Professional Documents
Culture Documents
Session - 2009-10
ORGANIC CHEMISTRY
TOPIC : GOC - I
CONTENTS :
IUPAC Nomenclature
Page No.1
IUPAC NOMENCLATURE
1.1
INTRODUCTION TO ORGANIC COMPOUNDS:Organic compounds are compounds of carbon and hydrogen and the following elements may also be
present: (Halogens, N, S, P, O). There are large no. of organic compounds available and large no of organic
compounds are synthesized every year.The most important reason for large no of organic compounds is the
property of catenation (selflinkage) in carbon.
Element
Bond Energy
CC
(strongest bond)
Si
SiSi
Ge
GeGe
Sn
SnSn
Pb
PbPb
Decreasing order
Size : CC>SiSi
(iii) Bond order (no. of covalet bonds b/w two atoms) (Directly)
Catenation in carbon: The element carbon has strongest tendency to show catenation or selflinkage due to
(a) its tetravalency so that it can form bonds with many elements as well as carbon itself.
(b) It can form multiple bonds (C = C, C C). Due to its small size, there is efficient colateral overlapping
b/w two Porbitals.
1.2
Page No.2
Ex.
Compounds
Classification
Unsaturated
Heterocyclic , saturated
Unsaturated
Saturated
Saturated, Alicylic
1.3
IMPORTANT TERMS:
Saturated compounds:
When all the valencies of an element are satisfied by covalent bonds.
Unsaturated compound:
When a compound contains one or more bonds (C = C, C = N, N = N, C = O or C C, C N, N N)
Molecular Formula (M.F.) :
The molecular formula of a compound indicates the actual number of atoms of each element present in one
molecule.
Structural Formula (S.F.):
It indicates the linkage due to covalent bond between different atoms in a molecule.
(i) Expanded Structural Formula (E.S.F.)
(ii) Condensed Structural Formula (C.S.F.)
(iii) Bondline Structural Formula (B.S.F.)
Ex.
M.F.
C3H8
Ex.
H
Ex.
M.F.
C4H10
E.S.F. H C C C H
H H H
C.S.F. CH3 CH2 CH3
E.S.F. H C C C C H
H H H H
C.S.F. CH3 CH2 CH2 CH3
B.S.F.
B.S.F.
or
B.S.F.
C.S.F.
M.F.
Ex.
CH 3 CH CH 2 CH 3
CH3
B.S.F.
M.F.
C6H12
C5H12
Homologous series :
Homologous series may be defined as a series of similarly constituted compounds in which the members
possess the same functional group, have similar chemical characteristics and have a regular gradation in
their physical properties. The two consecutive members differ in their molecular formula by CH2.
Calculation of Degree of Unsaturation (DU):(a) It is the hydrogen deficiency index (HDI) or Double Bond Equivalence (DBE)
Page No.3
2H
(b) H3 C H2C CH3
(DU O)
2H
CH3 C CH or CH2 = C = CH2 or
(d)
G.F.
D.U.
(i) CxHy
y
(x + 1)
2
(ii) CxHyOz
yo
(x + 1)
2
(iii) CxHyXs
ys
(x + 1)
2
(iv) CxHyNw
yw
(x + 1)
2
(v) CxHyOzXsNw
ys w
(x + 1)
2
Ex
DU = 4
(b) C6H5Cl
DU = 4
(c) C6Br6
DU = 4
(d) C5H11OCl
DU = 0
(e) C9H12N2
DU = 5
(f) C6N6
DU = 10
DU = 8
DU
S.F.
H
1.
C4H6
CC=C=C
H
H
H H
CCCC
CCCC
C=CC=C
CH2
C
Page No.4
2.
C2H2Cl2
=1
Total isomers = 3
3. C7H6O (Aromatic)
=5
4. C7H8 (Aromatic)
=4
Note : In case of the aromatic Compounds minimum DU = 4. That means at least 1 Benzene ring is
present.
Degree of carbon :
It is defined as the number of carbon atoms attached to a carbon atom.
H
|
|
H
C
|
Tertiary (3) carbon
|
3
H
C
|
Quaternary (4) carbon :
|
C
Superprimary :
(1)
Ex.
10 5 carbon
CH3 CH3
1
2 | 3|
4
5
CH3 C CH CH2 CH3
|
CH3
2 1 carbon
0
3 1 carbon
40 1 carbon
Page No.5
Ex.
1.4
Word Root: It indicates the no. of carbon atoms present in the main chain. It is represented as Alk.
Prefix : It is the first part of the name.
(i) Primary Prefix : Cyclo
(ii) Secondary Prefix : Normal substitutents and junior functional groups are treated as a substituent than
their name is treated as secondary prefix.
The following substituent groups are always cited in the prefix.
(i) R
Alkyl
(ii) R O
Alkoxy
(iii) X
halo (fluoro, chloro, bromo, iodo)
(iv) NO2
Nitro
(v) N = O
Nitroso
(vi) Junior functional group
The prefixes are always written in alphabetical order
The position of substituent group in the main carbon chain is mentioned by writing the number just before
the name of substituent by writing a small dash ().
Suffix :
(i) Primary Suffix:- It indicates saturation or unsaturation existing in the main chain.
ane single bond (saturated)
ene one = bond
diene If two double bonds
Polyene if plenty of double bond are present.
yne one bond
diyne two bond
(ii) Secondary Suffix:- It is used for the principal functional group.
1.5
Page No.6
(b) If number of carbon atoms are same in more than one longest chain then more substituted longest chain
will be the parent chain.
(c) If number of side chain are also same then that will be parent chain having its substituent at lower number.
CCCCCCCC
CCC
C
(2) Numbering
(a) Numbering is done from that side of the parent chain having it substituent at lower number
(lowest set of locant)
(b) If position of substituent are same from both the end of the parent chain, then numbering is done
from alphbetical order.
* If alphabets are also same then numbering is done from that side of the parent chain having its
substituent of substituent at lower number.
Methylpropane
CH3 CH3
CH3 CH CH CH3
2, 3-Dimethyl butane
CH3
CH3 C CH3
CH3
Ex.
CH3
CH3 CH CH3
Dimethyl propane
2-Methylbutane
Page No.7
C
CCCCC
3-Ethyl-2-methyl hexane
CCC
4, 4-Diethyl heptane
C
CCC
CCCCC
CCC
C
CCC
CCCCC
CCC
3-Ethyl hexane
1-Chlorobutane
CCCCC
Cl Br
3-Bromo-2-chloropentane
CCCCC
Br
Cl
2-Bromo-4-chloro pentane
CCCCC
CCC
CCCCCC
Cl
CCCCC
Br
Cl
Cl Cl
Br
H
CnH2n + 2 CnH2n + 1
Alkyl Radical
H
CnH2n CnH2n 1
Alkenyl Radical
H
CnH2n 2 CnH2n 3
Alkynyl Radical
R (structural formula)
Name
CH3
Methyl
CH3 CH2
Ethyl
Page No.8
CH3
|
(b) CH3 C CH3
|
H
CH3
3 2|
1
H
CH3 C CH2 Isobutyl
|
H
CH3
|
CH3 C CH3 Tert butyl
(Tertiary butyl)
|
5 (1 Ethylpropyl) nonane
5 (Dimethylethyl) nonane
Alkenyl
Alkyne
CH2 = CH2
CH3 CH = CH2
Alkynyl
CH2 = CH
ethenyl
Prop 1 enyl
Methylethenyl
Prop 2 enyl
Page No.9
CH3 C CH
CH3 C C
Prop-1-ynyl
CH3 C CH
CH2 C C H
Prop-2-ynyl
Phenyl
2.
Benzyl
3.
Benzal
4.
Benzo
5.
Tolyl
CH3
(o, m, p)
Methylene
7.
Alkylidene
8.
- naphthyl
9.
-naphthyl
(b) neo
(c) Di, Tri, Tetra of complex radical are considered for alphabetization
(2) Following are not considered for alphabetization
(a) Di, Tri, Tetra for simple radicals.
(b) Sec, Tert are not considered for alphabetization
(c) Bis , Tris
Page No.10
(ii)
C
C C CC
Isopentane or methylbutane
C
C C CCC
Isohexane or 2-methylpentane
(i)
C
C C C
(iii)
Conditions :-
Ans.
C
C CC CC
C
C
(3) Neo :
Q.
C
C CC
C
Neopentane
C
C C C C Neohexane
C
Ex.
Page No.11
(5) Tertiary :
First member
But-1-ene
CH3 CH = CH CH3
But-2-ene
CH3
CH3 CH CH2 CH = CH2
4-Methylpent-1-ene
Ex.
CH3
|
CH3 CH CH = CH CH3
4-Methylpent-2-ene
Cl
5
4
3
2
1
CH3 C CH2 CH2 CH = CH2
Cl
5, 5-Dichlorohex-1-ene
(a) C = C C = C
Buta-1,3-diene
(b) C C C C
Butadiyne
(c) C = C C C
Butenyne
1.6
CCCC=CC
1
2
1
Hex-4-en-1-yne
Hexa-1, 3, 5-triene
3
5
Page No.12
Ex.1
3-(2-Methylpropyl) hept-1-ene
Ex.2
4 -(1,1-Dimethylpropyl)-4-ethenylhepta-1,5-diene
Ex.3
3-Ethynylhexa-1, 5-diene
Ex.4
4-Ethenylhept-2-en-5-yne
Ex.5
Ex.6
2, 4-Dimethylpenta-1, 3-diene
Ex.6
2,3-Dimethylhex-1-en-4-yne
1.7
(B) Numbering:
(a) Lowest Locant
(b) Alphabetization
(C) Naming:
Prefix cyclo is used just before the word root if it constitutes the main chain.
If cyclic part is the main chain then the prefix cyclo is not considered for alphabetical order..
If cyclic part constitutes the side-chain (substituent) then prefix cyclo is considered for alphabetization:-
Ex:-
Cyclopropane
Cyclobutane
Page No.13
Cyclohexane
Cycloheptane
Cyclooctane
Methylcyclopropane
Ethylcyclopropane
Propylcyclopropane
1-Cyclopropylbutane
Cyclopentane
C C Cl
2-Chloroethylcyclopropane
Cl C C
Chloroethylcyclopropane
Cl
CCC
Cl
3
CCC
1-Chloro-3-cyclopropylpropane
Cl
CCC
1
2-Chloro-1-cyclopropylpropane
1-Chloro-1-cyclopropylpropane
CCC
1-Chloro-2-propylcyclopropane
Cl
2
3
Br
Cl
2-Bromo-1-chloro-3-fluoro-4-iodocyclohexane
I
Methylethylcyclopropane or isopropylcyclopropane
Cl
Br
1
6
1-Bromo-2-chloro-4-iodocyclohexane
6
5
1
2
3-Chlorocyclohex-1-ene
Cl
Br
6
1
2
3
5-Bromo-3-chlorocyclohex-1-ene
Cl
Page No.14
1.8
Class
Name
Suffix
Prefix
1.
R COOH
Alkanoic acid
Carboxy
2.
R SO3H
sulphonic acid
sulpho
3.
RCOCR
||
||
O
O
Alkanoic anhydride
anhydride
------------
4.
R COOR
Alkyl alkanoate
alkanoate (carboxylate)
Alkoxy carbonyl
5.
RCX
||
O
Alkanoyl halide
halo carbonyl
6.
R C NH2
||
O
Alkanamide
amide (carboxamide)
Carbamoyl
7.
RCN
Alkanenitrile
nitrile (carbonitrile)
cyano
8.
RCH
||
O
Alkanal
al (carbaldehyde)
formyl / Oxo
Alkanone
one
Oxo / Keto
ol
hydroxy
9.
RCR
||
O
10. R OH
Alkanol
11. R SH
Alkanethiol
thiol
mercapto
12. R NH2
Alkanamine
amine
amino
1.9
Page No.15
1.9.1
Carboxylic acid
F.G.
COOH
Prefix
Suffix
IUPAC name
Alkanoic acid
Carboxy
Rule : If first alphabet of sec. suffix is begin from a, i, o, u, y then e of primary suffix will be dropped.
Ex.
(1) HCOOH
Methanoic Acid
Ethanoic Acid
(3) C C COOH
Propanoic Acid
(4) C C C COOH
Butanoic Acid
(5) C C C C C C C C
1
COOH
2-propylhexanoic acid
COOH
(6)
Cyclopropanecarboxylic acid
(7)
CH2 COOH
Cyclopropylethanoic acid
COOH
3'
CCC
1'
2'
(8)
COOH
Ethanedioic acid
Propanedioic acid
Hexanedioic acid
(12)
Sulphonic acid
F.G.
Prefix
SO3H
Sulpho
Ex.
Suffix
Sulphonic acid
IUPAC name
Alkanes sulphonic acid
Methanesulphonic acid
(2) C C C C C
SO3H
Pentane-2-sulphonic acid
1.9.2
Page No.16
SO H
3
(3)
Cyclobutanesulphonic acid
1
(4) HOOC C C C C SO 3H
1.9.3
5-Sulphopentanoic acid
Anhydride
(a) R C O H + H O C R
Heat
H2O
R C O C R
O
Alkanoic anhydride
(b) Mixed Anhydride (according to alphabet)
CH3 COOH +
Ethanoic
acid
CH3 C O C C2H5
O
(1)
H C O C H
O
(2)
C
C
CCCOCCC
O
Methanoic Anhydride
(unstable )
2-Methylpropanoic anhydride
(3)
Butanedioic anhydride
(4) C C C C O C C C C
||
||
O
O
Butanoic anhydride
O
||
C
O
(5)
C
||
O
(6)
COC
O
(7)
Page No.17
1.9.4
Ester :
F.group
Prefix
Suffix
Name
C OR
Alkoxy Carbonyl
Oate
Alkyl....alkanoate
or
Alkanoyloxy
or
carboxylate
(Ester)
or
Alkyl.....Alkanecarboxylate
H2 O R C O R'
R C O H + H O R'
O
O
Example:(1) H C O CH3
Methyl methanoate
O
(2) C C C O C C C
Propyl propanoate
O
(3) C C O C C C C
Ethyl butanoate
C
(4) C C C O C H
Isobutyl methanoate
O
3
(5) C O C C C COOH
3-(Methoxycarbonyl)propanoic acid
O
(6) C C O C C COOH
3-(Ethanoyloxy)propanoic acid
(7)
(8)
O
(9)
O C CH2 CH3
O=C
OCH3
Prefix
CX
Halo Carbonyl
Suffix
Name
Alkanoyl halide
Oyl-halide
or
or
Carbonylhalide Alkane carbonyl halide
O = C Cl
Example:-
(1)
(2) CH3 C Cl
Ethanoyl chloride
(3)
Prop-2-enoyl bromide
(4)
Cl
C
(5) CH2 CH2 CH2 CH C Cl
COOH
O
5, 5-Dichlorocarbonylpentanoic acid
COOH
COOH
(6)
O
O
(7)
C CH2 CH CH = CH CH 2 COCl
Cl
CH 3
(8)
4-Bromocarbonyl-2-chlorocarbonyl-5-propanoyloxycycloexane-1-carboxylic acid
1.9.6 Amide:F.Group
Prefix
Suffix
Name
C NH2
Carbamoyl
amide
or
Carboxamide
Alkanamide
or
Alkane Carboxamide
Example:-
(1) H C NH2
Methanamide (Formamide)
Ethanamide (Acetamide)
N-methylethanamide
(4) CH3 C N C C C
N-butyl-N-propylethanamide
C
C
C
C
Page No.19
O = C NH2
(5)
Benzene carboxamide
O = C NH2
Benzene-1, 3-dicarboxamide
(6)
C NH2
O
COOH
(7)
C NH2
O
C NH CH3
(8) CH2
C NH CH3
O
Nitrile:-
(1) H CN
Methanenitrile
(2) CH3 CN
Ethanenitrile
Example:-
3-Methyl butanenitrile
CN
(4)
Cyclopropane-1, 2, 3-tricarbonitrile
CN
CN
CN
1.9.7
(5)
Benzene carbonitrile
(7)
CH2 CH CH2
CN CN CN
Propane-1,2,3-tricarbonitrile
(6)
Page No.20
1.9.8
Isocyanide :-
F.Group
Prefix
Suffix
Name
NC
Isocyano
Isocyanide
Alkyl Isocyanide
Example:-
(1) CH3 N C
Methyl isocyanide
Ethyl isocyanide
NC
(3)
Aldehyde:Prefix
F.Group
Name
CH = O
(1) HCHO
Methanal
Propanal
5, 5, 5-Trichloro pentanal
CH = O
(4)
Cyclohexane carbaldehyde
CH = O
(5)
Benzaldehyde/Benzene carbaldehyde
Ph
(6)
CH CH
Ph
CH = O
CH2Cl
CH = O
(7)
Benzene-1, 3-dicarbaldehyde
CH = O
(8) HOOC CH2 CH2 CH2 CH = O
5-Oxopentanoic acid
3-(2-Oxoethyl) pentane-1, 5-dioic acid
COOC2H5
(10)
Example:-
Suffix
1.9.9
Phenyl isocyanide
CH2 CH2 CH = O
Page No.21
1.9.10 Ketone:Prefix
F.Group
Name
one
Alkanone
Keto or oxo
C=O
Example:-
Suffix
Propanone
O
(2)
Cyclohexanone
O
(3)
Cyclohexane-1, 3, 5-trione
CH2 C CH3
(4)
2-(2-Oxopropyl) cyclohexanone
COOH
3-(3-Oxobutyl) cyclohexane -1-carboxylic acid
(5)
3-Oxobutanal
1.9.11 Alcohol:F.Group
Prefix
Suffix
Name
OH
Hydroxy
ol
Alkanol
2-Methyl Propanol
(2) CH 3 CH CH 2 CH 2 CH CH 3
CH 2 OH
CH 2 OH
2, 5-Dimethylhexane-1, 6-diol
HO
OH
(3)
OH
HO
Cyclohexane-1, 2, 3, 4, 5, 6-hexaol
OH
OH
(Glyceraldehyde) 2, 3-Dihydroxy propanal
(4) CHO
CH OH
CH2 OH
OH
Cl CH2 CH CH2
(5)
Example:-
O
OH
(6)
HO
OH
1.9.12 Amines:F.Group
Prefix
Suffix
Name
NH2
amino
amine
Alkan amine
(a) R NH2
1 = amine
Alkanamine
N Alkylalkan a min e
(R' )
(R )
N, N-Dialkylalkanamine
R'
(d) R N CH3
N-Ethyl-N-methylalkanamine
CH2 CH3
Methanamine
(2) C C C C C
NH2
Pentan-3-amine
(3) C C C NH C C
N-Ethylpropan-1-amine
(4) C C C N C
N-Ethyl-N-methylpropan-1-amine
Ex:-
C
C
N-Ethylpropan-2-amine
(5) C C C
NH C C
OH
(6) CH2 CH = CH CH CH3
NH CH2 CH3
NH Ph
If hetero atoms are count as a C atom in the parent chain then they are written as
(1) NH Aza
(2) O Oxa
(3) S Thia
(4) Se Selena
H
N
Example:-
(2)
H
N
(3)
CH3
Prefix
Suffix
Name
R O R'
alkoxy
Alkoxy alkane
Alkoxy + Alkane
less no.
more no.
of ' C'
of ' C'
Methoxymethane
(2) C O C C
Methoxyethane
(3) C O C C C
1-Methoxypropane
(4) C C C
O
C
2-Methoxypropane
C
(5) C C C O C C
1-Isopropoxypropane
1-(Methylethoxy) propane
OCC
(6)
Ethoxycyclohexane
(7)
Cyclopropoxycyclohexane
Br
OCCC
(8)
3-Bromo-6-chloro-2-propoxycyclohexan-1-ol
OH
Cl
In cyclic system, numbering always starts from senior most functional group.
OH
Br
(9)
6-Bromo-5-methoxycyclohex-2-en-1-ol
O CH3
OH
1
Br
(10)
3
6-Bromo-5-ethoxycyclohex-3-en-1-ol
OCC
Page No.24
Oxirane or Epoxyethane
(2) C C C
O
1, 3-Epoxypropane
(3) C C C
O
1, 2-Epoxypropane
Cl
(4) C C C
O
1-Chloro-2, 3-Epoxypropane
Polyethers:(1) C C O C C O C C
1
1, 2-Diethoxyethane
1
10
11
10
11
(2) C C O C C O C C O C C
3, 6, 9-Trioxaundecane
12
13
14
15
(3) C O C C C O C C O C C C O C C
2, 6, 9, 13-Tetraoxapentadecane
2
1
12
O7
(4)
11
10
1, 4, 7, 10-Tetraoxacyclododecane
H
Cation
2 e
Cyclopropenium ion
Cation
2 e
Cyclobutenium dication
Non-Benzenoid:
+
H
+
+
Page No.25
Anion
..
H
H
6 e
Cyclopentadienyl anion
H
H
6 e
CH3
(1)
Methylbenzene (Toluene)
CH3
CH3
(2)
CH3
(3)
CH3
CH3
(4)
CH3
Write structures of
CC
(i) Metadiethylbenzene
CC
CC
(ii) 1-ethyl-4-isopropylbenzene
CCC
(iii) Orthodiethenylbenzene
C=C
C=C
C
1, 2, 3-Trimethyl benzene
(Vicinal Trimethyl benzene)
C
1, 2, 4-Trimethyl benzene
(Unsymmetrical Trimethyl benzene)
Q.
C
C
1, 3, 5-Trimethyl benzene
(Symmetrical Trimethyl benzene)
Page No.26
Examples :
Isopropylbenzene (Cumene)
1.
CC
C
1-Chloro-4-methyl-2-nitrobenzene
2.
NO2
Cl
C=C
3.
CC=C
4.
3-Phenylprop-1-ene (Allylbenzene)
CH = CH CH3
5.
1-Phenylprop-1-ene
COOH
6.
COC
7.
SO3H
8.
C O C2H5
9.
O C CH3
10.
Phenyl ethanoate
C Cl
11.
NH C CH3
12.
N-Phenylethanamide
C NH CH3
13.
N-Methylbenzene carboxamide
Page No.27
CN
14.
CH = O
15.
16.
17.
CH3
OH
18.
Phenol
OH
19.
CH3
OH
OH
20.
o-Hydroxyphenol (Catechol)
OH
m-Hydroxyphenol (Resorcinol)
21.
OH
OH
22.
p-Hydroxyphenol (Quinol)(Hydroquinone)
OH
NH2
23.
Benzenamine (Aniline)
SH
24.
Benzenethiol
O
O C CH3
O
25.
COH
Page No.28
LECTURE NOTES
Session - 2009-10
ORGANIC CHEMISTRY
TOPIC : GOC - I
CONTENTS :
Isomerism
* Structure Isomerism
* Stereo Isomerism
Geomertical
Optical
Conformational
Page-29
Isomerism
Isomers:
Compounds with same general formula or molecular formula but different physical and chemical property.
Ex:-
Ex:-
Homologs:
Compounds with same general formula differing by same structural unit CH2 or molecular weight by 14
unit.
Ex:- CH3 OH and CH3 CH2 OH
Difference between isomers and homologs:-
Page-30
Structural isomers:
When two or more number of organic compounds have same molecular formula but different structural
formula these are called structural isomers.
Stereo isomers:
When two or more compounds have same Molecular Formual (M.F.) and same Structural Formula (S.F.) but
have different stereochemical formula (S.C.F.), these are called stereoisomers.
M.F.
S.F.
(i) CH3 CH2 CH = CH2
These are structural isomers.
For (ii), S.C.F. are
H3C
H
CH3
H3C
and
C=C
C=C
H
CH3
Stereocentre
These are stereoisomers.
H
Chain isomers :
They have different size of main carbon chain and / or side alkyl chain
(i) The two chain isomers should have same nature of F.G./multiple bonds/substituents (except R group)
(ii) The position of F.G./M.B./substituent (locants) is not. considered here.
Ex:-
Alkanes:(a) C1 C3
(b) C4H10
(c) C5H12
(d) C6H14
(i) CH3 CH2 CH2 CH2 CH2 CH3, (ii) CH3 CH CH2
(iii) CH3 CH2
CH3
CH3 ,
CH3
CH3
CH3,
CH3,
CH3
Ex.
Ans.
and
Chain Isomers
Page-31
Q.
Ans.
C C C C NH2,
C
C C C NH2
Positional isomers:
They have different position of locants Functional group (F.G.) or Multiple Bond (M.B.) or substituents in
the same skeleton of C-atoms.
Nature of F.G. or M.B. should not change.
The skeleton of C-atom should not change.
(1) C C C C C ,
CC C CC
(2) C = C C C ,
CC=CC
(3) C C C C C ,
CCCCC
(4) C C C C ,
C C C C OH
OH
Write all Positional isomers of Dichlorobenzene ?
Ex.
Cl
Cl
Cl
Q.
Cl
Q.
,
Cl
Cl Cl
Ans.
,
Cl
Cl
Ans.
Cl Cl
Cl
Cl
Cl Cl
Cl
Q.
Cl
Q.
Ans.
Cl
Ans.
Cl
C
(iii) C C C C C C
CC
(ii) C C C C C C,
(i) C C C C C C
Ex.
C6H12 (Cycloalkanes):(2)
(3)
(4)
(1)
Ex.
Page-32
(10)
Ans.
(6)
CC
(9)
CCC
(5)
C
CC
(7)
(11)
(8)
CC
Functional isomers:
They have different nature of functional group (F.G.). The chain and positional isomerism is ignored (not
considered).
Compound
Functional isomer
CCCC
Nil
CCC=C
Compound
CCCC
Isomer Functional
(a) C = C C = C Alkadiene
Remarks
(a), (b) are not functional isomers
Alkyne
(b)
Cycloalkene
among themselve
(c)
Bicyclo
(2)
C C C OH
Alcohol
CCOC
Ethers
(3)
C C CH = O
C C C
Aldehydes
O
Ketones
C C COOH
C C OC
Carboxylic acids
O
Esters
C C C NH2
..
(a) C C NH C
1 amine
2 amine
CCCN
Cyanide
(Propanenitrile)
C C NC
Isocyanide
(Ethane isocyanide)
(4)
(5)
(6)
..
(b) C N C
C
3 amine
Ex.
(1)
Important point :- Following compounds dont exist at room temperature therefore not consider as a structure
isomer
(ii) C C OH
(iii) C OH
(i) C = C OH
(iv) C OH
OR
(v) C O C = C
OH
OH
Page-33
Ans.
(i) C C C C C OH,
C
C C C C OH,
Q.
C C C C OH,
(7 alcohols)
C
C C O C,
C
C C C O C,
C C C O C,
C C C C O C,
C C C C C,
OH
C
C C C OH
C
C C C C C,
OH
C
C C C OH,
C
C C C O C C,
C
C C OCC
(6 ethers).
G.F.
CnH2n + 3N
n
(1) 3
M.F.
C3H9N
2 Amine (R NH R)
3 Amine R N R
R
G.F.
CnH2n + 1N
2
n
(1) 2
M.F.
C2H5N
1 Amine
(1) C = C NH2
Ethenamine
2 Amine
3 Amine
CC=N
CN=C
Ethanimine
N-Methylene methanamine
(Unstable at room temperature)
Q.
1 Amine (R NH2)
Q
Q.
G.F.
CnH2n 1N
n
2
M.F.
C2H3N
Ans.
CH2 = C = NH
HC C NH2
H3 C N
Metamers:
When two isomers have same functional group (containing a hetero atom O, N, S) but have different nature
of alkyl or aryl (aromatic radical) group attached to hetero atom, then these are called metamers.
Conditions:
(a) Same functional group
(b) Chain or position isomerism is not considered.
(c) >C = O (keto) group does not show metamerism
Following functional groups show metamerism
Ethers (All isomeric ethers are metamers)
(b) R NH R
2 Amines
(c) R N R
R''
(d) R S R
3 Amines
(a) R O R
Thioethers
Page-34
(e) R C O R
Esters
(f) R C O C R Anhydrides
O
O
(g) R S O R
Sulphonate esters
O
Q.
Ans.
Q.
OC
OCC
Q.
CCC NC
CC NCC
Ans.
and
Q.
Acyclic compound (A) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (A).
Ans.
C C
C C C C C8H18
C C
Q.
Cyclic compound (P) contains 18 1 H atoms, two types of C atoms. All H are identical. Identify (P).
Metamerism
Ans.
or
CH3
H3C O C CH3
Ans.
C
C
Compound X is an ether. It has 12 1 H atoms. It has 2 types of H-atoms and 3 types of C-atoms. Write it
Structural formula ?
C
Q.
Ans.
C
C
CH3
Page-35
Stereoisomers (Classification)
Stereoisomers :
The stereoisomers has different orientation of groups along a stereo centre. A stereocentre can be C = C
(any double bond), a ring structure, asymmetric carbon atom (*Cabcd). These isomers has same general
formula, structural formula and molecular formula but different stereochemical formula.
E.g.
CH3
C=C
H
CH3
CH3
H
H
(I)
C=C
(II)
H
CH3
CH3CH2CH=CH2
(III)
I, III
II, III
I, II
Positional
Positional
Stereoisomer
Configurational isomers :
Configurational isomerism arises due to different orientations along a stereocentre and these isomers can
be seperated and these isomers do not convert into one-another at room temperature. Therefore, they are
true isomers. They can separated by physical and chemical method.
E.g.
Cis2Butene
Trans-2-Butene
Conformational isomers :
When different orientations arise due to the free-rotation along a sigma covalent bond. Such isomers are
called conformational isomers.
E.g.
eclipsed ethane and
staggered ethane
These isomers change into each other at room temperature and can never be isolated. So these are not
considered as true isomers.
Geometrical Isomerism
1.
a
C=C
b
(I) b
The root form of geometrical isomers lie in restricted rotation.
a
b
a
(I)
Page-36
Condition
(i) Restricted rotation
(ii) The two groups at each end of restricted bond must be different.
1
3
C=C
2
4
Caa Caa
X
Caa Cbd
X
Cae Cbb
X
Cab Cab
Cab . Cbd
Cab Cde
(iii) In two geometrical isomer the distance between two particular groups at the ends of the restricted bond
must be changed.
Q.
(2) Propene
(6) 1, 2-Dideuteroethene
H2C = CH
(7) Phenylethene
Ans.
4, 5, 6
Nil
and
By E / Z
Q.
Which of the following compounds show geometrical isomerism after reaction with NH3.
O
||
(a) CH3 C CH3
O
||
(d) CH3 C H
(g)
Ans.
O
||
(b) H C H
O
||
(c) H C D
(e) Ph C CH3
||
O
(f) Ph C Ph
||
O
(h)
(i)
c, d, e, g, i
(b) Oximes
C = N OH :
These are prepared by reacting carbonyl compuond with hydroxyl amine (NH2 OH)
R
C=O
H
H2O
+ H2 NOH
R
C = NOH
H
(Aldoxime)
OH
C=N
H
(I)
(syn)
and
OH
C=N
H
(II)
(anti)
(1) Propanone
O
||
CH3 C CH3
(2) Butanone
O
||
CH3 CH2 C CH3
(3) 3-Pentanone
CCCCC
(4) Acetophenone
C 6H 5CCH 3
O
(5) Benzophenone
C 6H 5CC 6H 5
(6) Cyclohexanone
O
Me
(7)
Methyl Cyclohexanone
Ans.
2, 4, 7
Q.
The lowest molecular weight of acyclic ketone and its next homologue are mixed with excess of NH2 OH
to react. How many oximes are formed after the reaction ?
3
Ans.
Page-38
(c) Hydrazones
C = N NH2 :
H2O
C = O + H2N.NH2
H
hydrazine
C = NNH2
H
R
NH2
R
+
C=N
H
(I)
NH2
C=N
H
(II)
(Geo. diastereomers)
Q.
Ans.
Two chain isomer of a cycloalkanone which are next higher homologue of lowest molecular weight,
cycloalkanone reacted with hydrazine. Identify the structure and number of isomer of hydrazones prepared ?
..
..
N
NH2
NH
2
N
N ..
O +
+ H2N NH2
+
+
NH2
CH 3
CH3
O
CH
3
Number of isomer = 3
(3) Geometrical isomerism across azo compounds ( N = N )
(i) H N = N H (H2N2)
..
..
N=N
Ph
Ph
syn
..
Ph
..
N=N
anti
Ph
(i)
Restricted rotation
(ii)
(iii)
Page-39
Stereocentre:An atom or bond across which stereoisomerism exists (either G.I. or optical isomerism)
Those stereoisomers which are not mirror images of each other are called diastereomers. Those compounds which are non-superimposable mirror-images of each other are called enantiomers
are enantiomers
E/Z Nomenclature :
Z (Zussamen = together) a > b and e > d
(a)
(b)
<
(c)
<
(d)
>
Page-40
Ex.
Ex.
E
(iii) If the first atom has same atomic number but different atomic mass, that is isotopes. Then heavier
isotope has higher seniority.
(iv) If the group has unsaturation, then a hypothetical hypothetical equivalent in drawn for it and it is compared with other group for seniority.
(1)
(2) CH = CH2 < C CH
(Hypothetical)
Ex.
(1)
HC
C(CH3)3
C == C
E
CH2 CH = CH2
(2)
N
(3)
CH2 C(CH3)3
H2C = C = CH
C == C
CH
(4)
(5)
(6)
Page-41
Stereocentre = 2
Geometrical isomerism = 4
(a)
(b)
(c)
(d)
Ex.1
Ans.
Case III : Compounds with similar ends but odd number of stereocentre.
No. of Geometrical isomerism = 2n1 + 2
Ex.1
Ans.
n 1
2
CH3 CH = CH CH = CH CH = CH CH3
Stereocentre = 3
Geometrical isomerism = 6
(i)
>
(ii)
<
COOH
COOH
C=C
(iii)
H
COOH
H
C=C
>
COOH
Page-42
Page-43
Optical Isomerism
Some organic compounds can rotate the plane of plane-polarised light. Such compounds are called
optically active compounds.
The optically active compound can show optical isomerism.
Measurement of optical activity
It is measured by an instrument called polarimeter.
=
(1)
(5)
(3)
(6)
Recorder
(8)
Inference
Compound is optically inactive.
Optically active, dextrorotatory or d or (+).
Optically active, laevorotatory or l or ().
Specific Rotation:- The specific rotation of a compound indicates the optical rotation of unit concentration (1 g/mL)
present in a sample tube of 1 dm of path-length at given temperature and given wavelength of light. It is
represented as follows:-
t 25 C
[ ] 580 nm
where
Q.
Compound X has = +70 for 2 g/mL solution in sample tube of = 1 dm. Calculate ?
Ans.
(1)
(2)
70
= +35
2
Its concentration is made twice, the observed rotation() will be 140 but = 35
If = +70, it will be a
(i) d compound or (ii) compound of = (360 70) = 290
It can be decided by changing the concentration or by changing the length of the tube (c or ).
If concentration is reduced to half, d will have +35 and will have 145 (not distinguish) still halfed, it will
give +17.5 and 72.5 to distinguish.
(I)
(II)
With symmetrical
With asymmetric
molecule
molecule
[] = 0
[] 0
Optically inactive compounds:For symmetrical molecule optical rotation observed after interaction of light is zero.
Page-44
But in case of optically active compounds. The molecules are asymmetric in nature and show non-zero
optical rotation.
Centre of symmetry : - A centre of symmetry in a molecule is said to exist if a line is drawn from any atom
or group to this points and then extended to an equal distance beyond this point, meets the identical atom
or group.
Cl
H
C=C
H
R
Centre of symmetry
Cl
Centre of symmetry
Axis of symmetry : It is defined as Cn axis of symmetry that means of the molecule is rotated by
360
n
angle, then its original or identical or superimposable. The molecule is said to have n-fold axis of symmetry
Ex.
(180 rot )
Ex.
(C4 axis)
Ex.
(axis)
There is no relation whatsoever with chirality and axis of symmetry. Meso molecule does not have axis of
symmetry
no axis of symmetry
Page-45
360
angle and its mirror image is taken in the perpendicular plane of
n
Ex.
H
H
Me
Me
Me
180
rotation
(I)
Me
Me
Reflextion
(II)
Me
(III)
The dissymmetric molecules have two orientations in space. These two orientations are called
stereoisomers, optical isomers, enantiomers.
These are mirror images (enantiomers).
Non-superimposability of enantiomers:- The dissymmetric molecules are always non-superimposable
on their mirror-image orientations.
The non-superimposable orientations are non-identical orientations, so are called isomers.
Because of dissymmetry, these two isomers are capable of rotating plane-polarised light. So, these are
called optical isomers.
Page-46
Optically Active Carbon Compounds:If a carbon-atom is attached with four different group, then if does not have any element of symmetry. It is
known as asymmetric carbon atom, which is represented as *Cabde.
a
C*
e
d
If a molecule contains only one asymmetric carbon atom, then the molecule as a whole becomes chiral and
optically active and show optical isomers.
b
Centre of symmetry
Plane of symmetry
Optical active
H
C
(1)
Absent
Yes
No
Absent
Yes
No
Absent
Yes
No
Absent
No
Yes
H
C
(2)
Cl
H
C
(3)
Br
Cl
H
C
(4)
Br
Cl
F
Ex.1:- Mark the chiral objects:(i) Cup
(ii) Plate
(vii) Shoe
(viii) Glove
Ans.
(iii) Letter A
(iv) Letter G
(v) Fan
(vi) Door
Ex:-
(i) Butan-2-ol
CH3
C
H
C2H5
OH
Ex:-
CH3
H
OH
CH2CH3
///////////////////////
OH
Rules of writing Fisher Projection formula :(i) It is represented by a cross (+).
(ii) Groups at Vertical line are away from observer.
(iii) Groups at Horizontal line are towards the observer.
(iv) Central C atom of the cross is chiral.
(v) High priority group lies at the top of vertical line (IUPAC Numbering starts from top).
Page-47
(1) 2-chlorobutane
(2) Pentan-2-ol
*
(3) CH2 CH CH
OH OH O
Glyceraldehyde
*
*
(4) CH3 CH CH CH2 CH3
OH OH
Ex:-
CHO
CHOH
CHOH
CHOH
CHOH
CH2OH
(5) Glucose
OH
OH
OH
OH
Page-48
Configuration nomenclature in Optical Isomers :Relative configuration : The experimentally determined relationship between the configurations of two
molecules, even though we may not know the absolute configuration of either. Relative configuration is
expressed by D-L system.
Absolute configuration : The detailed stereochemical picture of a molecule, including how the atoms are
arranged in space. Alternatively the (R) or (S) configuration at each chirality centre.
(I) D - L System (Relative configuration) : Application on correct Fisher Projection Formula
This method is used to relate the configuration of sugars and amino acids to the enantiomers of glyceraldehyde. The configuration of (+)-glyceraldenyde has been assigned as D and the compounds with the same
relative configuration are also assigned as D, & those with (-) glyceraldehyde are assigned as L.
Examples :
Sugars have several asymmetric carbons. A sugar whose highest numbered chiral centre (the penultimate
carbon) has the same configuration as D-(+)-glyceraldehyde ( OH group on right side) is designated as a Dsugar, one whose highest numbered chiral centre has the same configuration as L-glyceraldehyde is designated as an L-sugar.
e.g.
S Sinister
Examples :
a
b
(3)
Q.
c
a
d
Now go from a to b, b to c.
(i) If it follows clockwise route, it is (R).
(ii) If it follows anticlockwise route, its configuration is (S).
Br
Br
Cl
F
(R)
Cl
F
(S)
Page-49
Me(c)
Ex:-
H(d)
Et(b) (d)
Pr
(a)
(b)
abc
Clock wise
(a)
Q.
(1)
Ans. R
(2)
Ans. R
(3)
Ans. S
same
same
same
same
different
Molecules with more than one chiral carbons:(I) Calculation of No. of optical isomer :Case I:- When all Chiral carbon atoms are differently substituted (all are dissimilar C*)
optical isomer = (2)n
Case II:- When all the Chiral carbon atoms are similar at ends.
n
(i) n = even
x = 2n 1 + 2 2
(ii) n = odd
x = 2n 1
Page-50
CH3
CH3
Molecules with two Asymmetric Carbon Atoms of Dissimilar Nature:(i) Structural formula
CH3 CH CH CH2 CH3
Cl
Cl
n
2
(ii) Optical isomer = 2 = 2 = 4
(iii) Stereochemical Formula:-
CH3
CH3
Cl
Cl
H H
Cl
Cl
Cl
Cl
H; Cl
Cl
C2H5
C2H5
I
[] = +x
C2H5
II
x
C2H5
III
+y
Analysis:(a)
I, II Enantiomers
I, III Diasteromers
II, III Diasteromers
IV
y
III, IV Enantiomers
I, IV Diasteromers
II, IV Diasteromers
n = 3,
x = 23 = 8 (4 d- pairs)
Ans.
Q.
(i)
(ii)
(ii)
(iii)
(iv)
(i) n = 2
(ii) x = 2n 1 + 2 2
= 3 (Optical stereoisomers).
Me
H
OH
OH
Me
(I)
(II)
Plane of symmetry present.
In (I and II)
Superimposable on its mirror image.
Thus, I and II are identical.
[] = 0, optically inactive.
Meso isomer
In (III) Specific rotation [] = +x
In (IV) Specific rotation [] = x
(III)
(IV)
Page-51
Meso isomers: The optical stereoisomers which have more than one asymmetric carbon atoms but have a plane of
symmetry are called meso compound.
They are achiral (optical rotation = 0).
They have [] = 0 due to internal compensation of optical rotation.
They are diastereomer of d pair. So, it has different physical properties than d -pair..
Presence of more than one asymmetric C atoms.
They are non resolvable.
Q.
COOH
OH
(1)
(2)
H
Ans.
OH
COOH
Cl
Me
Cl
(3)
(4)
Me
OH
H
(5)
*
OH
\\\\\\\\\\\\\\\\\\\\
(I)
2S
3S
4R
(II)
2S
3R
4R
(III)
2S
3 achiral
4S
(IV)
2R
3 achiral
4R
Optically active
Properties of Optical Diastereomers:The optical isomer which are neither mirror image nor superimpossible to each other are called optical
diastereomers.
Conclusion:- Optical Diastereomers have different physical properties, so these can be separated by normal
physical methods of separation.
(i) By fractional distillation (different B.P.)
(ii) By fractional crystallization (different solubility)
(iii) Chromatography (different solubility)
(iv) Differential Melting (M.P. diff.)
Page-52
Assertion:- All diastereomers have different polarities (Both Geometrical and Optical) True
Assertion:- Geometrical isomer are always diastereomers True
Chemical method of separation (resolution) by using optically active reagent:Separation of Racemic Mixture:- The enantiomers in a d pair have identical physical properties, so these
cannot be separated by normal physical methods of separation. The special method is used for separation
of d pair known as optical resolution.
General scheme of resolution:-
d+
+ d'
Racemic Optically
mixture
active
Reagent
Hydrolysis
Hydrolysis
d + d'
Example:-
Esterifica tion
Me
H
COOH
(d)
Et
Et
Me
+ OH
COOH
( )
H
D
(d')
H + H
(dd')
CO
O
(d')
O
D
( d ')
(dd')
Me
H
(d' )
CO
Me
Et
Me
Et
Me
Me
Pair of Diastereomers
Ester upon still hydrolysis will give back the carboxylic acid and alcohol.
(II) Separation of (d ) pair of alcohol by using optically active acid:-
Ph
+
H
(dd')
OC
O
Me
Me
Ph
Me
CO
O
D
(d' )
Me
Page-53
Diastereomers (Separable)
(obs)
100%
[]specific
Page-54
Asymmetric N:R' N
N R'
R''
R''
A nitrogen atom attached with 3 different groups (sp3) is chiral, asymmetric.
In case of acyclic compounds, the Nitrogen, having trigonal pyramidal shape undergoes rapid inversion of shape
at room temperature. So at room temperature, everytime a racemic mixture of d and forms exists.
This racemic mixture can never be resolved at room temperature.
Nitrogen converts into its enantiomer..
So, acyclic molecules with chiral nitrogen are chiral but optically inactive ([] = 0) and are non-resolvable.
If asymmetric Nitrogen atom is present in ring structure, then inversion does not take place and such molecules are
optically active [ ] 0 . (otherwise ring will break)
Ex:-
Me
N
[ ] 0
CCCCC
(Cumulated double bond)
CCCCC
(Conjugated double bond)
Alternate
C CCC C
(Isolated double bond)
Separated
e.g.
e.g.
The groups at the end of allene structure lie in same plane (ZX plane). Therefore it will have a plane of
symmetry (ZX plane). The molecules lacks molecular dissymmetry & it will not show optical activity hence
optical isomerism. But the compound will exist in two geometrical diastereomeric forms.
Page-55
(II) Case of spiranes : A similar case like allenes is observed in spiranes. The spiranes with even rings and
different groups at terminal carbons show optical activity & optical isomerism, while the spiranes with odd
rings shows geometrical isomerism.
(a) spiranes with even rings :
shows optical isomerism.
Page-56
CONFORMATIONAL ISOMERISM :
1.
Free Rotation : A sigma covalent bond undergoes free rotation at room temperature.
(CC, C O, CN, NN, OO)
2.
Conformers / Rotamers or conformations : The infinite number of spatial oreintation of molecule arises
due to free rotation along a sigma covalent bond
3.
Conformational Isomers : Those conformations which are most stable and have minimum P.E. are defined
as conformational isomers. These are not true isomers and can never be isolated.
4.
Conformational Energy : The rotational energy barrier is known as conformational energy. It is the P.E.
difference between conformational at potential energy minima and maxima.
5.
Angle of rotation/Dihedral Angle (D.H.A.)/Torsion Angle : The interfacial angle between the groups
attach at two -bonded atoms is defined as dihedral angle.
Projection formula
(a) Saw horse Projection formula
Ex.
CH3 CH3
H(a) H(c)
rotation
H
(b)
Eclipsed
H
(c)
H(b)
H(a)
Staggered
1
12.5 kJ / mol
Ex.
CH3CH2CH3
Page-57
Eclipsed
Staggered
CH3
60
120
H
II
Staggered
Eclipsed
HH
H
III
Eclipsed
CH3
H
H
H
H
H
IV
Staggered
Propane :
Butane :
Ex.
Ethyl-hydrogen repulsion is less than methyl-methyl repulsion. So draw the newman between C2 - C3
CH3
CH3
CH3
60
CH3
CH3
120
H
H
H
(I)
H
(II)
180
H
240
CH3
(IV)
300
CH3
H
H CH3 H H
(V)
360
Page-58
Conformational Isomers : Due to free rotation from 0 to 360 those conformations which are most stable
and have minimum P.E. are defined as conformational isomers.If these conformers have same energy then
there isomers are called degenerate isomers or equienergic isomers.
The conformational isomers with different energies are called non-degenerate isomers.
The conformational isomes lie at the P.E. minima in the P.E. diagram with respect to rotational angle.
Strains :
(i) Torsional Stran (eclipsing strain) :
It is defined as the electronic repulsion between the bond-pairs electrons of two adjacent eclipsed bonds. It
is active at torsional angles 0, 120, 240 in which the molecule has eclipsed conformation. It is considered
almost zero in the staggered conformation. (D.H.A. = 60, 180, 300)
(ii) Vander Waal strain :
It is the repulsion between the group attached at adjacent bonds. The vander waal strain is maximum in
eclipsed conformation, and minimum in anti conformation, while intermediate in gauche conformations.
It is almost zero for H-atom since the sum of vander waal radii is less than internuclear distance between two
H atom.
(iii) Angle Strain :
It arises due to distortion in normal bond-angles. In acyclic compounds, there is no distortion of bond-angle
due to free rotation. So, all conformations have zero angle strain in acyclic compound
Page-59
CH3
Ques. Draw conformation isomers of following compound CH3 CH CH CH3 with respect to C2 and C3 carbon
CH3 CH3
atoms.
H
H
H
60
H3C
180
CH3
CH3
CH3
CH3
CH3
120
CH
CH3 CH3 3
Eclipsed
H3C
CH3
H3CCH
CH3
H3C
CH3
H
Staggered
Page-60
CH2OH (Glycol).
CH2OH
OH
H
OH
H
(II) Gauche
Tartaric Acid :
COOH CHOH CHOH COOH
no. of Sterioisomers : 3
COOH
1. Meso
OH
OH
COOH
Page-61
2. d/
COOH
COOH
H
Meso
COOH
H
OH
OH
COOH
OH
OH
H
H
COOH OH
COOH
COOH
COOH
H H
COOH
OH
OH
COOH
OH
OH
OH
d/
COOH
COOH
COOH
OH
H
OH
COOH
H OH
OH
COOH
COOH
OH
HH
COOH H
OH
COOH
COOH
H
OH
OH
OH
COOH
COOH
OH
OH
H COOH OH
Page-62
LECTURE NOTES
Session - 2009-10
ORGANIC CHEMISTRY
TOPIC : GOC - I
CONTENTS :
Structure Identification
* Monochlorination
* Catalytic Hydrogenation
* Ozonolysis
* Elements detection
* Identification of Functional Group by Lab. Test
63
STRUCTURE INDENTIFICATION
Monochlorination:(a)
Cl / h
CH3Cl + HCl
(i) CH4 2
Cl / Sunlight
(ii) CH3 CH3 2 CH3 CH2Cl + HCl
Cl
Cl / h
2
(iii)
+ HCl
C
C
Cl2 / h
C C C Cl + HCl
(iv) C C C
C
C
Cl
Cl / h
2
(v)
+ HCl
Remarks:- When an alkane or a cycloalkane is treated with halogen (Cl2, Br2, F2, I2), a photochemical reaction takes
place and a C H bond cleaves and a C Cl bond is formed. If one H-atom is substituted by one halogen
atom. This is known as monohalogenation reaction.
Application:- If a molecule has more than one type of H-atom, then on monochlorination, it forms a mixture of
monochloroisomers. All these isomers are position isomers.
Conclusion:- Hence, it can be concluded that the total no. of position isomers (structural) of monochloro compounds
is equal to the number of different types of H-atoms present in the reactant. The different type of H-atoms are
also known as non-identical Hydrogens or non-equivalent Hydrogens or chemically different Hydrogens.
Ex.
Monochlori nation
2 Products (structure isomers)
(b) C C C C
Monochlori nation
2 Products (structure isomers)
(c) C C C C C
Monochlori nation
3 Products (structure isomers)
(d) C C C C
Monochlori nation
4 Products (structure isomers)
(a) C C C
C
CH3
Monochlori nation
5 Products (structure isomers)
(e)
Q.
Cl / h
only one monochloro isomer..
X(C5H12) 2
Ans.
X = Neopentane
Q.
Cl / h
Two monochloro
P(C6H14) 2
Remark : In aromatic hydrocarbons, the hydrogen atoms of the side-chain are chlorinated, but H-atoms of Benzene
ring are stable.
CH3
Ex.
CH2Cl
Cl / h
2
64
Q.
Cl / h
Two mohochloro
X(C8H10) (Aromatic) 2
Cl / h
One monochloro
Y(C8H10) (Aromatic) 2
Ans.
(X)
(Y)
Catalytic Hydrogenation of C = C; C C
General reaction:Ni
R CH2 CH2 R
(a) R CH = CH R + H2
Ni / Pt / Pd
R CH2 CH2 R
(b) R C C R + 2H2
H2
H2
R CH CH R R CH2 CH2 R
(Not isolated)
2H2 / Ni
(d)
(e)
3H2 / Ni
CH = CH2
H2 / Ni
room temperature
CH CH3
2
H 2/Ni
(100 150C)
(f)
H / Ni,
2
CH CH3
2
Remarks:(a) Alkenes, Alkynes, polyenes or polyynes can be hydrogenated by using catalysts Ni/Pt/Pd at room temperature.
(b) All C C bonds(C = C, C C) are hydrogenated. The reaction cant be stopped at any intermediate stage.
Exceptions:Aromatic bonds which are stable at room temperature but can be hydrogenated at high temperature.
It can be concluded that the hydrogenation product of an alkene or alkyne or any unsaturated compound is
always a saturated compound.
The no. of moles of H2 consumed by 1 mole of compounds is equal to the no. of bonds presents.
All positional isomers of alkenes or alkynes (due to multiple bond) always give same product on hydrogenation.
65
Ex:- C = C C = C + Cl2 X
Ex.
C CC
C Cl
2H2 / Ni
(1)
Cl
Y =
(X)
Cl / h
2
Y + Z
Z =
Cl
CH3
CH3
H / Ni
2
(2)
CH3
CH3
H / Ni
2
(3)
Q.
Cl / h
2
5 Monochloro product
5 Monochloro product
H / Ni
Cl / h
Z(only one monochloro product)
X(C4H6) 2 Y 2
Identify X, Y, Z
Ans.
DU = 2
X
Identify the lowest molecular weight alkane which gives four structural isomeric monochloro products ?
C C CC
Q.
Ans.
Cl
C5H12
= 72g
Ans.
C
C C C C,
C
Q.
Ans.
DU = 2
Q.
CCCCCC
2 monochloro product
Find the structural isomers of
product?
Q.
Q.
Ans.
Cl / h
2
A
C 8H17 Cl
(C8H18 )
(Only one type )
Identify A ?
66
Q.
Ans.
C C
C C CC
C C
Write all isomeric alkynes which produce an isomer of heptane which on further monochlorination gives
(a) three monochloro products.
Ans.
CC
(i) C C C C C
(b)
Ans.
two monochloro
Nil
Q.
Find the structure of lowest molecular weight hydrocarbon and maximum unsaturation which on hydrogenation produce such an alkane which gives two monochloro products ?
Ans.
C = C = C or C C C
Q.
Determine the M.W. of maximum unsaturated hydrocarbon which on hydrogenation gives C6H12 which on
further chlorination gives two monochloro.
C
(ii) C C C C C
C
CH2
Ans.
CH2
CH2
C6H6 = 78g
Ozonolysis:
It tells about position of unsaturation.
Remarks:(1)
(2)
(3)
The products are carbonyl compounds (aldehydes or ketones). This type of ozonolysis is known as reductive
ozonolysis.
(4)
General Reaction:- R CH = CH R
Ex:-
(1) O 3
R CH = O + O = CH R + ZnO + H2O
(2) Zn/H2O
(1) O 3
CH2 = O + CH2 = O
(2) Zn/H2O
(1) O 3
CH3 CH2 CH = O + O = CH2
(2) Zn/H2O
O3 / Zn
O / Zn
3 + OHC CH2 CHO (Propandial)
(4)
Applications:
The process is used to determine the position of C = C in a molecule.
If the products are rejoined, the position of C = C can be determined in the reactant molecule. All C = C (except
aromatic ones) undergo oxidative cleavage under normal conditions.
At higher temperature, the aromatic double bonds can also undergo ozonolysis.
O3
O = C C C C C = O + O = CH2
(1)
Zn
O ()
3
(2)
(4)
Q.
CH = CH CH3
low temperatur e
CH = O
(3)
Zn
O3 / Zn
+ O = CH CH3
O3
C6H5 CH = O
CH = CH
Zn
H / Ni
Cl / h
2 CnH2n 2 2
CnH2n1Cl
(P)
CnH2n 2
(Q )
(m products)
Single Compound
m3
(no isomer )
CH3
HCOOH + CH3 C COOH
CH3
Identify P ?
Ans.
P=
Q.
Find the structure of the hydrocarbon and the no. of monochloro products formed followed by hydrogenation.
Ans.
5 monochloro product
68
X
(Unsat. hydrocarbon)
H / Ni
2
Q.
Cl2
m products
h
(m 3 )
O 3 (Zn/H2O)
O
identify structure of X ?
Ans.
Q.
X =
H / Ni
2
X
(Unsat. H.C.)
Cl / h
2
m products
(m 7 )
O 3 (Zn/H2O)
C
X
Ans.
C=CC
Q.
Identify structure of X ?
Ans.
X is
Q.
H2
CCCCCC
X
O3 (Zn)
X is C C = C C = C C
69
Q.
O3
Zn, H2O
CH3
CH
3
O3
Zn, H2O
CH3
CH3
CH3
C C
+2
CH
3
Sol.
O O
Q.
Ex.1
(A) (C 9H18 )
Single monochloro produc
( Saturated
Hydrocarbon )
t
Cl2 / h
(B) (C8H18)
Cl / h
(C) (C 7H14 ) 2
s
Two monochloro products
( Saturated
Hydrocarbon)
Sol.
A=
or
Ex.2
C C
| |
B = CCCC
| |
C C
C =
Sol.
-Terpinene
Ex.3
Identify A & B
Sol.
A = CH3 C CH CH CH2
|
CH3
Ex.4
Identify A & m
A = Ph C C Ph
|
|
CH3 CH3
Sol.
m=3
Ex.5
H 2 / Ni
A
Cl / h n-products
2
O3
Zn/H 2O
H C H +
H C C CH2 CH2 C C H
Sol.
A=
n=7
71
1.1
1. Nitrogen
Test / Reaction
Remark
Lassaignes test
Na + C + N NaCN
2. Sulphur
Appearance
purple
2Na + S Na2S
Na2S + Na2[Fe(CN)5NO] Na4[Fe(CN)5NO.S]
3. Halogens
of
presence of sulphur
Lassaignes test
X + Na NaX
4. Phosphorus
pyrophosphate indicates
phosphorus
H3PO4 + Magnesia mixture MgP2O7 + H2O
2MgNH4PO4 Mg2P2O7 + 2NH3 + H2O
5. Nitrogen
and
Sulphur
Lassaignes test
FeCl
Na + C + N + S NaSCN
3 Fe(SCN)3
72
73
Lucas Reagent
[Conc. HCl + anhyd. ZnCl2]
ROH
3
2
1
White ppt.
R OH + HCl
white ppt
+ H2 O
cloudiness
R C C Ag (white)
R C C Cu (red)
RCOOH + RCOOH
2HCHO
2ROH + Na 2RONa + H2
R C CH + Ag+
R C CH + CuCl
Red ppt.
Na
R C C R
Acid formed.
= O Compounds
O3(ozone)
O3
H2C = CH2 + O3
--------------
NR
NR
NR
NR
Pink colour
Disappears
Reaction
Observation
Br2 / H2O
[Bayers reagent]
alk. dil. cold KMNO4
conc. H2SO4
conc. NaOH
KMnO4
LiAlH4
Reagent
(R OH)
R C CH
CC
CC
C=C/
CC
CC
Functional
Groups
Lucas Test
I. ter.alcohol
II. sec. alcohol
III. pri.alcohol
Presence of active H
Ozonolysis
Ozonolysis
Bromination
Hydroxylation
Inert paraffins
Remarks
74
Amides
Ester
CH3CHO
or ArCOCH3
or
R COCH3
R CHO
Ar OH
Enols
Functional
Groups
Sodium bicarbonate
test
Effervescence evolve.
Pink colour
disappear on heating.
Smell of NH3
NaOH, phenophthalein.
Conc. NaOH,
RCOONa + NH3
Schiffs reagent : p-Rosiniline hydrochloride saturated with SO2 so it is colourless. The pink colour is resumed by RCHO.
RCONH2 + NaOH
(pink)
Litmus test.
Iodoform reaction
Tollens test
Fehlings test
DNP-test
Test of
enols / phenols
Remarks
H2O + CO2
+ H2
Reaction
Blue litmus
Schifts Reagent *
I2 / NaOH
Tollens reagent
Red ppt.
2, 4-Dinitrophenyl hydrazine
(2, 4-DNP) solution
Fehling solution
A&B
Coloured ppt.
(violet, blue, green buff)
Observation
FeCl3 (Neutral)
Reagent
75
Violet colour
Blue colour
Amino acids
Molischs reagent
(10% -naphthol in alcohol).
R2NH
Sec. Amines
red colouration
Liebermann test
Effervescence of N2
Nauseating odour
(Carbylamine)
black ppt
Observation
Carbohydrate
CHCl3, KOH
Mullikens test
Reagent
Ar. amines.
ArNH2
Amines (pri.)
RNH2
Nitro
Compounds
(RCH2NO2) or
ArNO2
Functional
Groups
ArNHOH
C=N C
(Blue colour)
CO
CO
C
OH
CO
+ H2N.CHR.COOH
(Amino acid)
OH
OH
(Ninhydrin)
CO
CO
Benzenediazonium
chloride
Naphthol
N=N-Cl +
OH
N=N
OH
orange-red dye
+ 2H2O
N2Cl
NH2.HCl
ROH + N2 + H2O
NaCl + HNO2
+ HNO2
Ag
Ag
NaNO2 + HCl
R NH2 + HONO
Reaction
Ninhydrin test
Dye test
Carbylamine
Reaction
Remarks
Examples
1.
: Structure Determination
Ex. 1
Ex. 2
Ex. 3
Ex. 4.
2.
Ex.5
Which of the following will not give (+ve) L.S. test for Nitrogen.
(A) CH3CH2NH2
(B)
(C)
76
H2C = CH CH2 OH
Benzyl C+ , 1
Other Examples
Ex.1
Ans.
Ex.2
Ans.
Ex.3
Ans.
Ex.4
Ans.
77
Ex.5
Ans.
Ex.6
C4H8
Ans.
CH3 CH = CH CH3
Ex.7
(A)
Ans.
A=
Ans.
Ans.
O
||
CH3 C O CH3
Ans.
A=
Ex.8
Ex.9
Na metal ve
Ex.10
A (C7H8O)
FeCl3 (neutral)
ve
Lucas
ve
Reagent
Ex.11
Ans.
78
1.
Reagents
(I)
(a) CH3 CH2 COOH
(b) CH3 C O CH3
NaHCO3 (+)
NaHCO3 ()
Acidic odour
Fruity/Sweet
odour
Na metal (+)
Na metal ()
O
(II)
(a) Ph CH2 C OH
Same
O
(b) Ph C O CH3
Same
Same
O
(III)
(a) Ph CH2 CH = CH2
Br2/H2 O (+)
(b) Ph
Br2/H2O ()
Dil KMnO4 ()
(IV)
(a) CH3 CH2 CH2 OH
Na metal (+)
Na metal ()
Ceric Ammonium
Nitrate (+)
,, ()
(V)
CH3
(a) CH3 C OH
CH3
Lucas Reagent
instant turbidity
Na metal (+)
In 5 min.
Na metal (+)
(+)
In 30 min.
Na metal (+)
(+)
(VI)
(a) CH3 CH2 CH2 CH2 NH2
NaNO2/HCl
(N2 gas )
Na metal (+)
N2 gas not
liberated
Na metal (+)
2.
Ans.
A
C
D
F
G
H
I
J
(B) NaHCO3
(C) 2, 4-DNP
(D) AgNO3 + NH4OH
OH
3.
Sol.
T =
79
POC - II
Separation of binary mixture of organic compounds
Theory of separation : Organic compounds have different solubilities in different solvents. So they can be
separated by use of appropriate solvents.
The organic compounds derived from natural sources or prepared in the laboratory are seldom pure. They are
usually contaminated with other substances.
Purification means the removal of undesirable impurities associated with a particular organic compound, i.e
to obtain the organic compound in pure state.
1.
2.
Chemical methods:Chemical methods of separation depend upon the nature of the functional group present in the component.
Hence these can be applied to solid as well as liquid compounds.
A chemical method can be applied only when one of the components of the mixture is soluble in a particular
solvent while the other is insoluble in the same solvent .
Separation is the first step during the actual analysis of organic mixture. It is the most important step in the
sense that if separation is incomplete the result will not be correct because the impure compound will give
tests of different functional group and its melting point will also be very much different from that of the pure
compound obtained from complete separation.
(i)
(ii)
(iii)
(iv)
(1)
Most of the aromatic compounds are water insoluble due to large hydrophobic group of six carbon atom
Aromatic acids are insoluble in water but soluble in aqueous NaHCO3 solution or NaOH solution, due to salt
formation.
Aromatic hydroxy compounds are water insoluble but are soluble in aqueous NaOH solution due to salt
formation.
Aromatic amine (Aniline 1, 2, 3) are organic base and water insoluble but are soluble in aqueous HCl
solution due to salt formation.
Aliphatic compoud with atleast two functional group ( which can form H-bonding) are water soluble.
Ex. Diacids, diols. diamines, hydroxy acids ( OH, COOH), Amino acids ( NH2 , COOH) .
oxalic acid , malonic acid, maleic acid, fumaric acid, glycol, glycerol, sucrose, glucose.
80
Ex.1
Compound A
Compound B
Appropriate Solvent
(1)
H2O
(2)
H2O
81
(3)
Fructose
H2O
(4)
aq. NaHCO3
(5)
aq. NaOH
(6)
aq. HCl
Ex.2
Sol.
Ex.3
Identify I & II
Sol.
Q,
Ex.4
P+Q+R
Identify P, Q, R
Sol.
PI
Q II
R III
82
(1)
(2)
(3)
III
83