| — CHAPTER-5 | AROMATIC HYDROCARBONS | Avamatic hydvacavkens axe organic campaunds possessing axvama. | (amelt (Fragrance). Althaugh this atribudte is applicable for majouty of |‘ axamatic hydvocarkans, the tow ‘arematicity’ can be nucstigated by zonsideving modern theouiks. According to modeun sheowts. aromatic hydvoca- ‘vbons should be: “= planar ~cydie* ~ contains conjugated n-eledyon system. ~ contains (4n42)rt-2ledven system. |The commen, fealunes of avamatic hydrocavhans arc : 1 They ave highly stable. 2. They prefer to undergo substitution veaction Ahan addition reaction. 3. U buon auth spot flame. 4. They are walstant towards oxidation. Aromatic hydrocarbons always retain aheiy conjugated‘ Ti-vlectvon System, uahile aveying cu organic wackion. mis as possible by undergning subslitubian ‘action than addition reaction’. °since the nucleophile experiences repulse antevactons from the 2, dlecrons cloud of benzene ving .arematie hydrocarbons dn NOL nds, nucleaphilie substitutdan yeactiar. Bact for positively Ahaxged oly eobvophil zhe urtevacians auth St-electron coud of benzene ‘cing 45 highwr. try lappreach of s1-clectrons become Lasy and. avomahi, hydvocaxtons 5 ngien eledvaphilie substitution yeaction: /NITRATION Natvation is cauied out using a mimture of con-Hago, and. con. tines (nitvating miccture) at (00°C. Ut 23 an saample of cledvophilic subetisuan 1 } NO2 loorc netroberizene MECHANISM. The Llecwephilic. sxubatitution Jakes place iin three steps |LGeneration of electrophile H * t H-O—Noz + H*# —> NOs Noa —+ t20-+ Not 2. Attack &F electrophile on benzene The electvophite initially approach wt- electron doud to form a st canplet | Which suddenly changes to © Complere.c- complece which see gotsetabilised, thrvaugh vesonance. C +N} —> C No}: | NO» err NO2 Co Nos —>| ey. — Cyn o complex C)Loss of proton The eee vetained by the Lees of a proten | a NO2 | aN SULPHONATION Sulphonaiton is cavcied, ud by teating benzene uth conc-H2s04 at 60°C 03H conc. #2804 (oy 60°C . 2 : Benzene ‘sulphone acid.” MECHANISM a) Generation of electrophile ai Has04 A . H-O-so3H+ H+——> H~ oo S03H +H604 -——> H803 + H20-+HS04 H b) Atlack of electrophile S03H 603H gosh H cr 4 S03H—— = Ee, > OE eA° Loss of - proton a WD $03H ‘On Cm ; ae | HALOGENATION 1. CHLORINATION Chovinatian is .cowned.out by treating benzene auith Cla in presenceof Fecls. Fects act as a halogen cariey fer Louis acd: MECHANISM .. a) Generation of electrophilé Cle wad with Fecls sorects and ‘lecinphile "lb bbiaghila generation. As possible dus to Louis avidity of Fects ClHCl+ Fecls > Cl*-+Fecla | b)Etectrophile attack Se te c) Coss of proton o ao BROMINATION. Benzene is heated uuth' Bin aA, presence of FeBrga)Generation of ‘electrophile | Br- Br + FeBr3 ——> Br*+ FeB1y, b Attack of A = _ Br Br we SR Or Ce a CH Ohoss of proton ce 4g co” -Ht FRIEDEL CRAFTS _ALKYLATION Wn Fuiedel (vag Alkylation, benzene is dveated uith an alkyl halide ah presence of unbydvans AlCls Zo foun alkylated product. cH3 J cHac! /unhydraus Alcls @) MECHANISM a) Generation of electrophile ; Alkyl halide vat avith unhydvaus AICl3 to fou ihe slectvophile (methyl chloride) ; cHacl -F AlGla—> CHa +All 1) Flectrophile attack ee nay ae ne o ® cra OK Cfro8 — Cro fetc) Loss of proton Q ey cH3 CH H C2 Benzene when treated with prapyl chloide in Fuedel (rafts Mkylation giues Asopropiyl benzene (aamency drstoad. of propyl benzene. why? CHa-Ctle-CH3 ~CH2-CH2- Cc a . () GHa-CHa-CHa-Cl/AICI3 (0) (Popyl berviene) : munior | “" LS CHa~ CH-CH3 ° isopropyl benzene _@seneration of electrophile When propyl carbocation is genovated, as the antewmecuate. tt sunderge | carbocation Yeanmangoment an foun sopropyl cavhocabion which is mow stable than propyl cubation. Now the Jatipropyl carbocation couey oui, olecrophilie substitution to feum isopopyl-benzene as the mgjor Produc. “CHa-CHa~CHa-Cl-+AlCla——» CHa —CH2—CHa +AICIA J + hers CH3- CH-CH3 + AICI, Attack of electrophile chs ii CH3-C-CH3 \ x . ® ch-cHa (Shred ote om = - Cy|FRIEDEL'S CRAFTS ACYLATION, Oo In Fubdels (rast Aqylation,avamatic hydvecerbon is ducaded auth CH3cocl un presence of wthydvous AICls O=C-CH3 (0) suecoci/atr Cy cHacoci/Alcls, 1. Acetophenone ajgeneration o electrophile oO. ° Ul tl - CH3—C— Cl-+AIClIs —> CH3—C* + AICI4 | byElectrophile attack ; : ° P 2 G wo C- CH c-cks td Cc + cHa-C+ = (5 H s H aa Zz en —> A te i | 0) Loss of of pene ont CH3 bs CH3 “oF - at gyndthetic utility of Fund cepts sugltion alkylbenzores Friedel. vagts Aaylation As used to. puepane those which cannot be dovedly syrhonised aheaugh Alkylation veaainns. in dus waction. ane writially sponed Produc 48 cutjeded do dlemenson reduction to get Ine veduclion predud.| 0 | _ : i a : C—CH2-CH3 | g I cla | (°) 4+ cHa-cha-c-cl A> (0) | O=C-CH2-CH3 CHa-CH2-CH? | Zn (Hg)/HCl. Z Qemensan Reduc.ion bceictertatay OF SUBSTITUTION In substituted. dhe benzone.the substiluded wich 1s alwody puesert ir | ahe ving contvols the position of sncoming subslituents. The substitivents can be clastifted irilo dun types namely: Adiuating substituents axe electron wleasing in nature and they | wleases the sledwvan density to ae buvzene ving. The ving becames more dive for undergoing Suvdhor slecuophilic substitution: Hence they axe eumed, as adivaling substituents. | 2g: ~OH, NH2,-R,-X ner substituent -NH2 group. , ; : Gi NHa fi" NH2 Ge -3 a te 7in this case, the ovtho and para positions has highor densdy and, thu Arvoming electvaphiles. pr cfr to atlack at ecthoy ortho oy para positions in General the electvan releastig subslituonts ave puho, para diucors 2: Deackiuating | substituents / Pecan wuithcvauing subsiisnis Deactivating substituents axe eledyon “uidhdlcansing sn nabs ond. ‘ahey wuthdvaw electra density from she ving. Now the wng beens deartivated fey undergouig electaphili subeteuclinn. Hence Aes | subshituerts ave called deactivating substituents. a=0 £g:=COOH,-CN,C.NO2 dani se dhadttialing -Bat'os Wixe greUP | On yO oN eo Oyo ON FO" Nee O- —O-O-0 | Inthe case of election suithdvawing substduonts.zhe metapesasc has highor olectvon density ahan ortho ane. para positions ie flectran wuidndraung substituents ave meta divectors: INFLUENCE OF SUBSTITUENTS ON ELECTROPHILIC SUBSTITUTION A) Activating substituents ° ! Cansidey dhe elodteaphiis substiuction of Toluene.cHa CHS. cH3 See Gg | cane H2$04 02 a)outhe attack Hi 3 Hs CHs * CHS CHa | 2 NOGA Non Noo 083 |" ” | i athe atackane of the sanatng atucture As highly stanls. | “meta attack : ; ? cHs SENGHE fy cus H3 2 + N H p Co NO2 NO2 < NG? tg Noo | | o)pava. attack § | CH3 cH3 - a Z 5 i ¢ | \ by meta attack ¢ | CH3 CHa CH3 CH3 (O* 9-0-0 4 Noe H Noa H Noe wa. Opa CHa CHa CHa cHe + x | oO we CP <—. o —- we "Nos H” Noa Ho Noe _Ohe vesonating shruuye is ctabinUn the case of xlectuan veleasing substitution, ahe incomg elcetvephile caxty out olertvophilic substitutian at ortho aul paxa positions and stable vesonabiig aructurcs are Jovined . Herve for election veleasing substituents, oho and para axe the proforved sults for sleuvophibic subshitudion. > - 8) Rectan wwihdvauidig subsditucrs @nsider the nitration of nitrobenzene * NO2 NOz cane. HNO3 Co o> cone: H2504, Noa a m+ rutrebenzne dee | ne S-N=0 O-N=0 | | pene atiale \ 6-N=0 o- CJ ne By oo, th No2 NOa NOz Fer meta attack, all ane reaonalirg strucures are comparvaticly unélanle-% “O -N=0 O-N=0 O-N=0 0- N=o Co + “ N03 — [TS] o [J Oo FL x) > H Nor. HONO2 HW” Now | Fey pava atiack,one of ahe vesenaling stuudure is highly unstable. In Geneval,an ahe case of electron suthdvawing euubstetution, Ae. slectvophilis substitution takes place al meta position. Identify the products of the folloming woadtion CHO CHO () cla/Fecla Cl > cl CH3 CHa CHa (o) cane: #9504 oye" —_ . ° $03 be . o- methyl benzene é mmathyl honaovte \ sulphantc aed sulphonic acta