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Vidyamandir Classes

Aldehydes & Ketones Questions Based on CBSE Pattern

Type - 1
1. Draw the structural formula of 1-phenyl propan-1-one molecule.

2. Write the structure of 3-oxopentanal.


3. Write IUPAC name of following compound.
(i) CH3COCH2COCH3 (ii)

4. What is Tollens reagent? Write one usefulness of this reagent.

5. Identify A, B and C in the following reaction


dilH SO
2 4 dil NaOH
CH CH
HgSO
A B C
4

6. Illustrate the following reactions giving a chemical equation for each.


(a) Cannizzaros reaction (b) Clemmenson reduction (c) Reimer-Tiemann reaction.

7. Complete the following reactions by giving the missing starting material, reagent or product as required.

(i) (ii)

(iii)

8. Arrange as directed.
(a) Acetaldehyde, Acetone, Ditertbutyl ketone, Methyl tert butyl ketone Reactivity towards HCN
(b) Benzaldehyde, p-tolulaldehyde, p-nitrobenzaldehyde, Acetophenone Reactivity towards nucleophilic
addition.

9. How are the following conversions carried out?


(i) Propanone to propene
(ii) Benzaldehyde from toluene
(iii) Benzoic acid to benzaldehyde
(iv) Benzene to Benzyl alcohol

10. How you will convert


(i) propane nitrile to 1-phenyl propanone
(ii) Bromobenzene to 1-phenyl ethanol.

11. Explain why.


(i) Acetone is highly soluble in water but benzophenone is not.

VMC 1 Aldehydes & Ketones/Chemistry


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(ii) Reaction of aldehyde/Ketone with NaHSO3 can be used for their separation and purification.
(iii) -hydrogen of aldehyde/ketone is acidic in nature.

12. How would you account for the following.


(i) Aldehydes are more reactive than ketones towards nucleophiles.
(ii) The aldehyde and ketones undergoes a number of addition reactions.

13. An organic compound (A) which has characteristic odour, on treatment with NaOH it forms two compounds (B)
and (C), Compound (B) has molecular formula C7 H8O which on oxidation gives back (A). The compound (C) is a
sodium salt of an acid. When (C) is heated with sodalime it yields an aromatic hydrocarbon (D). Deduce the
structures of A, B, C and D. Write the sequence of reactions involved.

14. How are the following conversions carried out?


(i) Ethanol to Acetone
(ii) Benzene to Acetophenone
(iii) Benzaldehyde to benzophenone

15. An organic compound 'A' contain 69.77% carbon, 11.63% hydrogen and rest oxygen. The molecular mass of the
compound is 86. It does not reduce Tollens reagent but forms an addition compound with sodium hydrogen
sulphite and gives positive iodoform test. On vigorous oxidation it gives ethanoic and propanoic acids. Derive the
possible structure of compound 'A'.

16. Write the mechanism of the addition of Grignard reagent to the carbonyl group of a compound forming an adduct
followed by hydrolysis.

SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

Type - 1
O
||
1. Ph CO CH 2 CH3 2. CH3 CH 2 C CH 2 CHO

3. (i) Pentane-2, 4-dione (ii) Cyclopentane carbaldehyde

4. Ammonical solution of silver nitrate is called Tollens reagent. It is used as an oxidizing agent/test for CHO
group.

B CH 3 C H CH 2 CHO
5. A CH3 CHO ; | ; C CH3CH CH CHO
OH

Conc. KOH
6. (a) 2HCHO
CH 3OH HCOOK
formal dehyde Methanol Potassium formate

Zn Hg
(b) C O
HCl
CH 2 H 2 O

(c)

VMC 2 Aldehydes & Ketones/Chemistry


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7. (i)

(ii) BH3 , H 2 O 2 / OH, PCC


(iii) A ArCOONa , B CHI3 , C ArCOOH

8. (a) Ditert butyl ketone < methyl tert-butyl ketone < Acetone < Acetaldehyde
(b) Acetophenone < p-tolulaldehyde < benzaldehyde < p-nitrobenzaldehyde.

OH
9. (i) |
LiAlH 4 conc. H 2SO4
CH3 COCH 3
CH 3 C H CH3
CH 3CH CH 2

(ii) Etard reaction,

(iii)

(iv)

H O
2 CH CH C O
CH3 CH 2 CN C6 H 5 MgBr
CH3 CH 2 C NMgBr 3 2
10. (i) | |
C6 H5 C6 H5

(ii)

11. (i) Acetone can make hydrogen bonds with water but benzophenone can not make hydrogen bonds due to
steric hindrance of two phenyl groups.
(ii) Because the bisulphite compounds formed can again be converted back into parent aldehyde or ketone by
reacting with acid or Alkali
(iii) Because the carbanion formed is resonance stabilised.

12. (i) Because two alkyl groups in ketones reduces the positive charge on carbon of the carbonyl group more
effectively than in aldehydes/or sterically, the presence of two relatively large substituents in ketones
hinders the approach of nucleophile to carbonyl carbon than in aldehydes having only one such substituent.
(ii) Because of the presence of the sp2 hybridised orbitals (or bond ) of carbonyl carbon.

13.

VMC 3 Aldehydes & Ketones/Chemistry


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Cu 3 (i) CH MgBr
14. (i) CH3 CH 2 OH
573K
CH3 CHO

CH3 COCH3
(ii) H 2O / H
(iii) Cu,573K

(ii)

(iii)

15. C 69.77/12 5.81 5.81/1.16 5


H 11.63/1 11.63 11.63/1.16 10
O 18.60/16 1.16 1.16/1.16 1
Empirical formula C5H10O
Empirical formula mass 60 + 10 + 16 = 86. Hence molecular formula C5H10O. It is a ketone as it appears from its
reactions as upon oxidation gives ethanoic acid and propanoic acids, hence the compound is CH3COCH2CH2CH3.

16.

Adduct

Type - 2
1. Arrange the following compounds in increasing order of their boiling points.
CH3CHO, CH3CH2OH, CH3OCH3, CH3CH2CH3

2. Arrange the following compounds in an increasing order of their reactivity of nuclephilic addition reactions,
Ethanal, propanal, propanone, butanone.

3. Write the mechanism of the given reaction:


4. How will you distinguish between acetone and acetaldehyde?

5. Write Gatterman-Koch reaction. 6. Write Stephen reaction.

7. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition reactions.
Benzaldehyde, p-tolualbenzaldehyde, p-nitrobenzaldehyde, acetophenone

8. Predict the products of the following reactions

(i) (ii)

O
||
H
(iii) RCH CH CHO NH 2 C NH NH 2 (iv)

VMC 4 Aldehydes & Ketones/Chemistry


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9. Write structural formulae and names of the four possible aldol condensation products from propanal and butanal. In
each case indicate which aldehyde served as electrophile and which as nucleophile, (self aldol condensation).
O
||
(i) CH3MgBr Na metal CH3 Br
10. Complete the following reaction sequence : CH3 C CH3 (ii) H O
(A)
Ether
(B) (C)
2

11. How will you convert ethanal into the following compounds?
(i) Butan-1, 3-diol (ii) But-2-enal (iii) But-2-enoic acid

12. An organic compound with molecular formula C9H10O forms 2, 4-DNP derivative reduces Tollens reagent and
undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1, 2-benzene dicarboxylic acid. Identify the
compound.

13. An organic compound A contains 69.77% carbon, 11.63 % hydrogen and rest oxygen. The molecular mass of the
compound is 86. It does not reduce Tollens reagent but forms an addition compound with sodium hydrogen
sulphite and give positive iodoform test. On vigorous oxidation, it gives ethanoic acid and propanoic acid. Derive
the structure of compound A.

14. Write reactions and conditions for the following conversions.


(i) Benzaldehyde to benzophenone (ii) Acetaldehyde to crotonaldehyde
(iii) Propanal to butanone

15. Write down functional isomers of a carbonyl compounds with molecular formula C3 H6O. Which isomer will react
faster with HCN and why? Explain the mechanism of the reaction also. Will the reaction lead to the completion
with the conversion of whole reactant into product at reaction conditions? What will be the effect on the
concentration of the product on adding H+ & why.
16. Give reasons:
(i) Hydrazones of aldehydes are prepared in light acidic medium and not in high acidic medium.
(ii) Tollens reagent is reduced by benzaldehyde while Fehlings or Benedicts solution are not reduced by it.

17. How will you bring about the following conversion in not more than two steps?
(i) Propanone to propene (ii) Ethanol to 3-hydroxy butanal
(iii) Benzene to m-nitroacetophenone (iv) Benzaldehyde to benzophenone
(v) Bromobenzene to 1-pehnyl ethanol (vi) Benzaldehyde to 3-phenyl propan-1-ol

18. Complete each synthesis by giving missing starting material, reagent or products.

2 H NCONHNH
2
(i) C6 H 5 CHO (ii)
Benzaldehyde

C6 H5 CHO
Dil. NaOH
(iii) (iv)

CH3 CH 2 CHO

(v) (vi)

(vii)

19. Predict the product formed when cyclohexane-carbaldehyde reacts with following reagents.
(i) PhMgBr and then H3O+ (ii) Tollens reagent

VMC 5 Aldehydes & Ketones/Chemistry


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(iii) Semicarbazide and weak acid (iv) Excess ethanol and acid
(v) Zinc amalgam and dilute hydrochloric acid.

20. (i) Give the chemical tests to distinguish between:


(a) propanol and propanone (b) benzaldehyde and acetophenone
(ii) Arrange the following compound in an increasing order of their property as indicated :
acetaldehyde, acetone, methyl tert-butyl ketone (reactivity towards HCN)

21. (i) Identify A , B and C is the following sequence of the reactions


2 5 (i) C H MgCl (i) Conc. H SO
HBr / Peroxide
2 4 B
CH3 CHO
(ii) H O
A C
2

(ii) Predict the structures of products formed when benzaldehyde is treated with
(a) conc. NaOH (b) HNO3/H2SO4 (at 273-383 K)

22. A ketone A (C4H8O) which undergoes a haloform reaction gives compound B on reduction. B on heating with
sulphuric acid gives a compound C which forms mono-ozonide D. D on hydrolysis with zinc dust gives only E.
Identify A, B, C, D and E. write the reactions involved.
Cl2 NaOH 6 5 6 6 C H COCl
3 D E . C H / AlCl
23. Identify A, B, C, D and E in the given sequence : A CHCl3 B C
excess
24. An organic compound A (C3H6O) is resistant to oxidation but forms compound B (C3H8O) on reduction. B reacts
with HBr to form the compound C. C with Mg forms Grignard reagent D which reacts with A to from a product on
hydrolysis gives E. Identify A to E.
25. Give simple chemical tests to distinguish between the following pairs of compounds.
(i) Propanal and propanone (ii) Acetophenone and benzophenone
(iii) Phenol and benzoic acid (iv) Benzoic acid and ethyl benzoate
(v) Pentan-2-one and pentan-3-one (vi) Benzaldehyde and acetophenone
(vii) Ethanal and propanal

SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

Type - 2
1. CH3CH2CH3 < CH3OCH3 < CH3CHO < CH3CH2OH
Stronger the attractive forces, higher is the boiling point. Hydrocarbon are nonpolar having weakest attractive
forces; ethers are polar and aldehydes have strong dipolar interaction. Alcohol have maximum intermolecular forces
due to H-bonding.
2, Butanone < propanone < propanal < ethanal (as size of alkyl group increases, the reactivity decreases as
electrophilic character of carbonyl carbon decreases).

3. : CN H 2 O
HCN OH

4. CH3 CHO 2[Ag(NH3 ) 2 ] 3OH CH 3COO 2H 2 O 2Ag 4NH 3


Acetaldehyde Tollen 's reagent Silver mirror

Tollen ' s reagent


CH3 COCH 3 No reaction
Acetone

VMC 6 Aldehydes & Ketones/Chemistry


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H3O
5. 6. RCN SnCl 2 HCl
RCH NH RCHO

7. Acetophenone < p-tolualdehyde < benzaldehyde < p-nitrobenzaldehyde


Benzaldehyde & derivatives are more reactive than aromatic ketones. Nitro group, being electron withdrawing
(R effect) increases reactivity.

8. (i) (ii)

O
||
(iii) R HC CH CH N NH C NH 2 (iv)

9. (i) Propanal forms a nucleophile (carbanian/enolate ion) and also acts as electrophilic substrate.
OH CH 3
| |
CH3 CH 2 CHO CH3 CH 2 CHO
CH3 CH 2 CH CH CHO
3 hydroxy 2 methyl pentanal

(ii) Butanal forms a nucleophile (carbanian/enolate ion) and also acts as electrophilic substrate.
OH CH 2 CH3
| |
OH
CH3 CH 2 CH 2 CHO CH3 CH 2 CH 2 CHO CH3CH 2 CH 2 C H C HCHO

(iii) Propanal acts as electrophilic substrate, whereas butanal forms enolate ion (as nucleophile).
OH CH 2 CH3
| |
CH3 CH 2 CHO CH3 CH 2 CH 2 CHO CH 3CH 2 CH CHCHO
Pr opanal Butanal 2 ethyl 3 hydroxy pentanal

(iv) Butanal acts as electrophilic substrate, whereas propanal forms enolate ion (as nucleophile).
OH CH 3
| |
CH3 CH 2 CH 2 CHO CH 3CH 2 CHO CH 3 CH 2 CH 2 CH CH CHO
Butanal Propanal 2 methyl 3 hydroxy hexanal

O OH ONa O CH3
|| | | |
(i) CH3 MgBr Na metal CH3 Br
10. CH 3 C CH3
(ii) H 2 O
CH 3 C CH3 (A)
Ether
CH 3 C CH3 CH 3 C CH3
| | SN 2 |
CH3 CH3 CH3
(A) (B) (C)
2 methy 2 methoxy propane

4 3 2 1
Dil. NaOH NaBH 4
11. (i) 2CH 3CHO
(Aldol condensation)
CH3 CHOH CH 2 CHO
(Reduction)
CH3 CHOH CH 2 CH 2 OH
aldol Butan 1,3 diol

Dil. NaOH Heat


(ii) 2CH 3CHO
(Aldol condensation)
CH3 CHOH CH 2 CHO
H O
CH 3 CH CH CHO
3 hydroxy butanol 2 But 2 anol

VMC 7 Aldehydes & Ketones/Chemistry


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(i) Dil. NaOH 3 2 [Ag(NH ) ] OH


(iii) 2CH 3CHO
(ii) H O,
CH 3CH CHCHO
CH3 CH CHCOOH Ag
2 Tollen 's reagent, H But 2 enoicacid

12. (i) As the given compound with molecular formula C9H10O forms a 2, 4-DNP derivative and reduces Tollens
reagent, it must be an aldehyde.
(ii) As it undergoes cannizzaro reaction, hence CHO group is directly attached to the benzene ring.
(iii) On vigorous oxidation, it gives 1, 2-benzene-dicarboxilic acid, therefore, it must be an ortho-substituted
benzaldehyde. And, the only o-substituted aromatic aldehyde which have C9H10O molecular formula is
o-ethylbenzaldehyde.
Reactions:

13. C = 69.77%, H = 11.63 %


O 100 69.77 11.63 18.6 %

Element Percentage (x) Molar mass (y) Moles (x/y) Simple ratio
C 69.77 12 5.81 5
H 11.63 1 11.63 10
O 18.6 16 1.16 1
Empirical formula of given compound = C5H10O
86
Empirical formula mass = 5 12 + 10 1 + 1 16 = 86 n 1 n = 1.
86
Molecular formula = (C5H10O)1 = C5H10O
Since, it does not give Tollens test but gives positive iodoform test, it is a methyl ketone i.e., have COCH3
group.
Since, on oxidation it gives ethanoic acid and propanoic acic, it is pentan-2-one.
[O]
CH3 C CH 2 CH 2 CH3 CH3 COOH CH3 CH 2 COOH
||
O
Pen tan 2 one (A)
(Observe smaller alkyl group takes carbonyl group on oxidation)

VMC 8 Aldehydes & Ketones/Chemistry


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14. (i) Benzaldehyde to benzophenone

(ii) Acetaldehyde to crotonaldehyde


Dil. NaOH heat
2CH3 C H CH3 CH CH 2 C H CH3 CH CH C H
|| | || ||
O OH O O
Acetaldehyde 3-hydroxybutanl Crotonaldehyde

(iii) Propanal to butanone


[O] PCl
5 CH CH COCl
3 2 CH CH COCH (CH ) Cd
CH3 CH 2 CHO CH 3CH 2 COOH 3 2 3 2 3
Propanal Butanone

15. (a) Functional isomers of C3H6O are: CH3 CH 2 CHO and CH3 COCH 3
Propanal Propanone

Propanal, CH3CH2CHO will react faster with HCN because there is less steric hindrance and favourable
electronic factors. (More electrophilic than CH3COCH3 due to greater to + I effect of CH3-group).

(b) CN H 2 O
The reaction mechanism is as follows: HCN OH

The reaction does not lead to completion because it is a reversible reaction. Equilibrium is established.

(c) If a strong acid is added to the reaction mixture, the reaction is inhibited because production of CN ions
is prevented.

16. (i) In highly acidic medium the NH2 group of hydrazine gets protonated.

NH 2 NH 2 H
NH 2 NH3
Hydrazine Pr otonated hydrazine


Due to electron-withdrawing effect of NH3 group, the lone pair of electrons on the NH2 group of
protonated hydrazine is not available for nucleophilic attack on the C = O and hence hydrazone formation
does not occur.
(iii) Due to + R effect of benzene ring, the electron density in the carbonyl group of benzaldehyde increase.
This is turn, increases the electron density in the CH bond of aldehyde group. As a result , the C H bond
becomes stronger and hence only oxidising agent like Tollens agents;
Ag (NH 3 )2 (E 0.8 V) can oxidise C H to C OH to form carboxylic acids but weaker
Ag / Ag

oxidising agents like Fehlings solution or Benedicts solution (E 0.18 V) fail to oxidise
Cu 2 / Cu
benzaldehyde to benzoic acid. In general all three reagents oxidise aliphatic aldehydes but only Tollens
reagent oxidizes aromatic aldehydes.
LiAlH 4 H 2 SO 4 (Conc.)
17. (i) Propanone to propene : CH3 COCH 3 CH 3 C HCH3 CH 3CH CH 2
2[H] Heat
(Propanone) | Propene
OH

VMC 9 Aldehydes & Ketones/Chemistry


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Oxidation Aldol
(ii) Ethanol to 3-hydroxybutnal: CH 3CH 2 OH
CrO in anhy. medium
CH 3CHO CH 3CH(OH)CH 2 CHO
3 Ethanal 3 hydroxy butanal

(iii) Benzene to m-nitroacetophenone :

Oxidation 2 C H COC H Ca(OH)


(iv) Benzaldehyde to benzophenone : C6 H5 CHO
KMnO
C6 H5 COOH
Heat 6 5 6 5
Benzaldehyde 4 Benzoic acid Benzopheone

(v) Bromobenzene to 1-phenylethanol :

(vi) Benzaldehyde to 3-phenyl propan-1-ol

O
||
18. (i) C6 H 5 CHO H 2 NNHCONH 2
C6 H5 CH N NH C NH 2 H 2 O
Benzaldehyde semicarbazone Benzaldehyde semicarbazone

(ii)

(iii)

CH 3
(iv) |
Dil. NaOH
C6 H 5 CHO CH3 CH 2 CHO
C6 H5 CH C CHO
2 methyl 3 phenyl prop 2 en l al

(v)

(vi)

VMC 10 Aldehydes & Ketones/Chemistry


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(viii)

19. (i)

(ii)

(iii)

(iv)

(v)

20. (a) Propanone, because of the presence of COCH 3 group when treated with NaOH and I2, gives yellow
crystals of iodoform.
CH3 COCH3 4NaOH 3I2
CHI3 CH3 COONa 3NaI 3H 2 O
Propanol (CH3CH2CH2OH) does not contain CH3 CH group, so it does not give iodoform test.
|
OH
(b) Benzaldehyde contains CHO group which reduces the Tollens reagent into silver mirror.
This test is not given by ketones (acetophenone).

(ii) Methyl t-butyl ketone < acetone < acetaldehyde


i.e., [CH3COC (CH3) 3] < (CH3COCH3) < (CH3CHO) (Reactivity towards HCN)

VMC 11 Aldehydes & Ketones/Chemistry


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(i) C2 H5 MgCl
OMgCl (ii) H O Conc.H 2SO4
2 CH CH C H
21.(i) CH3 CHO | 3 2 5
CH 3 CH C2 H5 |
OH
(A)

HBr / peroxide
CH3 CH CHCH3
H 3C CH CH CH3
But 2 ene | |
(B)
H Br
2 bromobutane
(C)

(ii) (a)

(b)

22. Since, A give haloform test, it must contains COCH3 group. Thus, its possible formula is C2H5COCH3. On
reduction its gives 2-butanol which on dehydration give 2-butene (C). Ozonolysis of 2-butene gives only
acetaldehyde. The equation involved are:
[H] 2 4 Conc. H SO
CH3 COCH 2 CH3
LiAlH 4
CH3 CH CH 2 CH3 CH3 CH CH CH 3
(A) | (C)
Butan-2-one
OH
(B)

(A) gives iodoform reaction as:


CH3 COCH 2 CH3 3I2 4NaOH
CHI3 C2 H5 COONa 3NaI 3H 2 O

23.

24. The possible structures of the molecular formula C3H6O are CH3COCH3 (acetone) and CH3CH2CHO (propanal), the
former one is resistant to the oxidation. Thus, A is ketone, i.e., acetone.
(i) A on reduction gives B, thus B is a 2 alcohol, i.e., 2-propanol.
4 LiAlH
CH3 COCH 3 CH3CH(OH)CH3
(A) 2 propanol (B)

(ii) 2-propanol reacts with HBr to give 2-bromopropane.


OH
|
HBr
CH3 CHCH3 CH 3CHCH3
2 propanol |
(B)
Br
2 bromopropane
(C)

VMC 12 Aldehydes & Ketones/Chemistry


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(iii) C (2-bromopropane) gives D (Grignard reagent) with Mg.


Ether
CH3 CHCH3 Mg CH3 CH CH 3
| |
Br MgBr
(D)

(iv) D reacts with acetone (A) to give on adduct which on hydrolysis gives a 3 alcohol (E)

25. (i) Propanal and propanone : Propanone responds to iodoform test whererase propanal (CH3CH2CHO) due to
absence of CH3CO group does not.
2 NaOH, I
CH3 COCH 3 3NaOI CHI3 CH3COONa 2NaOH
Sodium Heat (Yellow ppt. Sodium
hypoiodite iodoform) acetate

(ii) Acetophenone and benzophenone : Acetophenone gives positive iodoform test whereas benzophenone
(C6H5COC6H5) does not.

(iii) Phenol and benzoic acid: Benzoic acid reacts with sodium bicarbonate to produce effervescences of carbon
dioxide whereas phenol (C6H5OH) does not.

(iv) Benzoic acid and ethyl benzoate : Benzoic acid reacts with sodium bicarbonate to produce effervescences
of carbon dioxide whereas ethyl benzoate (C6H5COOC2H5) does not.

(v) Pentan-2-one and pentan-3-one : Pentan-2-one responds positively towards iodoform test whereas
pentan-3-one (C2H5COC2H5) does not.
2 NaOH, I
CH3 CO CH 2 CH 2 CH 3 3NaOI
Heat
CHI3 CH3 CH 2 CH 2 COONa 2NaOH
Pentan-2-one Yellow ppt.

(vi) Benzaldehyde and acetophenone Acetophenone responds towards iodoform test positively wherease
benzaldehyde (C6H5CHO) does not.

VMC 13 Aldehydes & Ketones/Chemistry


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(vii) Ethanal and propanal : Ethanal responds positively towards iodoform test whereas propanal
(CH3CH2CHO) does not.
NaOH, I 2
CH3 CHO 3NaOI
Heat
CHI3 HCOONa 2NaOH
Ethanal Iodoform
(Yellow ppt.)

VMC 14 Aldehydes & Ketones/Chemistry


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Carboxylic Acids Questions Based on CBSE Pattern

Type - 1
1. Write IUPAC names of the following compounds :
CH3 CH CH 2 COOH
(i) | (ii) CH3CH2CH2COOC2H5
OH
2. Give chemical tests to distinguish between following pair of compounds.
(i) Benzoic acid and ethyl benzoate (ii) Methyl acetate and ethyl acetate

3. Illustrate the following reactions giving a chemical equation for each.


(a) Hell Volhard Zelinsky reaction (b) Decarboxylation

4. Arrange the following compounds in an increasing order of their acidic strength.


Benzoic acid, 4-nitrobenzoic acid, 3, 4 dinitrobenzoic acid, 4-methoxy benzoic acid.

5. Arrange the following compounds in an increasing order of their acid strengths


CH3 2 CHCOOH, CH3CH 2 CH Br COOH, CH 3CH Br CH 2COOH
A
6. Identify 'A' in the given reaction : RCOCl H 2
RCHO
7. How are the following conversions carried out?
(a) Benzoic acid to benzaldehyde (b) Ethyl cyanide to Ethanoic acid
(c) Benzoic acid from ethyl benzene (d) Benzaldehyde from toluene

8. How you will convert Bromobenzene to Benzoic acid?

9. How will you convert Benzaldehyde into hydroxy phenyl acetic acid?
10. State reasons for the following.
(a) Ethanoic acid is a weaker acid than benzoic acid.
(b) Monochloro ethanoic acid has a higher pka value than dichloro ethanoic acid.

11. Account for the following


(i) Among CH3COCl and CH3CONH2, CH3COCl is more susceptible to nucleophilic attack.
(ii) Benzoic acid does not undergo Friedal craft reaction.
12. An organic compound 'A' has the molecular formula C8H16O2. It gets hydrolysed with dilute sulphuric acid and
gives a carboxylic acid 'B' and an alcohol 'C' Oxidation of 'C' with chromic acid also produced 'B', 'C' on
dehydration reaction gives but-1-ene. Write equations for the reactions.
13. An organic compound 'X' undergoes acid hydrolysis to form two compounds Y and Z, Y reacts with Na2CO3 to
form A. A is heated with soda lime to form B (CH4). Y on reduction with LiAlH4 forms Z. Identify X, Y, Z, A, B
and write the reactions involved.
14. An organic compound (A) on treatment with acetic acid in presence of conc. H2SO4 produces (B), (A) on mild
oxidation gives (C). (C) reacts with 50% KOH followed by acidification with dil HCl generates (A) and (D), (D)
reacts with PCl5 followed by reaction with ammonia gives (E), (E) on dehydration produces hydrocyanic acid.
Identify the compounds (A) to (E) and write chemical reactions involved.
15. An organic compound (A) on treatment with ethyl alcohol gives a carboxylic acid (B) and compound (C).
Hydrolysis of (C) under acidified conditions gives (B) and (D). Oxidation of (D) with KMnO4 also gives (B). (B) on
heating with Ca(OH)2 and dry distillation gives (E) having molecular formula C3H6O . (E) does not give Tollens
test and does not reduce Fehling solution but forms a 2, 4 dinitrophenyl hydrazone. Identify A, B, C, D and E.
VMC 15 Aldehydes & Ketones/Chemistry
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SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

Type - 1
1. (i) 3-hydroxy butanoic acid (ii) Ethyl butanoate

2. (i) Benzoic acid gives brisk effervescence of CO2 with NaHCO3 solution
C6 H 5 COOH NaHCO3
C 6 H5 COONa CO2 H 2 O
(ii) When ethyl acetate is boiled with excess of NaOH solution and further if this alkaline solution is heated
with I2, it will give yellow ppt of iodoform.

CH3 COOCH 2 CH3 NaOH
CH3 COONa CH 3CH 2 OH

CH3 CH 2 OH 4I2 6NaOH
CHI3 5NaI HCOONa 5H 2 O
Iodoform
Methyl acetate when boiled with excess of NaOH gives methyl alcohol which does not give iodoform test.

2 Br / Re d P
3. (a) CH3CH 2 COOH
CH3 C H COOH HBr
|
Br
NaOH CaO
(b) RCOONa R H Na 2 CO3
4. 4-methoxy benzoic acid < Benzoic acid < 4-nitro benzoic acid < 3, 4 dinitro benzoic acid.
5. CH3 2 CHCOOH CH3CH Br CH 2COOH CH3CH2 CH Br COOH 6. (A) is Pd-BaSO4

7. (a)

H O / H
2 2 Br
(b) C2 H 5 CN
(Partial)
CH3CH 2 CONH 2
KOH
CH3 CH 2 NH 2

2HNO O
CH3 CH 2 OH
KMnO
CH3 COOH
4

(c)

(d)

8.

H 2O / H
9. ArCH CN OH
ArCHO HCN ArCH OH COOH

10. (a) It is because benzoate ion is stabilized due to resonance whereas CH 3COO is destabilized due to (+ I)
inductive effect.

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(b) Because the stability of conjugate base of monochloro ethanoic acid is less due to presence of one electron
withdrawing Cl group than in dichloro ethanoic acid.
11. (i) It is because Cl group is electron withdrawing therefore, increases +ve charge on carbonyl carbon.
(ii) Because Lewis acid catalyst AlCl3 gets bonded to the carboxyl group.

12. Compound 'A' hydrolyses to give carboxylic acid and alcohol hence it must be ester. Since oxidation of 'C' gives 'B'
hence both must possess equal number of carbon.
O
|| B C
Dil
CH3 CH 2 CH 2 C O CH 2 CH 2 CH 2 CH3
H SO
CH 3 CH 2 CH 2 COOH CH 3 CH 2 CH 2 CH 2 OH
Butyl butanoate A 2 4 Butanoic acid Butanol

2 H O
C CH3CH 2 CH CH 2
But 1 ene

13.

14.

15.

(E) does not give Tollens reagent test and does not reduce fehlings solution as it is ketone, hence it forms
2, 4 dinitrophenyl hydrazone.

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Type - 2
1. Illustratrate the decarboxylation reaction by giving a suitable example.
2. Arrange the following in decreasing order of their acidic strength. ClCH2COOH, CH3CH2OH, CH3COOH,
FCH2COOH, C6H5COOH.
3. Compound A was prepared by oxidation of compound B with alkaline KMnO4. Compound A on reduction
with lithium aluminium hydride gets converted back to compound B. When compound A is heated with
compound B in the presence of H2SO4, it produces fruity smell of compound C. To which family the compounds
A, B and C belongs to?
4. Arrange the following in decreasing order of acidic strength : CH2ClCOOH, HCOOH, CF3COOH, CCl3COOH.
5. What happens when methylbenzene is oxidized with alkaline KMnO4?
6. Given two uses of carboxylic acid
7. Given halogenation reaction of benzoic aicd
8. Show how each of the following compounds can be converted to benzoic aicd?
(i) Ethyl benzene (ii) Acetophenone (iii) Bromobenzene (iv) Phenylethene (styrene)
9. Which acid of each pair shown here would you expect to be stronger?
(i) CH3COOH or CH2FCOOH (ii) CH2FCOOH or CH2ClCOOH
(iii) CH2FCH2CH2COOH or CH3CHFCH2COOH

(iv)

10. Although phenoxide ion has more number of resonating structures than carboxylate ion, carboxylic acid is a
stronger acid then phenol. Why?
11. Steps of conversion of benzoic aicd to m nitrobenzyl alcohol.
12. Give reasons :
(i) Dichloroethanoic acid has lower pKa value than monochloro ethanoic acid.
(ii) Benzoic acid is a stronger acid than ethanoic acid.
13. Arrange the following compounds in increasing order of their property as indicated.
(i) Acetaldehyde, acetone, di-tert-butyl ketone, methyl tert-butyl ketone (reactivity towards HCN)
(ii) CH3CH2CH(Br) COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH {acid strength}.
(iii) Benzoic acid, 4-nitrobenzoic acid, 3, 4-dinitro benzoic acid, 4-methoxy benzoic acid (acid strength).
14. How are the following conversion carried out?
(i) Ethylcyanide to ethanoic acid (ii) Butan-1-ol to butanoic acid
(iii) Benzoic acid to meta-bromo benzoic acid
15. An organic compound (A) (molecular formula (C8H16O2) was hydrolysed with dilute sulphuric acid to give a
carboxylic acid (B) and alcohol (C). Oxidation of (C) with chromic acid produced (B). (C) on dehydration gives
but-1-ene. Write equations for the reactions involved.
16. Account for the following :
(i) Chloroacetic acid has lower pKa value than acetic acid.
(ii) Electrophilic substitution in benzoic acid takes place at meta-position.
(iii) Carboxylic acid have higher boiling points than alcohols of comparable molecular masses.

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17. An organic compound A (C7 H6Cl2) on treatment with NaOH solution gives another compound B(C7H6O). B on
oxidation gives an acid (C7H5O2) which upon treatment with a mixture of conc. HNO3 and H2SO4 gives a
compound D(C7H5NO4). B on treatment with Conc. NaOH gives compound E(C7H8O) and C6H5COONa. Deduce
the structures of A, B, C, D and E.
18. Identify A to E in the following sequence.
NH
3 A
2 Br / KOH HONO
2 D [O]
4 E Ca(OH) LiAlH
CH3CH 2 COOH B
C
CH3 COOH
Dil. HCl

19. Compound A (C6H12O 2) on reduction with LiAIH4 yields two compound B and C. The compound B on oxidation
gave D which on treatment with aqueous alkali and subsequent heating, furnished E. the latter on catalytic
hydrogenation gave C. The compound D on further oxidation gave CH3COOH. Deduce the structures of A, B, C, D
and E.
20. How will you prepare the following compounds from benzene ? You may use any inorganic reagent and any
organic reagent having not more than one carbon atom.
(i) Methyl benzoate (ii) m-nitrobenzoic acid (iii) p-nitrobenzoic acid
(iv) Pheynl acetic acid (v) p-nitrobenzaldehuyde
21. (i) Give chemical tests to distinguish between the following :
(a) Benzoic acid and ethyl benzoate (b) Benzophenone and acetophenone

(ii) Complete the following reactions :

(iii) Identify A, B and C in the sequence :

22. Some commercially important carboxylic acids are methanoic acid (formic acid), ethanoic acid (acetic acid) and
benzoic acid. These are used in various industries.
(i) How is methanoic acid manufactured? (ii) Give important uses of methanoic acid?
(iii) How is methanol converted into ethanoic aicd?
(iv) What are the important uses of ethanoic acid?
(v) Which salt of benzoic acid is used as food preservative?
23. Complete the following equations giving the names of the reactants and the products.
Anhyd.AlCl
(i) (CH 3COO)2 Ca (ii) C6 H 6
3 C H COCH
6 5 3
LiAIH
4
(iii) (CH 3 )2 CO

24. What is -hydrogen in a carbonyl compound? Write similarities and differences on the reactivity of the
compounds CH3CHO and C6H5CHO with the reagents.
(i) NaOH (ii) Tollens reagent
25. (i) Convert :
(a) Benzoic acid to benzaldehyde (b) Propanone to propane

26. An organic compound (P) having molecular formula C9H10O form an orange precipitate (Q) with 2, 4-DNP reagent.
Compound (P) gives a yellow precipitate (R) when heated in the presence of iodine and NaOH along with a
colourless compound(S). (P) does not reduce Tollens reagent or Fehlings solution nor it decolourises bromine
water. On drastic oxidation of (P) with chromic acid, a carboxylic acid (T) having molecular formula C7H6O 2 is
obtained. Deduced the structures of the compounds (P) to (T).

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SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

Type - 2
1. Decarboxylation refers to the reaction when the sodium salts of carboxylic acids are heated with sodalime, where
the carboxylic acid loses CO2 to form hydrocarbons.
Sodalime
e. g., CH3 COONa CH 4 Na 2 CO3
Sodium acetate
A mixture of Na OH and
CaO in 3 :1 ratio Methane

2. FCH2COOH > ClCH2COOH > C6H5CH2COOH > CH3COOH > CH3CH2OH


C6H5 group has weak I effect though much weaker than those of F and Cl therefore, C6H5CH2COOH is a much
stronger acid than CH3COOH but weaker than FCH2COOH and ClCH2COOH.
4 Alkaline KMnO
3. [B] [A]
[O]
Alcohol Carboxylic acid
LiAlH
4 Alcohol
Carboxylic acid or [A] [B] [C] H 2O
(A) (B) Acid Alcohol Ester
(Fruity smell)
4. HCOOH < CH2ClCOOH < CCl3COOH < CF3COOH

5. Benzoic acid is obtained

6. (i) As a coagulating agent in latex rubber industry


(ii) Ethanoic acid is used as vinegar in food industry

7.

8. (i)

(ii)

(iii)

(iv)

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9. (i) CH2FCOOH is a stronger acid (ii) CH2FCOOH is a stronger acid

(iii) CH3CHFCH2COOH is a stronger acid (iv)

10. (i) Phenoxide ion has non-equivalent resonance structures in which the negative charge is at the less
electronegative carbon atom
(ii) The negative charge is delocalized over two electronegative
oxygen atoms in carboxylate ion whereas in phenoxide ion the
negative charge is less effectively delocalized over one
oxygen atom and carbon atoms.

11. Benzoic acid to m-nitrobenzyl alcohol :

12. (i) Monochloroethanoic acid is a weaker acid than dichloroethanoic acid. That, why dichloroethanoic acid has
lower pKa value than monochloro ethanoic acid.
(ii) Due to positive inductive effect of methyl group, it destabilizes the acetate anion by intensifying the
negative charge. Therefore, benzoic acid is a stronger acid than ethanoic acid.
13. (i) The reactivity of a compound depends on the steric hindrance due to the groups present around the
carbonyl group. Greater the steric hindrance, less will be the reactivity of the compound. Reactivity
towards HCN is in following order .
Di-tertiary butyl ketone < methyl tertiary butyl ketone < acetone < acetaldehyde.
(ii) Alkyl group with +I effect decreases the acidic strength whereas with I effect increases the acidic
strength. Also, I effect decreases with distance.
Increasing order of acidic strength is (CH3)2CHCOOH < CH3CH2CH2COOH < CH3CH(Br)CH2COOH
< CH3CH2CH(Br)COOH
(iii) Electron donating group (OCH3) decreases the acidic strength whereas electron withdrawing group (NO2)
increases the same.
Increasing order of acidic strength is 4-methoxy benzoic acid < benzoic acid < 4 nitrobenzoic acid
< 3, 4-dinitrobenzoic acid.

2 H O / H NH
3 C H CONH C H NH KOH
14. (i) C2 H5CN
C2 H5COOH 2 5 2 2 5 2
Br 2
HNO 2 Alk.KMnO
4 CH COOH

C2 H5 OH 3
Ethanoic acid
K 2Cr2O7 / H 2SO4
(ii) CH3 CH 2 CH 2 CH 2 OH
CH3CH 2 CH 2 COOH
Butanol Butanoic acid

(iii)

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15. (i) Since, [A], produces carboxylic acid [B] and alcohol [C] on hydrolysis, compound [A] is an ester.
(ii) Alcohol [C] on oxidation produces acid [B]. It means both [B] and [C] have same number of carbon atoms,
i.e., four each.
(iii) The equations for all the above reactions are
O O
|| ||
Dil. H 2SO4
CH3 CH 2 CH 2 C OCH 2 CH 2 CH 2 CH3 CH3CH 2CH 2 C OH CH3CH 2CH 2CH 2 OH
Hydrolysis
Butyl butanoate [A] Butanoic acid [B] Butan-1-ol [C]

[O]
CH3CH 2 CH 2 CH 2 OH
CH3CH 2 CH 2 COOH
Chromic acid
Bu tan 1 ol (oxidation) Butanoic acid
[C] [B]
Conc. H SO
2 4
CH3CH 2 CH CH 2
Dehydration ( H 2O)
But 1 ene

16. (i) In chloroacetic acid, the chlorine shows I effect and creates less electron density on the oxygen of
carboxylic acid. Thus the release of proton becomes easier. In case of acetic acid, the state of effect is just
opposite i.e., CH3 group increases the electron density on the oxygen of carboxylic acid and thus, release
of proton becomes difficult. Thus, the former is more acidic (more is the acidity, lesser is the pKa value).
So, pKa value of chloroacetic acid is less than that of acetic acid.
(ii) Due to the resonance in benzoic acid, there is high electron density at meta-position (because o- and
p-position become deficient). So, electrophilic substitution takes place at meta-position.

(iii) In carboxylic acids the hydrogen bonding is much stronger than that in alcohols so they have high boiling
points.
17. Since, Compound A on treatment with NaOH gives C7 H6O, i.e. only one O atom is introduced, both the Cl atoms
must be present on the same carbon atom.
The molecular formula C7H6O suggest the structure of B is C6H5CHO. Thu, A must be C6H5CHCl2. The relevant
equations are as

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NH
3 CH CH CONH 2 Br / KOH
18. CH3 CH 2 COOH 3 2 2
CH3 CH 2 NH 2

Ethanamide Ethanamine
(A) (B)
HNO
2 CH CH OH [O] Ca(OH)
2 CH COCH 4 CH C HCH LiAlH
3 2 CH3 COOH 3 3 3 3
Dil.HCl
Ethnol (C) Acetic acid Acetone (D) |
OH
Pr opan 2ol
(E)
19. D gave CH3 COOH on oxidation, so it must be CH3CHO and it is obtained by the oxidation of B so, B is
CH3CH2OH.
Further, D being an aldehyde having H undergoes aldol condensation. The unsaturated aldehyde formed
gives (C) on hydrogenation. Thus compound (A) is CH3CO(CH2)3CH2OH and the reactions involved are as follows.
LiAlH
4 CH CH CH CH OH CH CH OH
(i) CH3 C CH 2 CH 2 CH 2 CH 2 OH 3 2 2 2 3 2
|| (A) (C) (B)
O
[O] [O]
(ii) CH3 CH 2 OH
CH3 CHO
CH3 COOH
(B) (D)
NaOH 2 H
CH3CHO CH 3 C HCH 2CHO CH 3CH CHCHO CH 3CH 2 CH 2 CH 2OH
(iii) Aldol Pd / C
(D) condensation | (C)
OH
20. (i) Benzene to Methyl benzoate :

(ii) Benzene to m-nitrobenzoic acid :

(iii) Benzene to p-nitrobenzoic acid :

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(iv) Benzene to phenyl acetic acid :

(v) Benzene to p-nitrobenzaldehyde

21. (i) (a) Benzoic acid being an acid produces brisk effervescence with NaHCO3 solution, while ethyl
benzoate does not.
C6 H5 COCH3 3I2 NaHCO3
C6 H5 COONa H 2 O CO 2
I
2 No reaction
C6 H5COC6 H5
NaOH
(b) Acetophenone with I2/NaOH gives yellow precipitate of iodoform but benzophenone does not
C6 H5 COCH3 3I 2 NaHCO3
C6 H5 COONa H 2 O CO2
I
2 No reaction
C6 H5COC6 H5 NaOH

(ii)

(iii)

O
||
473K H 2O / H
22. (i) CO NaOH H C ONa HCOOH
1atm
(ii) It is used in rubber, leather and electroplating industry
O
||
Rh
(iii) CH3OH CO CH3 C OH
Methnaol |
Ethanoic acid

(iv) It is used in the manufacture of rayon, plastic, rubber and in silk industries. It is used as a solvent, vinegar
is used in cooking and pickles.
(v) Sodium benzoate.

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AlCl
3
23. (i) CH3COCH 3 CaCO3 (ii)
(CH3COO) 2 Ca C6 H 6 CH3COCl C6 H 5COCH 3
anhydrous
LiAlH
4 (CH ) CHOH
(iii) (CH 3 )2 CO 3 2

24. H is the H-atom attached to C atom in aldehydes and ketones.


C H 2 CHO C H 2 COCH 3 ; Ph C H CHO
eg : | | |
HH HH H H
NaOH
* will given aldol formation, as OH (NaOH) will act as base.
CH3CHO
OH
|
OH
2CH3 CHO CH3 C H CH 2 CHO (aldol)
NaOH
* will given Cannizzaro reaction, as OH (NaOH) will act as nucleophile as there is
C6 H 5CHO
no H in C6 H5 CHO .
NaOH
2C6 H 5CHO C6 H5 CH 2 OH C 6 H5 COONa
* Both CH3CHO and C6 H5CHO will reduce Tollens reagent to give respective acids and white shinning
silver (Ag) precipitate.

25. (a)

Zn Hg
(b) CH3 COCH3
CH3CH 2 CH3
HCl
Propanone Propane

26.

(P) does not given Tollens or Fehling solution test it is ketone.

O O
|| ||
P must have CH3 C group as it gives Iodoform test. Hence P must be : C6 H5 CH 2 C CH3 (C9 H10 O)
(O)
C6 H5 CH 2 COCH3 C6 H 5COOH
H 2CrO 4

(S) : C6 H5 CH 2 COONa (R) CHI3 (iodoform)

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Vidyamandir Classes

Type - 3
Aldehydes, Ketones & Carboxylic Acids
1. Arrange the following in the increasing order of b.p.
CH2CH2 CH2CHO, CH3CH2CH2CH2OH ; C2H5 O C2H5, CH3CH2CH2CH2 CH3
General order of b.p. : (having nearly the same mol mass)
ROH > RCHO > RCOR > ROR > RO R > R H
alcohols aldehydes ethers hydrocarbons
Alcohols are high boiling due to strong intermolecular forces via H-bonding.
Aldehydes/Ketones are more polar than ethers and hence their dipole-dipole interactions are stronger.
Alkanes have only weak van der Waal forces.
CH3CH2CH2CH2OH > CH3CH2CH2CHO > C2H5OC2H5 > CH3CH2CH2CH2CH3

2. Similar to above : Arrange the given in increasing boiling points


CH3CHO, CH3 CH2OH, CH3 COCH3, CH3 CH2CH3, CH3COOH
CH3CH2OH > CH3COOH > CH3CHO > CH3COCH3 > CH3 CH2CH3 Explanation is given above.

3. Which of the two ; Benzaldehyde or propanal is more reactive towards nucleophilic addition reaction.
The carbon of benzaldehyde is less electrophilic than that of propanal (CH3CH2CHO). The polarity of

group in benzaldehyde is reduced more than in propanal, due to resonance:


The resonance (+R) effect is stronger than +I effect in propanal.

4. Arrange the following in increasing order of reactivity in nucleophilic addition reactions.


(i) Ethanal, Propanal, Propanone, Butanone
(ii) Benzaldehyde, p-Tolualdehyde, p-nitrobenzaldehyde acetophenone
O O
|| ||
(i) CH3CHO CH3CH 2 CHO CH 3 C CH3 CH 3 C C2 H 5
Ethanal Propanal Propanone Butanone
Reactivity depends upon polarization of group. Alkyl groups decreases polarity and hence
electrophilic character in aldehydes.
In ketones, steric factors due to two alkyl groups also decreases reactivity due to hindrance to the poor
stability of Nu- addition product (steric crowding).
(ii) p-nitrobenzaldehyde > benzaldehyde > p-Tolualdehyde > acetophenone

Electron withdrawing groups at o and p increases electrophilic character via Resonance. CH3 via
hyperconjugation decreases electrophilic character. Acetophenone is least reactive being ketone, due to +R
effect of ring and +I effect of alkyl group.

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5. Which acid of each pair is stronger of the two. Why ?


(a) CH3CO2 H and CH2FCO2H : FCH2COOH is stronger as F is a strong electron withdrawing group
pulling away electron cloud away from oxygen makes FCH2COOH a stronger one ; whereas CH3, an
electron donating group makes acetic acid weaker.
(b) CH2FCO2H and CH2ClCO2H : FCH2CO2H is stronger than ClCH2COOH as F as more
electronegative than Cl- atom making it strongly electron withdrawing and making acid much stronger.
(c) CH2FCH2CH2CO2H and CH3CHFCH2CO2H
CH3 C H CH 2 CO 2 H is stronger than C H 2 CH 2CH 2CO 2 H
| |
F F
(I) (II)
Since position of F in first (I) compound is nearer to COOH and that affects acidity to a greater extent.

(d)

CF3 group at p-position in is electron withdrawing via inductive effect and reverse hyperconjugation.

whereas CH3 exerts electron pushing/donating effect (via hyperconjugation) making acid weaker.

6. There are two NH2 groups in semi-carbazide, however only one is involved in the formation of semi-
carbazones.

Observe that p over N-atom is involved in resonance, hence this NH2 does not get involved in Nu-addition to
aldehyde and ketones.

The p over other amino group is available for Nu addition.

7. Cyclohexanone forms cyanohydrin in good yield


but 2, 4, 6-trimethylcyclohexanone does not.

Due to steric hindrance of two methyl groups near group, it becomes difficult for nucleophile to add and
thus 2, 4, 6-trimethyl cyclohexanone does not give good yield of cyanohydrin, as compared to cyclohexanone.

8. During the preparation of esters from a carboxylic acid and an alcohol in the presence of an acid catalyst, the
water or the ester should be removed as soon as it is formed.
O O
|| H
||
R C OH R OH R C OR H 2 O
The formation of esters is a reversible reaction. By removing ester or H2O makes sure that reaction goes forward
and ester is formed. So to avoid backward reaction i.e. hydrolysis of esters such an action is required.

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9. Although phenoxide ion has more number of resonating structures than carboxylate ion, carboxylic acid is a
stronger acid than phenol. Why ?
In phenoxide ion, there is negative charge over carbon atom of benzene ring in three resonating structure which is
not suitable for its low electronegativity. Whereas in carboxylate ion, negative charges rests on oxygen (a strongly
electronegative atom), which results in greater stability of ve charge in carboxylate ion. So carboxylate ion is more
strongly resonance stabilized than phenoxide ion ; hence carboxylic acids are more acidic than phenol.
Also equivalent structures in carboxylate can impart greater stability.

10. Acid anhydrides have high b.p. than corresponding acids.


Acid anhydrides are bigger size molecules than corresponding acids therefore have more surface area and more van
der Waals force of attraction. Hence they have high boiling points.

11. Arrange the following compounds in increasing order of their property as indicated:
(i) CH 3 C H 2CHCOOH, CH 3 CH 2CH 2COOH (acid strength).
|
Br
(ii) Benzoic acid, 4-nitrobenzoic acid, 3, 4-dinitro benzoic acid, 4-methoxy benzoic acid (acid strength).

(i) Alkyl group with +I effect decreases the acidic stength whereas I effect increases the acidic strength.
The strength of I effect decreases with distance of the electron withdrawing group from O H bond.

Increasing order of acidic strength is


(CH3)2CHCOOH < CH3CH2CH2COOH < CH3CH(Br)CH2COOH < CH3CH2CH(Br)COOH
[Br is an electron withdrawing group exerting I effect]
(ii) Electron donating group (OCH3) via +R effect in benzoic acid decreases the acidic strength where as
electron withdrawing group (NO2) via M and I effect increases the acidic strength.

Increasing order of acidic strength is:


4-methoxy benzoic acid < benzoic acid < 4-nitrobenzoic acid < 3, 4-dinitrobenzoic acid.
[Two nitro group increases acidity by a large factor]

12. Arrange the following in decreasing order of their acidic strength and give reason for your answer.
CH3CH2 OH ; CH3COOH ; ClCH2COOH ; FCH2COOH ; C6H5CH2COOH.
FCH2COOH > ClCH2COOH > C6H5CH2COOH > CH3COOH > CH3CH2OH
CH3CH2OH is very weak acid as ethyl group is a electron withdrawing group and its conjugate base, ethoxide ion is
very strong. CH3COOH is weakest of given acids as CH3 is an electron releasing group decreasing acidic strength.
C6H5CH2COOH is more acidic than CH3COOH, as C6H5CH2 is less electron releasing than CH3 group. Florine is
more strongly electronegative than chlorine making FCH2COOH more acidic than ClCH2COOH.

13. Arrange the following in decreasing order of their acidic strength. Give explanation for the arrangement.
C6H5COOH, FCH2COOH, NO2CH2COOH
NO2CH2COOH > FCH2COOH > C6H5COOH
Benzoic acid is stronger than acetic acid but when strong electron withdrawing groups such as NO2 and F are
present in acetic acid, the acidity of substituted acetic acid increases. Note that NO2 is more strongly electron
withdrawing than F making NO2CH2COOH more acidic than FCH2COOH.

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Amines Questions Based on CBSE Pattern

Type - 1
1. Give the IUPAC name of H 2 N CH 2 CH 2 CH CH 2

2. Give the chemical tests to distinguish between the following pairs of compounds
(a) Ethyl amine and Aniline (b) Methyl amine and Dimethyl amine

3. Illustrate the following reactions giving a chemical equation for each.


(a) Hoffmanns bromamide degradation (b) Gatterman reaction
(c) Gabriel phthalimide synthesis (d) Coupling Reaction

4. Complete the following reaction conditions.


O
||
LiAlH 4
(i) R C NH 2 H O
(ii) C6 H5 N 2 Cl H3PO2 H 2O

2

(iii) C6 H 5 NH 2 Br2 aq.


(iv) C6 H 5 N 2 Cl CH3COCl

(v) C2 H5 NH 2 HNO 2

5. How are the following conversions carried out?


(i) Benzene diazonium chloride to nitrobenzene (ii) Ethyl amide to methyl amine
(iii) Aniline to benzonitrile
6. How you will convert Aniline to p-nitro aniline?
7. Amine are basic substances while amides are neutral explain.
8. Account for the following observations
(i) pKb for anilines is more than that for methyl amine
(ii) Methyl amine solution in water reacts with FeCl3 to give a precipitate of ferric hydroxide.

9. Account for the following.


(i) Although amino group is o, p-directing in aromatic eletrophilic substitution but aniline on nitration gives a
substantial amount of m-nitroaniline.
(ii) Aniline does not undergo Friedal craft reaction.
(iii) Aromatic amines cant be prepared by Gabriel phthalimide synthesis.

10. In the following cases rearrange the compounds as directed


(a) In an increasing order of basic strength : C6H5 NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2
(b) In an increasing order of pkb value : C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
(c) In an increasing order of basic strength in aqueous solution : NH3, CH3NH2, (CH3)2NH, (CH3)3N
(d) In an increasing order of basic strength : Aniline, p-nitroaniline, p-toluidine.
11. An aromatic compound (A) on treatment with ammonia followed by heating forms compound (B), which on
heating with Br2 and KOH forms a compound (C) having molecular formula C6H7N. Give the structure of A, B and
C and write the reactions involved.
12. Compound (A) reacts with Sn and HCl and gives (B), (B) on reaction with Br2 water gives (C), (C) on diazatisation
gives (D), (D) on reaction with H3PO2 in aqueous solution gives 1, 3, 5 trinitrobenzene. (B) can also be obtained
form (E) by reaction with Br2 and KOH. Identify (A) to (E) and write chemical reactions.
VMC 29 Aldehydes & Ketones/Chemistry
Vidyamandir Classes

SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

Type - 1
1. But-3-en-1-amine

2. (a) Aniline forms an azo dye with benzene diazonium chloride through coupling reaction whereas ethyl amine
does not form an azo dye.
(b) Methyl amine undergoes carbyl amine reaction while dimethyl amine does not.
3. (a) RCONH 2 Br2 4 NaOH
RNH 2 Na 2 CO3 2NaBr H 2 O

(b)

(c)

(d)

4. (i) RCH2NH2 (ii) C6H6 + H3PO3 + HCl + N2 (iii)

(iv) (v) C2H5OH + N2 + H2O

5. (i)

(ii) CH3 CONH 2 Br2 4KOH


CH3 NH 2 K 2 CO3 2KBr 2H 2 O

(iii)

6.

7. In alkyl amines, due to + I effect of alkyl group, electron density on nitrogen increases, whereas in acid amides the
lone pair of electrons on the nitrogen atom is delocalised over the keto group, as a result, electron density on the
N-atom decreases.
8. (i) electron pair of nitrogen in aniline is involved in resonance.
(ii) Methyl amine in water gives OH ions which reacts with FeCl3 to give ppt. of Fe(OH) 3
CH 3 NH 3 OH
CH3 NH 2 H 2 O CH3 NH3 OH

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Fe3 3OH
Fe(OH)3
9. (i) During nitration, aniline converts into anilinium ion which is electron withdrawing and m-directing.
(ii) Because aniline forms salt with Lewis acid catalyst, AlCl3 used in Friedal craft reaction.
(iii) Because aryl halide do not undergo nucleophillic substitution with phthalimide.

10. (a) C6H5NH2 < C6H5N (CH3)2 < CH3NH2 < (C2H5)2 NH
(b) (C2H5)2NH < C2H5NH2 < C6H5NHCH3 < C6H5NH2
(c) NH3 < (CH3)3N < CH3NH2 < (CH3)2 NH
(d) p-nitro aniline < Aniline < p-toluidine.

11.

12.

Type - 2
1. Write the IUPAC names of the following compounds and classify them into primary, secondary and tertiary amines.
(i) C6 H5 NHCH3 (ii) CH3CH 2 2 N CH3
2. How will you convert Cl CH 2 4 Cl into hexane-1, 6-diamine ?

3. What is the best reagent to convert nitrile to primary amine ?


4. How will you convert ethanoic acid to methanamine.
5. Given the name of any two naturally occurring amines.
6. Write the IUPAC names of the following compounds.

(i) (ii)

(iii) CH3 CH 2 4 C H CN (iv) CH3 C H CH 2 C H CH3


| | |
CH3 NO2 NO2
7. Why cannot aromatic primary amines be prepared using Gabriel phthalimide synthesis ?
8. Write IUPAC name of CH3CH Br CH 2CONHCH3 .

9. Write chemical reaction aniline with benzoyl-chloride and write the name of the product obtained.

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10. Complete the following acid-base reactions and name the products
(i) CH3 CH 2 CH 2 NH 2 HCl
(ii) C2 H5 3 N HCl

11. Convert 3-methyl aniline into 3-nitro toluene


12. Arrange the following
(i) In increasing order of boiling point C2 H5 OH, CH3 2 NH, C2 H5 NH 2

(ii) In increasing order of solubility in water C6 H5 NH 2 , C2 H 5 2 NH, C2 H5 NH 2

13. How will convert


(i) Ethanamine into methanamine (ii) Ethanoic acid into propanoic acid
(iii) Methanamine into ethanamine
14. Accomplish the following conversions
(i) Nitrobenzene to benzoic acid (ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline
15. Arrange the following
(i) In decreasing order of basic strength in gas phase : C2 H5 NH 2 , C2 H5 2 NH, C2 H5 3 N and NH3

(ii) In increasing order of boiling point : C2 H5 OH, CH3 2 NH, C2 H5 NH 2

(iii) Increasing order of solubility in water : C6 H5 NH 2 , C2 H 5 2 NH, C2 H5 NH 2

16. (i) Rearrange the following in an increasing order of the basic strength :
C6 H5 NH, C6 H5 N CH3 2 , C 2 H 5 2 NH, CH3 NH 2
(ii) Arrange the following compounds in increasing order of basic strength in their aqueous solution :
NH3 , CH3 NH 2 , CH 3 2 NH, CH3 3 N

17. Amino compounds and their derivative are also used in making drugs. Analgesics are the chemical substances
which give relief from pain. Give answer of the following questions
(i) Novalgin, most widely used as analgesic belongs to which type of amine ?
(ii) Why should we avoid analgesic in case of minor head ache or fever below 100 F ?
(iii) Why should these not taken empty stomach ?
(iv) Give one more example of analgesic other than novalgin.
18. Account for the following
(i) Although amino group is o-and p-directing in aromatic electrophilic substitution reactions, aniline on
nitration gives a substantial amount of m-nitroaniline.
(ii) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(iii) Gabriel phthalimide synthesis is preferred for sythesising primary amines.
19. An aromatic compound A on treatment with aqueous ammonia and heating forms compound B which on heating
with Br 2 and KOH forms a compound C of molecular formula C6 H 7 N . Write the structures and IUPAC names
of compounds A, B and C.
20. Give one chemical test distinguish between the following pairs of compounds.
(i) Methylamine and dimethylamine (ii) Secondary and tertiary amines

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(iii) Ethylamine and aniline

SOLUTIONS - QUESTIONS BASED ON CBSE PATTERN

Type - 2
1. (i) N-methylbenzenamine (2) (ii) N-ethyl-N-methylethanamine (3)

2KCN alcohol (i) LiAlH


2. Cl CH 2 4 Cl
NC CH 2 4 CN 2 4 NH 2
4 H N CH
2
2KCN, (ii) H3O
Hexane-1, 6-dinitrile Hexane-1, 6-diamine
Ether

3. The best reagent to reduce nitriles is sodium/alcohol or LiAlH 4 and the product of this reduction is primary amines.

2 SOCl NH excess
3
4. Ethanoic acid to methanamine : CH3 COOH CH3COCl
CH3 CONH 2
Ethanoic acid Ethanoyl chloride Ethanamide
Br 2 / KOH

CH3 NH 2
Hoffmann bromaide reaction Methanamine
5. Alkaloids and proteins
6. (i) 4-nitromethoxybenzene (ii) N-ethyl-N-methylpropanamine
(iii) 2-methylheptanenitrile (iv) 2, 4-dinitropentane

7. The main step in the Gabriel phthalimide synthesis is a SN 2 reaction in which the nucleophile, phthalimide anion
displaces the halide ion from alkyl halides to form N-alkylphthalimide which by subsequent acid to alkaline
hydrolysis gives the corresponding aliphatic primary amine.
However in aryl halide, nucleophile substitution reaction does not occurs easily due to resonance in Ar X . That is
why aromatic primary amines cannot be prepared by Gabriel pthalimide reaction.
O
||
8. CH3 C H CH 2 C NH CH3
|
Br
3-bromo-N-methylbutanamide

9. The reactions and the product will be as under


10. (i) CH3 CH 2 CH 2 N H 3Cl
CH3 CH 2 CH 2 N H 2 H Cl
n-propylamine n-propylammonniumchloride


(ii) C2 H5 3 N H Cl C2 H5 3 N HCl
Triethylamine Triethylammoniumchloride

11.

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12. (i) Order of boiling point CH3 2 NH C2 H5 NH 2 C2 H 5OH

(ii) Order of solubility C6 H5 NH 2 C2 H5 2 NH C2 H5 NH 2


13. (i) Ethanamine to methanamine
HONO O O
CH3CH 2 NH 2
CH3 CH 2 OH
CH3CHO

K 2Cr2 O7 K 2Cr2O7 / H 2SO4
Ethanamine Ethanol
NH3 2 Br / KOH
CH3COOH CH3CONH 2
CH 3 NH 2
Heat
Ethanamine Methanamine
(ii) Ethanoic acid into propanoic acid
LiAlH
4 CH CH OH
2 CH CH I P/I KCN (alc.)
CH3COOH 3 2 3 2
Ethanoic acid Ethanol Iodoethane

2 H O / H
CH3CH 2 CN
CH3CH 2 COOH
Propane nitrile Propanoic acid
(iii) Methanamine to ethanamine
HONO P/ I
2 KCN (alc.)
CH3 NH 2 CH3OH CH3 I

N 2 , H 2 O
Methanamine Methanol Methyl iodide

2 5 Na / C H OH / Re duction
CH3CN
CH 3CH 2 NH 2
Methyl nitrile Ethanamine

14. (i)

(ii)

(iii)

15. (i) C2 H5 3 N C2 H5 2 NH C2 H5 NH2 NH3


(ii) CH3 2 NH C2 H5 NH2 C2 H5OH

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(iii) C6 H5 NH 2 C2 H5 2 NH C2 H5 NH 2

16. (i) The increasing order following of basic strength: C6 H5 NH 2 C6 H 5 N(CH3 ) 2 CH3 NH 2 (C2 H5 ) 2 NH
(ii) The increasing order of basic strength in their aqueous solution: NH3 CH3 3 N CH3 NH 2 CH3 2 NH
17. (i) It is tertiary amine.
(ii) These are habit-forming. So we should use them only in acute pain but not regularly. These contain tertiary
amino group.
(iii) These drugs are harmful for liver if used for long time. If these are taken empty stomach, they may cause
ulcer as some drugs contain aspirin and release salicylic acid causing ulcer.
(iv) Crocin, aspirin

18. (i) Nitration is usually carried out with a mixture of conc. HNO3 conc . H 2SO4 . So, in the presence of
these acids, aniline gets protonated to form anilinium ion. Therefore, in presence of these acids, the
reaction mixture consists of aniline and anilinium ion. NH 2 group in aniline is o, p-directing and

activating whereas the N H3 group in anilinium is m-directing and deactivating.
Now nitration of aniline mainly gives p-nitroaniline. In actual practice approx, 1 : 1 mixture of
p-nitroaniline and m-obtained.

(ii) Diazonium salts of aromatic amines are more stable than those of aliphatic amines due to delocalisation of
the positive charge on the benzene ring as shown below by the resonating structures.

(iii) Gabriel pthalimide synthesis produces primary amines only, without the traces of secondary or tertiary.
So, this method is preferred for the synthesis of primary amines.

19. (i) As the compound C with molecular formula C6 H 7 N is formed compound B on treatment with
Br 2 KOH (i.e., Hoffmann bromide reaction), compound B must be an amide and C must be an
amine. The amine having the molecular formula C6 H7 N is C6 H5 NH2 (aniline or benzenamine).
(ii) Since, compound B is from which it is formed must be benzamide C6 H5 CONH 2 .

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2 Br / KOH
C6 H5 CONH 2
C6 H5 NH 2
Benzamide (B)
Hoffmann bromamide reaction Benzenamine (C)
Since compound B is formed from compound A with aqueous ammonia and heating, compound A
must be benzoic acid or benzene carboxylic acid as acids on treatment with NH3 and subsequent heating
form amides.
(i) Aq. NH
3 C H CONH
C6 H5 COOH 6 5 2
(ii)
Benzenecarboxxylic acid Benzamide (B)
or banzoic acid (A)

A C6 H5 COOH (Benzene carboxylic acid), B C6 H5 CONH 2 (Benzamide) C C6 H5 NH 2


(Benzenamine)
20. (i) Carbylamine Test : Methylamine is a primary amine, therefore, it gives carbylamine test. When heated
with an alcoholic solution of KOH and CHCl3 , it gives offensive smell of methyl isocyanide. Since
dimethylamine is a secondary amine and hence does not give this test.

CH3 NH 2 CHCl3 3KOH CH 3 NC 3KCl 3H 2 O
Methylamine (Alc.) Methyl isocyanide
(1 amine) (Offensive smell)

CHCl / KOH alc.


3
CH3 2 NH
No reaction
Dimethylamine
(2 amine)

(ii) They can be distinguished by Libermann nitrosoamine test.


Secondary (2) amines on treatment with HNO2 give yellow coloured oily N-nitrosoamines.

CH3CH 2 2 NH HO N O CH3CH 2 2 N N O H 2 O
Diethylamine Nitrous acid N-nitrosodiethylamine
(Yellow colour)

N-nitrosodiethylamine on warming with a crystal of phenol and conc. H 2SO 4 , gives a green solution
which when made alkaline with aqueous NaOH turns deep blue and then red on dilution.
Tertiary amines do not gives this test.
(iii) Ethylamine CH3CH 2 NH 2 is a primary aliphatic amine while aniline C6 H5 NH 2 is a primary
aromatic amine.
With the reaction of nitrous acid HNO2 ; Ethylamine gives a brisk effervescence of N 2 gas with
formation of alcohol.
2 NaNO
CH3CH 2 NH 2 HONO
CH3CH 2 OH N 2 H 2 O
Dil. HCl 273 278 K
Ethylamine Ethanol

Aniline gives benzene diazonium chloride which on treatment with alkaline solution of -naphthol (2-
naphthol) gives an orange dye (Azo dye test).

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Type - 3

1. pKb of aniline is more than that of methylamine.


In aniline, NH2 group is attached directly to the ring. This result in delocalisation of p (unshared pair of
electrons) as it is in conjugation with -bonds of rings. Hence due to resonance, p is not available for protonation.
Whereas in methyl amine, electron releasing methyl group pushes electrons towards nitrogen making electron cloud
more easily available for protonating. Hence pKb of aniline is more i.e. less basic than methyl amine.

2. Ethyl amine is soluble in water, whereas aniline is not.


Ethyl amine, CH3CH2NH2 is soluble in water as it can form H-bonds with water molecules. In aniline, the large size
of benzene ring being hydrophobic makes it sparingly soluble.

3. MeNH2 (Methylamine) in water reacts with ferric chloride, FeCl3 to precipitate hydrated ferric oxide.

Methyl amine being basic in water release hydroxide ion. Now in water, OH ions precipitate out Fe3+ ions as
Fe(OH)3

4. Although amino group is o- and p- directing in aromatic substitution reactions, aniline on nitration gives a
substantial amount of m-nitro aniline.


Anilinium ion is formed by protonation, where N H3 ion is electron withdrawing group. N H3 group is a meta-
directing group which result in formation of m-nitro anline.

Aniline which is not protonated gives o and p-nitro products in a typical SE reaction.

5. Aniline does not show Friedal craft reactions.

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Aniline does not show Friedal craft acylation and alkylation due to salt formation with Lewis acid, AlCl3 (the
catalyst being used).

The positive charge over nitrogen makes it deactivating and hence no Friedal craft reactions.
+
6. Diazonium salt of aromatic amines, Ar N 2 Cl are more stable than those of aliphatic amines.

Primary aromatic amines form arene diazonium salts which are stable for a short time at low temperature due to
resonance.


No resonance in case of alkyl diazonium salts. (R N 2 Cl )

7. Gabriel pthalimide synthesis is preferred for primary amines synthesis (mainly).


It involves nucleophilic substitution using potassium pthalimide as nucleophile. Since it is a bimolecular
substitution (SN2), so mainly 1 (primary) halides are used as reactants giving mainly primary aliphatic amines.
Note that amines formed here are pure amines.

8. In this same reaction (above), aromatic primary amines cannot be formed. Why ?
Since it involves nucleophilic substitution, the anion, potassium pthalimide cannot do substitution in aromatic
halides to eventually form 1 aromatic amines.

9. Why are amines less acidic than alcohols of comparable molecular masses ?
(a) In alcohols, the polarity of O H bond is more than N H bond in amines.
(b) Also, the conjugate base of amines, i.e. aminium ion RNH2+ is very strong base as compared to conjugate
base of alcohols, i.e. alkoxides RO, since oxygen atom is more electronegative than nitrogen. Hence, amines are
less acidic than alcohols.

10. Why do primary amines have higher boiling point than tertiary amines.
The intermolecular association in primary amines is very high due to two hydrogen atoms bonded to nitrogen.
This results in stronger hydrogen bonding among molecules. Whereas tertiary amines do not show intermolecular
H-bonding due to lack of hydrogen atom.

11. Why are aliphatic amines more basic than aromatic amines ?
In aromatic amines, lone pair over nitrogen atom is not available due to resonance with -bonds of benzene ring.
In aliphatic amines, electron releasing (alkyl) groups push the electrons over N-atom making lone pair easily
available for accepting protons, i.e. making them more basic. (Also read answer of Q.1)

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+
12. C6 H 5 N (CH 3 )3 OH is stronger base than NH4OH.

C6 H5 N(CH3 )3 OH
C6 H5 N(CH3 )3 OH

C6 H5 N(CH3 )3 is highly stable as three methyl groups are electron releasing and thus stabilise positive charge on
nitrogen whereas no such effect is there in ion, which is not so stable.

13. Aniline is acetylated to get o- and p- bromo and nitro derivatives. Why ?

NHCOCH3 is moderately activating and hence less reactive towards nitration and bromination. The lone pair of
electrons on nitrogen of acetanilide interacts with oxygen atom due to resonance as shown.

So lone pair is less available for donation to benzene ring, but still it is o- and p- directing.

14. Arrange the following in increasing order of their basic strength:


(i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH
(ii) C2H5NH2, (C2H5)2 NH, (C2H5)3N, C6H5NH2
(iii) CH3NH2 , (CH3)2NH, (CH3)3 N, C6H5NH2, C6 H5CH2NH2
(i) C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2< (C2H5)2NH
(ii) C6H5NH2 < C2H5NH2 < (C2H5)3N < (C2H5)2NH

(iii) C6H5NH2 < C6H5CH2NH2 < (CH3)3N < CH3NH2 < (CH3)2NH

Explanation :
(a) Presence of electron donating alkyl group increases the basicity of amines. However, 3 amines in aqueous
solution are less basic due to steric hindrance ; resulting in poor solvation in H2O.
(b) Aliphatic amines are more basic than aromatic bases because in aromatic amines lone pair over N-atom
takes part in delocalization over benzene ring, so it is less available for donation.

15. What is the role of HNO3 in the nitrating mixture used for nitration of benzene ?
HNO3 acts as a base in the nitrating mixture and provide the electrophile, NO2 .

HNO3 H 2SO 4
H 2 NO3 HSO 4
Base Acid Conjugate acid

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Vidyamandir Classes

H 2 NO3
NO2 H 2O
Electrophile
16. What is the role of pyridine in the acylation reaction of amines ?
Pyridine being a base, is used to remove the side product i.e., HCl from reaction mixture.

17. Arrange the following compounds in increasing order of dipole moment.


CH3CH2 CH3 ; CH3CH2NH2 ; CH3CH2 OH.

As the bond polarity increases, dipole moment increases.


CH3CH2CH3 < CH3CH2NH2 < CH3CH2OH

18. A compound Z with molecular formula C3H9 N reacts with C6H5SO2Cl to give a solid, insoluble in alkali.
Identify Z.
Z[C 3H9N] is an aliphatic amine. On reaction with C6H5SO2Cl (Hinsbergs reagent), it gives a product insoluble in
alkali. It means that the product does not have a replaceable H-atom attached to the N-atom. So, compound Z is a
secondary amine (Ethyl methyl amine).
NaOH
CH3 N H C6 H5SO 2 Cl
CH 3 N SO 2C6 H5
Insoluble
| |
C2 H5 C2 H5
Ethyl methyl amine N-ethyl-N-methyl
[Z = C3H9N] benzene sulphonamide
(Insoluble in alkali)

19. A primary amines, RNH2 can be reacted with CH3 X to get secondary amine, R NHCH3 but the only
disadvantage is that 3 amine and quaternary ammonium salts are also obtained as side products. Can you
suggest a method where RNH2 forms only 2 amine ?
KOH / CHCl
3 2 H / Pd
RNH 2 RNC
RNHCH 3
or Na / EtOH
Primary Carbylamine Iso cyanide Secondary amine
amine reaction

Primary amines show carbylamine reaction in which two H-atoms attached to N-atoms of NH2 are replaced by one
C-atoms. On catalytic reduction, isocyanide (formed) produces secondary amine and not tertiary or quaternary salts.

VMC 40 Aldehydes & Ketones/Chemistry


Vidyamandir Classes

Organic Chemistry Practice Tests Based on CBSE Pattern

SET - 1

1. Accomplish the following conversions:


(a) Benzene to aniline (b) Propanoic acid to ethanoic acid
(c) Nitromethane to dimethylamine (d) Benzamide to toluene
(e) Cyclohexane to Hexane -1, 6-dioic acid (f) Benzene to benzophenone
(g) Methanamine to ethanamine (h) Chlorobenzene to p-chloroaniline

2. Give plausible explanation for each of the following:


(a) Carboxylic acids do not give the characteristic reactions of carbonyl group.
(b) Gabriel phthalimide synthesis is preferred for synthesizing primary amine.
(c) Alcohols act as both nuclephile as well as electrophile.
(d) During the preparation of ammonia derivatives from aldehydes or Ketones, pH of the reaction is carefully
controlled.

3. Arrange the following in increasing order of


(a) p-toluidine, N, N-dimethyl-p-toluidine, p-nitroaniline (basic strength)
(b) C2H5NH2, C6H5NHCH3, (C2H5)2 NH and C6H5NH2 (pKb values)
(c) (CH3)2 CHCOOH, CH3CH2CH (Br) COOH, CH3CH(Br)CH2COOH (acid strength)

4. Identify A, B and C in the following reactions:


Conc. H SO
2 4 A HBr aq. KoH
(a) C2 H5 OH B
C
443 K I 2 , NaOH

HC CNa Hg 2 / H
4C NaBH
(b) CH3 Br
A
B
KCN LiAlH
4 B
2 C HNO
(c) CH3CH 2 Br A
O C
NH
3 A 2 Br / NaOH
(d) C6 H5COOH B C

3 CH MgBr
2 H O/H O
(e) HCHO
A
B

5. An organic compound A (C7H6Cl2) on treatment with NaOH solution gives another compound B (C7H6O),
which on treatment with a mixture of conc. HNO3 and H2SO 4 gives a compound D (C7H5NO4). B on treatment with
conc. NaOH give E (C7H8 O) and C6H5COONa. Deduce the structures of A, B, C, D and E.
6. An organic compound A on heating with ammonia and cuprous oxide at a high pressure gave B. B on treatment
with ice-cold solution of sodium nitrate gave C. C when heated with copper powder & HCl gave A again.
Identify A, B and C.
7. An aliphatic organic compound A gave an analysis C = 61.01%, H = 15.25% and rest is N. The molecular mass of
compound is 59. On treatment with HNO2 compound A gave compound B which did not contain any N, the
compound B upon controlled oxidation gave another compound C which responded to iodoform test. Identify
the structures of A, B & C.

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8. An organic compound with the molecular formula C9H10O forms 2, 4-DNP derivative, reduces Tollens reagent and
undergoes cannizzaro reaction. On vigorous oxidation, it gives 1, 2- benzenedicarboxylic acid. Identify the
compound & write its IUPAC name.
9. Write a chemical test to distinguish between the following pairs of compounds:
(a) Propanal & propanone (b) Acetophenone & benzophenone
(c) Phenol & benzoic acid (d) Benzyl chloride & chlorobenzene
(e) Ethanol & propanol (f) Benzoic acid & ethyl benzoate
(g) Ethanamine & N-Methylmethanamine
10. Describe the following reactions giving an example of each:
(a) Cannizaro reaction (b) Cross-aldol condensation
(c) Kolble electrolysis reaction (d) HVZ reaction
(e) Etard reaction (f) Aldol condensation
(g) Willimson synthesis (h) Gabriel phthalimide synthesis

SET - 2
1. Accomplish the following conversions:
(a) Ethanoic acid to propanone (b) Acetone to t-butyl alcohol
(c) Benzoic acid to benzaldehyde (d) ethanol to propanone
(e) n-propyl alcohol to n-hexane (f) acetic acid to acetaldehyde
(g) acetic acid to ethyl amine (h) Ethanol to 3-hydroxybutanal

2. Give plausible explanation for each of the following:


(a) Sodium bisulphate is used for the purification of aldehydes and Ketones.
(b) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(c) Dipole momentums of aldehydes and ketones are higher than those of alcohols.
(d) Aniline does not undergo Friedal-crafts reaction.

3. Arrange the following in increasing order of


(a) CH3CH2CH2CHO, CH3CH2CH2CH2OH, H5C2OC2H5, CH3CH2CH2CH2CH3 (boiling points)
(b) CH3COOH, HCOOH, CH3CH2COOH, (CH3)3CCOOH (reactivity towards esterification)
(c) CH2ClCOOH, CHCl2COOH, CH3COOH, CCl3COOH (acid strength)

4. Identify A, B, C, D and E in the following reactions:


alc. KoH Br
2 B alc. KOH Hg 2 / H
CH3 C H CH3 A C
D
(a) |
Br
SOCl
2 A B KCN
(b) CH3CH 2 OH (c) (CH3 ) 2 CHCl CH CNa
A
AgNO 2
(d) CH3CH 2Cl A

(e)

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5. A compound A with formula C5 H10O, gave a positive 2, 4-DNP test, but negative Tollens test. It was oxidized to
carboxylic acid B with formula C3H6O2 when treated with alkaline KMnO4. Sodium salt of B gave hydrocarbon
C on Kolbes electrolytic reaction. Deduce structures of A, B and C and write the reactions involved.
6. An organic compound A has the molecular formula C 8H16O2. It gets hydrolysed with dil H2SO4 & gives a
carboxylic acid B and an alcohol C. Oxidation of C with chromic acid also produced B. C on dehydration reaction
gives but-1-ene. Write equations for the reaction involved. Also identify A, B and C.
7. A compound X (C2H4O) on oxidation gives Y(C2H4O2) X undergoes haloform reaction. On treatment with HCN
X forms product Z, which on hydrolysis gives 2-Hydroxy-propanoic acid.
(a) Write the structures of X and Y (b) Name the product when X reacts with dil. NaOH
8. An optically inactive compound A having molecular formula C4H9Cl on heating with alcoholic KOH gave B.
B on treatment with HBr gave C that can be resolved. Identify A, B & C.
9. Write a chemical test to distinguish between the following pairs of compounds:
(a) Benzaldehyde & acetophenone (b) Aniline & methylamine
(c) Chlorobenzene & chloroethane (d) ethanol & phenol
(e) aniline and N-methylaniline (f) iso-propylcohol & n-propylalchohol
10. Describe the following reactions giving an example of each:
(a) Reimer-Tiemann reaction (b) Swarts reaction
(c) Sandmeyer reaction (d) Wolff-Kishner reduction
(e) Kolbe reaction (f) Decarboxylation
(g) Clemmenson reduction (h) Wurtz-Fittig reaction

SET - 3 1 Mark

1. Direct nitration of aniline is not carried out. Explain why?


2. Write the IUPAC name of the following compound:
CH3 C C CH 2 OH
| |
CH3 Br

3. Arrange the following compounds in an increasing order of their acid strengths


(CH3)2CH COOH, CH3CH2CH (Br) COOH, CH3CH (Br) CH2COOH
4. Write the structural formula of 3-Ethyl -2, 5-dimethylhexan-2-ol.
5. Which is more basic PhNH2 or Ph2NH?
6. Write the IUPAC name of the compound:

7. What is meant by enantiomers?


8. Arrange the following compounds in increasing order of their boiling points:
CH3CHO , CH3CH2OH , CH3OCH3 , CH3CH2CH3
9. Write the structure and IUPAC name of the amide which gives propanamine by Hoffmann bromamide reaction.
10. Why is sulphuric acid not used during the reaction of alchohols with KI?

VMC 43 Aldehydes & Ketones/Chemistry


Vidyamandir Classes

2 Mark

1. Give the mechanism for acid catalysed hydration of an alkene froming an alcohol.
2. How will you bring about the following conversions?
(a) iso-propyl bromide to n-propyl bromide (b) Aniline to iodo benzene
3. Give a chemical test to distinguish between the following pairs of organic compounds:
(a) ethylamine and diethylamine (b) 2-pentanone and 3-pentanone
4. (a) Give an example of a zwitter ion.
(b) Which reaction is used for the preparation of pure aliphatic primary amines?
5. Propose the mechanism for the following reaction:
H 2SO4 conc.
CH3 CH 2 OH CH 2 CH 2 H 2 O
443K

6. Account for the following:


(a) Aniline does not undergo Friedal crafts reaction.
(b) 3-fluorobutanoic acid is stronger acid the 4-fluorobutanoic acid.
7. Predict the major product of acid catalysed dehydration of :
(a) 1-methyl cyclohexanol (b) Butan-1-ol
8. An alkyl halide (A) on reaction with magnesium in dry ether followed by treatment with ethanol gave
2-methylbutane. Write all the possible isomeric structures of A.
9. Explain as to why haloarenes are much less reactive than haloalknes towards nucleophilic substitution ractions.
10. Complete the following reactions:

(a)

(b)

3 Mark

1. How are the following conversions carried out?


(a) Benzil chloride Benzyl alcohol
(b) Methyl magnesium bromide 2-Methylpropan-2-ol
(c) Chlorobenzene Phenol
2. (a) Explain the mechanism of acid catalysed dehydration of ethanol at high temperature to yield ethoxyethane.
(b) What is meant by the term acetal?
3. Account for the following :
(a) The presence of base is needed in the ammonolysis of alkyl halides
(b) Ethylamine is soluble in water, whereas aniline is not.
(c) Ethers possess a dipole moment even if the alkyl groups in the molecule are identical.

VMC 44 Aldehydes & Ketones/Chemistry


Vidyamandir Classes

4. Complete each synthesis by giving the missing material, reagent or products:

2 H
(a) C6 H5 COCl (b)
Pd BaSO 4

2 H NCONHNH
2 _____
(c) CH3CHO

5. Convert:
(a) Nitrobenzene to phenol (b) Acetaldehyde to But-2-enal (c) Aniline to P-bromoaniline

6. Give reason for the following


(a) Sodium bisulphate is used for the purification of aldehydes & ketones
(b) Aromatic amines are weaker bases than aliphatic amines
(c) Methanol is miscible with water while iodomethane is not.
7. (a) Give plausible explanation for each of the following:
(i) The presence of a base is needed in the ammonolysis of alkyl halides
(ii) Aromatic primary amines cannot be prepared by Gabriel pthalimide synthesis.
CH3 N CO CH3
(b) Write the IUPAC name of |
C 2 H5

8. (a) An organic compound A with molecular formula C8H8O gives positive DNP and iodoform tests.
It doesnt reduce Tollens or Fehlings reagent and does not decolourise bromine water also. On oxidation
with chromic acid (H2CrO4), it gives a carboxylic acid (B) with molecular formula C7H6O2. Deduce the
structures of A and B.
(b) Which of the following two compounds would react faster by SN2 path: 1-bromobutane or 2-bromobutane
and why?
9. Write the structure of main products:
(a) Chlorination of benzene in the presence of UV light.
(b) Propene is treated with HBr in presence of benzoyl peroxide.
(c) Chlorobenzene is treated with NaOH at 623 K and high pressure.
10. Give two reactions that show the acidic nature of phenol. Compare the acidity of phenol with that of ethanol.

SET - 4 1 Mark

1. A hydrocarbon C5H12 gives only one chlorination product. Identify the compound.
2. Write the IUPAC name of the given organic compound CH2 = CHCH2COCH2CH3
3. Why are primary amines higher boiling than tertiary amines?
4. Point out the difference between chirality and chiral centre.
5. Write the IUPAC name: (CH3)3 C CH2COOH
6. Mention the chief use of quaternary ammonium salts derived from long chain amines.
7. Write the structure of 4-Methylpent-3-en-2-one.
8. A solution of KOH hydrolyses CH3CHClCH2CH3 and CH3CH2CH2CH2Cl. Which one of these is more easily
hydrolysed?

VMC 45 Aldehydes & Ketones/Chemistry


Vidyamandir Classes

9. Arrange the following in the decreasing order of their basic strength in aqueous solutions:
CH3NH2 , (CH3)2NH , (CH3)3N , NH3
10. Give reason for the following: Ortho-nitrophenol is more acidic than ortho-methoxyphenol

2 Mark

1. Explain the following terms with suitable example:


(a) retention (b) inversion
2. Explain giving reasons.
(a) Phenol has a smaller dipole moment than methanol
(b) Phenol undergoes electrophilic substitution reactions
3. P-methoxyaniline is a stronger base than aniline but p-nitroaniline is a weaker base than aniline. Explain
4. Explain the following.
(a) Acetaldehyde gives aldol condensation while formaldehyde does not.
(b) It is necessary to control the pH during the reaction of aldehydes or ketones with ammonia derivatives.
5. Name the reagent used in the following reactions:
(a) Oxidation of primary alcohol to carboxylic acid
(b) Butan-2-one to buta-2-ol
6. Which alkyl halide from the following pairs would you expect to react more rapidly by SN2 mehcanism? Explain
your answer.
CH3CH 2 CH 2 CH 2 Br or CH3CH 2 C H CH3
(a) |
Br
CH3 C CH 2 CH 2 Cl or CH 3 CH 2 C CH 2 Cl
(b) | |
CH3 CH3

7. An optically active compounds having molecular formula C7H15Br reacts with aqueous KOH to give a racemic
mixture of products. Write the mechanism involved for this reaction.
O
||
HCN H2O / H
8. Give the structures of A and B in the following reaction: CH3 C H A B

9. How will you bring about the following conversions?


(a) Acetic acid to methyl amine (a) Aniline to benzoic acid
10. Write the names of the reagents and equations in the conversion of
(a) Phenol to salicylaldehyde (b) Anisole to P-methoxyacetophenone

3 Mark
1. Account for the following observations:
(a) pKb for aniline is more than that of methylamine
(b) tert-butyl chloride reacts with aq. NaOH by SN1 mechanism while n-butyl chloride by SN2 mechanism.
(c) Aldehydes are more reactive than ketones towards nucleophiles

VMC 46 Aldehydes & Ketones/Chemistry


Vidyamandir Classes

2. (a) Out of C6H5CH2Cl and C6H5CHClC6H5, which is more easily hydrolysed by aqueous KOH & why?
(b) Write the structural formula for the organic molecules A, B, C and D in the following sequence of
reaction:
alc. KOH Br
2 B C 2 D alc. KOH H O
CH3 C H CH 2 CH3
A
| Hg 2 , H
Br
3. Explain the following giving example of each :
(a) Carbylamine reaction (b) Hoffmanns bromamide reaction (c) coupling reaction
4. (a) What is meant by racemic mxitre?
(b) Predict the alkenes that would be formed by dehydrohalogenation of 2- chloro-2-methylbutane with
sodium ethoxide in ethanol and identify the major alkene.
5. Give Reasons:
(a) P-nitrobenzoic acid has higher Ka value than benzoic acid.
(b) Acetone is highly soluble in water but benzophenone is not.
(c) Cyclohexane forms cyanohydrin in good yield but 2, 2, 6-trimethyl cyclohexanone does not.
6. Describe how the following conversions can be brought about:
(a) Cyclohexanol to Cyclohexan-1-one (b) Ethyl benzene to benzoic acid
(c) Bromobenzene to benzoic acid
7. Complete the each synthesis by giving the missing material, reagent or product:

(a) (b)

(c)

8. Write the IUPAC names of following compounds:


CH3
|
(a) CH3 CH CH 2 COCl (b) (c) CH3 C NH 2
| |
CH3 CH3

9. Explain why
(a) The dipole moment of chlorobenzene is lower than that of cyclohexyl chloride.
(b) Alkyl halides, though polar, are immiscible with water.
(c) Grignard reagent should be prepared under anhydrous conditions.
10. What is meant by the following terms? Give an example in each case:
(a) Oxime (b) Imine (c) Schiffs base

VMC 47 Aldehydes & Ketones/Chemistry