CBSE CHAPTERWISE SOLVED PAPERS ens-5 (ie i imeee CHAPTER 10 ee rT, Alcohols, Phenols and Ethers TOPIC 1 Alcohols and Phenols When a hydrogen atom in a hydrocarbon (aliphatic or aromatic) is replaced by one or more—OH groups, the compound is known as alcohols or phenols. In other words, hydroxy derivatives of aliphatic hydrocarbons are called alcohols while hydroxy derivatives of benzene are called phenols. 1.1 Nomenclature ‘The common name of an alcohol is derived from common name of alkyl group and adding the word alcohol to it. In IUPAC system, the name of an alcohol is derived from the name of the alkane by replacing ‘e’ of the alkane with the suffix ‘ol’, For naming polyhydric alcohols, the ‘e’ of alkane is retained and the ending ‘ol' is added. Cyclic alcohols are named using the prefix cyclo and considering - OH group attached to C - 1 ‘Common and IUPAC name of some alcohols ‘Common name TUPAC name Methyl alcohol Methanol Ethyl alcohol Ethanol CH,CH,CH,OH n-propyl alcohol Propan- on — 7 SS -propyl ale ropan-2-0l ca,y—a—cH, 1s0-propyl alcohol Propan. CH,CH,CH,CH, —OH n-butyl alcohol Butan-1-ol CH,—CH—CH,—CH, See-butyl alcohol Butan-2-0l onCHAPTER 10 : Alcohols, Phenols and Ethers 241 Compound ee TUPAC name on oo 7 fiyetnbennce a Oo Phenol Phenol a on Catechol Benzene-1, 2-diol cH, a o-ctesol 2-methyl phenol Structure of Alcohols and Phenols ‘The C—O bond length in phenol is slightly less than that of alcohol due to following reasons. (i) Partial double character due to resonance. ii) sp? hybridised state of carbon to which oxygen is attached. \ 2 pm H—c228_ 6: 136pm_ 6, HH? 108°" Fy 109° H Preparation of Alcohols sy acid catalysed hydration of alkenes, i.e. addition of H,0 on alkenes in the presence of an acid ‘as a catalyst. Unsymmetrical alkenes undergo Markownikoff's addition to yield secondary alcohols. Ht .R —CH—CH, Markownikotf addition | OH (ii) By hydroboration-oxidation of unsymmetrical alkenes, i.e. addition of diborane on alkenes followed by oxidation of HO, in presence of NaOH yields primary alcohols. ‘Anti-Markownikoff addition — RCH = CH, +H,0 CH;—CH 3CH,—CH, —CH, —OH+ B(OH), Prop: ene H,0/1130;, 3087 Propan-I-o (iii) By reduction of carbonyl compounds, i.e. aldehydes and ketones in presence of Raney Ni/Pd, LiAIH,, NaBH,. Aldehydes give primary alcohols while ketones give secondary alcohols. CH,+(H—BH,), Raney NI/Pd RCHO =, R—cH,OH or LAI, 1s maany Romo, 8 cH—on R Re ay Carboxylic acids are reduced to primary alcohols in excellent yields by LiAlH,, a strong reducing agent.242 @ Chapterwise CBSE Solved Papers : CHEMISTRY (iv) By the addition of Grignard’s reagent followed by hydrolysis with dil. HCl, mex HCHO — >» gives 1° alcohols RCHO a gives 2° alcohols, i R—C—R’ a gives 3° alcohols (v) By hydrolysis of alkyl halides with aqueous NaOH or KOH through Sy reaction. 1.3 Preparation of Phenols Opal + Noon site (C)-or nd eee wa 70H, oF O* oO) 1.4 Properties. of Alcohols and Phenols + Boiling point of alcohols and phenols are much higher than those of corresponding haloalkanes, ethers and hydrocarbons due to intermolecular H-bonding. Boiling point of alcohols increases with increase in the number of carbon atoms and decreases with increase in branching. + Alcohols and phenols are soluble in water due to intermolecular H-bonding. + Alcohols are less acidic than phenols because phenoxide ion [formed by the loss of H-atom] is stabilised by resonance but alkoxide ion is not. + Electron withdrawing groups like NO, X, increases the acidic strength of phenols due to the effective delocalisation of negative charge in phenoxide ion and this effect is more pronounced at o- and p positions than at m-positions. Therefore, correct order of acidity is p-nitrophenol > o-nitrophenol > m-nitrophenol. + Electron donating groups like —OCH,,—NH, do not favour the formation of phenoxide ion. Hence, decreases the acidic strength of phenols.CHAPTER 10 : Alcohols, Phenols and Ethers 243 + Primary alcohols are oxidised to carboxylic acid by acidified K CO, and to aldehydes by CrO, or PCC. see ondary alcohols on oxidation gives ketones. 3° alcohols undergo oxidation only under strong conditions. + phenols readily undergo electrophilic substitution reactions due to strong activating —OH group. + Phenol gives a mixture of o and p -nitrophenols on reaction with dil. HNO, at 293K. o-nitrophenol forms weak intramolecular H-bonding due to which it has lower melting point and boiling point, lower solubility in water and it is more volatile than p-nitrophenol which forms intermolecular H-bonding and hence, has high melting and boiling point, more solubility in water. Thus, both types of nitrophenols can be separated by steam distillation. + On treating phenol with CHCl, (chloroform) in the presence of sodium hydroxide, a —CHO group is introduced at o-position of benzene ring. This reaction is called Reimer-Tiemann reaction. + Sodium phenoxide (formed by reaction of phenol with NaOH) when heated with CO, at 400K under a pressure of 4-7 atm followed by acidification gives salicylic acid. This reaction is called Kolbe’s reaction. 1.5 Chemical Properties (i) Flow Chart for the Chemical Properties of Alcohols a a+ + RONa + Hat COOH [Etcaieationt R-OCOR’ + H,0 Lege ROCOR’ + R’COOH Seren R—OCOR’ + HCI ROH Wi _, Rx +H,0 [Alcohols] pay, }—+— R—Cl + POCI; + HCl Ee 3R—Br + HPO; | __SOCh__, rc} + $0, T+ HCIT |, with conc. H,S0, “?*} alkene is formed due to dehydration. _ ° alcohol —> Aldehyde —> Carboxylic acid | oxidation —> C2° alcohol — Ketones Dehydrogenation wiih Gusts 2° alcohol —> Ketones f 1° alcohol —> Aldehydes 3° alcohol —> Alkenes244 Qchapterwise cas! (ii) Flow Chart for Chemical Properties of Phenols Solved Papers : CHEMISTpy OH Br Br bvomophen Br (hep on ou Bry, OC . fuzoe Cs, 7 (Bletopitie nor oH Subst (mien reaction) Br OH (909 On wi Cone. H,80, SoH (Elect 7 = a OH SO,H (eon Cone. HNOs+ ON NO2 one. HS (Elccrphie (Cheap 2A,6ieophenl a NO} (plete ae) oH oH OH OH ‘NO; 2 coon J or * i > LJ {Elecrophile (nyamusecuar H-bonding) ae, reaction OH ‘salicylic acid " med er CHO (intermolcise - £00! oh tending) OH eine “Tema |aq NaOH, (i)CO,, (il) H* COOH, Hyon ‘COOH —— (Kolbe’s reaction) a }C0,, 5-7 atm pressure 720-140, (sos Shmi eacton) in Arn |CH,COcl COOH’ [Zndust +2n0 fi frenscono” oH [NayCr20, /H1,S¢ (Oxidation) cron COOH,CHAPTER 10: Alcohols, Phenols and Ethers ca 1.6 Methods to Distinguish Alcohols and Phenols (1) Phenols can be distinguished from alcohols by litmus test, phenols turn blue litmus red and produces violet colouration with neutral FeCl, and white ppt. of 2, 4, 6-tribromophenol with bromine water, whereas alcohols does not give this test (iv) Coupling reaction Phenols react with diazonium salts in weakly basic solution to form yellow or orange coloured azo dyes but alcohols do not react. Methods to distinguish between 1°, 2° and 3° alcohols (1) Lucas test Alcohols are soluble in Lucas reagent (conc. HCl and ZnCl,) while, their halides are immiscible and produces turbidity. 3° alcohols produces turbidity immediately, 2° alcohols produces after 5 minutes while 1° alcohols docs not produce turbidity at room temperature. (it) lodoform test All alcohols containing the group CH ,CH(OH) linked to carbon or hydrogen atom can be distinguished from other alcohols by the iodoform test. 4 * CH,CH,OH+41, +6NaQH ——+ CHI, +HCOONa +5Nal (Ethyl alcohol) Jodoform 4 CH,OH +1, +NaOH —— No reaction (Methyl alcohol) Phenols and alcohols can also be distinguished using this test. 1.7 Some Commercially Important Alcohols and Uses of Alcohol and Phenols (i) 100% ethanol is absolute alcohol and 95% ethanol is rectified alcohol + A mixture of 20% ethanol and 80% gasoline is the power alcohol. (ii) Uses + Alcohols are used as solvents, anti-freeze agent in the preparation of medicines as preservatives etc + Phenols are used to prepare bakelite, plastic for manufacturing of dyes and drugs in medicines in the preparation of phenolphthalein, etc.PREVIOUS YEARS’ EXAMINATION QUESTIONS TOPIC 1 @ 1Mark Questions 1.Write the IUPAC name of the following: CH, CH, — - pun C,H, OH 2. Write the IUPAC name of the following compound. HyC—O= 6 —OHy— OH CH, Br slindio 2017 3. Write IUPAC name of the given compound: (CHy—CHy—OH 4. Write the IUPAC name of the given compound omy ‘NO2 peti 2015 5. Write the IUPAC name of the given compound: HO—CH,—CH = 0— CH, CH, Foreign 2015 6. Which of the following isomers is more volatile : o-nitrophenol or p-nitrophenol? All india 2018 7. Name the alcohol that is used to make the following ester 0 i CH, —C— oH CH, CHy All india 20140 (CBSE 2018 Examination paper 8. Write IUPAC name of the following compound. Foraign 2014 HO—CH,—PH—CH,—OH OH 9. Of the two hydroxy organic compounds ROH and ROH, the first one is basic and other is acidic in behaviour, How is R different from R’? eihi 20190 40. How is toluene obtained from phenol? belhi 20190 11. o-nitrophenol has lower boiling point than p-nitrophenol. Explain. oelhizotac 42, How would you obtain ethane ~ from ethanol? All india 2013 ¢ , 2-diol 43. Draw the structure of hex-1-en-3-ol compound. path 2012 14, Draw the structural formula of 2-methylpropan-2-ol molecule. pelhizo12 45, Write the IUPAC name of the following compound Foreign 2012 CH) —CH = CH—CH—CH,—CH, OH 46. The C—O bond is much shorter in phenol than in ethanol. Give reason palhi zorec 17. How could you convert ethanol to ethene? Ail india 2011 48, Write the equations involved in the following reaction. Reimer-Tiemann reaction All india 2012 Or Write Reimer-Tiemann reaction giving an example. allindia 2011 19. Draw the structure of 2,6-dimethylphenol linda 2001 20. Write the chemical equation for the preparation of phenol from benzene using oleum and sodium hydroxide. oeihi zon 21. Write the structure of the molecule of compound whose IUPAC name is L-phenylpropan-2-ol. allindla 2010 22. Write the mechanism of acid dehydration of ethanol to yield ethene. All india 2015¢CHAPTER 10 : Alcohols, Phenols and Ethers Or Explain the mechanism of dehydration steps of ethanol. Ht CH,CH,OH—“> CH, =CH, + H,0 ‘eth! 20186, ll india 2013 @ 2 Marks Questions 23. (i) Arrange the following compounds in the increasing order of their acidic strength. p-resol, pnitrophenol, phenol (ii) Write the mechanism (using curved arrow notation) of the following reaction. H,0* + CH, =CH, —> CH, —CH, + H,0 ll india 2017 24. How are the following conversions carried out? ( Propene to propan-2-0l? (ii) Ethyl chloride to ethanal? 25. Write the mechanism of the following reaction. CH,CH,OH 5 CH,CH,Br + H,O Foreign 2014; Dethi 2014 26. How will you convert the following. (i) Propan-2- ol to propanone? (ii) Phenol to 2,4,6-tribromophenol? Delhi 2013 27. How will you convert (i) propene to propan-1-ol? Gii) ethanal to propan-2-ol? pelhi 2013 28. How will you convert (i) propene to propan-2-0l? i) phenol to 2,4,6- trinitrophenol? Delhi 2013 29. Explain the mechanism of acid catalysed hydration of an alkene to form corresponding alcohol. Allindia 2012 30. Explain the following behaviours. (i) Alcohols are more soluble in water than the hydrocarbons of comparable molec ular masses. Ini 2014 247 (ii) Ortho-nitrophenol is more acidic than ortho-methoxy phenol. Allindio 2012 31. How would you obtain pelhi zon ( picric acid from phenol? (ii) 2-methyl propanol from 2-methyl propene? 32. Account for the following. (® Propanol has higher boiling point than butane. (ii) Ortho-nitrophenol is more acidic than ortho-methoxy phenol. pethi zone 33. Account for the following. (@ The boiling points of alcohols decrease with increase in branching of the alkyl chain. (ii) Phenol does not give protonation reaction readily. Delhi zonc 34, How are the following conversions carried out (i) benzyl chloride to benzyl alcohol? (ii) methyl magnesium bromide to 2-methylpropan-2-0l? pelhi 2010 35. How are the following conversions carried out (i) Propene to propan-2-ol? Gi) Ethyl magnesium chloride to propan-1-ol? ethi 20.0 36. Write the mechanism of hydration of ethene to ethanol. Foreign 2010 37. Give one chemical test to distinguish between the following pairs of compounds. () Phenol and benzoic acid. (ii) 1-propanol and 2-propanol. pethi 2o10c (@ 3 Marks Questions 38. (a) How will you synthesis the following alcohol from appropriate alkene : OH (b) Write the mechanism of the following reaction All india 2019 CH,CH,OH “> CH= CH, + H,0248 39. (a) Show how you will synthesise the following alcohol by the reaction of a suitable Grignard reagent on methanal? Hypa Cie 1g —OH CH, (b) Write the mechanism of the following 19 reaction All indi CH,= CH, +H,0 "5 CH,CH,OH 40. (a) Butan-1-ol has a higher boiling point than diethyl ether. Why? (b) Write the mechanism of the following reaction : i 2CH,CH,OH > CH,CH,—O—CH,—CH, allindia 2018 Allindia 2019 41. (i) Complete the following reaction and suggest a suitable mechanism for the reaction : Bae 43K cx,cx,on “4 Gi) Why ortho-nitrophenol is steam volatile while para-nitrophenol is less volatile? 2018 ¢ 42. Predict the products of the following reactions. o Bat () CH,— cH =cH, —***_, ? co an,or on Gi) CH,oH =, ous7aK Gii) CHyCH,OH——> foreign 2015 43. How are the following conversions carried out (i) Benzy chloride to benzyl alcohol? (i) Ethyl magnesium chloride to propan-1-ol? Gii) Propene to propan-2-0l? all india 2015 44, (i) Write the mechanism of the following reaction. CH,CH,OH —"®*5 CH,CH,Br + H,0 (ii) Write the equation involved in Reimer-Tiemann reaction. ll india 2014 @ Chopterwise CBSE Solved Papers : CHEMISTRY 45. How are the following conversions carried out, (i) Propene > Propan-2-ol? i) Ethyl magnesium chloride + Propan-1-ol? Gi) Benzyl chloride — Benzyl aloohol? ain 46, Draw the er and name the product formed if the following alcohols are oxidised. Assume that an excess of oxidising agent is used. () CH,CH,CH,CH,OH Gi) 2-butanol (ii) 2-methyl-1-propanol beth 2012 47. How would you obtain the following. (i) Benzoquinone from phenol? Gi) 2-methyl propan-2-ol from methyl magnesium bromide ? (ii) Propan-2-0l from propene? AlLindia 201; Foreign 201 48. Account for the following: (i) The boiling point of ethanol is higher than that of methanol, Gi) Phenol is a stronger acid than an alcohol. (iii) Propanol has higher boiling point than butane. bethi zone (i) Describe the mechanism of hydration of ethene to yield ethanol. (i) Write Kolbe's reaction with an example. Allindia 20mc ( Describe the mechanism of acid catalysed dehydration of ethanol to yield ethene. (i) Describe the chemical test to distinguish between ethanol and phenol. ail india 20100 @5 Marks Questions 51. (a) How do you convert the following (@ Phenol to anisole i) Ethanol to propan-2-ol (b) Write mechanism of the following reaction HyS04 C,H,OH CH, = 49. CH, +H,0CHAPTER 10 : Alcohols, Phenols and Ethers (©) Why phenol undergoes electrophilic substitution more easily than benzene? Delhi 2019 52. (a) Account for the following : (@ o-nitrophenol is more steam volatile than p-nitrophenol. (ii) butyl chloride on heating with sodium methoxide gives 2-methylpropene instead of t-butylmethylether. (b) Write the reaction involved in the following (@ Reimer-Tiemann reaction )) Friedel-Crafts alkylation of phenol (©) Give simple chemical test to distinguish between ethanol and phenol. pelhi 2019 @ Explanations 4. TUPAC name of given structure CH; OH cr 2t— Gch, cH, —cH, “4s 3, 3-dimethylpentan-2-o1 H,¢—¢ = ¢—CH,—on CH Br 2-bromo:3-methylbut-2-en-1-o1 o 3. IUPAC name of the given compound is 2-phenylethanol o Tk ‘ NO, : TUPAC name 2,5- dinitrophenol o fe 4 5. HO—CH,—CH =c—CH, cH, TUPAC Name 3-methylbut-2-en-1-ol o 6. o-nitrophenol is more volatile due to chelation (weak intramolecular H-bonding). While, p-nitrophenol is less volatile due to strong intermolecular H-bonding which causes the association of molecules. 249 wy Due t-bonding F o-nitrophenol (Intramolecular H-bonding) H-bonding o OH 7. CH, —CH—cH, Propan 20 o 8. Propane -1, 2, 3-triol. o 9. | +helfect of alkyl group increases the basic cler of alcohols and —Hetfect of alkyl group increases the acidic character of alcoho's. In R—OH, R possesses only +/-effect, i.e. only alkyl groups which increases electron density on O-atom of O—H bond and hence, it shows basic character while, in R’OH, R’ possesses —I-effect in its alkyl chain which decreases electron density in ee o Cr aya, a, ad Orns Alc Phenol Thine) 11, In o-nitrophenol, intramolecular H-bonding occurs which makes it more volatile whereas, in p-nitrophenol intermolecular hydrogen bonding exists which makes it less volatile. That's why, o-nitrophenol has lower boiling point than p-nitrophenol o 12, cucu on SHH, CH, = ye a oa oH on o 13, én,— én,— én,— ¢u—Cn= cn, on Hex-ben- 3-01 io250 ou 14. ou —c, cH, 2methylpropan-2-01 o 15. CH,—CH = CH—CH—CH,—CH, H Hex-4- en-3-ol o 16. In phenol, C—O bond acquires partial double bond character due to resonance while, in alcohol, C—O bond has single bond character. (0) 17, cH cH OH EES, cH, CH, + HO Ethanol fnene (Dean) © 18. Reimer -Tiemann Reaction The reaction of phenol with chloroform in the presence of sodium hydroxide, a—CHO group is introduced at o-position of benzene ring. This reaction is known as Reimer-Tiemann reaction, The intermediate substituted benzal chloride is hydrolysed in the presence of alkali to produce salicylaldchyde. oH {) N8OH, 340. + CHO, ano is o-Nat Nat CH(OH)2 * 208, ua? a benzene ehaide ONa ae Dic Tne “aaa? yronbenalehyde (Salicyladehyde) (1) NOTE A small amount of phydroxybenzaldehyde is also formed. 19. on HCvg A cH 5 3 ‘ 2, 6-dlmethylpheno! to @ chapterwise CBSE Solved Papers : CHEMISTRY 20. $O5H ‘cid Sodium benzene Sodium phenoxide Phenol sulphonate o 21. eae ces ou 1-phenytpropan-2-o1 o ‘Sieps involved in acid catalysed dehyotation of alcohol are {Protonation of alcohol (i) Formation of carbocation (i) Elimination of proton 22. Ht —cH,—oH —# > CH, = CH + H, CH,—CHy- re ol re) Mechanism This reaction involves the following steps: ‘Step 1 Formation of protonated alcohol a/fH CHy—CH, —O—H+H* + CH; —CH,—OC Protonaed ethanol! (ethyi oxontum tn) 2) ‘Step U1 Formation of carbocation SAL vt crc, L$ — \ pr Rate determining “Ramet o_ cH, — ci, +110 Carbocation Step III Loss of proton to give alkene BCH GOH, ih = CH 23, (i) Blectron withdrawing groups such as —NO, increases the acidic character while, electron releasing group such as —CH, decreases the acidic character thus, the increasing order of acidic strength is,CHAPTER 10 : Alcohols, Phenols and Ethers 251 G-O-0 CH, NO, G-eresol) (Phenol) p-nitrophenol) (ii) The mechanism for the formation of fare is as follows: I, cuca, + HOO — cHy—CH, + 1,0 24, (i) Propene to propan-2-ol on maou cH, —cH = cH, —"°"_, cu, cc, pene ‘Sidonarsya) Pov o (ii) Ethyl chloride to ethanal 1H, — CH, — a cH, — cH,— on —2_5cH,—cHo °c cade Phanct— COWFEC Roane sation {Osésion o 25, CH,CH,OH on reaction with HBr follows S,2mechanism. HEr—> Ht + Br” Sy2 mechanism os + +H? —s cH, —cH,—OH, Step) Cj —CH, — Hs Za, wl step? we cn, “cH, Sn, —o] B5-cH, di a immed “oer Hc, + 4,0 26) Propan-2.a to propanone Hfo— ACH SORTS HEE ou mono a nm (ii) Phenol to 2,4,6 -tribromophenol on Br Br 35 ino ecaimey i Br aaecar ct - mm Fropene to propan-1-ol CHCH cH, + HBr cHcH cHBr cH, Ct, —CH,—On = rept bonis nn o AOTE Alternative method for converting propene to propanol is hydroboration-oxidation reaction,252 @chapterwise CBSE Solved Papers : CHEMISTRY CHy—CH=CH,+(H—BH,)) —+ CH —CH—CH, SHS, (cH, —CHy—CH,),BH Propene Diborane | i BH een 20H > (CH; —CH,— CH) 3B => > 3CH, — CH, — CH,0H+ B(OH) (CH, —CHe— CHB apa? 3CH — CHa — CH (i Ethanal to propan-2-ol 3-3 (CH, Omg! cH, oH Cee ae ee 7 HW n7 Neus a7 cy than ropa " Addut Propene to propan-2-ol Addition of H,S0, takes place in accordance with Markownikoff's rule while converting propene to propan-2-ol. CH,CH=CH, + 104, Bap o ou Propan-2ot (ii) Phenol to 2,4,6-trinitrophenol Nitration of phenol in the presence of conc. H,SO, and conc. HNO yields 2,4,6-trinitrophenol (picric acid). : OH on ON NO, 13504 0; + SHINO: Toone)” Pict NO2 2A intuophena trac aaa) o 29. | The steps involved in this process are () Protonation of alkene: (i) Nucleophilc attack of water on carbocation (ll) Deprotonation to form an alcoho! Following steps are involved in the acid catalysed hydration of an alkene. ‘Step I Protonation of alkene to give carbocation by electrophilic attack of H,0* as shown below: Hp+H'—Hp* ay a Protonated alcoholCHAPTER 10 : Alcohols, Phenols and Ethers 259 30. | () Consider polar nature of water as well as alcohol, presence o H-bonding | | (0) Acidity is the tendency to give a proton. It depends upon the stability of phenoxide ion formed (in case of phenols) Higher the stabilty of phenoxide ion, more willbe the acidic character. | (1) Due to the presence of polar — OH bond, alcohol molecules can form H—bonds with the water molecules and the water-alcohol interaction becomes stronger than the water-water or alcohol-alcohol interactions. That's why, alcohols are more soluble in water. H-bond Kw be ew Lo Baga pert Geel GO | | | R H R " R Intermolecular H-bonding between alcohol and water : Hydrocarbons, on the other hand, have no polar bond and hence, the water-hydrocarbon interaction remains weaker as compared to water-water or hydrocarbon- hydrocarbon interactions, i.e. hydrocarbons do not form H-bond with water. Thus, they remain insoluble in water. o (ii) Due to strong ~R and ~I-effect of the NO, group, electron density in the O—H bond decreases and hence, the loss of a proton becomes easy. 1 eo Ge no NO NY N 2 > effect -Retfec decreases the election a positive charge on the density in the O—H bond, ‘phenolic O-atom, makes makes release of proton easy the release of proton ea: Further, the o-nitrophenoxide ion left after the loss of a proton is stabilised by resonance. Thereby making o-nitrophenol a stronger acid In contrast, due to +R-effect of —OCH, group, the electron density in the O—H bond increases thereby making the loss of a proton difficult. o-H oH cf cH cr cH Furthermore, the o-methoxyphenoxide ion left after the loss of a proton is destablised by resonance because the two negative charges repel each other thereby making o-methoxy phenol a weaker acid. Thus, onitrophenol is more acidic than o-methoxyphenol. wo: o + Gt co cH o254 @chapterwise CBSE Solved Papers : CHEMISTRY 31. (i) on on NO, No, o Conc14N0y, = “onc.H;50, Prevod No; aie add a cH, 3cH, — HH, + BH, ———> (CH,),CHCH,] ,B "22> 3 (CH,),CHCH OH Dimcypepee HWaroborton ir -H905 or HC— a cHoH cH, 2>methyl propanol i 32, (i) Themolecules of propanol are held together by intermolecular hydrogen bonding while the molecules of butane have only weak van der Waals’ forces of attraction. Hydrogen bonds are much stronger so the boiling point of propanol is much higher than butane. A (Gi) Refer to solution 30 (ii). 0 + 33. (i) Since, branched chain alcohols have minimum surface arca, therefore, minimum force of attraction occur between them, hence boiling point decreases with increase in branching of alkyl chain. o (Gi) In phenols, the lone pairs of electrons on the oxygen atom are delocalised over the benzene ring due to resonance and hence, are not easily available for protonation. o 34. (i) SH CH,—OH oO ~ fe) Benzyl chloride Benzyl alcohol o 5 56 ‘eel ie (ii) CHyMger + cHy¢—cH,—>cH,—¢—cH, 2°, cn,—C—c, Medi magnesium [stoner 1 corde cH, cu, ‘opanane: 2-methyipropan-2-01 o 35. (i) CH, = CH—cH, 2%", cH,—cH—cH, Boers 1H Propan 201 © he oMac i 1 HCHO, cy, cH, —cH, —™2°5 cH,CH,CHOH a : “gone opera ‘chloride a 36. Refer to solution 29. 37. (i) Phenols do not give brisk effervescence of CO; on reaction with carbonates and bicarbonates while carbox acid gives. Ph—OH + NaCO, —> No reaction 2CH,COOH + NaC0,—> 2CH,COONa’ + H,0 + C0, T oCHAPTER 10 : Alcohols, Phenols and Ethers (4) Propan-2-o1 on reaction with sodium hydroxide and 1) (warm) gives a yellow precipitate of odoform (CHI) while, propan-l-ol gives. no such test CH, —CH—CH, +41, 9 CHIL CH COON a4 SNat on (roqan 2.00) 4511,0CH, ~CH, ~CHON+ a1, “5 No reaction (ovo 1-01) o 98. (a) Given, alcohol (2-methyl-2-butanol) canbe synthesised from 2-methyl-2-butene (alkene) as follows ‘OH 2-mnethyl-2-butene 2-methy-2-butanol (major) ut _ (by Ch, CH, —OH Ech, = cM, + HO Mechanism. Step 1, Addition of H* ion §-u/Mtven, cn, —9—n i ‘Step 11. Formation of carbocation cH, —CH, — cn, =e, Ln — ar, —dn, +19 H ‘Step 111, Formation of ethene (alkene) cH, 5 CH, — cH, =cH, +H" 7 W 39. ne + Cayeugar —> Cayce, oO cH, CH; OMgBr Melovnbr + Ci,— en.cu peer, Step 1 CH,CH,—OH + Ht—+ CH,—CHy eH Step 2 CH,CHy—On + CH;CH,-COT, SA # + enon. —p%cnon +140 h Step 3 CH, —cii-—GcngcHy —> t CHjCH,OCH,CH,+H* 41. (i) Refer to solution 22. (ii) Refer to solution 11. ae Taaoron CH,—CH,—CH,OH () Propane! i cayonor €V—on ten. nC Fon Bi 24.6 unbromophenol a) 42, (i) CH,—CH = CH, (ui) cu cuon “2”, cH, cHo pe o256 “emer gro i Ki OC + neon ic. oO Ca CH,OH chloride | —H+ enn schol a oO (ii) Refer to solution 35 (ii). o iii) Refer to solution 35 (i). o 44. (i) Refer to solution 25. wa (ii) Reimer-Tiemann Reaction Refer to solution 18. om 5. (i) Refer to solution 35 (i. o (ii) Refer to solution 35 (ii). o (iii) Refer to solution 43 ° o 46. (i) cHcH cH CHAO CH,CH,CH,COOH amine CD iy cH, —cH—cH,cH, 2 ou nana (CH, —C—CH,CH, J pbuanone —H) 8 u I I (iii) CH, —C—cHoH "cH, —C—cooH ‘dation | cH, “2methyoropanole ac (1) (ii) Refer to solution “ww, o i) Refer to solution 35 (i). o cH, ‘bmethy-- propanol 47. (i) 6 = em, Phenol 48. (i) Boiling point of alcohol increases with increase in the number of carbon atoms (increase in van der Waals’ forces). That's why boiling point of ethanol is higher than that of methanol. (1) @ Chapterwise CBSE Solved Papers : CHEMISTRY (ii) The phenoxide ion, produced by the loss of g proton by phenol, is stabilised by resonance due to delocalisation of the negative charge on the benzene ring. In contrast, alkoxide ion, h not stabilised by resonance. On the other hand, it is further destabilised by positive inductive effect of alkyl group. 5 ve Phenaxide fon Resonating structures of phenoxide ion tr bdS ROH = RO” +H* ‘Akoideion n (ili) Refer to solution 32 (i) o 49. (i) Refer to solution 29. o (ii) Kolbe’s reaction When sodium phenoxide [generated by treating phenol with NaOH) is heated with CO, at about 400 K and under 4 to7 atmospheric pressure, sodium salicylate is formed as major product, which on acidification Bives salicylic acid, e.g. Sodium phenoxide 9coond OH Rearrangement seataail on coo Hom’, Salicylic acid (2anydrony benzoic acid) 50. (i) Refer to solution 22. @CHAPTER 10 : Alcohols, Phenols and Ethers (ii) Ethanol when warmed with NaOH + 1, gives yellow ppt. of iodoform while phenol does not give this test 257 Step lt Formation of ethene by the elimination of a proton WH CH,CHOH + 4Nao1—>_cHt, L INL We cs ae hand todotorm Ho Ny 8 (ow pp rl H + HCOONa" + Nal+ H,0+ 2NaOH C,H,OH + NaOH —> No yellow ppt Phenol 51. (a) (i) Phenol to anisole o The acid used in step I is released in step 111. To drive the equilibrium to the right, cthene is removed as itis formed. (c) Phenol undergoes electrophilic substitution oH ONa ‘more easily than benzene because phenolic ion is ‘more stable than benzene. 52. (a) (i) Ino-nitrophenol, there exists intramolecular +NaoH >> H-bonding which ‘makes it more volatile a) whereas in p-nitrophenol, intermolecular ; 4 hydrogen bonding exists, which makes it Phen Path less volatile, — (ii) butyl chloride on heating with sodium 5 methoxide gives 2-methyl propene instead of -butyl methyl ether because, in case of 2° crct land 3° alkyl halides due to steric hindrance, " (b) (i) Reimer-Tiemann reaction On cating anisole phenol with CHCl, (chloroform) in. the presence of sodium hydroxide, a —CHO (i) Ethanol to propan2-l group is introduced at ortho position of cucnpu cH, —cHo 2" , —- => cH,—cHo ee, at hana Osta on ota Ve ie CHCh, cH,—¢—G gar 5 cHy—cH—on wet, N20H my ome heen ba War H Phew Intermediate (b) Mechanism co eae Step I Formation of protonated alcohol cHO it om, Ha lz Fast wee Bone ent ba i i sant Ethanol Frotonated alcohol (ii) Friedel-Crafts alkylation of phenol (Ethyl exonium ion) Step II Formation of carbocation It is the slowest step and hence, itis the rate determining step of the reaction. Hiatal it sow, | I He ergtn Ss Het m0 ft) HOH Catbocation HH os Oa Phenols when treated with alkyl halides in the presence of anhydrous AIC} undergo alkylation to form, me substituted eels =O0" ovcresol (Minor) Pal (major) Anya. Ally258 @ Chapterwise CBSE Solved Papers : CHEMISTRY (6) Ethanol when warmed with NaOH + ly gives yellow ppt. of iodoform while phenol does not give this test. CHCH,ON+4NaOH—> CHI, L + HCOONa +Nal +H,0 + 2NaOH ‘anal Iodolerm vow ty GJH,OH+ NaOH —> No yellow ppt. [TOPIC 2) Ethers + The substitution of a hydrogen atom in a hydrocarbon (aliphatic/aromatic) by an alkoxy (—OR) or by aryloxy (—OAr) group yield ethers, Ethers are represented as R—OR' and have general formula Cyan y 2 + Ethers are dialkyl derivatives of water or monoalkyl derivatives of alcohols. + The IUPAC name of ether is alkoxy alkane. The ethereal oxygen is taken with smaller alkyl group and forms a part of alkoxy group while, the larger alkyl group is considered to be a part of the alkane. e.g. The IUPAC name for CH —O —CH, is methoxy methane and for CH, -CH,0—CH,CH, is ethoxy ethane. + The isomerism commonly exhibited by ethers is metamerism. 2.1 Preparation of Ethers (i) By dehydration of alcohols in presence of protic acids at 413 K. (ii) Both symmetrical and unsymmetrical ethers can be prepared by Williamson’s synthesis. ‘The order of reactivity of alkyl halides for Williamson's synthesis reaction is primary > secondary > tertiary. (iii) To obtain best yield of tert-butyl ether by Williamson’s synthesis, the alkyl halide should be primary and alkoxide should be tert-butoxide. (iv) Aromatic ethers like anisole can be prepared by the reaction of sodium phenoxide with alkyl halides. 2.2 Properties of Ethers (i) Ethers have low boiling points than isomeric alcohols due to their inability to form H-bonds. (ii) Bthers are inert and thus are used as solvents in many reactions. (iii) Ethers on cleavage by acids give back alcohols and alkyl halides. The reaction proceed via Sy2 mechanism. Due to steric hindrance, the alkyl halide is always obtained from smaller alkyl group. (iv) Aromatic ethers on cleavage give phenol and alkyl halide.CHAPTER 10: Alcohols, Phenols and Ethers 259 Flow Chart for the Preparation and Chemical Reactions of Ether Preparation Chemical Properties RX + R-ONay —. BE ser kG RK + +R-O-R 2 proc] sd — J tether 2ron 4 och, ocny Reactions of Anisole * Electrophilic Substitution Reactions br Pbromoanisole ‘Man och, OCH NO, cone. HNO, . ‘on H,30y (Nitration) ‘ino ~ OCH, : (Major) a oct, ocn, |-— cocit, Se cncoa ; Aatyd A ede SSH ey “tts cocn, A-methoxpacctophenone ‘ison och, ocH, cn, a. agit 2-methorytoluene (ince) cHy “-methonytoucne (Major)PREVIOUS YEARS' EXAMINATION QUESTIONS TOPIC 2 @ 1 Mark Questions 1, Write the IUPAC name of the following compound. oy. Cy ——F— Cy, CH, All indo 2017 2. Write the IUPAC name of the given compound: Ct —-fH— GH, —0— CH,— Gi, CH, All india 2018 3. Write the equation involved in the reaction Williamson's ether synthesis. All indi. 2019 4. Write the IUPAC name of the following compound Ailll india 20126 NO» OCH; 5. Explain the following by giving one example. Friedel-Crafts acetylation of anisole. Delhi 201, 2010 6. Illustrate the following reaction by giving a chemical equation : Williamson’s synthesis Delhi 2010; All india 2010; Foreign 2010 7. Phenyl methyl ether reacts with HI to give phenol and methyl iodide and not iodobenzene and methyl alcohol. Why? Dethi 20100 @ 2 Marks Questions 8. Write the mechanism of the following reaction. Cone. M804 2CH,CH,OH > CH,CH,—O—CH,—CH, bethi 2016 Or Give mechanism of preparation of ethoxy ethane from ethanol. 20r0c 9. How is 1-propoxy propane synthesised from propan-1-ol? beihi 2010 @ 3 Marks Questions 10. State the products of the following reactions : (i) CH,CH,CH,OCH, + HBr —> i) OCjHs Co, Gil) (CH,);C—OCH, "+ foreign 2012 @ Explanations cH, I 1. Given, compound is cas 0 Gt, 2&4, —fu 4,0, : 2. Willlamson’s ether Synthesis R—X + R'ONa —> R—-O—R’+ NaX eg, CHiL+C,,0Na—s CHOCH, + Nal tat lade wetanetane 4. 1-ethoxy-2-nitroyclohexane. 0 anisole reacts with acetyl chloride in the presence of anhydrous AICI,, the acy! group is introduced. at ortho and para-positions..CHAPTER 10 ; Alcohols, Phenols and Ethers och, 0 anh +encocl “it. ankle cn oct, cH—cHy 8 + hoxyacetophenone (Minor) ccny A-methoxyacetophenone (maken (otal eg 6. Willlamson’s Synthesis When alkyl halide reacts with sodium alkoxide, ethers are formed. This reaction is known as Williamson's synthesis. Hy CMBr+ CHy—C—O-Nat_ —> Hy au CH) —C—O—CH, + NaBr cH, 2 ethoxy -2- methylpropane (1 7. Protonation of anisole (phenylmethyl ether) gives methyl phenyl oxonium ion. oHy—6 — a, H In this ion, O—CH, bond is weaker than O—CyH, due to partial double bond character because of resonance between the lone pair of electrons of O-atom along with sp?-hybridised C-atom of the phenyl ring. Therefore, attack by ion exclusively breaks the weaker O—CH, bond forming methyl iodide and phenol. The phenol formed does not react further to give aryl halides, Hears Chas boubleYond hacer Opa — OCrowscrys ron in o 261 lowing siops occur (0) Protonation of alcohol (i) Attack of nucioophite (li) Romoval of proton | Step | Protonation of Alcohol cy —cu,— uh CH) cH, —G: + chy en, =—9' E> cH, — cr, —3—cH,cH, + 1,0 " ‘Step 111. Removal of Proton cH ea (CH,—CH, —O—CH,—CH,+ H* favo cane @ 2CH,—CH,CH,OH + 1,80, ES 5 cHCH.cHe—cucH eH, i.e, primary halide is formed due to steric hindrance. {il) Tertiary iodide and primary alcohol are formed as reaction proceeds by S 1 mechanism. (i) CH,CH,CHOCH, + HBr —> CHCHCHON+ CH Br + Hs Br ‘romoethane (1) (ill) (CHy ,C—OGMH, + HL —> ony csp + CaLON ay oLe acme en MISCELLANEOUS QUESTIONS @ 2 Marks Questions 1. Define with equation : (a) Riemer-Tiemann reaction (b) Williamson's synthesis all india 2013 2. Write the equations involved in the following reactions: (a) Kolbe’s reaction (b) Friedel-Crafts alkylation of anisole All indio 2019 3. Name the different reagents needed to perform the following reactions : () Phenol to benzene. (ii) Dehydration of propan-2-0l to propene. (iii) Friedel-Crafts acetylation of anisole. (iv) Dehydrogenation of ethanol to ethanal. Foreign 2014 4. Name the reagents used in the following reactions : (@) Bromination of phenol to 2, 4,6-tribromophenol. (i) Butan-2-one to butan-2-ol. (iii) Friedel-Crafts alkylation of anisole. (iv) Oxidation of primary alcohol to carboxylic acid, Foreign 2014 5. Name the reagents used in the following reactions : @ Nitration of phenol to 2,4,6-trinitrophenol (i) Butanal to butanol. (iii) Friedel-Crafts acetylation of anisole. (iv) Oxidation of primary alcohol to aldehyde. Foreign 2014 6. Write the equations involved in the following reactions : ( Reimer-Tiemann reaction. (i) Williamson synthesis. 2 7. Write the equations involved in the following reactions : (i) Williamson ether synthesis. Gi) Kolbe's reaction. peihi 2014 @ 3 Marks Questions 8. What happens when (a) phenol reacts with conc. HNO? (b) ethyl chloride reacts with NaOC,H,? Write the chemical equations involved in the above reactions. all india 2019 9. Write the main products in each of the following reactions: CH; @ CHy~G-o—cHy+ Ht —+ bay (i) CHs—CH=cH, Bt CH2~ Gi atig0g07 Gi) CgHy—OH —020.N20H G) CO, HY all india 2016 10. Write the final products in each of the following reactions: CH; @ CHy-4-0—CHly +HI— ba, (i) CHy—CH,—CH—cH, 225, bu i) Ogg OF Fp at 205 11. How do you convert the following. ) Phenol to anisole? i) Propan-2-ol to 2-methylpropan-2-0l? (ii) Aniline to phenol? pethi 2015 12. (i) Write the mechanism of the following reaction. 2CH,CH,OH-, CH,CH,— O— CH,CH, (ii) Write the equation involved in the acetylation of salicylic acid. pelhi 2015 13. Give reason for the following. (@ Phenol is more acidic than methanol. (i) The C—O—H bond angle in alcohols is slightly less than the tetrahedral angle (109° 28 ).CHAPTER 10: Alcohols, Phenols and Ethers, i) (CH C-O-- CH, on reaction with, Wi aves (CH, )C— Land CHy OH as the main products and not (CN WC--O1 and CH, 1 attindle 208 14, Write the major product in the following equations, All india 20180 Wey (i) CHy CHO +? on ov (Oren, can SF —a (ii) CH, —Cl+ CH,CH,—ONa—> ? 18. Name the following according to IUPAC system, Delhl 20186 ween, ft CH,—CH, OH Je on, 6 i ks CH, | CH,—Cl (ii) CHy f CHy 46, How nre the following conversions carried out. (i) Propene to propan-2-0l? (ii) Benzyl chloride to benzyl alcohol? Gi) Anisole to p-bromonnisole? pathi 20180 17, Explain the following with an example for each : i) Kolbo's reaction (ii) Roimor-Tiemann reaction Gii) Williamson ether synthesis NLinglo 20140 18. Account for the following. (i) The boiling points of ethers are lower than isomeric aleohols. (ii) Ortho-nitrophonol is more acidic than ortho-methoxy phenol. 263 (iii) Preparation of ethers by acid dehydration of secondary or tertiary alcohols is not a suitable method oath! zone (@ 5 Marks Questions 19. (i) Write the products in the following reactions: on coo (€14,C01,0 nan W CH; (b) CH,—CH — 0— CHs—CHs | HI (©) CH,— CH = CH— CH,— oH Poe (ii) Give simple chemical tests to distinguish between the following pairs of compounds: (a) Ethanol and phenol (b) Propanol and 2-methylpropan-2-ol. 20. (i) Write the formula of reagents used in the following reactions: (a) Bromination of phenol to 2, 4, 6-tribromophenol. (b) Hydroboration of propene and then oxidation to propanol. (ii) Arrange the following compounds in 12017 (a) p-nitrophenol, ethanol, phenol (acidic character). (b) Propanol, propane, propanal Qboiling point). Write the mechanism (using curved arrowemotation) of the following reaction: CH, — CH,—OH, Hy—CH, —G— CH, CH +H (CHyCH OH H264 @ Explanations 1. (a) Riemer-Tlemann Reaction (On treating phenol with chloroform in the presence of sodium hydroxide, a—CHO group is introduced at ortho position of benzene ring resulting in salicylaldehyde. This reaction is known as Riemer-Tiemann reaction. oH ONa CHCl, cacy MoH, a0 Phenol Gila imemedste On cHo cHo salle (b) Refer to solution 6 of Topic 2. 2. The equations involved in the following reactions are (a) Kolbe’s reaction, on ONa oH coon NaoHt (10, wer Phenol Salleyie acid (b) Friedel-Craft alkylation of anisole on oc, OCH, Anbyd cH, ‘ach, + CHCl + Aisole — (atinor ou, (oan) 9. (i) Zn dust and heat OH zn dus i.e Phenol Benzene (ii) 85% HPO, (440K, OH | CH, —CH—cH, Propan-2-o1 @ chopterwise CBSE Solved Papers : CHEMISTRY {iti) Refer to solution 5 of topic 2. {iv) PCC (Pyridinium chlorochromate) CH, —CH,—0H 4 cH,—cHo hana bana (o17202) 4, (i) Aqueous bromine or bromine water (Br in H,0) oH OH Br Br snmnten +38, no? Penal Br 2.4. 6mbromaphena (Gi) Sodium borohydride (NaBH) 9 ll —cH,—cH,, Naty cH, — OH CH, —CH—cH, —cH, itan-2-l (iii) CH,Clin the presence of anhy. AICI, as acatalyst and CS, as a solvent. cH, cH, cH, Anh AlCl + CHCl AMEND Cl Fede rats Asiole ‘Atyiation) metho tohene (ine) OCH, ot cH “meth toluene (ian). (iv) Acidified potassium permanganate or acidified KE1D>. R—CHOH Vr ashot 84 5. (i) Conc. HNO, and conc. #50, on on ON, NO, ine. N04 ene HO Kit,» coon axK=a Phenol NO, 2Astniophenel ‘icc ac)CHAPTER 10 : Alcohols, Phenols and Ethers (ii) Hin presence of Pd cH, —CH, —cH, — otal cH, —CH,— cH, — cH oH vod CHO (iti) Refer to solution 5 of topic 2 (iv) Pyridinium chlorochromate (PCC), a complex of chromium trioxide (CrO ,) with pyridine and HCI and [0] cH,cH oH 5 cH cHo a Accubleirde (40172 = 2) 6 (i) Refer to solution 18 of Topic 1 a (ii) Refer to solution 6 of Topic 2 o (1) Refer to solution 3 of Topic 2 o (ii) Refer to solution 49 (ii) of Topic 1 0 8. (a) When phenol reacts with conc. HNO, then picric acid is obtained on A NO, FD) comet, Phenol Noy Picric acid (b) When ethyl chloride reacts with NaOC,H, then diethyl ether is obtained. cH,cit, cl + Na OCH, —> CHyCH, 0 GH +Nacl Diethylther| = Hy | WCtty—<—O—cHly + HI City 4 + CHO CH CHy m (Bitty (i) CHy—CH= cH, OSS —> 3cH, CH, CH,OH CTE alae ttre ocH, ocH, OCH, COOH (ii) ae + CO, (2 nydry benzoic aid) {sleylc acid) coo (hydroxy benzoic) 10. Final Product(s) of the given reaction are as following: (i) Refer to solution 9(i) oy o (ii) City —CH—CH—CHy SE Ow CHC -E ey ° o on CHO 2 hydroxy benzaldehyde Vsaleyaldehyde} o 11. (1) Penal wo enlacte,, OH OCH, sme atta) Pheol Anivole (ii) Propan-2-ol to 2-methylpropan-2-ol oH 10; 10 I CH; —CH— cH, AOS}, cy, _C_cH, “ho ‘xctone Propan-2l Suiar on wae _ =Ma1 OH) cH, CH, ‘Adduet 2emethylpropan-2-01 o camel, — oe (iil) Aniline to phenol NH 9 aniline Nicr Nanounich Game Plazorisation Benzene diagonium ne on Dil H, S08, tse + Natt Hel Phenol o 12. (i) The given reaction depicts the preparation of ther through dehydration of alcohols, CH, —CH, on 7H, ital ry CH,—0—CH, +0 hon ane Mechanism ‘This reaction proceeds through nucleophilic bimolecular substitution reaction, i.e. $2 mechanism. ‘The main steps are as follows: ‘Step 1 Protonation of alcohol cH, —cH, —G—H + #* > H + cH —cH,b—H ie266 @ chapterwise CBSE Solved Papers : CHEMISTRY ‘Step 1. Nucleophilic attack by unprotonated alcohol molecule on protonated alcohol molecule, : + cc, —8:+ cry —cn, CoC" > csc, —S— cinch, + 120 a A stow) H H ‘Step TH Loss of proton to form ethoxyethane. H Ip ks HCH, 9 cH, —cH, 54 cHycH, —3—cH.CH,+H* Ethoryethane on cock, COOH cH,CO. coon i 7 ON Ses, +cHcooH CH;CO: Conc. HySO, Acetic acid sales 2accobenic za Goria) o 13. (i) Refer to solution 48 (ti) of topic 1. (ii) In alcohols, both the oxygen and the carbon attached to it are sp?-hybridised. Two of the four sp?-hybridised orbitals of oxygen overlap separately with 1s-orbital of H and sp?-orbital of carbon of the alkyl group to form OH and C—O, o-bonds respectively, while the remaining two sp -orbitals contain lone pairs of electrons. ‘The C—O—H bond angle is slightly less (108.9") than the tetrahedral angle (109°28’) due to greater lone pair-lone pair repulsion than lone pair-bond pair repulsion. o In case of unsymmetrical ethers having two different alkyl groups, the alcohol and the alkyl halide formed depend on the nature of the alkyl group. If one of the alkyl group is tertiary, the alkyl halide is formed from the tertiary alkyl group. ony rin cH, —C—0cH, + HI—+ cH,—On + cH, —C—1 f Sul” ety aol I cH, cH, This is due to the reason that the reaction occurs by Sy] mechanism and the formation of products is controlled by the stability of the carbocation resulting, from the cleavage of C—O bond in protonated ether. Since, a ter-butyl carbocation is more stable than methyl carbocation, therefore, cleavage of C—O bond gives ‘methyl alcohol and the more stable tert-butyl carbocation. This carbocation then reacts with I~ ion to form. tert-butyl iodide. o 14 (iy cH,cu,on 4 cH,CH¢! + POC), + HCI ‘aieoraee 1H on a cus wy (+cat ‘ (voor) ane cus (Majo amen a (iil) CHy—C1 + CH,CH,ONS- —3cH,CHOCH, + Nacl ‘Mean ethane ro Br 1 2h 4 : cH, 2 Te wen —te—eH,—O,) (ii) Ce cH, Butan-2o1 2-methylbromobenzene 22-dimethyicbropropane oCHAPTER 10 : Alcohols, Phenols and Ethers 267 o 16. (i) Refer to solution 28 (i) topic 1. (ii) Refer to solution 34 (i) topic 1 o ocH, och, och, Br iii) By Gwethanaie * seid) Anisole -bromeanisole ‘liner Br p-bromoanisole o “sajor) 17. (i) Refer to solution 49 (ii) topic 1 o (ii) Refer to solution 18 of topic 1. 9 o (iti) Refer to solution 3 of topic 2. 18. (i) Boiling point is directly proportional to the intermolecular forces existing in a compound. Ethers have low polarity because they do not show any association by intermolecular hydrogen bonding. On the other hand, their isomeric alcohols have strong H-bonding and so their boiling points are high.) (li) Refer to the solution 30 (i) of topic 1. o (iii) Secondary and tertiary alcohols on dehydration lead to the formation of alkene and not ethers due to extra stability of 2° and 3° carbocation, Hence, not suitable. o 19. (i) (a) OH ‘OCOCH, coon COOH = speci acd sate ad asp cu, we «b) CH,— CH —O—CH,—CH, ieee at +CH,— CH,OH “ethoxy propane ‘shana H 2 lodopropane (c) cH, —cH =cH—cH,—oH 54 cH,— cH =cH— CHO But-2en-Ial @ But-2en-L-0! (il) (a) Ethanol and phenol Iodoform test is used to distinguish ethanol and phenol. Ethanol reacts with NaOH solution containing iodine. On heating, it gives a yellow precipitate of iodoform while phenol does not react. NaOH +1, —+ Nal +NaOl+H,0; CH,CH,OH + 3NaOI—> CHI, 1+ n—¢—OWa ‘beta ° OH + Na0l—> No reaction (b) Propanol and 2-methylpropan-2-ol Propanol is 1° alcohol while 2-methylpropan-2-ol is 2° alcohol. Victor-Meyer’s test is used to distinguish both of them. In this test, first the given alcohol is treated with P/, and then with AgNO, and HNO. The final product obtained gives different colour with NaOH. By identifying the colour produced, the alcohols are identified.268 Primary alcohols give blood red colour rcijon 225 RCH M4 RCH,NO, Yakchat O=H-Ay RENO, NOH [sou Bo Secondary alcohols give blue colour R R Yeuion 4, yous ABS), R,CHNO> R R ¥ alcoho! SEN OH, RC—NOD N=o sow sue cour 20. (i(a) Bromine in presence of water can carry out bromination of phenol to 2, 4, 6-tribromophenol. on oH Br, Br eee Phenol br 2,4, 6ribromophenol (b) Diborane (BH), reacts with propene to give tripropylboranes as addition product which on ‘oxidation with alkaline H,0,, give alcohols. 3CH,—CcH =cH, "4, (CH, —CH,—cH,),— B B(OH), + 3CH,—CH,—CH,—On (ii)(a)_Blectron withdrawing group such as NO, Increases the acidic character while electron releasing group such as —CH, decreases the acidic character. Morcover, the ‘phenoxide ion, produced by the loss of a‘proton by phenol, is stabilised by resonance duc to delocalisation of the negative charge on the benzene‘ing. Therefore, the increasing order of acidic character is on On CH,CH,OH < < than Phen! No, palo pent (b) Alcohols (CH,CH,OH) undergoes strong hydrogen bonding while hydrocarbon such as Propane does not exhibit hydrogen bonding, Aldehydes show hydrogen bonding but not stronger than alcohols. @ Chapterwise CBSE Solved Papers : CHEMISTRY CH,CH,CH, HBr > HI> HP (>) HI > HBr > HCl > HF () HF > HCI > HBr > HI (4) HF > HBr > HI> HCI 2. Boiling point of alcohol is comparatively higher than that of corresponding alkane due to (a) intermolecular hydrogen bonding (b) intramolecular hydrogen bonding (c) volatile nature (d) None of the above 3. The most suitable reagent for the conversion of RCHOH —+ RCHOis (a) KMnO, (b) K £10, (o)pce (a) cro, 4. The correct order of dehydration of alcohols is {ayl> 23° (o) B>ie> 3 (b) 3°> 2 >1¢ (d)ie> 3°> 2CHAPTER 10 : Alcohols, Phenols and Ethers Which of the following compounds is most acidic? (actly (bya, (cc = CHL (a) Cujo 6, Lucas reagent reacts fastest with {a) L-butanol (b) 2-butanol {c) 2-methyl-2-propanol(d) 2-methyl-1-propanol Which one of the following alcohols, is used as an antifreeze reagent and for making explosives? (a) Glycerol (b) Glycol (d) Phenol 8, The correct order of boiling point for primary (1°), secondary (2°) and tertiary (3°) alcohols is (ay> > (Po > (c) Ethanol (b) 38> 2°> 1° (a) > ¥°> 19 9, Picric acid is (2) 246-tribromophenot (b) 246-trinitrotoluene (cl 24.6-trinitrophenol {u) None of the above 10. Which of the following does not give iodoform test? (a) CH,0H (by cyioHt (e)(CHt),CHOH (4) All of these 11, The chemical name of anisole is (a) ethanoic acid (b) methoxy benzene (c) propanone (d) acetone 12. From Williamson's synthesis, preparation of which of the following is possible? (a) Only symmetrical ethers (b) Only asymmetrical ethers (c) Both (a) and (b) (2) None of the above 13. Williamson's synthesis of preparing dimethyl ether is a/an (a) electrophilic sibstitution ()5y1 reaction {c) electrophilic addition. (d) Sy 2 reaction 14, The major product of the reaction between tert-butyl chloride and sodium ethoxide is (a) 2-methylprop-l-ene _(b) I-butene (c) 2-butene (d) ethene 269 @ Explanations MI> HBr > HCl > HP. ‘This is due to the fact that, nucleophilicity of a halide fon increases with increase in size. As the size of halide ion increases from Pt 1", thus, 1 fon will be a better nucleophile followed by BrCl and P, Because of intermolecular hydrogen bonding in alcohols, they exist as associated molecules. Consequently, a large amount of energy 1s required to break these bonds and, therefore, their bolling points are higher than that of the corresponding hydrocarbons (hydrogen bonding is absent in hydrocarbons). Pyridinium chlorochromate (PCC) prevents further oxidation of aldehydes to carboxylic acid. ncn pn P> 1°, Hence, 2-methyl-2-propanol reacts fastest with Lucas reagent. 7. Glycerol is generally used as an antifreeze reagent and for making explosives. 8 Alcohols with same molecular weight are expected to have almost same boiling point, however two more factors other than molecular weight are important; they are namely H-bonding and surface area of molecule. Both these factors are least in 3° alcohols and maximum in 1° alcohols. Hence, 3° alcohols have least boiling point while 1° alcohols have maximum boiling point. 9 Pleric acid is 2,4,6- trinitro phenol iH OnN- NO; NOz 2A,6-triniuophenol 10. Compounds containing either CH ,CHOH or form yellow coloured fodoform. This test is called fodoform tst.CjH,0H contains nether CH, F4— oH nor CH, —C— group, thus it does not give lodoform test. Note Tie I; converts C,H,OH into CH CHO. That's why it @ Chopterwise CBSE Solved Papers : CHEMISTRY ‘OCH 11. Anisole It is an ether and the IUPAC name of ether is given as alkoxy alkane. So, its name is methoxy benzene. 12. From Williamson's synthesis, both symmetrical and asymmetrical ethers can be prepared, e.g For synthesis of symmetrical ethers CHs0-Nat + CH3Br —+ CHOCH) + NaBr Sodium Methyl Dimethyl ether mmetborde bromide (Symmeincal the) For synthesis of asymmetrical ethers cH, cH, CH — GON" +CHBr—vcH,—F—0— cH, cH, CH, Sodium tr-butaoxide Methylter-butyl ether {asymmetrical ether) +NaBr 13, R—X-7™4R—-O—R Given equation represents Williamson synthesis. It involves nucleophilic substitution of the halide {on from the alkyl halide by the alkoxide fon by S,2mechanism. 14, Sodium ethoxide is a strong base, so it causes dehydrohalogenation of 3° alkyl halide and gives, alkene. cH, cH, I a+ a» ali gives iodoform test thy — 1 pia 7 Ei eit u BAPE on 2mahvivop ene ‘er-butyl chloride Download Free Chapter Test Note [email protected] Visit : http://tinyurl.com/yxdhbs4x OR Scan the Code For solution to this test mail your; Name, School Name, City, Test Name (chapter) at