Arenes Introduction 1. Hydrocarbon that contain rings which stabilised by electron delocalisation are called aromatic hydrocarbon or arenes 2. The simplest yet most important member of the aromatic hydrocarbons is benzene Naming Aromatic Hydrocarbon • Monosubstituted alkylbenzene is named as derivatives of benzene. For example: CH3 methylbenzene (Toluene) CHO Benzaldehyde CH2CH3 ethylbenzene NH2 Aniline (Phenylamine) OH Phenol CH=CH2 Phenylethene (Styrene) COOH Benzeoic acid • The IUPAC system retains certain common names for some simpler alkylbenzenes. For example: Aniline, styrene, toluene. • When two or more substituents on a benzene ring, three structural isomers are possible. a) Location of two substituents may be indicated by the prefixs ortho, meta or para – 1,2 is equivalent to ortho, o– 1,3 is equivalent to meta, m– 1,4 is equivalent to para, pb) The order of decreasing priorities of common substituents is: COOH > SO3H> CHO> CN > C=O> OH> NH2> R> NO2> X Where R= alkyl group ; X= halogen CH3 1 CH3 OH COOH CH3 2 6 3 5 4 1,2-dimethylbenzene o-xylene 1,4-dimethylbenzene p-xylene CH3 Benzeoic acid Phenol CH3 CH3 CH3 1 Br 6 2 3 5 4 Br Br 2-bromomethylbenzene 3-bromomethylbenzene 4-bromomethylbenzene p-bromotoluene m-bromotoluene o-bromotoluene OH OH 1 NO2 6 2 5 3 4 NO2 2-nitrophenol o-nitrophenol 4-nitrophenol p-nitrophenol • When three or more groups are on the benzene ring, a numbering system must be used to locate them. For example, CH3 CH3 1 NO2 6 2 6 3 5 1 4 NO2 2,4-dinitromethylbenzene Br 2 3 5 4 NO2 2-bromo-4-nitrophenol • In more complex molecules, the benzene ring is named as a substituent on a parent chain. In this case, the C6H5- group is called a phenyl group. For example 1 2 3 4 2 3 4 5 CH2CH CHCH3 CHCH2CH2CH3 1 CH3 1-phenylbut-2-ene 2-phenylpentane Exercise • Name the following aromatic compounds CH2CH3 NO2 Cl CH3 Cl CH3 CH3 COOH COOH O2N H3C NO2 NO2 HO Reaction of benzene 1. Nitration • Nitration is the substitution of a nitro group, -NO2, for one of the hydrogen atoms on the benzene ring • Benzene reacts with a mixture of concentrated nitric acid and concentrated sulphuric acid • The product is nitrobenzene, a pale yellow liquid NO2 + HNO3 concentrated H2SO4 o <55 C refulx + H2O 2. Halogenation – This reaction involves substitution of a halogen atom for a hydrogen atom on the aromatic ring – In the presence of a catalyst or halogen carrier such as aluminium chloride, AlCl3, benzene is substituted by chlorine or bromine at room temperature. Cl AlCl3 + Cl2 room temp + HCl • The catalyst aluminium chloride, AlCl3, an electron-deficient compound which has only six electrons in its outer shell, accepts a lone pair of electrons from one of the chlorine atoms, which induces polarisation in the chlorine molecule. Cl Cl AlCl3 • The positively charged end of the chlorine molecule is now an electrophile and attacks the benzene ring. 3. Alkylation: Friedel-Crafts reaction • This reaction substitutes an alkyl group for a hydrogen atom on an aromatic ring • When benzene is warmed with chloromethane, CH3Cl and aluminium chloride (catalyst) under anhydrous conditions, a substitution reaction occurs and methylbenzene is formed CH3 + anhydrous AlCl3 + HCl CH3Cl warm – AlCl3 polarise the CH3 Cl molecule H3C Cl AlCl3 – The positively charged methyl group attacks the benzene ring and electrophilic substitution occurs H3C Cl AlCl3 H CH3 CH3+ + AlCl4CH3 CH3 + H+ 4. Acylation • Involves substitution of an acyl group, RCO, for a hydrogen atom on the aromatic ring. • When benzene is added to ethanoyl chloride and AlCl3, under anhydrous conditions, a substitution reaction occurs and phenylethanone is formed. O O C AlCl3 + H3C C CH3 + HCl Cl heat Exercise • Write the structural formula for the producta formed from Friedal Crafts alkylation or acylation of benzene with (a) CH3CH2CH2Cl (b) CH3CH2CH2COCl 5. Sulphonation • Involves substitution of an –SO3H group for a hydrogen atom on the aromatic ring. • If benzene and [H2SO4] are reflux together for several hours, benzenesulphonic acid is formed: + concentrated H2SO4 SO3H reflux + H2O Benzenesulphonic acid Reaction of methylbenzene 1. Reaction with chlorine • When chlorine, Cl2, is bubbled through boiling methylbenzene in strong sunlight or uv light, substitution takes place on the methyl group: CH2Cl CH3 Cl2, boil uv light CHCl2 CCl3 • If Cl2 is bubbled through methylbenzene in the absence of uv light but in the presence of AlCl3, the ring is substitutes. A mixture of two isomers is obtained. • White fumes of HCl are given off • Electron density of the benzene ring more strongly at the 2and 4- positions CH3 CH3 Cl + Cl2 AlCl3 + HCl room temperature roo m AlC l3 tem per atu re CH3 + HCl Cl 2. Reaction with HNO3 • When methyl benzene is added to HNO3 and concentrated H2SO4, at room temperature, a mixture of 2- and 4-nitromethylbenzene CH3 CH3 NO2 + HNO3 H2SO4 room temperature roo m HS 2 tem O4 per atu re + H2O CH3 + H2O NO2 • If the temperature is raised, two or three nitro groups, NO2 are introduced CH3 CH3 NO2 O N 2 NO2 2,4-diphenylmethylbenzene NO2 NO2 2,4,6-triphenylmethylbenzene 3. Reaction with CH3I (Friedal craft alkylation) • When methlbenzene is added to CH3I in AlCl3 at 20 oC, a mixture of 1,2dimethylbenzene and 1,4-dimethylbenzene is CH formed CH 3 3 CH3 + CH3I AlCl3 room temperature roo m AlC tem l3 per atu re + HI CH3 + HI CH3 4. Reaction with CH3COCl (FriedalCraft Acylation) • • The reaction of an acyl chloride with an aromatic hydrocarbon is known as FriedalCraft acylation. Involves substitution of an acyl group, RCO-, for a hydrogen atom on the aromatic ring in the presence of CH CH AlCl3. O 3 3 O + H3C C C Cl ethanoyl chloride AlCl3 80oC CH3 + HCl Al 80 o Cl3 C CH3 + HCl C O CH3 Exercise • Write the structural formula for the products formed by Friedal Crafts acylation or alkylation of methylbenzene with (a) C6H5COCl (b) CH3CH2Br 5. Reaction with SO3 • When methylbenzene is added to fuming H2SO4 containing SO3 at 0oC, a mixture of 2and 4-methylbenzenesulphonic is obtained. CH3 CH3 2 1 H2SO4 + SO3 + H+ o 0 C 2-methylbenzenesulphonic acid H 0 SO3H 2 SO 4 o C CH3 4 + H+ 1 SO3H 4-methylbenzenesulphonic acid 6. Oxidation of alkylbenzene • Alkylbenzenes are oxidised to benzoic acid on prolonged reflux with KMnO4 or K2Cr2O7 R KMnO4 / K2Cr2O7 COOH + H2O + CO2 • Example CH3 + 3 [O] KMnO4 / K2Cr2O7 reflux CH2CH3 + 6 [O] KMnO4 / K2Cr2O7 reflux COOH COOH + H2O + 2H2O + CO2 Exercise • Predict the products from treatment of each of the following compounds with KMnO4 / H2SO4 under reflux. CH3 (a) CH3 (b) CH3 (c) CH2CH2CH3 CH3 CH3 Exercise • Name compound P, Q, R and S below CH3 CH3 CH3 R AlCl3 P+Q NO2 fuming H2SO4 4-methylbenzenesulphonic acid (S) Br Exercise • Draw the structural formulae of the organic products formed when methylbenzene reacts with (a) Concentrated nitric acid and concentrated sulphuric acid at room temp (b) Chlorine in the presence of anhydrous aluminium chloride (c) Chloromethane in the presence of aluminium chloride