CPP

IIT-JEE
Class – XII
ALDEHYDE & KETONE

Methods of Preparation : Aldhydes & Ketones

1. The reactant that lead to products (A) and (B) on ozonolysis are :
O O O

H H
H

(A) O (B)

(IV)
(I) (II) (III)

(A) I, II, III (B) I, III, IV (C) I, II, IV (D) II, III

2. Which of the following is a correct name for (CH3)2C=CHCOCH3?

(A) 2-methyl-2-penten-4-one (B) 4-methyl-3-penten-2-one
(C) 1,3-dimethyl-2-pentenal (D) isopentenone

3. Which of the following compounds could not be converted to pentanal in one or two steps?
(A) 1-pentyne (B) trans-5-decene (C) 2-pentanone (D) 1-pentanol

4. CH3CH2CN  CH3CH2CHO
The above conversion can not be brought about by
(A) DIBALH; H2O (B) Lithium tritertiary butoxy aluminium hydride; H2O
(C) SnCl2; HCl (D) (i) LiAlH4, (ii) H2O

5. O
CH 3CH 2CH 2OH  CH 3CH 2CH 2CCH 2CH 2CH 3
 Select the sequence of reagents which can bring about the above conversion satisfactorily :
+
(I) (i) PBr3 (ii) Mg Dry ether (iii) CO2; H (iv) SOCl2 (v) (CH3CH2CH2)2CuLi
(II) (i) PBr3 (ii) Mg Dry ether (iii) CO2; H+ (iv)CH3CH2CH2MgBr
(III) (i) KMnO4 (ii) Ca(OH)2 / 
(IV) (i) PBr3 (ii) KCN (iii) CH3CH2CH2MgCl followed by H+/ H2O.
(A) II and III (B) I and IV (C) II and IV (D) I and III

Nucleophilic Addition Reactions and Acetals – Ketals.

6. The most reactive compound towards formation of cyanohydrin on treatment with KCN followed by
acidification is
(A) benzaldehyde (B) p – nitrobenzaldehyde
(C) m-nitrobenzaldehyde (D) p – hydroxybenzaldehyde

FIITJEE Page 1
7. 18 (i) HCl
CN + C 2H5OH 
(ii) H2O

Where the organic product P is:

18
O O
(A) (B)
OC2H5 OC2H5
18
O O
(C) (D)
OC2H5 OC2H5
18 18

8. O

Br CH3MgBr ; Where the organic product P is:

   P
H3C
H3C H3C
CH3
(A) Br (B)
H3C O
OMgBr
H3C
O
O
(C) CH3
(D)
CH3
CH3

9. What is the product of the following reaction?


HO CH3OH H
CHO  ?
heat –H2O

HO CH(OCH3)2 CH(OCH3)2
OCH3
O O
(A) (B) (C) (D)

10. Which of the following amines would be best chosen for preparing an enamine derivative from
cyclohexanone?
(A) dimethylamine (B) ethylamine (C) trimethylamine (D) hydroxylamine

11. Heating cyclopentanone with either: I ethyl amine, or II diethylamine, together with an acid catalyst leads
to different results. Which of the following best describes this difference?
(A) I gives an imine & II fails to react (B) I gives an enamine & II fails to react
(C) I gives an imine & II gives an enamine (D) I gives an enamine & II gives an imine

12. The Wittig reaction takes place between a carbonyl compound and a phosphorus ylid. Which of the
following represents the dipolar contributor to such an ylide?

(A) I & II (B) II only (C) III only (D) I & IV


13. O 
HCN Possible product(s) is/are :
Ph C H 
(pH = 9-10)

 OH  OH
(R) Ph C H (S) Ph C H
CN  CN 
(III) O OH (IV) O OH
(R) Ph C CH Ph  (S) Ph C CH Ph
(A) Only (I) and (II) (B) Only (III) and (IV) (C) Only (II) and IV) (D) All of these

FIITJEE Page 2
14. The reagent semicarbazide, NH2CONHNH2, reacts with simple aldehydes and ketones (R2C=O) forming
crystalline derivatives called semicarbazones. Which of the following represents the structure of a
semicarbazone?
R
R
N
N
(A) R (B) R N CONH2
NH – NH2
O H
H
O NH
R N R O
(C) NH (D) N
R N R N
H H
15. Two equivalents of the Wittig reagent (CH3)2C=CH-CH=P(C6H5)3 were allowed to react with a C4H4O2
compound. The chief product was 2,11-dimethyl-2,4,6,8,10-dodecapentaene,
(CH3)2C=CH(CH=CH)3CH=C(CH3)2.
What was the C4H4O2 compound used in this reaction?
(A) 2-butyne-1,4-diol (B) 1,2-cyclobutanedione (C) 1,3-butadien-2,3-diol (D) 2-butenedial
16. Which of the following reactions would not be a useful way of preparing 1-phenyl-2-butanol?
(A) phenylacetaldehyde + ethylmagnesium bromide(B) butanal + phenylmagnesium bromine
(C) propanal + benzylmagnesium bromine (D) 1-phenyl-2-butanone + NaBH4

17. Which of the following reactions would not be a useful way of preparing 2-phenyl-2-butanol?
(A) 2-butanone + phenylmagnesium bromine
(B) acetophenone + ethylmagnesium bromide
(C) cis-2,3-dimethyloxirane + phenylmagnesium bromide
(D) ethylphenylketone + methylmagnesium iodide

18. What product or products are expected from acid-catalyzed hydrolysis of the following compound?
O

O
(A) only the starting material itself (no reaction) (B) benzaldehyde and 2,2-dimethyl-1,3-propanediol
(C) benzoic acid and 2,2-dimethyl-1,3-propanediol (D) 2-phenyl-1,3-propanediol and acetone

19. Which of the following may be classified as an acetal?

O O
O
OCH3
O O O O OH
(I) (II) (III) (IV)
(A) I & II (B) III & IV (C) only IV (D) all but IV

20. Formulas for four ethyl ethers are drawn below. Two are cleaved by aqueous acid much more easily than
the other two. Which ethers are more easily hydrolyzed?

(A) I and II (B) II and III (C) III and IV (D) I and IV

21. Which of the following compounds (I through V) should not be classified as an acetal?

(A) II & III (B) IV

(C) I (D) none (they are all acetals)

FIITJEE Page 3
 Aldol Condensation and Cannizaro’s Reaction
22. D

D  OH  X  Y
( conc .)

O
( 2 moles)
Where X and Y are:
D D
O D O D
(A) D and (B) H and
OD OH
- H - D
O O
D D
O D O D
(C) H and (D) D and
OH OH
- H - D
O O

23. O
OH–

H3C CHO 
Where the product P is:
O
CH3

(A) (B) OH
O

OH O

(C) (D)
CHO

24. O
H2C
1. OH
 CH3  X (ultimate )
 
2. 

O
The product X is:
O

(A) (B) CH3

(C) (D)
O
O

25.
 2 
H3O / Hg SeO 2 OH (conc .)
   X   Y   Z
; Where Z is:

H
O
O

(A) COOH (B)

OH O

-
(C) COO (D)
OH

26. In the cannizzaro reaction given below :


OH
Ph CHO   Ph CH2 OH PhCOO
the slowest step is
(A) the attack of OH at the carbonyl group. (B) the transfer of hydride to the carbonyl group.
(C) the abstraction of proton from carboxylic acid. (D) the deprotonation of Ph – COOH.

27. A mixture of benzaldehyde and formaldehyde on heating with aqueous NaOH solution gives:
(A) benzyl alcohol and sodium formate. (B) sodium benzoate and methyl alcohol.
(C) sodium benzoate and sodium formate. (D) none

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28. Aldol condensation will not be observed in
(A) chloral (B) phenyl acetaldehyde
(C) hexanal (D) none of these
29. O O OH

OH
C6H5 C C C6H5   C6H5 C COO

C6H5
the above reaction is known as
(A) Beckmann rearrangement. (B) benzil-benzilic acid rearrangement
(C) benzoic condensation. (D) aldol condensation.

30. Identify the final product (z) in the following sequence of reactions.
Cold KMnO
4 4 OH HIO –
 (X)  (Y)  (Z)


OH OH
(A) (B)
OH O

(C) (D)
O O

31. Which of the following compounds would not be a possible product from the mixed aldol reaction of
acetaldehyde and butanal?
(A) 3-hydroxybutanal (B) 2-ethyl-3-hydroxybutanal
(C) 3-ethyl-2-hydroxyhexanal (D) 3-hydroxyhexanal

32. An aldol condensation is used to prepare 1,3-diphenyl-2-propenone, C6H5CH=CHCOC6H5. Which

combination of reactants will lead to this product?
(A) enolate donor=acetaldehyde; carbonyl acceptor=benzaldehyde
(B) enolate donor=phenylacetaldehyde; carbonyl acceptor=phenylacetaldehyde
(C) enolate donor=acetophenone; carbonyl acceptor=benzaldehyde
(D) enolate donor=propiophenone; carbonyl acceptor=benzaldehyde
33. Which of the following compounds exchanges the largest number of hydrogens for deuterium when
treated with KOD in D2O?
(A) 3-methyl-1,2-cycloheptanedione (B) 2-methyl-1,3-cycloheptanedione
(C) 5-methyl-1,3-cycloheptanedione (D) 6-methyl-1,4-cycloheptanedione
34. Treatment of cyclohexanone with an excess of H218O produces 18O labeled cyclohexanone. Which of the
following is a likely intermediate in this isotope exchange? (the isotope is not name(D)
(A) 1-cyclohexen-1-ol (B) 1,1-cyclohexanediol (C) 2-cyclohexen-1-one (D) 1,2-cyclohexanediol
D O / OH –
35. (Me)(Et)CHCOPh 2   (Me) (Et)CDCOPh + OD + H2O
If the reactant of this reaction is enantiomerically pure dexorotatory isomer, product will be:
(A) a racemic mixture (B) a meso product (C) dextrorotatory isomer (D) laevorotatory isomer

O
36.


The above conversion can be brought about by

(a) (i) cold KMnO4 (ii) HIO4 (iii) PhCO3H
(b) (i) O3/H2O (ii) Ca(OH)2/
(c) KMnO4 /  (ii) DIBALH; H2O
+
(d) (i) Cold KMnO4 (ii) HIO4 (iii) excess Ag (iv) Ca(OH)2/
(A) Only b, c and d (B) Only b (C) Only a, b and c (D) Only b and d


FIITJEE Page 5
37. Which of the following compounds would be the major product from aldol condensation of 6-ketoheptanal?
CH3
H3C O
O O
(A) (B) (C) O (D)
CH3 H

38. The Wieland-Miescher ketone is an important synthetic intermediate. Its formula is shown below. What
starting materials would be suitable for preparing this compound by a combination of Michael and aldol
reactions?
O

O
Wieland-Miescher Ketone
(A) 4-methyl-2-cyclohexen-1-one and 3-butenal
(B) 2-methylcyclohexane-1,3-dione and 3-buten-2-one
(C) 2-methyl-2-vinyl-3-cyclohexen-1-one and acetaldehyde
(D) 2-methyl-2-cyclohexen-1-one and 1,4-dichlorobutan-2-one

39. 2,2-Dimethyl-1,3-propanediol is coveniently prepared by heating 2-methylpropanal with excess

formaldehyde and Ca(OH)2. What sequence of reactions takes place in this synthesis?
(A) dehydrogenation to 2-methyl-2-propenal followed by addition of formaldehyde
(B) dehydrogenation to dimethylketene followed by addition of formaldehyde
(C) a crossed aldol reaction followed by a crossed Cannizzaro reaction
(D) a crossed Cannizzaro reaction followed by a crossed aldol reaction

40. A bis-aldol dimerization of 1-phenyl-1,2-propanedione, C6H5COCOCH3, gives which of the following?

O
O
C6H5 C5H5

(A) C6H5 (B)

C6H5
O
O
C5H5
O
(C) (D) C6H5
C6 H5
C6H5 O

41. What donor and acceptor reactants should be used to prepare the following compound by an aldol
reaction?

(A) acceptor = formaldehyde; donor = propanedial (B) acceptor = 1,3-propanediol; donor = ethanal
(C) acceptor = propanal; donor = formaldehyde (D) acceptor = formaldehyde; donor = propanal
42. What donor and acceptor reactants should be used to prepare the following compound by an aldol
condensation (or Claisen-Schmidt reaction)?

(A) acceptor = cyclopentanone; donor = benzaldehyde

(B) acceptor = benzaldehyde; donor = cyclopentanone
(C) acceptor = phenylacetaldehyde; donor = cyclopentanone
(D) acceptor = cyclopentanecarbaldehyde; donor = toluene

FIITJEE Page 6
43. Which of the following isomers is most acidic ?
(A) 3,4-hexanedione (B) 2,5-hexanedione (C) 2,4-hexanedione (D) hexanedial

44. Which of the following aldehydes, used alone, will undergo an aldol reaction?
(A) formaldehyde, CH2O (B) butanal, CH3(CH2)2CHO
(C) benzaldehyde, C6H5CHO (D) 2-propenal, CH2=CHCHO

Oxidation and Reduction

45. The appropriate reagent for the transformation :
O

CH3 CH3

HO HO

(A) Zn – Hg / HCl (B) (I) NH2 – NH2 (II) OH–

(C) both (A) & (B) (D) none of these.
46. Under Wölf Kishner reduction conditions, the conversion which may be brought about is
OH OH

(B)
(A) H OH

O
O OH

(C) (D)

47. In the Baeyer Villiger oxidation of ketone to ester i.e.

18 18
O O
ArCO 3H  ArCO2H
R   R

R' OR'
The rate of reaction depends upon the nature of R and Ar. The maximum rate of oxidation is observed
when :
CH3
CH3

(A) (B) and Ar =

R’ = Ph and Ar = R' =
CH3
H3C
OCH 3 NO2

and Ar =
(C) R' = and Ar = (D) R' = Cl

CH3
OCH3 NO 2

48. The reduction:

O OH

O O O O

can be brought about by

(A) LiAlH4 (B) NaBH4 (C) Clemmensen’s reduction (D) WolfKishner
49. A C5H8 hydrocarbon is reacted with BH3 in THF, followed by oxidation with alkaline hydrogen peroxide.
Treatment of the resulting product with PCC in CH2Cl2 produces a chiral ketone, formula C5H8O. What
hydrocarbon best fits these facts?
(A) 1-methylcyclobutene (B) methylenecyclobutane
(C) vinylcyclopropane (D) cyclopentene

50. How can 1,1,1,2,2-pentadeutero-3,3-dimethylpentane, C2H5C(CH3)2C2D5, be prepared from 3,3-dimethyl-

2-pentanone?
(A) (i) NaOD in D2O (excess); (ii) LiAlD4 in ether; (iii) D2O workup
(B) (i) Wolff-Kishner reduction with N2D4 in ROD; (ii) NaOD in D2O (excess)
(C) (i) Zn & DCl in CH3CO2D; (ii) LiAlD4 in ether; (iii) D2O workup
(D) (i) NaOD in D2O (excess); (ii) HSCH2CH2SH + BF3; (iii) D2 + Raney Ni catalyst

FIITJEE Page 7
51. Which of the following reaction sequences would be best for converting cyclohexanol to
methylenecyclohexane, (CH2)5C=CH2 ?
(A) (i) H3PO4 & heat; (ii) CH2I2 + Zn(Cu) (B) (i) PCC in CH2Cl2; (ii) CH3MgBr; (iii) H3PO4 & heat
(C) PCC in CH2Cl2; (ii) (C6H5)3P=CH2 (D) CH2N2 & heat

52. Which of the following reactions would not be useful for converting 4,4-diethylcyclohexanone into
1,1-diethylcyclohexane?
(A) Wolff-Kishner reduction (N2H4, strong base & heat)
(B) Clemmensen reduction (Zn/Hg, acid & heat)
(C) thioacetal reduction (i HSCH2CH2SH & BF3; ii H2 + Raney Ni)
(D) LiAlH4 in THF & heat

53. A C5H12O compound is optically active, and is oxidized by PCC in CH2Cl2 to an optically active C5H1OO
product, which is racemized in acid or base. Which of the following best fits these facts?
(A) 2-pentanol (B) 2-methoxybutane (C) 2-methyl-1-butanol (D) 3-methyl-1-butanol

54. You have two C6H10O ketones, I and II. Both are optically active, but I is racemized by treatment with base
and II is not. Wolff-Kishner reduction of both ketones gives the same achiral hydrocarbon, formula C6H12.
What reasonable structures may be assigned to I and II?
(A) I is 3-methyl-4-penten-2-one; II is 4-methyl-1-penten-3-one
(B) I is 2-methylcyclopentanone; II is 3-methylcyclopentanone
(C) I is 3-methylcyclopentanone; II is 2-methylcyclopentanone
(D) I is 2-ethylcyclobutanone; II is 3-ethylcyclobutanone

Test for Aldehydes and Ketones

55. The compound that will not form iodoform on treatment with alkali and iodine is
(A) acetone (B) ethanol (C) diethyl ketone (D) isopropyl alcohol

56. The conversion ; CH3-CH=CH-CHO  CH3-CH=CHCOOH can be effected by

(A) alk. KMnO4 (B) K2Cr2O7/H+
(C) ammoniacal AgNO3 (D) SeO2 reduction

57. The products X, Y and Z obtained from acid hydrolysis of P, Q and R, respectively, can be distinguished by :
Ph OCOCH3 Ph OCOCH3

x y
CH3 H3C

Ph OCOCH3

z
C 2H 5
(A) Tollen’s reagent test for Y vs X or Z and Fehling solution test for X vs Z.
(B) Fehling solution test for Y vs Z or X and FeCl3 test for X vs Z
(C) Tollen’s reagent test for Y vs X or Z and iodoform test for X vs Z
(D) FeCl3 test for Y vs X or Z and iodoform test for X vs Z.

58. Which one of the following ketones will respond to FeCl3 test and azodye test and will simultaneously
liberate H2(g) upon treatment with Na metal but will fail to form oxime?
O O O O

(A) (B) (C) (D)

H3C
O

59. A C7H12O2 compound gives a positive Tollens' silver mirror test and a positive iodoform test. Which of the
following would satisfy these facts?
(A) 2-hydroxy-3,3-dimethylcyclopentanone (B) 2,5-heptanedione
(C) 2,2-dimethyl-3-ketopentanal (D) 2,2-dimethyl-4-ketopentanal

2 NaOH / I
60. CH3 CH2CH(OH)CH3   CHI3  B. B is

(A) CH3CH2COOH (B) CH3CH2COONa (C) CH3CH2CHO (D) CH3CH2CH2OH

FIITJEE Page 8
 Miscellaneous
61. Which of the following will be most readily dehydrated in acidic conditions.
(A) O OH (B) OH

H3C CH3 H3C CH3

(C) O (D) O

CH3
H3C CH3 H3C

OH OH

62. Acetaldehyde reacts with (R)-1,2-propanediol (acid catalyst) to give two isomeric acetals. What is their
isomeric relationship?
(A) they are constitutional isomers (B) they are diastereomers
(C) they are enantiomers (D) they are conformers

63. Base induced elimination of 3-chlorocyclohexanone I is much faster than elimination of cyclohexyl
chloride II. What is the major factor accounting for this difference?
(A) the halogen in I is less hindered (B) the halogen in I is forced to be axial
(C) elimination of I produces a more stable conjugated double bond
(D) I rapidly forms an enolate anion, and this immediately eliminates a stable chloride ion

64. Which of the following optically active compounds will be racemized on treatment with warm alcoholic
sodium ethoxide?

(R)-2,2,6- (R)-2,2,5- (R)-2-methyl-2- (R)-4-methyl-2-

trimethylcyclohexanone trimethylcyclohexanone phenylcyclohexanone cyclohexen-1-one
I II III IV
(A) I and II (B) I and III
(C) I and IV (D) all compounds will be racemized

65. Reaction of C6H5CHBr2 with NaOH in aqueous THF is likely to produce which product?
(A) C6H5CHBrOH (B) C6H5CH(OH)2 (C) C6H5CHO (D) C6H5CO2H

66. Which reaction or sequence of reactions would be best used to convert cyclohexanone to cis-1,2-
cyclohexanediol?
(A) PCC in CH2Cl2 and base (B) (i) NaBH4; (ii) H3PO4 & heat; (iii) OsO4 in pyridine
(C) (i) NaBH4; (ii) H3PO4 & heat; (iii) C6H5CO3H (D) (i) NaBH4; (ii) OsO4 in pyridine

67. Which of the following procedures would not be suitable for preparing 3-methyl-1-phenyl-1-butanone,
C6H5COCH2CH(CH3)2?
(A) (i) C6H5COCH=CHCH3 + (CH3)2CuLi in ether; (ii) H3O+ workup
(B) (i) benzene + (CH3)2CHCH2COCl & AlCl3 (ii) H3O+ workup
+
(C) (i) C6H5MgBr + (CH3)2CHCH2CHO in ether; (ii) H3O workup; (iii) PCC in CH2Cl2
+
(D) (i) (CH3)2CHMgBr + C6H5COCH3 in ether; (ii) H3O workup; (iii) PCC in CH2Cl2

68. The lithium enolate base from cyclohexanone reacts with alkyl  
halides, often in different ways. As shown here, methyl iodide and tert- CH3 O Li
butyl bromide react to give different organic products, I and II, together H3C C Br

with lithium halides. What are the products from these reactions? CH3 CH3 I
II   I
(A) I is 2-methylcyclohexanone; II is 2-t-butylcyclohexanone THF THF

(B) I is 1-methoxycyclohexene; II is 1-t-butoxycyclohexene

(C) I is 2-methylcyclohexanone; II is 1-t-butoxycyclohexene
(D) I is 2-methylcyclohexanone; II is a mixture of cyclohexanone and
2-methylpropene

FIITJEE Page 9
 Subjective Questions

69. When benzaldelhyde reacts with a peroxy acid, the product is benzoic acid. With the help of this
experimental result, compare the migratory aptitude of phenyl group with that of hydrogen.

70. What would be the major product that would result from a Baeyer-Villiger oxidation of 3-methyl-2-butanone?

71. Write structural formulas for the products formed when propanal reacts with each of the following reagents.
_ +
-
(a) NaBH4 in C2H5OH (b) Ag2O, OH (c) CH 3 C H- P (C6 H 5 )3
+ + +
(d) Ag(NH3)2 (e) i. BrCH2CO2C2H5, Zn; ii. H3O (f) HSCH2CH2SH, H , then Raney Ni

72. Give structures for the compounds through A to E

H2CrO4 i.CH3MgBr ii.H3O+ H+ /Δ
Cyclohexanol  A(C6 H10O)   B(C7 H14O) 
i.O3 ii.Zn/H+ i.Ag 2O,OH- ii.H+
C(C7 H12 )  D(C7 H12O 2 )   E(C7 H12 O3 )

73. Provide the missing reagents and intermediates in the following synthesis.

74. What are the intermediates A-C and what stereoisomeric form of glyceraldehyde would you expect to
obtain ?
PCC/CH2Cl2 CH3OH/H+
CH2 =CHCH2 OH   A(C3 H4 O)   B(C5 H10 O2 )
coldKMnO4,OH- H3O+
  C  C5 H12 O4    glyceraldehyde

75. Compounds A and D do not give positive Tollen’s test; however compound C does. Give structures for A-D.
HOCH2CH2OH, H+ Mg,Et2O
4-Bromobutanal   A(C6 H11 O2 Br)  
i.CH3CHO ii.H+ CH3OH,H+
B(C6 H11 MgO 2 Br)   C(C6 H12 O2 )   D(C7 H14 O2 )

76.

77. Show how you accomplish the following syntheses.

78. Show what compound(s) result from complete hydrolysis of each of the following?

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79. With 1-butanol as your only organic starting compound, devise a synthesis of 5-nonanone.

80. Propose reagents for the following reactions

(a) benzene  bromobenzene  phenylmagnesium bromide  benzyl alcohol  benzaldehyde
(b) toluene  benzoic acid  benzoyl chloride  benzaldehyde
(c) ethyl bromide  1-butyne  butanone
(d) 2-butyne  butanone
(e) benzene  acetophenone
(f) benzoyl chloride  acetophenone
(g) CH3(CH2)4CO2CH3  hexanal

81. Starting with benzyl bromide, show how would you synthesise each of the following?
(a) C6 H 5 CH 2 CHOHCH 3 (c) C6 H 5 CH=CH-CH=CHC6 H5
(b) C 6 H5 CH 2 CH 2 CHO (d) C6 H 5CH 2 COCH 2 CH 3

82. Write the products of the following reactions.

83. Write the product of the following reactions.

a) CH 3OCCH 2 CCl +  CH 3  2 CHCH 2 CH 2  CuLi 

2
O O
b) NCCH 2 CH 2 CCl +  CH 3  2 CHCH 2 CH 2  CuLi 

2
O

84. Write equations for all steps in the synthesis of the following from propionaldehyde.
(a) n-propyl alcohol (b) propanoic acid
(c) -hydroxybutyric acid (d) sec-butyl alcohol
(e) ethyl methyl ketone (f) 2-methyl-3-pentanol

85. Trimethylphosphine is much less expensive than triphenylphosphine. Why is trimethylphosphine unsuitable
for making phosphorous ylides ?

86. Dihydropyran reacts readily with an alcohol in the presence of a trace of anhydrous HCl to form a
tetrahydropyranyl (THP) ether.

+ ROH H+ 

O O OR
Dihydropyran THP ether
(a) Write the mechanism of the above conversion.
(b) THP ethers are stable in aqueous base but hydrolyse rapidly in aqueous acid. Write the products of
acid hydrolysis of THPether.

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 CLIP
IIT-JEE
Clip Class – XII
ALDEHYDE & KETONE
1. Assign structures to compounds L through R
(R)-(+)-1-bromo-2,4-dimethylpentane + Mg  L
L + (CH3)2CHCH2CHO, then H2O  M ( C12H26O ), a mixture
M + CrO3  N ( C12H24O )
N + CH3MgBr, then H2O  O ( C13H28O ), a mixture
O + POCl3/pyridine  P ( C13H26 ), a mixture
P + H2/Ni  Q ( C13H28 ) + R ( C13H28 )
(optically active) ( optically inactive)

2. Assign structures to compounds S through W

1-heptyne + LiNH2  S (C7H11Li)
S + 1-chloro-3-bromopropane  T (C10H17Cl)
T + Mg; then n-C10H21CHO; then H+  U (C21H40O)
U + H2, Lindlar’s catalyst  V (C21H42O)
V + CrO3  W (C21H40O)

3. Account for the following reaction.

KOH  C H CH=CHNO +H O
(a) C6 H5 CHO+CH 3 NO 2  6 5 2 2
C2 H5ONa
(b) C6 H 5 CHO+C6 H5 CH 2 CN  C 6 H5 CH=C(C 6 H5 )CN

4. Give the structures of A-C

C 6 H5 OCH 2 Cl+PPh 3 ,then t-BuOK 
A
A+ethyl methyl ketone 
 Ph 3 PO+B
B+dil.aqueous acid 
 C(C5 H10 O) + PhOH

5. Give the structure of D

(a) C6 H5 COCH 2 CH 2 CH 2 CH 2 Br + PPh 3 ,then t-BuOK 
 D(C11H12 )

6. In the alkaline solution, 4-hydroxy-4-methyl-2-pentanone is partly converted into acetone. Show all the
steps involved.
7. What reagents would you use to bring about each step of the following syntheses ?

FIITJEE Page 12
 O

H
a) CHO
H

O
O
O

b)

8. When (CH3)2CHCHO and Ba(OH)2/H2O are heated in a sealed tube, the reaction produces only

(CH3)2CHCH2OH and (CH3 ) 2 CHCO 2 2 Ba . Provide an explanation.
9. What starting compound would you use in an aldol cyclisation to prepare each of the following ?
O O
O

a) b) c)

10. Aldol Condensation proceeds by carbon-carbon bond formation between an enolate donor and a carbonyl
acceptor. For each of the following aldol products (1 through 5) select a donor and an acceptor compound
from the list at the bottom (compounds A through H).
Aldol Product Donor Acceptor

CHO
CHO
(A) (B) O (C) (D) H2C — O

O O
CO2C2H5
(E) (F) H2C (G) (H) CHO
CO2C2H5 CH3 CH3

FIITJEE Page 13
11. Although the enol form of acetoacetic ester (CH3COCH2COOEt) is an alcohol, it does not have a higher
boiling point than the keto form (actually it boils somewhat lower). Explain.

12. Upon treatment with dilute NaOH, 3-methyl-2-butenal, (CH3)2C=CHCHO, yields a product of formula
C10H14O, called dihydrocitral. What is the likely structure of the product ?

13. There are three dioxane isomers: 1,2-dioxane, 1,3-dioxane, 1,4-dioxane. One of them acts as a normal
ether, one of them is a potential explosive, and the third one rapidly hydrolyses in dilute acid. Write the
hydrolysis products of the third one.

O O
O
O O
O
1, 2-dioxane 1, 3-dioxane 1, 4-dioxane
explosive
14. Propose a reasonable mechanism for the following reaction.

N N

OH
+ HCHO H+ 
 OH

*****
Answer Key
1. C 2. B 3. C 4. D 5. B 6. B 7. D 8. C 9. C 10. A
11. C 12. D 13. D 14. B 15. D 16. B 17. C 18. B 19. A 20. B
21. D 22. D 23. A 24. D 25. C 26. B 27. A 28. A 29. B 30. C
31. C 32. C 33. D 34. B 35. A 36. D 37. A 38. B 39. C 40. A
41. D 42. B 43. C 44. B 45. B 46. D 47. C 48. B 49. A 50. D
51. C 52. D 53. C 54. B 55. C 56. C 57. C 58. B 59. D 60. B
61. A 62. B 63. C 64. C 65. C 66. B 67. D 68. D
Subjective Questions Answers
69. Migratory aptitude of H > Ph
70. CH3COOCH(CH3)2
71. (a) n-propyl alcohol (b) propanoic acid
(c) 2-pentene (d) propanoic acid
(e) CH3CH2CH(OH)CH2COOC2H5 (Reformatsky reaction)
(f) propane

72.

73. (a) i) NaOH ii) (CH3)2SO4 or CH3I (b) PCC

(c) BrZnCH(CH3)COOEt (d) LiAlH4; H2O

74. (a) CH2=CHCHO (b) CH2=CHCH(OCH3)2 an acetal

(c) HOCH2CH(OH)CH(OCH3)2 glyceraldehyde HOCH2CH(OH)CHO
Racemic mixture of glyceraldehyde is obtained.

FIITJEE Page 14
75.

76.

77. (a) Ag+ 2. HOCH2CH2OH/H+ 3. LiAlH4 4. H+

(b) reduction of ketone after the protection of aldehyde group

78. (a) OH (b) O

O OH
+ OH +
HO H
(c) OHC–CHO + H2NCH2CH2NH2 (d) OH
+ HOCH2CH2OH
OH
79.

CH3CH2CH2CH2 — C — Cl

80.
(a) 1.Br2 /Fe 2.Mg/THF 3.HCHO;H + 4.PCC/CH 2 Cl 2 or PDC (e) CH3COCl/AlCl3 or (CH3CO)2O/AlCl3
(b) 1.hot KMnO4 2.SOCl2 3.H 2 /Pd-BaSO4 or DIBALH;H 2 O (f) (CH3)2 CuLi or (CH3)2Cd
(g) DIBALH;H+
(c) 1.HC  C- Na + 2.HgSO4 /H 2SO4
(d) HgSO4 /H 2SO4 or Hg(OAc)/H 2O; NaBH 4

81. (a) 1.Mg/THF 2.CH 3CHO;H + (c) 1.NaOH 2.PCC/CH 2 Cl 2 3.PhCH=CH-CH=PPh 3

(d) 1.Mg/THF 2. CH2CH2CHO; H+ 3. PCC/CH2Cl2
(b) 1.Mg/THF 2.Ethylene oxide;H + 3.PCC/CH 2Cl 2

82. (a) CH3CH2CH2(CH=CH2)2(OH) (b)

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83. (a) CH 3OCOCH 2 COCH 2 CH 2CH(CH3 ) 2
(b) NCCH 2 CH 2 COCH 2 CH 2CH(CH 3 ) 2

84. (a) LiAlH4;H2O (b) KMnO4 or Ag+

+ +
(c) 1.KCN; H 2. H /  (hydrolysis of cyanide to carboxylic acid)
(d) CH3MgBr; H+ (e) oxidation of the product of d
(f) isopropyl magnesium halide; H+

85. In the preparation of phosphorous ylides, a strong base is used to remove the  -hydrogen. If
trimethylphosphine is used, one will have more than one type of -hydrogens and side products result.

86. H+ ROH
a)
+
O O O OR

O ( an acetal )

b) HO H + ROH

Clip
1. L-
(R) CH2MgBr
(R)
M- OH
(a mixture of diastereomers)
(R) & (R)
(S)

N- O

(R)

O- OH
(a mixture of diastereomers)
(R) & (R)
(S)
P- (or)

Q-

(R, R)
R-

(R, S) meso compound

2. S CH3 -(CH 2 )4 -C  CLi + NH3

T CH3 -(CH 2 )4 -C  C-(CH 2 ) 3 -Cl
U CH3 -(CH 2 ) 4 -C  C-(CH 2 ) 3 -CH(OH)-C10 H 21
H H

V CH3 – (CH2)4 – C = C – (CH2)3 – CH(OH) – C10H21(cis)

W CH3 – (CH2)4 – C = C – (CH2)3 – COC10H21

H H
3. Both a and b are aldol type of reactions. In a,  -hydrogen is removed from CH3NO2 and in b, it is removed
from PhCH2CN.

FIITJEE Page 16
4. A- C6H5-O-CH=PPh3 B- CH3CH2C(CH3)=CH-O-Ph
C- CH3CH2CH(CH3)CHO (formed through acetal)

5.

6. Aldol reaction is reversible. And given reaction is reverse of aldol reaction.

7. (a) 1. O3; Zn/H+ or KMnO4; HIO4 2. H+ or OH-
+ + -
(b) 1. O3; Zn/H or KMnO4; HIO4 2. H or OH
8. (CH3)2CHCHO undergoes Cannizaro reaction despite the presence of  -hydrogen. Given products are
the result of Cannizaro reaction.

9. O O O O
a) c)
b)
H
O O

10. 1. Donor-C Acceptor-C 2. Donor-E Acceptor-D 3. Donor-B Acceptor-A

4. Donor-G Acceptor-G 5. Donor-F Acceptor-B
11. The enol form has intramolecular hydrogen bonding.
12. O

13. 1, 3-dioxane is an acetal so it hydrolysis quickly.

14. N bearing a lone pair works as a nucleophile which attack on formaldehyde then the carbon of the
formaldehyde woks as an electrophile and attacks at the benzene ring.

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