CHAPTER PRACTICE PROBLEMS (CHEMISTRY) FIITJEE

GENERAL ORGANIC CHEMISTRY & ISOMERISM

Q.1. Why cyclic 1, 2-diketones exist mainly in the enolic form?

Q.2. Write the following free radicals in the order of increasing stability.

CH3, 1, 2, 3, allyl, vinyl

Q.3. Arrange the following compound on the basis of increasing basic strength
O

NH
O
||
NH3 CH3 – NH2 CH3  C  NH2 O

I II III IV

Q.4. The allene 2, 3-pentadiene does not have a chiral carbon but is resolvable into enantiomers.
Draw an orbital picture that account for its chirality.

Q.5. What will be specific rotation of caniine, the toxic component of poison hemlock, if a solution
containing 0.75 gm/10 mL is placed in a one dm polarimeter tube and its observed rotation of
298K is +1.2°?

Q.6. O O
O

H3C CH3
O

(i) (ii)

Why in (i) enol form is more stable whereas (ii) mainly exists in keto form

Q.7. Write down the correct decreasing order of following compound

OH OH OH OH
(a)
, , , (acidity)

OCH 3 NO 2 CH3
I II III IV
NH2 OH NH2
O

(b) NH H2C
(Basicity)
, , , NH2
I II O III IV
+ + + +
CH CH CH C

, , and (carbocationic stability)

(c)

IV V VI VII
CH 2
CH 2 HC C

(d) , , and (stability of free radical)

VIII IX X XI

Q.8. (a) Write the following in the increasing order of acid strength.
CCl3COOH, NH3, HCOOH, CH3COOH, CH3CONH2
(b) Write the following in the decreasing order of basic strength
- -
C6H5 NH2 , HO , NH3 , NH2 , (CH3)2N, CH3OH, CH3NH2

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CHAPTER PRACTICE PROBLEMS (CHEMISTRY) FIITJEE
Q.9. Arrange the following in increasing order of the property as indicated in the bracket against
each
OH OH OH OH

(a)
(acidic property)
O NO2 CH3
H3C
I II III IV
-
CH2
H3C
-
(b) C CH3 (carbanion stability)
H2C
H3C -
CH2 CH3

I II III IV
NH2 NMe2 NMe2
Me Me

basic property
(c)
I II III

Q.10. Arrange the following in their decreasing order of basicity

O O O CH3

H3C NH2 , H 3C N CH3 , H3C NH2 , NH 3

Q.11. Why guanidine is basic in nature.

Q.12. Mark the asymmetric carbon atoms and give the number of optical isomers in the following
compounds. (i) CH3(CHOH)2 – COOH (ii) HOOC(CHOH)2COOH
Q.13. Write all the stereoisomers of the following acid.
CH3CH = CH CH COOH
|
CH3
Q.14. Which of the following compound is stronger acid and why?

CH

CH

(i) (ii)

Q.15. Arrange the following compound in their decreasing order of enol content.
O O O O

H3C CH3 , H3C CH3, H3C CH3 , H3C O

O O

Q.16. Arrange the following singlet carbene in their decreasing order of stability. Give reasons.
   
CH2 , CF2 , CHCl , CCl2
Q.17. 2, 4, 6 trinitrotoluene is relatively acidic compound. Explain why this proton is easily removed
from the methyl group?
Q.18. Though enol form is less stable than keto form, phenol exists in enol form, why?
Q.19. Why is pyridine much weaker base than aliphatic amines?
Q.20. Why is 2, 6-dimethyl-4-niotro phenol stronger acid than 3,5-dimethyl-4-nitrophenol

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CHAPTER PRACTICE PROBLEMS (CHEMISTRY) FIITJEE
ANSWERS
1. The main driving force for enolization is relief of the electrostatic repulsion that occurs where
the two electrophilic carbonyl groups are adjacent to each other.
O O H
O O

(minor) (major)
Enol form will also stabilize due to intramolecular H-bonding’.

2. Vinyl  Methyl 1°  2° 3°  Allyl

3. II  I  III  IV
O
 
CH3  NH2 , H – NH2 ,
H3C C NH2
+I effect -I efect
O

NH

4. The allene has non-planar character. The two double bond systems in 2,3-pentadiene are at
right angle to each other. Due to this it has no plane of symmetry and its mirror images are not
super-imposable and the allene is capable of existence in (+) and (–) enantiomers.
H3C H H CH3

C C C C C C

H CH3 H 3C H

In allene, the central carbon atom is sp hybridised and linear while the two terminal carbon
atoms are sp2 hybridized and trigonal. The two unhybridized p-orbitals on a sp hybrid carbon
atom are perpendicular. So the two -bonds must also be perpendicular. Allene itself is a
chiral, however, if some substituents are added to allene the situation is different and it
becomes chiral as in the case of 2,3-pentadiene.

 obs 0.75 gm
5. Specific rotation []D = Given C (conc) =
C 10mL
( 1.2 )
[]D = = +16° Where  = length of the solution in decimetres
 0.75 
1  
 10 

H3C CH3
C C
6. In O O rotation about the single bond is possible which helps in minimizing repulsion
O O

between two – C = O dipoles whereas in this rotation is not possible and so in order
to reduce two – C = O dipole repulsion molecule prefers enol form which is also stabilized by
hydrogen bonding.
O O O CH3

C C C C

H3C CH3 H3C O

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CHAPTER PRACTICE PROBLEMS (CHEMISTRY) FIITJEE
H
O O

7. (a) III> I > IV > II (b) III > IV > I > II

(c) VII < VI < IV < V (d) X < VIII < IX < XI

8. (a) NH3 < CH3CONH2 < CH3COOH < HCOOH < CCl3COOH
(b) NH2- > OH- > (CH3)2N > CH3NH2 > NH3 > C6H5NH2 > CH3 OH

9. (a) II < IV < I < III (b) I < IV < III < II (c) I < II < III

H3C O H3C
10.
NH2 NH3 H3C NH

H3C NH2 H3C

O
11. In Guanidine lone pair on any one of the nitrogen atoms is always available for donation as a
base.
–
NH NH

+
H 2N NH2 H2N NH2
If any of the nitrogen gets protonated, even then also we have a lone pair available for donation
as a base.
+
NH2 NH2

+
H2N NH2 H2N NH2
Hence Guanidine is a stronger base
OH OH
12. i)
H3C C C COOH

H H
There are two (even) asymmetric carbon atoms (*), but the molecule cannot be divided into
symmetrical halves. So the number of d- and l- isomers, a = 2n = 22 = 4, and the no. of meso
forms m = 0
So, total number of stereoisomers = a + m = 4 + 0 = 4
OH OH

ii) COOH C C COOH

H H
There are two (even asymmetric carbon (*) atoms and the molecule can be divided into
symmetrical halves, so the number of d- and l-isomers a = 2n–1 = 22–1 = 2, and the number of
meso forms, m = 2 (n/2)-1 = 20 = 1
Total number of stereoisomers = 2 + 1 = 3

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CHAPTER PRACTICE PROBLEMS (CHEMISTRY) FIITJEE
H H H H H3C H H CH3
13. (i) (ii)
C C C C C C C C

H C C H
H3C C C CH3
CH3 H3C H CH3 H3C H
H H
COOH HOOC COOH HOOC

14. Carbanion which results from loss of H+ from (ii) is less stable because rings lose co planarity
due to steric repulsion and therefore are not involved in stabilization of –ve change through
resonance in (i) where all rings are tied to each other.

O O O
O
15.
H3C O H3C CH3 H3C CH3
H3C CH3

O O

   
16. C H2  C HCl  C Cl 2  C F2
In all singlet carbene, the stability increase as it is attached with halogen compound because

halogen can have p – p conjugation with carbon. p-p conjugation for C F2 as it is 2p-2p,

where as in C Cl 2 it is 2p – 3p.

17. The proton is removed easily because the anion formed after, removal of the proton is stabilized
by resonance with three NO2 groups as shown

CH2 O CH2 O
CH3 O
+ N N
N O2N
O2N Base O O
O

ON2

N 2O N2 O
N2 O

18. OH O
H
H

Enol form is much more stable than keto form because of great stability associated with
aromatic ring which is absent in keto form.

19. In aliphatic amines lone pair lies in sp3 hybridized nitrogen whereas in pyridine lone pair lies in
sp2hybridized nitrogen. So in pyridine nitrogen atom has more hold over this lone pair of
electrons, decreasing its availability.

20. Anion derived from 3, 5-dimethyl-4-nitrophenol is less acidic due to steric hindrance nitrogroup
is forced out of the plane of ring and thus is unable to stabilize negative charge on anion
through resonance



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