7 R. K. MALIK'S riitramanovs,neoica son, non eax NEWTON CLASSES Enjoys unparalleled reputation for best results in terms of percentage selection www.newtonclasses.net HALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS — XI TARGET CBSE Haloathanes and haloarenes are formed bythe replacement of hydrogen atoms in an aliphatic or aromatic hydrectbon, respectively by halogen atoms Haloskanes contain halogen atoms tached to thes hybriized carbon atom of alkyl ‘f0up, whereas haloaanes contain halogen) atached os hybridized carbon toms) ofan aryl group. On the bass of number af halogen atoms, haloakenes and haloaenes re classified as mono. dbo polyalogen com pounds (0) Inthe case of compounds containing sp? €-X bond (x =F, lB. these can be alkyl halides alii halides or benz halides (b)_Inthe ase of compounds containing sp?C-X bond, these an be vnc halides ra halides {@)_Inthe ate ofcompounds containing 3p -X bond, these canbe alkyl halides. ‘Allo halides ate named by the akyl group followed by the halide. n IUPAC system, these are named as halosubstituted hydro- ‘carbons. Halaarenes are the common as wll as IUPAC names of ay halides Since halogen atoms are more electronegative than carbon, the carbon-halogen bond of alkyl hallde Is polarized: he carbon atom bears a partial postive charge whereas the halogen atom bears a partial negative charge. Preparation of (a) Haloalkanes: + From alcohols by nucleophile substitution (Sy eactons wth halogen acids (FX), phosphorus halides or thionyl chloride + Free-radical halogenation of alkanes {By addition of haloges acids and halogens to alkenes {From sver salts of carboxylic acids Hunsciecker teaction with Cl, and Br; Birnbaum. Simoni reaction with + Byhalogen exchange (aky| iodides and Nuorides) Finkelstein reaction Swarts reaction (b) Haloarenes: {= By electrophilic substitution with halogens to arenes + By conversion of primary aromatic amine to diazonium salt and replacement of ciazonium group with ~Cl and “Br (Sandmeyer’ reaction, Physical properties + Those are colorless when pure, and develop color when exposed to light Many volatile halogen compounds have sweet smell Methyl and ethyl chlorides, methy| bromide and chlotefluocomethanes are gases at (00m temperature. Higher members are liquids or solids ‘These are slightly soluble in water but completely soluble in organic solvents Due to strong dipole-dipole and van der Waals forces of attraction, boling points of organahalagen compounds are higher than the corresponding hydrocarbons + Para isomers have higher melting points than ortho or meta isomers {The density increases with increase in number of carbon atoms, halogen atoms and atomic mass of the halogen atom Chemical properties «Their =X bond is polar and Is tesponsible for nucleophilic substitution elimination reactions and reaction with metals, * They exhibit chirality Office.; 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-t, Ph.; 0661-2662523, 9635508812, 7546645949 NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES + Their hydrolysis with aqueous alkal or mois slvr oxide leads o alcohol formation, + On reaction with RON, they form ethers (Williamson's synthesis 8. Chemical reactions (a) Haloalkanes: ‘= Nucleophilic substitution Substitution nucleophilic unimolecular (5,1) «Substitution nucleophilic bimolecular (42) «+ Elimination reactions ) CHACH,CHICH CHIC HCL fe) CHCHLCICH) CH (a) (CH)CCHACHIBNC A, (ec) CH,CHICHICHIBNCH, (0) CHYCICH cH, 8 ig) CHACICINCH)CH,CH, (ip) CHCH=C(CICH,CHICH), (i) CHCHACHC(BrNCHS), U) PCIGHCHCHCH), (i) MMCICH,CHACHCICHy (0) BrCgHyCHICHICHCHy Solution « ow CH, —cH cH cH, Terre four carbon atomsin longest posbecarbon chan (outane tthe second carbon gtoup eatached andthe third «carbon CH group is attached, Therefore the IUPAC name is 2-chloro-3-methylbutane, andit isa secondary alky! halide because the halogen atoms attached tothe secondary carbon atom, oH ot 04, HCH, cr ‘There ae six carbon atoms in longest possible carbon chain hexane), atthe third carbon Cl group is attached and at the fourth bon CHs group is attached. Therefore, the IUPAC name is 3-cloro-4-methylhexane andi isa secondary ally halide because ‘the halogen is attached tothe secondary carbon atom. Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII Hs CH=CH CCH cH There are four earbon atoms in the longest carbon chain (butane), and atthe fst carbon atom ~I group i attached and to the second carbon atom two methyl (CH,) groups ae attached, Therefore, the IUPAC name Is |iodo-22-dimethylbutane and it isa primary ally halide because the halogen Is attached tothe primary carbon atom. CH Be od a Hs ‘There are four catbon atoms in the longest carbon chain and atthe fist carbon phenyl group and bromo (Bt) group are attached ‘and tothe third carbon atom two methyl groups are attached. Therefore, the IUPAC name is 1-bromo-3,3-dimethy-t-phenylbu tane and tis a secondary benzylic halide because the halogen and phenyl gloups are attached tothe secondary carbon atom. Hy Be Cy CH CHC, There are four carbon atoms in the longest carbon chain and at the second carbon atom bromo (8?) groupis attached and at the third carbon atom methyl (CH) group i attached. Therefore, the IUPAC name s2-bromo-3-methylbutane and itis a secondary allyl halide because the halogen is attached tothe secondary carbon atom, Gas oh eG 8 &, q oH, There are four cron atomsin the longest cabo han ano theistarbon atom bromo tou isatached othe second {atbon som ty group and met (CH) goup ate sta Therefore thelUPAC ram's bromo? ey 2 methyl tan an tsa primary al Rade hea the lagen atachedo he pmary carbon ston. a 1 HCH, Ch Hy Ga ‘Tere are five carbon atoms inthe longest carbon atom chain and to the third carbon atom chloro (C) and methyl (CH) groups ate attached. Therefore, the IUPAC name Is 3-chioro-3-methypentane and itis 2 teary ay! halide because the halogen i attached tothe tertiary carbon atom, $ Hs HCH C—O HH, “Thete are six carbon atoms in the longest carbon atom chain and the second carbon contains the double bond, tothe third carbon atom chiro (Ci) group is attached and tothe ith carbon atom methy/ (CH) group is attached. Therefore, the IUPAC name is 3-hloro-5-methylhex-2-ene and itis vinyl halide because the halogen atom is attached to vinylic carbon atom. er Cy CH=CH, cH, ‘There are five carbon atoms inthe longest carbon atom chain, double bond Is present atthe second carbon atom, and to the fourth carbon atom methy (CH) group and bromo (81) group are attached. Therefore the IUPAC name Is 4-bromo-#-methyl- [pent-2-ene and its anally halide because the halogen atom i attached to allylic carbon atom. Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES ‘The IUPAC name is 1-chloro-4(2-methylpropy) benzene and itis an aryl halide because the halogen is attached tothe arylc catbon. r Hy C—CHs on Sac ‘The IUPAC name is 1-chloromethy/-3-2”-dlmethylpropy!) benzene and its a primary benzylic halide because the halogen is attached to side chan of benzene (benzylic Catom) which s primary carbon atom, cH HO Oh ar ‘The IUPAC name is |-bromo-2-1"-methylpropyi) benzene and it is an ary halide because the halogen atom Is atached to the aryl earbon atom, Textbook Exerdses 1. How are alkyl halides classified? There ae four alkyl bromides with the formula CHB. Write thelr structural formulas and classify ‘each as to whether it sa primary, secondary or tertiary alkyl bromide. Solution (Organic compounds containing a halagen atom as. functional group are called aly hades. They ae classified as {a}, Primary alkyl halide: Alky| halides containing primary C atom are called primaty alkyl halides. A primary carbon ator is 2 ‘carbon atom linked to only ane carbon atom. bi, Secondary alkyl halide: Alkyl halides containing secondary Catom are called secondary alky halides. A secondary carbon atom isa carbon atom linked to two neighboring carbon atoms. (c)_ Tertiary alley halide: Aly halides containing tertiary C atom are called tertiary alkyl halde. A tertiary carbon atom sa carbon _atom linked to three neighboring carbon atoms. ‘The four ally! bromides with formula CBr are: Oho — GO CHSCH,CHcHBr Br ‘Bromabusane 2 romobutane In Buy bromide ec Buy bride Primary Secondary Position isomers (CHsaCHCH,8r (cr) c8r 1 8romo 2 methprane rome 3 metyloropne Bury brome! ite uty! brome) Primary Tertiary Chain isomers 2. Wt structural formulas for each ofthe following: Four primary ay! halides wit the formula CH, 8 (b) Three secondary ally! halides with the formula CsHy Br (@) tertiary alkyl halide with the formula C,H, Br Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII Solution ‘The structural formuls ofa chemical compound is a graphical representation ofthe molecular structure, showing how the atoms are arranges. (a) Alkyl halides containing halogen attached to primary C atom are called primary aly! halides. Four primary alkyl halides with the formula C8 are (i) CHYCHACH,CHACHBe WW) Ch CHC, — CHB ‘omapentane be ‘frome J methytutene (Cyc ar Hs roma 2-meoutane () Ally halides containing halogen attached to secondary C atom are called secondary lk halides. Three secondary alky halides with the formula C,H ,Brare w er i Br (il) CH=CH CH Chip —CHs Hy —CH— CH, —CH CH, CH —CH—CH—H Be rompaiiie T 3 tromopentane Hs 2 rome} ethan (c)_ Allyl halides containing halogen attached to tertiary C atom are called tertiary ally! halide. tertiary aly! halide withthe formula CH, Hs Oy FOO be 2 tromo:? methyoutane 10.2. NOMENCLATURE Conceptual Questions 1. Give the IUPAC names ofthe following compounds: be CHCHCDCHENCH, ot CHE,CBKCIF © cicH.caec,sr (a) €ay,ccl fe) CH,Clo-CicH),CHENCH, (0, (ChyACCHCCgHp Solution a Ge CH OHHH “There are four carbon atoms inthe longest carbon atom chain and tothe secand carbon atom brome (Br) groups attached and tothe third carbon atom chloro (Cl) group is attached, Therefore, the IUPAC name s -bromo-3-chiorobutane. roa Lol nal “There are two carbon atoms in longest possible carbon chain tothe frst carbon fluoro (F), bromo (Brand chloro (C) groups are attached and tothe second carbon atom two fluoro (F} groups are attached. Therefore, the IUPAC name will be I-bromo-t chloro-1,2,2-tfluoroethane. CyB ‘Tete are four carbon atoms in longest possible carbon chain, tothe fst carbon atom ofthe longest chain bromo (Br) group is attached, between the second and third carbon atoms triple bond is present and tothe fourth carbon atom chloro (I) group is attached. Therefore the IUPAC name wl be 1-bromo-4-chiorobut-2-yne. Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETMALIK'S NEWTON CLASSES aaa ‘Thete are three carbon atoms in the longest posible carbon atom chain, tothe first carbon atom three chloro (CD) groups are attached, tothe second carbon atom one chloro (Cl) and one tichloromethyl groups are attached and to the third carbon aton ‘agnin tree chlor (Cl groups are attached. Therefor, the IUPAC name willbe 2+rchloromethy)11,1.2.33,3-heptachloropro. pane. oy Fl Op ee Ce! Hy There are four carbon atoms in the longest posible carbon chain, tothe fist carbon atom one chloro (i) and one iodopheny! {group are attached: and tothe third carbon, two methyl (CH,) groups are attached. Aso, there is double bond present between the fist and the second carbon atoms. Therefore, the IUPAC name Is 1-chloro-1-4-lodopheny/)3.3-dimethylbut-1-ene, 2, Write the structures of the fllowing organic halogen compounds. (ncert) (a) 2-Chloro-3-methylpentane {b) p-Bromochlorobenzene (a) ¥-Chloro-+ethyicyclohexane (d) 242-Chloropheny!-1-iodooctane {@) Perfluorobenzene (f) tert Burytedohoptane (a) 1-Brome-4see-butyl-2-methylbenzene (h) 14 Dibromobut-2-ene Solution do er al al ‘ eyo, a (a) ey tC 6H — CH) — EHC, — Hy cc Oe GFE (9) CHy—CH— crc Be—CHy CH=CH CH — Br ‘ ° sch, oH, Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII 5. Write the isomers of the compound having the formula CHy8r Solution ‘The Isomers of compound with the formula CH Br are: a dye yaar Gy OO, CHCHACHCH) + HCL chsgtenich, + gb —e CaneHCHLCHy + He A ‘The resulting fre radicals react with chlorine o give the corresponding alkyl chlorides. n-Buty radical gives ony I-clorobutane; s8¢-buty radial gives only 2-chiorobutane. secur acl Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII CCHSCH,CHCH, + Cly ——> CHCH,CH.CH,S + “Gt uy rac "vrata in Buylehonde) OAseHCHLCH + Ge —> CHEHEHLOH, + a sec Butyl acl 2Chiorbutane sec Buty chore Now. if on each collision of a chlorine atom with a butane molecule hydrogen abstraction takes place then the mburyi/se butyl radical ratio, and hence the 1- 2"> I Hy Che--He-CHyCH,CHyCH,——Cl---He-“CHCH,CHs Tianation saeforabirction —Tanion ste fox abtractin, of prmary hydrogen ‘la secondary hdrogen [hydrocarbon CyH;9 does notreact with chlorine in dark butgives single menechloro compound CeHsCtin bright sunlight. entity the hydrocarbon. (NCERT) Solution Hyp belongs tothe group of hydrocarbon with general molecular formula C,H, Therefore, tcan be either an alkene ora cycloal kane’ As hydrocarbon doesnot react with chlorine in the dark, It cannot be an alkene; soit must bea cycloalkane. Again, the hydro- Catbon gives a single monechloro compound, C;HyCl in bright sunlight Since a single monochioro compound is formed, the hydrocarbon must contain H atoms that are all equivalent. Ako, sal Hatoms of acycoalkane are equivalent, the hydrocarbon must ‘bea cyclolkane, Thus, the said compound is eyelopentane. Qo Ox 3 cytopentane (Hy ‘The reactions involved inthe question are: 4. Wite te equations forthe preparation of odebutane fom butanol) -chlrobutane and (but -ene Solution 0) CHy—CHy—Cly—CH,—OH + HI > Cy — CH, CH CH) 1 + HQ vata Veaobuane (8) Cty OCH —Cj—CI + Nal E> CHy— CCH, — CF Nac © yay — cee + He 2s yc) Oy — CH, — Br cy CH) CH=CH + Nae Previous Years’ CBSE Questions 1. Complete the following reaction equations (a) CaN —> HM, a + Br, WOH Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES CoHSNZCI + KIS HGF KCN, OB) Hcg, eruennaaonium lodobennene ea + Bs 8c) — cH Br tiene wo OMA 12.0bromoethane thene 10.5 PHYSICAL PROPERTIES Conceptual Questions 11 Which wil have a higher boing point: 1-Chloroethaneor2chlro-2-methyloutane? Give reasons Solution ‘Since the molecular mass of2- R—H+ MgioHx Gugrarreageen ane “Therefore. Grignard reagents must be prepared under anhydrous concitions 4. pDichlorobenzene has higher meking point and ower solubility than those of o-and mrisomers Discuss Solution q . Oo o 0 . t san en nian pDichlorobenzene is more symmetrical than o- and m-somers Fortis reason, it fits more closely than o-and m-\somersin the cys tallatice, Therefore, more energy is required to break the crystal atice of p-ichlorobenzene. Asa result p-dichlorobenzene has @ higher melting point and lower solubility than o-and m-isomers. 10.6 CHEMICAL REACTIONS Conceptual Questions 4, Differentiate between chiral and achiral molecules. Solution A chiral moleculeisa type of molecule that lacks an internal plane of symmetry and thus has anon-superimposable microrimage The presence of an asymmetric carbon atom (carbon atom withthe four different groups attached) isthe cause of chirality inthe mole- cules. For example, utan-2-0.An achiral molecule sone which is superimposable on its mirror image. For example, propan-2-oL, oa Ga Ben Sees cncntontintesenigne ante Me GHs GHs | ¥ i Low teh Lt op ok Hs Y a Hy Y CH iy G& & sae NH he yeh ‘Therefore, there is one chiral atom in 2-aminobutane which is marked with *in the structure. Two stereoisomers are possible for 2-aminobutane. Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES (b) The structure of 3-bromopent-1-ene's “Therefore theres one chiral atom in3-bromopent-1-ene which s marked with *in the structure. Two sterecisomersare possible for 3-bromopent:I-ene. (o) The structure of1.2-dichloropropane is Ha “Therefore, there is one chiral tom in 1.2-dihloropropane which s marked with * Inthe structure. Two stereoisomers are poss ble for 1,2-dichloropropane. (4) The structure of 3-methylpent-1ene is Hs I CCC CH=CH, kK ‘Therefore thereis one chiral atom in3-methylpent-1-ene which is marked with *in the structure. Two stereolsomersare possible for -methy-t-pentene. 4, What are enantiomers? Draw the structures ofthe possible enantiomers of -methylpent-1-ene. Solution ‘stereoisomers which are non-superimposable mirror images of each other are called enantiomers, The possible enantiomers of Semethylpent-1-ene are: Hs Hy I I tN Pe) 4“ aN dict, Chic 5. Amange the following halides in order of increasing Sy2teactvty: CH,Cl CHyBr, CH,CH,CL (CH,)sCHCL Solution [As we knove that with the increase inthe iz of ally group, 542 reactivity ofthe coresponding aly! halide decreases. Further, we know that C-Ci bond is stronger than C-Br bond. Therefore, the increasing order of the given four alky| halides in tems of reactivity towards 5,2 reaction vl be (CH,),CHCl < CHsCH,Cl< CH,CI< CHB, 6. Which compound in each of the following pairs will react faster in Sy2 reaction with OH (a) CHsBr or CH4L(b)(CH,),CClor CHC? (NCERT) Solution {Since fon fa better leaving group than Brion therefore CH reacts faster than CH8r in Sy2 reactions with OF {Ib} The structures of(CH,),CCl and CH,Clare: Hy -G—a CH= CH “The 5,2 mechanism involves the attack ofthe nucleophile atthe atom bearing the leaving group. However In case of (CH) the attack ofthe nucleophile atthe carbon atom is hindered because ofthe presence of bulky substituents onthe carbon atom ‘bearing the leaving group.On the other hand, there are no bulky substituents on the carbon atom bearing the leaving group in (CHC. Hence, CHyCl reats faster than (CH)CClin $2 reaction with OH 17. Predict all he alkenes that would be formed by dehydrohalogenation of the following halides with sodium ethoxide in ethanol and identify the major alkene: (a) 1-Gromo-|-methyicyclohexane;(b) 2-chloro-2-methylbutane;()223-Limethy/-3-bromopentane, (NCERT) 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII Solurton (a) BH 4 4 4 4" Inthe given compound, all hydrogen atoms are equivalent Thus, dehydrohalogenation ofthis compound gives only onealkens. chy oH Co 0) a la Oa g—dh, oH, Hy In the given compound, there are two different sets of equivalent hydrogen atoms. Thus, dehydrehalogenation of the com- pound yields two alkenes CmcH— cl, + CH CCH, — ct I Hs Hs aor is Saytzefs rule implies that in dehydrohalogenation reactions, the alkene having a greater numberof ay! groups attached toa ‘doubly bonded carton atoms is preferably produced, Therefore, 2 methylbut-2-ene|s the major product inthis reaction. ae a badis Inthe ven compound there ae often sts of quale yrogen sons, Tus dehythaeoenaon of he com- Sooetees wheres chute a och Onin Emop oy cH ememainat, + Foo dudes bydy by aiesinto 30 re adpenion fon sczoitg saya ndellagerntion ars ha akere hag rarer ial rps ache ta the doy bonded eaten stom iptteabh famed Hence sAe-ametbent2-eel tema pot ns encton 2. ow wily bing about the loving entero? to ceeltobar ae fe hand romowtene 6) Propane -npropane Tamrac en (| Popenew pone ( chonas cin horde (a) taromometanetoprovenone tn) urtanetobiacane AY VCherobwane to racine th tenant ineean) sel (a) cryCH0H > cH Chioroethane cmc + Hay Soci CHC; +HC=C Na ——> CHyCHAC=CH NaCl Chlorsethare Sodium aceyide But tyne Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES CH — CH, M225 cHy— Hor "> CH=CH, “Ay Bic, —cHyor Ac, PS CH CHB > Cyc nor romoethane | 2.Dibromoethane fromoethene cicero PS Cc, Gor 22+ Cry Cth HNO, ‘-oreprpane —_a uct cron bedmé Benay alchohol hy —CHCH Sey hye —> CH=CH & Br — 1.2-Diromoprosane 0 os = ey HH A> Hy cH CH —Chhy—0H > Ch . Chloroethane Ethyl Muoride: Cy Es Che ES Oy conga, ES tm romney Os Hy Propanone creamer 2 aoLeHa, —S cCHmCe But zene br 2romobutane 2CHyCH:CH,CH,—C1+ 2Na 27" CHJCH,CH,CH,CH,CH,CH,CHy — . > CQ oh fensere Sromabenzene Write the structue ofthe major organic productin each of the following reactions: (a) CHCH,CHC+ nat E>) CHEB + KOH fe) CHYCHIBACHCH, + NUH —> (a) CCH, + KN (0) CQHsONa+CHCI——> __(()_CHCH,CH,OH+ SOC ——> (9) CHCHH=CH, + HBr > th) CHCH=CICHy)» + HBr ——> (NCERT) Solution CCHyCH,CH,CI + Nal SSS CHyCH,CHal + NaCl Chloropropane "Taman edopropane (CryCor + KOH 2 frome? methteropane ha —_e vcHtncjct, +naon 2 > COHOMCH,CH + Nabe tonne ats coyeryar+ Kew 22» CHEN + vectors Seam Gureatane CoWONe + GN oF CLOG + Hcl noe pomuurenaasian! SSS” asa CHAEHACHAOM + SOC —> CHYCHCH,C + $03 + HC tee ‘toepepne Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII CH; + HBr ES > CHyCH,CH,CH,—Br I GHCH=CICH,), + HBr > CHO CH 2 Methyl 2-ene ‘soon Methyl 2 L, 2 Bromo 2methylbutane 110, Write the mechanism of the following reaction: nBuBr + KCN "2 nBucny (NCERT) Solution ‘The given reaction proceeds through S42 mechanism. n this reaction, CN” acts as the nucleophile and attack the carbon atom to hich Bris attached. CN" ion isan ambident nucleophile and can attack ether through Cor Nn ths case, it attacks through the C oe a SNE PE os ee Bury bromide Bury cyanide 11, Arrange the compounds of each set in order of reactivity towards 52 displacement: {a}, 2-Bromo-2-methylbutane, I-Bromopentane,2-Bromopentane {b) -Bromo-3-meehylbutane, 2-Bromo-2-methyibutane, 2-Bromo-3-methylbutane {6} 1-Bromobutane,1-Bromo-2,2-dimethyipropane, |-Bromo-2-methylbutane, -Bromo-3-methylbutane. Solution (a) Br er I | CHYCHIONCH:CH Br CHCHCH,CHCH CHACHA, Vemopetie(")/— 3enopenin h, 2 4rome:-methfbutane ‘An Sy2reacton involves the approaching ofthe nucleophile othe carbon atom to which the leaving group I attached. When the nucleophile is sterically hindered, then the reactivity towards Sy2 displacement decreases. Due othe presence of substitu ents, hindrence ro the appreaching nucleophile increases inthe folowing order 1-8romopentane <2sbeomopentane < 2-Bromo-2-methylbutane Hence the increasing order of reactivly towards Sy2 displacements 2-Bromo-2-methylbutane yd a Colts —CH—CGoHls ——> CoHs—CH—GyHs yds aqueous KOH proceeds through the formation of carbocation the cabocaton|s stable, then the compoundiseasly Ite by equeous KOH Now igor reatboaton wf cH fos carbocation whe more sale than Tearbocaton Hence CHC Hs hry more ess than Chl by aqueous FOAL How the folowing conversions can be cated out? (a) Propeneto propanol fb) Ethanol tobutyne (6) -Bremapropane 0 2bromapropane (d) Tolueetoberzyakohol (e) eneanetoa-bromontrobencene (f) Benayacoelt2-phenlethaoic cd (9) Ehercltopropenentie’ _(h) Anne techloeberamne {) ethebutane 03, detyihesane ) 2Matyrtpropeneto. (8) Eychoridetopropanoicac I) Gut renetwn-buylodde Zehir 2 methane (m) 2.CHrepropane to propanol(*)opropy akohol tofodoform (0) Clorobeaane to p-nitrophenol (9) 2Btomapropane to (a) Chiocthane te butane (folie to phenyl sceyanule "bremoprepane Solution (a) Cyc, SS cH — cH, HBr > CHSCH,CH,OH (weenry 1 eKeK > obcus SH SoKmc4 Soo lodoethane Einene | “Ssano & Br Oyo Oe co a — Br dine CH.COoH Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII asciior yoo + ancien het omens enero ° na cy Hy CCH,CHCHCHCH;CH, + 2NaCl 24 Dimettyinenane jC, EN + KCI > cH, cH COOH chy) cy 5 chy Cy — Cyr 9 OCC twatiene ‘aan "remebutene in fuyiodise Hy CH=CH Hy HH, cy CH CH 8 2 Chovaeroeane Propane | "Se 1 bromopropane Fae? Hh hy OF =r 1 Propan oH ° cht, 22> tc, SS cy ‘eProp alchohol ""™" Propanone “eer ladoform a OO + &. 4 on hovobenzene rm-Chorontvobenzene _0-Chlrontrobenagne Charette ‘maior oH { 0 for thos Ww ay Gta cy aie > yc — yor — Someones cay 0H —c1 A Hy chy — CH) + aN! a has NH, ve Phen nocyanice Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NET18 R. K. MALIK’S NEWTON CLASSES 114, The treatment of ay! chlorides with aqueous KOH leads to the formation of alcohols but inthe presence of alcohol KOH, alkenes are major products. Explain. (NCERT) Solution Inan aqueous solution, KOH almost completely ionizes to give OH" fons. The OH lon strong nucleophile which leads the alkyl chloride to undergo a substitution reaction to form alcohol. R—Cl+KOH (aq) ——> R—OH+ KCI ‘byt ‘Neohel (On the other hand, an alcoholic solution of KOH contains alkoxide (RO” on, which isa strong base Thus it from the carbon ofthe alky chloride and form an alkene by eliminating a molecule of HCl. R—CHy—CH,—Cl + KOH (ale) ———> R—CH=CH + KCI + HL ‘ « Akane ‘OH ion isa much weaker base than AO" ion. Also, OH” ion s hight solvated in an aqueous solution and as a result the basic cha _acter of OH" ion decreases. Therefor, it cannot abstract a hydrogen from the fecarbon - Primary ally! halide C,Hy8r (A) reacted with alcoholic KOH to give compound (8). Compound (8) is reacted with HBr to give (C) ‘hich i an isomer of (A) When (A is reacted with sodium metal t gives compound (0), CeHyg which i diferent from the com- pound formed when n-butyl bromide i eacted with sodium. Give the structural formula of (A) and write the equation forall the reactions. (ncerr) Solution ‘There are two primary ally! halides having the formula, CHB. They are m-buty! bromide and isobutyl bromide CyB Hy EHH Bury! bromide CHs ‘Butyl remide ‘Therefore, compound (A) is either mbutyl bromide or iso-buty! bromide. Now, compound (A) reacts with Na metal to gle com- Pound (8) of molecular formula, Cy which is ifferent from the compound formed when n-butyl bromide reacts with Na metal. Hence, compound (A) must be so-buty bromide. 2CHACH,CH, CH 22s cy CH,CH,CH,CH, CHC, + 2B ries pe Chercher EEE CeHCR CCFO +240" Hy Gy Gy ‘50 Buy bromide 25 Oimethyhexane w o “Thus, compound (0) is 2,5-dimethyhexane. tis given that compound (A) reacts with alcoholic KOH to give compound (8). Hence, «compound (B) is 2-methyipropene. Hy —OH— CBr “CH, + HBr Hs Hs o-Biy broie 2 Merhyoropene iw a ‘Also, compound () reacts with HBrto give compound () which san isomer of (A). Hence, compound [Cs 2-bromo-2-methylaro- pane, Br Hs : cHs 2Methvoropene 2 Brome? methypropane o cepts E> ob tia (on tomer aA) Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XI 16. What happens when (a) rebut chiovides treated with leoholic KOH. (o)bromobenzenei treated with Mg inthe presence of dry ether. (c)_ chlorobenzene is subjected tohydrobyss (a) ethyl chloride treated with aqueous KOH. (e)_ methyl bromide i teated with sodkam inthe presence of ry ether. (methyl chlorides treated with KCN. (weer) Solution (2), When m-buty| chloride is treated with alcoholic KOH, the formation of but--ene takes place. This eaction isa dehydohaloge- ration reaction HCH CH CHC! > cy cH CH= Cy + KCI + H,0 Buy! Monge Boe () When bromobenrene is tested with Min the presence of dry ether, phenyimagnesium bromide Is formed, er MaBr I OO fromabearene _Phenyimagnesum brome {€) Chlorobenzene does not undergo hydrolysis under normal conditions. However, it undergoes hytrolysis when heated in an ‘aqueous sodium hydroxide solution 3t a temperature of 623 Kand a pressure of 300 atm to form phenol a QO robonz nen ety chloride treated with aqueous KOH, undergoes hydrolysis to form ethanol yc, 1 SY cr HOH + KI Ehyteiide eran ‘When methyl bromide i treated with sodium inthe presence of dry ether, ethane s formed. This reaction i known asthe Wurtz 2CH,—Br + Na 25 cH + 20 Metotanide thane en methy chloride strated with KCN t undergoes a substitution ection to giv methyl cyanide. ay—a rHen 82 cyeN HH ot ae Textbook Exercises ‘Show how you might usea nucleophilic substitution reaction of propyl bromide to synthesize each ofthe following compound (You ‘may use ary other compounds that are necessary.) (a) CHCH,CH,OH (b) CHyCH,CHal (a) cHycH,OCH,CHCH, (a) CH,CH,CH,-5-CH, ™ 9 HHH, (CH, COCH,CH,CH, fo) GH (h)_ CHcH,CH,eN W CHcH,CH,SH oa amma ay Solution fa) CHyCH,CHsBe+ NAOH — CH,CH,CH,OH + NaBr (0). CHCH,CH,Br + Nal CH/CH,CH,L+ NaBr (eo) CH,CH,CH,Br + CHyCH,ONa > CH,CH,CH,OCH,CH, + NoBr ()CHyCH,CH,Be + ChySNa + CH,CH,CH,SCHy + Nate Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NET20 R. K. MALIK’S NEWTON CLASSES te ; : (1) CHCH,CH,Br + NaN, + CHCHLCHN, | Nae (CHACH,CHyfir + CHyC—ONA—> CHSCH,CH,OCCH + Nabe @) Hs () CHsCH,CH,0r+ NaCN -» CH,CH,CHCN + Nar (ChyN + CHACH,CHBe > CHy—N—CH,CH,CHy Br cH (1) CHCHCH,Br + NaSH + CHCH,CH,SH + NaBr 2. Which ally! halide would you expect to react more rapidly by an Sy2 mechanism? Explain your answer (0) CHCH,CH,Br or (CH,).CHBr lb) CHsCH,CH,CH,Cl or CH,CH,CH,CHL le) (CH):CHCH,Clor CHCH,CH,CH,CI (@)_(CH),CHCH,CH,Cleor CH,CH,CHICHs}CH,CI (le) CiHeBr oF CH,CH,CH,CH,CH,CH,Cl Solution {a} 1-Bromopropane would react more rapidly because, being a primary halide its lss hindered {(b) odobutane, because iodide ion is a better leaving group than chloride ion {el_1-Chlorobutane, because the carbon bearing the leaving group is less hindered than in I-chloro-2-methylpropane. ()_1-Chloro-3-methytbutane, because the carbon bearing the leaving group is lss hindered than in 1-chloro-2-methylbutane, (e)_1-Chlorohexane, because itisa primary halide, Pheny halides are unreactive in 5,2 reactions Your tasks to prepare jo-propyl meth ether, CH,OCHICHs)s, by one ofthe following reactions. Which reaction would give the better yield? Explain your choice {a} CH,ONa + (CH,),CH > CHAOCHICH), () (CH,),CHONa + Hy! CHAOCHICH), Solution Reaction (b) would give the better yield because the desired reaction Is an $2 reaction, and the substrate Ia methyl halide. Use af reaction (a) would result in considerable elimination by an E2 pathway because the substrate isa secondaty halide ‘Atnough ethyl bromide and isobutyl bromide are both primary halides, ety bromide undergoes $y2 reactions more than 10 times faster than io-buty! bromide does, When each compound is treated with a strong base/nucleophile(CH,CH,0 0 buty bromide gives a greater vied of elimination products than substitution products, whereas with ethyl bromide ths behaviors reversed, What factor accounts fr these results? Solution {50 Butyl bromide is more sterically hindered than ethyl bromide because ofthe methyl groups onthe carbon atom HE PN HOE tar ec we ¥ ‘50-Butyl bromide Ethyl bromide This steric hindrance causes so-butyl bromide to react more slowly in S,2 reactions and to give elatvely more elimination (by an E2 pathway) when a strong base is used Explain the following observations: When tet butyl bromide i teated with sodium methoxidein a mixture of methanol and water, the cate of formation of ter-buty alcohol and tert-butyl methyl ether does not change appreciably a the concenteation of sodium ‘methoxideis increased, However, incregsing the concentration of sodium methoxide causes a marked increase in the rte at which {ert-buty| bromide disappears from the mixture, Solution {ert Buty alcohol and tert-butyl methyl ether ae formed via Sy mechanism. The rate ofthe reaction Is Independent of the eancen tration of methoxide ion (om sodium methoxide). Ths, however is only one reaction that causes tert-butyl bromide to disappear A ‘competing reaction that also causes ‘et-buty bromide to dsappear I an £2 reaction in whlch methoxide fon reacts with tert buryt bromide. This reaction is dependent on the concentration of methoxide ion: therefore, increasing the methaslde ion concentratlon ‘causes an increase in the ate of disappearance of tert-butyl bromide, (8) Consider the genera problem of converting a tertiary ally halide into an alkene, for example the conversion oftr-buty| chloride into 2:methyipropene. What experimental conditions would you choose to ensure that elimination i favored over substitution? (b) Consider the opposite problem, that of carrying out a substitution reaction on a tertiary alk! halide. Use as your example the conversion of tert buty chloride toter-buty| ethyl ether What experimental conditions vould you employ toensure the highest possibie yield ofthe ether? 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII Solution You shoul use. strong base, such as RO" at a higher temperature to bing about an €2 reaction (b) Here we want an Sy! reaction. We use ethanol at alow temperature so that elimination is minimized. 77. When the alky bromides (listed here) were subjected to hydrolysis ina mixture of ethanol and water (80% C,HyOH / 20% 0) a 55°C the rates ofthe reaction showed the following order: (CHsCr> CHyBr> CHCH,Br>(CH,),CHEe Provide an explanation for this order of reactivity Solution ‘wo ifferent mechanisms ae involved. (CH,),CBr reacts by an Sy mechanism, and apparently this reaction takes place faster. The ‘other three aly! halides react by an Sy2 mechanism, and thelr reactions ae slower because te nucleophile (1,0)'s weak The eac- tion rates of CHB, CH,CHB, and (CH,);CHBr are affected by the steric hindrance, ané thus their order of reactivity is CHsBr > (CH,CH,Br> (CH,),CH, {& Thereactionof 1 alkyl halides with nitrite salts produces both RNO, and RONO. Account for this behavior, Solution [tte ion i an ambident nucleophile. [foted [Nitite ion can attack through okygen resulting in the formation of ay! nitrites Als, It can atack through nitrogen resulting in the formation of ritralkanes, - ae Atte Ntroattane R ‘You have the task of preparing styrene (CeH,CH=CH,) by dehydrohalogenation of ether 1-bromo-2-phenylethane or 1-bromo-1 phenylethane using KOH in ethanol. Which halide would you chooseas your starting material to give the better yeld ofthe alkene? Explain youranswe. Solution ‘The bette led willbe obtained by using the secondary halide, 1-bromo-1-phenylethane, because the desired reaction is (2. Using ‘the primary halle wil esutin substantia 2 reaction as wel, producing the alcohol instead of the desired alkene. ‘Which ofthe following statements are true for S,2 reaction of haloalkanes? {a} Both the haloakane and the nucleophile ae involved in the transition state. {(b), The reaction proceeds with inversion of configuration a the substitution center. |e) The reaction proceeds with retention of optical activity [) The order of reactivity is 3°>2"> 1°> methyl [e) The nucleophile must have an unshared pair of electrons and bears a negative charge 0) The greater the nucleophilic of the nucleophile, the greater the rate of reaction Solution (a) Tue (b) Tee) Fale (a) False =e) Tue tf) Tre Complete these Sy2 reactions ” 4 of | i, Neato Se outta cys me Hs (a) (CH) N+ Cy CH,CHCHcHyBe + Nat AA Operas anorne 0 a as sonst SS Crs anicngcnia > to) -eryer emi, 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836608812, 7546846949 NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES i fs) q LOCCH, or worto-nae 2 Cr +naci ra sensory AGH, + aHCHS Na MS cacy + Nl © oF ms andoncer+ Nat AS cdHcyciig + Nase (a omg ct AS ch oct Hoc, () teornes ++ abr © Our» avencia 5 (Yayoi ™ D-aa 4 ity Orcas Show how you might synthesize the fllowing compounds from a haloakane and a nucleophile: @ cn ®) cre e Oy ° Ne 0) Ao @ 2 si ssaton oe on Coen o ona oon CO ec ‘a ; 8 o—c—cHy (4) CHYCH)) CHB + HS-Nat* —> CHyICH,),CHSH + Nabe (0) CHYCH) CH, + HC=C“Na* ——> CHy(CH,)sC=CH+ Nabe (9) CHyCHO-Na* + CHCA S cHycHOCHCH + Na SS ns SO raw structural formulas forthe alene() formed by treating each ofthe folowing halolkanes with sodlum ethoxide in ethanol ‘Assume that elimination is by an E2 mechanism. Where two alkenes are possible, use Saytzef rule to predict which alkene isthe ‘major product: Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII "Cfo "cy de oan — =X cone” oe 4 ‘Nong with substitution elimination occurs to yield 2,3-dimethyibut-2-ene (major) and 23-dlmethyIbut--ene (minoe {b)_-Methyicyclohexene is formed by dehalogenation of 1-chloro-1-methylcyciohexane by Sodium ethoxide in ethanol 4 of a Hy Gy now or rT 4 | tre -methyycohewane——_1 Methyeylohenane nom ew + Ke cH mld Not conjugated Predict the outcome ofthe folowing reactions: 4 (a) GiyCH:CN ()CHyICHYYCHANCH, 4 (©) CHCH)«CHANCH, ‘Starting with an appropriate alky| halide and using any other needed reagents, outline syntheses of exch ofthe following, When altemative possibiltis exis fora synthesis, you should be careful to choose the one that glves the better yield. (a) Butyl secbutylether ——(b)CH,CH,SCICH,),__()_ Methyl neopentyl ether (4) Methyl phenyl ether (e), CgHsCHCN Solution CHO EH > Om HEHEH bu ow avons, Soyencnen, cry ,cnar ATE eye —s—cH CH, e Hs Hy Hs [ = ow CF eOM EE Hh F—OHOTNNY —T chy —E— er 00H, OH cy oH 10) cayon > eyo nat 2 atyocny te) ego Lhe + na Temene Se ety 16. (Stem UPA ramet ean comp (0) Complete the following chemical equation: HCH CH=CH, + HBr Solution (a) ome butane (8) creamer, + Hrs CHCHCH Cree Aart ones in rman of primary ty hale nh case, resus formation of bromabutane 17. ile compound inthe folowing couples wlreactfasten 52 spacer and ty? {a} emopetan or empentane Ib) trom 2methyioutaneor2 bom 2-metybutane Setution (a) n2bromepertane the acarbon tached the bromine atom Bis frhe inked with we ay foun math ad po pbuh {romopertane Ik aached ws ony nett group which buy gtoun Tere 3 rmopeaare hes greater sterichindrance to nucleophilic attack than 1-bromopentane; and hence I-bromopentane is more reactive than 2-bro- mopentane'in 5,2 reaction, HCH cy EB CH) CH EHC | Bromopentane | be In -bvomo-2-methybutane, carbons attached one bully sc butyl group when 2-bromo-2-methylbutane. carbons atzached othe aly groups which re two mety groups and one ety! group. Therefore, -bvoma 2 methyouane ster greater src hindrance to nileophile attack han -bromo-2metyieutane Hence, I-bomne--metioutane is more ea the than 2brome--nethybtane Hs Os Hy —CHp—CH— CH, 8 CHy— CH, CH, 1 Bromo 2 methylbutane 4 2 Brome-2mathybutane Which product (or praducts) would you expect to obtain from each ofthe following reactions? In each pat give the mechanism (Sy1,5y2or elimination) by which each products formed and predict the relative amount of each product (i.e, would the product, be the only product, the major product, a minor product, et) (a) CHyCH,CHyCH,CH,Br + CH,CH,0- > (b) CHSCH,CH,CH,CH,Br + (CH),CO (2 (Cig car + cH:0- > (a) (CHy)sCBr + (CH),co- —** 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII a (ora (h) 3Chloropentane + CH3CO,; => 103 8romo-3-metiherane E> (8) 2370mociane + 1° E> sSehation {a} The major prot woul be csCHCHCHCH{ OCH (by an 52 mechanism) case the subatesrmaty and he ruleoph bases ot hinted sore ry CHyCryCrch, wou be produced by Earechanism (hy Themoorrodut wouldbe ChchccHCh oy an neha eventhough the substrate primary because base issvong and stencal hindered Sone CHICHYGH,CHCHOCTCH), woube produced by an Sy? mechan {e) Forallrectal purpose (CH),C-Ci(byan 2 mechoism) wuld be the ony produt because the sUbsuae stein and tebe song Some araner an lodide in sa very weak base and a good nucleophile Because the substrate i terary and the only nucleophiles the solvent, mechanism is Sy. The two products formed are cH, Hs cH PS ~OCHs cHs)¢ and (cH). (CHsCH-CHCH, Cs by an £2 mechanism) would be the major product because the substrates secondary and the base/nucleo- pile is a strong base. Some of the ether, CH,CH,CHIOCH,)CH, CH, would be formed by an Sy2 pathway ‘The major product would be CH,CH,CH(O;CCH)CH,CH by an Sy2 mechanism) because the acetate ion isa weak base. Some (CH,CH=CHCH,CH,CH, might be formed by an €2 pathway. CCH,CHACHCH) ane CH,=CHCH,CH, (by E2) would be major products and (S-CHsCHIOMICH,CH, (by $)2) would be minor product, Gly —Gh chy CHa omopertane & 2 Bromopentane Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES Int bromopentene, the a-carbon atom attached to Br atom is further inked to two alkyl groups but in 2-bromopentane itis ‘attached to only one ay! group. Therefore, 2-bromopentane sues greater sterichindrance to nucieaphilc attack than Ir: rmopentane. As a result 1-bromopentane is more reactive than 2-bromopentane in Sy2 reaction. (b) 1-Bromo-2-methylbutane will undergo 5,2 reaction faster than 2-bromo-2-methylbutane, Thus, the order of S,2 reaction is oe yO “GIG —Br> Gy — eG OH br |-trome:2methyibutane rome? methybutane 1-Brome-2:methylbutane proceeds by forming 1 carbocation while 2-bromo-2 methylbutane proceeds by forming 3° carboca- tion, The electron density on the cecarbon atom of the later compound is more due o presence of more alkyl groups. Ths increased electron density on the aecarbon atom repels the direct attack ofthe nucleophile and thus etards 5,2 reaction. It rather proceeds by 51 reaction 2. How would you differentiate between Sy! and 5,2 mechanisms of substitution reactions? Give one example ofeach. (CBSE 2010) Solution ‘5! reactions occur intwo steps and the reaction is of fist order whereas S,2 reactions occurin one step and the reactions of second ‘order In Sy! reaction, retention of configuration takes place whereas in $,2 reaction inversion of configuration takes place. Example of 542 reaction: H 4 H ow + role] ong sc Example ofS ection, see, (yer 2 Os ve wc ty oH b+ 0H” 4 (CHy),C—OH HC OH ‘4. Which ones inthe following pais of substances undergo 5,2 substitution reaction faster and why? Solution (a) A will undergo 5,2 reaction faster than 8 because Aisa primary halide, and as we know due to les steric hindrance primary On On ve OQ (&) Awillundergo Sy2 reaction faster than Bas iodine isa better leaving group due toislarger sz will be released faster in pres tence of incoming nucleophile ~~! ert a 6 5. (al. Why is itthat haloalkanes are more reactive than haloarenes towards nucleophiles? (b) Which one ofthe following reacts faster in an Sy reaction and why? q i Neo rg a ® Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII Solution (a) Haloarenes are less reactive towards nucleophilic substitution reaction because ofthe following factors (0) Resonance effect: Haloarenes are stabilzed due to resonance. ce %: xe x % C-O+0-0-0 < Difference in hybridization: The C atom in haloarenes is sp* hybridized, while in haloalkanes, itis sp” hybridized. The sp” hybridize carbon has a greater s character and is more electronegative than the sp hybridized carbon. S, in haloarenes (C-Xbond is shorter and stronger ficult 1o break} x 4 toyoiiaded op ioaaed (7 AN was i) Instabitty of phenyl cation: The phenyl cation is formed by the loss ofa halogen atom which isnot resonance stab lized () Compound A forms secondary carbocation, vile B forms primary carbocation. Greater the stability ofthe carbocation. faster isthe Sy] reaction. As secondary carbocations are more stable than primary carbocations, Areacts faster than 8, a HL AR, 0 o Chrapensne 2 -Chlorbatane (19 What are chital objects? Indicate che presence of center of chirality, any Inthe molecules of3-bromopent-I-ene. (CBSE 2007) Solution ‘The objects which are non-superimposable on their mirror images ae called as chiral objects For example, Hsia carbon eect 4h 2 Bromopent-1-ene 7. Identity whether the following pais of compounds are structural or geometrical somes: (esse 2007) creyceeenzamm omnes wl \ Nin ud Nee Solution (2) The two given compounds are geometrical isomers because the relative postions oftheir atoms or groups are different in space Hs R & Hid ya Hs (b} The two given compounds ae structural isomers as they have same molecular formula but different structures. Ky Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES 1, Wurtz action fas incase of tral halides. Explain Solution ‘The mechanism of the Wurtz reaction goes ike this: ‘One electron from the metals transferred tothe halogen to produce a metal halide and an alkyl radi RX MR EM The allyl radical then accepts an election from another metal atom to form an alkyl anion and the metal becomes cationic. This intr mediate has been isolated in several cases: RMoRM ‘The nucleophilic carbon of the alkyl anion then displaces the halide fon in another molecule through an Sy2 reaction, forming anew carbon-carbon covalent bond. RM? +RX RRO MEX” So in the third step, there I Sy2 reaction, Tertiary alkyl groups are very large groups. Thus, the ally anion will not be abl to attack another molecule ofthe ally halide due to steric hindrance o repulsion between molecules So, tertiary ally halides do not give this reaction. 1. Expalnthe following in one or two sentences [a)_ Displacement of cyanide and amide on is never observed in nucleophile substitution reactions. (b)RClis hydrolyzed to ROH slowly but the reaction i rapid fa catalytic amount of Kis added tothe reaction mixture. (e)_ Vinyl chloride s hydrolyzed more slowly than ethyl chloride. Solution (e) Displacement of cyanide and amide ions is never observed In nucleophilic substitution reactions because both of them are ambident nucleophiles, ~CN” and ~CONH, groups are strong nucleophiles. )ladide ion sa powerful nucleophile and hence reacts rapidly with RC to form Rl. R-CI+KI9R1+ KC Further.” is better leaving group than CI" ion, therefore, Ris more rapcly hydrolyzed than RCI to form ROH. Rel+KOH—+R-OH + KI {)_ Vinyl chloride has two resonance structures, 2 ‘The chloride on in vinyl chloride s not as reactive as in other ally chlorides due to resonance stabilization. The following two effets are observed due to esonance stablization, i) Carbon-chlorine bond in vinyl chlorce has some double bond character and is therefore, stronger than » pure single bond. \W)_ Carbon atom 32 hybridized and C-Ci bond lengths shorter (169 pm), and the bond is stronger than in ethy| halides (180 in) due to sp hybridization ofthe carbon atom, 3. Out of the various possible isomers of C,H,Cl containing a benzene ring, suggest the structure withthe weakest C-Clbond. Solution ‘The four isomers of HyCl are yO Q ‘Cl ~ I e-Chovotduene —mChloroteluene pChlootoluene Bony hide ‘Out ofthese, only benzy chloride isnot an ary chloride. This because, unice in aryl haldes, ts halogen atom snot atached the aro ‘maticring dectly.The C-Cl bond in benzyl chloride i the weakest and ready undergoes homolytic eavage togve benzyl radical, Opa +3 enaytdial Chlorine stom 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9836508812, 7546846949 NEWTONCLASSES.NETHALOALKANES AND HALOARENES [DRILL ASSIGNMENT] CLASS ~ XII ‘4 Optically active 24odobutane on treatment with Nalin acetone gives a product which does not show optical activity. Explain Solution Optically active Yodobutane on treatment with Nalin acetone undergoes racemization and hence the product does not show opt! cal activity as explained below: Hs Hs hm I Cech, HCH (Denorctaory) ——_Laevortaory When 2-iodobutane (is treated with "ion it undergoes Walden inversion to give 2-odabutane (il) which san enantiomer oft Then 2 odobutane l) undergoes Walden inversion to lve enantiomer (). tsa result of repetitions of these two Walden inversions, that Ultimately 2 50:50 mixture ofthe two enantiomersis obtained, 10.7 POLYHALOGEN COMPOUNDS Conceptual Questions 1. Givesome properties of feons. Solution Froon-12 (éichlorodifluoromethane, CFC) is commonly known as CFC. tis used asa refrigerant in reffigerators and air conditioners. It also sed in aerosol spray propellants such as body sprays, hal sprays, etc. However, It damages the azone layer. Hence, ts manufacture was banned in many counties in 1998, 2, Give the rade name and IUPAC name of benzene hexachlorde. Solution a a, a aya a ‘The IUPAC name of benzene hexachlovide ls hexachlorocyciohexane. Its commercially called gammexane (07 indane and is used as agyicltural pesticide. 2. Writ a reaction forthe preparation of carbon tetrachoride. Solution Hy +40, > Cc + AHCI 44. what happens when chloroform reacts with nitric acid? Solution Chloroform reacts with concentrated nittic acid to form nitro chloroform or chloropicin, which is used as an Insecticide and war gs CHC, + HNO; + CCI;.NOs + H,0 CChorferm Nie Chlerpienn wd 5. Give the uses offreon-12, DDT, carbon tetrachloride and iodoform. Solution Uses of Freon-12 Freon-12 dichiorodifuoromethane, CFC) s commonly known as CF. tis used as arefrigerantin refrigerators and air conditioners. Its also used in aerosol spray propellants such as body sprays, hair sprays, etc. However, it damages the azone layer Hence, its ‘manufacture was banned in many countries in 1994, Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0861-2662623, 9636608612, 7546846949, NEWTONCLASSES.NETR. K. MALIK’S NEWTON CLASSES Uses of DOT OT (pp Dichlorodiphenyltrichloroethane) sone ofthe best known insecticides. It is very effective against mosquitos and lice. But due its harmful effects, t's banned in most industrialized countles, Uses of carbon tetrachloride (CCl) (a). eis useefor manufacturing refigerants and propellants for aerosol cans () itis used as feedstock inthe synthesis of clorofluorocarbons and other chemicals. (cl. Itlsusedasa solvent inthe manufacture of pharmaceutical products. [Unt the mid 1960s, carbon ttrachioride was widely used asa cleaning fui, a degreasing agent in Industries a spot reamerin homes, and a fire extinguisher. Uses of iodaform (CHI) lodoform is used as an antiseptic. The antiseptic property of iodoform is only de tothe liberation of free iodine when it comes in contact with the skin. Textbook Exercises 1. (a) State one medicinal use each of chloroform and iodoform. (b) Whatare fons and how are they used?” Solution {a} Chloroform is used as an anesthetic lodoform is used as an antiseptic. The antiseptic property of iodoform is only due to the liberation of fee fodine when It comes in contact with the skin {b)Freon-12 (dichlorediftuoromethane, C,Cl,) is commonly known as CFC. [tis used a arefigerantin retigerators and ar condi toners It is also used in aerosol spray propellants such as body sprays, hair sprays, et. However, it damages the ozone layer. Hence, its manufacture was banned in many countries in 1994, 22. Whats the most important use of DDT Discuss the factors that lead to decline ofthis use. Solution DOT (p, p-Dichiorodipheny/trichloraethane) is one of the best known inectees. ts very effective against mosquitoes and lice. At avout that time the use of DDT to control insect pests in agriculture and forestry also began. Because of the ciscovery ofa widespread environmental contamination with DDT and its breakdown products and associated ecological damage, most industrialized coun- tres banned it use inthe early 1970s, Office.; 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2695608612, 7646846949, NEWTONCLASSES.NET