«+ Aromatic Compounds: CH | ~~ Side chain | ~ senzene ng (Benzene nucleus) “* Aromatic Halogen Compounds: Aryl halides (Arylalkylhalide) (Haloarenes) CHyX x oO (Phenyl methyl halide) (Phenyl halide) + X-atom is directly bonded + X-atom is directly bonded to C-atom of side chain. to C-atom of Benzene ring. Haloarenes (Ar-X): * These are the organic compounds in which X-atom is directly bonded to C-atom of benzene nucleus. + These are the halogen derivatives of benzene. For examples: Chlorobenzene = Bromobenzene lodobenzene cl a oO" O ; ~Ccl o-dichlorobenzene m-dichlorobenzene (1,2-dichlorobenzene) (1,3-dichlorobenzene) cl OH oO" f o-chlorophenol p-dichlorobenzene (2-chlorophenol) (1,4-dichlorobenzene) a Br om om a I 1,2,3-trichlorobenzene —_1-bromo-2-chloro-3-iodobenzene Note: G With respect to G, > 1,2 —= ortho (0) > 1,3 —> meta (m) > 1,4 —= para (p) + Isomerism: * Dihalogen substituted benzene shows following isomerism: a) 1,2-dihalobenzene (o-dihalobenzene) b) 1,3-dihalobenzene (m-dihalobenzene) ¢) 1,4-dihalobenzene (p-dihalobenzene) cal a cd 6 a, 8 o-dichlorobenzene m-dichlorobenzene _p-dichlorobenzene (1,2-dichlorobenzene) (1,3-dichlorobenzene) (1,4-dichlorobenzene) General methods of preparation: 1. By direct halogenation of benzene: Ho, x oo ekOR Ay 6 +oxx Say Oo + HX Benzene (X,) Halobenzene For examples: cH cl “+ che) fo 6 + HC Benzene (ClI,) Chlorobenzene 2. From Benzene diazonium chloride(BDC): (Sand Meyer's reaction): Nen-Cl cl + cucl, 4 o + CuCl, +N, BDC Cuprous chloride Chlorobenzene N=N-Cl Br + Cu,8r, 4 Oo + Cu,Cl + Np BDC Cuprous Bromide Bromobenzene » This reaction is called Sand Meyer's reaction. > If Cu-powder is used instead of Cu,Cl, or Cu,Br,, the reaction is called Gattermann reaction. cl Br cu/tor us Oo +N 2 Bromobenzene “+ Chemical properties: 1) Nucleophilic Substitution Reaction(NSR): > Haloarenes (Halobenzenes) are less reactive than haloalkane towards nucleophilic substitution reaction. & This is due to a) Resonance effect b) Hybridization effect ¢) Polarity effect a) Resonance effect: ey Resonance Hybrid Fig: Resonating structure of Halobenzene. > From above resonating structure of halobenzene, it is clear that C-X bond acquires partial double bond character which is shorter and stronger than C-X single bond exist in haloalkane. > Therefore, nucleophile cannot displace halogen atom from benzene ring easily. > Hence, it is less reactive than haloalkane towards nucleophilic substitution reaction. O why is ary! halide less reactive than alkyl halide towards nucleophilic substitution reaction? O Compare the reactivity of Chlorobenzene and Chloroethane towards nucleophilic substitution reaction. O Draw the resonating structure of a) Chlorobenzene b) Bromobenzene ¢) lodobenzene d) Fluorobenzene e) Halobenzene b) Hybridization effect: > In haloalkane, the C-atom of C-X bond is SP? hybridized where as in haloarene (halobenzene) the C-atom is SP? hybridized. Halobenzene > The SP, hybridized carbon with greater S-character is more electronegative as compared to SP, hybridized carbon. > Hence, X-atom is more tightly hold in halobenzene than that of in haloalkane. | Sp? hybridized Sp? hybridized -o- x Haloalkane > Therefore, nucleophile can not displace X-atom from benzene ring easily. > Hence, halobenzene is less reactive than haloalkane towards nucleophilic substitution reaction. ¢) Polarity effect: > sp2 hybridized C-atom in halobenzene is more electronegative than sp3 hybridized C-atom of haloalkane. > Therefore, C-X bond of halobenzene is less polar than that of haloalkane. > So, greater the polarity of C-x bond, higher will be the reactivity. > Hence, halobenzene is less reactive than haloalkane. > However, under drastic condition(vigorous condition; use of high temperature, high pressure, strong alkali, etc. halobenzene also undergoes nucleophilic substitution reaction. > Some important Nucleophilic substitution reactions of Haloarene are: 1) Action with dil. NaOH (or aq. KoH)(Hydrolysis) (Dow’s Process): ce ONa oH O + mont Qatar Chlorobenzene (5, Sod. Phenoxide Phenol 2. Action with alc. NH, (Ammonolysis): j Chlorobenzene — (alc.NH,) Aniline 3, Action with Cuprous Cyanide[Cu,(CN),] : / CN Pyridine/OMF/A + coger), sola © + NH,CI Chlorobenzene Phenylcyanide (Benzonitrile) NH, cu,0/8 1 200% 60atm + NH,CI + Reactions of Phenyl Cyanide: (OOH Hom Tomi ere Benzoic acid N ‘ONH, one wa tres genfamide H,-NH,, Phenyl Cyanide (Benzonitrile) uation NalcHor edurton Benzyl amine 2. Reduction: i) Ni-Al/NaOQH(KOH)/d } 2H oO + Hel Chlorobenzene Benzene 3. Electrophilic Substitution Reaction(ESR): > In halobenzene, electrophilic substitution(ESR) takes place at ortho and para positions. > This is due to resonance effect. Resonance Hybrid Fig: Resonating structure of Halobenzene. > From above resonating structures of halobenzene, it is clear that halogen(x) atom donates its lone pair electron to the benzene ring through resonance. > Asa result, electron density increases at ortho and para positions as compared to meta position. > Therefore, incoming electrophile is likely to attack on these positions resulting the formation of ortho and para substituted products. > This effect of halogen is called ortho-para directing effect. > On the other hand, halogen has powerful electron withdrawing inductive effect(- | effect) over its resonance effect. > Therefore, electron density finally decreases on benzene nucleus of halobenzene as compared to benzene. > Hence, electrophilic substitution reaction in halobenzene takes place slower than in benzene. > This effect of halogen is called ring deactivating effect. Q Why does electrophilic substitution reaction in halobenzene take place at ortho and para position? Q Halogen atom is ortho-para directing, why? OQ Halogen atom is ring deactivating even though it is ortho- para director, why? > Some important Electrophilic Substitution reaction of Haloarenes are: 1. Halogination: > Replacement of H-atom of benzene ring by X-atom. ql a ql cl Fec, Oo + Cl, ee o + 3 + HCl Chlorobenzene o-dichlorobenzene fy p-dichlorobenzene (Major) 2. Nitration: > Replacement of H-atom of benzene ring by NO, group. > Nitrating mixture = conc. HNO, + conc H,S0, > Nitrating mixture produces nitronium ion(NO,). al cl a Conc.H,S0, NO, + HNO, + + H,0 °- {cone.) itrochlorobenzene yo, Chlorobenzene p-nitrochlorobenzene (Major) 3. Sulphonation: > Replacement of H-atom of benzene ring by SO,H group. cd cl cl _-SOH + + H,0 o-chlorobenzene S0,H Sulphonic acid chlorobenzene sulphonic acid + H,S0, (fuming) Chlorobenzene (Major) 4, Fridel-Craft reaction: a) Friedel-Craft Alkylation: a a (a) CH. hy. AIC e) 6 + CHC! ivan Oy + 0 + HCl Chloromethane 0-chlorotoluene cH, Chlorobenzene p-chlorotoluene (major) b) Friedel-Craft Acylation: cl ° a Bow a a ant - + CHyC-Cl = + + HCI Chlorobenzene Ethanoyl chloride © 4 chioroacetophenone (Acetyl chloride) cock, pehlomacetophenone (Major) OR b) Friedel-Craft Acylation: cl g 09 oe g CCH, + CHYC ci, SG + + HCl creme OR(CIACO),O | oenereszrarerone Loc, Ethanoic anhydride . ; p-chloroacetophenone (Acetic anhydride) (Major) 4. Action with Sodium(Na) metal: a) Fi se O-O = vac Biphenyl (two molecules) b) Wurtz-Fittig reaction: cl 6 Na/A + CHC + NaCl Oo 2 Gry ether a Chlorobenzene Toluene 5. Action with Chloral (CCL, cd cl i H™ Conc.H,SO, CI5CaC-H + HO Qo a CCl,-C-H a Chloral cl a Dichlorodiphenyl Chlorobenzene trichloroethane (DDT) (two molecules) (2,2,1-trichloro-2,2-bis(4-chlorophenylethane * Uses of haloarenes: