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TARGET IIT JEE 2010

ORGANIC CHEMISTRY

GOC
ELECTRONIC DISPLACEMENT EFFECTS

Q.1 Which of the following statements is (are) true about resonance.


(a) Resonance is an intramolecular process.
(b) Resonance involves delocalization of both and electrons.
(c) Resonance involves delocalization of electrons only.
(d) Resonance decreases potential energy of a molecule.
(e) Resonance has no effect on the potential energy of a molecule.
(f) Resonance is the only way to increase molecular stability.
(g) Resonance is not the only way to increase molecular stability.
(h) Any resonating molecule is always more stable than any nonresonating molecule.
(i) The canonical structure explains all features of a molecule.
(j) The resonance hybrid explains all features of a molecule.
(k) Resonating structures are real and resonance hybrid is imaginary.
(l) Resonance hybrid is real and resonating structures are imaginary.
(m) Resonance hybrid is always more stable than all canonical structures.

Q.2 Consider structural formulas A, B and C:

(A) (B) (C)


(a) Are A, B and C constitutional isomers, or are they resonance forms?
(b) Which structures have a negatively charged carbon?
(c) Which structures have a positively charged carbon?
(d) Which structures have a positively charged nitrogen?
(e) Which structures have a negatively charged nitrogen?
(f) What is the net charge on each structure?
(g) Which is a more stable structure, A or B? Why?
(h) Which is a more stable structure, B or C? Why?

Q.3 In each of the following pairs, determine whether the two represent resonance forms of a single
species or depict different substances. If two structures are not resonance froms, explain why.
(a) and

(b) and

(c) and

Q.4 Which of the following statement is incorrect ?


(A) Contributing structures contributes to the resonance hybrid in proportion of their energies.
(B) Equivalent contributing structure make the resonance very important.
(C) Contributing structures represent hypothetical molecules having no real existance.
(D) Contributing structures are less stable than the resonance hybrid.

GOC [2]
Q.5 Which one of the following pairs of structures does not represent the phenomenon of resonance?
O O
|| |
(A) H 2C CH C H ; CH 2 CH C H

(B) CH 2 CH CH Cl ; CH 2 CH CH Cl
O O
|| |
(C) (CH 3 ) 2 CH C O ; (CH 3 ) 2 CH C O
O O
|| |
(D) CH 3 CH 2 C CH 3 ; CH 3 CH C CH 3

Q.6 In which of the following lone-pair indicated is involved in resonance :

(a) (b) (c) (d)


(e) CH2= CH C H 2 (f) CH2 = CH CH = N H

Q.7 In which of the following lone-pair indicated is not involved in resonance :



(a) CH2 = CH N H CH3 (b) CH2 = CH CH = O

(c) CH2 = CH O CH = CH2 (d) CH2 = CH C N

(e) (f)

Q.8 Which of the following is not a valid resonating structure of the other three?
+ + +
NH2 NH2 NH2 NH2
(i) (a) + (b) (c) (d)

O O O O
+ + + + +
NO NO NO NO
(ii) (a) (b) (c) (d)
+ + +
NH2 NH2 NH2 NH2


(iii) (a) CH 2 N O (b) CH 2 N O (c) CH 2 N O (d) CH 2 N O
| | | |
CH 3 CH 3 CH 3 CH 3

GOC [3]
Q.9 Draw the resonance forms to show the delocalization of charges in the following ions
O O
+
(a) CH3 C CH2 (b) H C CH = CH CH2 (c) CH2

(d) (e) O (f) + NH (g)


+ O



(h) (i) CH3 CH = CH CH = CH CH CH3

O

(j) CH3 CH = CH CH = CH CH 2

Q.10 Write stability order of following intermediates:


CH 3
|
(i) (a) CH 3 CH 2 (b) CH 3 CH CH 3 (c) CH 3 C
|
CH 3

(ii) (a) + (b) + (c) +



(iii) (a) (b) (c)


(iv) (a) (b) (c)



(v) (a) (b) (c) (d)


(vi) (a) CF3 CH 2 (b) CCl3 CH 2 (c) CBr3 CH 2

GOC [4]
Q.11 Write stability order of following intermediates:
CH 3
|
(i) (a) CH 3 CH 2 (b) CH 3 CH CH 3 (c) CH 3 C
|
CH 3



(ii) (a) (b) (c)


(iii) (a) (b) (c)


(iv) (a) HC C (b) CH 2 CH (c) CH 3 CH 2

Q.12 Rank the following sets of intermediates in increasing order of their stability.
(i) (a) C6H5+ (b) pNO2(C6H4)+ (c) pCH3(C6H4)+ (d) pClC6H4+

CH2 CH2 CH2

(ii) (a) (b) (c)

N OMe
O O

CH2 CH2 CH2


OH
(iii) (a) (b) (c)
OH
OH

(iv) (a) CF3 CH 2 CH 2 (b) CF3 CH 2 (c) CF3

(v) (a) CF3 (b) CCl3

Q.13 Write stability order of following intermediates:


CH 3
|
(i) CH 3 CH 2 (b) CH 3 CH CH 3 (c) CH 3 C
|
CH 3

(ii) (a) (b) (c)

GOC [5]
(iii) (a) (b) (c)


(iv) (a) HC C (b) CH 2 CH (c) CH 3 CH 2

(v) (a) (b) (c)

Q.14 Among the following molecules, the correct order of C C bond lenght is
(A) C2H6 > C2H4 > C6H6 > C2H2 (B) C2H6 > C6H6 > C2H4 > C2H2(C6H6 is benzene)
(C) C2H4 > C2H6 > C2H2 > C6H6 (D) C2H6 > C2H4 > C2H2 > C6H6

Q.15 Which of the following is (are) the correct order of bond lengths :
(A) C C > C = C > C C > C N (B) C = N > C = O > C = C
(C) C = C > C = N > C = O (D) C C > C = C > C C > C H

Q.16 C1 C2 bond is shortest in

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

Q.17 Which of the following has longest C O bond :

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

Q.18 CH2 = NH

I II III IV
Among these compounds, the correct order of C N bond lengths is :
(A) IV > I > II > III (B) III > I > II > IV
(C) III > II > I > IV (D) III > I > IV > II

Q.19 Compare the CN bond-length in the following species:

(i) (ii) (iii)

GOC [6]
Q.20 CH3O CH = CH NO2 I
CH2 = CH NO2 II
CH2 = CH Cl III
CH2 = CH2 IV
Which of the following is the correct order of C C bond lengths among these compounds :
(A) I > II > III > IV (B) IV > III > II > I
(C) I > III > II > IV (D) II > III > I > IV

Q.21

These are three canonical structures of naphthalene. Examine them and find correct statement
among the following :
(A) All C C bonds are of same length
(B) Cl C2 bond is shorter than C2 C3 bond.
(C) C1 C2 bond is longer than C2 C3 bond
(D) none.

Q.22 In which of the following pairs, indicated bond having less bond dissociation energy :
(a) CH 3 CH 2 Br & CH 3 CH 2 Cl

(b) CH 3 CH CH Br & CH 3 CH CH 3
|
Br

(c) &

(d) &

(e) &

(f) &

Q.23 Discuss the following observations:


(a) CCl bond in vinyl chloride is stronger than in chloroethane.
(b) Carbon-carbon bond length in ethene is shorter than in CH2 = CHOCH3
(c) CH3SH is stronger acid than CH3OH
(d) CH3CH2NH2 is stronger base than CH2 = CHNH2.

GOC [7]
Q.24 A canonical structure will be more stable if
(a) it has more number of bonds than if it has less number of bonds.
(b) the octets of all atoms are complete than if octets of all atoms are not complete.
(c) it involves cyclic delocalization of (4n + 2) electrons than if it involves acyclic delocalization
of (4n + 2) electrons.
(d) it involves cyclic delocalization (4n) electrons than if it involves acyclic delocalizationof
(4n) electrons.
(e) +ve charge is on more electronegative atom than if +ve charge is on less electronegative atoms.
(f) ve charge is on more electronegative atom than if ve charge is on less electronegative atom.

Q.25 Resonance energy will be more if


(a) canonical structures are equivalent than if canonical structures are non-equivalent.
(b) molecule is aromatic than if molecule is not aromatic.

Q.26 In each set of species select the aromatic species.


+ +
(i) (a) (b) (c) (d)
S

+
(ii) (a) (b) (c) (d)

+
(iii) (a) (b) (c) (d)

N
H
Q.27 Consider the given reaction:

+ 3H2 Pd /C

In the above reaction which one of the given ring will undergo reduction?

Br
Q.28 AgNO
3 A

Select the correct statement about product A.


(A) Product is aromatic (B) Product has high dipole moment.
(C) Product has less resonance energy (D) Product is soluble in polar solvent.

GOC [8]
Q.29 Which of the following pairs has higher resonance energy :

(a) & (b) &

(c) & (d) CH2 = CH OH & CH2 = CH CH = CH OH

(e) &

Q.30 Which of the following pairs has less resonance energy :

(a) & (b) & (c) &

(d) & (e) &

Q.31 Which of the following pairs has higher resonance energy :

(a) & (b) CH2 = CH O CH = CH2 & CH2 = CH NH CH = CH2


(c) CH 2 CH N H & HN CH N H (d) CH2 = CH F & CH2 = CH Br


(e) & CH2 = CH C H 2

Q.32 Which of the following pairs has less resonance energy :

(a) CO 32 & HCOO (b) & CH2 = CH CH 2


(c) & CH2 = CH CH = CH2 (d) & CH2 = CH C H 2

(e) &

Q.33 Which of the following pairs has higher resonance energy :



(a) CH3COOH & CH3COONa (b) CH2 = CH O & CH2 = CH OH

(c) & (d) &

(e) & CH2 = CH CH = CH CH = CH2

GOC [9]
Q.34 Explain why which compound is aromatic, antiaromatic or nonaromatic.
H
+
(a) N (b) N S (c) (d)
O O O
isoxazole 1,3-thiazole pyran pyrylium ion

O NH2
N
(e) (f) (g)
O N N O
H
1,2-dihydropyridine H
-pyrone
cytosine

Q.35 Identify less stable canonical structure in each of the following pairs :

(a) C H 2 O CH 3
CH 2 O CH 3 (b)

(c) (d)

(e)


CH2 CH2

Q.36 Identify more stable canonical structure in each of the following pairs :

O O CH2 CH2
(a) C C (b)

.. C C
H OH H OH Me2N OMe Me2N OMe

(c) (d)


(e) C H 2 CH CH O
CH 2 CH CH O (f)

GOC [10]
Q.37 Rank the following sets of intermediates in increasing order of their stability.

CH2 CH2

(i) (a) (b)


F Cl

CH2
CH2 CH2

CH2

(ii) (a) (b) (c) (d)

Cl N C N
O O

(iii) (a) CH 2 CH (b) CH 2 CH 3
||
O

Q.38 In each of the following pairs of ions which ion is more stable:

(a) (I) C6H5 CH 2 and (II) CH2=CH CH 2

(b) (I) CH3 CH 2 and (II) CH2 = CH

(c) (I) and (II)

(d) (I) CH 3 CH CH 3 and (II) CH 3 N CH 3


| |
CH 3 C CH 3 CH 3 C CH 3


(e) CH2CH=NH CH2=CHNH

O O
(f) +
CH3C=CHCHCH3 CH3CCH=CHCH3
+

O O O O
(g) CH3CCHCCH3 CH3C=CHCCH3

NH2 NH2
(h) +
CH3CH2CNH2 CH3CH2C = NH2
+

GOC [11]
Q.39 Select the least stable resonating structure in each of the following sets of carbocation.
O O
+ + +
(i) (a) CH2 = CH N (b) CH2 CH N
O O
O O
+ + + +
(c) CH2 CH N (d) CH2 CH = N
O O


(ii) (a) CH 2 CH CH CH NH 2 (b) CH 2 CH CH CH NH 2

(c) CH 2 CH CH CH NH 2 (d) CH 2 CH CH CH NH 2


(iii) (a) H 2 C CH CH = CH O CH3 (b) H 2 C CH = CH CH = O CH3

(c) H2C = CH C H C H O CH3 (d) H2C = CH CH CH = O CH3

Q.40 Rank the following sets of intermediates in increasing order of their stability.

(i) (a) (b) (c)

(ii) (a) (b)


CH2 CH2 CH2

H
(iii) (a) (b) H (c) C H
C H H
H
H C H
H

CH2 CH2 CH2 CH2

(iv) (a) (b) (c) (d)


CH3 CH2Me CH Me2 CMe3

Me Ph +
| |
(v) (a) Me C (b) Ph C (c) Ph CH 2 (d)
| |
Me Ph

GOC [12]
+
+
(vi) (a) (b) (c)

+
+
(d) (e)
+

Q.41 Which of the following groups cannot participate in resonance with other suitable group :

(a) COOH (b) CO O (c) COCl (d) NH 3

(e) C H 2 (f) C H 2 (g) CH 2 N
|
CH 3

Q.42 Identify electron donating groups in resonance among the following :


(a) CONH2 (b) NO2 (c) OCOCH3 (d) COOCH3
(e) CHO (f) NHCOCH3

Q.43 Identify electron withdrawing groups in resonance among the following :


(a) COOH (b) CONHCH3 (c) COCl (d) CN

(e) O CH = CH2 (f)

Q.44 Which of the following groups can either donate or withdraw a pair of electrons in resonance
depending upon situation :
(a) NO2 (b) NO (c) CH = CH2 (d) CHO
(e) NH2 (f) N = NH

Q.45 Which of the following groups can only withdraw a pair of electrons in resonance depending
upon situation :

(a) Ph (b) (c) (d)


(e) N Me3 (f) CONH2

Q.46 Which of the following group can participate in resonance with other suitable group :

(a) CH 2 O (b) CH 2 C H 2 (c) CH C H2 (d)
2


(e) (f) BH2 (g) P Ph
3

GOC [13]
Q.47 In which of the following molecules electron density in ring is minimum :

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

Q.48 In which of the following molecules electron density in ring is maximum :

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

Q.49 CH2 = CH CH = CH CH3 is more stable than CH3 CH = C = CH CH3 because


(I) (II)
(A) there is resonance in I but not in II (B) there is tautomerism in I but not in II
(C) there is hyperconjugation in I but not in II (D) II has more cononical structures than I.

Q.50 Consider the following statements:



(I) CH3O CH 2 is more stable than CH3 CH 2

(II) Me 2 CH is more stable than CH 3CH 2 CH2

(III) CH 2 CH CH2 is more stable than CH 3 CH 2 CH 2

(IV) CH 2 CH is more stable than CH 3 CH 2
Of these statements:
(A) I and II are correct (B) III and IV are correct
(C) I, II and III are correct (D) II, III and IV are correct

Q.51 Which one of the following molecules has all the effect, namely inductive, mesomeric and
hyperconjugative?
(A) CH3Cl (B) CH3CH = CH2
(C) CH 3 CH CH C CH 3 (D) CH2 = CH CH = CH2
||
O

Q.52 Hyperconjugation is best described as:


(A) Delocalisation of electrons into a nearby empty orbital.
(B) Delocalisation of electrons into a nearby empty orbital.
(C) The effect of alkyl groups donating a small amount of electron density inductively into a
carbocation.
(D) The migration of a carbon or hydrogen from one carbocation to another.

Q.53 Select the correct statement.


(i) Delocalisation of -electron is hyperconjugation.
(ii) Delocalisation of -electron is resonance.
(iii) Partial displacement of -electron is inductive effect.
(A) i & iii (B) ii & iii (C) i & ii (D) i, ii, iii

GOC [14]
Q.54 Arrange following compounds in decreasing order of electrophilic substitution.
CH3 CH3 H
CH3 HCCH3 CH3CCH3 HCCH3

(i) (ii) (iii) (iv)

(A) i > ii > iii > iv (B) iii > iv > ii > i (C) i > iv > ii > iii (D) i > ii > iv > iii

Q.55 Select correct statement:


(A ) NO2 and COOH group deactivates benzene nucleus for attack of E+ at o and p sites.
(B) NH2 and OMe group activates benzene nucleous for attack of E+ at o and p sites.
(C) NH2 and COOH group activates benzene nucleous for attack of E+ at o and p sites.
(D) NO2 and OMe group activates benzene nucleous for attack of E+ at o and p sites.

Q.56 In which of the following pairs, indicated bond is of greater strength :

(a) and CH 2 CH 2 (b) CH3 C CH and HC CH


(c) and CH 3 CH 2 Cl

(d) CH 2 CH CH CH 2 and CH 2 CH 2 CH 2 CH 3

(e) CH 2 CH CH CH 2 and CH 2 CH NO 2

(f) and

Q.57 Choose the more stable alkene in each of the following pairs. Explain your reasoning.
(a) 1-Methylcyclohexene or 3-methylcyclohexene
(b) Isopropenylcyclopentane or allylcyclopentane

(c) or

Q.58 Match each alkene with the appropriate heat of combustion:


Heats of combustion (kJ/mol) : 5293 ; 4658; 4650; 4638; 4632
(a) 1-Heptene (b) 2,4-Dimethyl-1-pentene
(c) 2,4-Dimethyl-2-pentene (d) 4,4-Dimethyl-2-pentene
(e) 2,4,4-Trimethyl-2-pentene

GOC [15]
Q.59 Compare heat of hydrogenation (Decreasing order)

(i) &

(ii) &

(iii) &

CH3
(iv) CH2 = CH CH & CH3 CH = C
CH3

Q.60 Compare heat of hydrogenation (Decreasing order)

(i)
A B D

(ii)

Q.61 (I) Stability order and (II) heat of hydrogenation orders.

(a) (b) (c) (d)

Q.62 Among the following pairs identify the one which gives higher heat of hydrogenation :

(a) and

(b) and

(c) CH3 CH = CH CH3 and CH3 CH2 CH = CH2

(d) and

GOC [16]
Q.63 Write increasing order of heat of hydrogenation :

(i) (a) (b)

(ii) (a) (b) (c) (d)

(iii) (a) (b) (c) (d) (e)

(iv) (a) (b) (c)

(v) (a) (b) (c) (HOH per bond)

(vi) (a) (b) (c) (HOH per benzene ring)

Q.64 Give decreasing order of heat of combustion (HOC):

(i) (a) (b) (c)

(ii) (a) (b) (c) (d)

(iii) (a) (b)

(iv) (a) (b) (c)

Q.65 Rank the following sets of intermediates in increasing order of their stability.
+

(i) (a) C (b) Ph CH 2 (c) (d) Me C Me
|
Me


(ii) (a) CH 2 CH (b) CH 2 CH CH 2 (c) CH2 (d) CH3

GOC [17]
CH2
CH2 CH2

(iii) (a) (b) (c)


Cl Cl

+ +
CH2 CH2 +
(iv) (a) (b) (c)

+ + +
(v) (a) (b) (c)


(vi) (a) (b) (c)

Q.66 Which of the following statements would be true about this compound :

(A) All three C N bonds are of same length.


(B) Cl N and C3 N bonds are of same length but shorter than C5 N bond.
(C) Cl N and C3 N bonds are of same length but longer than C5 N bond.
(D) Cl N and C3 N bonds are of different length but both are longer than C5 N bond

GOC [18]
ANSWER KEY
Q.1 (a), (c), (d), (g), (j), (l), (m)
Q.2 a = Resonance form, b= A, c = C, d= A & B, e=B&C, f = 0, g = B, h = B

Q.3 (a) is resonance form; (b) is not resonance form due to different number of l.p. and b.p.;
(c) is not resonance form due to different number of l.p. and b.p

Q.4 A Q.5 D Q.6 (b), (d), (e) Q.7 (b), (d), (e) Q.8 (i) a (ii) c (iii) c

O O
| |
Q.9 (a) CH 3 C CH 2 (b) H C CH CH CH 2

+ +
CH2 CH2 CH2 CH2 CH2
+ +
(c)
+

(d) +
(e) O O O O

+
(f) NH (g) (h)
O+
O

(i) CH3 CH CH CH CH CH CH3 (j) CH3 CH CH CH CH CH 2 ]

Q.10 (i) c>b>a (ii) b>c>a (iii) c>b>a (iv) b>c>a


(v) d>c > b>a (vi) a<b<c

Q.11 (i) a>b>c (ii) a>b>c (iii) a>c>b (iv) a>b>c

Q.12 (i) b < d < a < c (ii) b>c>a (iii) c>a>b (iv) c>a>b
(v) a>b

Q.13 (i) c>b>a (ii) c>b>a (iii) b>c>a (iv) c>b>a


(v) a>c>b

Q.14 B Q.15 A, C, D Q.16 D Q.17 B Q.18 C Q.19 iii > ii > i

Q.20 A Q.21 B

Q.22 (a) I, (b) II, (c) II, (d) I, (e) I, (f) I

GOC [19]

Q.23 (a) Due to resonance C H 2 CH = Cl+
(b) In CH2=CHOCH3, there is single bond character due to resonance

C H 2 CH = O+ CH3

(c) Conjugate base of CH3SH ie, CH3S is more stable than conjugate base of CH3OH, ie CH3O

(d) In CH2=CHNH2 lone pair of N is delocalized C H 2 CH = N H 2

Q.24 (a), (b), (c), (f) Q.25 (a), (b) Q.26 (i) a, b, d (ii) a, c (iii) b, c, d

Q.27 A Q.28 A, B, D Q.29 (a) II, (b) I, (c) II, (d) II, (e) II

Q.30 (a) II, (b) II, (c) II, (d) II, (e) II Q.31 (a) I, (b) II, (c) II, (d) I, (e) I

Q.32 (a) II, (b) I, (c) I, (d) II , (e) I Q.33 (a) II, (b) I, (c) I, (d) I, (e) I

Q.34 (a) A, (b) A, (c) N.A. (d) A, (e) A, (f) N.A. (g) A Q.35 (a) I, (b) II, (c) II, (d) II, (e) I
Q.36 (a) I, (b) I, (c) I, (d) I, (e) II, (f) II
Q.37 (i) a<b (ii) b>c>a>d (iii) a>b

Q.38 (a) I, (b) I, (c) II, (d) II, (e) II, (f) I, (g) II, (h) II Q.39 (i) c (ii) a (iii) c

Q.40 (i) a>b>c (ii) a>b (iii) c>a>b (iv) a>b>c>d


(v) d>b>c>a (vi) d>e>b>a>c

Q.41 (d) Q.42 (c), (f) Q.43 (a), (b), (c), (d), (f) Q.44 (b), (c), (f)

Q.45 (f) Q.46 (a), (e), (f), (g) Q.47 D Q.48 B Q.49 A

Q.50 C Q.51 C Q.52 B Q.53 D Q.54 C Q.55 A, B

Q.56 (a) I I , (b) I I , (c) I , (d) I , (e) I I , (f) I I Q.57 (a) i , (b) i , (c) ii

Q.58 (a) 4658, (b) 4638, (c) 4632, (d) 4650, (e) 5293 Q.59 (i) 2 > 1 (ii) 2 <1 (iii) 1 < 2 (iv) 1 > 2

Q.60 (i) D > C > B > A (ii) E > C > D > B > A Q.61 (I) d > c > b > a; (II) a > b > c > d

Q.62 (a) I, (b) I, (c) II, (d) I

Q.63 (i) b>a (ii) a>b>d>c (iii) a>b>c>d>e


(iv) b>c>a (v) a>b>c (vi) a>b>c

Q.64 (i) c > b > a (ii) a>b>c>d (iii) a>b (iv) c>b>a

Q.65 (i) a c > b > d (ii) d>b>c>a (iii) b>a>c (iv) a>c>b
(v) b>c>a (vi) b>c>a Q.66 C

GOC [20]

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