07

Organic Chemistry :
Some Basic Principles and
Techniques
Quick Revision
1. Classification On the basis of functional groups, organic compounds are classified into following
families or homologous series:

Organic Compounds

Single C—C Double/triple Halogen Oxygen containing Nitrogen containing

bond bond containing derivatives compounds compounds
containing compounds
Alcohol (R—OH) Amines
compound
Haloalkanes Haloarenes Ether (R OR) Aldehyde 1° amine (RNH2)
Alkyne R—X C6H5X Carbonyl compounds (RCHO)
(Alkanes) Alkene 2° amine (R2NH)
C C —C C — (where, X = F, Cl, Br, I) Ketone 3° amine (R3N)
Carboxylic acids
(RCOOH) (R COR) Aromatic amine (ArNH2)
Ester
(RCOOR) Nitro compounds (R NO2)
Carboxylic acid Amide (RCONH2) Cyanide (RCN)
derivatives Anhydride (RCO)2O Isocyanides (RNC)
Acid halide (RCOCl)

2. Nomenclature of Organic Compounds Step 4 Add suitable prefixes and suffixes along
Steps involved in IUPAC nomenclature are as with numerals to indicate the number and
follows: position of each side chain substituent or
Step 1 Locate the longest chain with as many functional group present in compound.
possible secondary functional groups Hence, according to these rules the IUPAC
along with multiple bonds. name of a compound can be written as :
Step 2 Select the root word corresponding to the Prefix + Root word + Suffix
length of longest possible chain.
Step 3 Number the longest possible chain Tells us about the Tells us about Tells us about the
branches or the length of principal functional
according to the rules to give an substituents except longest possible groups and multiple
identification number to each C-atom of in the case of chain. bonds mostly except
longest possible chain. multiple bonds. in case of halogens.
3. Fission of a Covalent Bond 4. Nucleophiles and Electrophiles
(i) Heterolytic cleavage or heterolysis (i) Nucleophiles or nucleophilic reagents An
Heterolysis electron rich species having a lone pair of
X æY æ æ æ ææÆ X + + Y -
electrons or is negatively charged species
(when X is less electronegative than Y ) which attacks on electron dificient areas is
Heterolysis
X æY æ æ æ ææÆ X - + Y + called a nucleophile (Nu••). e.g.
(when Y is less electronegative than X ) Negatively charged species like – –
Heterolytic cleavage results in formation of H - , Cl - , Br- , I- , carbanions, O H, - OR , S R ,
-
two types of species. These are : CN . Nucleophiles can also be seen in the
(a) Carbocation or carbonium ion If the form of neutral molecules with lone pair. e.g.
•• •• •• •• ••
carbon has sextet of electrons and a H 2 O, N H 3, R N H 2 , R OH, R S H, etc.
positive charge, then the species is called •• •• ••
carbocation (earlier called carbonium (ii) Electrophiles or electrophilic reagents
ion), e.g. CH +3 (methyl carbonium ion). An electrophile is defined as electron
It is trigonal planar with C-atom deficient species which attacks on electron
carrying-positive charge is sp 3 -hybridised. rich areas. e.g. : Positively charged species
like H + , Cl + , Br+ , I+ , NO+2 , SO+3 and
The order of stability of carbocations is
+ + + carbocations.
CH 3 < CH 3 CH 2 < (CH 3 )2 CH < (CH 3 )3 C + The electrophiles can also be seen in the
or methyl carbocation < 1°< 2 °< 3 °. form of neutral molecules,
••
e.g. carbenes
(b) Carbanion If the carbon of the (••CR 2 ), nitrenes (N R ), BF3 , etc.
obtained species is negatively charged 5. Inductive Effect (I-effect)
and have octet of electrons in its valence In a polar covalent bond, the electrons are shifted to
shell, then the species is called the more electronegative atom and hence, a polarity
carbanion. It is pyramidal in shape is developed in the bond. e.g. In a chain of carbon
with-atom carrying negative charge is atoms having C æ Cl bond, the C attached directly to
sp 3 -hybridised. the Cl-atom because of its less electronegativity
acquires some positive charge (δ + ).
The order –
of stability of carbanions is : δδδ + δδ + δ+ δ-
–
(C 6H 5 )3 C > (C 6H 5 )2CH – > C 6H 5 CH 2 C H 3 æ C H 2 Ææ CH 2 Ææ Cl
– 3 2 1
> allyl carbanions > CH 3 > (1°> 2 °> 3° This induction of polarity due to presence of
carbanions) polar bold in an organic molecule is called
(ii) Homolytic cleavage or homolysis This inductive effect.
cleavage involves movement of only one Types of Inductive Effect
electron, which is represented by half
(i) Negative inductive effect Atoms or groups
headed (fish hook) curved arrow. having greater electron affinity than hydrogen
Heat or
e.g. R——X !!" R• + X • are said to have - I -effect (electron attracting).
Light Alkyl free
radical Some of the - I -effect producing groups in
The neutral chemical species, thus formed decreasing order of inductive effect are
+ +
are called the free radicals. It is a planar
æR 3N > æNH 3 > æ NO2 > æ CN >
species in which C atom bearing odd electron
is sp 2 -hydridised. Like carbocations, the order æ SO3H > æ CHO > æ CO > æCOOH >
of stability of alkyl free radicals is æ COCl > æ COOR > æ CONH 2 > æF >
• • • • æ Cl > æ Br > æ I > æ OH > æ OR >
CH3 < CH2CH3 < CH(CH3 ) 2 < C(CH3 ) 3
Methyl Ethyl Isopropyl tert -butyl
æ NH 2 > æC 6H 5 > æH
free radical free radical free radical free radical (-I power in decreasing order with respect
(1°) (1°) (2°) (3°) to H.)
(ii) Positive inductive effect Atoms or groups (ii) Negative electromeric effect (- E -effect)
having lower electron affinity than hydrogen If the electrons of the double ( π ) bond are
are said to have + I effect (electron transferred to an atom of the double bond
withdrawing). other than the one to which the reagent
The order of +I-effect of some groups is as gets finally attached, then that effect is
follows : 3 °> 2 °> 1°or CH 3 . known as - E -effect.
6. Resonance Structure
These structures are hypothetical and individually – –
C O + CN !" C—O
don’t represent any real molecule. Benzene is a
resonance hybrid of following two canonical forms CN
6 6
9. Hyperconjugation
1 5 1 5
←æÆ ! The stabilising interaction that involves
2 4 2 4 delocalisation of σ-electrons of C—H bond of
3 3 Resonance
I II hybrid an alkyl group linked directly to an atom
of unsaturated system or to an atom having
7. Resonance Effect (R-effect)
unshared p -orbital, is called hyperconjugation.
The polarity developed with in a molecule due to +
interaction of two π-bond or of a π-bond with the CH 3 CH 2 has empty p -orbital, with which one
lone pair of electrons present on a fix atom is
of the CæH bonds of the methyl group align
called resonance effect.
in its plane and thus, the electrons of the
(i) Positive resonance effect (+ R-effect) CæH bonds can be delocalised into the
When the electrons move away from the empty p -orbital as shown below.
atom or substituent group attached to the
Hyperconjugation
conjugated system, the effect is called positive
resonance effect.In this effect, electron density C sp 3 —H 1s H
increases at certain places. e.g. Groups like bond
H
+
halogen, —OH, —OR,—OCOR,—NH 2 , C C
æNHR, —NR 2 show + R-effect. H H
(ii) Negative resonance effect (-R-effect) H Empty 2p-orbital
When the electrons are transferred towards of carbon
the atom or substituent group attached to the Orbital diagram showing
conjugated system, the effect is called hyperconjugation in ethyl cation
negative resonance effect.
10. Types of Organic Reactions and Mechanism
e.g. æ C == O, æ CN and æ NO2 show
—R-effect. The organic reactions can be categorised into
following five categories:
8. Electromeric Effect (E -effect)
(i) Substitution reactions
The polarity developed due to complete transfer Substituent
of a shared pair of π-electrons to any of the atoms hν or
linked directly to the multiple bond in the R — CH3 + X2 R—CH2 X + H X
520-670 K
presence of an attacking reagent is called the
Substitution product
electromeric effect.
(i) Positive electromeric effect (+ E -effect) These are further classified as follows :
If the electrons of the π-bond are transferred (a) Free-radical substitution The
to that atom of the double bond to which the reaction brought by free radicals are called
reagent gets finally attached, then that effect is free radical substitutions. e.g. Halogenation
known as + E -effect. e.g. of alkenes.
CH3 æ CH == CH2 + H+ æÆ + CH 4 + Cl 2 æææÆ
hν
CH 3Cl
CH3 æ CH æCH3 Methane HCl Chloromethane
(b) Electrophilic substitution reactions (iii)Addition reactions Reactions which involve
Anhydrous CH2R combination between two reacting molecules
AlCl3
+ R CH2 X + HX to give a single molecule of the product are
Friedel-Crafts´
alkylation
called addition reactions.
Such reactions are of typical compounds
(c) Nucleophilic substitution reactions These containing multiple bonds.
are usually written as S N (S-substitution,
N-nucleophile) and are of two types, i.e. R æ CH == CH 2 + HX æÆ R æ CH æ CH 3
unimolecular (shown as S N1) and bimolecular 
(shown as S N 2). X
(iv)Addition-elimination reactions These
These reactions are generally seen in alkyl
halides and alcohols. reactions involve addition of two molecules
with elimination of smaller molecules like
e.g. RX + KOH(aq ) æÆ ROH + KX H 2O, e.g. esterification.
(ii) Elimination reactions An elimination reaction H+
is one that involves the loss of two atoms or C 2H 5OH + CH 3COOH !
groups of atoms from the same or adjacent atoms Ethanol Ethanoic acid
of a substance leading to the formation of a CH 3COOC 2H 5 + H 2O
multiple (double or triple) bond. Ethyl acetate
Elimination reaction is given by those
(v) Rearrangement reactions These reaction
compounds which have a nucleophile as a
involve the migration of an atom or a group
leaving group, i.e.
from one atom to another within the same
" " " R "
—R,—S —R
– – – —
X, OH, OR, N2, N3, H3O, —N— molecule.
R R
e.g. CH 3 æCH 2 æCH 2 æCH 2 æBr
Elimination reactions are of two types : 1- bromobutane
Br
(a) α-elimination reactions
Anhyd. AlCl 3 
(b) β-elimination reactions ææææÆ CH 3 æCH 2 æCH æ CH 3
(i) H3O + 575 K
e.g. (CH3 ) 3 COH ææÆ (CH3 ) 2 C == CH2 + H2O 2- bromobutane
2-methylpropan-2-ol
(ii) Heat 2-methyl propene

Objective Questions
Multiple Choose Questions 2. Consider the following methane
molecule on paper.
1. Which of the following is a correct
H
representation of condensed formula for X
HOCH 2 CH 2 CH 2 CH(CH 3 )CH C H
(CH 3 )CH 3 ? H Y
H
(a) HO(CH2 )2 CHCH3CH(CH3)2
Here, X and Y are respectively
(b) HO(CH2 ) 3CH(CH3)CH(CH3)2 (a) dashed wedge, solid wedge
(c) HOCH2CHCH3CH(CH3)2 (b) solid wedge, dashed wedge
(d) None of the above (c) both are bonds in the plane of paper
(d) both are dashed wedge
3. In cyclic compounds, the bond-line (a) 1-chloro-2-nitro-4-methylbenzene
formula for chlorocyclohexane is (b) 1-chloro-4-methyl-2-nitrobenzene
(c) 2-chloro-1-nitro-5-methylbenzene
represented by which of the following
(d) m-nitro-p-chlorotoluene
representations?
Cl
Cl 9. The IUPAC name of the compound
(a) (b) O
O
Cl Cl H C
(c) (d) is ......... .

(a) 3-keto-2-methylhex-4-enal
4. Which of the following is a homocyclic (b) 5-formylhex-2-en-3-one
alicyclic compound ? (c) 5-methyl-4-oxohex-2-en-5-al
(d) 3-keto-2-methylhex-5-enal
(a) (b) (c) (d)
O
10. The IUPAC name of following
O S compound is
5. Which of the following compounds CH 3 æ CH æ CH æ CH æ CH 2 æ CH 3
is/are heterocyclic aromatic compound?   
(a) Furan (b) Thiophene CH 3 CH 3 CHO
(c) Pyridine (d) All of these
(a) 2-ethyl-3,4-dimethylpentanal
6. Which type of compound is shown by (b) 2,3-dimethyl-4-aldohexane
(c) 3-aldol-4,5-dimethyl hexane
the following structure ? (d) 1,3,4,5-tetraethyl butanal

(Naphthalene)
11. The IUPAC name for
(a) Alicyclic compound O O
(b) Benzenoid aromatic compound || ||
(c) Non-benzenoid aromatic compound CH 3 æ C æ CH 2 æ CH 2 æ C æ OH is
(d) Acyclic compound (a) 1-hydroxypentane-1,4-dione
7. In the following compounds, number of (b) 1,4-dioxopentanol
1° (primary) carbons is (c) 1-carboxybutan-3-one
(d) 4-oxopentanoic acid
CH 3
 12. The IUPAC name of the following
CH 3 æ CH æ C æ CH 2 æ CH 3 compound.
  HOCH 2 (CH 2 ) 3 CH 2 COCH 3 is
CH 3 CH 3 (a) 7-hydroxyheptan-2-ol
(a) 3 (b) 4 (c) 5 (d) 6 (b) 7-hydroxyheptan-2-one
(c) 2-oxoheptan-7-ol
8. The IUPAC name for (d) Heptan-2-oxo-7-ol
Cl
13. Neo-pentyl group is named as based on
NO2 IUPAC system on
(a) iso-pentyl
(b) neo-pentyl
(c) 2,2-dimethyl propyl
CH3
(d) 1,1-dimethyl
14. The IUPAC name of 18. Which of the following is the correct
CH3—CH—COOH is IUPAC name ?
(a) 3-ethyl-4, 4-dimethylheptane
(b) 4,4-dimethyl-3-ethylheptane
(c) 5-ethyl-4, 4-dimethylheptane
(d) 4,4-bis(methyl)-3-ethylheptane
Cl
(a) 2-(1-chlorophenyl) propanoic acid 19. IUPAC name of the following
(b) 2-methyl-(2-chlorophenyl) ethanoic acid compound is
(c) 1-methyl-(2-chlorophenyl) ethanoic acid
(d) 2-(4-chlorophenyl) propanoic acid
H3C CH3
15. The structure of iso-butyl group in an
organic compound is (a) 3,5-dimethylcyclohexene
CH3 (b) 3,5-dimethyl-1-cyclohexene
(c) 1,5-dimethyl-5-cyclohexene
(a) CH æCH2 æ
(d) 1,3-dimethyl-5-cyclohexene
CH3
(b) CH3 æCH2 æCH2 æCH3 20. IUPAC name of
(CH 3 ) 2 CH æ CH 2 æ CH 2 Br is
(c) CH3 æCH2 æCH2 æCH2 æ
(a) 1-bromopentane
CH3 (b) 2-methyl-1-4-bromobutane
 (c) 1-bromo-3-methylbutane
(d) CH3 æ C æ
(d) 2-methyl-3-bromopropane

CH3 21. Which of the following is not in
accordance to IUPAC system ?
16. Structure of 2-methyl-2-cyclohexen-1-ol (a) Br æ CH2 æ CH == CH2
is 1-bromoprop-2 -ene
OH CH3
OH CH3 
(a) (b) (b) CH3 æCH2 æ C æ CH2 æ CHCH3
CH3  
Br CH3
OH CH3
4-bromo-2, 4-dimethylhexane
(c) CH — CH — CH — CH —CH
(c) (d) 3 2 3

CH3 CH3
OH
2-methyl-3- phenylpentane
17. IUPAC name of the compound
(d) CH3 æ C æCH2 æ CH2CH2COOH
Cl CH 2 CH 3 
" !
C == C is O
! " 5-oxohexanoic acid
H 3C I
(a) trans-3-iodo-4-chloro-3-pentene 22. Cl æ Cl heterolytic fission gives
(b) cis-2-chloro-3-iodo-2-pentene (a) two free radicals (b) two carbonium ion
(c) trans-2-chloro-3-iodo-2-pentene (c) two carbanion
(d) cis-3-iodo-4-chloro-3-pentene (d) one carbocation and one carbanion
23. The most stable carbocation, among the (a) sp 3 (b) sp2
following is (c) sp (d) None of these
⊕
(a) (CH3) 3C æCH æCH3 29. The most stable carbocation, among the
⊕ following is
(b) CH3 æCH2 æCH æCH2 æCH3 ⊕
⊕ (a) (CH3) 3C æCH æCH3
(c) CH3 æ CH æCH2 æCH2 æCH3 ⊕
⊕ (b) CH3 æCH2 æCH æCH2 æCH3
(d) CH3 æ CH2 æ CH2 ⊕
(c) CH3 æCH æCH2 æCH2 æCH3
24. Which of the following free radicals is (d) CH3 æCH2 æCH2
⊕

the most stable ?

(a) Primary (b) Methyl 30. Among the following carbocations
(c) Secondary (d) Tertiary Ph 2C + CH 2 Me (I), PhCH 2CH 2CH + Ph (II) ,
25. When CH3 Cl undergoes homolytic Ph 2CHCH 2+ (III), Ph 2C(Me)• CH ⊕
2 (IV)
bond-fission the order of stability is
(a) carbon undergoes a geometric change from (a) IV > II > I > III (b) I > II > III > IV
tetrahedral to planar
(c) II > I > IV > III (d) I > IV > III > II
(b) hybridisation changes from sp 3 to sp2
(c) Both (a) and (b) 31. What is the correct order of decreasing
(d) None of the above stability of the following cations?
⊕ ⊕
26. Compare stability of free radicals. CH 3 — CH— CH 3 CH 3 — CH— OCH 3
•
I. CH 3 æ CH æ CH 3 I II
⊕
II. CH2 CH 3 — CH— CH 2 — OCH 3
• III
III. CH3 æ C(CH 3)2 (a) II > I > III (b) II > III > I
• (c) III > I > II (d) I > II > III
IV. CH 2 æ CH 3
32. Which one of the following is an
(a) II > I > III > IV (b) II > III > I > IV
intermediate in the reaction of benzene
(c) I > II > III > IV (d) IV > III > I > II
with CH 3Cl in the presence of
27. Which is the most stable carbocation ? anhydrous AlCl 3 ?
#
(a) Cl+ (b) CH3
(a) (CH3)3C (b) # +

# #
(c) —CH2 (d) (CH3)2CH (c) CH+3 (d)

33. Match the intermediates given in

28. Look at the figure below and find the Column I with their probable structure
hybridisation of carbon atom.
in Column II.
H
Column I Column II
+ C H A. Free radical 1. Trigonal planar
B. Carbocation 2. Pyramidal
H
C. Carbanion 3. Linear
Shape of methyl cation
Codes 40. Which has maximum stabilisation
A B C A B C energy as a result of resonance ?
(a) 1 1 2 (b) 1 2 3
(c) 1 3 2 (d) 2 1 3 O# O
#
34. Select the incorrect comparison as C—O
nucleophile. (a) (b)
(a) (CH3) 3CO# < OH# (b) H2O < NH3
# #
(c) RO# < RS# (d) R3P < R3N (c) CH2 == CHCH2 (d) CH3 CH2
35. Which has the highest nucleophilicity ?
(a) F - (b) OH- 41. Observe the effect carefully and predict
(c) CH-3 (d) NH2- the nature of it.
" "+
36. Which of the following compounds can C == C ! + H + æÆ C—C !
! " ! "
react with the Lewis base Cl - in a Lewis 
(Attacking reagent)
acid-base reaction ? H
(a) CH4 (b) AlCl3 Choose the correct option.
(c) OH- (d) CH-3 (a) Negative electromeric effect
(b) Resonance effect
37. An example of electrophile is (c) Positive electromeric effect
+
(a NO2 (b) NH3 (c) NO2 (d) H2O (d) Inductive effect

38. Electrophiles are electron seeking 42. Ethynic hydrogen is released most
species. Which of the following groups easily in
contain only electrophiles ?
+ (a) æC CH
(a) BF3,CH3, NO2
(b) AlCl3, SO 3, NO2+
(c) NO2+ , CH+3 , CH3 —C + == O (b) O2Næ æC CH
(d) C2 H-5 , C2H5 , C2H+5

39. Match the terms mentioned in Column I (c) æC CH

with the terms in Column II.
Column I Column II
(d) O2Næ æC CH
A. Carbocation 1. sp 2 hybridised carbon
with empty p-orbital
B. Nucleophile 2. Ethyne
43. Observe the orbital diagram showing
hyperconjugation in ethyl cation.
C. sp-hybridisation 3. Species that can receive
a pair of electrons Here A, B and C refer to
D. Electrophile 4. Species that can supply A
C
a pair of electrons. H
H H
Codes +
C C
A B C D
(a) 1 4 2 3 H H
(b) 1 3 4 2 B
(c) 1 3 4 2 (a) AÆ hyperconjugation, B Æ empty 2p -orbital
(d) 2 3 4 1 of carbon, C Æ C 3— H1s bond
sp
(b) AÆ inductive effect, B Æ i 2p-orbital of 47. Which is the incorrect resonating
carbon, C Æ C sp 2 — H1s bond
structure ?
(c) AÆ electromeric effect, B Æ empty
2p-orbital of carbon, C Æ C sp 3 — H1s bond (a) H2C== (b) H2C—
(d) AÆ resonance effect, B Æ i 2p-orbital of
carbon, C Æ C 3 — H1s bond
sp
(c) H2C— (d) H2C==
44. Choose the correct order of stability of
carbocation using the concept of
hyperconjugation. 48. The stability of Me 2C == CH 2 is more
CH3 CH3 than that of MeCH 2CH == CH 2 due to
" "
" " (a) inductive effect of the Me group
C3H—C , CH3—C , CH3 CH2 , CH3 (b) resonance effect of the Me group
CH3 H (c) hyperconjugative effect of the Me group
I II III IV (d) resonance as well as inductive effect of the
(a) I < II < III < IV (b) IV < III < II < I group
(c) III < IV < II < I (d) None of these 49. Hyperconjugation involves overlapping
45. The order of relative stability of the of which of the following orbitals.
contributing structures are (a) σ - σ (b) σ -p
•• (c) p -p (d) π -π
•O• •O •#
• • • •
 ⊕  50. Formic acid is a stronger acid than
CH2 == CH—C — H ←Æ C H2 —CH == C— H acetic acid. This can be explained using
I II
(a) +M effect
• •+
•O • (b) -I effect
- 
←Æ •
• CH 2 — CH == C — H (c) +I effect
III (d) -M effect
(a) II > I > III (b) I > II > III
(c) III > II > I (d) I = II = III
51. The arrangement of (CH 3 ) 3 C æ ,
(CH 3 ) 2 CH æ , CH 3CH 2 — when
46. Consider the following compounds, attached to benzene or unsaturated
NH2 NO2 group in increasing order of inductive
effect is
and (a) (CH3) 3C — < (CH3)2 CH — < CH3CH2 —

Aniline Nitrobenzene
(b) CH3CH2 — < (CH3)2 CH — < (CH3) 3C —
(I) (II) (c) (CH3)2 CH — < (CH3) 3C — < CH3CH2 —
Which of the following option is/are (d) (CH3) 3C — < CH3CH2 — < (CH3)2 CH —
true regarding I and II ?
52. Which of the following does not show
(a) I shows + R -effect, whereas II shows electromeric effect ?
–R-effect
(a) Alkene
(b) I shows –R -effect, whereas II shows
(b) Ether
+ R-effect
(c) Aldehyde
(c) Both I and II show +R -effect
(d) Ketone
(d) Both I and II show -R -effect
53. Match the ions given in Column I with ! CHO ! COCH3
(a) (b)
their nature given in Column II.
Column I Column II CHO CHO
1. Stable due to
A. CH 3 NO2
resonance
(c) (d)
⊕ 2. Destabilised due
B. F3 æ C
to inductive effect
⊕ 3. Stabilised by CH3 NO2
C. CH 3 æ CH æ CH 3
hyperconjugation

Codes
58. Electrophilic addition reactions proceed
A B C A B C in two steps. The first step involves the
(a) 1 2 3 (b) 2 3 1 addition of an electrophile. Name the
(c) 3 1 2 (d) 3 2 1 type of intermediate formed in the first
step of the following addition reaction.
54. Ionic species are stabilised by the H 3C æ HC == CH 2 + H + æÆ ?
dispersal of charge. Which of the
(a) 2° carbanion (b) 1° carbocation
following carboxylate ion is the most (c) 2° carbocation (d) 1° carbanion
stable?
O O 59. Which one is a nucleophilic substitution
|| || reaction among the following ?
(a) CH3 — C —O - (b) Cl—CH2 —C—O -
(a) CH3CHO + HCN æÆ CH3CH(OH)CN
O O
H+
|| F (b) CH3 æCH == CH2 +H2O æÆ CH3 æ CH æCH3
(c) F—CH2 —C—O - (d) CH—C—O– 
F OH
55. In which of the following compounds (c) RCHO + R′ MgX æÆ R —CH— R′

the carbon marked with asterisk is OH
CH3
expected to have greatest positive 
charge ? (d) CH3 æCH2 æCH æ CH2Br + NH3 æÆ
(a) *CH3 æ CH2 æ CI CH3
(b)*CH3 æCH2 æMg +Cl- 
CH3 æ CH2 æCH æ CH2NH2
(c) *CH3 æ CH2 æBr
(d) *CH3 æ CH2 æ CH3 60. Dehydration of alcohol is an example
56. Dichlorocarbene is generated by the of which type of reaction?
action of potassium-1- butoxide on (a) Substitution (b) Elimination
(c) Addition (d) Rearrangement
chloroform. This is an example of
(a) α-elimination Assertion-Reasoning MCQs
(b) β-elimination
(c) addition reaction
Directions In the following questions
(d) rearrangement reaction
(Q.No. 61-75) a statement of Assertion
followed by a statement of Reason is
57. Which one is most reactive towards given. Choose the correct answer out of
nucleophilic addition reaction ? the following choices.
(a) Both Assertion and Reason are correct 66. Assertion The names of straight chain
statements and Reason is the correct compounds are based on their chain
explanation of the Assertion.
structure and carry a prefix indicating
(b) Both Assertion and Reason are correct
the number of carbon atoms present in
statements, but Reason is not the correct
explanation of the Assertion. the chain.
(c) Assertion is correct, but Reason is incorrect Reason From CH 4 to C 4 H10 , the
statement. prefixes are derived from common or
(d) Assertion is incorrect but Reason is correct trivial names.
statement.
67. Assertion 2, 3-dimethylhept-5-ene is
61. Assertion Acyclic compounds consist CH 3
of straight or branched chain compounds.

Reason Alicyclic compounds contain CH 3 æ CH ==CH æ CH æ
carbon atoms joined in the form of a
CH 3
ring.

62. Assertion When a covalent bond is CH 2 æ CH æ CH 3
formed between atoms of different
electronegativity, the electron density is Reason The alkyl group do not get
more towards the more electronegative preference to the double bond.
atom of the bond. 68. Assertion Heterolytic fission involves
Reason Shift of electron density results the breaking of a covalent bond in such
in a polar covalent bond. a way that both the electrons of the
shared pair are carried away by one of
63. Assertion All the carbon atoms in the atoms.
H 2C == C == CH 2 are sp 2 - hybridised.
Reason Heterolytic fission occurs
Reason In this molecule, all the carbon readily in polar covalent bonds.
atoms are attached to each other by
double bonds. 69. Assertion A covalent bond may be
cleaved either by heterolytic cleavage
CH3 or by homolytic cleavage.
64. Assertion is
Reason Heterolytic cleavage of CH 3 Br
+ -
3-methylcyclohexene. will give C H 3 and Br.
Reason In numbering, double bonded 70. Assertion Carbanion has an octet of
carbon atoms get preference to the alkyl electorns.
group in cycloalkenes. Reason In carbanion, negatively
charged carbon atom is sp 3 -hybridised.
65. Assertion In bond-line structural
representations, only atoms specifically 71. Assertion Free radicals are short lived
written are oxygen, chlorine, nitrogen etc. and highly reactive.
Reason In bond-line structural Reason Free radicals are highly unstable.
representations, line junctions denote
carbon atoms bonded to appropriate 72. Assertion Inductive effect and
number of hydrogens required to satisfy resonance effect cause permanent
the valency of the carbon atoms. polarisation of bond.
Reason These involve electron When the group or atom release electron
displacements due to the influence of an density then electron density of conjugated
atom or a substituted group present in system increases while the group or atom
the molecule. attract/withdraw electron density then
electron density of conjugated system
73. Assertion Conjugated system show decreases.
abnormal behaviour, it contains The following questions (i-iv) are multiple
alternate single and double bonds in an choice questions. Choose the most
open chain or cyclic system. appropriate answer :
Reason In conjugated system, (i) In which molecule dipole moment is
π-electrons are delocalised and the the maximum?
system develops polarity. (a) CH3CH2 CH2 æ Cl
(b) CH3CH2 CH2 æ NO2
74. Assertion Energy of resonance hybrid
(c) CH3CH2 CH2 æ OH
is equal to the average of energies of all
canonical forms. (d) CH3 æ CH2 æNH æ C æ CH3

Reason Resonance hybrid cannot be O
presented by a single structure. (ii) In which benzene ring electron density
is maximum?
75. Assertion Polarisation of one σ bond O
caused by the polarisation of adjacent OCH3 O—C—CH3
σ bond is referred to as the inductive effect.
(a) (b)
Reason The substituents can be
classified as electron withdrawing or O
electron donating groups relative to
C—O—CH3 CH==O
hydrogen.
(c) (d)
Case Based MCQs
76. Read the passage given below and (iii) Which of the following system show
answer the following questions : abnormal behaviour in their properties
The electron displacements due to the (like-stability, polarity … etc.) ?
influence of an atom or a substituent group NH2 NH2
present in the molecule cause permanent (a) (b)
polarisation of the bond (called electronic
δδ+ δ+ δ–
effect), e.g. CH3 æCH2 æCH2 æ F . OCH3
In above example, polar C—F bond (c) (d)
induce polarity in the adjacent bonds.
Such polarisation of adjacent σ- bond is
referred to as the inductive effect. This (iv) The permanent displacement of
effect decreases rapidly as the number of electron through a chain involving
only σ-bonds is called
intervening bonds increases.
(a) inductive effect
The resonance effect is defined as the (b) hyperconjugation effect
polarity produced in the molecule by the (c) electromeric effect
interaction of two π-bonds or in conjugated (d) mesomeric effect
system.
Or (ii) CH3 CH2 Cl undergoes homolytic fission,
Which of the following is correct with produces
• • ⊕
respect to -I -effect of the substituents? (a) CH3 CH2 and Cl (b) CH3 CH2 and Cl -
(R = alkyl) ⊕ ⊕ •
(c) CH3 CH2 and Cl (d) CH3 CH2 and Cl -
(a) æNH2 >æOR > æF
(b) æNR2 < æOR < æF (iii) The shape of carbocation is
(c) æNH2 > æOR < æF (a) square planar
(d) æNH2 > æOR > æF (b) trigonal planar
(c) octahedral
77. Read the following passage and answer (d) trigonal pyramidal
the question accordingly. (iv) Compare stability of free radicals
•
An intermediate is a molecular entity, that I. CH3 æ CH æ CH3
is formed from the reactants and reacts
further to give the directly observed II. CH2
products of a chemical reaction. Most
•
chemical reactions are stepwise, that is III. CH2 æ CH(CH3 ) 2
they take more than one elementary step •
to complete. An intermediate is the IV. CH 2 æCH 3
reaction product of each of these steps, (a) II > I > III > IV (b) II > I > IV > III
except for the last one, which forms the (c) I > II > III > IV (d) IV > III > I > II
final very isolated. Also, owing to the short
lifetime, they do not remain in the product Or
mixture. The radical is aromatic because it has
In certain cases, they are separated and · 2
stored. For example matrix isolation and CH
low temperature. (a) 6p-orbitals and 6 unpaired electrons
Matrix isolation is a technique that is used (b) 7p-orbitals and 6 unpaired electrons
experimentally in physics and chemistry (c) 7p-orbitals and 7 unpaired electrons
that includes a material that has been (d) 6p-orbitals and 7 unpaired electrons
trapped with in an unreactive material.
Host matrix generally comprises guest 78. Read the passage given below and
particles that are generally embedded. answer the following questions :
Guest particles can be molecules, atoms When a single Lewis dot structure is
and ions. The guest is isolated within the unable to explain all the properties of a
host matrix. compound, two or more structures, called
The following questions (i-iv) are multiple the canonical forms or resonating
choice questions. Choose the most structures, are drawn to explain all the
appropriate answer: properties of that compound, then the
(i) Relative stabilities of the following actual structure of the compound is in
carbocations will be in the order between these canonical form and is
⊕ ⊕ ⊕ called the resonance hybrid of these
CH 3 , CH 3CH 2 , CH 2 OCH 3 canonical forms. This phenomenon is
(A ) (B ) (C ) called resonance.
(a) C > B > A The resonating structure are hypothetical,
(b) C < B < A i.e. have no real existence. The energy of
(c) B > C > A actual structure or resonance hybrid is
(d) C > A > B lower than, that of any of the canonical
forms. The difference between hybrid and Or
the energy of most stable (lowest energy) Which of the following show -R-effect ?
canonical form is called the resonance (a) æOR2 (b) æNHCOR
stabilisation energy or resonance energy. (c) æNH2 (d) æCOOH
The more the number of important
79. Read the passage given below and
canonical forms more is the resonance
answer the following questions:
energy. In case of resonating structures of
equivalent energy, resonance is of great In a polar covalent bond, the electrons are
importance. shifted to the more electronegative atom
In these questions (i-iv) a statement of and hence, a polarity is developed in the
Assertion followed by a statement of bond. e.g. In a chain of carbon atoms
Reason is given. Choose the correct having C—Cl bond, the C attached
answer out of the following choices : directly to the Cl-atom because of its less
electronegativity acquires some positive
(i) Which rules of resonating structures is
charge (δ + ). The carbon ( C2 ) that is
true ? +
I. The overall charge of system bonded directly to the Cδ also loose
remains same. some of its electron density due to more
+
II. The arrangement of atoms must be polar Cδ and hence, acquires somewhat
identical or almost same in less positive charge (δ ++ ). Similarly, the
resonance structure. next carbon ( C3 ) also acquires some
(a) Rule I positive charge but less than (δ ++ ) as
(b) Rule II
shown below :
(c) Both the rules
(d) Neither rule I nor rule II δδδ + δδ + δ+ δ-
CH3 æ CH2 Ææ CH2 Ææ Cl
(ii) There are how many resonance 3 2 1
structure of phenoxide ion ? This induction of polarity, due to the
(a) 4 (b) 5 presence of polar bond in an organic
(c) 6 (d) 3
molecule, is called inductive effect.
(iii) Which is more stable among the In these questions (i-iv) a statement of
following pair of resonance Assertion followed by a statement of
contributing structures.
Reason is given.
" "
Choose the correct answer out of the
R! C — O R—C O
(I) (II)
following choices :
(a) Structure I (a) Assertion and Reason both are correct
(b) Structure II statements and Reason is correct
(c) Both are equally stable explanation for Assertion.
(d) Can’t say (b) Assertion and Reason both are correct
statements but Reason is not correct
(iv) The relation between resonance and explanation for Assertion.
bond order is (c) Assertion is correct statement but Reason
no. of bonds
(a) B.O. = is incorrect statement.
no. of resonating structure
(d) Assertion is incorrect statement but
no. of π - bond Reason is correct statement.
(b) B.O. =
no. of σ - bond
no of σ - bond
(i) Assertion Polarisation of one σ-bond
(c) B.O. = caused by the polarisation of adjacent
no. of resonating structure
σ-bond is referred to as the inductive
(d) B.O.= no. of (σ + π) bond
effect.
Reason The substituents can be Various organic compounds are known
classified as electron withdrawing which came from non-living systems.
or electron donating groups relative to Carbon is known to form more than five
hydrogen. million compounds. The existence of such a
(ii) Assertion Formic acid is a stronger acid large number of compounds is due to some
than benzoic acid. unique properties of carbon.
Reason +R-effect phenyl group is In these questions (i -iv), a statement of
greater than -I -effect. Assertion followed by a statement of Reason
(iii) Assertion Allyl and benzyl carbonium is given. Choose the correct answer out of
ions are stable than propyl carbonium the following choices.
ions. (i) Assertion Saturated hydrocarbons are
Reason Electron releasing groups chemically less reactive.
stabilise carbonium ions. Reason All isomeric paraffins have same
(iv) Assertion When a covalent bond is parent name.
formed between atoms of different (ii) Assertion Olefins are unsaturated
electronegativity, the electron density hydrocarbons containing two hydrogen
is more towards the more atoms less than the
electronegative atom of the bond. corresponding paraffin.
Reason Shift of electron density Reason There is one triple bond
results in a polar covalent bond. between two carbon atoms in olefin
Or molecules.
Assertion Inductive effect and (iii) Assertion The IUPAC name for
resonance effect cause permanent CH 3CH == CH æC ≡≡ CH is
polarisation of bond. pent-3-en-1-yne and not pent-2-en-4-yne.
Reason These involve electron Reason While deciding the locants for
displacements due to the influence of double and triple bonds, lowest sum rule
an atom or a substituted group present is always followed.
in the molecule.
(iv) Assertion
80. Read the following passage and answer CH 3 æCH æCH 2 æCH æ CHO
the questions accordingly.  
Cl CH 3
The name carbon is derived from the latin
word ‘carbo’ which means coal. This is is 4-chloro-2-methylpentanal.
because it is the main constituent of coal. Reason Numbering is to be given
The amount of carbon present in the earth’s according to the alphabetical order of
crust and atmosphere is very small. In fact, substituents.
Or
all the living things, plants and animals, are
Assertion neo-hydrocarbons contain a
made up of carbon compounds.
quaternary carbon atom.
The compounds having organic origin are
Reason Whenever a carbon atom is
known as organic compounds. In morden
bounded to four carbon atoms it is
days organic compounds are not restricted
quaternary.
to living systems.
ANSWERS
Multiple Choice Questions
1. (b) 2. (a) 3. (c) 4. (b) 5. (d) 6. (b) 7. (c) 8. (b) 9. (a) 10. (a)
11. (d) 12. (b) 13. (c) 14. (d) 15. (a) 16. (b) 17. (c) 18. (a) 19. (a) 20. (c)
21. (a) 22. (d) 23. (c) 24. (d) 25. (c) 26. (b) 27. (c) 28. (b) 29. (c) 30. (b)
31. (a) 32. (c) 33. (a) 34. (d) 35. (c) 36. (b) 37. (c) 38. (b) 39. (a) 40. (b)
41. (c) 42. (d) 43. (a) 44. (b) 45. (b) 46. (a) 47. (b) 48. (c) 49. (b) 50. (c)
51. (a) 52. (b) 53. (a) 54. (d) 55. (a) 56. (a) 57. (d) 58. (c) 59. (d) 60. (b)

Assertion-Reasoning MCQs
61. (b) 62. (b) 63. (d) 64. (a) 65. (b) 66. (b) 67. (d) 68. (b) 69. (b) 70. (b)
71. (b) 72. (a) 73. (a) 74. (d) 75. (b)

Case Based MCQs

76. (i)-(b), (ii)-(a), (iii)-(b), (iv)-(a) or-(b) 77. (i)-(a), (ii)-(a), (iii)-(b), (iv)-(b) or-(c)
78. (i)-(c), (ii)-(b), (iii)-(a), (iv)-(a) or-(d) 79. (i)-(b), (ii)-(a), (iii)-(b), (iv)-(b) or-(b)
80. (i)-(b), (ii)-(c), (iii)-(a), (iv)-(c) or-(b)

EXPLANATIONS
1. The correct condensed formula for not have aromatic character. Homocyclic means
HOCH2CH2CH2CH(CH3 )CH(CH3 )CH3 it contains only C-atoms in ring, e.g.
is HO(CH2 ) 3 CH(CH3 )CH(CH3 ) 2 .
2. X is dashed wedge (bond away from observer)
and Y is solid wedge (bond towards observer).
In these formulas, the solid wedge is used to Cyclopentane Cyclohexane
indicate a bond projecting out of the plane of
paper towards the observer.
The dashed wedge is used to depict the bond
projecting out of the plane of paper and away
from the observer. Cyclohexene Cyclobutane
3. In cyclic compounds, the Cl 5. All the given compounds, i.e. furan, thiophene,
bond-line formula for pyridine are known as heterocyclic aromatic
chloro-cyclohexane is represented compounds.
by following formula :
6. Since, the given compounds contains benzene
4. Alicyclic (aliphatic cyclic) compounds contain nucleus, so naphthalene is a benzenoid aromatic
compound.
carbon atoms joined in the form of a ring but do
7. 1° carbons are attached directly to one carbon A compound containing both an alcohol and a
3° CH3 1° keto group is named as hydroxy alkanone since
2° the keto group is preferred over hydroxy group.
CH3—CH—C—CH2—CH3 13. CH3
4°
1° CH3 CH3 1°
CH3 —C—CH2 —
3 2 1
1° 1°
CH3
So, there are 5 primary carbons. 2, 2-dimethyl propyl
8. For tri or higher substituted benzene derivatives, Longest chain is of three carbons; two alkyl
the compounds are named by identifying groups at C 2 .
substituent, positions on the ring by following
the lowest locant rule. 14. The IUPAC name of compound is
2-(4-chlorophenyl) propanoic acid.
Substituent of the base compound is assigned
3 2 1
number 1 and then the direction of numbering CH3—CH—COOH
is chosen such that the next substituent gets the
1
lowest number. 2
The substituents appear in the name in 3
alphabetical order. 4
Cl
Cl
1
NO2
2 15 ‘iso’ means one Me group is present at side chain.
Hence, the structure of iso-butyl group is
3
4 CH3
CH3 
CH3 æC æCH2 æ
9. O
O 
H C H
1 3 4
2
5 ‘yl’ suffix is used to represent one æ H less than
6 the parent hydrocarbon.
æ CHO group gets higher priority (act as 16. Option (b) is the correct structure of 2-methyl
principal group) over > C == O and C == C 2-cyclohexen-1-ol.
group in numbering of principal carbon chain. OH
IUPAC name 3-keto-2-methylhex-4-enal. 1
6
2 CH3
10. 5 4 3 2
CH3CH—CH—CH CH2CH3 5 3
4
CH3 CH3 CHO
1 17. trans-2-chloro-3-iodo-2-pentene
IUPAC name is 2-ethyl-3, 4-dimethylpentanal. 4 5
Cl CH2CH3
2 3
11. When more than one functional group lie in the C == C
1
main chain, nomenclature is done according to H3C I
that functional group which has higher priority.
Carboxylic acid ( æCOOH) has more priority 18. The structure
than ketone ( > C == O). CH3
12. The correct IUPAC name of the given 
CH3 æCH2 æCH2 æC æ CH æ CH2 æCH3
compound HOCH2 (CH2 )3 CH2COCH3 is  
7-hydroxyheptan-2-one. CH3 C2H5
While writing IUPAC name, alkyl groups are greater is the delocalisation of odd electron and
written in alphabetical priority, thus lower hence, more stable is the free radical.
locant 3 is assigned to ethyl. • •
25. CH3 •• Cl ææÆ CH3 + Cl
Note Prefix di, tri, tetra are not included in Methyl free radical
alphabetical order. sp 2 -hybridised (with singly
occupied p -orbital)
19. The IUPAC name of given compound is H
3, 5-dimethyl cyclohexene. Bond angle 120°
C with three co-planar (C—H)
1 H H bonds)
2
6 Cl
5
sp 3 -hybridised carbon
3
H3C CH3 tetrahedral bond angle 109°28′
4
26. Among the given free radicals,
4 3 2 1
20. C H3 æ CH æ CH 2 æ CH 2 æ Br CH2 is most stable due to resonance.
 In the remaining free radicals, more the alkyl
CH3
groups bonded to the electron deficient carbon,
IUPAC name is 1-bromo-3-methylbutane. the more stable is the radical.
21. Option (a) is not in accordance with IUPAC Thus, the correct order of stability of given free
system. In IUPAC system of nomenclature, radicals is
preference is given to multiple bond than CH2 > CH3 C CH3 > CH2 CH3 > CH2 CH3
halogen substituent, so the correct name is (I) (IV)
3 2 1 (II) CH3 CH3
Br æ CH2 æ CH == CH2 (III)
3- bromoprop-1-ene
27. Benzyl carbocation is most stable due to
22. Heterolytic fission of Cl 2 gives one carbocation resonance
and one carbanion due to transfer of electron
(a) 3° alkyl
from shared pair of bonded electrons.
+ (b) 3° vinylic least stable
23. CH3 C H CH2 CH2 CH3 is the most stable (c) 1° benzyl most stable
carbocation among the given carbocations. It is (d) 2° alkyl
because the number of α-H atom attached to
+ Order is : (b) < (d) < (a) < (c)
carbocation is maximum in CH3 CHCH2CH2CH3. #
Thus, it has maximum number of #
—CH2 CH2
hyperconjugating structure hence, it is most
stable.
24. Stability order of free radical is as
# CH2 CH2
CH3
H3C
 #
CH3 — C • > % C•H > CH — CH
• •
> CH3
$ 3 2
Methyl 28. The shape of CH+3
may be considered as being
 H3C free radical derived from the overlap of three equivalent
CH3
Tertiary Primary C-( sp 2 )-hybridised orbitals with 1s-orbital of
free radical Secondary free radical
free radical each of the three hydrogen atoms.
Greater the number of alkyl groups attached to Each bond may be represented as C( sp 2 ) —H (1s)
the carbon atom carrying the odd electrons, sigma bond.
The remaining carbon orbital is perpendicular to 33. A Æ (1); B Æ (1); C Æ (2)
the molecular plane and contains no electrons.
H
Column I Column II Explanation

= 3σ-bonds A. Free radical Trigonal Free radicals are formed

+ C H planar by homolytic fission e.g.
⇒ sp2-hybridisation °
H CH 3 hybridisation sp 2
Shape of methyl cation
B. Carbocation Trigonal Formed by heterolytic
+
29. CH3C HCH2CH2CH3 is the most stable planar fission when carbon is
carbocation among the given carbocations. attached to a more
It is because the number of α-H atom attached electronegative atom e.g.
+
to carbocation is maximum in CH 3 hybridisation sp 2
⊕
CH3CHCH2CH2CH3. Thus, it has maximum C. Carbanion Pyramidal Formed by heterolytic
number of hyperconjugating structure. fission when carbon is
Hence, it is most stable. attached to more
30. The order of stability of carbocation is electropositive atom e.g.
3° benzylic > 2° benzylic >3° >2° > 1°. CH -3 hybridisation sp 3
Thus, the correct order of stability will be
34. Nucleophilic strength increases down the group
Ph H then
  R3 P > R3 N
Ph æ C æ CH2CH3 > PhCH2CH2 æ C æ Ph
+ +
(I) (II) but given comparison R3 P < R3 N is incorrect.
H Me 1
 
35. Electronegativity ∝
+ nucleophilicity
> Ph 2CH æ C+ > Ph æ C æ CH2
  ∴ CH-3 has the highest nucleophilicity.
H Ph 36. (a) CH4 + Cl – æÆ No reaction
(III) (IV)
31. Stability of the given cations can be understood (b) AlCl 3 + Cl – æÆ AlCl –4
Electron -deficient Lewis base
by the following structures
Al (Lewis acid)
+ +
CH3 CH CH3 ; CH3 — CH — O — CH3 ; (c) OH– + Cl – æÆ No reaction
I II (d) CH–3 + Cl – æÆ No reaction
Weak + I-effect of Strong + R-effect of
the two methyl groups —OCH3 group stabilises 37. Electrophiles are electron deficient species.
stabilises carbocation (I) carbocation (II)
Hence, among the given species, nitronium ion
+ +
CH3 — CH — CH2 OCH3 (NO2 ) due to lack of electrons act as
III
electrophile while all other given species due to
–I-effect of —OCH3
group destabilises the the presence of lone pair of electrons, act as
carbocation (III) nucleophile.
Hence, the stability of carbocation decreases 38. AlCl 3 , SO3 (Lewis acids), NO+2 , CH+3 ,
II > I > III. +
+ CH3 æ C ==O are electron deficient species.
32. CH3 group acts as an intermediate in the Hence, these acts as electrophiles.
reaction of benzene with CH3Cl in the presence 39. A Æ (1); B Æ (4); C Æ (2); D Æ (3)
of anhydrous AlCl 3 . This reaction is called as
Friedel-Craft alkylation.
Column I Column II Explanation 44. Greater the number of alkyl groups attached
A. Carbocation sp 2 -hybridised H 3C + is carbocation. to a positively charged carbon atom, the
carbon with Loss of e - makes its greater is the hyperconjugation interaction
empty p-orbital p-orbitals empty and stabilisation of the cation.
(sp 2 -hybridised Thus, the correct order of stability of carbo-
carbon) cation using the concept of hybridisation is
B. Nucleophile Species that can Nucleus loving, i.e. CH3
supply a pair of having negative | + + +
electron charge or excess of CH3 — C+ > (CH3 )2 CH > CH3 CH2 > CH3
electrons. |
C. sp-hybridisa Ethyne HC ≡≡ CH CH3
-tion (sp-hybridisation) (I ) ( II ) ( III ) ( IV )

D. Electrophile Species that Electron loving, i.e. 45. The order of relative stability of the
receive a pair positive charge or contributing structures are I > II > III.
of electron lack of electrons
:O:–

:
:O:
40. O +
CH2==CH — C — H CH2 — CH == C —H
C æ O– I II
+
:O:
–
Resonance in benzene nucleus as well as in : CH2 — CH == C —H
carboxylate ion. Thus, maximum stable. III
Thus, maximum resonance energy. The reason for this order is
41. In the given reaction, π-electrons of the multiple I. The resonating structure which is most
bond are transferred to that atom on which the stable has more number of covalent
attacking reagent get attached. So, it is an example bonds, each carbon and oxygen atom has
of positive electromeric effect complete octet and no separation of
(+E -effect). e.g. opposite charges.
+
C C + H+ C C II. Negative charge on more electronegative
(Attacking atom and positive charge on more
reagent) H electropositive atom.
42. Ethynic H is attached to (— C ≡≡ C —) system. III. Structure does not contribute as oxygen
æ NO 2 is electron-withdrawing and (C— H) bond has positive charge and carbon has
strength is weakened to a greater extent. Since, negative charge, hence least stable.
benzene nucleus is also resonance stabilised,
46 Aniline (I) shows + R -effect, whereas
hence (d) is correct option.
+ nitrobenzene (II) shows -R -effect. In +R
43. In CH3 C H2 (ethyl cation), the positively charged -effect, the transfer of electrons is away from
carbon atom has an empty p -orbital . One of the an atom or substituent group attached to the
C—H bonds of the methyl group can align in the conjugated system.
plane of this empty p-orbital and the electrons This electron displacement make certain
constituting the C—H bond in plane with this positions in the molecule of high electron
p-orbital can then be delocalised into the empty densities.
p-orbital as depicted below :
This effect in aniline is shown as :
Hyperconjugation
Csp3 — H1s " " "
:

(A) NH2 NH2 NH2 NH2 NH2

bond
H
(C)
H –
:
+ – :
H C C (B)
H empty 2p-orbital
:

H –
of carbon
-R -effect is observed when the transfer of 51. The inductive effect of the alkyl group on a
electrons is toward the atom or substituent saturated carbon chain follows the order
group is attached to the conjugated system, e.g. (CH3 )3 C— > (CH3 )2 CH — > CH3CH2—
in nitrobenzene this electron displacement can
be depicted as. However, when an alkyl group is attached to an
unsaturated system such as double bond or a
–:O –:O :
:
O – O benzene ring, the order of inductive effect is
:
O O O O

:
: : :
N N N N
actually reversed.
This effect is called hyperconjugation effect or
" " Baker-Nathan effect. Now, the reactivity order is
(CH3 )3 C — < (CH3 )2 CH — < CH3 — CH2 —
" 52. Electromeric effect implies complete transfer of
π-electrons in presence of a reagent. Since,
47.
simple ethers do not contain any multiple bond,
H2C H2C hence they do not show electromeric effect.
53. A Æ (1); B Æ (2); C Æ (3)
(a) (d)
Column I Column II Explanation
A. CH 3 NO2 Stable due to
H2C H2C— resonance
B. F3 æ C + Destabilised due – I effect of F
(c) to inductive effect creates electron
48. Me H deficiency at
C==C carbon C + .
Me H ⊕ +
has 6- hyperconjugate forms while D. CH 3 —CH Stabilised due to CH is attached to
MeCH2 H —CH 3 hyperconjugation two carbon. It can
also be stabilised by
C==C
H H hyperconjugation.
has 2- hyperconjugate forms
54. In all the given carbocations, the negative
Therefore, Me2C ==CH2 is more stable than charge is dispersed which stabilises these
MeCH2CH ==CH2 . carbocations.
49. Hyperconjugation involves overlapping of the Here, the negative charge is dispersed by two
σ-p-orbitals. It is a general stabilising interaction. factors, i.e. +R-effect of the carboxylate ion
It involves delocalisation of σ-electrons of C—H (conjugation) and I-effect of the halogens.
bond of an alkyl group directly attached to an These effects are shown below in the
atom of unsaturated system or to an atom with carbocations
an unshared system or to an atom with an
O
unshared p -orbital. ||
The σ-electrons of C—H bond of the alkyl (a) CH3 C—O
group enter into partial conjugation with the O
attached unsaturated system or with the | O
CH3 C==O ! CH3 C
unshared p-orbital. It is a permanent effect. O
50. Due to + I effect, electron density increases, O
||
which results in decrease in acidic character. (b) Cl CH2 C—O
Acetic acid, CH3 æ COOH has —CH3 group O
that shows + I effect, whereas no such group is | O
present in formic acid. Therefore, formic acid is Cl CH2 C ==O ! Cl CH2 C
O
a stronger acid than acetic acid.
O O
||
(c) F CH2 O—O
CHO CHO CHO C æ CH3
O
| O
F CH2 C==O ! F CH2 C > > >
O
(+R)
NO2 CH3
O
F || (–I, –M) (+I)
(d) CH C—O
F 58. When electrophile attacks CH3 æ CH ==CH2
O delocalisation of electrons can take place, in two
F | F O possible ways
CH C == O ! CH C ⊕
F F O CH3 æ CH ==CH2 + H+ æÆ CH3 æ CH æ CH3
As it is clearly evident from the above (2° carbocation)
⊕
structures, that +R-effect is common in all the CH3 æ CH2 æ CH2 (1° carbocation)
four structures, therefore, overall dispersal of
negative charge depends upon the number of As 2° carbocation is more stable than 1°
halogen atoms and electronegativity. Since, F carbocation thus first addition is more feasible.
has the highest electronegativity and two Note Stability of carbocations is the basis of
F-atoms are present in option (d), thus, dispersal Markownikoff's rule.
of negative charge is maximum in option (d). CH3
Note In above structure (a), methyl group (æCH 3 ) 
increases the density on C-atom. 59. CH3 æ CH2 æ CH æ CH2Br + NH3 æÆ
55. Electronegativity of Cl, Br, C and Mg follows CH3

the order Cl > Br > C > Mg CH3 — CH2 — CH — CH2NH2
*CH3 Æ æ CH2 Æ æ Cl ( - I-effect)
*CH3 æ← CH2 æ ← Mg +Cl - It is an example of nucleophilic substitution
reaction.
*CH3 Æ æ CH2 Æ æ Br ( - I-effect)
*CH3 æ CH2 æ CH3 (+ I-effect) 60. Dehydration of alcohol involves the loss of two
atoms or groups from the adjacent carbon
-l effect of Cl > Br. atoms, hence it is an example of β-elimination
Hence, CH3 æCH2 æCl has the greatest reaction.
positive charge.
61. Acyclic or open chain compounds are
K (t -butoxide) • also called aliphatic compounds and
56. CHCl 3 æææææÆ •CCl 2
Chloroform Dichlorocarbene consist of straight or branched chain of carbon
Since, the dominating group, i.e. hydrogen and atoms.
chlorine, here are lost from the same carbon CH3
atom, it is an example of α-elimination. 
CH3CH3 , CH3 æ CH æ CH3,
57. Reactivity of carbonyl compounds towards
Ethane iso - butane
nucleophilic addition reactions depends on the
presence of substituted group. Electron O O
withdrawing (– I , – M ) groups increases  
reactivity towards nucleophilic addition CH3 æ C æ H , CH3 æ C æ OH
reactions. Acetaldehyde Acetic acid
Alicyclic or closed chain or ring compounds Thus, bond Assertion and Reason correct and
contain carbon atoms joined in the form of a Reason is not the correct explanation of Assertion.
ring (homocyclic). Some examples of this type
of compounds are
66. The names of straight chain compounds are
based on their chain structure and end with suffix
‘-ane’, carry a prefix indicating the number of
carbon atoms present in the chain (except
from CH4 to C4H10 where the prefixes are
Cyclopropane Cyclohexane Cyclohexene derived from trivial names).
Thus, both Assertion and Reason are correct Thus, both Assertion and Reason are correct and
and Reason is not the correct explanation of Reason is not the correct explanation of Assertion.
Assertion. 67. In numbering to carbon chain, the parent carbon
62. When a covalent bond is formed between atoms chain is numbered in a manner so as to give
of different electronegativity, the electron lowest number to that carbon atom linked by
density is more towards the more double or triple bond even it violates the rules of
electronegative atom of the bond. Such a shift of saturated hydrocarbons so,
electron density results in a polar covalent bond. CH3 CH CH CH CH2 CH CH3
Bond polarity leads to various electronic effects 1 2 3 4 5 6 7
in organic compounds. CH3 CH3
Thus, both Assertion and Reason are correct is 4, 6-dimethylhept-2-ene.
and Reason is not the correct explanation of 68. Heterolytic fission occurs when the two atoms
Assertion. differ considerable in their electronegativities
63. Assertion is not correct but Reason is correct. and shared pair of electrons is carried by more
Hybridisation can be determined by counting electronegative atom.
σ-bond 69. A covalent bond may be cleaved either by
3σ 2σ 3σ heterolytic cleavage or by homolytic cleavage.
H2C== C == CH2 In heterolytic cleavage, the bond breaks in such
3σ - sp 2 hybridisation a fashion that the shared pair of electrons
remains with one of the fragments.
2σ - sp hybridisation " #
Correct assertion In H2C == C == CH2 , H3C — Br æÆ H3 C + Br
the central carbon is sp-hybridised whereas the In homolytic cleavage, one of the electrons of the
terminal carbons are sp 2 -hybridised. shared pair in a covalent bond goes with each of the
bonded atoms.
64. In naming cycloalkenes, number the ring to
•
specify the position of the double bonded R—X
Heat or light
R• + X
carbons and choose the direction of numbering Alkyl free
radical
so that the substituents get the lowest number.
The position of the double bond is not indicated Thus, both Assertion and Reason are correct and
because it is known to be between C -1 and C - 2. Reason is not the correct explanation of Assertion.
CH3 70. Both Assertion and Reason are correct but Reason
So, is 3-methycyclohexene. is not the correct explanation of Assertion.
71. Since free radicals contain odd electrons, so they
are short lived and they readily try to pair up the
65. In bond-line structural representations only odd electrons to form neutral molecules, that is
atoms specifically written are oxygen, chlorine, why they are highly reactive.
nitrogen etc. Also the terminal position denote
72. The electron displacements in an organic
methyl ( æCH3 ) group while line-junctions
molecule due to the influence of an atom or a
denote carbon atoms bonded to appropriate
substituted group present in the molecule cause
number of hydrogens required to satisfy the
permanent polarisation of the bond. Inductive
valency of the carbon atoms.
effect and resonance effect are examples of this (iv) The permanent displacement of electron
type of electronic displacement. through a chain involving only σ-bonds is
Thus, both Assertion and Reason are correct called inductive effect. It involves the
and Reason is the correct explanation of electron displacement along the chain of
Assertion. saturated carbon atoms due to the presence
73. Presence of alternate single and double bonds of a polar covalent bond at one end of the
in an open chain or cyclic system is termed as chain.
conjugated system. These systems often show Or
abnormal behaviour as in them the π- electrons – I -effect is related to the ability of
are delocalised and the develops polarity. substituent for the electron attraction
Examples are 1, 3- butadiene, aniline and capacity from the attached carbon atom, i.e.
nitrobenzene etc. it is based on electronegativity of an
Thus, both Assertion and Reason are correct atom. This effect increases with increase in
and Reason is the correct explanation of the electronegativity of an atom.
Assertion. From above, we can conclude that option (b)
74. Assertion is incorrect but Reason is correct. is correct.
Resonance hybrids are always more stable than — NR2 < — OR < — F (-I -effect)
any of the canonical structures would be, if they 77. (i) The dispersal of the charge stabilises the
existed. The delocalisation of the electrons carbocation. More the number of alkyl
lowers the orbital energies, imparting stability. groups, the greater is the dispersal of
The gain in stability of the resonance hybrid positive charge and therefore, more is the
over the most stable of the canonical structure is stability of carbocation.
called resonance energy. Thus, the correct order is
A canonical structure that is lower in energy ⊕ ⊕ ⊕

makes a relating greater contribution to CH2OCH3 > CH3 CH2 > CH3
resonance hybrid. C B A
Thus, the correct assertion will be energy of (ii) Homolytic cleavage results in the formation
resonance hybrid is equal to the sum of energies of free radical.
of all canonical forms in proportion of their Homolytic •
contribution towards the resonance hybrid. CH3CH2 — Cl ææææÆ CH3 C H2 + •Cl
fission
75. When a covalent bond is formed between atoms (iii) The shape of carbocation is trigonal planar
of different electronegativity, the bonding with positively charged carbon being
electrons are shifted towards the more sp 2 -hybridised.
electronegative atom. This is known as inductive
It is shown below :
effect and this unequal sharing of electrons
results in polar covalent bond. H
76. (i) Maximum polarity present in C æ NO2 + C H
bond so dipole moment of nitropropane is
the maximum amongst the given molecules. H
(ii) Electron donor tendency :
O
 (iv) Among the given free radicals, CH2
æ OCH3 > æO æ C æ CH3
(iii) Aniline is a conjugated system and it is more is most stable due to resonance. In the
polar than expected because NH2 group remaining free radicals, more the alkyl
release electron density towards benzene groups bonded to the electron deficient
nucleus rather than attract from benzene. carbon, more stable is the radical.
Thus, the correct order of stability of given ● -R-effect is shown :
free radicals is "
æCOOH, æCHO, ! C ==O, æCN,
CH2 > CH3 CHCH3 æNO2 etc.
(II) (I)
Or
In compounds exhibiting resonance, bond
> CH2 CH3 > CH2 —CH(CH3)2 order can be given by the formula.
(IV) (III) 79. (i) When a covalent bond is formed between
atoms of different electronegativity, the
Or Because of the presence of 7 p -orbitals and bonding electrons are shifted towards the more
7 unpaired electrons. It is aromatic in nature electronegative atom. This is known as
as these unpaired electrons delocalise in inductive effect and this unequal sharing of
p-orbitals. electrons results in polar covalent bond.
The structure of benzyl free radical is Thus, both (A) and (R) are correct but (R) is
not the correct explanation of (A).
(ii) Formic acid (HCOOH) is a stronger acid than
benzoic acid (PhCOOH) although (Ph-) group
is e - - attracting (-I -effect). This is due to the
+ R effect of phenyl group which is greater than
-I -effect.
78. (i) Both the rules are correct for resonating Hence, it decreases the acidic nature of benzoic
structure. acid.
I. The overall charge of system must remain (iii) The stability of carbonium ions is influenced
same. by both resonance and inductive effects. Allyl
and benzyl show resonance effect.
II. The arrangement of atoms must be
identical or almost same in every Thus, both (A) and (R) are correct and (R) is
resonance structures. the correct explanation of (A).
(ii) # (iv) When a covalent bond is formed between
O O O atoms of different electronegativity, the
electron density is more towards the more
# electronegative atom of the bond.
Such a shift of electron density results in a
polar covalent bond. Bond polarity leads to
# various electronic effects in organic
# compounds.
O O Thus, both Assertion and Reason are correct
and Reason is not the correct explanation of
# Assertion.
Or
The electron displacements in an organic
(Phenoxide ion)
molecule due to the influence of an atom or a
(iii) Structure I is more stable than structure II as substituted group present in the molecule cause
in structure II, the positive charge is present permanent polarisation of the bond. Inductive
on the highly electronegative oxygen. effect and resonance effect are examples of this
type of electronic displacement.
(iv) + R-effect is shown by :
Thus, both Assertion and Reason are correct
Halogen, æOH, OR, æOCOR, NH2 ,
and Reason is the correct explanation of
COR , OR2
Assertion.
80. (i) Both Assertion and Reason are correct but (iv) Assertion is correct but Reason is incorrect.
Reason is not the correct explanation of IUPAC name of
Assertion. Less reactivity of saturated 5 4 3 2 1
C H3 æ C H æ C H2 æ C H æ C HO
hydrocarbons is due to the presence of  
single bonds between carbon atoms. Cl CH3
(ii) Assertion is correct but Reason is incorrect.
is 4-chloro-2-methylpentanal, the compound
There is one double bond between two
consists of æ CHO as functional group. The
carbon atoms in their molecules and they
numbering is done from the functional
have the general formula C n H2n .
group. The numbering is done from the
(iii) Both Assertion and Reason are correct and functional group side, Cl and CH3 are
Reason is the correct explanation of substituents.
Assertion. When double and triple bonds
When writing the names of the compounds,
are present in a single compound lowest sum
it is written in alphabetical order.
rule is followed. Thus in
5 4 3 2 1 Thus, the name is given as 4-chloro-2-methyl
C H3 C H == C H æC ≡≡ C H pentanal.
Sum of locants (1 + 3) = 4. Or Assertion and Reason both are correct
In C H3 C H == C H æC ≡≡ C H statement but Reason is not the correct
1 2 3 4 5 explanation of Assertion. neo-hydrocarbons
Sum of locants ( 2 + 4 ) = 6 contain a quaternay carbon atom, i.e.
So it is named as pent-3-en-1-yne. ( CH3 ) 3 C æ .