CHAPTER 6 AROMATIC HYDROCARBON NORHASLINDA NASUHA FKK, UiTM PULAU PINANGCOURSE OUTCOME + Ability to explain the relationship between the structure, physical and chemical properties of the different bonds and functional group in organic compounds.(CO2) + Ability to explain each of functional group activity. (CO3) COURSE LEARNING OUTCOMES The student should be able to: - = Name benzene compounds = Explain aryl properties. = Predict, draw and name the products of functional groups reactions. = Draw the mechanistic pathway.BACKGROUND + Benzene (C;H,) is the simplest aromatic hydrocarbon (or arene). + Benzene has four degrees of unsaturation, making it a highly unsaturated hydrocarbon. + Whereas unsaturated hydrocarbons such as alkenes, alkynes and dienes readily undergo addition reactions, benzene does not. Br uy Ethylene ‘ (en alkene) EH Br Br Br, rae CeHs + No reaction + Benzene does react with bromine, but only in the presence of FeBr, (a Lewis acid), and the reaction is a substitution, not an addition Br, ‘substitution fi CH oat CaHsBr Br replaces H ‘wt ‘a RAY+ Proposed structures of benzene must account for its high degree of unsaturation and its lack of reactivity towards electrophilic addition August Kekulé proposed that benzene was a rapidly equilibrating mixture of two compounds, each containing a six-membered ring with three alternating x bonds. In the Kekulé description, the bond between any two carbon atoms is sometimes a single bond and sometimes a double bond. These structures are known as Kekulé structures oOo a Although benzene is still drawn as a six-membered ring with alternating x bonds, in reality there is no equilibrium between the two different kinds of benzene molecules. Current descriptions of benzene are based on resonance and electron delocalization due to orbital overlap. In the nineteenth century, many other compounds having properties similar to those of benzene were isolated from natural sources. Since these compounds possessed strong and characteristic odors, they were called aromatic compounds. It should be noted however, af that it is their chemical properties, and not their odor, that make them special oFStructure of Benzene Any structure for benzene must account for the following facts: 1 It contains a six-membered ring and three additional degrees of unsaturation. 2. Itis planar. 3. AllC—C bond lengths are equal The Kekulé structures satisfy the first two criteria but not the third, because having three alternating x bonds means that benzene should have three short double bonds alternating with three longer single bonds. nest were eo =e ghonbend =e + Iong bond \Z (exaggerates) ) ages) | This structure implies that the CC bonds 2 vis Sa ar ‘should have two different lengths. ree long bonds + Inbenzene, the actual bond length (1.39 A) is intermediate between the carbon—carbon single bond (1.53 A) and the carbon—carbon double bond (1.34 A). The C~C bonds in benzene are ciel Cesore | 63 Oi ‘equal and intermediate in length. 153A 130A t 1904 | Bonzone—A plonor moiseule a s 3° _ “ ey, 3 ro ces brieThe stability of Benzene Comparison of the hypothetical and observed heats of hydrogenation for benzene. ne with three “regular” C=C bends _ Og i oe |__| Benzene is 36 kcal/mol [ = ) lower in energy. AHP = 88.8 kealfmol NZ Sie AH? = —49.8 kcal/mol CO O (observed) The huge difference between the hypothetical and observed heats of hydrogenation for benzene cannot be explained solely on the basis of resonance and conjugation. aS+ The low heat of hydrogenation of benzene means that benzene is especially stable—even more so than conjugated polyenes. This unusual stability is characteristic of aromatic compounds. Benzene's unusual behavior is not limited to hydrogenation. Benzene does not undergo addition reactions typical of other highly unsaturated compounds, including conjugated dienes. Benzene does not react with Br, to yield an addition product. Instead, in the presence of a Lewis acid, bromine substitutes for a hydrogen atom, yielding a product that retains the benzene ring. H 24 py ANB Addition does nat occur. GC | +e It J Ny S ye a off Substitution occurs. | cr Y CF — 7 9 ‘An addition product would no longer contain a benzene ring. ‘A substitution product stil contains | abenzene ring. ‘ oe weg =Physical properties > Colorless liquid >» Melting point 5.5 Celcius > Boiling point 80.1 Celcius > Hydrophobic Benzene Uses Benzene is used in the production of many materials and products Including : styrene, some types of rubbers, lubricants, dyes,drugs, synthetic Detergents, insecticides, fumigants, solvents, paint removers and gasoline aSBenzene and Aromatic Compounds The Structure of Benzene + In benzene, the actual bond length (1.39 A) is intermediate between the carbon—carbon single bond (1.53 A) and the carbon—carbon double bond (1.34 A). oxo ots | OS) — C) [itscteamauiinen 153A wha 130A =e €u * a 4 “ = Hs $ H wr 2 r — sp* hybridized a, porbitals 9Nomenclature of Benzene Derivatives * To name a benzene ring with one substituent, name the substituent and add the word benzene. CHs (Fence | G-CHy (ta ethyl group CH chloro group tert-butyl group ethylbenzene ter-butylbenzene chlorobenzene + Many monosubstituted benzenes have common names which you must also learn. Ow Oe On toluene phenol aniline (methylbenzene) dyrenybercond (aminobenzene) ®+ There are three different ways that two groups can be attached to a benzene ring, so a prefix—ortho, meta, or para—can be used to designate the relative position of the two substituents. 1,2-disubstituted benzene 1,3-disubstituted benzene | 1,4-disubstituted benzene ortho isomer meta isomer para isomer er Br + a o~ WJ ortho-dibromobenzene or o-dibromobenzene or 1,2-dibromobenzene CL meta-dibromobenzene or m-dibromobenzene or 1,3-dibromobenzene para-dibromobenzene or p-dibromobenzene or 1,4-dibromobenzene+ If the two groups on the benzene ring are different, alphabetize the names of the substituents preceding the word benzene. + If one substituent is part of a common root, name the molecule as a derivative of that monosubstituted benzene Alphabetize two different substituent names: Br NO, <—nitro group re LZ — re F @-bromochloro- m-fiuoronitro- benzene benzene Use a common root name: toluene phenol = . NO2 Br CH, ‘OH p-bromotoluene o-nitrophenol 12For three or more substituents on a benzene ring: Number to give the lowest possible numbers around the ring. Alphabetize the substituent names. When substituents are part of common roots, name the molecule as a derivative of that monosubstituted benzene. The substituent that comprises the common root is located at C1. 1. 2; 1 0 ce cr P°CHCH.CH3 4 2 + Assign the lowest sel of numbers. + Alphabetize the names of all the substituents | é-chioro-1-ethy/-2-propylbenzeno | mples of naming polysubstituted benzenes esac 5 + Name the molecule as a derivative of the common root aniline. + Designate the position of the Nis group as“, and then assign the lowest possible set of numbers to the other substituents. | 2,5-dichioroaniline+ A benzene substituent is called a phenyl group, and it can be abbreviated in a structure as “Ph-”. i i cr abbreviatedas | Ph— phenyl group CoHs: ¢ Aphenyl group (CH;—) is formed by removing one hydrogen from benzene (C¢H,). + Therefore, benzene can be represented as PhH, and phenol would be PhOH. LH OH CY = | GHeA cr = | HOH PhH PhOH benzene phenol 14* The benzyl group, another common substituent that contains a benzene ring, differs from a phenyl group. CH.-? i CIN ecg Cr benayl group phenyl group CgH-CH.— CeHs— + Substituents derived from other substituted aromatic rings are collectively known as aryl groups. Examples of Sy 3 oe i aa sae Ly Ly ad cH Br CH;ELECTROPHILIC AROMATIC SUBSTITUTION + The characteristic reaction of benzene is electrophilic aromatic substitution—a hydrogen atom is replaced by an electrophile. Benzene has six x electrons delocalized in six p orbitals that overlap above and below the plane of the ring. These loosely held x electrons make the benzene ring electron rich, and so it reacts with electrophiles. Because benzene’s six x electrons satisfy Hiickel's rule, benzene is especially stable. Reactions that keep the aromatic ring intact are therefore favored. Electrophilic aromatic substi electrophile substitution of H by Eigure 18.1 Fieexamples Reaction Electrophile ‘of Seetrophiic aromatic subetitution [1] Halogenation—Replacement of H by X (Cl or Br) H nk A ype Oo S Fox “ x=ci at halide Xebr [2] Nitration—Replacement of H by NO, H KO, (eo HNO, Cr SS 1,80, % niltobenzene [3] Sulfonation—Replacement of H by SO:H 2 Of = HO, Denzenosulfonic acid [4] Friedel-Crafts alkylation— Replacement of H by R H LR ey A fe J] (esa AIC S akyl benzene Friedel-Cratts alkylation and (arene) acylation, named tor Chaves Fede’ and ames _(5]Friedol-Crafte cael of H by RCO Grafts who discovered the reactions in the nineteenth Hi x century, form new a eoct n sae CY O (Pane) ‘ Ais ketoneHALOGENATION + In halogenation, benzene reacts with Cl, or Br, in the presence of a Lewis acid catalyst, such as FeCl, or FeBr,, to give the aryl halides chlorobenzene or bromobenzene respectively, + Analogous reactions with |, and F, are not synthetically useful because I, is too unreactive and F, reacts too violently. 1 ee H o cl Chlorination ~ FeCl, chlorobenzene H Br Bro Fer, bromabenzeneMECHANISM 18.2 % Step [1] Generation of the electrophile Bromination of Benzene om + Feb = eB, Lewis base Lewis acid lectrophile (serves as a source ol Br*) Step [2] Addition of the electrophile to form a carbocation a H H H ee Bre Br Pus B reba — had = resonance: stabilized carbocation + FeBre Step [3] ees aie 6 Fame emma Th Bs FeBy + HBr ore + FeBr, eae *® Lewis acid-base reaction of Br, with Firs forms a species with a weakened and polarized Br- Br bord. This adduct serves 8a source of Br’ in the next step. # Addition ofthe electraphile forms a new C~Br bond and generates a carbocation This carbocation intermediate is resonance stabiized— three resonance structures ccan be drawn. # The Fer,” also formed inthis reaction is the base used in Step (3). “ FeBr.” removes the proton from the carbon bearing the Br, thus re-forming the aromatic ring, FeBr,, a catalyst, is also regenerated for another reaction cycle.NITRATION and SULFONATION * Nitration and sulfonation introduce two different functional groups into the aromatic ring + Nitration is especially useful because the nitro group can be reduced to an NH, group. NH, es en ~HeSO, 7 Section | Seage [ 18.14 nitrobenzene aniline H SO3H Sulfonation 55: HoSO4 benzenesulfonic acidGeneration of the electrophile in both nitration and sulfonation requires strong acid. Formation ofthe Nitronium lon ("NO or Nitration f aI uo tn | fa Q-N=0 \| t HON, + A080 —- HON, —> HO + + 10, sectrogtile Lewis stuctureIn sulfonation, protonation of sulfur trioxide, $03, forms a positively charged sulfur species (°SOsH) that acts a an electrophile, Formation of the Electrophile *SO,H for Sulfonation 0: 10: leaps _, i - 3 gs: + H70SO.H 8 NH = | *803H | + HSO, clectrophileFriedel-Crafts‘Alkylation and Friedel-Crafts Acylation + In Friedel-Crafts alkylation, treatment of benzene with an alkyl halide and a Lewis acid (AICI,) forms an alkyl benzene. Friedel-Crafts alkylation— General reaction OWN R Examples cr 2 AIC new C—C bond | + HCI alkyl benzene CH)CHy Oo _CHsCH.CI a | * + HCI AICls Sy a (CH) _{H),CCr ~ | . 7 HCI RICFormation of the Electrophile in Friedel-Crafts Alkylation— Two Possibilities ForchyCland t°RC:| Cliscty-G + “Ac, —> | chyCHy-C-Ack Lewis base Lewis acid Lewis acid-base complex A cry ime FRCL! cHy.c-ti + “All, —> (CHy,C,0-Acl, —> Lewis base Lewis acid + AC4 For Gh and 1° PCL te Les acid-base comple sl serves a he eect foeletohi aromatic suotuton, 4 With? and ACL the Lewis acid-base complex rcs futher to give 2 or! carbocation which snes a lerptile Crbocaton maton cccurs only wth 2 and} aylclondes, paca they aod more tbe caroctons; Friede!-Cratts Alkylation Using a 4° Carbocation (ck on C1 a ih "hi T + Hol + AR, y Sabo Veal " tivo mate | structures Addition ofthe electroohit 3° carbocation} forms a new carbon-cardon bond in Step (1). AICI; removes @ proton on the carbon bearing the new substituent, thus re-forming the aromatic ring in Step (2)+ In Friedel-Crafts acylation, a benzene ring is treated with an acid chloride (RCOCI) and. AICI, to form a ketone. + Because the new group bonded to the benzene ring is called an acyl group, thé transfer of an acyl group from one atom to another is an acylation. (9 REC A 9 B | — cca grou Friedel-Crafts acylation— | [~ ] . u ( c, "yl group ‘General reaction Mie, . ——— Rc zich Hel acid chloride eae H ° 2 Example). q J + & iors + 01 KS oH ct ag, LL new G—G bond S Formation of the Electrophite in Friedel-Crafts Acylation io, Lf sac, R Lowis acid a reconance-stabilizod acylium ion electrophileSubstituted Benzenes + Many substituted benzene rings undergo electrophilic aromatic substitution + Each substituent either increases or decreases the electron density in the benzene ring, and this affects the course of electrophilic aromatic substitution ® Donation of electron density to the ring makes benzene more electron rich. Withdrawal of electron density from the ring makes benzene less electron rich. Atoms more electronegative than carbon—including N, O, and X—pull electron density away from carbon and thus exhibit an electron-withdrawing inductive effect. # Polarizable alkyl groups donate electron density, and thus exhibit an electron- donating inductive effect. Considering inductive effects only, the NH, group withdraws electron density and CH, donates electron density. Electron-withdrawing inductive effect | [ Electron-donating inductive effect | CN f\ & )—NH, )—CHs V4 VS , Ky ad + Nis more electronegative than C. + Alkyl groups are polarizable, making i sf +N inductively withdraws electron density them electron-donating groups. wyOme Quin Electron-withdrawing groups OO: The electron-donating rasonance effect predominates. The olectron-withdrawing inductive effect predominates. ‘With a =CHO group, the inductive and resonance effects reinforce’ benzaldehyde structures ‘The polar C—O bond withdraws electron density from the ring inductively Resonance removes electron density as well. + five more resonance+ These compounds represent examples of the general structural features in electron- donating and electron withdrawing substituents. " Electron-donating groups Electron-withdrawing groups Oo | o =alkyl Z=NorO X= halogen Common electron-donating groups: Common electron-withdrawing groups + Alkyl groups + Halogens * Groups with an NorO atom bonded to | + Groups with an atom Y bearing a positive the benzene ring; N or O must have a charge (8° or +) bonded to the benzene ring lone pair. Electrophilic aromatic substitution is a general reaction of all aromatic compounds, A substituent affects two aspects of the electrophilic aromatic substitution reaction: 1. The rate of the reaction—A substituted benzene reacts faster or slower than benzene itself. 2. The orientation—The new group is located either ortho, meta, or para to the ‘ existing substituent. The identity of the first substituent determines the position of ¥ the second incoming substituent. sConsider toluene—Toluene reacts faster than benzene in all substitution reactions. The electron-donating CH, group activates the benzene ring to electrophilic attack. Ortho and para products predominate. The CH, group is called an ortho, para director. ae og Aas we (J aa + G i ais si sara 40% trace [e0% Consider nitrobenzene—lt reacts more slowly than benzene in all substitution reactions. The electron-withdrawing NO, group deactivates the benzene ring to electrophilic attack. The meta product predominates. The NO, group is called a meta director. No, Ay NO: | cy ee Co + 4 H;80, 2~no, ortho 7%All substituents can be divided into three general types: BMI ore, pars carectors and acuvators © Subst ents that activate a benzene in ortho and para. “tit, |B] ortho, para deactivators © Substituents that deactivate a benzene 1 [lines crestor Substituents that diveet substitution meta. ‘Alien rwext cnet tia vig: “cH0 con GA ~S00H | General structure “cn Gor) “S04 “NO, ARs AY sOrientation Effects in Substituted Benzenes + There are two general types of ortho, para R Ortho, para ~ directors and one general type of meta director. ors ai + Allortho, para directors are R groups or have a \A nonbonded electron pair on the atom bonded to. Z=N,O,o0rX the benzene ring. + All meta directors have a full or partial positive SY (8 or) charge on the atom bonded to the benzene ring Matal directors. | 2 Determine the Directing Effects of a Particular Substituent Step [1] Draw all resonance structures for the carbocation formed from attack of an eleetrophile E* at the ortho, meta, and pata positions of a substituted benzene (CjH.~A). ofginal substituent —» A ¢Sy——otno © There are at least three resonance structures for each site of reaction. NO2 p-bromonitrobenzene Let us consider the consequences of bromination first followed by nitration, and nitration first, followed by brominationPathway I, in which bromination precedes nitration, yields the desired product. Pathway II yields the undesired meta isomer. Pathway [1]: Bromination before nitration ortho, para director Br Br AL Bre SS HNO, =O No, | _ The ortho isomer can be 2} separated from the mixture, para preduct This pathway gives the desired product. HNO This pathway does NOT form O H,80," Feta" the desired product. ~ ta director ae) meta isomer