Re K. MALIK'S (rc ramanons, neoren + sonno, non ieee NEWTON CLASSES Enjoys unparalleled reputation for best results in terms of percentage selection www.newtonclasses.net ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS — XI 1. Aleohots are compounds wihose molecules havea hydroxy group attached toa carbon atom af an liphatic system, Compounds having a hycroxy! group attached directly to a benzene ring are called phenols. Ethers differ from alcohols in that the exygen atom of etheris bonded to two carbon atoms. 2. Classification (a) Aleahots and phenols may be clasifed as mono- di, trio polyhydric compounds depending on whether they contain ‘one, Wo, three or many hydroxy groups, respectively in their steuetures (b) Ethers ae classified into two types) Simple or symmetrical the alkyl or ary groups attached to the oxygen atom are the same and (b) mixed or unsymmetrical ifthe two groups are diferent. 2. Nomenclature (a). In alcohols the hydroxy! group has precedence over double bonds and triple bonds in deciding which functional group to same as the sufi, ‘= Commonly, alcohols ae called alkyl alcohols, such as methyl alcohol, ethyl alcohol, ete, Other alcohol include ale, benzylic and vinylic alcohols «According to1UPAC system, the name of an alcohols derived by substituting of an alkane with the suffix o Cycle alcohols are named by using the prefixcyco {b)_Thesimplest hydroxy derivative of benzene s phenol. Itisbotha common name and anlUPAC name, The terms ortho, meta and para are often used forts substituted compounds {c)_ Simple ethers are frequently given common functional lass names. One simply list alphabetical order both groups that {are attached to the oxygen atom and add the word ether. ‘+ IMIUPAC style ethers are named as alkoxyatkanes alkaxyalkenes and alkoxyarenes ‘+ Gjctic ethers can be named by using replacement nomenclature n which we relate the cyclic ether tothe correspond ing hydrocarbon rng system and use the prefix axa to indicate that an oxygen atom replaces aC, group. + Another way of naming ethersistoname the two alkyl groups attached tothe oxygen atom in alphabetical order and add the word eter. the two alky groups are the same, we use the prefix di for example, dimethyl ther «+ Inanother system, a cyclic three-membered ether isnamed oxirane and a four-membered ether called oxetane. 4. Structur {a In alcohols, the oxygen ofthe ~OH group is attached to carbon by a sigme (ct) bond formed by the overlapping ofan sp? hybridized orbital of carbon atom wit an sp* hybridized orbital of oxygen (b)_ In phenols, the -OH group is atached 10 5p" hybridized carson of an atomatie ring. {c)_Inethers, four electron pais that is, two bond pais and two lone pals of electrons on oxygen are aranged approximately ina tevahedral arangement 5. Preparation {a} -Aleohols from (a alkenes, (b) carbonyl compounds and (c) Grignard reagents, {b}_ Phenols from (a haloarenes, b) benzenesulphonic acid) diazonium salts and (€) cumene. {o)_ Ethers by a) intermolecular dehydration of alcohols; b) Williamson synthesis (reaction of alkyl halides with sodium alkox- 6} alkoxymercuration-demercuration and (a) rer-buty| ethers by alkylation of alcohols. 6. Physical Properties (a) Bolling points: «The boiling points of alcohots increase with increasing numberof carbon stoms and decrease with increaseinthe ranch- Ing of carbon chain. They have much higher boling points than comparable ethers or hydrocarbon. Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranc! |, Ph.s 0661-2562623, 9695508812, 7546845949R. K. MALIK’S NEWTON CLASSES «Ethers have boling points that are roughly comparable with those of hydrocarbons ofthe same molecular weight. They are ‘weakly polar and ths does nat affect ther boling points. + Inphenols, the ability to form strong intermolecular hydrogen bonds causes them to have higher boiling points than hydro- carbons ofthe same molecular weight. The boling pots increase withthe increase in number of carbon atoms. () Solubitity: The solubility of alcohol and phenolsin water i due to their abilty to form hydrogen bonds with water molecules, and it decreases with increase in sizeof alkyVaryl groups. The solubility of ethers in water resembles those of alcohols of the ‘same molecular mass ands very different fom those of hydrocarbons. 7. Important Reactions ‘Alcohols are versatile compounds (they can act as both electrophiles as well as nucleophiles). (a) Alcohols and phenols = Cleavage of O-H bond ‘acidification (react with active metas such as Na, K etc, tliberate H) esterification (react with organic acids to form esters) reaction with inorganic acids acylation reaction allylation reaction teacton with Grignard reagent + Cleavage of C-0 bond ‘action with hydrogen halides reaction with phosphorus trhalides reaction with ammonia reaction with thionyl chloride CH, —CH—CH, > CH) CH CH, + H,50, ‘1-Propy hyeogen ‘no Propy alkohol sulphate () Grignard reagents (RMgX) ae allyl or ary! magnesium halides. Te C-Mg bond in Grignard reagent isa highly polar bond &s carbons electronegative relative to electroposiive magnesium. Oue to ths polar nature of C-Mg bond, Grignard reagents are ‘very versatile reagents In organic synthesis. They react with aldehydes and ketones to form adducts, which decompose with dite HCl or dilute H,S0, to give primary, secondary and tertiary alcohols, hy mo, cms, ~ ah NS nemo, Ho Soko + G4 hat > 0 ag 28, Ss c—ont + mgtonn Hoe Se + CMa eco aoe if Hs Hs adduct o-Propeahel “The overall abjective sto ind the alkyl group of Grignard reagent to carbon of the carbony! group and hyd Formaldehyde gives primary alcohol, whereas all other aldehydes give secondary alcohols and ketones ive to oxygen. 2. Write three carbonyl compounds, which may be used to prepare the following compound, BA cH,0H Solution ‘The three carbonyl compounds use to prepare the compound oh Gach GOH oH CH GH CH= CH—CHO; CH —CH—CHO; CHCHO Os Hs Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0661-2662623, 9836600012, 7546845949,8 R. K. MALIK’S NEWTON CLASSES The rectog rows ah—t-cimat—cH0 Ms chy CHO a, by on anor hrs too be-onci0 hy by Brancaccio aya rmcrein by by, 3. Whats meant by hydroboration-oxidation reaction? iustrat it with an example. (weert) Solution “The addition of borane followed by oxidation Is known asthe hydroboration-oxidation reaction. Propan--ols produced by the hnydreboration-axidation reaction of propene. In this reaction, propene rects with ciborane (BH) to form trialy| borane as an ad tion product. This addition producti oxidized to alcohol by hydrogen peroxide inthe presence of aqueous sodium hydroxide. Hy — CH=CH, + BH) > Oy — CH) cH, CHB Propane Obrane 1 4 oon 0 [novo sCHy—CHy—CH)— OH + B10H)s 4 Youare given benzene, cone. H;50, nd NaOH, Write the equations forthe preparation of phenol using these reagents, (CERT) Solution SoH on '5. Give the equations of reactions forthe preparation of phenol from cumene, (wcert) Solution ‘Oxidation of cumene (2-phenylpropane or iso-propyl benzene) atthe benzylic position gives hydroperoside, which upon subsequent hydrolysis wth aqueous acid cleaves to give phenol and acetone Co ” New Hy —C—O0H On oO on oO se Corea ones comettqoowniie art Namen 4 We chemical ection fr the preparation of phen rom chlorobenzene. wwcerr) Solution ‘Base hydrolysis of chlorobenzene (Dow's process): The reaction occurs via the elimination-addltion mechanism via sodium phe nonide Intermediate, which on further heating with HCl produces phenol. This isa useful industrial method for synthesis of pheno bonded Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 9 7. ite the mechanism of hydration of ethene to yield ethanol. (ncerT) Solution ‘The mechanism of hydration of ethene to form ethanol involves three steps: ‘Step 1: Protonation of ethene to form carbocation by electrophilic attack of HjO* ° Za Ora W 4 ‘Step 2: Nueleophilcatack of water molecule on carbocation AP Rent LS. MW Sejiieriomieamiominc HHH 4 OH ret one (a) 1-Phenylethanol from suitable alkene. (b)Cyclohexyimethanol using an alkyl halide by an $2 reaction. (¢) Pentan-1-ol using a sultable aly! halide. Solution (2) Byacid-catalyzed hydration of phenylethene,1-phenylethanol can be synthesized. oma) xo oO +hoealY ob tonnes teeth (0) When chloromethylcyclohexane is treated with sodium hydroxide, cyclohexylmethanols obtained, cHact cHioH + NaOH —> + Nal CChorometnvlyconenane ———_Cylehenyethano! {c)_ When I-chloropentane is treated with NaOH, pentan-1-lis produced, (CHJCH,CH,CH,CH,C+ NAOH > CH,CH,CH,CH,CH,OH + NaCl "Ghlorpentane Penta ‘9, Show how would you synthesize the following alcohols from appropriate alkenes? (wcert) a ce ) wath fe St a ok 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.; 0651-2662623, 9836608812, 754684694910 R. K. MALIK’S NEWTON CLASSES Solution ‘The given alcohols canbe synthesized by applying Markovnikov’s ule of acid-catalyzed hydration of appropriate alkenes. @ Hs +H0 oN ‘As both alkenes give the desired product, so any alkene can be used, o on « 1 CCH C—O — Orc + H0 + CEE — CHCA, Hy Hy “Medheptan 4 wo He Achy Hy +420 > Cy FH CH oH nwa isn mn oy Gtmcd— 4 — 04 +140 vate O04 + OOOH, on maria 3 ba an So.we wit pent -eelnteaet pentane oan woh Nata — 4 (OY Pras —ar Ton saben rahe 10. Howarth ftoung cnn carieut? ween (Spee sPopan a 1b), enal coi Bez aol (2) Eigmagnetom hte Propane! a) Met mages brani» 2Methipopan 2 Setaton (et Mpopeelsslawedta ach waterinthe presence anata then propane, Oy Cm + HO Oem oa be ropa (theyre tet wth WOH alowed by acct then bea akhls produce ove uo Chon OO =O vee vena Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII u {@)_ When ethyl magnesium chlorides treated with formaldehyde, an adduct is produced which gives propan--ol on hydrolysis. ‘OMact on Lo wm | GHMgcl + HCHO ——> HCH Sy Hc + gion fh Formaldende magnesium Gs Gracy hone Propan tol (a). When methyl magnesium bromide is treated with propanone, an adducts produced which gives 2-methylpropan-2 oon hydro ysis Hy CH (CHy);C=0 + CH) —MoBr —> [CH —C—6 figBrl > MilOHIBr + CHy—C—OH ropsnone Methyl magnesium by ais Aeduct 2.Methyprapnn 2 ol Textbook Exercises 11. Show how you would utilize the hydroboration-oxiation procedure to prepare each ofthe following alcohols (a) 3,3-dimethy!-1 ‘butanol, (0) T-hexano,c)2-phenylethanol and (4) trans-2-methylcyclopentanol. rr) Hy Hy CH) — CHB Oy 0.080. ES ah Goh oH ci) 1b) crycH,CHCH,0H—c Us HCH CHYCHYCHLOH © vena eon he oa or me ruc C7 Cy _wwine 4 CH amore Kats + enantiomer manor (_ YOM ‘ 2. Show how you would use oxymercuration-demercuraton to prepare each of the following alcohols from the appropriate alkene: (a) 2-pentanol (b)1- ccKoK gt, bu by ” Dpeee e D-pe by © os on oncimdaion TES avencanc on 8 Deo, Samoa 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.; 0651-2662623, 9836608812, 75468469492 R. K. MALIK’S NEWTON CLASSES 3. Starting with isobutane, show how each ofthe following could be synthesize) tet Butyl bromide, (b)2-methylpropene, cob ‘bromide, (d isobuty/iodide()isobuty alcoho! (two ways} tert-butyl bromide and (a) sabutyl methyl ether, Solution oO oy as oo i % on EHO SP OnE, ie Ser Oh (CHC Ch, Ss CHCHCH Br & & my hte) cH oF oO Hs CAH Ecc! OLEH ES CKEHCHOH aye, — "en or sd Hy cy rhea, Hs cHscHCH oH os cH Hyco 5 cHscHH.OCH, 4. Give the structural forul of n alkene o alkenes fom which each akoho or glycol canbe prepared) Butar2- (8) methyl metiy pentan 2-0) ylopentanol nd) 1.2 popanedil, Solution (a) But ener but 2-ene can be prepared fom butan 2 on On (Hy CH CHC, > CHyCH—CH,CHy "> CH CHCH:CH; > CHyCH=CH—CHy + Cy mn! Potonte ste Peabo fawe ‘Mar ‘jer nen More highly substituted product will be the major product according the Saytzeff rule oe CHyCHaCH— Croc > cryCHencH—cHyCHyEy + CHACHYEH=CH—-CH—CH.CH, Moan 34 Werden ectene ‘ion ‘nan on at tnnte, 0 G—chachich + y= GOH) —OH Hs Hy Hy BMY 2 penton! 2 Met pent ene 3 Meth pont 2 ene ‘men ‘oj Oh, O+0=0-0, Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 13 ooo eh 0h 6h Gly —Ghy hme on OH OF Ot Hy '5. Write the equation forthe preparation of alcohols by reacting each of the following slkenes with sulphur aeld and water: (a) Propene, (b)1-butene and (c}2-pentene. Solution (a) Propene: This is typical of the reaction with unsymmetrical alkenes. An unsymmetial alkene has diffrent groups at either end ‘ofthe carbon-carbon double bond. sulphuric acid adds to an unsymmetrical alkene like propene, there are two possible ways In could add. You could end up with one ofthe two products depending on which carbon atom the hydrogen attaches itself to, However, in practice theres only one major product. GHyCH= CH +1250, —> CHyCHCH, “> iy -H— Cy 0504 on Propan-2-01 ‘Thisis inline with Markovrikovs rule which states that When a compound HX is added toan unsymmetrical alkene, the hydrogen becomes amtached tthe carbon withthe most hydrogens ‘attached tot already. In this case, the hydrogen becomes attached to the CH, group because this group has more hydrogens than the CH group, Notice that only the hydrogens directly attached tothe carbon atom at either end ofthe double bond count The onesin the Il, ‘group are totally irelevant. oy) on no al ‘CH CH, CH, ——> CHC CH uno cy) oH I HyC CH=CH — CH, CH > CHyCH:CH— CH) — CH Penean 3-3 Previous Yeas’ CBSE Questions +1. Name the reagents which are used in the following conversion: Butan-2-one to butan-2-0, Solution (DELHI 2008) ‘The reagent can be Ni, or IA, or NaBH, HOW I wm, tl We ne =e oy yes ee Hw 2. How can the following conversions be carted out: (a) Propene to propan-2-ol and (b) anisole to phenol? (Write the reaction only.) (cBse 2007) Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0661-2662623, 9836600012, 7546845949,W R. K. MALIK’S NEWTON CLASSES ‘Additional Questions 1. Wite a Grignard’s reagent to prepare the following alcohols: (a) -Phenyloutan-2-0,() 3-methypentan 3-0, (€) 2-methylpentan- 2.0 (@)2-phenyipropan-2-ol and ()3-methyl2-phenylbutan-1+ Solution a 9 cue on ey —€ 0 + mcr —s cht 29 cry foo by by ® 9 omect on ero CH, + cya] —> chery —t—creny > crema cre by by ” @ ogc on I I OE chet + chad —+ 0, —F CCH Sty yates by uy ™ @ ove " cyt Sone uma rout op oon bs by 9 uses ou nom | OS chy —cH— chy —C—H 1 hy Gy H+ aM) —+ Gy —EH cy —F—H Hs a, Cos cH, 2. How will you prepare phenol from benzene? Solution ‘Benzene sulphonated with oleum (H,S,0,) which forms benzene sulphonic acid. tis fused with NaQH at 623 K when sodium phe ‘oxide is formed, Acidification of sodium phenoxide gives phenol 50,4 $0,Na Ne oH enzene ——ensene Sod Sodium = Phenol sulphone benzene phenoude fad sulphonate 11.5 PHYSICAL PROPERTIES OF ALCOHOLS AND PHENOLS Conceptual Questions +1. Why isthe boiling point of glycol higher than ethanol? Solution ‘Molecules ofethanol form intermolecular hydrogen bonds using the hydroxyl (~OH) group. Incase of ethylene glyco. the number oF hydroxyl groups istwo and so the number of hydrogen bonds formed is more The boling point of glycols higher than that of eth ‘nol due to stronger hydrogen bonding. 2. Why do alcohols have higher boiling points than haloalkanes of the same molecular mass? Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 15 Solution “The hydroxy group creates polarity and forms hydrogen bonds with adjacent molecules and water, which lesds to association of molecules and stronger van det Waal forces of interaction, that, alcohols have higher melting and boling points than their core sponding alkanes. 5. Wny ae boiling points of phenols higher than the baling points of hydrocarbons ofthe same molecular mass? Solution ‘The C-OH bonds are more polarized than the C-X bonds in alky! halides. Therefore, dipole-dipole a ‘weaker than the dipole-dipole attractions (rising due to hydrogen bonds) in akohos. ‘4. Explain why propanol has higher bolling point than that ofthe hydrocarbon butane? (NCERT} Solution Propancl undergoes intermolecular hydrogen bonding because of the presence of -OH group, which butane does not have. Therefore ‘extra energy sequited to break these hydrogen bonds Fortis reason, propancl has higher bolting point than the hydrocarbon butane oh Ft GH Gh GH, 5, Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses. Explain thisfact. _(NCERT) Solution ‘Acohols form hydrogen bonds with water due to the presence of -OH group; however, hydrocarbons cannot form hydrogen bonds ‘ath water. As result alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses Ho - #9 --------0 - 1 1 1 R 4 R 9 - | 4 Textbook Exercises 1). Ethanol (molecular weight = 46.0 g mot) has a boiling point of 78.1 °C and propane {molecular weight = 44.09 mol“) hasa baling point of-42°C. Account fr the diferencein ther baling points Solution ‘The higher bolting point of ethanol is due tohydrogen bonds. Ethanol molecules can form hydrogen bonds with each other. Propane molecules ate held together only by weaker London forces. 2. Ethanol (molecular weight = 460 g mol”) is miscible in water, whereas propane (molecuh ‘Account forthe difference in water solubility. Solution Propane (CH;CH,CH,) has only carbon and hydrogen atoms. Between carbon and hydrogen atoms, no significant electronegativity difference exists, s0 propane has weak van der Waals attraction. Ethanol has OH bonds which form strong dipole-dipole attraction forces known a hydrogen bonds similar to water, Therefore, ethanol dissolves in water. weight 440 = g mol" is insoluble. 3. 1-Propanol i miscible in water and T-butanol has a water solubility of 80 g/100 mi. Account fr ths cferencein water solubility. Solution “The hydroxy! group of both the compounds can form hydrogen bond with water, However, n-butanol the alkyl chain is longer and the molecule has lowe solubility in water due to hydrophobic nature ofthe alkyl chain. “4. Propanoic acid and methyl acetate are constitutional isomers, and both ar liquids at room temperature, Oneof these compoundshas _aboilng point of 141°C; the other has a boling point of 57°. Which compound has wich boing point? 9 9 1 I CHCH,COHCHCOCHS Propanolc acid Methyl acetate Solution Propanoic acd has higher boling point of 141 °C, whereas methyl acetate has 57°C ass boiling point. This is because acid has tron- ‘ger hydrogen bonding as compared to ester. Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0661-2662623, 9836600012, 7546845949,16 R. K. MALIK’S NEWTON CLASSES 5. Arrange the compounds in each set in order of decreasing solubility in water (a) Ethanol butane, diethylether (6) Hexan-1-ol; Hexan-1,2-diolshexane Solution {a} Thedecreasing orders ethanol > diethylether > butane, Ethanol is highly soluble in water due to Is ablity to form very trong intermolecular hydrogen bonding, Solubility of ether in water is due to the formation of hydrogen bond between water and ether molecules. BH gr" 8 cts SW NH (8) The order is Hexan-1,2-diol > Hexan-1-ol > hexane. In 1,2-hexanedol there are two OM groups so there will be more intr ‘molecular hydragen bonding withthe H,O molecules. Hence, it wil be highly soluble in water. This wil be followed by hexanol mihone-Oh 6. romeucprfepoud ech oe ttt ner sce as We Gndelon BD ne Gy fo Geyer) CLCLCASHErCHOCHON ako,” onto oo I 1 (CHyCH,CHCHSCH, or CHsCH;CCH;CHy Solution (a) CH,OH » 4 (Nac (8) CHCH,CH,OH(e) on CHACCHs CHACH,CHCH,CH, ‘Additional Questions 1. Anhydrous CaCl snot recommended as a drying agent fr alcohols and amines. Explain why? ‘Solution ‘Alcohols and amines combine wth anhydrous CaCl to form complex. CaCl, + 3CHyCH,OH —> CaCl, 3CHsCH,0H 11.6 CHEMICAL REACTIONS OF ALCOHOLS AND PHENOLS Conceptual Questions 11. Arrange the fllowing compounds in the decreasing order of the property inccated against exch. Give reasons for your answer. (a) CHjCH,OH, CF,CH,OH, CClCH,OH ~ Acid strength, {b) 2 methyl 2 propanol, butan-1-ol and butan-2-l - Reactivity towards sodium. {c)_ butan'2-0| butan-I-o, 2-methyi-2‘propanol - Reactivity towards Lucas reagent. Solution {0} CFyCH,OH > CCI,CH,OH > CH,CH,OH ~ Acid strength Halogen exerts a effect, aso result there is decease inthe electron density in the O-H bond, Thus there Is weakening of (-Hbond and H* releases easly. is more electronegative than Cls0 its effects higher. Therefore, F,CH,OH Isa stronger acid than CCIjCH,OH while CHjCH,OH isa weak acid ) on Hs (CHsCH,CHsCHOH > CH,CH3CH—CH, > CHy—C— Cy ‘uta ‘tan 2 [ (aco alconod on beanie 2 Math? propane! Gaol leas reactive) ROH + Na —> RONa + H “The # effect ofthe ally! groups prevents the ionization of the O-H bond. Therefor, the eactvty of alcohols towards sodium decreases asthe acidic characte of alcohol decreases in the order 1°> 2°> 3°. Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 7 10) The protonation of alcohol followed by elimination of water leads tothe formation of carbonium fon. The stability of carboca tions is 3° > 2° > 1°. Therefore the reactivity of alcohols towards Lucas reagent follows the sequence 3°> 2° > 1" and the order |s2-methyl2-propanal > butan-2-0l> butar-I-ol Hs Hs, Fa HAS pce by é 2 ag ropa mene ton toa o ‘ cota + Her nde + HO faa Tutte ‘esta CAyCHLCHLCHLOH + HC) “== Wo reaction at room temperate 2. Why are phenols less nucleophilic than alcohols? Solution O-G-B-8-8 ‘The lone pairs of electrons onthe oxygen atom in phenol are delocalized over the benzene ring due to resonance and so they are not avaiable for protonation. The oxygen atom hasa positive charge. ROH + HY —> ROH, Nuceophle —_rotonated alcohol In alcohols the lone par of electrons on the O atom ae localized due to the absence of resonance. and hence are easly avaliable for protonation 3. Alcohols react with halogen acids or phosphorus halide to form haloalkanes but phenols donot form halobenzenes. Explain. Solution R—OH + HK > RK + H,0 ROH + PC, —= ACI + HyPO3 ROH + PCls —> RCI + POC, + HC Inalcohols, the C-0 bond in alcohols single bond and hence can be easly cleared by X"lons Inthe presence of halogen acids (HX) ‘or phosphorus halides o form haloalkenes.. O-&-$-8--5 tm phenols, the C-0 bond has some double bond character due to resonance, and hence cannot be easly cleared by X"ions in the presence of halogen acids or phosphorus halides to form halobenzenes, 4 Explain why phenols donot undergo substitution of the ~OH group lke alcohols. Bubb BS In phenols, the C-O bond has some double bond character due to resonance, and hence cannot be easily broken. Thus they usually ‘donot undergo reactions involving the ceavage of -OH bond, instead undergo a number of electrophilic substitution reactions ofthe Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0661-2662623, 9836600012, 7546845949,Is R. K. MALIK’S NEWTON CLASSES benzene ring. Thus, alcohols ae versatile compounds because they act both as nucleophiles as well as electrophiles, whereas phe ols usually act as nucleophiles only. 5. Of the two hydroxy organic compounds ROH and OH, the fst one is basic and the other Is acidic In behavior. How sR eifferent tome Setation Ae strenght sores flows the oder i I ORO ROH REO h oe Thebes eng of toes low the ve nde, an tf R60» RHO > RENO Tertary Secondary Primary ‘The electron releasing inductive effect would be maximum in tertlary alcohols, and minimum in primary alcohols. Thus, primary alcohols are the strongest acids and tertiary the weakest. 66. Why issulphuric acid not used during the reaction of alcohols with Klin the conversion of an alcohol tothe alkyl iodide? Solution ROH + Ki +HyPO,—> RI + KH2PO, + H20 H,50, isan oxidizing agent, and it oxidizes Hl produced during the reaction tol, thus preventing the reaction berween an alcohol ‘and Hl to form an allyl iodide, 2K\ + HS, —> 2KHSO, + 2H 2HI + H,S0, —>H,0 +1, + $0 To overcome this dificulty, 2 non-exiizing acid such as H,PO, is used instead of H,S0, 7. Whats the order of reactivity of HC, HBr and HI with alcohols? Solution Alcohols resct with halogen acids to form haloslkanes and water. The order of reactivity ofthe halogen acidsis HI> HBr > HCL Tiss ‘due tothe reason that Ion sa better nucleophile than BY lon which in tun, is better than CT” fon. The strength of helogen aids Hi>HBr > HCL 8, Whats the order of dehydration of primary, secondary and tertiary alcohols? Solution ‘The sepsinvolvedinthe dehydration of alcohol are) protonation, (mination of water o form carbonium ion and os of proton fom, adjacent carbon atom to form alkene. Since tertiary carbon stom s more table (3°>2* > 1"), the dehydration of alcohol follows the order Tertiary alcohol > Secondary alcohol» Primary alcohol ‘The dehydration of 2° and 3° alcohols always occursin the accordance with Saytzef's rule "9. Name any two reagents used for bringing about the oxidation of alcohols to carboxylic acids. Solution {a} Neutral acidic or alkaline KMnO, (0) Acidified KCr,0, RCH,OH +> RcHO > RCOoH TV Alconat Aldehyde Carbonic 10, While separating misture of ortho and para nitrophenols by steam distilation,narme the isomer which will be steam volatle. Give teasons. (NCERT) Solution Intramolecular hydrogen bonding is present in onitrophenol thats why itis steam volatile and intermolecular hydrogen bonding is present in p-nitrophenol which causes the association of molecules. Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 19 ae Ny” wpe 0 “ No---Ho- N. So ote pe 1. he ect tae rie tl Cp tts tea cee san Theme of inept Ha esreeeeerntosnsirer ae x ns Cm Oo sty ee (Pench tenho wate ° on However ethanol doesnot react with sodium hydroxide. The acidity of phenols more than that of ethanol because after losing 2 proton the phenoxide lon undergoes resonance and ges stabilized, whereas ethoxie fon does not +12, Explain why is onitrophenol more acidic than o-methoxyphenal? (weerr) Solution on oH Noy oc o-Nirephenal ——_@ Methoxyphena! ‘The nitro group ian electron withdrawing group. At ortho postion, this group decreases the electron density inthe O-H bond due towhich proton canbe lst easly. The structure thus formed is stabilzed by resonance; hence o-ntrophenol isa stronger acid. The ‘methoxy 0p i an electron releasing group, which increases the electron density in the O-H bond and hence the proton cannot ’be given out easly. That is why o-ntrophenol is more acidic than @-methoxypheno) 113 Explain how the -OH group attached toa carbon of benzene ring activates the ring towards electrophilic substhution? —(NCERT) Solution ‘The ~OH group isan electron-donating group. Thus, it increases the electron density in the benzene ring as shown in the given resonance structure of phenol. Thisis the reason why benzene ring goes for electrophilic substitution. +0—H +0—-H 6-H OH 9-0 G Y 14 Give the equations of the fllowing reactions: (NCERT) |e}, Oxidation of propan-1-l with alkaline KMnO, solution (b) Bromine in CS, with phenol [d)_DiluteHINO, with phenol (4) Tieating phenol with chloroform in presence of aqueous NAO Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0661-2662623, 9836600012, 7546845949,20 R. K. MALIK'S NEWTON CLASSES. Solution (8) Oxidation of propan-1-l with alkaline KMnO, solution cHycH,cH,oH =" cc#,cO0H Propan 3 Propanoi acd Gx =O: &y Siena whee ‘majo ‘Miner "6 Prenat (2) Dilute NHO, with phenol onroprens p Mtropnenot a) Treating phenol with chloroform in presence of aqueous NaOH d= Sq =o7-o" ree Sacyialdehyte +15. Explain the following with an example: (a) Kolbes reaction, (b) Relmer-Tlemann reaction, (c Willamson’s ether synthesis and (€) unsymmetrical ether (NCERT) Solution {8}, Kolbe's reaction: When phenolis treated with NaOH, sodium phenonide is produced. This when treated with CO, followed by ‘cidfication, undergoes electrophilic substitution to give salicylic acid asthe main product, b=620° otydronybeneok aid (soley aod) (6) Reimer-Tiemann reaction: When phenol is treated with chloroform in an alkaline medium (NaOH, an aldehyde group is lnttoduced a ortho position ina benzene rng, Ths on hydrelyss in the presence of alkali produces salicyaldenyde. on ‘ON b==|5- Prenat meer On =O": -o" Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 21 (€) Willamson’s ether reaction: is 2 method to produce symmetrical and unsymmetrical ethers by allowing alkyl halides to react with sodium alkoxides. Its an Sy2 reaction and works best with prima alkyl hades. Incase of secondary and tertiary halides, emination competes over substitution RX + R—GNa——> R—G—R+ NaK, Atytnaide Sedum aowise Fer Hs co Hy CHG fa + CH — Br ——> CH) —B—CH— CH + Nadir (4) Unsymmetrical ether: i is the ether which has diferent groups attached to the to sides af the oxygen atom (eg, ethyl methyl ether. The differences in the numberof carbon atoms that would be different onthe two sides ofthe ether. 116. Name the reagents used in the following reactions: (NcERT) {a} Oxidation ofa primary alcoho! to carboxylic acid (8), Oxidation ofa primary alcohol to aldenyde {¢)_Bromination of phenol to 24,6-tibromophenol {@)_ Benzyl alcohol to benzoic acid {e)_ Dehydration of propan-2-0l to propene Solution 0) Acidified potassium permanganate (b)Pysidinium chlorochromate (PCC) e}_ Bromine water (q) Aciified potassium permanganate _(e} 858% phosphoric acid (0) NaBH, or Lily 117, When 3-methylbutan-2-ls treated with Hr, the following reaction takes place: ncert) ¥ Hs —CH—CH—cHy > CH, —C— CH, — Cy Hy OH Hy ‘Give amechaniam for this teaton. soltion ‘The mechan ofthe given reaction involves the following steps: Step 1: Protonation yoy Oh OH, Gy On Oty OH anon 201 Step 2: Formation of secondary carbocation by the eimination of water molecule Ce 1c I by “One oO 1 cabocaton Step 3 Rearangementby the hyride-on shit & Oth AE oy FOO bay bi Lestabe cubation Stop 4: Nuelephic tack * —~ a by by 2 feome2ethy Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0661-2662623, 9836600012, 7546845949,2 R. K. MALIK’S NEWTON CLASSES Textbook Exercises 1. Give the structures and acceptable names for the compounds that would be formed when 1-butanol is treated with each ofthe following reagents: (a) sodium hydride; (6) sodium hydride, fllowed by 1-bromopropane:(€) phosphorus chloride; () thionyl chloride and e) refluxing concentrated HBr. Solution (2) CHJCH{CH;CHZONa Sostur-utonte (b}_CHyCH,CH,CH,OCH,CH,CHy | Proposyoutane (2) CHCHACH CHC! —Y-chiovoburane (A) sameas(e) (6) CHyCHCHACH,Br _|-tromobuiane 2. Complete the folowing reactions: (0) Phenol + Br ——> (a) Phenol + Br," > b)_ Phenol + HyS0g(conc) > 0) peresol + Br) ——> (6) Phenol + H,S0,{conc) > Solution (on (oH oH fon on 50 cy er aon 504K, S03 jon onan, OW on Br a Be ar br Gs 3. Without consuiting tables, elect the stonger acid from each ofthe following pais: {a} 4-Methypheno| and 4‘fuorophenol {b) 4Methylphenoland 4-nitrophenol [e)_4-Nitrophenol and 3-nitropheno! (d) 4 Methyiphenol and benzy| alcohol (e)_4-Fluorophenol and 4-bromophenol Solution (a) 4-Fluorophenol because a fluorine substituent san electron-withdrawing group while 2 methyl group isan electvon-eleasing ‘group, (b),4-Nitrophenol because 2 nitro group is more electron withdrawing than a methyl group. [c)_4Nitrophenol because the nitro group can exert an electron withdrawing eect through resonance effect. @ NS -o~ So In S-nitrophenol, thie resonance effects not possible. (2), 44kethyiphenol because tis a phenol, nat an alcoho {e}_ 4 Fluorophenol because fluorine is more electronegative than bromine. 44 Draw each molecule and the major organic product expected when each is reacted with H and heat: a) 2.-dimethyl-2-butanok (6) 23-cimethy!-3-hexanol and (c)2-methyleyclopentanol, Solution @ on o-oo) = oh T Hs CH CHa CH mao Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 23 o on Oy —EH—F Ah Gt “SBF FG OOH Oh Oh O44 Major 20h) — Gh F OOH Gh + HFC Gh Ot G4 inn ‘Mine © OH Hoty oy ot, “ad (wine jn 5. Draw the major producto each reaction. ® O% oo ed = cHCCHCH, > Oy OH a OH (a) oH cnycrycrcrscrs > F Solution ao oo chart —cr yc ccs Oy (0 Oh —cH= Hcy (Ob 6. Wite equations forthe reaction of 7-butanol a primary alcohol, with these reagents: (a) Na meta: (b) HBr, heat ()KCr,0>, H,S04, heat (d) SOCl, and (e) pyridinium chlorochromate (PCC). Solution a) CHCH,CH,CH,OH + Na > CH,CH,CH,CH,ONa +H, (8) AKCHLCHLOHOH + Hor = aLCHLCH CHB + 10 (6) HCH, CH,CHOH + K140) A> cHyCH,CH;COOH Serine (a) CAyCHLCHCH,0H + Soc, —> cHCH:CH,CH,CL+ $0, + Hal (eo) CHCH,CH,CH,OH + PCC —> CH,CH,CH,CHO ‘utara 7. Name the aleohol used to make the following esters: ane ® 8 om Me-0-oh crf—o—o4tn—or, selon er 8) Ogio —om by 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.; 0651-2662623, 9836608812, 7546846949Ey R. K. MALIK’S NEWTON CLASSES 8. Complete the following equations, and name the principal organic product(s) formed in each case: ai wes, (a) 2cHycroH () GHyCHcHoH te rycHrorncHycr, (8 cone —ocHyeH + Ho > seution (3) CH,CHLOH + H,504 > cHyCH O50, + HO oer "hare CH,CHOSO,H + CHyCH,OH > cH 0CHj0H, + H,504 Dheeyohane Over eacon 2CHjCHOH SMS cHjCHOCHOHy +0 ee cyanea SHS cxermane0 Propane Dehydration of alcohol to give alkene (OH 00, ol HCH CH,CHy “SS > cHyC—CH,H Patan 2-one @ } CHjcH.C —OcH,cH, + H,0 > cH,CH,COOH + CHCH,OH 9, Arrange these three compounds in the order of increasing acy: Ome OF WYO 3-Ethy/-I-hexanol isa primary alcohol. Wite the formulas of two diferent organic compounds that can be obtained by oxidizing this alcohol (cH,0H Sotuton rics °c oN, tho —b1—cyocn Ps He, b1—ca1 04, > Hoc, —di-ccn.ary a +} €thylhexanone 2-Ethythexanone acid senna 11. Wie the formula and the name of the chief product when the folowing alcohols are dehydrated to alkenes: opbos Co on Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 25 Solution (Gy Hs Hy (Hy —CH—CH— Cy > CH=CH CH=CH, + Hy CH — CH, a ‘Miron ‘Mayor “More highly substituted would be major product according to Saytzef' ule. 1) Ob—Gh—-CHOHOH, > yoo Hy LOH MCHC tomo totter on ‘Miso syn) 12, Inwhat important ways do phenols difer from alcohols? Solution {a} The C-0 bond in phenols has some double bond character due to resonance. Hence t cannot be easily cleaved by a nucleo- Phin contrast the C-O bond in alcohols isa pure single bond, and hence can be easily cleaved by a nucleophile. (b) Phenols are stronger acids than alcohols and react with aqueous alkall to form phenaxides or phenates, whereas alcohol does not react. ROH + NaOH —> No reaction Previous Years’ CBSE Questions 11. Name the reagents which are used in the following conversions: (a) primary alcohol to aldehyde and () phenol to 14-trlbromophe- ol (OELHI 2008), Solution (a) Pytidinium chiorochromate (PCO) a complex of chromium trioxide with pyridine and HCl ‘CHy—CH=CH—CH,OH “> CH; —CH=CH—-CHO (b) Aqueous bromine or bromine water 2A6:Tibremaphenal 2. Complete the folowing reaction equations: © Oo ser 1 or ms (DELHI 2009) on’ (a) n+ soc, S +50, +HeI Te Ho’ 606 , 6 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.; 0651-2662623, 9836608812, 754684694926 R. K. MALIK’S NEWTON CLASSES Additional Questions 1. Givea method of converting benzene to phenol ianitrobenzene. Solution 2. Predict which is stronger acid in each of the following pits: ) Phenol or eyclohexanot (0) Phenolorp-itrophenol __{c}_p-Nitrophenol or pchlorophenol () 24.8Ttinitrophenol or24-dinitrophenol —_(e) (CH,),CHOH or (CF,},CHOH _(f)_ Phenol or benzyl alcohol Solution (a) Phenol is more acidic than cyclohexanol because the electrons ofthe O-H bond are drawn into the benzene ring due to reso: ance. This factates the release of H* ions to form phenoxide ion, which i further stabilized by resonance. (b} NO, group hae both -R effect and ~1 effect but the -R effect predominates over ~1 effec. The electron withdrawing group withdraws electron, disperses the negative charge, stabllzes the phenxide fon with respect to phenol. and thus increases the acidic strength. So, pritrophenol is more acidic than phenol (@) Both ate electron withdrawing groups but p-nitrophenol is the stronger acid. The -NO, group has both -R effect and effect ‘but the -R effect predominates over the | effect. An -NO, group at ortho and para postion withdraws electrons of te O-H ‘bond towards itby stronger effect. Halogen (-Cl has both +R effect and effect but the - effect predominates over the #8 effet So, Cl withdraws electrons, dlspenses the negative charge, stabilizes the phenoxide ion with respect to phenol (2) Greater the number of electron withdrawing groups at ortho and para positions, mote acidic s the phenol. So, 2,4 6-trntrop hhenol is more acidic than 2, 3-dinitrephenol (e}_ Fteanelectron withdrawing group and stabilzs the alkoxide lon by dispersing the negative charge relative to alcohol Thus, the {acidic strength increases due tol effet ofthe F, the electron density inthe O-H bond decreases due to this electron deficiency ‘Thus the O-H bond gets weaker; and thus facitates the release of @ proton. Hence, (CF,),CHOH is the stronger acid 0) Phenolis stronger acid than benzyl alcohol. The ~OH group attached te benzene ring is much more acidic than the ~OH group ‘attached to an alkyl group. Phenols are stronger acids because the phenoxide ion left after the release ofa proton is stabilized by resonance, bu the alkoxide on isnot. |. Whatis the main product formed when phenol is subjected to Kelbe's reaction? Solution remain posecroma nla b= = -o- = cae samp Baca hatha when heelshyogente? setiion on v0 Coon iS) ret can! ‘5. Finish the following acid-base reaction, and preditifit will proceed inthe forward direction: HN, {HOH + cH,COONa ——> cH, Nc On + CHyCOON: SH ct ona + 043C00H on icOONa <> 6, ta + Phy Pes Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 27 ‘The reaction wil not proceed in the forward direction because (CH), CHO™ ion isa stronger base than CH,COO~ 6. Supply the missing reagents Aand 8. ors a OE = 08 +o som [A= p-CHC,H,$0,, base; B= NaCN in ethanol. 7. Draw the structure ofthe ionic species obtained when the following substance is treated with NaOH Nip OH Solution ‘The structure ofthe lon specesis Nay Oat Ho. 11.7 DISTINCTION BETWEEN 1°, 2°, 3° ALCOHOLS, IODOFORM TEST Conceptual Questions 1. Gwe a chemical test to distinguish between the following pairs of compounds: (a) OW on (0 cig cH,0H on and and (CBSE Sample Paper 2007) Solution a) Phenol gives violet coloration with FeCl solution but cyclohexanol does not. The vilet complex formed Is (CH,O} Fel™. 6) opropy| alcohol glves postive lodoform test but benzyl alcohol doesnot respond to iodoform test. OYE + MOH + h—> ye + HO + Ha on (CHj—C—CH + 3NaOl —> Cli + CH,COONa J odotorm \vehow pot) 2. How will you distinguish between the folowing pairs by chemical reactions? (a) CHO and CyH,CH,OH —(b). Phenol and benzoic acid Solution (2). Phenol gives violet color complex Fe(OCH,);)* with neutral FeCl, solution, whereas benzyl alcohol does not (b}_ Phenol reacts with neutral FeCl to form an ron-phenol complex ving vilet coloration. SCHSOH + FeCl, —> (CHO), Fe + 3HCI Phen Wolet But benzoic acid reacts with neutral Fel to give a buf-colored precipitate of fertic benzoate. AGSHGOH + FeCl ——* (CQH,COO), Fe + 3HCI enaok aid Fee benoate (aut coored pot) Benzoic acd produces effervescence when treated with an aqueous solution of Na,CO or NaHCO, while phenol does not Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9636608812, 754684694928 R. K. MALIK’S NEWTON CLASSES '3. How does Lucas reagent help in the distinction of primary, secondary and tertiary alcohols? Discuss the reactions involved. Solution ‘was test Alcohols reac with concentrated hydrochloric acid in presence of anhydrous zinc chloride to form alky| halides on nas nao Thetatesof econ wth ics eget con C+ 2A anus flow the ollowing ode: Tertiary lho > Secondary kool» mary aloha ‘Lucas test Is based on this order because formation of intermediate carbocation takes place. An unknown alcohol (monohydtic s Imbxed with cone. HCl and Zn, The following observations are made when the reaction i caried out t room temperature: )feloudiness appears immediatly, the alcohols tertiary {) fcloudiness appears within 5=10 min, the alcohols secondary {)_ Ifthe solution remains clear, that is, no cloudinesss formed, the alcohols primary Textbook Exercises 1). Describe a simple chemical test that could be used to lstinguish between members of each ofthe following pairs of compounds: (a) 4:Chlorophenol and 4-chloro-1-methyibenzene (0) 4-Methylpheno! and 4-methylbenzole acid {c)_ Phenyl vinyl ether and ethy phenyl ether (a) 4-Methyiphenol and 246-tinitropheno} () Ethyl phenyletherand 4-ethyiphenot Solutions {a} 4Chlorophenol wil dissolve in aqueous NaOH; 4.chloro-I-methylbenzene wil not (b) 4 Methylbenzoic acd wl solve in aqueous NaHCO, 4-methylphenol will not. {e)_ Phenyl vinyl ether wil react with bromine in carbon tetrachloride by altion (thus decolorizing the solution ethyl phenyl ether vwilnot. (a) 246-Trnitrophenol, because is 50 exceptionally acidic (pK, = 0:38), i will dissolve in aqueous NaHCO,, while 4-methyiphenol (pK, = 10.17) wil not {e},4Ethyipheno will dissolve in aqueous NaOH; ethyl phenyl ether will not. 2. Give a simple chemical test that will distinguish between the compounds in each ofthe following pairs: () Ethanol and dimethy ‘ether (b)-pentanol and T-pentene and () p-nethylphenol and methoxybenzene. Solution |e} Ethanol gives todoform test while dimethyl ether doesnot. (b).PPentene decolorizes bromine water and I-pentanol reacts with sodium, |e). PMethylphenol forms complex with FeCl solution. ‘Additional Questions 1, How willyou know whethera given OH group alcoholic or phenolic in nature? teristic colors with neutral FeCl, solution, while aliphatic alcohol does not. The olor may vary from violet to blue, ‘green or even red depending upon the nature of the phenol 2. Name the only primary alcohol that gives odoform test Solution Ethanolis the only primary alcohol that gives iadoform test. crycH,0n 22> cen > cyco 2+ cy + Hc00 23, Name one reagent that i used forthe distinction of primary secondary and tertiary alcohols. Solution Lucas reagents used to distinguish primary, secondary and tertiary alcohols, Lucas reagents equimolar mixture cone. HCl and ai drous ZnCl 3 Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2562623, 9836608612, 7646846949ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XI 29 11.8 SOME COMMERCIALLY IMPORTANT ALCOHOLS Conceptual Questions 1. Mention two important uses of methanol Solution (2) The largest use of methanol by fais in making other chemicals. About 408 of methanol s converted to formaldehyde which it ‘then used to produce products 2s diverse as plastic plywood, paints, explosives and permanent press textiles (b) Methanol isused on limited bass to fuel internal combustion engines. 2 What is usually added to ethyl alcohol to make it unfit fr ernking purposes? Solution Methanol and pytiine 23. Whatis rectified spit? Solution [tected sprit isa highly concentrated ethanol (959) which ha been pure by means of repeated dstilation. Rectified spit are Used in mixed drinks inthe production of iors fr medicinal purposes and asa household solvent. 11.9 PREPARATION OF ETHERS Conceptual Questions 1. How can diethyl ether be prepared from () ethyl odide and (b) ethyl alcohol? Solution (0) Wiltiamson ether synthests: The general reaction mechanisms as fllows 2 R08 LK NR ‘An example's the reaction of sodium ethoxide wit iodoethane to form diethyl ether and sodium chloride: Na*CHyO~ + Gis! —> GoHsOGaHy + Na’ (b}Ethy alcohol reacts with thionyl chloride to form 1-chloroethane. Its then treated with Mg dust to form Grignard regent, and ‘hen simply treated with ethyl aleahol to frm diethylether. GHJOH + SOCl,—> CHAS cHaMgcr ==> c,H,—0— Cals Dehn 2. Name the ally halide and scum alkoxide use to synthesize er-buy ey ether Solution Ay halde aed sodium akosde used tosyesetertbuty| thy ether are ety! bromide and sdium tert iii Hs CGO + Oye hE Om + Hr Hy Hy Secium srt side Ey temige tw Buyer Aone “nae! 3. Name the major product obtained when fe-buty bromides treated with sodium ethoxide Solution Hs Hs Fr ho EE Hy CH + GHGOH + Nabe Hy ter Buyoromide 2 Metiyiropene With ertiary alkyl halides, only elimination reaction occurs which give alkenes. n ths cas, it 's2-methy| propene.Ethoxideisastrong base, Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0651-2662623, 9636608812, 754684694930 R. K. MALIK’S NEWTON CLASSES “4. Name the reagent used to convert bromoethane to ethoxyethane or diethyl ether. Solution ‘illamson synthesis RONs + RK —> ROR + NaX. cHjci,0Na + CrjcHyBr Es yCHOCH CHS Nar Seoum honde tromecture “Detter 5. GiveIUPAC name ofthe folowing ether wwcer) (9) 00g a5 () yocrycryct (6) ON—C4—OCH40) oy 1) cryerncrsocrs fe WC ota rn OGHs cats Solution (a) 1-thoxy-2-methylpropane (0), 2chloro-t-methoxyethane (e) Anitroanisole (ch) methorypropane {e}_1-Ethoxy-4/4-dimethyleyclohexane (0) Ethoxybenzene |6. White the names of reagents and equations forthe preparation ofthe following ethers by Wliamsons synthesis: (NceRT) (a) -Prepoxypropane(b) ethexybenzene ——_(c). 2methoxy-2methylpropane (a) T-methoxyethane Solution (0) GHACHCHONa + CHACHsCHBe —> GHSCH)—O— CHC My + Nasr Sodium sroponde 1 Bromepropane 1 Propoxvprepane (1 ON OcHscH Seno —=(5 om Sodium Sromoethane ——_Ethoxybenaene phenonde cy) Hs Hs Cy —F—Om + Ose —> Foch) +e Hs cH Sedum2oeny-2orpinide Gemematane —4theny dete (2) CCH —ONa + CHy Br —> CHACH) OCH + Nabe Sechmethente Sromenethane —Aetamethane 2. strate wth examples the litations of Willason synthesis forthe preparation ofcerain types ethers ween Solution “The reaction of Wilamson synthesisinvlves 5,2 tack ofan alkoxide ion on primary aliythaide on a (CH, —C—ONa + cHy—Cl —> CHy—G—C—CHy + Nac dy dy However if secondary or tertiary ay! halides are taken then elimination would compete for substitution. As resulekenes would be produced. Alkexides ae nucleophiles as well as strong bases. Hence, they react with alkyl halides, which results in an elimination reaction. Hs (Cs CCl Nath CH —> CHy—CmecHy+ HOH + NaCl cH cH Terayakynalide wee Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 31 |8. How is -propoxypropane synthesized from propan-1-ol? Write the mechanism of this action, Solution 1-Proporypropane can be synthesized from propan-1-ol by dehydration. Propan-I-ol undergoes dehydration inthe presence of proticacid (such as H;S0, H;PO,) 10 glve |-propoxypropane, (NCERT) 2H CHC OH > CH, CHC —0— CH, CH CH, ‘ropa ot 1 Proponprosne ‘The mechanism sas fllows: Step 1: Protonation 4 \ cH,CHCH, BH HY — cycH,cH, OH ropa ‘Step2: Nucleophiicattack << , cat 5 a4 B+ oO AE — OHHH, BAH OOH HHO 4 H ‘Step 3: Deprotonation na Gh —oHOKEH —r BACH —O—CLEAEH He . 4 |-Proponypropane ‘9, Preparation of ethers by acid dehydration of secondary or tertiary alcohol snot asultable method. Give reasons, Solution The formation of ethers by dehydretion of alcohol is a bimolecular (52 reaction involving the attack of an alcohol molecule on a protonated alcoho! molecule. nthe case of secondary or etiary alcohols, nucleophilic attack by the alcoho molecule onthe proto nated alcohol molecule doesnot occur due to steric hindrance. Thus, elimination dominates substitution. Hence in place of ethers, alkenes are formed, (NceRT) Textbook Exercises 11. Give the common name of each ofthe following ethers. fa t ChigHOCHHLCHCH, fe) CHyCH.CH,CH,CH,00H,CH,CH,CH,CH, conocer Hy Hs Solution (a) ter-Butylmethylether () Buy opropy ether {c)_Dipentyl ether 2, Fourteen omerc saturated ethers have the formula M0, Witte structural frm for each ofthese ethers Solution (0) CHJCH,CH,CH,CH,OCH, | neiyeenane (6) CHJCH{CH,OCH,CH,CH, opomeopane ee [b) CHYCH,CH,CHLOCH,CH | einonbutone Ay—O— HIGH —O— OH, MCHC “GO Hs Hy ch, seenemywenene |-Metnony-2-methybvane |-Methoxyetnybuaane 19) yO PI—O—CHy OH, CHICO“ GC Hy GH—“O— GHC Hy Hs Hs ethonybutane ethoxy 2methylpropane 2 Froporrepane W G4 —GI-o—EH—a, (kG —CH—CH—-O— CH o Hy cH CH CH CH Hy CH —O—C— CH 2-2-Prepory! propane 2 Merhony 3 methyibutane I Hy 2.2hory 2 methyoropene Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. (0651-2562623, 9696608012, 754684594932 R. K. MALIK’S NEWTON CLASSES tm ) Hy Hy—C—Cy—-O—CHy CH —CHy—C—0—CH oy Hy | athoxy22-dmethypropane 1 Methony 1 metyutane ‘Additional Questions 1. Preparation of unsymmetrical ethers by Wliamson synthesis requires proper choice of reactants. Comment. Solution For the synthesis of unsymmetrical ether, proper choice of reactants is necessary since Willamson synthesis accurs by Sy2 mecha nism and primary alkyl halides are most reactive in Sy2 reaction, However, the alkoxide may be either 1°, 2° or 3°, for example, tert-butyl ethyl ether is prepared by treating ethy! bromide with sodium tert-butoxide, chy Oh t—oNe + crc A Cy COC CHy + Nar cH cy Sodium tersbutonde 3) Ehytromide(") ter Buylethyl ether ‘The above ether cannot be prepared by treating sodium ethoxide with tert-butyl chloride or bromide since under these conditions, alkene is the main product. « on os =F Br GOON > y—C my + GOH ar Detlneome Hs . potas for 2. Outline a scheme forthe synthesis of each ofa) ethyl methyl ether and (b) tert-butyl methyl ether. Solution (2) Ethyl methyl ether CCH0-Nat + C482» CHOC + Nate Stim tng ey rat = = = (0) ereguy meteor or on C—O 5 BE — 00 + a hs cs Settee Matt sain oe Si 2. How wilyou conver ty bromide int ity ether? Solution By Willson ether synthesis, There must bea primary lly halide otherwise an elmination ection wl occu Gath + GHO-Na > OCs Ch Soden Oltyther wemie Shemte 4. Giving conditions and reactions, convert HOH into C,H,OGH, Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XI 33 “Solution Dehydrati rong acids, such as sulphuric acid, can catalyze ethanols dehydration to form either diethyl ether or ethylene, 2CHyCHJOH—> CHJCH;OCH,CH, + H,0 (CHsCHOH—> HC = CH + HO However, the acid is luted by the water thats formed, which makes the reaction inefficient. Whether dlethy| ether or ethylene will predominate wll depend on the precise reaction conditions Hy CHyCH,OH] LAR CH OCHs ‘Alcohols undergo dehydration inthe presence of protic acids (H,$0,,H,PO,) The formation of the reaction product, alkene or ethet, ‘depends on the reaction conditions For example, as shown n the above reaction, ethanol is dehydrated to ethene inthe presence of sulphuric acd at 443 Kand at 413K, diethylether the main product. 5. Drawall he ethers corresponding to the formula C,H,,0, including stereoisomers. solution AN NN |. Which isthe best method to prepare ethoxycyclopentane via the Williamson method? = ' Onn 11.10 PHYSICAL PROPERTIES OF ETHERS Conceptual Questions 11. Why are higher ethers insoluble in water? Solution “The small esters are fail soluble in water, but solublity falls with chain length. Ester Formula Solubitity(g per 100mL of Water, Ethyl methanoate HCOOCH,CH, 10s Ethylethanoate cHyCOOCH,CH, 87 Ethyl propanoate CHscH,COOcH,CH Ww ‘The reason forthe solubility is that although ethers cannot form hydrogen bond with themselves, they can form hydrogen bonds swith water molecules. As the chain length increases, the hydrocarbon parts ofthe ester molecules start to getin the way of hydrogen bbond formation. This makes the process energetically lss profitable, and so solubility decreases. 2. How do you account forthe miscibility of ethoxyethane with water? (CBSE Sample Paper! 2008) Solution Ethoxyethane forms weak hydrogen bonds with water because the C-O bond is only slightly polarized. The ethyl group being hydro- phobic prevents extensive hydrogen bond formation 3. Why are Grignard reagents soluble in ether but not in benzene? Solution Grignard reagents form coordination complexes with ether but not with benzene, since the former have lone pair of electronsbut the latter donot Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0661-2662623, 9836600012, 7546845949,ET R. K. MALIK’S NEWTON CLASSES 4. Give reasons for the following {a} The C-O-C bond angle in ethers higher than the H-O-H angle in water though oxygen Isp? hybridized in both these cases (0) The dipole moment of ciethyl ether (1.18 0) is lower than that of water (14D) Solution (a) In ethers, the four electron pais thats, two bond pais and two lone pairs of electrons on oxygen are arranged approximately Jin tetrahedral patter, The bond angle Is slighty greater than H-O-H bond of water because of the repulsive interactions between the two bulky (-R) groups. DSL He MH wt tins o-Hbond ehh ioe ig mania ti nid ‘thigh dipole moment. In ethers, the C-O bonds are less polarized because of small difference in electronegativy. Hence the dipole moment of ether is less than that of water. 5. GWve reason forthe higher boiling point of ethanol in comparison to methoxymethane, (NcerT) Solution Ethanol undergoes intermolecular hydrogen bonding due to the presence of -OH group. xtra energy I required to break these hhydregen bonds. Methoxymethane does not undergo intermolecular hydrogen bonding, thus the boiling point of ethanel i higher than that of methoxymethane, Textbook Exercises 1. Account forthe fact that dipropyl ether has a higher boling point than diethylether Solution propyl ether has higher molecular mass and so the van der Waals forces of atraction in dipropyl ether are more than diethyl ether Hence, more energy would be required to break these forces, and so the boiling point i higher for dipropyl ether ‘Additional Questions 1. Dimethyl ether is completely soluble in water but diethyl ethers soluble in water to small exter. Solution Both dimethy! ether and diethylether form weak hydrogen bonds with water which accounts fo their subi In diethy| ether the hydrophobic hydrocarbon partis larger and therefore, mits the hydrogen bond formation. in water However, 2. How will you account forthe following: Ethers posses anet dipole moment even if they are symmetrical in structure? iahiing wR apes a ‘Te €-0 bons aon sigh plated the fees in the elecoonegtves feo nd anges al The C-0-< Tisirebar ial eas ann meetaneaces cant nae 11.11 CHEMICAL REACTIONS OF ETHERS Conceptual Questions 1 Explain that in arylalkyl ethers, (wcert) (a) the alkoxy group activates the benzene ring towards electrophilic substitution and (}tarects the incoming substituents to ortho and pare positions ina benzene ring, Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 33 Solution (2) In arf allyl ethers, one ofthe lone pais of electrons on the axygen atom i dawn into the benzene ring due tothe +R effect. This Increases the electron density inthe benzene ring thereby activating the benzene ring towards electrophilic substitution reactions. ‘Sor 2R on + ‘ & +88 a -O-0-0-0 _ ay () -Asseen fom the above resonating structures, the electron dens increases more at ortho and para postions as compared to ‘meta postion. So, the electrophilic attack takes place at orto and para positions respectively. 2, How does diethyl ether eat wih ) HBr a 373K () Hat 373Kand (late H,S0, under pressure? Solution (0) GHOGHs +H 5 CHO GHB (b) GHOGHs + HI) C,H,OH + Ce (©) GHyOCHS +1450. (at) —> CHsOH 2 Wit the chemical equations, when {a} Benzy phenyl ever reacts wih Hlat373K, {0} ere Butyl methyl ether eats with HBr at 373 K {c)_Tetahyrofuran reacts wth excess of Hr at 373K (a) Phenetole reacts with Hat 373K {e)_2€thorybutane reacts wth Hlat 373K (1) 2Methoxy-2-henyoropane react with Hat 373K Solution. - c-o¢ Yen Yan enn phen ster enlodide Pena Om os Cy —F 008 +H OOH Er by wenn dy seb ebay mete toma Note: When oneof the aly groups nan ethers tert a tera hades formed. ‘s yO td OG, on (Come 2 ants, oar is 07 een) 1Ateomchinne vas CO rons nol eral in foal Hs HiC-HsC H.C —HC—OGyHy + HI —> HyC—CHy CH —CHOH + Cs! Hy 2Ethonybuure Penan 2o ft o os Hy Cote —00H4 + HH OH as == oy chy 2 Methony2 pen Metronet Ayia “4. ite the equation ofthe reaction of hydrogen fide wth) -propoxypropane.b) methoxybenzene and () benzyl ethy| ther. (wcerT) Office.: 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph. 0661-2662623, 9836600012, 7546845949,36 R. K. MALIK’S NEWTON CLASSES selton (8) Hach ocr HS cHYCHLCH, OH + CHSCHLCH —I "osormonine Peniel—— odapmpere oct 7 O +Hi—| J+ cHs—I Methonybersene Phenol ladomethane ® Hy—0—GiHs fH +H + GHsOH Dene ey eter Benayiodiée Ethanol 5, White the mechanism of the reaction of Hi with methoxymethane. (NceRT) Solution The mechanism ofthe reaction of Hi with methoxymethane involves the following steps: Svep 1: Protonation of methoxymethane 4 Hy 00H C—O 41> ‘Step 2: Nucleophilicatack off 4 H +c —Gt— cH, > tery Otc > 1 + cH OH lodomethane Methanol ‘Step 3: When Hlisin excess and the reactions carried out at ahigh temperature, the methanol formed inthe second step reacts with another HI molecule and gets converted to methyl iodide an) I Hy Fi cry 9H + 1+ GHy on, —> cHy—14H,0 todomethane 6. te equations of the following reactions: ncert {a}, Friedel-Crafts eaction—alkyation of anisole ()_Niration of anisole {€)Bromination of anisole in ethancic acid medium (a). Friedel-Crafts acetyaton of anisole Solution ry field omc sind Neto OCH , ‘oct 0, 0 toa =. spc iceman Ansole 2 Ntvoansole ‘mj ‘wan ‘minor areal 2) Mentone meen eric macim () Friedel ot cern tomate oc coe, | + chycog = sine rma 2.Methony ‘aor ‘ann semophenone — acogherane ‘wine hap Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,ALCOHOLS, PHENOLS AND ETHERS [DRILL ASSIGNMENT] CLASS - XII 37 [Additional Questions 1. Complete the folowing reactions: 8) GHSOCaHs + HCI—> (b) GHOGHs + HE te) [ + 2HBr (excess) —> (3) CHy-=CH—GHONe + 1CHy—CH=CH, > te) CH — Hy seuton (a) GOGH + HCI» GcOH + CH (oy GOGH + ME 2 ail + HO oH) [J 120 wads, ya (a) C= CHCH,0-Na + IHC CH, “> CH= CHCHOCH CH=CH + Nal Dethe ©) tho AEs con Te! 2. Discus the following: Electrophilic substitution reactions in aromatic ethers. Solution In arylalkyl ethers, the + effect ofthe alkoxy group (-OR) increases the electron density inthe benzene ring, thereby activating the bbenzene ring towards electrophilic substitution reactions ce +R +6R ttn OR G-Y 0-0-0 oO NEN asm ai ig rc dc an sn nd pon i fe ee ee cata rses paoeaeney ime omogia aaa ora (a) Halogenation () Friedel-Crafts reaction (alkylation) & cts oc, cts ne 00, i “> soya SE, + Anisole Methyl ‘horde Hs 2Methory 4 Methony- ‘— ale toluene tolvene (Maron iM (tino ry (¢)Fredal-Crafts reaction (acylation) (4) Nitration cH OCH OCH, ‘cOCH i + aco + Oo a= Ptoanle cede cock, “ney Methony tarde seetophenone ain ‘ajo 606 , 6" Floor, Hariom Tower, Circular Road, Ranchi-1, Ph; 0851-2562623, 9836608812, 764884694938 R. K. MALIK’S NEWTON CLASSES 3. Write the reagent and equation in the conversion of anisole into 4-methaxyacetophenone Solution ‘Anisoe eacts with acetic anhydride to give 4-methoxyacetophenone. This is called acylation of anisole. 4 Methoxyacetophenone is synthesized in a Friedel-Crafts acylation of anisole wth acetic anhyatride, - at i i Cy robot ceaton-ce ten ne ‘wacom Office.: 606 , 6” Floor, Hariom Tower, Circular Road, Ranchi-1, Ph.: 0861-2662623, 2635608812, 7546845949,