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ORGANIC chemistry
IR
GENERAL ORGANIC CHEMISTRY
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(G.O.C)
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N
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2. In each of the following pairs, determine which of the following represent resonance forms of a
single species or depict different substances. If two structures are not resonance forms. Explain
why.
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(a) N N N and N N N
(b) N N N and N N N
(c) N N N and N N N
4. Choose the more stable alkene in each of the following pairs. Explain your reasoning.
(a) 1-Methylcyclohexene or 3-methylcyclohexene
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(c) or
5. Rank the following sets of intermediates in increasing order of their stability giving appropriate
reasons for your choice.
(a) C6H5 ,P NO2 (C 6H4 ) ,P CH3 (C6H4 ) ,P Cl C6H4
+ +
(b)
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2 H C
3
Hb
Ha
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(a) (I) C6H5 CH2 and (II) CH2═CH – CH2
(b) (I) CH3– CH2 and (II) CH2═ CH
CH2 CH2
(c) (I) and
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CH3 — CH — CH 3 CH3 N CH3
(d) (I) and
CH3 — C — CH3 CH3 C CH3
C
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Pd / C
C
A 3H2
C
B D
In the above reaction which one of the given ring will undergo reduction?
N
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14. In which of the following molecules resonance takes place through out the entire system.
O O
COOCH 3
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CH
2
COOCH 3
15. Which of the following groups cannot participate in resonance with other suitable group:
(a) ─ COOH (b) ─CO O (c) ─ COCl (d) ─ NH3
.S
(e) ─ C H2 (f) CH2 ═ N —
CH3
16. Which of the following group can participate in resonance with other suitable group:
CH2
(a) CH2═ O ─ (b) ─CH2─ C H2 (c) ─CH2─ C H2 (d) CH
3
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CH = CH—
(e) (f) ─BH2 (g) ─ P Ph3
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21. Which of the following groups can either donate or with draw a pair of electrons in resonance
depending upon situation:
(a) ─NO2 (b) ─NO (c) ─CH═CH2 (d) ─CHO
(e) ─NH2 (f) ─N═NH
22. Which of the following groups can only withdraw a pair of electrons in resonance depending upon
situation:
IR
CH CH
3 CH 3
3
O
O
(d) (e)
N
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NH2 NO 2
IR
30. Which of the following pairs has higher resonance energy:
(a) CH3COOH and CH3COONa (b) CH2═CH─ O and CH2═CH─OH
COO O
(c) and (d) and
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(e) and CH2═CH─CH═CH─CH═CH2
(c) and CH2═CH─CH═CH2 (d) and CH2═CH─ C H2
OH
(e) and
N
O O
(c) and
(e) H C
2
CH
2
and H C
CH
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O
(c) and (d) and
NO 2 NO 2 O O
(e) N and
H O
34. Which of the following pairs has higher resonance energy:
(a) and N
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N H
(b) CH2═CH─O─CH═CH2 and CH2═CH─NH─CH═CH2
(c) CH2═CH─ N H and HN═CH─ N H
(d) CH2═CH─F and CH2═CH─Br
CH2
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(e) and CH2═CH─ C H2
1 1 1
2 2 2
35. 3 3 3
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4 4 4
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.
N
36. Identify more stable canonical structure in each of the following pairs:
O O
(a) C C (b) C H2─C≡CH CH2═C═ C H
H OH H OH
(c) (d)
N
N CH 2 CH 2
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O O
(b) C C
H CH2 H CH2
O NH O NH
(c) C C
H H H H
(d)
CH2 CH2
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(a) CH3―CH2 Br and CH3―CH2 Cl
(b) CH3―CH═CH Br and CH3 CH―CH3
Br
O
C
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(c) CH3 Cl and CH ―CH
3 2 Cl
(d) CH2═CH CH═CH2 and CH2═CH CH2―CH3
(e) CH2═CH CH═CH2 and CH2═CH NO2
CH3
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39. In which of the following pairs, indicated bond having less bond dissociation energy
2
N
C C
CH2 CH2
O O O O
(d) C C (e) C C
and and
H2 N NH2 CH3 NH2 Cl Cl CH 3 Cl
O O
(f) C C
and
H2 N NH2 H NH2
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CH2
NH
CHO
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
IR
42. C1―C2 bond is shortest in
3
CH
2
CH CH CH
2 2 2 2 2
CH
1
CH
C 1 1 1 C
(a) (b) (c) (d)
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43. Among the following molecules, the correct order of C―C bond length is
(a) C2H6 > C2H4 > C6H6 > C2H2
(b) C2H6 > C6H6 > C2H4 > C2H2 (C6H6 is benzene)
(c) C2H4 > C2H6 > C2H2 > C6H6
(d) C2H6 > C2H4 > C2H2 > C6H6
44. CH3O―CH═CH―NO2 I
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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
N
(c) I > III > II > IV (d) II > III > I > IV
45. In which of the following molecules resonance is equivalent:
(a) HCO O (b) CH2═CH―CH═CH2
CHO
(c) (d)
NH2
46. CH2═CH―CH═CH―CH═CH2 I
CH2═CH― C H―CH═CH― C H2 II
C H2―CH═CH―CH═CH― C H2 III
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
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48. Among the following pairs identify the one which gives higher heat of hydrogenation:
49. Which of the following statements would be true about this compound:
NO 2
5
IR
1 3
NO 2 NO 2
Br
(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.
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50. Write resonating structures of complex formed when an electrophile ( E ) attacks on (i) and (ii)
position of naphthalene. Also state which is more stable?
51. The total number of contributing structure showing hyperconjugation (involving C—H bond)for the
following carbocation is [IIT-JEE 2011]
H3C CH2CH3
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O O
O O
(ii) (a) CH3 – CH2 – CH – C – O – H (b) CH3 – CH – CH2 – C – O – H
F F
O
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(c) CH2 – CH2 – CH2 – C – O – H
F
O O
(c) Cl – C – C – O – H
Cl
(iv) (a) CH3 – CH2 – O – H (b) CH3 – CH – O – H
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CH3
CH3
(c) CH3 – C – O – H
N
CH3
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O
(vi) (a) (b) (c)
•• •• ••
NH NH N
Me
•• ••
IR
NH2 NH2
•• ••
N N N
.S
(viii) (a) (b) (c)
O2N Me F
•• •• •• ••
NH2 NH2 NH2 NH2
NH3 Cl CH3 H
O NO2
N NO2 NO2
(i) (a) (b) O (c) (d)
•• •• ••
•• O – H •• O – H •• O – H
NO2 Cl CH3
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••
•• •• •• O – H ••
•• O – H •• O – H •• O – H
IR
•• ••
•• •• O – H •• O – H
•• O – H
Cl
(v) (a) (b) (c)
Cl
.S Cl
O O
C –O – H C –O – H COOH COOH
CH3 Cl Br
(vi) (a) (b) (vii) (a) (b)
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O O
O ••
•• C –O – H C –O – H
C –O – H ••
•• ••
OMe
••
(viii) (a) (b) (c)
N
••
OMe
••
•• OMe
••
O O
O
C –O – H C –O – H
C –O – H
NO2
(ix) (a) (b) (c)
NO2
N
O O
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OH OH OH OH
OH OH OH OH
NO2 F CH3
OH
IR
OH OH OH
OMe
(iii) (a) (b) (c) (d)
OMe
OMe
.S
OH OH OH
OH
NO2 NO2
•• •• ••
(ii) (a) CH3 – C – NH2 (b) CH3 – CH2 – NH2 (c) CH3 – C – NH2
N
O NH
••
•• ••
(d) NH2 – C – NH2
NH
••
••
NH2
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NH
NO2 CN OMe •• 2
•• •• ••
NH2 NH2 NH2
NO2
(v) (a) (b) (c)
NO2
NO2
IR
Me
Me
NMe2 NMe2 N
OMe
(vi) (a) (b) (c)
.S OMe
OMe
•• ••
NH2 NH2
Me
Me
N N
O O O O
O
•• •• ••
NH– C–CH3 NH2 NH– CH2 – CH3
N
•• •• ••
NH2 NH2 NH2
H
C–H
(ix) (a) (b) H (c)
H
C–H
H
C
H H
H
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H H H
NH2
IR
(c) (d)
N N
H
.S
N
H H CH3 H
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H H Me
N– Li+ N N N
NH2 C –NH2
(c) (d)
NO2 O
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IR
Q.10 Which one of the following phenols will show highest acidity?
CH3
OH H3C OH
(A) (B)
CH3 O2N
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NO2 CH3
CH3
OH
H3C OH
(C) (D)
H3C
H 3C NO2 NO2
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OH
(A) (B) (C) (D)
N
OH OH
N
d
CH3 CH3
(A) b > d > a > c (B) a > b > d > c (C) a > b > c > d (D) a > c > b > d
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O O O O O
O
(I) (II) (III)
(A) I > II > III (B) III > II > I (C) III > I > II (D) I > III > II
IR
Q.15 Arrange acidity of given compounds in decreasing order :
(I) CH3 – NH – CH2 – CH2 – OH (II) CH3 – NH – CH2 – CH2 – CH2 – OH
(III) (CH3 )3 N CH2 CH2 OH
OH
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COOH CH3CCOOH
O OH
(I)
(II) (III)
(A) I, II and III (B) I and III (C) II and III (D) I and II
Q.17 Say which pka belong to which functional group in case of following amino acids :
COOH
(i) cysteine : HS 1.8, 8.3 & 10.8
NH2
HO2C COOH
(ii) glutamic acid : : 2.19, 4.25, 9.67
NH2
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IR
OH OH OH OH
or or
(c) (d)
(e) or
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Q.20 Which of the following would you predict to be the stronger acid?
O O
COOH
(a) or N C – OH
O
N
N N N–H N N
(A) (B) (C) (D)
H H H
Q.24 In each of the following pair of compounds, which is more basic in aqueous solution? Give
an explanation for your choice:
(a) CH3NH2 or CF3NH2
NH
IR
(c) n-PrNH2 or CH3CN
(d) C6H5N (CH3)2 or 2,6-dimethyl-N-N-dimethylaniline
(e) m-nitroaniline or p-nitroaniline
Q.26 Choose the member of each of the following pairs of compounds that is likely to be the
weaker base.
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(a) H2O or H3O (b) H2S, HS–, S2– (c) Cl–, SH– (d) F–, OH–, NH2–, CH3–
(e) HF, H2O, NH3 (f) OH–, SH–, SeH–
NH2 NH2
NO2
OH OH
O O O O
CH3 CF3
(c) O– – C – C – OH or HO – C – C – OH (d) or
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CH3 NO2
(a)
CH3
(b)
CH3
(i) (ii) CH3 (iv)
(iii)
IR
NH2
(c)
N
N
(i) (ii) H
.S (iii)
Q.29 Arrange the basic strength of the following compounds.
(a) OH– CH3COO– Cl–
(i) (ii) (iii)
– –
(b) CH C CH2= CH CH3CH2–
(i) (ii) (iii)
(c) CH2= CHCH2NH2 CH3CH2CH2NH2 CH C – CH2NH2
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(d)
N
Cl
(e)
Cl Cl
(i) (ii) (iii)
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O
Q.32 Which is stronger acid, A or B and why?
COOH COOH
CH
H C
3
3 HC CH
3 3
C
HC
CH
3
3
(a) (b) HC
3
CH
3
HC CH
H C 3 3
CH
3
3
NO2 NO2
IR
Nb
H
Benzimidazole
Q.34 In the following structure, which is better site of protonation and why-oxygen or nitrogen?
.S O N CH
3
H
Q.35 Rank the following in increasing order of basic strength, explaining reason for your choice:
H H
+ N
NLi N
(i) (ii) (iii)
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Q.36 One of the indicated proton Ha or Hb, is approximately 1030 times more acidic than other, which is
more acidic and why?
H
H
H
H
N
Q.37 Number the following compounds in order of increasing acidity of indicated proton giving
mechanistic reasoning:
O H CH2 H CH2 CH2 H O H
I II III IV
Q.38 From the following pair. Select the stronger acid providing clear reasoning:
(a) O2N COOH or H C
3
COOH
NH2Cl NH2Cl
(b) or (c) or H C
3
CH
H C
CH
N+
N+
3 H C CH
3
3 3
H
H
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Q.2 Among the following the compounds having the highest enol content:
(A) CH3CHO (B) CH3COCH3
(C) CH3 – C –CH2CHO (D) CH3 – CO – CH2 – CO2CH3
IR
O
(A)
.S (B) (C) (D) None of these
N=O
HO OH
HO OH
OH
N
O O
HO O HO OH
(A) (B)
HO OH O O
O OH
O
O O
(C) (D) All of these
HO OH
OH
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(A) C – CH = C
O OH
(B) C – CH2 – C
OH O
(C) CH – CH = CH
IR
OH OH
(D) C – CH2 – C
O OH
.S
Q. 6 Tautomer in following is/are triad system:
O
(A) CH3COCH3 (B) CH3CH2NO 2 (C) (D) HCN
O OH
(A) (B)
N N O N HO N
| |
H (I) (II) H (I) (II)
N
O O
OH OH
C H–C C CH3– C
(C) NH2
(D) NH2
H NH CH3 NH
O
OH
C CH2 = C
(E) OH
CH3 OH
(I) (II)
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O O H O OH
C CH3 C O
(C) CH3 C CH3 C (D)
O CH2
O OH
IR
(I) (II) (I) (II)
H CH3
O
O O=C
C CH2 CH3
C CH2
(E) CH3 CH2 C
CH3 CH
.S O
(I) (II)
Q.9 In each of the following pairs which will have higher enol content:
COOEt O
(A) CH2 and C
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COOEt O O
N
O O O O
(C) C C and C C
O O O O
(D) C C and C C
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O O O
(C) and (D) and
O
Cl
Q.11 In each of the following pairs which will have less enol content:
IR
O OCH3 O OCH3
C C
and
(A) (B) O
and N N O
| |
H H
.S
Q.12 In each of the following stets of compounds write the decreasing order of % enol content.
O
(A)
O O
(I) (II) (III)
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(B)
O
(II) O O
O
(I) (III) (IV)
N
O O O O
O
(C)
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(E)
O H H
O O O O
C C C
C
Q.13 CD3 CD3 CH3 CH2 CH3
CH3 CH3
IR
Q.14 %enol content of acetylacetone in following solvents is found as:
Solvent % enol content
H2O 15
Liquid state 76
Hexane 92
Gas phase 92
.S
Explain the observation.
O Na O Na
+
Q.15
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(Minor) (Major)
NaOH H2O
O
N
H+/H2O OH
OH
(Major) (Minor)
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6. (a) CH2 = CH — Cl , CH 3 — CH 2 — Cl
B.L. ( < ) since has partial double bond caracter
IR
— (1s — 3P) (1S — 2P)
..
(d) In CH2 = CH — NH2
Lone pair on nitrogen is part of conjugation
7. iii > ii > i 8. Hc
9. (a) I, (b) I, (c) II, (d) II 10. A 11. (a), (c),(d),(g),(j),(l),(m)
.S
12. (a), (b) 13. (a),(b),(c),(f) 14. (b), (c) (f)
15. (d) 16. (a), (e), (f), (g) 17. (b), (d), (e)
18. (b), (d), (e) 19. (c), (f) 20. (a), (b), (c), (d), (f)
21. (b), (c), (f) 22. (f)
27. d 28. b 29. a
30. (a) II, (b) I, (c) I, (d) I, (e) I
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31. (a) II, (b) I, (c) I, (d) II, (e) I 32. (a) II, (b) I, (c) II, (d) II, (e) II
33. (a) II, (b) II, (c) II, (d) II, (e) II 34. (a) I, (b) II, (c) II, (d) I, (e) I 35. b
36. (a) I, (b) I, (c) I, (d) I,
37. (a) I, (b) II, (c) II, (d) I 38. (a) I, (b) II, (c) II, (d) II, (e) I, (f) I
N
50.
e
attack
extended conjugation
E
E
- attack cross conjugation
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CH3 OH NO2
ACIDIY, BASICITY
ANSWER KEY
Q.1 (i) a > b > c > d, (ii) a > b > c, (iii) c > b > a, (iv) a > b > c
IR
(v) c > b > a, (vi) a > b > c (vii) d > c > b > a (viii) d > c > b > a
(v) a > b > c (vi) a < b < c (vii) c > a > b (viii) b > c > a
.S
(ix) c > d > b > a
Q.3 (i) d > c > a > b (ii) a > b > c (iii) c > a > b > d (iv) d > b > c > a
(v) a > b > c (vi) b > a (vii) b > a (viii) c > b > a
(v) b > a > c (vi) c > a > b (vii) b > a (viii) c > b > a
(ix) c > b > a (x) a > b > c
N
Q.16 a
Q.18 (a) 3 < 2 < 1; (b) 1 < 2 < 3; (c) 3 < 2 < 1 (d) 2 < 1 < 3 (e) 2 < 3 < 1
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Q.24 (a) i, (b) ii, (c) i, (d) ii, (e) I Q.25 (a) i, (b) i, (c) ii Q.26 (a) 2; (b) 1 (c) 1; (d) 1; (e) 1;
(f) 3
Q.27 (a) 2 ; (b) 1; (c) 2; (d) 2 Q.28 (a) 3 < 2 < 1 < 4 (b) 1 < 2 < 3 < 4; (c) 3 < 1 < 2
Q.29 (a) 1 > 2 > 3; (b) 1 < 2 < 3; (c) 3 < 1 < 2; (d) 2 < 1 < 3; (e) 1 < 2 < 3
Q.30 (a) 2 < 1 < 3; (b) 1 < 2 < 3; (c) 3 < 1 < 2
IR
TAUTOMERISM
ANSWER KEY
Q.12 (a) 3 > 1 > 2; (b) 4 > 2 > 1 > 3; (c) 4 > 1 > 3 > 2 (d) 3 > 1 > 4 > 2 (e) 3 > 4 > 2 > 1
Q.13 3 > 1 > 2
N
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