_ NOMENCLATURE Benzene and its homologues are frequently called by the Common Names which are 2 IUPAC system. The homologues of benzene having a single alkyl group are named as -ylbenzenes. These are made of a benzene ring to which is attached the alkyl group. The alkyl sroup bonded to a ring carbon is designated as the Side-Chain. CH.CH. cua Toluene Ethylbenzene Cumene Bonners (Methylbenzene) (|sopropylbenzene) Dimethylbenzenes have the common name Xylenes. ‘The three isomeric xylenes are : CH. CHs CHg s i Oo. ‘CH CH ‘o-xylene mXylene f p-xyleneie tan i i i 1es, the positions of ‘Trimethylbenzenes are invariably assigned systematic nam« shown by numbers. The three isomeric trimethylbenzenes are named as follows : Fo CHs re a 4 oc oo” ia CHs H,C" cH, cat? CH3 1,2,4-Trimethylbenzene 1,3,5-Trimethybenzeng 1,2,3-Trimethylbenzene Aryl Groups. The groups resulting from arenes by dropping a H atom of the been sing called aryl groups (Ar). me 6 6 6 OME. Phenyl (Ph) o-Tolyl mTolyl pTolyl Aralkyl Groups. The groups derived by removal of H atom from the side-chain ar called ray groups. The groups furnished by toluene are I I O- OF OF Benzyl Benzal Benzo. STRUCTURE OF BENZENE ‘The structure of benzene has been derived as follows : (1) Molecular Formula. Elemental analysis and molecular weight determination showed that benzene had the molecular formula CH. This indicated that benzene was a highly unsaturated compound (compare it with n-hexane, CsH,,). @) Straight-Chain Structure Not Possible. Benzene could be constructed as a straight-chaino« ring compound having double (C=C) and/or triple (C=C) bonds. But benzene did not behave like alkenes or alkynes. It did not decolorize bromine in carbon tetrachloride or cold. aqueous potassium permanganate. It did not add water in the presence of acids. Bra/CCl, ee No Reaction Dilute cold Tao —> No Reaction Benzene KMInO, > No Reaction a ‘of Cyclic Structure. (a) Substitution of Benzene. Benzene reacted with eBr; (catalyst) to form monobromobenzene.SMOLOGUES Ss 691 CoH +. Br, ~FeBty clare Benzene cue HBr Moben; ect that only On monobrome and ny Womerie poe The Navoms in benzene Were ident pee ical, ure of Six CarbONS and to each IS Could be ct ( lucts Were obtained indicated that all six PRPC OMIy if benzene had a cyelic ition of Hydrogen drogen, Addition of Hydrogen, 0 give cyclohexane, lyst CoHs + 3H, We Ella Benzene Ta Usually i) Hoy Oy written as There were two objections : @ Ifthe Kekule's structure was correct, there should exist two ortho irs of dibromobenzene, In one isomer, the two bromine atoms should be on carbons that are iected by a double bond, as shown in structure (a). In the other isomer, the bromines should be on id, as shown in Structure (6). In fact, only one ortho-dibromobenzene Br Br Br. Br 2Brp O FeBr, 4 (a) (b) To overcome thi 442) in rapid eq is objection, Kekule further suggested that benzene was a mixture of two forms uilibrium, oe tures failed to explain why benzene with three double bonds did not give ther alkenes, For example, benzene did not react with HBror Bry inCCl,. >) Resonance Description of Benzene. The phenomenon in which two or more structures can ‘riten fora Substance which involve identical positions of atoms is called Resonance. The seal -_ © Of the molecule is said to be Resonance Hybrid of various possible alternative structures. “ative structures are referred to as the Resonance Structures or Contributing Forms. Kekule's struct "lon reactions like ot692 | CHAPTER 33 tructures is used to represent the re; double headed arrow (<>) between the resonance 5 our ey hybrid. Thus in the case of benzene, Kekule's structures (1) and (2) repre resonance structure” ‘Actual structure of the molecule may be represented as hybrid of these two resonance structures, by the single structural formula (3). a-O-9 1 2 3 tructures (1) and (2) are not the It should be clearly understood that the fesonance st structures of the benzene molecule. They exist only in theory. None of these structures adequate, represents the molecule. In resonance theory, we view the benzene molecule (which of courseis are i i i structures. entity) as being hybrid of these two hypothetical resonance stru Tok at the structures (1 and 2) carefully. All single bonds in structure (1) are double bonds structure (2), that is consider a hybrid of them, then the carbon-carbon bonds in benzene are neithe, single bonds nor double bonds. Rather, they are something halfway between. This is exactly What we find experimentally. Spectroscopic measurements show that benzene is planar and that all of jj carbon-carbon bonds are of equal length, 1.40 A. This value lies in between the carbon-carbon single bond length (1.54 A) and the carbon-carbon double bond length 1.34 A). \ / c=C K@) zC 1.344 140A Double-bond length Benzene-bond length 154A Single-bond length Resonance hybrid is more stable than any of its contributing structures. For benzene, the stability due to resonance is so great that 1-bonds of the molecule will normally resist breaking. This explains lack of reactivity of benzene towards addition. (© Molecular Orbital Structure of Benzene. The structure of benzene is best described in terms of the modern molecular orbital theory. All six carbon atoms in benzene are sp” hybridized. The sp” hybrid orbitals overlap with each other and with s orbitals of the six hydrogen atoms forming C-CandC-H o bonds (Fig. 33.1). s-sp* CHe bond QW c LO sp-sp° c-co bond OTRAS Formation of o-bonds in benzene.BENZENE AND ITS HOMOLOGUES sS 693 It fi ce the o-bonds 3 com Overlap of planar sp? orbitals, all carbon and hydrogen atoms in ene ie in the same plane, i‘ ‘O-bonds in benzene lie in one Plane and all bond angles are 120° \ } Co. ion Le HS eg 120" yen g Q H 4 Fig. 33.2. All o-bonds in benzene lie in one pl: All bond angles are 120°. CARES ‘Also each carbon atom in benzene possesses an unhybridized p-orbital containing one electron. ce p-orbitals are perpendicular to the plane of o-bonds, The lateral overlap of these p-orbitals jyces a molecular orbital containing six electrons (Fig. 33.3). One half of this x molecular orbital ‘above and the other half lies below the plane of the G-bonds. a— Porbitals Le Lee p=, - Ss Fig. 33.3. Formation of x molecular orbital in benzene. Khe (a) (b) ms in benzene are sp? hybridized. (a) The Orbital structure of benzene. All carbons ator is a iene overtap. Al carbon-carbon and carbon-hydrogen « bonds ed by oreo c bonds in benzene lie in one plane. (b) All carbon atoms in benzene have a p them. (c) The delocalized x molecular orbital is formed bythe rei ‘of the six porbi (c) These p orbitals overlap to forma delocalized x molecular \. i sees has actually shown that the stabilization energy of @ deletes t peolecnlen gene = benzene, is 36 kcal/mole compared to the p-orbitals forming € - nary FeiGrhichitiel S-cyclohexatriene (Kekule structure). Thus benzene gives substitution reactions : bility of the benzene ring is retained. er694 | CHAPTEN OLY sented : ‘There are three ways in which benzene can be repre: ind ~~ Co O be G: Hye ‘Short-hand H Kekule Expanded form structure representation i imply hexagon with a circle ing, hand representation of benzene is simp! v sie A Se else? pital. In this book short-hand representation has been used grt Se Kukale structure has been used only in describing the reaction mechanisms where we a "5 cl i track of the bonding electrons. INE RESONANCE ENERGY OF BENZE! : : Benzene's special stability is due to the formation of the delocalized n molecular orbital magnitude of this extra stability can be estimated by measuring the changes in heat of hydrogens Vmol, a va, that are associated with reactions. Hydrogenation of cyclohexene evolves 28.6 kcal Vahy typical for hydrogenation of alkenes. O Ee Na ©) + 28.6 kcal Hydrogenation of both double bonds of 1,3-cyclohexadiene evolves 54.4 kcal/mol, Approximately double the amount observed for cyclohexene. oj ens eo + 55.4 kcal ig three ordinary double bonds, The molecule of 1,3,5-cyclohexatriene (Kekule structure), containin; s to produce it yields benzene. We would, however, expect comles is hypothetical-any efforts hydrogenation of the unknown 1,3,5-cyclohexatriene to evolve approximately 3 x 28.6 or 85.8 kcalinol O aha ——> e + 85.8 kcal Hypothetical Cyclohexane 1,3,5-Cyclohexatriene Hydrogenation of benzene gives only 49.8 kcal/mole. oO PBHo\ o>. i) + 49.8 kcal ee ge ae makes these energy relationships more evident. The 36 keal difference between tie ar on be hydrogenation of benzene and that estimated for hydrogenation of a compoun! Rees ea een 's the added stability. This added stability is sometimes i energy is a measure of how stable resonance hybrid is than its extreme resonance structures, nachos .Ci (Cyclohexane) Fig. 3.4. Heats evolved on hyd rogenation of one mole of lic qaTiciTY (HUCKEL RULE) some cyclic compounds. “the aromatic compounds apparently contain alternate double and si : zy 5 c Je and single bonds in acyclic structure, mble benzens th eeerd peu vice ‘They undergo substitution rather than addition reactions. rr is called Aromatic Character or Aromaticity. Aromaticity is, in fact, a resel is characteristic 2 hybridi: Nottie yperty of the sp hybridized planar rings in which the p orbitals (one on each atom) allow cyclic alization of T electrons. On the basis of the above considerations, can be laid down criteria or rules which help us in wing whether a particular compound is aromatic or non-aromatic. Rule 1. An aromatic compound is cyclic and planar. Rule2, Each atom in an aromatic ring has a p orbit continuous overlap is possible around the ring. ule3, The cyclic 7 molecular orbital (electron cloud) formed by overlap of orbitals must contain (4n+2) Telectrons, where n= integer 0, 1,2, 3ete. This is known as Huckel Rule. les to the following examples : Let us apply these rul Benzene Cycloheptatriene Cyclooctatetraene Naphthalene Benzene. It is a cyclic and planar compound. Ithas ap orbital on each carbon of the ring involved 2 double bond, Ithas three double bonds and six qrelectrons, which isin. accordance with Huckel rule. tal, These p orbitals must be parallel so that a 4n+2=6 ors Ane » anne) ond n=l : ( ycloheptatriene. It is cyclic and planar. Ithas three double bonds and six W electrons Butone of rbons is saturated and does not possess @P orbital. Hence continuous overlap around the ring ic. 2 possible. This compound is, therefore, non-696 | CHAPTER 33 ; n each atom of the ring. Th Cyclooctatetraene. Itis cyclic and has ap orbital o1 Hicks satisfied, since there are 871 electrons. € 4n+2=8 equals 4n= ic. Moreover, it 6 ons .s been determined that cyclooet The compound is non-aromat has alctaene jg Janar but tub-shaped. : Ban Heterocyclic Aromatics, Heterocyclic compoun aromaticity rules. Examples of such heterocyclics are a Ooo Oe , H Pyridit Pyrole Uren Thiophene yridine yclic compounds pyrrole, furan, and thi Let us first consider the 5-membered heteroc . ; «d:(1) they are cyclic planar ; (2) each has a p orbital on every % atom ;and (3) each observes Huckel rule. For example, in furan there are four p orbitals on theo carbons, containing one electron each. The N atom (also sp” hybridized) has an unused pair electrons in a p orbital parallel with the other four p orbitals. The four p electrons of carbons and, twoelectrons of N atom form acyclic? MO. However, in furan and thiophene, there are two unused eleciny pairs with O or S atom, One of these is in a p orbital at right angles to the ring and is not tobe coun, Similarly, in pyridine with three double bonds, each ring atom has ap orbital, and the six electron, form the 7 MO. Therefore, the compound is aromatic. The unshared electron pair on nitrogen ig perpendicular to the ring and is not to be counted while applying Huckel rule. ds also behave as aromatic if they op Y the Applying aromaticity rules we fin v P oe H sp*-sp* Delocalized Delocalized LOD xMO MO Ne N WS H noh-bending electron pair (a) (b) Fig. 33.5. (a) In pyrrole, the five parallel i init i i the Porbitals containing six electrons form @ oes a te In ee i six p orbitals containing six electrons form & , the unused sp? orbital of nit ini electrons remains as such. regen contanng te ota Antiaroi ic, E matic compounds. Cyclic, planar and completely conjugated compounds that con slectrons are especially unstable and are said to be antiaromatic, For example, eye | antiaromatic and very unstable because it contains 4m electrons, ; | Cyclobutadiene is planar, cyclic and completely conjugated. It has 4x Cyclobutadiene electrons. Therefore, it is antiaromatic.iar ee AND pe ANNULENES 2 TTS Homo pt Ame annulene has been p; OGUES 697 see single and double bonds. et asa a is [6 . The ring size rer’ name eienzene 8 Jannulene and cyclooctaree ofa annulene of 080cyclic compounds having ne is, (8lonnutene toby number in brackets. Nzene O [6] annulene Cyclooctatet 's rule predicts tl rasenen He Hees planar cafe sie will be Lak ea eo Or example, [6lannulene ig ae have (4n+2) ic whereas (8]annulene is ’ points to Remember K ture and Reactivity of Benzene Benzene has a cyclic, planar, hexagonal 2 % onal structure, All ae my bond lengths are identical and are intermedi boot c=c oa Gontsabere MeN eetade tinaa tn ene ee hydrogens in i ternate single silos Seite aca I hye ae Se oe that in baa a yaar is replaced. Only one product is formed. Always mosubstituti < i “8 cee stitution leads to a single product. Disubstitution yields All carbon atoms in benzene are sp” hybridized. Typical reactions of benzene are substitution reactions. Addition reactions can be induced, but special conditions are necessary. 4 ENE, CeHg Benzene ring is present in all arenes and their derivatives. Therefore, our study omatic compounds must begin with that of benzene. This will lay a sound dation of the structural features and principles encountered in the study of all .s of aromatic compounds. (GE SCALE PREPARATION OF BENZENE (1) From Petroleum. We have already learnt that the Aromatization or Platforming of Co ion of petroleum naphtha yields a mixture of benzene, toluene, and xylenes. PUAIOs CHg(CH2)aCHs ore, 158m” i ate n-Hexane Benzene CH, PVAI2O3 4H, CHa(CHz)sCHs avr, sam” ya ‘Heptane poniene neHep' CH CH2CH3 tes a CHy + CHg(CHa)eCHs 00" 15 am n-Octane Ethylbenzene698 | cHaPteR 33 Benzene is recovered from the mixture by solvent extraction and fractional distillation IPurities ic is finally washed with water ; dried, and distilled. The frac Phenol) some toluene, and thiophene (C,H,S). This is refractionated and the fash” Collected between 80-82°C is almost pure benzene. Traces of thiophene present as impurity ig ae from the product by heating it with hydrogen under Pressure at 400°C in presence of a cataynrvd redistillation. Ystang Ni LENT any Heat” CHeCH2CH2CH, + Hos s Thiophene SMALL SCALE PREPARATION OF BENZENE Benzene is obtained on large scale from petroleum and coal-tar. The s laboratory scale are of academic interest only. Benzene is obtained : (D_ By passing acetylene through red-hot tube at 500°C aHo=on ote! O tube Acetylene Benzene (2) By heating benzoic acid or its sodium salt with soda-lime (NaOH + CaO). oO I C—ONa + NaH —%, © + Na,CO3 Sodium benzoate (3) By heating phenol with zinc dust. ©v-o + Zn o> + ZnO Phenol Benzene (@ By treating chlorobenzene with magnesium followed by treatment with dilute HCL O- * Oe =O Chlorobenzene Phenyimagnesium chloride PHYSICAL PROPERTIES OF BENZENE (1) Benzene is a colorless liquid, bp 80.1°C, mp 5.5°C : 2) Itis insoluble in water, forming the upper of two layers when mixéd. Itis miscible with aleobo, ether, and chloroform. (3) Benzene itself is a good solvent for many organic and inorganic substances e.g., fat, resi, and iodine, Its vapors are highly toxic which on inhalation produce loss of consciousness. Benzem® in the long run can prove fatal, destroying the red and white blood corpuscles. burns with a luminous, sooty flame, in contrast to alkanes and alkenes which usually bu! h flame. 5 ne and its derivatives show characteristic IR spectrum. The two bands near 1600 ci” * have been correlated with the stretching of the carbon-carbon bonds of the aroma sharp bands near 3030 cm” are caused by aromatic C-H bond. n-Butane thetic methods Benzene BenzeneREACTIO! BENZENE AND : eemrowemene Ronn SS on principal tyPes of reactions of Electrophilic Substitution Reacti n°? Addition Reactions Reactions 0 Oxidation Reactions ee N On: Bultonation Nitration ‘=O Halogenation Acylation Electrophilic aromatic ‘substitution reactions. FLECTROPHILIC SUBSTITUTION REACTIONS Benzene wee electrophilic Substitution reactions. The benzene ring with its delocalized trons is an el lectron-rich system. It is attacked by electrophiles, giving substitution products. reactions can be represented as : : i E e. i ema Se (O + H—Nu ‘Substitution product Where E* is any electrophile and Nu: is a nucleophile. Such reactions in which hydrogen atom of ‘aromatic ring is replaced by an electrophile are called electrophilic aromatic substitution reactions. GENERAL MECHANISM. All electrophilic aromatic substitution reactions follow the same -step mechanism : Step 1. Formation of an electrophile. E—Nu + [Catalyst] —* E* + Nu-{Cataiyst] Step2. The electrophile attacks the aromatic ring to form a carbonium ion. ~ Benzet Carbonium ion ne : : ahybrid of the following three structures: s resonance-stabilized. Itis 5 The intermediate ion it H {! E gh - GeOi} 700 | CHAPTER 33 Step 3. Loss of proton gives the substitution product. eR E Nu-Cataiyet SS + HONU + Cataiyat Carbonium ion Substitution product Why benzene undergoes electrophilic substitution reactions whereas alkenes . Feactions ? Both benzene and alkenes are susceptible to electrophilic attack because of thei, Telectrons. Both react with electrophiles to form stable carbonium i Terenas ons. oe coc +e — de uv \ Electrophilic addition to an alkene Electrophilic addition to benzene But similarity ends at this point. The carbonium ion produced from the alkene Usually combiag with a nucleophile to give the overall addition product : | eee oe * Nur —* Nu~G—Gae If this happened to benzene, the product would no longer be aromatic, The esonance energy (stabilizing energy) of benzene would be lost. Instead, the nucleophile removes a proton from the carbonium ion intermediate. The loss of proton allows the electrons from the C-H bond to 80 back, into the ring and regenerate the aromatic system, Net change is the replacement of a hydrogen atom by an electrophile : Hae E Oho (1) Halogenation. Benzene reacts with chlorine in the presence of FeCl; or AlCls at 0a temperature to form chlorobenzene. Iron powder can be used in place of ferric chloride (2Fe + 3Cly = 2FeCl,). a FeCl + Cli =a + HCl Benzene Chlorobenzene MECHANISM. Following steps are involved: Step 1. Formation of the electrophile (Cl*). cE + FeCl; —> cr + Fecly Step2. The electrophile attacks the benzene ring to form a carbonium ion. H ooh Benzene Carbonium ionHel + Foci, Br + HBr lobenzene or HNO,, Benzene ey : Py lodobenzene Nitric acid isan oxidizing agent and oxidizes Isto le + CuCl, lee nee Fluorine is very reactive. Polysubstitution takes ine atoms. 2) Nitration. Benzene reacts with concentrated nitric ric acid at 60°C to form nitrobenzene. ia Electrophile place and all benzene hydrogens are replaced by acid in the presence of concentrated NO, + HNO, #80, +. LBD Benzene MECHANISM. Following steps are involved : Nitrobenzene Step 1. Formation of the electrophile (NO}). HNO, + 2H,SOQ, ——> NO$ + 2HSOj + H,0° Step 2. The electrophile attacks the benzene ring to form a carbonium ion. H ce Os Benzene Carbonium ion Step3. Loss of proton yields nitrobenzene. Ham NO, (oe HSO;, Ci + HSO, Nitrobenzene iid leat 1 i trated sulfuric acid at 120°C or fuming sulfuric aci Ca Pee cS a Nate : Fuming sulfuric acid is concentrated sulfuric temperature to give benzenesulfor that contains added sulfur trioxide.702 | CHAPTER 33 Conc. Hex heat SO3H Fuming HeSO, Benzene Benzenesulfonic acid MECHANISM. Following steps are involved : 1, Electrophile is formed. In this reaction the el i Step pl e electrophile is sulfur troy, concentrated sulfuric acid, SO, is produced as follows. In fuming sulfi i 2 5 g Sulfuric acid, this step me 4 because the dissolved SO reacts directly. 2H2S0, === SO3 + H30* + HSO; Step2. The electrophile attacks the benzene ring to form a carbonium ion ° xo aH “ia. CEL. it ‘(ae SO; 2 ° Step 3. Loss of proton. H . A SEN S03 S03 +‘HSO; —> all + HS0, (from step 1) Step4. Addition of proton gives benzenesulfonic acid. SO,H SOs , ae + Hot —> or + HO (from step 1) Benzenesutfonic acid (4) Friedel-Crafts Alkylation. Benzene reacts with alkyl halides in the presence of aluminion chloride to form alkylbenzenes. For example, ik 3 O + CHC! ACh» Oo + HCL Benzene Toluene MECHANISM. Following steps are involved : Step 1. Formation of the electrophile (CH;*). CHCl + *AIC, —> GH + AIC Step 2. The electrophile attacks the benzene ring to give a carbonium ion. H ! Ot oe Chew Benzene Carbonium ion Step3. Loss of proton gives alkylbenzene. ‘eli ee Is ich c / + AIC Toluenei Of certain alkylbenzenes, the reaction e It is difficult to stop the i (D senzenes are also formed, 1°" When one alkyl ne ‘The alkyl groups often tend to io inthe presence of AICI, ai edn-propylbenzene, or Tearrange, For the product is lbopropyiNee when benzene is treated with n- ropyl Pylbenzene (also Bred called cumene) rather than the gts CH—CH, O * CHeCHcH,c) Ah, oO : Benzene 'sopropylbenzene This is because the Friedel-Crafts alkylation invol 1). These carbonium ions can undergo rearrange (Gel) Friedel-Crafts Acylation, Benzene Teacts w ‘pfaluminium: chloride to give aromatic ketones, Fore: ves formation of carbonium ion electrophiles ‘ment before attacking the benzene ring (Step 2). ith acid chlorides (or anhydrides) in the presence xample, a e C—CHy O + CHsG—c) ACs, Oo + HCI Benzene Acetophenone MECHANISM. Following steps are involved : Step 1. Formation of the electrophile (CH,—¢=0). ° ° I I i CHU cirea ace —>+ CHC + ACh _ Step2. The electrophile attacks the benzene ring to form a carbonium ion. 9 i i‘ Cho and Chew ¢ Carbonium ion Step3. Loss of proton gives an aromatic ketone. t C-CH A Hoe ae CHOLES AICI ita Acetophenone 1 halides ared from alky Bing ther than methyl, ethyl, or alkyl cannot be prepa Or ion nee alles been best prepared by Friedel-Crafts Acylati ul rearrangement, they are uence. For example, O° ° CcH,CHs oe 2 Zn(H9) ’ H. ala ae” GEGiees AICls n-Propylbenzene BenzeneAlkylbenzenes can also be prepared by treatment of benzene with alcohol or an alk presence of an acid catalyst. In each case the initial step involves the formation ofa stay eng fa ion. OH Pe tei - 1250, y oO CH; CHsCH= CH, HPO, Isopropylbenzene Benzene B. ADDITION REACTIONS (6) Addition of Hydrogen. Benzene reacts with hydrogen in the presence. of nickel (0r Plating in) catalyst at 150°C under pressure to form cyclohexane, Ni O + SHo i50°0, preseuts CO Cyclohexane Benzene © Addition of Halogens. Benzene reacis with chlorine (or bromine) in the presence of ly light to form benzene hexachloride (Hexachlorocyclohexane). ce} cl Cl uv O + 8Clh Taye cl cl Benzene cl Benzene hexachloride Benzene hexachloride (BHC) is a powerful insecticide. It is sold under the name Gammexane ot Lindane. MECHANISM. The above reaction involves a free-radical mechanism. UV Cl Toye Ch + Oh H. H. Cl " Hl Cl, H Chain io . O = Os & Cia vo it ae C. OXIDATION REACTIONS (8) Ozonolysis. Benzene reacts with yields glyoxal. ozone to give a triozonide which on treatment with Z0/#2 Q3 +302, 120. HCo=O atid > I CO Oo amas HC=O Benzene Glyoxal Triozonide of Phase Oxidation. Benzene undergoes oxidation with air/oxygen in the prese™ ide (V20s) at 450°C to form maleic anhydride.Benzene WV R REACTIONS jrch Reduction. Ben: ; 10) Bie’ nzene and its dei ahesadienes by treatment with jell GBA Sant reduced to nonconjugated irch reduction provides a convenient method for making a wide eet yi diene variety of interesting and useful 4 H i" HH Naor Li H Ni H H IHa(0), ROH a ‘i = a HH ne 4,4-Cyclohexadiene Writing’ Mechanism of ‘Electrophilic Aromatic ‘Substitution Reactions (i) All electrophilic substitution reactions follow the same 3-step mechanism : Step 1. Formation of an electrophile. Step2. The electrophile attacks the aromatic ring to give resonance-stabilized carbonium ion (also called arenium ion). substitution product. step3. Loss of proton gives the (2) Important electrophiles used in aro! jc substitution and their sources are * Electrophile Source cir Clp +AICls or FeCls Br Bra +AlBrs OF FeBrs NO HNO3+H2SO« SO Conc. HSO4 Fuming H,SOs Rt RX+AIXs (Xx=Clor Br) ROH + H* Analkene + i. i p—6=0 p—c—cl + ACs aa fx : G3) Substi so undergo el yrilic substitution. The group already present bint ae s fnere further substitution occurs (See Chapter 34). on the ring determines W