11 Alkyl Halides Alkyl Halides Alkyl halides are halogen substituted alkanes. A mmonohsloalkane is writen & RX, where X is any talogen atom (F, Cl, Rr and 1) The general formula of rmonohaloskanesis C,H, .X whilethatof'adiloukane KCH,X, Alkythatides ofa particular kind, in which halogen atom js attached to a saturated carbon, which in tum is linked to unsaturated carbon, arecalled allyl halides. And when halogen atom isattached to an unsaturated (sp*) carbon, they are called viny! halides. For example, u,c-cuicH (allyl iodide) Q oe (vinyl chloride) (vinyl chloride and ally bromide) Alkyl halides are classified as primary (1*), secondary (2°) or tertiary (3"), depending upen the type of carbon to which X is bonded. When X is bonded to carbon, which is bonded to one more carbon is called 1° halide ‘and their general representation is RCH,X. When X is linked to & carbon, which is bonded to two carbons is called 2° halides and is denoted by R,CHX. When X is bonded to @ carbon, which is attached to 3 carbons is called 3° halides and is designated as R,CX. CH, is unique (no: classified as 1°, 2% or 3%)as carbon is bonded to only hydrogens und is simply called methyl halide, Dihaloalkanes with both halogens on same carbon are called genuihalides and with halogen on adjacent carbors, se called vicinal dinalides. CHEMisTRY FCH.CH,CHFCH, FCH,CH,CHCHE JUPAC nomenclature of alkyl! halides TUPAC nomenclatute oF alky! halides with one halogen is haloalkanes and with two similar halogens is, ihaloalkanes. Ifthe hslogens present ae different, they are prefixed in alphabetical order, For example, CLCH.CH,CH,CH,CH, — CH,CHCH,CH.CH, i a I—chloropentane 2-chiloropentane CRICH.CHCH.CHS OLCH:CHOH.CH, cH a 3-chloropeniane 4 -chloro-2-methy butane ot hs CHAC-cH.cH, CHCHCHCH, a a 2ehloro-2ometyltutane ——-Pehlro-Smety butane Gh Hs cH g-cHsal oh GHOHCH-c1 ca ‘erro buns oN? 2-ameypopme FCHCHCH,CH, CHLCR,CH,CH, — FCH,CHFCH,CH, 1, L-difluorobutane 2,2-difluorobutane 1,2difluorobutane (gen) (vie) cH,CHFCHFCH, ifluerobutane 1, 4-ifluorobutane 2, 3-difluorobutane (vie) oe ot F,CH-CH-CH; FCH.CF-CH; is aes hare (fon ay bane (oem) wo)ng Hater HsCy.¢CHa HCl BrCH.CHCICHCL, Sree. 1, ueHow@pmpEne — 2_chloromethyi-, {dimethyl ‘oyclopentane jr By H H (CHy).C=CHCH.CI s-1, abiomocydobutane —T-chlor 3-metiyl-2-butne. Methods Of Preparation Of Alkyl Halides By using hydrogen halides ROW HS, RX +H.0 Ir must be noted thatthe HX used shouldbe dry, which is produced, in stu, as fllons 2NaCl+ HSO, Oy DCIT + NaSO, 2NaBr + HS, DH, 2HBrt + Na.SO, Nal + PO, 4, lt = 2NsP0, ee (2ome sarang fe prosuet, poss ble) R-X+H0 Details about $,1 and S,2 mechanism will be discussed later in this togie By using phosphorous halides ROOH + PCI, —» R-Cl + POCI, + HCL 3R-OH + PCI, > 3R-Cl + HPO, 3R-OH + PBr, 5 3R-Br +H,PO, 3R-OH + PI,» 3R-1+ HPO, Phosphorous halides are prepared by treating red phosphorous and halogen. The advantage of using Phosphorous alidenis that thereaxiion does not involve ‘carbocation intermediate so, itis fee from rearrangement may be noted that HPO, is used in place of H,SO, to prepare HI, This is because HI is & reducing agent and H,SO, being an oxidising agent can oxidize it ‘The above conversion af aleahol 1 sky halides proceeds via S,1 or 8,2 mechanism, Both the mechanisms are ‘operative during the reaction, having competition between them, The type of mechanism followed by an ‘alcohol depends on the structure of alcohol and the type ‘of solvent used for carrying cut reaction, By using SOCI, (thionyl chloride) R-OH + socl, fale, RCL + $0, + HIT The usefulness of this method is that there is no side product, which has to be separated. The side products are sgassousSO,,,which escape from he reaction mixtureand HCI, which formsa salt with the hase (pyridine), named. pytidinium chloride (C,H,N°Cr). The product alkyl chloride has 4 configuration inverted with respect tothe rea:tantalcobol (iit ischiral) inthe presence of pyridine base. In absence of base and polar solvent, the chiral alcohol gives alkyl chloride with retention of ‘configuration, Mechanism: Alcohol first reacis with SOCI, to form an intermediate chlorosulphite ester, which gives alkylchlorosulphiteand HCL In presence of pyridine, HCI reacis with itto give pyridinium (PyH') ion and chloride (CI ion. The Cr displaces the leaving group CISO 3 and chloro sulphite ‘ester decomposes to $0,, CP and RCI with inversion of configuration o @ RG Fc —> $0) BE ROSH ho& AG a +H Py+ HCl —> Py + cr Log —> crn sopser In the absence of a base and polar solvent, the chlorosulphite ester dissociates ino an intimate for—pair. The Cl of the anion of ion-pair attacks from the front side of Rta give retention afconfiguration. Theretention, is observed because Cl cannot reach the rear of the R' ‘group but is close toi front side Ro a $-0—> F a Noa Inamatelon-gir Bo RCI+ 80, ‘This referred asi (substitution nucteophilicinternal) ‘mechanism because a part of the leaving group detaches itself from the resto the leaving group during the process ‘and attacks the substrate By direct Halogenation of Hydrocarbons Rat 2%, ROX © HX Reactivity of above reaction with respect to type of hyérogen to be replaced fallows following order ‘Tertiary hydrogen > Secondary hydrogen > Primary hydrogen Jee CompenpiumAs ras the reactivity of halogen is concerned, Fis most by eating analkene with coresponding hydrogen halide reactive while I, is least restive. Infact, reaction with (HCL, HBr or Hl). The addition of these compounds 10 is reversible and is carried out in the presence of some alkene takes place according to Markownikov's rule, The ‘oxidising agents like HIO,, HNO, ete. 0 oxidise Hl reaction proccedsby elevtruphiliy addition of Hw give Mechanism of this reaction has already been di inthe lesson “alkanes more stable carbocation followed by attack of X~ Anié-Markownikoy addition of HBr can be achieved, if thereaction is caried eut in presence of peroxides (H,O, SOLVED EXAMPLE ‘orenzeyl peroxide oF di-trt~batyl peroxide). Addition ‘of HBr ‘o alkenes in the presence of peroxide follows EXAMPLE Ty free raga mechanism eee ee Creche Hs CHG CH Es cH cH CHB Br oi ree oC <= SOLVED EXAMPLE be EXAMPLE ei OXS ‘Major procuct of the reactions : ome BO wk al XK oS o§ < : : BC) + te Io 0-0: (me 06-070 sud Seal ie By halide Exchange (Finkelstein Reaction) “Arrange the following according to decreasing order mre , al ere achieved by treating them with Nal, using acetone as a = 2: solvent. Feasibility ofthisreaction is ducto the solubility mus Seite eeoasy ion. me oO ay (uy, : : wtom * n RCL ee RAE NaCl | RoBr GS? RH + NaBr (ula to (Dy > WT ‘The reaction proceeds by 5,2 mechanism andis possible Sol (A) Rcrmapiaeenacte So ae Dod. aes eee itan Sol, Sol. Sol. EXAMPLE, Which of the following compounds is most rapidly hydrolyzed by SN" mechanism, WGHtcl (d—cH,-cr=cH, (chy, €c1 wMeficier © SN‘ Reactions proceed through carbocation which (GH), CCl» (C.),C2ChRate-deternin tp) (oat sable carbocation So (C,H1).CCl is most apily hydrolyzed Opin (©) is coc, EXAMPLE Which of te allowing bromides te major produit cf thereaetion shown below, assuming that there are no carbocation rearrangement C,H, Br © EXAMPLE “Major product (P) in the Following reaction is CHy_D-<1 , (p) CH CH aw Yo @ Ya H H D D o Yor, o You a H @) Sol, Sol. CH,CH,COOAg + Br, Silver Propionate (No. of C= 3) Sol. EXAMPLE Pick out te comec equations = ()CHCH= CH, +HCI-> CH,CHCICH, (8) CH.CH= CH, + HBr—> CH.CH,CH,Br (©) CH,CH = CH, + HBr P20sée_, CH,CH,CH,Br (0) CH,CH= CH, + HI_P#88 , CH,CHICH, = CH-HCI—> CH,-CHCLCH, From Silver salt of carboxylic acid RCOOAS + X, SH, REX + AgXt + CO, (X,= C1, or Br,) “This reaction is called /funsdieker reaction. Mechanis The mechanism is uncertain but probably inthe frst step ‘acyl hypohlite is formed which then decomposes fire radicals, RCOOAg +X, —> RCOOX + AgX Initiation step RCOOX—> RCOO" + X* Propagation step: RCOO'— R* + CO, Rt + RCOOX—> REX + RCOO" “Then, the propagation stepsare repeated again. Chainean be terminated at any siage, when any (wo radicals will collide to fom a neutral molecule. In Hunsdieker reaction, the yield of Bris better than RCI because OBr bond is weeker than O-C] bond as well AgBr is less soluble than AgCI ‘The yield and ease of formation of R-X is DRX > PRX > FRX SOLVED EXAMPLE AMPLE Tn the Hunsdiecker reaction — (taba steer drone. Oh sites dane panei che th sien ee (Date of be dave ®) Tbe sae ie CH,CH,Br+C0,+Agbe ‘eth Bromide (he. ofc Nat ct At dane Phas ie cetoo Ais const example EW ena a aaa GONI=CHOH()NaE+ sctne (Nabe CHOH — (D)Nal¥CH.CoCH, © ) Jee CompenpiumCHBr+Nal “22 H+ Nabe Ethyl Bromide Ethyl fodide ‘This reaction is called "Finkelstein Reaction” exameLe AF C.HC1~ Agr GH Frac Theabore reaction is called (A)Hunsiedker (8)Svart (©)sirecker (Warts So. (B) CHLCI+ Agr —> CHE FAC This eaction scaled SWART" Reaction: Therefore option B is comect Preparation of Allylic or Benzylic Halides (i) Direct halogenation of any aromatic hydrocarbon preferably gives benzylic halide. This is because benzyl radical is resonance stabilized CHe-CHa X-CH-CHy Xd hy. ‘The reaction follows free radical mechanism, SOLVED EXAMPLE exameLe AEF ‘When Cl is passed through boiling toluene in presence of sunlight, benzotrichloride is obtained as the finel product. CHC CHCl, 62626 ‘This Resetion is chain Reaction. ‘There, fore this statement istrue. cel, Bencuitichloride (i) When alkenes are reacted with halogens at high Sol, temperature or in the presence of radiations or any reagent, which is able to provide halogen radicals in low concentrations, then ally! halides are produced. CH-CHCH, _*_, X-CH-CHCH High temperature, Wea =CH, (CH-CH=CH,*+Cl, 499 19 000 NBS in ee asehe cut -c1-cut, + By, | L* Br, ea, by (CH-CH=CH, cu-cu-cn, 24m , sot Cuemisrey. 5 A Hatdew Prepration of Polyhalides (ten OF et cit soc a diate ah a cucu, + x, ESET CH He x XxX (i) Addtionottulogen (Chor, waynes produces teal aha xx nicecu E> GH=cH 2 HOCH ce tte x x Mechanism of additionof halogen to alkenes and allynes hhas heen discussed in the lesson “alkemes” SOLVED EXAMPLE exampe AEF {A gem dichloride is Formed inthe reaction except (A) CH,CHO and PCI, (B)CH,COCH, and PCI, (©) CH, =CH, and C1, (D) CH, = CHCI and HCL © 1 aa Ethylene chloride ‘There fore option (C) is correct SOLVED EXAMPLE exams EF ‘Addition of BrCl, to propene in presence of peroxides gives 1,1, 1richloro-3-tromobutane 348 CH-CHOCH, + BrCCh——> CH -CH-CH_-CCl, 1 Br 1.1, l-trichlore-3-brome butane ‘Therefore statement is true EXAMPLE ATV The reaction of Vinyl chloride with hydragen iodide to give I-chlorc-I- iodocthane as a major product Product is formed A: tomarkovrikov’s RuleHates n cutcn-ci ts aie I roa 1-Chloro-2-iodo ethane But product is formed sccording to artimarkovaikovs rl cHtcrci-ly rat cl 2-Chloro-I-fodo ethane ‘Therefore statement is true Preparation of vinyl Halides. cHecH 2+ CH=CH ch=ctt SG? ‘ ‘The above reaction proceeds via electrophilic addition a8 follows co ap cHech ©" cH. Physical Properties The physical properties of alkyl halides are influenced by the polarity of C-X bond. The bond length of CX bond in alkyl halides follow the order Mel > MeBr > McCI> MeF. Vapour phase dipole moments in Me varies as MeCl> MeF > MeBr > Mel, This is because dipole moment depends on electronegatvity of halogen a8 well as on the bond length, The order of boiling points of alkyl halides is Mel > MeBr > MeC! > MeF, which is influenced by the decreasing van der Waal forces of attraction benween them. Among polyhalogen compounds, boiling point decreases as CCl, > CHCL, > CH,CI, > CHL This is ‘due to accumulation of CV’s on CH, increases 1 molecular mass and size, thus van der Waals forces incresses and boiling point also increases. ‘The densities of alkyl iodides and bromides is more than that of H,0 that the densities of alky| chlorides and {luorides in less than that of H,O. The order of densities ‘of alkyl halides and 1,0 is RI> RBe> 1,0 > RCI> RF and the densities of polychloro methane varies as CCI,>CHCI,>CH, > CH,CI. The alkyl halides are in general insoluble in water HHS CH=CH Gr a SOLVED EXAMPLE EXAMPLE EY "The caret uder af Uipols momen OTA RANI (RI>RBr= RCI RF (B)RE> RCI> RBr> RI (ORC RF ABER (D) None: © Sol. RCI> RF > RBr> RI Exception due to bond length Polarity oc EN difference pameLe Aly _ = Pick up the correct statement wbout alll halides (A) They show H-bonding (B) They are soluble in water (C) They are soluble in organie solvent (D) They do not contain any polar bond Sol (©) Fact Chemical Properties CCarbonhalagen bond in alt hides is por owing to thepartal postive charge on carbon and partial negative charge cn halogen, Due tothe positive charge on carton, fan muclcophile can stack the molecule and if itis « sirengcr nuckoptie than halide, itcan substitute halide ion So, nucleophile substitution reactions are the most common reactions of alkyl halides. Otier common Preparation of Organometallic Compounds RX RMsx ns Dy ener (Grignard reagent) Lix (Organo lithium ‘compound) Mechanism: RX + Li [REXP Li [RX > Re x Re Li RL ‘The extra electron in free radical anion occupies an antibonding molecular orbital tmust be noted thatthe reactivity oF alkyl halides fo form, ‘organometallic compounds inerezses from alkyl fluorides to alkyl iodies. Infact, alkyl fluorides do not respond to the reaction and alkyl chloride and aryl halides give considerable yield only if THE (tetrahydrofuran) is wed asa solvent, Further, more the stability of free radical, more will be reactivity of sky! halide to form ‘organometallic compound. Alkyl organometallic compounds ate good source of ccarbanions (as carbon is more electronegative than the meals) and are very useful in organic synthesis, Jee CompenniumSOLVED EXAMPLE exameLe AF ‘An alkylbromide (A) forms Grignatd’s reagent which ‘on treatment with water yields n-Hexane. (A) with sodium ‘ether forms 4, S-ethyl Wis- (A) CH (CH), Br (B) CH, (CH), CH(Br) CH, © CH. (CH), - CH(BA)CH, CH, (D) CH, (CH), CH(Br) CH=CH, Sok () CH,=(CH),- CH(BN) CH, CH, octane. EXAMPLE, ‘What are A&B inthe following reaction 1 vic wy S26 ©) Mabe CHONCH, Mec Mac! aycw.cno CHOHCH; © & Br ‘CHOHCH, (D)None of these So. (B) cect, bu ‘Thar fr option Bis some examete AF ‘What is product of the following reaction ? cl My Br B.0 A> Mec cl wml Ta @) Ment A og J J S Sok (C) CHEMisTRY (D) None of these / i Htdee rtho-dihalobenzene does not formed Grignard reagent, Therefore option (C) is coerect, Reduction of Alkyl Halides Rox Ricken RH ‘The reagents used forthe reduction of wlkyl halides t alkanes are Zn and CH,COOH, Zn and HCI, Zn and. NaOH, Zn ~ Cu couple and alcohol, aluminium amalgam and aleohel etc Wurtz Reaction 2R-X + Na —Bvater , RR ELIMINATION REACTIONS OF ALKYL HALIDE: E1 Elimination: Gis Gh Hic Sir ei eect. FB: CH; {Butyl bromide undergoes hydcolysis in wo steps, In the first rate-limiting step, the alkyl halide dissociates heterolytically. In the second step, the base forms an elimination product by removing proton froma carbon adjacent to the positively chargeé carbon, Increasing the concentration of base has no effect on the rate of the reaution cH cH, Step 1: chee, SS MS cH Ce + BF cH Hs oH cH. Step: CHrGo OS cet + HOt | Gngis: by, ‘When two elimination products can be formed, tie major product is generally the ene obtained by following, Saytel’ rules, ots CheCHe-C-Cl- HO —> CHs cH, CH, r (CH,CH=C_CH, + CH,CH,C=CH, + HO" + Cr (rar produc) (minor productHater ‘The energy profikediegram for this reaetion is ha : cnonele * bY cnondien ene | Ae ee CHCH=E-cH, + HE roaress of reacion > Rate of El reaction depends on the ease with which the leaving group leaves and the shility of the carbocation farmed. Thus, the relative reactivities of series of alk halides with thesame leaving group parallels he relative stabilities of ewbocations und the order is prevented ‘as 3° benzylic © 3° allylic > 2° benzylic ~ 2° allylic = 3 alkyl > I°benzylic © 1° allylic = 2°> 1° > vinyl Because El reaction invelves formation of carbocation as intermediate, so rearrangement of the carbon skeleton is also frequently observed, For example, oh: OCoren oe Hc cl Hs CO) Piven sere OY) Sonn c 2 eaboceion 2° earkocatn GHs Ot CH, cHorrcacn ceric, 8 crcrcronBroHcr m7 uemcroncHeHick, << oHcHcHBoncHce, In this example, the secondary carbocation undergoes a 1, 2-liydride sift to forma more stable secondary allylic carbocation E2 Reaction: Dehydrahalagenation is the elimination af « hydrogen ‘and a halogen irom an alkyl halide to form an alkene Dehydrohalogenation can take place by El and E2 mechanism, Reagent (9 Hot alcoholic solution of KOH or FtOEtOH, (ii) NaNH, (ii) LBuO-K* in -BuOHL bw -cwd- | i co aan Characteristics Of £2 Reactio 1. This isa single step, bimolecular resction 2. Ite second order renction 3. Kinetics > Rate x [R— X] [Base] Rate = k [R — X] [B] Rearrangment is rot possible 5. Forthe lower energy of astivation rani sate must be sable follows a soncerted mechanism 7. The orientation of proton & leaving group should be amiperiplanar 8. Here B -H is eliminated by base hence called B climinatio 9. Positional orientation of elimination -> Inmast El and E2 eliminations where there are two ar mare possible elimination products, the preduet with the most highly substituted double bond will predominate, This rule is called the saytzett or zaltsev nile. Reactivity towards E,-yR-1 > R-Br > R-CI> RF For example : Dehydrahlogenation of 2-bromo-2- rmeihylbutane can yield two preducts cH —— @ ak & Sy PLP cece ate) ga He sapzetforoduct CH en 8i8S ep —f rab cH, ©) 4 LE). chick, -c: Son, Hotman's product (teseaylas) Free eneroy \ cho! Progress of action Jee CompenpiumcH, «gh ee bx, -GH-EH— i, oe. KOH, Bch, Ch-CHE SCH, + CH, inaen (morestable akene) (less stable akene) CheGHorLor, +"CHLO" “EEA CHLCH=CHCH, + CH.=CHGRCH, L we es 2-bromodutane has two structurally different fB-earbons trom which proton can be removed, Thus, it Teads to the formation of 2 products (2—butene and T-butene). The antcoplaner transition state for the formation of two products is H-Son)" 1---6or i (ch.-GH-—=CHOH, lor GHoH.CH, a an hoon ~prome ‘The transition state leading to 2—butene is more stable than that leading to the formation of I—butene, a8 this transition state has more hyperconjugeble hydrogens Thus, 2-butene is a more stable product than I—butene ‘and is formed in greater quantity than |—batene. The ability of the product is governed by Saytzeff's rule (aecordingto which more substituted alkene isthe major Product) ° oot LS a ak. KOH i (cH, Chlorocycleoctane ent Formation of the hoffmann product Bulky bases can also accomplish dehydrohalogenations that do not follow the sayteetf rule, Due to steric hindrance, bulky base abstracts less hindered proton, ‘offen the one that leads fo formation of the Teast highly substituted product, called the Hoffmann product HCH, Lt cn,-b-b cw, —DoHCH, [| 2 CHCHOH” Hae H Ae got ae Ha CH, HE oo CHEMisTRY i Hatdow Hoch yl cic, Onn ea6 6h ssh KBr H tee deed Ke, cH, cH,-He. i Sere Sono 1 gam OH Be Bulky base: cH, (cy,cH ! I cH-c-8 (CH).CH=N: I \ on, 4 ouside Diisopropyamine (CRON ae y Triethylamine He cH, 2, e CH,CI> CH,Br> CH, Q) CHCl >CH,Br> CHL> CHF (3) CHl> CH,Br > CH,Cl> CHE (4) CHF > CH,Br> CH,CI> CH, Carbon-halogen bond is strongest among the following () CHCl (2) CH,Br 3) CHF Qn () CHL For a given alkyl group the densitics of the halides follow the order Q)RL=RBr= RCL (3) RBr< RI< RCI @)RI=RCI= Rar (@)RCL= RBr = RI Which of the following leads to the formation of an alkyl halide - () CHLOH 2) HOH Se, , (3) CHO _10+sc2ne 4504 (4) all Rad PB Ethyl bromide is industrially prepared from ()ethylaleohol + HBr (2) RBr < RCI > RE (2) RF > RCL> RBr> RI (3) RCL > RF = RBr = RI (4) None ity of alkyl halides is =~ Qs Arrange the following in decreasing order of stability Of their transition state during elimination by strong base CVouor 1 M1 heim y= > Q)1>ml>0 (@)1> > CuEemasrey. ul i Hatder en oll oY YY 1D] as the major product among the elimination prod- ucts is CH, od pono -oran &, owes cH, oo oS Propylidene chloride when hested with zine gives: (1) Ethene (2) Propene 3) 1-Butene (8) 3+Hexene Alkyl halide with alcoholic KOH gives ~ () Alcan (@) Acoholie walt G)Alkene (4) Alcohol In which of the following reactions major product is formed by Saytef?s rule — hy (y) Ce-cHiec a br 9) Cec 8 @ Cet a ou (0) UE -capre ena ca (a) Allthe aboveHates Qus Qu6 Qu CHCH CH Bre CH CH=CH, WeohoT Theabove reaction is an example of ... teacion, () substitution (2) elimination (3) addition (4) rearrangement ‘Consider the reaction given below. PhCH = CHBr 4» Which of the following will be formed as the major product ? ()PRCHCHO——(2)Ph—-C=CH @LO (4) PhCH = CHO, ‘The reagent(s) forthe following conversion, aoe H islare (1) Alcoholic KOH (2) Aleoholie KOH followed by NaNH, (3) Aqueous KOH followed by NaNH, (4) Z/CHOH Aliphatic Nucleophilic Substitution In nucleophile substitution, the atacking reagent (ousleophle) brings an elscuon pai tothe arate, which apes thispaio forma new bondand the avin troup goesaeay with an clectrn par When nucleophie isa solver, the reaton i aed sores BX Yo RY eX ica miceopile, which may he seul oe negatively charged while RX nay be neural rpostvelychuged Rett HO-—> ROHS F RA, NMe,—> RNMe, + R-WMe, + O# —> ROH + NM, FNMe, + *HS—> RSH, 4NMe, sehen an" ROH + NaX or KK + AGX Benet. |22™"_> R_O-R’ + Nak iste! 5. R_SH + KX or NaX |—BS™_s R_S_R’ + NaX RX ME _s R_NHR’ + HX [SNA > RNR + HX [Se RN's + HX jh CaN + RANE C 4 XT one-r > R-O=C-R' +" resto LX NF RLNO, + RLONO +X a In the reaction, CH,NH, + X + KOH -> CH,NC the ‘compound X is (CHC, @)cxcl, «cH, acc, “The less reactivity ofchlorine tom in CH, =CH =Cr is dueto (1) Inductive effect (@) Resonance sabilization G) Electromeric effect (4) Electronegativity ‘The reaction oftohuene with Cl inthe presenceof FeCl, gives X and reaction in presence of light gives Y. (1) X= benzyl chloride, Y= m-chlorotoluene (@)X ~ benzal chloride, 6) X= m-chlowtoluene, Y= p-chlorotoluene (4) X= o-and p-chiorotoluene, Y= tichloromerhyl benzene ~ecchloratoluene Deore embarking on the mechanism of nucleophilic sutstitution reactions in alkyl halides, we must know ccerain basic terms. Basicity And Nucleophilicity Nghe agin ciaaaamonin ee ee es Sac weenie ore oa cart coe are Se an cane eect pape ener ti Beuee a s —I | wee 2 a we aes ere cates B+ HAS =B-H+ Me han vekcacetuseies hace ere etch arr basicity is determined by the equilibrium constant, which moe GER maar vege ee Leas F-, CI, Brand F with their counter cation as Na’ and Se nsecnion cons BoC one a ecu nasi, CO oe Soa Jee Compenpiumpars can be separated. Onthe otherhand, nonpolar and Weakly polar solvents are unable to dissociate salts, so they exist as iompairs, The ion—pairing is strong when ins are small and kave high charge density. In novpolar and weakly polar aprotic solvents all the salt will exist ay fon~psits. The fou-pairing will be ‘srongest with the smallest anion (F-) and weakest with the Targestanion (IF), thus the reactivity of X" devreases with decreasing size. Thus, the nucleophilic order of XC in such solvents would be > Br> cho F In polar protic solvents, hydrogen bonding orion—tipole {teraction diminishes the reactivity of the anion, Suonger te interaction, lesseris the reactivity of anion, Fon will form strong H-bond with polar protic solvent while ‘weakest ion—dipole interaction will be with I"ion. Thus, the nucleophlisty order of X7 in polar protie solvent would be I> Br > Cr> F Polar aprotic solvents have the ability to solvate only ‘ations, thus anions are left free, The reactivity of anions isthen govenedby their negative charge density (ie. ther basic character). Thus, the order of nucleophilicty of X° in polar aprotic solvents would be Focreprer (On this basis, certain nucleophilicity orders are (In polar protic solvents, HS > HO" (Gi) In weakly potar apratic solvents, CSF > RBF > KF > NaF > LiF (ii) Bases are better nucleophiles than their conjugate acids. For example, OFF > H,0 and NH3> NH, (iv) In non-polar solvents, “CH, » “NH, >-OH > -F (¥) When nucleophilic and basic sites are same, nucleophilicity parallels basicity. For example. RO-> HO™> R= COO" (vi) When the stom bonded to nucleophilic site also has, an unshared pair of electrons, nucleophilicity of species increases, For example, HOO" > HOT and HaN-NH, > NH nd Pearson gave following order of for §,2 reactions in protic solvents. RS" > ArS > > CN7> OH" > N5 > Br > ArO™> Clr» pyridine > AeO- > HO. A Htden Several distinct mechanisms are possible for aliphatic nucleophilic substitution reactions. By far the most ‘common are Sand S,2 mechanisms S,’ REACTION $2 stands for substitution nucleophilic bimoleculas. In this mechanism, there is a backside sttack of the rnucloopile. The nucleophile approgshes the substrate from a position 180° away fromthe leaving group. The reaction is a one-step process with no intermediate, it involves a transition sate, The C-Y bond is formed as COX bond is broken. vedo mol Fe Kb + AR BOI The msg mosey ek C-X bn sop by thesmuanens foto ofC-Y bond. The op X mt eve a ¥ come in, bse oi an he Caton som haem hn 8 cto ni ote Sl tthe wan se, ond ing wd ond broking ate siltaeous Inthe trsion ste, he con hybrid with 2 atomic ial valle for overpping fit ees wih an ob ofte coming wee aera ‘overlaps with an orbital of the leaving group XO, The reaction is initiated by 2 Ju" beginning to overlap with thesmall lobe (tail) ofthe sp’ hybrid orbital bonding with, X. In onler to provide more bonding volume o give a stronger bond, thetail becomes the larger lobe (bead) and thehead becomes the tal, inverting the configuration of ‘cathon, The configuration of the original compound is ‘opposite than the compound abtained. Inversion in ‘configuration implies change in configuration from Rto S or $ to R and not from (+) to (~) oF (-) to (+). This, inversiva in configuration would be observed only when the leaving group and incoming nucleophile have same priority relative to other atoms or group of atoms Asi ur starts to hond o carbon, it les some ofits full ‘charge and in the transition state has ad charge, as docs X as it begins to leave as an anion. In S,2 mechanism, the frost side attack has never been observed. In hypothetical front side attack, both the nucleophile and nucleoluge (leaving group) would have to overlap with the same lobe of porbital whereas the backside attack involves the maximum amount of overlap throughout the course of reaction, During the transition state, the three non—reacting groups and the central ‘carbon atom are approximately co-planar. Cuemisrey. 13,Hatin odco-fofex|- ‘9's ina Sconiusion ae chert: R configuration (Nu and X are of same prety) Inthegiven representation it isclear thatthe carbon ators is linked tofive groups, so it ishighiy overcrowded, Due thigh overcrowding, it isensier tomake a decision thet bigger the groups attached to carbon, more unstable will be the transition state, Hence, steric factors play an important role in S,2 mechanism, Thus, the reactivity of alkyl halides towards §,2 reaction is as follows, R H 4 4 sig i ROG < REK < REX < HK R R 4 4 The rate lew far the $,2 reaction is Rate = k [R-X] [Nw] Rate of theS,2 reaction isdependenton the concentration ‘ef RX and Nu” both S,2 reactions are stereospecific because stereaisemerie reactants give stereochemically different products. They are also stereoselective hecause they form exclusively ot redominaatly only one ofa pessible pair of enantiomers ‘er one of the possible diastercoisomers Let ussee the effect of solvent polarity on therate of 2 reactions, For most ofthe S, reactions, the rate decreases with the increasing polarity of solvents so $,2 reactions ‘are more favoured in nor—polar solvents, We know that successful 8,2 displacements are ‘exothermic in natureand its energy profi cam be show “4 In general, ifwe change solvent that increases ANT would decrease the rate of S,2 reaction. AH" can be increased by decreasing H,,,orby increasing H,, orby doing both. Conversely, any change in solvent that deereases AH? will increase the S,2 rate and the decrease in AH" can be achieved hy increasing Hor hy deereasing H,, ot by doing both, Let us consider four charge—type of S,2 reactions and see the effect af change of solvent polarity on thers (@) Med OH —> MeOH +r (i) MeS*“Me +OH" —> Mc-OH + Me,S Gi Mese-Me +H, —> Nef, Mes (0) Me + NH Me Ba 2 * Tei ropecve vanstion tats ar shown ss ie (i) [Ho i) () | Increasing the polarity ofthe solvent stabilizes charged. ‘ground state species, thereby lowering H.,. and also stabilizes charged transition state that would lower H.. ‘The enthalpy of a fully charged ion is lowered more than ‘8 spocics with difased charge, In case of reactions (i), (ii) and (ii), the charge in the ‘transition state is more diffused than the charge on the reactant species. Thus, increasing the polarity af the solvent lowers H., more than H,,. Thus, increasing AH* and decreasing the rate. Hence, such reactions proceed ‘with faster rate in nonpolar solvents Butin reaction (iv), thereactants are uncharged while the transition state has diffused charge. Thus, increasing, solvent polarity lowers H,, butnotH, So, AH" decreases and the rate increases. Hence, such reactions proceed with «fester rate in polar solvents than in nonpolar solvents, Jee Compenoiumin general reactions with charged reactants the rate of S,2 reactions decreases wih inereasing polaity of solvent while for eastons with uncharged reactants, the §,2 rte increases with incressing polarity of solvent. Sy! Reaction SUI stnds for substiationnueleophic unimolecular. The ideal version of Sl consists of two steps. The fit step isthe slow ionization of the substrate and is rate limiting sep. The second ste isthe rapid reaction betwesn the carbocation and nucleopile RX ROS R+X” Step 1 (slow) R+Y—>RY Step 2 (fast) Solvent assists the ionization process, since the energy ‘of activation required for breaking ofthe hond is largely recovered fiom solvation of iens produced. In pure 5,1 reactions, solvent molecules assist the departure of leaving group from the front side. The carbocation generated by frst step has an sp* hybrifized carbon ie. the structure is flat (trigonal planar). Thus, nucleophile will be able to attack the carbocation from the frout side as well as from the rear side with equal ease, leeding to the formation of two isomers, ifthe chiral carbon is present in the substrate The basic difference in S,1 and S,2 mechanisms is in lhe timing of the steps. In the 8,1 mechanism, first X° leaves and then Y° attacks while in an $,2 process, the to things happen simultancously. The following order ‘of reactivity for S,1 is observed, RAL > R-Br>R-Cl > RF g t i 4 REX > REX > ROX > HEX R R 4 4 The rate law for the S,1 reaction is Rate = k [R-X] The rate ofS, reaction isindependent ofthe nucleophile used. Moreover, the carbocation formed are sp? hybridized and planar, so the attack oF nucleophile has almost equal chances of attack: from both the sides. So. ‘any optically active alkyl halide will give partial racemic mixture since before the formation of carbocation, the rmucleophile attacks from rear side Cuemisrey. 15 A Htden Now, let us observe the effect of solvent polarity on the rate of $1 reaction, Itis generally said that the rate of 1 reactions is favoured in polar solvents than in non— polar solvents, Successful S,1 reactions are exothermic in nature and their general energy profile can te shown Enthalpy > Progress ofreaction —> Let us consider the rate of solvolysis of -BuCt and, WMe,C-8me,, The solvolysis reaction of BuCl and uci Sin cd be rac () Mo,c-al "> Mee + cl? ‘Sabent (0) Fig Ho (Hast sen Me;C—OH g P g (ii) Me,c-SMe, —“°—> Mes¢ + MeS ow MeC-OH ‘The transition states forthe two reactions inthe slow sep ccan be shown as, &] an ([esé---Shan] In reaction (i), the ground state has no charge but transition state has diffused charge. Thus, an increase in o [west solvent polity decreases Hyg, which slo decreases AIP and thereby inerensing the rate of resction In action (i), the reactants cary full-fledged positive charge, while the transition state has diffused positive ‘charge. Thus, increase insolvent polariy lowers Hore than Hy, which increases AH? Hence, such reactions, proceed with faster raw in solvents with high polasityA Hates COMPARISION OF S,: AND S, REACTIONS (b) Resction rate & order (e) Steeoctemistry Sa Sz (a) Number of steps 2 steps 1 step ORL Re Re LriNe oRNUr A or (Ro NUH RN HY Rate = k [RL first order (6) Mobscusnty UUnmoocular (b) TS of chow se aa ‘ . R 5 HNus Inversion and retention (Partial racemization) Re L+:NuH oR: NUH eo Rate = ky [RL] [Nu]; second order Bimolecular FNitorGavos LE ith: NUP) SHIN .C.o (with: HN) Inversion of configuration (tackside aac (9) Reseting nudoophile (@) Stricture of R (h) Nature of Leaving group Nucloopilic olvent stable R ~ mayreact with added nucleeohile B25 > Me ‘Weakes! base is best leaving group, Le. F>Br>ch>F ‘Added nucleophile Me> > 2>3° Weakest base is best leaving group, le, F > Br > Ch > F (i) Nature of rudeophile ForHINu: (soWvent), rae « basicity of HNu: Inprote sovents, (i) Within @ pefodic table group, rate polarizablity of Nu (For same nucleophilic: site Fate a. basicity of Nu In polar aprote solvers, abastity of Nu ‘ate ( Sovent effect Rate a H-bonding ability and delectic constant Depends on charge type. Polar aprotic solvents leave most reactive Nu free. (1h) Determining factor ‘Stabilty of ‘Serie nnarance (Rearrangement ‘Observed Nat observed, excopt for alive (mn) Catalysis Lewis ard Bronsted acds: Ag’, AID, ZAC etc, No specific catalyst SOLVED EXAMPLE Steps and Il are - (A) bath $,1 (B)bothS,2 (OTS LIS, (D)IS,2 1151 EXAMPLE ZI) Sol (©) Inversion of configuration take place in SN? Reaction Ne ote pe St win 2 gy seasionN foo won tea E 1 aversion ofeontguration) Et = tt Therefore option C is comect ow|1 EXAMPLES ve For CH,Br+ OH ——> CHOH+ Br Me the rte of reaction is given by the expression- (A) rate = k [CH,Br] (B) rate = k [OH] b (©) rae ~k [CHB] [014 A (D) rate = k [CH,Br? [OH-? So.) 16 Jez ComPenpium:i Htdee Rate of reaction [r] = K [CH,Br] [OH] Sol. (B) Fact Therefore option (C) is corret exam. ZF wear ey (@) lw, () EH, ()_, The rae law forthe reaction, CH,CHO, entity, B & C- RCI+Na (g.) > ROH + NaCl given by, (A) Ethylalcaho, Ethyl chloride & Etsane rate =Ky [RCI]. The rate ofthe reasion will be (B) Ethane, Ethyihloride & CH,—CH,—OH (A) Doubled ondoublingthe concentration of sodium (©) Propane Propylehloride & hydroxide CH.-CH,—cH,-On (8) Hisived on reducing the concsntration of alkyl (D) All he above halide to halt Sot (B) (© Decreased on incteasing the temperate of the CH, 2b, c.H,Cl_8K0H, C.H0H reaction fal 1B] idl (D) Unaffected by increasing the temperature of the cl A renetion HHO Sol. (B) “There fore option (B) is core SN, EXAMPLE, Rate of re = K, RCI} Theoxtdiionof CCH by air &lightisprevenied by Rate of ex" doubled on doubling ean of halide Oat oo ee Si retin ivy ma Chee ree fore no of alk! group oa the carbon atom When the oxidation of CHCL, by sir & Light ItStowiy 5 hates rneraaee decomposes in to phosgene and hydrogen chloride. © Sennen shed to the halog Phoigene is exremely poisonous ga. ie CHCI, prevented the above reaction 1% C,H,0H is (D) None added. This retards the oxidation and converts the S°- — (B) phosgene formed into armlees carbonate Rate of Sy! reaction & Stability of carbocation COCI, +2C,H,OH—> (C.H,0), CO + 2HCL aa eed Eyl carbonate example Ze EXAMPLE, iy chloride + aq, KOH gives the product - Tsocyanide feaclion involves the intermediate (a) CHyCHAOH (B)CHs-CHy formation of- (©) Cilg-Cily (D)CHSCHOK (A):CCL, (BY'CH, —(C):CH> (D):CCl> Sok (A) Sol (A) CH, CHCl 25> CH-CH-OH cHel, 2, Bey Ch, + Cr Dickie Paco rhs cen, ap tay H H H Sol. R-N=CHCI _=HCl_, R- (Alkyl soeyanide) EXAMPLE ZY Finkelstein reaction is (A) 2CH3CHyCH+ Ag30 (dey) —> CH3CH,OCH CH3+ 2AgCI (B) CH CHB + + Nal CH3CHpI~NaBr (C)CH3CHyBr +Ag30 (moist) —> CHCH2OH + AgBr (D)CH3CHyCI + NaOcH;——> (CH3 CH2OCH3 + NaCl CHEMisTRY EXAMPLE ET Whenethyl bromide is weated with moist AgyO, main product is/are (A) Ethyl eer (B) Ethanol (©) Ethoxy ethane (D)All ofthe above () CH CHB > CH CH -0-CH CI —vencH-04 EXAMPLE Te eae Taga CU 2 Cives- (aynsncoon. ——@)LeH-COON ai (©)RNHZ+ HCOOH. (D)RCH.NH,* HCOOH wyHatin () RCH-N2c 10", RCHA-NH,+ HCOOH ‘Therefore option (D) is cone. EXAMPLE £5 ‘CHCI, + OH —> HOO" Intermediates of this reaction are~ (A): CCl @): CCl, (Cpboth (D) None © Sol. Sol, cre, 25 :Ga,—> 004 +r Dichlorobenzene ‘There fore option (C) is correct. Example EV Recemic mixiure is abtained due to halogenation of (A)mpentane (8) lsopentane (Opneopentane () Both A&B () Halogenstionofu-pentane and Isopentane ste produce chiral molecule asthe product. Molecule as the Product. Sol. H CH CH-CH CCH, Ay order 1 repentane Chiral molsule cu cH x | Le ch-iecHci, cH-tieci-cr, Ibopentane —- —®2_ Chiral molecule ‘There, fore option (D) is correct LIKMAD, CHT Gi sodectine,& So -b- ee Sol, KM0,, Oy sn — 6 a oeifeie (Seu tts Ot — a 18 Therefore option (B), (C), and (D)are correct EXAMPLE The products of reaction ofalegholisallver ethyl bromide are - (A) Ethyne (C)Nitroethane cD) CHB (B)Ethene (D)Ethyl nitrite Sol. Alootalic AgNO: (_H|-O-N-O + singe product (Ethyl nitrie) product (Nitro ethane) ‘Therelore option (C) and (D) are correct. Ambident Nucleophiles Some necleophils have lone par of electrons on more than oneatom andean attack through morethanone st. Such nucleophiles ae called ambident nucleophiles. In such cases, different products are posible dco tack through diffrent sites. Attack by a specific ste can be promoted under special conditions. Two well-known txamples are discussed in detail “Attack By CN- Nucleophile (°C = N:) RX OT RCN + RNC HX nitriles isonitrles In CN> carbon (negatively charged) will be a vot base ‘as compared to nitrogen. So, ifthe reaction proceeds via Sl mechanism, which preduces # fice carbocation (4 hard acid), then attack through nitrogen (hard base) will take place. But if the reaction proceeds via S,2 ‘mechanism (small positively charged carben is soft ws) then attack through carbon (soft base) will ake place. So, if we want to increase relative yield of niles, we ean uuse NaCN or KCN ete ina less polar solvent, which facilitates §,2 substitution. Similarly, if we want 10 increase the yield of isonitiles, we can use AgCN. Ag’ ‘oi favoursthe formation has very strong affinity for X" ‘of R’ and the reaction proceeds via S,1 mechanism, This ‘will result in attack by hard base giving R-NC. Further if we compare primary, secondary and tertiary allyl halides, formation of RNC should be favoured due to ‘move favourable $,1 substitution in tertiary alkyl halide But the exception is that tertiary alkyl halides undergo. climination and the yield decreases. This isbecause CN~ is 2 strong base, which can also cause elimination. reaction Jee CompenpiumAttack By NO, Nucleophile (-O-N= 0) nex 75 RONKO + RRO, E Tn NOG, oxygen (negatively charged) will bea had base «5 compared to nitrogen. So ifthe reaction proceeds via 1 mechanism, then attack through oxygen (hard base) will take place to produce alkane nitite. Butif the reaction takes place via §,2 mechanism then attack through niteogen (soft hase) takes place to give nitro alkane, |f we want to increase the yield of nitro slkane, the reaction should proceed via S,2 mechanism. ie. we ean use NaNO,, KNO, etc. Moreover, the yield will be best if we use primary alkyl nalide and less polar selvent. Formationof nitrite will dominate, i'we use tertiary alkyl halide, moce polar solvent and AgNO, because Ag” has ‘srong affinity for Xand can form s carbocation to force the reaction to proceed vie, | meckanisim. Primary alkyl halide with AgNO, chiefly gives nitro alkane but if secondary and trtiaty alkyl halides are used then AgNO, will yield nitrite as the major product. SOLVED EXAMPLE F Give the organic products ofthe following reactions. o: @ wears l_on acetone (6) I-PrBr + [SC =N2° (thiocyanate) EON > (©) BBr + [SC=N-T (thiocyanate) ME (@) CICH,CH,CHL + CN- acetone (One mole each) (© HINCH.CH,CHCHBr =! step A Hatdes Nucleophilic substitution in Allyl & Vinyl Halides Let us compare the S,1 and S,2 rates of allyl chloride and n-Pr chloride. Both allyl chloride (CH,=CHCH,C, ‘and n-Pr chloride are 1° RX, Towards $,2 rat, allyl chloride is more reactive than n-Pr chloride because the transition state of allyl chloride is stabilized by the overlay ‘of p-atomic orbital of the transition state with r—bond while such stabilization is not possible in propyl eine . (w- Fe PAG | [Pan “he oF 4 2 Towards S,1 rate also, ally chloride ismore reactive than, Pr chloride because the ally] carbocation is resonance stabilized while rpropyl carbocation is stabilized by Induction. chscihoni gy SE cndGida, > Bx-oteon OG Ae at tg The rate of $1 reaction forall chlorides faster than the, 2te while or propyl chor, 5,2 aes faster than 8, rate Now let us se the S,1 and S,2 reaction posbiity in vinyl halides in gener, vinyl hldesae ess reactive thn alk hails hetause C_Xbond in vinyl halide short and stronger than aly halides (hiss because of resonance in vityl halides, Sol The ncleopiles in (a,b) aad (6) ae abident since ' they each have morethanone reactive st. Ineach ese, g . the more nucleophilic atom reacts even through the other chcb}: > Gae-chek p. seen ber re a Thus, they are inert towards displacement reastions, 10 RN sO EEN BRO When thy show §,1 reaction, they wouldionize give \ sop vinyl eatons, which are very unstable beats the eabon onl bearing posiive charge i p hybridized. Mote the 5 character in carbocation, th less sabe it would be ¥ During 8,2 attack, backside atack of nucleophile is Aiticul becuse # would approach i the pla of the When the sucleopilc and leaving groups ae pat’ molecule wher it would be repelled by the telecon ofthesamemolecule.aninramoleculr displacement _—_dersityandifthere is mono dilkyaion at Cit weuld cxcursifwiuee.afive-orasirimemberdringcan———_equsesteic hindrance els. Ths, vinyl hes have ile form, for mo tendency to undergo S,1 and 8,2 reactions Cuenustay 1»ates SOLVED EXAMPLE Example EF Sol, Chlorobenzene and benzyl chloride can be distinguished by boiling with aqueous KOH followed by acidification with dil. HNO3 and subsequent treatment with AgNO, solution. cl + KOH — No reaction cHe CHCl > +e EE age “The statement is te EXAMPLE TY Sol. Sol. Sol, m-Chlorobromotenzene is an isomer of m-bromochlorobenzene ‘These names are of same compound So They are net isomer ‘Statement is wrong, EXAMPLE Todide ion isa better nucleophile than bromide ion (aq. solutions). [Nucleophilicity increase on going down is the group of the periodic table I> Bre>CP> ‘There, fore statement is true EXAMPLE, "An organic compound boiled with HNO, ,cooled and then treated with AgNO, a white pptis obtained, the ‘compound may be De) (B) © oO pac (D) CH=CH ~CH CH, cI BCD) -cl 20 9 Cpa CH, -CH-CH-CH,-cl EXAMPLE Ly ‘Which of the following statements are correct? (A) The C-Cl bond in chlorobenzene is shorter than inchleromethane (B) Tae C-Clbond in chlorobenzene has some double bond character (©) It is difficult to replace chlorine from chlorobenzene than from benzyl chloride (D) Chlorobenzene on further chlorination gives m— dichlorobenzene Sol (ABC) ‘The C-CI bond in chlorobenzene has some double bond character due to resonance double bond character ‘Therefore it is C-Cl bond is shorter than Chloromethane, and difficult to replace chlorine trom chlorobenzene than trom benzyl ehlorde “Therefore option (A), (B) and (C) ate correct EXAMPLE, Aryl halides are less reactive towards nucleophilic substitution reactions as compared to alkyl halides due to- (A) The formation of less stable carbonium ion (B) Resonance stabilization (©) Longer earbon-halogen bond (D) sp Hybridized carbon attached to halogen Sol (B.D) In an Arylhalides halogen stom directly attached to sp' hybridized carbon atom and C-X bond in Aryl halides have partial double bond character due to resonance. Thus, the halogen atom becomes firmly bonded to the aromatic ring and cannot for replaced exsily Jee CompenpiumThere, fore option, (B) and (D) is correct, Nucleophilic substitution in neopentyl halides Although aeopentyl halide is a 1° halide, it does net undergo nucleophilic substitution by $,2 mechanisra because its highly sterically crowded toe able to form 4 transition state. So, neopentyl halide has a greater tendency to undergo nucleophilic substitution by S.I mechanism, Although the initially formed ‘cathocation is aprimary carbocation, it rearranges give ‘@ more steble carbocation, which is then attacked by nucleophile to give corresponding produ. For example, Hs Gx CH G-CH-Br P8629 CHC BH, + Br ch, cH, (1 carbocation) Hs Be CH-G-CH-CH, <4 cH, E-CH.-CHs OH CHs (2-methyl butan-2-0)) 3" carbocation) Neighbouring Group Participation: There are some examples of retention of configuration in nucleophilic displacement reactions. The common feature for such nucleophilic displacernents is an atom cr greup-close tothe carton undergoing attack—which has atleast one electeon pair available on it, This neighbouring group can use its eletron pair to interact with the “backside’ of the earbon atom undergoing substitution, thus preventing attack by the external tnicleophilic reagent, Atack ean thus take place only “romihe font side’ lending toretntion of configuration Base bydrelysisofthe 1, 2-ehlorohydrinis fount vic 1.2- ae aes % 3 oH by the hydrolysis of theanalogous compound (Il), which Las] yields two ulcohols (the unexpected one in grewter yield) 0 w ny indicating the participation of the unsymmetrical intermediate (I) Cuemisrey aHates Me ye to ng 78 FM cps rot ec tig Goed-ch Za OH he ‘eo ‘ Som Se, te “Es-¢h (Unoeted modus) N : can also act as a neighbouring group participant in similar circumstances, eg. the hydrolysis of Me,NCH,CH,Cl, but the rate is markedly slower under comparable conditions than that for (I) SOLVED EXAMPLE Examee ZEV ‘Alkyl halides are insoluble in water because they do no form, Sok H-bond Example Z7¥ With aqueous KOH, alky! halides undergo... reaction but with hot alcoholic KOH, they with water undergo. reaction. Sol, __examrte ZF With potassium cyanide, alkyt halides give... while with silver eyanide ...... are the major products. Sol Alkyl cyanide, alky!isocyanide Example ZY Formaticn of phenel from chlorobenzene isan example of Substitution, elimination ‘aromatic substitution and occurs through intermediate Sol Nucloophilic, benzyne Intermolecular Versus Intramolecular Displacement Reaction A molecule with two functional grosps is called @ bifunetional molecule. Ifthe wo fanetional groups are able east with each omer, ovo kinds of reactions ean take place. In case of a molecule having both, 4 nucleophile an a leaving group, the nucleophile of one tmolecule can diaplace the leaving group of a second mnolecule ofthe compourd, Sich reactions, which take place between two different molecules, are called intermaecular reactions aes BICH,ICH).CHC- +q8¢-CHACH).CH BrCH,(CHa,CH.OCH-(CHz),CH:0- + Br 22 Alternatively, the nucleophile of molecule candisplace the leaving group of same molecule, leading to the formation of «ring compound. So, such reactions, which takes place within a single molecule are called one Inch cases, when the nucleophile and the leaving group, are part of the same molecule, inter as well as Intramolecular reactions, both can takes place. Which, reaction is more likely to cecur, can be determined by ‘theconcentration ofthe bifunctional molecule and by the size of the ring that will be formed by intramolecular reactions, Intramolecular reactions has an advantage in that the reacting groups are tethered close iogether (entropy facior) and thus donot have to wander through the solvent 1 find a group with which it react. As a result, a low concentration of reactant favours an intramolecular reaction because the two functional groups have a better chance of finding one another if they are in the same molecule, When an intramolecular reaction would form, a five orsix memberedring, it would be highly favoured ‘over the intermolecular reaction because ofthe stability ‘of $ and membered rings as they are less strained. Three ‘and four membered rings are highly strained, thus they are less stable than 5 and 6 membered rings, The entropy factor in 3 membered cing is so highly favoured that 3 membered rings are also formed with case inspite ofthe faci thatthey are too strained, The high activation energy for the formation of 4 membeted rings cancels the advantage gained by tethering, thus they are not easily formed ‘The likelihood thatthe reacting groupscan find each other decreases sharply forthe formation of 7 membered and larger rings, so the intramolecular reaction becomes less favoured as the ring size increases beyond 6. Over ° Aninexmoncab GHACH,,CH.O- ATHEAMORELI, 4 an fe ct Sh —> ee Jee Compennium