e alcohols, phenols ang hers according to the IupaG ystem of nomenclature: ; ‘olved in. preparation of alcohols from kenes, aldehydes, Ketones and poxylic acids; the reactions involved in the preparation of phenols from aloarenes, benzene sulphonic elds, diazonium salts ang eumene; 5 the reactions preparation of ethers EC GATS TOE and Ethers AleBhols, ptiénols and ethers are thé basic comp Jormation of detergents, ant nds for the iseptics and fragrances, ely, You have learnt that substitution of one or more hydrogen atom(s) from a hydrocarbon by another atom Cr 8 group of atoms result in the formation of an entirely new compound having altogether different properties and applications. Alcohols ‘and phenols are: formed when a hydrogen atom in a hydrocarbon, aliphatic and Aromatic respectively, is replaced by -OH group. These classes of compounds find wide applications in industry as well as in day-to-day life. For instance, have you ever noticed that/Ofdindry spirit used for! polishing ‘wObden furniture TS hlety- + compound cMaIS hydroxyl group; ethanol. The sugar we eat, the cotton used for fabrics, the paper we use for writing, are all made up of compounds containing -OH groups. Just think of life without Paper; no note-books, books, news- eS, CI etc, The ‘agazines carrying beautiful photographs | and nteresting stories would disappear Hom our Tite. It would have'been really a different world, An alcohol contains one or more hydroxyl (OH) group(s) directly attached to carbon atom(s), of an aliphatic system (CH;OH) while a phenol contains -OH group(s) directly attached to carbon atom(s) of an aromatic system (CjH,OH). The substitution of a hydrogen atom in a hydrocarbon by an alkoxy or aryloxy group (R-O/Ar-O) yields another class of compounds known. as ‘ethers’, for example, CH,OCH, (dimethyl ether). You may also visualise ethers as compounds formed byWL Classification 11.1.1 Alcohols— Mono, Di, Tri or Polyhydric alcohols a nydrony 67050 FBP ALSO, tom chemistry of three classe, and ethers. A Substituting the hydrogen 4! Phenol by an alkyl or aryl group. in In this unit, we shall discuss ry. compounds, namely — alcohols. P! heir study systematic kes tl a, The classification of compounds MA’ T, how are alcohols, Phen! hence simpler. Therefore, let us and ethers classified? e classified as mono- dic, tr. ‘whether they contain one, Oy Alcohols and phenols may b 01 ectively in their structures 9 compounds depending on ree or many: hydroxyl groups TesP! given below: oH, LOH CHon CHOH 7 ty OH SoH ee Tribydric Monohydric Dihydric e further classified according to Monohydric alcohols may b' hybridisation of the carbon atom to which the hydroxyl group ,, ’ attached, Mo Compounds containing .C,,~ OH bond: In this class of alcoho. the -OH group is attached to an sp” dybridived carbon atom of a, alkyl group. They are further classified as follows: Primary, secondary and tertiary alcohols: In these three'types « alcohols, the -OH group is attached to primary, secondary anj tertiary carbon atom, respectively as depicted below: \ —cH;0H >cu—-on PC-OH Primary (1°) Secondary (2°) _ Tertiary (3°) Allylic alcohols: In these alcohols, the —OH group is attached in a sp° hybridised carbon adjacent to the carbon-carbon double bond, that is to an allylic carbon. For example a -G- I CH,-CH-CH,-o}} CHy-CH-C-oH CHy-CH-C-o}1 ' 1 Primary Secondary Tertiary Benzylic alcohols: In these alcohols, the OH group is attached to a sp —hybridised carbon atom next to an aromatic ring. For example.H yt \ ania ‘CH,OH Cy ies ao 6-01 i ~(- ot Primary i Secondary Tertl lary Allyjic and benzylic alcohols may be secondary or terti Compounds cor : : a : —OH group onde ne C,»-OH bond: These alcohols contain led to a carbon-carbon double bond, 1.¢., to a vinylic carbon or as vinylic al to an aryl carbon. These alcohols are also known 11.1.2 Phenols OH OH Mone. Di OH OH oa an trhydrie CH, phenols A OH Trihydric Monohydric — Monohydrie _—_—Dihydric 11.1.3 Bthers Ethers are classified if the alkyl or aryl : to the Oxygen atom are Te Same, and CHOCH, be yan oe {wo groups are different. Diethyl ether, Se etricé the areuneymmetiealeterss ee Classify the following as primary, secondary and tertiary alcohols: CH, OQ : 0 Mes ¢ —CH,OH I H,C=CH- CH,OH CH, 3 0 on H-CH, ih CH,- CH; CH,- OH 8 * © wf curcH- Gn, AD (Ol ou i i) OY Alcohols: The common name of an alcohol is derived from the Common name of the alkyl group and adding the word alcohol fo it For example, CH,OH is methyl alcohol. / Identify allylic alcohols in the above examples. (\ 1.2 Vlomenclature pda Alcohols, Phenols and Ethersy xp), the name of an t 12, Class ‘the alcohol ig 2° sg ue ana a is derived from the name e cof alkane r this, the longest sears eal veatnted by numers ae ee pearest os chain yumbel and other sut hyd vga ne pelions of the OH Bn ators to which the are indleated ty using the numbers oa ¢ ‘e’ of alkane is rey attached, For naming polyhydrie alee Cr on groups is ae snd re ending’ a ae tat, etc before ‘al The sv “OH groupe are indicated by appropriate nes common and {s named as ethane-1, 2-diol, Table 11- ag names of a few alcohols as examples. Ble 11,1: Common and IUPAC ‘Common name Names of Some Aleohoy, sh Conn ety Methanol Methyl alcohol Seo alcohol | Propan-1-ol teopropy! alcohol | Propan-2-ol Butan-1-ol Butan-2-ol n-Butyl alcohol secButyl aleohol Isobutyl alcohol | 2-Methylpropan-1..) tert-Butyl alcohol | 2-Methylpropan-2-0) Ethylene glycol Glycerol Ethane-1,2-diol Propane -1, 2, 3-tridl Cyclic alcohols are named u the the —OH group attached to cite Prefix cyclo and considering OH OH oo Cyclohexanol —-2-Methyleyelopentanol is phenol. Ol involves a bei structure in its substit eee (1,2- disubstituted), meta (1.S-disubel capone -4-dlsubstituted) are often used in the cy stituted) and part names, Chemistry 326, ;OH Hy CH, CH, ‘OH OH Common seme = Phenol m-Cresol p-Cresol JUPAC name Phenol 2-Methylphenol_ -3-Methylphenol —_4-Methylphenol Dihydroxy derivatives of benzene are known as 1, 2-, 1, 3- and 1, 4-benzenediol. OH OH OH oO” ‘OH OH Goac aa re, =, ——aae \Aef thers: Common names of ethers are derived from the names of alkyl/ aryl groups written as separate words in alphabetical order and adding the word ‘ether’ at the end. For example, CHjOC;Hy is ethylmethy! ether. ble 11.2: Common and IUPAC Names of Some Ethers bert ee etc mrry TUPAC name Dimethyl ether Methoxymethane Diethyl ether ‘Ethoxyethane Methyl n-propyl ether 1-Methoxypropane Methyl phenyl ether Methoxybenzene (anisole) (anor (0CH,CHs a fa | ether Ethoxybenzene CyHsO(CH,),- CHy Heptyl phenyl ether 1-Phenoxyheptane cH0-CH ~CH, CH, | GjHy-O-CH,- CH, CH-CH, | Phenyl fbopenty! ether | 3- Methylbutoxybenzene | | Methyl (Sopropyl ether 2-Methoxypropane CH, CH O - CH;~ CH, - OCH, HC. CH, OC.H, - 1,2-Dimethoxyethane 2-Ethoxy- -1,1-dimethyleyclohexane (Bi Alcohols, Phenols and Etherssame, the prefix Ifboth the ally! groUPs we js diethyl ether, group, For example. C2807 nomenclature, ethers ay, to TUPAC Yet hich a hydrogen atom ts a bon deri inere R and eee as cap and any -OR e ay ce ales up is cl Parent Tes| ively. ivel ‘The names of a few euers a7e following compounds: ple I) Give TUPAC names of th HH (CH; - CH ~ 0-., AT CH,- cH - ch - cH CH,O! t 7 Hey Cl CH, CHs NO, ie fH a “Cy (i) 2-Bthoxypropane Solution {g 4-chtoré:2:3-dimethylpentan-1-o1 ( 4-Chioré:2,3-dimethylpe (i) 1-Ethoxy-2- (it 2,6-Dimethylphenol ntext ior 1.3 Name the following compounds according to TUPAC system. CH.OH CH,0H ; @ cHy-cu,-cH-cH-cH-cH, Al Hs GH OH THC cg, 1 1 CH, OH CH,Cl CH, OH 6) AO) H,C= CH CH CH, CH, Hh, Ai ct 0 =0- | Br OH CH, Br 11.3 Structures of In alcohols, the oxygen of the-OH group is attached to carbon y functional sigma (c) bond formed by the overlap of a sp” hybridised orbit Gi carbon with a sp’ hybridised orbital of oxygen. Fig. 11.1 depi reupe structural aspects of methanol, phenol and methoxymethane. 142 pm 96 pm x ilpm o. a 0; HM ¢ “ : H, og . * ag \ fat wScTrrcLa oy o MoH okny Ou Hu] 186pm W” f H [ps ] Methanol Phenol Methoxymethane rears) Je 11.1: Structures of methanol, phenol and methoxymethane Chemistry 828The bona 10: tetrahedral Angle (1090., ingle >, tn alcohols is slightly less than the = 28), I iy tf jh flectron et ton between the UNS bybrtacg tie leant ausched to =F of ‘bon 0 nang a. M) tn pew aromatic ring. The carl anol. THIS Phenol ts slightly less than that in met a cleat oUble bond hurler on aceount ofthe con on 11.4.4) ang gy TO" Pale of oxygen with the aromatic ring (Sect® attached, “HHT sp" hybridised ate of carbon to which oxygen lone patre or the four electron airs and two Pairs, 1.e., the two bond pi ‘tetrahedral weeleetrons on oxygen are arranged approximately 1n.@ 11.4 fulcohols and Phenols Alcohols wearetio of Alcohols — Pe cild catalysed hydration: Alkenes react with water in oe . In case of ngs to form alcohols \ddition reaction takes place in Secordance with Markoinikevs nil (Unit 15, Class 0). 2C=C< + Ho SR >e-0< H OH CHCH=cH,+ H0 S cH-cH-cH, I Mechanism a The mechanism of the reaction involves the following three steps: SS 1: Protonai alkene to form carbocationby'electrophilic’ H,0 + en) H H 1 +7 sesec + HOH -G-&0 +H SP 2: Nucleophilic attack of water on carbocation. H HH 1 € ‘ jegk as =C-CK + HG = -0=¢-0H SO 3: Deprotonation to form an alcohol. H :OH i 1 3b a. He + -C-C-OFH + HO > -C-C- +H,0 fel’ " ' 1829, Alcohols, Phenols and EthersAX rom carbonyl compounds . Chemistry 98305 wn; Diborane (BHs)2 reacts oat sg to give trialky! ide in the pre Aqui aleohol by hydrogen Pero™ i * hydroxide. , cH, + (H-BHh—? cH CH CH, ores H BH, \CH,-CH=CH, \ (CH,-CH,-CH),2 gieCHeCH (oH, CH,-CH),BiH * Is! H,0|3#1,0,, OH 3CH,-CH,-CH,-Oll + B(OH) Propan-1-ol bond takes f borane to the double na 8 manne thet the ora atom gets attached to the gpa atoms. The alcoho} 80 yydrogen ed by the addition of water i thas been forme ko’ rule. In ths in a way opposite to the Mar} alcohol is obtained to aluminium hydride (AIH). Aldehydes yield primary aloo whereas ketones give secondary alcohols. RCHO +H, Ps RCH,OH RCOR’ NABH R- CHR’ ou Ut By reduction of carboxylic acids and esters: Carboxylic are reduced to primary alcohols in excellent yields by lt aluminium hydride, a strong reducing agent. oma ) GAH, RCOOH ———> RCH,OH (i) HO However, LiAIH, is for preparing special chemic: " reduced to alcohol: erting them -4.4), followed by thetr reduction using hydrogen in the Presence of catalyst (catalytic hydrogenation): v Oh Rcoon- SOY, Rcoor 2, RcH0H+ ROH w Catalyst“ren Grignard reagents t 10, Class Xn) wiped by the reaction of Grignard reagents (Unit 10+ The fit an aldehydes and ketones a Teagent to ie of the reaction is the nucleophilic addition of ae ns Adduct yields an aloo gFOUP to form an adduct. Hydrolys! Cae Nig-x i - 0 Mg-x 0 k 7 Adduct Ho, ol) >C- OH + Mgonx R he reaction of gece for? all reactions using different aldehydes and ketones are a8 produces @ primary ‘alcohol, with other Hen Sidehydes, secondary © + RMX RcHoMgx ES RoH,OH + Mg(OHDx ‘alcohols and with ans fr E ’ 0 + RMex R-CH- oMgx 2:2, RCH. OH + MglOHIX r r Mgx —+ Ro. omgx 225 R-C- OH + Mg(OHK R R ‘You will notice that the Teaction produces a primary alcohol with in en } & secondary alcohol with other aldehydes and tertiary alcohol tones. Give the structures and IUPAC . oe eemucture and hhames of the products expected from . Gxfaple 12 | a) Catalytic reduction of butanal. b) Hydration of propene in the presence of dilute sulphuric acid, p) Reaction of propanone with methylmagnestum bromide followed by hydrolysis, a rd _ (@) CH;CH,-CH,-CH,-oH (b) cre CH ta cHet-on Solution Butan-1-ol HH H, Propan-2-ol 2-Methylpropan-2-ol RCOR + R’ 11.4.2 Preparation Phenol, also known as| was first isolated in the early of Phenols nineteenth century fro lowadays, phenol is commercially produced synthetically. In the laboratory, phenols are prepared from benzene derivatives by any of the following methods: Alcohols, Phenols and Ethers| AC From hatoarenes Chlorobenzene is fused with NaOH a! + pressure, Phenol is obtained by acidification of sodium ph. Produced (Unit 10, Class XI). \ cl Na’ OH 623 K, HCl O 2 From benzenesulphonic acid Benzene ts sulphonated with oleum and eaene Sulphonie ay formed is converted to sodium phenoxide on heating wip, *,, ‘Acidification of the sodium salt gives Phen SO,H OH Oleum () NaOH OO | _x From diazoniuim salts A diazonium salt is formed by treating am aromatic with nitrous acid (NaNO, + HCl} at 273-278 K. Diazonium Salts ie hydrolysed to phenols by warming with water or by treating = dilute acids (Unit 13, Class XI). eo NEb N.cl OH NaNO2 ho, +N, +Ha +HCl ‘Warm = Aniline Benzene diazonium chloride Phenol is manufactured from the hydrocarbon, cumene. Cumene (isopropylbenzene) is oxidised in the presence of air to cumen, hydroperoxide. It is converted to phenol and acetone by treating, with dilute aci of this 0 Oe CHs-CH CH; C-O-0-H Eke x CH, aft “ao? + CH,COCH, Cumene —_Cumene hydroperoxide __Chemistry sidations (4 Show how are the fol, Intext Ques Grignard reagent on methane Prepared by the reaction of a sultable CH,-CH-CH,OH Cites ar Write structuy 30s Fes of the products of the following reactions: CH, ~CH = CH, _H,0/H" " 2 TOU ° wt cure -OCH, 3 NaBH, —_ ah CH —CH,~CH— NaBH, - CH, CH—CHo CH, “HOH . D4 oo 11.4.3 Physical =~ Alcohols and Phenols cons 1 anda Propertic ist of two parts, an alkyl/aryl group ®* hydroxyl group, The properties of alcohols and phenols are chiefly due to the pero group, Bolling Points The bolling points of alcohols and phenols inerease with Increase in the umber of carbon atoms (increase in van der Waals forces). In alcohols, the boiling points decrease with increase of branching in carbon chain (because of decrease in van der Waals forces with decrease in surface ‘The -OH group in alcohols and phenols is involved in intermolecular hydrogen bonding as shown below: R R “ I wH-! Ro~n-d ~H-0 ok Ron OR H R een Reh a H-O~"H-O-H-O rey No It is interesting to note that boiling points of alcohols and phenols are higher in comparison to other classes of compounds, namely hydrocarbons, ethers, haloalkanes and haloarenes of comparable molecular masses. For example, ethanol and propane have comparable molecular masses but their boiling points differ widely. The boiling point of methoxymethane is intermediate of the two boiling points. ols, Phenols and Ethers _7 C. E cH, ch, 1 HyC —CHs Hg Cay Ethanol Methane />P- Moleciilar aa, Poy Mol s/b.p. Molecular -P- 24/231, ork orer0/248 K 4/231 K mainly due to the pre, ° ‘The high boiling points of alcohols are fa ine Se of intermolecular hydrogen bonding in them which ‘king in ethers and hydrocarbons. Solubili oo Solubility of alcohols and phenols in water is due to their ability to form hydrogen bonds with water molecules — a8 shown. The solubility decreases with Arrange the following sets of compounds in order of thelr increasing bolling points: vol tan-1-ol, butan-1:ol, butan-2-ol, ethanol, propan-1-ol, methano), eeiecneien n-butane, pentanal, ethoxyethane. Solution (a) Methanol, ethanol, propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-, (b) n-Butane, ethoxyethane, pentanal and pentan-1-ol. 11.4.4 Chemical Alcohols are versatile compounds. They react both as nucleophiles ang electrophiles, The bond between O-H is broken when alcohols react ag nucleophiles. H | i Alcohols as nucleophiles MO r-5-H+ ‘ - + RA0-C- —F RO-G- st ‘The bond between C-O is broken when they react as electrophiles. Protonated alcohols react in this manner, R-CH,-OH + H+ R-CH,-OH, | of ain gut —> Br-CH,+ H,0 k R R Protonated alcohols as electrophiles Based on the cleavage of O-H and C-O bonds, the reactions of alcohols and phenols may be divided into two groups: Chemistry 9334, owAS Resctions involving cleavage of 0-H bond ee @ alcohols and phenols Reaction with metals: Alcohols and phenols react with active Metals such as sodium, potassium and aluminium to yleld Sorresponding alkoxides/phenoxides and hydrogen. 2R-O-H +2Na —» 2R-O-Na+ Hy CH, a 8 Cliy-C-OH14 21—> 2 Cte 0 Als 3H, CH Hh, tert- Butyl alcohol Aluminium tert- butoxide OH - ONa Cem +Ha Phenol Sodium phenoxide Th addition to this, phenols react with aqueous sodium hydroxide to form sodium phenoxides. OH ONa - + NaOH —> +120 ‘Sodium phenoxide The above reactions show that alcohols and phenols are acidic in nature, In fact, alcohols and phenols are Bronsted acids 1.e., they can donate a proton to a stronger base (B:), OG 5-4 + Base Acid. Conjugate Conjugate a i acid base Acidity of alcohols: The acidic character of alcohols 1s due to the polar nature of O-H bond. An electron-releasing group (CH,, -CyH,) increases electron density on oxygen tending to decrease the polarity of O-H bond. This decreases the acid Strength. For this reason, the acid strength of alcohols decreases in the following order: a HOH® R>C- OH R* R7 R->- CH,0H > Alcohols, Phenols and Ethersemistry 33 Alcohols are, however’N AMlustrated by the reactor pro ROH eee gale ony Base ad © a a ‘This reaction shows that wale Ie oabove reach dong stronger acid) than alee te rato acceptor than yt N that Ikoxide fon 1S stronger i ton. ere suggests that alkoxides fe su areas tat ethoxide is a stronger base than o as well. It ae ‘y base . Iu tas Bronst © ty ar shared electron pairs On onvEeM. Which ote them proton acceptors. of phenol with me Act of phen Nd solum nydronde Indicate yy nature, The hydroxyl group: 1 Phen ring at, tach the sp? hybridised carbon of oe this, the charge a ay! electron withdrawing group: DM "i. resonance tr in phenol molecule, a8 depicte to be positive Struetya causes the oxygen of ~OH group (© ve. % (0-H +O-H +O-H UOH 5 Gs =r O-G ‘The reaction of phenol with aqueous sodium hy cy ids than alcohols indicates that phenols are stronger acids Sen. Sicohols and ya, Let us examine how a compound in which hydroxyl 9 attached to an aromatic ring is more acidic than the on, which hydroxyl group is attached to an alkyl group, ‘The ionisation of an alcohol and a phenol takes place as fol, +Ht Conjugate base reactions Due to the higher electronegativity of sp’ hybridised carb of phenol to which -OH is attached, electron density decreise on oxygen. This increases the polarity of O-H bond and resi in an increase in ionisation of phenols than that of alcohus Now let us examine the stabilities of alkoxide and phenoxi ions. In alkoxide ion, the negative charge is localised on ox} while in phenoxide ion, the charge is delocalise The delocalisation of negative charge (structures I-V)o 1 ta Chey? af % In substitute Phenols, the presence of electron withdrawing < Prenat Tae 8s nitro group, enhances the acidic strength of Present at spitct 18 more pronounced when such a group is delocatisat en”? 2nd para positions. It is due to the effective substituenttO® of negative charge in phenoxide ion when electron res &t, atthe or para position. On the other hand, not favouir then, groups, such as alkyl groups, in general, do in acd strona ration of phenoxide jon resulting in decrease . Cresols, for example, are less acidic than phenol. Table 11.3: pK, Values of some Phenols and Ethanol m-Niyzophenol ftrophenol Phenol _ ~--0-Cresol ‘m-Cresol P-Cresol Ethanol Nig From the above data, you will note that phenol is million times more acidic than ethanol. pan-1-ol, 4-methylphenol, phenol, 3-nitrophenol, 3,5-dinitrophenol, Solution 4, 6-trinitrophenol , > Alcohols and phenols react th CG ag Bla Alcohol gO 2H OH, Phenols.and Ethers =Asptrin possesses AC Reaction with hydrogen halides: Chemistry @3y Hy aa Ar/ROH +R> COOH =e AF/ROCOR'+ HO 10,0 aan Ar/ROCOR+R COOH Ar/R-Oll+ (RC (6H yarocor ec R/ArOHER COL id and acid anhydride 1, ‘The reaction with carbo ic acl — co ion Ie reversible, an erefore, a ‘rhe reaction with acd c loride 1s, ine) reat form* se. go as to neutralise HCI ormed. a eveaction. It shifts the fum to the rij formed during een of ace (CHCO) sroup i alot hand side. ‘as acetylation. Acetylation of salicylic acig phenols is known produces aspirin. COOH a OH e ACen + (CHyCO},O— LL Salicylic acid cooH Reactions involving cleavage of carbon - oxygen (C-O) bond in alcohols ‘The reactions involving cleavage of C-O bond take place only ty alcohol ; ‘Alcohols react with hydrogen halides to form alkyl halides (Refer Unit 10, Class XII). ROH +HX + R-X+H,0 ~ Reaction with phosphorus trihalides: Alcohols are converted to alkyl bromides by reaction with phosphorus tribromide (Refer Unit 10, Class XII). ration: Alcohols undergo dehydration (removal of a molecule ‘of water) to form alkenes on treating with aprotic acid ae ooo HPO, or eatalyets ouch axaniyarous te (Unit 13, Class XI). H* \cec’, -6-b- —B—> deect+H,0 tA - Ethanol undergoes dehydration by heating it with concentrated H,SO, at 443 K. CHLOH Fe = Clit HOler ancoPelary and tertiary alcohols are dehydrated under mild conditions, For example OH = Crtricr DEO os coy cry +th0 440 K My Hy onan, 4, 1,0 cH 158 K ee f alcohols follows the following order St¥e-ea8e of dehydration of ‘Tertiary > Secondary > Primary| 7 ‘The mechanism of dehydration af ethanol volves the following steps: carbocations Mechanism and etre case's Step 1: Formation of protonated alcohol. ena secondary HH - ns; tertlary W665 Yh ned gen are the easiest HH Ethanol (eyes \S# 2: Formation of carbocation: iis the slowest step and hence, the Tate step of the reaction. q GG Sam He-Os HO H HH Step 3: Formation of ethene by elimination of a proton. How HOY ee ae Hw a Hi Ethene The acid used in step 1 1s released in step 3, To drive the equilibrium to the right, ethene is removed as it is formed. 4“ Oxidation: Oxidation of alcohols involves the formation of a carbon- oxygen double bond with cleavage of an O-H and C-H bonds. HyG-0,H—+sc-0 Bond Such a cleavage and formation of bonds occur in oxidation reactions. These are also known as dehydrogenation reactions as these involve loss of dihydrogen from an alcofiol molecule, on the oxidising agent used, a primary alcohol is oxidised to an aldehyde which in turn is oxidised to a carboxylic acid. >» : 1989 Alcohols, Phenols: and EthersHu re > R-C=0 omdation, GeO’ non ee a RCHLOH ean cata acidified _pota, + agents such as ae ane oxidise gel carboxy ie aa rom alga janganate are use un i used a8 CHE OXIA pe aly eros anhydrous for the isolation of aldehydes. RCH, on LOSS Kono : : ofprimary alcohols to aldehyg, for oxidation a compig’® food yield i: cl. of Shronilum trioxide with pyridine and Hi on EOL CHs CH = CH- Cig CH, -CH = CH - CH, Secondary alcohols are oxidised t0 ketones by chromic any, (Croy. OH Sec- alcohol Ketone Tertiary aloohols do not undergo oxidation ae tno se reaétion conditions such as strong oxidis! CC bonds tak 0) ang elevated temperatures, cleavage of various C-C Do! €S Place and a mixture of carboxylic - acids containing lesser number On: RCHO of carbon atoms is formed. RCH,OHG73K > cu When the vapours of a pour CR rimary ofa secondary alcool 5 te Ee” PI are passed over he: Hi, ql g ‘OH 50H, ie 573K =CH, ding Biological oxidation of methanol and ethanol in the body produces the corresponc aldehyde followed by the acid. At times the alcoholics. by mistake, drink ethanol, with methanol also called | In the body, methanol is oxidi e blindne: ) Reactions of phenols Following reactions are shown by phenols only.=} BI FP pesrophile ‘aromatic substitution Uc ring are . the reactions tha lace on the aromatic ateeeeetile substitution eaetons Unit 13, Class XI, The -OH pile benzene ring activates it towards electrophvin pea It directs the incoming group to ortho ane five thereat the ring as these positions become electron ric! ctures ase nance effect caused by -OH group. The resonance strus ‘own under acidity of phenols. in emma Clectrophitic aromatic substitution reactions taking place oe ‘enol are as follows: Nutration: wit ture (298 1. ith dilute nitric acid at low temperature (2: Phenol yields a maixture af ortho and para nitrophenols OH OH OH NOa Dilute HNOs cy + HNO: ~ NOa o-Nitrophenol p-Nitrophenol the ortho and para isomers can be separated by steam distillation. o-Nitrophenol is steam volatile due to intramol hydrogen bonding while p-nitrophenol is less volatile due to intermolecular hydrogen bonding which causes the association of molecules. - Vy e e a0 cy No. HO-L DN. o-Nitrophenol p-Nitrophenol 6-Trinitrophenol (intramolecular (intermolecular , ‘strong acid due to H-bonding) H-bonding) With concentrated _nitric_acjd, phenol is converted to fi 2,4,6-trinitrophenol. The product is commonly known as picric ae acid. Th ield of ction product i OH On, No, Conc. HNO3 02 246 manphenol Nowadays picric acid is prepared by treating phenol first with_concentrated_sulphuric acid which converts it to phenol-2,4-disulphonic acid, and then with concentrated nitric acid to get 2-4,6-trintrophenol. Can you write the @quaqons- oT the reactions involve: Sifu Alcohols, Phenols and Ethersaa , different 1 with bromine, falogenation: On treating phen® imental con, A Hage tor med under afer eae of cnt ‘When the reaction Is carrie out at low temper x such as CHCl, or CO monobromophenols are forme - OH OH Br Bry in CSa, + 273K Br Major Minor ne takes place in of bene The usual halogentid, such as FeBr, (Unt 10, Clagg x presence of a ‘the halog ren molecule. In case of eno which polarises jecule takes place even in TEs du bi e mol es of bromine : eto” ct effect of -OH group. oi : §pPWhen. phenol is aatsis rete 2,4,6-irfbromophenol is formed as. OH OH a - Cm Uae ir 2,4,6-Tribromophenol le 11.5 Whtte the structures of the major products expected from the following Teactions: lononitration of 3-methylphenol Dinitration of 3-methylphenol ‘Mononttration of phenyl methanoate. Solution ‘The combined influence of -OH and -CH, groups determine the position of the incoming group. : OcOcH, OH OH OH ON. 0) © H, ies io; 0, . Kolbe's reaction ON, f@) and ‘CH 0, Phenioxide ion generated by treating phenol with sodium hydroxide Ne is even more reactive than phenol towards electrophilic aromatic substitution. Hence, it undergoes electrophilic substitution with carbon dioxide, a weak electrophile. Ortho hydroxybenzoic acid is formed as the main reaction product Chemistry 98425.on ONa on 2 ysragiaeens fad sey ee we ¥ tion a im ydroeet!?& Phenot with chloroform in the presence of eodtt 1 The ee gCHO group is introduced at ortho position of benzene This reaction is known as Reimer - Tiemann reaction. ‘The intermediate. lysed in the substituted ce sence of alka to produce salicy! lehyde. oH OH = n Nat O Nat CHO CHC, + aq NaOH HCL] CHO ys NaOH, —_> Salicylaldehyde Intermediate A Reaction &F Phenol with zine dust Penal 18 converted to benzene on heating with zinc dust. 1H ero Oxidation of Phenol with chromic luces a conjugated known as benzoquinone. 11.6 Give structures of the products you would expect when each of the y following alcohol reacts with (a) HCl -ZnCl, (b) HBr and (c) SOCl,. () Butan-1-ol es ({#)’2-Methylbutan-2-ol oe the major product of acid catalysed dehydration of 1 -methyleyclohexanol and (i) butan-1-ol 41.8 Ortho and para nitrophenols are more acidic than phenol. Draw the resonance structures of the corresponding phenoxide ions. 9 Write the equations involved in the following reactions:ea 4.5 Some Commercially ‘portant Alcohols Ingestion of ethanol acts on the central nervous ‘system. In moderate amounts, it affects Judgment and lowers inhibitions. Higher Chemistry 34 wa Methanol he prog hu Methanol, CH,OH, also known oOo meine ol} ne two cOMMeTClally jp, Methanol and ethanol are among tt alcohols, destructive distillation of wood. Produced by catalyiie hydrogenation of era at ys Pressure and temperature and 17 the pt ~oh catalyst, 2, Co + 2H, MBHO:CH0_, 4,011 200-300 ae 573-673 337K. It ig Methanol is a,colouflegs liquid and bolls at 3371 h polsonous in nature. Ingestion of even small quantities of Tethany titles causes even death, Mettan! ant can cause blindness and large qu! hes and chiefly for makey is used as a solvent in paints, varnis! formaldehyde. . Ethanol Ethanol, C,H,OH, is obtained commercially by fermentation, the far in molasses, sugar, oldest method is from sugars. The sug or fruits such as grapes is converted to.glucose and fructose, tom of which have the formula C;H,,00). in the presence of an enzym,. invertase. Glucose and fructose undergo fermentation in ,; Presence of another enzym hich is found i CHO, + HO BS 5C,H,0, + CatlnO, Glucose Fructose (CyHyO, 488° _, 90,1, 0H + 200, _In wine making, grapes are the source of sugars and Yeast. js gfapes ripen, the quantity of sugar increases and yeast grows on th, outer skin. When grapes are crushed, sugar and the enzyme come contact and fermentation starts. Fermentation takes place jy anaerobic conditions i.e. in absence of air. Carbon dioxide is Teleased during fermentation. ‘The action of zymase is inhibited once the percentage of alcotol sored exeoblo i person alr Got its Temontaton percent. Ifair gets into fermentation mixture, the oxygen ofair oxidises ethanol to ethanotc acid which in turn destroys the taste of alcoholic drinks. Ethanol is a colourless liquid with boiling point 351 K. Itis used as a solvent in paint industry and in the preparation of a numberof carbon compounds. The commercial alcohol is made unfit for. ers colour) a Nowadays, large quantities of ethanol are obtained by hydrationof ethene (Section 11.4).‘hydration there Alcohols under) eonols f protic acids TPR AerKO dehydration in the presence Of Ler oy ether depends ‘on w formation of the reaction product. anol 18 detyas othe reaction conditions. For example, CREE re resence of sulphuric at at CH,.CH, ny asa nae 7 wr H,S0, cH, 413K Ho The form: ation of eth bimolecular react (6.2) tm er is a nucleophilic volving the attack of aleohol molecule on a protonated alco} 7" H AD CH CHa ey CH CHO ttf CH,cH, at cHcn,6H > cHoH, Q- CH,CH, + H.0 Nas SAT CH.CH)— cH,CH,—> CH,CH-O-CH.CH, + H Acidic dehydration of alcohols, to give an alkene is also associated with substitution reaction to give an ether. The method is suitable for the preparation of ethers hat i rim: The alkyl group shor and the temperature be kept low. Otherwise the reaction favours the formation of alkene. The reaction follows S,1 path fowever, the dehydration of secondary and tertiary alcoho! to give corresponding ethers is unsuccessful as elimination competes over substitution and as a consequence, alkenes are easily formed. Can you explain why is bimolecular dehydration not appropriate for the preparation of ethyl methyl ether? —. wittiamson synthesis It is an important laboratory method for the preparation of eae eae oo symmetrical ant tnsymmetrical ethers. In this method, an alkyl ana halide is allowed to react with sodium alkoxide. R-X+R-ONa——> RY-R + Nax ofessor of Chemistry Ethers containing substituted alkyl groups (secondary ogértiary) j may also be prepared by this method. The reaction involves6,2wattack of an alkoxide ion on primary alky! halide. 345, Alcohols, Phenols and Bthers eeCH, cred Kn» beth Ir CH 3 cu, Hy tained ifthe alkyl halide j ; ee se any alkyl halides, elimination compe. substitution, Ifa te halide is used. an ween ee reactio1 nae e-anetypeg merci) CH,ONa with (CH9)sC-Br gives CH, . cH,-b-Br + Naij-CH,— fae +CHoH Hy ‘2-Methyipropene It is because alkoxides are not only nucleophiles but strong as well. They react with ally] halides leading to elimination rec 1.6 The following is not an appropriate reaction for the preparation t-butyl ethyl ether. e = C,H,ONa‘+ CH,—C-Cl —> cH,-C-OGH, on, CH, eit would be the major product of this reaction ? ‘Write a suitable reaction for the preparation of t-butylethy! ether, Solution The major product of the given reaction is 2-methylprop-1-ene, Its because sodium ethoxide is a strong nucleophile as well as a strong base. Thus elimination reaction predominates over substitution. CH, CH, lost w CH,-C- ONa + CH,CH,Cl —> SiC CH, cH, Phenols are also converted to ethers by this method. In this, phen! 1s used as the phenoxide molety. :ONa\ 0H nao Oo :O-R Chemistry,pagsical The C-O bonds in ethers are aipole net 6 Froperties — MOment. The wea Polar and thus, ethers Have AT het | | 6.3 polarit yreciab! Sem eae Where compare thse of the A 8 88 shown In the following cases: ' mia CHICHYACH, City 0-CyHly_ CHACH OH sf) M-Pentane Ethoxyethane _Butan-1-0) /K 309.1 307.6 390 The large diferenc ethers is due ¢ In bolling points of alcohols and to the presence of hydrogen bonding in alcohols. with water 1 : : cular mass; Both ethoxyethane and butan-1-0l 6° 1e 8. ., 7.5 an er 7 ‘Fespectively while penton ieaible with water. Can you explain i 1S essentially immi: Peale en thle Dbscraton Fis i oe to the ack that just Oe ike of bonds with wa Tiolecule aergenot ether can also form hydrogen meee as shown: > py chemical Me Cleavage.of C-0 bond in ethers Pe Reactions Ethers are the least reactive of the functional groups. The cleavage C-O bond in effers takes place unde drasue comaitions with excess of hydrogen halides, The reaction of dialkyl ether gives two allyl halide molecules, R-O-R + HX—> RX+R-OH R-OH+HX —>R-X+H,0 Alkyl aryl ethers are cleaved at the alkyl-oxygen bond due to the more stable aryl-oxygen bond. The reaction ylelds phenol and alkyl * halide, -R Hi sie O es , Ethers with two different alkyl groups are also cleaved in the same manner, R-o-R+HK—>R-X +R-o1 ler_of reactivity of hydrogen halides is as follows: HI> HBr > HCL\The cleavage of ethers takes place with concentrated or HBF at temperature. 847, Alcohols, Phenols and Etherstonatic ‘The reaction ofan ether wilh concentrated HI starts with Protonation of ether H. CH,CH, +H 2 CHO reagents are The reaction takes place with Be GF HI because ae Hctenty Rit Step 2: ibstituted carbon of th Todide ts a good nucleophile. It attacks the least su! Oren hol molecule by S,2 mech; fon formed in step 1 and displaces an alcoho! rn ae als, t-CH,CH, +1 Th with two the lus, in the cleavage of mixed ethers nature of alkyl groups. When Aloo and alkyl iodide formed, depend on the Secondly ai sme. dePeipent, iis the lower ally! UP that form x lodide (S,2 reaction). H Hy my T+CH,-o*cHcH, —> | r-cH,~-G "CCH | > CHT + CHC, When HI is in excess and the reaction is carried out at high temperatur, reacts with another molecule of HI and is converted to ethyl todige Step 3: ep Ae ky CH,CH, Ho +H-I @ CH,CH,~OQH + cH, (exe Che — CHCHI + HO However, when one ofthe alkyl group isa tertiary group, the hat formed is a tertiary halide. CHs CH Cacao +HI— CHOH +CHs—F-1 CHy CHy It is because in step 2 of the reaction, the departure of leaving gimp (HO-CH,) creates amore stable carbocation [(CH,sC'], and the reactin follows S,1 mechanism. oH ot |ncase of anisole, methyiphen! + + cH,-¢-6 —cH, 2% cu,—¢* + cxon | °xRUm ton, CuH,- 8 -CH 8 1H 1 u CH, formed by protonation of ether. Tht cH bond between O-CH, is weakt! I than the bond between ‘because the carbon of pheti! group is sp’ hybridised and thet is a partial double bond charac™Therefore the attack by Ion breaks O-CH bond to form” 1 hon do not react further to give halides because the SP” Eo a needed of phenol cannot ‘undergo nucleophilic substitution reat for conversion to the halide. ete major products that are formed by heating each of the following Example with HI. ethers CH, CH, I I a CHy-CHy-CH-CH,-O-CH,-CH, —(u) CH CH, CH-0-C CH; CH, CH, w Ore) Gis 0 ClHs-Cth-CH-CH.OH +CH,CH,I (i) CHjCH,CH,OH + CH CHCl Solution _ ot apo Ope | . re substitution . The alkoxy group (-OR) is ortho, para directing and activates the aromatic ring towards electrophilic substitution in the same way a5 in phenol. Ge +OR +0R dor :0R 3 <— =-> — — ava I I mM - Vv v _ ww alogenaton Phenylalkyl ethers undergo usual halogenation in the benzene ring, e.g., anisole undergoes bromination with bromine in ethanolc acid even in the absence of iron (Ill) bromide catalyst. It is due to the activation of b ring by the methoxy gFoup. Para isomer is obtained COON. CH, CH CHs Br, in Br Ethanoic acid i Anisole Br p-Bromoanisole o-Bromoanisole (Major) (minor)’ Alcohols, Phenols and Ethers\dergoes Friedel-Crans Friedel-Crafts reaction: Anisole un Le, the alkyl and acyl ae a Sea Sotto ‘ a reaction peeeme ner aluminium chloride (a Lewis mag = OCH, CH, Anhyd. AICI, Gee” 2-Methoxy- 41 Mate toluene ttuen (Minor) sc OCH oct +CH,COCL Ant. AIC Cock, Ethanoyl 2-Methoxy- 4Methoxy. chloride acetophenone Socrgptenone (Minor) ajor) Su Ntration: Anisole reacts with a mixture of concentrated ra and nitric dclds to yield a mixture of ortho and para nitroaniso.. o#0"0 2-Nitroanisole 4+ treacle (Minor) (Major) _Intext Questions prio ‘Write the reactions of Williamson synthesis of 2-ethoxy-3-methylpentane starting from ethanol and 3-methylpentan-2-ol. “11 Which of the following is an appropriate set of reactants for the preparation of 1-methoxy-4-nitrobenzene and why? ace . ONa 0 0 + CH,ONa + CHBr NO, Chemistry 350, A : |Lo o™ (ov (CH,),C-00,H, a, Summary according ) on the basis of the number of hydroxyl orn the -OH group is at bvbrdiation of the carbon atom, sp’ or sp" to j attached to the oxygen atom. * Ethers are classified on the basis of groups sottand 00 by tytn (1) by hydration of alkenes (i) in presence of an catalytic reduction and yo vation reaction (2) from carbonyl compounds by spared by (1) substitut (t) the action of Grignard reagents. Phenols may be Fe oup in aryl eulphosie atom in haloarenes and (i) sulphonic salts and (3) industrially from cre, oH SOUP (2) by hydrolysis of diazontum ‘Alcohols are higher bolling wee okole ant Phenols are classified ing than other classes of compounds, namely eT clcebsls 7 and rag kanes of comparable molecular masses. | The eh water takes perience nae to form intermolecular hydrogen bonding Alcohols and phenols are actéie in nature, Blectron withdrawing groupe in iol increase its acidic strength and electron releasing groups decrease it. Alcohols undergo nucleophilic substitution with hydrogen halides to yield allyl halides. Dehydration of alcohols gives alkenes, On oxidation, primary alcohols ee cae a oxidising agents and carboxylic’ acids with strong lc ererta na lary alcohols yield ketones. Tertiary alcohols are ‘The presence, of -OH group in phenols activates the aromatic ring towards electrophilic substitution and directs the incoming group to ortho and para positions due to resonance effect. Reimer-Tiemann reaction of phenol yields salicylaldehyde. In presence of sodium hydroxide, phenol generates phenoxide fon which is even more reactive than phenol. Thus, in alkaline medium, phenol undergoes Kolbe's reaction. . Ethers may be prepared by (i) dehydration of alcohols and (i) Williamson syathesis, The boiling points of ethers resemble those of alkanes while their solubility is comparable to those of alcohols having same molecular mass. The C-O bond in ethers can be cleaved by hydrogen halides. In electrophilic substitution, the alkoxy group activates the aromatic ring and directs the incoming group to ortho and para positions. (351, Alcohols, Phenols and Ethersa al oN Exercises ds: 11.1 Write IUPAC names of the following compoun CHy _ cH-CH,- CH-CH~CH,~ (0 Ctis-cH-cH-G-cHe = He-CH-CHE SPF Cc, T cae OH OH C,H, CHs OH CHy —-CH-CH- CH,-OH (it) CHy- CH-CH-CHs (iv) HO-CHy ‘ 2 on 6 OH OH OH CH, CH; CHy CH, OH OH w w) (wu) (wat) H ‘CH, oH CHy (tx) CH O-CH-CH-CH, (x) C,H,-O-C,H, CH, - 0-CH-CH;-CH, (xX) CH-0-CH,,(n-) (ail) CH-CH;-O-CH ‘CH-CH, cH, 11.2 Write structures of the compounds whose IUPAC names are as follows; -() 2-Methylbutan-2-ol (u) 1-Phenylpropan-2-ol (ii) 3,5-Dimethythexane -1, 3, 5+triol (tv) 2,3 - Diethylphenol () 1 ~ Ethoxypropane (vi) 2-Ethoxy-3-methylpentane (vil) Cyclohexylmethanol (viii) 3-Cyclohexylpentan-3-ol (x) 4-Chloro-3-ethylbutan-1-ol. (ix) Cyclopent-3-en-1-ol Draw the structures of all isomeric alcohols of molecular formula C;H,,0 y(t give their IUPAC names. Classify the isomers of alcohols in question 11.3 (i) as primary, secondary and tertiary alcohols. whe Explain why propanol has higher boiling point than that of the hydrocarbon, utane? yA nt are comparatively more soluble in water than hydrocarbons of parable molecular masses. Explain this fact. Orin is meant by hydroboration-oxidation reaction? Mlustrate it with an example. 7 Give the structures and IUPAC names of monohydric phenols of molecular a formula, C;H,0. 11 While separating a mixture of ortho and para nitrophenols by steam distillation, name. the isomer which will be steam volatile. Give reason. Ya cive the equations of reactions for the preparation of phenol from cumene. * {te chemical reaction for the preparation of phenol from chlorobenzene. 1 rit Yok wee the mechanism of hydration of ethene to yield ethanol. yu are given benzene, conc. H,SO, and NaOH. Write the equations for the ol Pe a gn of phenol using these reagents. Chemistry 352,4 Show How Will you syntheaige yy . T-phenylethanol from a suitable me alkene ‘cyolohexylmeth, a. Snel Using an alkyl halide by an Sy2 reaction ntan-1- pe ol using a suttable alkyl halide? 34 Give two reactions that show 2% of phenol with that of ethanal ” Site nature of phenol. Compare acidity 11.56 Explain how does the ~o7, activate It towards electophee sted 2 & carbon of benzene ring le substitution? 17 Give equations of the following rea, ctions: yy Af Oxidation of Propan-l-ol with alkaline KMnO, Bromine in CS, with phenol Dilute HNO, with Phenol, ‘Treat ) Treating Phenol wih chloroform in presence of aqueous NaOH. yi.18 Explain the following with an example, Kolbe's reaction. fi Retmer-Tiemann reaction, “gef Williamson ether synthesis, go Cnsymmetrical ether. Jie Write the mechanism of acid dehydration of ethanol to yield ethene. es the following conversions carried out? (i) pene -> Propan-2-ol, “afoaat chloride + Benzyl alcohol. Shen magnesium chloride + Propan-1-ol. . {Methyl magnesium bromide + 2-Methylpropan-2-ol. 1 Name, the reagents used in the following reactions: : ‘Oxidation of a primary alcohol to carboxylic acid. ae of a primary alcohol to aldehyde. jaf Bromination of phenol to 2,4,6-tribromophenol. CpBenay alcohol to benzoic acid. hydration of propan-2-ol to propene. {yj-Butan-2-one to butan-2-ol. | 92 Give reason for the higher boiling point of ethanol in comparison to methoxymethane. be §3581_Alcohols, Phenols and.3: 3 Give TUPAC names of the following Her 1 pm ONCOL ocH,cH.C cHocH,—cH—cH, i) cH wr c CH, CH, HE. ro CH,CH,CH,OCH, wa OCH, OCH, paration of the fo} 11.24 Write the names of reagents and equations for the pre lowing ethers by Williamson's synthesis: (u) Ethoxybenzene « () 1-Propoxypropane w) 1-Methoxyethane (i) 2-Methoxy-2-methylpropane ‘5 Illustrate with examples the pe nonin Preparation of certain types of ethers. 1-01? Write mechanie, “26 How 1s 1-propoxypropane synthesised from Proper wie of this reaction. tertiary alcoho 27 Preparation of ethers by acid dehydration of secondary OF * is not a suitable method. Give reason. ao ie the equation of the reaction of hydro ethyl ether. Air 1-propoxypropane_{y) methoxybenzene tivates “25 Explain the fact that in aryl alkyl ethers () the alkoxy, ghoul Sf ts the benzene ring towards electrophilic substitution A008 og the incoming substituents to ortho and para positions “80 Write the mechanism of the reaction of HI with methoxymethane. | Le equations of the following reactions: ) Friedel-Crafts reaction - allylation of anisole. itration of anisole. fomination of anisole in ethanolc acid medium. /) Friedel-Craft's acetylation of anisole. 4.32 Show how would you synthesise the following alcohols from appropriate alkenes? . A fe ont 11,25 When 3-methylbutan-2-0l is treated with HBr, the following reaction takes place: : of Williamson synthesis for y, Br CH,- CH- CH-CH, 1 1 CH, OH oy, Give a mechanism for this’ reaction, (Hint ; The secondary carbocation formed in step II rearranges to a mére stable tertiary carbocation by a hydride ion at from Srd carbon atom. 1 —HBY_, CHy-C=CH,-CH, 1