RAFFLES INSTITUTION YEAR 5 H2 CHEMISTRY 2017 Lecture Notes 12 -Arenes Lecturer: Dr Wong Poh Lee ‘Ms Lee Mei Yin Content ‘Arenes (exemplified by benzene and methylbenzene) 1. Introduction 2. Nomenclature of Benzene Derivatives 3. Benzene — Physical Properties 4. Structure of Benzene 5. Electrophilic Substitution Reactions of Benzene : 6. Reaction with Concentrated Nitric Acid 7. Reaction with Halogens 8. Friedel-Crafts Alkylation & Acylation 9. Other Reactions of Benzene 10. Methylbenzene 11. Reactions of the Side Chain in Alkylbenzenes 12. _Electrophilic Substitution of the Benzene Ring in Methylbenzenes 13, Effect of Substituent Groups 14. Summary Learning outcomes Candidates should be able to: (@) understand mechanisms in terms of organic structure and bonding (b) © @ © @ @ (hy recognise that the mechanisms of polar reactions involve the flow of electrons from electron-rich to ‘electron-poor sites ‘explain, in terms of delocalisation of 1 electrons, the difference between benzene and alkene: () reactivity towards electrophiles (i) _ preference of benzene to undergo substitution rather than addition reaction describe the chemistry of the benzene ring’as exemplified by the following reactions of benzene and ethylbenzene: (electrophilic substitution reactions with chlorine and with bromine (recognise the use of Lewis acid as catalysts) (i) nitration with concentrated nitric acid (recognise concentrated sulfuric acid as a Bransted-Lowry acid catalyst) (ii) Friedel-Crafts alkylation with halogenoalkanes (recognise the use of Lewis acid as catalysts) (describe the mechanism of electrophilic substitution in arenes, using the mono-bromination of benzene as an example (ii) describe the effect of the delocalisation of electrons in arenes in such reactions. describe the chemistry of the alkyl side-chain of benzene ring as exemplified by the following reactions of methylbenzene: (free-radical substitution by chlorine and by bromine (ii) complete oxidation to give benzoic acid predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes depending on reaction conditions apply the knowledge of positions of substitution in the electrophilic substitution reactions of monosubstituted arenes References ‘AcLevel Chemistry (by Ramsden) Chemistry in Context (by Hill and Holman) Organic Chemistry (by David Klein) Organic Chemistry (by LG. Wade) Website: wwnw.chemquide co.ukKE INTRODUCTION Arenes (2ls0 referred to as aromatic hydrocarbons) are hydrocarbons based on the benzene ring as a structural unit Examples of arenes (or aromatic hydrocarbons): © O« Orn O» benzene methybenzene ‘ethylbenzene alkylbenzene naphthalene felaone The term ‘aromatic’ (fragrant) was originally used because the first benzene-like compounds isolated have pleasant smells. However since the vapours are toxic, it is unwise to smell them. The term ‘aromatic’ has been retained to indicate certain chemical characteristics rather than odorous properties. An aromatic compound has special stability. For example, benzene is more stable than if it were to be formulated as a triene (refer to Section 4.2). Aromatic compounds are benzene and those compounds possessing the ring structure of benzene or other molecular structures that resemble benzene in structure and chemical behaviour. The chemistry of arenes will be exemplified by the reactions of benzene and methylbenzene. EA NOMENCLATURE OF BENZENE DERIVATIVES 2.1 Monosubstituted benzene derivatives ‘+ For many of these derivatives, the name of the substituent group is added as a prefix to the word ~benzene. Below are several examples. CH; CH,CH, Nos o ethylbenzene ethylbenzene nitrobenzene _ chlorobenzene. (0r toluene) * Other derivatives have special names which may show no resemblance to the name of the attached ‘substituent group. Some examples are given below. CHO. on NH COOH SO\H benzaldehyde phenol © phenylamnine benzoic acid benzenesulfonic (aniline) benzenecarboxylic acid) ‘acid2.2 Disubstituted benzene derivatives + For disubstituted benzene derivatives, numbers can be used to indicate the relative positions of the ‘two substituents. Br Br er, O O+ =O 4,2-dibromobenzene _—1,3-dibromobenzene _—_1,4-dibromobenzene evthe he fe + If the two substituent groups are different, the names of the groups prefix benzene in alphabetical order. Br CHs : NO, 2-bromomethylbenzene 3-nitromethylbenzene 4-chloronitrobenzene I-brena -2- my | baron Fe mdly! 3 -wtrhasene blow 4 nibobencna + If one of the two substituents is the kind that gives a special name to the moleoule, then the compound is named as a derivative of that special compound. If both substituents give derivatives with special names, then preference is given to the substituent of highest nomenclature priotty Br ho OH 2-bromophenol 4-nitrobenzaldehyde S-hydroxy benzoic acid + Examples of substituents ona side ch: CHC CH.CH,cl CHOICE, a 2-chloroethylbenzene (2-chioroethyl)benzene (1-chloroethy!benzene beddlove -2-elle bar zens 2.3. Polysubstituted benzene derivatives ‘+ If three or more groups are attached to the benzene ring, the numbering is in such a way as to keep the prefix numbers as low as possible and with preference given to the group of highest nomenclature priority ‘+ If one of the groups present gives rise to a compound with a special name, then only two positions of substitution are mentioned. CH on on Br Cl Cl cr ar NO, cH 2,4-dibromomethylbenzene 2-chloro-4-nitrophenol 2,5-ichiow-4-methylphenol 2¢-dibrom Lemlly| beware 32.4 The phenyl and aryl groups + Benzene ring is treated as a substituent and is called a phenyl group when ~ the substituent on the benzene ring has more than six carbon atoms ~ the highest priority functional group is not a substituent on the benzene ring + Phenyl and substituted phenyl groups afe called aryl groups. phenyl group | CHy-CH-CHy CH GH- ClCH, Caceee S-methyl-2-phenylheptane 2-phenylethanol benzyl group Or ‘CH)— Br Orw- vonzy bromide or CoHgCH— or (bromomethy))benzene [EA BENZENE — PHYSICAL PROPERTIES: + Benzene is a colourless liquid with a characteristic odour. + Itis non-polar, insoluble in water and less dense than'water, ed IME: Mid idemubos + tis soluble in all organic solvents, and is itself a good solvent for organic compounds. + Itfreezes at 5.5 °C and boils at 80 °C. + Like all aromatic compounds, it burns with a smoky and luminous flame, owing to its relatively high carbon content. ‘Benzene is a useful chemical “Benzene is a TOXIC chemicall bora iy wed Ur Ste: 1 ata 669 20| Gor i nd te vgs ar Hy hori fr petucin wane Se maties tae tere | O38, 2,803 an he wana ae nhiy 7/7 ee ‘aes Curae ich ewe oma paste ese ane | bacon 9a esane must neue 7" tmorandomaic tov Eecrect asoaet omeascomtpe | gs commit carcnognc Sastre’ ketone pel Somers, ge ond pose | area) i eset oscar sao ee Drea at tea peta a crecece a =EL struc [Candidates should be able to explain, in terms of delocalisation of electrons, the difference between benzene and alkene: |= reactivity towards electrophiles preference of benzene to undergo substitution rather than addition reaction F BENZENE 4.1 Resonance Structure of Benzene % Each of the six carbon atoms in benzene is sp? hybridised. There are three sp? hybrid orbitals and ‘one unhybridised p orbital for each carbon atom, Three sp* hybrid orbitals One unhybridised p orbital + Each C atom has three sp? hybri orbitals that are arranged in a trigonal planar manner. > Two sp? hybrid orbitals are used to Each carbon atom also has an unhybridised p orbital occupied by a single electron Each singly-filed p orbital overlaps sideways overlap head-on with the sp? hybia | “- with the adjacent p orbital on either side. orbitals of two adjacent C atoms to form two C-C ¢ bonds. ‘> One sp? hybrid orbital is used to overlap head-on with the 1s orbital of the H atom to form the C-H « bond > The benzene molecule is entirely planar + This continuous overlap of the p-orbitals results in a cloud of cyclic delocalised x electrons above and below the plane of the ring, ie. resonance is present in benzene, 2 All bond angles in the molecule are TOO foyarl planar { The unique properties of benzene are a | |. fesult of the resonance it possesses. | 4.2 Experimental Evidence of Resonancé Benzene (a) Carbon-carbon bond lenaths If benzene were to have a Kekulé structure (i.e. the cyclohexa-1,3,5-triene structure), there should be two kinds of carbon-carbon bonds in benzene: C-C bonds and C=C bonds. This is not the case. = 2 types of > All the =~ carbon-carbon u carbon- bonds modembenzene | Carbon bonds Kekulé benzene (resonance tybrid) | are identical X-ray diffraction studies actually show that all the carbon-carbon bonds in benzene are identical and equal in length. This agrees with the description of benzene as a resonance hybrid of two Kekulé structures.‘Compound ~ Bond ~ Bond lengthinm cyclohexane | carbon-carbon single bond C—C. 0.154 cyclohexene | carbon-carbon double bond C=C 0.133 benzene carbon-carbon bond C=C 0.139 ‘The measured carbon-carbon bond length (0.139 nm) in benzene is intermediate between the length of a C-C bond (0.154 nm) and that of a C=C bond (0.133 nm), = This indicates that the bonds have partial double bond character. 0 + 4@) —— | + Experimentally, enthalpy change of hydrogenation of cyclohexene = ~120 kJ mol cyclohexene ‘+ If benzene were to have the cyclohexa-1,3,5-triene structure, rare) a then its expected enthalpy change of hydrogenation a 3) (enthalpy change of hydrogenation of cyclohexene) (3) (~120) 360 kJ mot cyclohexa-1,3,5-triene ‘+ Experimentally, enthalpy change of hydrogenation of benzene = —208 kJ mol’ © + 3H) —— 0 ‘+ That is less exothermic than the expected value of corer =360 kJ mor, potential energy Py . - Gorse onan oycoherat,3.5criene enerar ie aH = @)(-120) = 182 kJ mol = 860 kJ mol” benzene Oo @ +3H,(9) es a (0 + Hig) 120 kJ mot Cj ‘+ The Kekulé structures, which contain localized x bonds, are not accurate representations of benzene. oH + Instead, benzene has a structure in which the six x electrons are delocalized. It is the delocalisation of the six x electrons that confers extra stability on benzene and gives benzene its aromatic character. + The extra stability of benzene is reflected by its resonance energy (or delocalisation energy or stabilisation energy), as shown in the diagram above.(c) Benzene undergoes substitution rather than addition reactions If benzene were cycohexa-1,3,S-triene, it is expected to undergo addition reactions which are characteristic of the alkenes. However, under conditions that cause an alkene to undergo rapid addition, benzene either reacts not at all or very slowly. If benzene undergoes addition reactions, its overall-aromatic character (ie. delocalisation of six x electrons) is destroyed, removing the extra stability associated with the delocalisation of the six x : O-» %& CL y Hence, the majority of reactions that benzene undergoes involve substitution in the ring, which takes place with overall retention of aromatic character, ie. retaining the delocalization of the six x electrons in the continuously overlapping p-orbitals. O-»—- Oe — The following properties are a result of the aromatic character of benzene: + All carbon-carbon bonds in benzene are equal and are intermediate in length between single and double bonds. + The enthalpy change of hydrogenation of benzene is less exothermic than expected. + Benzene undergoes substitution reactions rather than addition reactions, Representation of the Benzene ring The benzene is represented by a regular hexagon containing a circle. This representation is useful since it emphasizes the equivalence of the various carbon-carbon bonds. OQ sar never CI CS + Itis understood that a hydrogen atom is attached to each angle of the hexagon, ie. each carbon atom, unless another atom or group is indicated. + The straight ines represent the « bonds joining the carbon atoms. + The circle represents the cloud of six delocalised x electrons.HI_ELECTROPHILIC SUBSTITUTION REACTIONS OF BENZENE Candidates should be able to ‘= understand mechanisms in terms of organic structure and bonding ‘+ recognise that the mechanisms of polar reactions involve the flow of electrons from electron-ich to electron-poor sites + describe the chemistry of the benzene ring (as exemplified by the following reactions of benzene and methyleenzene) as involving electrophilic substitution reactions + _describe the effect ofthe delocalisation of electrons in arenes in such reactions + The availability of six x electrons in benzene makes the benzene ring electron ich. The benzene ring thus serves as a Source of electrons for electrophilic reagents. ‘+ The main reactions of benzene are characterised by electrophilic substitution in the benzene ring in which benzene reacts with an electrophile (E") which replaces one or more hydrogen atoms in the ring. Ors — electron-rich electrophile benzene + Examples of electrophilic substitution reactions of benzene (and related aromatic compounds) are: crema + nan OS) + sno, —ssaamBEHE HE. FP) 0, «yo halogenation + Fel, 2 | (eg. chlorination) © oa ors Hel AlCl, 3 | Friedel-Crafts alkylation + crcl es cH, + Hel + Each electrophilic substitution reaction of benzene involves essentially the following steps: Generation of the | « The electrophile, E*, is first generated in the reaction mixture. Clectrophile E* | « This is followed by a two-step electrophilic substitution reaction mechanism. Electrophilic Step 1 : ae attack by E* on HAE | 2 This carbon atom is sp? | the benzene ring <— hybridised. Udrbedod) to form a + gr — sow i carbocation [__femain sp? hybridised, Chg + This step is the slow step ie. the rate-determining step because it involves the destruction of the aromaticity of the benzene ring (ie. it destroys the extra stability associated with the delocalisation of the six electrons in the benzene ring), + In this step, the electrophile attacks the electron-rich benzene ring and takes two electrons of the six-electron x system to form a c bond to one carbon atom of the benzene ring. + The aromatic character of the benzene ring is destroyed and a carbocation is formed. This carbocation is resonance-stabilised but not aromatic. a carbocation 8from the carbocation to form the product Loss ofproton | Step 2 H. Z ‘al This step is a fast step. In this step, the carbocation intermediate loses a proton from the carbon atom that bears the electrophile, The two electrons that bonded this proton to carbon become a part of the delocalised n-electron system. The aromatic character of the benzene ring substituted product is formed, restored and the Energy Profile potential eneegy Summary of electrophilic substitution reactions of benzene reactoncooinate Fey > Eos. Reaction Reagent Catalyst Electrophile ‘Organic product Nitration ‘conc. HNO ‘cone. H:SO« NOs (CO) no; Halogenation (e.g. bromination) Bre FeBrs Br (for simplicity) Oye Friedel-Crafts alkylation AIC: rg R Friedel-Crafts acylation AIC R-G O Ove °ic EACTION WITH CONCENTRATED NITRIC ACID ‘Candidates should be able to describe the chemistry of the benzene fing as exemplified by the following reactions of benzene ‘and methylbenzene: + nitration with concentrated nitric acid (recognise concentrated sulfuric acid as a Brensted-Lowry acid catalyst) 6.1 The overall equation No, cone CONC. HaS0« + HNO, ———_> + #0 55% nitrobenzene (@ yellow oi) A nitrating mixture, containing concentrated nitric(V) acid and concentrated sulfuric(VI) acid carefully mixed together, is added to the benzene. The mixture is then refluxed in a water bath maintained at 55-60 °C. Keeping the temperature bel 60°C minimises the formation of a dinitrated product. 6.2 The reaction mechanism: Electrophilic Substitution 6.2.1 Bronsted-Lowry acid and base In the nitration of benzene, the electrophile is generated from the reaction between a Bronsted-Lowry acid and a Bronsted-Lowry base. ABronsted-Lowry acid is a__rehes ( Ht) dawer A Bronsted-Lowny base is a __praten CH) a cephor . 8.2.2 Rea ion mechanism The nitration of benzene involves the following stages: 1) Generation of the electrophile, NO:* (9 2H2SO, + HNO, = NOz* + 2HSOe + HsO* ‘Stops involved in generation of the electrophile NO-’ In the nitrating mixture, the HNOs acid acts as 2 Bronsted-Lowry base and accepts a proton from the Bronsted-Lowry acid H-SO. HsSOx + HNOs = HeNOs' + HSOe o ‘The reaction leads eventually to the formation ofthe nitronium ion (or nitty ion). HeNOs' = NO2* + HO @ HrSOc+ H20 > HSO+ HO" eo ‘Adding up (1) to (3) gives the overall equation for generation of electroptile 2H:S01+ HNOs = NOs! + 2HSOc + Hs0*2) Atwo-step electrophilic substitution reaction mechanism then follows: Step 1: Electrophilic attack by NO." sn ‘+ _ Inthis slow step, the NO-" ion acts as an electrophile and attacks the electron-rich benzene ring + 2 of the 6 x electrons in the benzene ring are used to form the C-N bond. Hence the aromatic character of the ring is destroyed. = this is the slow step of the reaction mechanism ‘+ A carbocation is formed. Note that the carbon atom bearing the NO; group in the carbocation is ‘sp* hybridised. The shape with respect to this carbon atom is tetrahedral. The rest of the carbon atoms on the benzene ring remain as sp? hybridised. Step 2: Loss of a proton from carbocation NO. fast + HO, nitrobenzene regenerated H. NO, NOz g or, 26h on ae + 1480, nitrobenzene _ regenerated °: + In this fast step, the unstable carbocation loses a proton to the HSO,-ion to form nitrobenzene, thus regaining the aromatic character. + H,S0, (catalyst) is regenerated 6.3. Electrophilic Substitution of more than one nitro group + During the nitration of benzene using the nitrating mixture, small quantities of white crystals of 1,3-dinitrobenzene (m.p. 90 °C) are almost invariably formed. + 1,3-dinitrobenzene can also be prepared as shown below: come, HNO, NO» no, NO ‘cone. HpSO,, he NO, S Ooms Or - Or ie c eee ‘major product minor products + Formation of 1,3,5-trinitrobenzene requires reacting benzene with fuming HNOs and cone. H:SO« for five days at 110 °C. Even under these conditions, the yield is only about 40 percent. teREACTION WITH HALOGENS Candidates should be able to + describe the chemistry of the benzene ring as exemplified by the following reactions of benzene and methylbenzen: electrophilic substitution reactions with chlorine and with bromine (recognise the use of Lewis acd as catalysts) describe the mechanism of electrophilic substitution in arenes, using the mono-bromination of benzene as an example TA Lewis a ce and base 3 ba Les The halogenation of benzene requires the use of a Lewis acid as a catalyst lai oth it, Pom ad) HY oH (bom Ho) no bese { ALewis acid is an___dlachon - pair accep A.Lewis base is an = pair dover 7.2 Halogenation: Generation of Electrophile Benzene does not react with chlorine or bromine in the dark. oO oo oO + po rcton Note: + The r-electron cloud in an alkene is easil ly brokén when reacting with halogens. However, the |) ‘same cannot be said for arenes. + The extra stability associated with the delocalization of the 6 n-electrons in benzene requires the use of a stronger electrophile in order to disrupt the x-electron cloud. In the presence of a suitable Lewis acid catalyst such as AICI or FeCh, benzene undergoes electrophilic substitution reaction with chlorine at room temperature. ci Feo +o, oe, + Hol orAiCh orFe In a similar way, benzene reacts with bromine to form bromoben: wene and hydrogen bromide in the presence of A/Brs or FeBrs Br FeBr, + 8, ——+ + Her or Bry orFe Note: * Analogous reactions with Ie and Fare not synthetically useful because [2 is too unreactive and Fs Feacts too violently, | -12-The catalyst is thought to work by inducing polarisation in the halogen molecule by accepting a lone Pair of electrons from it. Hence the catalyst functions as a Lewis acid, generating the CF electrophile Jae aid rb Note: ry * AlCis catalyst reacts readily with water. - ACIS) + OHO —> (AKH:O}eP"(aq) + (00) Gaol fet) a2) | agora 400) 4 = (AIHOMOH)*(aq) + HiO'(aq) | | «Hence the reaction can only proceed Ga. tM, ats EAU)” UH cay” | under anhydrous condition Iron filings can be used for the reaction since it is converted into FeCl or FeBr, in the reaction mixture (Le. FeChis often generated in situ from Fe and Clz while FeBrs from Fe and Br) 2Fe + 38% —> 2FeBrs 2Fe + 3Ch —> 2FeCh, 7.3. | ‘The reaction mechanism: Electrophilic Substitution Gece ceed Overall reaction: @ Fel Ovm =, a O-«w O-« Gia satcbemne (eyelow ah Reaction Mechanisr 7 ion of the electrophile, Cr" Generation of the electrophile, NOs" Ch + FeCis = Ch + [FeCuy- 2H2SO. + HNO; = NO3* + 2HSO. + H;0* Step 1: ‘Step 1: ~ not Nos 6. oy? ie oO OO Nor o benzene clcrophi carbocation vonzene ecg cartoaton Step 2: ‘Step 2: HO oct Go HNO, NO2 = tat - ts + tFecig” 2S + HOI + FeCl, + H80, + H,80, ctorenzne regenerated robenzene regneaea oN ; or 6 + cprecar O) + ner race oO ones arcrase _rseorted steered] Marking points for mechanism drawing: ¥ Name of mechanism ¥ Correct intermediate ¥ Equation for generation of electrophile ¥ Label slowfast steps ¥ Correct curly arrowsIEM_ELECTROPHILIC SUBSTITUTION: FRIEDEL-CRAFTS ALKYLATION & ACYLATION and methylbenzene ‘Candidates should be able to describe the chemistry of the benzene ring as exemplified by the following reactions of benzene Friedel-Crafts alkylation with halogenoalkanes (recognise the use of Lewis acid as catalysts) Gator een Alkylation with a halogenoalkane and a trace amount of anhydrous A/Ci; as catalyst is often referred to as a Friedel-Crafts alkylation, after Charles Friedel, a French chemist, and James Crafts, an American chemist, who developed this, reaction in 1877. Acylation is similar to that of alkylation except that, halide (RCOX or ArCOX) instead of a halogenoalkane (RX) is used. The acid halide provides the acyl group needed for the reaction The overall reaction oO AICI, + Ro] + HEI Note: A/Cis catalyst ‘The overall reaction Ah + Cry g=c1 —S G-CH + HO 3 3 reacts readily with water. Hence the reaction can only proceed under anhydrous condition. Generation of the electrophile R* RCI+ AIC, = R* + [AICH Step 1: rhe . Ove re Step 2: nee ro Oo + Hor + AlCl, Reaction mechanism: Electrophilic Substitution Generation of the electrophilic acylium ion cHy-E-o1 + AK, i Step 1: —_ . Co aks = & omg te SK, benzene a @X = tant i § i ra eX. cn E et) cot «pen A are slEM OTHER REACTIONS OF BENZENE _ ~ 91 Combustion Benzene burns in air with a sooty, smoky 415 flame. This sort of flame is charactenstic | O () + -0,) —> 6C0,g) + 3H,0() of all hydrocarbons containing a high | Percentage of carbon i 9.2 Reduction (catalytic hydrogenation) Benzene undergoes addition reaction with hydrogen in the presence of nickel catalyst at considerably higher temperature and pressure than for alkenes. = The higher temperature is needed because extra energy must be supplied to break up the delocalised x-electron system. Raney nickel + oH, 150°C Or simply 1, S_Neatayst * Ste “Tian temperatire igh pressure 9.3. Reactions that benzene DOES NOT undergo re evthelin no reaction acidified KMnO,(aq) - No decolourisation of Tat soda tox purple KMn0,(aq) ro rim wth, Be, alone © BrincCi, oe in the dark =no decoloursation of ‘dich bo Bry ergo 1 Foto). 1 aim no reaction Ni, 25°CMETHYLBENZENE ‘Candidates should be able to +) describe the chemistry of the aly! side-chain of benzene sng as exemplified by the folowing reactions of methybenzene: (free-radical substitution by chlorine and by bromine (i). complete oxidation to give benzoic acid + predict whether halogenation wil occur inthe side-chain or aromatic nuctous in arenes depending on reaction conditions 10.1. Introduction Methylbenzene (C;Hs) is the simplest alkylbenzene. Its structural formula is shown below. R where CH Ris an alkyl group ethylbenzene alkylbenzene + Like benzene, methylbenzene is a colourless liquid which is insoluble in water but soluble in organic solvents. It is itself a useful solvent. + Itmelts at -95 °C and boils at 111 °C. + When combusted, it bums with a sooty flame indicating that it has a relatively high C:H ratio, ‘+ Industrially, methylbenzene is obtained both from coal and from petroleum in the same way as benzene. 10.2 Reactions of methylbenzene and other'alkylbenzenes ethylbenzene has an aromatic portion (the benzene ring) and an aliphatic portion (the methyl group) => These two portions make different contributions to the chemical properties of methylbenzene and have a modifying effect on one another. - aromatic portion aliphatic portion ‘aromatic potion aliphatic portion =canundergo — - canundergo ~canundego —-canundergo electrophilic free radical electrophife free radical substitizion| ‘substitution ‘substitution substitution reactions reactions reactions reactions Methylbenzene undergoes two main types of reactions: © reactions of the alkyl side chain > free radical substitution > oxidation @ reactions of the benzene ring 2 electrophilic substitution (similar to benzene but at milder conditions) 16KEE REACTIONS OF THE SIDE CHAIN IN ALKYLBENZENES Candidates should be able to 5 * describe the chemistry ofthe alky| side-chain of benzene ring as exemplified by the following reactions of methylbenzene: (i) ftee-ragical substitution by chlorine and by bromine complete oxidation to give benzoic acid Predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes depending on reaction conditions 11.4. Free radical substitution of the alkyl side chain * The —CHs group in methylbenzene shows reactions expected of an alkyl group, for example, it can undergo free radical substitution reaction with chlorine, * The reaction occurs when chlorine is bubbled into boiling methylbenzene which is exposed to sunlight or ultraviolet fight. Ores + ch, —avioletiont Oproner + Hor (ctloromethy)benzene vile te Oprener+ cy, —Wtawoletight | Operon ec (Gichlorometty)berzene Livavolet ott Oyoren + ch, —weaioletsht Opes + HEI (Gictloromethybenzene * Bromination of methylbenzene takes place under similar conditions, forming the corresponding bromine derivatives. + The conditions employed here favour the formation of free radicals, and the reaction proceeds in a Similar way to the halogenation of alkanes (i.e. via free radical substitution mechanism). Worked Example 1m Describe the mechanism for the reaction between methylbenzene and chlorine in the presence of ultraviolet light to produce (chloromethyl)benzene. Solution Mechanism: Free radical substitution Step 1: Initiation PCat Step 3: Termination = Opis — 2a Bebe © Ome — Orem Ga eG —-O-aO) © Oma — Opoase ‘Then (8 (O(a “17.11:2" Oxidation ofthe alkyl side chain chain quite susceptible to oxidation, he side chain is oxidised, with only a carboxylic acid group (COOH) remaining to indicate the position of the original side chain. ‘+ This oxidation reaction is useful for the synthesis of carboxylic acids and the identification of alkylbenzenes. Although alkanes and benzene are quite unreactive toward the usual oxidising agents (e.g. acidified KMnO.), the benzene ring renders an aliphatic side Reagents and Conditions Reaction (if any) Observations * Decolourisation of Le Ete 6, (Fitts the ining reagent Galh.®, Cheers 674) 4 Formation of a_vhite precpitake of bensay pee ene aud. upon cooling. KMn0,(aq), KMnO.(aq), dllste H,SO,(aq) Note: Benzoic acid has limited solubility in water as its H,SO.(aq), heat CH, + 3) ————_———». COOH + H;0 large non-polar benzene ring interferes with the formation heat under reflux of hydrogen bonding between the -COzH group and | water. | Hee ray Hence, benzene is soluble in hot water but has poor | indesk. patho d || solubiyin cold water. It appears as'a white precipitate emg) ot daw when the reaction mixture is cooled, * Decolourisation of yu 1h Oy KWin0,(aq), dilute (if itis the limiting reagent) KMnOx(aq), Oro NaoHaa) Op-e00" ne aisocee coon |* Formation of a_buow-}auk pt NaOH(aq), heat heat under of MnO, refiux ~—— | ms ‘+ Formation of a_whit. posible ob berseye ound oh upon codling and acidification. K,Cr207(aa), G* K2Cre07(aq), r we hed : chy SMe H2S0%, no reaction ‘+ Orange KzCrz0;(aq) does not turn green, iSO.(aq), heat “heat underrefiux — (@t’A' level)ns using half equation method For stoichiometric calculations, the following equations are required to derive the stoichiometric ratios of the oxidising agent and reducing agent. Oxidation Pee gre | Oyen sano > Gyan save Reduction > + BH + Se7 > Mn2* + 4H halt-equation: MnO. + 8H* + Se-—> Mn2* + 410 Owatentin: |=) vttmar +o —> 6(C))-coon em oe no Oxidation of longer alkyl chai S. + Ethylbenzene or any other benzene derivative with an alkyl side chain (however long) will produce the same product, benzoic acid, ‘+ The rest of the alkyl side chain is destroyed, usually forming carbon di Example: CHCHACH, oa KWo). poor dikte 80, CHyCHy: + 15(0) HOOC: +3CO, + 51,0 Heat under reflux Note: Only a carboxylic acid group (i.e. COOH) remains to indicate the position of the original side chain. cont i . mod bong ct Let LH obaw 11.2.3 Criteria for oxidation of side chains on benzer YX if + Alkylbenzenes without a H atom bonded to the benzylic carbon atom (i. the carbon atom that is bonded to the benzene ring) do not undergo oxidation when heated with acidified KMnO. CH, KMnO4(aq), i dite #50, ‘CCH; = I heatunder reaction CH rf + The other criteria will be discussed in the later topics of Organic Chemistry. -19-Exercise 1: Identify the organic reactants or products for the following reactions (Note: Equations are not balanced) KWin0,(2q), dilute #80, 1 ee SO © Sareea le KWridg(ac), ite H,S0, , Opgirers —KMoQq(ag), litte 480, | ©r- onl i heat under reflux ee O)-cnsensen, —Mmowemraintis 4 a ‘ctCHals CH) Heat under reflux Cotte Exercise 2: Identify the reactant of the following reaction ~ (Note: Equations are not balanced) KO, (29) ite HS, coor Cichyg —AMNO «fea, dite HpSOx On + CO, +H,0 heat coon Possible structures of the reactant CoH (Hint: There are 3 possible structures) im t 0 acu O uals 8 Hs a ay Om cae CoHEEA ELECTROPHILIC SUBSTITUTION OF THE BENZENE RING IN METHYLBENZENES: + Consider the following electrophilic substitution reactions of methylbenzene: Ha conc. HNO, Note: - cone. HS, ‘+ Reaction takes place — at 30°C. + A mixture of fae pea is obtained Note: women Oats Or 5. O. + Faster rate of reaction relative to benzene. + A mixture of products Br minor product : is obtained. J ‘+ The presence of the -CHs group in methylbenzene affects both the reacti the electrophilic substitution reaction Using the nitration of methylbenzene as an example: and orientation of Effect on Reactivity (Le. the rate of the nitration reaction) Effect on Orientation (Le. the site of electrophilic attack) + A lower temperature (30 °C) is used for the nitration of methyibenzene (whereas nitration of benzene requires 55 - 60°C). * This shows that methylbenzene is more reactive than benzene towards nitration, ‘+ In this case, the ~CHs group is said to be an activating group. + The major products of mono-nitration of methylbenzene are 2-nitromethylbenzene and 4-nitromethylbenzene. + This shows that substitution by the -NO» group occurs chiefly at 2- and 4- positions relative to the ~CHs group. + As such the -CHs group is described as 2,4-directing (or ortho, para-directing). substitu abhd qrecbchow (srt. of ckudrophtte otk). KEEI__EFFECTS OF SUBSTITUENT GROUPS: ‘monosubstituted arenes, Candidates should be able to apply the knowledge of positions of substitution in the electrophilic substitution reactions of ‘When an electrophilic reagent attacks an aromatic ring, it is the group already attached to the ring that determines: > how readily the attack occurs (i.e. the reactivity of the ring), and 'D_ the position of substitution, “2h43.1. Relative reactivity ‘+ Reactivity in electrophilic substitution depends on the tendency of a substituent group to release or withdraw electrons. - A group that donates electrons or delocalize electrons into the ring activates the benzene ring towards electrophilic substitution reaction. - A group that withdraws electrons deactivates the benzene ring towards electrophil substitution reaction. eT Poe An activating group is electron-donating. A dea 1g group is electron. It withdrawing. It - increases the electron density in the| - decreases the electron density in the benzene ring and makes the ring benzene fing and makes the ring pave sueptible to eledrophilic Juss sw uptible te durbayhiler a } cHlocke . atfosk . - helps to disperse the positive charge in ~ tends to intensify the positive charge the intermediate carbocation and leads in the intermediate carbocation and to the stabilisation of the carbocation leads to the destabilisation of the carbocation A group attached to a benzene ring is, A group attached to a benzene ring is classified as activating if it activates the classified as deactivating if it deactivates the benzene ring towards electrophilic attack, ie. benzene ring towards electrophilic attack, i.e. the ring is more. reactive than benzene] |} the ring is less reactive than benzene towards towards electrophilic substitution reactions. electrophilic substitution reactions. + Examples of activating group: * Examples of deactivating group: “NH, -OH, ~CHs -NOz, ~COOH, ~CI G G 8 eat : Ow— — +e* € +others where G is CI, in this example. ‘+ Relative rates of electrophilic substitution decreasing rate of electrophilic substitution reaction oe hy i a-o y Oo > oO ©) Methylbenzene is more reactive than benzene towards electrophilic substitution reactions because the ~CHs group is an Yisanclectrondonaing Zi an Yen eecron dona ce aithaving group | Slestton-donatina group and hence_an land hence isa activating aroup. It increases the electron — deactivating group density in the benzene ring and makes it more susceptible to electrophilic attack. -22-Example: Nitration of benzene ring CHa OH a NOz omens! (O) 5 Prete = Activating Strongly activating Deaactivating Strongly deactivating Reagents Concentrated nitric acid ‘Concentrated nitric acid Dilute nitric acid Concentrated nitric acid Concentrated nitric acid ; Concentrated sulfuric acid fons | Concentrated suttue acid | Concentrated suture acid Concentrated sulfuric acid Condons | Concentrate sutur porated tc Rom temperature acca sult cla igh erate No, uw Hy On Reactivity Oo O < < < O < Hs ot om on 7 ¢ nos We Nr Noe oO eo Q wo 2 aor ¢ 5 products) Q O oF O oF O} 7 y ve No, Nos NOp Nop i Note: The -CHs, -OH , ~C/ groups are 2,4-dlrecting while the -NO2 group is 3-directing (refer to Section 13.2)etme ‘+ An inductive effect is the donation or withdrawal of electrons through « bonds due to the electronegativity difference lent on a benzene ring electron-donating or electron: ithdrawing? Substituents on a benzene ting donate or withdraw electrons through inductive and resonance effects. feu A resonance effect is the donation or withdrawal of electrons through x bonds due to the continuous p-orbital overlap of the ‘+ Alkyl groups have a sp® carbon. Since sp? orbitals have less s-character, its between atoms. substituent and the benzene fing. This results in delocaiisation of electrons, either towards or away from the benzene ring, bomen ae Example: -OH (refer to pg 25) Ifa substituent has a lone pair of electrons on the atom that is directly attached to the from C through the « bond. ‘+ The substituent is said to be electron- withdrawing by inductive effect. Electron- benzene ring, donating | Clecfonsare less tightly held and more | tone paris usually ina porbitl, anc casly donated to the benzene rng. canbe delocalised into the ring, + Tho substituent is said to be electron- + The substituent is said to be electron-donating donating by inductive effect ie iasomeees ence | Examples: -C-O,-NOz | Example CF (600 botow) = Hfasubsttents dict atcha othe = es hae sore benzene fing by an atom that is doubly or triply electronegative than C atom (on benzene Election | ie or contre bonded toa more electronegative atom, the = withdrawing 9). Thay pull et a electrons of the ring can be delocalised onto the substituent. ‘The substituent is said to be electron- withdrawing by resonance effect. + Consider chlorobenzene and phenol where there Is competion between electronwithdrawing inductive effect and the electron-donating resonance effect. Inductive effect Resonance effect = The Ci atom is more electronegative than C. + Hence the ~C! group is electron-withdrawing by inductive effect. cr into the ring, * A lone pair of electrons on the Cl atom can interact with the delocalised x-electron cloud of the benzene ring and delocalises = This increases the electron density in the benzene ring. ‘+ Hence the ~C/ group is electron-donating by resonance effect. Note: 24. + In this case, the inductive effect is stronger than the resonance effect. + This is because C/is in Period 3 = its p-orbitals are more diffuse leading to a less effective side-on overlap with the p-orbitals of the benzene ring. + Hence the overall effect of the —C/ group in chlorobenzene i ‘+ The -C/ group decreases the electron density in the benzene ring and makes the ring less susceptible to electrophilic attack. Itis said to be a deactivating group. electron-withdrawing.Inductive effect Resonance effect x O * The © atom is mote}. @ lone pair of electrons on the O atom can interact with the electronegative than C. | gelogalised m-electron cloud of the benzene ring and delocalises + Hence the -OH group | into the ring. is electron- = This increases the electron density in the benzene ring, withdrawing by ' inductive effect + Hence the -OH group is electron-donating by resonance effect, Note: + Inthis case, the resonance effect is stronger than the inductive effect. + Hence the overall effect of the -OH group in phenol is electron-donating. + The-OH group increases the electron density in the benzene ring and makes the ring more susceptible to electrophilic attack. It is said to be a stronaly activating group, 13.2 Orientation ‘+ A substituent group in the benzene ring not only activates or deactivates the ring, it also controls the Position of entry of an incoming group. + Depending on the position it directs an incoming group to, a Substituent group may be classified as - 2,4-directing group (or ortho, para-directing group) or - a3-directing group (or meta-directing group) z EE + A 24-directing group (e. + A3-directing group (e.g. -NOz) causes an an electrophile to attack chiefly at| electrophile to attack chiefly at 3-position position and 4-position relative to it. relative to it =I directs the incoming group mainly to| => It directs the incoming group mainly to the 2- and 4- positions relative to it. the 3-position relative to it + Examples of 2,4-directing group: + Examples of 3-directing group: “NH, -OH, ~CHs, ~Cl ~COOH, -NO;,-CHO CH Hy CH, No, NOp Le No, ‘ + NOS —> + Noy —> s NO2 No, ‘major product ee ‘major products13.3. Classification of substituent groups at Refer to the Data Booklet section 8 8 nya ay “The orentating effect of groups Effect of groups on electrophilic aromatic substitution: aromatic substitution reactions’ Substvent group Eliecton | Effect on Remarks reactivity | _orentaton NH : ‘+ Each substituent has a lone pair on an CNH strongly . ftom that i bonded to the carton atom ot =NR2 activating 2.4-drecting the aromatic ring. con «Each substiven! can donate electrons by —OCHs (-OCH2CHs, etc.) moderately 2 irectin resonance effect (delocalize electrons into -NHCOCH3 activating z ‘9 the ring). —CsHs weakly CHs (CH2CHs, etc.) activating | _?-4-directing _ oH Standard oF comparison weak QQ ARkcocks Sx 2-0r4- directing AA classification of substituents based on how each group affects the ‘reactivity of the benzene ring towards electrophilic substitution If there are two substituent groups in the benzene ring and their directing effects oppose each other, the directing effect of the more powerful activating group wins. Both groups direct to same position palsy 02 Eri at donb omy . (major product) ‘Opposing effects } jos a ies oH Her -26- 2a drab (major product) adeaby13.4 Orientation and Synthesis The order in which the various substituents are introduced into the benzene ring is important. Worked Example 2 Suagest reagents and conditions for the synthesis of -bromonitrobenzene from benzene 2 dann Br cent: HN Br ame. MSD, or —— 5 2-bromonitrobenzene I-biyme-) hirano Ov Wt -dimbng advatrs (CH.CH, ame Ino, 6. cent Hysdy 2% Exercise 3: DN binbng [cn.crsh ae Oe ce ‘Suggest reagents and conditions for the synthesis of 3-nitrobenzoic acid from ethylbenzene. Tay cme 0s, O ene A604 head Eola (ay) H$0y o 3 dity daddy (COOH QO NO, oH 27SUMMARY 14.1 Some reactions of benzene conc. HNOS cones combustion CO, + 1,0 ch Je Opa + wer 2_ © _ etecropte Fae Ors + nae) states reactions, Ni ‘ = Ops \ ere C-R+ Hel guleteres ACh © . 14.2. Some reactions of methylbenzene comic, oH : conc. HSO, Noy cho <2 =O Om No; = / a a Qk (limiting reagent) . a ch or oO - ore! a cheer re Br, (mtng eager en § ood Kiin0,(aq) acidified witvalue rsS0y = coo-tst is Ch CH Kwn0,(a0), dite NaoHaq) Teal -28.14.3. Electrophilic Substitution Reactions Nitration of benzene: Electrophilic Substitution No, ‘2H2SO«+ HNOs = NOz* + 2HSO.- + H30° oe 480, {a yellow oll) + Nos _slow Step 2: HL NO, NO, OS ener Can tichontre pnt Gioination of bozane Elecopic Substitution cl Ch + FeCls = Cr’ + [FeCl oO +o, eee + Ho) | Step t: cr Oia slow Hooch a lvcencine reget Frode rats Ay Electronic Substation 5 RCIWAlC «RCH a Reagents and condos: Ri, AIC O-* So Hon ©) + wea" HO) ner nc rsetOPTIONAL READING + Industrial sources of Benzene {a} From petroleum by catalytic reforming of hexane (b) From coal tar by fractional distilation of Poheat ‘coal ar serreropeaian + Laboratory preparation of Benzene (not in the syllabus but can be tested) ‘Owing to the abundance of benzene from industrial sources, itis rarely prepared in the laboratory, and the following reactions tend to be of academic interest only. {a) Decarboxylation of a sodium benzoate , sedasime + Decarboxylation isa O)-cooret + neon ASE + e360) |" teacton Yin which th wat ‘loments of carson dioxide are removed fom a Note Soda ime is @ mature of sodium and calcu hytrones made by adsng | compound concarated soaum hysronce souslon 1 auisime, W tunclons. 83) sodkt hhydroxide may te prelerabio to Sodium hydtaxce asa reagent because tis nt tquescer anaes sass less eadlyandithasa highermeling poi (b) Reduction of phenol Oya + aa © + 2 {c) Polymerisation of ethyne hested tube, 60-70°C ‘organo-nickel catabst 3 H-C=C-H + Reduction of benzene Benzene undergoes addition reaction with hydrogen in the presence of nickel catalyst at considerably higher temperatures than for alkenes. The higher temperature is needed because extra energy must be supplied to break up the delocalised n-electron system Raney rick ee 150°C The catalyst, Raney nickel, is a form of nickel with an extremely high surface area for catalytic activity. The catalytic hydrogenation of benzene is important industrially in the manufacture of cyclohexane, from which nylon is made. Other catalyst that can be used: Pt or Pd + Reduction of methylbenzene Methylbenzene reacts with hydrogen under the same conditions (je. catalyst + high temperature + high pressure) as benzene. Thus if a mixture of methylbenzene vapour and hydrogen is passed over finely divided nickel at 180 °C, methyicyclohexane is produced. Ni high temperature CH, + 3H, —Sitahlempersive | Ope +» epee om Other catalysts: Pt or Pd ‘+ Free radical addition of benzene