10 n (@) Lucas reagent is conc. HCI+ anhyd. ZnCl, HoH coon © Con Eg do cnon coon ‘Osecl Meo ales (0) Methana C0+2H, 204 5 cHOH wate es Highpesse | Meta! (©) C,H,OH and CH; -O~CH, are isomers. (&) Example R-CH,~ CH; - OH ABO) »R-CH= CH, + HO (&) 5-10 % methanol and remaing ethanol is called ‘methylated spirit. Its also known as denatured alcohol because it is unfit for drinking, i 7 ny Nen-on a) or Ch (e) {2 Phenol sme solblein NaOH and forme sls Cyn 6 og Sodas fheoxie @ (b). Giycols are dihydric alcohols (having two hydroxy! ‘grougs), Ethylene glycol i the first member ofthis series, cH,OH CH;OH (epi pet) ay ©) ciy-cit-cih-d-chy bu ba 2 meth: 2,4 pentane Br, © wo) 8038 125 Ho) Br SO,H 1. 6. n. 9, Hints & Solutions o) @ @ © (b) o © = OF grup i highly asnting This ype of electrophillic substitution reaction at ortho and para past InC,H,0H, 3 CH CHD Due to presence of lone pair of electrons on axygen, there occurs a small decrease in bond angle from the ‘normal tetrahedral bond angle (109°28") ‘Water gas ismixed with halfits volume of hydrogen The ‘mixture is compressed to approximately 200 - 300 atmospheres. It is then passed over a catalyst [2n0 + Cr,0,] at 300°C. Methyl alcohol vapours are formed which are condensed Cosa asi, con -oH R- CH) ~ OH aon deine cisoonin Gate tr att of Seeman retest, pactdhcitbbatd teectacatvonsda genres 3 caboeaon ihc, ese ac ben extcr-c, 2 egcrcxon OMepr — Primary alcoho! on oxidation give aldehyde which on tarts Geiss gre cate oad whats ieee aac gi as. (CH;CH,CH,0H —!°L, prop aleahol cHicH,cHo —!°L,cH,cH,COoH Hye [0], Hac n-on Oh, =o aco ae ‘sopropytalabol Ethylene oxide when treated with Grignard Reagent ‘ives primary alcohol Ketone ela 2o Bo a @ O) © RR a @ Cit, -OMax 1H,CH = CHCH, + CH,CH,CH = CH, Ms (ajo product) (bint pod) X29 (d)_ Glycerol is dehydrated by using dehydrating agent like 0, or cane $0, o KHSO, bt KSSO, ie of 7 = CH=CH, - OH + R-CH-C Mae on t 30. (@) Lucas reagent is anhydrous ZnCl, and cone. HCI. Itis ‘The compounds containing CH3—C-OH or sed to distinguish berween 1°, 2° and 3° alcohols i 3° alcohols — immediate turbidity ° alcohols -> turbidity ater S minutes cu,-ler (=H, alkyl or ary) give CHL, wth |, 1? alcohols - No turbidity at room temp. and NaOH. CH Cone. HCI, HBr and cone. HCI + ZnCl, all are i ‘nucleophiles, thus convert aleohols to alkyl halides Cis Satta tertiary stabil Renee eae However, cone, H,PO, is a good dehydrating agent du, ‘which converts an aleohol tan alkene fastest reaction with Lucas reagent NaBH, and LiAIH, attacks only carbonyl group and 31. (b) Phenol is more acidic than ethanol, Phenols can turn Faduce i neicocbal goo be litmus pape red but ethanol cannot do so. 32. (@ Solubility ofalcohol in water decreases with increase Cyl CH= cHCHO MHL, in molecular mass due to increase in water repelling coeds ally! partinaleohal cH, HOH Culls-CH=CHCHOH 3 (9 | 2 sHocl — [2 Simic ash Hy cH,c Phenol has active (acidic) hydrogen soit reacts with cH,OH CCH,Mal to give CH, and not anisole Nalco, CetigOH +CHjMgl —+CHt, +CeH1gOMal on CH - OH fe Since the compound is formed by hydration of an 54 co. alkene, togetthestructureofalkeneremoveamolecule ©) CHyChRCHEHAOH of water fom the alcohol as Hy cH cH, pce 82, cH, = CHCH, —— cH CH,CHCH, ==", CH, cH, 6-H. i" Tops CHA CHCH 2 5 CHa “E-CH soto lst (2 atweaton) cHOH CH CH os 1 | i) > 2c. cons cu cu—iensel nena CH,OH CHI CHI 3s) COM Ho ea, ie ny oa % @ cH; All the compounds except (C), we. | cio -c-ciotae ameddring seton of He £01 lycerol with excess HI cH 10 37. (b)_lodoform test can differentiate between ethyl alcohol Csecnon Ss and methyl alcohol. Ethyl aleoho! contains CH,CO Hy troup sot gives lodoform test whereas meth alechol does not give this test38 aL o uty ~Cr- City AEE CH -C- Cs on (A) 2-propanot acetone PL cr,coon seat aid () cHon- =", goons +HoOORA, ) (B) (&) c,Hson 4 cHcH,cr cH,cH,cN—"2"_,cH,CH,COOH one (©) Because of larger (three per molecule) number of intermolecular hydrogen bonding in case of glycerol (CH,OH- CHOH - CH, OH )as compared to ethanol (CH,CH,OH), the attraction between molecules of glycerol is more than that of molecules of ethanol. Due 1 this glycerol is more viscous than ethanol HH oH © Naot Na 0; 1H COOH ryote Salicylic cid ‘The intermediate is carbocation which is destabiised by C=O group (present on c-carban to the -OH group) in the first three cases. In (d), at-hydrogen is ‘more acidic which can be removed as water. Moreover, the positive charge on the intermediate carbocation is relatively away from the C=O group. ‘Among the given compounds only CH,OH does not give iadoform reaction (@) Due to H-bonding boiling point of C,H,OH is much higher than isomeric (CH,),0. dH Na © 00H, cs 5 coon crepe oO a Salicylate a Ne cl, -cicr, MOH, @ @ ) SL O) @ @ © © Na CH(OH); 2200, He a, Fi a HO Yi iH "HO. Reimer-Tiemann reaction ‘Aldol condensation is carried out on aldehydes or kedones having a-hydrogen atom in presence of base which abstracts a- H atom from aldchyde/ketane to form corresponding carbanion which is stabilised by resonance ° —™ u on HEH, cH ° o i I Hy0+ [CHy" -C- HCH; =C- 1] With Br, water, phenol gives? 4, 6-titromophencl. ou oO + ena 24, Tebronephenal CH.NH, cHOH + HNO, —> + Neo ‘Alkyl halides can be prepared by treating alcohol with soa CH,CH,0H +S0Cl, — CH CH C1+S0, + HCI “This reaction is known as Darzen's procedure Note» SOBr, and SOl, are not used in this reaction because SOBr, is less stable and SOL; does not exist. Perkin reaction involves reaction of aromatic aldehyde ‘with aliphatic acid anhydride in presence of sodium salt of the same acid as anhydride to form a, B- unsaturated acid. Celts CHO + (CHsCO), 0 SLO 5 CgHsCH = CHCOOH +CH;COOH ‘Wurtz reaction involves the reaction ofan alkyl halide with metallic sodium in dry ether to form higher hydrocarbon.84 © @ © @ © © @ @ ay RX+2Na+XR —S2_5R -R42NaX Cannizzaro reaction is given by aldehydes having no hydrogen atom to form a mixture of alechol and sodium salt of the acid. Iisa disproportionation reaction in which half ofthe aldehyde molecules are oxidised and other half reduced in presence of NaOH. 2CgHsCHO 2H, (CeHsCH30H + CgHsCOONa CCaisen reaction is the self condensation of esters having a-hydrogen atom in presence of strong base to ‘orm keto ester. 2CH,COOC,H, — SO, CHONe ° | cHydcH,coocH, " my oO +200 ent — ‘The most suitable reagent for converting aleohol to acetaldehyde is PCC. Other reagent will convert alcohol toacid b-bd Resonance sabato of phenaside ion (convent bare of penal) Conjugate base of ethyl alcohol, ie, C3H,0" does not show resonance. on o” ‘COOH (oman ah NICO) sche seid (eros CO, oh NaHCO) ‘o-Nitropheno! as intramolecular H-bonding ‘The reaction is an example of electrophilic aromatic substitution. Although both OCH, and CH, groups are op-directing, the OCH, group dominates. Produet (0) is favoured because the new coming group (Br) experiences east hindrance. CgHsONa+CgHs1—*-> CgHjOCgHs +Nal Pheneole In case of unsymmetrical ethers, the site of cleavage depends on the nature of alkyl group eg. Ciy-0-CyHy +t 278. cHyL+ CHO ‘Thealkyl halide is formed ftom the smaller alkyl group, 61 a CH ~C-CH; ~C-CH; CH ~ ‘ee fem a 6s 6 a. © © ° @) ) o) @ @ o © However, in case of tertiary alkyl ether following, reaction occurs. CH, -OC(CH,); +41 22K, serbuyl thy eer (CH,),C-1+CH,O8 ‘The alkyl halide is formed ftom the tertiary alkyl group and the cleavage of such ethers occurs by Sy1 ‘mechanism as the products controlled by the formation cof more stable intermediate tertiary carbocation from protonated ether OH O-R io mx Atay oO ox Williamson’s synthesis - CH; -CH; -ONa+C1-CH, =CH; > CH; ~CH; ~O-CH, ~CH; ‘Maximum enol content isin structure (b) because here the enol form is stabilised by H-bonding, ° 1 Acetone Dehydration of alcohols gives ethers CH,OH + HOOCCH; —> C,H,COOCH, +H,0 ethyl acetate (ester) ‘ty smell Reaction of sodium ethoxide with ethyl iodide to produce diethyl ether isknown as Williamson synthesis Itis a nucleophilic substitution reaction and proceeds viaS,2 mechanism, Jn Williamson's synthesis the reaction of alkyl halides with sodium alkoxwes give ethers. However, if the allyl halide is 3°, undergoes elmination to give an alkene cuckoo + qnptenm CyHs -O-CpHs +02 SR CH -CH(OOH)-0-CoHHs (CH,OCH, and C,HJOCH, are gases while CHOC H; (b.p 308K)is low boiling liquid Carboxylic acids ar stronger acids than phenols which intumare stronger than alcohols. Outofbenz aleohol and rifluoroethanol, the later is more acidic due tothe