96 Unit 5: SECTION 9 — ORGANIC COMPOUNDS Aromatic Compounds fic compound. In the old days something just had to be whiffy to qualify as an aromatic compo These days, they’re a bit more fussy about the definition. Arenes or aromatic compounds contain a benzene ring. Benzene has the formula C,H, — there are two ways of representing it The Kelle Strctare The Delcalised 5 Vora erate ete ee AI located ng NG etre Arenes are named in two ways. There's no easy rule — you just have to learn these examples: ‘Some are named as substituted benzene rings. | while others are named as compounds with a phenyl group (C,H,) attached «1 XO, cH | oH OH NH, : cH, horsberzere nitrobenzene |, 3dimethyibertone prerel_ 2metylphenel_phanyanine » 1) The Kekulé structure was proposed by Friedrich August Kekulé in 1865, —= — It consists of a ring of carbon atoms with alternating single and double bonds, which constantly flip between the two carbons. 2) Ifthe Kekulé model was correct, you'd expect there to always be three bonds with the length of 2 CC bond (154 pm) and three bonds with the length of a C=C bond (134 pm). 3) But X-ray diffraction studies have shown that all of the carbon-carbon bonds in benzene are the same length (139 pm) — i.e. they are between the length of a single bond and a double bond, Infrared studies have also shown that none of the carbon-carbon bonds in benzene are normal double or single bonds because they absorb energy at a different frequency. 4) So the Kekulé structure can’t be completely right. But it’ still sometimes used today, because it’s useful for drawing reaction mechanisms, 1) The delocalised model says that the p-orbitals of all six carbon atoms overlap to create mbonds 2) This creates two ring-shaped clouds of electrons — one above and one below the plane of the six carbon atoms. SO en er > Benzene is a planar (Hat) molecule Z it aot aring of carbon atoms withther — ™ hydrogens sticking out al ona lala. — 7 PRI —< 3) All the bonds in the ring are the same length because all the bonds are the same. So this model fits the X-ray diffraction and infrared data. 4) The electrons in the rings are said to be delocalised because they n't belong to a specific carbon atom. They are represented as a == ide the carbon ring rather than as double or single bonds. Gary woke up after the stag party to find himselh ina very delocalised orbit.Aromatic Compounds js -120 KJ mol, If benzene had 1) Cyclohexene h, : tion of -360 k) mol. hs as one double bond. When its hydrogenated, the enthalpy change NO," +H,0 HNO, + H,SO, > H,NO,* + HSO, echani 4) And here's the re This Ht ion reacts, with HS0, to reform the catalyst, 50, The nitroniu ion ‘An unstable The H+ ion is lost attacks the benzene ring __intermediate forms you need to keep the temperature below 55 5) Ifyou only want one NO, group added (mononitration), y ‘Above this temperature you'll get lots of substitutions. 1) Ifyou want to make benzenesulfonic acid (and you never know, one day you might.) you'll need to warm benzene to 40°C with fuming sulfuric acid for about half an hour. 2) Fuming sulfuric acid is basically sulfur trioxide, SO, dissolved in sulfuric acid. 3) The electrophile in this reaction is sulfur trioxide, and the mechanism is similar to the nitration one: Escaping fom ison breeze vith the pat Os i Teor wecvetic | ah | Berzenesulfonie acid eee An electrophile must have a prety strong postive charge tobe able to attack the stable benzene ring. Most compouy aren't polarised enough — but some can be made into stronger electrophiles using, a catalyst called a halogen carve Halogen carriers accept a lone pair of electrons from the halogen in the electrophile. As the lone pair of electrons is pulled away, the ae polarisation in the electrophile increases and sometimes a earbocation Ge ven forms. This makes the electrophile heaps stronger. Halogen carriers include aluminium halides, iron halides and iron, ‘Alcl, —> 8° Alcl nealkane halogen carrier = carbocation Unir 5: Sicrion 9 — OscaNte Corounos) ¥Reactions of Aromatic Compounds Friedel and Crafts discovered that a hak i ae overed that a halogenoalkane will react with benzene in the presence of a halogen carrier to produce an alkylbenzene, The halogen carrier used is usually aluminium chloride. AICI, : {ts another electrophilic substitution reaction — the electrophile is the carbocation (R:) made when the halogenoalkane reacts withthe halogen carrer First you need to form the electrophile:_RCI-+AICL, > R* + AICI, Then ican attack the benzene ring \iiied Tardis wrt ‘Abylbaraanes are nore reactive ha) | OO vee reaction shpat nubiles! | Sd S x you vsualy act polation ‘attacks the benzene ring removed by AICI. ye | 4 AICI, is very sensitive to hydrolysis, so the reaction is done in dry conditions — the reactants are refluxed in dry ether. Acyl chlorides (see page 59) are polar molecules — so they can easily lose their chlorine atoms to form carbocations. They react with benzene by electrophilic substitution in the presence of a halogen carrier — producing phenylketones. Handily, it’s very similar to the Friedel-Crafts alkylation reaction, You form the electrophile from the acyl chloride and the halogen carrier: _ RCOC! + AICI, > RCO* + AICI, Then it attacks the benzene ring: oe, The reaction mixture is heated A apl-g 0ego Ment: ic ae en te ccleenieiten under reflux with a dry ether. Xt=o0 Accel Tishuadic tela sees — +Hel +A, > Phenylketones are less reactive ~ x Geechee cine The carbocation (RCO) AnHatomis _pharletone__thhaencaiee | one substitution a attacks the benzene ring. removed by AIO. ete MIT S98) SSL QI. Describe the role of a halogen carrier in electrophilic substitution reactions. H.Q2 Draw the mechanism forthe reaction of benzene with chloromethane, CH,Cl, in the presence ofan AICI, catalyst “| Exam Question son No, 1 Two electrophilic substitution reactions of benzene are summarised in tis diagram: a Xx i) Name the product A, and the reagents B and C, oy E : i [4 marks] ‘ jive the conditions D. é . we s Git: ‘a mechanism for this reaction. gee! Write wo equations to show the formation ofthe eletropile, [2 marks] (2 marks) E. t i the product F, and the reagent 2a Oe the electrophile in this reaction? [mark] ee xgo electrophilic substitution reactions. [2 marks} )_ Explain why benzene and other arenes will undet ite contain the word ‘delocalised’. ve. Sor ee = itmakes them stable, and they don’t want to give it up for anythin ei delocalised (there el in el jough, because do those and still keep it intact reactions thougl they can ” : snes love the parti Jlectrophilic substitution bu can get them (0 Orcanic Compou100 tomes More Reactions yeni ite ra Jectron rings yet. Prepare yourself fo el You're not quite done with delocalised jes Will React With Ikene, like cyclohexene, double bond to give 2 dition reaction — itd J as a test for alkenes. with bromine water, The mecl 2 dibromoalkane- Seen Jecolorises the " Ifyou shake a cycloal bromine adds across the This is an electrophilic ad bromine water, and is used "t decolorise bromine water — itt benzene will undergo electrop! energy to bre fakes too much ac ar act ic substitution re ‘As you saw on the last page, sown. Bromine, Br,, isn’t strong enough el like FeBr,. it strongly polarises the Br, mol nzene on it to react with ber a stron elect? lectrophile lecule, creating First ofall you need to form the electrophile: Then it attacks the benzene ring: yr Br7fe-Br a bromine atom has been Fee BNET Brea the erm Oye ) S the catalyst 7) You end up with bromobenzene — a Br atom has been substituted IF you want to add groups to benzene, you have to use very harsh conditions in order to break that stable delocalised electron system. For example, benzene will react with hydrogen in the presence —>= ofa finely divided nickel catalyst at 150 °C and 10 atm to form cyclohexane. Use Methylben: lf you're doing any of the reactions on pages 98 to 100 in the lab, you'll probably use ethylbenzene or methoxybenzene as the reactant instead of benzene. y) 2). Because ofits delocalised electron ring, benzene isa really stable molecule. So its reactions are usually very slow. The CH, and OCH, groups in methylbenzene and methoxybenzene donate electrons tothe delocalised ring, increasing is electron density and making it more reactive. So they both react faster than benzene.” Mathylbenzene and methoxybenzene are both much les toxic than benzene too, You'll end up with slightly different products —but the basic reactions will work 3) 4) 5) few more reactions. remember it, take a peck at your Ag ak up the delocalised electron yy pphile that can attack the benzey for one of the H atoms. Methylbenzene oda eee La TeS Tne eee ‘alkene reacting with Br, — ifs YOUcay nt tions with strong electrophijeg But if you add a halogen can Ne ting, Nicatalyst_ + 3H, = Methoxybenzene so they're safer to use. just the same. Phenol is a benzene ring with an OH group substituted for one of the se we ee pt H atoms. Ithas the formula C,H,OH. Sth Other phenols can have various groups attached to the benzene ring here! _2-methyiphenal 4 choraphenl NO: 4-nitrophenot > Number the carbons = starting from the one 7 with the -OH group Cte eaayn’More Reactions of Aromatic Compounds 1) Ifyou shake phenol with orange bromine water, they will react, and the bromine water will be decolorised. a 2) Benzene doesn't react with bromine water (as you saw on delocalised ring af electrons, electrons in prrbitals page 100), so phenol’s reaction must be to do with the OH group. a 3) One of the electron pairs in a p-orbital of the oxygen atom overlaps = ne eee with the delocalised ring of electrons in the benzene ring, 4) This increases the electron density of the ring, especially at positions 2, 4 and 6, making it more likely to be attacked OH OH by the bromine molecule in these positions: (Youdort need to ec Br Se hers Gia a se deel lacy by UW Er a ons ate iene) ee So 5) The hydrogen atoms at 2, 4 and 6 are substituted by bromine Br atoms — it's an electrophilic substitution reaction. The product > 2,4,6-tribromophenol is 2,4,6-tribromophenol — it's insoluble in water and precipitates out ofthe mixture as a white solid. It smells of antiseptic On oH 1) Phenol will react with ric acid to give two isomers of nitrophenol, and water. —> 2) Nitrating phenol is much easier than nitrating benzene — that requires © concentrated nitric and sulfuric acids. 3) The difference is due to the activating effect of the OH group again ac No, and that’s also why you're most likely to get NO, groups at Aritrophenol positions 2 and 4 on the carbon ring, {QI Describe the conditions needed to get benzene to react with hydrogen to make cyclohexane. Q2 Draw the structures of methylbenzene and methoxybenzene. Q3 Write a balanced equation for the reaction between phenol (C,H,OH) and bromine (Br,). Q4 Draw the two isomers formed when phenol reacts with dilute nitric acid. Exam Questions 1 Benzene will react with bromine, Br,, in the presence of iron(III) bromide, FeBr, This reaction that takes place is an electrophilic substitution reaction. a) Write an equation for the formation of the electrophile. [1 mark) b) Draw out the mechanism for the reaction aes] ¢) Name the aromatic product formed. [1 mark] 2 Bromine water can be used to distinguish between benzene and phenol. a) Describe what you would observe when benzene is shaken with bromine water. [1 mark b)_Deseribe what you would observe when phenol is shaken with bromine water. Res) ‘ompound formed when phenol reacts with bromine water. [1 mark ) Name the aromatic c 4) Explain why phenol reacts differently from benzene with bromine water, [2-marks} ©) What type of reaction occurs between phenol and bromine? [1 marig 4 — more chemicals, more equations, more horror.. “actions of benzene (and, of course, reactions of benzene with other stuff stuck on it). earned the benzene and bromine mechanism, and the cheeky extra couple of benzene your favourite hat, throw itin the air give 2 loud cheer, and move on to amines... Unir 5: Section 9 — Oncanie Phenol Destination Ind that about wraps it UP. uy fe a ‘re quite sure ate perl tu ed