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of NCERT
Organic Chemistry
Questions
By
(i)
(ii)
Preface
The guiding principle in writing this book was to create
a textbook for students- a textbook that presents the
material in a way that they learn to solve all the questions of NCERT along with the strategy to approach
the problems.
In this book we mixed all our teaching experience of 10
yea rs a long with theora tica l a nd experimenta l
knowledge to generate a hand book for all students to
reason their way to a solution rather than memorize a
multitude of facts, hoping they dont run out of memory.
If you ask your teacher, senior or friend about NCERT,
then they will surely say that NCERT questions are very
important to solve before giving board exam or any competitive exam as it is the basic theme for any board or
competitive exa m a nd nearly a ll the questions a re
derieved from NCERT only.
But the problem in NCERT organic chemistry is that
there are a lot of intermixing of concept involve in same
chapter so many students get fear of it and generally
leave it by thinking that they can score good marks or
rank without it, but they are fooling themself.
Organic chemistry is very easy and conceptual subject
and need proper understa nding of the basics a nd
stretegy to solve the questions in corret manner.
This book will prepare your right mindset for learning
Organic Chemistry. This mindset is essentially the one
that focuses you on a small number of straight forward,
repeated, fundamental concepts and helps you to apply them in different ways to solve the variety of
problems you face in NCERT or other organic problems.
Ajnish Kumar Gupta & Bharti Gupta
(iii)
Acknowledgement
We are tha nkful to all the teachers who taught us
during the concept building session of our life specially
Dr. Nizamuddin sir, senior Chandra Vijay Rao and Dr.
Vijay Pratima Mittal madam.
We have written this book to remove the fever of
organic chemistry from mind of students.
We particularly want to thank many wonderful and
talented students whom we have taught over the years
who in turn taught us how to be a good teacher and
how we can help others.
We want to make this book as user friendly as possible,
and we will appreciate any comments that will help us
to achieve this goal in future editions.
Finally, this edition has been presented before you with
efforts to make it errors free. Any that remain are our
responsibility; if you find any, please let us know so they
can be corrected in future printing.
Ajnish Gupta & Bharti Gupta
Professors of Organic Chemistry
Ajnish@OrganicChemistry.co.in
09122057123
(iv)
Table of Contents
Unit
Topic
Page. No.
1. Organic Chemistry- Some basic
principle & techniques
01 - 46
2. Hydrocarbon
47 - 78
3. Haloalkane & Haloarenes
79 - 124
4. Alcohol, Phenol & Ether
125 - 172
5. Aldehyde, Ketone & Carboxylic acid 173 - 224
6. Amines
225 - 260
7. Biomolecules
261 - 282
8. Polymers
283 - 300
9. Chemistry in everyday life
301 - 313
(v)
Dedication
Dedicated to all those students who
are in fever of organic chemistry.
(vi)
Unit
Objective
This unit give you an understanding of Organic chemistry- Some basic principles and Techniques and covers following topics:
What is Organic chemistry, Representation of Organic compounds, Reason for the formation of large
number of organic compounds, Functional groups,
Homologue & Homologous series, Nature of C &
H, functional groups, Saturated & unsaturated molecules, Hybridiza tion, Classification of organic
compounds, Alkyl groups, IUPAC nomenclature
& Common name of Organic molecules.
Basic understanding of isomerism in organic chemistry.
Structural isomerism Chain, Position,
Function, Metamer, Tautomer. Stereoisomerism
Configurationa l & Conforma tional. Configurational Geometrical & Optical isomerism.
Electronic effects- Inductive effect, Basic concept
of resonance, General cases of resonance, Electron
flows in bond, How to draw resonating structures,
Stabiity of resonating structrue, Mesomeric effect, Hyperconjugation, Electromeric effect;
Reaction intermediate-Carbocation, Carbanion,
Free radicals, Carbene, Nitrene, Benzyne;
Concept of Acid and Base- How to find out relative Acidic & Ba sic strength, Sca le to measure
Acidic & Basic strength
Practical organic chemistry- Methods of purification of organic compounds, qualitative & quantitative analysis of organic compounds.
Solved Example:
Example 1.
How many and bonds are present in each of the following
molecules?
(A) HC CCH = CHCH3
Strategy.
To solve such questions, always expand the structure and count
the number of & bond keeping given basic in mind.
(A)
= 10
=3
(B)
H
=9
=2
Example 2.
What is the type of hybridisation of each carbon in the following
compounds?
(A) CH3 Cl
(B) (CH 3 )2 CO
(C) CH3 CN
(D) HCONH 2
(A) H C Cl 4 sp
(B)
O
CH 3 CCH3
sp3 sp2 sp3
(C) CH 3 C
sp
(E)
(D) HCNH 2
sp 2
CH 3 CH=CHC
sp
sp
sp
Example 3.
Write the state of hybridisation of carbon in the following
compounds and shapes of each of the molecules.
(A) H 2 C = O
(B) CH 3 F
(C) HC N
Strategy.
Similar to above question, first expand the molecule & then
count the number of bond for deciding the hybridization of
carbon.
H
(A) H
C =O
sp2
(B) H C F
3
H sp
HC
(C)
Strategy.
To expand the molecule in correct form, always keep in mind
the valencies of some common atoms such as i.e. carbon always
form 4 bonds in neutral case.
H H
H H
H,
F,
H HO H H
(A) HCCCCCH
(B)
Cl ,
Br ,
H H HH
HCC=CCCCCH
HH HH H HH
Example 5.
For ea ch of the following compounds, write a condensed
formula and also their bond-line formula.
(A) HOCH 2 CH 2 CH 2 CH(CH 3 )CH(CH3 )CH3
OH
(B)
N C CH C N
HO
NC
CN
Example 6.
Expand each of the following bond-line formulas to show all
the atoms including carbon and hydrogen.
(A)
(B)
(C)
OH
(D)
Strategy.
In bond line formula, the number of H at each carbon = 4 no.
of visible bond.
H
H
H
C
C H
C
H
H
C
C C
H
(A) H
C
C
H C
H
H H H H
H
H
H H
H H HH HHH H
(B)
HCCCCCCCCH
H H HH HH HH
(C) HC CCC
H
CH
H OH H
H HCH HCH H
(D) HC
CH
Example 7.
Structures and IUPAC names of some hydrocarbons are given
below. Explain why the names given in the parentheses are
incorrect.
(A) CH 3 CH CH 2 CH2 CH CH CH2 CH3
CH3
CH 3 CH 3
2,5,6-Trimethyloctane
[and not 3,4,7-Trimethyloctane]
(B)
CH 3 CH 2 CH CH 2 CH CH2 CH 3
CH 2 CH3
CH3
3-Ethyl-5-methylheptane
[and not 5-Ethyl-3-methylheptane]
Strategy.
(A) In writing the IUPAC name of organic compound, always
give minimum positions to substituents i.e. use lowest
locant for substituent.
(B) In writing the IUPAC name of orga nic compound on
identical position, numbering in chain starts according to
alphabets of substituent. The alphabet which comes first
are given lower position.
1
2
3
4
5
6
7
8
CH 3 CH 2 CH CH2 CH2 CH CH2 CH3
OH
CH 3
Strategy.
To write IUPAC name of any compound always use following
keys
(A) Use the concept of 2 prefix + 1prefix + Word root
+ 1suffix + 2suffix in sequence.
(B) Use the concept of position then alphabet then position if
functiona l group, multiple bond or substituents are
present.
(C) For giving minimum position functional group then
multiple bond then substituent.
(D) If more than one functional groups are present, then use
the concept of priority order.
(i)
1
2
3
4
5
6 7
8
CH 3 CH 2 CHCH 2 CH2 CHCH 2 CH 3
CH3
OH
6-Methyloctan-3-ol
O
(ii)
CH 3 CH 2 CCH 2 CCH 3
6
5
4 3
2 1
Hexane-2,4- dione
(iv) HC CCH=CHCH=CH 2
6 5 4
3
2
1
Hexa-1,3-dien-5-yne
Cl
(i)
(ii)
6
1 2 3 4 5
1 2 3 4 5
OH
(iii)
2
3
NO 2
(iv)
3
OH
4
(v) 7 6
3
5
2 1 H
O
Example 10.
Write the structural formula of :
(A) o-Ethylanisole
(B) p-Nitroaniline
(A)
(B)
NO 2
(C)
F
1 2 NO
6
2
(D) 5
3
4
Br
Ph
1 2
3
Br
4 5
Example 11.
Using curved-arrow notation, show the formation of reactive
intermediates when the following covalent bonds undergo
heterolytic cleavage.
(A) CH3 - SCH3
(B) CH3 - CN
(C) CH3 - Cu
Strategy.
In heterolytic bond cleavage, bond breaks to acquire negative
charge over more electronegative atom & positive charge over
less electronegative atom.
(A) CH 3 S CH 3
(B)
CH 3 CN
(C) CH 3 Cu
CH3 + S CH 3
CH 3 + CN
CH 3 + Cu
Example 12.
Giving justification, categorise the following molecules/ions as
nucleophile or electrophile:
+
Strategy.
To solve this question, remember the basic definition of nucleophile &
electrophile.
Nucleophiles- They are e rich species with complete octet with either
negative charge or with lone pair of electrons.
10
So nucleophiles are
while
Strategy.
Electrophilic centre is the electron deficient centre in the
molecule. They arises due to difference in electronegativity
between two atoms so electrophilic centre in above molecules
are
CH 3HC = O
H 3C C
H 3C I
Example 14.
Which bond is more polar in the following pairs of molecules:
(A) H 3 C - H, H 3 C - Br
(B) H 3 C - NH2 , H 3 C - OH
(C) H 3 C - OH, H 3 C - SH
Strategy.
Polarity of bond is judged on the basis of electronegativity
difference. Greater is the electronegativity difference, greater
is the polarity. So
(A) CBr bond is more polar than CH
(B) CO bond is more polar than CN
(C) CO bond is more polar than CS
Example 15.
In which CC bond of CH3 CH 2 CH 2 Br, the inductive effect is
expected to be the least?
11
CH2 CH 2 CH 2 Br
H
Example 16.
Write resonance structures of CH 3 COO - a nd show the
movement of electrons by curved arrows.
Strategy.
To write resonating structure of any molecule, first write the
structure of it and then put unshared electron or ve charge on
appropriate atoms, then draw arrow one at a time moving the
electron to get the other structure.
O
CH 3 CO
O
CH 3 C=O
Example 17.
Write resonance structures of CH 2 = CH - CHO. Indicate
relative stability of the contributing structures.
Strategy.
Resonating structure of CH2 =CHCHO will be
O
CH 2 =CHCH
I
O
CH 2 CH=CHCH
II
O+
CH 2 CH=CHCH
III
12
CH 3 COCH 3
I
CH 3 C=OCH 3
II
Strategy.
Ist structure is less contributor as it has atom with incomplete
octet while IInd structure is less contributor because of charge separation
of positive & negative charge.
Example 19.
+
13
(CH 3 )3 C CH 3 C H 2 CH 3
9 HC
3 HC
0 HC
Example 20.
On complete combustion, 0.246g of an organic compound gave
0.198g of carbon dioxide and 0.1014g of water. Determine the
percenta ge composition of ca rbon and hydrogen in the
compound.
Strategy.
% composition of C & H in compound will be
% of C =
% of H =
% of C =
12 0.198 100
21.95%
44 0.246
% of H =
2 0.1014 100
= 4.58%
18 0.246
Example 21.
In Dumas method for estimation of nitrogen, 0.3g of an organic
compound gave 50mL of nitrogen collected at 300K temperature
and 715mm pressure.
Strategy.
Volume of nitrogen collected at 300K and 715 mm pressure is
50 ml.
Actual pressure = 715 15 = 700 mm
14
273 700 50
= 41.9 mL
300 760
14 20
gN
1000
14 20 100
56.0%
1000 0.5
Example 23.
In Carius method of estimation of halogen, 0.15g of an organic
compound gave 0.12 g of AgBr. Find out the percentage of
bromine in the compound.
Strategy.
Molar mass of AgBr = 108 + 80 = 188 g/mol
188 g AgBr contains 80 g Br
15
Hence, % of Br
80 0.12
g Br
188
80 0.12 100
= 34.04%
188 0.15
Example 24.
In sulphur estimation, 0.157 g of an organic compound gave
0.4813 g of barium sulphate. What is the percentage of sulphur
in the compound?
Strategy.
Molecular mass of BaSO4 = 137 + 32 + 64 = 233 g
233 g BaSO4 contains 32 g S
So, 0.4813 g BaSO4 contains
% of S
32 0.4813
gS
233
32 0.4813 100
= 42.10%
233 0.157
16
Exercise Problems:
Exercise Problem 1.
Wha t are hybridisation states of each carbon atom in the
following compounds?
CH2 = C = O, CH 3 CH = CH 2 , (CH 3 )2 CO, CH2 = CHCN, C 6 H 6
Strategy.
To write the hybridiza tion of any atom, always count the
number of bond & lp of e. If
Sum of bond + lp = 2 sp hybridization
Sum of bond + lp = 3 sp2 hybridization
Sum of bond + lp = 4 sp3 hybridization
So hybridization state of each carbon atom will be
O
CH 2 =C=O
sp
CH 3 CH=CH2
sp 3
sp2
sp 2 sp2
sp2
CH 3 CCH 3
sp 3 sp2 sp3
sp2
CH 2 =CHCN
sp2
sp2
sp 2
sp
sp2
Exercise Problem 2.
Indicate the and bonds in the following molecules :
C 6 H 6 , C 6H 12 , CH2 Cl 2 , CH 2 = C = CH 2 , CH 3NO 2 , HCONHCH 3
Strategy.
To find total number of & bonds present in any molecule,
first expand the molecule and then look for single, double &
triple bond. Single bond are only bond, double bond have
17
H
H
H H HH
H
H
HH HH
H
H
Cl
Cl
H
H
H
H
O
O
N
Exercise Problem 3.
Write bond line formulas for : Isopropyl alcohol, 2,3-Dimethyl
butanal, Heptan-4-one.
Strategy.
To draw bond line formulas of any compound, first draw the
skelelon of ca rbon taking the help of word root of IUPAC
nomenclature & then add substituent or functional group on
appropriate position in it.
OH
O
3
7 6 5 4 32 1
Iso-propyl alcohol 2,3-Dimethylbutanal Heptan-4-one
1 H
Exercise Problem 4.
Give the IUPAC names of the following compounds :
(A)
18
(B)
CN
(D)
O
Cl
Br
Cl
(F) Cl 2 CHCH 2 OH
Strategy.
To write the IUPAC name of any compound, always use
(A) 2prefix + 1prefix + word root + 1suffix + 2suffix in
sequence.
(B) Use the concept of position then alphabet then position if
functiona l group, multiple bond or substituents are
present.
(C) For giving minimum position- Functional group- multiple
bond- Substituent.
(D) If more than one functional groups are present, then use
the concept of priority order.
(A)
(C)
CN
1
3
4
2
(B)
3-Methylpentane nitrile
5
Propylbenzene
4 5 6
7
1
3
2,5-Dimethylheptane
2 3 4
6
5
7
Cl Br
(D)
3-Bromo-3-chloroheptane
1
(E)
Cl 3 2 1 H
3-Chloropropanal
2
1
ClCHCH 2 OH
(F)
Cl
2,2-Dichloroethanol
Exercise Problem 5.
Which of the following represents the correct IUPAC name of
the compounds concerned ?
(A) 2,2-Dimethylpentane or 2-Dimethylpentane
(B) 2,4,7-Trimethyloctane or 2,5,7-Trimethyloctane
19
4
1 2 3
(D) But-3-yn-1-ol (correct)
But-4-ol-1-yne (incorrect)
20
HCOH
I
CH 3 COH
II
CH 3 CH 2 COH
III
O
CH 3 CH 2 CH2 COH
IV
O
CH 3 CH 2 CH2 CH 2 COH
V
CH 3 CCH2 CH 3
II
CH 3 CCH 2 CH2 CH 3
III
O
CH 3 CCH2 CH 2 CH 2 CH 3
IV
CH 3 CCH 2 CH 2 CH 2 CH 2 CH 3
V
CH 2 =CH2
I
CH 3 CH=CH 2
II
CH 3 CH 2 CH2 CH=CH 2
IV
CH 3 CH 2 CH=CH 2
III
CH 3 CH 2 CH 2 CH 2 CH=CH2
V
21
CH 3
CH 3 CCH 2 CHCH 3
(A)
CH 3
condensed form
&
bond line formula
2,2,4-Trimethylpentane
OH
(B)
OH O
HO
OH
OH
O
bond line formula
2-Hydroxy-1,2,3-propanetricarboxylic acid
HCCH 2 CH 2 CH 2 CH2 CH H
(C)
H
O
bond line formula
condensed form
Hexanedial
22
CHO
(A)
(B)
OMe
OH
OCH 2 CH 2 N(C 2 H 5 )2
(C)
Strategy.
CH=CH NO 2
CHO
Ether
(A)
OMe
OH
Phenol
NH 2
(B)
Aromatic 1amine
Ether
3amine
OCH 2 CH 2 N(C 2H 5 )2
(C)
CH=CH NO 2
Nitro
23
O2N
CH2
CH2
CH3
(more stable)
CH2
(less stable)
H
H C = CH CH 2
H+
24
(B) C 6 H 5 NO 2
(D) C 6 H 5 - CHO
(E) C 6 H 5 - CH2
(F) CH3 CH = CH C H 2
Strategy.
To write resonating structure of any molecule, first write the
structure of it and then put unshared electron or charge if
present on appropriate atom & then draw arrow one at a time
by moving the electrons to get other structures.
.OH
OH
OH
OH
OH
(A)
O O
O O
O O
N
O O
N
O
N
(B)
O
(C) CH CH = CH C H
3
CH 3 CH CH = C H
CH
CH
CH
CH
CH
CH2
CH 2
CH 2
CH 2
CH 2
(D)
(E)
(F)
CH 3 CH = CH CH 2
CH 3 CH CH = CH 2
25
(C) C 6 H 5 + CH 3 CO C 6 H 5 COCH 3
Strategy.
As stated above nucleophiles a re electron rich species with
either ve charge or with lone pair of electrons with complete
octct, while electrophiles are electron deficient species with
either positive charge, vacant orbital or incomplete octct. So,
26
CH 3 COO + H 2O
(A) CH 3COOH + OH
(Nucleophile but acts as a base)
(B)
CH 3 CCH 3 + CN
CH3 CCH 3
(C)
CH3 CCH 3
CN
(Nucleophile)
OH
H+
H CCH3
CN
O
CCH 3
+ CH 3 C
(Electrophile)
27
ACB
Cl H
|
CH3
28
(C) CH3 CH 2 Br O H
CH 2 CH 2 H 2 O Br
In this reaction 2 sigma bonds are broken & corresponding a pi
bond is formed, so reaction is elimination reaction.
CH 3
CH3
CH 3
Br
(B)
C =C
H
D
C= C
H
OH
(C) HCOH
HCOH
Strategy.
To find out structural & stereo isomers, always think for the
IUPAC name. If IUPAC of isomers a re different they a re
streuctural isomers but if they have same IUPAC name, then
they are stereoisomers.
To find out resonating structure, always look for the position
of bonding electron & non-bonding electron as position of
atoms remains same in all resonating structures.
29
(A)
Pentan-3-one
Pentan-2-one
H
C= C
(B)
D
C =C
H
D
H
Trans-1,2-Deuteroethene Cis-1,2-Deuteroethene
OH
HCOH
HCOH
(C)
(D)
30
O + OH
Br
+ E+
CH 3 O + OCH 3
O + H 2O
+ Br
E
+
. .
(A) CH 3 O
O CH 3
..
CH 3 O + O CH3
O
+ OH
(B)
+ H 2O
Br
+ Br
(D)
+ E+
31
C
C
C
CH 2 =CH2 + Br
Br
Cl
O > Cl
Cl
(3-I of Cl)
CH
O
C
O > Cl
(2-I of Cl)
CH 2
(1-I of Cl)
CH2
O
O > CH 3
(Repulsion with
1 CH3 group)
32
CH
CH 3 O
O > CH 3
CH3
(Repulsion with
2 CH3 group)
CH 3
(Repulsion with
3 CH3 group)
(B) Distillation
(C) Chromatography
Strategy.
(A) Crystallisation- In this process we convert an impure
compound into a pure crystals. This process is based on
the difference in the solubility of the compound and the
impurities in a suitable solvent. Here the impure compound
is dissolved in a solvent in which it is sparingly soluble at
room tempera ture but apprecia bly soluble a t higher
temperature.
Now solution is concentrated to get a nearly saturated
solution at higher temperature. On cooling the solution,
pure compound in the form of crystals separates.
The best exa mple of crysta llisa tion is iodoform
crystallisation with alcohol & benzoic a cid mixed with
naphthalene be purified by not water.
(B) Distillation- Distillation involves the process of heating a
liquid to convert it into the vapour and then condensing
the vapour to get back to the liquid.
This process of sepa ration is a pplied only for the
purification of liquid which boil without decomposition
a t a tmospheric pressure a nd contain non-vola tile
impurities. So mixture of two liquids having sufficient
difference in their boiling points can be separa ted and
purified by this process.
The best example are the separation of chloroform (bp
334K) & aniline (bp 457K) can be done by it.
(C) Chromatography- It is a technique for the separation,
purification & identification of constituents of mixtures.
Chromatography is based on the principle of selective
adsorption of components of a mixture between two phase
i.e. a stationary pha se and a moving pha se. Here the
33
34
Fe(OH)2 6 NaCN
Na 4 [Fe(CN)6 ] 2 NaOH
Sodium ferrocyanide
NaSCN
Sodium thiocyanate
Fe 3 NaSCN
Fe(SCN)3 3Na
Blook red colour
35
PbS
(Black ppt)
2 CH 3COONa
Na 4 [Fe(CN)5 NOS]
Sodium thionitroprusside
(violet ppt)
AgBr
NaNO 3
36
AgI
yellow ppt
NaNO 3
28
Volume of N 2 at STP
100
22400 Mass of the substance taken
37
38
.
.
solvent front
spot
X
base line
Observation on paper chromatograph
R f value =
39
Ag 2 S NaNO 3
(Black ppt)
Na S
Na 2 S
Na X
NaX
Exercise Problem 27.
40
41
Hence, this white ppt of PbSO4 will interfere with the following
test of sulphur.
(CH 3 COO)2 Pb NaS
PbS CH 3 COONa
Black ppt
However, if acetic acid is used, it does not react with lead acetate, so it
will not interfere in the test.
Exercise Problem 32.
An orga nic compound conta ins 6 9 % ca rbon a nd 4 .8 %
hydrogen, the remainder being oxygen. Calculate the masses
of carbon dioxide and water produced when 0.20 g of this
substance is subjected to complete combustion.
Strategy.
Calculation of mass can be done by following formula.
% of C =
69 =
2 Mass of H2 O formed
100
Mass of substance taken
2 Mass of H 2 O formed
100
18 0.2
So, mass of H2O formed = 0.0864 g.
4.8 =
42
% of Nitrogen =
% of Nitrogen =
1.4 2 10
56.0
0.5
43
100
143.5
Mass of substance taken
35.5
0.5740
100 = 37.566%
143.5
0.3780
32
Mass of BaSO 4 formed
100
233
Mass of substance taken
=
32
0.668
100 = 19.60%
233
0.468
(B) sp - sp3
(C) sp 2 - sp3
(D) sp 3 - sp3
Strategy.
To find out hybridised orbital first write hybridization of each
carbon & then report your answer.
So, hybridised orbitals involved in the formation of C2C3 bond
is sp2sp3.
44
(B) Fe 4 [Fe(CN)6 ]3
(C) Fe 2 [Fe(CN)6 ]
(D) Fe 3 [Fe(CN)6 ]4
Strategy.
In the Lassaignes test for nitrogen in an organic compound,
the Prussian blue colour is obtained due to forma tion of
Fe 4 [Fe(CN)6 ]3 .
FeSO 4 2 NaOH
Fe(OH)2 Na 2 SO 4
Fe(OH)2 6 NaCN
Na 4 [Fe(CN)6 ] 2 NaOH
4 Fe 3 3 Na 4 [Fe(CN)6 ]
Fe 4 [Fe(CN)6 ]3 12 Na
(C) CH3 CH 2 CH 2
(B) (CH3 )3 C
+
(D) CH3 CH CH 2 CH 3
Strategy.
Greater is the number of hyperconjugating structure, greater
is the sta bility of carbocation. So (CH 3 )3 C is most stable
carbocation.
CH 3
CH 3 CCH 2
CH 3
(0 HC)
CH 3
CH 3 C
CH 3
(9 HC)
45
CH 3 CHCH 2 CH3
(5 HC)
(B) Distillation
(C) Sublimation
(D) Chromatography
Strategy.
The best & latest technique for isolation, purification &
separation of organic compound is chromatography.
Exercise Problem 40.
The reaction :
CH 3 CH2 I +KOH(aq) CH 3CH2 OH +KI
is classified as :
(A) electrophilic substitution (B) nucleophilic substitution
(C) elimination
(D) addition
Strategy.
The reaction is classified as nucleophilic substitution reaction
as nucleophile (OH) attacks over carbon directly attached to I
to replace it with itself.
CH 3 CH2 I
CH 3 CH 2 OH + KI
HO
46
Hydrocarbon
Unit
Hydrocarbon
47
Hydrocarbon
Objective
This unit give you an understanding of Hydrocarbons
and covers following topics:
48
Hydrocarbon
Solved Example:
Example 1.
Write structures of different cha in isomers of a lkanes
corresponding to the molecular formula C 6 H 14 . Also write their
IUPAC names.
Stategy.
Whenever you have to draw the structures from a known
molecular formula, always follow these steps.
(A) Calculate DU
(B) Make the skeleton of carbon in decreasing order
(C) Take the help of chemically different H or position
So, structure possible for C 6 H 14 will be
Hexane
2-Methylpentane
2,2-Dimethylbutane
3-Methylpentane
2,3-Dimethylbutane
Example 2.
Write structures of different isomeric a lkyl groups
corresponding to the molecular formula C 5 H11 . Write IUPAC
names of alcohols obtained by attachment of OH groups at
different carbons of the chain.
Stategy.
To write the structures of different alkyl groups from a known
molecular formula, add a hydrogen & find DU first. DU will
give a clear cut picture, whether we have to think double bond,
ring or not.
49
Hydrocarbon
So, alkyl group possible for the molecular formula C 5 H11 are
OH
Pentan-3-ol
OH
Pentan-2-ol
OH
3-Methylbutan-1-ol
OH
OH
3-Methylbutan-2-ol
2-Methylbutan-2-ol
OH
HO
2-Methylbutan-1-ol
2,2-Dimethylpropan-1-ol
Example 3.
Write IUPAC names of the following compounds:
(i)
(iii) tetra-tert-butylmethane
50
Hydrocarbon
Stategy.
Whenever you have to write the IUPAC name of compound
written in condensed form, first write in bond line
representation & then use the general concept of IUPAC
nomenclature i.e. use the concept of 2prefix + 1prefix + word
root + 1suffix + 2suffix is sequence.
(CH 3 )3 C CH 2 C(CH3 )3
(i)
(Condensed form)
1 2 3 4 5
2,2,4,4-Tetramethylpentane
(CH3 ) 2 C(C 2 H5 )2
(ii)
(Condensed form)
34 5
1
3,3-Dimethylpentane
1 2 3 4
3,3-Bis-(dimethylethyl)-2,2,4,4-tetramethylpentane
Example 4.
Stategy.
Whenever you have to draw structures from given compound,
always take the help of word root. With the help of it, first
51
Hydrocarbon
draw the skeleton & then on it, attach the substituent, multiple
bond or functional group, whatever it is mensioned.
(i)
23 45 6
7
(ii)
3 45 6
Example 5.
Write structures for each of the following compounds. Why
are the given names incorrect? Write correct IUPAC names.
(i)
2-Ethylpentane
(ii) 5-Ethyl-3-methylheptane
Stategy.
As told earlier, first draw the structure & then think for correct
& incorrect name.
1
2
5
6
23 4
3
1
5
4
(i)
2-Ethylpentane
3-Methyl hexane
(Incorrect)
(correct)
In this case longest chain is of 6 carbon atom & not of 5 carbon
atom.
1
23 4 5 6
7
65 4 3 2
1
52
Hydrocarbon
(i)
Butanoic acid
COOH
CO
2
COOH
NaOH/CaO
CO
2
Example 7.
Write IUPAC names of the following compounds:
(i)
(CH 3 )2 CH CH = CH CH 2 CH
CH3 CH CH
C2H 5
(ii)
(iii) CH2 = C(CH 2 CH 2 CH 3 )2
(iv) CH 3CH2 CH2 CH2
CH 2 CH 3
Stategy.
To write IUPAC name of compound from structure, always
follows following concept.
(A) Use the concept of 2prefix + 1 prefix + word root +
1suffix + 2suffix.
(B) Use the concept of position then alphabet & then position
if functiona l group, multiple bond or substituents are
present.
(C) For giving minimum position functional group -multiple
bond - substituent.
(D) If more than one functional groups are present, then use
the concept of priority order.
53
Hydrocarbon
CH 3
(i)
(ii)
CH 3 CHCH=CHCH 2 CH
1
2
3
4
5 6
H 3CCHCH
8
7
CH 2 CH 3
9
10
2,8-Dimethyldeca-3,6-diene
2 3 4
8
5 6 7
1
Octa-1,3,5,7-tetraene
1
2 3
4
5
(iii) CH 2 =CCH 2 CH2 CH 3
CH 2 CH 2 CH3
2-Propylpent-1-ene
10 9 8 7
(iv) CH 3CH2 CH2 CH2
CH 2 CH 3
6 5
43
2
1
H3 CCHCH=CCH2 CHCH 3
CH 3
4-Ethyl-2,6-dimethyldec-4-ene
Example 8.
Calculate number of sigma () and pi ( ) bonds in the above
structures (i-iv).
Stategy.
To calculate the number of sigma & pi bond in any molecule,
first write the molecule in expanded form & then look for single,
double & triple bond. Single bond is only of bond. Double
bond contains 1 & 1. Triple bond have 1 & 2 bonds.
54
Hydrocarbon
H
HCH
H
(i)
H C C C = C C C H
bond = 33
bond = 2
H H H H H
H H
HCCCH
H
H
(Expanded form)
H C C H
H H
(ii)
H
C = C C = C C = C C = C
H H H H H H
bond 17
bond 4
H H H
CCCH
(iii)
C =C
H
bond 23
bond 1
H HH
H H
HCCCH
H H H
H H H H
H H
HCCCCH HCCH
(iv)
H H H
H
H C C C
H H H
H
H H H
bond 41
bond 1
C C C C H
H H
H
HCH
H
55
Hydrocarbon
Example 9.
Write structures and IUPAC names of different structural
isomers of alkenes corresponding to C 5 H 10 .
Stategy.
To draw the structure from molecular formula, as we have
discussed earlier, first calculate DU, then make the skeleton of
carbon in decreasing order & finally take the help of chemically
different position on that skeleton to make double bond over it.
So alkene with molecular formula C 5 H 10 will be
Pent-1-ene
Pent-2-ene
2-Methylbut-2-ene
2-Methylbut-1-ene
3-Methylbut-1-ene
Example 10.
Draw cis and trans isomers of the following compounds. Also
write their IUPAC names :
Stategy.
When two same atom or groups are present in the same side of
double bond, then we asign the configuration cis, and if
opposite, then we called as trans.
H
(i)
Cl
C =C
C =C
Cl
Cl
cis-1,2-Dichloroethene
H
Cl
trans-1,2-Dichloroethene
H 3C
CH 3
H 3C
C 2 H5
H 5C 2
C= C
(ii)
H 5C2
cis-3,4-Dimethylhex-3-ene
56
C2H 5
C =C
CH 3
trans-3,4-Dimethylhex-3-ene
Hydrocarbon
Example 11.
Which of the following compounds will show cis-trans
isomerism?
(i)
(ii) CH 2 = CBr2
(CH 3 )2 C = CH - C 2 H5
(iii) C 6 H 5 CH = CH - CH3
Stategy.
Those compounds which have restriction in rota tion &
restricted atom have different substituent, shows geometrical
isomeris.
(i)
H3 C
C2H 5
C =C
H
H3 C
(ii)
Br
C=C
Br
(iii)
CH 3
C6H 5
C =C
H
cis
H
C =C
H
trans
CH 3
(iv)
CH3
C =C
H
cis
Cl
H3 C
Cl
C =C
H
trans
CH 3
57
Hydrocarbon
Example 12.
Write IUPAC names of the products obtained by addition
reactions of HBr to hex-1-ene
(i)
Hex-1-ene
2-Bromohexane
1-Bromohexane
58
Hydrocarbon
By doing so, we will get following alkynes of 5th member of
alkyne series.
Hex-1-ene
(I)
Hex-3-yne
(III)
4-Methylpent-2-yne
(V)
Hex-2-yne
(II)
4-Methylpent-1-yne
(IV)
3-Methylpent-1-yne
(VI)
3,3-Dimethylbut-1-yne
(VII)
59
Hydrocarbon
Example 14.
How will you convert ethanoic acid into benzene?
Stategy.
To solve this question, first think for the conversion of ethanoic
acid to ethyne, as ethyne on high temperature trimerize to give
benzene as the product. So, conversion followsO
Cl /h
NaOH/CaO
2
CH3 C OH
CH 4
CH 3 Cl
Decarboxylation
Monochlorination
Na/dry ether
Cl /h
reaction
chlorination
2
CH3 Cl
CH 3 CH3
CH3 CH2 Cl
Wurtz
Mono
Br
addition
reaction
alc KOH
2
CH3 CH 2 Cl
CH 2 =CH 2
CH 2 CH 2
Elimination
reaction
alc KOH
Elimination
reaction
Br
Br
NaNH
2
C H2 CH 2 CH 2 =CHBr
HC CH
Br
Br
Elimination
reaction
873 K
60
Hydrocarbon
Exercise Problems:
Exercise Problem 1.
How do you account for the formation of ethane during
chlorination of methane ?
Stategy.
Halogenation of alkane is a free radical substitution reaction.
Cl /h
2
CH4
CH3 Cl HCl
. .
Cl
2 Cl
. . .
H C
H + Cl
HC
+ HCl
. . .
CH 3 + Cl
Cl
CH 3 Cl + Cl
..
..
..
Cl + Cl
CH 3 + CH 3
CH 3 + Cl
Cl 2
CH 3 CH 3
CH 3 Cl
61
Hydrocarbon
Exercise Problem 2.
Write IUPAC names of the following compounds :
(a) CH3 CH = C(CH 3 )2
(b) CH2 = CH - C C - CH3
(c)
(d)
CH 2 CH 2 CH = CH 2
CH3
(e)
(f)
OH
CH 3 (CH 2 ) 4 CH(CH2 )3 CH 3
CH 2 CH(CH 3 )2
(g)
CH 3 CH = CH CH2 CH = CH CH CH 2 CH = CH 2
C2H 5
Stategy.
To write IUPAC name of compound from structure, always
follows following concept.
(A) Use the concept of 2prefix + 1 prefix + word root +
1suffix + 2suffix.
(B) Use the concept of position then alphabet & then position
if functiona l group, multiple bond or substituents are
present.
(C) For giving minimum position functional group -multiple
bond -substituent.
(D) If more than one functional groups are present, then use
the concept of priority order.
62
Hydrocarbon
CH3
(A) CH 3 CH=CCH3
4
3
2 1
2-Methylbut-2-ene
1 2 3
4
(C)
Buta-1,3-diene
(B)
(D)
H2 C=CHC CCH 3
1 2
3 4 5
Pent-1-en-3-yne
4
3
2
1
CH 2 CH 2 CH=CH 2
4-Phenylbut-1-ene
4 3
5
2 CH 3
(E)
6 1 OH
2-Methylphenol
(F)
10
9
8
7
6
5
4
3
2
1
CH 3 CH 2 CH2 CH 2 CH 2 CHCH2 CH 2 CH 2 CH 3
CH2 CHCH 3
CH 3
5-(2-Methylpropyl)decane
10
9
8
7
6 5
4
3
2
1
(G) CH 3 CH=CHCH 2 CH=CHCHCH2 CH=CH 2
C 2 H5
4-Ethyldeca-1,5,8-triene
Exercise Problem 3.
For the following compounds, write structural formulas and
IUPAC names for all possible isomers having the number of
double or triple bond as indicated :
(a) C 4H 8 (one double bond)
(b) C 5 H 8 (one triple bond)
Stategy.
Whenever you have to draw the structures from a known
molecular formula, always follow these steps.
(A) Calculate DU
63
Hydrocarbon
(B) Make the skeleton of carbon in decreasing order
(C) Take the help of chemically different H or position. On the
basis of this a and b are
(a)
(b)
But-1-ene
But-2-ene
2-Methylpropene
Pent-1-yne
Pent-2-yne
3-Methylbut-1-yne
Exercise Problem 4.
Write IUPAC names of the products obtained by the ozonolysis
of the following compounds:
(i)
Pent-2-ene
(ii) 3,4-Dimethylhept-3-ene
(iii) 2-Ethylbut-1-ene
(iv) 1-Phenylbut-1-ene
Stategy.
Ozonolysis is a chemical method to find position of C=C or
C C bond in unknown compound. To find out the product
of ozonolysis, break the C=C bond & add two oxygen, one
at each double bonded carbon atom to get aldehyde or ketone
as general product.
C
O+O
Alkene
(Aldehyde or Ketone)
(i)
Pent-2-ene
2 1 H
Ethanal
3
+ H 1
2
Propanal
4 32
(ii)
3,4-Dimethylhept-3-ene
64
1
Butanone
+ O
Pentan-2-one
Hydrocarbon
O
(iii)
(iv)
Exercise Problem 5.
An alkene A on ozonolysis gives a mixture of ethanal and
pentan-3-one. Write structure and IUPAC name of A.
Stategy.
To get back from aldehyde, ketone to alkene in ozonolysis
reaction, write the structure of aldehyde or ketones in such a
way that their oxygen atoms pointing toward each other. Then
join the two ends of these through a double bond by removing
oxygen atom to get alkene.
2
1 O+ O
H
Ethanal
Pentan-3-one
4 5
1
2 3
3-Ethylpent-2-ene
(A)
Exercise Problem 6.
An alkene A contains three C C, eight C H bonds and
one C C bond. A on ozonolysis gives two moles of an
aldehyde of molar mass 44 u. Write IUPAC name of A.
Stategy.
Alkenes that contains 3 CC, 8 CH bonds & 1 CC bond
will be.
But-1-ene
But-2-ene
2-Methylpropene
65
Hydrocarbon
But from the question, it is indicated that A on ozonolysis
gives 2 moles of aldehyde of molar mass 44u i.e. CH 3 CHO.
So alkene must be symmetrical & hence
CH 3 CH
Ethanal
O+O
CHCH3
CH3 CH=CHCH 3
But-2-ene
Exercise Problem 7.
Propanal and pentan-3-one are the ozonolysis products of an
alkene? What is the structural formula of the alkene?
Stategy.
To get back from aldehyde, ketone to alkene in ozonolysis
reaction, write the structure of aldehyde or ketones in such a
way that their oxygen atoms pointing toward each other. Then
join the two ends of these through a double bond by removing
oxygen atom to get alkene.
3 2
2 1
3
4 5
1 O+O
H
Propanal
Pentan-3-one
6 5 2 1
43
3-Ethylhex-3-ene
Exercise Problem 8.
Write chemical equa tions for combustion rea ction of the
following hydrocarbons:
(i)
Butane
(ii) Pentene
(iii) Hexyne
(iv) Toluene
Stategy.
Chemical equations for combustion reaction of hydrocarbon
followsy
y
C x H y x O 2
xCO 2 H2 O
4
2
So,
66
10
10
C 4 H10 4 O 2
4 CO 2 H2 O
4
2
Butane
Hydrocarbon
C 4H 10 6.5 O 2
4 CO 2 5 H 2 O
10
10
C 5 H10 5 O2
5 CO 2 H2 O
4
2
pentane
C 5 H 10 7.5O 2
5 CO 2 5 H 2 O
10
10
C 6 H 10 6 O 2
6 CO 2 H2 O
4
2
Hexyne
C 6 H 10 8.5 O 2
6 CO 2 5H 2 O
CH3
Toluene
or C 7 H 8 7
8
8
O2
7 CO2 H 2 O
4
2
C 7 H 8 9 O 2
7 CO 2 4 H 2 O
Exercise Problem 9.
Draw the cis and trans structures of hex-2-ene. Which isomer
will have higher b.p. and why?
Stategy.
Cis & Trans structures of hex-2-ene are
cis-Hex-2-ene
trans-Hex-2-ene
Boiling point of any molecule depends on its intermolecular
forces i.e. hydrogen-bonding, dipole moment & vander waal
interaction.
67
Hydrocarbon
Exercise Problem 10.
Why is benzene extra ordinarily stable though it contains three
double bonds?
Stategy.
Benzene have extra ordinary stability inspite of 3 double bonds
due to its aromatic character. Due to aromaticity, there is cyclic
delocalization of electron density in the molecule and due to
this delocalization of electrons, molecule become stable.
Resonating structure
Resonance hybrid
Benzene
CH 2
(ii)
(iii)
Stategy.
As we have discussed in the above question, for a compound
to be aromatic, molecule must satisfy all the four conditions i.e.
68
Hydrocarbon
(i)
(iii)
p-nitrobromobenzene
(iii) p-nitrotoluene
(ii) m-nitrochlorobenzene
(iv) acetophenone?
Stategy.
Following conversion take place as below.
Br
?
(i)
NO 2
Br
Br
Br2 /AlCl 3
conc.H 2SO 4
Bromination
HNO 3
CH3
+
NO 2
NO 2 (minor)
(major)
69
Hydrocarbon
Cl
(ii)
NO 2
NO 2
conc.H 2 SO 4 /HNO 3
NO 2
Cl 2 /FeCl 3
Cl
In this reaction you have to first perform nitration followed by
chlorination as NO2 is meta directing group.
CH 3
(iii)
NO 2
CH 3
CH 3Cl
CH3
conc.H 2SO 4
AlCl 3
NO 2
HNO 3
CH 3
+
(minor)
NO 2
(major)
Now from fractional distillation, p-nitrotoluene should be
separated out.
Here again first alkylation has to perform as CH3 is orthopara directing in nature.
O
(iv)
CH 3
70
Hydrocarbon
Exercise Problem 14.
In the alkane H 3 C - CH2 - C(CH3 )2 - CH2 - CH(CH3 )2 , identify
1, 2, 3 carbon atoms and give the number of H atoms bonded
to each one of these.
Stategy.
On the basis of attachment of carbon with other carbon, carbon
is categorise into 4 types.
(A) Primary carbon (1C) It is the carbon attached with none
or 1 carbon.
(B) Secondary carbon (2C) It is the carbon attached with 2
carbon.
(C) Tertiary carbon (3C) It is the carbon attached with 3
carbon.
(D) Quaternary carbon (4C) It is the carbon attached with
4 carbon.
Hydrogens present on 1C, 2C & 3C are called as 1H, 2H &
3H respectively. So,
1
1
CH3
CH 3
1H = 15
1
2
2
1
CH 3 CH 2 CCH 2 CHCH3 2H = 4
4
3
3H = 1
CH3
1
Exercise Problem 15.
What effect does branching of an alkane chain has on its boiling
point?
Stategy.
Boiling point of any molecule depends on its intermolecular
force of attraction i.e. H-bonding, dipole moment, vander waal
force of attraction.
As in alkane, H-bonding & dipole moment is absent, so deciding
factor is vander waal force of attraction.
As va nde r wa al force of attraction surfa ce area and
71
Hydrocarbon
decrea ses with increase in bra nching. So boiling point also
decreases with increase in branching.
Exercise Problem 16.
Addition of HBr to propene yields 2-bromopropane, while in
the presence of benzoyl peroxide, the same reaction yields 1bromopropane. Explain and give mechanism.
Stategy.
Addition of HBr to propene yield 2-Bromopropane as a product
while in presence of benzoyl peroxide, 1-Bromo propane is
formed because nature & mechanism of chemical reaction in
both the cases are different.
Addition of HBr in absence of peroxide follow carbocationic
mechanism and follow Markownikoff rule while addition of
HBr in presence of peroxide follow free radical mechanism &
follow anti-Markownikoff rule.
Br
|
HBr CH CHCH
CH3 CH=CH 2
3
3
Mechanism:
HBr
+ Br
Br
CH 3 CH = CH2
CH 3 CH=CH2
CH3 CH CH 3
HBr/(PhCO)2O 2
Br
CH 3 CH CH 3
CH3 CH 2 CH 2 Br
Mechanism:
O
..
. ..
PhCO
OCPh
Ph + H
2 Ph
CO
2 Ph + 2 CO 2
Ph H + Br
CH 3 CH=CH2 + Br
CH 3 CHCH 2 Br
CH 3 CHCH 2 Br + H
Ph
72
Br
. . .
.
.
.
..
O
CH3 CH 2 CH 2 Br
Hydrocarbon
Exercise Problem 17.
Write down the products of ozonolysis of 1,2-dimethylbenzene
(o-xylene), How does the result support Kekule structure for
benzene?
Stategy.
To solve this question, first think for the both resonating
restructure of o-xylene. i.e.
Ozonolysis
O O
2 H3 C C C H + H C C H
O O
Ozonolysis
O O
H 3 C C C CH3 + 2 H C C H
O O
O O
CH3 C C H + H C C H + CH 3 C C CH 3
73
Hydrocarbon
Benzene
Conjugate base
(I)
Conjugate base
II
n-hexane
HC CH
Ethyne
HC C
Conjugate base
III
As conjugate base follows the order III > I > II as I of C C >
I of C=C while CC
follows the order
HC
Ethyne
>
Benzene
n-hexane
74
Hydrocarbon
Stategy.
(i)
?
HC CH
Red hot Fe tube
HC CH
873 K
Br
Br2
Br
alc KOH
CH2 =CH 2
CH2 CH 2 CH 2 =CHBr
CCl
4
Elimination
reaction
NaNH /liq NH
2
3
CH2 =CHBr
HC CH
873K
Cr2O 3 /V2 O 5
75
Hydrocarbon
It has 3 chemically different positions.
76
Hydrocarbon
CH3 (HC)
CH3 (HC)
>
NO 2 (M)
>
M
NO 2
(p-Nitrotoluene)
(B)
(Toluene)
(M)
NO 2
(p-nitrobenzene)
NO 2M
>
(Benzene)
M
NO 2
(m-Dinitrobenzene)
77
Hydrocarbon
CH 2 CH 3
CH 3CH 2 Cl/FeCl 3
RX
RR
Mechansim:
R X
R + R RR
RX + R' X
RR + R 'R' + RR'
+ CH 3CH2 CH3
78
Unit
79
Objective
This unit give you an understanding of Haloalkanes
and Haloarenes and covers following topics:
80
Solved Example:
Example 1.
Draw the structures of all the eight structural isomers that have
the molecular formula C 5 H 11Br. Name each isomer according
to IUPAC system and classify them as primary, secondary or
tertiary bromide.
Strategy.
This type of questions can be done by taking longest chain of
carbon containing substituent and then replacing methyl group
one by one at other carbons to obtain all isomers.
Br
2
I
1-Bromopentane
Br
II
1-Bromo-2-methylbutane
Br
Br
IV
III
1-Bromo-3-methylbutane 1-Bromo-2,2-dimethylpropane
Br
VI
3-Bromopentane
Br
VII
2-Bromo-3-methylbutane
81
H3 C
(i)
CH 3
H
Br
CH3
H
Br
H
H 3C
H3 C
(iv)
H
H
Br
H
CH 3
H
Br
H 3C
H3 C
(v)
(ii)
H 3C
H3 C
(iii)
(vi)
CH 3
H
Br
Strategy.
For writting IUPAC name of any organic compound, always
write 2 Prefix + 1 Prefix + Word root + 1 Suffix + 2 Suffix
in sequencial order.
82
H
4H
H
5
Br
(i)
H 3C
Trans-4-Bromopent-2-ene
H 3C
(iii)
23
1
2
CH 3
CH 3
3H
4
H
Br
(ii)
H 3C
3-Bromo-2-methylbut-1-ene
H 3C
3 H
H 5 4 Br
H 3C
Cis-4-Bromo-3-methyl
pent-2-ene
4
H3 C
H
2 H
(v)
H 3 1 Br
H
Trans-1-Bromobut-2-ene
12
4
3
CH 3
H
H 2 Br
H 1
(iv)
Cis-1-Bromo-2-methyl
but-2-ene
CH 3
12 H
H
Br
(vi)
H 3
3-Bromo-2-methylpropene
H
Example 3.
Identify all the possible monochloro structural isomers expected
to be formed on free ra dica l monochlorina tion of
(CH 3 )2 CHCH2 CH3 .
Strategy.
Monochlorination under the presence of light is used to identify
the type of H atom which are chemically different in alkanes.
As the given molecule contains 4 different H so it will give 4
monochloro product.
5
CH 3
4
CH 3 CHCH 2 CH 3
3
2
1
CH 3
CH 3 CHCH 2 CH 2 Cl
CH 3
CH 3 CH CH CH 3
Cl
1-Chloro-3methylbutane
2-Chloro-3-methylbutane
83
2-Chloro-2-methylbutane
CH3
Cl CH 2 CH CH2 CH3
1-Chloro-2-methylbutane
H
+ HBr
H H
(ii)
(iii)
Strategy.
This example tells about the reaction of C=C bond with HX
in absence or presence of peroxide.
Ph
(i)
Ph
+ HBr
H Br CH 3
Mechanism HBr H + Br
84
H
+H
(ii)
Ph +
CH 3 Br
nd
face
CH 3 CH2 CH = CH 2 + HCl
Br
Ph
H
Ph
CH 3
CH 3
H
(S)
Br
(R)
Racemic mixture
Cl
CH 3 CH 2 CH CH3
Mechanism HCl H + Cl
CH 3 CH 2 CH=CH2 + H
CH 3 CH 2 CHCH3
Cl
1 st face
+
CH 3 CH 2 CHCH3
2
nd
CH 3 CH 2
CH 3
H
(S)
Cl
+
H
face
CH 3 CH 2
CH3
Cl
(R)
Racemic mixture
Peroxide
(iii) PhCH 2 CH = CH 2 + HBr
PhCH 2 CH 2 CH 2 Br
Ph C O O C Ph
Ph + H
Br
O
2 Ph C O
2Ph + 2CO 2
Ph H + Br
85
.Ph
PhCH 2 CHCH2 Br
Ph
PhCH 2 CH 2 CH 2 Br
Example 5.
Haloalkanes react with KCN to form alkyl cyanides as main
product while AgCN forms isocyanides as the chief product.
Explain.
Strategy.
This question is based on ionic & covalent nature of cynide
and some short of knowledge of inorganic compound.
KCN is predominantly ionic and provides cyanide ion in
solution. Although both carbon & nitrogen atoms are in position
to donate electron pairs, the attack takes place mainly through
carbon atom and not through nitrogen atom since CC bond is
more stable than CN bond.
H
D
Cl KCN NC
T
(R)
H
D
T
(S)
Mechanism :
KCN K + CN
H
NC
D C
T
2
Cl SN NC
H
D
T
86
AgCN
CN
H
AgCN
D
T
D
T(S)
2
SN
Cl AgCl
CN
H
D
T
(S)
Example 6.
In the following pairs of halogen compounds, which would
undergo SN 2 reaction faster?
CH 2 Cl and
Cl;
I and
Cl
Strategy.
Always remember tha t SN 2 rea ction proceeds through
transition state.
Cl which in 2 in nature.
H
SN2
C H
Cl
Nu H
C H
Cl
TS
H
C H
Nu
87
In
2 nd case iodine
Example 7.
Predict the order of reactivity of the following compounds in
S N 1 and S N 2 reactions:
(i)
Strategy.
(i)
88
CH 3
CH 3
Ph CH 2 Br
CH3
Ph
Ph CH Br
Ph CH Br
(Less Hindered
More hindered)
Ph
Ph C Br
CH 3
Example 8.
Identify chiral and achiral molecules in each of the following
pair of compounds.
H
(i)
H3 C
Br
H
H 3C
Br
OH
(i)
HO H
(ii) H3 C
(i)
(ii)
H 3C
CH 3
Br
CH 3
OH
(ii)
89
(i)
HO H
(ii)
(iii)
H3 C
H3 C
CH 3
H OH
CH3 - CH 2 - CH 2 - CH 2 - Br
90
Cl
+ E+
H
E
But as chlorine have 3 lone pairs & due to one of the lone pair
it stabilizes the carbocation by resonance.
:Cl
+E
H
E
+Cl
H
E
Cl
+
H
E
Cl
H
E
91
Cl
+E+
Cl
Cl
H
H
E
+ E
(No extra stability)
:Cl
Cl
+E
Cl
Cl+
H
E
Cl
+
+
E H E H E H E H
(Extra stability due to more resonance structure)
92
Intext Problem:
Intext Question 1.
Write structures of the following compounds:
(i)
2-Chloro-3-methylpentane
(ii) 1-Chloro-4-ethylcyclohexane
(iii) 4-tert. Butyl-3-iodoheptane
(iv) 1,4-Dibromobut-2-ene
(v) 1-Bromo-4-sec. butyl-2-methylbenzene.
Strategy.
Structure of any organic compound follow the same basic
pattern of nomenclature i.e. 2 Prefix + 1 Prefix + Word root +
1 Suffix + 2 Suffix.
(i)
2-Chloro-3-methylpentane
2 Prefix
Cl
1 2
(ii)
3 4
1-Chloro-4-ethylcyclohexane
1Prefix Word root 1suffix
2 Prefix
Cl
1 2
6
5 4 3
2 Prefix
2
1
6
3 4 5
I
93
Br
1
4
3
Br
6
5
Br
1 2 CH
3
4
Intext Question 2.
Why is sulphuric acid not used during the reaction of alcohols
with KI?
Strategy.
Sulphuric acid is not used during the reaction of alcohol with
KI because sulphuric a cid is dehydra ting agent along with
oxidizing agent. It will produce alkene instead of alkyl halide
so 95% phosphoric acid is used to form alkyl iodide in reaction
with alcohol & KI.
HypotheticallyH 2 SO4 H + HSO4
CH 3 CH 2 OH +H
+ H HSO 4
CH 2 CH 2 O
H
CH2 = CH2
H H 2 O
H 2SO 4
94
H + H 2 PO 4
+ H
CH 3 CH 2 O
I
H 2O
CH3 CH 2 I
CH 3 CCl 2 CH 3
II
CH 3 CH CH2
CH 2 CH 2 CH 2
Cl
III
Cl
Cl
Cl
IV
Intext Question 4.
Among the isomeric alkanes of molecular formula C 5 H 12 ,
identify the one that on photochemical chlorination yields
(i)
A single monochloride.
II
III
95
Cl
Cl
Cl 2
h
Cl
Cl 2
h
Cl
+
+ Cl
Cl
Intext Question 5.
Draw the structures of major monohalo products in each of
the following reactions.
OH
+ SOCl 2
(i)
CH2 CH 3
(ii)
(iii)
(iv)
O2N
CH 2 OH
HO
Br2 , heat or
UV light
+ HCl heat
CH 3
+ HI
(vi)
96
heat
+ Br2 UV
light
(i)
Cl
Mechanismm:O
O
+ Cl S Cl HCl
O
O S SO
Cl
2
Cl (SN i )
(By nucleophilic
substitution internal)
Br
(ii)
Br2 , heat
or, light
O2N
O2N
Mechanism:Br
Br
2 Br
Br
Br
O2N
+ Br
HBr O N
2
O2N
(iii)
(Free radical)
(By Free radical formation)
OH HCl, Heat
HO
Cl
HO
Mechanism:-
HO
OH + H +
H H O
2
+ H
HO
O
HO
97
CH3
(iv)
Cl
HO
(By SN 1 reaction)
Cl
HO
CH 3
I
+ HI
Mechanism CH3 +
+H
+ CH 3
CH 3
I
CH 3 CH 2 Br
H3 C
I
H
Br
CH3 CH 2 I
H
(By SN 2 reaction)
+ Br2
(vi)
heat/UVlight
Mechanism:
Br
Br
2 Br
H
Br
HBr
Br
Br
98
Bromometha ne,
Dibromomethane.
Bromoform,
Chlorometha ne,
Cl
Cl
>
Intext Question 7.
Which alkyl halide from the following pairs would you expect
to react more rapidly by an SN 2 mechanism? Explain your
answer.
(i)
CH 3
(ii)
99
CH3 - CH 2 - CH 2 - CH 2 - Br
Br
CH 3 CH2 CH CH 3
1 alkyl halide
2 alkyl halide
(ii)
CH 3
CH 3 C Br
CH 3 CH2 CH CH 3
CH 3
2 alkyl halide
3 alkyl halide
(more favourable)
100
CH 3
CH 3CH2 CHCH 2Br
Intext Question 8.
In the following pairs of halogen compounds, which compound
undergoes faster S N 1 reaction?
Cl
(i)
Cl
and
Cl
(ii)
and
Cl
Strategy.
As earlia r sa id SN 1 rea ction proceed with formation of
carbocation as an intermediate. So more stable the carbocation,
more favourable the SN 1 reaction will be.
101
(i)
3 carbocation
(more stabilized by 3 +I effect & 9 HC)
Cl
2 carbocation
(Less stable)
Cl
Therefore
Cl
Cl
(ii)
2 carbocation
(more stable)
+
Cl
1 carbocation
(Less stable)
Cl
Therefore
Intext Question 9.
Identify A, B, C, D, E, R and R 1 in the following:
Br + Mg dry ether
R Br + Mg
dry ether
A
D2 O
H 2O
CH 3 CHCH3
D
CH 3 CH 3
H 2O
Mg
D
E
CH3 Na/ether R'X
CH 3
CH 3 CH 3
102
For SN1
dry ether
(Preparation
of GR)
Mg Br
A
H 2O
(R eaction of GR
by acidic H)
D O
CH 3 CH 3
CH 3 C C CH3
CH 3 CH3
Br
C
of G R)
Na /ether
(Wurtz
reaction)
CH 3
by acidic D)
Mg
CH3 C X
(G R)
CH 3
(R1X)
CH 3
H2 O
CH 3 C Mg
CH 3
(R eaction of GR
CH 3
by acidic H)
D
CH3
CH3 C Mg X
CH3
D
CH 3
C H
CH 3
E
103
Exercise Problems:
Exercise Problem 1.
Name the following halides according to IUPAC system and
classify them as alkyl, allyl, benzyl (prima ry, secondary,
tertiary), vinyl or aryl halides:
(i)
(CH 3 )2 CHCH(Cl)CH3
(ii)
(iii)
CH 3 CH 2 C(CH 3 )2 CH 2 I
(iv)
(v)
(vi)
CH3 C(C 2 H 5 )2 CH 2 Br
CH3 CH = CHC(Br)(CH 3 )2
(x)
p - ClC 6H 4 CH 2 CH(CH 3 )2
(xi)
m - ClCH 2 C 6 H 4 CH 2C(CH3 )3
104
CH3
CH3 CH2 C CH 2 I
2
(iii)
4
3
1
CH3
1-Iodo-2,2-dimethylbutane (1 alkyl halide)
Br
CH3
CH 3 C CH 2 CH C6 H 5
3
4
2
1
(iv)
CH3
1-Bromo-3,3-dimethyl-1-phenylbutane
(2 benzylic halide)
CH 3 Br
(v)
CH 3 CH CH CH 3
4
3
2
1
2-Bromo-3-methylbutane (2 alkyl halide)
C2H 5
(vi) CH 3 C CH2 Br
C2H 5
or
4
5
CH2 CH3
3
CH 3 C CH2 Br
CH2 CH3
1
2
3-Bromomethyl-3-methylpentane
(1 alkyl halide)
105
Cl CH 3
CH 3 CH = C CH 2 CH CH3
(viii)
1
2
3 4
5
6
3-chloro-5-methylhex-2-ene (2 vinyl halide)
Br
CH 3 CH = CH C CH 3
1
2
3 4
5
(ix)
CH 3
4-Bromo-4-methylpent-2-ene (3 Allyl halide)
1
CH 2 CH CH3
(x)
CH 3
Cl
1-Chloro-4-(2-methylpropyl)benzene
Aryl halide
(xi)
106
CH 3
1
2
CH 2 C CH 3
3
3
2 CH 3
1 CH 2 Cl
1-Chloromethyl-3-(2,2-dimethylpropyl)benzene
1 Benzyl Halide
Exercise Problem 2.
Give the IUPAC names of the following compounds:
(i)
CH 3 CH(Cl)CH(Br)CH 3
Br
(i)
CH 3 CH CH CH 3 2-Bromo-3-chlorobutane
4
3
2
1
(ii)
F Br
2 1
HC C Cl 1-Bromo-1-chloro-1,2,2-trifluoroethane
F F
4
3 2 1
(iii) Cl CH 2 C C CH 2 Br 1-Bromo-4-chlorobut-2-yne
Cl
Cl Cl C Cl
2
1,1,1,2,3,3,3-heptachloro-21
(iv) Cl C
C Cl
trichloromethylpropane
3
Cl Cl C Cl
Cl
107
(v)
Br
1
3 4
2
CH3 C CH CH 3
Cl
3-Bromo-2,2-bis-(4-chlorophenyl) butane
CH 3 CH 3 3 2
CH 3 C CH 4
I
1
(vi)
CH 3
1-Iodo-4-(1,2,2-trimethylpropyl)benzene
Exercise Problem 3.
Write the structures of the following orga nic ha logen
compounds.
(i)
2-Chloro-3-methylpentane
(ii) p-Bromochlorobenzene
(iii) 1-Chloro-4-ethylcyclohexane
(iv) 2-(2-Chlorophenyl)-1-iodooctane
(v) Perfluorobenzene
(vi) 4-tert-Butyl-3-iodoheptane
(vii) 1-Bromo-4-sec-butyl-2-methylbenzene
(viii) 1,4-Dibromobut-2-ene
Strategy.
Cl
Cl
4
3
5
2
(i)
1
(ii)
2-Chloro-3-methylpentane
108
Br
p-Bromochlorobenzene
(iii)
1-Chloro-4-ethylcyclohexane
(iv)
Cl
8
2 3 4
6
1
5 7
2-(2-chlorophenyl)-1-iodooctane
I
(v)
(vi)
F
F
Perfluorobenzene
1 2
4 6 7
5
I
4-tert-Butyl-3-iodoheptane
(vii)
Br
1 2
3
4
1-Bromo-4-sec-butyl
-2-methylbenzene
5
Br
(viii)
4 Br
1 2 3
1,4-Dibromobut-2-ene
Exercise Problem 4.
Which one of the following has the highest dipole moment?
(i)
CH 2 Cl 2
CCl 4
109
Exercise Problem 5.
A hydrocarbon C 5 H 10 does not react with chlorine in dark but
gives a single monochloro compound C 5 H9 Cl in bright sunlight.
Identify the hydrocarbon.
Strategy.
Cl 2 / Dark
No reaction
C 5 H10
Cl 2 /h
A
C5 H 9Cl (Single monochloro product)
only one type of H
CH3
CH3
Cl 2 / h
so, CH 3 C CH3
CH3 C CH2 Cl
CH3
CH3
Exercise Problem 6.
Write the isomers of the compound having formula C 4 H 9 Br .
Strategy.
Isomers of C 4 H 9 Br
Br
Br
Br
Br
II
III
IV
Exercise Problem 7.
Write the equations for the preparation of 1-iodobutane from
(i)
1-butanol
(ii) 1-chlorobutane
(iii) but-1-ene.
110
(i)
OH
(ii)
Cl
KI
B H /THF
H2O 2/OH
(iii)
HI
OH
2 6
Exercise Problem 8.
What are ambident nucleophiles? Explain with an example.
Strategy.
Ambident nucleophiles are those which can attack from two
or more than two place resulting in formation of two or more
products.
Ex
O
R C NH
O
R C = NH
CH3 Br or CH 3 I
Strategy.
(i) CH3 I > CH3 Br
Here I is better leaving group than Br
(ii)
CH3
CH 3 Cl > CH3 C Cl
CH3
111
1-Bromo-1-methylcyclohexane
(ii) 2-Chloro-2-methylbutane
(iii) 2,2,3-Trimethyl-3-bromopentane.
Strategy.
Br
HBr
EtONa/EtOH
(i)
+
(minor) (major)
Cl
EtONa/EtOH
(ii)
(iii)
HCl
Br
+
(minor) (major)
EtONa/EtOH
HBr
+
(E)
(major)
(Z)
Ethanol to but-1-yne
1-Chlorobutane to n-octane
(x)
Benzene to biphenyl
112
OH
OH
(ii)
HI
HC CH/NaNH 2
(1 eq)
Br
HI
Br
Br2 /h
Br
Br2 / h
Br
Br
KOH/alc
NO 2
(iii)
OH HI
B 2H 6
H 2O 2 / OH
CH3
I AgNO 2
NO 2
CH 2 OH
(iv)
CH 3
CH 2 Cl
CH 2 OH
H2 O /
Cl 2 /h
(v)
Br
Br2 /CCl 4
Br NaNH2
liq NH 3
(vi)
OH
HF/BF
OH
(vii) H C Br
3
i) CH3 -C -H
Mg/Ether
H 3 C Br
CH 3 MgBr
ii) H3O+
OH
CH 3 CH CH3
113
(viii)
H O/H+
OH
H SO (conc)
2
4
Cl
(ix)
Cl Na/THF
Wurtz reaction
(x)
Na
Ether
(Fitting reaction)
114
(ii)
Acetone
Heat
ethanol
Heat
water
aq. ethanol
(iv) CH3 CH 2 Br + KCN
(v) C 6 H 5ONa + C 2 H 5 Cl
(vi) CH 3 CH 2 CH 2 OH + SOCl 2
115
Strategy.
acetone
(i) CH3 CH 2 CH 2 Cl + NaI
CH3 CH 2 CH2 I
(ii)
CH 3
CH 3
Ethanol
CH 3 C Br +KOH
CH 3 C = CH 2
CH 3
Br
OH
H2O
(iii) CH 3 CH CH 2 CH 3
CH 3 CH CH 2 CH 3
aq acetone
(iv) CH3 CH 2 Br + KCN
CH 3 CH2 CN
O CH2 CH3
(v)
C 6 H5 ONa + CH3 CH 2 Cl
(vi) CH 3 CH 2 CH 2 OH + SOCl 2
CH 3 CH 2 CH 2 Cl
Peroxide CH CH CH CH Br
(vii) CH3 CH 2 CH = CH 2 + HBr
3
2
2
2
Br
(viii) CH 3 CH = C
+ HBr
CH 3 CH2 C CH 3
CH 3
CH3
CH 3
2
nBuBr + KCN
nBuCN
Strategy.
Br + KCN
116
EtOH H 2 O
CN
CN
Br
CN
CN
Br
(ii)
Br
Br
Br
>
>
Br
>
>
(decreasing order of SN 2 )
Br
(iii) Br
> Br
>
Br
> Br
CH 2
(Less stable)
117
CH
(More stable)
Cl
>
Cl
Cl
Cl
>
Cl
Propene to propan-1-ol
Benzene to 4-bromonitrobenzene
(vi)
(vii)
Ethanol to propanenitrile
2-Chlorobutane to 3, 4-dimethylhexane
(x)
2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi)
118
But-1-ene to n-butyliodide
Chlorobenzene to p-nitrophenol
Aniline to phenylisocyanide
Strategy.
OH
(i)
H2O 2/OH
) B
BH
2 6
OH
(ii)
OH
OH
Br2
CCl 4
H2 SO 4
180C
Br
Br
alc KOH
Br
NaNH
NaNH2
CH 3 -CH2 -I
HC CH
HC C Na
CH3 CH 2 C CH
?
Br
(iii)
Br
alc KOH/80
Br
CH 3
HBr
Br
CH2 OH
?
(iv)
CH 3
CH2 Cl
Cl 2/h
CH2 OH
aq KOH
119
(v)
Br
NO 2
Br
Br2/FeBr3
HNO 3+H2SO 4
Br
CH 2 - OH
Ph CH 2 C OH
?
(vi)
CH2 OH
COOH
KMnO 4 /OH
COCl
PCl 5
CH2 COOH
(i) CH 2 N 2 /Ag 2 O
(ii) H 2 O /H
?
(vii) CH 3 - CH 2 - OH
CH 3 - CH2 - C N
SOCl
KCN
2
CH3 CH 2 OH
CH 3CH 2 Cl
CH3 CH 2 C N
Cl
NH 2
?
(viii)
NH 2
(ix)
Cl
Cl
NaNO 2/HCl
0-5C
Cl
N 2Cl
KCl
(Sandmeyer reaction)
?
Na/Et O
(Wurtz reaction)
120
(x)
Cl
HCl
Cl
(Markownikoff rule)
OH
(xi)
Cl
(xii)
OH
H O/H+
KCN
CN
Cl
I
-
BH
H2O 2 /OH
) B
3 (
HI
OH
Cl
OH
(xiii)
Cl
alc KOH/80C
OH
(xiv)
B2H6 (
H2O 2 /OH
) 3B
OH
CHI 3
OH
NaOH/I 2
CH 3 C ONa + CHI 3
OH
Cl
?
(xv)
NO 2
Cl
OH
KOH/
High T
CH 3COCl
O
O
OCCH 3 OCCH 3
NO 2+
OH
H 2O/H +
NO 2
NO 2
121
(xvi)
Br
Br
HBr/(PhCO) O
alc KOH/
2 2
Br
(xvii)
Cl
Na/THF
Cl
(Wurtz reaction)
?
(xviii)
Cl
Cl /FeCl
2
3
Na/Ether
(Fitting reaction)
CH 3
CH 3
?
(xix) CH 3 C Br
CH 3 CH CH 2 Br
CH 3
CH 3
CH 3
EtOH/
CH 3 C Br
CH 3 C = CH 2
CH 3
CH 3
CH 3
HBr
CH 3 C = CH 2 (PhCO)2 O2 CH 3 CH CH 2 Br
N C
NH 2
?
(xx)
NH 2
N C
CHCl 3/KOH
122
In presence of H 2 O
H O H + OH OH + H 2 O
In presence of ROH
R O H +OH RO +H 2 O
alc KOH
Isomers of C 4 H9 Br
Br ,
1 Alc
Br
2 Alc
HBr
C
Isomer of A
Na
C 8 H18
D
Different from the reaction of
n-butyl bromide with Na.
B
Br ,
,
1 Alc
Br
3 Alc
123
A=
Br
HBr
Br alc KOH
Na
dry ether
(i)
Br
Mg/dry ether
(ii)
Mg
Br
(Grignard reagent)
Cl
(iii)
HO
CH3 - CH 2 - OH
Na/dry ether
(v) CH3 - Br
Wurtz reaction CH 3 - CH 3
KCN
(vi) CH 3 - Cl
CH 3 - CN
124
Unit
125
Objective
This unit give you a n understanding of Alcohol,
Phenol & Ether and covers following topics:
126
Solved Example:
Example 1.
Give IUPAC names of the following compounds:
(i) CH 3 CH CH CH CH 2 OH (ii) CH 3 CH O CH 2 CH 3
Cl CH 3 CH 3
CH 3
H3 C
OH
CH 3
(iii)
(iv)
NO 2
OC 2 H 5
Strategy.
(i)
(ii)
5
4
3
2
1
CH 3 CH CH CH CH2 OH
Cl CH 3 CH 3
4-Chloro-2,3-dimethylpentan-1-ol
3
2
CH 3 CH O CH 3 CH 3
1
CH3
2-Ethoxypropane
OH
H3 C 6 1 2 CH
3
(iii)
3
4
2,6-Dimethylphenol
NO 2
OC H
2 1 2 5
(iv)
1-Ethoxy-2-nitrocyclohexane
Example 2.
Give the structures and IUPAC names of the products expected
from the following reactions:
(a) Catalytic reduction of butanal.
127
OH
Butan-1-ol
(Reduction can be carried out
by LiAH 4 or NaBH4)
(A)
H 2 O / H 2 SO 4
(B)
OH
Propan-2-ol
(C)
CH 3MgBr
OMgBr
H 2O
OH
2-Methylpropan-2-ol
Example 3.
Arrange the following sets of compounds in order of their
increasing boiling points:
(a) Pentan-1-ol, butan-1-ol, butan-2-ol, ethanol, propan-1-ol,
methanol.
(b) Pentan-1-ol, n-butane, pentanal, ethoxyethane.
Strategy.
Boiling point of compount depends on extent of hydrogen
bonding with other molecule and molecular weight. Lower the
molecular weight, lower the boiling point & larger the hydrogen
bonding, larger the boiling point, so order of increasing boiling
point follow.
OH
(A) CH 3OH< CH 3CH 2 OH<CH3 CH 2 CH 2 OH <CH 3 CH 2 CHCH3
< CH3 CH 2 CH 2 CH 2 OH < CH 3CH2 CH2 CH2 CH2 OH
128
Example 4.
Arrange the following compounds in increasing order of their
acid strength: Propan-1-ol, 2,4,6-trinitrophenol, 3-nitrophenol,
3,5-dinitrophenol, phenol, 4-methylphenol.
Strategy.
Acidic strength depends on the stability of conjugate base, more
stable the conjugate base, more acidic the molecule will be.
OH
O 2N
O2N
NO 2
NO 2
NO 2
NO 2
(Conjugate base is stabilize due to M &
I of NO2 along with ortho effect)
OH
NO 2
NO 2
(Conjugate base is stabilized due to I of NO2)
OH
O
O 2N
NO 2
NO2
O 2N
(Conjugate base is stabilize due to two I of NO2)
OH
129
CH 3
CH 3
(Conjugate base is destabilize due to
+I nature of methyl group)
OH
<
OH
<
NO 2
CH3
OH
OH
<
<
O2N
O2N
NO 2
NO 2
NO 2
Example 5.
Write the structures of the major products expected from the
following reactions:
(a) Mononitration of 3-methylphenol
(b) Dinitration of 3-methylphenol
(c) Mononitration of phenyl methanoate.
Strategy.
OH
(A)
Mononitration
CH3
130
OH
CH3
So
OH
OH
OH
NO 2
OH
+
O2N
CH 3
NO 2
1,2,3 substitution 1,2,4 substitution 1,2,4 substitution
(without IUPAC) (without IUPAC) (without IUPAC)
CH 3
CH 3
CH 3
(B)
OH
Mono
nitration
CH3
O2N
OH
O 2N
CH 3
CH 3
NO 2
Mono
nitra tion
OH
CH 3
NO 2
(C)
O
OCH
Mono
nitration
O
OCH
NO 2
(1,2-substitution)
NO 2
(minor)
(1,4-substitution)
(major)
131
(i)
CH3 C OC 2 H5
CH 3
(i)
CH 3
CH 3
C 2 H 5ONa
CH 3 C Cl
CH 3 C = CH2
CH 3
OEt
CH 3 C = CH2
CH 3
CH 3
CH 3 C O CH2 CH3
CH 3
(t-butylethyl ether)
Example 7.
Give the major products that are formed by heating each of
the following ethers with HI.
CH3
(i)
132
CH 3 CH 2 CH CH 2 O CH2 CH3
(ii)
CH 3
CH 3 CH 2 CH 2 O C CH2 CH 3
CH 3
(iii)
CH2 O
Strategy.
CH3
CH 3
+
HI
(i) CH 3CH2 CHCH 2 OCH 2 CH 3
CH 3CH2 CHCH 2 OCH 2 CH 3
H
CH 3
+
CH 3 CH 2 CHCH2 OCH2 CH 3 I
SN 2
CH 3
CH 3 CH 2 CHCH2 OH
+
CH 3 CH 2 I
CH3
(ii)
HI
CH 3
CH3 CH 2 CH 2 OCCH 2 CH 3
H CH 3
CH 3
CH 3CH2 CH2 OCCH 2 CH 3
H CH 3
+
CH 3 CH 2 CH 2 OH
+
CH3
CH3 CCH 2 CH 3
+
133
CH 3
I
CH2 O
HI
CH 2 O
H
+
CH 2 + HO
CH2 O
H
+
CH2
CH2I
134
Intext Problem:
Intext Question 1.
Classify the following as primary, secondary and tertia ry
alcohols:
(i)
CH 3
CH 3 C CH2 OH
CH 3
(ii) H 2 C = CH CH 2 OH
OH
CH CH 3
(iii) CH3 CH 2 CH 2 OH
CH 2 CH CH3
OH
(v)
(iv)
(vi)
CH 3
CH = CH C OH
CH 3
Strategy.
Primary (1) alcohol is that alcohol which is attached to primary
carbon, secondary (2) alcohol is that one which is attached to
secondary carbon while tertiary (3) alcohol is one which is
attached to tertiary carbon.
(i)
CH 3
CH 3 C CH 2 OH (Primary alcohol)
CH 3
(ii)
CH 3 = CH CH 2 OH (Primary alcohol)
(iv)
(Secondary alcohol)
135
CH2 CH CH 3
(Secondary alcohol)
OH
(vi)
CH 3
CH = CH C OH
(Tertiary alcohol)
CH 3
Intext Question 2.
Identify allylic alcohols in the above examples.
Strategy.
Allylic alcohol is that alcohol which is attached to allylic position
CH3
CH = CH C OH
are allylic
CH3
alcohol.
Intext Question 3.
Name the following compounds according to IUPAC system.
(i)
CH2 OH
CH 3 CH 2 CH CH CH CH 3
CH2 Cl
CH3
(ii)
CH 2 OH
CH 3 CH CH 2 CH CH CH 3
OH
CH 3
OH
(iii)
Br
(iv) H2 C = CH CH CH 2 CH 2 CH3
OH
136
CH 3 C = C CH2 OH
CH 3 Br
Strategy.
(i)
1
CH 2 OH
5
4
3 2
CH 3 CH 2 CH CH CH CH3
CH2 Cl
CH3
3-Chloromethyl-2-(methylethyl)pentan-1-ol
(ii)
1
CH 2 OH
6
5
4
3 2
CH 3 CH CH 2 CH CH CH3
CH3
OH
2,5-Dimethylhexane-1,3-diol
(iii)
OH
1 2
3 Br
3-Bromocyclohexanol
1
2
3
4
5
6
(iv) CH 2 = CH CH CH 2 CH 2 CH 3
OH
Hex-1-en-3-ol
(v)
4
3 2 1
CH 3 C = C CH 2 OH
CH 3 Br
2-Bromo-3-methylbut-2-en-1-ol
Intext Question 4.
Show how are the following alcohols prepared by the reaction
of a suitable Grignard reagent on methanal ?
CH 2 OH
(i)
CH 3 CH CH 2 OH
CH 3
(ii)
137
MgBr
for second
Mechanism;
+
O MgBr
(i)
CH 3 CH MgBr +H C H
CH 3
CH 3 CH C H
CH 3 OH
CH 3 CH CH2 OH
CH 3
+
O MgBr
MgBr O
+H C H
(ii)
H 2 O /H
H 2O
H
OH
+
Intext Question 5.
Write structures of the products of the following reactions:
(i)
CH 3 CH = CH 2
O
(ii)
H 2O /H
CH 2 C OCH 3 NaBH
4
O
(iii) CH 3 CH 2 CH CHO
NaBH 4
CH 3
138
(i)
CH 3 CH = CH 2
CH 3 CH CH 3
OH
CH 3 CH CH 3
OH
CH 2 C O CH 3 NaBH 4
O
(ii)
H 2O
CH 2 C O CH3
O
(iii) CH 3 CH 2 CHCH
CH 3
NaBH 4
CH3 CH 2 CHCH 2 OH
CH3
Intext Question 6.
Give structures of the products you would expect when each
of the following alcohol reacts with (a) HCl ZnCl 2 (b) HBr
and (c) SOCl 2 .
(i)
Butan-1-ol
(ii) 2-Methylbutan-2-ol
Strategy.
OH
(i)
OH
(ii)
HCl - ZnCl 2
Cl
HBr
SOCl 2
HCl - ZnCl 2
HBr
SOCl 2
Br
Cl
Cl
Br
Cl
139
1-methylcyclohexanol and
(ii) butan-1-ol
Strategy.
OH
H 2SO 4
H 2 O
(i)
OH
(ii)
H
(major)
H 2 SO 4
O
H
H+
H
+
H
(major)
Intext Question 8.
O
N
O
O
O
N
O
N
O
N
OH
O
N
O
H+
N
O
140
N
O
O
N
N
OO
N
O O
N
O O
N
O O
N
O O
OH
>
NO 2
OH
>
NO 2
(ortho have intramolecular H-bonding
so have less acidic character)
Intext Question 9.
Write the equations involved in the following reactions:
(i)
Reimer-Tiemann reaction
OH
CHCl 3 /KOH
(i)
OH
CCl 4 /KOH
CHO
COOH
OH
(i) CO 2 /NaOH
(ii) H 2 O /H
COOH
141
OEt
NaOH
EtOH +
EtO H OH EtO
Cl
OEt
EtO
OH
O
OH
O CH2 CH3
CH 3 CH 2 Cl
Br
(i)
+ CH3 ONa
NO 2
142
(ii)
+ CH 3Br
NO 2
Br OCH 3 OCH 3
CH 3 O
(Method I)
N
NO 2
O
N
O
OCH 3
+ CH3 Br
(Method II)
N
O
NO 2
(iii)
OC 2 H 5 Conc.H SO
2
4
Conc.HNO 3
OC 2 H 5
+ HBr
HI
(iv) (CH 3 )3COC 2 H5
Strategy.
..
+
CH 3 CH2 CH 2 OCH 3
H
143
+
Br
CH3 CH 2 CH 2 OCH 3
CH 3 CH 2 CH2 OH + CH 3 Br
..
OC H
2
H
+
OC 2 H 5
H+
(ii)
H
+
OCH 2 CH3
OH
Br
OC 2 H 5
(iii)
NO 2
+ CH 3CH2 Br
OC 2 H 5
NO 2
OC 2 H 5
+
NO 2
H+
+
(CH 3 )3COC 2H 5
H
+
(CH 3 )3 COC 2 H 5
CH 3
CH3 C + + C 2 H 5 OH
CH 3
CH 3
CH 3 C +
CH 3
CH 3
CH3 C
CH 3
144
Exercise Problems:
Exercise Problem 1.
Write IUPAC names of the following compounds:
(i)
(ii)
CH3
CH 3 CH CH C CH 3
CH 3 OH CH3
H 3 CCHCH 2 CHCHCH 2 CH 3
OH
OH C 2 H 5
(iii) CH 3 CH CH CH 3
OH OH
(iv) HO CH 2 CH CH 2 OH
OH
(v)
CH 3
OH
CH 3
(vi)
OH
CH 3
(vii)
OH
(viii)
CH 3
CH 3
(ix) CH 3 O CH2 CH CH 3
CH 3
CH 3
OH
(x) C 6 H 5 O C 2H 5
(xi) C 6 H 5 O C 7 H 15 (n-)
(xii) CH 3 CH2 O CH CH 2 CH 3
CH3
145
(i)
(ii)
CH
5
4
3 2 31
CH 3 CH CH C CH 3 2,2,4-Trimethylpentan-3-ol
CH3 OH CH3
1
2
3
4
5
6
7
CH 3 CH CH2 CH CH CH 2 CH3
OH
OH C 2 H 5
5-Ethylheptane-2,4-diol
1
2
3
4
(iii) CH 3 CH CH CH 3 Butane-2,3-diol
OH OH
1
2
3
(iv) HO CH 2 CH CH 2 OH Propane-1,2,3-triol
OH
CH 3
4
CH 3
3
2 1 OH
1 2
(v)
(vi)
OH
2-Methylphenol
4-Methylphenol
CH
5 3
6
4
(vii)
3
2 1 OH
CH 3
2,5-Dimethylphenol
CH3
6 1 OH
5
2
(viii)
4
3 CH3
2,6-Dimethylphenol
1
2
3
(ix) CH 3 O CH2 CH CH 3 1-Methoxy-2-methylpropane
CH3
146
2-Methylbutan-2-ol
(ii)
1-Phenylpropan-2-ol
(iii) 3,5-Dimethylhexane-1,3,5-triol
(iv)
2,3-Diethylphenol
(v)
1-Ethoxypropane
(vi)
2-Ethoxy-3-methylpentane
(vii) Cyclohexylmethanol
(viii) 3-Cyclohexylpentan-3-ol
(ix)
Cyclopent-3-en-1-ol
(x)
3-Chloromethylpentan-1-ol
Strategy.
(i)
OH
2-Methylbutan-2-ol
(ii) 1-Phenylpropan-2-ol Ph
OH
(iii) 3,5-Dimethylhexane-1,3,5-tiol
OH
(iv) 2,3-Diethylphenol
HO
OH OH
CH 2 CH 3
CH 2 CH 3
OCH2 CH3
CH2 OH
147
(viii) 3-Cyclohexylpentan-3-ol
(ix) Cyclopent-3-en-1-ol
(x)
HO
3-Chloromethylpentan-1-ol HO
Cl
Exercise Problem 3.
(i)
2
3 1
Pentan-1-ol
I
32 1
OH
3-methyl
butan-1-ol
IV
HO
4
1 2 3
2-Methyl
butan-1-ol
VII
148
OH
OH
4 2 1
5
3
Pentan-2-ol
II
32 1
OH
3-Methyl
butan-2-ol
V
OH
2
3
1
2,2-Dimethyl
propan-1-ol
VIII
4 3 2
1
OH
Pentan-3-ol
III
2 3 4
OH
2-Methyl
butan-2-ol
VI
1
Primary alcohol
II
Secondary alcohol
IV
Primary alcohol
VI
Tertiary alcohol
Secondary alcohol
Exercise Problem 4.
Explain why propanol has higher boiling point than that of
the hydrocarbon, butane?
Strategy.
Propanol has higher boiling point than buta ne because of
presence of intermolecular H-bonding. Additional energy is
required to break that H-bonding.
CH 3 CH 2 CH 2 O
H
H
O CH2 CH2 CH 3
Exercise Problem 5.
Alcohols a re compa ratively more soluble in water tha n
hydrocarbons of comparable molecular masses. Explain this
fact.
Strategy.
Solubility of any molecule in water depends upon extent of
hydrogen bonding with water. Alcohol form H-bonding with
water but hydroca rbon does not. So alcohol ha ve more
solubility in water than hydrocarbon.
HO
HO
R
H
Exercise Problem 6.
149
(i) BH 3
(ii) H 2O 2 /OH
CH3 CH2 CH 2 OH
CH 3 - CH 2 - CH 2 - BH2
CH3-CH = CH2
CH 3 - CH = CH 2
H - BH 2
CH 3 -CH=CH 2
3 CH 3 CH 2 CH2 OH
Exercise Problem 7.
Give the structures and IUPAC names of monohydric phenols
of molecular formula, C 7 H 8O.
Strategy.
Monohydric phenol with moecular formula C 7 H 8 O will be
OH
OH
CH3
2-Methylphenol
OH
CH 3
3-Methylphenol
CH3
4-Methylphenol
Exercise Problem 8.
While separating a mixture of ortho and para nitrophenols by
steam distillation, name the isomer which will be steam volatile.
Give reason.
Strategy.
Ortho-nitrophenol will be steam volatile because of presence
of intramolecular hydrogen bonding in it.
O
N
O
O-Nitrophenol
150
OH
O
+ CH3 C CH 3
i) O 2
ii) H 2 O /H +
CH3
H3 CCH
CH 3
H 3CCOOH
O2
CH 3
CH 3
H3 C C O O H
CH3
CH 3 C O
H 3C C O O H
H + /H 2 O
CH3
CH 3 C O
+
H2 O
H
CH3
O
CH3C
OH
OH
CH3 C CH 3 +
OH
NaOH
623K,300Atm
151
Cl
H OH
H 2O
OH
H 2 O
Benzyne
H 2O /H +
CH 3 CH2 OH
+
CH 2 = CH2 H CH 3 CH2
H 2O
H
CH 3 CH 2 O H
+
CH 3 CH2 OH
OH
i) NaOH
ii) H +
152
Alkene ?
Ph CH CH 3
OH
H 2 O /H +
Ph CH CH 3
+
SN
H+
OH
Ph CH CH 3
CH 2 OH
CH 2 Br
CH 2 OH
NaOH
H2O
OH
CH 3 -CH 2 -CH 2 -CH 2 -CH2 -Br KOH CH3 -CH2 -CH 2 -CH 2 -CH 2 -Br
OH
ONa
Na
+
+
NaOH
1
H2
2
ONa
+ H 2O
OH
H
CH 3 CH 2 OH
CH3 CH2 O
153
O
N
OH
OCH 3 H +
O
OCH3
154
OH
OH
OH
OH
- E+
-
OH
E
OH
+
alkaline KMNO 4
OH
Br2 /CS 2
(ii)
CH3 CH2 C OH
OH
Br
Br
OH
OH
dilute HNO 3
(iii)
OH
(iv)
OH
CHCl 3 /NaOH
OH
NO 2
NO 2
CHO
155
Kolbes reaction.
OH
CO 2
COOH
Salicylic acid
+
OH
OH
O H
O
CO
O
O
H COH
OH
COOH
OH
CHCl 3 /KOH
CHO
Salicyldehyde
Cl
Cl
OH
ClCH H O ClC
ClCCl
2
Dichlorocarbene
Cl
Cl
..
OH
O
KOH
156
O
ClC Cl
Cl
CCl
Cl
CCl H OH
Cl
CCl
H
O
KOH
OH
O
O
OH
H
COH
CH
CHO
H
CH 3ONa
CH 3 CH 2 O CH 3
H
2
CH 3 O + H 3 C C Br SN CH 3 O CH 2 CH 3
Methoxyethane
H
H 2O
CH 3 CH 2 O H+ H O CH 3
CH 3 CH 2 O CH 3
R
R
(Both alkyl group is different so
unsymmetrical ether)
H 2O
H 2 SO 4/
CH 2 = CH2
157
H+ + HSO 4
H
CH 3 CH2 OH +H+
HSO 4
CH 2 CH 2 O H H SO CH 2 = CH2
+
2
4
(E2 )
H
Propene Propan-2-ol.
OH
H2 O / H
H 2O
OH
H +
(ii)
CH 2 Cl
CH 2 OH
CH 2 Cl
CH 2 OH
KOH
2
SN
?
(iii) CH3 CH 2 MgCl
CH 3 CH 2 CH 2 OH
O
CH3CH2 MgCl + H C H
CH 3 CH 2 CH 2 OH
158
CH 3 CH2 CH2 O Mg Cl
H 2 O /H +
?
(iv) CH 3 MgBr
O
CH 3MgBr + CH 3 C CH3
O MgBr
H 2O /H +
OH
?
Primary alcohol
Carboxylic acid.
2.
K 2 Cr2 O 7
3. CrO 3
? aldehyde
(ii) Primary alcohol
(iii)
Br
OH
Br
Br
159
Br
OH
Br
CH2 OH
(iv)
Br
O
COH
(v)
2.
K 2 Cr2 O 7
2.
H 3 PO 4
3. Al 2 O 3
4.
ThO 2
(vi)
OH
2. LiAlH 4
3. Al-isopropoxide(MPV reduction)
Exercise Problem 22.
Give reason for the higher boiling point of ethanol in comparison
to methoxymethane.
Strategy.
Boiling point depends on extent of hydroden bonding for nearly
same molecular weight compound. More the H-bonding, more
will be the boiling point. Ethanol form intermolecular Hbonding but methoxymethane can not.
160
HO
HO
CH 2 CH 3 CH 2 CH 3 CH2 CH3
C 2 H5 OCH 2 CH CH 3
CH 3
CH3
(v)
(vi)
OC 2 H 5
OC 2 H 5
Strategy.
(i)
1
2
3
C 2 H5 O CH 2 CH CH3 1-Ethoxy-2-methylpropane
CH 3
(ii)
2
1
CH 3 O CH2 CH 2 Cl 1-chloro-2-methoxyethane
1
3 2
O CH 3
3
2
1
(iv) CH 3 CH 2 CH 2 O CH 3 1-Methoxypropane
(v)
2
4-Ethoxy-1,1-dimethylcyclohexane
4 3
OC 2 H 5
161
Ethoxybenzene
OC 2 H 5
1-Propoxypropane
(ii) Ethoxybenzene
?
X
CH3 CH2 CH2 O CH 2 CH 2 CH3
CH 3 CH 2 CH 2 O K + CH 3 CH2 CH2 Cl
SN
(ii) X
O CH 2 CH 3
OK
+ CH 3 CH2 Cl
(iii)
OCH3
OK
+ CH 3 Cl
(iv) X
OCH3
OCH3
+
CH3 CH 2 O K +CH 3 Cl
162
O CH2 CH3
CH 3CH 2 OCH3
RO
R R'
CH 3
CH 3 ONa
CH 3 C = CH 2 + CH 3 OH
Mechanism:CH 3
CH 3O CH 3 C Br
H CH 2
CH 3
E2
CH 3 C = CH2
163
NaOH
CH 3 CH 2 CH 2 OCH2 CH 2 CH3
Mechansim:+
CH 3 CH2 CH2 O H + OH
CH 3CH2 CH2 O + CH 3 CH 2 CH 2 I
SN
CH 3 CH2 CH2 O Na
2
CH 3 CH 2CH2 OCH 2 CH 2 CH 3
CH 3
CH 3
CH 3 CO
CH 3 C +
+ H H 2O
CH
CH 3
CH 3
CH 3
CH 3 CCH 2
+
164
CH 3 COH
CH3
CH 3 CH3
CH 3 COCCH3
CH3 CH3
(Less favourable)
CH 3
CH 3 CCH 2
+
CH 3
CH 3 CCH 2
(More favourable)
1-propoxypropane
HI
CH3 CH 2 CH 2 - O - CH 2 - CH 2 - CH 3
?
H I
H
+
H
+
(ii)
CH 3 CH 2CH2 OH
+
CH 3CH2 CH2 I
O CH 3 HI ?
O CH3 H I
O CH 3 I 2
SN
H
OH + CH 3I
165
(iii)
CH2 O CH 2 CH 3
HI
CH 2 O CH 2 CH 3
H
+
CH
+
CH2 O CH 2 CH 3
+ CH 3 CH2 OH
H
+
CH 2 I
CH 2
I
OR
E+
OR
OR
OR
E
+
OR
OR
OR
166
+
CH 3 O CH3 H I CH 3 O CH 3 I
H
CH3 OH +CH3 I
OCH3
R
(Minor)
OCH3
+
R
(Major)
167
R + +AlX4
(Electrophile)
OCH3
+ R
OCH3
OCH3
+
+ R
(Stable)
(Least stable)
R
(stable)
(C) Deprotonation
OCH 3
H R
OCH3
OCH 3
+ R
H
OCH3
R
OCH 3
NO 2
(Minor)
OCH3
+
NO 2
(Major)
Mechanism
Similar to above question mechanism follows three steps
(A) Formation of an electrophile
(B) Attack of an electrophile
(C) Deprotonation
168
O
O
+
H O N H O + N
2
O
O
O
H
Nitronium ion
(Electrophile)
+
+
OCH3 OCH 3 OCH3
H O S O H + H O N
O
OCH 3 OCH 3
OCH 3 +
OCH 3
NO
NO 2
2
OCH3
NO 2
OCH 3
Br
Br2 / CH 3 COOH
OCH3
+
(Minor)
Br
(Major)
OCH 3 OCH 3
OCH 3 +
OCH 3
NO 2
NO 2
OCH3
+
NO 2
169
OCH3
O
CH 3 C Cl /AlCl 3
O
OCH 3
CCH3
(Minor)
CCH3
O
(Major)
O
+ CH3 C +
OCH 3
+ CH3 C+
O+
O
CH 3 C +
OCH 3
+ COCH 3
OCH3
CH 3 C
OCH 3
O
C CH 3
OCH 3
H CR
CCH3
O
O
Friedel-Craft acylation is carried out in presence of acid halide
& lewis a cid such a s AlCl 3 , FeCl 3 etc. which ma ke a cyl
carbocation, which is an electrophile for acylation reaction. As
ortho & para position is more electron rich so ortho & para
product will be formed as product.
170
(i)
OH
OH
(iii)
OH
(ii)
(iv)
OH
Strategy.
(i)
Alkene ?
or
(ii) Alkene
+ H O
2
OH
H +
OH
H2 O / H+
or
(iii) Alkene
OH
OH
H 2O /H +
OH
H 2O
H
(iv) Alkene
OH
H 2O
OH
H 2O /H +
H2 O
H
OH
or
171
H+
H2 O
OH
H +
HBr
CH 3 C CH 2 CH 3
CH 3
CH 3 CH CH CH 3
CH 3 OH
HBr
CH 3 CH CH CH 3
CH3 O
H
CH3 CH CH CH 3
CH 3
CH 3 -C-CH-CH 3
CH3
Br
Br
CH 3 -C-CH 2 -CH 3
CH 3
172
Unit
173
Objective
This unit give you an understanding of Aldehyde ketone & Carboxylic acid and covers following topics:
174
Solved Example:
Example 1.
Give na mes of the reagents to bring about the following
transformations:
(i)
Hexan-1-ol to hexanal
(i)
OH
(ii)
O
?
175
CHO
?
(iii)
F
CHO
i) CrO2 Cl 2 , Ac 2O
ii) H 2O /H
(iv) CH 3 C
DIBAL-H
CH 3 C H
(v)
DIBAL-H
OH ?
CH 3 C H
H
O
O
CH 3 C H
176
H 3C O
H
O CH
O H
Ozonide
Zn H 2O
O
2 CH 3 C H
Example 2.
Arrange the following compounds in the increasing order of
their boiling points:
CH 3 (CH2 )2 CHO, CH 3 CH 2 CH 2 CH 2 OH,
H 5 C 2 OC 2 H 5 , CH 3 (CH 2 )3 CH 3
Strategy.
Boiling point depends on following factors in decreasing order
for nearly same mol. wt.
Intermolecular H-bonding > Intramolecular H-bonding > Dipole
moment > Vander waal force.
So increasing order of boiling points of following molecules
follows.
CH3 CH 2 CH 2 CH 2 CH 3 < H5 C 2 OC 2 H5 <
CH3 CH 2 CH 2 CHO < CH 3 CH 2 CH 2 CH 2 OH
Example 3.
177
O
H
O
H
O
H
Example 4.
An orga nic compound (A) with molecula r formula
C 8 H8 O forms an orange-red precipitate with 2,4-DNP reagent
and gives yellow precipitate on heating with iodine in the
presence of sodium hydroxide. It neither reduces Tollens or
Fehlings reagent, nor does it decolourise bromine water or
Baeyers reagent. On drastic oxidation with chromic acid, it
gives a ca rboxylic a cid (B) ha ving molecula r formula
C 7 H 6 O 2 . Identify the compounds (A) and (B) and explain the
reactions involved.
Strategy.
C 8 H8 O
A
2,4-DNP
178
2,4-DNP
NN
NO 2
H 3C
CH 3
Ph
I 2 /NaOH
NO 2
Ph COONa +CHI3
COOH
H2 CrO 4
Example 5
Write chemical reactions to affect the following transformations:
(i)
O
?
OH
OH
(e) K 2 Cr2 O 7
(ii)
CH 2 OH
CH 2 COOH
?
179
CH2 Br
HBr
CH 2 CN
KCN
KBr
H2 O
CH 2 COOH
H 2O /H
COOH
Br
?
(iii)
NO 2
NO 2
MgBr
COOMgBr
CO 2
Mg/THF
NO 2
NO 2
NO 2
(iv)
H3 C
NO 2
COOH
CH 3
COOH
H 2 O /H +
HOOC
COOH
COOH
(vi)
COOH
COOH
O
OH
180
Intext Problem:
Intext Question 1.
Write the structures of the following compounds.
(i)
- Methoxypropionaldehyde
(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-Oxopentanal
(v) Di-sec. butyl ketone
(vi) 4-Fluoroacetophenone
Strategy.
(i)
(iii)
OCH 3
0 H
O
OH O
(ii)
CHO
OH
12
2 1 H
(iv)
(v)
sec butyl group
Intext Question 2.
4 3
2 1 H
O
2 1O
CH 3
(vi) 3
F4
(i)
+ C2H 5
Cl
Anhyd. AlCl 3
CS 2
Hg 2 + ,H 2SO 4
181
(iv)
2. H 3O +
NO 2
Strategy.
O
(i)
+ C2H 5
O
Cl
Anhydrous AlCl 3
Cl
C 2 H5 C Cl +AlCl
Cl
C 2 H 5 C + + AlCl 4
+H
+ C2H 5 C+
(ii)
C2H 5
CS 2
O
C 2 H5
O
(C 6 H 5CH2 )2 Cd + 2CH3 C Cl
H+
Et
O
C6H 5 C Cl + C 6H 5 CH 2 Cd CH 2 C6 H5
O
CH 3 C CH 2 C 6 H5
(iii) CH C C H
3
CH3 C CH
Hg 2+ ,H 2 SO 4
Hg 2+
CH3C
O
CH 3 C Cl
CH 2 C 6 H5
CH
Hg +
182
CH3C
Hg +
Hg
H + H
O
OH
CH 3 C=CH
CH3 C=CHHg
O
CH 3 CCH 2 Hg
Hg
O
CH 3 CCH 2 Hg
[H]
CH 3 CCH 3
CHO
CH3
i)CrO 2 Cl 2
(iv)
(Etard reaction)
ii)H 2O /H +
NO 2
Intext Question 3.
NO 2
Strategy.
Boiling points depends upon following factors in decreasing
order
H-bonding > dipole-dipole interaction > Vander waal force
so increasing order of boiling points of following compounds
follows
O
CH 3 CH 2 CH3 < CH3 OCH3 < CH 3 CH < CH3 CH2 OH
Intext Question 4.
Arrange the following compounds in increasing order of their
reactivity in nucleophilic addition reactions.
(i)
183
CH 3 -C-CH 2 -CH 3 < CH 3 -C-CH 3 < CH 3 -CH 2 -C-H < CH3 -C-H
(ii) Aldehydes are more reactive than ketone due to steric factor
& electronic factors. Electron withdrawing group present
in carbonyl compound increases the partial positive charge
on carbonyl carbon but electron donating group decreases
the reactivity due to decrease in partial +ve charge. So,
O
C CH 3
<
CHO
CHO
<
CHO
<
CH3
NO 2
Intext Question 5.
Predict the products of the following reactions:
(i)
O
H+
+ HO NH2
(ii)
O2N
O
+ NH2 NH
NO 2
O
+
(iii) R CH = CH CHO + NH 2 C NH NH 2 H
184
(iv)
Strategy.
(i)
O
H+
+ HO NH 2
+
OH
H+
OH
+
OH
H
+NOH
H
(ii)
OH
2H
OH
H
+NOH
H
H 2NOH
NH
NOH
O2N
O
+ NH2 NH
NO 2
O
NO 2
H 2 NN
H
OH
H NO
2
NN
NO 2
H
NO 2
OH
NO 2
NN
H H
NO 2
NO 2
NN
H
NO 2
O
H+
?
(iii) R CH = CH CHO +H2 N C NH NH 2
O
OH
+
H
RCH=CHCH
RCH=CHCH
+
185
OH H2 N-N-C-NH2
OH H
O
RCH=CHCHNNCNH2
H
RCH=CHCH
H +
1
OH H
O
O
3
2
RCH=CHCHNNCNH 2 CH 3 CH=CHCH=NNCNH 2
H
H
O
CH 3 + CH CH NH H+
3
2
2
(iv)
OH
O
CH 3 H
+ CH3
OH H
C NCH2CH3
CH 3
OH
+ CH 3 H 2 N-CH 2 -CH 3
H
1
OH H
2
3
C NCH 2 CH3
C=NCH 2 CH 3
CH 3
CH3
Intext Question 6.
Give the IUPAC names of the following compounds:
(i)
PhCH 2 CH 2 COOH
CH 3
(iii)
186
COOH
(iv)
O2N
NO 2
3
2
1
Ph CH 2 CH2 COOH 3-Phenylpropanoic acid
(ii)
4
3 2
1
CH 3 C = CH COOH 3-Methylbut-2-enoic acid
CH 3
CH3
COOH
12
2-Methylcyclopentane-1-carboxylic acid
(iii)
NO 2
6 COOH
5
1
(iv)
2,4,6-Trinitrobenzenecarboxylic acid.
O 2 N 4 3 2 NO 2
Intext Question 7.
Show how each of the following compounds can be converted
to benzoic acid.
(i)
Ethylbenzene
(ii) Acetophenone
(iii) Bromobenzene
Strategy.
CH 2 CH 3
COOH
(i)
COOH
KMnO 4 /
(ii)
COOH
CH 3
187
O
CH 3
I 2 /NaOH
Br
(iii)
OH
COOH
?
Br
MgBr
Mg/THF
(iv)
O
O Na H2 O /H
CH = CH2
COOMgBr
CO 2
H 2O /H
COOH
+
COOH
COOH
KMnO 4 /
Intext Question 8.
Which acid of each pair shown here would you expect to be
stronger?
(i)
CH3 CO 2 H or CH 2 FCO 2 H
188
COOH or H 3C
COOH
O
O
+
H
CH 3 C OH
CH 3 C O
(I)
O
O
H +
F CH 2 C OH
F CH 2 C O
(II)
O
O
H +
Cl CH 2 C OH
Cl CH 2 C O
(II)
O
FCH2 CH 2 CH2 CO
(I)
189
(II)
(iv) F3C
COOH or H 3C
COOH
O
C O
COOH
H +
CF3
CF3
(I)
COOH
COO
H +
CH 3
CH 3
(II)
COOH
>
CF3
CH3
190
Exercise Problems:
Exercise Problem 1.
What is meant by the following terms ? Give an example of the
reaction in each case.
(i)
Cyanohydrin
(ii)
Acetal
(iii) Semicarbazone
(iv) Aldol
(v)
(vi) Oxime
Hemiacetal
(vii) Ketal
(viii) Imine
(ix) 2,4-DNP-derivative
(x)
Schiffs base
Strategy.
(i)
HCN
H/R
CN H/R
Cyanohydrine
+ OH
ROH / H+
OH
H
R ORH
RO
R
ROH
R ORH
OH
H
OH
OR
ROH
ROH
OR OR
R
H/R
191
OH
H
R/H
OH
O
H
NNCNH2
R/H
H/R H
NNCNH 2
H/R H
NNCNH2
R/H
H
(Semicarbazone)
OH
O
CH 3 CH CH 2 C H
O
HO CH2 C H
O
CH 2 C H
O
H C = CH 2
O
O
HC=CH 2 CH 3 CH
OH
O
CH 3 CHCH2 CH
-hydroxyaldehyde (Aldol)
192
ROH / H +
+ OH
ROH
OH
H H +
H
OR
(Hemiacetal)
NOH
H
H
OH
R
NOH
NOH
+
NOH
H
R
H/R
H/R
R/H Oxime
O
R
OH
H
ROH
ROH
OH
R H + R
OR R
H+
H 2O
ROH
R ORRH +
RO
OR
R
R
Ketal
O
R
H/R
H
+
NH
R
H/R H
NH 3
OH
R
H
H 2O
NH
NH
R
H/R
R/H
(Imine)
193
H
H
R
NN
NN
NO 2
H NO 2
2,4-DNP
NO 2
R/H
H NO 2
2,4-DNP derivative
O
H/R
H
+
NR
R
H/R H
RNH 2
OH
R
H
H 2O
NR
NR
R
H/R
R/H
(Schiff's base)
Exercise Problem 2.
Name the following compounds according to IUPAC system
of nomenclature:
(i)
194
CH 3
O
CH 3 CH CH 2 CH 2 C H 4-Methyl pentanal
5
4
3
2
1
(ii)
4
5
6
CH 3 CH2 C CH CH 2 CH 2 Cl
1
2
3
C 2H 5
6-Chloro-4-ethyl
hexan-3-one
O
(iii) CH 3 CH = CH C H But - 2 - enal
4
3
2
1
CH 3 O
(v) CH 3 CH CH 2 C C CH 3 3,3,5-Trimethylhexan-2-one
3
6
5
4
2 1
CH 3
CH 3
O
(vi) CH 3 3C CH2 C OH 3,3-Dimethylbutanoic-acid
2
4
1
CH 3
CHO
1
2
(vii)
4-Hydroxybenzenecarbaldehyde
43
OH
Exercise Problem 3.
Draw the structures of the following compounds.
(i)
3-Methylbutanal
(ii) p-Nitropropiophenone
(iii) p-Methylbenzaldehyde
(iv) 4-Methylpent-3-en-2-one
(v) 4-Chloropentan-2-one
(vi) 3-Bromo-4-phenylpentanoic acid
(vii) p,p-Dihydroxybenzophenone
(viii) Hex-2-en-4-ynoic acid
195
O
(i) 3-Methylbutanal CH 3 CH CH 2 C H
4
3
2
1
(ii) p-Nitropropiophenone
O2N
CHO
(iii) p-Methylbenzaldehyde
CH 3
(iv) 4-Methylpent-3-en-2-one
(v) 4-Chloropentan-2-one
O
2 1
5 4 3
Cl O
5 4 3 2 1
Ph
3 2 1 OH
(vi) 3-Bromo-4-phenylpentanoic acid
4
5
Br O
O
C
(vii) p,p-Dihydroxybenzophenone HO
5
6
3
4
OH
1 OH
Exercise Problem 4.
Write the IUPAC names of the following ketones and aldehydes.
Wherever possible, give also common names.
(i)
196
(iv) Ph CH = CH - CHO
(v)
(vi) PhCOPh
Strategy.
Structure
(i)
Common Name
O
CH 3 C CH 2 CH 2 CH2 CH2 CH3
Heptan-2-one
Br
(ii)
CH 3 O
CH 3 CH 2 CH CH 2 CH C H
6
5
4
3
2
1
4-Bromo-2-methylhexanal
O
(iii) CH 3 CH2 CH2 CH2 CH 2 CH2 C H
7
6
5
4
3
2
1
Heptanal
O
(iv) Ph CH = CH C H
3
2
1
3-Phenylprop-2-enal
Cinnamaldehyde
CHO
(v)
Cyclopentane carbaldehyde
O
Ph C Ph
(vi) Diphenylmethanone
Benzophenone
Exercise Problem 5.
Draw structures of the following derivatives.
(i)
197
(i)
(ii)
Ph
NN
O + NN
NO 2
NO 2
H
H
H NO 2
H NO 2
Benzaldehyde 2,4-DNP 2,4-Dinitrophenylhydrazone
of benzaldehyde
H
NOH
NOH
H
Cyclopropanone Hydroxylamine Cyclopropanone oxime
O
CH 3 O
CH 3 OH /
H
(iii) H3 C
Acetaldehyde
O+
OCH 3
H
H
Acetaldehydedimethylacetal
O
N N C NH 2
H
Cyclobutanone Semicarbazide
(iv)
N N C NH 2
H
Semicarbazone of
cyclobutanone
(Hexan-3-one)
H
(v)
O
H
O
(Ethane-1,2-diol)
(vi)
198
CH 3OH(1 eq)/H
H
H
Formaldehyde
OH OCH3
H
H
Methylhemiacetal of formaldehyde
(i)
i) PhMgBr
ii) H 3O +
O MgBr
O
H PhMgBr
Ph
OH
+
H 3O
O
H Tollen's reagent
(ii)
O
H
Tollen's reagent
O Ag
H 2 N N C NH 2 /H +
(iii)
O
H
H
H
O
N N C NH 2
H
H+
N N C NH 2
H
199
(iv)
OH
O
H H+
+ H EtOH
H+
OH
OEt
+
H H
H 2O
OEt
OEt
OEt
+ H EtOH
H+
(v)
Zn Hg / HCl
Methanal
(ii) 2-Methylpentanal
(iii) Benzaldehyde
(iv) Benzophenone
(v) Cyclohexanone
(vi) 1-Phenylpropanone
(vii) Phenylacetaldehyde
(viii) Butan-1-ol
(ix) 2,2-Dimethylbutanal
Strategy.
Those aldehyde which have - H when treated with base give
-hydroxy aldehyde, which is called as aldol, and condensation
200
aldol
O
O
OH
HCCH 2 H O HCCH 2
2
H
O
HC=CH 2
O
O
H OH
CH3 CHCH2 CH
O
O
HC=CH 2 CH 3 CH
OH
O
CH 3 CHCH2 CH
OH
O
HCH
OH
O
O
HC H+HCH
OH
O
O
HCOH+HCH
H
O
O
HCO H + HCH
H
O
HCONa + CH 3OH
201
O
O
OH
H C H
H C O + CH 3OH (Show cannizzaro
Methanal
reaction)
(ii)
OH
CHO
CHO
2-methylpentanal
CHO
H 2O/H
CHO
CHO
OH CHO
(Show aldol reaction)
OH
H
Ph
H
(iii) Ph
OH
(Benzaldehyde)
O
Ph
H Ph
OH
Ph
Ph
O
O H +Ph
H
OH
OH + Ph
H
OH
O
Ph
O + PhCH 2 OH
(Show cannizzaro reaction)
(iv)
OH
Ph
Ph
Benzophenone
202
H OH
OH
H 2O
(v)
OH
(vi)
H OH
Ph
H OH
Ph
OH
O
HOH
Ph
(vii)
Ph
O
H
Ph Ph
Ph Ph
(Show aldol type raction)
O
H
Ph
O
Ph
H OH
Ph Ph
O
OH
Ph Ph
(Show aldol reaction)
OH
(viii)
(ix)
OH
H
2,2-Dimethylbutanal
O
H
OH
H
OH
O
O H +
O H +
(show cannizzaro reaction)
O
OH +
203
Butane-1,3-diol
(ii) But-2-enal
(i)
H3 C
HO
OH
Butane-1,3-diol
Ethanal
O
OH
O
NaBH
OH
CH 3 C H
CH 3 CH CH2 C H [H] 4
Aldol
Ethanal condensation
OH
OH
CH3 CH CH 2 CH 2
Butane-1,3-diol
(ii)
O
CH 3 C H
O
?
H
But-2-enal
O
CH 3 C H
OH H O
CH CH C H E CB
1
O
CH 3 CH = CH C H
But-2-enal
OH
CH3
Aldol
con densation
O
(iii) CH 3 C H
O
CH 3 C H
204
O
?
OH
But-2-enoic acid
OH
Aldol
OH H O
CH3 CH CH C H H O
2
O
CH 3 CH = CH C H
Exercise Problem 9.
Write structural formulas and names of four possible aldol
condensation products from propanal and butanal. In each
case, indicate which aldehyde acts as nucleophile and which
as electrophile.
Strategy.
O
O
CH 3 CH 2 C H + CH 3 CH 2 CH 2 C H
OH
O
CH 3 CH C H
H
OH
CH3 CH CHO
Nucleophile
(Electrophile)
OH
CH 3 CH 2 CHCHCHO
CH3
OH
CH 3 CH 2 CH2 CHCHCHO
CH 3
O
CH 3 CH 2 CHCH OH CH3 CH 2 CHCHO
H
(Nucleophile)
205
OH
CH 3 CH 2 CHCHCHO
CH2 CH 3
OH
CH 3 CH 2CH2 CHCHCHO
CH2 CH3
C 9 H10O
Tollen's
Reduce it Presence of aldehyde.
reagent
Cannizzaro
+Ve Presence of aldehyde without H.
reaction
C
COOH
[O]
Presence of skeleton
COOH
C
206
C
Alcohol
H 2O / H +
CrO 3
[O]
H2 O
H 2O/H
Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tertbutyl ketone (reactivity towards HCN)
207
<
O CH 3
CH3 C C CH 3
CH 3
<
CH 3
CH 3 CHCOOH
208
CH 3 CH 2 CH COO
(I)
Br
CH 3 CH CH2 COO
(II)
CH 3
CH 3 CH COO
(III)
CH3 CH 2 CH 2 COO
(IV)
COOH
(I)
COOH
COO
NO 2
NO 2 (I, M)
(II)
COOH
COO
NO
NO 2 2
NO 2 (I)
NO 2 (I, M)
(III)
COOH
COO
OCH 3(+M, I)
(IV)
OCH 3
209
(i)
O
Tollen's test
Black ppt
CH 3 CH 2 CH NaOH/I
2
No Yellow ppt
(Propanal)
O
Tollen's test
CH 3 CCH 3
(Propanone)
I 2 /NaOH
Yellow ppt
O
CH3 NaOH /I2
(ii)
No ppt
ONa + CHI
(Yellow ppt)
(Acetophenone)
O
NaOH /I2
No yellow ppt
(Benzophenone)
OH
(iii)
NaHCO 3
(Phenol)
COOH
NaHCO 3
COONa
+ CO 2 (evolution of CO 2 )
(Benzoic acid)
210
(iv)
O
COH NaHCO
CO 2 evolution is seen
(Benzoic acid)
O
COEt NaHCO
3
No CO 2 evolution
(Ethyl benzoate)
(v)
I 2 /NaOH
ONa + CHI 3
yellow ppt
(Pentan-2-one)
I2 / NaOH
No yellow ppt
O
(Pentan-3-one)
O
(vi)
CH I /NaOH
2
No yellow ppt
(Benzaldehyde)
O
C CH3 I /NaOH
2
O
C ONa + CHI 3
yellow ppt
O
I 2 / NaOH
yellow ppt
(vii) CH3 C H
(Ethanal)
O
I /NaOH
CH3 CH2 C H 2
No yellow ppt
(Propanal)
211
Methyl benzoate
(v) p-Nitrobenzaldehyde.
Strategy.
(i)
O
C OCH3
(Benzene)
(Methyl benzoate)
CH 3
CH 3 Cl /AlCl 3
(Friedel-craft
alkylation )
KMnO 4 /H +
O
+
CH 3OH / H
COH (Esterification)
(oxidation)
O
COCH 3
COOH
(ii)
(Benzene)
NO 2
(m-nitrobenzoic acid)
CH3
CH 3Cl/AlCl 3
(Friedel-craft
alkylation)
KMnO 4 /H +
oxidat ion
COOH
HNO 3 /H 2 SO 4
Nitra tion
COOH
(iii)
NO 2
212
COOH
NO 2
CH 3
CH3
NO 2
HNO 3 /H 2SO 4
CH 3
+
NO 2
(Separation by fractional distilation)
COOH
KMnO 4 /H +
NO 2
NO 2
CH2 COOH
(Phenylacetic acid)
(iv)
CH3
CH 3Cl/AlCl 3
(Friedel-craft
alkylation)
CH2 Cl
CH 2 Cl
Cl 2 /h
(Free radical
substitution)
CH 2 CN
CH2 COOH
+
H 2O/H
(Hydrolysis)
KCN
(Nucleophilic
substitution)
CHO
?
(v)
NO 2 (p-nitrobenzaldehyde)
CH3
CH 3Cl/AlCl 3
HNO 3 /H 2 SO 4
CH 3
NO 2
(Friedel-craft
alkylation)
CH3
CHO
CH 3
+
NO 2
(i) CrO 2 Cl 2
(ii) H 2O/H
NO 2
NO 2
213
Propanone to Propene
(ii)
(iii)
Ethanol to 3-Hydroxybutanal
(iv)
Benzene to m-Nitroacetophenone
(v)
Benzaldehyde to Benzophenone
(vi)
Bromobenzene to 1-Phenylethanol
Strategy.
(i)
O
CH 3 C CH 3
Propanone
O
CH 3 C CH3
(ii)
CH3 CH = CH 2
Propene
OH
LiAlH 4
H 3O +
(R eduction)
CH 3 CH = CH2
CHO
COOH ?
Benzoic acid
O
COH SOCl
Benzaldehyde
O
CCl H / Pd - BaSO
2
4
(Rosenmuld
reduction)
214
H 2 SO 4 /
CH 3 CH CH 3 Elimination
CHO
CH 3 CH 2 OH
OH
O
CH 3 CH CH2 C H
3-Hydroxybutanal
PCC
oxidation
O
NaOH
CH 3 C H aldol reaction
OH
O
CH 3 CH CH2 C H
COCH 3
?
(iv)
NO 2
m-nitroacetophenone
Benzene
COCH 3
COCH 3
CH 3COCl /AlCl 3
HNO 3 /H 2 SO 4
(F.C. acylation)
(Nitration)
CHO
NO 2
O
?
(v)
Benzaldehyde
Benzophenone
OH
H PhMgBr
Br
O
Cu
OH
?
(vi)
Bromobenzene
Br
CH CH3
1-Phenylethanol
O
Mg/THF
i) CH 3 C H
MgBr
+
ii) H 2O /H
OH
CH CH 3
215
Ph
?
(vii)
CH 2 CH 2 CH 2 OH
Benzaldehyde
Ph CH = O
3-Phenylpropan-1-ol
Ph CH = CH COOH
CHO
LiAlH 4
Ph CH = CH COOH
Ph CH 2 CH2 CH2 OH
OH O
?
(viii)
Benzaldehyde
CHO
CH C OH
- Hydroxyphenylacetic acid
OH
OH
+
H O/H
CHCN 2
HCN
COOH
CHCOOH
CH 2 OH
?
(ix)
Benzoic acid
COOH
NO 2
m-nitrobenzyl alcohol
COOH
HNO 3 / H 2 SO 4
CH2 OH
LiAlH 4
NO 2
NO 2
Acetylation
216
Ex.
CH 3 C Cl /AlCl 3
Cl
C CH 3 C CH 3
+
O
HCH
O
HCO H + CH3 O
O
HCO H + CH 3 O
O
HCONa+CH3OH
CH3CH + CH3CH2CH
CH3 O
OH
CH 3CH=C CH
217
OH CH3 O
OH CH3 O
O
OH
CH3CH=CCH CH3CHC CH
CH3CHC CH
CH3
H
, - Unsaturated aldehyde
O
O
CH 3 C CH2 C OH
(i)
COOH
KMnO 4
KOH, heat
(ii)
COOH
O
C
(v)
218
[Ag(NH 3 )2 ]+
CHO
CHO
(vi)
SOCl 2
heat
NaCN/HCl
COOH
C 6 H 5CHO
dil. NaOH
+
CH 3CH2 CHO
NaBH 4
H
CrO 3
(ix)
OH
(x)
CH2
CHO
(i) O
3
(xi) (ii) Zn H O 2
2
Strategy.
CH 2 CH 3
(i)
COOK
KMnO 4
KOH/Heat
COOH
(ii)
SOCl 2
COOH
O
CCl
CCl
O
(iii)
O
O H
CH H N C N NH
2
2
O
(iv)
O
CH = N N C NH 2
H
O
Ph C Cl / AlCl 3
Friedel-cra ft reaction
219
(v)
(vi)
Ag (NH 3 )2
CHO
COO
OH
CN
(Cyanohydrine
H
COOH formation)
NaCN/HCl
COOH
O
O
dil NaOH
(vii) PhC H +CH 3 CH 2CHO
Ph CH = C C H
CH 3
(Cross aldol condensation)
O
O
OH
O
(i) NaBH 4
CH3CHCH 2COC 2 H5
(viii) CH 3CCH2 COC 2 H5
+
(ii) H
(ix)
OH
CrO 3
in presence of CrO 3 .
(x)
(i) BH
CH 2 (ii) H O3 /NaOH
2 2
CHO
(iii) PCC
(i) O 3
(ii) Zn H 2 O
220
HO
CN
HCN
No reaction
221
Tollen's
An organic reagent Ve Absence of aldehyde group
compound
O
NaHSO 3
C=69.77%
Addition product Reaction of R-C-H/R
H=11.63%
O
I2 /NaOH
O=100
+Ve Presence of C CH 3
(69.77+11.63) [O]
CH 3 COOH + CH 3CH2 COOH
=18.56%
222
At.
mass
12
1
16
Relative
atomic mass
69.77/12=5.8
11.63/1=11.63
18.56/16=1.16
Simple ratio
of moles
5.8/1.16=5
11.63/1.16=10
1.16/1.16=1
whole
no. ratio
5
10
1
O
CH 3 -CH 2 -CH 2 -C-CH 3
Tollen's
Ve
test
OH
NaHSO 3
CH3 CH2 CH2 C CH 3
I 2 /NaOH
[O]
SO 3 Na
CH3 CH2 CH2 COO Na + + CHI3
CH3 COOH + CH3 CH 2 COOH
223
(Less contributing)
O
RC O
O
RC=O
224
Amines
Unit
Amines
225
Amines
Objective
This unit give you an understanding of Amines and
covers following topics:
226
Structures of amines.
Classification of amines.
Nomenclature of amines.
Preparation of amines.
Physical properties of amines.
Chemical reactions of amines.
Methods of preparation of diazonium salt & its
chemical reactions
Important diazonium salt in synthesis of aromatic
compounds.
Amines
Solved Example:
Example 1.
Write chemical equations for the following reactions:
(i)
(i)
NH 3
2
SN
HCl
C 2 H 5NH2
C 2H 5 Cl
HCl
2
(SN )
(Ethylchloride) (Ethylamine)
C 2 H 5 NH
C 2 H5
(N-Ethylethanamine)
C H Cl
2 5
C 2 H 5 NC 2 H5
C 2 H 5 NH
HCl
2
(SN )
C2H 5
C 2H 5
(N-Ethylethanamine)
(N,N-Diethylethanamine)
C 6 H 5CH2 Cl
(ii)
NH 3
HCl
(SN1)
Benzylchloride
C 6H 5 CH 2NH2
Benzylamine
CH 3Cl
HCl
(SN 2 )
C 6 H 5CH2NCH 3
H
N-methylphenyl
methanamine
CH Cl
C 6 H5 CH 2 N CH 3 3
C 6 H5 CH 2 N CH 3
HCl
H
2
CH 3
(SN )
N-methylphenyl
N,N-Dimethylphenyl
methanamine
methanamine
Example 2.
Write chemical equations for the following conversions:
(i)
227
Amines
Strategy.
(i)
CH 3CH2 Cl
(ii)
KCN
2
SN
LiAlH
4
CH 3 CH 2 C N Reduction
CH3 CH 2 CH 2 NH2
C 6 H5 CH2 Cl KCN
C 6 H 5 CH 2 C
2
SN
H 2/Ni
C 6H 5 CH2 CH 2 NH 2
Example 3.
Write structures and IUPAC names of
(i)
(ii)
C NH 2 Br2 /NaOH
Benzamide
NH 2
Aniline
Ph C N H OH Ph C NH
Br Br
Ph C N Br OH
H
H
O
Ph NH 2
228
H 2O
Ph N = C = O
Ph C N Br
Amines
Example 4.
Arra nge the following in decreasing order of their basic
strength:
C 6 H 5NH2 , C 2 H 5 NH 2 , (C 2 H 5 )2 NH, NH3
Strategy.
Basic strength depends upon the availability of electron pair
on nitrogen atom. More the available electron, more the basic
molecule will be. So basic strength of following compounds
follows.
NH 2
CH 3 CH2 N H > CH 3 CH 2 NH 2 > NH 3 >
2+I
CH 2 CH 3
+I
Resonance
Example 5.
How will you convert 4-nitrotoluene to 2-bromobenzoic acid ?
Strategy.
COOH
Br
CH 3
?
NO 2
CH 3
Br2
CH 3
CH3
CH 3
Br NaNO2 /HCl
Br H 3PO 2
Br Sn /HCl
05C
NO 2
NO 2
step I
step II
NH 2
step III
N 2 Cl
step IV
CH 3
COOH
KMnO
/OH
Br
Br
4
step V
229
Amines
Note step I is bromination which is govern by CH3 group.
It is because of the reason that in disubstituted benzene when
one group is EDG & other is EWG, the EDG will decide the
position of incomming electrophile.
Step II is reduction which convert NO 2 into NH2 .
Step III is diazotization which convert NH2 into N 2 Cl.
Step IV is removal of N 2 .
Step V is oxidation.
230
Amines
Intext Problem:
Intext Question 1.
Classify the following amines as primary, secondary or tertiary:
N(CH 3 )2
NH 2
(i)
(ii)
(iii) (C 2 H 5 )2 CHNH 2
(iv) (C 6H 5 )2 NH
Strategy.
So,
NH 2
(i)
H3 C N CH 3
3 amine
H
(iii) CH 3CH2 C NH 2 1amine (iv) CH 3 CH 2 NH 2 amine
CH 2 CH 3
CH2 CH 3
Intext Question 2.
(i)
231
Amines
Strategy.
(i)
NH 2
NH 2
II
I
NH 2
III
IV
NH 2 (1 amines)
VI
H
N
VII
(ii) I
N
(2 amines)
VIII
Butan -1-amine
II
Butan-2-amine
III
2-Methylprop-1-amine
IV
2-Methylprop-2-amine
N-Methylpropan-1-amine
VI
N-methylproan-2-amine
(3 amines)
VII =
N-Ethylethanamine
VIII =
N,N-Dimethylethanamine
232
Amines
Intext Question 3.
How will you convert
(i)
(i)
Benzene
Aniline
NO 2
HNO 3 / H 2 SO 4
Nitration
NH 2
Sn/HCl
reduction
H3 C N CH3
?
(ii)
Benzene
N,N-Dimethylaniline
NO 2
HNO 3 /H 2 SO 4
NH 2
Sn/HCl
reduction
Nitration
CH 3I
1 eq
NH2
H 2N
(Hexane-1,6-Diamines)
(iii) Cl (CH ) Cl
2 4
Cl (CH 2 )4 Cl
CH 3I
(1 eq)
HNCH 3 H3 CNCH 3
KCN
LiAlH
4
NC (CH 2 )4 CN reduction
H 2 N CH 2 (CH 2 )4 CH 2 NH 2
233
Amines
Intext Question 4.
Arrange the following in increasing order of their basic strength:
(i) C 2 H 5 NH 2 , C 6 H5 NH 2 , NH 3 , C 6H 5 CH 2 NH 2 and (C 2 H 5 )2 NH
(ii) C 2 H 5 NH 2 , (C 2 H 5 )2 NH, (C 2 H 5 )3 N,C 6 H 5NH 2
(iii) CH3 NH 2 , (CH 3 )2 NH, (CH3 )3 N,C 6 H 5 NH 2 , C 6H 5 CH 2 NH 2 .
Strategy.
CH 2 NH 2
NH 2
< NH 3<
(i)
NH 2
CH 2 CH 3
(ii)
CH 2 CH 3
< CH 3 CH 2 NH
NH 2
CH 2NH2
<
(iii)
CH3
< CH3 N < CH 3 NH 2 < CH 3 N H
CH3
CH 3
Intext Question 5.
Complete the following acid-ba se reactions and name the
products:
(i)
CH 3 CH 2 CH 2 NH 2 +HCl
(ii) (C 2 H5 )3 N + HCl
Strategy.
(i)
CH 3 CH 2 CH 2 NH 3Cl
(ii)
234
(C 2H 5 )3 N + HCl
CH3 CH 2 N CH 2 CH 3 Cl
CH2 CH3
Amines
Intext Question 6.
Write reactions of the final alkylation product of aniline with
excess of methyl iodide in the presence of sodium carbonate
solution.
Strategy.
CH3 I
+
H 3 C N CH3
NH2
CH 3 I(excess)
HI
NH2
CH 3 I
HI
CH I
NCH3CH 3 I
CH3
NCH3 3
HI
H
CH3
+
NCH3 I
CH3
Intext Question 7.
Write chemical reaction of aniline with benzoyl chloride and
write the name of the product obtained.
Strategy.
NH 2
O
Cl
Aniline Benzoylchloride
O
Cl
+ H2 N
HCl
N
H
N-phenylbenzenecarboxylate
235
Amines
Intext Question 8.
Write structures of different isomers corresponding to the
molecular formula, C 3 H9 N. Write IUPAC names of the isomers
which will liberate nitrogen gas on treatment with nitrous acid.
Strategy.
Isomers of C 3 H 9 N
2C + 2 - H + N
= O System is saturated with only
2
single bonds without ring. So
DU =
NH2 ,
1 Amines are
NH 2
H CH 3
H
2 amine is
3 amine is CH 3 N CH 3
CH 3
1 amines librate N 2 gas on treatment with HNO 2 . So they
are
(a) propan-1-amine
(b) propan-2-amine
Intext Question 9.
Convert
(i)
Convertion
NH2
CH 3
?
NO 2
CH 3
3-Methylaniline 3-Nitrotoluene
236
Amines
N2 Cl
NH 2
NaNO 2 / HCl
CH 3
KNO 2
05C
NH 2
NO 2
CH3
Br
CH 3
Br
(ii)
Br
1,3,5-Tribromobenzene
Aniline
NH2
Br
Br2
NH 2
N 2 Cl
Br H PO Br
Br NaNO 2 Br
3
2
H2 O
Br
HCl
Br
Br
Br
237
Amines
Exercise Problems:
Exercise Problem 1.
Write IUPAC names of the following compounds and classify
them into primary, secondary and tertiary amines.
(i)
(CH3 )2 CHNH 2
(v) C 6 H 5NHCH3
Structure
1 amine
1 amine
N-Methyl
propan-2-amine
2 amine
CH 3 CH NH 2
CH 3
(iii) CH 3 N CH CH 3
H CH3
CH 3
(iv) CH 3 C NH 2
CH 3
(v)
N CH 3
H
238
2-Methyl
propan-2-amine
1 amine
N-Methylaniline
2 amine
N-Ethyl-N-methyl 3 amine
ethanamine
3-Bromoaniline
1 amine
Amines
Exercise Problem 2.
Give one chemical test to distinguish between the following
pairs of compounds.
(i)
CH 3 NH2 & CH 3 N H
CH 3
Methylamine librate N 2 gas on treatment with nitrous acid but
dimethylamine does not, because it is a test of primary amine.
239
Amines
(v) Aniline & N-methylaniline
Aniline on reaction with NaNO 2 /HCl at low temperature
followed by a ddition of -naphthol give red dye but Nmethylanilinc give yellow oily drop of nitroso compounds with
treatment with NaNO2/HCl.
Exercise Problem 3.
Account for the following :
(i)
NH
H
240
(Resonance stabilization of
negative charge)
Amines
+
CH 3 NH2 H CH3 NH2 (Inductive effect destabilize
negative charge)
O H
H
..
CH3 N H 3 OH
CH 3 NH2 + H OH
FeCl 3
Fe3 3Cl
2 Fe 3 6 OH
2 Fe(OH)3 or
Fe 2 O3 .3 H2 O
Hydrated ferric oxide
(brown ppt)
NH2
NH 3
HNO 3 /H 2 SO4
NO 2
NH3
NH 2
H
NO 2
NO 2
(v) Aniline react with lewis acids such as FeCl 3 , AlCl 3 to form
a complex which deactivate the benzene ring. So this
deactivated benzene ring do not give Friedel-craft reaction.
NH 2 +AlCl 3
H Cl
+
N Al Cl
H Cl
Complex formation
241
Amines
(vi) Gabriel phthalimide synthesis is very useful method for
the synthesis of pure primary amine. Here phthalimide is
first converted into potassium salt which on heating with
alkyl halide, give N-alkylphthalimide which on hydrolysis
give primary amine is pure form.
O
NH
O
+ RI
EtOH/KOH
O
Phthalimide
NR
NK
Salt
O
N-alkylphthalimide
RNH 2 +
COOH
H2 O
COOH
1amine Phthalic acid
Exercise Problem 4.
Arrange the following:
(i)
242
Amines
Strategy.
Arrange the following
(i)
>
< H 3C NH 2 < CH 3 CH 2 N H
CH 2 CH 3
NH 2
NH2
<
(a)
NO 2
p-nitroaniline aniline
NH 2
(b)
<
CH3
p-toluidine
H N CH 3
<
CH 2 NH 2
<
243
Amines
(vi) Increasing order of solubility in water follows
NH2
< CH 3 CH2 N H < CH3 CH 2 NH 2
CH 2 CH 3
Exercise Problem 5.
How will you convert:
(i)
(ii)
(i)
CH 3 C OH
Ethanoic acid
O
CH 3COH
(ii)
NH 3/
CH 3 NH 2
Methanamine
O
Br2 /KOHa
CH 3CNH Hoffmann
CH 3NH 2
bromide
CN ?
CN H2 O/H+
NH 2
Partial
hydrolysis
Br2 /OH
NH 2 Hoffmann
bromamide
reaction
NH 2
244
Amines
(iii) CH 3 OH
Methanol
CH 3 OH
O
CH 3 C OH
Ethanoic acid
HI
CH 3 I
(iv) CH 3 CH 2 NH2
Ethanamine
(v)
Br2 /NaOH
O
CH 3 C OH
Ethanoic acid
H 2O
CH 3 CN H+ CH 3 C OH
CH 3 NH 2
Methanamine
NaNO2 /HCl
H 2O /
CH 3 CH 2 NH2
CH 3 NH 2
KCN
CH 3 CH 2 OH
KMnO 4 /H +
O
O
NH 3 /
CH 3 C NH2
CH 3 C OH
O
CH 3 CH2 C OH
Propanoic acid
O
LiAlH 4
KCN
HI
CH 3 CH2 I
CH 3 C OH
CH 3 CH2 OH
O
+
H 2O / H
CH 3 CH2 CN
CH 3 CH 2 C OH
?
(vi) CH 3 NH2
Methanamine
CH3NH 2
NaNO 2
HCl
CH 3 CH 2 NH2
Ethanamine
CH 3Cl
KCN
CH 3 CN
CH 3 CH 2 NH2
LiAlH 4
H 2O
H+
O
CH 3 C OH
NH 3 /
O
CH 3 C NH 2
245
Amines
(vii) CH3 NO 2
Nitromethane
CH 3 N CH 3
H
Dimethylamine
CH I
3
CH 3 NO 2 Sn /HCl CH 3 NH2 (1 eq)
CH3 N CH 3
H
O
(viii) CH 3 CH2 C OH
Propanoic acid
O
CH 3 C OH
Ethanoic acid
Br2
NaOH
CH 3 CH 2 C OH CaO
CH 3 CH 3 h CH3 CH 2 Br
O
CH 3 C OH
KMnO 4 /H
KOH
CH 3 CH 2 OH
Exercise Problem 6.
Describe a method for the identification of primary, secondary
and tertiary amines. Also write chemical equa tions of the
reactions involved.
Strategy.
Primary, secondary & tertiary amines ca n be identified by
nitrous acid test.
A. Sample
NaNO 2 /HCl
B.
-naphthol
C.
Sample
NaNO 2 /HCl
246
Amines
D. Sample
NaNO 2 /HCl
No change/No reaction.
E.
Chemical reactions
(A) RNH2
(B) ArNH2
(C)
NaNO 2 /HCl
NaNO 2 /HCl
(R/Ar)2NH
RCl + N2
ArN2Cl
NaNO 2 / HCl
-naphthol
HO
N=N
R/ArNN=O
R/Ar
NR NaNO 2 /HCl R
N
R
R
Exercise Problem 7.
(D)
N=O
Carbylamine reaction
(ii) Diazotisation
(iii) Hofmanns bromamide reaction
(iv) Coupling reaction
(v) Ammonolysis
(vi) Acetylation
(vii) Gabriel phthalimide synthesis.
Strategy.
Short notes on
(A) Carbylamine reaction It is used to test primary amine
whether aliphatic or aromatic. When primary amine is
247
Amines
heated with chloroform in presence of KOH then
isocyanide is obtained, which have foul smell. This reaction
is called as carbylamine reaction.
R/Ar NH2
KOH /CHCl 3
R/Ar NC
(Isocyanide with foul smell)
NH 2
N 2 Cl
NaNO 2 / HCl
05C
Br2 /KOH
RNH2 + K 2 CO 3 + KBr + H 2O
Ph N 2Cl
P
NH 2
= 8 10
N=N
(Orange dye)
NH 2
N=N
(Yellow dye)
PhN 2Cl
P
248
HO
= 47
Amines
(E) Ammonolysis When alkyl halide is treated with NH3 ,
then cleavage of CX bond by ammonia take place. This
reaction is called as ammonolysis.
R
NH
RX HX3
RNH2
RX
(1Amine)
RNH
RX
RNR
RX
RNRX
R
R
R
(2Amine) (3Amine) (overall product)
or
O
R O C CH3
to decrea se the
acetylation.
O
NH 2
HN C CH3
CH 3 C Cl
OH
O
O C CH 3
CH 3 C Cl
249
Amines
by alka line hydrolysis give prima ry a mine. It ha s a
limita tion tha t a roma tic prima ry amine ca n not be
prepared by this reaction as no SN 2 reaction occur over
ArX.
O
O
EtOH
NH KOH
O
O
+R X
NK
SN
H O
2
NR NaOH
COONa
R NH 2 +
(1amine)
COONa
Exercise Problem 8.
Accomplish the following conversions:
(i)
250
Amines
NH2
NO 2
N 2 Cl
NaNO 2 /HCl
0-5C
Diazotization
Sn/HCl
(Reduction)
Nitrobenzene
KCN
Nucleophilic
Substitution
COOH
CN
H 2O / H +
Hydrolysis
Benzoic acid
NO 2
Br2 /AlCl 3
Nitration
Bromination
Br
Benzene
OH
Sn/HCl
Reduction
N2 Cl
KOH
Nucleophilic
substition
Br
m-bromophenol
NH2
NaNO /HCl
2
Diazotization
Br
Br
CONH 2
NH3 /
Benzoic acid
NH 2
Br2 /NaOH
Hoffmann bromamide reaction
251
Amines
(b) First convert benz oic a cid into benz ene by
decarboxylation & then take the help of nitration &
reduction.
NH 2
COOH
conc. H 2 SO 4 /HNO 3
CaO/NaOH
Decarboxylation
NH 2
Sn/HCl
Reduction
Nitration
Aniline
Benzoic acid
Br
Br2 / H 2O
NH 2
N 2 Cl
Br NaNO / HCl Br
Br
2
Diazotization
Bromination
Aniline
Br
Br
Br
Br NaBF /
4
Fluorination
Br
2,4,6-Tribromofluoro benzene
CH 2 Cl
KCN
SN 2
CH 2 CH 2 NH 2
H 2 / Ni
reduction
Benzyl chloride
2-Phenylethanamine
252
Amines
Cl
Cl
Cl
Chlorobenzene
Sn/HCl
Reduction
NO 2
NH 2
p-chloroaniline
NH 2
(CH 3CO)2 O
Nucleophilic
substitution
NHCOCH 3
Br2 /AlCl 3
Bromination
H 2O/H
hydrolysis
Br
p-Bromoaniline
Br
Aniline
NH 2
+
O
CH
C N
P2 O 5
Dehydration
Benzamide
DIBAL - H
Partial
Reduction
CH 3
Zn Hg / HCl
Clemmenson
reduction
Toluene
78C
Aniline
CN
KCN
Nucleophilic
substit ution
DIBAL-H
Partial reduction
78C
CH 2 OH
CHO
H 2 /Ni
reduction
Benzyl alcohol
253
Amines
Exercise Problem 9.
Give the structures of A, B and C in the following reactions:
(i)
OH
NaOH+Br
NaCN
2
CH3 CH 2 I
A
B
C
Partial hydrolysis
H O/H+
NH
CuCN
2
3
(ii) C 6 H 5N 2 Cl
A
B
C
LiAlH
HNO
KCN
4
2
(iii) CH3 CH 2 Br
A
B
C
0C
NaNO 2+HCl
H2O/H+
Fe/HCl
(iv) C 6 H 5NO2
A
C
273K
NH
NaNO /HCl
3
NaOBr
2
(v) CH3 COOH
A
B
HNO
C H OH
Fe/HCl
2
6 5
(vi) C 6 H 5NO 2
A
B
C
273K
Strategy.
(i) CH 3CH2 I
NaCN
SN
OH
CH3 CH 2 CN Partial
A
hydrolysis
CH 3CH2 NH 2
C
(ii)
C 6 H5 N 2 Cl
CuCN
Nucleophilic
substitution
O
CH 3 CH 2 C NH 2
B
Na OH /Br2
Hofmann bromamide
reaction
H O / H+
C 6 H5 CN 2
C 6 H 5 COOH
Hydrolysis
A
B
C 6 H 5 CONH2
C
NH 3
254
HNO 2
0C
Amines
(iv) C 6 H5 NO 2
Fe/HCl
reduction
C6 H5 NH 2
A
NaNO 2/HCl
273K
C6 H 5N 2 Cl
B
C 6 H 5OH
C
(v)
CH 3COOH
NH 3
H 2 O/H +
NaOBr
CH3 CONH2
Hoffmann
A
bromamide reaction
NaNO 2 /HCl
CH3 OH
C
CH 3 NH 2
B
HNO 2
(vi) C 6 H5 NO 2 Fe/HCl C 6H 5 NH 2
C 6 H5 N 2 Cl
reduction
273K
A
B
N=N
OH
C 6H 5OH
Diazo-coupling
reduction
Strategy.
Such type of questions can be done by first making an equation
from statement so that everything is visible by our eyes. The
equation for this statement will be
aq NH 3 /
A
Aromatic
Compound
Br2 / KOH
C6 H 7 N
C
Molecular
formula
255
Amines
The deciding reaction will be B to C a s it is a Hoffma nn
bromamide reaction i.e. conversion of amide into amine.
As A on treatment with NH3 give B (Amide) so A must be
carboxylic acid. So overall reaction will be
O
COH
C NH 2
NH 2
Br2 /KOH
aq NH 3 /
A
Benzene carboxylic
acid
(ii) C 6 H 5N 2 Cl + H 3 PO 2 + H 2 O
(iii) C 6 H 5NH2 + H 2 SO 4 (conc.)
(iv) C 6 H 5 N 2Cl + C 2 H5 OH
(v) C 6 H 5NH2 + Br2 (aq)
(vi) C 6 H 5NH2 + (CH 3CO)2 O
(i) HBF
(vii) C 6 H 5 N 2Cl
(ii) NaNO /Cu.
2
Strategy.
(i)
256
CHCl 3 / KOH
C 6 H 5NC
Iso-nitrile
Amines
(ii) C 6 H 5 N 2Cl +H 3 PO2 + H 2 O
C 6 H5 N 2 Cl
conc. H 2SO 4
(C 6 H5 NH 3 )2 SO 4
Br
NH 2
Br
Br
257
Amines
O
HNCCH 3
NH2
(CH 3 CO)2 O
N 2 BF4
N2 Cl
HBF4
NO 2
NaNO2/Cu/
O
+ RX
N K SN 2
O
ArX
NR
H 2 O/H +
RNH2
O
No reaction
258
Amines
Strategy.
Nitrous acid rea cts differently with a romatic & aliphatic
primary amine.
NH2
N2 Cl
HNO 2
NH2
OH
HNO 2
259
Amines
group in aliphatic amine donates electron density towards
nitrogen and increases the available e density by +I while
phenyl group is aroma tic a mine withdra ws electron
density from nitrogen by M, So aliphatic amines are more
basic than aromatic amines.
NH 2
NH 2
>
in basic strength.
260
Biomolecules
Unit
Biomolecules
261
Biomolecules
Objective
This unit give you an understanding of Biomolecules
and covers following topics:
262
Biomolecules
Intext Problem:
Intext Question 1.
Glucose or sucrose are soluble in water but cyclohexane or
benzene (simple six membered ring compounds) are insoluble
in water. Explain.
Strategy.
Solubility of any molecule in water depends on H-bonding with
water molecule & dipole moment. Greater is the extent of Hbonding or dipole moment, greater is the solubility in water.
Glucose & sucrose can form H-bonding with water molecule
hence soluble but cyclohexane & benzene are non-polar and do
not form H-bonding with water and hence insoluble in water.
Intext Question 2.
What are the expected products of hydrolysis of lactose?
Strategy.
La ctose is a disaccha ride formed by combina tion of two
monosaccharide units - D-Galactose & - D-Glucose. Hence
hydrolysis of lactose give its monosaccharides - D-Galactose
& - D-Glucose.
CH 2 OH
CH 2 OH
O
HOH
HO H
H H O OH
O
OH H H
H OH H H
H OH
-D-Galactose
CH2 OH
HO H O OH
H OH H H
H OH
-D-Galactose
H OH
-D-Glucose
Lactose
H2 O
CH 2 OH
H H O OH
HO OH H H
H OH
-D-Glucose
263
Biomolecules
Intext Question 3.
How do you explain the absence of aldehyde group in the
pentaacetate of D-glucose?
Strategy.
Free aldehyde group in any molecule react with hydroxylamine
to form oxime as a product but pentaacetate of D-glucose does
not react with hydroxylamine indicating the absence of free
aldehyde group.
CH2 OAc
O OAc
H H
AcO OAc H H
Hydroxylamin e
No reaction.
H
OAc
Penta acetate of D-Glucose
Intext Question 4.
COOH
R
NH 2
H
COO
R
NH 3
H
Zwitter ion
264
Biomolecules
Intext Question 5.
Where does the water present in the egg go after boiling the
egg?
Strategy.
This question is based on denaturation of protein i.e. when an
egg is boiled, its globular protein gets denatured and water
present in egg probably gets either absorbed or adsorbed during
this denaturation & gets disappears.
Intext Question 6.
Why cannot vitamin C be stored in our body?
Strategy.
This question is asked to check the knowledge of soluble &
insoluble a vitamines.
As Vitamic-C (Ascorbic acid) is water soluble so it is regularly
excreted in urine from the body and can not be stored.
Intext Question 7.
What products would be formed when a nucleotide from DNA
containing thymine is hydrolysed?
Strategy.
To solve such question, first think for the atta chment of
nitrogenous bases of DNA & RNA along with sugars.
When nucleotide from DNA is hydrolysed, it will give its sugar
component i.e. deoxyribose suga r; phosphoric a cid &
nitrogenous bases i.e. Guanine (G), Adenine (A), Thymine (T)
& cytosine (C).
Base
Sugar Phosphate
H2 O
+
n H
Nucleotide
265
Biomolecules
Intext Question 8.
When RNA is hydrolysed, there is no relationship among the
qua ntities of different bases obtained. What does this fact
suggest about the structure of RNA?
Strategy.
This question is to check the knowledge of single stranded
structure of RNA.
As we know that DNA molecules has a double strand structure
and four complementary nitrogenous bases paired with each
other.
Cytocine (C) pairs with Guanine (G) while Thymine (T) pairs
with Adenine (A).
Due to such pairing structure, DNA produces the products in
definite molar ratio.
But in case of RNA, base pairing is not observed, So RNA on
hydrolysis, different quantities of bases are observed.
This fact suggest about single stranded structure of RNA.
266
Biomolecules
Exercise Problems:
Exercise Problem 1.
What are monosaccharides?
Strategy.
Monosaccharides are the smallest unit of sugars which can
not be further hydrolysed. They have carbon ranges from C3
C7. On the basis of aldehydic or ketonic group present, they
are simply consider as aldose or ketose sugar of following types.
C 3
Triose
C 4
Tetrose
C 5
Pentose
C 6
Hexose
C 7
Heptose
Exercise Problem 2.
What are reducing sugars?
Strategy.
Reducing sugars are those sugars which have presence of either
aldehyde, ketone or hemiacetal linkage while non-reducing
sugars are those which have only acetal linkage in it.
All monosaccharides & disa ccha rides (except sucrose) are
reducing sugar.
In terms of chemical reaction, they reduces Fehling solution &
Tollens reagent.
Exercise Problem 3.
Write two main functions of carbohydrates in plants.
Strategy.
There are many functions of carbohydrates in plants but the 2
main functions are
(i)
267
Biomolecules
Exercise Problem 4.
Classify the following into monosaccharides and disaccharides.
Ribose, 2-deoxyribose, maltose, galactose, fructose and lactose.
Strategy.
As we know that monosaccharides are smallest unit of sugar
which can not hydrolysed but disa ccharide are simply the
compound formed by combination of 2 monosaccharide units.
Ribose, 2 -Deoxyribose, Ga la ctose & Fructose a re
monosaccharide while Maltose & Lactose are disaccharides.
O
HOH 2 C
H
OH
H
H
OH OH
Ribose
CH2 OH
HO H O OH
H OH H H
H OH
Galactose
HOH 2 C
H
OH
H
OH H
2-Deoxyribose
HOH 2 C
H HO
CH 2 OH
OH H
Fructose
HO
CH 2 OH
CH 2 OH
O
H H
H
H H O OH
O
OH H H (Maltose)
HO OH H
H OH
-D-Glucose
CH2 OH
HO H O
H OH H H
H OH
-D-Galactose
268
H OH
-D-Glucose
CH 2OH
H H O OH
(Lactose)
O
OH H H
H OH
-D-Glucose
Biomolecules
Exercise Problem 5.
What do you understand by the term glycosidic linkage?
Strategy.
Glycosidic linkage is simply the ether linkage between two
monosaccharide when combines to form disaccha ride or
polysaccharides.
CH2 OH
H H O H
HO OH H
HOH2 C
O
H HO
CH 2 OH
OH
H
H OH
-D-Fructose
-D-Glucose
Glycosidic linkage
(Sucrose)
Exercise Problem 6.
What is glycogen? How is it different from starch?
Strategy.
Glycosen is a polysaccharide or simply the carbohydrate which
is stored in animal body. It is generally stored in liver, muscle
& brain. When body needs glucose, enzymes break down the
glycogen to glucose. On the other ha nd, sta rch is a
polysaccha ride which is stored in plants. It consists of two
components i.e. amylose & amylopectin. Amylose is water
soluble component and makes nearly 15-20% part of starch
while amylopectin is water insoluble component & ma kes
nearly 80-85% part of starch.
Exercise Problem 7.
What are the hydrolysis products of
(i)
sucrose and
(ii) lactose?
Strategy.
To solve such question, you must know the structure of sucrose
& lactose.
269
Biomolecules
CH 2OH
H H O H HOH 2C O H
H HO
O
CH 2 OH
HO OH H
OH H
H OH
-D-Fructose
-D-Glucose
(Sucrose)
+
H O
2
H
CH2 OH
H H O H
HOH2 C O OH
+
H HO
HO OH H OH
HO
CH 2 OH
OH H
H OH
-D-Glucose
-D-Fructose
CH2 OH
CH2 OH
O OH
HO H O
NH
O
OH H H
H OH H H
H OH
-D-Galactose
H OH
-D-Glucose
H2 O H +
CH 2OH
CH 2 OH
HO H O OH
H H O OH
+
H OH H H
HO OH H H
H OH
-D-Galactose
H OH
-D-Glucose
Exercise Problem 8.
What is the basic structural difference between starch and
cellulose?
Strategy.
The basic structural difference between starch & cellulose is
seen in nature of glucose molecules.
270
Biomolecules
Starch consists of amylose & amylopectin, which are made up
of -D-Glucose unit. Here amylose unit consist of linear chains
of glucose linked in C1C4 manner wheras amylopectin consists
of these linear chains further linked in C1C6 manner.
Cellulose consist of only -D-Glucose molecules that are linked
to each other in C1C4 manner.
CH 2 OH
CH2 OH
CH 2 OH
O
O
O H
H H
H
H 5
H
H
H
H
4
1
4
1
4
1
O OH H
O
O
OH H
OH H O
H
OH
-Link
OH
OH
-Link
Amylose
CH 2 OH
CH2 OH
O
O H
H H
H
H
H
4
1
4
1
O OH H
O
OH H
H
OH
OH
O
-Link
Branch at C 6
CH2 OH
CH2
CH 2 OH
O
O
H H
H
H 5
H
H H O H
H
4
1
4
1
4
1
O OH H
O
O
OH H
OH H O
H
OH
H
H OH
-Link
-Link
Amylopectin
OH
271
Biomolecules
HOH2 C
HOH 2 C
HOH 2 C
H
O OH
O O
O O OH
O O OH
OH
OH
OH
-links
Cellulose
Exercise Problem 9.
What happens when D-glucose is treated with the following
reagents?
(i)
HI
Strategy.
(i)
H
HO
H
H
272
Bromine w ater
COOH
OH
H
OH
OH
CH2 OH
Gluconic acid
H
HO
H
H
Biomolecules
(iii) HNO3 is a strong oxidising agent which convert aldehyde
as well as CH2OH group into carboxylic acid.
CHO
OH
H
OH
OH
CH2 OH
D-Glucose
H
HO
H
H
HNO 3
COOH
OH
H
OH
OH
COOH
Glucaric acid
H
HO
H
H
2,4DNP
Glucose
Ve
Schiff base
(ii) Glucose
Ve
NaHCO
2
(iv) Pentaacetate of glucose
No reaction.
273
Biomolecules
i.e. from diet. Out of 20 naturally occuring amino-acids, 10 are
essential amino acids. They are
(i)
Valine
(ii)
Leucine
(iii) Isoleucine
(iv) Arginine
(v) Lysine
(vi) Threonine
(vii) Methionine
(viii) Phenylalanine
(ix) Tryptophan
(x)
Histidine
Glycine
(ii)
Alanine
(iii) Glutamine
(vi) Asparagine
(vii) Serine
(viii) Cysteine
(ix) Tyrosine
(x)
Proline
Peptide linkage
(iii) Denaturation.
Strategy.
(i)
H O
H O
H2 N
C OH + H N
COH
R
H R'
Amino acid(I)
Amino acid(II)
H O
H O
H 2N
CN
COH
R
H R'
Peptide linkage
274
Biomolecules
(ii) Primary structure:- Every polypeptide in a protein has
amino acids linked with each other in a specific sequence
and this sequence of amino a cid is called as prima ry
structure of that perticular protein. Any change in primary
structure of protein creates different protein.
(iii) De na turation:- When a protein in its native form is
subjected to physica l cha nge such a s cha nge in
temperature, or some chemical change such as change in
pH, the hydrogen bond present in the secondary structure
of protein get disturbed. Due to this change the protein
globules gets unfold and helix get uncoiled and protein
loses its biological activity. This loss of biological activity
of protein is called as denaturation of protein.
In this denaturation, secondary & tertiary structures of protein
gets destroyed but the primary structure of protein remains as
such.
Some common examples of denaturation of protein is the
coagulation of egg on heating & curdling of milk.
Exercise Problem 13.
What are the common types of secondary structure of proteins?
Strategy.
This
question
is
ba sed
on
understa nding
of
(i)
possible
- helix hydrogen bonds by twisting into a right handed
screw i.e. helix with the -NH- group of each amino acid
reside hydrogen bonded to CO of an adjacent turn of
the helix.
275
Biomolecules
This structure resembles the pleated fold of drapery, so is called
as -pleated sheet.
Exercise Problem 14.
What type of bonding helps in stabilising the -helix structure
of proteins?
Strategy.
The -helix structure of protein is stabilized by intramolecular
hydrogen bonding between CO & NH group of different
peptide bonds.
O
...
...
...
H O
..
N
C
...
O
..
N
..
.
HO
.. C.
.. O..
C N
H
O
...
N
..
H
N
..
C
276
Biomolecules
Strategy.
Differentiation between globular proteins & Fibrous proteins
are as follows:
SN.
Globular proteins
Fibrous proteins
1. In th i s pr ote in s , po ly
pe pt ide s chains are
arranged as a coils.
2. Globula r protei ns h ave
spherical shape.
COH
..
NH 2
H
COO
R
NH 3
H
Zwitter ion
277
Biomolecules
reactions occurring in the living organism.
All enzymes are proteins and made up of amino acids only.
On the basis of its functions, it is of 2 types
(A) Endoenzymes- They have intracellular function.
(B) Exoenzymes- They have extracellular function.
Enzymes may be made up of only amino acids but can also be
associated with a non-proteinous part. In that case it is called
as coenzyme.
Exercise Problem 18.
What is the effect of denaturation on the structure of proteins?
Strategy.
During the denaturation of a protein, its secondary & tertiary
structures are destroyed but primary structures remains intact.
During this process, globular proteins are converted into fibrous
protein and biological activity of the protein is lost.
Exercise Problem 19.
How are vitamins classified? Name the vitamin responsible for
the coagulation of blood.
Strategy.
Vitamins are cla ssified into 2 groups on the ba sis of their
solubility in water or fat.
(i)
(ii) Fat soluble vitamins- These vitamins are soluble in fats &
insoluble in water. Fat soluble vitamins are vitamins A, D,
E & K.
The vitamin responsible for the coagula tion of blood is
vitamin K.
Exercise Problem 20.
Why are vitamin A and vitamin C essential to us? Give their
important sources.
278
Biomolecules
Strategy.
All vitamins are essential for us as they protect us from different
diseases. Every vitamin is specific in it function.
Deficiency of vitamin A cause Xerophthalmia or nightblindness while deficiency of vitamin C cause scurry or
bleeding of gums.
The main source of vitamin A is fish liver oil, carrots,
butter & milk while main source of vitamin C is citrus
fruits, amla & green leafy vegetables.
Exercise Problem 21.
What are nucleic acids? Mention their two important functions.
Strategy.
Nucleic acids are the biomolecules which are found in the nuclei
of living orga nisms in the form of nucleoproteins or
chromosomes.
Nucleic acids are of 2 types.
(A) DNA (Deoxyribonucleic acid)
(B) RNA (Ribonucleic acid)
The two important functions of nucleic acids are
(i) DNA, due to its replica tion property, tra nsmits
hereditary cha ra cteristics from one genera tion to
another.
(ii) DNA & RNA help in the protein synthesis in the cell.
RNA synthesises the protein and DNA has the message
for this synthesis.
Exercise Problem 22.
What is the difference between a nucleoside and a nucleotide?
Strategy.
The main difference between nucleoside and a nucleotide are
as follows:
279
Biomolecules
Nucleoside
SN.
1. Nucleoside is combination
of nitrogenous base & sugar
unit.
2. 4 nucleosides are
(A) Adenosine =
Adenine + ribose
(B) Guanosine =
Guanine + ribose
(C) Cytidine =
Cytosine + ribose
(D) Deoxythymide =
Thymine + Deoxyribose
3. The structure of nucleoside
is
HOH 2 C O Base
H
H
H
OH OH
Nucleotide
Nucleotide is combination of
nitrogenous base, sugar unit
& phosphoric acid.
4 nucleotides are
(A) Adenylic acid =
Adenosine + H3PO4
(B) Guanylic acid =
Guanosine + H3PO4
(C) Cytidylic acid =
Cytidine + H3PO4
(D) Uridylic acid =
Uridine + H3PO4
The structure of nucleotide is
O
OPOCH 2 O Base
O
H H
H
H
OH OH
280
Biomolecules
281
Biomolecules
SN.
DNA
RNA
Structural difference
1. The pentose sugar present in
The pentose sugar present
DNA is deoxyribose.
in RNA is ribose
2. Pyrimidine base present in
DNA is cytosine & thymine.
4.
Functional difference
1. It has a unique property of
replication.
It has no property of
replication.
It controls protein
synthesis.
282
Polymers
Unit
Polymers
283
Polymers
Objective
This unit give you an understanding of Polymers and
covers following topics:
284
Classification of polymers.
Types of polymerization reactions.
Molecular mass of polymers.
Biodegradable polymers.
Polymers of commercial importance.
Polymers
Solved Example:
Example 1.
CHCH(C 6 H 5 ) is a homopolymer or a copolymer?
n
Strategy.
CHCH(C 6 H 5 ) is a homopolymer of styrene.
n
285
Polymers
Intext Problem:
Intext Question 1.
What are polymers ?
Strategy.
Polymer is a compound of la rge molecules ha ving high
molecular mass. It is formed by joining small repeating units of
small basic unit, monomer by the process of polymerization.
Ex- Polythene, Polystyrene etc.
Intext Question 2.
How are polymers classified on the basis of structure?
Strategy.
On the basis of structures, polymers are classified into 3 classes.
(A) Line ar polymer- They a re high density polythenes,
polyvinyl chloride etc.
(B) Bra nche d cha in polyme r- They ha ve low density
polythene.
(C) Cross-linked or network polymers- bakelite & melamines
etc.
Intext Question 3.
Write the names of monomers of the following polymers:
H
(i)
(ii)
N(CH2 )6 N
O
C(CH 2 )4 C
n
C (CH 2 )5 N
n
(iii) CF CF
2
2
n
Strategy.
To solve such question look over the linkage & then make the
monomer unit.
286
Polymers
(i)
N(CH 2 )6 N
H
O
H 2O
C(CH 2 )4 C
OH
n
H2 N(CH 2 )6 NH 2+
Hexane-1,6-diamine
(ii)
C (CH 2 )5 N
n
O
H2 O
HO C (CH 2 )5 NH2
6-Aminohexanoic acid
CF2 =CF2
(Tetrafluoroethene)
Intext Question 4.
Classify the following as addition and condensation polymers:
Terylene, Bakelite, Polyvinyl chloride, Polythene.
Strategy.
Addition polymers are obta ined from polymerisa tion of
unsaturated monomers while condensation polymers a re
obtained from condensing the monomer units conta ining
287
Polymers
functional group by removing some neutral molecules such as
H2O, CH3OH etc.
Addition polymer- Polyvinyl chloride & Polythenes
Condensation polymer- Terylene, Bakelite
Intext Question 5.
Explain the difference between Buna-N and Buna-S.
Strategy.
Buna-N & Buna-S are synthetic rubber & are copolymer formed
by adding 2 monomer units. The difference in both these
copolymer lies in their composition.
Buna-N is formed by polymerisa tion of Buta-1 ,3-diene &
acrylonitrile while Buna-S are formed by polymerisation of Buta1,3-diene & styrene.
CN
n CH2 =CHCH=CH 2 + n CH 2 =CH
CN
CH 2 CH=CHCH 2 CH2 CH
n
Buna-N
Ph
n CH2 =CHCH=CH 2 + n CH 2 =CH
Ph
Intext Question 6.
CH 2 CH=CHCH 2 CH2 CH
n
Buna-S
288
Polymers
Eastomer < Plastics > Fibres.
So first classify the given polymer into the above classes & then
arrange them in increasing order of force. So increasing order
of their intermolecular forces follow.
(i)
289
Polymers
Exercise Problems:
Exercise Problem 1.
Explain the terms polymer and monomer.
Strategy.
Polymers are the compound of large molecules having high
molecular mass. They are formed by joining small repeating
units of small units which are called as monomers, by the
process called as polymerization.
n CH 2 =CH 2 Polymerisation
Ethene
(Monomer unit)
CH 2 CH2
n
Polythene
(Polymer)
Exercise Problem 2.
What are natural and synthetic polymers? Give two examples
of each type.
Strategy.
Natural polymer- They are those polymers which are found
in anima ls & plants. They are also called as bio-polymers.
Examples are- Starch, Cellulose, Proteins etc.
Synthe tic polyme r- They are those polymers which are
synthesized with the help of chemicals in industries. They are
also called as men-made polymer. Examples are- Polythenes,
Nylon-6,6, Nylon-6 etc.
Exercise Problem 3.
Distinguish between the terms homopolymer and copolymer
and give an example of each.
Strategy.
Homopolymer- They are those polymer in which a single type
of monomer is used. Example- Polythene, Polystyrene etc.
Copolymer- They are those polymer in which more than on
monomers are used. Example- Buna-N, Buna-S etc.
290
Polymers
Exercise Problem 4.
How do you explain the functionality of a monomer?
Strategy.
Functionality of a monomer means the number of bonding sites
present in it. i.e. functionality of ethene, Propene, Styrene is
one and that of ethylene glycol, adipic acid & hexamethylene
diamine is two.
CH 2 =CH 2
H 2 NCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 NH2
(one)
(two)
Exercise Problem 5.
Define the term polymerisation.
Strategy.
Polymeriz ation is the process of formation of polymers by
joining several monomer units by covalent bond.
n CH 2 =CH 2 Polymerization
Ethene
(Monomer)
CH 2 CH2
n
Polythene
(Polymer)
Exercise Problem 6.
Is (NH-CHR-CO)n , a homopolymer or copolymer?
Strategy.
NHCHRCO is a homopolymer as it has single monomer
n
unit of H 2 NCHRCOOH
R
NCHC
H
n
(Polymer)
R
H2 O
H2 NCHCOOH
(monomer)
Amino acid
291
Polymers
Exercise Problem 7.
In which classes, the polymers are classified on the basis of
molecular forces?
Strategy.
On the basis of intermolecular forces, polymers are classified
into mainly four classes.
(A) Elastomers
(B) Fibres
Exercise Problem 8.
How can you differentiate between addition and condensation
polymerisation?
Strategy.
The differentiation between a ddition & condensa tion
polymerisation are as follows.
SN. Addition polymerization Condensation polymerization
1. In this polymerization,
monomer units have a
double bond or triple bond
in their molecule. These
re pre sent s t he ir
functionality.
2. Addition polymerization
is generally chain growth
poly meri za tio n a s
monomer units combines
c o n t i n o u s l y w i t h o ut
loosing anything.
In t h is po l ym eri z a tio n ,
monomer units have specific
fun c tio n al g rou p wh ic h
represent their functionality.
Condensation polymerization
is generally step growth
p olym eri za tio n as so me
molecules such as water,
alcohol continously removes
at each step of growth of
poymer.
3. E x a mp l e o f a dd i t i on Example of condensation
p o l y m e r i z a t i o n i s polymerization is terylene,
polythenes, polystyrenes nylon-6 etc.
etc.
292
Polymers
Exercise Problem 9.
Explain the term copolymerisation and give two examples.
Strategy.
Copolymerization- It is the polymerization reaction in which
more than one monomer units polymerize to form a copolymer.
The two most common examples are
(A) Buna-N:- It is a copolymer formed by the copolymerization
of two monomers- Buta-1,3-diene & acrylonitrile.
CN
CH 2 =CHCH=CH 2 + CH 2 =CH
Buta-1,3-diene Acrylonitrile
CN
CH 2 CH=CHCH 2 CH2 CH
n
Buna-N
(B) Buna-S:- It is a copolymer formed by the copolymerization
of two monomers- Buta-1,3-diene & styrene.
Ph
CH 2 =CHCH=CH 2 + CH 2 =CH
Buta-1,3-diene
Styrene
Ph
CH 2 CH=CHCH 2 CH2 CH
n
Buna-S
293
Polymers
General reaction:
CH 2 =CH2
ethene
(PhCO)2O 2
CH2 =CH 2
Polythene
Mechanism:
(A) Chain initia tion ste p- In this step free radicals are
generated from benzoyl peroxide.
O
..
PhCO
. . .
OCPh
2 Ph
CO
2 Ph + 2 CO 2
Ph + CH 2 =CH 2
PhCH 2 CH 2
PhCH 2 CH 2 + CH 2 =CH 2
PhCH2 CH 2 CH2 CH 2
(C) Chain termination step- In this step, all the free radicals
formed, combines together to form neutral molecules.
. .
.
Ph + Ph
Ph Ph
PhCH 2 CH 2 + PhCH2 CH 2
PhCH 2 CH 2 CH2 CH 2 Ph
294
Polymers
Examples are polythenes, polyvinyl chloride, polystyrene etc.
Thermosetting polymers- Those polymers which on heating
do not soften and can not be remoulded are called thermosetting
polymers.
On heating they undergo extensive cross-linking in moulds and
becomes infusible.
Examples are bakelite, Urea-formaldehyde resins etc.
Exercise Problem 12.
Write the monomers used for getting the following polymers.
(i)
Polyvinyl chloride
(ii) Teflon
(iii) Bakelite
Strategy.
(i)
COOC
(Benzoyl peroxide)
Exercise Problem 14.
295
Polymers
CH3
CH 3
CH 2 =CCH=CH 2 + CH 2 =CCH=CH 2
1
2 3
4
(2-Methylbuta-1,3-diene)
CH 3
CH2 C=CHCH 2
n
1
2 3 4
(Natural rubber)
296
Polymers
Strategy.
(i)
Styrene
CH2 = CH CN
Acrylonitrile
CH 2 CH2
HOC
OH OH
Ethylene glycol
O
COH
Terephthalic acid
(i)
C(CH 2 )8 C
NH(CH 2 )6 NH
n
297
Polymers
NH
(ii)
NH CH 2
N
NH
Strategy.
(i)
O
O
C(CH 2 )8 C
NH(CH2 )6 NH
n
HO H
Polymer
HO C(CH 2 )8 COH
+
H2 N(CH 2 )6 NH 2
NH
H OH
N NH CH 2
N N
H 2O
NH
O
H 2 N N NH 2
+ HCH
N N
NH (Formaldehyde)
2
(Melamine)
298
Polymers
Strategy.
Dacron is formed by the condensation polymerization of glycol
& terephthalic acid. During this condensation, a molecule of
water goes out at each step growth of polymer.
This polymeriz a tion rea ction ta ke pla ce a t 4 2 0 -4 6 0 K
temperature in presence of Zinc acetate antimony trioxide as a
catalyst.
O
COH
n HOCH2 CH 2 OH + HOC
Ethylene glycol
Terephthalic acid
420460 K
(CH 3COO)2 Zn/Sb 2O 3
O
OCH 2 CH2 OC
Dacron
O
C + H2 O
n
299
Polymers
CH 3
CH 2 CH 3
n HOCHCH 2 COOH
3-Hydroxybutanoic acid
+ n HOCHCH 2 COOH
3-Hydroxypentanoic acid
Polymerization
CH3
CH 2 CH3 O
O CH CH2 C O CH CH 2 C + H2 O
PHBV
n
300
Unit
301
Objective
This unit give you an understanding of Chemistry in
everyday life and covers following topics:
302
Intext Problem:
Intext Question 1.
Sleeping pills a re recommended by doctors to the patients
suffering from sleeplessness but it is not advisable to take its
doses without consultation with the doctor. Why ?
Strategy.
Sleeping pills contains drug that may be anti-depressant or may
be transquilizer so they may affect the nervous system of body
or may creat anxiety, stress, irritability or excitement. So they
must strictly used under the supervision of a doctor. If not,
then uncontrolled & over dosage can cause harm to the body
and mind because in higher doses they acts as a poisons for
body.
Intext Question 2.
With reference to which classifica tion has the statement,
ranitidine is an antacid been given?
Strategy.
This statement refers to the classification of drugs according to
pharmacological effect because it may neutralize the acidity of
stomach.
Intext Question 3.
Why do we require artificial sweetening agents ?
Strategy.
Natural sweetners such as sucrose & glucose provides calories
to the body. These extra calories are ha rmful for diabetic
patients, so a artificial sweetener are used to control intake of
calories & act as a substitute of sugar for diabetics.
Intext Question 4.
Write the chemical equation for preparing sodium soap from
glyceryl oleate and glyceryl palmitate. Structural formulae of
these compounds are given below.
(i)
303
CH 2 OCOC 15 H 31
CH2 OH
3 NaOH/
CHOC 15 H 31
CH 2 OCOC 15 H 31
Glyceryl palmitate
(ii)
3 C 15 H 31COONa + CHOH
Sodium palmitate CH OH
2
(soap)
Glycerol
CH 2 OCOC 17 H 33
CHOCOC 17 H 33
CH2 OH
3 NaOH/
CH 2 OCOC 17 H 33
3 C 17 H 33 COONa + CHOH
Sodium oleate CH OH
2
(soap)
Glycerol
Intext Question 5.
Following type of non-ionic detergents are present in liquid
detergents emulsifying agents and wetting agents. Label the
hydrophilic and hydrophobic parts in the molecule. Identify
the functional group(s) present in the molecule.
C 9 H19
O (CH 2 CH 2O )x CH 2 CH 2 OH
(x = 5 to 10)
Strategy.
Hydrophobic part in non-pola r part in the molecule while
hydrophilic part is that which creats polarity and is responsible
for hydrogen bonding with water.
C 9 H19
O (CH 2 CH 2 O)x CH 2 CH 2 OH
Hydrophobic part
Hydrophilic part
304
Exercise Problems:
Exercise Problem 1.
Why do we need to classify drugs in different ways ?
Strategy.
Drugs are generally the complex organic molecules so different
types of classification to it is beneficial for the people related to
different fields. Knowing pharmacological effect makes it easy
for doctors to remember their name.
It also makes the correct medicine available to the patient as
first aid such as an antacid, can be used in case of excessive
acidity in stomach.
In the same way, other types of classification helps the scientist,
drug manufacturers, students, chemist etc to remember their
name.
Exercise Problem 2.
Explain the term, target molecules or drug targets as used in
medicinal chemistry.
Strategy.
Targe t mole cule s or drug ta rget- Drugs interact with
biomolecules present in our body such a s proteins,
ca rbohydra tes, lipids & nucleic a cid a nd hence these
biomolecules are called as target molecule or drug target.
Drugs possessing some common structural features may have
the same mechanism of action on target.
Exercise Problem 3.
Name the macromolecules that are chosen as drug targets.
Strategy.
Biomolecules present in the body are the drug targets such as
proteins, carbohydrates, lipids, nucleic acids, enzymes etc.
Exercise Problem 4.
Why should not medicines be taken without consulting doctors ?
305
306
307
308
309
NH 2 O
N
H
Alitame O
OH
Cationic detergents
310
CH 3
CH 3 CH CH 2 CH
SO 3Na
ABS detergent
C 17 H35COONa CaCl 2
(C 17 H 35 COO)2 Ca 2 NaCl
(soap) (in hard water)
(White ppt)
311
312
Hydrophilic
(ii)
Hydrophobic Hydrophilic
(iii)
Hydrophobic
Hydrophilic
313
314