Chuong 2: Phan ting ciia cac hp chat hitu co 1. Pham mg hina cer: Ks rn i 2. Gigi thigu vé phan img thé than hach 3. Gidi thigu vé phan img tach logi 4, Phan img eta alcohol 5. 6. Phan img thé than din tr hong phuromg 7. Phan i i thigu vé phan img céng: phan img cia alkene alkane 8, Polymer va phan img tring hgp 9. Téng hop hop chat hitu co‘Chuong 2: Phan img cia cdc hgp chit hitu co 1. Phan ding hitu co: loi mé du Cac hop chat hiru co trai qua nhigu phan ting khéc nhau. Trong phan img thé (substitution reaction), mt nguyén tit, mOt ion hay mOt nhom trong phan tir duge thay thé bing nhém khac. Day 1a mot s6 vi du vé phan ting thé: CH,Cl + NaOH “+ CH,OH + NaCl (cy,c0 (CHy)sCBr + HO (CH,);COH + HBr CoHy + HNO; B24. CHO) + H:0 sit dung durge ghi trén mai tén. Trong phin img dau ti ‘Trong méi phuong trinh, dung mi nguyén ti Cl treng phan tir CHCl duge thay thé boi nhém -OH. ‘Trong phan img thir hai, nguyén tir Br trong phan te (CH3)sCBr duge thay thé boi nhom -OH, va o phan img thir ba, nguyén ttr H trong phin ti CoHy duge thay thé boi nhém -NO;. Me div m&i phin ting ddu Ia phan dng thé nhung ching xy ra theo cde co ché khac nhau ‘Trong phan ng cng (addition reaction), mt phan tir cOng vao néi d6i hay néi ba cia mot phan tir khéc. Sau day li hai vi du: Trong phan img tich logi (climination reaction), cée nguyén tir hoe nhém ni véi nguyén tir bén canh bj tack logi dudi dang mt phan tir nh6. Théng thudng, phan ting tach loai dn dén thir ty cia néi gita hai nguyen ur ké c@n tang nhu eae phan img dudi day: 1,805 Ee oS cH,+ 1,0 2HBr Phan img dau tién minh hoa ring alkene e6 thé duge digu ché tir alcohol (ROL). Phan img. thir hai, trong d6 hai phan tir HBr bj logi va tgo ra alkyne, la mét vi dy cia phan ting tach logi hai tin, Khi mét phan tir hétu co thye hién phan tig ehuyén vj (rearrangement reaction) (hay phan img déng phan héa isomerization reaction), khung suén carbon ciia phan tir duge slip xép lai.‘Chuong 2: Phan img cia cdc hgp chit hitu co cutictes, A> cucrcrcier Vi dy 2.1: Xae djnh logi phan dng hu cv Cae phan img sau la phan img thé, phan ding eng, phan img tach ‘vj. (Trong mdi phuong trinh sau, H* va Pb la xite tac). @ ° ° (CljCHCONa + CHyBr. ——+ (CH);CHCOCH, + NaBr Cat a (© 2CHOH > CH,OCH, + H:0 (d) cyclohexanol + cyclohexene + water (6) 2-butyne +2 Hy > butane © (a) Bai vi nguyén tit Br trong CH3Br duge thay thé boi nhém (CHs),CHCOO nén phan img a 1a phan ing thé, (b) Phan img cé sy thay ddi khung suit cdu tric (cdu tao) nén phan img b la phan tng chuyén vj. (c) Khi viét phuong trinh phan ing ra CH3OH + CH3OH —> CH3OCH3 + H20, ching ta thdy nhom -OH & mét phan tir duge thay thé béi nhom CH3O- . Phan img c li phan img thé. on ‘on aie O- no ; @ Phan tg tach logi OH va H tir hai nguyén tir carbon ké cn & cyclohexanol. Vi phan ting d la phan (ng tach Losi (e) Trong phan ting nay, alkyne chuyén héa thanh alkane, Nguyén tir H dure e6ng vio ndi tba nén phan tng e la phan img cng. cue ‘CH,+ 2H, ——* CH,CH,CH,CH, ‘Vi dy A: Cae phan img sau la phan tng thé, phan img cOng, phan img tich logi hay phan img‘Chuong 2: Phan img cia cdc hgp chit hitu co ‘chuyén vj ay Feb, + By Br + HBr es aene (b) on a ae tee yo Vi dy B: Phin logi cae phan dng sau i phan dng thé, phan dng cong, phan dng tach ogi hay phan img chuyén vi. (@) cricu,c,cri.br + (cH),0-K" —» cuycu.ci (b) - CH.CL+ NICH.CH,), ——e cn (©) CH,CH;C=C'Na* + CHyCH;Br —+ CH,CH.C=CCH,CH, + NaBr H+ KBr + (CH,),OW “c yy + CT 2. Gidi thigu vé phan tng thé than hgch ‘Trong phin nay, ching ta s® xem xét ede de tramg quan trong cia phan Ging thé lién quan dn cdc hop chat trong dé cée nhém chire duge néi véi carbon lai héa sp’. Ching ta sé tap trung chit yéu ‘vao phan img thé haloalkane. Trong mét haloalkane, nguyén tir carbon néi véi halogen lai héa sp’. Vai nhiing thay déi thich hyp, ede khai nigm hge trong phan nay 6 thé duge sir dyng dé hiéu phan img iné cna cac hgp chat knac. Vid sirthay thé ciia nguyén tir CL trong CH3CI bai nhém OH tao ra methanol CHCl+OH > CHOH+Cr 1) Lo@i plain ding nay la phan dng thé than hgeh (nucleophilic substitution reaction), boi vi ion hydroxide la ehat than hach (nucleophile) - chat tim kiém cac tim c6 mat d6 dign tir thap trong phan tit. Chit thin hgch gidu dign tir va m6 cho d CHCl durge xern nhur thi C duge goi la thin dign tit, Chat than dign tir (clectrophile) la chat bj tin e6ng boi chat than hach u dO: digu ti, Cle tir cho phan tir khdc. Nguyén tir C trong, dign tir vi nguyén tir Cl kéo mat d6 dign tir ra xa nguyén tit C; nguyén tir u digu td chia nguyen ti dhiéu digu ed. Troy phan dug wen, hydroxide tin céng vao nguyén tir C thiéu dign tt, thay thé ion chloride, ion CI’ duge goi la nh6m xuit (leaving group). ‘Chat than hach, thuéng duge viét tit la Nu, c6 thé mang dign tich am hay trung hda dign, nhung méi chat than hach phai chira it nhat m6t ddi dign tir khong ding chung. Chat than hach li base Lewis. Phan tmg thé thin hach cia haloalkane duge mé ta theo mét trong hai phwong trinh téng quat sau:‘Chuong 2: Phan img cia cdc hgp chit hitu co Nib + (27.2a) Nucleophile Electrophile (substrate) Nas + —| (27.20) Nucleophile Eleetrophile (substrate) ‘Trong phan img thé than hgch, ndi (1 u xanh) gidta carbon va nhém xuat bj bé gay va ndi méi (mau d6) duge tao thanh bing céch sir dung ddi dign tir ddc than cia chat than hach. C§p electron tir néi bi bé gay tre thanh déi dign tir 06 lap & nhém xuét. Sy can bing wu dai sy tao thanh san phim thé néu nhom xwat la base yéu hon chat than hach. Phan tmg thé cua haloalkane xay ra qua mot trong hai co ché. Trude khi kiém tra cdc co ché, ching ta cing xem xét mt sb phan img thé than Bach oy thé sau dy: Nat [CHC ae - + CHCH, Boa ‘Trong phin img nay, ion CHsC=C’ la chét thin hach va CHsCH,Br la chit thin dign ti. Carbon a thiéu dign tir (6+), la nguyén tir ciia chét than dign tir bi tin cdng boi chat than hach. Boi vi ca hai chat thin hach va nhém xuat déu la base Lewis, nén ching ta c6 thé ding khai m acid= base dé thiét lap phan img trén. lon CHsC: ich am 6 trén C, mt nguyén tr rét nho Khi so sinh véi Br, vi dy CHsC=C’ Ia base manh hon Br’. Bai vi phan img tgo ra base yéu hon nén phan ling xay ra nh da vi Nguoe lai véi vi du trén, phan img thé sau khdng xay ra vi ca hai phan img déu tao thanh base ‘manh hon nucleophile: HO> + H;C—H = HjC—OH +H (H7 isa stronger base than OH”) Br + CH;CH,—OH == CHC Br + OH” (OHT isa stronger base than Br) Co ché phan ting thé than hach Sy1 va Sy2 Nghién ctu héa hoe, bat dau tir nhiing nim 1890, da chi ra ring phan img thé than hach c6 lign quan dén hei loai eo ché, Phan tng gita chloromethane va ion hydroxide (2.2), ¢6 van te phan ting ti Ig véi ndrg dé chit than hgch va than dién tir: =KOH)[CH3Cl] vain toc‘Chuong 2: Phan img cia cdc hgp chit hitu co Co ché eiia phan ing nay lién quan dén bude xée dinh van tc ludng phan tir ma 6 6 nhom than hach tién gan carbon than dign tir va dng thoi nhém xuat ra di. Su tién vao va ra di cita céc nhém xiy ra cing mot hie duge goi la. concerted step, nh hinh ve sau: nnhém hydroxy! trong truimg hgp nay) d& carbon trong néi phan cue carbon-chloro), Dy la co ché Sy2, v6i S 1a thay thé (substitution), N Ta than hach (nucleophilic) va 2 la luong. phan ci nly van te pl ing 18 2). Sud ocular (96 pln can gia vau gi dog quySt phan tmg Sy2 duge trinh bay trong, OFF va chloromethane. ton hydroxide tén edng vio phia d6i dign nguyen Cl, va ndi C-CI bit dia h 2.1, trong dé trang thai chuyén tiép duge tgo thanh béi ion ditt, dng thoi réi C-O bat dau hinh thanh, tao re trang thai chuyén tiép (transition state) nhur hinh -vé. Trong co ché $2, chat than hgch cho chat than dign tir di dién tir tao thanh ndi c6ng héa tr), WW o- |o~ fe oon Transition HOH Reaction progress Hinh 2.1: Sod} phin img Sx2 dign cdc néi dang tao thanh va dang dirt gay. Dudng nét dirt Cé bing chimg nao tng hd co ché va trang thai chuyén tiép mae din nay khOng? Bau tién, cng thie van the goi ¥ day la phan tig lung phiin ti; ther hai 18 nam 1893, Paul Walden xée nhgn ip nhur hinh 2.2. Walden phat halogen la tha tinh thi edu hinh tai cée carbon thi tinh bj dao ngugc, nghfa la edu trie phan we duge sy tao thanh trang thai chuyén ign ra ring néu nguyén tir C néi voi dio nguege va mBt d6i phan c6 wu hinh ngurge Iai due tao thanh. Vi vay, khi (S)-2-iodobutane thre hign phan img shé than hach béi nhém hydroxide, hyp chit (R)-2-butanol durge tgo thanh (Hinh 6‘Chuong 2: Phan img cia cdc hgp chit hitu co 2.2). Sw nghich chuyén edu hinh nay chinh la sy ade nhgn co ché ning phan tir da duge dé nghj va trang thai chuyén tigp nam lign két. cu.cH, guys 3- o Ho” | acLi'— |it0 1 | 9 HOCom yy + cH CH, Reactants ‘Transition state Products Hinh 2.2: Sy nghich chuyén cau hinh trong co ché phan tmg Sx2 it chit thin hgch? ‘Chuang ta thdy ring mot phan tir hoge mot jon c6 doi dign tw dde than c6 thé hoat dong nhur ‘Sy khic bit gia mot base mét chat cho didn tir trong phan img vai mét proton hofe carbon thin dign tir. Trong ef hai terimg, hgp, mét néi msi duge hinh thanh. Khi néi véi proton, chit cho ddi dign tir phan img nhur la mét base. Khi néi véi carbon, 46i dign tir phan img nhu 1 mdt chat than hach. Cac nha héa hoe sir dyng thuat ngtr tinh base (basicity) va tinh than hach (nucleophilicity) khi dé cép dén xu huong ciia chat cho d6i electron phan ing nhur 1a mt base hay chit than hach trong mt phan tng. Tinh base la su do ludng xu huing cia chit cho doi dign tt phan Ging véi proton. Tinh than hgch 1a syr do luong ‘mt chat than hach phan img véi carbon than dign tir nhanh nhur thé nao, Chuing ta sir dung hing s6 cin bing (Ks) khi so sinh tinh base eta ede phan ti hay ion, va do dé tinh base li mét de tinh efin bing nhiét déng hoc (equilibrium thermodynamic property). Khi so sénh tinh thin hach cia cée phan tir hay ion, ching ta so sénh te d phan img cua ching véi carbon than dign tit, va vi vay tinh than hach 1a die tinh dng hoc (kinetic property). Mot phan tir hay ion voi d6i dign tir dée than ¢6 thé phan tg nw Ia base hoe chat than hach. Vi dy ion methoxide CH;0" vita la base manh vira la chat than hach tét. ea 5 —— cH,o—cn,cn, + Nuvleophile Fleetrophile ° ogo, | cng—n+ E+ — cH — , cn, Bue Acid Vi vay, didu quan trong 1a phai hiéu cdc yéu t6 anh hudng dén tinh base cling nhu cae yéu t6 nh hung dén tinh than hach.‘Chuong 2: Phan img cia cdc hgp chit hitu co ‘Vi dy 2.2: Xae djnh chat than hach, than tir, nhom xuiit, acid va base Phan hiét duge chit cho déi dign tir phan dng nhur 1 mOt base hay la mdt chit than hach rit quan trong. Sau day 14 mét sé phan img co ban. Trong mdi trudng hyp, xdc dinh chdt cho doi ign tir hogt dong nhu 1a base Bronsted-Lowry hay chét than hach. Sau dé, xéc dinh acid, chét than dign tir, nhom xuat thich hgp. Cudi cing, str dung mai tén dé chi sy di chuyén ctia dign ti. ® ° ° I CHS + CH,CH,O—s—cn, —— cH,scH,cH, + 0—s—cH, Et nyt oy neg \, © ; cua —a+ fk W o © (a) Trong phurong trinh dud dy, tée chit va sén phim durgetrinh bly véi ttc da ‘tir d6c than. Ching ta thdy ring mét néi méi duye hinh thanh gidta sulfur va carbon, va ndi gidra carbon va oxygen bj bé gay. CHS" la chat than hach, CHsCH20SO3CHs la chat thin dign ti (hay chat nén substrate), va OSO>CH; la nhém xuét. Mai tén dé chi su di chuyén cia dién tir 0: Nucleophile Etectropile Leaving group (b) Trong phan img nay, NH2” phan img tao NH. Boi vi cOng thie héa hge cua nhing chat nay khée nhau béi mét proton duy nbit, ching ta biét sng NII, vA NIT IA mét efip acid-base liga hgp. NH. li Beansted-Lowry va (CH3);CHCHB1CH li acid i. Ye Ee cH, ae ‘ Fr i a ee nc SD Va Gien a @ nc Nw ft Base Acid‘Chuong 2: Phan img cia cdc hgp chit hitu co (© Chiing ta thay tir phwong trinh dudi day, mot lign KEL m6i earbon-oxygen duge wo thanh va mét ndi carbon-chloro bj bé giy. Phin tir HCOOH la chat thin hach va CHsCHCI la chat than dign tir, va CI'la nhom xuat. Electophile Nucloophile Leaving soup Vi dy A: Trong mdi phin img sau diy, xéc dinh chat cho d6i dign tir hoat dng nhur Ta base Bronsted-Lowry hay cht thin hgch, Xée djnh chit nao 1a acid, chat thin dign tir, nhém xudt va sir dung mii téa dé chi sw di chuyén cia cde din tr. (a) CHsI + NaOH — CHsOH + Nal (b) NoOH + CHsCH2CH2CO.H_ » CH\CH;CH;CO;Na + H,0 Vi dy B: Trong méi phan ting sau day, xc dinh chit cho doi dign tir hoat ding nhu la base Bronsted-Lowry hay chat thn hach. Xac dinh chat nao la acid, chat than dign tir, nhom xuat va sir dung mdi tén dé chi syr di chuyén cita cée dign ti. (a) NH:Na + CH3CH:OH — CH3CH2Na +NH3 (b) (CHs)xCHCH:CH,Br + CHsSNa — (CH:):CHCH:CH:SCHs + NaBr Co ché phan ing thé than hgch tgi haloalkane khde ¢6 vin te phan tg ti 1g véi chi duy nhat néng 49 haloalkane. Vi dy, phan ting gitta 2-bromo-2-methylpropane trong dé HO 1 chat than hack: (CHy)sCBr+ H20 > (CH3)COH + HBr 6 cng thite van téc la vain te = k{(CH3)sCBr] Céng thie van téc nay goi y giai doan quyét dinh van phan tmg la don phan tir (unimolecular). Co ché phan tmg duge trinh bay trong hinh 2.3. Giai doan dau tién la giai doan chgm don phan «, ma 0 d6 haloalkane ion hoa wo tanh ion bromide va carbocation, Carbocation 6 dang phiing va carbon mang dign tich duong lai hoa sp’. Trong giai doan hai, carbocation ngay |p tite phan tg véi chat than hach, phan tt HO trong truing hgp nay, tao ra avid lin hgp iia alcohol (alcohol bj proton héa). Trong lugng thira nude, alcohol bi proton héa ngay lap tire phan ly tao thanh alcohel trung hoa dign va ion hydronium H30".‘Chuong 2: Phan img cia cdc hgp chit hitu co Step 1: Formation of a carbocation (slow) He cH, Carbocation Step 2: Nucleophilic tack of earbucation (Last) HO CH, oH Carbocation —__Nucleophile (clectrophile) Step 3 Loss of proton (fast) HC H HC enti —OH + H,0° inh 2.3: Co ehé pha Giai doan dau tién tgo thinh carbocation, Day 14 giai doan chém, quyét dinh van téc phan img. Trong giai doan hai, chit cho déi dign tir (chat than hach) tin céng carbon than dign tir ctia carbocation, tao thanh néi c img Syl Co ché nay 1a Syl, voi S 1a thay thé (substitution), N 14 than hach (nucleophilic) va 1 1a don phan tir (unimolecular) (sé phan tir tham gia vio giai dogn quyét dinh van téc phan img la 1). Sod phan img Sw1 duge trinh bay trong hinh 2.4, hinh gom ba trang thai chuyén tiép va hai trung gian. 10‘Chuong 2: Phan img cia cdc hgp chit hitu co On, HC .C—OH + H,0* tion progress Hinh 2.4: So dé phan tg gitta butyl bromide va nuée Carbocation durge tgo thanh trong giai dogn quyét dinh van téc phan img e6 dang phiing. Neguyén te C trung tém trong carbocation trung gian bj lai héa. Van dao p edn lai durge str dung dé tao lin két méi. Sau d6, nguyén tir C trung tim ciia ion 2,2- dimethylethyloxonium (trung gian thit hai) lai héa. Ngoai cong thire van téc, c6 bling ching nao chimg t6 su tn tai ciia carbocation phing? Lin nifa, ching ta sit dung mét haloalkane thi tinh va nghién citu tinh thi tinh cia sin phim. Khi mét trong eae ddng phan eas 3-bromo-3-methylhexune phan dng voi nude, san phém ta Ow hyp dea loan quyét dinh trign cia 3-methyl-3-hexanol. Trung gian carhocation duge tao thanh trong gi van tée phan img e6 edu trie phing. Phan tir nude (chat than hach) c6 thé tao m6t ndi méi trén ca hai mat cua carbocation trung gian. Diéu nay din dén két qua hn hgp sin phim cde d6i phan (Hinh 2.5). Sy tao thnh hén hop tiéu trién xac nhiin cho giai doan quyét dinh van t6c phan img don phin tir trong co ché Sy. ou fv HOPS cHcHc, Hed Ho LO, CHC CHCHCH, ——_-R3-methyl--evanol no ane cHcH, Ye“ Ki Na Planar achiral $-3-me Anexanol Hinh 2.5: Sir tgo thanh han hgp tiéu trién trong phan img Sy 1 uw‘Chuong 2: Phan img cia cdc hgp chit hitu co Khi nao la.co ché Sy1_ va khi nao 1a co ché $y2? Dé tra li edu hoi nay, ching ta edn thao lug ngn gon mot s§ nghién ciru dong hoc thuc hign béi Christopher Ingold va Edward Hughes vao nim 1937. Bo tée d6 phan ting dudi nhimg digu kign the nghigm khae nhau e6 thé cung edp edi hin sau vé co ché phan img. Vi dy, xem xét t6c dé cia cde phan img bac hai sau day gita bromoalkane va cht thin hach CI’: S12 Rr + cl = RCI + Br ‘Theo quan diém nhigt dong lyre hoe, sy thé Br° béi Cl duge wu dai béi vi Br la base yéu hon CT. Van téc phan img phy thude ding ké vao dé phan nhénh ca carbon a. cH; (CHyBr > CHCHsBr > CHCH,CHyBr > CHSCHBr > CHCBr du, day, Relative rte 1200 40 16 1” Too slow to measure (for $y2) ‘Trong co ché Sx2, chit than hach tdn céng tim than dign tir & phia ddi dién voi nhom xudt, thuong goi la tn cong phia sau (backside attack). Bi vi chat than hach tin edng tir phia sau eva carbon a, ning nhom thé cng kénb di vOi carbon a s€ gay Kho khiin eho chit thin hgeh ti phia sau nhiéu hon. Sy can tri chat thn hgch tuong tic vii carbon thin dign tr a mot vi dy cia chuéng ngai lap thé (steric hindrance). Sy tén céng phia sau cia bromomethane la nhanh nhat vi cb chung ngai lp thé nhd nhét (Hinh 2.6). 2%? B Bromomethane Bromoethane _1-Methylbromoethane _ 1,1-Dimethylbromoathane 2.6; M6 hiinh space-filling cua bromomethane, bromoethane, I-bromoethane, va 1,1= dimethylbromoethane ‘Cée mo hinh durge nhin tir hung tn c6ng thuan Ii cua chat than hgch vao earbon «tr phia sau. Khi s6 nhém methyl néi véi carbon « ting thi duvmg vaio dign tich dong mot phin trén carbon a gidm. ‘Tuy nhién phia sau cia I,1-dimethylbromocthane lé gan nhur hoan toan bi khéa khdi sur tin cng cia chat thin hach va vi vay chét nay khdng thue hién phan ting Sx2,thay vao d6 la phan tng thé than hach Sw 2‘Chuong 2: Phan img cia cdc hgp chit hitu co Sy thay thé nhém alkyl anh huéng gi dén van tée phan mg Sy? Khi khdo sit mot logt cde bromoalkane phin img vai nude, thir tu dé phan tng duoc quan sat nhw sau: R—Br + HO —> R—OH + HBr Syl reactivity: CH3Br < CH3CH2Br < (CH3)2CHBr < (CH3)3CBr carbon: methyl primary secondary tertiary ‘Thir ty dé phan ig, ngugc chiéu véi thir ty dO phan img 6 phan tmg Sy2, theo thir ty do ben cita carbocation. D6 phan ting lign quan dén d6 bin cia carbocation béi vi bude quyét dinh van t6e trong phan tmg Sy! 1a sy tgo thanh carbocation (Hinh 2.4) Dé bén céc carbocation nhur sau: Relative stability: CHs* < CHsCH3* < (CHs),CH* < (CH;);C* Least stable Most stable Vi vay, cde tée chat hoge diéu kién phan ing wu dai sy tgo thanh carbocation sé ting te 46 phan img Syl Tuy nbién, diéu quan trong cin nin man i ee carbocation khong bén, int lt khong ben theo nghia théng thudng. Carbocation la trung gian hoat dong vi khoang thoi gian tn tai ngin, Carbocation tam cap, nhu (CH3);C’, c6 thai gian séng khoang 10" gidy trong nude, trong khi ‘earbocation nhj edip, nhur (CH3)CH", e6 théi gian séng khoang 10°” gidy trong nuée. Sy giai thich cho 6 bén tueng déi cia methyl, carbocation nhat, nhi, tam cp 1a gi? Nhém alkyl lam bén sy gidi thich lam thé nao nhém alkyl bén héa carbocation 1a mét vin dé con nhiéu tranh cai. Mét giai thich dya trén khai nigm siéu lién hop (hyperconjugation), duge minh hoa trong hinh 2.7 cho carbocation nhdt jp CHsCH2'. Carbon carbocation vi ching ¢6 vai trd cho dign ti. Tuy nl duong dign lai héa sp’. Xung quanh nguyén tir carbon mang dign tich dong, sy siip xép cde nguyén tir khac tao tam gide phing va van dao 2p tréng vudng géc voi mit phing lai hoa. Nguyén tir cacbon lin cén lai héa sp’. va tao ndi o voi nguyén tr hydrogen. Cac néi C-H e6 thé cho mat do electron vao vin dgo 2p tréng, nhu dé nghj bing cée mai tén nét dirt trong hinh 2.7. Néu nhidu nhém alkyl hign dign trong mdt carbocation, thi cic twong tae kiéu ny xay ra nhidu hon, va két qua 1a lm ting dé bén cia carbocation. Vi vay, carbocation tam cap bén hon carbocation nhj cap, va carbocation nhj cp bén hon carbocation nhat cp. Boi vi khéng cé nhém alkyl nao hign dign trong: carbocation methyl, nén carbocation memyl la kem bén nhdt; trong tye té, no durge cho rang khong ~e bao git duge tgo thanh, ve Hinh 2.7: Higu img siéu lién hgp (hyperconjugation) lam bén carbocation B‘Chuong 2: Phan img cia cdc hgp chit hitu co Céch gidi thich khée vé syr bén hoa ciia carbocation 18 do eée nhém alkyl. Tuy nhién, tat ca n tir lign két voi Bat ké loi giai cc gidi thich déu c6 chung mot diém: su cho mat d6 dign tir tir cic orbital diy cic orbi | 2p trdng trén nguyén tir carbon mang dign tich duong ciia carbocs thich nao, cde nhém alkyl déu gitp bén héa carbocation; vi vay khi sé tang, d6 bén cia carbocation eding nhur t6c d6 eta phan img Sy! ting. Vi dy 2.3: Nhan biét phan tng Syl va Sy2, dy-doan sin phim Xét cde phan img sau, trong mdi trubng hyp phan img thé cé xay ra khGng? Néu c6, xdc inh san phim va d8 nghj eo ché phan img. (a) CN’ + CH3CH,CH,Cl > (b) Br + CH3CH30H (a) CH;OH + (CH,)sCCI (trong methanol) > © (a) Chit than hach la ion CN’, chat than dign ti 1a chloropropane, va nhom xuat la ion Cl «lon CN’ [a base manh hon ion CI nén hing sé can bing cho phan img nay Ién. Chloropropane 1a haloalkane nhit c&p, nén co ché phan tmg la SN; va sin phim 1a |-cyanopropane (CH3CH3CHCN. (b) Chat than hach la ion Br’, chat than dign tir la cthanol, va nhom xuat la ion OIL", OIT 1a. base manh hon ion Br’ nén hing s6 céin bang cho phan tmg nay nh6 hon mét. Khéng c6 phan ting. nio xay ra. (c) Chat shan hach la CH;OH, chai thn dign tir la t-butyl chloride, va nhém xuit la ion Cl Trong trudng hgp nay ching ta phai biét tinh base cia CHsOH so véi CI dé quyét dinh chiéu phan ting xay ra. Néu gid dinh ring tinh base eiia CH;OH va ion CF nhur nhau, edn bing sé duge thiét lp. Tuy rhién, ching ta dang str dung long thira methanol (methanol 1a dung mdi) nén edn bing djch chuyén theo hudng igo ra san phdm (nguyen M Le Chételier), San phim 1a rert-butyl methyl ether, (CHs)sCOCHs, eo ché phan ing 14 Sw vi chat thin dign tir a haloalkane tam cép. ‘Vi du A: Dur doan cdc phan ting sau 6 xay ra khéng va dé nghi cor ché c6 kha nang. (a) CHSC + CH3Br> (b) CI + CHsCHSCN > (0) CH NH + (CHCl > ‘Vi dy B: Tir cac thong tin sau day, trinh bay cor ché phan ing. (a) Phan img thye hign trong acetone (propanone) 4‘Chuong 2: Phan img cia cdc hgp chit hitu co xe = (b) Mt mau chi chira mét déi phan (R hay S) cita m6t hgp chat quang hoat goi la tinh khiér quang hoe (optically pure). Mot mau tink Khi quang hoc 2-iodobutane duge hda tan trong methanol. Dung dich thu duge la sec-butyl methyl ether khong e6 tinh quang hogt. Anh hwéng cia dung méi trong phan tg Sy1 va Sy2 ‘Chat than hach trong phan img thé thuong la ion mang dign tich am hay phan tir phan cye. Vi vay dé hoa tan vat ligu ban dau, chiing ta thudng str dung dung mdi phan cye. Tuy nhién, ban chat cia dung méi va dic biét cach phan tir dung méi tuong tic véi chat thin hach déng vai tro quan trong trong viée quyét dinh phan img xy ra theo eo ché Syl hay Sy2. Dé hiéu r@ higu ting cila dung. méi cn phan bigt dung méi proton (protic solvent) vi dung mdi phi proton (aprotic solvent). Dung mai proton Ia dung mdi ma phan tir cha né e6 nguyén tir hydrogen lién két véi nguyén tir 4m dign, nhu oxygen hay nitrogen. Nucée, methanol, ethanol, acid acetic vai methylamine ki ahiing vi du cia dung moi proton phan eve (polar protic solvent). Dung m6i phi proton 1 nhimg dung moi ma phan tir ea né khOng 6 nguyén tt hydrogen lién két v6i nguyén t6 4m dign. Dung moi phi proton 6 thé phan exe hose khong phan cue. MOL x6 vi dy vé dung mdi phi proton phin cye: acewne, diethyl ether, dimethylsulfoxide (DMSO), dimethoxyethane (DME), dimethylformamide (DMF), dimethylacetamide (DMA), hexamethylphosphoric triamide (HMPT). Mét sé vi dy vé dung moi phi proton khdng phan eye: hexane, benzene, g g Do AN oe Nye acetone diethylether dimethylsulfoxide _dimethoxyethane ‘OMSO) (OME) {i ° a phy Ay ok ! | / methylformamide dimethylacetarride_hexamethylphosphoric triamide (owe) (oma) Loai dung méi nao wu dai phan img Sy1? Giai dogn quyét dinh van t6e trong phan ing St 1a giai doan tao thanh carbocation va anion. Néu dung méi khéng lam bén héa cdc ion nay, phan img. Sul st khong xty ra, Dung mdi proton ¢6 6 phin eye cao, nhur nude va methanol, thée diy phan {img 8x1 hai vi dung mai nay hén héa cf carbocation va anion, twemg tyr nhur céich nic fam én cfc ion ciia mudi khi hoa tan mudi vao nude. Phin tir cia dung moi proton phén eye lim bén 15‘Chuong 2: Phan img cia cdc hgp chit hitu co carbocation bing cach cho déi electron chwa lién két tir nguyén tir oxygen hay nitrogen, va lim bén cc anion théng qua sv tao thanh lign két hydrogen. Logi dung méi nao wu dai phan img Sx2? Dung méi phi proton phan cue hoat déng tét nhat cho phan ting Sy2. Phan img Sy2 gdm mét gi ign tir. Hoat tinh eta chat than hach s€ bj gidm néu phan tir dung mdi cé kha ning (go ign két hydrogen véi chat than hach. Khi phén tir dung mi tao lién két hydrogen véi chdt thin hach, mdi loan trong dé chat than hach tan céng chat than phan tur chat than hgch bj bao quanh béi m6t Ip v6 dung méi, ean tr phan ting gida chét than hach vva chit than dign tir (Hinh 2.8). Sir dung dung moi phi proton sé trénh duge sur tgo thanh tien két hydrogen va do 46 dung méi phi proton thie dy phan ting Sy2. Solvent shell Solve n-ipole interactions. Weak ion-dipleintersctions.% ) tng Hinh 2.8: Tuong téc chit than hach - dung moi va anh hung eta dung moi én tinh than hach (a) Khi twong tic ion-ludng eye manb, tinh thin hach giam, Chit thin hach bi solvate héa ‘manh boi dung moi va sy tin cOng vao carbon than dign tir bj can tro. (6) Khi trong téc fon- ludng cyc yéu, chit thn hach khdng bj solvate héa manh va sy tin céng vao carbon than dign tur it bj can try hon bai dung méi. Cae yéu anh hudng dén tinh than hach Tinh than hach Li sir do luving kha nang chit thin bach tin eng carbon than dign tir mang nhom xudt nhanh nhu thé nao. Nhung diéu gi tao nén mt chat than hgch tt? Khong c6 méi lién he rio gift tinh thin hgch wa tinh hase ‘Tinh than hach 4 mie tinh chét ding hoe (lid quan dén the AB phan img) va tinh base la m6t tinh chat nhiégt dong hoc (lién quan dén do bén nhigt dong hoc cia base). hhudng gitta tinh base va tinh than hach. Ca tinh thin hach va tinh base du phy thude vio d@ 4m dign, kich thude va sy lai héa etia nguyén tir Nhiéu tai ligu gidi thich sy tuong quan trong ‘mang d@i electron chu lign két; sir bat dinh xtr dign tich; va higu img ciia nhém cho va rit dign tir. ‘Tuy nhién, chiéa huéng trong tinh than hach phy thude vao nhimg yéu t6 khée nia, nhur tuong tic 16‘Chuong 2: Phan img cia cdc hgp chit hitu co iia chit than hach va dung méi, higu img lap thé, va ban chat cia chat than dign tit. Do dé, chiéu hung trong tinh than hach khéng phai lite nao ciing theo chiéu hudng trong tinh base, Sau day la mot sé nguyén téc ching ta cé thé sit dung dé hiéu chiéu huéng trong tinh than hach. Khi 4p dung cdc nguyén tic nay, diém tham chiéu ciia ching ta 14 nguyén tu than hach, chat ma sit dung d6i dign tir cha lign két cha né tao néi véi chat than dign ti. 1. Chit thin hach mang dign tich am s@ phan (ing nhanh hon chat than hach khong mang dign tich. Vi dy, HO’ la chat than hach mgnh hon H;0, va CHsO" la chét than hach manh hon CH;OH. ‘Nguyen tir mang dign tich am sé hp din tam than dign tw hon ka nguyén tir khong mang dign hoge mang mt phan din tich 4m. 2. Khi so sinh ede phan tt hay ion c6 nguyén tir than hach nim cing mot hing cua bing hé théng tuan hoan, 46 4m dign cua nguyén tir than hach la yé Juan trong béi vi né anh hudng dén kha ning cia in tir chua lién két tgo noi véi nguyén tir thn dign tir. Trong ede anion sau day, nguyen tir than hach 6 chu ki thir hai, F*¢6 tinh than hach king bing HC’ vi F am dign hon C, vi vay d6i dign tr chua lién két @ F° sin sang tao ndi kém hon d6i dign tir chua lién ket HyC’. Increasing electronegativity of the nucleophilic atom, H.C > HN” > HO > F Tnereasing nucleophilicity ‘Doi khi cé thé dy doan anh hudng ciia cae yéu t6 khde, nhu la sy bat dink xt tich hay sw hign dign efia nkdim cho va rit dign tit. Vi dy, day ede chit thin hach san dy durge sip xép theo thie ty gidm tinh than hach. Tat cd ede nguyén tir than hach trong ede ion 6 chu ki hai eta bang phan laoj tuan hoan. N~ > CH,O~ > HO~ > HCOO- nucleophilic HN’ 1a chit than hach manh nhdt vi N kém 4m dign hon O, vi vay d6i dign tir chua lin két trén N dé ding tg0 n6i hon d6i dign tir chura lién két trén O, CHO" e6 tinh than hgch hon HO” bai vi trong dung dich nhém CH, cho dign tir va diéu nay lam cho d6i dign tir chua lign két trén © kém bén hon va hoat tinh hon. HCOO’ la chat than hach yéu hon HO™ vi ién tich am bat dinh xtr (dign tich Am durge chia déu trén hai nguyén tir oxygen), vi vay HCOO” sé kém hogt tinh hon HO, 3. Chit thin hgch mang dign tich &m hogt tinh hon trong dung mdi phn eye phi proton so véi trong dung mdi phan eye proton. Trong dung mdi phan eye proton, anion bj solvate hoa manh hon va dan dén kém hoat tinh hon (Hinh 2.8). ‘Chiéu huéng hoat tinh cua day cac cht thin hach trong mét s6 truéng hgp ¢é thé hoan toan dao nguge khi thay di dung méi. 7‘Chuong 2: Phan img cia cdc hgp chit hitu co Proticsolvent. «> BE > Cr > protic solvent 4. Khi so snh ede chat than hach ma nguyén tir thén hgch & cing mot nhém eda bang phan Jogi tuin hoan, tinh than hgch thuding tng khi kich et (va do d6 kha nang phan eye) eta nguyén tr than hach tng. Nguyén tir than hgch edng I6n va cng phan cye, dim may dign tick cing d& bi bién dang hudng vé phia nguyén tir carbon than dign tit. Sy bién dang ctia dim may dign tich vé phia nguyén tir carbon than dign tir lim giam nding Iugng ciia trang théi chuyén tiép va lim ting téc 46 phan img (Hinh 2.9). eneigy enetsy " More boning Large, highly polarizable nucleophile Transition state @ o Hinh 2.9: Higu tmg cia kha nang phan eve eiia chat than hach trong phan tng Sx2 (a) Sy tao thénh trang thai chuyén tiép trong co ché Sx2 bao gm sy chuyén mat d6 dign tir tir chat than hach dén van dao tréng trén C. Béi véi chat than hach lén hon va phan eye hon, sy chuyén mat d9 dign tir xdy ra sém hon (tai khoding cfich 1én hon) va két qua la trang thai chuyén tiép 6 nding lugng thép hon nhu trong hinh (b). Bai vi te 46 phan img ting khi nang. Iugng hoat hia giém, chit than hach cng phan eye phan tmg cing nhanh. Luu ¥ ring twong, tic dung moi - chit than hach (khéng trinh bay 6 dy) ciing anh hung dén kha nang tao néi cia chit than hgch véi carbon than dign t. 5. Cie nhom céng kénh bén canh nguyén tt than hach Lam giam hoat tinh cia chat than hach ‘vi nhiing nhém nay can tro vige tiép can ciia chat than hach vé phia nguyén tir than dién tir. Vi du, so sinh hoat tinh gitta ion methoxide va fert-butoxide: 18‘Chuong 2: Phan img cia cdc hgp chit hitu co Fast Slow Dy trén m6 hinh space-filling cia ion (CHs)sCO™ va ion CHO’, st tiép cn carbon than dign tir CHsBr boi nguyén tir oxygen than higeh cha (CHs);CO” bj edn td dng ké nhung boi nguyen ti oxygen than hach ciia CH3O’ thi khéng. Vi vay, (CHs):CO’ c6 tinh than hach yéu hon CHO” Bang 2.1phan logi m6t s6 chat thn hach thudng gap. Tuy nhién diéu quan trong li phai sir dung bang nay cn than. Tinh than hach ciia d6i dign tir phy thudc vao nhiéu yéu t6, chi mét trong. 86 46 lign quan dén chinh edu trie ctia chat than hach. Tinh than hach cing phy thude vao dung moi va ban chat ciia chat thin Bang 2.1: Phan logi ce chat than hach thong dung Chit than hach manh_ “Vn t6c | Chat than hack tt Van t6c | Chat than hach kha Vain te NC Cyanide 126000 | HO" Hydroxide 16000 | Cr Chloride 1000 HS’ Thivlate 126000 | Br Bromide 10000 | CH;COO™ Acetate 30 TF Iodide 80000 | Nv Azide 8000 | F Fluoride 80 NH; Ammonia S000 | CH3OH Methanol I NOs" Nitrite 5000 | H:0 Nurse 1 Van toc Ia van te tong d6i. Van te 100 nghia la chat than hach phan tng nhanh gap 100 Tan so véi nude, 19‘Chuong 2: Phan img cia cdc hgp chit hitu co ‘Tom tit phan img Syl va Sy2 Trong phan nay. ching t6i xem xét hai co ché khéc nhau cia phan mg thé xy ra tai nguyén tur carbon lai hia sp*. hy sinh xay ra, Phan ting Sy1 va Sy2 canh tranh lin nhau. Cie phan tt trong m@t hé théng sé lun phan img theo con dudmg 6 mite nang lugng thap nhat, Tuy thuge vao cde chat phan img vi digu kign phan img, con during e6 mite nang hegng thép nhat cho phan ing thé e6 thé 1a phan tng Sy1 hodie Sx2 hodic phan img gitta hai phin img nay. Bang 2.2 tom tit mot sé ¥ tuéng chinh xée dinh sy két hgp cila chat phan img va cdc diéu kign phan img sé thiic day mgt phan tmg thé theo co ché Sw1 hoge Sy2. Bang 2.2: Hoat tinh tuong d6i ciia haloalkane CH 4 4 4 rye—f-x tye—f-x wpe x Hy CH, cH, 4 Chat than dign we ¥ 2 ° Methyl bp bén cua 10 carbocation bén 10 carbocation khong bén carbocation Hogt tinh Sy oO phi ne Syl tan Khéng Syl Hogt tinh $2 Khdng S92 Po pin ng Sy? Hine Carbon « Chusdng ngai lip thé Khang o6 chung ngai lip Dung mdi Dung mdi phan eye proton Dung mdi phan cue phi proton thie day phan ting Sy1 thie day phan img Sy2 ‘Vi dy 2.4: Dy doan phan éng thé xy ra theo co ché Syl hay Sx2 Phan ding thé sau xay ra theo co ché Sx! hay Sx2? San phim tgo thanh la gi? Trinh bay cde bude ciia co ché va str dung mai tén dé chi chiéu di chuyén cia dign tir. Br (B)2-bromo-t-methylpentane © Methanol la chat thin hgch va haloalkene 1a chét than dign tir. Nguyén tir O tuong déi nho va khéng phan cue kim nén CH3OH la chat than hach yéu. Mét chat thin hach yéu khéng wu dai phan img Sy2. Mac khée, dung mdi phan ce proton sé bén héa carbocation. Vi cl thin hach yéu va dung méi phn cyc proton, ching ta dy doan phan img xay ra theo co ché Sy1. 20‘Chuong 2: Phan img cia cdc hgp chit hitu co Carbocation 190 thanh phan dng voi dung méi CH3OH (phan img dung moi giai solvolysis reaction) tgo thinh ether proton héa. San phim cudi cing Ia ether, durge tao thinh khi mét proton chuyén tir ether proton héa dén phan tir dung méi CH3OH. Boi vi CH3OH cé thé tic kich vao carbocation tir hai phia nén sin phim gdm hai ding phan Igp thé R va 8. Cée bude din ra nhu sau: Step Formation ofa carbocation n cH, 4 cH, a a ae ee: He cu cr, ne~* Seu cn, Step 2: Naleopilic attack by CH,OH rN . H CH,CHCH,), Hoy? ° ¢ fh i 3G) a oi ee Ves or | Hew Sag a nyeZ SHCHICH), ye 3 ‘Step 3: Lass of proton o solvent (ignoring sereochenistry) 4 4 rt) He € cH,cicu, —- a, ‘ciency, (wae(S) 8 ' i, AN, Hg HC a < ee o Phan img tao ra hin hop tiéu trién gim hai déi phn (R) va (S)-2-methoxy-4- methylpentane. Vi dy A; Dy oan cae phan Ging sau xay ra theo eo ché Sy1 hay Sy2. Chi 18 ting bude trong eo ché, sir dung mii tén dé chi sy di chuyén cia diga tit va goi tén sin pham tao thinh. we AA. + crysna 22 (62.4 Vi dy #5: Phan ung sau xay ra theo eo ché Swi hay Suz? Br 1 a CH, + 0 > CH,CH,CHCH,CH, CH,CHCHCH,CH, + 10 —— CH,CH,CHCH,CH, 3. Gi6i thigu vé phan tng tach I a‘Chuong 2: Phan img cia cdc hgp chit hitu co Trong phin trude, ching ta théy ring haloalkane o6 thé tham gia phan ting thé, trong dé nguyén tir halogen bi thay thé bai mét nhém khéc. Haloalkane cé thé tham gia phén tmg tach loai, trong d6 nguyén tr halogen va nguyén tir hydrogen ndi véi carbon bi logi ra khdi phan tir, Phan (mg tach logi ca haloalkane 6 thé xiy ra theo nhiéu co ché khac nhau, Néu giai doan quyét dinh vain te phan img la don phan tr (unimolecular), thi co ché phan img la E1. Néu gi doan quyét dinh van téc phan img 1a luong phan tr (bimolecular), thl co ché phan ting 1a E2, Trong phan nay, ching ta sé khao sat cdc co ché nay va thao ludn sy canh tranh gitta phan tng tach logi va phan img thé. Co ché phan tng El va E2 Trong tt ea ede phan ting da duge khao sit dén lie nay, d6i dign tir cho phan img nhur la mot base hoac chit thin hach. Vi du, khi 2-bromo-2-methylpropane, mét haloalkane bic ba, dure hoa tan vao methanol, hai sin phim khéc nhau duge igo thinh. San phim chinh (81%) la sn phim thé mong dgi, 2-methoxy-2-methylpropane. Phan ting xay ra theo co ché Sy1 cn, con ‘ Sw HAC wi wd “cH, 2-tomo-2-met propane 2ometnny 2 (ls) propane San phdm phy (19%) la 2-methylpropene. Phuong trinh héa hoe cho sy hinh thanh sin phim phy duye md tidudi day: He HE H \ cos \, nego Pa + i He h 2-bromo-2-methylpropane 2-methy!propene fica) Cae nghién eu dng hoe cho thay, van tbe phan img nay chi phy thuge vio néng d6 iia haloalkane: véin téc = k{(CHs)sCBr] Boi vi phan img la phan img tich loai theo déng hoe bac nhét nén duge goi la phan ing EA. Co ché cho phaa img E1 duge trinh bay trong hinh 2.10. Giai dogn dau tién la giai dogn chim bao gm sy hinh thinh cia mét carbocation. Giai dean nay ging nhur giai doan dau tién ciia co ché 2‘Chuong 2: Phan img cia cdc hgp chit hitu co Syl. Trong giai dogn thir hai, mOt phan tir methanol phan ting nhur la mot base (khong phai la mot chit thn hach) va loai bé mét proton khéi carbocation, tao thinh alkene. Chi ¥ ring proton bi loai Khoi nguyén tir carbon ké bén nguyén tir carbon tich dign durong cila cacbocation, carbon f. So 4d phan (mg E1 due trinh bay trong hinh 2.11 Step I: Formation ofa carbocation (slow) Step 2: Removal of proton fom the carbocation (fast) -, yeas LL. on) eh, + cus — Ac HC iW a Hinh 2.10: Co ché phiin img El nels Ne sei P yey uc 8 5 e ™~N ‘Transition IC === Cin HW | ne \" ‘Tramition +cHOH Reaction progres Hinh 2.1 Giai doan dau 1a qua trinh thu nhigt cao bao gdm sy tao thanh carbocation. Trong trang thai chuyén Br bj bé gay mét phan. Trong giai doan hai, CHsOH hoat - Reaction progress Hinh 2.12: So dé phan img E2 gitta butyl bromide va CHyCH:0" trong methanol Dy doan san phdm tach loai chinh ‘Trong cée phan ting tach loai ma ching ta da nghién ettu cho dén gid, chi eS mot sin phim tach logi. Tuy nhién, thuémg xay ra traémg hop e6 nhiéu hon mot san phim tich loai. Vi dy, trong 4 H / + och, + 387 W cr, I -butene (185%) (27.4a) phe \, / Hy \ 7 \ iH W i srans-2-butene (67%) cis-2-butene (15%) + HOCH, + (7.40) ‘Trong I-butene, lién két di C=C 6 cudi mgch carbon, va trong cae déng phan cis va trans 2- butene, ni C=C 6 gitta mach. Luu y ring phin img ¢6 sw uu dai hay cé tinh chon Ioe manh cho vige tao thanh ni ddi 6 gitta mach (82% so véi 18%). Khi cé thé c6 nhiéu hon mét san pham tach loai, ligu ching ta cé thé dy doan duge sin phim nao la san phdm chinh? Théng thuéng, san phdm chinh cia phan img tach loai sin phdm bén nhat. Trong so dé dui day, cdc alkene due sip xép theo thir ty ting dn d6 bén: 25,‘Chuong 2: Phan img cia cdc hgp chit hitu co sya = nen PONV SNS NS eens ec weecnt ey eae Ares peed 2 vere Abe ae : : : R ® R Wn c ® KR \. ‘Thi ty d6 bén nay dya trén dit ligu thye nghigm (nhigt cua phan img hydrogen héa). Chiéu hung vé do bén ca alkene durge 16m tat trong phat biéu sau day: ‘58 lang cic nim thé alkyl lien ker vit carton op ctia alkene cing ton, alkene dé came ban. Noi chung, alkene mang nhiéu nhém thé bén hon alkene mang it nhém thé. Ngoai ra, cdc nh6m alkyl céng kénh cé xu hudng cang xa nhau ra cing tot, vi dy: dong phan trans ben hon dong phan cts. Hay tre Igi phan img (27.4) va gidi thich vé ty 18 cae sin phim thu durge, Cée alkenes e6 lién két doi gitta mgch la san pham chinh béi vi ching e6 nhiéu nhém thé hon va trang thai chuyén tiép iia nhimng alkene nay ¢6 nang lugng thép hon trgng thai chuyén tiép ciia alkene mang it nhém thé, ‘Trong hai alkene ¢6 néi doi 6 gitta, ddng phan érans bén hon (trang thai chuyén tiép cua déng phan nay ¢6 nang lugng thép hon) va do 46 déng phan irans 1a san phim chinh, ‘Thong thudng, sin phim chinh trong phan img tach logi li alkene mang nhiéu nhém thé nhat nhung cing cé nhimg ngoai Ig cho quy tic nay. Sy hinh thanh alkene mang nhiéu nhom thé nhat xyéu edu base logi bd mét proton tir nguyén tir corbon bge hai hoge bge ba. Duong vao nguyén tir hydrogen trén nauyén tit carbon bac hai hode bac ba bi can tré bs céic nhém lan en, Cae base nho hw OH", CHyO", hay CHsCH;0" 66 thé vugt qua cée nhom nay kha d& dang nhung cée base Ion hon nhur (CHs)sCO™ thi khéng thé. Base véi kich thirde lim s& um tién tin eng c4e nguyen tr hydrogen bj 16 ra nhiéu hon (tréng trai hon), tao thanh alkene mang it nhém thé. Trong cdc phan img sau day, cing mt chat nén phan img véi nhidu base khac nhau. Trong phan ing dau tién, base vGi kich thude nho hon, it bj chuéng ngai lap thé hon duge sir dung va san pham tach loai chinh la alkene mang nhiéu nhom thir hai, base voi kich thud hon. Trong phan é ¢ lon hon, bj chusng noni tap thd nhidu hem Aug: it ng vA cin phim tich lng chinh IA alkene mang it shim thd 26‘Chuong 2: Phan img cia cdc hgp chit hitu co cH, HC ne W ‘cH, H.C 13% 2-butene 2-methyl--butene 2-bromo-2-methylbatne 6 vi tri “anti” d6i voi nhom xuat, ‘Déi vai phan img E2, nguyén tir H trén carbon f ph cdu nay dat ra mét su gidi han cho céc sin phim tich logi duge tgo thinh tir haloalkane 2°. Chi ‘¥@ phan dng nay s® duge thao lugn trong chuong tinh hoa hu co chuyén nga Phan ing thé va phan tng tach logi: Tom tit ‘Chang ta thay rang céc haloalkane c6 thé trai qua nhiéu phan tng: Sy2, Sy1, £2, hoge El. Ve nguyén th, tt cf fe phn img niy dé canh tranh vi nhau, va © thé c6 mot loat sin phim of thé Khi xae dinh ligu mot phan img sé xy ra theo co ché mio Sy2, Syl, E2, hoy E1, ching ta phai xem xét nhiéu yéu t6. Ban chat cua chat cho cp electron 1a gi? Né la mét chat than hach tét hay la mot base manh? Né c6 bj can tre Kip thé Khong? Ban chat cia chat than hach la gi? N6 e6 bj edn tro ve mgt lgp thé khong? Con vé dung mdi sav? NO thie dy sy hink thanh carbocation (phn ing, Sy1, 1)? Ligu n6 lim ting hoe gidm tinh than hach cua chat cho eap electron? Mét sé nguyén tic huéng din dy két qua doan phan img va co ché duge trinh bay trong hinh 2.13, nhung hy nhé ring luén tn tgi ede trudmg hop ngoai Ig. Bé sir dung tét nhat ede nguyén tic nay, chiing ta can theo cae bude sau; 1. Trinh biy tt cd cdc dign tich hinh thie vé dign tich mot phan trén nguyén tir ¢6 ching. 2. Xée dinh chat cho cp electron va chat nhin cp electron (chat than dign tir) 5. Xem xet ede chdit than dign tu: fa nha, nhy hay tam ep? A. Xem xét chit cho ep dign tir: lA chat than hach mgnh hay yéu? La base mgnh hay yéu? CO bj can tro vé mat lap thé khéng? 5. Dung 10i 1a dung moi proton hay phi proton? 6. Xée dinh xem ligu phan img chii dao sé la Sy2, F2, hoc Syl, Fl (hy nhé ring Syl va EI ludn xay ra eting mot lic). 27‘Chuong 2: Phan img cia cdc hgp chit hitu co Cae huéng din duge trinh bay theo dang hinh céy quyét dinh (decision tree) véi sy xem xét 46 manh tinh base cia chat cho cp electron :B, va mot s6 yéu t6 khic gdm higu img lap tl than hach, higu img dung moi. Yes / Is:Basterically hindered strong base? 1s:Bastwong X° rnucleophil a (a) YeyIs :B a stoong base? Yey Is-Ra good nucleophile? () Is:Ba strong base? Is the solvent polar? Is the solvent polarand protic? © Minh 2.13: Tém tét phan tng $y2, £2, Syl va E1 cho haloalkanc abit, nhj va tam ep (a) Haloalkane 1° trai qua phan img Sy2 ho&c E2. (b) Haloalkane 2° trai qua phan tng Sy2, 2, Syl va EL. Céc h6p mau dé 6 thim mot sé Inu y. Déi véi alkene e6 ndi doi gitta mach c6 thé c6 déng phan lap thé (£) va (Z). Khi m6t haloalkane 2° trai qua phan imgSy2, ¢6 sur nghjch chuyén céu hinh ()<>(S). Trong dung méi phan eye proton, haloalkane c6 thé phan tg voi mot chit than hach yéu tao san phim Sy1 va El. (c) Haloalkane 3° trai qua phan img Sw1, El, vi E2. Methyl halide (CHsX) khéng duoc dé cfip 6 day chi trai qua phan img Sy2. 28‘Chuong 2: Phan img cia cdc hgp chit hitu co D6i véi haloalkane 1° (Ilinh 2.13a), ede phan ing o6 thé la Sy2 va E2. Khong ¢6 phan img ‘Sw vi carbocation 1° khéng bén, Néu chat cho dign tir :B, la mét base manh bi can tro vé mat lap 1 hi phan tng E2 sé chiém wu thé bai vi chat cho dign tir sé kh6ng thé tn céng nguyén tir carbon than dign tir tir phia sau. Thay vio d6, mét proton sé bj logi bo khéi carbon #. Néu :B khéng bj can {ro lap thé, thi n6 sé phan img nhur la mt chat than hach va tn céng carbon than dign ti tir phia sau theo phan tmg Sy2. Néu :B 1a mét chét than hach manh, nhur f, “CN, RS", hay RO’, thi phan img ‘Sy2 sé xy ra kha nhanh. Néu :B 1a mét chat than hach yéu, thi phan img Sy2 sé xay ra kha cham. 16i v6i haloalkane 2° (Hinh 2.13b), kha ning xay ra nhiéu logi phan tg la nhigu nhét. Néu chat cho dign tila mét base manh, thi phan img tich logi E2 la phan img chinh va sin phim chink la alkene véi néi déi gitta mach. Néu :B la m6t base yéu nhung 1a mét chat than hgch manh hode tt, nhur I, “CN, RS" hay RCO’, t ‘cue phi proton. Diéu quan trong can nhé la néu carbon « trong haloalkane thi tinh, shan img Sx2 sé phan img chinh la Sy2, dic bigt néu sit dung dung méi phan dao nguge céu hinh cia carbon a, Néu :B 1a mot base yéu va cling la mot chat than hgch kém, nhur HO hoe ROH, phan img Sw! s@ chiém uu thé khi str dung dung mdi phan cue proton. Cée phan tir cla dung méi sé déng vai trd chat than hach trong trudng hgp nay. San phim El cling sé duge tao phan Sy. ‘bi vdi cae haloalkane 3° (Hinh 2.13¢), ede phan img e6 thé la Swl, EI, hay E2. Phan img, thanh cing vi s ‘Sy2 kho xay ra vi carbon « bj chuéng ngai lp the lén cho vige tan céng tit phia sau. Néu :B la mot base manh, nhu RsCO™ hay RO’, phan mg tich loai E2 sé la phan img chiém wu thé. Néu :B la mot base yéu (va la mét chat than hach kém), nhu H;0 hoac ROH, thi phan img chinh sé la Syl cing an phim El cing duge tgo thanh, khi dung mi phan cye proton duge sir éung. Diéu quan trong can nhé 12 néu carbon a thd tinh, sin pham Sy1 bao gdm mt hdn hgp cde déng phan lap thé (x) vas). ‘Vi dy 2.5: Dy doan phan ing Sy2, E2, Sql va E1 Dy dodn san pham va co ché cho mdi phan img sau day. @ (CHy),COH euen,cuciyps + «ery co-na BSEON Br ° o CHCHCH, + CHC —O-Na* E> cHCH,CHC © (a) Chat than dign tt CHyCH2CH:CH:Br 1a haloalkane nat edp. (CHs)sC 1a base man bj chuéing ngai lap thé, 29‘Chuong 2: Phan img cia cdc hgp chit hitu co He at 8 \__ chy,con CHCHCH,CHB: |, ww —0 A> alc ne Strong base (primary) (bik, stray hindered) Mfc dit m@t base manh ciing thong 1a mét chat than hach manh, nhung sy cong kénh cia ‘base khéng uu dai phn mg thé va phan img tach loai E2 sé cho ra san phim chin. I fo \n Phan (mg thé Sy2 tgo san phim CHsCH;CH,CH20C(CHs)s, nhung san phim thé 1a san phim phy. (b) Chait hin dign tit aloalkane nh edp. Chait cho cap electron li base yeu (base hyp ciia acid yéu) va bai vi né mang dign tich am nén la chat than hach tat, dae biét la trong dung mdi phan eye phi proton. Phan img chinh sé la phan ting Sy2. ness °. —s ca, lctwphile Weak tase Sy proct (secondary) (good nucleophile “ono (6) Phan tir dung m ‘ing la chét cho c§p dign ti. Phan ting bao gdm m6t haloalkane nhj cap va mot base yéu/chat than hach yéu trong dung moi phan cue proton. Nhimg diéu kign nay khong wu dai phan tg Sx2 hay E2 nhung wu dai Syl va El. Swi va El xay ra déng thoi. Carbocation nhj cap bén, dac biét la trong dung méi phan cye proton, nh H20. Bai vi H20 la base yéu va la chat than hgch kha nén phan tmg thé sé trdih hon phan tmg tach Logi. Br on 1.0 CHCH.CHCH.CH, + 1,0 Se CHCHCHCH,CH, or CHCH=CHCH,CH, + HEE Electwophile Weak base Syl EL (secondary) (weak nucleophile) (min) (minor) Vi dy A: Dir dodn sin phim va ea ehé cho phan img sau day. (CHjCH,CH;Br | CH3S-Nat “> 30‘Chuong 2: Phan img cia cdc hgp chit hitu co ‘Vi dy B: Dy doan san phim thé va san phim tich Togi o6 thé 66 trong phan dng sau day. San phim nao la saa phim chinh? (CHy,CHOM (Emmy + (cy cHo-nat ECON cucu \ = Te, Phan tng Sy1 va El ¢6 duge sit dung trong tong hop hitu co? Ban tom tit 6 hinh 2.13 cho thdy phan tmg Syl va E1 xdy ra déng thdi. Do d5, phan ing Sy 1 va El cia haloalkane thudng khéng duge sit dyng dé tong hgp cde hgp chat khéc. Hon naa, mot rac réi khée xudt hign trong phan img SN1 va El 1a sy sp xép lai carbocation 44 tga thanh mfe trang gian kde bin hom trade Khi sin phimSul va FT durge hinh thanh, trung gi Vi dy, khi 2-bromo-3-methylbutane duge dun néng v6i nude. Sin phim Sy! chinh khdng phai la 3- methyl-2-butancl, thay vito dé la 2-methyl-2-butanol. ou, cH cu Ho | Hep + WO t= Ne 4a wr HEA — + Hobe on 1 on 2-tomo-3-mety bane 2imetyl2twanol 3th 2 bata ‘rap cae Sin phim chinh duge tgo thanh la do sy sip xép lai carbocation 2°, duge tgo thanh khi ndi C- Br trong 2-bromo-3-methylbutane bj gy va giai phéng ion Br’. Nhu nghi dui day, e6 hai céch sip xép lai (a) vi (b). Nhimg cach sap xép Iai nay la vi dy vé chuyén vj hydride (hy¢ride shift). Hou ji ty , oy nia el SK : Pies, Rete H Jess stable than A 3° carbocation ‘mow stable than 2° ‘Cch sip xép (b) khéng xay ra vi nd tgo ra carbocation 1° khéng bén, Cach sip xép (a) chuyén sarbocation 2° thanh carbocation 3° bén hon, Carbocation 3° din dén sy tao thanh sain phdm thé chinh. ai 31‘Chuong 2: Phan img cia cdc hgp chit hitu co Bat ett hic nao mét carbocation tgo thank, sir chuyén yj luén €6 thé xay ra, va sy chuyén vic thé bao gém su di chuyén cia cdc nhom methyl hay alkyl. Voi nhiéu kha nang cé thé phat sinh trong phan tmg Syl va E1 nhur thé, that khé khan trong vige dy doan hoge kiém soat phan img. Vi vay, khong e6 bat ngi gi khi phan mg Syl va EI khong duge sir dung nkigu trong téng hop hitu eo. 4. Phan ting cia alcohol Rugu thong duge sir dung trong téng hgp hiru co vi chang dé dang chuyén déi thanh cae hgp chit khac. Trong chuong 1, ching ta thdy ring alcohol 1° ¢6 thé bj oxi héa thanh aldehyde hose acid carboxylic va alcohol 2° c6 thé bj oxi héa thinh ketone, Alcohol phan img véi carboxy! ester. Trong phin 2, alcohol ROH phan img oahu 1a chat thin hach trong phin img thé voi haloalkane R’X tgo thanh ether ROR’. Mét s6 phan img cia rugu duge t6m tit trong Bang 2.3. ‘Trong phin nay, ching ta t§p trung vao phan ting rong dé nhom -OH bj thay thé boi nguyen tir halogen (phan img thé) hay logi nude (phan tng tach log. Bang 2.3: Mot s6 phan img cia alcohol Logi phan ang Phuong t Deprot ROH + Na —> RO"Na® + 1/2H Caos ROH +2 > aldehyde, ketone or carboxylic acid Esterificati ROH + R'COOH => R'COOR + H;0 Substitution ROH® + R'X —> ROR’ + HX ROH® + HX —> RX + H,0 Elimination ROHL alkenes Na;CryO/H2SO, hay PCC/CH2Cly. PCC 1a pyridinium chlorochromate. °ROH phan img nhu la chit thin hach trong phan img nay. °ROH phan tng nhur la chat than dign tir trong phan img nay Phin dng thé va phan ing tach logi cita alcohol Nhém -OH ciia alcohol c6 thé bi thay thé hing nguyén tir halogen hay bj logi duedi dang nurée trong nhing diéa kign thich hgp. Hay cing xem xét cdc phan img thé sau (CH CH2CH;0H + Nal —> CH3CH2CHpl + NaOH (does not occur) CH3CH)CH,OH + HI —+> CH;CH3CHyI + H;0 (occurs slowly) than dign tir va HO” 1 nhém xudt. Mg dit ion I” 1a mot chat ‘Trong ca hai phan img, IIa el than hach tét, nhung ion HO" cé tinh base manh va ld nhom xudt kém. Vi vay phan img dau khong, 2‘Chuong 2: Phan img cia cdc hgp chit hitu co xay ra, Tai sao phan ting thir hai xay ra durge? Trong sy hign dign cua acid manh, nguyén tit oxygen ciia nhém -OH bi proton héa, tao thinh R-OH)”. Bi ‘6i alcohol bi proton héa, nhém xuat la HO thay vi HO”, Boi vi H;0 li base yéu hon HO nén sé la nhom xuat tét hon. Trong phan img thir hai, é Sy2: carbon @ trong CHsCH2CH;OH Ia nnhat edp (khOng bi can tr lap thé) va I la chat than hgch tt. Co ché phan ting duge trinh bay trong hinh 2.14. digu kign phan dmg hoan toan phit hop cho phan img a, +H cr,ch, — GH + Hot == cHcH,— QT + 0 “ “1 ee eT AN, { easton is 1° Nucleophule substitution (8,2) 1,—I + 10 rsleopile Hinh 2.14: Co ché phan img gitta CHsCH,OH va HI Bude dau tién thugn nghich, trong 46 nguyén tt oxygen eta nhém chite alcohol bi proton hoa. Buse thir hai la sy tae kich than hach vao carbon a cua I. Bi vi carbon a 1a hat cdp va T'1a chat than hach manh nén phan img xay ra theo co ché Sx2 ‘Néu alcohol tam cép nhu la (CH3);COH duge str dung thay cho alcohol nhat cdp trong phan lung mu hai, phan ung mé xay ra theo co ché Spt, DOI Vi phia sau cua carbon @ tong alconol tam. cp bj can tre lp thé va chét than hach khé e6 thé tiép cn duge. Nhur trong hinh 2.15, phan img thé bao gém sy tao thinh carbocation theo sau Id sy tée kich thin hgch eta. Carbocation duge bén hh6a boi cde nhém alkyl cho dign ti. 8 ace oe een eriggc—tf Toy = cH ye— OT + HO keen Ht 4 _ iy 1) “a 1 Nock ccearbon is 3° substitution (Syl) cnyc—e — (cnyc—1 finh 2.15: Cor ché phan img gitta (CHs)sCOH va HI 3‘Chuong 2: Phan img cia cdc hgp chit hitu co Nhur da biét, phan tmg tach loai canb tranh v6i phan ing thé. Sy tich loai nurde khdi alcohol la mét phuong phip quan trong dé téng hop alkene. Sur loai nude khdi alcohol goi la phan img dehydrate héa (dehydration reaction). Dang tng quat cia phan img dehydrate hoa nhur sau: ue » oO aioe mae mo Vi du, phan img dehydrate héa cia 2-methyl-2-butanol. oi ar HS0, / \ ne ee en ae Lud in, ncn tamigiivme —— 2amty nate nies) aang Sur dehydrate héa alcohol can xtic tac acid. Xitc téc acid proton héa alcohol dé nhém xuat sé 1a HO (nh6m xuat t6t) thay vi li HO" (nhém xudt kém). Dé thiic dy phan img tach logi (dehydrate hh6a) vugt tri so véi phan img thé céc acid 11,805 hay IIsPOy dim de duge sir dung hon la cée acid HI hay HBr (nhé ring I’ va Br’ la chat than hach manh, néu ding HI va HBr, phan img thé sé uu dai hon phan img tach logi). Phan img dehydrate héa cia alcohol tam cép xay ra theo co ché E1 (a) Protoration of the alcohol cn, cn, ne ucue Minor Hinh 2.16: Co ché phan img dehydrate héa xtic tée bling acid cba 2-methyl-2-butanol 34‘Chuong 2: Phan img cia cdc hgp chit hitu co ‘Co ché ciia phan ting dehydrate hoa xtc tac bing acid ciia 2-methyl-2-butanol duge trinh bay 6 hinh 2.16, Bude dat ién fa su proton héa alcchol. Tiép theo la phan img dehydrate héa xay ra theo eo ché E] tgo ra sin phdm 2-methyl-2-butene (sin phim chinh: san phim mang nhiéu nhém thé) va 2-methyl-1-butene. Phan img dehydrate héa cia alcohol nhj cip thuding xay ra theo co ché E1, nhung cing c6 thé xy ra theo co ché E2. Ethanol, alcohol nhit cp, thye hign phan img dehydrate héa theo co ché 2 nhur dui day: ‘Vi dy 2.6; Dy doan san phim cia phan tg véi alcohol Dy doan san phim cua cae phan img sau day. Dé nghi eo ché thich hgp cho phan tg, str dung mai tén 43 chi sy di chuyén eta dign tit (a) L-propanol + codium hydroxide 24. (b) (R)-2-bromo-3-methylbutane + ethanol =" © (a) L-propanol CHsCHsCH,OH Ii alcohol bje nhit. Khong 66 phin Ging thé hay phan img Lich loai (dehyidrate hoa) nao xay ra trong digu kin nhur vay. (b) 2-bromo-3-methylbutane CHsCHBrCH(CHs)2 li haloalkane 2° va Br ta base yéu va la nh6m xuat t6t. Ethanol CHsCH;OH Ia base yéu va cling la chat than hach yéu, Dung mdi phan eye: proton. Trén co sé cdc thong tin nay, chung t0i két luan ring phan dmg Sy1 va El sé xay ra (Xem hinh 2.12), Rurie du tién trang 08 cor ché Sul_vA EI 1A sy hinh thinh carbocation: He ewer, ne~ ewcny, (R}2-bromo-3-methylbutane ‘M6t khi carbocation da hinh thanh, phan tng thé ho&c phan img tich logi déu 6 thé xay ra. Bude tiép theo eta phan img thé nhur sau: 35‘Chuong 2: Phan img cia cdc hgp chit hitu co HCH, (ay ands) " * sche B——C—cHCH), ——e HcH,C— —CHCH), + CH,CH, eH cH, Randi) ‘Trong so dé trén, chat than hach ¢6 thé tin c6ng vio carbocation & ca hi |. Vi vay, e% hai dng phan lap thé (R) va (S) duge tgo than Buse tigp theo cia phan img tach logi duge trinh bay dudi day. Phan img téch logi tgo ra hai ju nhom thé, alkene va san phim chinh la alkene mang nl H | a mi ve hoon Laru §: 6 edu (a), NaOH khéng thé deproton héa CHLCILOH duge, nhung NaNILz thi 66 thé. (pK, (NH) khong 34 nén pK, (NHz) khoaing 14 - 34 = -20). cau (b), carbocation co thé chuyén vj tgo carbocation bén hon nén sé co nhiéu san phém thu duge trong phan img thé va phan tmg tach logi. G day ching ta khdng khéng bin dén sur chuyén vj nay. ‘Vi dy A: Dy doan san pham cua cdc phan tg sau day. Dé nghj co ché thich hgp cho phan tng, str dung mii tén dé chi sy di chuyén cita dign tr. (@) (R)-2-butanol SEE (b) 1-propanol = Vi dy B: Dy doan san phim cia cdc phan img sau day. Dé nghi co ché thich hop cho phan img, str dung mai tén dé chi sy di chuyén cia dién wr. (a) 3-methyl--butanol + hydrogen iodide —+ _ (b) 2-methyl-2-propanol + sodium —> 5. Gi6t thigu vé phiin king cng (addition reaction): phan dmg ea alkene ‘Trong phin trie, ching ta tip trung vao eae phan img lién quan dén dai dign tir e@ lip 66 thé hoat déng nhu [a base Lewis ho§c cht than hach. Trong phan nay, ching ta sé théo ludn cdc phan 36‘Chuong 2: Phan img cia cdc hgp chit hitu co ing ita alkene, ur fa (CH3)2C-CHb va thay ring ndi 6 uhdng phan ti nay eding 66 thé hoat dong nnhir li hase | ewis hoje chat thin hach Phan img dac trung cia ankene (va alkyne) la phan img cOng hai nhém thé, X va Y, vao méi carbon cia néi doi hay ndi ba. Trong phan nay, ching ta sé tip trung cha yéu vae phan tmg cong. cia ankene véi phuong trinh tong quét duge hién th dudi day \ C+ XY —— cc / \ | | Niu minh hoa trong Hinh 2.17, n6i gita hai nguyén ti Ving hoat tinh trong alkene la ns carbon trong alkene cd mat d6 dign tir cao & phia trén va phia dudi mat phing cha cic nguyén tit ‘v6i carbon sp”, Dign tir trong ndi + khong duge gid chat nhur cdc dign tir trong cic lién két o, va ching bj kéo vé phia nguyén tir than dign tir. Sy chuyén mat d6 electron tir lign két 7 cia mot alkene dén chit thin dign tir la dj diém chung trong cée phan img ching ta thio hyjn trong phan nay. Upper half ofthe bond . | Hinh 2.17; So dd biéu dign lign két zrtrong alkene Méi nguyén tir carbon trong néi déi li carbon sp” va tao ba ee | néi o. Néi oduge biéu din bing duong nét lién, hinh ném nét ditt iu nt met en, MU AO i t trén va phia durdi mat phiing ciia cde nguyén tir ndi véi carbon sp” Lower half ofthe a bond 1G Wuny udi 2 eda alkene © phi Phan ting eng hydrogen: phan img hydrogen héa (hydrogenation) Cong Hs vio néi d6i cia alkene tgo thanh alkane. Phan tg nay rét chm, tritkhi sir dung cht xiic téc kim loai min, nhu Ni, Pd, Pt, hay Rh. Vi du, phan tng hydrogen hod propene, CHsCH=Cl biing céch sir dung chat xtic téc kim loai Pt nhu dui day: CH=CH + Hy CH,CHy So dé mé ta co ché ciia phan img nay duge trinh bay trong Hinh 2.18. Phan img hydrogen héa xiie tée ca alkene 1a m6t phan img quan trong quy trinh céng nghiép. 7‘Chuong 2: Phan img cia cdc hgp chit hitu co Nisurtace a Hinh 2.18: So dé mé ta co ché cia phan tmg hydrogen héa xtc tac kim loai cla C2Hs (a) Hz va C2Hs hap phy lén bé mat kim logi, lam yéu ndi H-H va ni pi trong C2Hy. (b) Nguyen tir H néi voi nguyén Ur carbon va chuyén CoH, thanh CoH. va gid hdp ra khoi b& mau kim loai. Chi tiét cu thé vé co ché nay vin dang cdn tranh lua, Hydrogen héa ed alkyne twong ty nh hycrogen héa alken. Phan img hydrogen héa xtc tie kim logi cia alkyne eng tao thanh alkane, trit khi sir dung chat xie tic dae bigt goi la chat xi tée Lindlar. Chat xie tée Lindlar bao gém barium sulfate duge phi kim logi palladium va “bi nhiém Ge" Véi quinolone. Trong chit xtic tic Lindlar, hogt tinh xc tée cia palladium giam va sy hydrogen héa cia alkyne dimg lai 6 viée tao alkene. Cc phurong trinh héa hoc duréi day minh hoa phan img hydrogen hoa 2-butyne, sit dung chat xc téc Pt va chat xtc téc Lindlar, Luu y ring khi mt chat xtc te kim Joai tinh khiét durge sir dung, phan img hydrogen héa alkyne tiéu thy hai mol hydrogen cho mdi mol alkyne. Khi ding chat xtc tac Lindlar, chi e6 déng phan lap thé cis (Z) duge tgo ra, Hai nguyén tr hydrogen duge ong vio tir cig mét phia. HyC—C=C—CHy + 2H, "+ CH,CH,CH,CHy, CO a ow, Lindlar's Heeme—oy +m Se Quinoline dirge sir dung trong W in xiic tie Lindlar dé lim gid ‘5(9 omer only hoat tinh ciia Pd Phin ding cng hydrogen halide HX Phan tmg cng HX vio alkene theo phuong trinh ting quat sau day. 38‘Chuong 2: Phan img cia cdc hgp chit hitu co \ L_| ‘e +H—x —+ ne / oe 1 | [Atkene Hydrogen aide Hatesthane Co ché cua phan tg nay gdm hai bude, nhu duge mé ta 6 hinh 2.19. Trong bude dau tién (Hinh 2.19), nguyén tir H durong dign mot phin cng vio mt trong hai nguyén tit carbon eiia lién két ddi, tg0 ra mOt carbocation. Vé nguyén tie, nguyén tir H ¢6 thé eGng vao mét trong hai nguyén tir carbon, nhumg trén thyc té, né wu tién cng vao nguyén tir carbon mang it nhom thé nhat vi khi nhém thé ¢6 thé lam bén carbocation, 6 dign tich duong 6 trén nguyén tir carbon meng Ml (Nhac lai: nhém alkyl giup én dinh carbocation.) Trong bude thir hai (Hinh 2.19b), ion Br hoat dong nhur mot chat than hgch va tin cong carbon mang dign tich duwong cua carbocation @ cu, H —+ nc—c—e bh: ; o™ “ H carbocation ¥ carbocation less stable) (more sable) » Be > HCCC Major product cH h 2.19: Co ché phan img cOng than dign tir ca HBr vao 2-methyl-1-propene ‘Néu phan ting thye hign trong dung dich nuéc, hdn hp sin phim duge tao ra. Dé tranh digu nay, c6 thé durge thye hign phan img bing cach din khi HCI, HBr, hoge HI qua elkene tinh khiét hoje bing each thyre hign phan (mg trong mot dung mai khong cé tinh than hgch. Phan ting eng nuse: phan tg hydrate héa (hydration) Phan tmg 2éng nuée vio alkene theo phuong trinh tng quat sau day. \_/ H50,/H,0 | | + won EE yc eon 1 | Alken Water Ateobol 39‘Chuong 2: Phan img cia cdc hgp chit hitu co Phan mg chi xay ra trong dung dich acid va c6 thé duge thuee hign trong hn hop gbm I1sSOq va H>O (thudng li 50% H»SOs theo thé tich). Co ché phan img tuong tu co ché céng HX vao alkene. N6 bao gdm su hinh thanh carbocation, theo sau d6 la sy tin cng than hach (Hinh 2.20), ‘Trong buse dau tién, mOt nguyén tt H tir HO" eng vao carbon mang nhiéu nguyén tir H nhdt, tg0 ra carbocation (Hinh 2.20a). Bude thit hai, phan tir nuréc hoat dng nhu chat than hech tén céng vao carbon mang dign tich dong cia carbocation (Hinh 2. 206). Bude thir ba, proton éurge loai bo, tgo ra rugu (Hinh 2.20c). @ HE H Hg ry H da He Ne | cr, AON cc cn, ne H H | cH © Hinn 2.20; Co ché phan img ong nude vo 2-methyl-I-propene xtc tae bing acid Phin ing eng halogen: phin ing halogen héa (halogenation) Halogen X; c6ng vao alkene tgo ra san phdm la dihalide. Khi hai halogen néi ké in nhau, dihalide duge goi la vieinal dihalide. Khi hai halogen néi_v Gihalide duge goi la geminal dihalide. (x = Coes Alkene Halogen al dialide Phan tig trén xay ra d8 ding & nbigt d6 phong khi halogen li Cl, hay Brs. Dung méi khéng, ruse (nonaqueous solvent) nhir CHCl; hay CCl: duge sit dung dé ngdn ngita sur hinh thanh eiia cdc san pham khac. Co ché cho phan img c6ng X2 vao alkene khac biét dng ké so véi cdc co ché trinh 40‘Chuong 2: Phan img cia cdc hgp chit hitu co bay phan trade (cOng IX va 11,0). Bude dau tién cia co ché la sy hinh thanh cu ion halonium (bridged halonium ion), chit khong phai 1a carbocation (Hinh 2.21a). Trong ion halonium, nguyén tir halogen duge lién két véi hai carbon va nguyén tir halogen mang dign tich duong. Cha y ring cde carbon va halogen trong ion halonium théa quy tée bat tir (octet rule), Luu ¥ vé syt di chuyén cia dlign tir xdy ra trong sy hinh thanh eta ion halonium. Cap electron trong lién két rela alkene hudng t6i nguyén tir chlorine. Khi idu nay xay ra, mOt cp electron tir mot nguyén tir chlorine hung tei ‘mé6t trong hai nguyén tir carbon va lién két Cl-Cl dang gay. 6 bude tiép theo (Hinh 2.21b), ion Cl tn cong mot nguy€n tir carbon trong ion halonium ti phia sau boi vi cu ion halonium d& chan sy tin cOng tir phia true. ‘cn, Vieinal dibalide Hinh 2.21: Co ché phan tg chlorine héa ciia 2-methyl-1-propene 6. Phiin ing thé thin dign tir trén nhan hurong phuong (cleetrophilie aromatic substitution) ‘Chang ta da thdy trong phan trude alkene thuéng tham gia cdc phan img céng. Véi benzene, phan img cng nhur minh hoa dui day khong xay ra. x Aiioncs | a S ‘not occur ( Jey Se [ LA Benzene va cée din xudt cua né thong phin img voi chét than tir trong cdc phan img thé, Phuong trinh tng quat cho phan img gitta benzene va chit than dign ti BY nhur sau: H E ey 1— ee aL‘Chuong 2: Phan img cia cdc hgp chit hitu co Phan ting la phan img thé than dign tir bai vi mt trong nhiing nguyén tik hydrogen cia benzene duoc thay thé béi chat thn dién tir E. Co ché phan img gém hai bude (Hinh 2.22). Trong bude dau tin, chét than dign tir nan mt c§p electron tir hé théng ela ving benzene dé hinh thanh carbocation, CcHsE* duge goi la ion arenium. Trong bude thir hai, ion arenium mit mot proton. Vé co bin, phan img thé than dign tir theo trinh ty &6 1g - tch Togi, Luu ¥ ring trong bude Y’ khong hoat d6ng nhu 1a chat thin hach tan céng vao nguyén tir carbon mang dién tich duong cia ion thir hai, Y" hoat dng nhu mét base va tin céng vao nguyén tir H trén carbon ndi ve arenium vi hai I do: ‘Thir nhit, dign tich duong cua ion arenium khéng phai dinh vj trén mot nguyén tir carbon mi né durge chia 36 bing nhau trén ba carbon (Hinh 2.23) va do dé eée carbon nay chi mang mét phan dién tich duong. Thir hai, quan trong hon, néu Y~tén cng va tgo lién két ‘véi mét trong cic carbon mang dign tich dong mét phin 46, sin phim thu duge khéng huong phuong va do do kém bén hon. © SS Hinh 2.23: Ba cdu triic dong gop tuong duong nhau cho cau trie Col Phan ing nitrate héa (nitration): phan dng thé -H bing -NO, é thay thé nguyén tir H ca benzene bang nhém nitro -NO», benzene phan img voi hin hyp: acid sulfuric (H)SO4) va acid nitric (HINO;). Phin tmg cia HSO, vi HINOs tao ra ion nitronium NOs" HNO; + 2H3$0, — O=N*=0 + H,0* + 2HS0, Phan tng nitrat hoa benzene gdm hai bude. Budc dau tién, nguyén tir nitrogen cia ion nitronium nh§n d6i dign tir tir hé théng cia ving benzene, ndi C-N dugc hinh thanh. 2‘Chuong 2: Phan img cia cdc hgp chit hitu co = | I 10: Bude thir hai, ion arenium bj deproton héa bri HSO,' tao ra nitrobenzene 10: ; I. ae —s—g —— | + HoO—S—on 2 1: 6 Ninbenzne Phan tng halogen héa (halogenation) Benzene cé thé chuyén héa thanh chlorobenzene hay bromobenzene bing cach cho benzene phan (img véi Cl: hay Brz dust sy hign dign ca xite tic thich hop. Phuong trinh phan img cho nhimg chuyén héa nay nhu sau: cl AIC, +a, + HEL ‘Trong céc phan img nay, chit x trung gian s¢ phan ting véi benzene. Vi dy Cl; sé phan ting véi AICI; tgo thinh C\"AICLy va phan hha benzene dign ra nhu sau: tie phan img véi Cla vA Bry tao thinh chat trung gian, chat cl AY J + HCI + AICI, A 43,