ALCOHOLS, PHENOLS AND ETHERS hols, phenols and ethers are structurally related compounds and may be AleMerivatives of water. Alcohols and phenols are obtained from water by fie ae of its hydrogens by alkyl and aryl groups, respectively. Ethers are from water by replacing both of its hydrogens by two alkyl, two aryl or one ‘gone aryl gTOUPS. OH B H-0-H R-O-H R-O-R water An alcohol an ether Phenol Both alcohols and phenols have the hydroxyl (-OH) functional groups while 4, nctional group of ether is oxo (-O-). In alcohols the hydroxyl.group is jubed to an aliphatic carbon atom, while in phenols the hydroxyl group is directly doched to an aromatic ring. ALCOHOLS UClassification of Alcohols. Compounds in which a hydroxyl group is attached to an aliphatic carbon tn are called alcohols. Alcohols are classified as monohydric, dihydric and pdr, depending upon the number of hydroxyl groups they contain in their niteules. Alcohols containing one hydroxyl group in their molecules are called tnchydric alcohols and the alcohols containing two and three hydroxyl groups different carbon atoms in their molecules are called dibydric and trihydric ‘abols, respectively. The alcohols having more than one hydroxyl group in their “tcules are generally called polyhydric alcohols. CH,OH GHLOH Eston d 2 CHOH toad HOH “OH gene’! Dikydrie alcohol CH20H P (two-OH group) Trihydric alcohol (three - OH group) beng uievarlo aloohols are further classified as primary (prim), vooondary (see-) ‘guy 'Y (tert-) aloohols depending on whother the - OH group is attached to a "Secondary or a tertiary carbon atom. me CH, plac goH °ScHOH CHy -¢- OH Mary alcoho) CHg CHy , Secondary alcohol merilary alcohol BOR ace ‘Scanned wth CamScanetGe 298 ORGANIG 92 Methods of preparation of Alcohols : 1. Hydrolysis of Alkyl Halides. Alkyl halides react with Gey hydroxide to form alcohols. Cty Wy. Ye H,O0 CHyCH, -Br + NaOH 429, cH,CH,OH + NaBr This method is of limited use because the alkyl halides are theme, obtained from alcohols. However, this method does have some industrial inp, particularly for the hydrolysis of those alkyl halides which are obtaineg by the halogenation of hydrocarbons. CH, CHCl CH,OH hv OH Toluene Benzyl chloride Benzyl alcohol 2. Hydration of Alkenes. The acid - catalyzed addition of an alcohol. The acids most commonly used to catalyze the hydration of alkene fulphuric acid and phosphoric acid. The addition of water te the double bond Markovnikov's rule. Alkenes react with sulphuric acid to produce allyl hye sulphates which on dilution with water followed by heating are hydrolas alcohols. ‘CH, = CH, + H,SO, — cH sCH,0SO,0H ps, CH,CH,0H +H,80, en CH, 1 CH;-C=CH, + HOH RE HESOs, CH, ~C-cH, 2-methyl-1-propene ou 2-methyl-2-propanol ot yield primary alcohols except a ‘ols. This method is generally used Acid - catalyzed hydration of alkenes do n yields enly secondary and tertiary aleoh Production of. alcohols on industrial scale, 3. Hydration through Hydroboratio, bond with the i Dinkvboranes, which on oxid, borane add; BH,. i diethyl ether or in tetrahy fiat crmborati drofuran (THF) with the -0) being attached to ane it addition of water to double bond), 8CH;CH =CHy + THF! BH, (CH,CH,CH,),B : F201 sy1,cH0 : ~H,0 4. By Oxymerouration Demerour, HH o00 i . ‘ation. Additi to an allen? 4 achieved indirectly through oxymercuration . dene Alkenes - ‘Seanne wth CamScanetyo, PHENOM AND JEN RE poke» eee orate #8 Wator-tolvahydhoturan wohution tf eae elt on rodtuction with Nalllty yield alec wy two coo pantkowrni boy actelition “Wand Ont eg MRO LOL a 8 ay Na nit : Renee > ROR OB, got OH ET TO yHeny On Reels : OH Theo CO CHL ou onols com Grignard Reagent, Urymard 1 (reneta with aldehydes or “eto form an Addition compound whieh on hydrolyaie with dilute acid gives Uhe Mraning alcohol, Kormakdehyde with Grignard aqovier other Chan formaldehyde form secondary alcohols and keto alcohols yal aygont gives primary alcohol wa yield iat esti 8 1 . \ Hot ye Ce Oe RMgX RG OMX Ms RCH, OL HOME X . primary alcohol u ul 1 . . Wyo! | ay C © O#RMRX — OMgX =) R-G- OW HOMgX CHy CHy 0 CHy a It 1 HyO" I €ily-C- Hy RMX > RG OMX “Py RG OW HOM X CHa CHa QBy tho action of Grignard reagent on epoxides. Grignard reagents react with atylene oxide (opoxide) to give an addition product which on hydrolysin yields mimary alcohol. Jy —) CHyCHyCH,OMgl He, CH;CH,CH,OH + Med! OH CHMgl + CHy = GH. A, Y Addition product 1-Propanol Ethylene oxide By the reduction of aldehydes, ketones, acide and esters. Alcohols can be “ily prepared by the reduction of aldehydes and ketones either by hydrogenation * Presence of metal catalyat such as Ni, Pt or Pd or by the use of chemical “cing agonta auch as Lidl Hy or NaRH,. RCHO + Hy a4 R-CH,OH ou.’ i cay My ~C-CHy +H, -NLy Hy -CH-CHy ‘tle hydrogenation has a drawback that it also reduces other functional groups Won C{,~C @C-, -C HN, -NOy ote, if present in the molecule, Raa eee ‘Seanne wih CamScanetORGANIC CHEMIsy», RY CH, CH =CHCHO + Ha _Niy CHjCH,CH,CH,OH : good yiled of aleebols fromm aldehydes, Ketones, sence thereal solution, One advan eters, acid chlorides and acid inhydrides in ethert a4 caters nt is thal jmjges not, reduce the olefinic bond and hence can ray. Bert aldehydes, ketones, ete, insaturated alcohols ether, (RCH,0),AlLi 41,0, 4RCHyOH + ANOH)s + LiOK 4RCOOH + 3LiAIHy —— (RCH,O)4 AILI + 2LiAIO2 + 42 L4H,0 4RCH,OH + AlOH)s 300 LiAH, gives Ve! unsaturate ARCHO + LiAIHy + LiOH i) LiALH. CHy(CHy)y4COOC2Hs oun, CHy(CHy)\«CH20H + CoHsOH (ii) Ho! Palmity] alcohol Ethyl plamitate CH,COOH OUiay Ha Leer, CH,CH,0H dc t is stable in aqueous solution Sodium borohydride (NaBH) is insoluble in ether bu (LiAIH, is destroyed by water). It is therefore generally used for the reduction of ‘ketones, NaBH, is much less reactive and therefore water-soluble aldehydes, and shore selective and reduces only aldehydes and ketones. 4RCHO + NaBH, —~> (RCH,0),BNa 3H20, 4RCH,OH +NaHBO3 NaB RCOCH,CH,COOH NaBH, RcHOHCH,CH,COOH 9.3 Industrial Preparation of Alcohols ‘At one time, most methaitol was produced by the was called "wood alcohol". Today. btained from natural gas. Methane nd at a temperature of 900°C. Manufacture of Methanol. destructive distillation of wood and therefore, fost methanol is manufactured from methane ol gas is passed with steam over Ni under pressure ai CH, + H,0() Nis co + 3H, The mixture of CO and Hp gases is passed over a heated co] under pressure to produce methanol, ; Cu, 260" Co + aH, £42607. 70atm, oH OH Manufacture of Ethanol, Ethanol is the alcohol of wine, boor, whiskey and ‘simile boverages and can bu made by tho fermentation of sugars in the presonce ® yeast. pper catalyst ‘The main sources of sugars are molasses (waste from cane-sugar industries): jes down 10 ‘The molasses is diluted with water so that the i concentration of sugar com aaa aS It is boiled and acid is added till its pH becomes 4. Tis solution known is mixed with yeast and kept at 36°C in large tanks, The following tions are involved in the fermentation of sugars. i ‘Scanned wth CamScanetNOLS AND ETHERS 01+ st) CoHy20, + CoHy,05 Glucose Fructose celln5 4 = 2C,H;OH + 2C0, source for sugar is starch, then the starchy materials are converted into eth ated with malt, from germinating barley and contains the enzyme ich is Ure “ghis enzyme converts starch into maltose which is then subjected to 9 wsortion with yeast to get ethanol Fe Diasta: (CiHlioOs)n +9/2 He RET Sy n/2 Crate Starch Maltose cylin + H,0 Maltese, 20,1,.0, Maltose glucose Zymase CiHuOs pont? 2CzHsOH+ 200, ‘The crude alcohol thus obtained is subjected to fractional distillation whereby ethanol called ‘rectified spirit’ is obtained. To obtain 100% pure ethanol, ‘ed. as absolute alcohol, it is mixed with benzene. Benzene forms a azeotrope 4h ethanol and water. Azeotropic distillation of the mixture gives three major ations, The first fraction contains a .mixture of benzene, ethanol and water, the ‘ead fraction contains benzene and ethanol and the final fraction is pure ethanol 1 industrial purposes is produced by the acid - catalyzed Most ethanol fo: siration of ethene. CH, -CH, + H,0 224, cH, cH, OH {Physical Properties of Alcohols toxic liquids and are miscible with water in all Lower alcohols are colourless, %ortions, Their water solubility may be attributed to intermolecular hydrogen i “ting between the molecules of alcohols and water. But with the increase in the ‘ster of carbon atoms, the solubility of alcohols in water decreases gradually ng isomeric aleohols, the solubility inereases with the increase in branching. For ma tert - butyl alcohol is cor:pletely miscible with water, but the other three i “Haleohols are only moderately soluble in water. £ H-0-----H---+--H-0 i i i 1 1 \ R R R H R H Hydrogen bonding between Hgdipgen bonding in leohol molecules Alec ‘choi and water molecules regular inerease with the inerease in the mage boiling points of alcohols show & ! : van der Waals interactions. Among - °f carbon atoms due to increase in ‘Scanned wth CamScanetORGANIC CHEN, 302. isomeric alcohols, as branching increases the boiling points decrease. Boiling ma of alcohols are much higher than those of the corresponding alkanes, The Tela, ~ high boiling points of alcohols can be attributed to association of molecules 4") hydrogen bonding. i Table 9.1 Physical Properties of Alcohols M.pt. Bopt Density Seiuhigy Name Formula (2O)_(2C)_(at 20°C) (6/100em? 85 Methanol CH,OH -97 65 0.792 : Ethanol CH,CH,OH -115 78.3 0.789 » 1-Propanol CH,CH,CH,OH -126 97.0 0.804 w 1-Butanol CH,(CH,),CH,OH -90 118.0 0.810 79 1-Pentanol CH,(CH,),CH,OH -79 138.0 0.815 23 isobutyl alcohol (CH3),CHCH,OH -108 108 0.802 100 sec-butyl alcohol CH,CH,CHOHCH, -114 99.5 0.807 125 tert - butyl alcohol (CHy);COH_ +25.5 82.5 0.789 . 9.5 Chemical Reactions of Alcohols Chemical reactions of alcohols involve either O-H or C-O bond cleavage Some of the important reactions of alcohols are described below. 1. Reaction with Active Metals (Alcohols as acids). Alcohols react with active metals like Na, K or Mg to form alkoxides with the evolution of hydrogen gas. 2CH3CH,OH + 2Na > 2CH,CH,O-Na + Hy Bases like NaH, NaNH, and Grignard reagents also react with alcohels forming alkoxide ions. : CH;CH,OH + NaH” —~> CH;CH,O-Ne& + Hy CH; CH, OH + Ne NH; —+ CH,CH,O-Ne’ + NH CyH, OH + CHyMg Br —> CH, + MgBr(OCy H,) i The above reactions show that aleohols are acidic in nature. This is beet | thee the O ~ H bond in aleohols is rolar and allows the release of the hydrogen #0 “as proton (H*). However, alcohols are slightly weaker acids than water. This * because the alkyl groups in alcohols have a electron - releasing inductive effect. T! release electrons towards the oxygen atom so that it becomes negatively This negative charge on oxygen makes the release of positive proton more diffi! “he order of acidity of alcohols is methyl > primary > secondary > tertiary alcohol 2, Resetion with carboxylic acids (esterification). Alcohols react x carboxylic acids on heating in the presence of catalytic amount of sulphuric #4 ‘Scanned wth CamScanetVOLS AND ETH. ction is known as esterificution, The reaction in rovernible ward di ‘veeton o ren.oving water as soon aus it ia formed Sone. H,SO, cHcooH + CyHj0H == one. H,S04' eer protenating agent as well as dehydrating agent. Only : alahols give | yields of esters, Steric hindrance. is an important factor Fpeniication. c a me ied alkyl group is either the alcohol or the acid will ter the rate of esterification and also shift the equilibrium more to the left a down - . the esterification reaction. The order of ractivity of an alcohol with given CHACOOCH, + HyO Fait acid is, therefore, as: Primay alcohol > Secondary alcohol > ‘Tertiary alcohol. © tye mechanism of esterification is as follows: | 0 +0H ou onl i] ’ M" 1 0, t con BS CH, -C-OH (> CH, -C-OH CoMON ou, C- Olle ,OH GH, - cy oH OH, ~ ° 1+ i -H’ a,-¢- OH ho CHy -¢ aIL, cH, -C-00,H5 OCoHs, OCoHs isReaction with Acid Halides and Acid Anhydrides (Acetylation) liwhols react with acid halides and acid anhydrides to form esters. CH, COCI + CHy CH, OH —> CH,COOCH,CHy + HCl 1a a {%,-C-0-C-CHy + CgH,0H —> CHs -C-OCzHy + CH,COOH (Asticanhydide Ethyl acetate Mormation of Inorganic Esters. Alcohols react with inorganic acids containiag ‘oa such as sulphuric acid and phosphoric acid, to form esters. “30H + HO-SO, OH +HOCH, 220+ CHyOSO,0CHs or (CHs):80. methyl sulphate ethylating agent. Phosphoric acid with les (5 sulphate (an ester) is used as a m f alcohol is used, dialkyl and tralkyl a |.0% yield alkyl phosphates. If excess o} 4 phosphoric acid are produced. Hi, hai CHOH EHSOH, (11,0),P0 : CH0),POOH » (CHOg PO, SEO? CH,OPO(OH)2 p,q (NO? " 6 Soar . : on dihydrogen Dimethyl hydrogen rimoths a es aD : phosphate , phosphate ares stant in biochemical reactions. , be |. phosphoric acid are extremely impo lides or Thionyl chlorides. tio f hal kuttions of Alcohols with phosphorv® ‘ i he at react with os aed ne hie pentahalides oF thionyl chlorid to form alkyl ‘Scanned wth CamScanetRGANIC CHEM)s 304 ORGANIC CHEMIS1; + 3CHgCH Br + HyPQs 3CH,CH,OH + PBry ——? 3CHgCH2Br + HyPOs cHi,0 __5 CH,CH,Br + POBr, + HBr CHjCH,0H + PBrs i CHyCH,OH + SOCl, ——> CHCH,C! + S02 * HC secondary and Tertiary alcohols Distinguish between primary, 6. Dehydration of Alcohols. When alcohols are heated with strong acids such , sulphuric acid, they undergo dehydration (elimination of water) to form alkenes, nT ease of dehydration is tert-> sec-> primary which is also the order of stability of tt carbonium ions. Conc. H,SO, vont 21, CH, =CH, + H20 CHjCH,OH —Ta59q 2 2 60 %. HSO. CH -CHy - CH-CH3 >> CH - CH = CH CH + H20 I 170°C OH CHa Hs 20 %. H,SO4 -C-0H 2 2""4, CH;-C=CH, + H,0. CHs ~G-OH aC 3 2 + He CHs 7. Reaction with Halogen acid (Lucas test) Alcohols react with halogen acid to form alkyl halides. The order of reactivity of the halogen acids is HI > HBr > HC1 and the order of reactivity of alcohols is tertiary > secondary > primary. Hydrogen chloride does not react with primary or secondary alcohols unless zinc chloride is added to the reaction mixture as well. Zinc chloride serves as a catalyst. A solution of zinc chloride in concentrated hydrochloric acid is used as the basis for a simple test (called the Lucas test) to differentiate between primary, secondary and tertiary alcohols. In this test, alcohols are treated with a solution of zinc chloride in conc. HCI (Lucas reagent) to form alkyl halides. Tertiary alcohols react with Lucas reagent immediately at room temperature to give an insoluble layer of the alkyl chloride, Secondary alcohols take several minutes to react and primary alcohols do not react with Lucas reagent unless they are heated. Zn Cl, + HCl RCH, OH “Fig; > ROH, CI + H,0 Ron 2nClz + HCl Rad ono “in S minutes’ _/CHO! + H20 Zn Cly + HCl (CH3)3 COH fame diately (CH3)3CCl + H,O 8, Oxidation. Acohols can be oxidized. The nature of the product depends on the type of alcohols and conditions of the reaction. Most widely used oxidizing agents a" CrO3 +CHsCOOH,K,Cr,0; + H2SO, or KMnO, + KOH. Oxidation of alcohols can be used to distinguish between primary, secondary and tertiary alcohols. The alcohol is treated at room temperature with K,Cr,0; in sulphuric acid (orange solution). ‘Scanned wth CamScanetops DUENOLS AND Eris ye sears 305 "alcohols are first oxidized to aldehydes a ae same number of carbon atoms and t and then to carboxylic acids pink Is give s and the orange sol e ot is give a ket ie solution turns green, at Ble leaner iene the same number of carbons and the tio ry alcohols are resistant to oxidation and solution ain orange KCr:07 + H2804, oy a 3CHO ——_—_ lo] Ki6n0; + 1,50,” CH,COOH Orange solution A becomes green K Cr,07 + HySO. " BoHoH ao CH; -C-CH3 cy Orange solution becomes green CHs | K Cr 07 + HySO ‘i ¢y-G-08| EES SCBn Fins range CH3 Most oxidizing reagents oxidizes a primary alcohol to the carboxylic acid mic oxide CrO3 in dilute H,SO, and acetone called the Jones enough to change the prim-alcohol to aldehyde and secondary ly. The Jones reagent has no effect on the double bonds present setly. Chro agent is milder dhol to ketone on) athe molecule. CH,CH,CH,OH ones reagent, ¢4,CH,CHO particularly useful for secondary alcohols to these conditions. The reaction proceeds through Cyomic acid oxidation is due to the saility of the product, ketones, initially formed chromate ester. H H HO MI RL + RL od oH +H,CrO,=—=_ >C- OHa+ HCrO; =o YY o-(7-0H ——» Scxidary aleohol R “OA chromate ester Ry © =0+ HACrOy R® Aketone teh svg different products when their ‘Dehydrogenation. Di ves of alcohols give different P = feta avalos cee Calgoo 2C. Primary and secondary alco tag dehydrogenation forming aldehydes and ketones, Se ‘ertiary Is are not dehydrogenated but “undergo dehydration forming 20°08" CH, CH, OH Cu, 300°C, ory, CHO + Hy ‘Scanned wth CamScanet306 EM OH 4 CH, ~CH-cH, S30PC, cH, - C- CH, + Hy CHy CHa CH, ~C- on C307, oy, au 1:0 CHy CHs 6.7 POLYHYDRIC ALCOHOLS Compounds containing more than one -OH group attached 0 the aly carbon atoms are called Polyhydric alcohols or polyols. They are fut! classified according to the number of -OH groups present in the molecules, | Polyhydric alcohols containing two and three -OH groups in their moeaig, are called dihydric alcohols (or diol) and trihydric alcohols (or triols), Tespectivels :| diol with both -OH groups attached to the same carbon are called-gem ~ diols, Te! Prefix gem comes from germinal. Most gem-diols are unstable and underp| Spontaneous decomposition to give the corresponding carbonyl compound and water | on o ¢ j i ~C-OH —> -C- +H,0 unstable carbonyl compound A diol having two hydroxyl groups present at 1,2-positions are called 1,244 or vicinal diol and commonly known as glycol. 9.7 Glycol (Ethylene glycol) Glycol is prepared as follows: 1. Acid-catalyzed hydrolysis of ethylene oxide which is made by the & oxidation of ethene at high temperature in the presence of a silver catalyst, produé glycol. (commercial) . CH CH, =CH, +40, 48, [", H,0° CH,OH 800°C" cH” CH,OH 2. By passing ethylene into cold dilute alkaline Potassium permanganate solution © CH, = CHy + (H,0 +0) 10, + OH CHa ~ GH OH OH H “dibromoethane with aq. NayCOy solution. 4 CH,Br I + 2Na,0 —» CEO, CH,Br ores i + 2Ni ‘Scanned wih CamScanet 3. By Hydrolysis of 1,2