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Chap 4 General Organic Chemistry Exercise
Chap 4 General Organic Chemistry Exercise
CHEMISTRY
ALLEN
Study Package
For – JEE (Advanced)
JEE-Chemistry
EXERCISE-01 CHECK YOUR GRASP
SELECT THE CORRECT ALTERNATIVE (ONLY ONE CORRECT ANSWER)
1. Carbanion is a :-
(A) Base (B) Nucleophile (C) Both (A) and (B) (D) None
2. Electrophile is :
(A) H 2O (B) NH 3 (C) AlCl 3 (D) C 2 H 5NH 2
3. Which of the following species has a pyramidal shape-
(A) CH 3 + (B) BF3 (C) CH 3– (D) C H 3
4. Increasing order (least basic first) of basic strength is shown by the set
(A) ClNH 2 , NH 3 , CH 3 NH 2 (B) ClNH 2 , CH 3 NH 2 , NH 3
(C) NH 3 , ClNH 2 , CH 3 NH 2 (D) CH 3 NH 2 , ClNH 2 , NH 3
5. The decreasing order of acid strength indicated by the following sequence of reaction is :-
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CH3
(C) CH3–C–CH=CH2 (D) CH3–C=CH2
CH3 CH3
H 3O
12. In the reaction CH 3CN CH 3COOH
heat
CH2 CH2 CH2 CH2
Cl NO2 OCH3
(a) CH3O– –CH2 (b) –CH2 (c) CH3– –CH2 (d) CH 3— C H 2
17. The increasing order of base strength of Cl –, CH 3 COO – , —OH and F — is : NODE6 E :\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-05\General organic chemistry\Eng\Exercise.p65
O O O O
H– C–OH H– C = O H H–C–O–H H–C–O–H
I II III IV
Which of the following order is correct for the stability of the four contributing structures.
(A) I > II > III > IV (B) I > II > IV > III (C) I > III > II > IV (D) I > IV > III > II
19. Which of the following carbonium ion is most stable
(A) Ph 3 C + (B) (CH 3 ) 3 C + (C) (CH 3 ) 2 CH + (D) CH 2 CH—CH 2+
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21. Match List- I with List- II and select the correct answer using the codes given below -
List-I (Stability) List -II (Reason)
H3C CH3
C
(A) > CH 3+ (1) Inductive effect
Br
(B) H3C–C < CH3– (2) Resonance
CH3
CH3
(C) H3C–C > H 3C–CH 2+ (3) Hyperconjugation and resonance
CH3
• H3C •
CH2 CH2
(D) > CH3 (4) Hyperconjugation and inductive effect
Codes :
(A) A - 2 ; B - 3 ; C - 4 ; D - 1 (B) A - 3 ; B - 1 ; C - 4 ; D -2
(C) A - 4 ; B - 3 ; C - 1 ; D - 2 (D) A - 3 ; B - 4 ; C - 2 ; D - 1
22. Which of the following compounds is the strongest base -
23. In which of the following molecule all the effect namely inductive, mesomeric & hyperconjugation operate:
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CH3 CH3
OH ONa
SO3Na COOH
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COOH
• •
(C) (Ph) 2C = C(Ph) 2 CH3 (D) CH 2 = CH 2 CH3
H
CH3–C–CH2
1,2 shift
27. A (Major) ; Here A is :
CH3
CH3–C–CH3 CH–CH2
(A) (B)
H
(C) CH3–C–H2C– (D) CH3–C= CH2
Ph
CH2CH3 •CHCH3
•
:O
O O O
Cl + HCl
(A) (B) HO–C–H+ C–H HO–C–H + H–C–H
H H H
H–CH2 H
H shift –
(C) CH3 –C CH3 –C–CH2 HO
(D) CH 3 CH 2 CHO CH 3 C HCHO H 2 O
CH3 H
30. The Ka values of alcohols, water and phenol are of order 10–17, 10–14 and 10–10 respectively. Which of the
following reactions is possible :
(I) C 6 H 5 O + H 2 O C 6 H 5 OH + OH (II) C 2H 5 O + H 2O C 6 H 5 OH + OH
(A) Both I and II (B) only II (C) only I (D) neither of two
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CH2 CH2
(A) CH 3 (B) CH 2 CH – CH 2 (C) (D)
NO2
32. Stability of :
CH3
(I) C H 3 – C H = C H – C H 3 (II) CH3– C = C – CH3 (III) CH3– C = CH2 (IV) CH3– C = CH – CH3
CH3 CH3 CH3
H2O
33. –MgBr + CH2—CH2 [A] ; the product (A) is :
O
H H
H
(A) CH 3 – CH 2 (B) CH3– C – CH3 (C) (D) (CH3)2C – CH2
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CH3
H3C H3C
(A) CH3 – CH2
(B) CH3– CH2– CH2 (C) CH– CH2 (D) 3C C – CH2
H
H3C H3C
37. Which of the following will react fastest with conc. HCl :
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OCH3
+ NaNH2 Product
Br
The product (P) and reaction (R) are :
OCH3 OCH3
NH2 NH2
(A) ; addition-elimination (B) ; elimination addition
OCH3 OCH3
(A) RCH 2 OH 2 R C H 2 (B) R 2 CH OH 2 R 2 C H
(C) R 3 C OH 2 R 3 C (D) all have same E act.
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NH2
N N N
H H
I II III IV
(A) I > II > III > IV (B) II > III > I > IV (C) II > IV > I > III (D) II > III > IV > I
2. The correct order of increasing dissociation constant of the following compound is :-
OH OH OH OH
NO2 NO2 NO2
NO2
NO2
NO2 NO2
I II III IV
(A) II < IV < I < III (B) IV < III < I < II (C) IV < II < I < III (D) IV < I < II < III
3. In the following arrange the H (numbered) for their ease of displacement during acid base reaction :
(2)
(3) OH
HO
H NaNH2(liquid NH3)
(1) 2 equivalent
(A) 1 > 2 > 3 (B) 3 > 2 > 1 (C) 3 > 1 > 2 (D) 2 > 3 > 1
4. Which one of the following is the strongest base in aqueous medium :-
(A) (C 2 H 5 ) 3 N (B) C 2 H 5 NH 2 (C) NH 3 (D) (C 2 H 5 ) 2 NH
5. The correct order of acid strength of the following compound is -
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N N N
H H
I II III
the order of basicity is -
(A) III > II > I (B) II > III > I (C) I > II > III (D) II > I > III
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OH OH COOH CCH
I II III IV
(A) II < I < III < IV (B) IV < II < I < III (C) I < II < IV < III (D) IV < I < II < III
10. Which of the following is the most acidic
(A) CH 2 = CH 2 (B) HC CH
11. Which of the following substituents will increase the acidity of phenol -
(A) –NO 2 (B) –CN (C) –CHO (D) – CH 3
O
(x) (y) (z)
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O O
O
(A) y > x > z (B) x < y < z (C) y > z > x (D) x < z < y
16. Rank the following alkenes in order of decreasing heats of hydrogenation (largest first):
O
I III
H–N –C–N(C2H5)2
II
N
CH3
(A) I (B) II (C) III (D) all are equally basic
19. Which of the following substituted carboxylic acids has the highest K a value :
20. Which of the following compounds yield most stable carbanion after rupture of (C 1 –C 2 ) bond :
O O
(A) CH3—C—CCl3 (B) CH3—C—CBr3
1 2 1 2
O
(C) CH3—CH2—C—CI3 (D) None of these
1 2
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N N
21.
H NH2
pyrrole (I) pyridine (II) aniline (III)
O O
(A) CH3–CH–CH=CH2 > CH3–C=CH–CH3
CH2
•
(B) CH 2=CH–CH=CH–CH 2• > CH2–C–CH–CH3
CH3
(C) CH2=C–CH2 > CH 3 –CH=CH– CH 2
O
(D) —O < CH3–C–O
O
(A) CH 3 COOH (B) —OH (C) CH3—C—CH2—CN (D) NaNH2
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—Br
(A) —Br (B) –CH=CH–CH2Br (C) (D) —Br
NH2 CH2–NH2
—CH3 —NH2
(A) (B) CH 3 –OH (C) (D) H 2 O
C6H5 H C6H5
OH H
(B) C6H5
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(A) C6H5 (C) either of the two (D) none of the two
H
OH O
(A)
(B)
OH OH
CH2
(C) (D) All of three
OH
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OD
D NaOH
33. [Intermediate] P. Product is :
CO2 D
OD OD
HOOC D DOOC D
(A) (B)
OH
DOOC D
(C) (D) Reaction not possible
O
+ ClCH2COOC2H5 Base
(A)
Cl
O
CCOOC2H5
(A) (B)
CH2COOC2H5
O O
(C) CHCOOC2H5 (D) CHCOOC2H5
35. Which of the following intermediate is most likely to be formed during addition of HBr on crotonic acid :
36. Which will give most stable cation upon strong heating :
CH2–Cl Cl
CH2
(A) (B) (Ph) 3C–Cl (C) (D) CH
CH2–Cl
Cl
37. (A); Here (A) is :
—Cl
H
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F
–F
38. Cl – C – C – F [X] ; Here [X] is :
Cl F
F F F F
(A) Cl – C = C – F (B) Cl – C = C – Cl (C) Cl – C = C – F (D) C l – C = C – F
Cl F Cl F
H3C CH3
H3C CH3 CHCl3
C C KOH
39. H H the reaction proceeds via :
H H
(A) carbene (B) Carbon free radical (C) Carbocation (D) Carbanion
Cl
:C Cl
40. (A) ; Here A is :
••
N
H
Cl
Cl
(A) (B) Cl
(C) (D)
N N N
N
H
41. Which of the following can give benzyne :
Cl Cl
(A) NaNH2 (B) (C) NaNH2 (D) All
H N2 Br
(A) I < II < III < IV (B) II < III < IV < I (C) I < III < IV < II (D) I < IV < II < III
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CH3
(I) CH 3 CH 2 CH 2 CH 2 Cl (II) CH3CH2CH – CH3 (III) CH3CHCH2 – Cl (IV) CH3–C – Cl
Cl CH3 CH3
(A) SN1 ; I < III < II < I V (B) SN2 ; IV < II < III < I
(C) (A) and (B) both are correct (D) Both incorrect
44. Cyclopentyl ethyl ether can be obtained by :
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CH3
1
6 2 NH2
48. (A) . The most probable structure of intermediate A is :
5 –Cl
3
4
•• ••
(A) singlet H – N
•
• (B) triplet H – N
•
• (C) singlet –C (D) triplet –C–
•
•
(A) carbene (B) (C) Benzyne (D)
•
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CH3 CH3 H
(A) CH3–C–CH2 (B) CH3–C– CH–C–H
H CH3 H
CH3
(C) CH3–C–CH–CH3 (D) all
Ph
2
Hg
OH
(A) (CH 3 )3 C — C H 2 (B) (CH3)3C CH—CH2 (C)
(D) all
•
CH2CH3 CHCH3 + HCl
(B) Cl•
O O O O
(C) HO–C–H+ H– C–H HO– C–H + H–C–H
H H
CH3
(D) CH3 –C
Hydride
shifting
CH3 –CH–CH2
CH3 CH3
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56. Methyl benzylic carbonium ion is the most stable one, hence it will react fastest consider the following
reaction :
Br CH3 SN2
+ OH (P) ; product (P) will be :
H H
H CH3 HO CH3
(A) (B)
HO H H H
OH
H CH3 CH3
H
(C) (D)
H H H H
OH
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Br Br Br
(A) Br (B) Br
Br
Br
(C) (D)
Br
CH2
CH3
O OH
60. Product ; major product of the reaction can be :
O
CH3
( i ) Zn
61. CH3COCH3 + BrCH2COOEt
( ii ) H 2 O / H
(A) ; the product (A) is :
OCH3 OH
CH3
(A) C (B) CH3–C–CH2COOEt
CH3 Br
CH3
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OH
(A) (B) (C) (D)
63. The most probable structure for (P) in the following reaction is :
conc H2SO4
2 (P)
64. Which of the following alcohols is dehydrated most readily with conc. H2SO4 ?
OCH3 NO2 Cl
65. Dehydration of alcohols by conc. H2SO4 takes palce according to following steps :
H H H
CH3 CH3
1,2–H shift –H
step -III CH3–C–CH3 step -IV CH2=C–CH3
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Cl
+ CHCl3 KOH +
N N CHO N
H H
(A) (B)
Cl
C
H Cl
(I) (II) (III) ••
(IV)
N CCl2 N N N
H
(A) I and IV (B) I and III (C) III and IV (D) I, III and IV
conc. H2SO4
67. Major product is :
OH
Qu e. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ans . D C B D A C D D B D A ,B,C C B B B
Qu e. 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
Ans . D D B A A B,D A ,C A ,B,C C C B A ,B,C ,D B,D A ,D A ,B,D
Qu e. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45
Ans . A B C D C C C A A D D A A A B
Qu e. 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Ans . C A B C B C C A B D A B C A B
Qu e. 61 62 63 64 65 66 67
Ans . B C C B C B C
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1. Out of benzene, ethylene and acetylene, the carbon-carbon bond is longest in ...................... .
2. The cyclopentadienyl cation is ...................... while cyclopentadienyl anion is ............... .
3. The type of delocalization involving sigma bond orbitals with bond or vacant orbital is called ..............
4. Hydroperoxide ion is a stronger ...................... but weaker ................... than hydroxide ion.
5. Catalytic hydrogenation of cis-2, 3-diphenyl-2-butene gives..................... .
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HOOC SO3H
HO CCH
Column-I Column-II
(A) Strongest acidic group in P (p) 1
(B) Weakest acidic group in P (q) 2
(C) Number of Intra molecular (r) 3
H-Bonding in P
(D) Number of mole of hydrogen (s) 4
gas that is liberated on reaction
of 'P' with excess of sodium metal if
one mole of P is used
2. Statement-I : Me 3 C is more stable than Me 2 C H and Me 2 C H is more stable than the Me C H 2 .
Because
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Statement-II : Greater the number of hyperconjugative structures, more is the stability of carbocation.
3. Statement-I : Cyclopentadienyl anion is much more stable than allyl anion.
Because
Statement-II : Cyclopentadienyl anion is aromatic in nature.
4. Statement-I : CH 3OCH 3 and C 2 H 5OH have comparable molecular masses but boiling point of C 2 H 5OH
is higher than dimethyl ether.
Because
Statement-II : C 2H5OH forms intermolecular H-bonding while CH3OCH3 forms intramolecular H-bonding.
IV III II I
5. Statement-I : In the compound, C H 3 — C H 2 — C N , the most electroegative carbon is II.
Because
Statement-II : Carbon atom II has more s-character.
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CH3 CD3
(I) (II)
Because
Statement-II : Carbocation (II) has more positive inductive effect of –CD 3 group as compared to –CH 3
group.
8. Statement-I : Carbon-oxygen bonds are of equal length in acetate ion.
Because
Statement-II : Bond length decreases with the multiplicity of bond between two atoms.
9. Statement-I : The potential energy barrier for rotation about C=C bond in 2-butene is much higher than
that in ethylene.
Because
Statement-II : Hyperconjugation effect decreases the double bond character.
10. Statement-I : Pyrrolidine (II) is more basic than pyrrole (I).
•• ••
N N
H H
(I) (II)
Because
Statement-II : Protonated pyrrole has resonance stabilization of positive charge in aromatic ring.
Comprehension # 1
The intramolecular delocalisation of and /non-bonding electrons without any change in the position of
atoms is called resonance. Delocalisation may occur in conjugated system involving carbon atom and atom
other than the carbon. Delocalisation makes system stable. More is the number of resonating structures,
more is the stability of the system. A conjugated structure is least stable when a higher electronegative atom
has positive charge and when identical charges are present on adjacent atoms.
1. The decreasing order of stability of the following resonating structures :
•• – + +
••–
CH2=CH—Cl CH2—CH=Cl CH2—CH= Cl is -
(I) (II) (III)
(A) I > II > III (B) II > III > I (C) III > II > I (D) I > III > II
2. If A is Ph CH 2 and B is CH 2 =CH— CH 2 , the greater number of resonating structure is of -
(A) A (B) B (C) both A and B (D) None of these
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+
O OH OH OH
4. Examine the structures I and II for nitromethane and choose the statement correctly :
•• ••–
O O
+ +2
——
—
CH3—N ••–
CH3—N ••–
O O
••
(I) (II)
(A) II is less important because electrons have shifted to oxygen
(B) II is less important because nitrogen has sextet of electrons
(C) II is acceptable and important structure
(D) none of these
5. Examine the following two structures for pyrrole and choose the correct statement given below :
+
•• ••
N N–
O O
(I) (II)
(A) II is not an acceptable resonating structure because carbonium ions is less stable than nitride ion
(B) II is not an acceptable resonating structure because there is charge separation
(C) II is not an acceptable resonating structure because nitrogen has ten valance electrons
(D) II is an acceptable resonating structure
6. Delocalization of electrons increases molecular stability because :
(A) Potential energy of the molecule decreases
+
(A) C H 3 (B) CH 3 — C H — CH 3 (C) CH 3 — C H 2 (D) CH3—C—CH3
CH3
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NO2
(A) (B) (C) (D)
3. In which of the following cases, the carbocation (I) is less stable than the carbocation (II) ?
+ +
CH2 CH2
+ +
(A) C 6 H 5 — C H 2 (I), CH 2 = CH— C H 2 (II) (B) (I), (II)
+ + + ⊕
(C) CH 2 = C H (I), CH 3 — C H 2 (II) (D) H 3C— C H 2 (I), CH2— CH2 (II)
⊕ F
+ +
4. The most stable and the least stable carbocation among (I), CH 2=CH— C H 2 (II), C 6H 5— C H 2 (III)
and CH 3 — C H — CH 3 (IV) are respectively :
NH2
NH2 NH2 NH2
(A) I > II > III > IV (B) IV > III > II > I (C) II > I > IV > III (D) I > IV > III > II
2. Which of the following is most acidic :
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:
O + O O + O
N N
(I) (II)
(A) carbon-nitrogen bond length structure I is greater than that in structure II
(B) carbon-nitrogen bond length in structure I is less than in structure II
(C) carbon-nitorogen bond length in both structure is same
(D) It can not be compared
4. Arrange the following carbocation in the increasing order of stability :
CH2 CH2 CH2
CH3
CH3–CH CH–CH3
CH3 NO2 CH3 NO2
(I) (II) (III)
(A) I < II < III (B) II < III < I (C) III < II < I (D) III < I < II
Comprehension # 4
1-Butene (A) and 1,3-Butadiene (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 conjugate system. Following are some of the conjugate
system.
O O
CH2=CH–C–H CH2=CH–C–OH
acrolein acrylic acid benzene
in such systems, electron shifting takes place consecutively giving permanent polarity on the chain. This
type of -electron shift in the conjugate systems is called mesomeric effect or resonance.
Rule s for re sona nce for ms :
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:
2. Which of the following statement is incorrect -
(A) In a resonance hybrid all the molecules are the same. A resonance hybrid cannot be expressed by any
single structure.
(B) The value of the resonance energy of any resonance hybrid is not an absolute value
(C) The energy of hybrid structures is always less than that of any resonating structure
(D) Only one individual resonating structure explains all characteristics of the molecule
3. Choose the correct option about stability of resonating structure :
O O
Cl :
Cl N N
O O
C O
O O
(C) < (D) H–C–O > CH3–C–O
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Tr u e / Fals e
1. F 2. F 3. T 4. F 5. F
F i ll i n t h e B lank s
1. benzene 2. antiaromatic, aromatic 3. hyperconjucation 4. nucleophile, base
5. 2,3-diphenylbutane (optically inactive, meso)
Matc h th e C o lu m n
1. (A) p,s ; B q,r ; (C) q,s ; (D) p,s 2. (A) q ; (B) p ; (C) p ; (D) r
3. (A) p ; (B) q ; (C) p ; (D) q
A s s er ti o n - R eas o n Q u es ti o ns
1. B 2. A 3. A 4. C 5. A
6. C 7. D 8. B 9. D 10. C
C o mp rehe ns i o n B as ed Q u e st i o ns
C o mp re he ns i o n #1 : 1. (A) 2. (A) 3. (B) 4. (B) 5. (C) 6. (C)
C o mp re he n s i o n #2 : 1. (D) 2. (C) 3. (C) 4. (D) 5. (B)
C o mp re he ns i o n #3 : 1. (C) 2. (B) 3. (B) 4. (B)
C o mp re he ns i o n #4 : 1. (A) 2. (D) 3. (C,D)
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(a)
N N
NH2 NH2
H
(I) (II) (III) (IV)
(b)
CH3
CH3 CH3
(I) (II) (III) (IV)
NH2
(c)
N
N
H
(I) (II) (III)
2. Rank the following intermediates according to the stability (most stable first).
⊕ ⊕ ⊕ ⊕
(a) CH 3 CH 2 CH 2 C H 2 , CH 3 C HCH 2 CH 3 , (CH 3 ) 2 C CH 2 CH 3 , (CH 3 ) 3 C
• • • •
(b) CH 3 CH 2 CH 2 C H 2 , CH 3 C HCH 2 CH 3 , (CH 3 ) 2 C CH 2 CH 3 , (CH 3 ) 3 C
3. Rank the following intermediates according to the stability (most stable first).
— — — —
(a) CH 3 CH 2 CH 2 C H 2 , CH 3 C HCH 2 CH 3 , (CH 3 ) 2 C CH 2 CH 3 , (CH 3 ) 3 C
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(b) CH 2 •• , CH 3 CH •• , C 6 H 5 CH •• , ( C 6 H 5 ) 2 C ••
4. Show why the phenolate ion, C 6 H 5O –, has a greater resonance stabilization than phenol, C 6 H 5OH.
5. Is phenol a stronger acid than acetic acid. Explain your answer with proper reasoning.
6. Arrange all these numbered H in order of their decreasing acidic strength.
H
4
O O
H H
1 2
OH
3
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OH OH
COOH SO3H OH
CH2OH
(I) (II) (III) (IV)
10. Why a cation like is not possible.
O
H OH
11. (A) Product.
O
H3O
12. CH 2=CHCHO + C 2H5MgBr P ; Here P is :
13. Within each set, select the compound which is more reactive in nucleophilic addition at carbonyl carbon :
(I) CH 3 COCH 2 CH 2 Br or CH 3 COCH 2 Br (II) CH 3 CHO or CH 3 COCH 3
(III) CH 3 COCH 3 or CH 3 –CO–CF 3 (IV) PhCHO or CH 3 CHO
14. Rank of the following compounds in increasing order of electrophilicity :
O CH2 NH
(I) F3C H (II) CH3 H (III) CH3 OH
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O O O O
(A) H3C–C–NH2 ; CH3 –C–Cl ; CH3 –C–OAc; H3C–C–OCH3
(I) (II) (III) (IV)
O O O O
(B) H3C–C–Cl ; CH3CH2 –C–Cl ; (CH3)2CH–C–Cl ; (CH3)3C–C–Cl
(I) (II) (III) (IV)
O O O
(C) CH3 –C–OCH3 ; CH3 –C– OCH2CH3 ; H3C–C–OCH3
(I) (II) (III)
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Cl Cl
AlCl3/ AlCl3
(A) CH3–CH2 (B) CH3–C= O
CH3
KOH/Alc. HBr
(C) CH3–C–Cl (D) CH2=CH–CH=CH2 A
40°C
CH3
–80°C
B
O
O–C–CH3 OH
AlCl3 AlCl3
(E) E (F) + CO + HCl G
O
N (CH3)3 C Cl
AlCl3
OH O
(G) CH3–CH2 –CH–CH3 H (H)
(C) , , ,
O O
O O
C–O C=O O–H C
O
OH C OH NO2
O
(D) ; ; ;
O–H
N(CH3)3
19. In the case of CH3–CH2–CH–CH3 OH, less stable 1-Butene is obtained. Why ?
20. When carbene attacks cis 2-butene singlet gives cis product while triplet gives trans product. Why ?
78
E
1. (a) I > III > II > IV (b) IV > III > II > I (c) II > I > III
⊕ ⊕ ⊕ ⊕
2. (a) (CH 3 ) 3 C > (CH 3 ) 2 C CH 2 CH 3 > CH 3 C HCH 2 CH 3 > CH 3 CH 2 CH 2 C H 2
• • • •
(b) (CH 3 ) 3 C > (CH 3 ) 2 C CH 2 CH 3 > CH 3 C HCH 2 CH 3 > CH 3 CH 2 CH 2 C H 2
— — — —
3. (a) CH 3 CH 2 CH 2 C H 2 > CH 3 C HCH 2 CH 3 > (CH 3 ) 2 C CH 2 CH 3 > (CH 3 ) 3 C
••
7. In –C=C–F, lone pair - p conjugation will be more due to more overlaping of orbitals involved in conjugation.
8. Phenol is more acidic as after loss of H+, phenoxide ion is Resonance stabilised. No such resonance is seen
in conjugate base of cyclohexanol.
9. II > I > III > IV
10. Due to the non-planar structure.
O
OH
11. 12. CH2=CH–C–C2H5
H
NODE6 E :\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-05\General organic chemistry\Eng\Exercise.p65
E 79
+ + +
+ O O O
(b) +
O O O
O O O O
(c) CH2—C—CH3, CH2—C—H, CH2—C—NH2 , CH2—C—CH2—OCH3
2. For the following compounds, arrange the labelled proton in increasing order of their ease of
deprotonation :
1
H
O
3
C C—H 3
H
2
(i) H (ii) CH2
CH2 C
H
1 2 O O
H
3. Benzene sulphonic acid is a stronger acid than benzoic acid, explain.
4. Which is a stronger acid, A or B and why ?
COOH COOH
(I)
NO2 NO2
(A) (B)
(A) (B)
80
E
N
H
Benzimidazole
7. In each of the following pair of compounds, which is more basic in aqueous solution ? Give an explaination
for your choice :
NH
(i) Which of the indicated H is abstracted rapidly by bromine radical and why ?
Ph Hc
Hb
Ha
(ii) One of the indicated proton H a or H b, is approximately 10 30 times more acidic than other, which is
more acidic and why ?
H
H
Ha
Hb
10. Compare the bond dissociation energies of C—H bonds in the following
NODE6 E :\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-05\General organic chemistry\Eng\Exercise.p65
H
(i) H—CH 2 —CH 2 —CH 2 —CH 3 (ii) CH3
(iii) (CH 3 ) 3 C—H
H3C
11. The most stable intermediatr y carbocation and major product in following reactions :
H
(i) [C ] Product
OH
(ii) H Product
[C ]
OH
OH
HBr
(iii) O [C ] Product
E 81
2
N •• CH3 CH3
–N N
••
(a) CH3 (b)
N
••
1
(I) (II)
Ag
A
KOH H
(c) + CHCl3 C+ D (d) [E]
••
N
Et Et
H
OD
D
(e) NaOH (i) CO2
[Intermediate] (ii) D
F
OH
O dil H
(a) + [A]
H HO C5H5
Me
H Me H–Cl
[A]
(b) –O–O–H [B] (c)
O–H
C2H5
3-Hydroperoxycyclohexene
MeO
Me
O BF3
(d) [B] (e) OTs KI
A+ B
82
E
HNO2 P–Ts–OH
(i) (ii)
H
HO
HO NH2
OAc
O H HClO4
(iii) (iv) THF
Me H
O O O H
O NH O N NH O
H–N NH NH
O
NaOH H3O
(A) H+
O
O
O
NaOH H3O
+
(B)
CHO
2-equivalent 1-equivalent
NaOH
(C) CHO
NODE6 E :\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-05\General organic chemistry\Eng\Exercise.p65
OH
H2SO4 CH3 H
(i) CH3–CH2–CH–CH3 C C
H CH3
trans
CH3 CH2
NaOH
(ii) CH3–C–Br alc.
CH3 –C
CH3 CH3
H OAC
CH3 CH3
(iii) CH3–CH–CH–CH3 C C
H H
cis
E 83
Br H
–CH –CH2 NaOH –CH= CH2
(iv) alc.
Br H
NaOH Ph H
–CH–CH2–CH3 C= C
(v) alc. H CH3
CH3OH
19. Y H2C—CHCH3 CH3OH X ; Here X and Y respectively are.
CH3ONa H
O
OH
H3C CH3 14
CH2=CHCH2Cl 200°C
21. P; Here P is.
O
H
22. [X] ; most likely the compound [X] is.
R R
O
O
23. H OH ; the above intermediatory involves.
O
24. Suggest the product of the reactions :
H
/H N NC
H CHCl3
(A) CH3–CH= CH2 (B) NaOH
O
N2Cl
–C–H NaOH
(E) D (F) F
O2N —— C –CH3
OH H
(G) P (H) NaOH
OH
Cl N
OH
84
E
O
+
O O O O
(c) CH2—C—NH2 < CH2—C—CH2—OCH3 < CH2—C—CH3 < CH2—C—H
N Basic
6. Lone pair of the basic nitorgen is fully available with
:
Benzimidazole
7. (i) CH 3NH 2, (ii) H2N—C—NH2 (iii) PhNH 2
NH
8. (i) H c > H a > H b (ii) H a : Conjugate base is aromatic
9. Acidic strength stability of anion formed after removal of H + number of e – withdrawing groups.
1
B.D.E.
stability of intermediate formed
E 85
86
E
(R is alkyl group)
decreasing order of inductive effect is-
(1) (CH 3 ) 3 C– > (CH 3 ) 2 CH– > CH 3 CH 2 –
(2) CH 3 –CH 2 – > (CH 3 ) 2 CH– > (CH 3 ) 3C–
(3) (CH 3 ) 2 CH– > CH 3 CH 2 – > (CH 3 ) 3 CH–
(4) None of these
2. In the anion HCOO– the two carbon-oxygen bonds are found to be of equal length. What is the reason
for it- [AIEEE 2003]
(1) Electronic orbits of carbon atoms are hybridised
(2) The C=O bond is weaker than the C–O bond
(3) The anion HCOO – has two resonating structure
(4) The anion is obtained by removal of a proton form the acid molecule
3. The correct order of increasing basic nature for the bases NH 3, CH 3NH 2 and (CH 3) 2NH is-[AIEEE 2003]
(1) CH 3 NH 2 < NH 3 < (CH 3 ) 2 NH
(2) (CH 3 ) 2 NH < NH 3 < CH 3 NH 2
(3) NH 3 < CH 3 NH 2 < (CH 3 ) 2 NH
(4) CH 3 NH 2 < (CH 3 ) 2 NH < NH
4. Consider the acidity of the carboxylic acids- [AIEEE 2004]
(i) PhCOOH (ii) o–NO 2 C 6 H 4 COOH
(iii) p-NO 2 C 6H 4 COOH (iv) m-NO 2 C 6 H 4 COOH
which of the following order is correct for acidic strength-
(1) i > ii > iii > iv (2) ii > iv > iii > i
(3) ii > iv > i > iii (4) ii > iii > iv > i
5. Which of the following is the strongest base- [AIEEE 2004]
NODE6 E :\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-05\General organic chemistry\Eng\Exercise.p65
E 87
O O
(1) (d) , (c), (b), (a) (2) (a), (b), (c), (d)
(3) (c), (b), (a), (d) (4) (b), (c), (a), (d)
10. Ter tiary alkyl halides are practically inert to substitution by SN 2 mechanism because of [AIEEE-2005]
(1) (C 6 H 5 )3 C (C 6 H 5 )2 C H (CH 3 )3 C (CH 3 )2 C H
(2) (C 6 H 5 )2 C H (C 6 H 5 )3 C (CH 3 )3 C (CH 3 )2 C H
(3) (CH 3 )2 C H (CH 3 )3 C (C 6 H 5 )3 C (C 6 H 5 )2 C H
NODE6 E :\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-05\General organic chemistry\Eng\Exercise.p65
(4) (CH 3 )2 C H (CH 3 )3 C (C 6 H 5 )2 C H (C 6 H 5 )3 C
15. CH 3 Br + Nu – CH 3 – Nu + Br –
The decreasing order of the rate of the above reaction with nucleophiles (Nu – ) A to D is [ A I E E E - 2 0 0 6 ]
[Nu – = (A) PhO – , (B) AcO –, (C) HO –, (D) CH 3O – ]
(1) D > C > B > A (2) A > B > C > D
(3) B > D > C > A (4) D > C > A > B
16. The correct order of increasing acid strength of the compounds is [AIEEE-2006]
(a) CH 3 CO 2 H (b) MeOCH 2 CO 2 H
Me
(c) CF 3 CO 2 H (d) CO2 H
Me
(1) d < a < c < b (2) d < a < b < c
(3) a < d < c < b (4) b < d < a < c
88
E
OH
— +
O Na
17. + CHCl 3 + NaOH
CHO
H
H
(1) + (2) + E (3) + (4) + H
E
E
H E
20. Arrange the carbanions, (CH 3 ) 3 C , CCl 3 , (CH 3 ) 2 CH , C 6 H 5 CH 2 , in order of their decreasing stability :-
(4) CH 3 2 CH CCl 3 C 6 H 5 CH 2 CH 3 3 C
21. The correct order of increasing basicity of the given conjugate base (R=CH 3 ) is :- [ A I E E E- 2 0 10 ]
E 89
O
(I) (II) (III) (IV)
N N N N
H H H
the order of basicity is as follows :
(1) IV > III > II > I (2) II > III > I > IV
(3) I > III > II > IV (4) III > I > II > IV
26. Dipole moment is shown by :- [AIEEE-2012(Online)]
(1) trans-2, 3-dichloro- 2-butene (2) 1, 2-dichlorobenzene
(3) 1, 4-dichlorobenzene (4) trans-1, 2-dinitroethene
27. Among the following chloro-compound having the lowest dipole moment is :- [AIEEE-2012(Online)]
Cl Cl Cl H
(1) CH 2 Cl 2 (2) CH 3 Cl (3) C=C (4) C=C
H 3C H H 3C Cl
28. In the below mentioned compounds the decreasing order of reactivity towards electrophilic substitution
(1) (iii) > (i) > (iv) > (ii) (2) (iv) > (i) > (ii) > (iii)
(3) (ii) > (iii) > (i) > (iv) (4) (i) > (ii) > (iii) > (iv)
29. Among the following the molecule with the lowest dipole moment is :- [AIEEE-2012(Online)]
(1) CHCl 3 (2) CH 2 Cl 2
(3) CCl 4 (4) CH 3 Cl
30. The most basic compound among the following is :- [AIEEE-2012(Online)]
(1) Acetanilide (2) Benzylamine
(3) p-Nitro aniline (4) Aniline
90
E
+
CH2
+ +
CH2=CH–CH2 ; CH3–CH2–CH2 ; is :- [JEE(MAIN)-2013]
I II
III
(1) III > II > I (2) II > III > I (3) I > II > III (4) III > I > II
33. Arrange the following compounds in order of decreasing acidity : [JEE(MAIN)-2013]
OH OH OH OH
; ; ;
(1) II > IV > I > III (2) I > II > III > IV
(3) III > I > II > IV (4) IV > III > I > II
NODE6 E :\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-05\General organic chemistry\Eng\Exercise.p65
1. Which one of the following has the smallest heat of hydrogenation per mole ? [IIT-93]
(A) 1–Butene (B) trans–2–Butene
(C) cis–2–Butene (D) 1, 3–Butadiene
2. What is the decreasing order of strength of bases OH, NH , HCC, CH –CH [IIT-93]
2 3 2
(A) CH3–CH2 > NH2 > HCC > OH (B) HCC > CH3–CH2 > NH2 > OH
(C) OH > NH2 > HCC > CH3–CH2 (D) NH2 > HCC > OH > CH3–CH2
OH OH OH OH
NO2
CH3 NO2
I II III IV
O O O
O
92
E
R R R H R R R R
NH O
CH3–C CH3CH2NH2 (CH3)2NH CH3CNH2
NH2 , , ,
1 2 3 4
(A) 2 > 1 > 3 > 4 (B) 1 > 3 > 2 > 4 (C) 3 > 1 > 2 > 4 (D) 1 > 2 > 3 > 4
10. Which of the following is least stable : [IIT -2005]
(A) CH3–O=CH–CH–HC=CH2 (B) CH3–O=CH–CH=HC–CH2
(C) CH3–O–CH–CH–HC=CH2 (D) CH3–O–CH=CH–HC–CH2
11. Among the following, the least stable resonance structure is - [IIT -2007]
O O
(A) N (B) N
O O
O O
(C) N (D) N
NODE6 E :\Data\2014\Kota\JEE-Advanced\SMP\Che\Unit-05\General organic chemistry\Eng\Exercise.p65
O O
Me Br
⊕
F PhS Na
dimethylformamide
NO2
F F SPh SPh
(A) (B) (C) (D)
⊕ ⊕ ⊕
O O ⊕
(A) II > IV > I > III (B) I > II > III > IV (C) II > I > IV > III (D) I > III > II > IV
14. Statement-I : p-Hydroxybenzoic acid has a lower boiling point that o-hydroxybenzoic acid.
Because
Statement-II : o-Hydroxybenzoic acid has intramolecular hydrogen bonding. [IIT 2003]
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
15. Statement-I : Bromobenzene upon reaction with Br 2/Fe gives 1, 4-dibromobenzene as the major product.
Because
Statement-II : In bromobenzene, the inductive effect of the bromo group is more dominant than the mesomeric
effect in directing the incoming electrophile. [IIT 2008]
(A) Statement-I is True, Statement-II is True ; Statement-II is a correct explanation for Statement-I
(B) Statement-I is True, Statement-II is True ; Statement-II is NOT a correct explanation for Statement-I
(C) Statement-I is True, Statement-II is False.
(D) Statement-I is False, Statement-II is True.
16. Out of anhydrous AlCl3 and hydrous AlCl3 which is more suluble in diethyl ether ? Explain with reason.
[IIT 2003]
17. Match Ka values with suitable acid : [IIT 2003]
Ka Acid
94
E
OH
19. Which of the following is more acidic and why ? [IIT 2004]
NH3 NH3
F
(I) (II)
20. The compound that does NOT liberate CO 2 , on treatment with aqueous sodium bicarbonate
solution, is - [JEE ADVANCED 2013]
(A) Benzoic acid (B) Benzenesulphonic acid
(C) Salicylic acid (D) Carbolic acid (phenol)
21. The hyperconjugative stbilities of tert-butyl cation and 2-butene, respectively, are due to
(A) p (empty) and * electron delocalisations [JEE ADVANCED 2013]
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