(CHEMISTRY) CHAPTER PRACTICE PROBLEMS Give mechanism for the following transformations . i ) ocHcr=te, oH = O = Hye" * ~ onuns . oy > i i 00H oe wf Ser @ on ° sore. C(cH)y aC: CiCHs)s = + Her Oxy 0190 f)— 9-c0CH, on : “OO, Give reasons for the following (a) o-Nitropenol is steam - volatile but both m - and p nitrophenols are not, {b) Phenol fs more acide then cyclohexanol but less acide than benzoic acid (6) The OH group in phenol is ortho, para ~ directing and highly activating in eleciphilic aromatic substitution reactions (a) 2,4, 6 Trinitrophenol liberates COs from NaHCO but phenol does not. {c) Reaction of phenol with HsSO. at 60°C gives mainly 0 ~ hydrexybenzenesulphonic acd but at 100°C gives mainly p ~ hydronybenzenesulphonie acid () Friedel ~ Crafts allylation of phenol with alkyl halides in presence of anhydrous AlCl, is unsatisfactory. {g) Cyclohexanol reacts with HBr to give cyclohexyl bromide but phenol does not react. OxOxOxOx¢- — oN © scanned with Oken Scannero c I ore mood * L* JO" . qi FHo=HotHo. | ‘O):2 tect stant 69 HOOOTHO'HOON'D:(0) NO'HOTHOO'' (a) BNOTH'D“(¥) _(H) STONGHG |: SaaMsSNv |_ QAUSTINGHO)] SWaTdOUd AQLLIVUd WALAVHS © scanned with Oken Scanner(CHAPTER PRACTICE PROBLEMS | (CHI we oko = a Cprecoss 0 (C)-ssoer1e—(C) coor hur. “OC-06 @ ona RB -Hes Coe mck @ (24), 6-o po, ae ),6-OH, 1490. —+(0H,), 641.044, PO, ae oH chy os — ae Ho" (0%), moe Worcs © scanned with Oken Scanner[CHAPTER PRACTICE PROBLEMS [(CHEMISTRY) Oo On ZH aa on I , Ye ate ® a a a anyone” 8 tyne” “Sr oe ” > a hen onde le, (iin hock, j onli A = ‘cH, Ow oars) 6b 8 7] “OC On Oy. OO, | 3. (a) e*Nitrophenol involves intramolecular hydrogen bonding while m ~ and p-nitrophenol und interme hye bonding The apparent molecular an of he wo ae er (oy The conjugate base of cyclohexanol, ie. CHO" does not have any resonance stabilization. phenoxide lon (conjugate base of phenol i resonance stabilized, The benzenecarbonvate fine conjugate base of tenzenccarborglic acid i more resonance stabilized then the phenox {on The greater the resonance stabilaation of conjugate base, the more isthe sci { © scanned with Oken Scanner| CHAPTER PRACTICE PROBLEMS (CHEMISTRY) (q) The nitro groups at 2, 4 and 6 positions in 2,4,64rinitrophenol withdraws electrons by Fesonance and hence increases the acidity considerably. Thus, 2,4,6-trinitraphenol is more acidic than carbonic acid (NCOs). Hence itis able to liberate CO? from NaHCO, (0) Phenol undergoes Lewis acid ~ base reaction with AICIy as follows: GH, -OH+ AIC, —=0,H,9- AlCl, =—=26,H,0A0C, + HCI 4 So, AlCl becomes less available to react with R - Cl to form R-CLAICI, (the potential clectrophile), Moreover, coordination of OH with AlCls deactivates the ring. (@) Cyclohexanol reacts with HBr either by Syl or Sx2 mechanism, or by both. Neither Sy1 nor Sx2 reaction ia possible with phenol, HXOXOXOXE- a © scanned with Oken Scanner(CHEMISTRY) TICE PROBLEMS PHENOLS CHAPTER PRAC' Preditthe products (A), (B) (6 et in each ofthe folowing sequences of actions fa) HOH (A) 28224 (B) SEC) (8) caCH= CH pRB A) p10) 10) 1 opon as) ii H0)—FS-(0) (8) pons (0) 2 (0) 9(0) te I, on {Corsa zs (a) S22 (0) } 9 CRN A) +) (0) oH e CL ESO) oct, 8) CoH AAS (a) 08) } o oon (C)— sn) 0) ABE) BCA) 0) es (C) (1 cpKoH—RE-o(4) 25-6) —“9-(0) (0) 0 oh “tmigjocme (q) (6) 50 (6) chs (ca, BBB (A) 808) (8) cron (x) a> (a) ane (0) ® ¢ ; ‘oon (4) S80) = 90) I (81 con+co, sa (a) 406) | @ eo i seat (a) “OPO. ‘COOH © scanned with Oken Scanner