Electronic Effect

ELECTRONIC EFFECTS
Contents
Topic Page No.
Theory 01 - 03
Exercise - 1 04 - 20
Answer Key 42 - 45
Syllabus
Resonance and hyperconjugation, Polarity and inductive effects in alkyl halides; Reactive
intermediates produced during homolytic and heterolytic bond cleavage; Formation, structure
and stability of carbocations, carbanions and free radicals, acidic strength & basic strength.
Name : ____________________________ Contact No. __________________

ELECTRONIC EFFECTS AND THEIR APPLICATIONS
ELECTRONIC EFFECTS
Permanent Electronic Effects : Permanent electronic effects are mainly divided into following categories:
(1) Inductive Effect (2) Mesomeric
(3) Hyperconjugation (4) Reverse hyperconjugation
Inductive Effect (Polar nature of covalent bonds)
The displacement of an electron (shared) pair along the carbon chain due to the presence of an
electron withdrawing or electron releasing groups in the carbon chain is known as Inductive Effect
(effect).

C---- C ---- C -- G (G : functional group)

C ---- C ---- C -- G
But the effect is insignificant beyond third carbon atom.
This effect is transmitted through the chain of bonds and diminishes. with increasing chain
length.
I group :
The group which withdraws electrons is known as I group and its effect is known as I effect.
I power of various group & cation.
> > > NO2 > SO2R > CN > CHO > COOH > F > Cl > Br >
I > OR > OH > C CH > NH2 > C6H5 > CH = CH2 > H.
I power of groups in decreasing order with respect to the reference H
+ I group :
The group which donates or gives electron is known as + I group and effect is known as + I effect.

Alkyl groups, O , CO O are + I groups.
(a) + I power of different type groups and anions :
> > C(CH3)3 > CH (CH3)2 > CH2 CH3 > CH3 > D > H
+ I power in decreasing order with reference to H
(b) + I power of same type of alkyl groups :
+ I power number of Cs in same type of alkyl group
For example
Resonance
When a molecule or ion can be represented by two or more structures which have the same
arrangement of atomic nuclei but differ in distribution of electrons, the phenomenon is called as
Resonance. The various structures are called contributing or resonating structures. None of these
structures truly represents all the properties of that molecule or ion. The actual structure is a resonance
hybrid of several contributing structures.
Physical & Inorganic By A-479 Indra Vihar, Kota Organic Chemistry By

NV Sir Ph. - 9982433693 (NV Sir) 9462729791(VKP Sir) VKP Sir
B.Tech. IIT Delhi M.Sc. IT-BHU ELECTRONIC EFFECT # 1
In the molecule if resonance is present then mesomeric effect may be present or may not be present.
Resonance generally occurs when there is a conjugation of -bonds (alternate double-single-double
bond arrangement) known as conjugated system.
Conjugate positions of the molecule :

Type of Conjugates
(i) , conjugation (ii) Positive charge, conjugation
(iii) Negative charge, conjugation (iv) Odd electron, conjugation
(v) Lone pair, conjugation
Mesomeric Effects : This is of following types :
+ M effect (+R) :
C or
When flow of e pair (movement) starts from the group (G). It takes place when G has a lone pair
or an extra electron (in ion).
Groups which shows '+ m' effect are :
> NH2 > NHR > NR2 > OH > OR > NH C R > O C R > Ph, CH3 > F >
|| ||
O O
Cl > Br > I, N = O.
M effect ( R) :
C C G or
When e pair movement takes place towards G from the molecule.

Groups which can show m effect are
NO2 > C N > SO3H > CHO > C R > C OH

|| ||
O O
Hyperconjugation
When (C H) sigma electrons are in conjugation to pi bond, this conjugation is known as (CH),
conjugation, excessive conjugation or hyperconjugatioon.
Structural requirement for hyperconjugation:
(A) Compound should have at least one sp 2 -hybrid carbon of either alkene alkyl carbocation or alkyl
free radical.
(B) -carbon with respect to sp 2 hybrid carbon should have at least one hydrogen.
If both these conditions are fulfilled then hyperconjugation will take place in the moelucle.
(C) Hyperconjugation is of three types :
(i) (C H), conjugation : This type of conjugation occurs in alkenes.
(ii) (CH), positive charge conjugation : This type of conjugation occurs in alkyl carbocation.
(iii) (CH), odd electron conjugation : This type of conjugation occurs in alkyl free radicals-

Reverse Hyperconjugation :
The phenomenon of hyperconjugation is also observed in the system given below :
X
|
C C = C where X - halogen
|
Application of Electronic Effects :

Stability of Alkenes
Carbon-carbon double bond length in alkenes
Stability of Alkyl Carbocations
Stability of Alkyl free radicals :
Electron releasing (or donating) power of R in alkyl benzene :
Aromaticity :
Aromatic Character : [The Huckel (4n + 2) rule]
The following three rules are useful in predicting whether a particular compound is aromatic or nonaromatic.
1. Aromatic compounds are cyclic and planar.

2. Each atom in an aromatic ring is sp2 or sp hybridised.
3. The cyclic molecular orbital (formed by overlap of p-orbitals) must contain (4n + 2) electrons, i.e., 2,
6, 10, 14 ........ electrons. Where n = an integer 0, 1, 2, 3,..............

PART - I : OBJECTIVE QUESTIONS
* Marked Questions are having more than one correct option.
Section (A) : Inductive Effect
A-1. The inductive effect :

(A) implies the atom's and groups ability to cause bond polarization
(B) increases with increase of distance
(C) implies the transfer of lone pair of electrons from more electronegative atom to the lesser
electronegative atom in a molecule
(D) implies the transfer of lone pair of electrons from lesser electronegative atom to the more
electronegative atom in a molecule
A-2. Which of the following orbital overlaps is involved in the formation of the carboncarbon single bond in
the molecule HC C CH = CH2
(A) sp3 - sp3 (B) sp2 - sp3 (C) sp - sp2 (D) sp3 - sp
A-3. Inductive effect involves :

(A) Delocalisation of - electrons (B) Partial displacement of - electrons
(C) Delocalisation of - electron (D) Displacement of lone pair electrons.
A-4. Which of the following has incorrect direction of Inductive effect.
CH3 O O
-
C OH C O
(A) (B) (C) (D) CH3 C CH2 CH3

O
CH3
A-5. Decreasing I effect of given groups is -

(a) CN (b) NO2 (c) NH2 (d) F
(A) b > a > d > c (B) b > c > d > a (C) c > b > d > a (D) c > b > a > d
Section : (B) Resonance and Mesomeric Effect

B-1. Which of the following resonating structure contributes equally to the resonance hybrid.

(A) CH3 C CH CH CH3 CH3 C CH C H CH3
| |
CH3 CH3
+
(B) CH3 C NH2 CH 3 C = NH 2
|| |
O
O-
-
O O
(C) CH3 C CH3 C
O- O
+ -
(D) CH2 = CH CH = O CH 2 CH = CH O
Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

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ELECTRONIC EFFECT # 4
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B-2. Which of the following compounds have delocalisation of -electrons ?
(A) (B)
(C) CH3CH2NH CH2 CH = CH2 (D) CH2 = CH CH2 CH = CH2
B-3. Which of the following statements is not true about the resonance contributing structures of a resonance
hybrid -
(A) Contributing structures contribute to the resonance hybrid in proportion of their energies
(B) Equivalent contributing structures make the resonance very important
(C) Contributing structures represent hypothetical molecules having no real existence
(D) Contributing structures are less stable than the resonance hybrid
B-4. Which of the following is not a pair of resonating structures ?

..
(A) H C NH ; H C NH (B) CH CH = CHCH ; CH CH CH = CH
3 3 3 2 2
(C) ; (D) ;
B-5. In which of the following delocalisation of -electron is possible.

(A) CH2 = CH CH2 CHO (B) CH2 = CH CH = O
(C) CH3 CH CH3 (D) CH2 = CH CH2 CH = CH2
|
OH
B-6. Which of the following species have conjugated system ?

:
(A) (B) (C) CH 2 = C = CH NH 2 (D) All of these
B-7. The type of hybrid orbitals used by C and N in the formation of CN bond in pyrrole NH is :
(A) sp2 and sp3 (B) sp2 and sp (C) sp2 and sp2 (D) sp2 and s
B-8. Which type of orbitals C and O use in the formation of CO bond in furan, O
(A) sp2 and sp3 (B) sp2 and sp (C) sp2 and sp2 (D) sp2 and p

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B-9. Which is the most stable resonance form ?
(A) (B)
(C) (D)
B-10. I CH2 CH CH CH CH CH2

II CH 2 CH C H CH CH C H 2

III C H 2 CH C H CH CH C H 2
Among these three canonical structures (through more are possible) what would be their relative
contribution in the hybrid :
(A) I > II > III (B) III > II > I (C) I > III > II (D) III > I > II
B-11. I II III
The stability order of these canonical structures is :

(A) I > II > III (B) II > III > I (C) I > III > II (D) III > I > II
B-12. Which of the following statements is NOT true ?

(A) Resonance forms must obey normal valency rules
(B) Resonance forms are in equilibrium
(C) The hybrid is more stable than the individual resonance forms
(D) Resonance forms differ only in the distribution of electrons
Section (C) : Hyperconjugation and Application of Electronic Effects

C-1. The correct order of decreasing hyperconjugative effect of the following compounds is -
(A) CH3CH=CH2 > CH3CH2CH=CH2 > (CH3)2 CHCH=CH2
(B) (CH3)2 CHCH=CH2 > CH3CH=CH2 > CH3CH2CH=CH2
(C) (CH3)2 CHCH=CH2 > CH3CH2CH=CH2 > CH3CH=CH2
(D) CH3CH2CH=CH2 > CH3CH=CH2 > (CH3)2 CHCH=CH2
C-2. Which of the following molecule has longest C=C bond length ?
CH3
|
(A) CH2 = C = CH2 (B) CH3 CH = CH2 (C) CH3 C CH CH2 (D) CH3 C CH2
| |
CH3 CH3

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C-3. In hyperconjugation there is overlap between :
(A) p- and -orbitals (B) 2 - orbitals (C) d-and--orbtial (D) -and - orbitals
C-4. Hyperconjugation phenomenon is possible in :
(A) (B) CH2 = CH2
(C) C6H5 CH = CH2 (D) CH3 CH2 CH = CH2
C-5. The decreasing order of bond length of C = C bond in the following compounds is:
I II III IV
(A) II > I > IV > III (B) III > I > II > IV (C) IV > II > I > III (D) IV > I > II > III
C-6. Which one of the following compounds maximum electron density on aromatic ring :
(A) (B) (C) (D)
C-7. Which of the following statements is true about this molecule .
(A) C1-C2 and C3-C4 bonds are of same length.

(B) C1-C2 bond is shorter than C3-C4 bond.
(C) C1-C2 bond is longer than C3-C4 bond.
(D) C1-C2 and C2-C3 bonds are of same length.
C-8. Which of the following statements is true about this molecule ?
(A) C5-N bond is longer than C1-N and C3-N bonds.

(B) C5-N bond is shorter than C1-N bond and latter is shorter than C3-N bond.
(C) All three C-N bonds are of same length.
(D) C1-N and C3-N bonds are of same length but they are longer than C5-N bond.
a b c
C-9. Which of the CC single bond is strongest in H 3C CH CH CH CH CH 3 :
(A) a (B) b (C) c (D) All equal
a
C-10. Predict the relative bond lengths a and b, in napthalene b
(A) a > b (B) a II > III (B) I > III > II (C) I > II = III (D) all equal
C-12. In which of the following molecules electron density in ring is minimum :
(A) (B) (C) (D)
C-13. In which of the following molecules electron density in ring is maximum :
(A) (B) (C) (D)
Section (D) : Aromaticity

D-1. Which has the most aromatic nature ?
(A) (B)
(C) (D) All having same aromatic character
D-2. Which of the following is aromatic species ?

(-)
(A) (B) (C) (D) All
N
H
D-3. Which of the following is anti-aromatic species ?

fuEu esal si zfr , j ksesfVd i zt kfr gS\
+
(A) (B) (C) (D)

N S
D-4. Which is the most aromatic in character ?
(A) (B)
N S
H
(C) (D) All having same aromatic character

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D-5. Which is the most aromatic in character ?
(A) (B) (C) (D)
N S O N
D-6. Identify the aromatic compound ?
(A) (B) (C) (D)
Section (E) : Reaction Intermediate

E-1. The species CH 3 CHCH3 is less stable than -

(A) (CH3)3 C+ (B) CH3 CH2CH2 (C) CH3 CH 2 (D) CH3
E-2. Homolytic fission of a hydrocarbon will liberate :

(A) Carbonium ions (B) carbanions (C) free radicals (D) carbenes
E-3. Heterolytic fission of carbon-chlorine bond produces :

(A) two free radicals (B) two carbonium ions
(C) two carbonions (D) one cation and one anion
E-4. Which carbocation is least likely to form as an intermediate?

(A) (C 6 H 5 )3 C (B) (C) (D) CH 2 CH
E-5. Which allylic carbocation is the most stable carbocation :
(A) CH3CH CH (B) CH3CH CH
(C) C6H5 CH CH (D) All have same stability
E-6. Arrange stability of the given carbocations in decreasing order :
I II III IV
(A) I > II > III > IV (B) III > II > I > IV (C) IV > I > II > III (D) II > III > I > IV

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E-7. Which of the following carbocation is most stable?
CH3
CH3 + CH3 CH3
+ C CH3 + +
(A) C CH3 (B) (C) C CH3 (D) C
H3C H3C HO H3C OH
OH
E-8. The most unstable carbocation is

(A) CH3 C H2 (B) Cl CH2 C H2 (C) C H2 CHO (D) C H2 O CH3
E-9. Nonplanar cation is :
(A) (B) (C) CH3 (D) (CH3)3C+SbF6
E-10. The stability order of following carbocation is :
I II III IV
(A) I > II > IV > III (B) III > I > II > IV (C) IV > II > III > I (D) II > IV > III > I
E-11. Most stable radical among following.
(A) (B) (C) (D)
E-12. Arrange the following radicals in decreasing order of their stability.
(I) (II) (III) (IV)
(A) IV > I > III > II (B) IV > III > II > I (C) I > II > III > IV (D) IV > III > I > II
E-13. Consider the following carbanions -

(a) CH3 C H2 (b) CH2 = C H (c) CH C
Correct order of stability of these carbanions in decreasing order is -
(A) a > b > c (B) b > a > c (C) c > b > a (D) c > a > b
E-14. Arrange the following carbanions in decreasing order of stability :
I II III IV
(A) III > I > IV > I (B) III > II > I > IV (C) I > III > II > IV (D) III > I > II > IV

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E-15. Arrange the following radicals in decreasing order of their stability.
(I) (II) (III) (IV)
(A) III > II > IV > I (B) III > IV > II > I (C) III > II > I > IV (D) II > III > IV > I
E-16. Rank the followIng radIcals in order of Decreasing stability
I II III IV
(A) III > II > I > IV (B) III > II III > II > IV (D) III < II < I < IV
Section (F) : Acid

F-1. Consider following acid
ClCH2COOH, CH3COOH, CH3CH2COOH
I II III
Correct order of theIr pH value.
(A) III < II < I (B) I < II < III (C) I < III < II (D) II < I < III
F-2. Which one of the following is most acidic ?

(A) Phenol (B) 2-chlorophenol (C) 3-chlorophenol (D) 4-chlorophenol
F-3. Which of the following has the most acidic hydrogen ?

(A) 3-hexanone (B) 2, 4-hexanedione
(C) 2, 5-hexanedione (D) 2, 3-hexanedione.
F-4. In following acid, the correct increasing order of acidic strength acid
I. HCOOH II. CH3COOH III. C6H5COOH
(A) I < II < III (B) II < I < III (C) III < II < I (D) II < III < I
F-5.
I II III
Arrange following phenol in increasing order of Pka value
(A) I < II < III (B) III PhSO3H > PhCH2OH > PhOH
(B) PhSO3H > PhOH > PhCH2OH > PhCH2OH
(C) PhCO2H > PhOH > PhCH2OH > PhSO3H
(D) PhSO3H > PhCO 2H > PhOH > PhCH2OH

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F-7. Give the correct order of increasing acidity of the following compounds -
(I) (II)
(III) (IV)
(A) II < I < IV < III (B) IV < II < I < III (C) I < II < IV < III (D) IV < I < II < III
F-8. Among the following compounds, the strongest acid is :

(A) HC CH (B) C6H6 (C) C2H6 (D) CH3OH
F-9. Amongest the following compounds the strongest acid is :
(A) (B) (C) (D)
F-10. Which one of the hydrocarbon is the most acidic ?
(A) (B)
H3 C CH3 H3 C CH3
|
|
CH3
|
H3C CH3 H3C

|
|
|
|
(C) (D)
|
|
|
H3C H3C H
||
|
CH3
|
H3C CH3
|
H CH3
F-11. Arrange Increasing order of their Ka value.

oxalic acid, succinic acid,
I II
malonic acid, adipic acid
III IV (all dibasic)
(A) III < II I > IV (C) I > III > II > IV (D) II > I > III < IV
F-12. (CH3)3COH is less acidic than (H 3C)3SiOH because :

(A) Carbon is more electronegative than Si (B) (CH3)3SiO is stabilized due to p- d-
(C) Bigger size of silicon than carbon (D) None of these
F-13. Arrange pH of the given compounds in decreasing order :

(1) Phenol (2) Ethyl alcohol (3) Formic acid (4) Benzoic acid
(A) 1 > 2 > 3 > 4 (B) 2 > 1 > 4 > 3 (C) 3 > 2. > 4 > 1 (D) 4 > 3. > 1 > 2

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F-14. Find the order of reactivity of labelled hydrogen with NaNH2.
(A) 1 > 2 > 3 (B) 3 > 2 > 1 (C) 3 > 1 > 2 (D) 2 > 3 > 1
F-15. Use resonance arguments to rank the following in order of increasing acidity .
(A) Hc < Ha < Hb (B) Ha < Hb < Hc (C) Hb < Hc < Ha (D) Hc < Hb < Ha
F-16. 1,3-cyclopentadiene has a pK a = 15 whereas simple cycloalkanes have pK a > 50 with respect to
their conjugate bases . This is because :
(A) 1, 3-cyclopentadiene is aromatic.
(B) 1, 3-cyclopentadiene is anti-aromatic.

(C) 1, 3-cyclopentadine is non-aromatic.
(D) 1, 3-cyclopentadiene is non-aromatic with an aromatic conjugate base.
(Z)
(W) HO OH
H
F-17. The most acidic H CH2OH(X) is :
O O
OH
(Y)
Vitamin-C
(A) X (B) Y (C) Z (D) W
F-18. HOCN HN=C=O

(Cyanic acid) (Isocyanic acid)
Loss of proton from these two acids produces :
(A) same anion (B) different anions (C) same cation (D) different cations

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2 moles NaNH 2
F-19. A . The product (A) will be :
(A) (B)
(C) (D)
Section (G) : Base
G-1. What is true about the following equilibrium ?

H
K
H + H3CC CH + H3CC CK
|||
||
|
H
|
(A) It will be almost completely shifted to the left

(B) It will be almost completely shifted to the right
(C) The equilibrium constant is very close to one
(D) The equilibrium constant is zero
G-2. Select the decreasing order of relative basic strengths of following species :
OH, NH2, H C C, CH3 CH2
(A) CH3 CH2 > NH2 > H C C > OH (B) H C C > CH3 CH2 > NH2 > OH
(C) OH > NH2 > H C C > CH3 CH2 (D) NH2 > H C C > OH > CH3 CH2
G-3. Select the decreasing order of relative basic strengths of following species :
(I) (CH3)3 (II) (CH3)2 (III) (CH3)3 (IV)
(A) (I) > (II) > (III) > (IV) (B) (III) > (IV) > (II) > (I) (C) (I) > (II) > (IV) > (III) (D) (II) > (IV) > (III) > (I)

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G-4. Which is maximum basic in nature ?
(A) (B) (C) (D)
G-5. Which of the following shows the correct order of decreasing basicity in aqueous medium ?
(A) (CH3)3N > (CH3)2NH > CH3NH2 > NH3 (B) (CH3)2NH > (CH3)3N > CH3NH2 > NH3
(C) (CH3)2NH > CH3NH2 > (CH3)3N > NH3 (D) (CH3)2NH > CH3NH2 > NH3 > (CH3)3N
G-6. Give the correct order of decreasing basicity of the following compounds ?
C6H5NH2 (C6H5)2NH (C6H5)3N C6H11NH2
I II III IV
(A) I > II > III > IV (B) IV > III > II > I (C) IV > I > II > III (D) III > II > I > IV
G-7. Arrange the following in Decreasing order of their PKa value -

I. CH2=CHCH2NH2, II. CH3CH2CH2NH2 , III. CHCCH2NH2
(A) I > II < III (B) II > I > III (C) III > II > I (D) II < III > > > >
(B) > > > > >
(C) > > > > >
(D) > > > > >
G-9. Which of the following is the strongest base -
(A) (B) (C) (D)
G-10. (I) (II)
(III) (IV)
The correct order of decreasing basicity of the above compound is -

(A) I > II > III > IV (B) II > I > IV > III (C) III > IV > II > I (D) II > I > III > IV
G-11. The correct order of basicities of the following compounds is
(a) (b) CH3CH2NH2 (c) (CH3)2NH (d)
(A) b > a > c > d (B) a > c > b > d (C) c > a > b > d (D) a > b > c > d

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G-12. In the following compounds
(I) (II) (III) (IV)

The order of basicity is -
(A) IV > I > III > II (B) III > I > IV > II (C) II > I > III > IV (D) I > III > II > IV
G-13. Select the order of basic strength.

(I) R4 N OH (II) R3N(III) R2NH (IV) RNH2 (if R = Me)
(A) (I) > (III) > (IV) > (II) (B) (IV) > (III) > (I) > (II)
(C) (II) > (IV) > (III) > (I) (D) (II) > (IV) > (I) > (III)
G-14. Order of basic strength in the following compounds.

.. ..
.. NH2 NH2
NH2
(I) (II) (III)
CH3 NO2
(A) II > I > III (B) I > II > III (C) III > II > I (D) II > III > I
O
NH2 C CH3 NH2
Cl NH2 CH3
I II III
(A) I > II > III (B) III > I > II (C) III > II > I (D) II > I > III
NH2 NH NH2
(I) (II) (III)
(A) III > I > II (B) III > II > I (C) I > II > III (D) II > I > III

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G-17. Which nitrogen in LSD is most basic ?
(1)
O
HN (3)
(2) CN(C2H5)2
N
CH3
(A) 1 (B) 2 (C) 3 (D) All are same basic
PART - II : MISLLANEOUS QUESTIONS
COMPREHENSION
Comprehension # 1
But-1-ene (A) and Buta-1,3-diene (B) differ not only in the number of bonds, but (B) also has and
bonds at alternate positions. This type of the system is called conjugated system. Following are some of
the conjugate system
In such systems, electron shifting result into permanent polarity. This type of -electron shift in the conjugate
systems is called mesomeric effect.
Rules for stability :

(i) Structures with more covalent bonds are more stable than other structures
(ii) Structures in which all of the atoms have a complete valence shell of electrons (i.e., the noble gas
structure) are especially stable and make large contributions to the hybrid.
(iii) Structure that carry negative charge on a more electronegative atom and positive charge on less
electronegative atom are comparatively more stable.
1. In which of the following compound, delocalisation is not possible
(A) (B) (C) (D)
2. Select the correct option related to stability of following structure.
(A) > (B) <
O
||
(C) < (D) > CF3 C O

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Comprehension # 2
Hyper conjugation : It is delocalisation of sigma electron with p-orbital. Also known as -conjugation or
no bond resonance.
May takes place in alkene, alkynes, carbocation, free radical, benzene nucleus.
Necessary Condition : Presence of at least one hydrogen at saturated carbon which is with respect to
alkene, alkynes, carbocation, free radical, benzene nucleus.
3. Which of the following alkenes have maximum number of hyper conjugation structure.
(A) CH3CH=CHCH3 (B) (C) (D)
4. In which of the following species hyperconjugation is not possible
(A) (B) (C) (D)
5. Select the incorrect statement.

(A) Hyperconjugation is a permanent effect.
(B) CH2=CHCH3 shows hyperconjugation.
(C) Stability of alkenes directly related to number of hyperconjugation structures.
(D) C6H5CH3 does not show hyperconjugation.
Comprehension # 3
Hyperconugation describes the orbital interaction between the -system and the adjacent -bond of the
substituent group (s) in organic compounds. Hyperconjugation is also called as Baker and Nathan
effect. The necessary and sufficient condition for the hyperconjugation are :
(i) compound should have at least on sp2-hybrid carbon of either alkene, carbocation or alkyl free
radical.
(ii) -carbon with respect to sp2-hybrid carbon should have at least one hydrogen.
Hyperconjugation are three types :-
(i) (CH), -conjugation
(ii) (CH), positive charge conjugation
(iii) (CH), odd electron conjugation
The hyperconjugation may be represented as
H H
|
H C CH = CH2 H C = CH CH2
| |
H H
H
|
H C = CH CH2
|
H
H
|
H C = CH CH2
H
Number of resonating structures due to hyperconjugation = (n + 1 ) where n is number of -hydrogen.
Greater is the number of such forms, more is the stability of species under consideration.
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6. Hyperconjugation is possible in which of the following species ?
CH3
|
(A) CH CH (B) C6H5CH3 (C) CH2=CH2 (D) CH3 C CH = CH2
3 2 |
CH3
7. Which of the following carbonium ions will show highest number of hyperconjugation forms ?
CH3 CH3
| |
(A) CH3CH 2 (B) CH3 CH (C) CH3 C (D) CH3 CH2 C
| | |
CH3 CH3 CH3
8. Which of the following alkenes will show maximum number of hyperconjugation forms ?
(A) CH2 = CH2 (B) CH3 CH = CH2
CH3
|
(C) CH3 CH2 CH = CH2 (D) CH3 CH CH = CH2
Match the column
9. Match the column.

Structure No. of -Hydrogen C =C bond length in
(A) CH3CH=CH2 (X) 0 (P) 1.34
(B) CH3CH2CH=CH2 (Y) 1 (Q) 1.35
(C) (Z) 2 (R) 1.37
(D) (W) 3 (S) 1.39

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10. Match the correct order for stability of following carbocation :
ASSERTION / REASONING
DIRECTIONS :
Each question has 5 choices (A), (B), (C), (D) and (E) out of which ONLY ONE is correct.
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1.
(C) Statement-1 is True, Statement-2 is False.
(D) Statement-1 is False, Statement-2 is True.
(E) Statement-1 and Statement-2 both are False.
11. Statement-1 : m-Nitrobenzoic acid is less acidic as compared to p-nitrobenzoic acid.

Statement-2 : Acetic acid is stronger acid than benzoic acid but formic acid is stronger acid than both
12. Statement-1 : Ortho substituted benzoic acids are stronger than benzoic acid
Statement-2 : Ortho substituent tends to prevent coplanarity of COOH with ring. Thus resonance is
diminished which increases acidic strength (ortho effect)
13. Statement-1 : Salicylic acid is much stronger than its m-, p-isomers and benzoic acid itself.
Statement-2 : It is due to steric inhibition of resonance, as OH group forces COOH out of the plane of ring
14. Statement-1 : Pyrrolidine () is more basic than pyrrole ()
Statement-2 : Protonated pyrrole has delocalisation of positive charge in aromatic ring.
15. Statement-1 : The Pka value of acetic acid is lower than that of phenol.
Statement-2 : Phenoxide ion is more resonance stabilized.
16. Statement-1 : Acetate ion is more basic than the methoxide ion.
Statement-2 : The acetate ion is resonance stabilized.

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PART - I : MIXED OBJECTIVE
Single Correct Answer Type

1. Consider the follownig carbocations -

(a) CH3 C H2 (b) CH2 = C H (c) CH2 = CH C H2 (d) C6H5 C H2
Stability of these carbocations in decreasing order is -
(A) d > c > a > b (B) d > c > b > a (C) c > d > b > a (D) c > d > a > b
2. Consider the following compounds -
(a) (b) (c) (d)

Arrange these compounds in decreasing order of their basicity :
(A) a>b> c > d (B) b > c > a > d (C) d > a > c > b (D) d > a > b > c
3.. Which free radical is the most stable -

(A) C6H5 C H2 (B) CH2 = CH C H2 (C) CH3 C H CH3 (D) CH3 C CH3
|
CH3
4. Which carbocation is the most stable -

CH2
(A) (B) (C) (D)
Cl
5. Which of the following carboxylic acids is most acidic in character -

(A) o-methyl benzoic acid (B) m-methyl benzoic acid
(C) p-methyl benzoic acid (D) Benzoic acid
6. Which one of the following is strongest acid -

(A) 2-chloropentanoic acid (B) 3-chloropentanoic acid
(C) 5-chloropentanoic acid (D) 4-chloropentanoic acid
7. The most stable carbanion is-
(A) CH3CH2 CH2 (B) CH3CC (C) CH3CH= CH (D) CH3 C =CH2

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8. Correct order of nucelophilicity -
(A) CH3 < NH2 < OH < F (B) F < OH < CH3 < NH2
(C) OH < NH2 < F < CH3 (D) F < OH < NH2 < CH3
9. Hydrogen bonding is maximum in

(A) Ethanol (B) Diethyl ether (C) Ethyl chloride (D) Triethylamine
10. Benzoic acid is less acidic than salicylic acid because of

(A) Hydrogen bond (B) Inductive effect (C) Resonance (D) none of these
11. In a reaction of C6H5Y, the major product (>60%) is m-isomer, so the group Y is
(A) COOH (B) Cl (C) OH (D) NH2
12. Which one of the following orders is correct regarding the I effect of the substituents ?
(A) NR2 < OR > F (B) NR2 > OR > F
(C) NR2 < OR < F (D) NR2 > OR < F
13. Which one of the following compounds will be most easily attacked by an electrophile ?
(A) (B) (C) (D)
14. The weakest acid among the following

(A) CH3COOH (B) CH3CO 2OH (C) ClCH2COOH (D) CH3CH2COOH
15. The correct order of boiling point for primary (1), secondary (2) and tertiary (3) alcohols is
(A) 2 > 1 > 3 (B) 3 > 2 > 1 (C) 1 > 2 > 3 (D) 2 > 3 > 1
16. Which of the following is most acidic ?

(A) m-chlorophenol (B) benzyl alcohol (C) phenol (D) cyclohexanol
17. Among the following the strongest base is

(A) C6H5NH2 (B) p-NO2C6H4NH2 (C) mNO2C6H4NH2 (D) C6H5CH2NH2
18. Strongest acid out of the following

(A) CH3COOH (B) ClCH2COOH (C) CH3CH2COOH (D) (CH3)2CHCOOH
19. Increasing order of acid strength among p-methoxyphenol, p-methylphenol, and p-nitrophenol is
(A)p-nitrophenol, p-methoxyphenol, p-methylphenol
(B) p-methylphenol, p-methoxyphenol, p-nitrophenol
(C)p-nitorphenol, p-methylphenol, p-methoxyphenol
(D) p-methoxyphenol, p-methylphenol, p-nitorphenol

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20. In the following compounds
(I) (II) (III) (IV)

the order of acidity is
(A) III > IV > I > II (B) I > IV > III > II (C) II > I > III > IV (D) IV > III > I > II
21. Most powerful leaving group in following -

(A) NH2 (B) OH (C) CH3 (D) F
22. (I) (II) (III) (IV)
Increasing order of stability is

(A) I < III < II < IV (B) IV < III < II < I (C) III < IV < II < I (D) II < IV < III < I
23. Increasing order of acidity in para methyl (I), chloro (II), amino (III), and nitro (IV) benzoic acids is
(A) III < II < I < IV (B) I < II < IV < III (C) III < I < II < IV (D) II < I < III < IV
24. Increasing order of basic strength of following compounds is

C6H5NH2, (CH3)3N, (C6H5)2NH, C6H5NHCH3
(I) (II) (III) (IV)
(A) III < IV < I < II (B) III < I < IV < II (C) I < III < II < IV (D) II < IV < III < I
25. The compound that is most reactive towards electrophilic nitration is

(A) Toluene (B) Benzene (C) Benzoic acid (D) Nitrobenzene
26. The most unlikely representation of resonance structures of p-nitrophenoxide ion is :
(A) (B) (C) (D)
27. Consider the following three halides -

(1) CH3 CH2 Cl (2) CH2 = CH Cl (3) C6H5 Cl
Arrange C Cl bond length of these compound in decreasing order -
(A) 1 > 2 > 1 (B) 1 > 3 > 2 (C) 3 > 2 > 1 (D) 2 > 3 > 1

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28. Arrange the following in increasing basic strength-
(a) CH3NH2 (b) (c) Cl CH2 NH2 (d) CH2 NH2 (e) NH3
Correct answer is -
(A) (a) < (b) < (c) < (e) < (d) (B) (a) < (b) < (c) < (d) < (e)
(C) (b) < (c) < (d) < (e) < (a) (D) (c) < (b) < (e) < (d) < (a)
29. Arrange in increasing pKa

(a) CH3CH2COOH (b) CH3CH2CH2COOH (c) CH3COOH
Correct answer is-
(A) (c) < (a) < (b) (B) (b) < (a) < (c) (C) (a) < (c) < (b) (D) (b) < (c) < (a)
30. Arrange in increasing basic strength

(a) Cl CH2 COOH (b) Cl CH2 CH2 CH2 COOH (c) Cl CH2 CH2 COOH
Correct answer is-
(A) (a) < (c)< (b) (B) (b) < (a) < (c) (C) (c) < (b)< (a) (D) (a) < (b) < (c)
31. Which one of the carbaions is most stable?
(A) (B) (C) (D)
32. What is the correct increasing order of bond lengths of the bonds indicated as I, II, III and IV in
following coumpounds -
(A) I < II < III < IV (B) II < III < IV < I (C) IV < II < III < I (D) IV < I < II < III
33. Which of the following is least stable ?
(A) (B) (C) (D)
34. Which one of the following is most stable carbocation ?

(A) CH2 CH C H2 (B) C H (C) CH CH C H (D) None of these
3 3
35. Which of the following ions is most stable :

(A) CH3CH2 C H2 (B) CH3 C HCH2CH3 (C) (CH3)3 C (D) (CH3)3 C . C H2

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36. The most stable carbanion is -
(A) methyl carbanion (B) primary carbanion
(C) seccondary carbanion ion (D) tertiary carbanion
37. Which of the following statements is wrong ?

(A) a tertiary free radical is more stable than a secondary free radical
(B) a secondary free radical is more stable than a primary free radical
(C) a tertiary carbonium ion is more stable than a secondary carbonium ion
(D) a primary carbonium ion is more stable than a secondary carbonium ion

38. The species CH3 C HCH3 is less stable then-

(A) (CH3)3C (B) CH3CH2 C H2 (C) CH3 C H2 (D) CH3
39. Most stable carbocation is -

(A) CH3 CH 2 (B) CH 2 CHCl2 (C) CH 2 CH2Cl (D) CH 2 CH2NO 2
40. Strongest acid among the following is -

(A) CF3COOH (B) CCl3COOH (C) CBr3COOH (D) CH3COOH
41. Among the following which one is most basic-
(A) NH3 (B) CH3NH2 (C) CH3CH2NH2 (D) CH2 NH2

|
Cl
42. Which one of the following is the weakest base -
(A) (C2H5)3N (B) (C2H5)2NH (C) C2H5NH2 (D) NH3
43. Which of the following alkenes will react fastest with H2 under catalytic hydrogenation conditions -
(A) (B) (C) (D)
44. M effect of -CCl3 can be explained on the basis of

(A) effect (B) + R effect
(C) negative hyper conjugative effect (D) none
45. Which of following has maximum hydrogenation energy.

(A) CH3 CH2 CH = CH2 (B) CH3 CH = CH CH3
cis
(C) CH2 = CH CH2 CH2 (D) All have the same

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46. Polarisation of electrons in acrolein may be written as -

(A) C H2 = CH CH = O (B) C H2 = CH C H = 0

(C) C H2 = C H CH = 0 (D) C H2 = CH CH = O
47. In which compound delocalisation is not possible -

(A) 2-butene (B) 1, 3-butadiene (C) 1, 3, 5-hexatriene (D) Benzene
48. Consider the following compound :
C H2 = C H C H = C H2
1 2 3 4
carbon-carbon bond length between C2 and C3 will be -

(A) 1.54 (B) 1.3
(C) Less than 1.54 and greater than 1.33 (D) 1.21
49. + R power of the given groups -

(a) O (b) NH2 (c) OH (d) NHCOCH3
increasing order is -
(A) a > b > c > d (B) d > c > b > a (C) a > c > b > d (D) a > d > c > b
50. In pyridine ; Number of conjugated electrons are -
(A) 6 (B) 8 (C) zero (D) 5
51. Which of the following is corect for stability of phennoxide ion -

(A) resonating structure of benzene ring
(B) localization of -electron in phenoxide ion
(C) delocalization of -electrons in phenoxide ion
(D) all of the above
Multiple Correct Answer Type
52. In which of the following pairs the first one is the stronger base than second.
(A) , (B) , (C) , (D) CH3NH2, CH3OH
53. Which of the following are not non-aromatic ?
(A) (B) (C) (D)

N

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54. Which of the following are aromatic ?
+
(A) (B) (C) (D)
(+)
55. In which of the following first carbocation is more stable than second one.
(A) , (B) ,
(C) , (D) ,
56. In which of the pair of carbanion have first more stable than second.
(A) (B)
(C) (D)
PART - II : SUBJECTIVE QUESTIONS
1. Show the direction of Inductive-effect in following compounds.
COONa COOH
CH3
(P) (Q) (R) (S)
COOH OH NaO
2. Arrange following compounds in decreasing order of their dipolemoment.

I II III IV
(x) CH3CH2NO2 CH3CH2NH2 CH3CH2F CH3CH2CN
(y) CH3CH2COOH CH3CH2OH CH3CH2Cl CH3CH2NH2
3. Which of the following cases have incorrect direction of I effect.
(P) (Q) (R) (S) CH3 CH2 MgBr
(T) (U) (V)

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4. Identify more stable resonating structure.
(i) and (ii) and
(iii) and (iv) and
5. Write the stability order of following resonating structures :

I II I II
(P) (Q)
(R) (S)
6. Which of the following compounds have delocalized electrons ?

O
||
a. CH 2 CHCCH 3 f.
b. g.
c. h. CH3CH2NHCH2CH = CHCH3
d. i. CH3CH2NHCH = CHCH3
e. CH2=CHCH2CH = CH2 j. k.

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7. For each pair of ions, determine which ion is more stable.
(A) and (B) and
(C) and (D) and
(E) and
8. In the following sets of resonating structure, label the major and minor contributors towards resonance
hybrid.
(a) (b)
(c)
(d)
9. Identify the major contribution in following resonance structures:
NH 2 NH 2
| |
(a) NH2 C NH2 NH2 C

(I) (II)
O O O
|| || ||
(b) CH3 C C CH3 & CH3 C CH= CH3
(I) (II)
(c) &
(I) (II)
(d) CH3 OH & CH3 = H
(I) (II)

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10. Find the number of hydrogens involved in hyperconjugation in the following compounds ?
11. Write the stability order of following carbocations
I II III IV
12. Write stability order of C=C bond present in following compound.
13. Write the number of hyperconjugable hydrogen atoms of following species :

(a) (b) CH3 CHCH2CH3
(c) C=CHCH3 (d) CH3CH=CHC2H5

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14. Write the stability order of following alkene :
CH3 CH3
| |
(I) (II) CH3CH=CHCH3 (III) C=C (IV) CH3 C CH CH C CH3
| |
CH3 CH3
15. The central carbon-carbon bond in 1, 3-butadiene is shorter than that of n-butane. Why ? [JEE-98]
16. What is aromaticity ?
17. Explain why the following systems are not aromatic ?
(i) (ii) (iii)
18. Classify the following as aromatic, antiaromatic and nonaromatic compounds.
(1) (2) (3) (4) (5)
(6) (7) (8) (9) (10)
(11) (12)
19. Benzene and [10] Annulene both have (4n + 2) -electron in ring and all bonds are conjugated even then
only benzene is aromatic explain.
20. Why cyclooctatetraene is nonplanar.
21. Which of the following is aromatic

H
+ + +
(a) (b) (c) (d)

+ -
H H
(e) (f) (g) (h)
H
H H
(i)
H H
H

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22. Arrange the given species in decreasing order of their nucleophilicity ?
H2O
23. Write nucleophilicity order in the following compound.
24. Which of the following carbocation is more stable and why ?
25. Arrange the following carbocations in decreasing order of their stability :

(i) (A) CH3CH2 CH2 (B) CH3 CH CH2 (C) CH3 CH CH2 (D) CH3 CH CH2
| | |
F Br Cl

(ii) (A) CH3 CH2 C H2 (B) CH3 C H CH2 CH3 (C) (CH3 )3 C (D) C H3
(iii) (A) (B) (C) (D)
(iv) (A) (B) (C) (D)
(v) (A) (B) (CH3CH2)2 (C) (CH3CH2)3 (D)
26. Rank the following free radical in increasing order of their stability and give appropriate reasons.

B.Tech. IIT Delhi
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27. Order of stability carbocation is :
CH3 CH3
| |
(A) CH3 O CH2 CH2 CH CH2 (B) CH O CH CH2 C CH3
3 2

CH3 CH3
| |
(C) CH3 O CH2 CH CH CH3 (D) CH3 O C H CH 2 CH CH3
28. Write the order of Ka following compounds :

I II III IV
(P)
(Q)
(R)
(S)
29. Write the order of ease of deprotonation of labelled Hatoms.
30. Although phenoxide ion has more number of resonating structures than benzoate ion, benzoic acid is a
stronger acid than phenol. Why ? [JEE-97]

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31. Find the order of Ka of following compounds.
(p) (A) (B) (C) (D)
(q) (A) (B) (C) (D)
(r) (A) (B) (C) (D)
(s) (A) (B) (C) (D)
32. Which nitrogen is more basic
(a) (b)
33. Arrange the following species in order of decreasing basicity.
(p) (A) (B) (C)
(q) (A) H2O (B) H2N (C) HO
(s) (A) (B) (C) (D)

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(t) (A) (B) (C) (D)
(u) (A) (B) (C) (D)
(w) (A) (B) (C) (D)
34. Dimethylamine is stronger base than trimethylamine. Explain. [JEE-98]
35. Write the order of Kb of following amines :

I II III
(P) (CH3)3N (CH3)2NH CH3NH2 (Gaseous phase)
(Q) (CH3)2NH CH3NH2 (CH3)3N (H2O as solvent)
(R) (C2H5)2NH (CH3CH2)3N C2H5NH2 (H2O as solvent)
36. Write the increasing pkb values for following anions.

CH3 , NH2 , OH , F
37. What is the effect of electron releasing and electron withdrawing groups on the basic strength of aniline.
38. Write the decreasing order of basic strength of following compounds.
(I) (II) (III)

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PART - I : IIT-JEE PROBLEMS (PREVIOUS YEARS)
* Marked Questions are having more than one correct option.
1. CH2 = CH is more basic than HC C. Explain. [JEE-2K(M), 1/100]
2. Which of the following acids has the lowest value of acid dissociation constant : [JEE-02(S), 3/90]
(A) CH3CHFCOOH (B) FCH2CH2COOH (C) BrCH2CH2COOH (D) CH3CHBrCOOH
3. Match the Ka values : [JEE-03(M), 2/60]
4. Write resonating structure of the compound . [JEE-03(S), 2/60]
5. Which of the following represent the given mode of hybridisation sp2 sp2 sp sp from left to right.
[JEE-03(S), 3/84]
(A) H2C = CH C N (B) HC C C CH (C) H2C = C = C = CH2 (D)
6. A , The product A will be - [JEE-03(S), 3/84]
(A) (B) (C) (D)

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7. What is the acidity order of x, y & z ? [JEE-04(S), 3/84]
(A) x > y > z (B) x > z > y (C) y > z > x (D) z > y > x
Excess of CH COONa
8. 3
[JEE-05(S), 3/84]
The products will be :
(A) + CH3COONa (B) + CH3COOH
(C) + CH3COOH (D) + SO3
9. Which will be the least stable resonating structure : [JEE-05(S), 3/84]

(A) CH2 = CH O CH3 (B) C H 2 CH = CH OCH3

(C) C H2 CH = CH CH = CH3 (D) CH2 = CH CH = CH3
10. NaHCO
3 ; NaHCO
3 [JEE-06, 3/184]

A mixture of benzene sulphonic acid and paranitrophenol react with NaHCO3 separately. The gases produced
are respectively.
(A) SO2, CO2 (B) SO2, CO (C) SO2, NO2 (D) CO2, CO2
11. Among the following, the least stable resonating structure is : [JEE-07, 3/162]
O
+ O +
(A) (B) N (C) + N (D)
+
O O

12. Hyperconjugation involves overlap of the following orbitals [JEE-08, 3/163]

(A) (B) p (C) p p (D)
13. The correct stability order for the following species is : [JEE-08, 3/163]
(A) (II) > (IV) > (I) > (III) (B) (I) > (II) > (III) > (IV)
(C) (II) > (I) > (IV) > (III) (D) (I) > (III) > (II) > (IV)

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14. The IUPAC name of the following compound is : [JEE-2009, 3/160]
(A) 4-Bromo-3-cyanophenol (B) 2-Bromo-5-hydroxybenzonitrile

(C) 2-Cyano-4-hydroxybromobenzene (D) 6-Bromo-3-hydroxybenzonitrile
15. The correct stability order of the following resonating structures is : [JEE-09, 3/160]
(A) (I) > (II) > (IV) > (III) (B) (I) > (III) > (II) > (IV)
(C) (II) > (I) > (III) > (IV) (D) (III) > (I) > (IV) > (II)
16. The correct acidity order of the following is : [JEE-09, 3/160]
(A) (III) > (IV) > (II) > (I) (B) (IV) > (III) > (I) > (II)
(C) (III) > (II) > (I) > (IV) (D) (II) > (III) > (IV) > (I)
17. The total number of basic groups in the following form of lysine is : [JEE-10, 3/163]
18. Among the following compounds, the most acidic is : [JEE-2011]

(A) p-nitrophenol (B) p-hydroxybenzoic acid
(C) o-hydroxybenzoic acid (D) p-toluic acid
19. The total number of contributing structures showing hyperconjugation (involving C-H bonds) for the follow-
ing carbocation is : [JEE-2011]
20. Which of the following molecules, in pure form, is (are) unstable at room temperature ? [JEE-12, 3/136]
O
O
(A) (B) (C) (D)

B.Tech. IIT Delhi
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PART - II : AIEEE PROBLEMS (PREVIOUS YEARS)
1. In which of the following species is the underlined carbon having sp3 hybridisation ? [AIEEE 2002]
(1) CH3COOH (2) CH3CH2OH (3) CH3COCH3 (4) CH2=CHCH3.
2. Which of the following compounds has wrong IUPAC name ? [AIEEE 2002]
(1) CH3CH2CH2COOCH2CH3 Ethylbutanoate (2) 3Methylbutanal
O
||
(3) 2Methyl-3-butanol (4) CH3CHCCH2CH3 2Methyl-3-pentanone
|
CH3
3. In the following benzyl/allyl system
R CH = CH2 and
(R is alkyl group)
decreasing order of inductive effect is : [AIEEE-2002]
(1) (CH3)3 C > (CH3)2CH > CH3CH2 (2) CH3CH2 > (CH3)2CH > (CH3)3C
(3) (CH3)2CH > CH3CH2 > (CH3)3C (4) (CH3)2C > CH3CH2 > (CH3)3CH
4. The IUPAC name of CH3COCH(CH3)2 is [AIEEE 2003]

(1) Isopropylmethyl ketone (2) 2-Methyl-3-butanone
(3) 4-Methylisopropyl ketone (4) 3-Methyl-2-butanone.
5. The correct order of increasing basic nature for the bases NH3, CH3NH2 and (CH3)2NH is : [AIEEE-2003]
(1) CH3NH2 < NH3 < (CH3)2NH (2) (CH3)2NH < NH3 < CH3NH2
(3) NH3 < CH3NH2 < (CH3)2NH (4) CH3NH2 < (CH3)2NH < NH3
6. The IUPAC name of the compounds is [AIEEE 2004]
(1) 3,3-Dimethyl -1-hydroxycyclohexane (2) 1,1 -Dimethyl-3-hydroxycyclohexane

(3) 3,3-Dimethyl-1-cyclohexanol (4) 1,1-Dimethyl-3-cyclohexanol
7. Which one of the following does not have sp2 hybridized carbon ? [AIEEE 2004]
(1) Acetone (2) Acetic acid (3) Acetonitrile (4) Acetamide
8. Among the following acid which has the lowest pKa value ? [AIEEE-2005]
(1) CH3CH2COOH (2) (CH3)2CH COOH (3) HCOOH (4) CH3COOH
9. Amongst the following the most basic compound is [AIEEE-2005]

(1) p-Nitroaniline (2) Acetanilide (3) Aniline (4) Benzylamine
10. The IUPAC name of the compound shown below is [AIEEE 2006]
(1) 2-Bromo-6-chlorocyclohex-1-ene (2) 6-Bromo-2-chlorocyclohexene

(3) 3-Bromo-1-chlorocyclohexene (4) 1-Bromo-3-chlorocyclohexene

B.Tech. IIT Delhi
M.Sc. IT-BHU
11. The increasing order of stability of the following free radicals is : [AIEEE-2006, 3/220]

(1) (C6H5)3 C < (C6H5)2 C H < (CH3)3 C < (CH3)2 C H

(2) (C6H5)2 C H < (C6H5)3 C < (CH3)3 C < (CH3)2 C H

(3) (CH3)2 C H < (CH3)3 C < (C6H5)3 C < (C6H5)2 C H

(4) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H < (C6H5)3 C
12. The correct order of increasing acid strength of the compounds [AIEEE-2006, 3/220]
(a) CH3CO2H (b) MeOCH2CO2H (c) CF3CO2H (d)
(1) d < a < c < b (2) d < a < b < c (3) a < d < c < b (4) b < d < a < c
13. The IUPAC name of [AIEEE 2007, 3/120]
(1) 5,5-Diethyl-4, 4-dimethylpentane (2) 3-Ethyl-4, 4-dimethylheptane

(3) 1,1-Diethyl-2, 2-dimethylpentane (4) 4,4-Dimethyl-5, 5-diethylpentane
14. Which one of the following is the strongest base in aqueous solution ? [AIEEE-2007, 3/120]
(1) Trimethylamine (2) Aniline (3) Dimethylamine (4) Methylamine
15. The IUPAC name of neopentane is : [AIEEE 2009, 4/144]

(1) 2, 2-dimethylpropane (2) 2-methylpropane
(3) 2, 2-dimethylbutane (4) 2-methylbutane
16. Arrange the carbanions, (CH3)3 C , C Cl3, (CH3)2 C H, C6H5 C H2 in order of their decreasing stability :
[AIEEE-2009, 4/144]
(1) (CH3)2 C H > C Cl3 > C6H5 C H2 > (CH3)3 C (2) C Cl3 > C6H5 C H2 > (CH3)2 C H > (CH3)3 C
(3) (CH3)3 C > (CH3)2 CH > C6H5 CH2 > CCCl3 (4) C6H5 CH2 > CCl3 > (CH3)3 C > (CH3)2 CH
17. The correct order of increasing basicity of the given conjugate bases (R = CH3) is : [AIEEE-2010, 4/144]
(1) RCO O HC C R N H2 (2) R HC C RCO O N H2
(3) RCO O N H2 HC C R (4) RCO O HC C N H2 R

B.Tech. IIT Delhi
M.Sc. IT-BHU
NCERT QUESTIONS
1. Show by arrow I effect in the following molecules
(a) CH3 CH = CH NO2 (b)
2. Arrange for acidic strength order CH3COOH, ClCH2COOH, Cl2CHCOOH, Cl3CCOOH
3. Draw resonating structure for following molecules , CH2 = C = O ,
4. By drawing resonating structures of following molecules, Judge whether the group attatched to ring exerts
+ m or m effect.
5. Which of them is more basic :
(a) (b)
6. Which of them is more basic (a) (b) (c)
7. Arrange the following free radicals in increasing order of stability
8. Write tautomer of butanone and cyclohexanone.
9. Arrange the following carbocation s in stability order-
1. H2.
2.
10. Resonance energy of benzene is 36 Kcal mol, but that of toluene is 37.5 Kcal mol. Why ?

B.Tech. IIT Delhi
M.Sc. IT-BHU
Exercise # 1
PART - I
A-1. (A) A-2. (C) A-3. (B) A-4. (D) A-5. (A) B-1. (C) B-2. (B)
B-3. (A) B-4. (B) B-5. (B) B-6. (D) B-7. (C) B-8. (C) B-9. (C)
B-10. (A) B-11. (D) B-12. (B) C-1. (A) C-2. (D) C-3. (D) C-4. (D)
C-5. (B) C-6. (B) C-7. (B) C-8. (D) C-9. (B) C-10. (B) C-11. (A)
C-12. (D) C-13. (B) D-1. (A) D-2. (D) D-3. (D) D-4. (B) D-5. (D)
D-6. (B) E-1. (A) E-2. (C) E-3. (D) E-4. (C) E-5. (C) E-6. (B)
E-7. (C) E-8. (C) E-9. (A) E-10. (D) E-11. (C) E-12. (B) E-13. (C)
E-14. (D) E-15. (C) E-16. (A) F-1. (B) F-2. (B) F-3. (B) F-4. (D)
F-5. (B) F-6. (D) F-7. (B) F-8. (D) F-9. (B) F-10. (A) F-11. (C)
F-12. (B) F-13. (B) F-14. (B) F-15. (A) F-16. (D) F-17. (C) F-18. (A)
F-19. (A) G-1. (A) G-2. (A) G-3. (A) G-4. (B) G-5. (C) G-6. (C)
G-7. (B) G-8. (C) G-9. (A) G-10. (B) G-11. (D) G-12. (D) G-13. (A)
G-14. (A) G-15. (B) G-16. (A) G-17. (B)
PART - II
1. (A) 2. (C) 3. (D) 4. (C) 5. (D) 6. (B) 7. (C)
8. (B) 9. (A) - W, S ; (B) - Z, R ; (C) - Y, Q ; (D) - X, P
10. (A) - r ; (B) - p ; (C) - q 11. (C) 12. (A) 13. (C) 14. (C) 15. (C)
16. (D)
Exercise # 2
PART - I
1. (A) 2. (C) 3. (A) 4. (B) 5. (A) 6. (A) 7. (B)
8. (D) 9. (A) 10. (D) 11. (A) 12. (C) 13. (D) 14. (B)
15. (C) 16. (A) 17. (D) 18. (B) 19. (D) 20. (D) 21. (D)
22. (B) 23. (C) 24. (B) 25. (A) 26. (C) 27. (A) 28. (C)
29. (A) 30. (A) 31. (A) 32. (D) 33. (A) 34. (A) 35. (C)
36. (A) 37. (D) 38. (A) 39. (A) 40. (A) 41. (C) 42. (A)
43. (A) 44. (C) 45. (A) 46. (A) 47. (A) 48. (C) 49. (A)
50. (A) 51. (C) 52. (ACD) 53. (ABD) 54. (ACD) 55. (BCD) 56. (BC)
PART - II
CH = CH2
COOH
CH3 COONa
1. (P) (Q) (R) (S)
COOH
OH NaO
C CH
2. Decreasing order of dipolemoment for given compounds
(x) : I > IV > III > II ; (y) : I > III > II > IV
3. Cases P, S, T, V has incorrect direction of I effect.
4. (i) 2 ; (ii) 2 ; (iii) 1 ; (iv) 2
5. (P) I > II ; (Q) II > I ; (R) I > II ; (S) II > I

B.Tech. IIT Delhi M.Sc. IT-BHU
6. a, d, f, g, i, j 7. A (II), B(I), C(II), D(I), E(I)
8. (a) I minor (b) I minor (c) I minor (d) I minor
9. (A) II (B) II (C) I (D) II
10. (I) 12 (II) 9 (III) 6 (IV) 4 (V) 3
(VI) 2 (VII) 1 (VIII) 6 (IX) 3 (X) 4
(XI) 0 (XII) 0 (XIII) 4 (XIV) 6
11. IV > III > II > I 12. b>a 13. (a) 3, (b) 5, (c) 9, (d) 5
14. I > III > II > IV
15. 1, 3-Butadiene shows delocalisation.
CH2 = CH CH = CH2 CH = CH
So bond between second & third C-atoms show partial double bond character. Hence bond length is
shorter than C C bond in n-butane.
16. Aromaticity comes through resonance. Only those molecules can be aromatic which have very high
resonance energy. Only those molecules has sufficiently high amount of resonance energy to becomes
aromatic which
(a) are cyclic (b) are planar (c) contains (4n +2) number of -electrons in ring.
(d) Does cyclic resonance between (4n + 2) number of -electrons
Where n = 0,1,2,3,4 ..........
17. (i) It has sp3 carbon in ring. (ii) One C is sp3 hybridised. (iii) It has 8 electrons. It is Antiaromatic.
18. Aromatic : (1), (2), (3), (4), (5), (6), (8)

Antiaromatic : (7), (9), (10), (12)
Nonaromatic : (11)
19. Benzene has all 6 hydrogen atoms in the plane. It does not have any vander waal or steric repulsions. So
it remains planar and aromatic. On the other hand [10]-annulene has inner hydrogen atoms (1, 6) which
are very close to each other causing steric or vander waal's repulsion. To minimise this the ring is twisted
this destroys coplanarity of all 2p-orbitals. So annulene is non aromatic.
20. Cyclooctatetraene is nonplanar due to its tub-shaped structure.
21. All are aromtic 22. > > > H2O 23. III > II > I > IV 24. B>A
25. (i) (A) > (C) > (D) > (B) (ii) (C) > (B) > (A) > (D). (iii) (A) > (D) > (C) > (B)
(iv) (C) > (B) > (D) > (A) (v) ((D) > (C) > (B) > (A)
26. IV > III > II > I 27. (D > C > B > A)

28. (P) II > I > III > IV ; (Q) II > I > III > IV ; (R) II > III > IV > I ; (S) I > IV > III > II
29. 1>4>2>3
Acidic strength order is SO 3 H > COOH > CCH > CH 3
30.

In resonting structure of phenoxide negative charge is present on C-atom (which is less electronegative)
while in benzoate ion, negative charge is present on more electronegative O atom. Hence in resonating
structure, if negative charge is present on more electronegative atoms it is more stable in comparison to
that resonating structure which have negative charge on less electronegative atoms.
31. (p) A>B>C>D (Order of Ka) (q) A > B > C ~_ D (Order of Ka)
(r) (A) > (D) > (C) > (B) (s) (A) > (B) > (D) > (C)
32. (a) X (b) X
33. (p) C>B>A (q) B>C>A (s) (D) > (B) > (C) > (A)
(t) (D) > (A) > (C) > (B) (u) (C) > (B) > (A) > (D) (w) (A) > (C) > (D) > (B)
34. Due to better solvation in polar protic solvent.
35. (P) I > II > III ; (Q) I > II > III ; (R) I > II > III

36. CH3 < NH2 < OH < F
37. ERG increases the basic strength because they tend to stabilise protonated aniline, on the other hand,
EWG decrease the basic strength they tend to destabilise the protonated aniline.
(G stabilises the cation) (G' destabilises the cation)
38. I > II > III

Exercise # 3
PART - I
1. Carbon has higher percentage s character in HCC, due to which higher electronegativity.
2. (C)
3. (a) (ii) (b) (iii) (c) (iv) (d) (i) (e) (v)
4. 5. (A) 6. (A) 7. (A) 8. (B) 9. (A)
10. (D) 11. (A) 12. (B) 13. (D) 14. (B) 15. (B) 16. (A)
17. 2 18. (C) 19. 6 20. (B,C)
PART - II
1. (2) 2. (3) 3. (1) 4. (4) 5. (3) 6. (3) 7. (3)
8. (3) 9. (4) 10. (3) 11. (4) 12. (2) 13. (2) 14. (3)
15. (1) 16. (2) 17. (4)

Exercise 4
O
-
+ + - -
1. (a) CH 3 CH CH NO2 (b)
- -
2. CH3COOH < ClCH2COOH < Cl2CHCOOH < Cl3CCOOH
3.
+ + .. 2
C H2 C O , N = N = N N N N
..
+
CH 2 = C = O
NHCCH3 NHCCH3
O O
4. (a) NH C CH3 (+M group)
||
O
O
CCH3 O O CH3 O
O CH3 O CH3 CH3
C C C C
CCH3
(b) CCH3 (m effect group)

O
5. is more basic due to lone pair of N atom is not delocalized.
6. is more basic due to sp 3 hybridised N atom.
7. V < III >
+
+ +
(2) > >
10. Greater resonance energy of is caused by hyperconjugation effect of CH3.

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ELECTRONIC EFFECTS

Name : ____________________________ Contact No. __________________

(a) + I power of different type groups and anions :

Physical & Inorganic By A-479 Indra Vihar, Kota Organic Chemistry By

Conjugate positions of the molecule :

Mesomeric Effects : This is of following types :

When e pair movement takes place towards G from the molecule.

NO2 > C N > SO3H > CHO > C R > C OH

Physical & Inorganic By A-479 Indra Vihar, Kota Organic Chemistry By

Application of Electronic Effects :

1. Aromatic compounds are cyclic and planar.

Physical & Inorganic By A-479 Indra Vihar, Kota Organic Chemistry By

A-1. The inductive effect :

A-3. Inductive effect involves :

A-4. Which of the following has incorrect direction of Inductive effect.

(A) (B) (C) (D) CH3 C CH2 CH3

A-5. Decreasing I effect of given groups is -

Section : (B) Resonance and Mesomeric Effect

Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

(C) CH3CH2NH CH2 CH = CH2 (D) CH2 = CH CH2 CH = CH2

B-4. Which of the following is not a pair of resonating structures ?

B-5. In which of the following delocalisation of -electron is possible.

B-6. Which of the following species have conjugated system ?

(A) (B) (C) CH 2 = C = CH NH 2 (D) All of these

Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

B-10. I CH2 CH CH CH CH CH2

The stability order of these canonical structures is :

B-12. Which of the following statements is NOT true ?

Section (C) : Hyperconjugation and Application of Electronic Effects

Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

C-4. Hyperconjugation phenomenon is possible in :

(A) (B) CH2 = CH2

(C) C6H5 CH = CH2 (D) CH3 CH2 CH = CH2

(A) (B) (C) (D)

C-7. Which of the following statements is true about this molecule .

(A) C1-C2 and C3-C4 bonds are of same length.

C-8. Which of the following statements is true about this molecule ?

(A) C5-N bond is longer than C1-N and C3-N bonds.

(A) a > b (B) a < b (C) a = b (D) None of these

Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

C-12. In which of the following molecules electron density in ring is minimum :

(A) (B) (C) (D)

C-13. In which of the following molecules electron density in ring is maximum :

(A) (B) (C) (D)

Section (D) : Aromaticity

(C) (D) All having same aromatic character

D-2. Which of the following is aromatic species ?

D-3. Which of the following is anti-aromatic species ?

(A) (B) (C) (D)

D-4. Which is the most aromatic in character ?

(C) (D) All having same aromatic character

Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

(A) (B) (C) (D)

D-6. Identify the aromatic compound ?

(A) (B) (C) (D)

Section (E) : Reaction Intermediate

E-2. Homolytic fission of a hydrocarbon will liberate :

E-3. Heterolytic fission of carbon-chlorine bond produces :

E-4. Which carbocation is least likely to form as an intermediate?

E-5. Which allylic carbocation is the most stable carbocation :

(A) CH3CH CH (B) CH3CH CH

(C) C6H5 CH CH (D) All have same stability

E-6. Arrange stability of the given carbocations in decreasing order :

Physical & Inorganic By A-479 Indra vihar, kota Organic Chemistry By

Name : __________ Contact No.