Alcohols, Phenols and Ethers 7.2 Nomenclature cm 2 HEE (mario i 2 10. 1. CH; The correct IUPAC name of cH—¢—CH,CHis {a) tert-butyl afcohot I (b) 2,2-Dimethyipropanol () 2-Methylbutan-2-o1 (4) 3-Methylbutan-3-ol | OH (2020) © Write the IUPAC name of the following : CHa i CHy—C—CH—CH, ti HC, OH (2018)(f) | Write the IUPAC name of the following compound : HsC— C= C— CH,— OH | H3C Br (al2017) © Write the IUPAC name of the following compound : awe CH,OH (A12017)(%3) | Write the IUPAC name of the following compound : CH; I CHy-O~C—CH CHy (a12017) Write the IUPAC name of the given compound. ‘CH —CH,— OH cr (412016) Write the IUPAC name of the given compound : me NO, (Denn 20159(89) | Write the IUPAC name of the given compound : CHy=C—CH,— OH i CHy (a12015) | Write the 1UPAC name of the given compound: HOCH, —CHee ~CHy i CH, (Foreign 2015) | Name the following according to IUPAC system = CHa ~CH— CH, —CH OH (172, Dethi 2015¢) Write IUPAC name of the following compound : HO—CH,—CH—CHy—OH | OH (Foreign 2014) | | 1s. Previous Years’ CBSE Board Questions y 7.3 Structures of Functional Groups | 12. TheC —O—H bond angle in alcohol is {a} slightly greater than 109°28" {b) slightly less than 109°28" (c) slightly greater than 120° (4) slightly less than 120° (Term!, 2021-22)() . Assertion (A) : The C—O~H bond angle in alcohols is slightly less than the tetrahedral angle. Reason {R) : This is due to the repulsive interaction between the two lone electron pairs on oxygen, (a) Both Assertion (A) and Reason (R) are correct ‘statements, and Reason (R) is the correct ‘explanation of the Assertion (A). (b) Both Assertion (A) and Reason (R) are cori ‘statements, but Reason (R) is not the explanation of the Assertion (A). (©) Assertion (A) is correct, but Re: incorrect statement. (d) Assertion (A) is incorrect, but Re: correct statement, (202 74 Alcohols and Phenols Cem 14. Which of the following alcohols will not undergo ‘oxidation? (a) Butanol (b) Butan-2-o1 (c) 2-Methylbutan-2-01 (d) 3-Methylbutan-2-ol (2023) nC, In the reaction R — OH + HCl 24 RCI + H,0, What is the correct order of reactivity of alcohol? (a) 19<2°< 3" (b) 1°> 3> 2° (6) 19> 2>3° (d) 3°> 19> 2° (2023) Read the passage given below and answer the following ‘questions (Q.No. 16 to 18): Alcohols and phenols are acidic in nature. Electron withdrawing groups in phenol increase its acidic strength and electron donating groups decrease it. Alcohols undergo nucleophilic substitution with hydrogen halides to give | alkyl halides. On oxidation primary alcohols yield akdehydes with mild oxidising agents and carbaxylic acids with strong oxidising agents while secondary alcohols yield ketones. ‘The presence of — OH groups in phenols activates the ‘ring towards electrophilic substitution. Various important products are obtained from phenol like salicylaldehyde, salicylic acid, pric acid ete. Arr rrr16. Which of the following alcohols is resistant to ! ‘oxidation? i {@) CHs-C-OH th) CHy-CH—GH CH; CHy () CH3—CH,—OH = (d) CHj—OH &) 17. Which of the following groups increases the acidic | 72 character of phenol? (a) CH,0- (b) CH3- () NO2- (d) Allof these &) 18. Consider the following reaction: i eH t (NaOH, CO, (CHC, + 0g. NaOH y = aH aH" the products X and Yare OH CHO COOH fa) X= Y= ‘OH OH IH CHO COOH (b) x= Y- COOH ‘OH © Y= OH CHO IH OH | ‘COOH CHO 25. (d) x= Ye i (Term |, 2021-22) | 19. Inthe following reaction, (CH3—CH=CH—CH,—OH PCC, the product formed is (a) CH; —CHO and CHyCH,OH (b) CH; —CH=CH—COOH (©) CH;—CH=CH—CHO (d) CH3—CHy—CH—CHO (Term 1, 2021-22)(i) Which of the following acids reacts with acetic anhydride to form aspirin? (a) Benzoic acid (b) Salicylic acid {c)_ Phthalic acid (@) Aceticacid {Term |, 2021-22) 21. Assertion (A) : o-nitrophenol is a weaker acid than p-nitrophenol. Reason (R) : Intramolecular hydrogen bonding makes ortho isomer weaker than para isomer, {a) Both assertion (A) and reason (R) are correct | statements, and reason (R) is the correct explanation of the assertion (A). {b) Both assertion (A) and reason (R) are correct statements, but reason (R) is not the correct explanation of the assertion (A). (€) Assertion (A) is correct, but reason (R) is incorrect statement. (d) Assertion (A) is incorrect, but reason (R) is correct statement. (2020) The conversion of an alkyl halide into an alcohol by aqueous NaOH is classified as {a) a dehydrohalogenation reaction {b) a substitution reaction {c)_ anaddition reaction (d) adehydration reaction (2020) Assertion (A) : Alcohols have higher boiling point than alkanes of comparable molecular mass. Reason (R) : Alcohols have intramolecular hydrogen bond. (a) Both Assertion (A) and Reason (R) are correct ‘Statements, and Reason (R) is the correct explanation of Assertion (A). Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation of Assertion (A). (€) Assertion (A) is correct, but Reason (R) is incorrect statement. Assertion (A) is incorrect, but Reason (R) is correct statement. (b) (d) |. Carry out the following conversion: Phenol to salicylaldehyde Carry out the following conversion: Propene to propanol (1/5, 2020)(6r) >. Predict the reagent for carrying out the following. conversion: Phenol to benzoquinone (1/5, 2020, 2019) '. Predict the reagent for carrying out the following. conversion: Phenol to 2,4,6-tribromophenol (1/5, 2020) . Write the preparation of phenol from cumene. (1/3, 2020) . How can you convert the following? Phenol to chlorobenzene. (1/3, 2020) (61) ). How can you convert the following? Sodium phenoxide to o-hydraxybenzoic acid. (1/3, 2020) OR Write the equation involved in the following reaction: Kolbe’s reaction (1/2, Al 2019, Delhi 2014¢) . How can you convert the following? Ethanol to propanenitrile. (1/3, 2020)32. Give reason for the following: Phenol is more acidic than ethanol. (1/3, Al2017C, 2015) (in) Write the equation involved in the acetylation of salicylic acid, 33. (Delhi 2015) © 34. Which of the following isomers is more volatile : o-nitrophenol or p-nitrophenol? 35. Write the equation involved in the following reaction : Reimer -Tiemann reaction. (172,A12014) HET 22 marks) 36. Predict the products of the following reactions : () CH,CH,OH CuS73K,, na Betas (i) CgHsOH— > (2023) 37. following: (a). Whyis phenol more acidic than cyclohexanol? {b) Give one chemical test to distinguish between (2023) the two. Account for the following: (i) Phenol is a stronger acid than an alcohol. (ii increase in branching of alkyl chain. OR rite the mechanism of the following reaction fite the equation involved in Reimer-Tiemann tion. structures of the products formed when : Propan-2-olis heated with Cu at 573K. (ii) Salicylic acid is treated with (CH3CO),0/H". (2021C) 40. Carry out the following conversions : (i) Phenol to Anisole (ii) Aniline to Phenol (2021¢) 41 undergo acid catalysed dehydration faster and why? (2/5, 2020) (a) How are the following conversions carried out? (i) Propene to propan-2-ol (ii) Benzyl chloride to benzyl alcoho! (2020€, 2/3, Delhi 2015C)(ip) Give the mechanism for the formation of ethanol from ethene. 42. 43. (2/5, 2020, Al 2015) Write the major product(s) of the followingreactions CH)—OH mi 8 Q a, OK (i) (CHy)sCOH- E> (273, 2020)(0) (Delhi 2014)(n) For the pair phenol and cyclohexanol, answer the | The boiling point of alcohols decreases with | (2023) © Out of t-butyl alcohol and n-butanol, which one will | 47. 51. 52. | sa ». (a) Show . How do you convert the following? (a) Phenol to Toluene (b) Ethanol to Ethanal (2019) the chemical reaction with bond movements and arrows for the nucleophilic attack of water on carbocation in acid catalysed hydration of alkenes. (b) Give IUPAC name for the following : OH HC. CHy (2019C) Write the structures of the main products in the following reactions : ° CH,—C—OCH3 NaBH, @ CY “oa P aw ano tte (2/3, 2018)(i) Explain the mechanism of dehydration steps of ethanol. CHCH,0H E> CHy=CH+H,0 (2/3, 2018C, Delhi 2015C) Write the product(s) in the following reactions OH ‘COOH a Cr oe ,, (ii) CH; —CH=CH—CH,—OH—~9? (2/5, Dethi 2017) Give simple chemical tests to distinguish between the following pairs of compounds: {i)_ Ethanol and phenol (ii) Propanol and 2-methyipropan-2-ol. (2/5, Delhi 2017) Arrange the following compounds in the increasing order of their acid strength: p-cresol, p-nitrophenol, phenol Write the mechanism (using curved arrow notation) of the following reaction : CH= cH a CH3+H,0 (412017) (a) (b) Write the structure of the products when butan-2-ol reacts with the following : (a) CrOy (b) SOCl, (a12017) i) Write the main product(s) in each of the following reactions: By, () CHy— CH= CH, wont (ii) Cg —OH MEOH, weo,F (Dethi 2016)54. Write the final product(s) in each of the following reactions: “ CHa CH, — GH— CH CHB79K OH () CHCly + aq. NaOH arn (Demmi 2016) Write the mechanism of the following reaction: CH3CH;0H "5 CHaCH»Br+H,0 (Al 2014, 2/3, Foreign 2014) Name the reagents used in the following reactions: Bromination of phenol to 2,4, 6-tribromophenol (ii) Butan-2-one to Butan-2-o1 i (ii) Friedel-Cratts alkylation of anisole (iv) Oxidation of primary alcohol to carboxylic acid i) CoHs—OH 55. 56, (Foreign 2014)(Gr) | 57. Name the different reagents needed to perform the following reactions: (i) Phenol to Benzene i) Dehydration of propan-2-ol to propene i) Friedel-Crafts alkylation of anisole (iv) Dehydrogenation of ethanol to ethanal (Foreign 2014) | are the following conversions cartied out? ropene to Propan-2-ol i yl chloride to Ethanal (Delhi 2014¢) thefollowingwithanexampleforeach: olbe's reaction, | ji) Reimer-Tiemannreaction (2/3,Al2014C)(R) MEM omens) 60. (1) Why is the C—O bond length in phenol less than that in methanol? (il) Arrange the following in order of increasing | boiling point: Ethoxyethane, Butanal, Butanol,n-Butane {ili) How can phenol be prepared from anisole? Give | reaction. (2023) | How do you convert the following : (Any three) {a) Phenol to picric acid (b) Propanone to 2-methylpropan-2-o1 (€) Phenol to anisole (d) Propene to propan-1-ol (2023) | ‘Write the product(s) of the following reactions : OH 0) Oe 61, 62. | 65. OH COOH O° O + CH MgBr 22> (2020) (Ka) 63. Write the products of the following reactions : () CHs—CHy;—O—CH + HI OH Orn OCH; iin + cHjcoct “AC, ag ag) Give one chemical test to distinguish between the following : {a) Phenol and 1-propanol {b) Ethanol and dimethyl ether {) 1-propanol and 2-methyi-2-propanol (2019) {a) Show how will you synthesise the following alcohol prepared by the reaction of a suitable Grignard reagent on methanal? CHa — GH—CH,— OH CH {b) Write the mechanism of the fotlowit CH, =CH, + H,0—-> CH,CH,01 (a) How will you convert the following: (i) Phenol to benzoquinone (ii) Propanone to 2-methylpropan-2-ol (b) Why does propanol have higher boiling point than that of butane? (2019¢) How do you convert the following? (i) Phenol to anisole (li) Propan-2-ol to 2-methylpropan-2-o1 (iil) Aniline to phenol (Delhi 2015) Predict the products of the following reactions: OBMy @ CHy—CH= cH, Bote 8 i) CgHgOH 252 cws7aK (ii) CHycH,oH 9p (Foreign 2015) How are the following conversions carried out? (0) Benzyl chloride to benzyl alcohol (i) Ethyl magnesium chloride to propan-t-ol (ii) Propene topropan-2-0l. (AI 2015C, 2014C) (a) Write the mechanism of the following reaction: Her CHyCHjOH——> CH,CH,Br+H,0 (b) Write the equation involved in Reimer-Tiemann reaction, (Delhi 2014)HEE (5 marks) 71. (a) Howdo you convert the following : (Phenol to anisole (ii) Ethanol to propan-2-ol? (b) Write mechanism of the following reaction: W806 oy HOH -ZES45 CH, = CH, + HzO 75. () Why phenol undergoes electrophilic substitution more easily than benzene? (Delhi 2019) © 72. (a) Account for the following: (i) o-nitrophenol is more steam volatile than © p-nitrophenol (ii) t-butyl chlor ‘on heating with sodium methoxide gives 2-methylpropene instead — of t-butyimethylether. (b) Write the reaction involved in the following : (i) Reimer—Tiemann reaction i) Friedal~Crafts alkylation of phenol 76. 77. (c) Give simple chemical test to distinguish — between ethanol and phenol. (Delhi 2019) (An) 73. (a) Write the formula of reagents used in the following reactions : ( Bromination of phenol to 2.4,6- tribromophenol 78. 79, (i) Hydroboration of propene and then © oxidation to propanol. range the following compound groups in the easing order of their property indicated: P-ritrophenol, ethanol, phenol (acidic character) h) propanol, propane, propanal (boiling point) Write the mechanism (using curved arrow notation) of the following reaction: + _cHyCH,OH CH3— CH— OH, OF = 81. CH3— CH)— 9- CH,— CHy +H,0 | ui (Delhi 2017)(3) 7.6 Ethers 82. Mm 74, Assertion (A): (CHq)C—O—CH, gives (CH,)3C—I and CH,OH on treatment with Hi. Reason (R): The reaction occurs by S,1 mechanism. (a) Both Assertion (A) and Reason (R) are correc statements, and Reason (R) is the correct ‘explanation of the Assertion (A). (b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct explanation of the Assertion (A). 83. | 84, 85. {c) Assertion (A) is correct, but Reason (R) is — incorrect statement. (d) Assertion (A) is incorrect, but Reason (R) is correct statement. (2020) E86. Assertion (A) : The C-O-C bond angle in ethers is slightly less than tetrahedral angle. Reason (R): Due to the repulsive interaction between the two alkyl groups in ethers. {a) Both Assertion (A) and Reason (R) are correct statements, and Reason (R) is the correct ‘explanation of the Assertion (A). (b) Both Assertion (A) and Reason (R) are correct statements, but Reason (R) is not the correct ‘explanation of the Assertion (A). (€) Assertion (A) is correct, but Reason (R) is wrong statement. {d) Assertion (A) is wrong, but Reason {R) is correct statement. (2020) (3) iL mark) Carry out the following conversion : t-Butyl chloride to t-butyl ethyl ether(1/3, 2020) (Er) Predict the reagent for carrying out the following conversions : Anisole to p-bromoanisole (1/3, 2020) Write the equation for the preparation of 2-methyl- 2-methoxypropane by Williamson synthesis. (1/3, 2020) Write the equations involved in the following reaction: Friedel-Crafts alkylation of anisole. (1/2, Al Write the structure of the main produ following reaction: OC2Hs +HI——> (v3, Write the product in the following reaction: i CH3—CH—O—CH,—CH, 4274? (1/5, Delhi 2017) Write the main product(s) in the following reaction : CH, CHy—F—O— Chg +1 —> Hy (1/3, Delhi 2016, 1/2, Al 2016) How is the following conversion carried out? Anisole to p-bromoanisole (1/3, Delhi 2015C) ‘Write the equationinvolved inthe followingreaction: Williamson synthesis (1/2, Al 2014, Delhi 2014C, 1/3,A12014C) HEE 02 maris) Write the mechanism of the following reaction : 2CH;CH,OH 47> CHyCH,OCH,CH, +H,0 (2/3, 2020, 2/3, Al 2017, Delhi 2016, 2015) Predict the major product obtained when t-butylbromide reacts with sodium methoxide. Also, give its (ii) Mlustrate hydroboration - oxidation reaction IUPAC name. (2019C) © 87. Give reasons for the following: / withan example. — (i) Boiling point of ethanol is higher in comparison | 89. Give the structures of final products expected from tomethaxymethane. the following reactions : (il) (CH)gC-O—CH on reaction with HI gives # , a CH,OH and (CH,),C-—12s the main products and (i) Hydroboration of propene followed by oxidation not (CH3);C—OH and CHI. (2/3, Al 2015)(in) | with H,O, in alkaline medium. HEY 03 mars | (il) Dehydration of (CH),C-OH by heating it with 88. (i) Give mechanism of the following reaction E 20% HPO, at 358 K. H,SO | CHCH OWS i Heatingot (_)— CH,-0 €Switnia. HCH, —O—CH,CH3+H,0 | (2020) An) [ aN : CBSE Sample Question (a == | 7.2 Nomenciature | (elimination of water (d) formation of anester. (Term |, 2021-22) Wm ‘Which of the following reactions is used to prepare 1. Identify the secondary alcohols from the following set: salicylaldehyde? (i) CHsCH,CH(OH)CH3 | (a) Kolbe's reaction (ii) (CzHs),COH | (b) Etard reaction OH (c)_ Reimer- Tiemann reaction (d) Stephen's reduction (fermi, OH Lower molecular mass alcohols are (a). miscible in limited amount of water ‘CH, | (b) miscible in excess of water (€)_ miscible in water in all proportions a) (i)and (iv) (b) (and Gi (d) immiscible in water. (Term |, 2021 (©) (and ti) (a) (0).(ii) and (ivy Phenol does not undergo nucleophilic substitution (Term|, 2021-22) | _reaction easily due to (a) acidic nature of phenol 7.4 Alcohols and Phenols (b) partial double bond character of C—OH bond Ee | (©) partial double bond character of C—C bond 2. The major product of acid catalysed dehydration of | _ (4) instability of phenoxi (Term |, 2021-22) 1-methylcyclohexanol is What would be the reactant and reagent used to {a) 1-methylcyclohexane | obtain 2,4-dimethylpentan-3-ol? (b) 1-methylcyclohexene | (a). Propanal and propyl magnesium bromide {c)_ A-cyclohexyimethanol | (b) 3-Methylbutanal and 2-methyl magnesium iodide $0) rmetyyanecisctroranal ing (€) 2-Dimethylpropanone and methyl magnesium 3. The boiling points of alcohols are higher than those iodide of hydrocarbons of comparable masses due to i) Siethiiiropanal! and dossrogel am th lec ersten | iodide (Term, 2021-22) ( Pee | 9. o-Hydroxybenzyl alcohol when reacted with PCI. (¢) dipole-dipole interaction eee ee Ib (d) van der Waats' forces. (Term), 2021-22) | _ivesthe product as (IUPAC name) 4. During dehydration of alcohols to alkenes by heating (2) o-tyydromybenzy! chloride with concentrated H,SO,, the initiation step is (b) 2-(chloromethy!) phenol (a) protonation of alcohol molecule | (c)_ o-chloromethylchlorobenzene {b) formation of carbocation (d) 4-hydroxymethyl phenol. (Term, 2021-22)(@) Ais true but . (d) Ais false but Ris true. (2022-23) . Williamson's synthesis of preparii EYE 2 marks) 10. When 3-methylbutan-2-ol is treated with HBr, the following reaction takes place: imettyyl ether is i afan a | (a) Sytreaction CHy-CH-CH-CHy HES CHy—C—CH—CHy (b) elimination reaction (0 Sy2reaction ___CHs OH CHS (4) nucleophilic addition reaction. Give amechanism for this reaction. (2020-24, fem 2021-22) 7.6 Ethers |. Assertion : Methoxyethane reacts with HI to give ethanol and iodomethane. 0 Reason : Reaction of ether with HI follows Sy2 111. What would be the major product of the following mechanism. reaction? | (@) Assertion and reason both are correct Cols = CH, = OCgHs +HBr+A+B statements and reason is correct explanation (a) A= C,HsCH,OH.B = C,Hy i for assertion. (b) A=CyHsCH,OH, B = CHs8r | (b) Assertion and reason both are correct A= CgHsCHy,8 = CyHsBi i statements but reason is not correct ii An CjcHiyae B-c4H,004 (2022-23) ee ee CoHsCH2Br, B = CoH | (© Assertion is correct statement but reason is 12. Givenbeloware twostatementslabelledas Assertion wrong statement. (A) and Reason (R). | (@) Assertion is wrong statement but reason is Assertion (A) : An ether is more volatile than an | correct statement. (2020-21) alcohol of comparable molecular mass. Psa ee Reason (R): Ethers are polar in nature. i m ri ‘ tthe mostperopriateanewerfromtheoptions | 1 Weite the equations forthe folowing reat nero | [a) Salicylic acid is treated with acetic a low: | the presence of conc. H,SO,. th A and R are true and R is the correct {b) tert-Butyl chloride is treated wi planation of A | ethoxide. Both A and R are true but Ris not the correct (c) Phenol is treated with chloroform explanation of A. | presence of NaOH. (2022-23) Detailed 224 OEMs Cyne 1. (c):2-Methylbutan-2-ol | Phenylorop-2-en- tool SHaoH 3 1 2 Gay Gt ra dH cHy (CH;— O— C—CH3 . & CH 3.3~ Dimethripentan-2-ot | 2Methony-2-methytpropane GE) | 6. 2-Phenylethant-ol > Always identify longest carbon chain. 7. 2,5-Dinitrophenol 2 Take phenol as a parent compound. 49-23 Emmg 3 Hef ttt Hy 2+Bromo-3-methylbut-2-en1-01 | 8. 2-Methylprop-2-en-1-019. 3-Methylbut-2-en-1-o1 COOH COOH 9 10. Butan-2-0l OH o-€-CHy 41. Propane-1,2,3-triol 20. (b): AERO. 12. (bl: —O—H bond angle in alcohol is 108°9’ which is slightly less than 109°28.. Saisie cai 13, (a): TheC—O—H bond angle in alcohols is slightly | 24 (a):Intramolecular H-bonding present in less than the tetrahedral angle due to greater fone pair- : ‘ : lone pair repulsions than lone pair-bond pair repulsions. _ °Titrophenol makes it weaker acid than p-nitrophenol 22 (b):RX+ NaOH —+ROH + NaX aamg This is a substitution reaction. ‘> Apply VSEPR theory. | 23, (a):In alcohols, intramolecular hydrogen bonding is 14. (¢):Butanol:CHy — CHy— CH, —CH,—OH present, resulting in higher boiling point than alkanes of (2*alcohot) | Comparable molecular mass. Butan-2-ol: CH;—CH, —CH—CHs (2°alcohol) OH ONa on i Na0H.340K cH 4, H 2 + CHCl, HOH SOK I 2-Methylbutan-2-0l: HC -C-—CH,—CH3(3* alcohol) PH i CH HO cae | 4 Na 1 Salicylalderyde 3-Methylbutan-2-ol: CH ~ € = CH ~ CH (2* alcohol) 1 I Ether OH CH; | 25, CH;—CH=CH2+(H—BH2)2 does not undergo oxidation, hence in © Propene iat oe 4 itan-2-ol, Laxidationis not possible. cH,CH=CH, cHy—cH—cH, H+ Hx Are ZnCl, eto» RX+H;0 Il a / nucleophilic substitution reaction in which -OH cen @ sroup gets replaced by -X group. It involves formation of | (CHACH,C! Cis carbocation. As we know, with Lucas reagent. cachet Primary alcohols - No cloudiness. 3H:02 Secondary alcohols - Cloudiness appearsin 5S minutes ~OH.H,0, (CHsCHrCHa)8 Tertiary alcohols - Cloudiness appears immediately Thus, the reactivity order is 3° > 2° > 1° 3CH3CH,CH,OH + H3B03 16. (al: Tertiary alcohols do not undergo oxidation. fometa 17. (¢):—NO, acts as EWG and increases the polarity _ of O—H bond resulting in increased acidic character of oH o phenol. 18. | Br Br &, ez Oo or 19. (c}:CH3—CH=CH—CH,OH PSE > Phenol CH3—CH=CH—CHO | 2.46-Tribromophenol34. @-Nitrophenol is more volatile than p-nitrophenol jue to the presence of intramolecular H-bonding. p-Nitrophenol shows intermolecular H-bonding. oe ve vt COOH 28. CH3—CH S O-—O-H “ Oo steHjco,o "4 % 2 Salicylic acid OCOcHs Cumene COOH HCOOH + ‘Aspirin cHeomtih Os aF 29. Zn a, be Ontat “Se on ee CE@ (intramolecular H-bonding) > Benzene undergoes electrophilic substitution reaction: with Clofanhy. FeCl 30. Kolbe's reaction : When sodium phenoxide is heated with carbon dioxide under pressure, it gives salicylic acid. (intermolecular H-bonding) ° ONe ou ct That's why, o-nitropheno! has lower boiling point than OONa Oo +0, Aga ow | prnitrophenol. 35. Reimer-Tiemann reacti Sod saiyate . 1H ONa nol Hc a, Naot oOo an a OS oH OK = NaCl.-H,0 4 ‘COOH OH ONa CHO gine ‘CHO Salicylic acid aa 31. CH3CH,OH Ae CHsCH,Br MENS CHSCHCN sale blaine Ethanol thy bromide Propanenitrile | 36. (i) CH3CHOH SY373%5 CH,CHO 32. Phenol is more sade than alcohol. It can be OH explained on the basis of that alcohol on losing H” ions bests er forms alkoxide ion and phenol forms phenoxide ion. | (i) CgHsOH — > ‘The greater acidity of phenol is due to the stability of the | phenoxide ion which is resonance stabilised, | L OH o 2446 -ribromophenal | 37. (a) Phenol is more acidic than cyclohexanot due = +H" | to resonance effect or delocalisation of n-electrons in a —, benzene which stabilises the negative charge present esonance st | on O-atom while in cyclohexanol, alkyl group is present On the other hand, alkoxide ionshows no such resonance | which shows #1 effect that, destabilises the negative stabilisation. | charge and hence, removal of H-atom becomes difficult. | (b) Phenol gives violet colour with neutral FeCl, solution while cyclohexanol does not. 38. (i) Phenol is a stronger acid than an alcoho! due | to the stabilisation of phenoxide ion through resonance. Due to higher electronegativity of sp” hybridised carbon ‘of phenol to which ~OH is attached, electron density decreases on oxygen. This increases the polarity of O-H ‘> More stable the conjugate base, higher isthe acidity.bond and results in an increase in ionisation of phenol | than that of alcohol. Thus, removal of proton is easier in case of phenol as compared to alcohol. (ii) The boiling point of alcohol decreases with increase in branching of alkyl chain due to a decrease in surface | area, The decrease in surface area decreases the van der Waals forces of attraction causing a decrease in the boiling point. or (i) Mechanism of dehydration : The H” ion of acid acts ‘as electrophile and attacks at the oxygen atom of alcohol having lone pair of electrons to give an oxonium salt. CHs—CH,—OH, HLH, cH, 6-H H xonium sa (rotonatedaleohol) Water is removed from protonated salt to gi carbocation (ethylium ion). As formation of intermediate is aslow step. hence this step israte determining step CHy—CH,—0€ Hz—CH, Ceo a H thyurion As ethylium ion (carbocation) is highly reactive species, it will try to be stabilized as soon as possible by the removal of proton to give alkene. This is afast step. Shay 76H, “HS CH=CH, ation is formed as intermediate, so it of carbocation is also possible which ‘more than one products. The major product ling to Saytzetf rule. ‘OH ONa NaOH. 340K CHO wo CoH Rac -H0? Prenat ree CHO itu NaCl Saealdehyde 98. CHS CH Hy 22% cH —C—CHy i oH ° Propan-2-l Propanone ; COOH cH,CON wy + > cH,Co sae acid OcocH, COOH +CH,COOH ~G==626 cH,—cl “0 FQ | os OCHs 40. ) Gn O en O nicr +No+HCl Phenol 41. Acid’ catalysed dehydration of ‘alcohols follows carbocation mechanism. CH CH; cHy—¢= —OH+H" oH E<- H diy CH3H CHs “4,0 AE SCH OC CH 3" carbocation {more stable) CHyCH;CH,CH,0H + H*—> CH,CH,CH,CH,OH, #25. CH CH,CH,CH, 1 carbocation less stable) Hence, dehydration of tert-butanol (which forms 3° carbocation) is faster than n-butanol (which forms primary carbocation). ‘> The relative ease of dehydration of the order :3°>2°> 1° H 42. (CHyCH= CH, “E2t> CH; —CH —CHy Propene Propan-2-0l CH,CI CH,OH "2" 8 Benzyichloride Benzylalcohol . neseust Hse — cH, Ethene HC — CH, — OH -H3C — CH, Ethanot bu. OH, Hyc— ¢—0n 59 Hye — Fact Hi0 573K CH CHy 2-Methylpropan-2-0l 2-Methvipropene45. .O-O% CHsCH,OH S22 cHyCHO Ethanol Ethanal (b) nzene 1-Phenylethanol catalysed dehydration of alcohols at high temperature takes place with formation of acarbocation. - Mechanism : The dehydration of ethanol involves the _ following steps: |. Formation of protonated alcohol, U1. Formation of carbocation. HHH H ibs d fone 7? Ethyl carbocation UL. Formation of ethene by elimination of a proton. hb fixe =U +H i | HH Ethene OH COOH Hyco, * cH,co7? OCOCHy {COOH + CH,COOH 49. (i) i Aspirin nce |G) CHy—CH=CH—CH,0H ——> Beenie Hy — CH= CH—CHO I But-2-enal PCC is an oxidising agent, oxidises 1° and 2° alcohols toaldehyde and ketone respectively. | 50. (@) Distinction between ethanol and phenol can be + done by FeCl, test. Phenol gives a violet colouration with | FeCly solution while ethanol does not. | 6CgHsOH + FeCls — 9 [Fe(CgHs0),]"" + 3H" + 3HCI | Phenol Violet colouration | GHsOH + FeCls —> No violet colouration (i) Propanol (1° alcohol) and 2-methylpropan-2-ol | (3° alcohol) can be distinguished by Lucas test. With Lucas reagent (conc. HCI and anhyd. ZnCI,), 1° alcohols show no | cloudiness while 3° alcohols show cloudiness i i OH OH 1H a0 -O- CH No, p-Cresol Phenol —_p-Nitrophenol ‘2 Electron donating groups at p-position decrease acidity while electron withdrawing groups increase acidity. Var | tb) CHa _ CHy— CH, +H,0 52. ig a, iy Soy Butan-201 3 I CHy—C—CH,CH3, Butar2one gu (b) CHy—CH—CH,—CHy 22%, 4 Sorte (CHy—CH—CH,—CH; | 2-Chlorobutane hae a (BH 53. (i) CHy— CH=CH, ae? CH3CH,CH,OH Propanot> Hydroboration-oxidation of alkene takes place as addition of water to alkene in anti-Markovnikov’s manner. OH (ag. NaOH ‘COOH or (ii) CgHsOH co, Salicylic acid cw573K 54. (i) CHyCH2—CH—CH, cH | ° OH il CH3CH,—C—CH, Butan-2-one OH ‘CHO . 9.CHCI,+ a9. NOM (ii) CiHs—OH D> Saleyladetyde 55. The react proceeds ‘of configuration takes place during the reaction. 56. i) ii) (i) Bromine water, (Br2iaq) Lithium aluminium hydride, (LiAIH,) or Ha/Ni ‘Ally! halide in the presence of anhydrous aluminium chloride, CH3Cl and AICletanny) ified potassium permangante, KMnO, and H,0° {i) Zine dust Concentrated H5O, Aiky! halide in the presence of anhydrous aluminium chloride, CHCl and AICI, (anhy) tiv) liv) Cuat$73K 1H HS, 58. (i) CHs3CH= CH, Rt» CHy— CH CH, Prope Propan-2-0! (ii) CHyCH,Cl + KOH jg —> CH3CH OH Eth chloride Ethanol S73K Jee ° W CH,—C—H Ethanal through nucleophilic - substitution bimolecular (5,2) mechanism, as shown | | 59. (i) Kolbe's reaction : When sodium phenoxide is heated with carbon dioxide under pressure, it gives salicylicacid. OH on Na Sod salicylate 0. le OH on Salicylic acid (ii) Relmer-Tlemann reaction : OH ONa 4-7atm + CO2 ~ZooK Sod. phenoxide Salicylaldehyde 60. (i) Due to resonance, C=O bond acquires some | partial double bond character. So, in phenol, C—O bond + length is smaller than methanol. (ii) Butanol > Butanal > Ethoxyethane > n-Bu | (17.70) (748%) (346) (1 | The boiling point of alcohol is higher in to hydrocarbons and ethers of comparable masses due to intermolecular hydrogen bonding. | The boiling points of aldehydes and ketones are hi | than hydrocarbons and ethers of comparable molecular | masses. | The boiling point of ether is higher than alkanes of comparable molecular masses but is much lower than that of alcohols. i OCHs OH Ai) Opn. — oO +CH3—X i Anisole Phenol Alkyl aryl ethers reaction with HX results in the cleavage | of R=O bond instead of Ar—O bond as Ar—O bond is more stable due to double bond character. | 61. (a) Phenol when treated with concentrated nitric | acid gives 2, 4, 6-trinitrophenol, OH OH O, NO, cone. HP 2 oO = NO, 2.4. 6-Trinitropherol (Phere acid)(b) CHyMgBr + CH;COCHs—> BrMg-O-C(CHa): Propanone pro HO-C(CH,); + Mg(OH)Br 2Metioropana OH OCH; © Qenom => bs, oe O- ony (0. CHa CHa tear? CHaCHsCHOH Propani-ol an eC) a COOH cH:cow,, " cH,co™ OcocH, on +CH;COOH ae Hos +CH,Mger 2°, +Mg(OH)Br ene OOt +HI> eH eee +CHy! brincs, or “aK” i Gass, ii) ‘OCH, ea och, COC! oO cH oct Amc o a “ a satan Toe suateronorbaen 64, Test to distinguish between: (a)_ Phenol and 1-propanol : Phenols react with neutral FeCl, solution to give blue, violet or green colouration whereas alcohols do not react with neutral FeCl; | solution. (b) Ethanol and dimethyl ether : When ethanol is | heated with iodine and aqueous NaOH solution at | 333-343 K, a yellow ppt. of iodoform is produced. Dimethyl ether do not undergo this test CH;CH,OH + 41, + 6NaOH—* 5 CHI, + HCOONa +5Nal+5H20 | (c) 1-propanol and 2-methyl-2-propanol_: When 2-methyl-2-propanol (3° alcohol) is treated with Lucas reagent at room temperature. turbidity appears | CHy= CH>—> CHy— | immediately. 1-propanol (1° alcohol) does not react with Lucas reagent at room temperature, hence no turbidity is | formed. | 65. (@) HCHO + (CH), CHMgBr—> OMgBr ae Ha CH —CH,OH CH Hy—CH — CHa CHy o H,S0,—"H* +HSO, —H+H'==H-G ae —H gers CHy+ Hy 66. (afi) iD-2 Benzoquinone ts ie Patera > cH ‘OMgBr CHs ft mg OH + cHy-¢—on eth? Spe i CH, | (vb) Propanol has higher boiling point than but | presence of intramolecular H-bonding. 67. (i) Phenol to anisole OH ONa’ Hy Gro G* Phenol Avivole Propan-2-ol to 2-methylpropan-2-ol Hs CH Ch SPE cy — CH OH ° Propan-2-ol on Carty creme 1 ‘WHO CH, 2Methyipropan-2-ol (ii) Anitine to phenol NH, ii) CH — Nicr OH oO 24 O)emrone Aniline 68. () CHy—CH=CH, asst a CHyCH,CH,OH1H {b) Acid catalysed dehydration of alcohols at high Br Br | temperature takes place with formation of a carbocation. (CeHs0H ———> Mechanism : The dehydration of ethanol involves the i, | following steps: 246-Trtromopheno! Step I: Formation of protonated alcohol. (iii), CHyCH,OH “22%, cH CHO CH,CI CH,OH Nao) on OO Benzyl choride Benzyl alcohol (ii) Ethyl magnesium chloride on addi to formaldehyde followed by hydrolysis gives propan-1-ol Dry ether i CH3— CH2MgCl+H—C—H Ethyl magnesium ‘chloride Step Ill : Formation of ethene by elimination of a proton. r CHy— CH,— CH,—OMgCl me | Al H. H Hy— CH, — CH,—OH. | He ro Pe a f HH Ethene H i HO. | (©) Phenolundergoes electrophilic substitution reaction Gi) CHyCH= CH, TES} CHy — CH=CH, i aaah ‘ani nga 70. (a)The reaction proceeds through nucleophilic | effect of -OH group attached to benzene ring. tc ae alan Bena | 72. {a) (i) o-Nitrophenol is more volati Hee lie | pitrophenol due to the presence of i e+ bh foe | Hebonding. p-Nitrophenol shows int ‘OH A Nous | Hebonding. ‘Tearsition tate ZH NS orp Br—C—=CH, +OH é Hi i & Inversion of configuration takes place during this reaction. | (b) Reimer=Tiemann reactios e-Nitrophenat ONa i — H-bonding) CHC 20. NAOH, CHCl, aon | wo{O)-nZ rs eo a / 8-_0-O-N Nac “H,0 PNitrophent , | {ntermoleclar H-bonding CHO tues CHO | That's why o-nitrophenol has lower boiling point than Rec | penitrophenol. Thisis because tert-alky! halides undergo elimination OH ONa* Hg | instead of substitution, CH; CHybr 71. ta) Q +NaQH ~© 6 i | chy ¢— CLE NOC Hs a> i CH; Cs oe Gi CHyCH,OH FES) CH CHO HEE, PCH ACH — CHy | CHy— C= CH + C,HsOH + NaCl Ethanol Propan2-ol 2emethylpropene{b) (i) Reimer-Tiemann reactior chs tet CHCl} 2NaoH =nacl “4,0 Na Oe on G* == 5.9 real oH p Chest ct aise8 (€)_ Distinction between ethanol and phenol can be _ done by FeCl test. Phenol gives a violet colouration with FeCl solution while ethanol does not. 6CyHgOH + FeCl; —9 [Fe(CyHs0),)* + 3H" + 3HCI Phen Violet calouration HOH + FeCl —> No violet colouration 73, (a)(i) Br2/H,0 (ii) BHyin THF/H,0,, OH" Ethanol < phenol < p-nitrophenol ne < propanal < propanol ‘iver CH; x Ha 74, (a) 06 —OCH;+HI->CH;— cH, CHy 75. (d):In ether, the C—O—C bond angle is slightly | greater than the tetrahedral angle due to the repulsive © interaction between the two bulky(-R) groups. 76. The given conversion is not possible by treating sodium ethoxide with t-butyl chloride or bromide | since, under these conditions an alkene ie, isobutylene (2-methylpropene) will be the main product. If however, t-butyl bromide is heated with a weak nucleophile such - as pure ethanol both substitution and elimination occur _ in which substitution product predominates. Thus, CH cH;— tL Br V8 ty CH; (CHs)3—C— OCH,CH + CHy—C=CH, tee-Bityletryether (90K) 2Metheropene (20K) 9—CHy—CHs +H,0 | G—leaoH i ' -OCH3 groupis o/p directing group. CH, © 78. HxC—Br+Na—O— —¢—CHs sala CMs | Hie Gan Chis Nab CH3 2.Methy-2-methoxypropane OCH, Anntry. AICI, 79, _ fale A + CHSC -Fcdet Crats : extn Anzole OCH; OCH CHy + OCHs " O # te Oey sc fn | 81. CHy3—CH—O—CH,CH; ——> 9H H3—CH—CH,+CH,CH,! CHy Hy | 82. CHy—C—OCH,+ HI ->CH3—C—1+CHj0H H3 Hy &: OCHs OCH3 fain oO" = Cts S 84. Williamson ether synthesis : Alkyl halide when treated with sodium alkoxide gives dialkyl ether. | GHsONa+CzHsCl—>CzHs— O— CoH + NaCl | 85. Mechanism : The formation of ether is nucleophilic bimolecular reaction.Step 1:CH3—CH2— G—H+H’—> (i) Hydroboration-oxidation reaction : Diborane (B2H,) 1 adds on alkane to give trialkyl boranes which on oxidation CHs—CH,—O—H | withhydrogen peroxide in presence of alkali give alcohols. | CHyCH=CH2 HH-BHa}2—, Step ll:CH;—CH,— CHa CH CHa H BH, 4 a 4,0 be i _—(cH,cH,cH,) aH etd cu, —cH,— O—CH,—CHs | [CH:CHe CH (CHSCH CH,)38— Step Ill: CH3—CH cH, | 3CHsCH;CH,OH + BIOH) <3 — CH3—CH,— O—CH,—CH3+H" saerko (8H). oo 4 / | 89. (i) 3CHy—CH=CH, Ter] 86. CHy—C—Br+NaOCHs iesian? i 3CH;—CH.—CH,—OH Propanel CH; we Gra CH, —C=CH,+CH,OH + NaBr cHy—¢—0H ERPS Hac cmc, met ropene | I 87. () Ethanol has higher boiling point because of | cH CH strong intermolecular hydrogen bonding whereas in CHat OH methoxymethane, molecules are held by dipole-dipole interaction. (ii) When the alkyl group is a tertiary group. the halide formed is tertiary halide. The departure of leaving group reates a more stable carbocation (3°) and the Syi mechanism. "1. (a): 6) CHCH,CHOHICH, (second a CH Gi) (CaHs)3COH (tertia I lo — CH, 3% CH) —C*+CH,OH : es dan day Mii) (phenol, not an alcohol) CH CHa | OH cry £81, cH; -¢-1 | cs dy dy tiv) : {secondary alcohol) (0.77) 88. (i) Mechanism : The formation of ether is | rwscleophilic bimolecular action am . Hs by Step!:CH;—CH,— G—H+H’—> ‘OH 5 cs — & H3—CH,—O—H {-Methyleyclohexane! ——_1-Methyleyelohexene Al According to Saytzeff rule, highly substituted alkene is Stepll:CH;—CH,— 9—H+CHy—CH,£Q—H —_ major product. Here, dehydration reaction takes place, alkene is formed due to the removal of a water molecule. H i (1) he | 1H? .cHy—CcH,— O—CH,—CHy | 3 (a):Aleohols form intermolecular hydrogen bonds. So, alcohols have higher boiling points than hydrocarbons sis | of comparable masses. (0.77) Step Ill: CH3 — CH, —"Q — CHy— CH3—> | 4. (a):Protonation of alcohol molecule is initial step in —CH,— O—CH;—CH3+H" | dehydration of alcohols to alkenes.Step 1: Formation of protonated alcohol i ae Hee Hew Ben-¢-¢-9'n HoH HH teal Protnsted aed {ethy! cxonium ion) Step 2: Formation of carbocation : It is the slowest step and hence the rate determining step of the reaction. HOH OH HOW eur to iii H—-C—C7O—H S=H—C—C+H,0 I ye if (0.77) 5, (c):Reimer-Tiemann reaction is used to prepare salicylaldehyde, Kolbe's reaction to prepare salicylic acid, Etard reaction for benzaldehyde and Stephen's reduction Ethene for aldehyde. OH OH CHO + CHCl + 3NaOH —> +3NaCl+2H,0 Salicylaetyde (077) : Lower molecular mass alcohols are able to form ‘s with water. Hence, they are miscible in ‘oportions. (0.77) 1 does not undergo nucleophilic reaction easily due to partial double bond ‘of C= OH bond. (0.7) ‘@. (d):2-Methylpropanal and iso-propyl_ magnesium | react to form 2,4-dimethylpentane 3-ol. H I CHy—CH—C=0+ (CH3),CHMgl —> ! {so-propyimagnesium CH "aase 2Methylpropanat H 4 1 51 i (CHylzcH—G—OMigt “> (CHgl;cH—C—OH CHICHs)2 CHICH3) 24-Dimetiyoentar-0t (0.77) © 9. (b):24Chloromethyl) phenol is formed. CH,OH CH,CI OH OH +PCl;—> (0.77) 10. i OGG _ CH #9 CH,— CH CH CHy CH; OH CH; QH2 (12) * } CH3—CH—CH—CH. (CH3— CH— CH — CH. a FHF cl Snr BF ty eee Hs ay Q a 1L:2-hydride shite CHy—¢— CH= CHy CHy=C— CH CHy CHa Br —— I cig=e — CH, — CH3 + Br” > CHs-C —CH,—CH3 CHs CH (1) CH (1/2) H I 1A. (d)sCgHsCHZOCgHs +H’ —>CgHsCH2OC Hs ae CgHsCH,Br+CgHsOH w (8) 12. (b): As hydrogen bonding does not exist ar is more volatile than alcohol. 13. (c):Itis Sy2reaction. In this, alkoxide ion reacts with primary alkyl single step to formether) CHyBr S498, CHOCH, +NaBr 14. (a):CH3CH,OCH3 + HI-+ CH3CHZOH + CH! 15. (a): Aspirin is formed. coon OH “ OCH +(CH,CO),0 > +CH3COOH ‘Acetylsalicylic acid, spirin) (0.77) (a) COOH | Salicylic ac (a) {b) (CHy)3Cct —Setmetbanide_, (CH3),C=CH2 (1) 2-Methytpropene | (0 o-hydroxybenzaldehyde will be formed. OH OH O CHC, H oO 3N20H Oo (a)