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Aldehydes, Ketones and Carboxylic Acids: Solutions
Aldehydes, Ketones and Carboxylic Acids: Solutions
Solutions
SECTION - A
Objective Type Questions
CH3
|
CH3 — CH — C— CH2 — CH2OH
||
O
(1) 1-Hydroxy-4-methylpentan-3-one (2) 2-Methyl-5-hydroxy-3-pentanone
(3) 4-Methyl-3-oxo-1-pentanol (4) Hexanol-1-one-3
3
5 4 2 OH
1-hydroxy-4-methylpentan-3-one
CCl3 – CHO
2, 2, 2 – trichloroethanal
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182 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
C CH3
Ca(CH3COO)2 Dry
CH3 CH3
R
7. CH3 — CH2 — C CH
Butanone, R is
H3O
2+
R Hg
9. An alkene of molecular formula C9H18 on ozonolysis gives 2,2-dimethylpropanal and butan-2-one, then the
alkene is
(1) 2,2,4-trimethylhex-3-ene (2) 2,2,6-trimethylhex-3-ene
(3) 2,3,4-trimethylhex-2-ene (4) 2,2,4-trimethylhex-2-ene
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 183
Sol. Answer (1)
(1) O3
+
(2) Zn
CHO
(i) O
10. X 3
(ii) Zn H O
O. 'X' can be
2
CH3
(1) (2) (3) (4)
O If Z is (–I) effect group, then reactivity will increases because such gp increases more partial the
Z
charge density on carboxyl carbon. Which inhances nucleophilic substitution (SN) reaction and nucleophilic
addition reaction.
14. Correct order of reactivity of CH3CHO, C2H5COCH3 and CH3COCH3 with HCN
(1) CH3CHO > CH3COCH3 > CH3COC2H5 (2) C2H5COCH3 > CH3COCH3 > CH3CHO
(3) CH3COCH3 > CH3CHO > C2H5COCH3 (4) CH3COCH3 > C2H5COCH3 > CH3CHO
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184 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
E – Nu E+ + Nu–
Nu
Since, the first step is attack of Nu on carbonyl carbon, so more is the positive charge on carboxyl ‘C’ more
the probability of attack on it. Because of this, the reactivity order follows as
> >
15. The increasing order of the rate of HCN addition to compounds A–D is
(A) HCHO (B) CH3COCH3 (C) PhCOCH3 (D) PhCOPh
(1) A < B < C < D (2) D < B < C < A (3) D < C < B < A (4) C < D < B < A
Sol. Answer (3)
O O
O
H CHO > > C CH3 > C
CH 3 CH3
Because more is the positive charge on carboxyl carbon more is the reactivity.
O O O
|| || ||
Ph — C— Ph CH3 — C— H CH3 — C— CH3
(i) (ii) (iii)
(1) (i) > (ii) > (iii) (2) (iii) > (ii) > (i) (3) (ii) > (iii) > (i) (4) (i) > (iii) > (ii)
Sol. Answer (3)
O
O
CH3 CHO > > C
Because more is the positive charge on carboxyl carbon more is the reactivity.
O OH O
CH3 OH
CH3
(1) (2) (3) (4)
CH3 CH3
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 185
Sol. Answer (2)
O O
(i). CH3MgBr
+
(ii). H3O
CH3
CH3MgBr tautomerism
OMgBr O H
+
(ii). H3O
CH3 CH3
R
R
18. Reaction CO + HCN R—C—OH is
R
CN
(1) Electrophilic substitution (2) Nucleophilic addition
(3) Nucleophilic substitution (4) Electrophilic addition
Sol. Answer (2)
R
R + –
O + H CN R—C—OH
R
CN
This is nucleophilic addition.
19. Reaction of aldehyde with HCN followed by hydrolysis gives a compound which shows
(1) Optical isomerism (2) Geometrical isomerism
(3) Metamerism (4) Tautomerism
Sol. Answer (1)
H H H
+
H3O
R C O R C OH R C OH
–
CN CN COOH
(Optically active)
Due to presence of chiral center.
NaCN H O
20. (CH3 )2 CO
(HCl)
A
3
B.
CN COOH
A B
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186 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
O
||
(1) C6H5OH (2) C6H5 C— C6H5
O O
|| ||
CH3 — C— (CH2 )2 — C— CH3
O O O O
OH
(1) (2) (3) (4)
CH3 CH3 CH3
O
O O
OH
H3C C CH2 CH2 C CH3
More H3C
acidic ‘H’ OH
O O
1 2 3 4 5
H2C C CH2 CH2 C
CH3
+ H2O
O O
H 2
3
1 –H2O
4
5 CH3
HO
CH3
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 187
24. What will be the product, when carboxy phenol, obtained by Reimer-Tiemann's process, is deoxidised with Zn
powder?
OH CHO
CHO
(1) (2)
OH COOH
(3) (4)
OH COOH
COOH
Zn
Dust
25. Benzyl alcohol and sodium benzoate is obtained by the action of concentrated sodium hydroxide on
benzaldehyde. This reaction is known as
(1) Perkin reaction (2) Cannizzaro reaction
(3) Sandmeyer reaction (4) Claisen condensation
Sol. Answer (2)
– –
CHO + OH COO +
OH
This is Cannizzaro reaction.
26. When m-chlorobenzaldehyde is treated with 50% Ba(OH)2 solution, the product(s) obtained is(are)
OH OH
–
COO CH2OH
CH—CH
(1) (2) +
OH OH OH
OH OH
–
COO CH2OH
CH—CH
(3) + (4)
Cl Cl Cl Cl
–
CHO –
COO
OH OH
+
(50%)
Cl Cl Cl
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188 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
COOH
OH
28. Which of the following compound will exhibits positive Fehling test as well as iodoform test?
(1) Methanal (2) Ethanol (3) Propanone (4) Ethanal
Sol. Answer (4)
H3C O
–
+ I2 / OH
30. Trichloroacetaldehyde, CCl3CHO reacts with chlorobenzene in presence of sulphuric acid and produces
Cl
Cl
(1) Cl C Cl (2) Cl C Cl
CH2Cl H
OH
(3) Cl C Cl (4) Cl CH Cl
Cl CCl3
Sol. Answer (4)
H
+
H
CCl3 CHO + Cl Cl C Cl
CCl3
(DDT)
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 189
31. An aromatic compound 'X' with molecular formula C9H10O gives the following chemical tests
(i) Forms 2,4-DNP derivative
(ii) Reduce Tollens reagent
(iii) Undergoes Cannizzaro reaction and
(iv) On vigorous oxidation, 1,2-benzenedicarboxylic acid is obtained
The compound
CHO O CHO
C2H5 CHO C
(1) (2) (3) CH3 (4)
CH3 C2H5
C2H5
Sol. Answer (1)
CHO
+ 2, 4 DNP Test
+ Tollen's Test
+ Cannizzaro reaction
O
OH(–)
32. CHO + 'X' CH CH C . Identify 'X'
293K
O
(1) CH2—CHO (2) CH2–CH2–OH (3) C CH3 (4) CH CH2
O
CHO + C CH3
–
OH
O
CH CH C
COOH
Benzene –1, 2-dicarboxylic acid.
COOH
C O KOH COO + OH
–
CH3
CH3 CH2
36. The major product obtained on reaction of phenol with sodium hydroxide and carbon dioxide is
(1) Benzoic acid (2) Salicylaldehyde (3) Salicylic acid (4) Phthalic acid
Sol. Answer (3)
–
OH + CO 2 + OH OH
COOH
37. Which of the following does not give benzoic acid on hydrolysis?
(1) Phenyl cyanide (2) Benzoyl chloride (3) Benzyl chloride (4) Methyl benzoate
Sol. Answer (3)
+ H2O
Cl OH
K Cr O , H
CH3CHO
2 2 7
CH3COOH
39. A liquid was mixed with ethanol and a drop of concentrated H2SO4 was added. A compound with a fruity smell
was formed. The liquid was
(1) CH3OH (2) HCHO (3) CH3COCH3 (4) CH3COOH
Sol. Answer (4)
+
H
+ Ester
CH3 OH
CH 3 OH
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 191
Sol. Answer (2)
COOH
OH
This is most acidic because of ortho effect.
41. CH3 COOH
PO
X . Identify X
2 5
+
OH HO P2O5
43. Which of the following presents the correct order of the acidity in the given compounds?
(1) CH3COOH > BrCH2COOH > ClCH2COOH > FCH3COOH
(2) FCH2COOH > CH3COOH > BrCH2COOH > ClCH2COOH
(3) BrCH2COOH > ClCH2COOH > FCH2COOH > CH3COOH
(4) FCH2COOH > ClCH2COOH > BrCH2COOH > CH3COOH
Sol. Answer (4)
FCH2COOH > ClCH2COOH > BrCH2COOH > CH3COOH
> >
> >
Because the S.O of CB' is
As, the acidic strength order 1 > 2 > 4 > 3.
So, BrCH2CH2CO2H is weakest acid and hence it has smallest value of dissociation constant.
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192 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
45. Which of the following acids has the smallest value of dissociation constant?
(1) CH3CHFCOOH (2) FCH2CH2COOH
(3) BrCH2CH2COOH (4) CH3CHBrCOOH
Sol. Answer (3)
As, the acidic strength order 1 > 2 > 4 > 3. So, BrCH2CH2CO2H is weakest acid and hence it has smallest
value of dissociation constant.
BrCH2CH2COO H
BrCH2CH2COOH
COOH COOH
Cl2/FeCl3
Cl
(m - chlorobenzoic acid)
47. In esterification
(1) OH– of acid is replaced by C6H5OH (2) H+ of acid is replaced by sodium metal
(3) OH– of alcohol is replaced by chlorine (4) OH– of acid is replaced by RO– group
Sol. Answer (4)
R – O H + HO – C – R
R O C R
P
CH3COOH + Cl2 ClCH2COOH + HCl
is called
(1) Hell-Volhard-Zelinsky reaction (2) Birch reaction
(3) Rosenmund reaction (4) Hunsdiecker reaction
Sol. Answer (1)
P
CH3 C OH + Cl2 Cl CH2 COOH
+
HCl
This is H–V–Z reaction.
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 193
COOH
NH3
49. A. Identify 'A'
COOH
(1) Benzene (2) Phthalimide (3) Benzamide (4) Acetaldehyde
OH NH3
N H Phthalimide
OH
O O
(3) Salicylic acid gives violet colour with neutral ferric chloride as well as brisk effervescence with sodium
bicarbonate
SECTION - B
Objective Type Questions
O O
O
(1) SeO2
(2) HIO4 O O
H2SO5 O
O
O C OH
(3) CaO
+ CaCO3
C OH
Cyclobutanone
O
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194 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
2. In the reaction
CHO
Conc. KOH
+ HCHO Product
O O
OH COOH
CH2 CH CHO
–
CHO COO CH2OH
–
OH –
+ HCHO HCOO + +
+ CH3OH
LiAlH4
CH = CH – CHO Product
3. .
CHO CH2OH
LiAlH4
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 195
Sol. Answer (2)
O
–
OH
CH3 CHO H C CH CH CH3
E&Z
O O
C
CH3
_
I2/OH
–
O
CHI3 +
CH3
O H O
O CH3
H O
Hydrogen bonding
7. Aromatic aldehydes undergoes condensation on heating with an ethanolic solution of KCN. This reaction is
called as
(1) Perkin reaction (2) Benzoin condensation
(3) Claisen condensation (4) Cannizzaro’s reaction
Sol. Answer (2)
O OH
–
CHO + CN C CH
(1) CCl3CHO (2) (CH3)3CCHO (3) CH3CH2CHO (4) Both (1) & (2)
–
CHO OH Cannizzaro reaction
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196 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
MgBr
dry
ether H2O
9. HCN + A B, B is
MgBr
dry
HCN +
This is wrong question because acid base reaction will dominate over nucleophilic addition reaction.
10. The reactivity of carbonyl compounds towards nucleophilic addition reaction gets affected by
(1) Magnitude of positive charge on carbonyl carbon atom
(2) Steric hindrance
(3) Presence of electron withdrawing groups surrounding carbonyl group
(4) All of these
Sol. Answer (4)
R electrophilicity
O
R Steni Hindirance
11. Which of the following statement is incorrect about the reaction of ammonia derivatives with carbonyl compounds?
(1) pH of solution is maintained between 3 to 4
(2) Addition of ammonia derivatives occurs followed by elimination of H2O
(3) At very low pH (less than 3) ammonia derivatives are protonated and do not act as nucleophile
(4) At very high pH reaction becomes explosive
Sol. Answer (4)
At very high temperature and at high pH reaction becomes explosive.
12. An organic compound does not reacts with Tollen’s reagent but undergoes Baeyer Villiger oxidation. The compound
is CHO
O
(1) CH C–CH2COCH3 (2) (3) CH3CHO (4) CH 3 – C – CH 3
O
Sol. Answer (4)
No Tollen's test
+ B.V. Oxidation
13. When HCOOH acid is heated with conc. H2SO4, the gas evolved is
(1) Only CO2 (2) CO + CO2 (3) SO2 + CO2 (4) CO
Sol. Answer (4)
HCOOH H2SO4
CO
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 197
O3/Zn
14. H2O Product. The product is
(3) O (4)
CHO
CHO
CHO CHO
Sol. Answer (3)
H
O3 / Zn
15. Clemmensen reduction of a ketone is carried out in the presence of which of the following?
(1) H2 and Pt as catalyst (2) Glycol with KOH
(3) Zn-Hg with HCl (4) LiAlH4
Sol. Answer (3)
Zn-Hg with HCl. (Clemmensen reduction)
CH 3
Which of the above compound(s), on being warmed with iodine solution and NaOH, will give iodoform?
(1) a, c & d (2) Only b (3) a, b & c (4) a & b
Sol. Answer (3)
–
I2, OH
CH3CH2OH CHI3
–
I2, OH
CHI3
–
I2, OH
CH3 CH OH CHI3
CH3
O O
CH3 C CH2 CH3 C CH2
H – –
OH O
CH3 C CH3
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198 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
–
+ I2, OH No reaction
19. Which of the following reactions will not result in the formation of carbon-carbon bonds?
(1) Friedel-Craft’s acylation
(2) Reimer-Tiemann reaction
(3) Cannizzaro reaction
(4) Wurtz reaction
Sol. Answer (3)
Cannizzaro reaction do not involve C—C bond formation.
OH OH
CH2–C–CH3 (CH2)2–C–CH3
(3) (4)
CN CN
KCN H O LiAlH
CH3 Br A
3
B 4
ether
C,
H LiAlH
CH3 Br CN CH3CN
CH3COOH
4
CH3CH2OH
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 199
22. The correct order of decreasing acid strength of trichloroacetic acid (A), trifluoroacetic acid (B), acetic acid (C) and
formic acid (D) is
(1) A > B > C > D (2) A > C > B > D (3) B > A > D > C (4) B > D > C > A
Sol. Answer (3)
F Cl
F Cl
23. An organic compound 'A' on treatment with NH3 gives 'B' which on heating gives 'C' when treated with Br2 in
presence of KOH produces ethylamine. Compound 'A' is
CH3
24. Which one of the following products is formed when adipic acid is heated?
Adipic acid O
C Cl + H2O C OH
OH O C CH3
O
COOH COOH
+ CH3 C Cl
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200 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
27. Which one of the following compounds will react with NaHCO3 solution to give sodium salt and carbon dioxide?
(1) Acetic acid (2) n-hexanol (3) Phenol (4) Both (2) & (3)
Sol. Answer (1)
O
O
– +
+ NaHCO 3 CH3 C O Na + CO 2+ H2O
CH 3 OH
R C OH + PCl5 R C Cl
31. Propionic acid with Br2 / P yields a dibromo product. Its structure would be
Br
Br
Br
Br
Sol. Answer (1)
Br
CH3 C COOH
Br
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 201
32. In a set of reactions, ethyl benzene yielded a product D.
KMnO4 Br2 C2H5OH
CH2CH3 KOH B FeCl3 C H
+ D
‘D’ would be
COOC2H5
CH2–CH–COOC2H5
(1) (2)
Br Br
Br COOH
(3) (4)
Br OCH2CH3
CH2COOC2H5
Sol. Answer (1)
O O
COOH COOH C Et C O Et
KMnO4 Br2 OH
+3 +
Fe H
Br Br Br
(B) (C) (D)
Phenol
X Y Z
Zn 3 CH Cl
alkaline
dust anhydrous AlCl3 KMnO 4
Br / P excess of NH
34. CH3 CH2COOH 2
A
3
Y.
The product Y is
(1) Lactic acid (2) n-propyl amine (3) Ethylamine (4) Alanine
Sol. Answer (4)
Br
Br2/P
H3C CH2 CO2H H3C CH CO2H
(A)
NH3
(xs)
NH2
H3C CH CO2H
Alanine
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202 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
O
16 18 dil. H2SO4
35. CH3 – C – O – H + R – O – H
Major product.
Product of the reaction is
O O
18 16
(1) CH3 – C – O – R (2) CH3 – C – O – R
O
18
(3) R – C – O – CH3 (4) R – C – O – R
16
Sol. Answer (1) O
O
16 + R
1
O 18
OH
+
H , H
O
18 1
CH3 C O R
36. Which of the following is the correct sequence of decreasing reactivity towards hydroxide ion promoted hydrolysis
among the following compounds?
O H O H O H O H
NO2 || | || |
|| | || |
CH3–C–N CH3–C–N CH3–C–N NO2 CH3–C–N
+
P2 O 5 H /H2 O
37. CH3CH2COONH4 X Y.
Y and X respectively are
(1) CH3CH2COOH, CH3CH2CN (2) CH3CH2CN, CH2CH2COOH
(3) CH3CH2CH2COOH, CH3CH2CH3 (4) CH3CH3, CH3CH2COOCH3
Sol. Answer (1)
+
P2O5 H
CH3CH2COONH4 CN COOH
(X) (Y)
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 203
39. The relative reactivities of acyl compounds towards nucleophilic substitution are in the order of
(1) Acyl chloride > Ester > Acid anhydride > Amide
(2) Acyl chloride > Acid anhydride > Ester > Amide
(3) Ester > Acyl chloride > Amide > Acid anhydride
(4) Acid anhydride > Amide > Ester > Acyl chloride
Sol. Answer (2)
O O O O O
SECTION - C
OH O OH O O
Sol. Answer (2)
O O
H
(i) OH(–)
+ H
(ii)
O
2. Consider the reactions :
+
Cu / [Ag(NH3)2]
X A Silver mirror observed
573 K –OH,
(C2H6O)
–OH,
Y
O
NH2 – NH – C – NH2
Z
Identify A, X, Y and Z [NEET-2017]
(1) A-Methoxymethane, X-Ethanoic acid, Y-Acetate ion, Z-hydrazine
(2) A-Methoxymethane, X-Ethanol, Y-Ethanoic acid, Z-Semicarbazide
(3) A-Ethanal, X-Ethanol, Y-But-2-enal, Z-Semicarbazone
(4) A-Ethanol, X-Acetaldehyde, Y-Butanone, Z-Hydrazone
Sol. Answer (3)
Since 'A' gives positive silver mirror test therefore, it must be an aldehyde or -Hydroxyketone.
Reaction with semicarbazide indicates that A can be an aldehyde or ketone.
Reaction with OH– i.e., aldol condensation (by assuming alkali to be dilute) indicates that A is aldehyde as
aldol reaction of ketones is reversible and carried out in special apparatus.
These indicates option (3).
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204 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
+ –
Cu [Ag(NH3)2] ,OH
CH3–CH2OH CH3–CHO CH3–COOH
573 K
(X) (A)
ethanal
O
OH
–
H2N – NH – C – NH2 OH
CH3 – CH – CH2 – CHO
O
3-Hydroxybutanal
CH3 – CH = N – NH – C – NH2
(Z)
CH3 – CH = CH – CHO
(Y)
But-2-enal
3. The correct structure of the product A formed in the reaction
O
H2(gas, 1 atmosphere)
A
Pd/carbon, ethanol
is [NEET-(Phase-2)-2016]
OH O OH OH
O O
H2(gas, 1 atm.)
Pd/carbon, ethanol
O
O
I II III
is [NEET-(Phase-2)-2016]
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 205
5. Reaction of a carbonyl compound with one of the following reagents involves nucleophilic addition followed by
elimination of water. The reagent is [Re-AIPMT-2015]
(1) Hydrocyanic acid (2) Sodium hydrogen sulphite
(3) A Grignard reagent (4) Hydrazine in presence of feebly acidic solution
Sol. Answer (4)
Feebly acidic
C = O + H2N – NH2 C – OH
NH
NH2
–H2O
C = N – NH2
6. Which one of the following esters gets hydrolysed most easily under alkaline conditions? [Re-AIPMT-2015]
OCOCH3 OCOCH3
(1) (2)
Cl
OCOCH3 OCOCH3
(3) (4)
O2N H3CO
Sol. Answer (3)
Since –NO2 has strong –I and –R effect, it will favour hydrolysis of ester most.
8. Treatment of cyclopentanone O with methyl lithium gives which of the following species?
[AIPMT-2015]
(1) Cyclopentanonyl biradical (2) Cyclopentanonyl anion
(3) Cyclopentanonyl cation (4) Cyclopentanonyl radical
Sol. Answer (2)
CH3 Li —
O O
CH3
9. An organic compound "X" having molecular formula C5H10O yields phenyl hydrazone and gives negative response
to the Iodoform test and Tollen's test. It produces n-pentane on reduction. 'X' could be : [AIPMT-2015]
(1) n-amyl alcohol (2) Pentanal (3) 2-pentanone (4) 3-pentanone
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206 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
X
[C5H 10O] yields phenylhydrazone which confirm the presence of carbonyl gp.
O
It gives negative response to the iodoform test and tollen's test which confirm the absence of C CH3
gp.
Therefore, from above condition it is obvious that ‘X’ is 3-Pentanone.
O
H3C CH2 C CH2 CH3
10. Which of the following will not be soluble in sodium hydrogen carbonate? [AIPMT-2014]
(1) 2,4,6 -trinitrophenol (2) Benzoic acid
(3) o-Nitrophenol (4) Benzenesulphonic acid
Sol. Answer (3)
o-nitrophenol is weaker acid than HCO3–.
11. Which one is most reactive towads Nucleophilic addition reaction? [AIPMT-2014]
CHO CHO
CHO COCH3
(1) (2) (3) (4)
CH3 NO2
COCl
(1) + H2 in presence of Pd-BaSO4 (2) +CO+HCl in presence of anhydrous AlCl3
COOH CH3
(3) + Zn/Hg and conc. HCl (4) +CrO2Cl2 in CS2 followed by H3O+
13. The correct order of decreasing acid strength of trichloroacetic acid (A),trifluoroacetic acid (B), acetic acid (C) and
formic acid (D) is [AIPMT (Prelims)-2012]
(1) A > B > C > D (2) A > C > B > D (3) B > A > D > C (4) B > D > C > A
Sol. Answer (3)
Electron withdrawing group increases the acidic character.
CF3COOH > CCl3COOH > HCOOH > CH3COOH
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 207
14. In the following sequence of reactions
KCN H O LiAlH
CH3– Br A
3
B 4
ether
C,
the end product (C) is [AIPMT (Prelims)-2012]
(1) Acetaldehyde (2) Ethyl alcohol (3) Acetone (4) Methane
Sol. Answer (2)
+
KCN H3O
CH3Br CH3CN CH3COOH
A LiAlH4
B ether
CH3CH2OH
50% KOH
Cl
[AIPMT (Prelims)-2012]
–
CH2OH COO
– CH2OH COO
(1) (2) +
+
Cl Cl OH OH
–
CH2OH CH2COO CH2OH OH
(3) + (4) +
Cl Cl OH OH
Sol. Answer (1)
–
CHO COO
50% OH
+
KOH
Cl Cl Cl
16. Which of the following acids does not exhibit optical isomerism? [AIPMT (Prelims)-2012]
(1) Lactic acid (2) Tartaric acid (3) Maleic acid (4) -amino acids
Sol. Answer (3)
Maleic acid.
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208 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
18. Acetone is treated with excess of ethanol in the presence of hydrochloric acid. The product obtained is
[AIPMT (Prelims)-2012]
OH OC2H5
(1) (CH3)2C (2) (CH3)2C
OC2H5 OC2H5
O O
COCl
H2
Pb – BaSO4
A
21. In a set of reactions m-Bromobenzoic acid gave a product D. Identify the product D
COOH
SOCl2 NH3 NaOH
B C Br2
D
[AIPMT (Prelims)-2011]
Br
A
COOH NH2
CONH2 SO2NH2
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 209
Sol. Answer (4)
O
COOH COCl C – NH2 NH2
–
SOCl2 NH3 Br2, OH
Br Br Br Br
(B) (C) (D)
22. Which one is a nucleophilic substitution reaction among the following? [AIPMT (Prelims)-2011]
(1) CH3CHO + HCN CH3CH(OH)CN
H
(2) CH3CH = CH2 + H2O CH3– CH – CH3
OH
(3) RCHO + RMgX R – CH – R
OH
CH3 CH3
23. Clemmensen reduction of a ketone is carried out in the presence of which of the following?
[AIPMT (Prelims)-2011]
(1) H2 and Pt as catalyst (2) Glycol with KOH
(3) Zn-Hg with HCl (4) LiAlH4
Sol. Answer (3)
Zn-Hg
C O HCl CH 2 ; clemmensen reduction .
24. An organic compound 'A' on treatment with NH3 gives 'B' which on heating gives 'C' when treated with Br in
the presence of KOH produces ethylamine. Compound 'A' is [AIPMT (Mains)-2011]
O
CH3 – CH2 – C – NH2
(C)
KOH + Br2
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210 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
25. Match the compounds given in Column-I with Column-II and select the suitable option using the code given below
Column-I Column-II
a. Benzaldehyde (i) Phenolphthalein
b. Phthalic anhydride (ii) Benzoin condensation
c. Phenyl benzoate (iii) Oil of wintergreen
d. Methyl salicylate (iv) Fries rearrangement [AIPMT (Mains)-2011]
(1) a(ii), b(iii), c(iv), d(i) (2) a(ii), b(i), c(iv), d(iii)
(3) a(iv), b(i), c(iii), d(ii) (4) a(iv), b(ii), c(iii), d(i)
Sol. Answer (2)
Fact.
26. The order of reactivity of Phenyl magnesium bromide (PhMgBr) with the following compounds
CH3 CH3 Ph
C = O, C = O and C=O
H H3C Ph
[AIPMT (Mains)-2011]
(1) I > III > II (2) I > II > III (3) III > II > I (4) II > I > III
Sol. Answer (2)
Electron density increases from I to III on carbonyl carbon.
27. Given are cyclohexanol(I), acetic acid(II), 2,4,6-trinitrophenol (III) and phenol(IV). In these the order of decreasing
acidic character will be [AIPMT (Prelims)-2010]
(1) III > II > IV > I (2) II > III > I > IV (3) II > III > IV > I (4) III > IV > II > I
Sol. Answer (1)
O
O2N NO2
NO2
Maximum resonance stabilized and maximum-I and –M effect due to three –NO2 groups, therefore more acidic
than CH3COOH.
CH2CH3 KMnO4 Br C H OH
B
C D
2 2 5
KOH FeCl3 H
COOH COOC2H5
(3) (4)
OCH2CH3 Br
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 211
Sol. Answer (4)
COOH COOC2H5
Br2 C2H5OH
COOH FeCl3 H+
Br Br
C D
B
29. Among the given compounds, the most susceptible to nucleophilic attack at the carbonyl group is
[AIPMT (Prelims)-2010]
30. Which of the following reactions will not result in the formation of carbon-carbon bonds ?
[AIPMT (Prelims)-2010]
Which of the above compound(s), on being warmed with iodine solution and NaOH, will give iodoform ?
[AIPMT (Mains)-2010]
(1) a, c and d (2) Only b (3) a, b and c (4) a and b
Sol. Answer (3)
O OH
Terminal CH 3 C or CH3 C show positive iodoform test.
32. Propionic acid with Br2|P yields a dibromo product. Its structure would be [AIPMT (Prelims)-2009]
Br Br
(1) H–C–CH2COOH (2) CH2Br–CH2–COBr (3) CH3–C–COOH (4) CH2Br–CHBr–COOH
Br Br
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212 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
33. Trichloroacetaldehyde, (CCl3CHO) reacts with chlorobenzene in presence of sulphuric acid and produces
[AIPMT (Prelims)-2009]
Cl
OH
(1) Cl C Cl (2) Cl C Cl
H Cl
Cl
(3) Cl CH Cl (4) Cl C Cl
CCl3 CH2Cl
Sol. Answer (3)
35. The relative reactivities of acyl compounds towards nucleophilic substitution are in the order of
[AIPMT (Prelims)-2008]
(1) Acyl chloride > Ester > Acid anhydride > Amide (2) Acyl chloride > Acid anhydride > Ester > Amide
(3) Ester > Acyl chloride > Amide > Acid anhydride (4) Acid anhydride > Amide > Ester > Acyl chloride
Sol. Answer (2)
36. Acetophenone when reacted with a base, C2H5ONa, yields a stable compound which has the structure ?
[AIPMT (Prelims)-2008]
CH—CH— C=CH—C–
(1) (2)
OH OH CH3 O
CH3 CH3
CH—CH2C
(3) (4) C C
CH3 O
OH OH
Sol. Answer (2)
37. Which of the following presents the correct order of the acidity in the given compounds ?
[AIPMT (Prelims)-2007]
(1) FCH2COOH > CH3COOH > BrCH2COOH > ClCH2COOH
(2) BrCH2COOH > ClCH2COOH > FCH2COOH > CH3COOH
(3) FCH2COOH > ClCH2COOH > BrCH2COOH > CH3COOH
(4) CH3COOH > BrCH2COOH > ClCH2COOH > FCH2COOH
Sol. Answer (3)
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 213
39. Reduction of aldehydes and ketones into hydrocarbons using zinc amalgam and conc. HCl is called
[AIPMT (Prelims)-2007]
(1) Wolf-Kishner Reduction (2) Clemmensen Reduction
(3) Cope Reduction (4) Dow Reduction
Sol. Answer (2)
O
Zn(Hg), HCl
R – CHO & R R Clemmensen reduction
The correct decreasing order of their reactivity towards hydrolysis is [AIPMT (Prelims)-2007]
(1) (b) > (d) > (a) > (c) (2) (b) > (d) > (c) > (a) (3) (a) > (b) > (c) > (d) (4) (d) > (b) > (a) > (c)
Sol. Answer (1)
41. Which of the compounds with molecular formula C5H10 yields acetone on ozonolysis ? [AIPMT (Prelims)-2007]
(1) 2 – Methyl – 1 – butene (2) 2 – Methyl – 2 – butene
(3) 3 – Methyl – 1 – butene (4) Cyclopentane
Sol. Answer (2)
43. A carbonyl compound reacts with hydrogen cyanide to form cyanohydrin which on hydrolysis forms a racemic
mixture of –hydroxy acid. The carbonyl compound is [AIPMT (Prelims)-2006]
(1) Acetaldehyde (2) Acetone (3) Diethylketone (4) Formaldehyde
Sol. Answer (1)
OH
–
CH3 CHO CN CH3 CH
CN
O
(1) CH3 – CH2 – CH2C – CH3 (2) (CH3)2C = O
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214 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
45. Self condensation of two moles of ethyl acetate in presence of sodium ethoxide yields
[AIPMT (Prelims)-2006]
(1) Ethyl butyrate (2) Acetoacetic ester (3) Methyl acetoacetate (4) Ethyl propionate
Sol. Answer (2)
OH
CH = CH – CH2 – CH
CH3
X is
(1) H2/Pt (2) Zn-Hg/HCl (3) Li/NH3 (4) NaBH4
Sol. Answer (4)
CH2 CH3
NaBH4 CH3
O OH
CH3
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 215
50. In Tollen’s test, aldehydes
(1) Are oxidised to acids (2) Are reduced to alcohol
(3) Neither reduced nor oxidised (4) Precipitate Ag+ as AgCl
Sol. Answer (1)
+ –
R – CHO + 2Ag + 3OH
–
R – COO + 2Ag + 2H2O
51. Which of the following compound will undergo self aldol condensation in the presence of cold dilute alkali?
H
will undergo aldol reaction.
O
52. Which of the following compounds will give positive test with Tollen’s reagent?
(1) Ar2C = O >R2C = O > ArCHO > RCHO > H2C = O (2) H2C = O > R2C = O > Ar2C = O > RCHO > ArCHO
(3) H2C = O > RCHO > ArCHO > R2C = O > Ar2C = O (4) ArCHO > Ar2C = O > RCHO > R2C = O > H2C = O
54. The oxidation of toluene with CrO3 in the presence of (CH3CO)2O gives a product A, which on treatment with
aqueous NaOH, produces
CrO3
CH3 (CH3CO)2O
CHO
55. When aniline reacts with oil of bitter almonds (C6H5CHO) condensation takes place and benzal derivative is
formed. This is known as
(1) Schiff’s base (2) Benedict’s reagent (3) Million’s base (4) Schiff’s reagent
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216 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
C O + H2N
H
C N
H
Schiff's base
HCHO OH
No Aldol
+ –
CH 2 = CH – C = O CH2 – CH C–O
H H
H H
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 217
CN
H3O
61. + CH3MgBr P
OCH3
OH O
CHO COOH
CH – CH3 C – CH3
O
CN
CH3
H3O
+ CH3MgBr
OCH3
OCH3
H . OH
62. In this reaction CH3CHO + HCN CH3CH(OH)CN CH3CH(OH)COOH an asymmetric centre is generated.
The acid obtained would be
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218 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
OH
63. A and B in the following reactions are R–C–R HCN/ B
A R—C
KCN
O R CH2NH2
CN
(1) A = RRC , B = H3O
OH
CN
(2) A = RRC , B = H2O/OH
OH
CN
(4) A = RRC , B = LiAlH4
OH
OH OH
HCN B
R C R + R C R R C R
KCN LiAlH4
O CN CH2 NH2
64. Compound A has a molecular formula C2Cl3OH. It reduces Fehling’s solution and on oxidation, it gives a
monocarboxylic acid B. If A is obtained by the action of chlorine on ethyl alcohol, then compound A is
(1) Methyl chloride (2) Monochloroacetic acid (3) Chloral (4) Chloroform
Sol. Answer (3)
Charly, answer is Chloral.
65. Which one of the following on treatment with 50% aqueous sodium hydroxide yields the corresponding alcohol
and acid?
66. An ester (a) with molecular formula, C9H10O2 was treated with excess, of CH3MgBr and the complex, so formed,
was treated with H2SO4 to give an olefin (b). Ozonolysis of (b) gave a ketone with molecular formula C8H8O which
shows +ve iodoform test. The structure of (a) is
(1) H3COCH2COC6H5 (2) C2H5COOC6H5
(3) C6H5COOC2H5 (4) p-H3CO C6H4 COCH3
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 219
Sol. Answer (3)
O OH
+
CH3 H
C – O C2H5 + CH3MgBr C C CH2
CH3 CH3
O3, Zn
O
C – CH3 + HCHO
SECTION - D
Assertion-Reason Type Questions
1. A : Aromatic aldehydes are less reactive than aliphatic aldehyde towards nucleophilic addition reaction.
R : In case of aromatic aldehyde, steric hinderance and –I effect of phenyl ring is present.
Aromatic aldehydes are less reactive than aliphatic aldehyde towards nucleophilic addition reaction because
of +M effect of benzene decreases the positive charge density on its carbonyl carbon of aromatic aldehyde.
O O
C C
H R H
+ 1 + 2
t t
ec ec
eff eff
+I
+M
O O
C > C
Order of nucleophilic R H H addition reaction.
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220 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
Ka order HCO2H > C6H5CO2H { But C6H5 – group shows +I & +R effect }
O
||
4. A : H2N—C—CH3 can give iodoform reaction.
O
||
R : Cl—C—CH3 can also give iodoform reaction due to presence of –COCH3 group.
Both of them do not give iodoform reaction because both have gp NH2, & Cl which do not allow haloform
reaction.
Because of presence of two –CH3 group on -‘C’ the -‘H’ is less acidic. So, it also gives Cannizzaro
reaction.
P.C.C. KMNO4
R CH2 OH
O.A.
; Ethanol undergoes aldol condensation reaction but it have only 3-H atom.
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 221
8. A : Formaldehyde undergoes Cannizzaro reaction in the presence of H.
R : Formaldehyde has two -Hydrogen atoms.
Sol. Answer (4)
O
C , Formaldehyde undergoes Cannizzaro reaction in presence of base, as it zero -‘H’.
H H
–
– O
O
> H3C CH2
Stability order of conjugate base
Resonance stabilized
OH
> H 3C CH2 OH
OH
Because ethanol have 3 -‘H’ and I2 + NaOH is oxidising agent also, which oxidises to
H3C CH2
12. A : Nitration of benzoic acid gives ortho and para derivatives of nitrobenzoic acids.
R : Carboxyl group is activating group.
Sol. Answer (4)
–CO2H is a deactivator because of its –M effect it gives meta product.
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222 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
O
O
C
C
H
H3C H
Order of nucleophilic addition reaction
t
t ec
eff
ec eff
+I +M
Aldehydes are easily oxidised to acid because of presence of ‘H’ atom on carbonyl carbon which can be
converted into –OH group, without involving the cleavage of any other bond.
But aromatic aldehyde (benzaldehyde) however do not reduce Fehling solution or Benedict solution. The
weaker oxidising agent. like Fehling's solution (or Benedict solution) fail to oxide benzaldehyde because the
C – H bond in aldehyde is strong (due to the increase of electron density in C – H bond of the aldehyde group)
and hence stronger oxidising agent are required.
O O
H2O
Cl3C C Cl3CH + C
H HO H
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Solution of Assignment (Set-2) Aldehydes, Ketones and Carboxylic Acids 223
Sol. Answer (1)
Acetate ion is less basic than methoxide ion because acetate ion is resonance stablised.
Stability order >
1
As basic strength order
Stablity order
(i) O3
3
(ii) Zn/H2O
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224 Aldehydes, Ketones and Carboxylic Acids Solution of Assignment (Set-2)
Because of strong - I effect of ‘3’ ‘F’ atom. at – c, its conjugate base is more stable.
S.O of conjugate base.
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