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), MEDICAL
+ BOARD, NDA, X & IX
Chapter 21
S
HI S S
Principles and Techniques
SE
NC L K’
Solutions
LI
A
SECTION - A
ON A
Objective Type Questions (One option is correct)
C
1. Compound having molecular formula C5H12O cannot show
M
(1) Tautomerism (2) Position isomerism
(3) Metamerism (4) Functional isomerism
Sol. Answer (1)
Factual
.
RA
+ NaHCO3
WT
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
CH3 CH3
CH
CH3
CH3—CH—C—CH
CH3
CH3 CH
CH3 CH3
S
HI S S
(1) 3-diisopropyl-2,4-dimethylpentane (2) 2, 4-dimethyl-3-diisopropylbutane
SE
NC L K’
(3) 2, 4-dimethyl-3-3-bis(1-methylethyl) pentane (4) None of these
Sol. Answer (3)
5 carbon in longest chain
4.
LI
At conjugated position – NO imparts
A
(1) + M and + I effect (2) – M and – I effect (3) + M and – I effect (4) – M and + I effect
Sol. Answer (2)
O (delocalization of p of double bonded N is difficult)
ON A
–N
C Me
M
Et
.
(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.
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
S
HI S S
highly unstable More stable
due to presence
SE
of positive charge
NC L K’
on highly en. sp—N
LI H
(2) OH (3)
OH
(4)
A
HO OH
Sol. Answer (3)
H
ON A
C OH is least acidic.
M
H3C C
H3C
(1) O2N CH2—H
NE K
(2) CH2—H
H3C
RA
WT
H3C C
H3C
CH3
R.
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.
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
S
O
HI S S
Sol. Answer (4)
SE
In (1), (2) and (3) hyperconjugate effect is absent.
NC L K’
11. Most acidic species among the following is
O O S S O O
(1)
LI O
(2)
S
(3)
O O
(4)
A
Sol. Answer (2)
Because its conjugate base is stabilized by p-d back bonding.
ON A
12. What is the index of hydrogen deficiency in the molecule C12H17NO?
C
(1) 4 (2) 5 (3) 6 (4) 7
M
Sol. Answer (2)
17 1
Index of hydrogen deficiency (12 1)
2
.
= 13 – 8 = 5
NE K
bond
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
O O
H SbF5 + [SbF6]
–
H NaOEt +
F
O O
NH2
CH3—C C—H CH3—C C
S
HI S S
16. Out of the given reactive intermediates which will be attracted towards the magnetic field?
SE
(1) Carbocation (2) Carbanion (3) Carbon free radial (4) Nitrene
NC L K’
Sol. Answer (3)
Carbon free radicals will have unpaired electrons and hence it will be attracted towards the magnetic field.
(1)
LI (2) (3) (4)
A
Sol. Answer (3)
Due to symmetrical structure neopentane will have most efficient stacking and hence highest melting point.
ON A
C
18. Which of the following species cannot behave as electrophile?
M
(1) BCl3 (2) AlCl3 (3) NH4+ (4) SO3
Sol. Answer (3)
NH4 does not have vacant orbital of appropriate energy.
.
RA
N
R.
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
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
S
HI S S
SE
NC L K’
(1) One atom (2) Three atom (3) Four atom (4) Five atom
Sol. Answer (3)
(2)
(3)
LI – (1)
A
(4)
ON A
O
C
M
23. The compounds and are
O
(1) Chain isomers (2) Metamers (3) Position isomers (4) Both (1) & (2)
Sol. Answer (4)
.
CH3
H3C – C – CH3 CH3
R.
25. Which of the following compound will give blood red colour while doing the Lassaigne’s test for N?
NH2
CH
S
HI S S
27. Which of the following group will have the strongest electron donating mesomeric effect?
SE
H
NC L K’
O Me N O
(1) N (2) N (3) C=O (4) O–C
O Me H3C R
LI
Electron donating mesomeric effect of a group depends upon size, electronegativity and lone pair availability
A
of key atom.
is an aromatic cation.
NE K
RA
O
(1) CH3 – C – CH3 (2) CH3 – O – H (3) CH3 – C C – H (4) H
R.
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
S
is most acidic because it generates most stable aromatic conjugate base.
HI S S
SE
32. Resonance is not possible in
NC L K’
(1) (2) NH3 (3) NO2 (4) BH2
O
LI
Nitrogen cannot form five bonds due to absence of vacant low energy d orbital
A
33. Which of the following compounds will have highest enolic content?
ON A
O
C
M
(1) (2) CH3COCH2CHO (3) CH3CHO (4) CH3COCH3
O O H
NE K
H
RA
WT
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)
CH2
I
II III
S
(1) III > I > II (2) I > III > II (3) III > II > I (4) II > III > I
HI S S
Sol. Answer (1)
IIIrd is aromatic (most stable) and IInd is antiaromatic (least stable)
SE
NC L K’
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
LI
Sol. Answer (2)
A
H 3C H
C = O ----- H — O
H
ON A
C
37. Correct stability order of the given free radicals is
M
CH3 CH3
(1) CH2 > > CH3— C > (CH3)2CH (2) > CH2 > CH3–C– > (CH3)2CH
CH3 CH3
.
CH3 CH3
NE K
> CH3–C– > CH2 > (CH3)2CH CH2 > CH3–C– > (CH3)2CH >
RA
(3) (4)
WT
CH3 CH3
Sol. Answer (2)
R.
Allyl C—H bond has lesser bond dissociation energy than benzylic C—H bond and hence corresponding allyl
free radical is more stable.
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.
S
41. Which of the following is correct order of dipole moment of o, m and p-methyl benzonitrile?
HI S S
CH3 CH3 CH3 CH3 CH3 CH3
SE
CN CN
NC L K’
(1) > > (2) > >
CN CN
CN CN
CH3 CH3 CH3 CH3 CH3 CH3
LI CN
> >
CN
A
(3) (4) > >
CN CN
CN CN
ON A
Sol. Answer (2)
C
CH3– is electron donating group and –CN is electron withdrawing group 12 22 – 212cosθ
M
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
.
RA
It can be separated.
WT
43. Which of the following compounds will give negative Lassaigne’s test for Nitrogen?
NO2
N
R.
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.
S
HI S S
Hyperconjugation involves -p conjugation.
SE
NC L K’
48. 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
LI
Sol. Answer (1)
A
49. The correct stability order for the following species is [IIT-JEE-2008]
ON A
O
C (I) (II)
M
O
(III) (IV)
.
(1) (II) > (IV) > (I) > (III) (2) (I) > (II) > (III) > (IV) (3) (II) > (I) > (IV) > (III) (4) (I) > (III) > (II) > (IV)
NE K
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)
OH
CN
Br
S
HI S S
(3) 2-Cyano-4-hydroxybromobenzene (4) 6-Bromo-3-hydroxybenzonitrile
SE
Sol. Answer (2)
NC L K’
OH
LI CN
A
Br
2-Bromo-5 hydroxy benzonitrile.
ON A
52. In the following carbocation, H/CH3 that is most likely to migrate to the positively charged carbon is
C [IIT-JEE-2009]
M
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
NE K
H H H H
1 + 5 +
2 4
H3C—C —C—C —CH3 CH3—C—C—C—CH3
R.
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.
S
H H
HI S S
O O
Most acidic Stabilized by strong
SE
intramolecular hydrogen
NC L K’
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
LI
Sol. Answer (2)
A
H (sp) H
C=C=C
H H
(sp2) (sp2)
ON A
(Allene)
C
M
SECTION - B
Objective Type Questions (More than one options are correct)
1. Which of the following bicyclic compounds are isomers?
.
NE K
RA
All of them have same molecular formula hence, they 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
S
HI S S
Sol. Answer (1, 3, 4)
SE
NC L K’
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)
LI
Molecular formula C4H9Cl only represents saturated alkyl chloride. Therefore metamerism is not possible.
A
5. Out of the given isomeric hydrocarbons which will undergoes rearrangement reaction in acidic medium?
ON A
(1) (2) (3) (4)
C
M
Sol. Answer (2, 3)
+H
(1)
Stable tertiary
.
carbocation
NE K
RA
+H
WT
(2)
Stable tertiary
carbocation
(No rearrangement
R.
possible)
CH2
CH 3
(1) CH2 CH — CH2 (2) C (3) C (4)
CH 3
CH3
CH2
(1) CH3 — C — C — O (2) (3) — CH (4)
CH3 CH3
CH3 CH 3
+
CH3—C + CO
+
CH3—C—C = O
CH3 CH 3
S
CH—CH3 +
HI S S
CH3
SE
NC L K’
+ +
CH2
LI
A
8. Formic acid is more acidic than
(1) Benzoic acid (2) Acetic acid
ON A
(3) Phenol (4) Benzene sulphonic acid
C
Sol. Answer (1, 2, 3)
M
In benzoic acid +R effect of benzene in acetic acid. +I effect of CH3–group and in phenol formation of less
stable resonating structures makes formic acid more acidic.
9. Which of the following will have C O bond length almost similar to C — O bond length?
.
O O
O
(4) O C O
NE K
+ +
CH2
(3) HC C H2 C CH CH3 CH2 (4)
Me Me
Sol. Answer (1, 2, 4)
S
In CH and + there is no hydrogen
3
HI S S
SE
NC L K’
+
In CH2 , stability is due to overlapping of p-orbital
LI
(1) Geometrical isomerism (2) Position isomerism (3) Metamerism (4) Chain isomerism
A
Sol. Answer (1, 2)
Cl
ON A
Cl – CH = CH – Cl can show geometrical isomerism and CH 2 CH is its position isomer
C Cl
M
13. A compound having molecular formula C4H10O can show
(1) Metamerism (2) Functional isomerism (3) Chain isomerism (4) Position isomerism
.
RA
14. Which of the following correctly represents the order of quality mentioned in bracket?
WT
(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)
R.
sp, sp2 & sp3 have 50%, 33% and 25% s-character
N N
H NH2
(I) (II) (III)
(1) I is more basic than II (2) II is more basic than I and III
(3) III is more basic than II (4) I is weakly acidic
Sol. Answer (2, 4)
Due to higher Kb for II, it is more basic than I and II
NO2
Sol. Answer (1, 2, 3, 4)
S
HI S S
CCl3 is more stable than CF3– due to presence of d-orbital in CCl3 hence CHCl3 is more acidic than CFCl3.
SE
NC L K’
17. Which of the following correctly represents the stability of reactive intermediate?
+
(1) CH3–CH2 < CH3OCH2 (2)
CH2 CH2
LI CH3
A
(3) > (4) CH3–CH3–C < CH3CH2
CH3
NO2 CH3
ON A
Sol. Answer (1, 2, 3)
C
M
CH3 —O— CH2 is a resonance stabilized carbocation.
|
RA
NH2
WT
O O H
H 2N H NH2
Ph OH Ph
C N and C N
S
HI S S
H H OH
SE
Geometrical isomers
NC L K’
H H H Me
and
Me Me Me H
LI Geometrical isomers
A
21. The compounds which cannot react with NaOH is/are
ON A
OH
C
M
(1) CH3 C CH (2) NH3 (3) C2H5OH (4)
than H2O)
RA
(1) sp3 in acetamide (2) sp2 in pyridine (3) sp2 in pyrrole (4) sp in methyl cyanide
WT
O
R.
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
Sol. Answer (1, 3)
2
N N N
Invalid resonating structure because of extension of octet around 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
S
25. In Lassaigne’s test, the sodium extract of an organic compound containing both N and S on treatment with FeCl3
HI S S
solution produces a blood-red colour. The appearance of this blood red colour is due to
SE
(1) [Fe(SCN)4]– (2) FeCl2(SCN) (3) [Fe(SCN)(H2O)5]2+ (4) Na4[Fe(CN)5NOS]
NC L K’
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
LI
conformations (if any), is(are) [IIT-JEE-2011]
A
H H H
(1) C—C (2) H—C C—C (3) H2C = C = O (4) H2C = C = CH2
H 2C CH2 CH2
ON A
Sol. Answer (2, 3)
C
M
H
C H
H
C
sp C C C O
2
C
H sp
2
H
H
.
RA
WT
H
H
C C C is non-planar
R.
H
H
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
S
28. Among P, Q, R and S, the aromatic compound(s) is/are [IIT-JEE-2013]
HI S S
Cl
SE
NC L K’
AlCl3
P
NaH
Q
(NH4)2CO3
R
LI OO
100-115 °C
A
O
HCl
S
ON A
(1) P (2) Q (3) R (4) S
C
Sol. Answer (1, 2, 3, 4)
M
AlCl3
Cl AlCl4 (P)
(i)
(AROMATIC)
Na
.
NaH
(Q) + H2
(ii)
NE K
(AROMATIC)
RA
WT
(NH4)2CO3
R
(iii) 100–115ºC
O O
R.
(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
O OH Cl (S)
(iv)
(AROMATIC)
S
In hyperconjugation p (empty) electron delocalization for tert-butyl carbocation and * electron
HI S S
delocalization for 2-butene will take place.
SE
NC L K’
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
LI
Sol. Answer (1, 3, 4)
Common name IUPAC name
A
OH
(1) tert-butanol 2-methylpropanol
ON A
C
(3) OH n-butanol butan-1-ol
M
SECTION - C
NE K
RA
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
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
O O
H
H
More stable
S
2. In which of the following solvent percentage enol content is maximum for 2,4-pentanedione?
HI S S
(1) CH3CN (2) H2O (3) n-Hexane (4) Ethanol
SE
Sol. Answer (3)
NC L K’
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
LI
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.
A
1. Write the IUPAC name of the following compound
ON A
CN
C
M
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
.
(4)
RA
(5)
WT
CN
(3)
(2)
R.
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
S
(1) 5-(3,3-dimethyl cyclobutyl) 1,2,2,3-tetra ethyl cyclohexane
HI S S
(2) 5-(3,3-dimethyl cyclobutyl) 1,3-diethyl 2,2-dimethyl cyclohexane
SE
(3) 1,2,2,3-tetra ethyl 5-(3,3-dimethyl cyclobutyl) cyclohexane
NC L K’
(4) None of these
Sol. Answer (1)
Fact
LI
Comprehension-III
A
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
ON A
affecting the stability of conjugate acid or base are electronic effect like resonance effect and inductive effect acting
C
upon the species.
M
1. Which of the following is strongest acid?
OH OH OH OH
CH3
(1) (2) (3) (4)
.
CH3
CH3
NE K
O
R.
NO2
NH2 NH2
..
(1) N (2) .. (3) (4)
N OCH3
H
CH3 OCH3
Sol. Answer (4)
S
+R effect of –OCH3 predominates over –I effect
HI S S
Comprehension-IV
SE
NC L K’
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.
1.
LI
Which of the following is incorrect hyperconjugative structure?
A
H H H H
H C H H C H H C H H C H
ON A
(1) (2) (3) (4)
C
M
Sol. Answer (3)
H is released as H+ not as H–
RA
WT
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)
S
and
HI S S
STATEMENT-2 : [10]-Annulene is a non-aromatic compound.
SE
Sol. Answer (4)
NC L K’
All C—C bonds are not equal in [10]-Annulene.
HO O OH
4.
LI
STATEMENT-1 : is less acidic than
A
HO
O
Br
.
5. STATEMENT-1 : When is treated with excess of Ag+ ion. One mole of the compound reacts
Br
NE K
Br
RA
Br
WT
(X)
and
STATEMENT-2 : Ag+ is a Lewis acid hence it reacts with Br– ion on which is a Lewis base.
Sol. Answer (4)
Compound (X) will give only two moles of AgBr.
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.
S
and
HI S S
STATEMENT-2 : Cyclopentanone has two hydrogen atoms attached to the carbon atom adjacent to carbonyl
SE
group.
NC L K’
Sol. Answer (1)
O OH
LI
Tautomers
A
10. STATEMENT-1 : CH3 CH2 CH2 is less stable than CH3 – N – CH2
ON A
|
C H
M
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.
.
and
RA
WT
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
14. STATEMENT-1 : Bridge head carbocation is less stable than Bridge head carbanion.
S
HI S S
and
STATEMENT-2 : C atom in carbocation is sp2 generally hybridized.
SE
NC L K’
Sol. Answer (2)
Carbocation and carbanion are generally sp2 and sp3 hybridised
LI SECTION - E
A
Matrix-Match Type Questions
1. Match the following
ON A
Column-I Column-II
RA
Carbonyl compounds, unsaturated alcohols and ethers are possible. This can also exhibit geometrical
isomerism
C4H11N can form 1°, 2° & 3° amines which are functional isomer.
S
(C) 0.37 gm of a given compound gave 0.631 gm AgBr (r) Equivalent mass of acid is 122
HI S S
(D) 0.122 gm of an organic acid required (s) 72.6% Br
SE
NC L K’
N
10 cm3 NaOH for neutralisation
10
Sol. Answer A(p), B(p, q), C(s), D(s)
LI 12 Mass of CO2
(A) Percentage of C = 44 Mass of organic compound 100
A
12 1.10
100 66.6%
ON A
44 0.45
C 2 Mass of H2 O
M
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
NE K
RA
WT
2
Percentage of H = 100 7.40%
27
7
R.
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
S
(D) Carbene (s) Stabilized by resonance
HI S S
Sol. Answer A(q, r, s), B(p, s), C(r, s), D(p, q)
SE
Carbocation is electrophile and stabilised by +I effect resonance and hyperconjugation.
NC L K’
Carbanion is nucleophiles and stabilized by resonance and –I effect
Free radical is electrophile and stabilised by resonance and hyperconjugation.
Carbene can act as electrophile and nucleophile both.
LI
A
5. Match the carbocation in column-I with the effect which is major, stabilizing factor for it in column-II
Column-I Column-II
ON A
C
(A) (p) Aromatic character
M
RA
+
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
S
HI S S
CH3
SE
NC L K’
(C) (r) Hyperconjugation effect is observed
LI
Sol. Answer A(p, r, s, t), B(p, q, s, t), C(p, q, r, s, t), D(p, r, s, t)
A
Resonance is possible in A and B. B and C are aromatic. (C) and (D) have hyperconjugation effect due to
-hydrogen.
7. Match the compounds in Column I with their characteristic test(s)/reaction(s) given in Column II.
ON A
[IIT-JEE-2008]
CColumn I Column II
M
(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
NE K
RA
WT
R.
(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
2.
How many intermediates are possible (excluding stereoisomer) when above mentioned molecule is attacked
by 1 equivalent H+?
Sol. Answer (6)
S
HI S S
SE
NC L K’
Sol. Answer (4)
LI F F F F
A
Hence positive charge is delocalized over four atoms.
5. How many bicyclic isomers are possible for the molecular formula C6H12O?
.
6. How many of the given species will evolve CO2 with NaHCO3?
OH OH OH
CH CH2
R.
HO O O
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.
9. Amongst the following, the total number of compounds soluble in aqueous NaOH is [IIT-JEE-2010]
H3C CH3
S
N COOH OCH2CH3 OH
HI S S
CH2OH
SE
NC L K’
NO2 OH CH2CH3 COOH
CH2CH3
LI
A
N
H3C CH3
ON A
C
Sol. Answer (4)
M
Carboxylic acids and aromatic alcohols dissolves in aqueous NaOH.
COOH OH OH COOH
.
, , ,
NE K
RA
N
WT
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
+
S
HI S S
SE
, , , ,
NC L K’
12. The number of resonance structures for N is [JEE(Advanced)-2015]
OH
NaOH
N
LI
A
Sol. Answer (9)
ON A
OH O
C NaOH
M
–H2O
O O O
.
NE K
RA
II III IV
WT
O
R.
O O O
III VI VII
O O
VIII IX
SECTION - G
Multiple True-False Type Questions
1. STATEMENT-1 : Phenol is more acidic than benzoic acid.
S
(1) T F T (2) F F F (3) F T F (4) T T F
HI S S
Sol. Answer (2)
SE
NC L K’
Phenol is less acidic than benzoic acid due to less stability of C6H5O– than C6H5COO–. Fluorobenzene is
more reactive than chlorobenzene.
O
2.
LI
STATEMENT-1 : CH3 O CH2 is more stable than O N CH2 .
A
STATEMENT-2 : + is antiaromatic molecule.
ON A
C
STATEMENT-3 : Phenoxide is more stable than ethoxide.
M
(1) F F T (2) T T F (3) F T F (4) T F T
..
In CH3 O
.. CH2 , resonance is effective. + – is aromatic (10 e–). Phenoxide is resonance
NE K
RA
stabilised.
WT
SECTION - H
R.
OH OHC HO
OH CHO CHO OH
I II III IV
Increasing solubility
in water
Greater the number of inter molecular hydrogen bond with solvent molecule higher the solubility.
OH O O NH2
N
I II III
OH
IV V VI
S
Sol.
HI S S
Increasing boiling point
SE
Strongest hydrogen bond is present in III. While weakest intermolecular force of attraction is present in VI.
NC L K’
3. For the given pair of compounds, identify the compound you expect to have the higher boiling point and explain
your reasoning.
LI N — H and NH2
A
Sol. NH2
ON A
C
To predict relative boiling points, look for differences in
M
(i) Hydrogen bonding
(ii) Molecular weight and surface area and
(iii) Dipole moment
.
RA
WT
I II
R.
+ 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.
Sol.
H
CH2OH CH2 O CH2
H+ H
(H2O being a rearrangement
good leaving of carbocation
group)
CH2 elimination
of H
CH3
S
HI S S
CH3
SE
NC L K’
CH2 Ring expansion
to bring release –H
A
CH2 – OH + CH2
H
ON A
C
M
Ring expansion
Hydride shift
CH3
.
NE K
RA
-H elimination
WT
R.
OCH3 OCH3
NH2
or
NH2
OCH3
NH2
Sol. is less stable, as a methoxyl group has negative (electron-withdrawing) inductive effect so
OCH3
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.
S
HI S S
SE
H; ; ;
NC L K’
I II III IV
LI
Sol. Only III can be deprotonated by NaOEt as its conjugate base is aromatic.
A
10. Pick out the correct statements about the barrier of rotation about the indicated bond in the given compounds
O
ON A
C
M
I II III IV
.
RA
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
N N
N N
N
N
H N N
H
I II III IV
S
HI S S
(1) I > II > IV > III (2) III > IV > II > I (3) IV > III > I > II (4) II > I > III > IV
SE
Sol. Answer (4)
NC L K’
Conjugate acids of I and II are stabilized by resonance.
LI OMe O—Me
A
Me Me
N N CH2
Me CH2 Me
ON A
(I) (II)
C
M
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
NE K
RA
14. What would be the major product of the given reaction? Justify mechanistically for the formation of your product?
R.
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.
D D D D
(1) and are identical compounds
D D D D
S
HI S S
(2) and are structural isomers
SE
NC L K’
D D
D D
(3) and are identical compounds
LI
A
D D
ON A
D D
C
(4) and are structural isomers
M
RA
WT
17. Species in which all C—C bonds are not equal is/are
R.
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?
[Equatorial conformer] 18
K
[Axial conformer] 1
[Equatorial conformer]
Percentage equatorial conformer 100
[Equatorial] [Axial conformer]
18
S
100
18 1
HI S S
SE
= 95%
NC L K’
Percentage axial conformer = 5%
LI
A
(1) (2) (3) (4)
ON A
I II
III IV
C
M
Sol. Answer (2)
Maximum delocalization of positive charge occur in II.
20. For which of the following compound tautomerization reaction is very slow?
.
O—H O O—H O
NE K
(1) C C (2) C C
RA
O O
R.
(3) (4)
H
O O
O O
H
Sol. Answer (1)
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.
Sol. Ph2CHNa Ph3 CH
Ph2 CH2 Ph3 CNa
23. Consider the following tautomeric equilibrium
Me
S
H Me
HI S S
Et3N 50%
D2O 50%
SE
NC L K’
H H
H
LI
(1) This interconversion is an intermolecular process (2) It is an intramolecular process
A
(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.
ON A
24. Most stable and least stable species respectively among the following are
C
M
O
O O
S S
S O S S
O O
O O
I II III IV
.
Maximum delocalization of negative charge is taking place in II. Electro negativity of S is less than oxygen.
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)
S
Except naphthalene all three compounds can trap free radicals due to presence of oxygen.
HI S S
SE
NC L K’
LI
A
ON A
C
M
.
NE K
RA
WT
R.