Aldehyde and Ketone (DPP)

Aldehydes and Ketones Exercise:1 Q. 1

The formation of cynohydrin from a ketone is an example of (1990) (A) Electrophilic addition (B) Nucleophilic addition (C) Nucleophilic substitution (D) Electrophilic substitution

Q.2

The enolic form of acetone contains : (A) 9 sigma bonds, 1 pi bond and 2 lone pairs (B) 8 sigma bonds, 2 pi bonds and 2 lone pairs (C) 10 sigma bonds, 1 pi bond and 1 lone pair (D) 9 sigma bonds, 2 pi bonds and 1 lone pair

Q.3

m-chlorobenzaldehyde on reaction with conc. KOH at room temperature gives: (A) Potassium m-chlorobenzoate and m-hydroxybenzaldehyde [IIT 1991] (B) m- hydroxybenzaldehyde and m- chlorobenzyl alcohol (C) m-chlorobenzyl and m-hydroxybenzyl alcohol (D) Potassium m-chlorobenzoate and m-chlorobenzyl alcohol

Q.4

Hydrogenation of benzoyl chloride in the presence of Pd and BaSO4 gives: (A) Benzyl alcohol (B) Benzaldehyde [IIT 1992] (C) Benzoic acid (D) Phenol

Q.5

An organic compound C3H6O does not give a precipitate with 2,4-Dinitrophenyl hydrazine reagent and does not react with metalli meta llicc sodium. sod ium. It could be: [IIT 1993] (A) CH3CH2CHO (B) CH3COCH3 (C) CH2= CH–CH2OH (D) CH2= CH –O –CH3

Q.6

Under Wolff Kishner reduction conditions, the conversions which may be brought about is? [IIT 1995] (A) Benzaldehyde into Benzyl alcoho l (B) Cyclohexanol into Cyclohexane (C) Cyclohexanone into Cyclohexanol (D) Benzophenone into Diphenylmethane

Q.7

In the reaction, P is

R I S . J . N [IIT 1990]

[IIT 1995]

CH3 CO CH3 (A) CH3COCHO (C) CH3COCH2OH

SeO2

P + Se + H2O (B) CH3COOCH3 (D) None

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1

OH –

–

Q.8

In the Cannizzaro reaction given below, 2Ph –CHO     Ph –CH2OH + PhCO2 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 the carboxylic a cid (D) the deprotonation of Ph–CH2OH [IIT 1996]

Q.9

Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is[IIT 1997] (A) MeCOCl (B) MeCHO (C) MeCOOMe (D) MeCOOCOMe

Q.10

In a Cannizzaro reaction the intermediate which is the best hydride donor is: [IIT 1997]

R I S . J . N H

H

–

–

(A) C6H5 – C – O

(B) C6H5 – C – O –

OH

O

H

H

–

O –

O

(C)

(D)

O –

O2N

O –

CH3O

Q.11

CH3CHO + H2 NOH  CH3 – CH = N – OH. The above reaction occurs at : (A) pH = 1 (B) pH = 4.5 [IIT 1997] (C) Any value of pH (D) pH = 12

Q.12

Among the following compounds, which will react acetone to give a product containing > C = N – (A) C6H5 NH2 (B) (CH3)3 N [IIT 1998] (C) C6H5 NHC6H5 (D) C6H5 NHNH2

Q.13

The product obtained via oxymercuration (HgSO4 – H2SO4) of 1- butyne would be

O

(A)

CH3CH2 –C –CH3

(B) CH3CH2CH2CHO

(C) CH3CH2CHO + HCHO

[IIT 1998]

(D) CH3CH2COOH + HCOOH

Q.14

Which of the following will undergo aldol condensation: (A) Acetaldehyde (B) Propanaldehyde (C) Benzaldehyde (D) Trideutero acetaldehyde

[IIT 1998]

Q.15

Which of the following will react with water: (A) CHCl3 (B) Cl3CCHO (C) CCl4 (D) ClCH2CH2Cl

[IIT 1998]


2

Q.16

A new carbon-carbon bond formation is possible in: [IIT 1998] (A) Cannizzaro reaction (B) Friedel-Crafts alkylation (C) Clemmensen reduction (D) Reimer-Tiemann reaction

Q.17

Which of the following has the most acidic hydrogen: (A) 3-hexanone (B) 2, 4-hexanedione (C) 2,5-hexanedione (D) 2, 3-hexandione

Q.18

The appropriate reagent for the following transformation:

[IIT 2000]

R I S . J . N [IIT 2000]

O

CH2CH3

CH3

HO

HO

–

(A) Zn (Hg), HCl (B) NH 2 NH2, OH (C) H2/Ni

(D) NaBH4

Q.19

A mixture of benzaldehyde and formaldehyde on heating with aqueous NaOH solution gives: [IIT 2001] (A) benzyl alcohol and sodium formate (B) sodium benzoate and methyl alcohol (C) sodium benzoate and sodium formate (D) benzyl alcohol and methyl alcohol

Q.20

Compound A (molecular formula C3H8O) is treated with acidified potassium dichromate to form a product B(molecular formula C3H6O). B forms a shining silver mirror on warming with ammonical silver nitrate. B when treated with an aqueous solution of H2 NCONHNH2. HCl and sodium acetate gives a product C. Identify the structure of C. [IIT 2002] (A) CH3CH2CH= NNHCONH2

(B) CH3 – C = NNHCONH2

CH3

(C)

(D) CH3CH2CH= NCONHNH2

CH3 – C = NCONHNH 2 CH3

Q.21

1- propanol and 2- propanol can be best distinguished by: [JEE 2001] (A) Oxidation with alkaline KMnO4 followed by reaction with Fehling solution (B) Oxidation with acedic dichromate followed by react ion with Fehling solution (C) Oxidation by heating with copper followed by reaction with Fehling solution (D) Oxidation with concentrated H2SO4 followed by reaction with Fehling CHO OHC (i) NaOH (excess) 100°C

Q.22

[IIT 2003]

+

(ii) H /H2O

CHO OHC

any one of the products formed is:


3

COOH

HOOC

CH 2OH

CH 2 OH

(A)

(B)

COOH CH2OH

CH 2OH

HOOC COOH

CH 2OH

O O

(C)

(D)

R I S . J . N COOH

CH2OH

O

O

OCOCH3

Q.23

P Q

Q.24

Acidic      OCOCH3 Hydrolysis

Products formed by P & Q can be differentiated by :

[IIT 2003] (A) 2,4 DNP (B) Lucas reagent (ZnCl2) conc. HCl (C) NaHSO3 (D) Fehlings solution The order of reactivity of phenyl Magnesium Bromide with the following compounds is : [IIT 2004] O

H3C

O

CH3

(I)

H 3C

O

H

Ph

(II)

(A) II > III > I (C) II > I > III

Ph

(III)

(B) I > III > II (D) All react with the same rate

COOH

Q.25

CHO CH3COONa + X       

MeO What is X? (A) CH3COOH

[IIT 2005]

MeO

(B) BrCH2, COOH

(C) (CH3CO)2O

(D) CHO –COOH

Q.26

The smallest ketone and its next homologue are reacted with NH2OH to form oxime. (A) Two different oximes are formed (B) Three different oximes are formed (C) Two oximes are optically active (D) All oximes are optically active [JEE 2006]

Q.27

Cyclohexene on ozonolysis followed by reaction with zinc dust and water gives compound E. Compound E on further treatment with aqueous KOH yields compound F. Compound F is: [JEE 2007]


4

(A)

Q.28

CHO (B)

CHO (C)

CO2H

COOH (D)

CO2H

Statement-1 : Glucose gives a reddish-brown precipitate with Fehling's solution. because Statement-2 : Reaction of glucose with Fehling's solution gives CuO and gluconic acid. (A) Statement-1 is true, Statement-2 is True; Statement-2 is a correct explanation for Statement-1 (B) Statement-1 is True, Statement-2 is True; St atement-2 is NOT a correct explanation for Statement-1. (C) Statement-1 is True, Statement-2 is False. (D) Statement-1 is False, Statement-2 is True. [JEE 2007]

R I S . J . N

Paragraph for Question Nos. 29 to 31(3 questions) Reimer-Tiemann reaction introduces an aldehyde group, on to the aromatic ring of phenol, ortho to the hydroxyl group. This reaction involves electrophilic aromatic substitution. This is a general method for the synthesis of substituted salicylaldehydes as depicted below:

OH



O Na

OH

CHO

(I)

CHO

aq. HCl

(Intermediate)

Q.29

Q.30

Q.31

CH3

CH3

CH3

(I) III II Which one of the following reagents is used in the above reaction? [JEE 2007] (A) aq.NaOH + CH3Cl (B) aq. NaOH +CH2Cl2 (C) aq. NaOH + CHCl3 (D) aq. NaOH + CCl4 The electrophile in this reaction is: (A) : CHCl (C) : CCl 2

[JEE 2007]

+

(B) CHCl2 (D) : CCl3

The structure of the intermediate I is: 



O Na

CH3

O Na

CHCl2

(B)

O Na

CH2OH

CCl3

(C)

CH3





O Na

CH2Cl

(A)

[JEE 2007]

(D)

CH3

CH3


5

Q.32

Match the compounds/ion in column-I with their properties/reaction in Column- II. Indicate your answer by darkening the appropriate bubbles of the 4 × 4 matrix given in the ORS. [JEE 2007] Column-I (A) C6H5CHO

Column-II (P) gives precipitate with 2,4- dinitrophenylhydrazine (Q) gives precipitate with AgNO3 (R) is a nucleophile (S) is involved in cyanohydrin formation

(B) CH3C  CH – (C) CN (D) I –

R I S . J . N

Paragraph for Question No.33 to 35

In the following reaction sequence, products I, J and L are formed. K represents a reagent. Hex-3-ynal

Q.33

1. Mg / ether 1. NaBH 4 2. CO2 K       I        J    2. PBr 3 3. H3O

Cl

Me

O

The structure of the product I is:

H2    Pd / BaSO 4 quinoline

L

[JEE 2008]

Me

Q.34

(A)

Me

Br

(B)

(C)

Me

Br

(D) Me

Br

Br

The structures of compounds J and K, respectively, are: (A) Me

COOH & SOCl2

[JEE 2008]

(B) Me

O & SO2Cl2

Me (C)

Q.35

COOH & SOCl2 (D) Me

COOH & CH3SO2Cl

The structure of product L is: (A) Me

CHO

[JEE 2008]

(B) Me

CHO

(D) Me

CHO

CHO (C) Me


6

Paragraph for Question No.36 to 38

A tertiary alcohol H upon acid catalysed dehydration gives a product I. Ozonolysis of I leads to compounds J and K. Compound J upon reaction with KOH gives benzyl alcohol and a compound L, whereas K on reaction with KOH gives only M. O H3C Ph M=

Q.36

H

R I S . J . N Ph

Compound H is formed by the reaction of :

[JEE 2008]

O

(A)

O

CH3

Ph

+ PhMgBr

(C)

O

(C)

Q.37

Ph

+ PhCH2MgBr

O

H

+ PhCH2MgBr

(D)

Ph

Me

H

+

Ph

The structure of compound I is:

Ph (A)

Ph (C)

MgBr

[JEE 2008]

CH3

H3C

Ph

H

Ph

(B)

H

Ph

CH3

H3C

CH3

(D)

H Q.38

CH3

Ph

Ph

CH2Ph

H

The structures of compounds J, K and L, respectively are : (A) PhCOCH3, PhCH2COCH3 and PhCH2COO – K + – + (B) PhCHO, PhCH2CHO and PhCOO K – + (C) PhCOCH3, PhCH2CHO and CH3COO K (D) PhCHO, PhCOCH3 and PhCOO – K +

[JEE 2008]

Paragraph for Question Nos. 39 to 41

A carbonyl compound P, which gives positive iodoform test, undergoes reaction with MeMgBr followed by dehydration to give an olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which undergoes Intramolecular aldol reaction to g ive predominantly S.


7

P Q.39

1. MeMgBr       2. H , H2O 3. H2SO4 , 

2. Zn,H2O

2. 

The structure of the carbonyl compound P is: (A)

[JEE 2009]

Me

(B)

Me

O (C)

O O

Me

R I S . J . N (D)

Et

O

Q.40

1. OH

1. O

3     R      S Q 

Me

The structure of the products Q and R, respectively, are

[JEE 2009]

O

H

Me

(A)

Me

,

COMe

Me

Me Me

O

(B)

H COMe

,

Me

Me

Me Me

O

H

,

(C)

Me

CHO

Et

Me Et O

Me

(D)

CH3

,

CHO

Me

Me Et

Q.41

The structure of the product S is :

[JEE 2009]

O

(A)

(B)

Me

Me

O Me


8

O

O

Me

(C)

(D)

Me

Me

R I S . J . N EXERCISE-2

Q.1

C6H5 –CHO + CH3 –COOC2H5

CH3CH2 Q.2

NaOC 2H5

     

C2H5OH and heat

(i) KCN/H2SO4

C=O

(ii) LiAlH4

H

(D).

[IIT 1995]

[IIT 1996]

D

Q.3

Acetophenone on reaction with hydroxylamine- hydrochloride can produce two isomeric oximes. Write structure of the oximes. [IIT 1997]

Q.4

An aldehyde (A) (C11H8O), which does not undergo self aldol condensation, gives benzaldehyde and two mole of (B) on ozonolysis. Compound (B), on oxidation with silver ion, gives oxalic acid. Identify the compounds (A) and (B). [IIT 1998] O O CHC6H5 (C)

Q.5

Q.6

( i)LiAlH

4       (D)

( ii) H ,heat

What would be the major product in each of the following reaction?

[IIT 1998]

[IIT 2000]

Ph

Base

O

Q.7

Identify (A), (B) and (C), and give their structures. O

CH3 O

CH3

Br 2

NaOH

A + B H

+



Q.8

[IIT 2000]

C(C7H12O)

Five isomeric para-disubstituted aromatic compounds A to E with molecular formula C8H8O2 were given for identification. Based on the following observations, give structure of the compounds. (i) Both A and B form a silver mirror with Tollen's reagent; also, B gives a positive test with FeCl3 solution (ii) C gives positive iodoform test. (iii)D is readily extracted in aqueous NaHCO3solution. 9


(iv) E on acid hydrolysis gives 1,4-dihydroxybenzene.

[IIT 2002]

Write structures of the products A, B, C, D and e in the following scheme.

Q.9

[IIT 2002]

O Cl2/FeCl3

CH2CH2CH 3

–

Cl

Q.10

Na-Hg

A

B

HCl +

CH2= CHCH2O Na

HNO3/ H2SO4

H2/ Pd/C

D

C

E

Ans.

R I S . J . N B

A,D

A

A,B,D

B

B, D

B

B

A

A

Q.No.

21

22

23

24

25

26

27

28

29

30

Ans.

C

C

D

C

C

B

A

C

C

C

Q.No.

31

A

B

C

D

33

34

35

36

Ans.

B

P, S

Q

Q,R, S

Q,R

D

A

C

B

Q.No.

37

38

39

40

41

Ans.

A

D

B

A

B

HCl

C6H12

C6H13Cl + (C) (B) (D)

ozonolysis

(E)

ozonolysis NaOH (A)       (F) + (G)      NCOONa + 1°alcohol (D) is isomer A. E gives negative test with Fehling solution but gives iodoform test. F and G gives Tollen's test but do not give iodoform test. Identify A to G. [IIT 2003]

Q.11

Which of the following disaccharide will not reduce. Tollen's reagent?

[IIT 2005]

CH2OH

CH2OH O

HO

(A)

H

H

O HO

H

H

H

O

OH H

OH

O

OH

(B)

OH

HO

CH2O

HOH2C

H

H

H

O

H

H

OH

OH H

HO

O

OH H

H

H

(Q)

H

(P)

EXERCISE-1 Q.No.

Ans. Q.No.

1

2

3

4

5

6

7

8

9

10

B

A

D

B

D

D

A

B

A

D

11

12

13

14

15

16

17

18

19

20

32

EXERCISE-2


10

CH 3CH 2

Q. 1

OH C

C6H5CH = CHCOOC2H5 Q.2 (D)

CH 2NH 2

H

(a racemic mixture)

Q.3

C6H5 – C – CH 3

C6H5 – C – CH3

R I S . J . N N – OH

and

HO – N

syn

anti (isomers)

CH= CH –C  C – CHO

CHO CHO Ag+ +2 COOH

Ozonolysis

Q.4

(A)

CHC6H5

(Oxalic acid)

Base

Q.6

O

O

CH3

C –CH3

Q.7

O

Br

(D)

O

Ph

Ph

+ Base (C)

COOH

(B)

C 6H5CHO

Q.5

COOH

O

CH3 COONa + CHBr 3

Br 2 + NaOH

CH3

O

(A)

(B)

(C)

O

CHO

Q.8

(A)

CHO

or

OCH 3

CH 2CHO

C – CH3

(C)

(D)

(B)

CH 2OH

OH

COOH

OH

O – CH = CH2

(E)

CH 3

OH


11

NO 2

O

Q.9

(C)

(B)

(A)

Cl

Cl

Cl

Cl

Cl

Cl NO 2

NH 2

R I S . J . N Bu

(D)

Bu

(E)

Cl

Cl

O –CH2 –CH = CH 2

Q.10

Bu

Bu

C – Pr

Me3C – CH = CH2 (A)

O –Pr

Me2C – CHMe2 + Me3C – CH–Me Cl (B)

Cl (C)

alc.KOH

(A)

Ozonolysis

HCHO + Me3C – CHO (G) (F)

NaOH

HCOONa + Me3C – CH2OH (1° alcohol)

Q.11

In structure (P) both the rings are present in acetyl form therefore it will not hydrolyse in solution that's why Fehling solution cannot react with this. In structure (Q) one ring present in the form of hemiacetal. This will hydrolysed in solution it can reduce Fehling solution.


12

Aldehyde and Ketone (DPP)

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