GOC - 2 and Reaction Mechanism

1. In the following benzyl/allyl system

R – CH = CH2 and
(R is alkyl group)
decreasing order of inductive effect is : [Ref. Arihant] [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—
Sol. CH3 group has + I effect, as number of – CH3 group increases the inductive effect increases.

2. Arrangement of (CH3)3C–, (CH3)2CH –, CH3 – CH2 – when attached to benzyl or an unsaturated group in
increasing order of inductive effect is [AIEEE 2002]
(1) (CH3)3C – < (CH3)2CH – < CH3–CH2 (2*) CH3–CH2 – < (CH3)2CH – < (CH3)3C –
(3) (CH3)2–CH – < (CH3)3C – < CH3–CH2 (4) (CH3)3C – < CH3–CH2 – < (CH3)2CH –
Sol. CH3 group has + I effect, as number of – CH3 group increases the inductive effect increases.

H2O
3. The reaction : (CH3)3 C – Br   (CH3)3C – OH [AIEEE 2002]
(1) elimination reaction (2*) substitution reaction
(3) free radical reaction (4) displacement reaction

4. In the anion HCOO– the two carbon-oxygen bonds are found to be of equal length. What is the reason for it?
(1) electronic orbitals of carbon atom are hybridised [AIEEE 2003]
(2) the C = O bond is weaker than the C – O bond
(3*) the anion HCOO– has two equivalent resonating structures
(4) the anion is obtained by removal of a proton from the acid molecule.
Sol. HCOO– exists as
–
O O
|
–
H–C–O H–C=O
So, the carbon-oxygen bonds are found to be of equal length.

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 [Ref. Arihant]
Sol. Except the amines containing tertiary butyl group, all lower aliphatic amines are stronger bases than ammonia
becaues of + I (inductive). The alkyl groups, which are electron releasing groups, increase the electron
density around the nitrogen there by increasing the availity of the lone pair of electrons to proton or lewis
acids and making the amine more basic. The ovserved order in the case of lower memebers is found more
basic. The observed order in the case of lower members is found to be as secondary > primary > tertiary.
This anomalous behaviour or tertiary amines is due to steric factors i.e., crowding of alkyl groups cover
nitrogen atom from all sides and thus makes it unable for protonation.
Thus the relative strenth is in order (CH3)2 NH > CH3NH2 > NH3.

6. Consider the acidity of the carboxylic acids: [AIEEE 2004]

(i) PhCOOH (ii) o– NO2C6H4COOH (iii) p– NO2C6H4COOH (iv) m– NO2C6H4COOH
(1) i > ii > iii > iv (2*) ii > iii > iv > i (3) iii > ii > iv > i (4) ii > iv > iii > i
COOH
COOH COOH | COOH
| | |
NO2
Sol. < < <
|
NO2 NO2
E.W.G. increases the acidity of benzoic acid, o-isomer will have higher acidity then corresponding m and p
isomer due to orthoeffect.

RESONANCE AIEEE_GOC-II - 1
 As M group (i.e., NO2) at p-postion have more pronounced electron withdrawing effect than as – NO2 group at
m-position ( – 1 effect)

7. The decreasing order of nucleophilicity among the nucleophiles [AIEEE 2005]

O
||
(1) CH3C – O– (2) CH3O– (3) CN– (4) H3C S O
|| ||
O O
(1) (1), (2), (3), (4) (2) (4), (3), (2), (1) (3*) (2), (3), (1), (4) (4) (3), (2), (1), (4)

8. The increasing order of the rate of HCN addition to compounds A - D is [AIEEE 2006]
A. HCHO B. CH3COCH3
C. PhCOCH3 D. PhCOPh
(1) A < B < C < D (2) D < B < C < A (3*) D < C < B < A (4) C < D < B < A
Sol. Addition of HCN to carbonyl compounds is a characteristic nucleophilic addition reaction of carbonyl
compounds.
Order of reactivity :

> >

The lower reactivity of ketones over aldeydes is due to + 1-effect of the alky (R) group and steric hindrance.
As the size of alkyl group increses, the reactivity of the ketones further decreases.

> >

The aromatic aldehydes and ketones are less reactive than their aliphatic analogous. This is due to the +R-
effect of the benzene ring.
PhCOH > PhCOCH3 > PhCOPh
From the above information, it is clear that increasing order of the rate of HCN addition to compounds HCHO,
Ch3COCH3, phCOCH3 and phCOPh is
PhCOPh < PhCOCH3 < CH3 COCH < HCHO
9. The increasing order of stability of the following free radicals is [AIEEE 2006]
(1*) (CH3)2 H < (CH3)3 < (C6H5)2 H < (C6H5)3
(2) (C6H5)2 < (C6H5)2 H < (CH3)3 < (CH3)2 H
(3) (C6H5)2 H < (C6H5)3 H < (CH3)3 < (CH3)2 H
(4) (CH3)2 H < (CH3)3 < (C6H5)3 < (C6H5)2 H
Sol. The order of stability of free radical is as follows:
tertiary > secondary > primary.
Benzyl free radicals are stabilised by resonance and hence are more stable than alkyl free radicals. Further
as the number of phenyl group attached to the carbon atom holding the odd electron increases, the stability
of a free radical increases accordingly i.e.
(CH3)2 H < (CH3)3 < (C6H5)2 H < (C6H5)3

10. CH3Br + Nu–  CH3Nu + Br–

The decreasing order of the rate of the above reaction with nucleophiles (Nu–) A to D is:
[Nu– = (1) PhO– , (2) AcO–, (3) HO–, (4) CH3O–] [AIEEE 2006]
(1*) D > C > A > B (2) D > C > B > A (3) A > B > C > D (4) B > D > C > A

11. The correct order of increasing acid strength of the compounds [AIEEE 2006]

RESONANCE AIEEE_GOC-II - 2
 Me
(1) CH3CO2H (2) MeOCH2CO2H (3) CF3CO2H (4) CO2H is
Me
(1) B < D < A < C (2) D < A < C < B (3*) D < A < B < C (4) A < D < C < B

Sol. Effect of substituent on the acid strength of aliphatic acids.

(i) Acidity decreases as the + I - effect of the alkyl group increases.
HCOOH > CH3COOH > (CH3)2 CHCOOH > (CH3)3 CCOOH
(ii) Acidity decreases as the – I-effect as well as number of halogen atoms decreases.
FCH2COOH > CICH2COOH > BrCH2COOH > ICH2COOH > CH3COOH
F3CCOOH > F2CHCOOH > FCH2COOH > CH3COOH
(iii) Electron donating substituents like – R , – OH, – NH2 etc. tend to decrease while electron withdraw
ing substituents tend to increase the acid strength of substituted acid.
On the basis of given information the relative order of increasing acid strength of the given com
pounds:
(CH3)2 COOH < CH3 COOH < CH3 OCH2COOH < CF3COOH

12. The organic chloro compound, which shows complete stereochemical inversion during an SN2 reaction, is
[AIEEE-2008, 3/105]
(1) (CH3)3CCl (2) (CH3)2CHCl (3*) CH3Cl (4) (C2H5)2CHCl
Sol. CH3Cl show complete stereochemical inversion during an SN2 reaction.

13. Arrange the carbanions, (CH3)3C, CCl3, (CH3)2 CH, C6H5 CH2 in order of their decreasing stability :
[AIEEE-2009, 4/144]
(1) (CH3)2 CH > CCl3 > C6H5 CH2 > (CH3)3 C (2*) CCl3 > C6H5 CH2 > (CH3)2 CH > (CH3)3 C
(3) (CH3)3 C > (CH3)2 CH > C6H5 CH2 > CCl3 (4) C6H5 CH2 > CCl3 > (CH3)3 C > (CH3)2 CH

14. Which of the following on heating with aqueous KOH, produces acetaldehyde ? [AIEEE-2009, 4/144]
(1) CH3CH2Cl (2) CH2ClCH2Cl (3*) CH3CHCl2 (4) CH3COCl
KOH H O
2
Sol.  
  CH3CHO


Cl CH3
CH3
Sol. Cl > CH 2 > C—H > C CH3
C
Cl CH3 CH3
Strong –I effect –m effect of phenyl +I effect of 2 CH3 +I effect of 3 CH3
of Cl and bonding
with vacant d-orbital

15. Consider the following bromides : [AIEEE-2010, 4/144]

The correct, order of SN1 reactivity is

(1*) B > C > A (2) B > A > C (3) C > B > A (4) A > B > C
Sol. Rate of SN1 reaction  stability of carbocation

16. The main product of the following reaction is : [AIEEE-2010, 4/144]

C6H5CH2CH(OH)CH(CH3)2  conc. H2SO4

RESONANCE AIEEE_GOC-II - 3
 (1*) (2)

(3) (4)

Sol. Conc. H SO
2 4
 
  

Hshift   +
  
H / 

52. Which of the following is not a pair of resonating structure :

(1)  CH =C=O (2) 

2

(3)  (4) CH3–CH=CH–CH=O 

53. S1 : Resonating structures have different hybridisation.

S2 : All resonating structures of every compound is always equally contribute to their resonance hybrid.
S3 : More stable resonating structure contribute more in resonance hybrid.
S4 :  and  bonds both take part in resonance.
(1) T T T T (2) F F T F (3) T F T F (4) F F F F

54. (t-butyl) 3º > (isopropyl) 2º > (ethyl) 1º >

Stability of carbon free radical order can be explained by :
(1) Hyperconjugation only. (2) Hyperconjugation and resonance.
(3) Hyperconjugation and -effect. (4) Only -effect

55. Which of the following is not correctly matched.

Column-I Column-II
(1) – NH2 + M, –

(2) – M, –

(3) + M, –

(4) + M, +

56. Which of the following represents a pair of resonating structures :

RESONANCE AIEEE_GOC-II - 4
 (1) , (2) CH2=CH–CH=CH2,

(3) , (4) ,

57. In which of the following molecule all effect such as -effect, resonance and hyperconjugation is observed.

(1) (2) (3) (4)

58. Decreasing order of hyperconjugation for alkyl benzene is -

(1) > > (2) > >

(3) > > (4) > >

59. S1: Correct order of + I effect is (CH3)3C– > (CH3)2CH–>CH3–CH2–>–CH3

S2 :Correct order of acidic strength F–CH2COOH > NO2–CH2–COOH > Cl–CH2–COOH > CH3–CH2–COOH

1
S3 : Stability of alkene 
H
(1) TTT (2) TFT (3) TFF (4) FTF

49. Which of the following has maximum electron density at benzen ring.

(1) (2) (3) (4)

54. Decreasing order of enol content amongst the following

(i) CH3–CH=O (ii) (iii)

RESONANCE AIEEE_GOC-II - 5
(iv) (v)
(1*) v > iv > iii > ii > i (2) iii > ii > iv > v > i (3) iv > v > i > iii > ii (4) v > iv > ii > iii > i

RESONANCE AIEEE_GOC-II - 6