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ORGANIC CHEMISTRY
Chapter 1
Learning Outcomes
a.
c.
i.
Homolytic
ii.
Heterolytic
f.
Lewis acids
ii.
Cations
iii.
Lewis bases
ii.
Anions
iii.
Learning Outcomes
h. State the main types of organic reactions
i.
Addition
ii.
Elimination
iii.
Substitution
iv.
Oxidation
i.
j.
NO2, -CN, -COOH, -COOR, C=O, -SO3H, -X(halogen), -OH, -OR, -NH2, -C6H5
are electron receptors
ii.
l.
i.
ii.
PUSAT ASASI
SAINS
i.
CH
CH
3
OH and C6H5OH
Classification of C and H
Carbon
Carbon atoms can be classified by the number of other carbon
atoms that are directly attached to it.
In CH4, the carbon is unique (no other carbon attached), and there
is no classification for it.
1 - Primary carbons, are carbons attached to one other carbon.
2 - Secondary carbons are attached to two other carbons.
3 - Tertiary carbons are attached to three other carbons.
4 - Quaternary carbons are attached to four other carbons.
Since a carbon atom normally cannot bond to more than four other
carbons, there is no higher classification for carbon atoms than the
quaternary carbon.
Classification of C and H
H
CH3
H3C
1C
CH3
2C
CH3
H3C
CH3
H3C
CH3
H3C
CH3
3C
PUSAT ASASI SAINS
4C
Classification of C and H
Hydrogen
Primary hydrogen are the ones that are directly connected to a
primary carbon.
Secondary hydrogen connected to the secondary carbon.
Tertiary hydrogen connected to tertiary carbon.
There is no quaternary hydrogen due to limited bonding of carbon
atom to just four.
Classification of C and H
o
1
H
1
H
1o
H C
H1
H2
C
o
H2
1o
H C
1o
H
o
3
H
1o
H C
1o
H
o
1
H
Classification of C and H
EXERCISE 1.8: Classify all carbon and hydrogen atoms in the
following compounds.
H
H
H
H
Classification of C and H
H
H
10
H
30
H
H
10
H
20
10
H
10
H
H
H
hydrogen's class follow
the carbon it attached to
30
10
20
30
10
Heterolytic Cleavage
unsymmetrical
one of the fragments takes both the electrons
leaving none on the other.
The product of this bond-breaking are two charged particles
h o m o ly t ic
c le a v a g e
Example:
Cl 2
Cl
Cl
X:Z
X
Example:
Cl
H 2O
Cl
Nucleophile (:Nu-)
Electron-rich reagent (ve charged anion);
tries to donate e- to electrophile in reactions; proton/ nucleus
lover,
Lewis base
H
H
H
H
-bond is electron-rich
acts as a nucleophile
attracts electrophiles
Electrophiles
Name
H+
Hydrogen ion
H3O+
Hydronium ion
R-C+
carbocation
R-C+=O
carbonyl ion
NO2+
Nitronium ion
Cl+
Chloronium ion
AlCl3
Aluminium trichloride
FeCl3
Iron trichloride
BF3
Boron trifluoride
H2SO4
Sulphuric acid
HCl
Hydrochloric acid
HBr
Hydrogen bromide
H2O
water
Name
CNOHR-CXN3-
cyanide ion
hydroxide ion
carbonion
halide ion
azide ion
bisulfide
ammonia
amine
alcohol
-bond (alkene)
-bond (aromatic)
-bond (enols)
sodium borohydride
lithium aluminium hydride
water
HS
NH3
R-NH2
R-OH
R=C
C=C (aromatic)
R-C(OH)=C
NaBH4
LiAlH4
H2O
PUSAT ASASI SAINS
:Nu
Nu
Reaction Intermediates
an intermediate is a molecular entity that is formed from the
reactants (or preceding intermediates) and reacts further to give
the directly observed products of a chemical reaction.
Most chemical reactions are stepwise, that is they take more than
one elementary step to complete.
Reaction Intermediates
Three types of reaction intermediates
Reaction Intermediates
Free radicals
formed when one of the weak bonds is broken and odd number of
electrons remains in the valence shell of the bonded atoms
Instead of electron pair there is a movement of a single electron.
Free radicals are not stable which makes them highly reactive
species.
The most common organic reaction involving free radicals is the
free radical substitution reactions of alkane and alkyl halides.
A free radical carbon has 7 electrons in its valence shell (4+ 3
shared electrons from other atoms).
Indicated by a curved, halfheaded arrow
PUSAT ASASI SAINS
-+
-+
+ -
-+ + -
Reaction Intermediates
Carbocation
carbon atom acquires a positive charge and also bears three
bonds such that it has a sextet of electrons.
Carbocations are electrophile
1 Primary carbocation: The positively charged carbon atom is attached
to only one alkyl group.
2 Secondary carbocation: attached to two alkyl groups.
3 Tertiary carbocation: attached to three alkyl groups.
Reaction Intermediates
Carbonion
A molecule in which the carbon atom bears a negative charge.
Similar to carbocation, there are also primary, secondary and
tertiary carbonions.
Carbonions are nucleophiles
their stability depends upon various factors:
Inductive effect: If an electronegative atom is near to the charge then
it will stabilize the molecule
Hybridization of the charge bearing atom
The extent of conjugation
-+
-+
+ -
-+ + -
Addition
Substitution
Elimination
Rearrangement
Oxidation
Reduction
Condensation
E
Cl
C
Cl
:Nu
Cl
Cl
E
H
H
Nu
Addition Reaction
limited to chemical compounds that have multiple bonds, such as
alkenes or alkynes
2 types: electrophilic addition and nucleophilic addition.
General reaction mechanism:
:Nu
Nu
Cl
+
H
Cl
Cl
Cl
H
H
dichloroethane
PUSAT ASASI SAINS
Br
L
OH
H 2O
s lo w
HBr
:Nu
-
fa s t
Nu
:Nu
fa s t
Nu
H 2O
OH
HBr
Br
O H
+ Br
H 3O
OH
HBr
Nu
L
:Nu
Nu
Strength of nucleophile
Nature of leaving group
Nature of solvent
Cl
N aO H
OH
NaCl
HO
Cl
O H
Na
H
C
H
Cl
OH
NaCl
Step 1
X
H3C
H3C
Z
Step 2
:B
C
H
X
C
N aO H
NaBr
CH3
Br
H3C
Br
CH3
CH3
Step 2
OH
CH3
H
H
C
H
CH3
CH3
CH3
H2O
Na Br
:B
H
H
C
H
C
L
B-H
H3C
Cl
NaO H
H2C
CH2
H2O
Cl
H
H
C
H
H
C
Cl
H
H
H2O
Cl
OH
N H 2O H
cyclohexanone
O
H 2S O
cyclohexanoxime
caprolactam
rearrangement reaction
[O ]
R
OH
10 alcohol
[R ]
[O ]
H
aldehyde
[R ]
OH
carboxylic acid
H
CH3
(2Z)-but-2-ene
H
2
Pt or Pd or N i
H3C
CH3
H
n-butane
NHNu
3
:Nu
H3C
O O
O
ClL
H3C
+L
HCl
Nu NH
2
O
:Nu
Nu
Nu
+
H3C
Cl
NH3
H3C
NH2
HCl
H
Cl
O
O
H
ClCl
C
H
Cl
OH
Cl
OH OH
Effect of distance:
HO
O- H
H C
H3C
H3C H
C O
OH
OH
O
H
H3C
NH2
H
NH2
H
aniline
methanamine
O
+
-H
NH2
NH2
NH2
-
NH2
End of Chapter 1