Cls Jeead-17-18 Xi Che Target-4 Set-2 Chapter-12
Cls Jeead-17-18 Xi Che Target-4 Set-2 Chapter-12
Cls Jeead-17-18 Xi Che Target-4 Set-2 Chapter-12
Solutions
SECTION - A
Objective Type Questions (One option is correct)
1. Compound having molecular formula C5H12O cannot show
(1) Tautomerism (2) Position isomerism
(3) Metamerism (4) Functional isomerism
Sol. Answer (1)
Factual
+ NaHCO3
(1) (2) C C—H + NaOH
H H
O
OH
C
(3) + NaHCO3 (4) OH
+ NaHCO3
O O
O
C H C
O C ONa
+ NaO OH
+ .
O
CO2 + H2O C
HO OH
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56 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
CH3 CH3
CH
CH3
CH3—CH—C—CH
CH3
CH3 CH
CH3 CH3
Me
Et
(1) 3-methyl-6-ethylcyclohexene (2) 6-ethyl-3-methyl cyclohexene
(3) 3-ethyl-6-methyl cyclohexene (4) 6-methyl-3-ethyl cyclohexene
Sol. Answer (3)
Priority of Et is alphabetically higher.
(1) I and II (2) III and IV (3) III and II (4) I and III
Sol. Answer (4)
Conjugate base of nitromethane (CH3—NO2) is stabilized by very strong – I and – M effect of – NO2 group
O O O
H—CH2—N CH2—N CH2—N
O O O
B
Very stable
conjugate base
Conjugate base of CH3—F is only stabilized by – I effect of F atom hence it is less stable and CH3F is
least acidic.
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 57
7. Correct order of acidic strength for the given species
I II III IV
(1) I > II > IV > III (2) II > IV > III > I (3) III > I > IV > II (4) I > III > IV > II
Sol. Answer (4)
CH3—C — CH3—C —
B
— N—H —N
highly unstable More stable
due to presence
of positive charge
on highly en. sp—N
H3C C
H3C
(1) O2N CH2—H (2) CH2—H
H3C
H3C C
H3C
CH3
CH3
C
CH3
(3) CH2—H (4) CH3—H
CH3
C
CH3
CH3
Sol. Answer (3)
CH3
CH3
C
CH3
CH2—H
CH3
C
CH3
CH3
Therefore, indicated C—H bond in (3) is weakest.
OH is least acidic.
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58 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
10. In which of the following all electronic effects namely inductive, mesomeric and hyperconjugative effects are
present?
O
O
CH3
(1) (2) (3) (4)
H3C CH3
O
Sol. Answer (4)
In (1), (2) and (3) hyperconjugate effect is absent.
O O S S O O
(1) (2) (3) (4)
O S O O
17 1
Index of hydrogen deficiency (12 1)
2
= 13 – 8 = 5
14. Which of the following experimental techniques can be used to detect carbon free radicals in a reaction mixture?
(1) Magnetic susceptibility method (2) Polarimetry
(3) NMR-spectroscopy (4) IR-spectroscopy
Sol. Answer (1)
This method indirectly gives some information about the presence of unpaired electrons.
(1) NaOEt NH 2
(1) (2)
Et-OH NO 2
O
SbF5
(3) (4) CH3 — C C — H
NaNH2 /NH3
F
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 59
Sol. Answer (3)
O O
H SbF5 + [SbF6]
–
H NaOEt +
F
O O
NH2
CH3—C C—H CH3—C C
16. Out of the given reactive intermediates which will be attracted towards the magnetic field?
(1) Carbocation (2) Carbanion (3) Carbon free radial (4) Nitrene
Sol. Answer (3)
Carbon free radicals will have unpaired electrons and hence it will be attracted towards the magnetic field.
N
3
sp
H
20. Which of the following is most acidic?
NH2 OH NH2
(1) (2) NH2 (3) CH3 – O – H (4) C
N
H H2N NH2
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60 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
21. Threedimensional arrangements which can be interconverted into one another due to rotation along a single
bond are known as
(1) Conformers (2) Diastereomers (3) Chain isomers (4) Positional isomers
Sol. Answer (1)
Conformers are formed due to rotation about single bond
(1) One atom (2) Three atom (3) Four atom (4) Five atom
Sol. Answer (3)
(2)
– (1)
(3)
(4)
O
23. The compounds and are
O
(1) Chain isomers (2) Metamers (3) Position isomers (4) Both (1) & (2)
Sol. Answer (4)
Both have different carbon chain length.
CH3
H3C – C – CH3 CH3
25. Which of the following compound will give blood red colour while doing the Lassaigne’s test for N?
NH2
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 61
26. The most stable free radical is _________
CH
27. Which of the following group will have the strongest electron donating mesomeric effect?
H
O Me N O
(1) N (2) N (3) C=O (4) O–C
O Me H3C R
(1) CH3 CH CH3 (2) (3) (4)
30. Which of the following double bond in the given molecule is most reactive towards a strong protic acid?
Me A C
Me
B D
Me
(1) A (2) B (3) C (4) D
Sol. Answer (1)
Attack of H+ on double bond (A) gives most stable carbocation.
CH 3
+ CH3
CH3
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62 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
33. Which of the following compounds will have highest enolic content?
O O H
H
Cl Cl Cl
I II III
the correct order of reactivity of chloride is
(1) I > II > III (2) III > II > I (3) II > I > III (4) II > III > I
Sol. Answer (4)
Stability order is
+ + +
(Antiaromatic)
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 63
35. Which of the following represents the correct order of stability of the given carbocations?
CH2
I
II III
(1) III > I > II (2) I > III > II (3) III > II > I (4) II > III > I
Sol. Answer (1)
IIIrd is aromatic (most stable) and IInd is antiaromatic (least stable)
36. Which of the following organic molecule cannot form hydrogen bond in pure state but can form the same in
water?
O
(1) (CH3CH2)2NH (2) CH3CHO (3) CH3CH2COOH (4) CH 3–C –NH 2
CH3 CH3
CH3 CH3
(3) > CH3–C– > CH2 > (CH3)2CH (4) CH2 > CH3–C– > (CH3)2CH >
CH3 CH3
Sol. Answer (2)
Allyl C—H bond has lesser bond dissociation energy than benzylic C—H bond and hence corresponding allyl
free radical is more stable.
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64 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
40. In which of the following molecules positive charge is not delocalized because of resonance?
NH NH2
Me
Me
(1) C (2) (3) C—N (4) C
H3N NH2 Me Me NH2 NH2
Sol. Answer (1)
Nitrogen atom cannot form five bonds due to absence of vacant d-orbitals.
41. Which of the following is correct order of dipole moment of o, m and p-methyl benzonitrile?
CH3 CH3 CH3 CH3 CH3 CH3
CN CN
(1) > > (2) > >
CN CN
CN CN
CH3 CH3 CH3 CH3 CH3 CH3
CN CN
(3) > > (4) > >
CN CN
CN CN
Sol. Answer (2)
CH3– is electron donating group and –CN is electron withdrawing group 12 22 – 212cosθ
42. Which of the following reagents can be used to separate benzoic acid from a mixture of Benzoic acid, Phenol,
Benzaldehyde and Toluene?
(1) aq. HCl (2) aq. NaHCO3 (3) Diethyl ether (4) NaOH
Sol. Answer (2)
When benzoic acid reacts with NaHCO3 it forms water soluble sodium benzoate and hence through extraction.
It can be separated.
43. Which of the following compounds will give negative Lassaigne’s test for Nitrogen?
NO2
NH2 N
(1) (2) N N (3) (4)
44. A mixture contains four solid organic compounds A, B, C and D. On heating, only C changes from solid to vapour
state. The compound (C) can be separated from the mixture by
(1) Distillation (2) Kinetic resolution (3) Crystallization (4) Sublimation
Sol. Answer (4)
Solid is directly converted to vapour.
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 65
46. The number of structural isomers for C6H14 is [IIT-JEE-2007]
(1) 3 (2) 4 (3) 5 (4) 6
Sol. Answer (3)
47. Among the following, the least stable resonance structure is [IIT-JEE-2007]
O O O O
(1) (2) N (3) (4)
N N N
| | | |
O O O O
49. The correct stability order for the following species is [IIT-JEE-2008]
O
(I) (II)
O
(III) (IV)
(1) (II) > (IV) > (I) > (III) (2) (I) > (II) > (III) > (IV) (3) (II) > (I) > (IV) > (III) (4) (I) > (III) > (II) > (IV)
Sol. Answer (4)
I & III are stabilized by resonance, hyperconjugation and + inductive effect.
order is (I) > (III) > (II) > (IV)
OH OH COOH COOH
Cl CH3
(I) (II) (III) (IV)
(1) (III) > (IV) > (II) > (I) (2) (IV) > (III) > (I) > (II) (3) (III) > (II) > (I) > (IV) (4) (II) > (III) > (IV) > (I)
Sol. Answer (1)
COOH COOH OH OH
CH3 Cl
(+I effect) (–I effect)
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66 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
OH
CN
Br
OH
CN
Br
2-Bromo-5 hydroxy benzonitrile.
52. In the following carbocation, H/CH3 that is most likely to migrate to the positively charged carbon is
[IIT-JEE-2009]
H H
1 + 5
2 4
H3C—C —C—C
3
—CH3
HO H CH3
(1) CH3 at C-4 (2) H at C-4 (3) CH3 at C-2 (4) H at C-2
Sol. Answer (4)
H H H H
1 + 5 +
2 4
H3C—C —C—C
3
—CH3 CH3—C—C—C—CH3
53. The correct stability order of the following resonance structures is [IIT-JEE-2009]
– – – –
H2C N N H2 C— N N H2 C— N N H2 C— N N
(I) (II) (III) (IV)
(1) (I) > (II) > (IV) > (III) (2) (I) > (III) > (II) > (IV)
(3) (II) > (I) > (III) > (IV) (4) (III) > (I) > (IV) > (II)
Sol. Answer (2)
Resonating structures having maximum number of covalent bonds are more contributing. Among
charge separated resonating structures, structures where opposite charge are close enough are more
contributing.
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 67
54. Among the following compounds, the most acidic is [IIT-JEE-2011]
(1) p-nitrophenol (2) p-hydroxybenzoic acid
(3) o-hydroxybenzoic acid (4) p-toluic acid
Sol. Answer (3)
O H O
–
C C
O –H O
H H
O O
Most acidic Stabilized by strong
intramolecular hydrogen
bonding
55. In allene (C3H4), the type(s) of hybridisation of the carbon atoms is (are) [IIT-JEE-2012]
(1) sp and sp3 (2) sp and sp2 (3) Only sp2 (4) sp2 and sp3
Sol. Answer (2)
H (sp) H
C=C=C
H H
(sp2) (sp2)
(Allene)
H3C NH2 N NH HN N
H2N NH
I II III IV
(1) IV > I > II > III (2) IV > II > III > I (3) I > IV > III > II (4) II > I > IV > III
Sol. Answer (1)
NH2
H2N NH
IV
Resonance with two NH2 groups increases electron density on 'N' of NH
NH
Lesser increase of electron density on = NH due to
only one resonance with one –NH2
CH3 NH2
sp2
N
–
N This LPe is not available as it is involve in aromatic Sextet.
H 'N' is bonded to sp2 C on both sides.
III
N
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68 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
SECTION - B
Objective Type Questions (More than one options are correct)
1. Which of the following bicyclic compounds are isomers?
CH3
+ BuLi
(3) CH3—C—OH H (4)
CH3
Sol. Answer (1, 2)
O O O
h
Ph—C—O—O—C—Ph 2Ph—C—O
h
R—O—Cl R—O + Cl
3. Species which will exhibit geometrical isomerism among the following is/are
T D
CH3
H
C C C N—OH
(1) (2) Br (3) (4) N2H2
H 3C
H Me
Sol. Answer (1, 3, 4)
4. Which of the following molecular formula will exhibit functional isomerism as well as metamerism?
(1) C4H10O (2) C4H11N (3) C4H8O (4) C4H9Cl
Sol. Answer (1, 2, 3)
For molecular formula C4H11N only saturated amines are possible (1°, 2° & 3° amines are functional isomers)
Molecular formula C4H9Cl only represents saturated alkyl chloride. Therefore metamerism is not possible.
5. Out of the given isomeric hydrocarbons which will undergoes rearrangement reaction in acidic medium?
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 69
Sol. Answer (2, 3)
+H
(1)
Stable tertiary
carbocation
+H
(2)
Stable tertiary
carbocation
(No rearrangement
possible)
CH3
CH2
(1) CH3 — C — C — O (2) (3) — CH (4)
CH3 CH3
Sol. Answer (1, 3, 4)
CH3 CH 3
+
CH3—C + CO
+
CH3—C—C = O
CH3 CH 3
+
CH—CH3 +
CH3
+ +
CH2
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70 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
9. Which of the following will have C O bond length almost similar to C — O bond length?
O O
O
(1) (2) (3) (4) O C O
CH2
(3) HC C H2 C CH CH3 CH2 (4)
Me Me
Sol. Answer (1, 2, 4)
In CH3 and there is no hydrogen
+
In CH2 , stability is due to overlapping of p-orbital
14. Which of the following correctly represents the order of quality mentioned in bracket?
(1) sp – sp > sp2 – sp2 > sp3 – sp3 (bond energy) (2) sp – sp3 > sp – sp2 > sp – sp (polarity in bond)
(3) sp3 – s < sp2 – s < sp – s (% s character) (4) sp3 – sp3 > sp2 – sp2 > sp – sp (bond stability)
Sol. Answer (1, 2, 3)
sp, sp2 & sp3 have 50%, 33% and 25% s-character.
N N
H NH2
(I) (II) (III)
OH OH
NO2
CCl3 is more stable than CF3– due to presence of d-orbital in CCl3 hence CHCl3 is more acidic than CFCl3.
17. Which of the following correctly represents the stability of reactive intermediate?
+
(1) CH3–CH2 < CH3OCH2 (2)
CH2 CH2
CH3
(3) > (4) CH3–CH3–C < CH3CH2
CH3
NO2 CH3
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72 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
O O H
H 2N H NH2
20. Which of the following can exhibit geometrical isomerism?
H H
(1) C6H5CH = N – OH (2) (3) (CH3)2C = C(CH3)2 (4)
Me Me
Sol. Answer (1, 4)
Ph OH Ph
C N and C N
H H OH
Geometrical isomers
H H H Me
and
Me Me Me H
Geometrical isomers
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 73
Sol. Answer (1, 2, 3)
OH– cannot neutrallise CH3—C CH, NH3 and C2H5OH due to their very low acidic strength (weaker acids
than H2O)
O
CH—C—NH
3 2 N N CH3 — C N
sp2 sp
sp 2
sp2 H
23. Which of the following Lewis structures are valid resonating structures for the azide ion?
N
–
(1) N—N—N (2) N N N (3) N N N (4)
N N
N
N N Invalid structure because position N atom is changing as well as no. of -electrons are also
changing.
24. In the given compound the hybridisation states of C atom is/are not
25. In Lassaigne’s test, the sodium extract of an organic compound containing both N and S on treatment with FeCl3
solution produces a blood-red colour. The appearance of this blood red colour is due to
(1) [Fe(SCN)4]– (2) FeCl2(SCN) (3) [Fe(SCN)(H2O)5]2+ (4) Na4[Fe(CN)5NOS]
Sol. Answer (1, 2, 3)
All of three are possible and (4) is Prussian blue coloured
26. Amongst the given options the compound(s) in which all the atoms are in one plane in all the possible
conformations (if any), is(are) [IIT-JEE-2011]
H H H
(1) C—C (2) H—C C—C (3) H2C = C = O (4) H2C = C = CH2
H 2C CH2 CH2
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74 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
H
H
C C H
H C C
H H
Non-planar in many conformations due to rotation along.
C2 — C3 bond.
27. Which of the following molecules, in pure form, is (are) unstable at room temperature? [IIT-JEE-2012]
O
O
The compound is antiaromatic and hence unstable at room temperature. The other compound
–
O O
+
is also unstable at room temperature due to partial positive charge at carbonyl C-atom
Cl
AlCl3
P
NaH
Q
(NH4)2CO3
R
100-115 °C
OO
O
HCl
S
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 75
Sol. Answer (1, 2, 3, 4)
AlCl3
Cl AlCl4 (P)
(i)
(AROMATIC)
Na
NaH
(Q) + H2
(ii)
(AROMATIC)
(NH4)2CO3
R
(iii) 100–115ºC
O O
(NH4)2CO3 2NH3 + CO2 + H2O
IMPE
+ NH3
O O O O NH2 O NH2 OH
H
H H H H
N N N
IMPE
–2H2O
HO OH O OH
(R) AROMATIC
HCl
(iv) O OH Cl (S)
(AROMATIC)
29. The hyperconjugative stabilities of tert-butyl cation and 2-butene, respectively, are due to [IIT-JEE-2013]
(1) p (empty) and electron delocalisations
(2) * and electron delocalisations
(3) p (filled) and electron delocalisations
(4) p (filled) and electron delocalisations
Sol. Answer (1)
In hyperconjugation p (empty) electron delocalization for tert-butyl carbocation and * electron
delocalization for 2-butene will take place.
30. The correct combination of names for isomeric alcohols with molecular formula C4H10O is/are
[JEE(Advanced)-2014]
(1) Tert-butanol and 2-methylpropan-2-ol
(2) Tert-butanol and 1, 1-dimethylethan-1-ol
(3) n-butanol and butan-1-ol
(4) Isobutyl alcohol and 2-methylpropan-1-ol
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76 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
H3C Cl
Cl CH3
1 1
2 2
(1) (2) 4-chlorotoluene
1-chloro-4-methylbenzene 3
3
4 4
CH3 Cl
SECTION - C
Linked Comprehension Type Questions
Comprehension-I
Tautomerism, strictly defined could be used to describe the reversible interconversion of isomers. Interconversion
of isomers is due to mobility of an atom or a group.
R R
R—HC—C O R—CH C—O
H H
In the above examples the composition of the equilibrium mixture is of course, governed by the relative
thermodynamic stability of the two forms under the particular conditions being studied.
1. In which of the following tautomeric equilibrium concentration of right hand product is more than left hand
product?
H
O O
O O CH3 O
(1) CH3—N CH2—N (2)
O O—H H3C O H2C OH
O OH O
O OH O
(3) (4) C
EtO OEt EtO OEt
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 77
Sol. Answer (3)
In dienone phenol tautomerism phenol form is more stable due to its aromatic character.
O O
H
H
More stable
2. In which of the following solvent percentage enol content is maximum for 2,4-pentanedione?
(1) CH3CN (2) H2O (3) n-Hexane (4) Ethanol
Sol. Answer (3)
In non-polar solvent enol content would be maximum
Comprehension-II
Names of organic compounds are under the latest guide line of IUPAC. IUPAC means international union of
pure and applied chemistry. The main rules are longest chain rule, lowest number rule etc. We have to include
the rules for naming the substituents, multiple bonds and even functional groups.
CN
CN
(1) 3,3-Diethenyl pentane1,5-dinitrile (2) 3,ethenyl,3-ethyl pentane 1,5-dinitrile
(3) 3,3-diethenyl pentane 1,5-dicyanide (4) None of these
Sol. Answer (1)
(4)
(5)
CN
(3)
(2)
CN
(1)
OH
2. , IUPAC name is
OH
(1) 3,3-diethenyl pentane 1,5-diol (2) 2,2-diethenyl propane 1,3-diol
(3) 2, 3-diethenyl propane 1,3-diol (4) 3,3-diethenyl propane 1,3-dialcohol
Sol. Answer (2)
(3)
(2) OH
(1)
OH
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78 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
Comprehension-III
Weak Acid does not dissociate completely into its ions. It is in equilibrium with its conjugate base. Greater is the
K
stability of conjugate base, greater is value of k for that equilibrium making the equilibrium move in (HA a H++A–)
forward direction. i.e., more is the degree of dissociation of that acid. Same is the case for weak bases. Factors
affecting the stability of conjugate acid or base are electronic effect like resonance effect and inductive effect acting
upon the species.
OH OH OH OH
CH3
(1) (2) (3) (4)
CH3
CH3
Sol. Answer (1)
Alkyl group (electron donor) decreases acidic strength of phenol
2. Which of the following is having most acidic -Hydrogen?
O
(1) CH3—NO2 (2) CH2 NO2 (3) NO2 CH NO2 (4)
NO2 NO2
Sol. Answer (3) O
H
NO2
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 79
3. Which of the following is most basic due to +R effect of any substituent?
NH2 NH2
..
(1) N (2) .. (3) (4)
N OCH3
H
CH3 OCH3
Sol. Answer (4)
+R effect of –OCH3 predominates over –I effect
Comprehension-IV
Hyperconjugation is defined as No bond resonance. The concept of hyperconjugation arose from the discovery
of electron releasing pattern for alkyl groups. It involves electrons of C–H bond. Greater the number of C–H
bond ( -hydrogen atom w.r.t. double bond) more will be hyperconjugative structures, more will be stability. Heat
of hydrogenation of alkene are affected by hyperconjugative effects.
H H H H
H C H H C H H C H H C H
SECTION - D
Assertion-Reason Type Questions
1. STATEMENT-1 : In naphthalene all C—C bonds are equal.
Naphthalene
and
STATEMENT-2 : Like benzene naphthalene is also aromatic.
Sol. Answer (4)
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80 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
HO O OH
and
STATEMENT-2 : Conjugate base of phenol is resonance stabilized.
Sol. Answer (4)
Infact squaric acid is more acidic than phenol.
Br
5. STATEMENT-1 : When is treated with excess of Ag+ ion. One mole of the compound reacts
Br
Br
Br
(X)
6. STATEMENT-1 : A compound with odd number of nitrogen always contains odd molecular weight.
and
STATEMENT-2 : Nitrogen has odd molecular mass.
Sol. Answer (3)
Molecular mass of nitrogen is 14.
7. STATEMENT-1 : Aldehydes and ketones having same molecular formulae are structural isomers.
and
STATEMENT-2 : Aldehydes and ketones are metamers.
Sol. Answer (3)
Aldehydes and ketones cannot be metamers.
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 81
8. STATEMENT-1 : Carbocationic rearrangement is known as electrophilic rearrangement.
and
STATEMENT-2 : Carbocations are stabilized by both hyperconjugation and +I effect.
Sol. Answer (4)
Carbocationic rearrangement is known as nucleophilic rearrangement.
Tautomers
10. STATEMENT-1 : CH3 CH2 CH2 is less stable than CH3 – N – CH2
|
H
and
STATEMENT-2 : Carbocation with adjacent hetero-atom like N, O are less stable.
Sol. Answer (3)
If ‘N’ or ‘O’ are attached to carbocation. These groups participate in the delocalization of +ve charge.
1
Angle strain of cyclic compound.
stability
O
||
12. STATEMENT-1 : Keto form is less stable than enol form.
O
||
and
STATEMENT-2 : Enol form is stabilized by aromaticity.
Sol. Answer (1)
O OH
O
OH
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82 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
13. STATEMENT-1 : Aniline undergoes Friedel-Craft alkylation more readily than Toluene.
and
STATEMENT-2 : Aniline undergoes fast electrophilic substitution than Toluene.
Sol. Answer (4)
Aniline does not follow Friedel-Craft reaction.
14. STATEMENT-1 : Bridge head carbocation is less stable than Bridge head carbanion.
and
STATEMENT-2 : C atom in carbocation is sp2 generally hybridized.
Sol. Answer (2)
Carbocation and carbanion are generally sp2 and sp3 hybridised
SECTION - E
Matrix-Match Type Questions
1. Match the following
Column-I Column-II
(Molecular formula) (Type of isomerism)
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 83
3. Match the following
Column-I Column-II
(Estimation) (Percentage)
(A) 0.45 gm organic compound gives 1.1 gm (p) 66.6% C
CO2 and 0.3 gm H2O 7.4% H
(B) C : H : N ratio in compound 18 : 2 : 7 (q) 26% N
(C) 0.37 gm of a given compound gave 0.631 gm AgBr (r) Equivalent mass of acid is 122
(D) 0.122 gm of an organic acid required (s) 72.6% Br
N
10 cm3 NaOH for neutralisation
10
Sol. Answer A(p), B(p, q), C(s), D(s)
12 Mass of CO2
(A) Percentage of C = 44 Mass of organic compound 100
12 1.10
100 66.6%
44 0.45
2 Mass of H2 O
Percentage of H = 18 Mass of compound 100
2 0.3
100 7.4%
18 0.45
18
(B) Percentage of C = 100
66.66%
27
2
Percentage of H = 100
7.40%
27
7
Percentage of N = 100
26%
27
80 Mass of AgBr
(C) Percentage of Br = 188 Mass of compound 100
80 0.631
100
72.6
188 0.37
N
(D) 10 cm3 of alkali required acid = 0.122 g
10
0.122
1000 cm3 of 1 N alkali required acid = 1000 10
10
= 122 g
But 1000 cm3 of 1 N alkali contain 1 gm equivalent of the alkali which must react with 1 gm equivalent
of acid.
Equivalent weight of acid = 122
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84 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
4. Match the carbocation in column-I with the effect which is major, stabilizing factor for it in column-II
Column-I Column-II
5. Match the carbocation in column-I with the effect which is major, stabilizing factor for it in column-II
Column-I Column-II
+
CH3 CH has 6 –H for hyperconjugation and 2 methyl groups for + I effect
CH3
+
is aromatic resonance stabilised cation
CH3 –O– CH2 is resonance stabilised because it can form CH3 – O CH2
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 85
6. Match the following
Column-I Column-II
+
(A) (p) Resonance stabilisation
O
CH3
7. Match the compounds in Column I with their characteristic test(s)/reaction(s) given in Column II.
[IIT-JEE-2008]
Column I Column II
(A) H2N—NH3Cl (p) Sodium fusion extract of the compound gives Prussian blue
colour with FeSO4
NH3l
(B) HO (q) Gives positive FeCI3 test
COOH
(C) HO NH3Cl (r) Gives white precipitate with AgNO3
(D) O2N NH—NH3Br (s) Reacts with aldehydes to form the corresponding
NO2
hydrazone derivative
Sol. Answer A(r, s); B(p, q); C(p, q, r), D(p)
SECTION - F
Integer Answer Type Questions
1. One mole of a compound with molecular formula C30H43N absorbs 8 moles of H2 gas under catalytic
hydrogenation. Then what is the ratio of number of bonds to the number of rings in the compound?
Sol. Answer (4)
43 1
Degrees of unsaturation in the compound = 31 = 31 – 21 = 10
2
Out of which 8 bonds are present
bond 8
Hence 4
ring 2
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86 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
2.
How many intermediates are possible (excluding stereoisomer) when above mentioned molecule is attacked
by 1 equivalent H+?
Sol. Answer (6)
F F F F
Hence positive charge is delocalized over four atoms.
5. How many bicyclic isomers are possible for the molecular formula C6H12O?
Sol. Answer (0)
Index of hydrogen deficiency is 1.
Bicyclic system is not possible for this.
6. How many of the given species will evolve CO2 with NaHCO3?
OH OH OH
HO O O CH CH2
O2N NO2 O OH OH
, , , , H
,
O
HO HO OH
NO2
O O OH OH
NO2 NO2
, , , ,
O
O NO2
Sol. Answers (3)
Trinitrophenol, squaric acid and Vth product can give CO2 with NaHCO3.
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 87
8. The total number of structural dihaloderivatives possible in n-pentane are ____.
Sol. Answer (9)
(1, 1), (1, 2), (1, 3), (1, 4), (1, 5), (2, 2), (2, 3), (2, 4), (3, 3)
Dihaloderivatives are nine different compounds.
9. Amongst the following, the total number of compounds soluble in aqueous NaOH is [IIT-JEE-2010]
H3C CH3
N COOH OCH2CH3 OH
CH2OH
N
H3C CH3
COOH OH OH COOH
, , ,
N
H3C CH3
10. The total number of contributing structures showing hyperconjugation (involving C-H bonds) for the following
carbocation is [IIT-JEE-2011]
H3C CH2CH3
+
HC
3 CHCH
2 3
+
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88 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
11. The total number of cyclic isomers possible for a hydrocarbon with the molecular formula C4H6 is
[IIT-JEE-2010]
Sol. Answer (5)
Index of hydrogen deficiency in the compound C4H6 is 2. Therefore either bicyclic compound or cycloalkenes
are possible as cyclic isomers.
Possible isomers are
, , , ,
OH O
NaOH
–H2O
O O O O
II III IV V
O O O
III VI VII
O O
VIII IX
+ + +
+
and are non-aromatic while and are antiaromatic compounds.
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 89
SECTION - G
Multiple True-False Type Questions
1. STATEMENT-1 : Phenol is more acidic than benzoic acid.
Phenol is less acidic than benzoic acid due to less stability of C6H5O– than C6H5COO–. Fluorobenzene is
more reactive than chlorobenzene.
O
2. STATEMENT-1 : CH3 O CH2 is more stable than O N CH2 .
..
In CH3 O
.. CH2 , resonance is effective. + – is aromatic (10 e–). Phenoxide is resonance
stabilised.
SECTION - H
Aakash Challengers Questions
1. Rank the given species in the increasing order of water solubility?
OH OHC HO
OH CHO CHO OH
I II III IV
Increasing solubility
in water
Greater the number of intermolecular hydrogen bond with solvent molecule higher the solubility.
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90 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
2. The given six compounds are similarly sized, very similar molecular weight and number of electrons, but the
boiling point of these compounds are quite different (30°C–141°C). Rank these compounds in the increasing
order of boiling point (lowest boiling first)
OH O O NH2
N
I II III
OH
IV V VI
Strongest hydrogen bond is present in III. While weakest intermolecular force of attraction is present in VI.
3. For the given pair of compounds, identify the compound you expect to have the higher boiling point and explain
your reasoning.
N — H and NH2
Sol. NH2
I II
+ In triphenyl methyl carbocation positive charge can be delocalized in all the 3 ring systems
C
causing the lowering of energy and making the carbocation very stable.
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 91
Sol.
H
CH2OH CH2 O CH2
H+ H
(H2O being a rearrangement
good leaving of carbocation
group)
CH2 elimination
of H
CH3
CH3
CH2 – OH + CH2
H
Ring expansion
Hydride shift
CH3
-H elimination
OCH3 OCH3
NH2
or
NH2
OCH3
NH2
Sol. is less stable, as a methoxyl group has negative (electron-withdrawing) inductive effect so
OCH3
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92 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
NH2
8. Aromatic amines are weakly basic, whereas is strongly basic, explain this unusual behaviour.
Sol. Planarity between lone pair of nitrogen and electron of ring is lost due to two bulky groups on ortho position.
H; ; ;
I II III IV
Sol. Only III can be deprotonated by NaOEt as its conjugate base is aromatic.
10. Pick out the correct statements about the barrier of rotation about the indicated bond in the given compounds.
I II III IV
I II III IV
(1) II < I < IV < III (2) IV < III < I < II (3) II < I < III < IV (4) III < IV < II < I
Sol. Answer (3)
Stronger acids have more stable conjugate base.
–H
Least acidic
Lesser delocalization
of negative charge,
hence least stable
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 93
12. Order of basicity of the following species is
N N
N N
N
N
H N N
H
I II III IV
(1) I > II > IV > III (2) III > IV > II > I (3) IV > III > I > II (4) II > I > III > IV
Sol. Answer (4)
Conjugate acids of I and II are stabilized by resonance.
OMe O—Me
Me Me
N N CH2
Me CH2 Me
(I) (II)
O—Me OMe
Me Me
N CH2 N CH2
Me Me
(IV) (III)
(1) I < III < IV < II (2) I < IV < III < II (3) I < IV < II < III (4) IV < I < II < III
Sol. Answer (3)
More number of covalent bonds more contributing structures.
14. What would be the major product of the given reaction? Justify mechanistically for the formation of your product?
H2SO4
CH2—OH
Sol. Alcohols in the presence of H+ will result into formation of carbocation which will result into the formation of
more stable carbocation.
HNO3
NO2
Sol. HNO3 generates NO 2 ion through self ionization which attacks on aromatic ring to give the desired product.
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94 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
D D D D
(1) and are identical compounds
D D D D
(2) and are structural isomers
D D
D D
(3) and are identical compounds
D D
D D
(4) and are structural isomers
17. Species in which all C—C bonds are not equal is/are
18. Consider the following equilibrium between two conformers of methyl cyclohexane
Me
Keq
Me
Me at axial Me at equatorial
position position
What is the percentage of axial conformer if the equilibrium constant for the given equilibrium is 18?
Sol. Answer (5)
[Equatorial conformer] 18
K
[Axial conformer] 1
[Equatorial conformer] 18
Percentage equatorial conformer
100 100 = 95%
[Equatorial] [Axial conformer] 18 1
Percentage axial conformer = 5%
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Solutions of Assignment (Set-2) Organic Chemistry : Some Basic Principles and Techniques 95
19. Most stable carbocation among the following is
I II
III IV
20. For which of the following compound tautomerization reaction is very slow?
O—H O O—H O
(1) C C (2) C C
F2C CH3 HF2C CH3 H2C CH3 H3C CH3
O O
(3) (4)
H
O O
O O
Sol. Answer (1) H
In case of highly fluorinated enols the enol form is less stable than keto form. Yet enol form can be kept at
room temperature for long periods of time because the tautomerization reaction is very slow.
22. A solution of the sodium salt of diphenyl methane, Ph2CHNa in diethyl ether is orange, due to absorption of
light in the blue region by the delocalized diphenyl methide ion, when colorless triphenyl methane is added,
the color changes to red. Explain this result. Would you expect the addition of diphenyl methane to the sodium
salt of triphenyl methane, in diethyl ether to result in a change in color from red to orange? Give explanation.
Sol. Ph2CHNa Ph3 CH
Ph2CH2 Ph3 CNa
H H
H
Correct statement about the above equilibrium is
(1) This interconversion is an intermolecular process (2) It is an intramolecular process
(3) Interconversion involves carbanion intermediate (4) Interconversion involves carbocation intermediate
Sol. Answer (2)
In the given example neither carbanion is formed nor carbocations is formed.
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96 Organic Chemistry : Some Basic Principles and Techniques Solutions of Assignment (Set-2)
24. Most stable and least stable species respectively among the following are
O
O O
S S
S O S S
O O
O O
I II III IV
O O O O
NH3 H—C CH3—S—OH
O—H HH
O
I II III IV
(1) II > I > III > IV (2) IV > II > I > III (3) III > IV > II > I (4) II > IV > I > III
Sol. Answer (2)
IV > II > I > III
Decreasing acidic strength
CH—CH2 OH OH
O
O
OH OH
(1) (2) H (3) (4)
HO OH
Sol. Answer (2, 3, 4)
Except naphthalene all three compounds can trap free radicals due to presence of oxygen.
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