnisevar,. =H o But -2-ene (Major) NOTE In thisreaction, another praduc,but--ene would also be formed as 4 minor product which being a less ‘substituted product. : Soll CH2—CHs a, uviight 34. (i) Aniline to bromobenzene SO ee : ON" r NE Neencr Br ‘ty obemene CH—CH, Naxopsa wet mak, usin LY Ol Onn: ‘eactio). 1-(L-bromoedy}-¢-nlobenzene (1) : 3 BromobenneJoloalxanes ond Halocrenes op 10% wr 2-chloroacetophenone a spenzene 10 enlor® ° Predicts Ay a ee H,c—C—cl_ Z tees ERLANG, cclondvenzene ——_dhlaride 2 chlooactophenone syrwetnane to butane o 2c cHfl+2Ne = cae ge cimecaed acca “routane > wren crobenzene is weated with Cl /FeCly, andl p-products are formed a OBO + OF a ciorobenzene 1, 2dichloabemene ‘oso 14 diclorobenzene rai) 2 (Ale) OFF | pee crm cty MT 6 ce (ota produc) (ney Ba. [eS 4c — Cll, — CH, — CH=CH, Teatl-ene 9) (on protect 0 ‘46, (0) oiling point ofa compound depends upon the surface area HEH the surface area, higher willbe the boling point ofa compound, Surface area decreases with increase in rene if the compound has branching its Paling point wl decrease. That's why, n-butyl bromide Being (OD 37% KS straight chain alkyl halide has Higher boing point than tertiary butyl bromide (346 K) which i 2 hrighly branched alkyl halide. oy ‘A mixture containing two enantiomers in equimolar amounts have “eft optical rotation, as the rotation A ra te molecules of one isomer (enantiomer) is exactly canceled DY at ‘equal and opposite rotation caused by the same number of molecules of other isomer (enantionns) ‘Such a mixture is known as racemic caused e gince, enantiomers have equal and opposite specificrotations, 2 racemic mixture exhibits no optical activity. o “The reactivity of haloarenes towards nucleophilic substitution reaction! £2 be increased by the presence of rae reagon withdrawing group (—NO, )at orto and para-postions This because NO, group at ortho and saspositions withdraw electron density from the benzene ting sind thus, facilitates the nucleophilic attack rar Mparenes, The carbanion thus formed is stabilised Uhrough reson ‘The negative charge appeared at or and para postion with respect to the halogen substituent is stabilised byNO, gTOuP- ‘The mechanism can be shown as:280 Attack at p-position a fe on Ch cou Ron! fe =! a &# ton 25) M a N Pe, fre on Sons SX AO OS : saa a0 5,08 cy con ic nS) a wl |e NX N Jes ore oN ° 8 2 5 ; ayconh Ac Oy Don, ° co es Ba! ANS ° 8 | ascouh. “ cates Cyt it is very clear that electron density is rich at ortho and para-positions. 0 0 jy todide 10m 5 @ 40, ndru0es Sx (a) (2)2-butanol and ths, ay (Gi) Refer to soba the byt From the above resonating structures, So, presence of EWG will faiitate nucleophilic attack at ortho and para-postions. 437, (i) Referto solution 23 (i). Butan-1ols optically inactive compound du to the absence of asymmeticC-atom or CHEN +KCl a wa @ cas \ie—c cy re chore 2-methyl benzene cH a ‘einer ey meth bengene (Mae) a sa 0 uaa eye pase i ce ras lide on be se han ey roe e Mamnnpemenmrny rs 2) 2 baana at Tce, otal AGH © (iy Refer soon 2 a ee idaien fairs Sieber ad ETO Siesa aero e rateb | resus apse moma eam Siena avon wate meee (ii) Consider reactive nature of Grignard’s reagent with water. 41. (i) Refer to solution 33 (ti). (ii) Refer to solution 23 (i) (iii) Refer to solution 23 (i) 42, Refer to solution 37 (iii).sle which is mits mirror image is ‘4a. (i) Anobject or molect non-superimposable 0 a fon Psral and the property of being CTS calcd em ax chirality, €g- lactic acd, ;CH(OH)COOH Pe a eal HO—¢—H E COOH coon Mirror o (i) CH,—CH— CHCA, is more easily a hydrolysed by KOH because this hydrolysis cccurs through Si mechanism and this ally balide forms a more stable 2" carbocation than CH, — CH,— CH, — CHC which forms a less stable 1° carbocation as Sy1 depends on stability of carbocation. o (ii) Refer to solution 24 (i) o ‘44, (i) Haloalkanes easly dissolve in organic solvents because both are covalent in nature (like dissolves like). Also, the steric effect in hhaloalkanes is not more as seen in the ease of hhaloarenes. o (Gi) A mixture containing two enantiomers in equal proportions will have zero optical rotation. Such mixtures are called racemic mixtures, ¢-. (2) butan-2-0l o (ii) = CHy—CH-Br | CHC (Stable carbocation) ‘The carbocation intermediate formed from. (CiH,)CH(C,H) Br is more stable because itis stabilised by two phenyl groups due to resonance, $0 (CqHs)CH (C/A) Bris more reactive towards Sy1 reaction. @ Chapterwise CBSE Solved Papers ; CHEN << t ore +bromo-2 methylbutane fs Incorrect IUPAC name 3; 46. (i) Refer to solution 26. 47. (i) (a) Benzyl chloride when treated with Nore the steric hindrance, slower ging a= So. order of reacvty ie 1*> 2age | rae! (i) -bromopentane > 2-bromopentane 2- bromo-2-methylbutane (ii) 1-bromo-3-methylbutane > ny 3-bromo-2-methylbutane > 2-bromo-2-methyibutane q bromo isa functional group it should be sven cover met group. Thus, the correct name shal 2-bromo-3-methylbutane. (ii) L-bromobutane > 1-bromo-3-methybutane > 1-bromo-2-methylbutane> l-bromo-2,2 (CH,),C—OH+ Br s,1 mecha of eaction aco! formation of carbocation res the j racemisation takes place. YA) intermediate a0 mechanism of ov inva substitution reaction, the nds InSeeacion depends upon the concentration te ahe reactants 4-e. on both haloaliane and. iil, e.g in the reaction between methyl "@roxide ion to form methanol, depends on the concentration of nucleo chloride and hy rate of reaction both the reactants. ransition state} (Transition state) 4 / —> HO 4 +f Baers (Inverted product) yn of transition state and ) of configuration wad Itinvolves the formatio inversion (Walden inversion) take place. 50. (i) Refer to solution 33 (i), 51.) | Symmety ofthe moleoule is rlted tous cota | (ii) Refer to solution 23 i). e (ii) Refer to solution 18, o o ltlco stn waren and sohbity. ANGWorrtehen ee | ahigher meting point. Mae ‘The melting point of p-is ace desieobsen aie A orto wise ghey ee pentose ee soa pc ecg a ee Se tinea cee sae ° (i) Refer to sluion 29 i iy | Diference tes n the mode and extent of dissociation of KOH in the presence of afferent sovents. OH isa good nucleophile while C,H.0" isa song base. In aqueous solution, KOH is almost ‘completely ionised to give OF fons which being a strong nucleophile gives a substirution reaction on alkyl halide to form alcohol. CH,—CH,—CH,—Br ATKOS, CH CH CHO ‘But an alcoholic solution of KOH contains alkoxide ions RO- which being much stronger pase than OH" ions preferentially eliminates @ aclecule of HCL from an alkyl chloride to form alkenes. o he KOH congue: "cx, —cH= Oh