MS CHAUHAN ADVANCE

400 BH3,THF (P) Pyridinium Chloro Chromate (PCC) (Q) 20. CH3—CH == CH2 H2O2,O–H CH2Cl2 Hg(OAc)2,H2O (R) Pyridinium Chloro Chromate (PCC) (S) NaBH4,HOs CH2Cl2 Relationship between products (Q) and (S) is: (a) Positional isomer (b) Chain isomer (c) Stereoisomer (d) Functional isomer 21. In the reaction, O ¾1¾. A¾l(Hg¾), b¾en¾zen¾e, h¾e¾at ® X, the product (X) is : 2. H2O, heat (a) O (b) OH O HO (c) (d) O 22. Rank the following in order of increasing value of the equilibrium constant for hydration, K hyd. (smallest value first). O O O (CH3)3CCC(CH3)3 (a) 1 < 2 <3 1 23 (d) 2 < 3 < 1 (b) 3 < 1 < 2 (c) 2 < 1 < 3 O 23. O ¾¾® O SS Above conversion can be achieved by: (b) NH 2 — NH 2 KOH D (a) Zn(Hg),HCl (d) H 2 Ni (c) LiAlH 4 https://t.me/studyzee

401 24. Which sequence represents the best synthesis of hexanal ? CH 3CH 2CH 2CH 2CH 2CH == O Hexanal O || (a) 1. CH 3CH 2CH 2 CH 2Br + NaC ºº CH (b) 1. CH 3CH 2CH 2CH == CH 2 + CH 3 C OOH 2. H 2O, H 2SO 4 ,HgSO 4 2. CH 3MgBr, diethyl ether 3. H 3O + O 4. PCC, CH 2Cl 2 || (d) 1. CH 3CH2CH2CH2MgBr + H 2C — CH 2 (c) 1. CH 3CH 2CH 2CH 2 C CH 3 O 3. LiAlH 4 2. H 3O + O || 3. PCC, CH 2Cl 2 2. CH 3 C OOH 4. H 2O 5. PCC, CH 2Cl 2 O 25. ¾H¾NO¾¾3 ®( A) ¾C¾a(O¾H¾)2 ®(B), Product (B) in this reaction is : (a) O O O O (d) (b) (c) CH2OH CH2O HO H HO H CH — Ph 26. H OH (?)x H O, OH OH H H CH2 — OH CH2 — OH Compound (x) in the above reaction is : O O || || (a) Ph — C — CH 3 (b) Ph — C — H O O || || (c) Ph — CH 2 — C — H (d) Ph — CH 2 — C — CH 3 https://t.me/studyzee

402 O || 27. Ph — C— CH 3 ¾N¾aN¾O¾2 ®( A) ¾ A¾C 2¾O¾®( B) ¾H¾3O¾+ ®(C) HCl heat Product (C) of the above reaction is : (a) Ph — CO 2H O || OO (b) Ph — C — CO 2H || || (c) Ph — C — C — H O || (d) Ph — C — CH 2OH O || 28. ¾H¾—¾C —¾¾H ®( A) ¾A¾gN¾O¾2 ® (B) ; Product (B) of the reaction is : 2HCl (a) Ph — CH 2 — NO 2 (b) Ph — CH 2 — ONO (c) Ph — CHO (d) Ph — O — N == O O 29. ¾B¾¾r2 ® ( A) ; 0.75 mole %, (100%) AlCl3 Et2O Product (A) of the above reaction is (bromination occur not in the benzene ring) : O Br O (a) Br (b) O Br (c) O C CH3 (d) Br +ive Iodoform test –ive Tollens test 30. C6H12O3 ¾ ¾ ¾H¾2O ¾¾® Positive Tollens test A drop of H2SO4 Compound (A) is : O O OCH 3 || | || (a) CH 3 — C— CH — CH 2 (b) CH 3 — C — C — CH 3 | | | OCH 3 OCH 3 OCH 3 https://t.me/studyzee

O 403 || (c) CH 3 — C — CH 2 — CH — OCH 3 O || | (d)H — C — CH 2 — CH 2 — CH — OCH 3 OCH 3 | OCH 3 31. C 16H 16 ¾O¾¾3 ® (B) ¾N¾H¾2—¾NH¾2 ® ; Reactant (A) in this reaction is : (A) C 8H8O HO- D Ph CH3 Ph CH3 (a) C == C (b) C= =C Ph CH3 CH3 Ph Ph Ph (d) both (b) and (c) (c) C= = C CH3 CH3 P C7H14O2 H3OÅ 32. O—O—H 1-methyl1-cyclohexyl +ive +ive +ive test with hydrogenperoxide Iodoform 2-4 DNP CrO3 test test Compound (P) is : O || (a) CH 3 — C — CH 2 — CH 2 — CH 2 — CH — CH 3 | OH O OH || | (b) CH 3 — C — CH 2 — CH — CH 2 — CH 2 — CH 3 O || (c) CH 3 — C — CH 2 — CH 2 — CH 2 — CH 2 — CH 2 — OH O OH || | (d) CH 3 — C — CH — C — CH 3 || CH 3 CH 3 https://t.me/studyzee

404 33. Correct order of reactivity of following compounds towards Grignard reagent? O O O || || CH3—C CH 3 — C — H H — C— H (III) (I) (II) (a) I > II > III (b) II > I > III (c) II > III > I (d) I > III > II CH2 ¾ 34. CH3 ¾ CH ¾ CH ¾ CH2 ¾ OH ¾H¾CH¾¾O ® ( A) ; Product (A) is : TsOH, D 93% OH (a) (b) (c) (d) O I 35. (CH3)3CO ¾ C ¾ CH2 ¾ CH2 ¾ CH — — OCH2CH2CH3 ¾K¾O¾H ® H2O D OH OCH3 Total number of products obtained in above reaction is : (a) 2 (b) 3 (c) 4 (d) 5 https://t.me/studyzee

405 36. What reagent and/or reaction conditions would you choose to bring about the following conversion? O CH == O + HOCH 2CH 2OH ¾® O (a) 1. LiAlH 4, 2. H 2O (b) H 2O, H 2SO 4, heat (c) H 2O, NaOH, heat (d) PCC, CH 2Cl 2 O || MeI excess 37. ¾K¾H ¾exc¾e¾ss ® 81% yield ; Product of the reaction is : O O O O || || || || (a) (b) (c) (d) 38. HO O || C ¾® HO The above reduction can be best carried out by : (a) Clemmensen reduction (b) Wolff-Kishner reduction (d) None of these (c) NaBH 4 39. CH 3 — C ºº CH ¾H¾gS¾O¾4 ®( A) dil. H2SO4 CH 3 — C ºº CH ¾(¾1)B¾H3¾×TH¾F ® (B) (2) H2O2/ HO- Product ( A) and (B) is differentiated by: (a) 2-4-DNP (b) NaOI (c) Na-metal (d) NaHSO 3 https://t.me/studyzee

406 O 40. ¾H¾C¾N ®( A) ¾L¾iAl¾H¾4 ®(B) ¾N¾aN¾O¾2 ®(C) OH | HCl OH CH2 End product (C) in above reaction is : (d) OOO (a) (b) (c) 41. Compound (X) C 4H 8O, which reacts with 2, 4-DNP derivative and gives negative haloform test is : O || (a) CH 3 — C — CH 2 — CH 3 (b) CH 3 — CH — CHO | CH3 OH OH | (c) (d) CH 3 — CH 2 — CH — CH 3 42. When a nucleophile encounters a ketone, the site of attack is : (a) the carbon atom of the carbonyl (b) the oxygen atom of the carbonyl (c) both the carbon and oxygen atoms, with equal probability (d) no attack occurs as ketones do not react with nucleophiles 43. The correct order of rate of reaction toward nucleophilic addition reaction: CHO CHO CHO O || O C – Ph || CH3 - C - Et NO2 OMe (d ) (e) (a) (b) (c) (b) a > b > d > c > e (d) a > b > e > d > c (a) a > b > c > d > e (c) a > d > e > b > c 44. The structure O OH would be best classified as a(an) : (a) Acetal H (c) Hydrate (d) Cyanohydrin (b) Hemiacetal 45. Which of the following pairs of reactants is most effective in forming an enamine ? O O || || (a) CH 3CH 2 CH + [(CH 3 )2 CH]2 NH (b) + CH 3 — NH — CH 3 https://t.me/studyzee

407 O (d) None of these form an enamine. || (c) (CH 3 )3 CCH + (CH 3 )2 NH 46. The reaction of C 6H 5CH == CHCHO with LiAlH 4 gives : (a) C 6H 5CH 2CH 2CH 2OH (b) C 6H 5CH == CHCH 2OH (c) C 6H 5CH 2CH 2CHO (d) C 6H 5CH 2CHOHCH 3 O 47. ¾ ¾Na¾BH¾4 ®( A) ¾ ¾H+¾®(B) ; Product (B) of the reaction is : D O O O OO (a) (b) (c) (d) OH OH 48. Which of following compound is hemiacetal ? H OH HO OMe O OH (a) (b) (c) (d) all of these O 49. Ph — CH 2 — C ºº N ¾L¾TDH¾AF ® ¾C¾H¾3I® 71% ; End product of the reaction will be : (a) Ph — CH 2 — CH 2 — NH 2 (b) Ph — CH 2 — NH 2 (c) Ph — CH — C ºº N (d) Ph — CH == C == N — CH 3 | CH3 O || 50. Ph — CH == CH — C — CH 3 ¾® Ph — CH == CH — CO 2H Above conversion can be achieved by : (b) I2 NaOH followed by H + (d) LiAlH 4 (a) KMnO 4, D followed by H + (c) H 2 Pt OH 51. ¾H¾3O¾¾Å ® Products ; Product of the reaction is/are : O O CH2 OH OH (a) (b) OH (c) HCHO (d) Both (a) and (c) OH OH OH https://t.me/studyzee

408 ¾S¾eO¾2 ® (A); Product (A) of the reaction is : O || 52. O OH O O O O || || || || O (a) (b) (c) (d) O || CH3 53. COCH3 ¾B¾r2¾+Na¾O¾H ® (A) + CHBr3 ; Product (C) of the reaction is : D ¾¾H+® (C) D OO OO || || || Br || CBr3 (a) (b) (c) CH3 (d) OO OO ¾H¾3O¾¾Å ® (A) + 2 Glycol 54. Product (A) of the reaction will be : OO || || (a) CH 3 — CH 2 — C — CH 2 — C — CH 2 — CH 3 OO || || (b) CH 3 — CH 2 — C — CH 2 — CH 2 — C — CH 3 OO || || (c) CH 3 — CH 2 — C — CH 2 — C — CH 3 OO || || (d) CH 3 — C — CH 2 — C — CH 3 O || 55. R — C — H ¾R¾-N¾H¾2 ® R — CH ==N — R. This reaction gives best yield at : (a) pH 1 - 2 (b) pH 4 - 5 (c) pH 10 - 11 (d) pH 13 - 14 56. An aromatic compound A of the molecular formula C 8H10O on reaction with iodine and dilute NaOH gives a yellow precipitate. The structure of the compound is expected to be: (a) C—CH3 (b) C 6H 5CHOHCH 3 O (c) CH3 CH2OH (d) CH3 OH CH3 https://t.me/studyzee

409 57. Compound A (molecular formula C 3H 8O) is treated with acidified potassium dichromate to form a product B(molecular formula C 3H 6O). B forms a shining silver mirror on warming with ammonical silver nitrate, B when treated with an aqueous solution of NH 2NHCONH 2 and sodium acetate gives a product C. Identify the structure of C. (a) CH 3CH 2CH == NNHCONH 2 (b) CH 3C|== NHHCONH 2 CH3 (c) CH 3C| == NCONHNH 2 (d) CH 3CH 2CH == NCONHNH 2 CH3 58. In the reaction, the acid obtained will be : CH3CHO + HCN ¾® CH3CH(OH)CN ¾H¾-O¾¾H ® CH3CH(OH)COOH (a) D-isomer (b) L-isomer (c) (80%D + 20%L) mixture (d) (50%D + 50%L) mixture 59. In the following sequence : CH 3CH 2Cl ¾N¾aC¾N ® (i) ¾N¾i H¾¾2 ® (ii) ¾a¾cet¾ic a¾nhy¾dri¾¾de® (iii), Product (iii) is : (a) CH 3CH 2CH 2NH 2 (b) CH 3CH 2CH 2CONHCH 3 (c) CH 3CH 2CH 2NHCOCH 3 (d) CH 3CH 2CH 2CONHCOCH 3 O || O C – H ¾K¾HM2On¾O,¾D4 ® ¾H¾3O¾¾Å ® (G) 60. O Product (G) is : O HO CO2H || (b) O C – OH (a) HO – CH2 O O (d) O || C–H HO CO2H (c) HO 61. Carbonyl compounds can generally be converted to hydrocarbons by : (a) H 2 Pt (b) LiAlH 4 (c) N 2H 4-KOH/D (d) K 2Cr2O7 - H 2SO 4 62. Et (1) ¾OAg32¾O¾® (A); Product (A) is : ¾(¾2) (3) NaBH4 (4) HÅ O OO O O O (c) (d) (a) (b) Et Et Et Et https://t.me/studyzee

410 63. Which statement about the aldol condensation is correct ? (a) A Lewis acid is commonly used as a catalyst (b) The initial step is probably the formation of a carbanion (c) A Lewis base is employed to induce carbocation formation (d) The carbon chain is lengthened through the elimination of 1 mole of water 64. A compound gives a positive test with I2 NaOH and is extracted from benzene by saturated NaHSO 3. It may be : (a) CH 3(CH 2 )4 CHO (b) CH 3(CH 2 )3 COCH 3 (c) CH 3CH 2COCH 2CH 3 (d) CH 3(CH 2 )4 CH 2OH 65. Which of the following compounds on reaction with excess CH 3MgBr and subsequent hydrolysis will give a tertiary alcohol? (a) C 2H 5CHO (b) C 2H 5CO 2CH 3 (c) C 2H 5COOH (d) CH3CH—CHCH3 O N ¾ OH 66. A + B ¾¾¾® Reactant (A) and (B) is : (a) Ph ¾ CH 2 ¾ CH == O + NH 2 ¾ OH (b) Ph ¾ CH == O + NH 2 ¾ OH O O || || (c) Ph ¾ C ¾ CH 3 + NH 2 ¾ NH 2 (d) Ph ¾ C ¾ CH 3 + NH 2 ¾ OH O O (b) 67. CH 3 ¾ || ¾Ca¾(O¾H)®2 ( A) C ¾ OH D Product (A) is : (a) O OH (c) (d) OH 68. Which of the following does not form a stable hydrate on addition of H2O ? O O OO || || || (a) Ph — C — C — C — Ph (b) O (c) O O O (d) https://t.me/studyzee

69. Consider the following sequence of reactions. 411 Ketone A ¾1¾. C¾2H¾5M¾gB¾r ® B ¾H¾2S¾O4¾, h¾e¾at ® C ¾1¾. O¾3 ® H 2. H2O -H 2O 2. Zn, H2O + O O The ketone (A) is : (d) (a) (b) (c) O O O O 70. In the reaction, + CH3COCH3 ¾E¾tO¾Na ¾EtO¾¾H ® X, the product (X) is : heat H3C CH3 H3C CH3 (a) (b) OH CH3 CH3 (c) C (d) C CH3 CH3 71. The conversion of acetophenone into benzoic acid can be achieved by its reaction with : (a) sodium hydroxide followed by acidification (b) iodine and sodium hydroxide, followed by acidification (c) hydroxylamine followed by reaction with H2SO4 (d) m-chloroperoxobenzoic acid 72. In which of the following compounds the methylenic hydrogens are the most acidic ? (a) CH 3COCH 2CH 3 (b) CH 3CH 2COOC 2H 5 (c) CH 3CH 2CH(COOC 2H 5 )2 (d) CH 3COCH 2CN 73. Which is the major product of the following reaction ? O ¾NHH¾¾2ÅOH® OH OH OEt OH (a) (b) (c) (d) N ONH2 NHOH OH O 74. Ph ¾ || ¾ OH ¾SO¾Cl®2 ( A) ¾¾H¾2 ® ( B) C Pd- BaSO4 Product (B) is : https://t.me/studyzee

412 O (b) Ph ¾ CH 2 ¾ OH || (d) Ph ¾ CH == CH 2 (a) Ph ¾ C ¾H (c) Ph ¾ CH 2 ¾ Cl 75. The presence of unsaturation in organic compounds can be tested with : (a) Schiff's reagent (b) Tollens' reagent (c) Fehling's reagent (d) Baeyer’s reagent 76. Which of the following gives iodoform test ? (a) CH 3CH 2OH (b) C 2H 5CHO (c) (CH 2OH)2 (d) None of these 77. Which of the followingb-keto carboxylic acid does not undergo decarboxylation on heating ? CO2H (a) (b) O CO2H O CO2H CH3 (c) O (d) None of these Br O || ¾P¾C¾C ®( A) ¾H¾2C¾==¾CH¾Mg¾Br ®(B) ¾N¾H¾4Cl ¾H2¾O ®(C) 78. HOCH 2CH 2CH 2 — C— OCH 2CH 3 (1 molar equivalent) O || ¾K¾O¾H ® ¾H¾3O¾¾Å ® ¾(¾CH¾3 —¾C )¾2¾O ®(D) H 2O Pyridine Product (D) is : O || O — C — CH 3 O | || (a) H 2C == CH — CH — CH 2 — CH 2 — C — OH (b) H 2C == CH — CH 2 — C — CO 2H | OH OO || || (c) H 2C == CH — C — CH 2 — CH 2 — C — O — C — CH 3 | OH O || (d) H 2C == CH — CH 2 — CH — CH 2 — C — O — H | OH https://t.me/studyzee

413 79. The compound shown in the below undergoes racemization on reaction with aqueous acid. H OH O Which of the following structures best represents the intermediate responsible for this process? OH H OH OH H OH (a) (b) (c) (d) O OH OH HO OH 80. The final product of the following sequence of reaction is : (CH 3O) 2 CHCH 2CH 2CH 2Br ¾M¾g ® H¾2C¾==®O ¾Hh¾3eOat®+ O O || || (a) CH 3O C CH 2CH 2CH 2CH 2OH (b) CH 3 C CH 2CH 2CH 2CH 2OH O OO || || || (c) H C CH 2CH 2CH 2CH 2OH (d) H C CH 2CH 2CH 2 C H 81. The amino ketone shown below undergoes a spontaneous cyclization on standing. What is the major product of this intramolecular reaction ? O CCH3 CH2CHNH2 | CH3 O (a) (b) CH3 (d) CH3 (c) NH2 https://t.me/studyzee

414 82. Compound (A) C 6H12O is optically active. Compound (A) give negative Tollens test and positive test with 2-4-di-nitro phenyl hydrazine. Identify A. O O || || (a) CH 3 — C — CH 2 — CH — CH 3 (b) CH 3 — C — CH — CH 3 | | CH3 CH 2 —CH 3 O O || || (d CH 3 — C — CH 2 — CH 2 — CH 2 — CH 3 (c) H — C — CH 2 — CH — CH 3 | CH 2 —CH 3 83. ¾(¾1)E¾t2¾O ® ( A) ; Product (A) of the reaction is : (2) H3OÅ 99% O NO2 O NO2 (a) (b) O NO2 O NO2 (c) (d) 84. O MgBr ( N) ¾N¾H¾4¾Cl ®(O) ¾H¾Cl¾(co¾nc¾.)®(P) ¾K¾OH¾(4¾mo¾la¾r)®(Q ) Product (Q) will be : H2O cold ethanol, D (a) (b) (c) (d) OH (d) Ph — CH 3 85. Ph — CH 3 ¾C¾rO¾2C¾l2 ®( A) ¾c¾on¾c.KO¾¾H ® Ph — CH 2OH + (B) Product (B) of above the reaction is : (a) Ph — CO 2H (b) Ph — CO - (c) Ph — CHO 2 https://t.me/studyzee

415 86. CHO H ¾(¾i)K¾C¾N ® Product ; Product obtained in the reaction is : OH (ii)H+ CH2 — OH D-(+)-Glyceraldehyde (a) Diastereomer (b) Racemic (c) Meso (d) Optically pure enantiomer O 87. ¾N¾H¾2O¾H ®( A) ¾H¾¾+ ®(B) ¾L¾A¾H ®(C); Product (C) of the reaction is : (a) (b) (c) (d) 88. C ºº N + CH 3MgBr ¾H¾3Or® ( A) ¾N¾aO®I (B) + (C) 14 Product (A) and (C) is : O O 14 (a) C ¾ CH3 ; CHI3 O (b) C ¾ CH3 ; CHI3 (c) C ¾ CH3 ; CHI 3 (d) CH2 ¾ CHO ; CHI 3 14 14 OH O || 89. | ¾P¾CC® Ph ¾ CH ¾ CH 3 ( A) ¾N¾H2¾¾¾NH¾¾¾C ¾¾N¾H®2 (B) Product (B) is : CH 3 O O | || || (a) Ph ¾ C == N ¾ C ¾ NH ¾ NH 2 (b) Ph ¾ C == N ¾ NH ¾ C ¾ NH 2 | O CH 3 O || || (c) Ph ¾ CH == N¾N¾ C ¾NH 2 (d) Ph ¾ CH == N ¾ C ¾ NH 2 | CH 3 https://t.me/studyzee

416 O 90. ¾2¾EHtOr¾H® (P) Product (P) is : (b) Acetal (c) Alcohol (d) Alkane (a) Hemiacetal 91. ; Product of rearrangement is : O OMe (Oxyallyl cation) (a) CH2 (b) O OMe OMe O CH2 (c) (d) OMe OMe O Keq OH CN RC R 92. + HCN R R Reactant K eq. a PhCHO O b O c || d Ph — C — CH 3 O || CH 3 — C — H The correct order of decreasing value of K eq. is : (a) a > b > c > d (b) d > a > b > c (c) d > b > a > c (d) d > a > c > d https://t.me/studyzee

417 93. Product (B) of the given reaction is : O O O + HO OH H+ Me — O — S (B) (b) O OH (A) OMe SO3Me O Me OMe O O (a) O O (c) base SO2OMe OO (d) 94. End product (C) of the reaction is : OO HO OH ( A) ¾2¾Ph¾Mg¾¾Br ®(B) ¾H¾3O¾¾Å ®(C) OEt H+ O O OH (c) OH O OH O Ph (b) Ph (d) Ph Ph Ph Ph OEt (a) OH does not undergo self aldol condensation 95. (A) O3 Ph — CHO + 2b ¾A¾g+® oxalic acid C11H8O Compound (A) will be : (b) Ph — C ºº C — CH == CH — CHO (a) Ph — C ºº C — C ºº C — CHO (c) Ph — CH == CH — C ºº C — CHO (d) Ph — CH == CH — C == CH — CO 2H O OH Product ; Product of the reaction is : 96. (62% yield) Catalyst TsOH 0°C, 2h (molecular sieves) (a) O O OO (b) OO (d) O O (c) https://t.me/studyzee

418 97. Which pair of reactants compounds may be used to make given acetal ? O CH2 — OH O + — OH (a) +| (b) — OH O CH2 — OH O + OH (c) (d) OH OH + OH OO 98. CHO ¾H¾¾Å ®(B) ; (A) & (B) are isomers ; Isomer (B) is : (A) CH2 O O O (a) O (b) O H OH O CH2 O O O O (d) H (c) H OH OH OH 99. ¾P¾CC® ( A) OH ¾P¾CC® (B) (A) and (B) is differentiated by : (a) NaH (b) 2-4 DNA (c) Tollen’s reagent (d) NaHSO 3 https://t.me/studyzee

419 100. Which of the following pairs cannot be differentiated by Tollens' reagent ? 101. (a) Benzaldehyde and benzyl alcohol (b) Hexanal and 2-hexanone (c) 2-Hexanol and 2-hexanone (d) Pentanal and diethyl ether An optically active compound C 6H12O gives positive test with 2, 4-dinitrophenyl hydrazine, but negative with Tollens' reagent, what is the structure of the compound ? OO || || (a) CH 3 — C — CH 2 — CH 2 — CH 2 — CH 3 (b) H — C — CH — CH 2 — CH 2 — CH 3 | CH 3 O O || || (c) CH 3 — C — CH — CH 2 — CH 3 (d) CH 3 — CH 2 — C — CH — CH 3 | | CH 3 CH 3 102. Compound (A) C 6H12O 3, when treated with I2 in aqueous sodium hydroxide gives yellow precipitate. When A is treated with Tollens reagent no reaction occur. When A is hydrolysed and then treated with Tollens reagent, a silver mirror is formed in test tube. Compound (A) will be : O O OCH 3 || || | (a) CH 3 — C — CH 2 — CH 2 — CH — OH (b) CH 3 —C —C — CH 3 | | OCH 3 OCH 3 O O || || (c) CH 3 — C — CH 2 — CH(OCH 3 )2 (d) H — C — CH 2 — CH 2 — CH(OCH 3 )2 103. CH 2 — CH 2 — CO 2H ¾ ¾D¾¾® A ¾N¾H¾2—¾NH¾2 ® B ¾h¾e¾at ®(C), Product (C) obtained is : | BaCO 3 KOH CH2 — CH2 — CO2H O (a) CH 3 — CH == CH — CH 2 (b) (c) N — NH2 (d) https://t.me/studyzee

420 104. Which of following does not react with NaHSO 3 (sodium bisulphite)? 105. OO || || (a) CH 3 — C — H (b) CH 3 — C — Et OO || || (c) Et — C — Et (d) Ph — CH 2 — C — CH 3 CH2 — CH2 — CH2 — NH2 ¾R¾anH¾e2y ¾Ni ® ( A) ; Product (A) is : O (a) (b) O N H (c) (d) NN O 106. HH O O (a) +CH 2 == CH — CH 2 — Br ¾K¾O¾H ® ( A) ; Product (A) is : (75%) CH2 — CH == CH2 O — CH2 — CH == CH2 O O (b) O O O O (c) CH2 — CH == CH2 (d) CO2H CH2 — CH == CH2 107. ¾(¾1)M¾e-¾Li(e¾xce¾s¾s) ® (A) ¾ ¾I2¾¾® (B) + CHI 3 ; Product (B) in this reaction is : (2) HCl H2O NaOH CO2Na CO2Na CO2Na CO2Na (a) (b) (c) (d) https://t.me/studyzee

421 O 108. DD D Arrange the following reagent in the correct order in which above transformation is carried out : (a) KOD D 2O ,H + D ,LiAlH 4 (b) H + D ,KOD D 2O ,LiAlH 4 (c) KOD D 2O ,LiAlH 4 ,H + D (d) LiAlH 4 ,H + D ,KOD D 2O O || 109. CH 3 — C— H ¾H¾C¾N ®( A) ¾H¾3O¾¾Å ®(B) ¾¾®(C) ¾L¾iAl¾H¾4 ®(D) ¾H¾IO¾4 ® HCHO + (E) D Compound (C)can show geometrical isomerism. Product (E) of the reaction will be : O O || || (a) CH 3 — C — CH 3 (b) CH 3 — CH 2 — C — H (c) CH 3 — CHO (d) HCHO 110. Arrange in their increasing order of equilibrium constants for hydration ? O O O O || || || || CH 3 — C — CH 3, CH 3 — C — H, CH 3 — C — CH 2 — Cl, H — C — H, (A) (B) (C ) (D) O || Cl — CH 2 — C — H (E ) (a) A < B < C < D < E (b) A < C < B < E < D (c) A < C < E < B < D (d) C < A < B < E < D 111. End products of the following sequence of reactions are : O C — CH3 ¾1¾. I2¾+N¾aOH¾¾, D ® 2. H+ 3. D (a) yellow ppt. of CHI3, O (b) yellow ppt. of CHI3, O (c) yellow ppt. of CHI3, O (d) yellow ppt. of CHI3, CHO COOH COOH O COOH https://t.me/studyzee

422 112. (1) EtONa Ph — CH 2 — CN ¾ ¾ ¾ ¾ ¾O ¾¾® (P) ; Product (P) of the reaction will be : || (2)CH3 —C —Cl (3) H3OÅ D O O || || (a) Ph — CH 2 — C — H (b) Ph — CH 2 — C — CH 3 O O || || (c) Ph — CH — C — H | (d) Ph — CH — C— CH 3 CH3 | O CH3 113. C — H ¾(¾i)N¾aC¾N ® Products. Products of the reaction are : (ii) H2SO4 (a) Racemic mixture (b) Diastereomers (c) Meso (d) Mixture of meso compound and optically active compound 114. ( A) ¾¾Hg¾SO¾4 ® (B) ¾L¾iAl¾H4® (C) dil. H2SO4 recemic mixture \\ reactant (A) is : (a) CH 3 ¾ C ººCH (b) HC ººCH (c) CH 3 ¾ C ººC ¾ CH 3 (d) Ph ¾ CH == CH 2 O || ¾N¾aN¾O¾2 ® 115. CH 3CH 2 — C— CH 3 ; Major product of this reaction is : HCl O O || || (b) CH 3 — CH 2 — C — CH == N — OH (a) CH 3 CH — C— CH 3 | NO O (d) CH 3 — CH 2 — C — CH 3 || || N —OH (c) CH 3 — C — C — CH 3 || N —OH https://t.me/studyzee

423 O 116. ¾((¾12))N¾HH+,2¾OD¾H®( A) + (B). Product (A) & (B) are : (a) (c) (3) LiAlH4 H N N—H (b) & & OH & NH OH NH (d) & 117. + CH 3NO 2 ¾N¾aO¾¾H ® A ¾H¾¾Cl ® ( B). Product (B) is : nitromethane D 93% (a) HO CH == CH — NO2 (b) OH CH == CH — NO2 (c) (d) HO O (1) HCN 118. ¾ ¾ ¾ ¾ ¾¾® ( A) . Product (A) is : (a) (2) LiAlH4 (3) NaNO2 H+ major O O (b) (c) (d) https://t.me/studyzee

424 O Cl ¾a¾lc.¾KO¾H ®( A). Product (A) is : 119. Cl O (2 mole) O (a) (b) C O O (c) (d) HO OH O HCN OH || (catalyst) | 120. R — C — R R —C— R | CN Which of following can be used as a catalyst in the above reaction? (a) Cl - O (d) HSO - || 4 (b) CH 3 — C — O - (c) Et — O - 121. Arrange the following carbonyl compounds in decreasing order of their reactivity in nucleophilic addition reaciton. CHO CHO COCH3 CHO NO2 CH3 (i) (ii) (iii) (iv) (a) ii > iii > i > iv (b) ii > i > iv > iii (c) iii > ii > i > iv (d) iii > i > iv > ii 122. The following reaction were carried out. H O ¾ ¾I2 ¾NaH¾CO¾3 ® OH The final product formed in the above reaction sequence is : H O (a) ONa (b) O I I I O H https://t.me/studyzee

425 I H H (d) O (c) O OI ONa OH I O 58% Me3C — C — CH2 — Br 123. Me3C — C — CH3 (A) (B) 54% OH O 68% Me3C — CH — CH2 — Br Me3C — CH — CH2 (C) A. Yield of each step as actually carried out in the laboratory is given above. What is overall yield of reaction? (a) 42% (b) 31% (c) 21% (d) 60% B. What is the appropriate reagent to carry out above synthesis, i. e. , A, B, C respectively are : (a) Br2 H + , LiAlH 4 ,H Å (b) Br2 H + ,NaBH 4 ,HO - (c) NBS, AlCl 3 ,HO - (d) Br2 HO - ,BF3 ,HO - OH 124. ¾ ¾ ¾3NHi¾2 ¾®( A) ¾C¾u ®(B) ¾N¾H¾2O¾H ®(C) ¾H¾¾Å ®(D) ¾H¾O¾- ®(E) ; (High temp & pressure) Product (E) is : (a) Nylon 66 (b) Nylon 6 (c) Styrene (d) Polystyrene 125. Methyl vinyl ketone on reaction with LiCuMe 2 gives a major product, whose structure is : (a) Me Me (b) Me O Me HO (c) Me Me O (d) Me HO https://t.me/studyzee

426 126. Which of following is in capable to show iodoform test ? O (a) CH3 OH | (b) Ph — CH == CH — CH — CH 3 OH H2C == CH CH3 O H (c) (d) CH2 — C — CH3 D OO || || 127. CH 3 — C— CH 2 — CH 2 — C— CH 3 ¾(N¾H 4¾)2¾CO®3 ( A) ¾C¾Cl 3¾CO¾2Na® (B) D D (major) Product (B) of above reaction is : (a) (b) (c) (d) 128. O EtO2C CO2Et ¾¾H3O¾+ ® A ; Product obtained is : O D (a) O O OH CO2Et (c) (d) None of these (b) O OO 129. ( A) ¾L¾iAl¾H 4® (B) Hr Diastereomers Symmetrical ¾D® Ketone Reactent (A) is : O || O (b) CH 3 ¾ C ¾ CH 2 ¾ CH 3 || (a) CH 3 ¾ C ¾ CH 3 (d) CH 3 ¾ CH 2 ¾ CH 2 ¾ CH == O O || (c) CH 3 ¾ CH 2 ¾ C ¾ CH 2 ¾ CH 3 https://t.me/studyzee

427 130. 4 + x LiAlH 4 ¾e¾th¾er ® ¾H¾3O¾¾Å ® + Li + and Al 3+ Salt Value of x in above reaction is : (a) 1 (b) 2 (c) 3 (d) 4 131. ( A) ¾N¾H¾2O¾H ®(B) ¾H¾2S¾O¾4 ®(C) ¾H¾3O¾¾Å ®(D) + ( E ) ¾C¾HC¾¾l3 ® CH 3 — N =®= C D KOH, D (D) ¾S¾OC¾l2 ®(F ) ¾(¾i)P¾hM¾gBr¾(ex¾ces¾s)®(G) ¾H¾¾Å ®(H ) ¾C¾H2¾I2 ® (ii) HÅ D Zn Cu Molecular weight of compound (A) is : (a) 58 (b) 120 (c) 60 (d) 182 O || — H ¾a¾qu¾eou¾s ac¾¾id ® ( A) 132. Ph 2CH — C + enol + aldehyde 81% 2% 17% Product (A) of above reaction will be : (a) Ph — C == CH — O OH | | (b) Ph 2CH — CH 2 Ph OH O | || (d) Ph 2CH — C — CH 3 (c) Ph 2CH — CH — OH 133. Which of the following will form stable hydrate ? (a) CCl 3CHO (Chloral) (b) (Ninhydrin) (c) (CF3 )2 CO (d) All of these 134. The pH at which maximum hydrate is present in an solution of oxaloacetic acid: OO O || || || H — O — C — C — CH 2 — C — O — H pK a = 2.2 pK a = 3.98 (a) pH = 0 (b) pH = 12 (c) pH = 4 (d) pH = 6 https://t.me/studyzee

428 135. Arrange their stabilities of given gem- diols in decreasing order. OH OH OH (I) OH (II) OH (III) OH (a) I > II > III (b) III > II > I (c) I > III > II (d) III > I > II 136. Maximum hydration takes place of : 137. O O O O || || || || (c) CH 3 CH- C CH 3 (a) CF3 C CF3 (b) CH 3 C CH 3 | (d) C 6H 5 C C 6H 5 Cl The conversion, PhCN ® PhCOCH 3, can be achieved most conveniently by reaction with: (a) CH 3MgBr followed by hydrolysis (b) I2 — NaOH, CH 3I (c) dil. H 2SO 4 followed by reaction with CH 2N 2 (d) LAH followed by reaction with CH 3I O 138. D Zn(Hg)/HCl (B) O (A) H–O In the above reaction, product (B) is: (a) (b) (c) (d) OH 139. ( A) ¾L¾iAl¾H4® (B) ¾Hr® O O O (c) (d) D Structure of A is : O (a) (b) https://t.me/studyzee

429 140. O O3 HCHO+(A) Ph – NH2 (B) O Product (B) is : O O || || (a) Ph — NH — C — CO 2H (b) Ph — NH — C — CH 2 — CO 2H (c) O N – Ph (d) O O O N Ph CO2H 141. To carry out above conversion, arrange the following reagents in correct order. O 3 Zn EtONa / EtOH D NaOCl H+ (1) (2) (3) (4) (a) 1 ® 3 ® 2 ® 4 (b) 1 ® 2 ® 4 ® 3 (c) 1 ® 3 ® 4 ® 2 (d) 1 ® 2 ® 3 ® 4 142. HOCH 2 O | || H 2C = CH - CH 2 - CH 2 - C - OH ¾C¾H3¾T-sCO¾-HCH¾¾3 ® ( A) ¾(¾CHO¾33)2¾S ® (B) + HCHO | CH 2 - CH 3 Product (B) is: CH2 O CH3 O CH3 C (a) H — C — CH2 — CH2 — C O Et CH3 OO CH3 (b) H — C — CH2 — CH2 — C C Et O O CH2 O CH3 C CH3 (c) H — O — C — CH2 — CH2 — C O OO Et (d) H — C — CH2 — C C CH3 Et O CH3 https://t.me/studyzee

430 O Br CHO 143. C—H CHO a b Identify appropriate reagents for the above reaction: (a) a = Br2 CCl 4, b = aq.KOH (b) a = Br2 H + , b = aq. KOH (c) a = Br2 H + , b = alc.KOH (d) a = Br2 HO - , b = aq.KOH OH OH 144. ¾P¾hC¾H¾O ®( X ) ; Product (X) of this reaction is : Me H+ 96% (a) Me Ph Ph CH CH O O (b) O (d) (c) 145. The K eq. values in HCN addition to following aldehydes are in the order : OO O HH H MeO Me2N (I) (II) (III) (a) I > II > III (b) II > III > I OH (c) III > I > II (d) II > I > III 146. (1) CH3—C—CN K1 O +HCN CH3 OH K2 O (2) CH3—C—CN +HCN H H elation between K1 and K 2 is : (a) K1 = K 2 (b) K1 > K 2 (c) K 2 > K1 (d) K1 = K 2 = 1 https://t.me/studyzee

431 147. Which of the following is correct for the reaction ? O + HCN ¾p¾H=¾9 to¾1¾0 ® ( A) (a) A is cyanohydrin (b) Nucleophilic-addition reaction (c) The above reaction is not shown by alkenes (d) All of these 148. Which of the following compounds (i through v) should not be classified as an acetal ? H CH3O OCH3 OO OO O O CH3 (i) (ii) (iv) O O (iii) (v) (a) ii and iii (b) iv (c) i (d) none (they are all acetals) 149. In which of reactions final product is NOT a ketone : (a) CH 3 — C ºº C — H ¾N¾aN¾H¾2 ®( A) ¾C¾H3¾¾– I ®(B) ¾H¾gS¾O¾4 ®(C) H 2SO 4 (b) H — C ºº C — H ¾N¾aN¾H¾2 ®(C) ¾C¾H3¾—¾CH2¾¾– I ®(D) ¾H¾g (¾OA¾c)2¾, H2¾O ®(E) NaBH4, H- O || (c) R — C — OH ¾N¾aO¾¾H ®( A) ¾C¾H3¾¾– I ®(B) (d) 1-butyne ¾N¾aN¾H¾2 ®( A) ¾C¾H3¾¾– I ® ( B) (1) ¾BHH2O¾3×2T/H¾HFO¾s ® (C ) ¾(¾2) 150. The reaction of ethyl methyl ketone with Cl 2/excess OH – gives the following major product (a) ClCH 2CH 2COCH 3 (b) CH 3CH 2COCCl 3 (c) ClCH 2CH 2COCH 2Cl (d) CH 3CCl 2COCH 2Cl 151. The product obtained from the following sequence of reactions is CH 3 — C º CH ¾H¾gS¾O¾4 ® A ¾N¾aB¾H¾4 ® B H 2SO 4 (a) propanol (b) 2-propanol (c) 1-propanol (d) propanhe https://t.me/studyzee

432 O OCH3 152. Which of the following shows oxidation of reactant. OO (1) (2) (3) (4) CH2 == CH2 ¾® CH3—CH2—Cl (a) 1 (b) 1, 2 (c) 1, 2, 3 (d) All of the above O 153. The enolate ion that reacts with to form O O O OO O (a) (b) (c) (d) OO O R 1H2/Pd S Al2O3 T 154. CH3—C—CH3 NaNH2 P HCºCH Q H3O+ D What is the final product T. OH O (a) H3C—C == C—C—CH3 (b) CH3—C—CH3 CH3 H2C == CH CH3 CH3 (c) CH3—C == CH—CH3 (d) CH3 == C—CH == CH2 https://t.me/studyzee

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

434 Level - 2 1. Select the best choice for example (A to L) from the examples (a to n) given below. Write your choice in the box given. A. An acetal derivative of a ketone. B. A chiral ketone. C. An aldehyde that gives a aldol condensation with itself. D. An oxime derivative E. A reagent that reduces aldehydes to 1°- alcohols. F. An a, b-unsaturated ketone. G. A reagent that oxidizes aldehydes to carboxylic acids. H. A reagent that reduces ketones to alkanes. I. An enamine derivative of a ketone. J. An intermediate in imine formation. K. A cyclic hemiacetal. L. A cyanohydrin derivative. CH3 OH O (a) (b) (c) CN OH OH (f) Zn(Hg)H 3O(+ ) O CH3 (d) R NHR' (e) H OO (g) (h) NaBH 4 aq. alcohol (i) H (j) Ag(NH ) (+ ) OH (-) (k) HO OCH3 2 N (l) CH3 C OCH3 3 CH3 CH3 https://t.me/studyzee

435 O (m) N (n) CH3 CH2 C H 2. The following questions refer to the compounds (A to G) shown below : Which compounds are Which compounds are Which compound are i. reduced by sodium ii. hydrolyzed by hot iii. oxidisized by borohydride ? aqueous acid ? CrO 3 pyridine? AE AE AE BF BF BF CG CG CG DH DH DH O O OO A. B. H C. D. O E. O O O O HO F. G. O H. O H 3. Match the column: Column (I) Column (II) (p) racemic mixture O ¾L¾iAl¾H4® (q) Diastereomers (a) (r) Nu-addition reaction O (s) Nu-Substitutions reaction (b) ¾((1¾2))K¾HCrN® (c) Ph ¾ CH 2 ¾ Cl ¾K¾CN® O (d) ¾(¾1)(¾C2H) ¾H3Mrg¾Br® https://t.me/studyzee

436 4. Complete the following table. REACTANT REAGENT(S)/ MAJOR ORGANIC CONDITIONS PRODUCTS O A a. CH3 H 2 Pd - C in ethanol (solvent) B b. COOCH3 H + H 2O D C COOCH3 D O CH3 O c. H –+ CH3 (CH 3) 2 C— P(C 6H 5) 3 O 1. Li + [(CH 3)2Cu]- d. in dry ether 2. H + H 2O e. E OH - ethanol D 5. Comprehension Consider the following reactions and answer A and B. OO (CH3)3 C C CH3 ¾5(¾8a%)® (CH3)3 C C CH2 Br ¾5(¾4b%)® (CH3)3 C OH Br ¾6¾8%® (CH3)3 C O C CH2 C CH2 H H A. Suggest a reagent appropriate step (a) the synthesis. (a) HO - Br2 (1mole) (b) H + Br2 (1 mole) (c) both (a) and (b) (d) None of these https://t.me/studyzee

437 B. Yield of each step as actually carried out in laboratory is given above each arrow. What is overall yield of the reaction ? (a) 60% (b) 21% (c) 40% (d) 68% 6. Reaction 1. O C — H¾(¾1)A¾c2O¾, A¾cON¾a,¾D ®( A) (2)H3O Å , D O || ¾A¾l(O¾CH¾Me¾2¾)3 ®(B) Reaction 2. Ph — CH == CH — C — CH 3 CH3— CH—OH | CH3 OH | Reaction 3. ¾(¾1)N¾a¾OI ®(C) Ph — CH == CH — CH — CH 3 (2)HÅ Degree of unsaturation present in compound (A + B + C) is ? 7. Within each set, which compound should be more reactive toward carbonyl addition reaction ? AB Set (1) O O Set (2) || || CH 3 — C — CH 2 — Br CH 3 — C — CH 2 — CH 2 — Br OO O || || || CH 3 — C — C— CH 3 CH 3 — C — CH 2 — CH 3 Set (3) CH 3O CH == O O 2N CH == O Set (4) O O || || C—H CH 3 — C — H Set (5) O O https://t.me/studyzee

438 CHO Set (6) Set (7) N N CHO Set (8) | | H H OO O O O C—H O C—H CHO CHO Cl Set (9) O O || C C — CH 3 Set (10) O O || || CH 3 — C — CH 2 — CH 3 C—H 8. Match the Column (I) and Column (II). (Matrix) Column (I) Column (II) O Formation of six member (A) ¾ ¾ ¾HC¾N ¾¾®( A) ¾L¾iAl¾H¾4 ®(B) ¾N¾aN¾O¾2 ®(C) (p) ring takes place traces of KOH HCl O (B) ¾N¾H2¾O¾H ®( A) ¾H¾¾+ ®(B) ¾L¾A¾H ®(C) (q) Final product is Ketone https://t.me/studyzee

OO 439 || || (r) Final product formed will (C) CH 3 - C - CH 2 - CH 2 - CH 2 - C - H ¾H¾O¾– ®( A) give positive Tollens test D Ph Final product formed will ¾H¾¾Å ®( A) (s) react with 2,4-DNP. (D) CH3 (2,4-di-nitrophenyl D OH OH hydrazine) 9. Consider reactions A through F. Those carbon atoms undergoing change, as part of a functional group, are marked as C12, C14 or starred. In the cases shown, each carbon atom has either been reduced or oxidized. Your job is to identify the change in oxidation state that has occurred for each of the marked carbon. Reaction C 12 C 14 A. CH 3 CH == CH 2 ¾B¾¾r2 ® CH 3CHBrCH 2Br Reduced Reduced Oxidized Oxidized 12 14 Reduced Reduced Oxidized Oxidized B. CH 31C2H == CH 2 ¾(¾ii)H¾(i2)OB¾22,HN6¾aO¾H ® CH 3CH 2CH 2OH Reduced Oxidized Reduced 14 Reduced Oxidized Oxidized C. CH 3CH 2 C* H == O ¾N¾aB¾H¾4 ® CH 3CH 2CH 2OH Reduced D. CH 3CH 2 C* H == O Ag(+ ) CH 3CH 2CO 2H Oxidized ¾H¾2O¾, pH¾>¾8 ® E. CH 3CO CH 2 C O 2H ¾H¾e¾at ® CH 3COCH 3 + 12 14 O == C == O F. H 2 C == C(OH)C 2H 5 ¾t¾aut¾ome¾riza¾tio¾n ® H 3CCOC 2H 5 Reduced Reduced Oxidized Oxidized 12 14 10. Consider the possible formation of an aldehyde or ketone product when each of the ten compounds in the column on the left is treated with each of the reagents shown in the top row. Check the designated answer box if you believe an aldehyde or ketone will be formed. Assume that the reagents may be present in excess. For each checked reaction, try to draw the structure of the major product (s). https://t.me/studyzee

440 Starting PCC C5H5NHCrO3Cl Jone's Reagent CrO3 in aq. acid Pb(OAc)4 [or HIO4] H3Or (i) BH3 in THF (ii) H2O2 + NaOH OH CH3 CH3 CH3 CC CH3 CH2 OH CH3 CH3 OH CH3 CH3 CH3 OH CH3 H3C CH3 C=C H3C CH3 CH3 HO OH HO C2H5 OH CH3 CH3 https://t.me/studyzee

441 11. Comprehension Wittig reaction : The reaction of a phosphorus ylide with an aldehyde (or) ketnoe introduces a carbon-carbon double bond is place of the carbonyl bond. O CH2 || || R — C — R + Ph 3P == CH 2 ¾® R — C — R + Ph 3P == O Mechanism : O OQ Å || Q Å | R – C – R + CH2 – PPh3 P|Ph3 ¾® R — C— CH 2 | (Nucleophilic addition R reaction) (betaine intermediate) CH2 ­ || ¯ O == PPh 3 + R — C — R O — |PPh3 | ¬¾ R — C — CH 2 | R (oxaphosphetane intermediate) Driving force of the reaction is high bond energy of (P == O) . (DH = –ve) O A. + Ph 3P == CH 2 ¾® (A) (major), Major product (A) is : CH2 CH3 CH3 CH – CH3 (a) (b) (c) (d) O || B. CH 3 — C — CH 2 — CH 2 — CH 2 — CH 2 Å ¾ P¾h-¾Li ® ( A) , Major product (A) is : — PPh 3 D CH3 CH2 CH3 (a) (b) (c) (d) HH CH3 ¾P¾h3¾P ® (A) , Major product (A) is : C. CH3 O (a) cis-2-butene (b) trans-2-butene (c) iso-butene (d) 1-butene https://t.me/studyzee

442 O OO || || || D. CH 3 - C -(CH 2 )3 - C - CH 2 - P(OEt)2 ¾N¾a¾H ® ( A) (cyclic). Product (A) is : OOO O CH3 CH3 (a) (b) (c) (d) CH3 E. Identify major product in given intramolecular Wittig reaction : O || Rxn.-1 ¾® CH 3 — C — CH 2 — CH(CO 2Et)2 + H 2C == CH — Å PPh 3 ¾N¾a¾H ®( A) CH = O Rxn.-2 ¾® QÅ + H 2C == CH — Å PPh 3 ¾¾® (B) ONa Product (A) and (B) respectively are : (a) CO2Et & O CH3 CO2Et (b) CO2Et & O (c) CO2Et & O (d) F. CO2Et CO2Et CO2Et & CO2Et CH2 – Br (1) ¾Ph3¾P (2¾¾mo®le) (A) ; product (A) is : (2) 2Ph-Li ¾ (3) CHO CH2 – Br | CHO (a) (b) (c) (d) https://t.me/studyzee

12. Match the column : 443 (a) Å Column (I) Column (II) Conversion Reagent Me3N O NH 2 NH 2 HO Q , D CH3 (p) (Wolff-Kishner reduction) ¾® (b) Zn(Hg), HCl O Å (q) Me3N (Clemmensen reduction) O ¾® O (c) O OH LiAlH 4 O (r) ¾® OH HO (s) None (d) O OH ¾® https://t.me/studyzee

444 13. Comprehension ( A) ¾H¾gS¾O 4® (B) ¾((1¾2))N¾HarB¾/HD4® CH 3 ¾ C ¾ CH 2 ¾ CH 3 || dil. H2SO4 CH ¾ CH 3 A. Reactant (A) is : (b) HC ºº C ¾C ¾C ¾C (a) CH 3 ¾ C ºº C ¾ CH ¾ CH 3 | | C¾C CH 3 (c) CH 3 ¾ CH ¾ C ºº CH (d) CH 3 ¾ C ºº C ¾ CH 2 ¾ CH 2 ¾ CH 3 | CH 2 ¾ CH 3 O (b) B. Product (B) is : O (a) O O (c) (d) https://t.me/studyzee

445 ANSWERS — LEVEL 2 1. A – l; B – g; C – n; D – k; E – h; F – c; G – j; H – f; I – m; J – d; K – e; L – b 2. i – A, B, C, E, F; ii – D, G, H; iii – B, E, F 3. a - p,r; b - r; c - s; d - p, r OH B : Ph — CH 2 — COOH; C : Ph — CH == C / CH 3 ; | \\CH 3 4. A : Ph — CH — CH 3; OO CH2 — C — CH3 D: CH3; E: CH2 — C — CH3 O 5. A – b; B – b 6. A + B + C = 17 7. set 1 – A; set 2 – A; set 3 – B; set 4 – B; set 5 – A; set 6 – B; set 7 – B; set 8 – B; set 9 – A; set 10 – B 8. A – p, q, s; B – p; C – p, q, s; D – p, q, s 9. A : both are oxidized; B : C12 is reduced, C14 is oxidized; C : reduced; D : oxidized E : C12 is reduced, C14 is oxidized; F : C12 is reduced, C14 is oxidized https://t.me/studyzee

446 10. Compound PCC C5H5NHCrO3Cl Jone's Reagent CrO3 in aq. acid Pb(OAc)4 [or HIO4] H3O+ (i) BH3 in THF (ii) H2O2 + NaOH OH # ##    #  ##  ## CH3 CC CH3 ###   CH3 CH3 # ## CH2 OH      # # ## # ## ### CH3 CH3  # OH  CH3 CH3 CH3 OH # # # CH3 H3C CH3 C=C ### H3C CH3 CH3 # # # HO OH   # HO C2H5 CH3    CH3 OH 11. A – a; B – a; C – b; D – b; E – a; F – b 12. a – q; b – s; c – r; d – p 13. A. (c) B. (d) https://t.me/studyzee

447 8 ALDOL AND CANNIZARO REACTION Level - 1 1. Compound A and B, both were treated with NaOH, producing a single compound C. OO CH3 CH3 + ¾¾HO¾- ® C. Compound (C) is : OH heat (A) OH O (B) O C — CH3 (a) (b) O O O (c) (d) https://t.me/studyzee

448 O O C — CH3 ? 2. ; This conversion can be achieved by : OH CH3 CH3 (a) Dehydration, Hydrolysis (b) Retro aldol and further condensation (c) Perkin condensation & Clemmensen reduction (d) Clemmensen and Perkin condensation 3. This is an example of an intramolecular aldol reaction : O ¾¾H2S¾O¾4 ® (A); Product (A) is : H 2O O OO O O (a) (b) (c) (d) OO || || 4. CH 3 — C — CH 2 — CH 2 — CH 2 — CH 2 — C — H ¾¾HO¾- /¾D ® ( A) ; Product (A) is : (73%) O O C ¾ CH3 O CH3 C ¾ CH3 (a) (b) (c) (d) CHO 5. Ph — CH == CHCHO + CH 3CH == CHCHO ¾¾ba¾se ®( A) 87% ; Product of this reaction is : EtOH, D (a) Ph — (CH == CH)2 — CHO (b) Ph — (CH == CH) 3CHO (c) Ph — (CH == CH)4 CHO (d) Ph — CH == CH — CH == CH — CH 3 6. CH 3CHO ¾1¾0%¾N¾aO¾H ® ¾¾® ¾¾H¾2 ® (A) ; Product (A) of the reaction is : 5°C D Ni (a) propanol (b) ethanol (c) butanol (d) pentanol https://t.me/studyzee

449 O || C – CH3 7. (A) ¾¾NaO¾¾H ® . Reactant (A) is : D OO OO || || || || (a) CH 3 - C - (CH 2 )5 - C - CH 3 (b) CH 3 - C - (CH 2 )4 - C - H OO O || || || (c) H - C - (CH 2 )5 - C - H (d) CH 3 - C - (CH 2 )4 - CH 2 - OH O CH 3 || | 8. CH 3 - C - CH 2 - C - CHO ¾¾KOH¾, ¾H2¾O ® ( A); Product A is: | CH 3 O OO O (a) (b) (c) (d) O || 9. ¾¾LD¾A ® ( A) ; Product A is: CH3 -CH2-I (major) O O O O || || || || (a) (b) (c) (d) 10. The reaction , CHO + conc. NaOH ¾¾he¾at ® , products Identify the product. CHO CH(OH)2 (b) O (a) COO¯ CH(OH)2 (d) CH2OH COO¯ (c) COO¯ https://t.me/studyzee