MS CHAUHAN ADVANCE

350 CO2H ¾K¾2C¾r2O¾7 ® (P); Product (P) is : OH D 9. O O CO2H CO2H (d) (a) (b) (c) 10. Which of the following react with HBr at faster rate ? OH (a) OH (b) CH3 OH (c) CH3 OH (d) CH3 O O OH CH2 – OH 11. CH3 – C || | (d) KMnO 4 C – OH ¾¾® CH3 – CH Above conversion can be done by : (a) NaBH 4 (b) LiAlH 4 (c) PCC CO2H 12. ¾2¾CH¾3O¾H ® (A) ; Product (A) is : H2SO 4, D CO2H O || CO2CH3 CO2CH3 CO2CH3 C – CH3 (a) (b) (c) (d) CO2CH3 CO2H CO2CH3 C – CH3 5 OH OH Ph || O 4 1 6 Ph ¾H¾2S¾O¾4 ® (P) ; Unknown (P) of the reaction is : 13. 2 99% yield 3 O Ph 1|| Ph 5 6 Ph (b) 4 5 1 6 (a) Ph 3 C 42 2 3 O OH || 6 1 Ph 5 1 Ph 5 Ph (d) 4 C Ph (c) 6 2 4 32 3 https://t.me/studyzee

14. Predict the major product of the given reaction. 351 OH OMe OH ¾H¾¾+ ® (A); Product (A) is : OMe OMe (b) (a) O (c) O (d) OMe MeO O 15. Identify the major product, H+ OH Product O O OH O (a) (b) (c) (d) O 16. O OO O ¾H¾¾+ ® (A); Product (A) is : O O OO O O OO (d) O (a) (b) (c) O OCH3 OCH3 17. ¾L¾iAl¾H¾4 ® (A) Major; product (A) is : CO2CH3 O OH OCH3 OCH3 OH OCH3 (d) (b) (c) (a) CH2OH OH OH CH2OH https://t.me/studyzee

352 OH 18. ¾ I¾2 + NaOH CHI 3 + ( A); Compound (A) is : ¾ ¾® OH (Iodoform) (Resorcinol) OO || || O (b) H – O – C – (CH 2)2 – C – OH ONa O || (a) (d) CH 3 – (CH 2)3 – C – ONa CO2Na O CH2 || (c) CH 3 – CH 2 – CH 2 – CH 2 – C – OH OH 19. ¾H¾2C¾rO¾4 ® (A). Product (A) is : (3º alcohol) OH (a) No reaction (b) (c) (d) CO2H O O 20. ¾(¾1)C¾H3¾-Li(¾exc¾e¾ss)®( A) ¾¾I2 ®(B) + CHI 3 ¯; Compound (B) is : (a) (2) HÅ NaOH 21. O O –+ CO2Na CO2Na –+ O Na O Na (b) (c) (d) OH ¾H¾-¾Br ® Major product obtained in the reaction is : 18OH CCl 4 (a) O O18 (b) (c) OH Br Br (d) OH https://t.me/studyzee

353 22. Consider the following alcohols, CH2OH CH2OH (II) O2N (I) CH2OH CH2OH (III) CH3O (IV) Br The order of decreasing reactivities of these alcohols towards nucleophilic substitution with HBr is: (a) III > I > IV > II (b) III > I > II > IV (c) I > III > IV > II (d) I > III > II > IV O O O 23. ¾N¾aB¾H4® (P) O O ¾L¾iAl¾H4® (Q) O O Sum of number of alcoholic groups in product (P) and (Q) is: (a) 1 (b) 2 (c) 3 (d) 5 24. In presence of dil. HCl, compound A is converted to a constitutional isomer (B), compound B is: O NO2 || HO NH – C (a) NH2 O NO2 (b) NH2 OH NO2 || | O–C O–C | H OH OO O–C (c) NH2 NO2 (d) C H NH2 Ar https://t.me/studyzee

354 CH3 N CrO3ClQ (A) (ten carbon atom) 25. CH3 | CH3 OH H (a) dichloro methane (b) O (c) (d) O CO2Et OH CH2OH O 26. LiAlH4 ; Product of the reaction is: (a) Racemic (b) Diastereomer (c) Meso (d) Optically pure OH 27. CO2H (1) EtLi (3.5 eq) ( A) ; Chemist added extra 0.5 mole of Et-Li (2) H +, H 2O 65%yield in above reaction to obtain product (A), which is? OO OH || || O || Et (b) C – Et (a) O O || || (c) Et Et (d) 28. CH2OH O Major product of above esterification reaction is: HO + Ph – C – O – H HCl O (a) O OH (b) CH2 – O – C – Ph || HO O Ph O (d) || O – C – Ph CH2 – O – Ph (c) HO HO https://t.me/studyzee

14C label OCOR 355 29. OTs ¾R¾CO¾2H® ; + OCOR no label (a) SN1 (b) SN2 (c) SN — NGP (d) SN — Ar HO ¾¾A¾c2O¾® (A); Product (A) of reaction is : O 30. || 100°C O O || NH2 O O O OH (a) (b) (c) (d) NH2 NH NH NH O || || O O OH N CrO3ClQ, (PCC).CH2Cl2 H Product of the reaction is : 31. CH3 – C – OH CH3 OH CHO CO2H O (a) (b) (c) (d) OH OH OH 32. Which is the best reagent to convert isopropyl alcohol to isopropyl bromide ? CH3 CH3 CH3 – CH – OH ? CH3 – CH – Br (a) HBr (b) SOBr2 (c) Br2 (d) CH 3MgBr https://t.me/studyzee

356 NH2 Ph OH A 33. HNO2 H CH3 Ph Major product obtained in the above reaction is : O H CH3 (b) O CH3 H (a) Ph — C Ph — C Ph Ph (c) Racemic (d) Diastereomers 34. OH ¾H¾IO4® (A) ¾((12¾)) LHi¾+AlH¾4 (¾ex¾ces®s) (B) OH Total number of stereoisomers of product (B) will be: (a) 2 (b) 3 (c) 4 (d) 5 O S – C – CH3 1. HO– 35. 2. H+ Major product of the reaction is : O – C – CH3 O SH SH (a) (b) (c) S (d) O O OH OH O S – C – CH3 36. HOQ O – C – CH3 O SH SH (a) (b) (c) S (d) OH OH https://t.me/studyzee

357 O CH3 OH 37. O CH 3MgBr H+ KMnO 4 (cold dil.) CrO 3 H+ D (4) (1) (2) (3) For the above conversion the correct order of reagents used is : (a) 1 ® 2 ® 3 ® 4 (b) 1 ® 4 ® 3 ® 2 (c) 1 ® 4 ® 2 ® 3 (d) 2 ® 3 ® 4 ® 1 CH3 CH3 (y) CH – C H – CH3 C – CH2 – CH3 (x) CH3 | CH3 OH 38. CH3 C — C H – CH3 OH CH3 O (2º alcohol) (3º alcohol) Find missing reagents. (a) x = LiAlH 4 , y = NaBH 4 (b) x = LiAlH 4 AlCl 3 , y = LiAlH 4 (c) x = LiAlH 4 , y = LiAlH 4 AlCl 3 (d) x = H 2 Ni , y = H 2 Pt 39. In solvolysis of 1, 2-dimethyl propyl p-toluene sulfonate in acetic acid at 75ºC, (alkene + substitution products) will be formed by mechanism ? (a) SN2 , E 2 (b) SN2 , E 1 (c) SN1 , E 2 (d) SN1 , E 1 O 40. O ¾L¾iAl¾H4® (A) ¾¾¾® xAc2O O (B) x = moles of anhydride consumed (a) 1 (b) 2 (c) 3 (d) 4 41. Identify product when (R) – and (S) – 2 – butanol reacts with (R,R) tartaric acid in acidic medium. (a) Racemic (b) Diastereomer (c) Meso (d) Pure enantiomer https://t.me/studyzee

358 42. An alcohol of formula C 9H12O reacts with Na 2Cr2O7 to form a compound having formula C 9H10O. The original alcohol might be : OH | (a) CH2 – CH2 – CH2 – OH (b) CH – CH2 – CH3 C|H3 C|H3 C – OH (d) CH – CH2OH (c) | CH3 43. An optically active alcohol of formula C 9H12O 2 produced the following compound when refluxed with KMnO 4 . OO HO –– C C –– OH The original compound showed these properties also : C9H12O2 Na H2 liberated (A) Br2 no rapid reaction CrO3/H+ C9H8O3 cool What is structure of (A)? OH OH CH3 OH OH (a) (b) (c) (d) both (a) and (b) OH CH3 CH3 44. Which are not cleaved by HIO 4 ? II : glycol I : glycerol IV : methoxy-2-propanol III : 1, 3-propenediol (b) I, II (a) I, II, III, IV (d) III, IV (c) II, III 45. Which of the following reactions require an oxidising agent ? (a) CH 3 — CH == CH 2 ¾® CH 3 — CH 2 — CH 3 (b) CH 3 — CH 2OH ¾® CH 3CHO (c) CH 3 — CH 2Cl ¾® CH 3 — CH 3 (d) CH 3 — CH 2OH ¾® CH 3 — CH 2Cl 46. What is the major product of the following reaction ? O NaBH4 product CO2H https://t.me/studyzee

OH OH O 359 OH (a) (b) (c) (d) CO2H CO2H CH2OH CO2CH3 47. Which of the esters shown, after reduction with LiAlH4 and aqueous workup, will yield two molecules of only a single alcohol ? (a) CH 3CH 2CO 2CH 2CH 3 (b) C 6H 5CO 2CH 2C 6H 5 (c) C 6H 5CO 2C 6H 5 (d) None of these 48. For the following reaction, select the statement that best describes the change. RCH 2OH + PCC [C 5H 5NH + ClCrO - ] ¾¾® 3 (a) The alcohol is oxidized to an acid, and the Cr(VI) is reduced (b) The alcohol is oxidized to an aldehyde, and the Cr(VI) is reduced (c) The alcohol is reduced to an aldehyde, and the Cr(III) is oxidized (d) The alcohol is oxidized to a ketone, and the Cr(VI) is reduced 49. What is the product of the following reaction ? CH3 CH3 CH3 H OH HO H H3C CH3 OsO4(cat.), (CH3)3CCOOH H OH H (CH3)3COH,HO– H OH HO H H OH C == C H CH3 CH3 2 3 CH3 1 (a) Only 1 (b) 1 : 1 mixture of 2 and 3 (c) Only 2 (d) 1 : 1 : 1 mixture of 1, 2, and 3 50. An organic compound B is formed by the reaction of ethylmagnesium iodide (CH3CH2MgI) with a substance A, followed by treatment with dilute aqueous acid. Compound B does not react with PCC in dichloromethane. Identify A ? O O (c) H 2C == O O || || (d) H2C – CH2 (a) CH 3 — C — H (b) CH 3CH 2 C CH 3 51. Which of the following reagents would carry out the following transformation ? (D = 2H) O ? OH CCH3 | C| CH3 D (a) NaBD 4 in CH 3OH (b) LiAlH 4 , then D 2O (c) NaBD 4 in CH 3OD (d) LiAlD 4 , then D 2O 52. Which sequence of steps describes the best synthesis of 2-methyl-3-pentanone ? O https://t.me/studyzee

360 (a) (1) 1-Propanol + (CH 3)2CHMgBr, diethyl ether (2) H 3O + (3) PCC, CH 2Cl 2 (b) (1) 1-Propanol + Na 2Cr2O7 , H 2SO 4 , H 2O, heat (2) SOCl 2 (3) (CH 3)2CHCl, AlCl 3 (c) (1) 1-Propanol + PCC, CH 2Cl 2 (2) (CH 3)2CHLi, diethyl ether (3) H 3O + (4) Na 2Cr2O7 ,H 2SO 4 ,H 2O, heat (d) (1) 2-Propanol + Na 2Cr2O7 , H 2SO 4 , H 2O, heat (2) CH 3CH 2CH 2Li, diethyl ether (3) H 3O + (4) PCC, CH 2Cl 2 53. Diols (I-IV) which react with CrO 3 in aqueous H 2SO 4 and yield products that readily under go dercarboxylation on heating, are : OH (I) HO (II) HO OH OH (III) HO (IV) OH OH (a) I and II (b) II and III (c) II and IV (d) I and IV 54. Which of following compounds are not oxidized by HIO4 ? CH 3 — CH — OH CH 3 — C == O (1) | (2) | CH 2 — OH H — C == O CH 3 — C == O CH 3 — C == O (3) | (4) | CH 3 — C == O CH 3 — CH — NH 2 O CH 2 — OCH 3 || (5) O (6) | (7) C — OH CH 2 — OH | CH 2 — OH (a) 5, 6, 7 (b) 4, 5, 6, 7 (c) 6, 7 (d) 3, 4, 5, 6, 7 CH2OH 55. OH TsCl ( A) ¾¾¾¾¾® (B) 84%; Final product (B) will be : 80°C ¾¾¾¾® Pyridine 0°C (HMPT Solvent) https://t.me/studyzee

OO O 361 (a) (b) (c) (d) O 56. Unknown (A) in the reaction (given in Q. 55) is : CH2OH CH2 – OTs OTs (a) OH (b) CH2 – CH3 O (c) OH (d) 57. In the given table, identify the incorrect option. The digit in box indicate the moles of that substance. Reactant HIO 4 HCO2H HCHO consumed formed formed OH | 21 2 (a) HO – CH 2 – CH – CH 2 – OH OH OH OH | || 3 2 1 (b) R – CH – CH – CH – CH 2 – OH OCH 3 | 0 0 (c) HO – CH 2 – CH – CH 2OH 0 OH OCH 3 || (d) HO – CH 2 – CH – CH 2 111 58. Succinic acid ¾¾D®( A) ¾N¾H¾3 ®(B) ¾B¾¾r2 ®(C); Product (C) will be : D KOH CH 2 – CO 2H CH 2 – CO 2H CH 2 – CO 2-K + CH 2 – CO 2H (a) | (b) | (c) | (d) | CH 2 – CH 2 – NH 2 CH 2 – NH 2 CH 2 – NH 2 CH 2 – CH 2 – Br https://t.me/studyzee

362 59A. Given are the structures of cyclic D-glucoside. Moles of HIO 4 consumed with X and Y are ......... respectively: RO CH CHOR O OH HO O OH OH OH OH CH2 – OH CH2 – OH (X) (Y) (a) 2, 2 (b) 3, 3 (c) 2, 3 (d) 3, 2 B. Moles of formic acid formed in X and Y respectively are: (a) 1, 2 (b) 2, 1 (c) 2, 3 (d) 3, 2 C. Moles of HCHO formed are: (b) 2, 2 (a) 1, 1 (d) 2, 1 (c) 1, 2 60. In which of the following group, each member gives positive iodoform test ? (a) methanol, ethanol, propanone (b) ethanol, isopropanal, methanal (c) ethanol, ethanal, isopropyl alcohol (d) propanal, propanol-2, propanone 61. H 2O18 + Na ¾® ( A) + (B) (base) O || CH 3 – C – O – CH 2 – CH 3 + ( A) ¾® (C) + (D) alcohol Product (C) of the reactions is: O O 18 || || (b) CH 3 – C – O – H (a) CH 3 – C– O– H O 18 || (d) CH 3 – C – O QN aÅ O (c) CH 3 — || 18 – C— O O O 62A. H2 0.1 M NaOH ¾¾¾¾¾® ( A) ¾¾¾¾¾® (B) + (C) NO2 (Ph 3P)3 RhCl H2O (Contains no nitrogen) O (Methanol) Product (B) of the reaction is : https://t.me/studyzee

363 OH COQ2 (a) (b) NO2 NO2 O C – O – CH3 O C–O (c) (d) NO2 NO2 O HO B. Product (C) of above reaction is : HO OH OH (a) (b) (c) (d) OO OO 63. Two unknown compounds X and Y, both having molecular formula C 4H 8O, give following results with four chemical tests. Bromine Na metal Chromic acid Lucas reagent decolourises bubbles Compound X No reaction No reaction Orange to Green No reaction Compound Y No reaction No reaction Compound X and Y respectively are : O || (a) CH 3 – CH 2 – C – CH 3 ; (b) OH ; O OO || (c) O ; OH (d) CH 3 – CH 2 – CH 2 – C – H ; 64. O O LiH CH3Br H3O + COH ¾¾¾¾¾¾® L ¾¾¾® M ¾¾¾® N + CH 3OH dimethoxy ethane Product (N) is : O (a) CH3 (b) C – CH3 O OH (c) || | (d) CH – CH3 C—O—H https://t.me/studyzee

364 65. Assign the structure of major product (X) of the reaction given below. O CH – COH CH3CH2OH SOCl2 (X) | HCl(g), D D OH OO || || (a) CH – C – OH (b) CH–C–OEt | | OEt Cl OO (c) CH – C – Cl (d) CH=CH–C–O–Et | OEt Cl O O || 66. CH — C — OCH2 — CH3 + CH3 – COH HCl (A) + (B) ethyl-2-chloro acetic acid D, 1.5 h (contains chlorine) 2-phenyl acetate (7 mole) (1 mole) Product (A) and (B) respectively in the above reaction are : OO (a) CH–C–OH, CH 3–C–OCH 2CH3 | Cl O O || || (b) CH – C – OEt, CH3 – C – OCH3 | Cl O O || || (c) CH – C – OEt, CH3 – C – OH | Cl O || (d) CH2 – Cl, CH3 – C – OH O || 67. H 2C = CH – C – OCH 3 + CH 3CH 2CH 2OH ¾¾¾® ( A) + CH 3OH methylacrylate n-butyl alcohol TsOH, D bpt,145°C bpt 65°C bpt 81°C bpt 117 °C Product (A) of above reaction is : O || O || (b) H 2C == CH – C – O – CH(Me)2 (a) H 2C == CH – C – OCH 2CH 2CH 3 O O || || (c) H 2C – CH 2 C – OCH 3 | (d) H 3C – (CH 2)4 – C – O – CH 3 OCH 3 https://t.me/studyzee

OH 365 (d) C 6H 6O 3 68. OH 3Ac 2O ¾® OH (acetic anhydride) In above reaction molecular formula of glycerol increases by : (a) C 4H 4O 2 (b) C 6H 6O 6 (c) C 6H 6O 2 69. Give the best conditions for this transformation: OCH3 H3C O H3C OCH3 (a) CH 3OH,H + (cat.),heat (b) H 2O,H + (cat.),heat (c) Mg,ether,CH 3OH (d) SOCl 2 ,CH 3OH 70. Give the major organic product of the following reaction. O (1) sodium acetylide ¾¾¾¾¾¾¾¾¾¾® Product (2) H2O,H+ to neutralize O OH (a) (b) HO (d) (c) OH OH (1) MeMgBr PCC (A) OH OH (B) (2) H3OÅ 71. H+ (C) NaBH4, EtOH (D) Product (D) in above reaction is : OH OH OH OH (a) (b) OH OH OH (c) OH (d) https://t.me/studyzee

366 72. Select the best method for the preparation of the following compounds : OH OH and CH3 CH3 (MCPBA = Metachloro per benzoic acid ) (a) reaction of cyclohexanone with CH 3Li (b) reaction of 1-methylcyclohexene with Hg(OAc)2 followed by NaBH 4 (c) reaction of cyclohexene with BH 3;NaOH H 2O 2, following by CH 3Br (d) reaction of cyclohexene with MCPBA, followed by CH 3MgBr 73. Identify the reagents (1-4), required for the transformations shown and arrange them in correct order. Ph Ph Ph Ph Ph Ph 1 H+ H OO HOH2C CH2OH O2 Ph OH HO OO OH OH H Ph Ph Ph Ph 43 H Ph O O O (1) LAH (LiAlH 4 ) (2) OsO 4 (3) NaIO 4 (4) NaBH 4 (a) 1 ® 3 ® 4 ® 2 (b) 2 ® 3 ® 1 ® 4 (c) 2 ® 1 ® 3 ® 4 (d) 1 ® 2 ® 3 ® 4 74. Which describes the best stereochemical aspects of the following reaction ? CH3 ¾H¾–¾Br ® Product Ph CD3 OH (a) Inversion of configuration occurs at the carbon undergoing substitution. (b) Retention of configuration occurs at the carbon undergoing substitution. (c) Racemization (loss of configuration) occurs at the carbon undergoing substitution. (d) The carbon undergoing substitution is not stereogenic 75. Which of following is an example of Pinacol-Diazotization ? OO || ¾ N¾aN¾O¾2 ® || (a) Me 2C – CMe 2 ¾A¾g¾+ ® Me – C – CMe 3 (b) Me 2C – CMe 2 HCl Me – C– CMe 3 || | | OH Br OH NH 2 https://t.me/studyzee

O O 367 || OH (c) Me 2C – CMe 2 ¾H¾¾Å ® Me – C – CMe 3 H+ || R (d) R R OH OH R 76. ( A) ¾H¾3O¾Å ® B + C ; (B) and (C) both give +ve iodoform test. Compound (A) is : C 5H10O H | (a) CH 3 – CH = CH – O – CH 2 – CH 3 (b) CH 3 - C - O - CH 2 - CH 3 | CH 3 (c) CH 3 – C – O – CH 2 – CH 3 (d) both (b) and (c) || CH 2 77. A solution of Ph 3CCO 2H in conc. H 2SO 4 gives (X) when poured into methanol X is : OO || || (a) Ph 3C – C – O – CH 3 (b) Ph 2CH – C – O – CH 3 (c) Ph 3C – OCH 3 (d) Ph 3C – CH 3 OH 78. ¾P¾yTris¾dCi¾lne ® ( A) ¾L¾iAl¾H¾4 ® (B) Product (B) of the above reaction is : Cl (a) (b) (c) (d) 79. In the given pair of alcohol, in which pair second alcohol is more reactive than first towards hydrogen bromide? CH3 OH H OH OH (b) and (a) and CH – CH3 | OH (c) CH 3 — CH — CH 2 — CH 3 and CH 3 — CH 2 — CH — CH 2 — OH | | OH CH3 (d) CH 3 — CH — CH 2 — CH 3 and (CH 3)2 C — CH 2 — CH 3 || OH OH https://t.me/studyzee

368 80. Rank the transition states that occur during the following reaction steps in order of increasing stability (least ® most stable) 1. H 3C — + 2 ¾® CH + + H 2O 3 OH 2. + ¾® (CH 3) 3C + + H 2O (CH 3) 3C — OH 2 3. + ¾® (CH 3) 2CH + + H 2O (CH 3)2CH — OH 2 (a) 1 < 2 < 3 (b) 2 < 3 < 1 (c) 1 < 3 < 2 (d) 2 < 1 < 3 81. HO OH ¾M¾nO¾2 ® (A), Product (A) is : (a) O == C OH (b) HO CHO | CH2 O O H (c) HO C—H (d) HO C—O—H 82. In which of the following reactions hydrogen gas will not be evolved ? (a) CH 3 — CH 2 — OH ¾N¾a ® (b) CH 3 — CH 2 — OH ¾¾K ® (d) CH 3 — CH — OH ¾C¾H3¾Mg¾Br ® (c) CH 3 — CH — OH ¾¾Al ® | | CH3 CH3 (A) PBr3 Mg, ether Grignard reagent (C) 83. Na2Cr2O7 (D) H3O (3, 4-dimethyl 3-hexanol) H2SO4 (B) When Grignard reagent reacts with (B) product (D) will obtained. Reactant (A) of the above reaction is : OH (a) (b) OH (c) (d) OH OH 84. ( A) ¾L¾iAl¾H4® 2( B) ; structure of (A) is : (Chiral alcohol only) OO || || (a) CH 3 ¾ CH ¾ C ¾ O ¾ CH ¾ CH 3 (b) CH 3 ¾ CH ¾ C ¾ O ¾ CH 2 ¾ CH ¾ CH 3 || || Et Et Et Et O (c) O (d) O OH O 85. ¾¾¾® NO2 NO2 https://t.me/studyzee

369 Above conversion can be acheived by : (a) LiAlH 4 (b) NaBH 4 (c) H 2 / Ni (d) CrO 3 OH O | || CH–COH 86. + EtOH ¾H¾¾Cl ® (86%) (Mandelicacid) Identify product of above Fischer esterification reaction : O -Et O | (b) Ph – CH – C = O O (a) Ph - CH - CO 2H || (c) Ph - CH - CO 2Et (d) Ph - CH - C - Et | | OH OH O CH3 CH2CH2COH 87. ¾C¾H3¾Li ®( A) ¾C¾H3¾Li ® (B) ¾H¾3O¾Å ® (C) O O Product (C) of the above reaction is : O OH OH OH || | || (a) CH 3 - C - CH 2 -CH 2 -C - CH 3 (b) CH 3 - C - CH 2 - CH 2 - C - CH 3 | || CH3 CH3 CH3 OO OO || || || || (c) CH 3 - C - CH 2 - CH 2 - C - CH 3 (d) CH 3 - C - CH 2 - C - CH 3 88. What is the major product of the following reaction ? OH | CH 3 - CH 2 - CH 2 - OH ¾ P¾yri¾CdrinOe¾3co¾ld ® Product - CH OH O OO | || || || (a) CH 3 - CH - CH 2 - C - H (b) CH 3 - C - CH 2 - C - H OO OH O || || | || (c) CH 3 - C - CH 2 - C - OH (d) CH 3 - CH - CH 2 - C - OH https://t.me/studyzee

370 89. The major reason that phenol is a better Bronsted acid than cyclohexanol is that : (a) it is a better proton donor. (b) the cyclohexyl group is an electron donating group by induction, which destabilizes the anion formed in the reaction by resonance. (c) phenol is able to stabilize the anion formed in the reaction. (d) the phenyl group is an electron withdrawing group by induction, which stabilizes the anion formed in the reaction. 90. Which of these reagents would accomplish the following reduction ? O OH || | N ºC - CH 2 - C - CH 2 - CH = CH 2 ¾® N ºC - CH 2 -C - CH 2 - CH = CH 2 H (a) NaBH 4 (b) LiAlH 4 (c) 1 mole H 2, poisoned catalyst, low pressure (d) H3O+ CH – CO2Et CH – CH2 – OH || || 91. ¾(¾¾A)® ¾M¾nO¾2 ® (B) Identify A and B : CH – CO2H CH – CHO (a) A = NaBH 4 , B = (b) A = NaBH 4 , B = CH – CHO CH – CO2H || || (c) A = LiAlH 4 , B = (d) A = LiAlH 4 , B = 92. Ph - CH 2 -CH - CH 3 ¾¾K ® ¾C¾2H¾5¾Br ® ( A) | OH Product (A) in above reaction is: (a) Ph - CH 2 -CH - CH 3 , (inversion) (b) Ph - CH 2 -CH - CH 3, (retention) | | OEt OEt (c) Ph - CH 2 -CH - CH 3, (racemic) (d) Ph - CH = CH - CH 3 | O OEt 93. || H+ ( X ) + H 2O ; Identify X: Ph - C - O - H + CH 3 - O18 - H O || (a) X = Ph - C - O18 - CH 3 (Trans esterification ) https://t.me/studyzee

371 O || (b) X = Ph - C - O18 - CH 3(Esterification reaction) O || (c) X = Ph - C - O18 - CH 3 (Saponification) O || (d) X = Ph - C - O - CH 3 (Hydrolysis) O O || || NO2 ¾H¾¾+ ® R –O–C NO2 94. R - OH + H - O - C Fastest rate of reaction will be when R is : (a) CH 3 - (b) CH 3 - CH 2 (c) CH 3 - CH - CH3 | | CH3 (d) CH 3 - C - | CH3 95. Select the correct statement. (a) Solvolysis of (CH 3)2C = CH - CH 2 - Cl in ethanol is over 6000 times greater than alkyl chloride (25ºC) (b) CH 3 - CH = CH - CH 2 - OH when reacts with HBr give a mixture of 1-bromo-2-butene and 3-bromo 1-butene (c) When solution of 3-buten-2-ol in aqueous sulphuric acid is allowed to stand for one week, it was found to contain both 3-buten-2-ol and 2-buten-1-ol (d) All of these OH OH 96. CH2–OH ¾® ; Above transformation can be carried out by : (a) H + D , Zn(Hg), HCl (b) HIO 4 ,LiAlH 4 (c) HIO 4 ,H + D (d) H + D , HIO 4 97. H 2C = CH - CH 2 - CH 2 -CH - CH 3 ¾S¾OC¾l2 ® ( A) ¾O¾3 ¾Z¾n ® (B) ¾N¾aB¾H¾4 ® (C) | Pyridine (H2O) C 5H9ClO OH Compound (C) is : OH | (a) CH 3 -CH - CH 2 -CH - CH 3 | Cl (b) HOCH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - Cl Cl | (c) HO - CH 2 - CH 2 - CH 2 -CH - CH 3 (d) HO - CH 2 - CH 2 -CH - CH 2 - CH 3 | Cl https://t.me/studyzee

372 98. Iodoform can be obtained on warming NaOH and iodine with : (a) CH 3CH 2CH(OH)CH 3 O || (b) (CH 3)2CH C C 2H 5 (c) CH 3 — C — OCH 3 (d) (CH 3)2CHCH 2OH || O 99. Which of these is a reducing agent ? (a) CrO 3 H + (b) KMnO 4 (c) LiAlH 4 (d) O 3 100. CH2 ¾ ¾(ii()i¾.).H(2¾BOH23¾)O2H¾¾- ® (P); Product (P) in the reaction is: CH3 O (a) CH2OH (b) OH (c) O (d) OH CH3 | 101. CH 3 — CH 3 ¾ ¾Na¾c2Coor2l¾O¾7 ® ( P ); Product (P) in the reaction is: —C | OH CH3 CH3 | | (a) CH 3 —C = CH 2 (b) CH 3 —CH — CH 3 CH3 CH3 | | (c) CH 3 —C — O —C — CH 3 (d) No reaction | | CH3 CH3 102. 1, 2, 3 – butanetriol undergoes oxidative cleavage of HIO 4 . During this process (a) 1 equivalent of HIO 4 consumed & HCO 2H & H 3C - C - CO 2H are formed || O (b) 2 equivalents of HIO 4 consumed & HCO 2H, HCH = O & CH 3 - CH = O are formed (c) 3 equivalents of HIO 4 consumed & HCO 2H (2 eq.) & 1 eq. of CH 3CO 2H are formed (d) 2 equivalents of HIO 4 consumed & 2 eq. of HCO 2H & 1 eq. of CH 3CH = O is formed OO || || CH3 – CO C – OCH3 103. ¾(¾i)L¾iAlH¾4 ® ( A) ; Product (A) of the reaction is : (ii)H2O (96%) OH OH OH CH2 – OH OH CH2OH O (a) (b) (c) (d) https://t.me/studyzee

373 OO || HÅ || 104. R - C - O - R ' + R' ' OH R - C - O - R ' ' + R' OH 105. Above reaction is/an example of : (b) saponification (a) esterification (d) hydrolysis (c) trans-esterification What is the major organic product of the following sequence of reactions ? O (CH 3) 2CHCH 2OH ¾P¾B¾r3 ® ¾M¾¾g ® H2C CH2 ¾ H¾3O¾+ ® ? OH (b) (CH 3)2CHCH 2CH 2OH (d) (CH 3)2CHCH 2CH 2CH 2OH | (a) (CH 3)2 CHCH CH 2CH 3 OH | (c) (CH 3)2 CHCH 2CHCH 3 106. The structure of the product formed in the reaction given below is : ¾¾H+® D OH OH (a) (b) (c) (d) O O CHO O | 107. CH - OH ¾2¾HI¾O¾4 ® Products obtained in the above reaction are : 108. | 109. CH 2 - OH (a) HCHO,HCO 2H (b) HCHO, 2HCO 2H (c) CO 2 ,2HCO 2H (d) CO 2 ,HCHO, HCO 2H CHO | (CH - OH)3 + 4HIO 4 ¾® Products obtained are : | CH 2 - OH Aldo pentose (a) 4HCO 2H, HCHO (b) 4CH 2O, HCO 2H (c) CO 2, 4HCHO (d) CO 2 ,3HCO 2H, HCHO CHO CH 2OH | (i) (CH - OH)3 ¾ 4¾HI¾O¾4 ® Product | ¾5¾HI¾O¾4 ® Product (ii) (CH - OH)4 | | CH 2 - OH CH 2 - OH https://t.me/studyzee

374 Ratio of moles of formic acid obtained in reaction (i) and reaction (ii) is : (a) 3/4 (b) 4/5 (c) 1 (d) 5/4 110. Which of the following compound gives 2HCHO, CO 2, HCO 2H when oxidised by periodic acid? 111. CH 2 _ OH CHO CH 2 - OH CHO 112. | | | | 113. C == O (a) (CH - OH) 2 (b) (CH - OH)2 C == O (d) | | | CH - OH CH 2 - OH (c) | | CH 2 - OH CH 2 - OH (CH - OH)2 | CH 2 - OH Hydration of 3-phenylbut-1-ene in dil. H 2SO 4 will give mainly : (a) 3-Phenylbutan-1-ol (b) 3-Phenylbutan-2-ol (c) 2-Phenylbutan-2-ol (d) 2-Phenylbutan-1-ol Decarboxylation of sodium salicylate with soda lime forms : (a) Salicylic acid (b) Phenol (c) Benzene (d) None of these MeO – CH O ¾ ¾xHI¾O¾4 ® What is the maximum value of (x) ? | CH – OH | CH – OH | CH – OH | HC | CH2 – OH (a) 1 (b) 2 (c) 3 (d) 4 114. O CH2 – OH (A) LiAlH4 ( B) H3OÅ ( C). Product C is : (a) (c) CH – CO2Et CH2 – OH CH3 H+ O O (b) CH2 – CH – OH CH – CH2 – OH CH3 O CH3 O OH (d) C – CH3 CH2 – CH2 – OH CH3 https://t.me/studyzee

115. (A) + CH 2 - OH ¾ P¾yri¾di¾ne ® CH2 – O C=O; 375 | CH2 – O O CH 2 -OH || (d) CH 3 - C - OEt Reactant A of the above reaction is : O O || || (c) CH 3 - C - Cl (a) CH 3 - C - CH 3 (b) COCl 2 O OO OO OO O 116. (A) (B) (C) (D) CO2CH3 CO2CH3 CH2 – OH CHO CHO Identify correct combination : CH 2 - OH (c) (C) = KMnO 4 (d) (D) = H 3O Å (a) (A) = | (b) (B)= NaBH 4 CH 2 - SH 117. In the Libermann's nitroso reaction, sequential changes in the colour of phenol occurs as : 118. 119. (a) Brown or red ¾® green ¾® deep blue (b) Red ¾® deep blue ¾® green 120. (c) Red ¾® green ¾® white (d) White ¾® red ¾® green Ethanol when reacts with PCl 5 gives A, POCl 3 and HCl. A reacts with dry Ag 2O to form B(major product) and AgCl. A and B respectively are : (a) C 2H 5Cl and C 2H 5OC 2H 5 (b) C 2H 4 and C 2H 5OC 2H 5 (c) C 2H 6 and C 2H 5OC 2H 5 (d) C 2H 6 and C 2H 5NO 2 O || CH 3 -S- Cl || 14 (B) ¾H¾3O¾Å ® CH 3 - (CH 2) 3 - OH ¾ ¾ ¾O¾¾® (C) ET3N ( A) ¾K¾C¾N ® Product (C) is : (b) CH 3 - (CH 2) 3 - 14 CO 2H (a) CH 3 - (CH 2)3 - CO 2H O || (c) CH 3 - CO 2H (d) CH 3 - C- O - H 14 Choose the best synthesis of phenyl n-propyl ether. OH 1. Na metal (b) H3C OH ¾1¾. N¾a m¾e¾tal ® (a) ¾ 2¾. C¾H3C¾H2¾CH2¾Br/¾® 2. Ph -Br polar,aprotic solvent https://t.me/studyzee

376 CH3 O (c) ¾ 2¾.1C.¾HNa3C¾mHe2t¾-a¾lBr ® (d) OH OH H3C ¾1¾. N2¾a. HmB¾er¾tal ® 121. ¾N¾a2¾Cr2O¾7 ¾H2S¾O¾4 ® The product obtained is : HO O O O (a) O (b) O (c) (d) None of these HO H CO2H 122. What is true for the equilibrium reaction ? 123. OO || || CH 3 - C - OH + CH 3 - OH cat. CH 3 - C - O - CH 3 + H 2O (a) The use of equimolar quantities of CH3OH and CH3COOH will give the greatest yield of the ester at equilibrium (b) Removal of water will increase the amount of ester at equilibrium (c) Addition of CH3COOCH3 will cause the formation of equal an equal number of moles of water (d) Application of pressure increases the amount of ester at equilibrium PCC (Pyridinium chloro chromate) is a good reagent for which of the following transformations ? O OH OH O (a) Cl (b) CO2H OH O CO2H (c) (d) 124. How many primary alcohols (including stereoisomers) are possible with formula C 5H12O ? 125. (a) Two (b) Three (c) Four (d) Five 1-Phenylethanol can be prepared by the reaction of benzaldehyde with the product obtained in the reaction between: (a) CH 3I and Mg (b) C 2H 5I and Mg (c) CH 3Br and AlCl 3 (d) CH 3OH and ZnCl 2 https://t.me/studyzee

377 126. 0.092 g of a compound with the molecular formula C 3H 8O 3on reaction with an excess of 127. CH 3MgI gives 67.00 mL of methane at STP. The number of active hydrogen atoms present in a molecule of the compound is : (a) one (b) two (c) three (d) four Migratory aptitude of the following in decreasing order is : OMe Cl Me (a) (b) (c) (d) (a) a > c > b > d (b) a > d > b > c (c) a > d > c > b (d) b > c > a > b 128. The major product formed in the reaction is : CH2R ¾H¾3O¾+ ® ? OO (a) + RCH 2OH (b) CH2R O HO O (c) + RCH 2OH (d) O CH2R HO CHO HO OH 129. Reaction of R-2-butanol with p-toluenesulphonyl chloride in pyridine then LiBr gives : 130. 131. (a) R-2-butyl bromide (b) S-2-butyl tosylate 132. (c) R-2-butyl tosylate (d) S-2-butyl bromide Optically active 2-octanol rapidly loses its optical activity when exposed to : (a) dilute acid (b) dilute base (c) light (d) humidity If (±) 2-methyl butanoic acid were esterified by reaction with (±) 2-butanol, how many optically active compounds would be present in the final equilibrium reaction mixture ? (a) 2 (b) 3 (c) 4 (d) 6 OH O PBr3 W Mg X (1) V Y CH3 — C — Cl Z (2) H3O+ ether Na2Cr2O7 V Product Z of above reaction is : https://t.me/studyzee

378 O O O – C – CH3 O – C – CH3 (a) O (b) O O – C – CH3 (d) O – C – CH3 (c) H OH 133. C ¾L¾iAl¾H¾4 ® (A) ; Identify the product : AlCl 3 (a) No reaction (b) HH O C || (c) (d) Ph — C — Ph 134. (EtO)2CHCHO + CH 3MgI ¾ ¾H3O¾Å ® (A) 135. Product obtained in the above reaction is : OO OH || || | (a) CH 3 — C — C — H (b) CH 3 —CH — CHO O (d) CH 3 —CH — CH 2 — OH || | (c) CH 3 — C — CH 2 — OH OH Reaction - (1): CH 3 — CH == CH — CH 3 ¾K¾MCon¾lOd¾4 ® (A) ¾N¾aIO¾¾4 ® (B) 2 mole Reaction - (2): CH 3 — CH == CH — CH 3 ¾K¾Mn¾O 4¾Na¾IO¾4 ® (C) 2 mole Product (B) and (C) respectively are : (a) CH 3CHO, CH 3CO 2H (b) CH 3CO 2H, CH 3CHO (c) CH 3CHO in both reaction (d) CH 3CO 2H in both reaction OH 136. TsCl A LiAlH4 B ; Product (B) is : Pyridine, 25°C Pyridine, 25°C https://t.me/studyzee

379 Cl (a) (b) (c) (d) 137. ¾¾® HO – (CH 2)6 – OH, this conversion can be achieved by (a) O 3, Zn, then LiAlH 4 (b) O 3 H 2O 2, then LiAlH 4 (c) cold dil. KMnO 4 ,HIO 4 , then LiAlH 4 (d) All of these 138. Which of the following alcohol on treatment with HCl give 3-chloro-3-methyl cyclohexene as a product ? CH3 CH3 OH CH3 (a) (b) (c) (d) All of these OH OH 139. (a)RCO 3H (A); Product of the reaction is : 140. ¾¾¾¾¾¾ H¾+ ,¾H2¾O ® 141. (b) CH3MgBr (c) CH3 OH OH OH (a) (b) (c) (d) CH3 CH3 OH Esterification (shown below) is a reaction converting a carboxylic acid to its ester. It involves only the carbonyl carbon. Esterification of (-) -lactic acid with methanol yields (+)-methyl lactate. Assuming that there are no side reactions, what is true about this reaction ? OH ¾C¾H3¾O¾H ® OH OH OCH3 HCl O O ( -) (+) (a) An SN2 process has occurred, inverting the absolute configuration of the chiral center (b) An SN1 reaction at the chiral center has inverted the optical rotation (c) A diastereomer has been produced; diastereomers have different physical properties including optical rotation (d) Optical rotation is not directly related to absolute configuration, so the change in sign of rotation is merely a coincidence Which of the following sets of reagents, used in the order shown, would successfully accomplish the conversion shown ? O C| H3 || CHCH2CH2CH3 CCH3 ¾¾® https://t.me/studyzee

380 (a) CH 3CH 2CH 2MgBr; H 3O + ; PCC, CH 2Cl 2 (b) CH 3CH 2CH 2MgBr; H 3O + ; H 2SO 4 , heat PCC, CH 2Cl 2 (c) (C 6H 5 ) 3 + C&& HCH 2CH 3 , B 2H 6 ; CH 3CO 2H P- (d) (C 6H 5) 3 + C&& HCH 2CH 3; H 2O P- 142. O || CO2Et ¾(¾1) ¾H3O¾¾+ ® Product ; Product of the reaction is : (2)D O O O O O || CHO || || CH3 || (c) (d) (a) (b) 143. Which of the following compound on hydrolysis followed by heating gives a product, which 144. gives positive iodoform test? 145. O CO2Et || C –CH3 (a) CH 3 - CH -C - CH 2 - CH 3 (b) || | O CO2Et (c) CH 3 - CH - CO 2Et O O | || || (d) C – O – Et CO2Et Treatment of a 2° OH with CrO 3 H 2SO 4 yields an/a : (a) aldehyde (b) carboxylic acid (c) ester (d) ketone Esterification of the acid P with the alcohols Q will give : H CH3 OH CO2H CH3 (S)-P (±)-Q (a) only one enantiomer (b) a mixture of diastereomers (c) a mixture of enantiomers (d) only one diastereomer 146. O CO2Et ¾H¾2O¾/¾D ® product EtO2C O https://t.me/studyzee

381 Identify major product of the reaction, when the given compound is hydrolysed and heated strongly: O OH OH CO2H CO2H (c) (d) (a) (b) O CO2H HO2C OH O 147. find out the reactivity order with LiAlH 4 : (a) A > B > C > D (b) B > C > D > A (c) D > C > B > A (d) B > D > C > A 148. Find out the reaction in which obtained product give positive isocyanide test: (a) (b) (c) (d) 149. In the above given compound how many functional group reduced by LAH (Lithium aluminium hydride ) and SBH (sodium borohydride) respectively ? (a) 4, 4 (b) 4, 3 (c) 3, 4 (d) 4, 2 150. An unknown compound (A) (molarmass = 180) on acylation gives a product (molar mass 151. = 390) than find the number of hydroxyl group present in compound (A). (a) 5 (b) 6 (c) 10 (d) 1 Which of the following compound is differentiated by NaHCO 3 as well as by NaOH ? CO2H OH OH CH2—OH (a) (b) https://t.me/studyzee

382 CH2—OH OH OCH3 CO2H (c) (d) 152. Arrange the following compounds in order of their reactivity toward LiAlH 4 . OO O CH3 O N i ii iii (a) i < ii < iii (b) i < iii < ii (c) ii < i < iii (d) ii < iii < i 153. Choose the statement that is true about A, B and C in the following separation scheme. Ether Evaporate A layer Naphthalene Diethyl HCl Ether Evaporate B Ether layer .N. Aqueous Make basic with H layer 10% NaOH tetrahydro- H2O isoquinoline Aqueous Evaporate C layer (a) A = tetrahydroisoquinoline, B = naphthalene and C = inorganic ions such as Na + and Cl - (b) A = naphthalene, B = tetrahydroisoquinoline and C = inorganic ions such as Na + and Cl - (c) A = inorganic ions such as Na + and Cl - ,B = naphthalene and C = tetrahydroisoquinoline (d) A = inorganic ions such as Na + and Cl - ,B = naphthalene and C = tetrahydroisoquinoline OH O 154. CH2—OH ¾ ¾x¾HI ® value of x is : O—CH3 CH2 (a) 2 (b) 3 (c) 4 (d) 5 155. CO2H ¾N¾aB¾H¾4 ® ( A) ¾H¾¾r ® (B) D Cyclic CH2—CHO https://t.me/studyzee

Compound (B) is : 383 O O COOH (b) (a) OH O (c) O (d) (a) and (c) both 156. 1-Phenoxypropane is treated with excess of conc. HI at 0° C and the mixture of products is 157. treated with thionyl chloride. The products formed are (a) n-propanol + Chlorobenzene (b) Phenol + n-propyl iodide (c) n-propyl chloride + Chlorobenzene (d) n-propyl chloride + Phenol Amongst the following compounds, the compound having the lowest boiling point is (a) OH (b) OH (c) O (d) OH OH 158. Which statement/s are true about products P & Q. (A) CH3—CH == CH—CH2—OH SOCl2 P ether (6 member T.S.) (B) CH3—C| H—CH == CH2 SOCl2 Q OH ether (6 member T.S.) (a) P & Q are position isomers (b) P show geometrical isomerism but Q not (c) P º CH 3 — CH — CH == CH 2 Q º CH 3 — CH ==CH — CH 2 — Cl | Cl (d) P º CH 3 — CH ==CH — CH 2 — Cl Q º CH 3 — CH — CH == CH 2 | Cl O R | 159. (i) BBr3 Product (ii) H2O https://t.me/studyzee

384 Which of the following is/are possible end product of the above reaction? OH Br || (a) (b) (c) R Br (d) both (a) and (c) ANSWERS — LEVEL 1 1. (c) 2. (a) 3. (b) 4. (c) 5. (b) 6. (b) 7. (b) 8. (a) 9. (b) 10. (b) 11. (b) 12. (b) 13. (a) 14. (a) 15. (a) 16. (a) 17. (d) 18. (a) 19. (b) 20. (a) 21. (a) 22. (a) 23. (d) 24. (a) 25. (b) 26. (b) 27. (b) 28. (b) 29. (c) 30. (c) 31. (b) 32. (b) 33. (a) 34. (b) 35. (b) 36. (c) 37. (c) 38. (c) 39. (d) 40. (c) 41. (b) 42. (b) 43. (d) 44. (d) 45. (b) 46. (a) 47. (b) 48. (b) 49. (a) 50. (b) 51. (a) 52. (c) 53. (c) 54. (c) 55. (b) 56. (a) 57. (d) 58. (c) 59. A-d 59. B-b 59. C-a 60. (c) 61. (c) 62. A-b 62. B-b 63. (b) 64. (c) 65. (b) 66. (a) 67. (a) 68. (d) 69. (a) 70. (c) 71. (b) 72. (d) 73. (d) 74. (c) 75. (b) 76. (d) 77. (c) 78. (c) 79. (d) 80. (c) 81. (c) 82. (d) 83. (a) 84. (b) 85. (b) 86. (c) 87. (c) 88. (b) 89. (d) 90. (a) 91. (c) 92. (b) 93. (b) 94. (a) 95. (d) 96. (b) 97. (c) 98. (a) 99. (c) 100. (a) 101. (d) 102. (b) 103. (c) 104. (c) 105. (d) 106. (c) 107. (b) 108. (a) 109. (c) 110. (d) 111. (c) 112. (b) 113. (b) 114. (b) 115. (b) 116. (d) 117. (b) 118. (a) 119. (b) 120. (a) 121. (a) 122. (b) 123. (b) 124. (d) 125. (a) 126. (c) 127. (b) 128. (c) 129. (d) 130. (a) 131. (c) 132. (b) 133. (c) 134. (b) 135. (a) 136. (c) 137. (d) 138. (d) 139. (b) 140. (d) 141. (c) 142. (b) 143. (b) 144. (d) 145. (b) 146. (c) 147. (b) 148. (a) 149. (d) 150. (a) 151. (c) 152. (d) 153. (b) 154. (b) 155. (a) 156. (b) 157. (c) 158. (a,c) 159. (d) https://t.me/studyzee

385 Level - 2 1. Consider the pairs of ethers, numbered I through V, shown below. To the right of each pair is a description of reaction conditions to be applied to each. One compound of the pair will react more rapidly than the other. Which ether of the two will be more rapidly cleaved? Write your answer in box. (A) Ether Pairs (B) Cleavage Conditions H3C O—CH(CH3)2 & O—CH3 Treated with HBr in I. H3C CH 3CN, 40°C H3C O—C(CH3)3 & C2H5 O—CH3 Treated with H 2SO 4 II. H3C C2H5 in CH 3CN, 40°C O— & O Treated with H 2SO 4 in CH 3CN, 40°C III. Treated with 5% aqueous CH3O OH H 2SO 4 , 25°C & IV. O OH O OCH3 V. O CH(CH3)2 & O CH(CH3)2 Treated with 5% aqueous H 2SO 4 , 25°C https://t.me/studyzee

386 2. Comprehension (a) CH 3 - CH 2 - CH 2 - CH 2 - CH 2 - OH (b) CH 3 - CH 2 - CH 2 -CH - CH 3 | OH CH3 | (c) CH 3 - CH 2 -CH - CH 2 - CH 3 (d) CH 3 - CH 2 -C - OH | | OH CH3 CH3 CH3 | | (e) CH 3 -CH - CH 2 - CH 2 - OH (f) CH 3 -CH -CH - CH 3 | OH CH3 CH3 | | (g) HO - CH 2 -CH - CH 2 - CH 3 (h) CH 3 -C - CH 2 - OH | CH3 Above compounds (a) to (h) are isomers of C 5H12O. Based on the above isomer answer the following (A to F). A. Which isomer is most reactive towards dehydration by conc. H 2SO 4 ? B. Which isomer will undergo rearrangement when treated with conc. H 2SO 4 ? C. Which isomers on dehydration with conc. H 2SO 4 give alkene which is capable to show geometrical isomerism ? D. Which isomer is least acidic ? E. Which isomers on dehydration give most stable alkene ? F. Which isomer on dehydration with conc. H 3PO 4 undergo maximum rearrangement ? https://t.me/studyzee

387 3. Comprehension [O] [O] [O] R — CH3 [H] R — CH2 — OH RCHO RCO2H [H] (alkane lowest alcohol aldehyde [H] (acid highest oxidation no.) oxidation no.) [O] = Oxidation [H] = Reduction Consider the above sequence and answer A to F. A. Conversion (CH 3 - CH 3 ¾® CH 3 - CH 2 - OH) alkane ¾® alcohol is achieved by: (a) Br2 hn, alc. KOH (b) Br2 hn, aq. KOH (c) Br2 CCl 4 , LiAlH 4 (d) Br2 CCl 4 , NaBH 4 B. Conversion R - CH 2 - OH ¾® R - CHO can be done by: (a) PCC CH 2Cl 2 (b) Cu, 300ºC (c) CrO 3 (d) All of these C. Conversion R - CHO ¾® R - CO 2H can be done by: (a) KMnO 4 (b) H 2CrO 4 (c) K 2Cr2O7 (d) All of these D. Conversion R - CO 2H ¾® R - CHO can be done by: (a) LiAlH 4 (b) NaBH 4 (c) DIBAL – H (d) All of these E. Conversion R - CHO ¾® R - CH 2 - OH can be done by: (a) LiAlH 4 (b) NaBH 4 (c) H 2 Ni (d) All of these F. Reduction R - CH 2 - OH ¾® R - CH 3 can be done by: (a) LiAlH 4 (b) NaBH 4 - AlCl 3 (c) H 2 - Ni (d) Red P + HI 4. Which of the following is true for 3-methylbutanal ? a. This compound may be classified as an aldehyde. b. This compound may be classified as a ketone c. An aldol reaction takes place on treatment with NaOH solution. d. There is no reaction with LiAlH 4 in ether solution. e. An excess of CH 3 MgBr in ether reacts to give 4-methyl-2-pentanol. f. Wolff-Kishner reduction gives butane. g. This compound is an isomer of 3-pentanone. https://t.me/studyzee

388 5. This problem is an introduction to the planning of multistep syntheses. For use, you have six reactant compounds (A through F) ; and eight reagents (1 through 8), shown below. Following these lists, five multistep syntheses are outlined. For each of these, certain reactants or reagents must be identified by writing an appropriate letter or number in designated answer boxes. Write a single letter or number, indicating your choice of the best reactant or reagent, in each answer box. Reactant Compounds : O O O OO OH O O (A) (B) (C) (D) (E) (F) Reagents : (2) PCC [CrO 3 in pyridine + HCl] (1) Jones’ reagent [Na 2Cr2O7 in H 3O+ ] (4) Sodium borohydride NaBH 4 (3) Sodium hydride NaH (6) Phosphorus tribromide PBr3 (8) Magnesium turnings in ether (5) Thionyl chloride SOCl 2 (7) Aluminium trichloride AlCl 3 CH2 – OH (1) Reagent R¾e¾age¾n¾t ® O (2) reactant O 1. ¾(3¾) ¾H3¾O(¾+)¾¾¾® C9H12O2 H O Reactant R¾ea¾ge¾nt¾® C3H6O2 (1) Reagent 2. C ¾¾¾¾¾¾® (2) Reactant Reagent heat (1) Reagent O O – CH2CH2CH3 3. OH (2) Reagent C6H10O2 (1) Reactant ¾¾ ¾ ¾¾¾® ¾¾ ¾ ¾¾¾® (3) CO2 (4) H3O(+) heating with catalytic acid 4. Reactant Reagent C3H6O (1) NaOH solution OCOCH3 C ¾¾¾¾¾¾® (2) Reagent OCOCH3 ¾¾ ¾ ¾ ¾¾® (3) Reactant 5. Reactant ¾(1¾)R¾ea¾ge¾nt¾® C3H7Br (1) Reagent OH B (2)Reagent (2) Reactant ¾¾ ¾ ¾ ¾¾® (3) H3O(+) https://t.me/studyzee

389 6. Which of the following is true for 3-methyl-2-butanone? a. It may be prepared by CrO3 oxidation of 2-methyl-2-butanol. b. Its reaction with NaBH 4 gives a secondary alcohol. c. It may be prepared by acidic Hg 2+ catalyzed hydration of 3-methyl-1-butyne. d. It forms a silver mirror on treatment with [Ag(NH 3 ) 2 ]+ . e. This compound is an isomer of 4-penten-1-ol. 7. Which of these methods would serve to prepare 1-phenyl-2-propanol? a. Addition of benzyl Grignard reagent to acetaldehyde (ethanal). b. Addition of phenyl lithium to propylene oxide (methyloxirane). c. Addition of phenyl Grignard reagent to acetone (2-propanone). d. Acid-catalyzed hydration (addition of water to) of 2-phenyl-1-propene. e. Addition of methyl Grignard reagent to acetophenone (methyl phenyl ketone). f. Addition of methyl Grignard reagent to phenylacetaldehyde. 8. Match the Column (I) and (II). Column (I) Column (II) Reaction Name of Reaction (a) ¾H¾¾+ ® (p) Pinacol-Pinacolone rearrangement D OH OH https://t.me/studyzee

390 ¾N¾aN¾O¾2 ® (q) Semi-Pinacol reaction (b) (r) Pinacolic-Diazotization (c) 2HCl OH NH2 ¾H¾¾+ ® D O (d) ¾(¾1)T¾sC¾l, ® (s) (2)Et 3N, D Pinacol fashion reaction OH OH Column (II) 9. Match the Column (I) and (II). Products CH3 Column (I) 14 Reactant OCH3 (a) CH3 ¾ ¾C¾H3O¾H¾® (p) CH3 OH (q) CH3 H2SO 4 Conc. (r) CH3 (s) OCH3 (b) CH3 ¾(¾1)N¾a¾H ® CH3 OH OCH3 (2) CH3I (c) CH3 ¾(¾1) H¾¾Br ® OH (2) Mg (3) CH3I (d) OCHH3¾(¾11)4N¾a ® (2)C H3I https://t.me/studyzee

391 10. Reaction 1. HO CH2 – OH 5HIO4 H H C == O H OH OH CH2OH Reaction 2. HO CHO 5HIO4 H H H OH H OH OH CH2OH Ratio of moles of formaldehyde obtained in the reaction (1) and reaction (2) ? 11. Comprehension Di-tert-glycols rearrange in the presence of acid to give a-tertiary ketones. The trivial name of the simplest glycol of this type is pinacol, and this type of reaction therefore is named pinacol rearrangement (in this specific case, the reaction is called a pinacol-pinacolone rearrangement). The rearrangement involves 4 steps. one of the hydroxyl groups is protonated in the first step. A molecule of water is eliminated in the second step and a tertiary carbocation is formed. The carbocation rearranges in the third step into a more stable carboxonium ion via a [1, 2] rearrangement. In the last step, the carboxonium ion is deprotonated and the product ketone is obtained. Me Me Me Me Me Me Å Me HO Å O–H HO OH H2SO4 HO Å – H2O 1,2-shift (I) (II) (III) Me OH2 Me Me Me Me Me Me Me Me O Me Pinacol (IV) Me – HÅ Me Me Pinacolone A. What is R.D.S. of pinacol-pinacolone rearrangement ? (a) I step (b) II step (c) III step (d) IV step https://t.me/studyzee

392 Et Ph CH3 Ph B. HO OH + HO OH H2SO4 D Et Ph CH3 Ph How many products obtained in above reaction ? (a) 1 (b) 2 (c) 3 (d) 4 OH O (d) C. CH2–Cl ¾A¾gN¾O¾3 ® P D Product 'P' is : O Cl O O (b) (c) (a) CH3 CH3 D. CH3 CH3 NaNO2 (A) HCl OH NH2 Product (A) is : CH3 CH3 O CH 3 (b) CH3 CH3 || | (a) CH 3 — C — C — CH 3 OH OH | CH 3 (c) (d) None of these Subjective Problems O CH==O 1. ( A) ¾4¾m¾oles¾of ¾PC¾C ® CH==O O Maximum number of moles of Ac 2O consumed by reactant ( A) is : https://t.me/studyzee

ANSWERS — LEVEL 2 393 1. I – B; II – A; III – A; IV – B; V – B O H 2. A – d; B – a, c, e, f, g, h; C – a, b, c; D – d; E – d, e, f, g, h; F – e 3. A – b; B – d, C – d, D – c, E – d; F – d 4. a, c, e, g CH2 – OH (1) Reagent 3 R¾e¾age¾n¾t 2® O (2) reactant d 5. ¾(3¾) ¾H3¾O(¾+)¾¾¾® C9H12O2 Reactant R¾ea¾ge¾nt¾1® C3H6O2 (1) Reagent 5 +& O C ¾¾¾¾¾¾® (2) Reactant A O Reagent 7 O – CH2CH2CH3 heat OCOCH3 OCOCH3 (1) Reagent 6 OH (2) Reagent 8 C6H10O2 (1) Reactant C ¾¾ ¾ ¾¾¾® ¾¾ ¾ ¾¾¾® (3) CO2 (4) H3O(+) heating with catalytic acid Reactant Reagent 2 C3H6O (1) NaOH solution C ¾¾ ¾ ¾ ¾¾® (2) Reagent 4 ¾¾ ¾ ¾ ¾¾® (3) Reactant F Reactant ¾(1¾) R¾ea¾ge¾n¾t 4® C3H7Br (1) Reagent 8 OH B (2) Reagent 6 (2) Reactant C or F ¾¾ ¾ ¾ ¾¾® (3) H3O(+) 6. b, c, e 7. a, b, f 8. a – p, b – r, c – s, d – q 9. a – s, b – r, c – q, d – p 10. Ratio of reaction I and II = 2 11. A – b; B – b; C – c; D – a Subjective Problems 1. 4 https://t.me/studyzee

394 7 ALDEHYDES AND KETONES Level - 1 1. ¾N¾2H¾4 ¾KOH¾H¾2¾O ® ( A) ; Product A is : (Wolff - Kishner reduction) major (a) (b) Cl O OH (c) O NO2 (d) NO2 https://t.me/studyzee

395 O CH2 — CH3 C — CH3 2. CH2 — CH2 — NMe3 CH2 — CH2 — NMe3 Above conversion can be achieved by : (a) Wolf-Kishner reduction (b) Clemmensen reduction (c) LiAlH 4 (d) NaBH 4 O 3. CH3 ¾ C ¾ CH2 ¾ CH2 ¾ CH ¾ CH2 ¾¾® CH3 ¾ (CH2)3 ¾ CH ¾ CH2 O O Above conversion can be achieved by : (a) Wolff- Kishner reduction (b) Clemmensen reduction (c) HS — CH 2 — CH 2 — SH, following by Raney Ni (d) None of these O C — CH3 4. ¾Z¾n(H¾¾g)® ; Product of the Clemmensen reduction is : HCl NO2 OH OH CH2 — CH3 CH — CH3 CH2 — CH3 CH2 — CH3 (a) (b) (c) (d) NO2 NO2 NH2 NO2 OH O OH | || | 5. CH 3 — CH — CH 2 — CH 2 — C — CH 3 ¾® CH 3 — CH — (CH 2 )3 — CH 3 Above conversion can be achieved by : (a) Wolff-Kishner reduction (b) Clemmensen reduction (c) LiAlH 4 (d) NaBH 4 https://t.me/studyzee

396 O C — CH3 CH2 — CH3 CH2 — CH3 CH2 — CH3 Zn(Hg) (A) HCl 6. NHHO2–—/DNH2 (B) OH OH Cl Cl (P) (Q) (R) Identify product (A) & (B) from the given product P ,Q , R: (d) A = R , B = P (a) A = P , B = Q (b) A = Q , B = R (c) A = Q, B = P O 7. C — CH3 HO ¾Z¾n(H¾¾g)®( A) ; Identify the A. (a) HCl HO CH2 — CH3 (b) Cl (c) OH Cl (d) O C — CH3 8. ¾ ¾ ¾ ¾HNO¾2-H,¾4D ¾ ¾¾® (A) ; Product (A) is : (Wolff - Kishner reduction) CH2 — CH2 — Br CH2 — CH3 (a) (b) CH2 — CH2 — OH https://t.me/studyzee

397 (c) (d) CH2 — CH2 — Br CH — CH3 Br 9. ; Above conversion can be carried out by : (a) Clemmensen reduction (b) Wolff-Kishner reduction (c) LiAlH 4 (d) NaBH 4 10. Increasing order of equilibrium constants for the formation of a hydrate: O OO O NH2 NH2 O2N (I) (II) (III) (IV) (a) IV < III < II < I (b) IV < III < I < II (c) I < II < III < IV (d) II <III < I < IV 11. CººC OCH3 ¾H¾gS¾O4® (A) Product (A) is: (a) O (c) C—CH2 dil. H2SO4 Major product O OCH3 (b) C—CH2 OCH3 CH2—C OH OCH3 OCH3 (d) CH2—CH OH https://t.me/studyzee

398 ¾H¾2¾O ® (A) 12. Predict the product of hydrolysis of the above molecule. O CO2H (a) (b) (c) (d) OH OH OH OH , This conversion can be achieved by : 13. OH O (b) Me 2CO H + ,KMnO 4 ,H 3O + (a) Me 2CO H + ,H 3O Å ,KMnO 4 HO - (d) KMnO 4 NaIO 4, H 3O + ,Me 2CO H + (c) KMnO 4 NaO 4 , Me 2CO H + , H 3O + 14. O ¾H¾3O¾¾Å ® A + B. Compound (A) & (B) can be differentiated by: (a) 2-4-DNP (b) Fehling solution (c) Lucas reagent (d) NaHSO 3 O || 15. ¾H¾OH¾, H¾+ ¾cata¾ly¾st ® ( A) + H — C — OMe ; Product (A) is : 20°C,15 min Methyl formate (a) (b) (c) (d) https://t.me/studyzee

399 P QR O 16. O Reagents to carry out above conversion, P, Q, R respectively are : (a) H 2C == CH — CH 2 — Br,(HO Q ),[HO Q , D], Wacker-process (b) H 2C == CH — CH 2 — Br(HO Q ), Wacker-process, HO Q , D (c) Wacker process, H 2C == CH — CH 2 — Br(HO Q ),HO Q(D) (d) Wacker process, HO Q(D),H 2C == CH — CH 2 — Br(HO Q ) O CO-2 O R C¾O¾O¾H 17. + ¾® Above reaction is a Baeyer Villiger rearrangement of an asymmetric ketone with magnesium mono peroxo pthalate hexahydrate (in the drawing, Mg +2 is omitted for clearity) Identify major product. OO R OH R O (a) (b) (c) (d) 18. , Above compounds can be differentiated by following reagent: (a) 2-4 DNP (Brady reagent) (b) Tollen's reagent (c) Lucas reagent (d) NaHSO 3 OH OH OH 19. OH PCC (excess) (A) 1 equivalent (B) CH3MgBr (C) NaBH4 (D) H+ H3O+ Product (D) will be : OH OH OH (b) OH CH ¾ CH3 (a) OH OH (c) OH OH (d) https://t.me/studyzee