Carbonyl Compounds 1

Level-I

Chapter 13
Aldehydes, Ketones and
Carboxylic Acids

Solutions (Set-1)

Very Short Answer Type Questions :

1. What product is formed when CH3COOH reacts with PCl5?
PCl5
Sol. CH3 COOH ⎯⎯⎯ → CH3 COCl + POCl3 + HCl
O
2. Write IUPAC name of
CH3
Sol. 2-Methylcyclohexanone.
3. Write chemical equation for the following chemical reactions:
Benzonitrile is converted to benzophenone.
C N Ph—C N.MgBr COPh
H3O+ Br
Sol. + PhMgBr + Mg
NH2
4. Draw the structural formula of Hex-2-en-4-ynoic acid.
O
||
Sol. CH3 — C ≡ C — CH = CH — C— OH .
5. Give one chemical test to distinguish between acetaldehyde and benzaldehyde.

Sol. Acetaldehyde gives positive iodoform reaction while benzaldehyde does not.
6. How are formalin and trioxane related to methanal?
Sol. Formalin is 40% aqueous solution of HCHO and trioxane is a trimer of HCHO.
7. How can we distinguish formic acid and acetic acid chemically?
Sol. Formic acid gives silver mirror with Tollen’s reagent while acetic acid does not give this test.
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
2 Aldehydes, Ketones and Carboxylic Acids Solutions of Assignment (Level-I) (Set-1)
8. How can we obtain Propan-2-ol from ethanal?
OMgBr OH
| +
|
H2O/H
Sol. CH3 CHO + CH3MgBr ⎯⎯→ CH3 — CH — CH3 ⎯⎯⎯⎯ → CH3 — CH— CH3
9. What product is obtained when CH3COOH reacts with PCl5?
Sol. CH3 COOH + PCl5 ⎯⎯→ CH3 COCl + POCl3 + HCl .
COOH
10. Compare the acidic strength of following acids i.e., (i) HCOOH (ii) CH3COOH and (iii) .
COOH
Sol. HCOOH > > CH3COOH.
Short Answer Type Questions :

11. Arrange the following compounds in increasing order of their boiling points:
CH3CH2CH2CHO, CH3(CH2)2CH2OH, C2H5—O—C2H5, CH3(CH2)3CH3
Sol. All have comparable molecular masses so deciding factor is their intermolecular forces of interaction, which
are strongest in alcohol and weakest in alkane. Therefore
CH3(CH2)3CH3 < C2H5—O—C2H5 < CH3CH2CH2CHO < CH3(CH2)2CH2OH
12. Complete the following equations:
COOH SO3/H2SO4
(i)
(ii) CH3 CONH2 + HNO2 ⎯⎯→
(iii) CH3 CHO + C6H5NHNH2 ⎯⎯→
COOH
Sol. (i)
SO3H
(ii) CH3COOH + N2 + H2O
(iii) CH3CH == N —NH—C6H5 + H2O
acetaldehydephenylhydrazone
13. Describe the following reactions:
(i) Cannizzaro reaction
(ii) Cross aldol reaction
Sol. (i) Cannizzaro reaction: Aldehydes which do not contain any α-H atom undergo disproportionation on
treatment with conc. alkali in which one molecule is oxidised and another is reduced.
H H
Ex. C O+ C O + conc. KOH CH3OH + HCOOK
H H
Solutions of Assignment (Level-I) (Set-1) Aldehydes, Ketones and Carboxylic Acids 3
(ii) Cross Aldol condensation: When aldol condensation is carried out between two different aldehydes or
ketones both containing α-H atom, it is Cross Aldol condensation.
OH
CH3—CH—CH2CHO
dil.
CH3CHO + CH3CH2CHO OH
NaOH
CH3—CH—CH—CHO
CH3
OH 4 possible products
CH3CH2—CH—CH—CHO
CH3
OH
CH3CH2—CH—CH2CHO
14. Write reactions with conditions for following conversions:
(i) Methylbromide to acetic acid
(ii) Benzene to toluene
H O/H+
Sol. (i) CH3Br + KCN(aq) ⎯⎯→ CH3 CN ⎯⎯⎯⎯
2
→ CH3 COOH
anh. AlCl3
CH3
(ii) + CH3Cl F.c. alkylation
15. Account for the following observations:

(i) Oxidation of toluene to benzaldehyde with CrO3 is carried out in presence of acetic anhydride.
(ii) Melting point of an acid with even number of carbon atom is higher than those of its neighbours with odd
number of carbon atoms.
Sol. (i) Acetic anhydride is used to stop the reaction at benzaldehyde otherwise the end product must be benzoic
acid.
(ii) Acids with even no. of carbon atoms fit into crystal lattice more readily than odd ones, hence they have
higher lattice energy and higher melting point.
16. How can you convert?
(i) Acetaldehyde to acetone
(ii) Acetylene to acetone
KMnO /H+ Ca(OH) dry

Sol. (i) CH3 CHO ⎯⎯⎯⎯⎯
4
(O)
→ CH3 COOH ⎯⎯⎯⎯→
2
(CH3 COO)2 Ca ⎯⎯⎯⎯⎯
distillation
→ CH3 COCH3 + CaCO3
O
||
CH3 Cl H2O/HgSO4 ,H2SO4
(ii) HC ≡ CH + NaNH2 ⎯⎯→ CH ≡ C — Na ⎯⎯⎯⎯ → HC ≡ C — CH3 ⎯⎯⎯⎯⎯⎯⎯⎯ → CH3 — C— CH3
17. Arrange the following in order of increasing boiling points:

(i) C2H5OC2H5, C4H9COOH, C4H9OH
(ii) C3H7CHO, CH3COC2H5, C2H5COOCH3, (CH3CO)2O
Sol. (i) C2H5OC2H5 < C4H9OH < C4H9COOH
(ii) C3H7CHO < CH3COC2H5 < C2H5COOCH3 < (CH3CO)2O
18. State reasons for the following:

(i) Monochloroethanoic acid is a weaker acid than dichloroethanoic acid.
(ii) Benzoic acid is a stronger acid than ethanoic acid.
O
||
Sol. (i) Cl ← CH2 — C— OH < Cl ← CH — COOH
↓
Cl
Presence of –I effect and EWG increases the H+ releasing tendency of carboxylic acid.
O
COO H
(ii) > CH3 C O H
Benzene ring withdraws electrons towards itself due to resonance and increases its acidic strength while
—CH3 group is electron releasing which decreases its acidic strength.
19. (a) How will you obtain an aldehyde by using following process?
(i) Dehydrogenation
(ii) Catalytic hydrogenation
(b) Why do aldehydes behave like polar compounds?
Cu
Sol. (a) (i) R — CH2OH ⎯⎯⎯→
573K
R — CHO + H2
Pd. BaSO
(ii) R — COCl + H2 ⎯⎯⎯⎯⎯
Xylene
4
→ R — CHO + HCl
(b) Due to presence of C O i.e., carbonyl group aldehyde molecules are polar.
20. How will you do the following conversions in not more than two steps?
(i) Propanal to butanone
(ii) Propanoyl chloride to dipropylamine
(iii) Propanoic acid to propenoic acid
OH O
| ||
(i) CH3MgBr K 2Cr2O7
Sol. (i) CH3 CH2CHO ⎯⎯⎯⎯⎯→ + CH2 — CH— CH2CH3 ⎯⎯⎯⎯ + → CH3 — C— CH2 — CH3
(ii) H3 O conc. H
CH CH CH NH Zn/Hg
(ii) CH3 CH2COCl ⎯⎯⎯⎯⎯⎯⎯
3 2 2 2
→ CH3 — CH2CONH — CH2CH2CH3 ⎯⎯⎯⎯⎯
conc. HCl
→ C3H7NHC3H7
dipropylamine
Cl
|
(iii) Red P/Cl2
CH3 CH2COOH ⎯⎯⎯⎯⎯ alc. KOH
→ CH3 — CH — COOH ⎯⎯⎯⎯→ CH2 = CH — COOH
21. Draw the structure of a carbonyl group and indicate clearly
(i) Hybridised state of carbon
(ii) The σ and π bonds present
(iii) The electrophilic and nucleophilic centres in it.
δ+ π δ–
Sol. (i) C O hybridised state of C is sp2
σ
σ
(ii) σ Cπ O 3σ bonds and 1π bond on C atom.
(iii) C O
Electrophilic centre
Nucleophilic centre
22. Give reasons for the following:

(i) Carboxylic acids do not give characteristic reactions of carbonyl group.
(ii) Treatment of benzaldehyde with HCN gives a mixture of two isomers which can not be separated even
by careful fractional distillation.
(iii) Sodium bisulphite is used for the purification of aldehydes and ketones.
Sol. (i) Due to resonance position of carbonyl group is changing
–
O O
+
R—C—O—H R—C OH
hence these compounds do not give reactions of carbonyl group.

(ii) On nucleophilic addition of HCN to benzaldehyde, it forms two optical isomers which have same physical
properties, hence can not be separated by fractional distillation.
O OH OH
C—H + HCN *C—CN NC—C
H H
(iii) Aldehydes and ketones form addition products with NaHSO3, whereas impurities don not react and are left
behind. Addition products which were earlier crystallised can be easily reconverted to aldehyde and ketone.
OH
|
H3 O+
CH3 CHO + NaHSO3 ⎯⎯→ CH3 — CH— SO3Na ⎯⎯⎯→ CH3 CHO + NaHSO3
23. Complete the following series of reaction:

K Cr O NaOBr SOCl NH
(i) CH3 CH2 OH ⎯⎯⎯⎯→
2 2 7
H SO
A ⎯⎯⎯⎯
2
→ B ⎯⎯⎯
3
→ C ⎯⎯⎯⎯ →D
2 4
KCN HO PO
(ii) CH3 CH2Cl ⎯⎯⎯ → A ⎯⎯⎯→
2 2
−OH
B ⎯⎯⎯
2 5
→A
C H OH CH MgBr CH MgBr
(iii) CH3 COOH ⎯⎯⎯⎯⎯
2 5
con. H SO
→ A ⎯⎯⎯⎯⎯
3
+ → B ⎯⎯⎯⎯⎯
3
+ →C
2 4 H3O H3O
[O] SOCl NaOBr NH

Sol. (i) CH3 CH2 OH ⎯⎯⎯ → CH3 COOH ⎯⎯⎯⎯
2
→ CH3 COCl ⎯⎯⎯
3
→ CH3 CONH2 ⎯⎯⎯⎯ → CH3NH2
A B C D
O
|| −
KCN OH P2O5
(ii) CH3 CH2Cl ⎯⎯⎯ → CH3 CH2C ≡ N ⎯⎯⎯→
HO
CH3 CH2 — CNH2 ⎯⎯⎯→
−H O
CH3 CH2CN
2 2 2
A A
O OH
|| |
C2H5 OH CH3MgBr CH3MgBr
(iii) CH3 COOH ⎯⎯⎯⎯⎯⎯
conc. H2SO4
→ CH3 COOC 2H5 ⎯⎯⎯⎯⎯ + → CH3 C— CH3 ⎯⎯⎯⎯⎯ + → CH3 C — CH3
H3O H3 O
A B |
CH3
C
24. Would you expect benzaldehyde to be more or less reactive in nucleophilic addition reactions than propanal?
Explain.
Sol. Benzaldehyde is considered to be lesser reactive than propanal due to reduced polarity of carbonyl group.
– – –
H O H O H O H O
C C C C
+ +
25. Write the names of reagents and equations in the conversions of

(i) Phenol to salicylaldehyde
(ii) Anisole to p-methoxyacetophenone
OH ONa OH
CHO CHO
60°C H+
Sol. (i) + CHCl3 + 3KOH
Chloroform
Salicylaldehyde
It is Reimer Tiemann reaction.
OCH3 OCH3
anh. AlCl3
(ii) + CH3COCl p-methoxyacetophenone
Ethanoyl chloride
Anisole
C—CH3
26. Give chemical tests to distinguish between following pairs of compounds:

(i) Propanoyl chloride and propanoic acid
(ii) Benzaldehyde and acetophenone
Sol. (i) Propanoyl chloride does not give brisk effervescence with NaHCO3(aq) but propanoic acid does so.
(ii) Acetophenone gives yellow ppt of iodoform with I2 and NaOH whereas benzaldehyde does not show this
reaction.
27. Write IUPAC names of the following compounds:
OCOCH3
(i)
Br
(ii) HOOC — CH2 — C = CH — COOH

|
CH3
COOH
Br
(iii)
HO NO2
Sol. (i) Methyl 4-bromobenzoate
(ii) 3-Methylpent-2-ene-1,5-dioic acid
(iii) 6-Bromo-3-hydroxy-5-nitrobenzoic acid
28. How will you convert?
(i) Ethanal to methane
(ii) Ethanol to propanone
[O] NaOH NaOH, Δ

Sol. (i) CH3 CHO ⎯⎯⎯ → CH3 COOH ⎯⎯⎯⎯ → CH3 COONa ⎯⎯⎯⎯
+ CaO
→ CH4 + Na2CO3
[O] Ca(OH)2 CH3COO dry

(ii) CH3CH2OH CH3COOH Ca CH3—CO—CH3 + CaCO3
CH3COO distillation
29. Write chemical equations, for the following reactions:

(i) Action of conc. NaOH on 2,2-Dimethyl propanal
(ii) Action of dil. NaOH on propanal.
CH3 CH3 CH3

| | |
conc. NaOH
Sol. (i) CH3 — C — CHO ⎯⎯⎯⎯⎯⎯⎯⎯
Cannizzaro reaction
→ CH3 — C — COONa + CH3 — C — CH2OH
| | |
CH3 CH3 CH3
OH
|
dil. NaOH
(ii) 2CH3 — CH2CHO ⎯⎯⎯⎯⎯
Aldol cond.
→ CH3 — CH2 — CH— CH — CHO
|
CH3
30. Write balanced chemical equations for the following reactions:

(i) Thionyl chloride reacts with benzoic acid
(ii) Acetic acid is treated with Red P and HI
(iii) Acetic acid is treated with Zn metal.
COOH COCl
Sol. (i) + SOCl2 + SO2 + HCl
Red P
(ii) CH3 COOH + 6HI ⎯⎯⎯⎯ → CH3 — CH3 + 3I2 + 2H2 O
(iii) 2CH3 COOH + Zn ⎯⎯→(CH3 COO)2 Zn + H2
Long Answer Type Questions :

31. Write structures of organic compounds A to F in the following sequence of reactions
OH
Zn conc. HNO Br H /Pt HNO H O+

⎯⎯⎯
Δ
→ A ⎯⎯⎯⎯⎯
H SO
3
→ B ⎯⎯⎯
2
Fe
→ C ⎯⎯⎯→
2
D ⎯⎯⎯⎯
HCl
2
→ E ⎯⎯⎯→
3
F
2 4
OH NO2 NO2 NH2

Zn conc. HNO3 Br2 H2/Pt
Sol. Fe
Δ conc. H2SO4
Br Br
A B C D
OH N2Cl
H3O+ NaNO2 + HCl
or HONO
Br Br
F E
32. (a) How can the following compounds be obtained?
(i) Acetic acid from acetylene
(ii) Acetone from acetic acid
(iii) Acetaldehyde from acetic acid
(b) In what way can acetic acid be distinguished from acetone?
H SO [O]
Sol. (a) (i) HC ≡ CH + H2 O ⎯⎯⎯⎯
2
HgSO
4
→ CH3 CHO ⎯⎯⎯ → CH3 COOH
4
Ca(OH) dry distillation

(ii) CH3 COOH ⎯⎯⎯⎯→
2
(CH3 COO)2 Ca ⎯⎯⎯⎯⎯⎯ → CH3 COCH3 + CaCO3
LiAlH4 Cu
(iii) CH3 COOH ⎯⎯⎯⎯ → CH3 CH2 OH ⎯⎯⎯→ CH3 CHO + H2
573 K
(b) Acetone shows iodoform reaction and gives yellow ppt of CHI3 with NaOH and I2, acetic acid does not
give this reaction.
33. Write chemical reactions to show the following conversions:
(i) Butanol to butanoic acid
(ii) 3-Nitrobromobenzene to 3-Nitrobenzoic acid
(iii) 4-Methylacetophenone to Benzene-1,4-dicarboxylic acid
(iv) Cyclohexene to Hexane-1,6-dioic acid
CrO −H SO
Sol. (i) CH3 CH2 CH2CH2OH ⎯⎯⎯⎯⎯⎯→
3 2 4
Jones Reagent
CH3 CH2 CH2 COOH
O OMgBr
Br MgBr C COOH
+
Mg CO2 H3O
(ii)
dry ether dry ice
NO2 NO2 NO2 NO2
COCH3 COOK COOH
KMnO4/KOH dil. H2SO4
(iii) terepthalic acid
CH3 COOK COOH
KMnO4–H2SO4 COOH
(iv) Δ COOH
34. How will you synthesise the following by using a Grignard reagent?
(i) 2,2-Dimethylpentanoic acid
(ii) But-3-enoic acid
(iii) 2-Phenylpropan-2-ol
CH3  CH3  CH3

|  |  |
→ CH3 CH2CH2 — C — MgBr  ⎯⎯⎯⎯
Mg/ether (i) CO2
Sol. (i) CH3 CH2CH2 — C — Br ⎯⎯⎯⎯ ⎯ → CH3 CH2 CH2 — C — COOH
|  |  (ii)H+ |
 
CH3  CH3  CH3
(ii) CH2 = CH — CH2Br ⎯⎯⎯→

Mg
ether
CH2 = CH — CH2MgBr ⎯⎯⎯⎯
(i) CO
(ii) H
→ CH2 = CH — CH2 COOH
+
2
O OMgBr OH
MgBr C CH3 C CH3
+
+CH3–C–CH3 H3O
(iii)
CH3 CH3
35. (a) Why has monochloroethanoic acid higher pKa value than dichloroethanoic acid?
(b) Give formulas of compounds A and B
dry ether PCl
CH3MgBr + CO2 ⎯⎯⎯⎯→ + A ⎯⎯⎯
5
→B
H3O
(c) Identify compounds A and B

SOCl LiAlH
CH3 COOH ⎯⎯⎯⎯
2
→ A ⎯⎯⎯⎯
4
→B
Sol. (a) Out of Cl—CH2COOH and Cl — CH— COOH , the later one has two —Cl atoms and more electron
|
Cl
withdrawing influence hence it is more acidic having lesser pKa value.
H O+ PCl
(b) CH3MgBr + CO2 ⎯⎯→ CH3 COOMgBr ⎯⎯⎯→
3
CH3 COOH ⎯⎯⎯
5
→ CH3 COCl
A B
SOCl LiAlH
(c) CH3 COOH ⎯⎯⎯⎯
2
→ CH3 COCl ⎯⎯⎯⎯
4
→ CH3 CH2 OH
A B
36. Which out of each pair is expected to be a stronger acid?

(a) CH3COOH or HCOOH
OH
(b) CH3COOH or
COOH
(c) or HCOOH
(d) CH2 — COOH or CH2 — COOH

| |
Cl Br
COOH COOH
OH
(e) or
OH
COOH COOH
(f) or
O2N H3C
Sol. (a) HCOOH

(b) CH3COOH
(c) HCOOH
(d) Cl—CH2—COOH
COOH
OH
(e)
COOH
(f)
NO2
37. How will you convert

(a) Butan-2-ol to 2-methylbutanoic acid
(b) Propanoic acid to acetic acid
(c) (CH3)2C == CH—COCH3 to (CH3)2C == CH—COOH
OH I MgI
| | |
PI3 Mg/dry
Sol. (a) CH3 CH2 — CH— CH3 ⎯⎯⎯ → C2H5 — CH — CH3 ⎯⎯⎯⎯
ether
→ C2H5 — CH — CH3
H O/H+ CO2
C2H5 — CH — COOH ←⎯⎯⎯⎯
2
−MgI(OH)
⎯ C2H5 — CHCOOMgI
| |
CH3 CH3
NH , Δ Br /KOH
HONO (O)
(b) CH3CH2COOH ⎯⎯⎯⎯
3
−H O
→ C2H5CONH2 ⎯⎯⎯⎯→
2
C2H5NH2 ⎯⎯⎯⎯ → CH3CH2OH ⎯⎯⎯⎯⎯→+ CH3COOH
2 K2Cr2O7 /H
+4NaOH + 3I2
(c) (CH3)2C CH—COCH3 (CH3)2C CH—COONa + CHI3 + 3NaI + 3H2O
H3O+
(CH3)2C CH—COOH
38. Give reasoning for the following:

(a) CH3COO– ion is more stable than C2H5O– ion
(b) Tertiary butylbenzene does not give benzoic acid when oxidised with KMnO4
(c) Carbon oxygen bond lengths in formic acid are different but are the same in sodium formate.
Sol. (a) In acetate ion there is delocalisation of –ve charge which is not possible in ethoxide ion.
–
–
O O O –
CH3—C CH3—C CH3—C C2H5 — O
O – O O
(b) To oxidise the alkyl group attached to benzene ring atleast one α-hydrogen must be present e.g., toluene
gets oxidised to benzoic acid but tert butyl group has no α-H hydrogen hence it does not oxidise with
KMnO4.
+
(c) H —C — O —H H —C O—H Formic acid
–
O O
H —C — O H —C O Formate ion
–
O O
In formate ion contributing structures for anion are equivalent while these are not the same in formic acid.

Level-I
Chapter 13
Aldehydes, Ketones and
Carboxylic Acids
Solutions (Set-2)
[Aldehydes and Ketones (Preparation and Reactions)]
OH OH
+
H
1. C C A
(Major)
CH3O OCH3
CH3 CH3
Major product A is
CH3
(1) C C
CH3O OCH3
CH3
CH3O
O
(2) C C CH3
CH3O
CH3
(3) Both (1) & (2)
O
(4) C C
CH3O OCH3
CH3 CH3
Sol. Answer (1)
OH OH OH2 OH
H+
C C C C
H3CO OCH3 H3CO OCH3
–H2O
CH3 CH3 CH3 CH3

CH3
O H O H
Rearrangement
C C
C C
H3CO OCH3 H3CO OCH3
CH3
CH3 CH3 CH3
O
+
–H
C C
H3CO OCH3
CH3
Migrating power of p-tolyl is more than m-anisyl.
2. CH 3 CHO + LiAlH 4 ⎯⎯→ CH3 CH 2 OH
Nucleophile added in this reaction is
(1) AlH−4 (2) Li+ (3) H+ (4) H –
Sol. Answer (4)

LiAlH4 → Li+ + Al3+ + 4H–
O O– O —H
|| – | H 3O+ |
CH3 — C — H + H CH3 — C — H CH3 — C — H
| |
H H
2+
PhMgBr (Cu )
3. Complete the reaction : Ph − CH = CH − CHO ⎯⎯⎯⎯⎯⎯⎯ → Product
+
H3O
(1) Ph – CH – CH – CHO (2) Ph – CH – CH2 – CHO

Ph OH Ph
(3) Ph – CH – CH – CHO (4) Ph – CH – CH2 – CH2 – OH

OH Ph Ph
Sol. Answer (2)
δ δ
Ph
— CH — CH —
Ph — CH — —O CH — CH —
— CH — O MgBr
Ph ⊕
H3O
PhMgBr Ph
CH — CH —
— CH — O
Ph
H
Ph
CH — CH 2— CHO
Ph
H Nu
4. C=O Product . Product may be
D
(1) Meso (2) Racemic (3) Inversion (4) All of these

Sol. Answer (2)
Product may be recemic, because carbonyl carbon is sp2 hybridised and has planar shape. So, Nu– attacks
on front as well as back side.
O
Conc.
5. CH 3 – C – CH 2 – CH 3 Product
HNO3
The product is
(1) CH3COOH (2) CH3CH2COOH + HCOOH
(3) CH3CH2CH2COOH (4) No reaction
Sol. Answer (1)
O
Conc . HNO 3
CH3 C CH2 CH3 ⎯⎯ ⎯ ⎯ ⎯ → 2CH3COOH
According to Popoff’s rule, carbonyl group goes with less complex alkyl group.
O
SeO2
6.
O O OH
O
OH
(1) (2) (3) O (4)
O
Sol. Answer (1)
O O
O
SeO2
In this reaction, active methylene group (—CH2—) is oxidised to C—

— O group.
O
7. LiAlH4
A
The product predominates is
HO H HO H O
(1) (2) (3) (4)
Sol. Answer (1)
O
HO H
LiAlH4
H 2O
LiAlH4 does not reduce double bond. If double bond is conjugated with phenyl system then double bond is
reduced by LiAlH4.
O
C A
CH3
8. H2N H2N
A is
(1) Zn – Hg/HCl (2) NH2 – NH2/OH – (3) Both (1) & (2) (4) NaBH4
Sol. Answer (2)
O
C
NH2NH2/OH–
CH 3
:
H2N H 2N
In this reaction, Zn — Hg/HCl is not used because in acidic medium, —NH2 group is affected.
9. Which of the following carbonyl oxygen will form strongest hydrogen bond with H2O molecule?
O O O
O
H H
(1) (2) (3) (4)
H H
Sol. Answer (2)
forms strongest hydrogen bond with H2O molecule because in this case carbonyl carbon readily attains
+ve charge due to aromaticity
O O
10. The compound —C—CH3 can be exclusively oxidized into —C—OH by
(1) NaCN followed by hydrolysis (2) NaOI followed by H3O+

(3) KMnO4 hot followed by hydrolysis (4) K2Cr2O7 followed H3O+
Sol. Answer (2)
O O O
|| || – + H3 O ||
NaOI
C — CH3 C — O Na + CHI3↓ Δ
C — OH
The above conversion is known as iodoform reaction.

11. An organic compound [x], C5H8O reacts with hydroxylamine to form [y], [y] in the presence of conc. H2SO4
gives δ-lactam. [x] neither give Benedicts test nor it respond positively towards haloform test. The compound
[x] is
O
H3C O
(1) (2) (3) —
—O (4)
O
Sol. Answer (3)

O N — OH H
|
H2NOH Conc. H2SO4
N
C O
Beckmann Rearrangement
(x) C5H8O (y)
δ - la ctam
O
PCl5, 0ºC (i) LiNH2(3eq) Na / NH3
12. C—CH3 [A]
(ii) Et – Br
A is
O
(1) C—CH2—CH2—CH3 (2) CH2—CH2—CH2—CH3
Ph H Ph Et
(3) C C (4) C C
H Et H H
Sol. Answer (3)
O Cl Cl
|| PCl5 LiNH2
C — CH3 C — CH3 C—
— CLi
—
0°C (excess)
Et — Br
Ph H Na/NH3
—
C—
—C C—
— C — Et
H Et (Birch Reduction)
13. CHO + (x)

CH3COONa
+
H3O
CH CHCOOH
The compound x is
(1) CH3COOH (2) BrCH2—COOH (3) (CH3CO)2O (4) CHO—COOH
Sol. Answer (3)
14. 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)
15. 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)
CHO (i) conc. NaOH

16. + ?
(ii) H2O/H
CHO
COOH COOH COOH CH2OH

(1) (2) (3) (4)
COOH CH2OH OH CHO
Sol. Answer (2)
17. 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 is
CHO O CHO
C2H5 CHO C
(1) (2) (3) CH3 (4)
CH3 C2H5
C2H5
Sol. Answer (1)
18. The correct order of reactivity of PhMgBr towards given compounds
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)
19. 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
OH(–)
20. CHO + 'X' CH CH C . Identify 'X'
293K
O
(1) CH2—CHO (2) CH2–CH2–OH (3) C CH3 (4) CH CH2
Sol. Answer (3)
O O
|| ||
21. The diketone CH3 — C— (CH2 )2 — C— CH3 on intramolecular aldol condensation gives the final product
O O O O
OH
(1) (2) (3) (4)
CH3 CH3 CH3
Sol. Answer (3)

22. Enol content is high test in
(1) Acetone (2) Acetophenone (3) Acetic acid (4) Acetyl acetone
Sol. Answer (4)
NaOH
23. 2C6H5 CHO ⎯⎯⎯⎯ → C6H5 CH2 OH + C6H5 COONa
The similar reaction can take place with which of the following aldehyde?
(1) CH3CHO (2) CH3CH2CHO (3) (CH3)3CCHO (4) CH3CH2CH2CHO
Sol. Answer (3)
[Carboxylic Acids (Preparation and Reactions)]
HBr, Peroxide (i) Mg/Et2O

24. Consider the following sequence of reaction : hν
[A] [B] . The final product
(ii) CO2
+
(iii) H3O
[B] in the reaction would be :
CH3
O
C OH
(1) C OH (2)
O
O O
(3) C OH (4) CH2 C OH
Sol. Answer (4)
HBr, Peroxide Mg
CH2 CH2— Br Et2O
CH2 MgBr
O
( i) CO
CH2 C OH ←⎯ ⎯⎯2 ⎯
(i i) H 3O +
25. Which of the following would be the best synthesis of benzoic acid from bromobenzene?
+
H3O
(1) Br + KCN [A]
+
H3O
(2) Br + AgCN [A]
Mg (i) CO2
(3) Br [A] +
THF (ii) H3O
Mg (i) KCN
(4) Br [A] +
THF (ii) H3O
Sol. Answer (3)

O
||
Mg (i) CO2
Br THF
Mg — Br C — O — Mg — Br
+
O (ii) H3O
||
C — OH
Benzoic Acid
26. Which of the following conversion is known as Stefen's reduction?
1. LiAlH4
(1) —C N 2. H3O
+ —CH2—NH2
1. SnCl2, HCl
(2) —C N 2. H2O, Δ
—CHO
1. Na, C2H5OH
(3) —N C —NH—CH3
2. H2O
O O
Pd/BaSO4
(4) —C—Cl —C—H
H2(1 eq.)
Sol. Answer (2)
SnCl2/HCl H2O
C—
—N CH — NH CHO
This is known as Stephen’s reduction.

27. Alanine can be obtained from acetaldehyde by the following sequence of reactions
H
|
HOOC—C—NH2
|
CH3
Alanine
(1) Reaction with NaCN and NH4Cl followed by acidic hydrolysis

(2) Reaction with HCN, acidic hydrolysis and finally reaction with NH3
(3) Reaction with HCN, followed by NH3 and finally acidic hydrolysis
(4) Reaction with NaHSO3, followed by NH3 and finally acidic hydrolysis
Sol. Answer (1)
CH3 CH3 OH NH3 CH3 NH2 H3O+ CH3 NH2

C—
— O + HCN C C C
CH3 H CN H CN H COOH
Acetaldehyde Alanine
α O γ O
28. H – C H–C
β O–H δ O
(I) (II)
(C – O) bond length designated by α, β, γ and δ are in order

(1) α = γ < β = δ (2) α < β < γ = δ (3) α < γ = δ < β (4) α = β = γ = δ
Sol. Answer (3)
γ O α O
In, H C due to complete resonance, γ = δ, While in H C , partial resonance is present. So,
βO H
δ O
α < β.
29. Which of the following carboxylic acid is most reluctant to form ester with a given alcohol in the presence of
a catalytic amount of concentrated H2SO4?
CH3 O O O O
|
(1) CH3—C—C (2) —C (3) CH3—C (4) F3C—CH2—C
| OH OH OH OH
CH3
Sol. Answer (1)

CH 3 O
| ||
CH3 — C — C is most reluctant to form ester with alcohol due to presence of bulky group.
| OH
|
CH 3
30. Which of the following aromatic acids is most acidic?
COOH COOH COOH COOH

OH
(1) (2) (3) (4)
OH
OH
Sol. Answer (2)
31. Which one of the following orders of acid strength is correct?
(1) RCOOH > HC ≡ CH > HOH > ROH (2) RCOOH > ROH > HOH > HC ≡ CH
(3) RCOOH > HOH > ROH > HC ≡ CH (4) RCOOH > HOH > HC ≡ CH > ROH
Sol. Answer (3)
32. The correct order of acidic strength of the carboxylic acid is
(1) Formic acid < Benzoic acid < Acetic acid (2) Formic acid < Acetic acid < Benzoic acid
(3) Acetic acid < Formic acid < Benzoic acid (4) Acetic acid < Benzoic acid < Formic acid
Sol. Answer (4)
COOH
NH3
33. Δ A. Identify 'A'
COOH
(1) Benzene (2) Phthalimide (3) Benzamide (4) Acetaldehyde

Sol. Answer (2)
[Acid Derivatives (Preparation and reactions)]

34. Among the given compounds
O OH O
C O OH O OH
C C C
OH OH
HO OH
HO
OH HO OH
OH
(I) (II) (III) (IV)
The order of decreasing acidity is

(1) III > IV > I > II (2) I > IV > II > III (3) III > I > IV > II (4) III > I > II > IV
Sol. Answer (3)
Due to ortho effect, (III) and (I) are most acidic. If —OH group is present at p-position w.r.t. —COOH group,
then it becomes less acidic.
O
(i) DIBAL-H (1 eq)
35. CH 3CH 2 – C – O – C 2H 5 +
A+B
(ii) H3O
A and B are respectively

(1) CH3CH2CH2OH + C2H5OH (2) CH3CH2CHO + C2H5OH
(3) CH3CH2CHO + CH3CHO (4) CH3CH2CH2OH + CH3CHO
Sol. Answer (2)
O
CH3CH2 C OC2H5 ⎯ (i) Di isobutyl
⎯ ⎯⎯⎯ ⎯→ CH3 — CH2CHO + C2H5OH
alu min ium hydride
(ii) H3O +
36. Consider the following sequence of reactions.

O
(i) PhMgBr H2N—C—NH—NH2
C N + [A] [B]
(ii) H3O
Major product [B] of the given reaction would be

O
C—NH—NH2
O N
(1) C—NH—NH—C—NH2 (2) C
O
NH—C—NH2
N
(3) C (4) C—NH2
Sol. Answer (3)
(i) PhMgBr
C—
—N C
||
+
(ii) H3O O
||
O [A] H2N — C — NH — NH2
N — NHCO NH2
||
C
[B]
37. Consider the following sequence of reactions.
O
Pd/CaCO3 HO—(CH2)3—OH/H
C—Cl [A] [B]
H2 (1eq)
The products [A] and [B] are respectively
H H O
(1) C—
—O and —C
O
O O
(2) C—OH and C—O—CH2—CH2—CH2—OH
O H O
(3) C—OH and —C
O
O O
(4) C—H and —CH2—CH
O
Sol. Answer (1)
O O H
|| || H O — (CH2)3 — O H /H
+ | O
Pd/CaCO3
C — Cl C—H C
H2(1 eq.) O
38. Which reagent or sequence of reagents would best accomplish the following synthesis?
OEt O
?
O O
O
(1) (i) LiAlH4 (ii) H+, Δ (2) (i) NaBH4 (ii) dil. H2SO4 (iii) conc.H2SO4
(3) (i) Na / NH3 (ii) NaBH4 / H+, Δ (4) (i) Mg / Et2O (ii) LiAlH4 , (iii) H+, Δ
Sol. Answer (2)
O O ?O–
|| OEt || OEt || O
OEt
–
H (from EtO
O NaBH4) O– O O
||
39. 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)
40. The compound which is not reduced by LiAlH4 is
(1) Cyclohexanone (2) 2-Methyl-1-butanol (3) Ethyl benzoate (4) ω-caprolactam
Sol. Answer (2)
Alcohols can’t be reduced by LiAlH4. Only carbonyl compound, carboxylic acid and acid derivatives are
reduced by LiAlH4


Carbonyl Compounds 1

Uploaded by

Copyright:

Available Formats

Carbonyl Compounds 1

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Carbonyl Compounds 1

Uploaded by

Copyright:

Available Formats

Level-I

Very Short Answer Type Questions :

C N Ph—C N.MgBr COPh

4. Draw the structural formula of Hex-2-en-4-ynoic acid.

5. Give one chemical test to distinguish between acetaldehyde and benzaldehyde.

8. How can we obtain Propan-2-ol from ethanal?

9. What product is obtained when CH3COOH reacts with PCl5?

Sol. CH3 COOH + PCl5 ⎯⎯→ CH3 COCl + POCl3 + HCl .

Short Answer Type Questions :

CH3CH2CH2CHO, CH3(CH2)2CH2OH, C2H5—O—C2H5, CH3(CH2)3CH3

CH3(CH2)3CH3 < C2H5—O—C2H5 < CH3CH2CH2CHO < CH3(CH2)2CH2OH

12. Complete the following equations:

(ii) CH3 CONH2 + HNO2 ⎯⎯→

(iii) CH3 CHO + C6H5NHNH2 ⎯⎯→

(ii) CH3COOH + N2 + H2O

(iii) CH3CH == N —NH—C6H5 + H2O

13. Describe the following reactions:

(i) Cannizzaro reaction

(ii) Cross aldol reaction

15. Account for the following observations:

KMnO /H+ Ca(OH) dry

17. Arrange the following in order of increasing boiling points:

18. State reasons for the following:

22. Give reasons for the following:

hence these compounds do not give reactions of carbonyl group.

23. Complete the following series of reaction:

[O] SOCl NaOBr NH

25. Write the names of reagents and equations in the conversions of

It is Reimer Tiemann reaction.

26. Give chemical tests to distinguish between following pairs of compounds:

(ii) HOOC — CH2 — C = CH — COOH

[O] NaOH NaOH, Δ

[O] Ca(OH)2 CH3COO dry

29. Write chemical equations, for the following reactions:

CH3 CH3 CH3

30. Write balanced chemical equations for the following reactions:

(iii) 2CH3 COOH + Zn ⎯⎯→(CH3 COO)2 Zn + H2

Long Answer Type Questions :

Zn conc. HNO Br H /Pt HNO H O+

OH NO2 NO2 NH2

Ca(OH) dry distillation

CH3 COOK COOH

CH3  CH3  CH3

(ii) CH2 = CH — CH2Br ⎯⎯⎯→

(c) Identify compounds A and B

36. Which out of each pair is expected to be a stronger acid?

(d) CH2 — COOH or CH2 — COOH

Sol. (a) HCOOH

37. How will you convert

38. Give reasoning for the following:

CH3 CH3 CH3 CH3

Migrating power of p-tolyl is more than m-anisyl.

2. CH 3 CHO + LiAlH 4 ⎯⎯→ CH3 CH 2 OH

Nucleophile added in this reaction is

(1) AlH−4 (2) Li+ (3) H+ (4) H –

Sol. Answer (4)

(1) Ph – CH – CH – CHO (2) Ph – CH – CH2 – CHO

(3) Ph – CH – CH – CHO (4) Ph – CH – CH2 – CH2 – OH

Sol. Answer (2)

(1) Meso (2) Racemic (3) Inversion (4) All of these