Chapter 5 ALCOHOLS, PHENOLS AND ETHERS INTRODUCTION | Allyic and benzylic alcohols may be primary, secondary or fertiary. T/F 2 Draw sec-Buty! alcohol 3. Common name of CH, CH- CH is - OH 4, Draw isobuty| alcohol 5. For naming polyhydric alcohols, the ‘' of alkane is replaced by cl. T/F 6. Draw ortho-cresol 1. Common name of -() OH uo w oF on Q OH 8 Draw Anisole (NEET) OH 4. Draw Phenetole 10. Common name of -C;H1,-O- CH= CH,~ CH—CH, CH. CH,OH IL IUPAC name of - () H.C. CH, (iid) 1 OCH, CH, - CH, - CH - CH CH- CH, ' CHCl CH NO, (i) on (jv) HC = CH - CH - CH, - CH, ~ CH. 1 OH 12. The bond angle in alcohol is shightly more than the tetrahedral angle T/F 18. Bond angle in ether is eighty higher than alcohol because - ALCOHOLS AND PHENOLS PREPARATION OF ALCOHOLS. 4. cH,-cH=cn, 22, D,O 15, CH,-CH=CH, 22>— on reaction with B2H6 give trialky!boranes. 17. Sqp/Anti addition takes place in B2H6 18. Hydroberaton oxidation Ren flow markomikow/art-markomikov rule 1A. Ring expansion and rearrangement takes place in HBO (Hydroboration-oxidahion). T/F 20. CH3-CH-CH2 + (BH8)2. H20/0H., 21. CH3-CO-CH-CH2 « (BH3I2 20/04, 22. Reagents used in Oxymercuration demercuration (OMDM) ran are - (2) 23. Syn/anti addon takes place in OMDM. 24, No ring expansion and rearrargement takes place in OMDM, T/E 25, CH3-CH=CH2 + H20 __HalGH3C0012/NoBHY SS . 6 H,O' H,0,/OH™ S Hg(OAc), 24, RCHO + H2/Pd > 30. RCOR' + NaBHls/H20 > 31 Esters, carboxylic acids and acid chloride are only reduced by LiAlH4/NoBHs. 32. LiAIH4+ and NaBH4s do not reduce C=C. 1/F 33. Reducing agents which reduce = bond are - (\4) 3b. Ester LAIH4/H30. 35. CH3CHO LinD4/H30., 36. CH3CHO Liatt,/D30., 31 Commercially acide are converted 40 oleohol by - 38. RCO-R + R-MGX afer hydrolysis give - 34. Ester on ran with Grignard reagent produces |°/2°/3° alechol PREPARATION OF PHENOLS 40. Phenol is also known as - LA + NaQH _623K/3000Im_, BB on acidification —> Phenol, Identify A & B. SO.H wot dm:Nib 43 NaNO, 4 OB yy eH na Warm 4b, Draw cumene. cH, f CHy-CH on 45 OQ» A wee (NEED ° CH;-C —OCH, 46. cy i Nabit, oO _~ PHYSICAL AND CHEMICAL PROPERTIES 47 The solbiity of alcohol decreases with increase in size of the alkyW ary) group. T/F 48 Phenol is more acide than oleahol.T/F 44. Water is more acide than methanol T/E 50. Phenol isa stronger acid than water. 1/F 51 Phenol molecules are more stable than phenoxde ions. T/F 52 Arrange o-ntrophenol p-nitrophenol, m--nitrophenaln order of acide strength 53 Arrange o-flucrephenol p-florophenol m-faorophenol in order of acidic shrength 5h, Arrange o-eresol p-eresel and moreso in order of acide strength 55. Arrange o-methoxyphenol p-methoxypherol and m-methonyphena in order of acide strength CHEMICAL REACTION OF ALCOHOL 56 ROH + Na > OH ok +2Na—> 58 The reaction with acid chloride is carried out in the presence of @ _______ so as to neutralise HCI which is formed during the reackion COOH 54 OH “ + (CH,CO),0-> 60. Arrange Cl.OH-RO- ard R-CO-O- in order of their leaving tendency. 61 Lucas reagent is - (NEET) 62. Lucas test is a test to find -—— 63, How does Lucas reagent differentiate between 1°.2°3° alcohol? (NEET) 6h, How does Lucas reagent cause turbidity ? 65. Order of I°, 2°, 3° alcohol in its ease of dehydration is - 66. Dehydration of alkohol happens by treating it with - (5) OH OH 61 cH-e—¢-cn, cu, 6H, 68. RCHZOH (im presence of acidified KMn() —> 64. RCH2OH (in presence of Cr03) —> 10. CH3-CH=CH-CHZOH (in presence of PCC) —> TI Sec-alcohols are oxidised fo _____ in Cr03, Ta. RCH20H _Cu/Si3K , 73. R-CH(OH)-R’ _Gu/S73K_, (NEET) CH, hm? 8 soy bon, on 573K b. MnO, MnO, 16, Mn02 oxides only allge or benzylic alechol T/F CHEMICAL REACTIONS OF PHENOL T1 Ortho and para nitrophenel can be separated by technique. (NEED 8. prvitrophenol has intra/intermolecular H bonding 1A. Direct nitration of phenol by cone. HNO3 gives poor yields of picric acid. T/F 80. To get good yield of picric acid what ic done? OH i Mapa an wie pasacl Farad ae = . jr P brim CS, Ose 82. Phenol + Br2/H20 — A. Identify A and also its colour. oH od Bh Reagents in Reimer-Tiemann reaction are ~ OH 85. OQ CHC, + aq NaOH. (NEET) +> 86 Intermediate electrophile formed in Rimer-fiemann reaction that attack benzene is - (NEET)2 87 oO CHCL NaOH on 88 + Zn ou 34 Na,Cr.0,, 780, SOME COMMERCIALLY IMPORTANT ALCOHOLS. 90. Methanol is also known as - Zn0-CrO2 es 200-300 atm 573-673 K 92. CILH220N + H20 —> Glucose + Fructose, eneyme used in this ran - 43. Glucoce —> CZHSOH + C02, enzyme used in thie ran ~ 4b. Action of aymase is inhibited once the X of alcohol formed reaches -—X 45, Commercial elohol is made unfit for drinking by ming - (2 46. The above process is caled - ETHERS 4 CO+2H, PREPARATION OF ETHERS 1. CH3CH20H HeSOK/43K 98. Alcohol in low temp. conditions form ether. I/F 499. Ether formation is a Snl/Sn2 reaction. 100. Write Williamson synthesis reaction - (NEET) 101. If 3° alkoxide ion is used, no ether is formed T/F 102. If 3° alky) halide is used. no ether is formed T/F 103. The BP. of alcohol is less than ether for the same molar mass, T/F | CHEMICAL REACTIONS 104. Least reactive functional group is ~ 105, Aryl-onygen bond ie more atable than alkyl-oxygen bond. T/F 106, The order of reactivity of hydrogen halides with ether is - 107. CH3-0-CH2-CH8 + Hl >108. If a Ferhary alkyl group is present inthe ether. the reaction process through mechariam,ofheruize it proceed through et 104. CHs-C—O-CHy +HI—> CHs & QoQ sn OcH, Br in Ethanoie acid Il 1 Victor meyer test isnot given by !°/ 2°/ 3° alcohol (NEET) 1, Aspirin is acetylation product of - (NEET Ith. Oil of winter green is - (NEEDANSWERS + INTRODUCTION LT 2. CH,~ CH - CH,~ CH, 1 OH 3. Isopropyl alcohol 4. CH, - cH ~CH,-OH CH, oF CH, OH 1. Catechol resorcinol, hydroquinone or quinol OCH; OCH,CH; 8 O ‘ (0, Phenyl Isepenty! ether IL) 2-E+hony-J-dimethyleyeehexane (i) |-Ethouy-2-nitrocyelehexane (i) 4-Chloro-3-ethyl-2-(methylethy)-butan--el (iv) Hex-I-en-3-ol iF |8. OF repulion between bulky alkyl groups on either side of + ALCOHOLS AND PHENOLS iy, CH,- CH - CH,D ou 5, CH,- CH ~ CH, op 16, Alkene 11. Syn 18, Antimarkovrikov re WF 20. CH3-CH2-CH2-OH 21, CH3-CO-CHIOW)-GH3, this product is formed because the terminal carbon have partial we charge due to resonance with C=0 22, Ha(CH3C00)2/NaBHY 23. Anti 24 T 25. CH3-CH(OH)-CH3 OH 26. eS OH n —— FS" — OH 28. 24. R-CH2-OH 30. R-CHIOW-R’ 31 Lidl 32.7 33 Pa/H2, BZH6, Na/Ethanol Raney Ni? 3h Alcohol 35. CH3-CHIOH)-D 36, CH3-CH2-0D 31, By converting them to esters followed by reduction using H2/Pd (or any other metal i RCOR + R'MgX —> R-C- omgx 225 R Re R-C- OH + Mg(OHDX R 343° 40, Carbolic acida “ O . o 42 A- Phau . Phenol wes B- ee CH, CH; C-0-0-H 45.A- Q B- CH,COCH, OH Ch 1G —OCH, 46 ° WIT 4B WF 80.T SIF 52 prritrophenel > o-rtrophenel > m--ritrophenal 53 o> p>m 5h. m> poe 55.m>o>p 56 RONG $1 2 +He 58. baselpyridine) 54 COOH OCOCH, + CH,COOH 60. Cl > R-CO-0- > OH- > RO- [Tip - Strong acid have good leaving conjugate base. Ax HCI > RCOOH > HZ0 > ROH in terms of acidity their conjugate base stabilty order ie aso the same and hence the leaving tendency] 61 ZnC2/HCI 62. the ‘degree’ of alcohol ie. I, 2°, 3° 63° aleohol - No turbidity 2° aleahel - Turbidity after 5 min, 3° oleahol - turbidty immediate 64. R-OH + Lucas reagent —> R-X. which in inzlube in Lucas reagent hence give turbidity 65.3°>2°>/° 66. Protc acid (eg. -Cone. H2SOl or H3PO4), P205/A. A203/D, Zn, POCIB/Pyrdine CH, 2 61. CH ¢— C-CaHts This pingclepinacglone ss, rearral reachon 68. R-COOH 69. RCHO 10. CH3-CH=CH-CHO Tl. Ketone 72, RCHO BROR ory I CH,- ¢- OH 14 CH, Oo ‘A 16.T TI, Steam distillation 18. Intermolecular H bonding aT 80. First phenol is sulphonated than nitratedOH OH FT Br + Minor Major IH Br Br, be 8 white precipitate Br 84, CHEIR ag NaOH CHO 85. Cy 86. CCi2 (dichlorocarbene) 81. + ZnO 88 84. R-O-R' + NaX 10 F 102. T 103. F 104. Ether 105. T 106. Hl > HBr > HCI 107. CH3-1, CH3-CH2-0H 108. Sol, Snd CH, 1 101, CH,OH +CH)—C-1 CH o Oe Qn OCHs OCH, Br Uh + Br p-Bromoanisole 0-Bromoanisole (Major) (minor) I. 3° [Victor mayer give red colour with I°, blue colour uith 2° and remaine celurless with 3° alechol ae no reaction with HNO2 occur] 13. Saheyie acid Ils. Methy! salicylate