ALCOHOL, PHENOLS & ETHERS [JEE ADVANCED PREVIOUS YEAR SOLVED PAPERS] JEE ADVANCED Single Correct Answer Type BHCC —0GH, Cay 1. Ethyl alcohol is heated with cone. H,S0, the product, ° formed is & GH 4. GH, (ITE 1980)Which of the following is soluble in water? a. CS, b. HOH CCl, 4. CHCl, (IIT-JEE 1980) . Which ofthe following is basic? a. CH,—CH,—OH ce. H-O-0-H b, OH—CH,—CH,—OH d. H,C—C—OH i ° (IT-JEE 1981) ‘The compound which reacts fastest with Lucas reagent at room temperature is a. butan-1-ol », butan-2-01 2methylpropan-I-old. 2-methylpropan-2-o1 (IT-JEE 1981) ‘A.compound that gives a positive iodoform testis a. L-pentanol . 2-pentanone e. 3pentanone 4. pentanal (IT-JEE 1982) 5. Diethyl ether on heating with cone. HI gives two moles of ‘a. ethanol », iodoform . ethyl iodide 4. methyl iodide (IT-JEE 1983) 2 ‘An industrial method of preparation of methanol is ‘a. catalytic reduction of carbon monoxide in presence of Zx0-Cr,0; by reacting methane with team at 900°C witha nickel catalyst ce. by reducing formaldehyde with lithium aluminium hydride 4. by reacting formaldehyde with aqueous sodium hydroxide solution (IIT-JEE 1984) ‘When phenols treated with excess bromine water, it gives. ‘a. mbromophenol —_b. o-and p-bromophenol ‘e. 2,4-dibromophenol d. 2, 4, 6-tribromophenol (IT-JEE 1984) ). HBr reacts fastest with a. 2-methylpropan-2-ol bi propan-I-ol © propan-2-o1 4. 2-methylpropan-I-ol (IT-JEE 1986) 10, ML. 2 1B ‘Which ofthe following compounds ‘methyl ethyl ketone? ized to prepare a, 2-Propanol b 1-Butanol fe. 2-Butanol @. Butyl alcohol (IT-JEE 1987) Hydrogen bonding is maximum in ‘a. ethanol ’. diethyl ether . ethyl chloride 4, triethyl amine (IT-JEE 1987) In CHjCH,OH, the bond that undergoes heterolytic cleavage most readily is acN bCo © CH 4. 0-H (ITT-JEE 1988) Phenol reacts with bromine in carbon disulphide at low temperature to give 16. 7. 19. '. o-and p-bromophenol 4. 2.4.6rbromophenol (UT-JEE 1988) Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH gives a. o-cresol b. peeresol . 2,4-dihydroxytoluene d. benzoic acid (IT-JEE 1990) ‘The products of combustion ofan aliphatic thiol (RHS) at 298 K are a. COs(g), H,O(g), and SOx(2) b. CO,(g), H,0(), and SOx(8) € COx(), H;00), and SO,(g) 4. CO,{g), H,0(), and SO;0) (IT-JEE 1992) ‘When phenol is reacted with CHC1, and NaOH followed by acidification, salicylaldehyde is obtained. Which ofthe following species are involved in the above-mentioned reaction as inermedae? O% Se a ° (fen a Be (ITJEE 1995) “The order of reactivity ofthe following alcohols towards cone. HCLis re | oH oh - m-bromophenol ‘e. p-bromiphenol OH 7 ow - Istoms b I>Ill>I>1V ce IV>Ml>i>1— d. IV>Il> I> (IT.JEE 1997) Benzene diazonium chloride on reaction with phenol in ‘basic medium gives 1. diphenyl ether €. chlorobenzene . p-hydroxy azobenzene . benzene (IIT-JEE 1998) ‘The compound that will react most readily with NaOH to form methanol is a (CH) NT b. CHOCH, © (CH)ST 4. (CHCl (IT-JEE 2001) |-Propanol ané 2-propanol can be best distinguished by 1. oxidation with alkaline KMnO, followed by reaction with Fehling solution . oxidation with acidic dichromate followed by reaction ‘with Fehling solution oxidation by heating with copper followed by reaction with Fehling solution 4. oxidation with concentrated H,SO, followed by reaction with Fehling solution (TIT-JEE 2001)on = + CHS! Tao Cam” 10 = 1. CyHOCH, b. GH,OCH, CHOC Hs 4. C,Hy1 (ITEJEE 2002) 22, The product of acid catalyzed hydration of2-phenylpropene ‘a. 3-phetyl-2-propanol b. 1I-phenyl-2-propanol 2phenyl-2-propanol d. 2-phenyl-I-propanol (IIT-JEE 2004) 23, Thebest method to prepare cyclohexene from cyclohexanol is by using a conc. HCI-+ZaCl; . HBr i. conc. HyPO, 4. cone. HCI (UT-JEE 2005) 24. The increasing order of boiling points of the below. ‘mentioned alcohols is L. 1,2-dihydroxybenzene IL. 1,3-dihydroxybenzene TIL. 1,4-dihydroxybenzene TV. Hydroxybenzene a [. “CHC, ca, is © CC, 3. The structure of the interme 8x 6Ni a C b o Hy Hy 6 a CH,OH g 8x e . LCC, Hs A tertiary alcohol H upon acid catalysed dehydration gives a Passage 2: ‘product I. Ozonolysis of [leads to compounds J and K. Com= ‘pound J upon reaction with KOH gives benzyl alcohol and ‘compound L, whereas K on reaction with KOH gives only M. ‘ur ae Q ne \ on 4. Compound H is formed by the reaction of ° ° JK mmo & 3 smc & ow San ° ° * © J armcttane © NS a co ‘The structure of compound lis PhCH HC. _ Ph 2 =< Bad wm Sn Ph chy Hse © wom wa 6. The structures of compounds J, K and L respectively, are ‘&. PhCOCH,, PHCHCOCH, and PhCH,COO”K* >. PhCHO, PhCH,CHO and PhCOO- K* © PhCOCH,, PhCH,CHO and CH,COO” K* 4. PhCHO, PhCOCH, and PRCOO” K*Matching Column Type Following questions have matching lists. The codes for the lists have choices (a), (b) (c), and (d) out of which ONLY ONE is correct. 1. Match the following, choosing one item from column I and the appropriate item from Column IL (UT JEE 1983) Column 1 ‘Column T (@) Williamson's synthesis | (p) er Aleohol @)Newal FeCl test_—_|(q) Ether (© Laces test (©) Phenol 2, Match the chemical conversions in List I with the appropriate reagents in List I and select the correct answer using the code given below the lists: (JEE Advanced 2013) o> a— = ai @ om —- —on? MOF © CY. -o 3. Be ed —X 4. OBR . Codes: © @ © 6 az3go14 bese cog ttta <3 24 1 Integer Answer Type 1, The number of resonance structures for N is > COC iat ce cdemet m8 2. The number of hydroxyl group(s) in Q is CIEE Advaned 2015) a te KMaO ences) WOO) ep cmmestmnicg HOw en Assertion-Reasoning Type 1, Read the following statement and explanation and answer as per the options given below: Statement (8): Solubility ofn-alcoholsin water decreases ‘with inerease in molecular weight. Explanation (E): The relative proportion of the ‘hydrocarbon part in alcohols increases with increasing molecular weight which permits enhanced hydrogen bonding with water. a. Both (S) and (F) are correct and (B) is the correct explanation of (S), ’b. Both (S) and (E) are correct but (E) is not the correct explanation of (S). . (S) is correct but (E) is wrong. 4. (S)is wrong but (E)iscorrect. (INT-JEE 1988) Fill in the Blanks Type 1, Ethanol vapour is passed over heated copper and the product is treated with aqueous NaOH. The final product, is (IT-JEE 1983) 2. The acidity of phenol is due to the of its anion, (IT-JEE 1984) 3. Formation of phenol from chlorobenzene is an example of Aromatic substitution. (IIT-JEE 1989) 44. Phenol is acidic because of resonance stabilization ofits ‘conjugate base, namely UTE-JEE 1990) 5. Aliphatic ethers are purified by shaking with a solution of ferrous salt to remove which are formed on prolonged standing in contact with air, T-JEE 1992) 6. Glycerine contains one hydroxyl group. (IT-JEE 1997) True/False Type 1. The yield oFketone when a secondary alcohol is oxidised ‘smote than the vied of aldehyde when a primary alcohol is oxidise. IT-JEE 1983) 2. Sodium ethoxide is prepared by reacting ethanol with ‘aqueous sodium hydroxide. AIT-JEE 1986) Subjective Type 1. An organic liquid (A), containing C, H and O with boiling point: 78°C. and possessing a rather pleasant odour, on heating with concentrated suphuric acid gives a gaseous product (B)-with the empirical formula, CH, °B: decolourises bromine water as well as alkaline KMnO, solution and takes up one mole of Hp (per mole of “B") in the presence of finely divided nickel at high temperature Identify the substances ‘A’ and °B'._(ITF-JEE 1979), 2 A’compound (X) containing C. H and O is unreactive towards sodium. It does not add bromine. Italso does not react with Schiff’ reagent, On refluxing with an excess of hydriodic acid, (X) yields only one organic product (Y). ‘on hydrolysis, (Y) yields anew compound (Z) which can bbe converted into (Y) by reaction with red phosphorus and iodine. The compound (Z) on oxidation with potassium permanganate gives a carboxylic acid, The equivalent ‘weight of this acid is 60, What are the compounds (X), (¥) and (Z)? Write chemical equations leading to the ‘conversion of (X) 10 (¥). (IT-JEE 1981)13. Write the structural formula of the main organic product, formed when: ethanol > (UIT-JEE 1985) 4, Predict the structure of the product in the following reaction (LIT-JEE 1996) Ph _ww waar C 5. Indicate steps which would convert: (IITJEE 1982) i. propanol from-2-propanol (in three steps) fi, ethylaleohol to vinyl acetate (in not more than 6 steps) ‘Complete the following with appropriate reagent: (UT-JEE 2003) 7. ‘State with balanced equations what happens when: ‘Acetic anhydride reacts with phenol in presence of a base. (IT-JEE 1982) ‘What happens when: (IIT-JEE 1991) Ethylene glycol is obtained by the reaction of ethylene ‘with potassium permanganate. 9. Give reasons for the following: (UT-JEE 1987) 4. Sodium metal can be used for drying diethyl ether but ‘ot ethanol. 4. Phenol is an acid but it does not react with sodium bicarbonate 10, Give reason in one or two sentences forthe following. ‘Acid catalysed dehydration of butanol is faster than that of n-butanol. (IIT-JEE 1988) 11. An alcohol A, when heated with cone. H,S0, gives an ‘alkene B, When B is bubbled through bromine water and the product obtained is dehydrohalogenated with excess of sodamide, a new compound Cis obtained. The compound C gives D when treated with warm dilute of H3S0, in presence of HgSO,. D can also be obtained either by oxidizing A with KMaO, or from acetic acid through its calcium salt. identify A, B,C and D. (IIT-JEE 1983) 12, Show witha balanced equation, what happens when the “p-xylene is reacted with concentrated sulphuric acid and the resultant product is fused with KOH’. (OT-JEE 1984) 13, A compound of molecular formula C,H0 is insoluble water and dilute sodium bicarbonate but dissolves in dilute aqueous sodium hydroxide. On treatment with bromine water, it readily gives a precipitate of, CyHLOBry. Write down the structure of the compound. (IIT-JEE 1985) 14, Give a chemical testsuggest a reagent to distinguish between methanol and ethanol. (IIT-JEE 1985) 15, Given reason in one o two sentences for the following “o-nitrophenol i steam volatile, whereas p-nitrophenol is not’ (IIT-JEE 1985) 16. Suggest a reason forthe large difference between boiling point of butanol and butaral, although they have almost the same solubility in water. (IT-JEE 1985) 117. Indicate steps which would conver: i. Phenol to acetophenone HL Acetic acid tosert-butyl alcohol (IIT-JEE 1989) 18, Complete the following with appropriate structures (IT-JEE 1992) on on cHO t(o) 19. Compound X' (molecular formula, C,H,0) does no react appreciably with Lucas reagent at room temperature but fives a precipitate with ammonical silver nitrate. With excess of MeMgBr, 0.42 g of "X” gives 224 ml of CH, at ‘STP. Treatment of "X’ with Hy in presence of Pt catalyst followed by boiling with excess HI, gives -pentane. ‘Suggest structure for °X’ and write the equation involved (IT-JEE 1992) 20, When r-butanol and n-butanol are separately treated with «few drops of dilute KMnO,, in one case only the purple colour disappears and a brown precipitate is formed. Which of the two alcohols give the above reaction and. ‘what isthe brown precipitate? (IT-JEE 1994) 21. Predict the product inthe following reactions: (IIT.JEE 1994) CH +(CHy),CHCH,OH BS 5... 22, 3,3-Dimethylbutan-2-ol loses a molecule of water in the presence of concentrated sulphuric acid to give {etramethylethylene as a major product. Suggests suitable ‘mechanism. (IT-JEE 1996) 23, A compound D (CyHy0) upon treatment with alkaline solution of iodine gives a yellow precipitate. The filtrate ‘on acidification gives a white solid E (C;H,0,). Write the structures of D and E and explain the formation of E. (IIT-JEE 1996) An optically active alcohol A (C,H,,0) absorbs two moles of hydrogen per mole of A upon catalytic hydrogenation and gives a product B. The compound B is resistant 10 ‘oxidation by CrO, and does not show any optical activity Deduce the structures of Aand B. —(IIT-JEE 1996) 25, Predict the stroctues ofthe intermediates/products in the following reaction sequence: (IT-JEE 1996) gome 0. C}+[ So tigiea. OO) tiie o 26. Predict the major product inthe following reactions (IIT-JEE 1997) dango ° Oo 1 ~ ome 27, 2,2-Dimethyloxirane can be cleaved by acid (H). Write ‘mechanism, (UT-JEE 1997) 28 Which of the following is the correct method for symhesizing methyl-e-butyl ether and why’? (IT.JEE 1997) 1. (CHy,CBr + NaOMe > fi, CH,Br + NaO -1-Bu > 29, Write the intermediate steps for each of the following reaction. (IIT-JEE 1998) 31. A biologically active compound, bombykol (CH) {s obtained from a natural source. The structure of the ‘compound is determined by the following reactions. (IT.JEE 2002) ‘a, On hydrogenation, bombykol gives a compound A. CyH,.0. which reacts with acetic anhydride to give anester. 'b, Bombykol also reacts with acetic anhydride to give another ester, which on oxidative ozonolysis (Oy H,0,) gives a mixture of butanoie acid, oxalic acid and 10-acetoxydecanoie acid, Determine the number of double bonds in bombykol Write the structures of compound A and bombykol. How ‘many geometrical isomers are possible for bombykol? 32, An organic compound (P) of molecular formula C,H Ois tweated with dil, H,SO, to give two compounds (Q) and (R) both of which respond iodoform test. The rate of reaction ‘of (P) with dil, HjS0, is 10" faster than the reaction of ‘ethylene with dil. H,S0,, Identify the organic compounds, (P), (Q) and (R) und explain the extra reactivity of (P) (QIT-JEE 2008) 30, How would you synthesis 4-methoxyphenol from 33 Kdemify(X) and (¥) in the following reaction sequence. ‘bromobenzene in NOT more than five steps Sate clearly (II JEE 2008) the reagents used in each and show the structures of a ° intermediate compounds in your synthetic scheme. *Oon dcn, IT-JEE 2001) CD 00 epee! Answer Key IEE Advanced Matching Column Type Poa anny eee 1. (a) (ith) Vins (0) 1p) Ba Le. ub Ba. 44. 5b Integer Answer Type 6c. ha Bd a. 10. c. 1 24 ha Ba Wh wd 1b Assertion-Reasoning Type ed Ihe RR a Me c. ae asic zat oe aid Fill in the Blanks Type M4 Mme Ba. 1. aldol (B-hydroxybutanal) “Multiple Correct Answers Type 2 resonance sain | nucleophilic 4. Phenoxide fon Lae 2ad 2b dad Sac 6b. Te aed. 8. a,b,c. etree: SuSeeacieny TruelFalse Type Linked Comprehension Type 1. Tre 2. False he de 6. Bho 4b SaHints and Solutions JEE ADVANCED Single Correct Answer Type Je, 203H,0H S25 cH +10 2b, Enanol (C,H,OH) forms hydrogen bonding with water Hence, is soluble in water 4.8 te ote recy of abo wk Lacs reagents ter > ten Ua et is bated on te difeece inh tee yes fo tots ving 6c ls carbon) owas Lacs agen (2 mi tv ot ony aad syns de de) ‘oom tempers. ROH +HCI 224 ReI+H,0 The eri sols pda bi ned, he son yas ge uty wit 3-10 ten nde pany ‘olson give at al atom terperte ence 2-mainprapa-2-0 (a ao ress ses 5.0. Compound ving CCH, group show psive odo form test. " ° Hence, CHy—CHly~CH,—C—CH (etanone 2) gives this test. ‘ ° CHLOGH, +21 Ys 26,H 4,0 Tea, CON, +H, 22 cH,oH on on Be Br a nian) Br 3 Ae Titenopteaa ‘coe pe ‘The -OH group in pheno, being activating group, feciiates Secondary > Primary due to stability of imermediste carbocation, 10.¢. Secondary alcohols oxidize to produce ketone. CH,CHOHCH,CH, —°- cH,CocH,CH, 1. H-bonding s maximum in ethanol because His bonded to high EN clement ic. O atom. 12.4, Reaction of alcohol with Na indicates that (O—H) bond is ‘most realy broken (2ROH + 2Na —» 2RONa + H,) ud enc &* 8 14.4. CyH,CH, Chere) Es Cyt, CCI, EE, c,H,C(01, #4 c,H,COOH 15.b, RSH, e., CH, SH) + 30,8) -» COs) + S048) +24,00) 46-4. Riemer-Tiemann reaction involves electrophilic substation ‘on the highly reactive phenoxide ring HCCI, + OH" + H,0+":Cc1, Ec,—er+ cc aa. a Ole ymin Abenaeede 17.€. The order of reactivity depends upon the stability ofthe carbo- cations formed, Stability of carbocations is in the order. CH, CHCH, < FCH,CH, CHCH, I> 1>1 18. (O)-sen-a+#{O)-onet ean aad19. a, Compound (CH,),N'T is mos reactive dv to) beter lea ing group, andi) de tothe fet that the methyl group, with positive N, is mot more electron deficient Hence this group is more reactive towards nucleophile, OH” > CHON + (CH) N + (CHt)y- ROH CHYOHA(CH)N CH 20. Feblng slton ina weak oxidizing agent which can oxiire aliphat ldehyde bat ot ketone Primary alohols undergo oxtion wih ltalne KMOO,, acti chromate and cone. SO, give aids, whereas wth Cathey give aldehydes 4 CHCH,CHO vp rang tn) CH,CHOHCH,—>CH,COCH, ce Fates in) 21. b, This reaction is an example of Williamson's synthesis. CHO" will abstract proton from phenol converting the later Into phenoxide ion. But C,H,O" isa better nucleophile than (CeHjO" (Phenoxide) ion because inthe former the negative charge is localised aver oxygen. while in the late laed over the whole molecular framework. So. {on that would make nucleophilic attack at ethyl iodide 10 give iehy| ether (Williamson's synthesis). 22.6. Addition of water to 2-phenylpropene follows Markownikov's rule. » » t HEE cH, — CCH, on Bb. Cone. HC, HBr and conc. HCI » Za all ae ceo, thas convert alehols fo aig hades. However, cone. HPO, isa good dehydrating agen which convens an alcool f0 a0 aiken: 24.4. Among the given compounds, hydoxybenzene (V) has least tila ss tnd therefore poss est baling por. Among the three isomeric ditydonybezcnes. 2dihydrosben- eve foms intraneleculr H boning with the res wl tet form internleclr H-bonding lean to lowest boing Print. On the other hand 1.dhydronytenzene (I) and La Eitydrorybemene i) do ot undergo chelation, hence hey wil invave extensive inermaecula HHtonding eating 10 Fisher bling pint. Further intrmolecular hydrogen bond. ings stongetin he p-somer tha the isomer ence former as highest bp Thos the decreasing order of bling ponte is trsisi, 25,d. PASO;H + NaHCO, —+ PhSO,Na+ H,0+ CO, P-NOs —Cjlle-OH + NaHCO, -> p NO; ~ GH,ONs +H,0 +00, Since bot (1) and (Il) are stronger acids than HyCOs, they ate ‘capable of evolving CO, with NaHCO,, HCO? +H® —+H,0+C0,7 2.8. Crone cle: ye) + CHB 27.6. This reaction proceeds via carbocation OCH, group has 4R effect It increases the stability of the carbocation. Cor oo7e- gro Multiple Correct Answers Type Lage -AGids are more acidic than phenol and phenols are more acidic than alcohols. p-Nitrophenot i stronger acid than phenol dve 1o-R and -L effects p-Methoxyphenol is weaker than phenol de to (+R and I) eects. So, phenol is less acidic than acetic acid and p-itopheno ‘The reaction involves electrophilic substitution on the highly reactive pheaoxde ion, Here the electophile is dichlorocarbene formed by the action ‘of song alkali on chloroform. CHC, +O + C5 +H,0 (Reaction occurs due 10 Ligh acidic stength of Hof CHC) CCF CC, +c able duct doit resonance) ann be OR f on oy. oo i Sateende (onan) a “The mechanism of this reaction is represented as follows. cn cfRen-{)-on > csc n-)-on secaictieg- 7) 4d. ‘The aromatic ethers ae cleaved to give phenol as one of the ‘roduets as C—O bond i resonance stabilize.Croc eC )-on site) Saye (0° is O and p directing tothe incoming electophile o @ wy av) ‘roduc of reaction of phenol with NSOWB is sodium salt of 2.4, bromophenol. Hence, species), (I), (I) are formed. ‘as intermediate 6b. on Br, Bro Br, Br | AaBr{3.0 agua er Be SO3H fro Br ° ‘Common name [TUPAC name [On DG ter-butanot | 2-methylpropan-2-01 Zou | mbotanot butan-I-ol D>, Jiscbuptaeatt | met prop Babe. o-n (), (and (tare probable postions as per electronic effect ‘of OH group where clectophile can attack and due o steric hindrance at (11) and (11) positions bulky electrophiles are not prefered lke I only prefered at position I, Bromine at posi tions I and I while chlorine at al tre positions. on pear ‘OL OH ou a ‘CMey ae ‘(CMe be oh aka P Tea eu Linked Comprehension Type Passage 1 tee. Reagents for Reimer-Tiemann reaction are ag. NaOH + cHcl, 2e OW + CHC == : CCl, +140 CCl + CF +: CCI, (Diehloroearbene) Passage 2 Aer analysis of questions, we know that the given compound (M) m6 Sn mS thse pt ty KF npn : ‘The compound Kis PRC =O T cH, 2Pr—C =O 80, ph =CH—C—Ph 1 eT cH, Compound K (ie. PHC ‘of compound I cH, “Therefore the compound I may be Scac-py Lenin ci @ o w XO ph—clty—O8 Oo Terabe! De: “Thus J seems 1 be CgHjCHO and hence Lis PhCH=C —Ph ' : cH [Now to solve the above said questions: 4b. As we know from above reaction sequence, compound (1) is Ph-CH=C —Ph and iis formed by catalytic dehydration 1 cH, (ecid catalysed) ofa teary alcohol (compound H). Therefore compound Hisou Ph-cHa—C—Ph cHy on PACH Ch ase Phcllc \ by @ o i (F1 can be formed by the action of PA’ “CH with PRCHMgBe as follows ° 1 ‘Mabe AS +PHCHMaBr—+ ¢—CHPh Pa cH ie cH $.a, The compound (Dis Ph CHy on 6.4, From the above sequence of reactions the structures of com: pounds JK and L respectively ae -O and PHCOO™K™ o Matching Column Type ©): > 0:70) ‘8. Williamson's synthesis i used forthe preparation of eter. 1 Phenol gives distinct colour with neural FeCl, solution. Lucas test is used for distinction between 1°, 2° and 3° alcohols. @ p. —C-NOE = (0"isa strong base and removes PO eee ee ae ete eat ‘bromie) : rtgorer, (Markovnikoy Twos (Son SSsiton come, * i (Antimarkovnikoy ] witeror a on and stack of Hand BH, i sym aros the double bond. Integer Answers Type Lo CRrcprcoR eo” Cyeco" 2a forgo OF CHSCHs Koepoe gos Assertion-Reasoning Type 1c. The solubility of alcohols in water can be exhibited du tothe formation of hydrogen bond between the highly polarized -OH roups preset both in alcohol and water. However. in higher alcohols the hydrocarbon character (alkyl chain) of the mot- cule increases and tus alcohols tend to resemble hydrocarbon (which ae insoluble in water) and hence the solbility in water decreases. When the ratio of Co OH is more than 4, alcohols. ‘ave lite solabilit in water So statement is correct but expla ation snot the Blanks Type 1. alot (B-nydroxybutaal cv,cH4,08-S-.cH,cHH0 SES y,—cHICH,CHO 2 resonance sbiization on nucleophilic 4 Phenoxide ion 5. peronides. On sanding in contact with sir, ethers are converted Foto unstable peroxides (R,0 —» 0) which ae highly explo- sive even in low concentrations. Hence ethers always purified before cillaon. Purification (mova of proxies) canbe dove by ashing eter with a solution offers sal (which reduces peroxides to alcohols) ot by distillaion with cone SO, (which oxidies peroxides) 6. Secondary. (CH,OH—CHOH—CH,OH—lycerine) ‘True/False Type 1. True: Since 1° alcohol on oxidation first gives aldehyde and then acid. But 2 alcohol on oxidation gives ketone.2 False: Ethanol is not acidic enough to react with ag, NaOH. Thus ‘sodium ethorie (C:HONa) is prepared by te reaction of Na ‘metal with ethyl alcohol. 2C\H,OH + 2Na + 2C,H,0Na+ HP Subjective Type 1. The compound with emptical formula ‘CH,’ can either be alkene or excloalkane, An organic liquid containing “0” canbe cof that on heating with cone. H,SO, can form alkene. Due tow bp the alcobol wil be of lose malar mass "A" is HOH and "Bis GH, HoH HS cH eyo cee CH,OH CyH,+alk KMn0, — | cH,oH yi, +H; 5 GH, 2. The unreactivty ofthe compound (X) towards sodium ind ‘cates that its neither an acid nor an alcohol, fuer its unreac: tivity towards Schifs base indicates that it isnot an aldehyde, ‘The reaction of compound (X) with excess of HI to form only cone product indicates that it shouldbe an ether ‘helo te oe eto 0-H gy Bt apo es ™ @ ron "#1. coon @ amo Since the carboxylic acd has equivalent weight of 60, it mas. be acetic acid (CHCOOH), hence Z must be ethyl alcobel, (Y) ethyl iodide and (X) diethyl ether. CyHy-0-C,Hg+ 215 2C,Hg1 esytero yt 2" 2¢,H,0H —S82,.cH,COOH, mgr) 8 pee ey 3. CaHOH —B> CH,CHO CHCHO + 31, + Nuon BE COONS + CHI, + 3H,0 + 3Nal 44. The reaction is Finkelstein halide exchange and takes place by ‘$2 eaction mechanism, Br is replaced by I following Sy2 mechanism. There will be ‘Walden inversion of configuration at the place of substitution. HP sa Ph——H Meo—}—H Zeewse” — Meo—}— Ht Ph Ph © 5. hk CH,CHOH)CH, 492. ,cH, CH=CH, eed I -a0 PL, cH, CH,CH;Br 8" CH, CH,CH,OH a tent 1. uM CH,CH,OH 42. cH, «CH, BiCH, CHB EN CHa ict cy, cHococH, cH,cH,on "2, cH,cooH Bid HS. 28, cH, =cHOCOCH, ‘Vay on \ coon 6.601405 ocoaurcsam, (SY ae or oi ose COOH conco,0 tine on coc I oO +(CH;CO),0 M20, Oo +CHyCOOH Pescelte Gil +KMaO, +08" —+ CHLOH 2 Se bx.01 eset Lana conais ative hydrogen tm My ~ OH at trace with sodium meal to form vedhinciboxide and Tern il cer aa benzene ane such yop ttm and hence do ot ec wt sou and ths ean be ‘id by met son A Phenol(s weaker ai) act with NBHCO, (a weaker base) 10 frm phenorde on stoner bse) and carne ald (asuenger act) GyHOH + NaHCO, —=GH,ONA+ H,00, a ee Since acid-base equilibria Ne towards the weaker sid and treater bas, peol docs mot decompose NaltCOy and the ‘ove eli ies towards the et Deidation of lobo fllows El mechani that involves the formation of carbons eaton normed, Since 3 Cartocuon (ome incase of roan) s more sablehan 1 MnO; (formed in n-butanol), the dehydration inthe former proceeds faster than in the later, ‘The sequence of reaction as follows: New om Aleghol ay Ale compound 5" rece aT OS Ze J inten (CHCOO):Caappears thatthe compound C is an alkyne, benee D must be an aldehyde or Ketone, Further since D ean be abined frm Acetic acid through its elcium sal it may be either acetalde- Ihyde or acetone. Hence going back, A is is-propanol, which explains the given se of reactions. b ckscyoncny gr cHicHe cect Ny Ales cece MONO CHa ‘©. @yAcevone ne Lecueoope. arco ‘cient Hence At opropy all, CH, CHOH-CH, Bis popene, Cy CH= CH, Cis propyee,CHjC= CH D ispetone, Cy -CO- CH, Hs ts us wwe, = og Gam GG cH cH cH Gain bpdeeing 13. L Taecompound (C;H,0)is soluble in ag. NaOH butinsolble in NaHICO,, indicating ito havea phenolic group. 4 The compound, on treatment with Br, water, gives ‘CyH,OBr, Taking into account of molecular formulae of the ‘wo compounds, the parent compound seems 1 be cresol Wh, Bromination ofthe compound reveals that it is m- \ wor | MEE oS) “oo OT wean “ho, “Lage Ng CHCl, + NaOH (Reimer-Tiemann reaction) Ont 6G, Me Me° (SOsH is deactivating and meta dreting) WNOH foe NaySO5 om a (Resorcinl) |. Since the compound X (CHO) does not react appreciably with Lucas reagent, it indicates thatthe compound has & primary alcoholic group (-CH,O#), Reaction ofthe compound X with ammonical sive nitrate 0 sive precipitate indicates that it hasan acetylenic hydrogen stom, ie, =C—H grouping is present. UWL Treatment of X with H/P followed by boiling with excess Mitgt pam tes hb mpd su yatta Som Cntr oases omy amie log oc ttese-cn,-cici.0 vale mae omen OE natty ne? 0%) Ateag w w=) Tie sv ti fr be compan nin tne ‘nescprc wehs omte pen a Satna ast wens fon 0. ako al och asTe= 22 2a 26 fw fe comp = Aeon fe cordL HcaccH,cH,.cH,on A825 AgC = CCH,CH,CH,OH | IL HCsCcH,cH,.cH,on HM, MBrC = C.CH,CH,CH,OMgBr+ CH, M. HeccH, cH, chon CH,CHCHCH,CH,OH —*-> CH,CH,CH,CH,CH, 20, r-Butanol gives the following reaction in which the purple colour of KMnO, changes t0 brown, fert-Alcobols are not coxidisable easily with alkaline KMnO, hence purple colour of KMn0, remains same, {HCHCH,CH,OH + KaMo0, —> CHCHACH, COOK + Mao, no, L+KOH =a OE ‘The brown preci ct 21. Cally + (CHs)>-CH-CHy-OH- 22, The steps involved inthe suggested mechanism areas follows ‘8 The protonation of hydroxyl group. cH, cH D Hi H,c—C —cH—cH, 4 H,c_¢ — cH—cH, a Teel cH, On cH, "0H, 230imdydatn 2 1 The removal of H,0 to form a secondary (2°) carbonium cH cH, Hc—C— cH — cH #24 cH, eu —cH, 1-08, ou, The conversion of 2° carbonium to the more sable 3° C)-coon 24, a. Since (B) is resistant 1 oxidation, it must be 1r-alcobol 1. Since (B)isoptically inactive, it mast havea least wo alkyl ‘roups similar. CH 2+ CH, ‘Thus the posible structure of alcohol (B) is ether cH, cH, H I CH,CH,CH,— C—OH or CH\CH,—C—OH 1 1 cH cH,CH, Hence the conesponding compound (A) is either cH, cH t ' Cit=ceH—C— On or CH=C—C—oH 1 ca, cH.cH, However he compound (A) is opty active, so (A) and tence also (B) shold have right sie str. cH cH, 1 I cHt=c—C—08 —%cnjcH,—C—on 1 i cucu, cucn,° omesr Cs Cg, ‘OMe ‘och; on ci scrson tt ot ate 21, "Te ono ing le caved via 2 mechanism ME. 3 ge HC He ne Banc ONG 7 tice " Ti Seog We, ne ‘OH OH — 28, The method givenin i isthe comet method forthe formation of eter because metho (ads alkene a the main product 5° ally halides ar easily dehyobalogente by tae like — oct, (CHiy,C8r 22%, (CH ,C-CH, Atk halides show Sy more easly i. CH,Br+NaOC(CH,), —> CH) —O—CCH,), ~COSCQ ACO, i ® on 5 » © 8% 0) moe WHO Ry Ola = | ome owe oe Fused | ee... + MeHSO,, ONs Seda sahot 4 Matoy pes ncn ia 31. Given Aspen orxor0 Cita Cyto ser ee s [vee Ester theese, CH.CHCHCOOH ‘Boe cid i »,Co01 $0 acocttyctiyxcooH coon fale accord et |. Hydrogenation of bombykol (C 4H)g0) 10 C,,HOCA) Indicates the presence of two double fonds in bomb ko Ii. Reaction ofA with acetic anhydride o form ester indicates the presence of an alcoholic group in A and hence also ia Dbombykol IIL, Products of oxidative ozonolysis of bombyko ester suggest the srvcture of bombykol (CHYCH,CH,COOH + HOOC.COOH + HOOC,(CH;),.C#;0Ae CCHsCH:CH,CH~CH—CH-CHCH)g CHOAE The structure of the bombykol ester suggest that bornbykol has the following stactare: CH,CH,CH,CH=CH-CH=CH{CH,),-CH,OH (Bombyko!) tnd the structure ofA is CH CH,CH,CH,CH,CH,CH4(CH,)y (CH,OH oC ,H,0H. Four geometrical simers are posible forthe above bombykol structure (as it has double bonds), yo ACH CHLON Wy City NeAE Sia sq eae! a H sa 1 ee N.city,cton ney et Ky we not NH32. L. Moleclar formula of P, C0 indicates 1° of unsaturation. Soit should have double bond. 1 Acidic hydrolysis of P to Q and R, both of which responds iodoform est indcates that Qand R should have following structure (CH,CH,OH, (CH,),CHOH, CH/CHO or CH,COR ‘The only possible linkage that can explain such hydrolysis is eter. The possible structure for P should be either ofthe fl Towing two structures which explains all the given reactions CHy-CH—Q—CHCH pee [CH,CHO=*CH,=CHOH]) + HOCH(CHt)2 (Qt Bo pon item et cuts or CHCH,-Q-—CacHy J spoon ge fit ervenusto-Cmc 0-€ a ath beens xara reactive of Ptoward di. H,SO, than ethylene is due 19 formation of highly stable carbocation hs H,C-CH—0-CH(CHs: oF CHsCH.—O0-C—CH (Stabile by +R CH=CH WH, CHSCiy effect of or group) extn = OS age OF" ae, “HO ieee rakenim (shnemnet (coon cH ow a Not Tawcoot reeset id 1st Gobet