12.ALDEHYDES, KETONES AND CARBOXYLIC ACIDS-f (2)
12.ALDEHYDES, KETONES AND CARBOXYLIC ACIDS-f (2)
12.ALDEHYDES, KETONES AND CARBOXYLIC ACIDS-f (2)
(1.) p-cresol reacts with chloroform in alkaline medium to give the compound A which adds
hydrogen cyanide to form the compound B. The latter on acidic hydrolysis gives chiral
carboxylic acid. The structure of carboxylic acid is
(b.)
(a.)
(c.) (d.)
(2.) Following reaction is used to prepare alkane from sodium salt of carboxylic acid. The name of
reaction is [Page: 383]
− +
RCO O N a ⎯⎯⎯⎯⎯
NaOH &CaO
Heat
→ R − H + Na 2CO3
(a.) Decarboxylation (b.) Kolbe electrolysis
(c.) HVZ reaction (d.) None of these
Codes
A B C D
(a.) r q p s
(b.) p q r s
(c.) s p q r
(d.) p s q r
20
(4.) Match the structure given in Column I with the name given in Column II [Page: 360]
Column I Column II
(structure) (Name)
p) 2-methyl cyclohexanone
(I)
q) 3-bromo benzaldehyde
(II)
r) cyclohexane carbaldehyde
(III)
s) 1-phenylpropan-1- one
(IV)
Codes
I II III IV
(a.) pqrs (b.) rsqp
(c.) srpq (d.) rsqp
(5.) In which of the following solvent, carboxylic acid is/are soluble? [Page: 379]
(a.) benzene (b.) ether
(c.) chloroform (d.) All of these
(6.) Assertion: Carboxylic acids are reduced to alkanes on reaction with HI in presence of red
phosphorus.
Reason: Melting point of carboxylic acid shows a regular pattern. [Page: 381]
(a.) Both A and R are correct and R is the (b.) Both A and R are correct but R is not
correct explanation of A. correct explanation of A.
(c.) A is correct but R is incorrect. (d.) Both A and R are false.
Which of the following statement is incorrect for above reaction? [Page: 367]
(a.) Aldehyde and ketone has its sterically (b.) For aldehydes, the position of equilibrium
hindered to give the required product. lies to right hand side.
(c.) For ketones, the position of equilibrium (d.) The product formed is water soluble.
lies to left hand side.
21
(8.) Acyl chloride is hydrogenated over catalyst, palladium on barium sulphate. This reaction is
called [Page: 362]
(a.) Stephen reaction (b.) Rosenmund reduction
(c.) Birch reduction (d.) Wolff–Kishner reduction
(9.) Assertion: Strong oxidising agents oxidise toluene and its derivatives to benzoic acid.
Reason: Chromyl chloride and chromic oxide stop the oxidation of toluene at aldehyde stage.
[Page: 362]
(a.) Both A and R are correct and R is the (b.) Both A and R are correct but R is not
correct explanation of A. correct explanation of A.
(c.) A is correct but R is incorrect. (d.) Both A and R are false.
(a.) – Benzaldehyde
(d.) HCHO – formaldehyde
(c.) − OXO − − bromopropane
(12.) Which of the following statement is correct for Fehling’s test? [Page: 369]
(a.) Fehling’s solution is an aqueous copper (b.) Aldehydes on heating with Fehling’s
sulphate solution. reagent give green precipitate.
(c.) Ketones does not give positive Fehling’s (d.) Aromatic aldehydes also reduces
test. Fehling’s solution.
(a.) (b.)
22
(c.) (d.)
(14.) The carboxylic carbon is less electrophilic than carbonyl carbon because of [Page: 375]
(a.) bond polarity (b.) resonance
(c.) carbocation formation (d.) carbanion formation
(15.) Aldehydes are more reactive towards nucleophilic addition reactions than ketones because of
[Page: 366]
(a.) inductive effect (b.) steric effect
(c.) Both (a) and (b) (d.) None of these
(17.) In the reaction given below, the total number of intermolecular aldol condensation products
formed ‘Y’ is
(a.) 1 (b.) 2
(c.) 3 (d.) 4
(18.) The product formed by the reaction of an aldehyde with a primary amine is [NEET-2016, Phase
II, Page: 368]
(a.) Ketone (b.) Carboxylic acid
(c.) Aromatic acid (d.) Schiff base
(19.) Which of the following does not act as mild oxidising agent? [Page: 369]
(a.) Tollen’s reagent (b.) Fehling’s reagent
(c.) Benedict’s reagent (d.) Alk. KMnO4
(20.) A compound A has molecular formula C2Cl3OH. It reduces Fehling’s solution and on oxidation
gives a monocarboxylic acid B. A can be obtained by the action of chlorine on ethyl alcohol. A
is
(a.) chloroform (b.) monochloroacetic acid
23
(c.) chloral (d.) methyl chloride
(22.) Assertion: Carbon−oxygen bond length in formic acid are 1.23 Å and 1.36 Å.
Reason: Formic acid gives rise to nucleophilic. [Page: 375]
(a.) Both A and R are correct and R is the (b.) Both A and R are correct but R is not
correct explanation of A. correct explanation of A.
(c.) A is correct but R is incorrect. (d.) Both A and R are false.
(23.) The correct common name for the given structure is [Page: 358]
(24.) Which of the following reaction is not used to synthesis carboxylic acids? [Page: 377]
RCOCl ⎯⎯⎯ → RCOOH + Cl−
+
(a.) H 2O
(b.) RCOCl ⎯⎯⎯⎯
OH/H 2O
→ RCOO− + Cl− ⎯⎯⎯
H3O
→ RCOOH
(c.) ( C6H5CO )2 O ⎯⎯⎯
H O
2
→ 2C6H5COOH
(d.)
(26.) The major product (X) formed in the reaction is [Page: 384]
24
(a.) m-nitrobenzoic and (b.) p-nitrobenzoic acid
(c.) o-nitrobenzoic acid (d.) None of these
(27.) Methanal, ethanal and propanone are miscible with water in all proportions because they [Page:
365]
(a.) form hydrogen bond with water (b.) polar bond
(c.) have high molecular mass (d.) none of these
(28.) The type of reaction shown by aldehydes and ketones is [Page: 366]
(a.) electrophilic addition reactions (b.) nucleophilic addition reactions
(c.) free radical addition reactions (d.) none of these
(29.) Assertion: During reaction of carboxylic acids with NaHCO3, the CO2 evolved comes from
carboxylic acid and not from NaHCO3.
Reason: Carbonic acid is a stronger acid than carboxylic acid. [Page: 379]
(a.) Both A and R are correct and R is the (b.) Both A and R are correct but R is not
correct explanation of A. correct explanation of A.
(c.) A is correct but R is incorrect. (d.) Both A and R are false.
(30.) Compound (A) [molecular formula C3H8O] is treated with acidified K2Cr2O7 to form a product
B (molecular formula C3H6O). B forms a shining silver mirror on warming with ammoniacal
silver nitrate. ‘B’ when treated with an aqueous solution of H 2NCONHNH2.HCl and sodium
acetate gives a product ‘C’. The structure ‘C’ is
(a.) CH 3CH 2 CH = NNHCONH 2 (b.) ( CH3 )2 C =NNHCONH2
(c.) ( CH3 )2 C =NCONHNH2 (d.) CH 3CH 2 CH = NCONHNH 2
(33.) Which of the following is the incorrect use of carboxylic acid? [Page: 384]
25
(a.) HCOOH is used in rubber, textile, dyeing (b.) Ethanoic acid is used as solvent and as
and electroplating. vinegar in food industry.
(c.) Sodium benzoate is used in perfumery. (d.) Ester of benzoic acid is used in
perfumery.
(a.)
(b.) CH 3CH = CH 2OH
(c.)
(d.)
(36.) Which of the following is the simplest aromatic aldehyde carrying the aldehyde group? [Page:
359]
(a.) benzene carbaldehyde (b.) benzaldehyde
(c.) cinnamaldehyde (d.) Both (a) and (b)
(38.) Which of the reagent can be used to oxidise primary alcohols to carboxylic acid? [Page: 375]
(a.) KMnO4 in neutral, acid or alkaline media (b.) K2Cr2O7
(c.) CrO3 in acidic media (d.) All of these
26
(a.) Both A and R are correct and R is the (b.) Both A and R are correct but R is not
correct explanation of A. correct explanation of A.
(c.) A is correct but R is incorrect. (d.) Both A and R are false.
(40.) Match the structure given in column I with common name given in column II [Page: 374]
Structure Common name
Codes
I II III IV
(a.) q p r s (b.) r p s q
(c.) r q p s (d.) p q s r
(42.) The intermediate ‘Y’ formed in the following reaction is [Page: 369]
(a.)
(b.)
(c.)
(d.)
(43.) Boiling points of aldehydes are higher than hydrocarbons. It is due to [Page: 365]
(a.) weak molecular association (b.) high intermolecular hydrogen bonding
(c.) high molecular masses (d.) None of these
27
(44.) The reagent in following reaction is [Page: 363]
(Reaction) (Product)
Codes
I II III IV
(a.) r s q p (b.) q r s p
(c.) p q r s (d.) r q p s
(47.) Assertion: Fehling’s solution can be used to distinguish benzaldehyde from acetaldehyde.
Reason: The C—H bond of CHO group in benzaldehyde is stronger than C—H bond of CHO
group in acetaldehyde. [Page: 369]
(a.) Both A and R are correct and R is correct (b.) Both A and R are correct but R is not
explanation of A. correct explanation of A.
(c.) A is true but R is false. (d.) Both A and R are false.
28
(a.)
(b.)
(c.)
(d.)
29
TOPIC WISE PRACTICE QUESTIONS
TOPIC 1: Methods of Preparation of Carbonyl Compounds
1. Calcium acetate, on heating, gives:
1) acetic anhydride 2) acetone 3) acetaldehyde 4) ethyl alcohol
2. Benzaldehyde can be prepared by the hydrolysis of
1) benzal chloride 2) benzotrichloride
3) benzyl chloride 4) benzonitrile
3.
Reactant X is:
1) CH3Cl 2) CH2Cl2 3) CHCl3 4) CCl4
OH −
4. In the Cannizzaro reaction given below 2C6 H5CHO ⎯⎯⎯ → C6 H5CH 2OH + C6 H5COO −
1) attack of OH– at the carbonyl group.
2) transfer of hydride ion to the carbonyl group.
3) abstraction of proton from the carboxylic acid.
4)feprotonation of C6H5CH2OH.
5. The end product 3) in the following sequence of reactions is
30
8.
31
TOPIC 2: Properties of Carbonyl Compounds
16. The reactant (X) in the reaction
20.
Product (A) of the reaction is
1) propanol 2) ethanol 3) butanol 4) pentanol
21. The presence of unsaturation in organic compounds can be tested with:
32
1) Schiff's reagent 2) Tollens' reagent 3) Fehling's reagent 4) Baeyer's reagent
22. Which carbon atoms are most susceptible to nucleophilic attack ?
−
24. CH3COCH 2Cl ⎯⎯⎯⎯ OH ,Cl2
→ Product P is
1) ClCH 2 COCH 2 Cl 2) CH 3COCHCl 2 3) both a and b 4) ClCH 2 COOH + CH 3Cl
25. Formalin is an aqueous solution of
1) fluorescein 2) formic acid 3) formaldehyde 4) furfuraldehyde
26. (CH3)2C = CHCOCH3 can be oxidized to (CH3)2C = CHCOOH by
1) Chromic acid 2) NaOI 3) Cu at 300 °C 4) KMnO4.
27. Aldehydes and ketones will not form crystalline derivatives with
1) sodium bisulphite 2) phenylhydrazine
3) semicarbazide hydrochloride 4) dihydrogen sodium phosphate.
28. Which of the following compound will undergo self aldol condensation in the presence of cold dilute
alkali ?
1) CH2 = CH-CHO 2) CH C – CHO 3) C6H5CHO 4) CH3CH2CHO
29. Appropriate reducing agent for the following conversion is–
33
32. Arrange the following carbonyl compounds in decreasing order of their reactivity in nucleophilic
addition reaction.
34. Arrange the following compounds in order of their reactivity toward LiAlH4.
34
37. Acetone is treated with excess of ethanol in the presence of hydrochloric acid. The product obtained is :
35
4) none of these form an enamine
43. Less reactivity of ketone is due to
1) + I inductive effect decreases positive charge on carbonyl carbon atom
2) steric effect of two bulky alkyl groups
3) sp2 hybridised carbon atom of carbonyl carbon atom
4) Both (1) and (2)
44. Which of the following statement is false?
1) Cannizzaro reaction is given by aldehydes in presence of alkali
2) Aldol condensation is given by aldehydes in presence of alkali
3) Aldol condensation is given by aldehydes and ketones in presence of acids
4) None of the above
45. The most acidic hydrogen for the following compound
1) 2 2) 1 3) 4 4) 3
46.
In the above sequence of reaction X and Y are respectively
1) H2/Pt ; Br2 2) KMnO4; H2/Pt 3) KMnO4 (aq); HI/P 4) NH2 – NH2/KOH, HI/P
47. Hydrolysis of an ester may be achived under acidic as well as basic conditions. Pick up the correct
statement regarding this.
1) Acidic hydrolysis is faster than alkaline hydrolysis.
2) Alkaline hydrolysis is faster than acidic hydrolysis.
3) Both occur at the same rate.
4) In both, the first step is protonation of the —OH part of the —COOH group.
48. When propionic acid is treated with aqueous sodium bicarbonate, CO2 is liberated. The ‘C’ of CO2
comes from
1) methyl group 2) carboxylic acid group 3) methylene group 4) bicarbonate
49. Formic acid is obtained when
1) calcium acetate is heated with conc. H2SO4
2) calcium formate is heated with calcium acetate
3) glycerol is heated with oxalic acid at 373 K
4) acetaldehyde is oxidised with K2Cr2O7 and H2SO4.
36
50. An ester is boiled with KOH. The product is cooled and acidified with concentrated HCl. A white
crystalline acid separates. The ester is
1) methyl acetate 2) ethyl acetate 3) ethyl formate 4) ethyl benzoate
51. The cyanohydrin of a compound on hydrolysis gives an optically active a-hydroxy acid. The compound
is
1) diethyl ketone 2) formaldehyde 3) acetaldehyde 4) acetone
52.
53. Acetic anhydride reacts with diethyl ether in presence of anhydrous AlCl3 to give :
1) CH3CH2COOH 2) CH3CH2COOC2H5 3) CH3COOCH3 4) CH3COOC2H5
54. CH3COOH ⎯⎯ A
→ CH3COCl . What is A?
1) PCl5 2) Cl 2 3)HCl 4) COCl2
55. The compound not soluble in acetic acid is :
1) CaCO3 2) CaO 3) CaC2O4 4) Ca(OH)2
56. In the following reaction
59. Which of the following can not be oxidised to give carboxylic acid?
37
60. Which one of the following is not resonance form of the enolate ion formed from aceto acetic ester ?
61.
38
64. Carboxylic acids are more acidic than phenol and alcohol because of
1) intermolecular hydrogen bonding 2) formation of dimers
3) highly acidic hydrogen 4) resonance stabilization of their conjugate base
65. Which of the following represents the correct order of the acidity in the given compounds?
1) FCH 2 COOH CH3COOH BrCH 2 COOH ClCH 2 COOH
2) BrCH 2 COOH ClCH 2 COOH FCH 2 COOH CH3COOH
3) FCH 2 COOH ClCH 2 COOH BrCH 2 COOH CH3COOH
4) CH 3COOH BrCH 2 COOH ClCH 2 COOH FCH 2 COOH
2) Formyl cation C HO
1) Dichloromethyl cation
39
4. Predict the correct intermediate and product in the following reaction: [2017]
Identify A, X, Y and Z
1) A-Methoxymethane, X-Ethanol, Y-Ethanoic acid, Z-Semicarbazide.
2) A-Ethanal, X-Ethanol, Y-But-2-enal, Z-Semicarbazone
3) A-Ethanol, X-Acetaldehyde, Y-Butanone, Z-Hydrazone
4) A-Methoxymethane, X-Ethanoic acid, Y-Acetate ion, Z-hydrazine.
6. Of the following, which is the product formed when cyclohexanone undergoes aldol condensation
followed by heating? [2017]
7. The correct statement regarding a carbonyl compound with a hydrogen atom on its alphacarbon, is:
[2016]
1) a carbonyl compound with a hydrogen atom on its alpha-carbon never equilibrates with its
corresponding enol.
40
2) a carbonyl compound with a hydrgen atom on its alphacarbon rapidly equilibrates with its
corresponding enol and this process is known as aldehyde-ketone equilibration.
3) a carbonyl compound with a hydrogen atom on its alpha-carbon rapidly equilibrates with its
corresponding enol and this process is known as carbonylation.
4) a carbonyl compound with a hydrogen atom on its alpha-carbon rapidly equilibrates with its
corresponding enol and this process is known as ketoenol tautomerism.
8. The product formed by the reaction of an aldehyde with a primary amine is [2016]
1) Schiff base 2) Ketone 3) Carboxylic acid 4) Aromatic acid
9. An organic compound 'X' having molecular formula C5H10O yields phenyl hydrazone and gives
negative response to the iodoform test and Tollen's test. It produces n-pentane on reduction. 'X' could be
:- [2015]
1) 2-pentanone 2) 3-pentanone 3) n-amyl alcohol 4) pentanal
10. Treatment of cyclopentanone with methyl lithium gives which of the following species?
[2015]
1) Cyclopentanonyl cation 2) Cyclopentanonyl radical
3) Cyclopentanonyl biradical 4) Cyclopentanonyl anion
11. The enolic form of ethyl acetoacetate as below has: [2015]
13. The reaction that does not give benzoic acid as the major product is:- [2019-ODISSA]
(1) (2)
(3) (4)
14. Which of the following acid will form an (a) Anhydride on heating and (b) Acid imide on strong
heating with ammonia? [2019-ODISSA]
41
(1) (2) (3) (4)
15. Identify compound (A) in the following reaction: [2019-ODISSA]
(1) Benzoyl chloride (2) Toluene (3) Acetophenone (4) Benzoic acid
16. Reaction between benzaldehyde and acetophenone in presence of dilute NaOH is known as [2020]
1. Cross Aldol condensation 2. Aldol condensation
3. Cannizzaro’s reaction 4. Cross Cannizzaro’s reaction
17. Identify compound X in the following sequence reactions. [2020]
CCl3
1) 2) 3) 4)
18. The product formed in the following chemical reaction is [NEET-2021]
42
Choose the correct answer from the options given below
1) a-iii, b- ii, c – i, d – iv 2) a-i, b- iv, c – iii, d – ii
3)a-ii, b- iii, c- iv, d – I 4)a – iv, b- i, c – ii, d – iii
20. The intermediate compound ‘X’ in the following chemical reaction is: [NEET-2021]
+
21. RMgX + CO2 ⎯⎯⎯
dry
ether
→ Y ⎯⎯⎯
H 3O
→ RCOOH What is Y in the above reaction? [NEET-2022]
1) RCOO − Mg + X 2) R3CO- Mg+ X 3) RCOO − X + 4) ( RCOO )2 Mg
43
1) Both Statement I and Statement II are correct
2) Both Statement I and Statement II are incorrect
3) Statement I is correct but Statement II is incorrect
4) Statement I is incorrect but Statement II is correct.
23. Match List- I and List – II [NEET-2022]
List – I List – II
(Products formed) (Reaction of carbonyl compound with)
a)Cyanohydrin i) NH OH
2
b) Acetal ii) RNH
2
c)Schiff’s base iii) alcohol
d)Oxime iv) HCN
Choose the correct answer from the options given below
1) (a)-(iii), (b)- (iv), (c)- (ii), (d)- (i)
2) (a)-(ii), (b)-(iii), (c)-(iv), (d)-(i)
3) (a)-(i), (b)-(iii), (c)-(ii), (d)-(iv)
4) (a)-(iv), (b)-(iii), (c)-(ii), (d)-(i)
24. Which one of the following is not formed when acetone reacts with 2- pentanone in the presence
of dilute NaOH followed by heating? [NEET-2022]
1) 2)
3) 4)
44
NCERT LINE BY LINE QUESTIONS – ANSWERS
(1.) c (2.) a (3.) c (4.) b (5.) d
(6.) c (7.) a (8.) b (9.) b (10.) c
(11.) c (12.) c (13.) c (14.) b (15.) c
(16.) a (17.) a (18.) d (19.) d (20.) b
(21.) c (22.) b (23.) b (24.) d (25.) c
(26.) a (27.) a (28.) b (29.) d (30.) d
(31.) b (32.) a (33.) c (34.) a (35.) c
(36.) d (37.) a (38.) d (39.) c (40.) b
(41.) b (42.) a (43.) a (44.) a (45.) d
(46.) b (47.) a (48.) c (49.) b (50.) c
(2.) (a) The given reaction is known as decarboxylation. Carboxylic acids lose CO2 to form hydrocarbons
when their sodium salts are heated with sodalime (NaOH and CaO in ratio of 3:1).
− +
RCO O N a ⎯⎯⎯⎯⎯
NaOH &CaO
Heat
→ R − H + Na 2CO3
(3.) (c) A → s, B → p, C → q, D → r
(4.) (b) I → r, II → s, III → q, IV → p
(5.) (d) Carboxylic acids are soluble in less polar organic solvents like benzene, ether, alcohol, chloroform
etc.
(6.) (c) A is correct but R is incorrect.
(7.) (a) Only statement (a) is incorrect. Other statements are correct. Corrected statement is “the aldehydes
and ketones which are not sterically hindered on reaction with NaHSO3 give bisulphite addition
product”.
45
(8.) (b) Acyl chloride is hydrogenated over catalyst, palladium on barium sulphate. This reaction is called
Rosenmund reduction.
(9.) (b) Both A and R are correct but R is not the correct explanation of A.
(10.) (c) Highly branched carboxylic acids are less than unbranched acids. The +I effect of alkyl groups in
branched acid increases the magnitude of negative group. Thus, –COOH group is shielded from solvent
molecules and cannot be stabilized by solvation as effectively as in unbranched carboxylic acids.
(11.) (c) The incorrect match is
(c).
(12.) (c) Only statement (c) is correct. Other statements are incorrect. Fehling’s reagent is a mixture of two
solutions, i.e. Fehling’s solution A and B. Fehling’s solution A is an aqueous copper sulphate and
Fehling’s solution B is an alkaline sodium potassium tartarate. When an aldehyde is heated with
Fehling’s reagent, a reddish brown precipitate is obtained.
(13.) (c) Alkyl benzene on reaction with alk. KMnO4 produces aromatic carboxylic acids. The entire side
chain is oxidized to the carboxyl group irrespective of length of side chain.
(14.) (b) The carboxylic carbon is less electrophilic than carbonyl carbon because of resonance. The possible
resonance structures are as follows:
(15.) (c) Aldehydes are more reactive towards nucleophilic addition reactions than ketones because of
inductive effect and steric effect. Greater the number of alkyl groups attached to the carbonyl group,
greater the electron density on carbonyl carbon. Thus, it lowers the attack of nucleophile and hence,
reactivity decreases. Due to steric hindrance, the attack of nucleophile on carbonyl group becomes more
difficult.
(16.) (a) But-2-ene on ozonolysis gives two molecules of acetaldehyde
46
(17.) (a)
(18.) (d) The product formed by the reaction of an aldehyde with 1° amine is Schiff’s base.
(19.) (d) Alkaline KMnO4 does not act as a mild oxidising agent. It act as a strong oxidising agent whereas
Tollen’s reagent, Fehling’s reagent and Benedict’s reagent act as a mild oxidising agent.
(20.) (b) Molecular formula of A is C2 Cl3OH . As (a) reduces Fehling’s solution and on oxidation gives a
monocarboxylic acid (b), it means (a) must be an aldehyde ( CCl3CHO ). This is further confirmed by
the reaction
C2 H5OH + Cl2 ⎯⎯ → CH 3CHO ⎯⎯ → ( CCl3CHO )
OCl2
(21.) (c) The given reaction is Cannizzaro reaction. Aldehydes which do not have an α-H atom undergo self-
oxidation and reduction reaction on treatment with conc. alkali.
(22.) (b) In carboxylic group, the characteristic nucleophilic additions are not shown because of the resonance
in carboxylate ion which resists for addition of HCN and NaHSO3 as well as reactions involving
replacement of carboxylic oxygen by reagents.
(23.) (b) − bromobutyraldehyde is the common name for the given structure. The location of the substituent
in the carbon chain is indicated by Greek letters , , , , etc.
(24.) (d) Reaction (d) is not possible. The corrected chemical equations is as follows:
C6 H5COOCOCH3 ⎯⎯⎯
H2O
→ C6 H5COOH + CH3COOH
Benzoic ethanoic Benzoic acid ethanoic acid
anhydride
(25.) (c) NaOCl is the reagent ‘X’ present in the given reaction. It is formed inside from Cl 2 and NaOH. The
reaction is haloform reaction.
(26.) (a) Benzoic acid on nitration gives m-nitrobenzoic acid.
(27.) (a) Methanal, ethanal and propanone are miscible with water in all proportions because they form
hydrogen bond with water.
(28.) (b) Aldehydes and ketones undergo electrophilic addition reactions. The carbonyl group being polar
behaves as an electrophile in the presence of nucleophile. Thus, the nucleophile readily attacks the
electrophilic carbon atom of carbonyl group and gives nucleophilic addition reactions.
(29.) (d) During reaction of carboxylic acids with NaHCO3, CO2 evolved comes from NaHCO3. Carboxylic
acid is a stronger acid than carbonic acid.
(30.) (d) As B forms a shining silver mirror on warming with ammoniacal silver nitrate, B must be an aldehyde
which can be obtained by the oxidation of alcohols. The complete series of
CH3CH 2CH 2OH ⎯⎯⎯⎯ K 2 Cr2 O7
H 2SO4
→ CH 3CH 2CHO ⎯⎯⎯⎯⎯
H 2 NCONHNH 2
→ CH 3CH 2CH = NCONHNH 2
(A) ( B) (C)
47
(31.) (b) ‘X’ in the above reaction is Cu2O. Reaction involved is as follows:
RCHO + 2Cu 2+ + 5OH – ⎯⎯ → RCOO– + ‘X’ + 3H 2O
(32.) (a) The IUPAC name is 3-methylcyclopentanone. The substituents are prefixed in alphabetical order
along with numerals indicating their positions in the carbon chain.
(33.) (c) Incorrect statement is (c). Sodium benzoate is used as a food preservative
(34.) (a) The ‘X’ in reaction is CH3 − CH ( OH ) = CH 2CHO 3-hydroxybutanal. It is an aldol reaction.
Complete reaction is an follows:
CH3CH ( OH ) − CH 2CHO ⎯−⎯
dil • NaOH
2CH3 − CHO ⎯
H2O
→ CH3CH = CHCHO
But − 2 − enal
(35.) (c) Amides on hydrolysis produces acids in the presence of H or OH- as catalyst. Reaction involved is
+
as follows:
C6 H5CONH 2 ⎯⎯⎯ H3O +
→ C6 H5COOH + NH 3
Benzamide Benzoic acid
(36.) (d) Benzene carbaldehyde and benzaldehyde is the simplest aromatic aldehyde carrying the aldehyde
group.
(37.) (a) The product formed are HCOOH and CH3COOH. In presence of strong oxidising agent like HNO3
ketones are oxidised to carboxylic acids
CH3COCH3 + 3O ⎯C⎯⎯⎯ onc.HNO3
→ HCOOH + CH3COOH
(38.) (d) Primary alcohols are readily oxidised to carboxylic acids with common oxidising agents such as
potassium permanganate (KMnO4) in neutral, acidic or alkaline media or by potassium dichromate
(K2Cr2O7) and chromium trioxide (CrO3) in acidic media.
(39.) (c) The carbon-oxygen double bond in carbonyls is polarised due to higher electronegativity of oxygen
relative to carbon.
(40.) (b) I → r, II → p, III → s, IV → q
(41.) (b) FCH 2 COOH ClCH 2 COOH C6 H 5CH 2COOH CH 3COOH (acid strength) Reason
• More the electron withdrawing nature of substituent, more is the acidic strength.
• Direct attachment of C6H5 group increases acidity due to resonance and sp2 hybridisation.
• Alcohols are weakly acidic than carboxylic acids.
48
(42.) (a) The intermediate ‘Y’ is C = N − NH 2 . In this reaction, aldehyde or ketone is heated with hydrazine
and KOH in high boiling solvent glycol to give hydrocarbon.
(43.) (a) Boiling points of aldehydes are higher than hydrocarbons. It is due to weak molecular association.
(44.) (a) The reagent involved in the given reaction are CO, HCl, Anhyd. AlCl3/CuCl.
Addition of NaHSO3
Addition of alcohols
Addition of ammonia
(47.) (a) Fehling test is positive with acetaldehyde but no reaction occurs with benzaldehyde.
CH3CHO +Cu 2+ +5OH− ⎯⎯ → CH3COO− + CH2O + 3H2O
The +R effect of phenyl group increases the electron density on the carbon atom of C = O group in
benzaldehyde.
(48.) (c)
(49.) (b) The correct order of acidity is III > II > I. The presence of electron withdrawing group on the phenyl
of aromatic carboxylic acid increases their acidity while electron donating groups decrease their acidity.
(50.) (c) Ais correct but R is incorrect. Aldehydes which contain α–hydrogens undergo aldol condensation.
1. 2)
49
+
2. 1) C6 H5CHCl2 ⎯⎯⎯⎯H / H2O
→ C6 H5CHO + H 2O
3. 3)
4. 2) Transfer of hydride ion to the carbonyl group is the slowest step of the reaction.
5. 3)
6. 3) Open the ring containing oxygen atoms you will get the products.
7. 4)
8. 1)
9. 1)
10. 2)
11. 2)
12. 2) Formyl chloride is unstable at room temperature.
13. (1) Alkanenitriles (other than methanenitrile) benzonitrile give ketones with Grignard reagents.
14. 2)
15. 2)
17. 3)
a)
b) In the reduction of carbonyl group with LiAlH4 or NaBH4, a hydride ion is transferred from the
metal to the carbonyl carbon (nuclephilic addition)
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18. 3)
23. 3)
51
26. (2) Chromic acid and KMnO4 will cleave the molecule at the site of double bond while Cu at 300°C
cannot oxidise COCH3 to COOH. The only reagent suitable for this conversion is NaOI or NaOH + I2
(iodoform test):
( CH3 )2 C = CHCOCH3 ⎯⎯⎯NaOI
→ ( CH3 )2 C = CHCOOH + CHI3
27. 4) Dihydrogen sodium phosphate (NaH2PO4) does not have a lone pair of electrons on the P atom. As
such it cannot act as a nucleophile and hence does not react with aldehydes and ketones.
28. (4) Aldehydes which contain a a -hydrogen on a saturated carbon, i.e., CH3CH2CHO undergo aldol
condensation.
29. (4) LiAlH4/H2O, NaBH4/H2O and Na/C2H5OH will reduce only –CHO
30. (1) In this reaction, one molecule is oxidised and other is reduced simultaneously.
31. (2) O is more electronegative than C.
32. (2) Aldehyde will be more reactive than ketone.
33. 2)
34. 4)
35. 3)
36. 4) The intermediate is carbocation which is destabilised by C = O group in the first three cases. In 4),
– hydrogen is more acidic which can be removed as water. Moreover, the positive charge on the
intermediate carbocation is relatively away from the C = O group.
37. 4)
38. 4) R – CH = O + H2N – NH2 → R – CH = N – NH2 Such reactions take place in slightly acidic medium
and involve nucleophilic addition of the ammonia derivative.
39. 2) It is iodoform reaction. Both give a yellow precipitate of CHI3 (iodoform) with iodine and alkali.
40. 1) Enolic form predominates in compounds containing two carbonyl groups separated by a – CH2 group.
This is due to following two factors.
(i) Presence of conjugation which increases stability.
(ii) Formation of intramolecular hydrogen bond between enolic hydroxyl group and second carbonyl
group which leads to stablisation of the molecule. Hence the correct answer is III > II > I.
41. 2)
52
45. (1) Hydrogen atoms attached C2 are most acidic due to presence of electrons withdrawing groups on
both sides.
46. 3) KMnO4 converts – CH3 group of toluene into – COOH while HI reduces – COOH group into – CH3
group.
47. 2) Alkaline hydrolysis is irreversible because here RCOO– is isolated ; moreover the product RCOO–
stabilizes itself due to resonance.
48. 4)
49. 3)
50. 4)Methyl acetate and ethyl acetate on hydrolysis give CH3COOH which is a liquid. Similarly, ethyl
formate on hydrolysis will give formic acid which is also a liquid. Only ethyl benzoate on hydrolysis
will give benzoic acid which is a solid
51. 3)
53. 4)
54. 1) CH3COOH ⎯⎯⎯ PCl5
→ CH3COCl + HCl
A is PCl5 . It can also be SOCl2
55. 3) CaC2 O 4 is the only compound of Ca which is not soluble in acetic acid. This property of Ca is used in
inorganic salt analysis.
56. 2) X = R − CH− COOH; Y = R − CHCOOH
| |
Br NH2
57. 2) At high temperature, esters containing -hydrogen atom undergo pyrolysis to give ketene and
alcohol.
59. (4) Primary and secondary alkyl groups are oxidised to give carboxylic acid, while tertiary alkyl group
remains unaffected.
53
60. (2) The structure 2) differs in the position of H hence not resonating structure.
61. (2) Grignard reagent forms addition product with bubbled carbon dioxide which on hydrolysis with HCl
yields benzoic acid.
2. 3) Carboxylic acids have higher boiling points than aldehydes, ketones and even alcohols of comparable
molecular mass. This is due to more extensive association through intermolecular H-bonding.
3. 3) Mechanism :
54
4. 3) Hydration of alkynes give ketones.
5. 2) Since 'A' gives positive silver mirror test therefore, it must be an aldehyde of a-Hydroxyketone. Also,
reaction with OH– i.e., aldol condensation (by assuming alkali to be dilute) indicates that A is aldehyde
as aldol reaction of ketones is reversible and carried out in special apparatus. It indicates that A is an
aldehyde
6. 1)
7. 4) Keto-enol tautomerism is possible only in those aldehydes and ketones which have atleast one
ahydrogen atom, which can convert the ketonic group to the enolic group. e.g.
55
8. 1) Schiff base is formed when 1° amine reacts with aldehydes.
9. 2)
does not give iodoform test due to absence of group. It also does not give Tollen’s test.
On reduction it gives n-pentane
10. 4)
11. 4) Enolic form of ethyl acetoacetate has 18 sigma and 2 pi-bonds as shown below:
12. (4) Any substituent in the carbonyl compound that increases the positive charge on the carbonyl carbon
will increase reactivity towards nucleophilic addition. − NO 2 shows – M effect hence
56
14. 1)
15. 1)
CHO+CH3-C-C6H5 CH=CH-CO-C6H5
16.
This is example for cross aldol condensation
17. 4)
18. 3)
57
OH
CH2 C OCH3
CH3
19. 3)a-iv, b-1 c-ii, d-iii
20. 4)
CH 3 CHO
⎯⎯⎯⎯ →
Cr2O2Cl2 +
Cs2 ⎯⎯⎯
H 3O
→
O O MgX
|| | +
21. R − MgX + C → R − C ⎯⎯⎯
H 3O
→ RCOOH
|| ||
O O
58