Kuliah Kimia Organik Lanjut s1

KIMIA ORGANIK LANJUT
(ADVANCED ORGANIC CHEMISTRY)

Referensi : March, J ; Advanced Organic Chemistry : reactions,
mechanisms, and structure, 3 rd, Jhon Wiley @ Sons, NY 2004
Dosen : Dr. H. Djaswir Darwis, MSc, DEA
Dr. Mai Efdi, MS
Prof .Dr. Yunazar Manjang
Dr. Afrizal.
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IKATAN KIMIA TERLOKALISASI
(LOCALIZED CHEMICAL
BONDING)

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PENDAHULUAN

PEMBENTUKAN IKATAN ANTAR
ATOM KIMIA ORGANIK

The Atom
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Periodic Table
Li: solid, Cs: liquid, Ar: gas, Tc: synthetic
Number of protons
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Kearomatisan : Huckel
4n + 2 elektron
n = 0 atau pos integer
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Ikatan kovalen
Molekul terjadi adalah berupa ikatan atom dengan atom yang berasal
dari penggabungan elektron dari masing-masing atom.
Ikatan kovalen hampir mirip dengan ikatan metalik yang merupakan
penggabungan elektron.
Pada senyawa organik maka ikatan kovalen adalah ikatan yang
terbentuk dari 2 elektron dari masing-masing atom.
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A more detailed model of covalent bonding requires a consideration of
valence shell atomic orbitals. For second period elements such as carbon,
nitrogen and oxygen, these orbitals have been designated 2
s
, 2p
x
, 2p
y
& 2p
z
.
The spatial distribution of electrons occupying each of these orbitals is shown
in the diagram below.

The valence shell electron configuration of carbon is 2
s
2
, 2p
x
1
, 2p
y
1
& 2p
z
0
.
If this were the configuration used in covalent bonding, carbon would only be
able to form two bonds.
Molecular Orbital
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In order to explain the structure of methane (CH
4
), the 2s and three 2p orbitals must be converted
to four equivalent hybrid atomic orbitals,each having 25% s and 75% p character, and designated sp
3
.
These hybrid orbitals have a specific orientation, and the four are naturally oriented in a tetrahedral fashion.

Hybrid Orbitals
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s-orbitals have a spherical symmetry surrounding a single nucleus,
-orbitals have a cylindrical symmetry and encompass two (or more) nuclei.
In the case of bonds between second period elements, p-orbitals or hybrid atomic orbitals
having p-orbital character are used toform molecular orbitals.
For example, the sigma molecular orbital that serves to bond two fluorine atoms together is
generated y the overlap of p-orbitals (part A below), and two sp3 hybrid orbitals of carbon
may combine to give a similar sigma orbital. When these bonding orbitals are occupied by a
pair of electrons a covalent bond, the sigma bond
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. The hydrogen molecule provides a simple example of MO formation.
In the following diagram, two 1s atomic orbitals combine to give a sigma
() bonding (low energy) molecular orbital and a second higher energy
MO referred to as an antibonding orbital. The bonding MO is occupied
by two electrons of opposite spin, the result being a covalent bond.
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the orbital may be formed from two p-orbitals by a lateral overlap, as shown in
part A of the following diagram.Since bonds consisting of occupied -orbitals (pi-
bonds) are weaker than sigma bonds, pi-bonding between two atoms occurs only
when a sigma bond has already been established.
Thus, pi-bonding is generally found only as a component of double and triple
covalent bonds.
Since carbon atoms involved
in double bonds have only
three bonding partners, they
require only three hybrid
orbitalsto contribute to three
sigma bonds. A mixing of the
2s-orbital with two of the 2p
orbitals gives
three sp
2
hybrid orbitals,
leaving one of the p-orbitals
unused. Two sp
2
hybridized
carbon atoms are then joined
together by
sigma and pi-bonds (a double
bond), as shown in part B.
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A Chime model of the p and orbitals of a double bond may be examined by .
The p-orbitals in this model are represented by red and blue colored spheres,
which represent different phases, defined by the mathematical wave equations
for such orbitals.
Finally, in the case of carbon atoms with only two bonding partners only two
hybrid orbitals are needed for the sigma bonds, and these sp hybrid orbitals
are directed 180 from each other. Two p-orbitals remain unused on each sp
hybridized atom, and these overlap to give two pi-bonds following the formation
of a sigma bond (a triple bond), as shown below.
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The Shape of Molecules

Methane Ammonia Water
Configuratio
n
Bonding
Partners
Bond
Angles
Example
Tetrahedral 4 109.5
Trigonal 3 120
Linear 2 180
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H
2.20
Electronegativity
Elements
Li
0.98
Be
1.57
B
2.04
C
2.55
N
3.04
O
3.44
F
3.98
Na
0.90
Mg
1.31
Al
1.61
Si
1.90
P
2.19
S
2.58
Cl
3.16
K
0.82
Ca
1.00
Ga
1.81
Ge
2.01
As
2.18
Se
2.55
Br
2.96
Electronegativity differences may be transmitted through connecting covalent bonds by an inductive
effect. Replacing one of the hydrogens of water by a more electronegative atom increases the acidity
of the remaining OH bond. Thus hydrogen peroxide, HOOH, is ten thousand times more acidic
than water, and hypochlorous acid, ClOH is one hundred million times more acidic. This inductive
transfer of polarity tapers off as the number of transmitting bonds increases, and the presence of more
than one highly electronegative atom has a cumulative effect. For example, trifluoro ethanol, CF3CH2
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1A 2A 3A 4A 5A 6A 7A 8A
1
H
1s
1

2
He
1s
2

3
Li
1s
2

2s
1

4
Be
1s
2

2s
2

5
B
1s
2

2s
2
2p
1

6
C
1s
2

2s
2
2p
2

7
N
1s
2

2s
2
2p
3

8
O
1s
2

2s
2
2p
4

9
F
1s
2

2s
2
2p
5

10
Ne
1s
2

2s
2
2p
6

11
Na
[Ne]
3s
1

12
Mg
[Ne]
3s
2

13
Al
[Ne]
3s
2
3p
1

14
Si
[Ne]
3s
2
3p
2

15
P
[Ne]
3s
2
3p
3

16
S
[Ne]
3s
2
3p
4

17
Cl
[Ne]
3s
2
3p
5

18
Ar
[Ne]
3s
2
3p
6

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Replacing one of the hydrogens of water by a more
electronegative atom increases the acidity of the remaining
OH bond.
Thus hydrogen peroxide, HOOH, is ten thousand times
more acidic than water, and
hypochlorous acid, ClOH is one hundred million times more
acidic.
This inductive transfer of polarity tapers offas the number of
transmitting bonds increases, and the presence of more than
one highly electronegative atom has a cumulative effect.

For example, trifluoro ethanol, CF3CH2OH is about ten
thousand times more acidic than ethanol, CH3CH2OH.
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Bond Energy

Since reactions of organic compounds involve the making
and breaking of bonds, the strength
of bonds, or their resistance to breaking, becomes an
important consideration. For example, the
chlorination of methane, discussed previously, was induced
by breaking a relatively weak Cl-Cl
covalent bond.
Bond energy is the energy required to break a covalent
bond homolytically (into neutral fragments).
Bond energies are commonly given in units of kcal/mol or
kJ/mol, and are generally called bond
dissociation energies when given for specific bonds, or
average bond energies when summarized
for a given type of bond over many kinds of compounds

Configuration Bonding Partners Bond Angles Example
Tetrahedral 4 109.5
Trigonal 3 120
Linear 2 180
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Standard Bond Energies
Single Bonds H
*

Single Bonds H
*

Multiple Bonds H
*

HH 104.2 BF 154 C=C 146
CC 83 BO 123 N=N 109
NN 38.4 CN 73 O=O 119
OO 35 NCO 86 C=N 147
FF 36.6 CO 85.5 C=O (CO
2
) 192
SiSi 52 OCO 110 C=O (aldehyde) 177
PP 51 CS 65 C=O (ketone) 178
SS 54 CF 116 C=O (ester) 179
ClCl 58 CCl 81 C=O (amide) 179
BrBr 46 CBr 68 C=O (halide) 177
II 36. CI 51 C=S (CS
2
) 138
HC 99 CB 94 N=O (HONO
2
) 143
HN 93 CSi 83 P=O (POCl
3
) 110
HO 111 CP 73 P=S (PSCl
3
) 70
HF 135 NO 55 S=O (SO
2
) 128
HCl 103 SO 87 S=O (DMSO) 93
HBr 87.5 SiF 132 P=P 84
HI 71 SiCl 86 PP 117
HB 90 SiO 110 CO 258
HS 81 PCl 79 CC 200
HSi 70 PBr 65 NN 226
HP 77 PO 96 CN 213
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How to show the formation
Its like a jigsaw puzzle.
You put the pieces together to end up
with the right formula.
Carbon is a special example - can it
really share 4 electrons: 1s
2
2s
2
2p
2
?
Yes, due to electron promotion!
Another example: lets show how water is
formed with covalent bonds, by using an
electron dot diagram
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Water
H
O
Each hydrogen has 1 valence
electron
- Each hydrogen wants 1 more

The oxygen has 6 valence
electrons
- The oxygen wants 2 more
They share to make each
other complete
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Water
Put the pieces together
The first hydrogen is happy
The oxygen still needs one more
H O
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Water
So, a second hydrogen attaches
Every atom has full energy levels
H O
H
Note the two
unshared pairs of
electrons
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Multiple Bonds
Sometimes atoms share more than
one pair of valence electrons.
A double bond is when atoms share
two pairs of electrons (4 total)
A triple bond is when atoms share
three pairs of electrons (6 total)
Know these 7 elements as diatomic:
Br
2
I
2
N
2
Cl
2
H
2
O
2
F
2

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Dot diagram for Carbon dioxide
CO
2
- Carbon is central
atom

( more metallic )
Carbon has 4 valence
electrons
Wants 4 more
Oxygen has 6 valence
electrons
Wants 2 more
O
C
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Carbon dioxide
Attaching 1 oxygen leaves the
oxygen 1 short, and the carbon 3
short
O
C
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Carbon dioxide
Attaching the second oxygen
leaves both of the oxygen 1 short,
and the carbon 2 short
O
C
O
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Carbon dioxide
The only solution is to share more
O
C O
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Carbon dioxide
O
C O
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Carbon dioxide
O
C O
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Carbon dioxide
O
C O
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Carbon dioxide
O
C O
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Carbon dioxide
O
C O
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Carbon dioxide
Requires two double bonds
Each atom can count all the
electrons in the bond
O
C O
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Carbon dioxide
Each atom can count all the electrons in
the bond
O
C O
8 valence
electrons
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Carbon dioxide
the bond
O
C O
8 valence
electrons
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Carbon dioxide
the bond
O
C O
8 valence
electrons
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How to draw them?
Use the handout guidelines:
1) Add up all the valence electrons.
2) Count up the total number of
electrons to make all atoms happy.
3) Subtract; then Divide by 2
4) Tells you how many bonds to draw
5) Fill in the rest of the valence
electrons to fill atoms up.
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Example
NH
3
, which is ammonia
N central atom; has 5
valence electrons, wants 8
H - has 1 (x3) valence
electrons, wants 2 (x3)
NH
3
has 5+3 = 8
NH
3
wants 8+6 = 14
(14-8)/2= 3 bonds
4 atoms with 3 bonds
N
H
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N H H
H
Examples
Draw in the bonds; start with singles
All 8 electrons are accounted for
Everything is full done with this one.
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Example: HCN
HCN: C is central atom
N - has 5 valence electrons, wants 8
C - has 4 valence electrons, wants 8
H - has 1 valence electron, wants 2
HCN

has 5+4+1 = 10
HCN

wants 8+8+2 = 18
(18-10)/2= 4 bonds
3 atoms with 4 bonds this will require
multiple bonds - not to H however
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HCN
Put single bond between each atom
Need to add 2 more bonds
Must go between C and N (Hydrogen is full)
N H C
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HCN
Put in single bonds
Needs 2 more bonds
Must go between C and N, not the H
Uses 8 electrons need 2 more to
equal the 10 it has
N H C
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HCN
Put in single bonds
Need 2 more bonds
Must go between C and N
Uses 8 electrons - 2 more to add
Must go on the N to fill its octet
N H C
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Another way of indicating bonds
Often use a line to indicate a bond
Called a structural formula
Each line is 2 valence electrons
H H O
=
H H O
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Bond Dissociation Energies...
The total energy required to break the
bond between 2 covalently bonded
atoms
High dissociation energy usually
means the chemical is relatively
unreactive, because it takes a lot of
energy to break it down.
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Standard Bond Energies
Single Bonds H
*

Single Bonds H
*

Multiple Bonds H
*

HH 104.2 BF 154 C=C 146
CC 83 BO 123 N=N 109
NN 38.4 CN 73 O=O 119
OO 35 NCO 86 C=N 147
FF 36.6 CO 85.5 C=O (CO
2
) 192
SiSi 52 OCO 110 C=O (aldehyde) 177
PP 51 CS 65 C=O (ketone) 178
SS 54 CF 116 C=O (ester) 179
ClCl 58 CCl 81 C=O (amide) 179
BrBr 46 CBr 68 C=O (halide) 177
II 36. CI 51 C=S (CS
2
) 138
HC 99 CB 94 N=O (HONO
2
) 143
HN 93 CSi 83 P=O (POCl
3
) 110
HO 111 CP 73 P=S (PSCl
3
) 70
HF 135 NO 55 S=O (SO
2
) 128
HCl 103 SO 87 S=O (DMSO) 93
HBr 87.5 SiF 132 P=P 84
HI 71 SiCl 86 PP 117
HB 90 SiO 110 CO 258
HS 81 PCl 79 CC 200
HSi 70 PBr 65 NN 226
HP 77 PO 96 CN 213
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Molecular Orbitals are...
The model for covalent bonding
assumes the orbitals are those of
the individual atoms = atomic orbital
Orbitals that apply to the overall
molecule, due to atomic orbital
overlap are the molecular orbitals
A bonding orbital is a molecular
orbital that can be occupied by
two electrons of a covalent bond
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Molecular Orbitals - definitions
Sigma bond- when two atomic
orbitals combine to form the
molecular orbital that is
symmetrical along the axis
connecting the nuclei
Pi bond- the bonding electrons are
likely to be found above and below
the bond axis (weaker than sigma)
Note pictures on the next slide
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- Pages 230 and 231
Sigma bond is symmetrical along the axis
between the two nuclei.
Pi bond is
above and
below the bond
axis, and is
weaker than
sigma
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Bond Dissociation Energies
Bond dissociation energy is the total energy
required to break the bond between two
covalently bonded atoms.
A typical carbon-carbon single bond has a
bond dissociation energy of 347 kJ. The
ability of carbon to form strong bonds helps
to explain its stability.
They are unreactive partly because the
dissociation energy of these bonds is high.

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Resonance is...
When more than one valid dot diagram is
possible.
Consider the two ways to draw ozone (O
3
)
Which one is it? Does it go back and forth?
It is a hybrid of both, like a mule; and shown by a
double-headed arrow found in double-bond
structures!

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Resonance in Ozone
Neither structure is correct, it is actually a
hybrid of the two. To show it, draw all
varieties possible, and join them with a
double-headed arrow.
Note the different location of the double bond
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Resonance
Occurs when more than one valid Lewis
structure can be written for a particular
molecule (due to position of double bond)
These are resonance structures of benzene.
The actual structure is an average (or hybrid)
of these structures.
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Resonance in
a carbonate
ion (CO
3
2-
):
Resonance in an
acetate ion
(C
2
H
3
O
2
1-
):
Polyatomic ions note the different
positions of the double bond.
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Resonance structures are structures that
occur when it is possible to write 2 or more
valid electron dot formulas that have the
same of electron pairs for a molecule or
ion.
Electrons do NOT change position
Bond lengths are an average of possible
bond lengths.
Bonds become a hybrid of all the possible
bonds.
Increases stability within the atom
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V S E P R
Valence Shell Electron Pair Repulsion
(DAYA DORONG DARI PASANGAN ELEKTRON VALENSI YANG
TIDAK BERIKATAN PADA ORBITAL IKATAN)
Predicts the three dimensional shape of
molecules.
The name tells you the theory:
Valence shell = outside electrons.
Electron Pair repulsion = electron
pairs try to get as far away as
possible from each other.
Can determine the angles of bonds.
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Exceptions to the Octet
Some molecules exist with an odd of e
-

NO
2
has 7 valence e
-
Paramagnetic containing 1 or more
unpaired e
-
Appear heavier in magnetic fields

Diamagnetic contain only paired e
-

O
2

Recently discovered its paramagnetic
Suggesting unpaired e- but double bonds
make senseResonance is suggested
VSEPR Theory
(Valence Shell Electron Pair Repulsion Theory)

Because electrons repel, molecules adjust
shape so the electron pairs are as far
apart as possible.
Unshared pairs of e
-
are also important
when trying to predict shape.
Methane forms a tetrahedron with angles
of 109.5
O
(tetrahedral angle).
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Some common shapes:
linear triatomic, trigonal planar, bent triatomic,
pyramidal, tetrahedral, trigonal bipyramidal
Linear triatomic
Trigonal planar
Formaldehyde
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Water
105
o
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Ammonia
107
o
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Tetrahedral
Methane
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Trigonal
bipyramidal
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VSEPR
Based on the number of pairs of
valence electrons, both bonded and
unbonded.
Unbonded pair also called lone pair.
CH
4
- draw the structural formula
Has 4 + 4(1) = 8 ( 4 from C and 4x1 from H)
wants 8 + 4(2) = 16 (see structure 8 of C and 4x2 of H)
(16-8)/2 = 4 bonds ( bond formation of structure)
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VSEPR for methane (a gas):
Single bonds fill
all atoms.
There are 4 pairs
of electrons
pushing away.
The furthest they
can get away is
109.5
C H H
H
H
This 2-dimensional drawing does
not show a true representation of
the chemical arrangement.
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Angle of 4 atoms bonded
Basic shape is
tetrahedral.
A pyramid with a
triangular base.
Same shape for
everything with
4 pairs.
C
H H
H
H
109.5
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Ammonia (NH
3
) = 107
o

Water (H
2
O) = 105
o

Carbon dioxide (CO
2
) = 180
o

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Methane has an
angle of 109.5
o
,
called tetrahedral
Ammonia has an
angle of 107
o
,
called pyramidal
Note the unshared pair that is repulsion for other electrons.
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DEDE KIM-UA
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Polar Bonds and Molecules
- keelektronegatifan
- vsepr
- Konstanta dielektrikum
- sudut ikatan
-- polaritas
OBJECTIVES:
Describe how
electronegativity values
determine the distribution
of charge in a polar
molecule.
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Electronegativity?
The ability of an
atom in a molecule
to attract shared
electrons to itself.
Linus Pauling
1901 - 1994
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Table of Electronegativities
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H
2.20
Electronegativity
Elements
Li
0.98
Be
1.57
B
2.04
C
2.55
N
3.04
O
3.44
F
3.98
Na
0.90
Mg
1.31
Al
1.61
Si
1.90
P
2.19
S
2.58
Cl
3.16
K
0.82
Ca
1.00
Ga
1.81
Ge
2.01
As
2.18
Se
2.55
Br
2.96
Electronegativity differences may be transmitted through connecting covalent bonds by an inductive
effect
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DEDE KIM-UA
87
Replacing one of the hydrogens of water by a more
electronegative atom increases the acidity of the
remaining OH bond.

Thus hydrogen peroxide,
HOOH, is ten thousand times more acidic than
water,
hypochlorous acid, ClOH is one hundred million
times more acidic.
This inductive transfer of polarity tapers off as the
number of transmitting bonds increases, and the
presence of more than one highly electronegative
atom has a cumulative effect.
For example, trifluoro ethanol, CF3CH2- O-H
OBJECTIVES:
Describe what happens to polar molecules when
they are placed between oppositely charged metal
plates.
Evaluate the strength of intermolecular attractions
compared with the strength of ionic and covalent
bonds.

Identify the reason why network solids have high
melting points.
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Bond Polarity
Covalent bonding means shared
electrons
but, do they share equally?
Electrons are pulled, as in a tug-of-
war, between the atoms nuclei
In equal sharing (such as
diatomic molecules), the bond
that results is called a nonpolar
covalent bond
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When two different atoms bond
covalently, there is an unequal
sharing
the more electronegative atom will
have a stronger attraction, and will
acquire a slightly negative charge
called a polar covalent bond, or
simply polar bond.
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Bond Polarity
Consider HCl
H = electronegativity of 2.1
Cl = electronegativity of 3.0
the bond is polar
the chlorine acquires a slight
negative charge, and the
hydrogen a slight positive charge
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Only partial charges, much less
than a true 1+ or 1- as in ionic bond
Written as:
H Cl
the positive and minus signs (with
the lower case delta: )
denote partial charges.
o
+
o

+
and

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Can also be shown:

the arrow points to the more
electronegative atom.
how the electronegativity can also
indicate the type of bond that tends
to form

H Cl
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A polar bond tends to make the
entire molecule polar
areas of difference
HCl has polar bonds, thus is a polar
molecule.
A molecule that has two poles is
called dipole, like HCl
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The effect of polar bonds on the
polarity of the entire molecule depends
on the molecule shape
carbon dioxide has two polar bonds,
and is linear = nonpolar molecule!
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How Polar molecules
The effect of polar bonds on the
polarity of the entire molecule depends
on the molecule shape
water has two polar bonds and a bent shape;
the highly electronegative oxygen pulls the e
-

away from H = very polar!
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When polar molecules are
placed between oppositely
charged plates, they tend to
become oriented with respect
to the positive and negative
plates.

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Attractions between molecules
They are what make solid and liquid
molecular compounds possible.
The weakest are called van der
Waals forces - there are two kinds:
1. Dispersion forces
weakest of all, caused by motion of e
-

increases as e
-
increases
halogens start as gases; bromine is
liquid; iodine is solid all in Group 7A

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Dipole interactions
Occurs when polar molecules are
attracted to each other.
2. Dipole interaction happens in
water
positive region of one molecule
attracts the negative region of
another molecule.
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Occur when polar molecules are attracted
to each other.
Slightly stronger than dispersion forces.
Opposites attract, but not completely
hooked like in ionic solids.
H F
o
+
o

H F
o
+
o

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Single Covalent Bonds
A single covalent bond is one in which two atoms share
a pair of electrons.
Structural formulas are chemical formulas that show
the arrangement of atoms in molecules and polyatomic
ions.
Chemical Formula Structural Formula
H
2
H-H
H
2
O
NH
3
CH
4

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Unshared pairs (lone pairs) are pairs of
valence electrons that are not shared
between atoms.
When carbon forms bonds with other
atoms, it usually forms four bonds.
CH
4
C
2
H
6
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Double & Triple Covalent Bonds
Double covalent bonds share two pairs
of electrons.
CO
2
O=C=O

Triple covalent bonds share three pairs
of electrons.
N
2
:N=N:

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Coordinate Covalent Bonds
Two nuclei are attracted to a lone pair of
electrons (e
-
)
A bond in which one atom shares an entire pair
of electrons (lone pair) with another atom.
Typically forms polyatomic ions
In structural formulas, you can show coordinate
covalent bonds as arrows that point from the
atom donating the pair of electrons to the atom
receiving them.

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KEPOLARAN
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When e- pairs are not shared equally
between atoms
Due to differences in electronegativity
Polar covalent bond an uneven sharing
of e
-
between 2 nonmetals
Non-polar covalent bond an even
sharing of e
-
between 2 nonmetals

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The lower case Greek
letter delta shows that
atoms involved in the
covalent bond acquire
only partial charges,
much less than 1+ or
1-
The polarity of a bond
may also be
represented with an
arrow pointing to the
more electronegative
atom

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IKATAN LEBIH LEMAH DARI
IKATAN KOVALEN
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For example in
:
Hydrogen bonding
the attractive force caused by hydrogen bonded
to N, O, F, or Cl
N, O, F, and Cl are very electronegative, so this
is a very strong dipole.
And, the hydrogen shares with the lone pair in
the molecule.
This is the strongest of the intermolecular
forces.
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Hydrogen bonding defined:
When a hydrogen atom is:

a) covalently bonded to a highly electronegative atom,
b) is also weakly bonded to an unshared electron pair of
a nearby highly electronegative atom.
The hydrogen is left very electron deficient (it only had
1 to start with!) thus it shares with something nearby
Hydrogen is also the ONLY element with no shielding
for its nucleus when involved in a covalent bond!
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Hydrogen Bonding
(Shown in water)
H
H
O
o
+
o
-
o
+
This hydrogen is bonded covalently
to: 1) the highly negative oxygen,
and 2) a nearby unshared pair.
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Hydrogen bonding allows H
2
O to be a
liquid at room conditions.
H
H
O
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Dipole Interactions
o
+
o

o
+
o

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Hydrogen Bonding
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Attractions Between Molecules
There are several kinds of molecular
attractions.
The weakest attractions are
collectively called van der Waals
forces, which are named after the
chemist who discovered them,
Johannes van der Waals.
Van der Waals forces consist of two
types: dispersion forces and dipole
interactions.
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Van der Waals Forces
Dispersion forces are the weakest of all
molecular interactions and they are
caused by the motion of electrons.
The strength of dispersion forces increases as
the of electrons increases
Dipole interactions occur when polar
molecules are attracted to one another.
The slightly negative region of a polar
molecule is attracted to the slightly positive
region of another polar molecule.
Similar but much weaker than ionic bonds
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Hydrogen Bonds
Hydrogen bonds are
attractive forces in
which a hydrogen
covalently bonded
to a very
electronegative
atom is also weakly
bonded to an
unshared electron
pair of another
electronegative
atom.

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Hydrogen Bonds
Usually the electronegative atom is
oxygen, nitrogen, or fluorine, which has a
partial negative charge. The hydrogen then
has the partial positive charge.
Hydrogen bonding is usually stronger than
normal dipole forces between molecules.
Because oxygen has two lone pairs, two
different hydrogen bonds can be made to
each oxygen.
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http://www.northland.cc.mn.us/biology/Biology1111/animations/hydrogenbonds.html
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Hydrogen Bonds in DNA
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Order of Intermolecular attraction strengths
1) Dispersion forces are the weakest
2) A little stronger are the dipole interactions
3) The strongest is the hydrogen bonding
4) All of these are weaker than ionic bonds
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Polar Molecules
In a polar molecule, one end of the
molecule is slightly negative and the other
end is slightly positive.
The electrically charged regions are called
poles.
A molecule that has two poles is called a
dipolar molecule or dipole.
The effect of polar bonds on the polarity of
a molecule depends on its shape.
CO
2
H
2
O
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Polar or Non-Polar
Molecule?
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Atom H C N O F Cl Br I
Valence 1 4 3 2 1 1 1 1
Moment dipole and Charges

A large local charge separation usually results when a
shared electron pair is donated unilaterally. The three
Kekul formulas shown here illustrate this condition.

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Despite having two polar covalent bonds, carbon dioxide is
non-polar. The reason for this is the molecule's linear geometry:
The electrons are pulled in equal but opposite directions,
causing them to cancel one another.
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Water has two polar
covalent bonds, but the
polar covalent bonds pull
electrons to the oxygen's
region of the molecule, to
make the molecule polar.
The reason for this is the
molecule's bent
geometry: The electrons
are not pulled in equal
and opposite directions,
despite the bonds being
identical.
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Hyperconjugation
Hyperconjugation in organic chemistry is the stabilizing interaction that results
from the interaction of the electrons in a sigma bond (usually C-H or C-C) with an
adjacent empty (or partially filled) non-bonding p-orbital or antibonding orbital or
filled orbital to give an extended molecular orbital that increases the stability of
the system. Only electrons in bonds that are to the positively charged carbon
can stabilize a carbocation by hyperconjugation
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The stabilisation arises because the orbital interaction leads to the electrons being
in a lower energy orbital

Let's consider how a methyl group is involved in hyperconjugation with a
carbocation centre.
First we need to draw it to show the C-H o-bonds.
Note that the empty p orbital associated with the positive charge at the
carbocation centre is in the same plane (i.e. coplanar) with one of the C-H o-
bonds (shown in blue.)
This geometry means the electrons in the o-bond can be stabilised by an
interaction with the empty p-orbital of the carbocation centre.
(this diagram shows the similarity with resonance and the structure on the
right has the "double bond - no bond" character)
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Hyperconjugation has an effect on several chemical properties

.
Bond length: Hyperconjugation is suggested as a key factor in shortening of sigma bonds (
bonds) in such systems. For example, the single C-C bonds in 1,3-butadiene and
methylacetylene are approximately 1.46 angstrom in length, much less than the value (1.54
angstrom) found in saturated hydrocarbons. This is due mainly to hyperconjugation that gives
partial double-bond character of the bond.

Dipole moments: The large increase in dipole moment of 1,1,1-trichloroethane as compared
with chloroform can be attributed to hyperconjugated structures.

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1.The heat of formation of such molecules are
greater than sum of their bond energies; and the
heats of hydrogenation per double bond are less
than the heat of hydrogenation of ethylene.

1.Stability of carbocations:
(CH
3
)
3
C+ > (CH
3
)
2
CH+ > (CH
3
)CH
2
+ > CH
3
+
The C-C bond adjacent to the cation is free to
rotate, and as it does so, the three C-H bonds of
the methyl group in turn undergoes the stabilization
interaction. The more adjacent C-H bonds are, the
larger hyperconjugation stabilization is.
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STEREOCHEMISTRY
(stereokimia)
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* isomers ADALAH BERBEDA SENYAWA TETAPI SAMA RUMUS MOLEKUL
For example, in the case of the C4H8 hydrocarbons, most of the isomers are constitutional.
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OPTIS AKTIF DAN KHIRALITAS

OPTIS AKTIF : MOLEKUL YANG DAPAT MEMUTAR BIDANG SINAR YANG TERPOLARI SASI TIDAK BERIMPIT
DENGAN BAYANGAN CERMIN
SENYAWA KHIRAL.: MOL. ORG YANG KE 4 IKATAN PD ATM C TERIKAT DENGAN ATOM ATAU MOL. YANG
BERBEDA-BEDA.

N
C
H
3
C
H
H
N
H
3
C
CH
2
CH
3
H
H
OH
COOH
H
C
H
OH
COOH
H
3
C
:
:
sp
3
sp
3 sp
3
sp
3
N - simetris
C - simetris
C - asimetris
N - asimetris
Khiral
Khiral
Akhiral
Akhiral
Contoh : atom N dan C tetrahedral
146 DEDE KIM-UA
enantiomer
* are stereoisomers that are mirror images of
each other. Much as a left and right hand are
different but one is the mirror image of the
other
are stereoisomers whose molecules are
nonsuperimposable mirror images of each
other.

Enantiomers have
- when present in a symmetric environment
-identical chemical and physical properties
except for their ability to rotate plane-
polarized light by equal amounts but in
opposite directions.

A solution of equal parts of an optically-
active isomer and its enantiomer is known as
a racemic solution and has a net rotation of
plane-polarized light of zero.
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Enantiomers are stereoisomers whose molecules are
nonsuperimposable mirror images of one another
Objects that are superimposable on their
mirror images are said to be achiral
CH
3
CH
2
C
H HO
CH
3
CH
2
C
H
CH
3
CH
3
OH
Interchanging any two groups at a chiral
centre (stereocentre) that bears four
different groups converts one enantiomer
into another
Involves a tetrahedral sp
3
atom
CH
3
C
OH
CH
2
CH
3
2-Butanol
H
Chiral Centre
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One structure can be superimposed on another
If any of the groups
attached to the
tetrahedral atom are
the same, the centre
is achiral.
The ultimate way to test for
molecular chirality is to construct
models of the molecule and its
mirror image and then determine
whether they are superimposable
A molecule will not be chiral if it possess a
centre or plane of Symmetry
2-Propanol
CH
3
C
OH H
CH
3
C
CH
3
H HO
CH
3
Screwdriver is achiral
Socks are achiral
Golf club is chiral
Gloves are chiral
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Properties of Enantiomers
Enantiomers have identical melting points and boiling points
Enantiomers have identical solubilities in solvents
Enantiomers have identical spectra and refractive index
Enantiomers interact, and react with achiral molecules in the same manner
Enantiomers interact and react with other chiral molecules at different rates
Enantiomers rotate plane-polarised light by equal amounts but in opposite
directions
Plane-polarised light
Oscillation of electrical field of ordinary light
occurs in all possible directions
Polarimeter is a devise used to measure the effect of plane-polarised light on an
optically active compound
Chiral molecules are optically active
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No Correlation between the direction of rotation of plane
polarised light and the absolute configuration of a molecule
Clockwise Rotation (+) dextrorotatory
Anti-Clockwise Rotation (-) levorotatory

C
CH
2
CH
3
H
2
C
CH
3
H
HO
C
CH
2
CH
3
H
2
C
CH
3
H
Cl
(R)-(+)-2-Methyl-1-butanol
(R)-(-)-1-Chloro-2-methylbutanol
Same Configuration
An equimolar mixture of two enantiomers is called a Racemic Mixture
It is Optically Inactive
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In chemistry (particularly organic
chemistry and biochemistry), a
Fischer projection is a two-
dimensional representation of a
three-dimensional organic
molecule by projection. All bonds
are depicted as horizontal or
vertical lines. The carbon chain
is depicted vertically, with carbon
atoms represented by the center
of crossing lines. The orientation
of the carbon chain is so that the
C1 carbon is at the top
Fischer projection of D-glucose
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The structure must not be flipped over or rotated 90 degree
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.

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Some physical properties of the isomers of tartaric acid are given in the following table.

(+)-tartaric acid: []
D
= +13 m.p. 172 C
()-tartaric acid: []
D
= 13 m.p. 172 C
meso-tartaric acid: []
D
= 0 m.p. 140 C

Fischer projection formulas provide a helpful view of the configurational relationships
within the structures of these isomers. In the following illustration a mirror line is drawn
between formulas that have a mirror-image relationship. In demonstrating the identity of
the two meso-compound formulas, remember that a Fischer projection formula may be
rotated 180 in the plane.
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(natural) tartaric acid
L-(+)-tartaric acid
dextrotartaric acid
D-(-)-tartaric acid
levotartaric acid

(1:1)
DL-tartaric acid
"racemic acid"
mesotartaric acid
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ISOMER STRUKTURAL
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* isomers ADALAH BERBEDA SENYAWA TETAPI SAMA RUMUS MOLEKUL
For example, in the case of the C4H8 hydrocarbons, most of the isomers are constitutional.
C4H8
C4H8
C4H8
C4H8
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Selasa.
Kamis, 22-10-09
Jumat, 23-10-09
Configurational Stereoisomers of Alkenes
alkynes are linear, there is no stereoisomerism associated with the carbon-carbon triple bond.
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Assignment of a cis or trans prefix to any of these isomers can only be done in an
arbitrary manner, so a more rigorous method is needed.
* based on a set of group priority rules,
assigns a Z (German, zusammen for together) is equivalent to cis or
E (German, entgegen for opposite) is equivalent to trans
to designate the stereoisomers Z and E.

The Sequence Rule for Assignment of Alkene Configurations

Assign priorities to double bond substituents by looking at the atoms attached directly
to the double bond carbons.
The higher the atomic number of the immediate substituent atom, the higher the priority.
For example,
H < C < N < O < Cl. (priority increases left to right)

(Different isotopes of the same element are assigned a priority according to their atomic mass.)

If two substituents have the same immediate substituent atom, move to the next atom (away
from the double bond) until a difference is found.
For example, CH3 < C2H5 < ClCH2 < BrCH2 < CH3O.
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Extreme Conformations of Ethane

Name of
Conformer
Wedge-Hatched
Bond Structure
Sawhorse
Structure
Newman
Projection

ANALISA KONFORMASI
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KONFORMASI ENANSIOMERIK
Conformations of meso-Tartaric Acid
Fischer
Projection
A
eclipsed, achiral
B
staggered, chiral
C
staggered, achiral
D
staggered, chiral
190 DEDE KIM-UA
.

The 1,2-Dichlorocyclohexanes The 1,3-Dichlorocyclohexanes

Stereoisomerism in Disubstituted Cyclohexanes
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KARBOKATION
(KARBONIUM ION)
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Ph3C-OH + H2SO4 Ph3C
+
HSO4
-
+ H2O (Ph stands for a phenyl substituent)
A carbocation (pronounced "carbo-cat-ion") is an ion with a positively-charged
carbon atom.( carbonium ion )
The charged carbon atom in a carbocation has only six electrons in its outer
valence shell instead of the eight valence electrons that ensures maximum stability
(octet rule).
The carbon cation is unstable and very reactive, seeking to fill its octet of valence
electrons as well as regain its neutral charge.
Order of stability of examples of
tertiary ( III ), secondary ( II ), and primary ( I ),
alkyl
An alkyl group is a group such as methyl,
CH3, or ethyl, CH3CH2. These are groups
containing chains of carbon atoms which
may be branched. Alkyl groups are given
the general symbol R.

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Some examples of primary carbocations include:

Notice that it doesn't matter how complicated the attached alkyl group is. All you are
doing is counting the number of bonds from the positive carbon to other carbon atoms.
In all the above cases there is only one such link.
Using the symbol R for an alkyl group, a primary carbocation would be written as in the
box.
Primary carbocations
In a primary (1) carbocation, the carbon which carries the positive charge is only
attached to one other alkyl group.
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Secondary carbocations
In a secondary (2) carbocation, the carbon with the positive charge is attached
to two other alkyl groups, which may be the same or different.

Examples:
A secondary carbocation has the general formula shown in the box. R and R' represent
alkyl groups which may be the same or different.
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A tertiary carbocation has the general formula shown in the box. R, R' and R" are alkyl
groups and may be the same or different.

Tertiary carbocations

In a tertiary (3) carbocation, the positive carbon atom is attached to three alkyl groups,
which may be any combination of same or different.
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Structure:

Alkyl carbocations are sp
2

hybridised, planar
systems at the cationic C
centre.
The p-orbital that is not
utilised in the hybrids is
empty and is often shown
bearing the positive
charge since it represents
the orbital available to
accept electrons.
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The stability of the various carbocations

The "electron pushing effect" of alkyl groups
You are probably familiar with the idea that bromine is more electronegative
than hydrogen, so that in a H-Br bond the electrons are held closer to the
bromine than the hydrogen. A bromine atom attached to a carbon atom would
have precisely the same effect - the electrons being pulled towards the bromine
end of the bond. The bromine has a negative inductive effect.
Alkyl groups do precisely the opposite and, rather than draw electrons towards
themselves, tend to "push" electrons away
This means that the alkyl group becomes slightly positive (+) and the carbon they are
attached to becomes slightly negative ( -). The alkyl group has a positive inductive effect.
This is sometimes shown as, for example:

The arrow shows the electrons being "pushed" away from the CH
3
group. The plus sign
on the left-hand end of it shows that the CH
3
group is becoming positive. The
symbols + and - simply reinforce that idea.
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The importance of spreading charge around in making ions stable

The general rule-of-thumb is that if a charge is very localised (all concentrated on one atom)
the ion is much less stable than if the charge is spread out over several atoms.
Applying that to carbocations of various sorts . . .

You will see that the electron pushing effect of the CH
3
group is placing more and more
negative charge on the positive carbon as you go from primary to secondary to tertiary
carbocations. The effect of this, of course, is to cut down that positive charge.
At the same time, the region around the various CH
3
groups is becoming
somewhat positive. The net effect, then, is that the positive charge is being
spread out over more and more atoms as you go from primary to secondary to
tertiary ions.
The more you can spread the charge around, the more stable the ion becomes.

Order of stability of carbocations: primary < secondary < tertiary

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The stability of the carbocations in terms of energetics

When we talk about secondary carbocations being more stable than primary ones, what
exactly do we mean? We are actually talking about energetic stability - secondary
carbocations are lower down an energy "ladder" than primary ones.
This means that it is going to take more energy to make a primary carbocation than a
secondary one.
If there is a choice between making a secondary ion or a primary one, it will be much
easier to make the secondary one.
Similarly, if there is a choice between making a tertiary ion or a secondary one, it will be
easier to make the tertiary one.
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Stability:

The general stability order of simple alkyl carbocations is: (most stable) 3
o
> 2
o
> 1
o
>
methyl (least stable)

This is because alkyl groups are weakly electron donating due to hyperconjugation and
inductive effects. Resonance effects can further stabilize carbocations when present.

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Mechanism

MEKANISME
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STEREOKIMIA ION KARBONIUM
Mekanisme sesuai dengan reaksi Substitusi Nukleofiik order 1.
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-Karbokation berumur pendek
-Karbokation tidak dapat diisolasi
-Karbokation dapat bergabung dengan spesies yang mempunyai pasangan elektron

R
+
Y
-
R
Y +
- Kehilangan proton dari atom yang bertetangga dengan ion karbonium
C Z H
+
C Z
+
H
+
- Penataan ulang (rearrangement)
CH3
CH CH2
H
+
+
H
CH2 CH
CH3
- Adisi
R
+ +
+ C C
C C R
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Carbanions
|
C:

|

The conjugate bases of weak acids,
strong bases, excellent nucleophiles.
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1. Alpha-halogenation of ketones
C C
H
O
+ X
2
OH
-
or H
+
C C
X
O
+ HX
X
2
= Cl
2
, Br
2
, I
2
-haloketone
o
H
3
C
C
CH
3
O
+ Br
2
, NaOH
H
3
C
C
CH
2
Br
O
+ NaBr
acetone -bromoacetone
o
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O
+ Cl
2
, H
+
O
Cl
+ HCl
2-chlorocyclohexanone
C CH
3
O
+ Br
2
, NaOH
C CH
2
Br + NaBr
O
-bromoacetophenone
o
cyclohexanone
acetophenone
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Alpha-hydrogens: 1
o
> 2
o
> 3
o

CH
3
CH
2
CH
2
CCH
3
O
2-pentanone
+ Br
2
, NaOH
CH
3
CH
2
CH
2
CCH
2
Br + NaBr
O
1-bromo-2-pentanone
Hydrogens that are alpha to a carbonyl group are weakly acidic:
H
3
C
C
CH
3
O
H
3
C
C
CH
2
O
+ OH
+ H
2
O
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R
C
CH
2
O
R
C
CH
2
O
"enolate" anion
Hydrogens that are alpha to a carbonyl are weakly
acidic due to resonance stabilization of the carbanion.
The enolate anion is a strong base and a good nucleophile
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Mechanism for base promoted alpha-bromination of acetone:
H
3
C
C
CH
3
O
H
3
C
C
CH
2
O
+ OH
+ H
2
O
RDS
H
3
C
C
CH
2
O
+
Br Br
H
3
C
C
CH
2
Br
O
+ Br
1)

2)
Rate = k [acetone] [base]
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RDS = rate determination step
Mechanism for acid catalyzed halogenation of ketones. Enolization.
H
3
C
C
CH
3
O
H
3
C
C
CH
3
OH
+ H
+
H
3
C
C
CH
3
OH
+ :B
H
3
C
C
CH
2
OH
+ H:B
H
3
C
C
CH
2
OH
+ Br Br
H
3
C
C
CH
2
Br
OH
+ :Br
H
3
C
C
CH
2
Br
OH
H
3
C
C
CH
2
Br
O
+ H
enol
1)

2)

3)

4)
219 DEDE KIM-UA
R
C
CH
3
O
Oxidation of "methyl" ketones. Iodoform test.
+ (xs) OI
R C
O
O
+ CHI
3
NaOH + I
2
R
C
CH
2
I
O
R
C
CHI
2
O
R
C
CI
3
O
+ OH
R C CI
3
O
OH
good
leaving
group
220 DEDE KIM-UA
Carbanions. The conjugate bases of weak acids;
strong bases, good nucleophiles.
1. enolate anions
2. organometallic compounds
3. ylides
4. cyanide
5. acetylides

221 DEDE KIM-UA
Aldehydes and ketones: nucleophilic addition

Esters and acid chlorides: nucleophilic acyl substitution

Alkyl halides: S
N
2
C
O
+ YZ
C
OY
Z
C
W
O
+ Z C
Z
O
+ W
R X
+ Z
R Z + X
Carbanions as the nucleophiles in the above reactions.
222 DEDE KIM-UA
2. Carbanions as the nucleophiles in nucleophilic
addition to aldehydes and ketones:
a) aldol condensation
crossed aldol condensation
b) aldol related reactions
c) addition of Grignard reagents
d) Wittig reaction
223 DEDE KIM-UA
Carbanions as the nucleophiles in nucleophilic addition to
aldehydes and ketones:
c) addition of Grignard reagents
Grignard reagents are examples of organo metallic
carbanions.
C
O
+ RMgX
C
OMgX
R
224 DEDE KIM-UA
a) Aldol condensation. The reaction of an aldehyde or ketone
with dilute base or acid to form a beta-hydroxycarbonyl product.
CH
3
CH=O
dil. NaOH
CH
3
CHCH
2
CH O
OH
acetaldehyde
3-hydroxybutanal
CH
3
CCH
3
O
dil. NaOH
CH
3
CCH
2
CCH
3
O OH
CH
3
acetone
4-hydroxy-4-methyl-2-pentanone
225 DEDE KIM-UA
CH
3
CH=O
dil. NaOH
CH
3
CHCH
2
CH O
OH
acetaldehyde
3-hydroxybutanal
OH
CH
2
CH=O
CH
3
CH
+
O
CH
3
CHCH
2
CH O
O
+ H
2
O
+ H
2
O
nucleophilic addition by enolate ion.
226 DEDE KIM-UA
H
3
C
C
CH
3
O
OH
H
3
C
C
CH
2
O
H
3
C
C
CH
3
O
H
3
C
C
O
C
H
2
C
O
CH
3
CH
3
+ H
2
O
+ H
2
O
H
3
C
C
O
C
H
2
C
OH
CH
3
CH
3
dil. NaOH
227 DEDE KIM-UA
CH
3
CH
2
CH=O + dil. NaOH
CH
3
CH
2
CHCH
2
CH
2
CH
OH
O
CH
3
CHCH O
alpha!
CH
3
CH
2
CH
CH
3
CH
2
CHCHCH
OH
CH
3
O
O
228 DEDE KIM-UA
O
dil. OH
-
O
OH
OH
O
O
O
O
+ HOH
229 DEDE KIM-UA
dil. H
+
O
+ H
2
O
O
With dilute acid the final product is the ,-
unsaturated carbonyl compound!
230 DEDE KIM-UA
CH
2
CH O
phenylacetaldehyde
dil NaOH
CH
2
C
H
CH
OH
CH=O
dilute H
+
CH
2
C
H
C CH=O
note: double bond is conjugated
with the carbonyl group!
+ H
2
O
231 DEDE KIM-UA
NB: An aldehyde without alpha-hydrogens
undergoes the Cannizzaro reaction with conc. base.
CHO
benzaldehyde
conc. NaOH
COO
-
CH
2
OH
+
232 DEDE KIM-UA
Crossed aldol condensation:
If you react two aldehydes or ketones together in an
aldol condensation, you will get four products. However, if
one of the reactants doesnt have any alpha hydrogens it can be
condensed with another compound that does have alpha
hydrogens to give only one organic product in a crossed
aldol.
CH
3
CH
2
CH + H
2
C O O
CH
3
CHCH
2
OH
CH O NaOH
233 DEDE KIM-UA
If the product of the aldol condensation under basic
conditions is a benzyl alcohol, then it will spontaneously
dehydrate to the ,-unsaturated carbonyl.
CH=O + CH
3
CH
2
CH
2
CH=O
dil OH
-
CH=CCH=O
CH
2
CH
3
CHCHCH=O
OH
CH
2
CH
3
-H
2
O
234 DEDE KIM-UA
A crossed aldol can also be done between an aldehyde and a
ketone to yield one product. The enolate carbanion from the
ketone adds to the more reactive aldehyde.
C CH
3
O
acetophenone
+
CH
3
CH=O
acetaldehyde
dil OH
-
CCH
2
O
C
H
OH
CH
3
235 DEDE KIM-UA
b) Aldol related reactions:
CH=O + CH
3
NO
2
KOH
CH=CHNO
2
+ H
2
O
CH
2
NO
2
CH=O +
CH
2
C N
NaOEt
CH=C CN
CHC N
+ H
2
O
236 DEDE KIM-UA
Perkin condensation
CH=O + (CH
3
CO)
2
O
CH
3
COONa
CH=CHCOOH
H
2
C C
O
O
C CH
3
O
CH
OH
CH
2
C
O
O
C CH
3
O
+ H
2
O
H
C C
H
C
O
O
C CH
3
O
hydrolysis of
anhydride
+ CH
3
COOH
237 DEDE KIM-UA
d) Wittig reaction (synthesis of alkenes)
1975 Nobel Prize in Chemistry to Georg Wittig
C O + Ph
3
P=C
R'
R
ylide
C
O
C R'
R
PPh
3
C C
R
R'
+ Ph
3
PO
CH
2
CH=O +
Ph
3
P=CH
2
CH
2
CH=CH
2
+ Ph
3
PO
Ph = phenyl
238 DEDE KIM-UA
C
O
C R'
R
PPh
3
C C
R
R'
+ Ph
3
PO
P
Ph
Ph
Ph
C
R
R' C
O
ylide
nuclephilic addition by ylide carbanion, followed by loss of
Ph
3
PO (triphenylphosphine oxide)
239 DEDE KIM-UA
O
+
Ph
3
PCHCH=CH
2
CHCH CH
2
+ Ph
3
PO
240 DEDE KIM-UA
3. Carbanions as the nucleophiles in nucleophilic acyl
substitution of esters and acid chlorides.
a) Claisen condensation
a reaction of esters that have alpha-hydrogens in basic
solution to condense into beta-keto esters
CH
3
COOEt
ethyl acetate
NaOEt
CH
3
CCH
2
COOEt
O
+ EtOH
ethyl acetoacetate
241 DEDE KIM-UA
CH
3
COOEt
NaOEt
CH
3
CCH
2
COOEt
O
+ EtOH
CH
3
C
OEt
O
CH
3
C OEt
O
CH
2
COOEt
nucleophilic acyl substitution by enolate anion
OEt
CH
2
COOEt
Mechanism for the Claisen condensation:
242 DEDE KIM-UA
ethyl propionate
CH
3
CH
2
CCHCOOEt
CH
3
O
ethyl 2-methyl-3-oxopentanoate
OEt
CH
3
CH
2
COOEt
OEt
CH
3
CHCOOEt
CH
3
CH
2
C
O
OEt
CH
3
CH
2
C
O
OEt
CHCOOEt
CH
3
243 DEDE KIM-UA
CH
2
COOEt
NaOEt
CH
2
C
O
CHCOOEt
ethyl phenylacetate
CHCOOEt
CH
2
C
O
OEt
CH
2
C
O
CHCOOEt
OEt
OEt
244 DEDE KIM-UA
Crossed Claisen condensation:
COOEt
+ CH
3
COOEt
NaOEt
C
O
CH
2
COOEt
ethyl benzoate
HCOOEt + CH
3
CH
2
COOEt
ethyl formate
H C
O
CHCOOEt
CH
3
OEt
245 DEDE KIM-UA
COOEt
COOEt
CH
3
CH
2
COOEt
OC
2
H
5
+
C
O
C
O
OEt
CHCOOEt
CH
3
COOEt
COOEt
2 CH
3
CH
2
COOEt
NaOC
2
H
5
+
C
O
C
O
CHCOOEt
CH
3
CHCOOEt
CH
3
ethyl oxalate
246 DEDE KIM-UA
EtOCOEt
ethyl carbonate
+
COOEt
CH
2
COOEt
ethyl malonate
NaOEt
C CH
O COOEt
COOEt
EtO
CH
3
CH
2
COOEt
ethyl propionate
+
O
cyclohexanone
NaOEt
CH
3
CH
2
C
O
O
enolate from ketone in nucleophilic acyl substitution on ester
O
247 DEDE KIM-UA
b) Coupling of lithium dialkyl cuprate with acid chloride
R C
Cl
O
+ R'
2
CuLi
R C
R'
O
nucleophile = R'
248 DEDE KIM-UA
4. Carbanions as nucleophiles in S
N
2 reactions with RX:
a) Corey-House synthesis of alkanes
R
2
CuLi + RX R-R
b) metal acetylide synthesis of alkynes
RCC
-
M
+
+ RX RCCR
c) Malonate synthesis of carboxylic acids

d) Acetoacetate synthesis of ketones
5. Michael Addition to ,-unsaturated carbonyl
compounds
249 DEDE KIM-UA
Carbanions are the conjugate bases of weak acids and
are therefore strong bases and excellent nucleophiles
that can react with
aldehydes/ketones (nucleophilic addition),
esters/acid chlorides (nucleophilic acyl substitution),
and
alkyl halides (S
N
2), etc.
250 DEDE KIM-UA
Reactions involving carbanions as nucleophiles:

1. Alpha-halogenation of ketones

2. Nucleophilic addition to aldehydes/ketones
a) aldol and crossed aldol
b) aldol related reactions
c) Grignard synthesis of alcohols
d) Wittig synthesis of alkenes

3. Nucleophilic acyl substitution with esters and
acid chlorides
a) Claisen and crossed Claisen
b) R2CuLi + RCOCl
251 DEDE KIM-UA
4. SN2 with alkyl halides
a) Corey-House
b) metal acetylide
c) Malonate synthesis
d) Acetoacetate synthesis

5. Michael Addition to ,-unsaturated carbonyl
compounds
252 DEDE KIM-UA

253 DEDE KIM-UA
Carbanions II
Carbanions as nucleophiles in S
N
2 reactions
with alkyl halides.
a) Malonate synthesis of carboxylic acids
b) Acetoacetate synthesis of ketones
c) 2-oxazoline synthesis of esters/
carboxylic acids
d) Organoborane synthesis of acids/
ketones
e) Enamine synthesis of aldehydes/ketones
254 DEDE KIM-UA
Malonate synthesis of carboxylic acids.
1. Diethyl malonate has acidic alpha-hydrogens

2. When reacted with sodium metal, the ester is converted
into its conjugate base (an enolate anion)

CO
2
CH
2
CH
3
CH
2
CO
2
CH
2
CH
3
CO
2
CH
2
CH
3
CH
2
CO
2
CH
2
CH
3
Na
CO
2
CH
2
CH
3
CH
CO
2
CH
2
CH
3
+ Na
+
+ H
2
255 DEDE KIM-UA
3. The enolate can be used as the nucleophile in an S
N
2
reaction with a 1
o
or CH
3
alkyl halide.

4. Upon hydrolysis, the substituted malonic acid will
decarboxylate when heated.

5. Product is a carboxylic acid derived from acetic acid.
CO
2
Et
CH
CO
2
Et
+ R-X
S
N
2
CO
2
Et
CH
CO
2
Et
R
CO
2
Et
CH
CO
2
Et
R
H
2
O, H
+
heat
CO
2
H
CH
CO
2
H
R
- CO
2
heat
CH
2
CO
2
H R
256 DEDE KIM-UA
C
CH
2
O
C
O
OEt
OEt
diethyl malonate
Na
C
CH
O
C
O
OEt
OEt
Na
RX
C
CH
O
C
O
OEt
OEt
R
H
+
,H
2
O
heat
C
CH
O
C
O
OH
OH
R
heat
-CO
2
CH
2
COOH
Na
C
C
O
C
O
OEt
OEt
R
R'X
C
C
O
C
O
OEt
OEt
R
H
+
,H
2
O
heat
C
C
O
C
O
OH
OH
R
-CO
2
heat
R
CHCOOH R
R'
R'
R'
257 DEDE KIM-UA
CH
2
COOH R
CHCOOH R
R'
The malonate synthesis makes substituted acetic acids
with one or two alkyl groups on the alpha carbon.
for example: synthesis of 4-methylpentanoic acid
CH
3
CHCH
2
CH
2
COOH
CH
3
start with diethyl malonate and isobutyl bromide
258 DEDE KIM-UA
C
CH
2
O
C
O
OEt
OEt
diethyl malonate
Na
C
CH
O
C
O
OEt
OEt
Na
C
CH
O
C
O
OEt
OEt
H
+
,H
2
O
heat
heat
-CO
2
CH
3
CHCH
2
Br
CH
3
CH
3
CHCH
2
CH
3
C
CH
O
C
O
OH
OH
CH
3
CHCH
2
CH
3
CH
3
CHCH
2
CH
2
COOH
CH
3
259 DEDE KIM-UA
Malonate synthesis of 2-methylpentanoic acid

Start with diethyl malonate and methyl bromide and n-propyl
bromide.
CH
3
CH
2
CH
2
CHCOOH
CH
3
260 DEDE KIM-UA
C
CH
2
O
C
O
OEt
OEt
diethyl malonate
Na
C
CH
O
C
O
OEt
OEt
Na
C
CH
O
C
O
OEt
OEt
H
3
C
C
C
O
C
O
OEt
OEt
H
3
C
C
C
O
C
O
OEt
OEt
H
3
C CH
2
CH
2
CH
3
CH
3
Br
Na
CH
3
CH
2
CH
2
Br
H
+
,H
2
O
heat
-CO
2
heat
CH
3
CH
2
CH
2
CHCOOH
CH
3
261 DEDE KIM-UA
Acetoacetate synthesis of ketones.
1. Ethyl acetoacetate has acidic alpha-hydrogens.

2. When reacted with sodium metal, the ester is converted
into its conjugate base (an enolate anion).
3. The enolate can be used as the nucleophile in an S
N
2
reaction with a 1
o
or CH
3
alkyl halide.
4. Upon hydrolysis, the substituted acetoacetic acid will
decarboxylate when heated.
5. Product is a ketone derived from acetone.
CO
2
CH
2
CH
3
CH
2
COCH
3
CH
3
CCH
2
CO
2
Et
O
262 DEDE KIM-UA
C
CH
2
O
C
O
CH
3
OEt
ethyl acetoacetate
Na
C
CH
O
C
O
CH
3
OEt
Na
RX
C
CH
O
C
O
CH
3
OEt
R
H
+
,H
2
O
heat
C
CH
O
C
O
CH
3
OH
R
heat
-CO
2
CH
2
CCH
3
Na
C
C
O
C
O
CH
3
OEt
R
R'X
C
C
O
C
O
CH
3
OEt
R
H
+
,H
2
O
heat
C
C
O
C
O
CH
3
OH
R
-CO
2
heat
R
CHCCH3 R
R'
R'
R'
O
O
263 DEDE KIM-UA
CH
2
CCH
3
R
CHCCH
3
R
R'
The acetoacetate synthesis makes substituted acetones
with one or two alkyl groups on the alpha carbon.
for example: synthesis of 5-methyl-2-hexanone
CH
3
CHCH
2
CH
2
CCH
3
CH
3
start with ethyl acetoacetate and isobutyl bromide
O
O
O
264 DEDE KIM-UA
C
CH
2
O
C
O
CH
3
OEt
ethyl acetoacetate
Na
C
CH
O
C
O
CH
3
OEt
Na
C
CH
O
C
O
CH
3
OEt
H
+
,H
2
O
heat
heat
-CO
2
CH
3
CHCH
2
Br
CH
3
CH
3
CHCH
2
CH
3
C
CH
O
C
O
CH
3
OH
CH
3
CHCH
2
CH
3
CH
3
CHCH
2
CH
2
CCH
3
CH
3
O
265 DEDE KIM-UA
Acetoacetate synthesis of 3-methyl-2-hexanone

Start with ethyl acetoacetate and methyl bromide and n-
propyl bromide.
CH
3
CH
2
CH
2
CHCCH
3
CH
3
O
266 DEDE KIM-UA
C
CH
2
O
C
O
CH
3
OEt
Na
C
CH
O
C
O
CH
3
OEt
Na
C
CH
O
C
O
CH
3
OEt
H
3
C
C
C
O
C
O
CH
3
OEt
H
3
C
C
C
O
C
O
CH
3
OEt
H
3
C CH
2
CH
2
CH
3
CH
3
Br
Na
CH
3
CH
2
CH
2
Br
H
+
,H
2
O
heat
-CO
2
heat
CH
3
CH
2
CH
2
CHCCH
3
CH
3
O
ethyl acetoacetate
267 DEDE KIM-UA
Synthesis of 2,5-hexanedione
CH
3
CCH
2
CH
2
CCH
3
O O
C
CH
2
O
C
O
CH
3
OEt
ethyl acetoacetate
Na
C
CH
O
C
O
CH
3
OEt
Na
C
CH
O
C
O
CH
3
OEt
H
+
,H
2
O
heat
heat
-CO
2
CH
3
CCH
2
Br
O
CH
3
CCH
2
O C
CH
O
C
O
CH
3
OH
CH
3
CCH
2
O
CH
3
CCH
2
CH
2
CCH
3
O O
268 DEDE KIM-UA
Synthesis of 2,4-pentanedione
CH
3
CCH
2
CCH
3
O O
C
CH
2
O
C
O
CH
3
OEt
ethyl acetoacetate
Na
C
CH
O
C
O
CH
3
OEt
Na
C
CH
O
C
O
CH
3
OEt
H
+
,H
2
O
heat
heat
-CO
2
CH
3
C
O
C
CH
O
C
O
CH
3
OH
CH
3
C
O
CH
3
CCH
2
CCH
3
O
H
3
C C
Cl
O
O
using the carbanion
in a nucleophilic acyl
substitution
269 DEDE KIM-UA
Biological Synthesis of Fatty Acids.

Enzyme = fatty acid synthase
(multifunctional enzyme)

Condensing Enzyme (CE)
Acyl Carrier Protein (ACP)
270 DEDE KIM-UA
HS CH
2
CH
2
NHCCH
2
CH
2
NHCCHCCH
2
O
O O
OH
CH
3
CH
3
P O
O
O
-
P
O
O
-
N
N
N
N
NH
2
O
H O
H H
H H
P O
O
-
O
O
-
Coenzyme A
271 DEDE KIM-UA
Acetyl CoA
CH
3
C S
O
Malonyl CoA
O C
O
CH
2
C
O
S
272 DEDE KIM-UA
O
OH OH
H H
H H
O P -O
N
N
N N
NH
2
O
O
HO
H
H
H
H
O
P
O
HO O
-O
N
+
C
NH
2
O
nicotinamide adenine dinucleotide phosphate
NADP+
N
C
O
NH
2
H H
NADPH
P -O
O
O
-
NADPH is a biological reducing agent
NADP+ is a biological oxidizing agent
biological oxidation/reduction
273 DEDE KIM-UA
C
E
A
C
P
SH SH
C
E
A
C
P
SH SH
ACP = acyl carrier protein
CE = condensing enzyme
acetyl CoA
malonyl CoA
C
E
A
C
P
S S
C C
CH
3
O
CH
2
O
C
O
-
O
CO
2
C
E
A
C
P
S SH
C
CH
2
O
C O
CH
3
2NADPH 2NADP
+
C
E
A
C
P
S SH
C
CH
2
O
CH
2
CH
3
1
2
3
274 DEDE KIM-UA
C
E
A
C
P
S S
C C
CH
3
O
CH
2
O
C
O
-
O
CO
2
C
E
A
C
P
S SH
C
CH
2
O
C O
CH
3
2
C
E
A
C
P
S S
C C
CH
3
O
CH
O
C
OH
O
C
E
A
C
P
S SH
C
HC
O
C O
CH
3
CO
2
H
->enolate
nucleo.acyl
substitution
decarboxylation
275 DEDE KIM-UA
C
E
A
C
P
S SH
C
CH
2
O
CH
2
CH
3
C
E
A
C
P
SH S
C
CH
2
CH
2
CH
3
O
malonyl CoA
C
E
A
C
P
S S
C
CH
2
CH
2
CH
3
O C
CH
2
C
O
-
O
O
CO
2
C
E
A
C
P
S SH
C
CH
2
C
CH
2
O
O
CH
2
CH
3
4
5
6
-> enolate
nucleophilic
acyl substitution
-CO
2
276 DEDE KIM-UA
C
E
A
C
P
S SH
C
CH
2
C
CH
2
O
O
CH
2
CH
3
7
C
E
A
C
P
S SH
C
CH
2
CH
2
CH
2
O
CH
2
CH
3
2NADPH 2NADP
+
C
E
A
C
P
SH S
C
CH
2
CH
2
CH
2
CH
2
CH
3
O
8
9
malonyl CoA
277 DEDE KIM-UA
Overall:
step 1) malonyl CoA and acetyl CoA transfer the acetyl and
malonate to the carrier enzyme (CE) and acyl carrier
protein (ACP) respectively.
step 2) enolate carbanion from malonate (ACP) nucleophilic
acyl substitution on the acetyl (CE) followed by
decarboxylation.
step 3) reduction of the ketone to a hydrocarbon.
step 4) transfer of the carboxylate from CE ACP to CE.
step 5) malonyl CoA transfers malonate to the carrier enzyme.
step 6) enolate from malonateetc.
278 DEDE KIM-UA
Biological synthesis of fatty acids is analogous to the
malonate synthesis of carboxylic acids.
The enolate carbanion from malonate acts as a
nucleophile in a nucleophilic substitution on the acetyl-
CE followed by decarboxylation.
Each series puts the three carbon malonate on the ACP
and then decarboxylates the substitution product
resulting in lengthening the carbon chain by two
carbons at a time.
Naturally occuring fatty acids are even numbered
carboxylic acids.
279 DEDE KIM-UA
297 DEDE KIM-UA
Organic Photochemistry

Luminol Light as a product

Experimental Objectives
We have used spectroscopy to study the structure of organic compounds. In most
cases the spectroscopic process of irradiation of an organic molecule, followed by
absorption and reemission causes no permanent change in the molecule.
In organic photochemistry, we will be studying the effects of photons (of sufficient
energy) that do cause permanent chemical change in the molecule or photons that
are created by a chemical process. Here electromagnetic radiation (light) will be
studied as both a product of a chemical process.
298 DEDE KIM-UA
Organic Photochemistry
I. Introduction
1. In most chemical reactions molecules are in their ground electronic
states.
2. In photochemical reactions one or more of the reacting molecules are
promoted by absorption of light (visible to UV) to an electronically
excited state Light as a chemical reagent

3. In some photochemical processes a molecule is formed which is
already in an electronically excited state. When this molecule returns
to its ground state, light is produced. Light as a chemical product

C
O
OH
C
OH
C
OH
O
+ +
Benzophenone Isopropanol Benzopinacol
Acetone
hv
2
NH
NH
O
O
NH
2
O
O
O
O
NH
2
H
2
O
2
,
-
OH
K
3
Fe(CN)
6
+ Light
299 DEDE KIM-UA
A. Excited States and the Ground State
1. Electrons can move from the ground state to an excited state if energy is
supplied, in a photochemical reaction this energy is in the form of light
2. The energy difference between electronic energy levels is quantized, so
only light of discrete frequencies will cause a transition to occur.
E = hv (h = Plancks constant, v = frequency))

3. The frequencies of light that correspond to the energy difference
between electronic energy levels in covalent bonds fall in the visible to
ultraviolet region of the spectrum.
4. Functional groups that contain bonds that undergo a given absorption
are called chromophores
t
t
-
Ground State
t
t
-
Excited State
Many frequencies
of light bombard
the chemical bond
The energy levels of chemical bonds are
quantized! E = hv
Only a photon of the exact energy will be
absorbed and cause promotion of an
electron to the excited state
300 DEDE KIM-UA
B. Singlet and Triplet States
1. In most organic molecules all electrons in the ground state are paired with
each member of the pair possessing an opposite spin (Pauli principle)
2. If one of the electrons is promoted to another orbital of higher energy, the
promoted electron is no longer constrained by the Pauli principle and may
posses either a parallel or opposite spin to its former partner
3. If a molecule contains two unpaired electrons of the same (or parallel) spin
is called a triplet
4. If a molecule contains two unpaired electrons of opposite spins it is called
a singlet
t
t
-
Ground State
t
t
-
Triplet Excited State
hv
t
t
-
Ground State
t
t
-
Singlet Excited State
hv
301 DEDE KIM-UA
B. Singlet and Triplet States
5. In principle there is a triplet state for every corresponding singlet state

6. By Hunds rules the excited triplet state should be lower in energy than the
corresponding excited singlet state (it costs more energy to pair an
electron than place it in a new orbital)

7. It would seem then, that the promotion of a given electron from the ground
state could result in either an excited triplet state or excited singlet state,
just a different amount of energy is required

8. This is not the case because these transitions may be forbidden by the
rules of quantum mechanics.

9. These restrictions are known as selection rules:
Spin-forbidden transitions: transitions where a electron changes its
direction of spin are forbidden. To change spin involves a change in
angular momentum.
Therefore singlet-triplet and triplet-singlet transitions are forbidden and
singlet-singlet and triplet-triplet transitions are allowed
Forbidden in this case indicates highly improbable.
These transitions do occur, slowly and with low intensity.
The difference in rate between an allowed transition and a forbidden
one lead to the difference between many photochemical processes.

302 DEDE KIM-UA
C. Types of Excitation
1. When an electron on an organic molecule is promoted it usually goes from
the highest occupied molecular orbital

2. (HOMO) into the lowest unoccupied molecular orbital (LUMO)

3. The four possible electronic excitations that are possible (in order of
increasing energy):

1. o o*
2. n o* (n denotes an electron from a lone pair)
3. t t*
4. n t*

* Denotes an excited state

1. In cases where the bond undergoing transition is the only one between the
atoms involved; the transition causes bond breakage
303 DEDE KIM-UA
Simplest type of Photochemical Transition: Color
C
H
C
H
H
H
t
t-
Ground State
t
t-
Many wavelengths
of light - visible
to UV
E = hv
One frequency
of light
corresponding
to the energy of
the transition is
reemitted
t
t-
For ethylene, the v of light that is absorbed and reemitted is in the ultraviolet
region of the spectrum (165 nm)

The corresponding wavelength is referred to as
max
304 DEDE KIM-UA
If the double bond is conjugated, delocalization (resonance) causes the
electrons within the conjugated system to be lower in energy.

Likewise, the difference in energy between t and t* is also reduced.
Therefore the t t* transition occurs with light of longer and longer
wavelengths (lower v, lower E)

Visible light (800 to 400 nm, red to violet); UV (400 to 200 nm)
(remember shorter wavelength, higher frequency, higher energy)
max
= 165 nm
max
= 217 nm
max
= 256 nm
max
= 364 nm
305 DEDE KIM-UA
With enough conjugated double bonds, the t t* transition will occur in
the visible region of the spectrum and perceived as color:
|-carotene,
max
= 455 nm
lycopene,
max
= 474 nm
N
H
H
N
O
O
indigo
|-carotene from carrots, orange; lycopene from tomatoes,red;
Indigo, the dye used in blue denim; blue
306 DEDE KIM-UA
OH
OH
O
O
NO
2
H
2
NNH
2
O
O
O
O
NO
2
NH
3
NH
3
- 2 H
2
O, A
HO(CH
2
CH
2
O)
3
H
NH
NH
O
O
NO
2
NH
NH
O
O
NH
2
Na
2
S
2
O
4
-
OH, H
2
O
Luminol
3-Nitrophthalic
acid
Hydrazonium
salt
3-Nitrophthalhydrazide
Synthesis of Luminol:
307 DEDE KIM-UA
Luminol a more complex transition that generates light
Before moving on, introduce some nomenclature:

S - singlet state
T - triplet state
0, 1, 2 - as subscripts denote energy level, 0 = ground state

* - an excited state

For every electronic energy level, there is a set of vibrational energy levels:
E
n
e
r
g
y
Interatomic Distance
within bond
Dissociation
V
o
V
4
V
3
V
2
V
1
308 DEDE KIM-UA
II. The Fate of Excited Molecule: Physical processes - Luminol

Physical processes undergone by electronically excited molecules:

S
0
+ hv S
1
Excitation

S
1
S
0
+ hv Fluorescence

S
1
T
1
(or vice versa) Intersystem Crossing

T
1
S
1
S
0
+ hv Phosphorescence

S
1
+ A(S
0
) S
0
+ A(S
1
) Singlet-singlet transfer
(photosensitization)

T
1
+ A(S
0
) S
0
+ A(T
1
) Triplet-triplet transfer
(photosensitization)
309 DEDE KIM-UA

Fluorescence:

S
1
S
0
+ hv

Is an immediate form of radiative decay for an excited electronic state as
the electron is going from an excited state to a ground state of the same
type (singlet to singlet, triplet to triplet) which is allowed by the selection
rules

Because of the non-radiative decay (production of heat to change
vibrational energy levels) often observed in this transition the photon
produced may not match the frequency of the photon absorbed

We are familiar with fluorescence in the vivid appearance of fluorescent
green and orange dyes (DayGlo colors) which absorb in the ultraviolet
region of the spectrum and fluoresce in the visible.
310 DEDE KIM-UA
II. The Fate of Excited Molecule:
Physical processes

Fluorescence:
The sequence leading
to fluorescence:

After initial absorbtion of a
photon, the vibrational states of
the excited state undergo
radiationless decay by giving up
energy to their surroundings.

A radiative decay then occurs
from the lowest vibrational
energy level of the excited state
to the ground electronic
state.
S
1
S
0
311 DEDE KIM-UA

Phosphorescence:
Fluorescence

T
1
S
1
S
0
+ hv

Intersystem crossing

Because intersystem crossing is a forbidden process which occurs
with low intensity with low probability phosphorescence is a slow
process where photons may be emitted over a period of fractions of
seconds to hours

Phosphorescence is responsible for the light from fireflies (luciferin),
luminol and Cyalume
312 DEDE KIM-UA
The sequence leading
to phosphorescence:

The intersystem crossing
is the key step, where
T
1
S
1
.

The triplet state acts
as a slowly leaking
reservoir, in that this
transition is normally
spin-forbidden
T
1
S
1
S
0
T
1
S
1

Phosphorescence:
313 DEDE KIM-UA
We can study many of these transitions through the
chemiluminescence of luminol:
NH
NH
O
O
NH
2
Luminol
-
OH
N
N
O
O
NH
2
N
N
O
O
NH
2
-
OH, H
2
O
2
K
3
Fe(CN)
6
- N
2
O
O
O
O
NH
2
* O
O
O
O
NH
2
* O
O
O
O
NH
2
Triplet excited state
(3-aminophthalate
anion)
Singlet excited state
(3-aminophthalate
anion)
hv
(light)
Here the triplet
excited state is
formed chemically
by the degradation
of this dianion
314 DEDE KIM-UA
Energetically:
Energy
O
2
+
Luminol dianion
Peroxide intermdediate
Intersystem
crossing Fluorescence
emission
- hv
T
1
vibrational
energy levels
S
1
vibrational
energy levels
3-Aminophthalate
dianion
S
0
Ground state
N
2
photon
315 DEDE KIM-UA
Other Example: Light Sticks: Cyalume
Light sticks contains a thin glass vial that contains an alkaline (basic)
solution of hydrogen peroxide suspended in a solution of diphenyloxalate
and an organic dye.

When the inner vial is broken two successive nucleophilic substitution
reactions occur to form an unstable 4-membered ring.

This ring decomposes by a pathway that forms a excited triplet electronic
state on the oxygen of one of the two molecules of carbon dioxide
produced.

Normally, if this electron decayed to the ground state the photon released
would be in the UV region. In the presence of the dye, however,
photosensitization occurs (triplet to triplet).

T
1
+ A(S
0
) S
0
+ A(T
1
)

The excited dye molecule undergoes phosphorescence to give a photon in
the visible region of the spectrum (dye dependant).
316 DEDE KIM-UA
O C C O
O O
Cl
Cl
Cl
Cl
Cl
Cl
Cyalume
O C C O
O O
HO OH
O OH + H
2
O
O C C O
O O
O
OH
O
C C O
O
O
O
OH
HO
-
+
HO
-
C C O
O
O
O
O
+ H
2
O
C C O
O
O
O O
C C O
O O
O O
+
+
C C
O O
O O
reverse [2 + 2]
cycloaddition
C
O
O
C
O
O
*
dye
C
O
O
+
dye
*
dye + hv (visible light)
Cyalume:
317 DEDE KIM-UA
Luciferin (fireflies): Similar to cyalume in the formation and degradation of a
4-membered ring followed by phosphorescence
N
S
S
N
H
OH
O
HO
Luciferin
ATP
S
N
H
O
O
AMP
+ pyrophosphate
S
N
O
O
AMP
- H
+
O O
S
N
O
O
AMP
O
O
S
N
O
O
AMP
O
O
R
N
S
HO
R
R
R
S
N
O
+ AMP
O
O
R
S
N
R
O
S
N
R
O
+ CO
2
*
= R
Oxyluciferin
318 DEDE KIM-UA
Intermolecular Forces and Liquids
and Solids
319 DEDE KIM-UA
A phase is a homogeneous part of the system in contact with
other parts of the system but separated from them by a well-
defined boundary.
2 Phases
Solid phase - ice
Liquid phase - water
11.1
320 DEDE KIM-UA
Intermolecular Forces
11.2
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular
41 kJ to vaporize 1 mole of water (inter)
930 kJ to break all O-H bonds in 1 mole of water (intra)
Generally,
intermolecular forces
are much weaker
than intramolecular
forces.
Measure of intermolecular force
boiling point
melting point
AH
vap

AH
fus
AH
sub

321 DEDE KIM-UA
Types of Intermolecular Forces
1. Hydrogen Bond (strongest)
11.2
The hydrogen bond is a special dipole-dipole interaction between the hydrogen
atom in a polar N-H, O-H, or F-H bond and an electronegative O, N, or F atom. IT
IS NOT A BOND.
A H

B A H

A
or
A & B are N, O, or F
322 DEDE KIM-UA
Hydrogen Bond
11.2
323 DEDE KIM-UA
Why is the hydrogen bond considered a
special dipole-dipole interaction?
Decreasing molar mass
Decreasing boiling point
11.2
324 DEDE KIM-UA
2. Ion-Dipole Forces
Attractive forces between an ion and a polar molecule
11.2
Ion-Dipole Interaction
325 DEDE KIM-UA
11.2
326 DEDE KIM-UA
3. Dipole-Dipole Forces
Attractive forces between polar molecules
Orientation of Polar Molecules in a Solid
11.2
327 DEDE KIM-UA
4. Dispersion Forces van der Walls forces/London forces (weakest)
Attractive forces that arise as a result of temporary dipoles induced in
atoms or molecules
11.2
ion-induced dipole interaction
dipole-induced dipole interaction
328 DEDE KIM-UA
Intermolecular Forces
4. Dispersion Forces Continued
11.2
Polarizability is the ease with which the electron distribution in the atom or
molecule can be distorted.
Polarizability increases with:
greater number of electrons
more diffuse electron cloud
Dispersion forces
usually increase with
molar mass.
329 DEDE KIM-UA
S
What type(s) of intermolecular forces exist between each of the following
molecules?
HBr
HBr is a polar molecule: dipole-dipole forces. There are also dispersion forces
between HBr molecules.
CH
4

CH
4
is nonpolar: dispersion forces.
SO
2

SO
2
is a polar molecule: dipole-dipole forces. There are also dispersion forces
between SO
2
molecules.
11.2
330 DEDE KIM-UA
Properties of Liquids
Surface tension is the amount of energy required to stretch or increase the
surface of a liquid by a unit area.
Strong
intermolecular
forces
High surface
tension
11.3
331 DEDE KIM-UA
Cohesion is the intermolecular attraction between like molecules
11.3
Adhesion is an attraction between unlike molecules
Adhesion
Cohesion
attracted to glass
attracted to each other
332 DEDE KIM-UA
Viscosity is a measure of a fluids resistance to flow.
11.3
Strong
intermolecular
forces
High viscosity
333 DEDE KIM-UA
Maximum Density
4
0
C
Ice is less dense than water
Density of Water
11.3
Water is a Unique Substance
334 DEDE KIM-UA
A crystalline solid possesses rigid and long-range order. In a crystalline solid,
atoms, molecules or ions occupy specific (predictable) positions.
An amorphous solid does not possess a well-defined arrangement and long-range
molecular order.
A unit cell is the basic repeating structural unit of a crystalline solid.
Unit Cell
lattice
point
Unit cells in 3 dimensions
11.4
At lattice points:
Atoms
Molecules
Ions
335 DEDE KIM-UA
11.4
336 DEDE KIM-UA
11.4
337 DEDE KIM-UA
Types of Crystals
Ionic Crystals Ion-Ion interactions are the strongest (including the intermolecular
forces (H bonding, etc.)
Lattice points occupied by cations and anions
Held together by electrostatic attraction
Hard, brittle, high melting point
Poor conductor of heat and electricity
CsCl ZnS CaF
2

11.6
338 DEDE KIM-UA
Types of Crystals
Covalent Crystals Stronger than IM forces but generally weaker than ion-
ion
Lattice points occupied by atoms
Held together by covalent bonds
Hard, high melting point
11.6
diamond graphite
carbon
atoms
339 DEDE KIM-UA
Types of Crystals
Molecular Crystals
Lattice points occupied by molecules
Held together by intermolecular forces
Soft, low melting point
11.6
340 DEDE KIM-UA
Types of Crystals
Metallic Crystals Typically weaker than covalent, but can be in the low end of
covalent
Lattice points occupied by metal atoms
Held together by metallic bonds
Soft to hard, low to high melting point
Good conductors of heat and electricity
11.6
Cross Section of a Metallic Crystal
nucleus &
inner shell e
-

mobile sea
of e
-

341 DEDE KIM-UA
An amorphous solid does not possess a well-defined arrangement and long-range
molecular order.
A glass is an optically transparent fusion product of inorganic materials that has
cooled to a rigid state without crystallizing
Crystalline
quartz (SiO
2
)
Non-crystalline
quartz glass
11.7
342 DEDE KIM-UA
Types of Crystals
11.6
343 DEDE KIM-UA
Chemistry In Action: High-Temperature Superconductors
344 DEDE KIM-UA
E
v
a
p
o
r
a
t
i
o
n

Greatest
Order
Least
Order
11.8
C
o
n
d
e
n
s
a
t
i
o
n

T
2
> T
1

345 DEDE KIM-UA
The equilibrium vapor pressure is the vapor pressure measured when a dynamic
equilibrium exists between condensation and evaporation
H
2
O (l) H
2
O (g)
Rate of
condensation
Rate of
evaporation
=
Dynamic Equilibrium
11.8
346 DEDE KIM-UA
Molar heat of vaporization (AH
vap
) is the energy required to vaporize 1 mole of a
liquid.
ln P = -
AH
vap
RT
+ C
Clausius-Clapeyron Equation
P = (equilibrium) vapor pressure
T = temperature (K)
R = gas constant (8.314 J/Kmol)
11.8
C = constant (depends on P & T)
347 DEDE KIM-UA
The boiling point is the temperature at which the (equilibrium) vapor pressure of
a liquid is equal to the external pressure.
The normal boiling point is the temperature at which a liquid boils when the
external pressure is 1 atm.
11.8
348 DEDE KIM-UA
The critical temperature (T
c
) is the temperature above which the gas cannot be
made to liquefy, no matter how great the applied pressure.
The critical pressure (P
c
) is
the minimum pressure that
must be applied to bring
about liquefaction at the
critical temperature.
11.8
349 DEDE KIM-UA
M
e
l
t
i
n
g

11.8
F
r
e
e
z
i
n
g

H
2
O (s) H
2
O (l)
The melting point of a solid or the
freezing point of a liquid is the
temperature at which the solid and
liquid phases coexist in equilibrium
350 DEDE KIM-UA
Molar heat of fusion (AH
fus
) is the energy required to melt 1 mole of a solid
substance.
11.8
351 DEDE KIM-UA
11.8
352 DEDE KIM-UA
S
u
b
l
i
m
a
t
i
o
n

11.8
D
e
p
o
s
i
t
i
o
n

H
2
O (s) H
2
O (g)
Molar heat of sublimation (AH
sub
) is
the energy required to sublime 1 mole
of a solid.
AH
sub =
AH
fus
+ AH
vap
( Hesss Law)
353 DEDE KIM-UA
A phase diagram summarizes the conditions at which a substance exists as a
solid, liquid, or gas.
The triple point is where all 3 phases meet.
Phase Diagram of Water
11.9
354 DEDE KIM-UA
11.9
355 DEDE KIM-UA
Wheres Waldo?
Can you find
The Triple Point?
Critical pressure?
Critical temperature?
Where fusion occurs?
Where vaporization
occurs?
Melting point
(at 1 atm)?
Boiling point
(at 6 atm)?
Carbon Dioxide
356 DEDE KIM-UA
11.9
357 DEDE KIM-UA
Chemistry In Action: Liquid Crystals
358 DEDE KIM-UA
ALDEHYDES AND KETONES
359 DEDE KIM-UA
Aldehydes and Ketones
O 1s
2
, 2s
2
2p
2
2p
1
2p
1
3 sp
2
orbitals
C
H
R
O C
R
R
O
Aldehyde
Ketone
C
H
H
O
lone Pairs
tbond - two overlapping 2p orbitals
obond
obond- overlapping 1s
H-orbital and sp
2
C-orbital
360 DEDE KIM-UA
C O
H
3
C
H
118
o
121
o
C C
H
H
H
H
118
o
121
o
o
o+
C O
H
3
C
H
C O
H
3
C
H
Resonance Structures
Most Reactive Group
telectrons + polarisation
Useful in Synthesis
al aldehydes, one - ketones
C O
H
H
C O
H
3
C
H
C O
CH
3
CH
2
H
C O
CH
3
CH
2
CH
2
CH
2
H
Methanal
(formaldehyde)
Ethanal
(acetaldehyde)
Propanal
Pentanal
361 DEDE KIM-UA
O
H
H O
H
H
Benzaldehyde
trans-Cinnamaldehyde
Formalin, 35-40% formadehyde in water
Preservative that reacts with
proteins causing them to resist decay
Coelacanth, prehistoric fish
O
H
Acrolein (2-propenal)
S
H
Thiopropionaldehyde
(propanethiol)
- lachrymator from chopped onion
- lachrymator and pleasant "odour"
from barbacuing meat
362 DEDE KIM-UA
Propanone
(ACETONE)
Butanone
Acetophenone
Benzophenone

O
H
3
C
CH
CH
2
CH
3
CH
3
3-Methyl-2-pentanone
O
H
OCH
3
OH
Vanillin
CH
3
O
Carvone
(spearmint flavour)
O O
H
3
C CH
3
Butadione
(butter flavour)
O
H
3
C CH
3
O
CH
3
O
O
H
3
C C
H
2
CH
3
363 DEDE KIM-UA
Carbonyls readily undergo Nucleophilic Attack
ANHYDROUS
Conditions are required for
imine formation
O
C
RNH
2
o
o+
O
C
N H
H
R
O
C
N H R
H
O
C
N H R
H
C
N
R
- H
2
O
Imine
Reaction between an amine and a carbonyl compound
364 DEDE KIM-UA
Condensation Reaction Elimination of water
C O
C H
3
C H
3
N N
H
H H
H
C N
C H
3
C H
3
N
H
H
+
hydrazine
acetone
hydrazone of acetone
Emil Fischer, Nobel Prize 1902
C O
C H
3
C H
3
N N
H H
H
O
2
N
O
2
N
C N
C H
3
C H
3
N
H
NO
2
NO
2
+
2,4-diphenylhydrazine
acetone
DNP test for aldehydes & ketones gives crystalline hydrazones
- H
2
O
- H
2
O
365 DEDE KIM-UA
Professor Victor Grignard (1912 Nobel Prize)
Developed this chemistry with Professor P. A. Barbier
C R O
H
Protonation
H
H
2
O
Alcohol
C R
X
H
H
X = I or Br
o+
o
C
H
H
MgX R
o
o+
RCH
2
MgX
Grignard Reagent
Mg
Ether
C R
X
H
H
X = I or Br
o+
o
C
H
H
Li R
o
o+
RCH
2
Li
Organolithium Reagent
Li
Ether
C O
R Li
o+
o
o
o+
C R O
Li
ADDITION
366 DEDE KIM-UA
MgBr
C O
H
H
Ether
C
H
H
O MgBr
H
3
O
+
C
H
H
O H
Benzylalcohol
C O
MgBr
+
Ether
C OH
Triphenylmethanol
Benzyl Group
Phenyl, Ph Group
Ph
2. H
3
O
+
Organometallics add to carbonyls to give alcohols
367 DEDE KIM-UA
O
C
H H
O
C
R H
O
C
R R
MgI Ph MgI Ph MgI Ph
O
C H H
H
Ph
O
C R H
H
Ph
O
C R R
H
Ph
+
+
+
Primary alcohols
Secondary alcohols tertiary alcohols
Ketone
Aldehydes
Formaldehyde
Nucleophilic Addition Reactions
your adding Ph

_
368 DEDE KIM-UA
Mg
Br
O
CH
2
CH
3
CH
3
CH
2
O
CH
2
CH
3 CH
3
CH
2
.. ..
.. ..
Ethers (Lewis base) stabilize the
Grignard Reagent making it
more reactive
Organometallic Reactions must always be done under anhydrous conditions
Mg Br
H
O
H
H
+o
o
OH
_
+
Grignards are powerful bases and
will deprotonate water
369 DEDE KIM-UA
CARBOXYLIC ACIDS and
ESTERS
370 DEDE KIM-UA
Carboxylic Acids
O
C
O H H
2
O +
O
C
O
H
3
O +
pKa = 4 - 5 , water = 16
We can distinguish a water-insoluble carboxylic acid and phenol from
an alcohol
O
C
O H NaOH +
O
C
O
H
2
O
Na
Benzoic acid
Sodium Benzoate
371 DEDE KIM-UA
Highly Polar
Low molecular weight acids show Appreciable Solubility in Water
High Bpt Extensive H-bonds to themselves and water
Carboxylic Acids
Methanoic acid
Ethanoic acid
Propanoic acid
4-Bromo-2-ethylpentanoic acid
O
H OH
O
CH
3
OH
O
CH
3
CH
2
OH
O
OH
Br
O
C
C OH
HO
O
Ethanedioic acid (oxalic acid)
rhubarb
O
OH
O
HO ( )
n
n = 1 = malonic acid
n = 2 = succinic acid
n = 3 = glutaric acid
HO
2
C CO
2
H
CO
2
H
CO
2
H
Terephthalic acid
Phthalic acid
372 DEDE KIM-UA
Esterification condensation reaction, where H
2
O is lost
Alcohol part appears first in the name
O
CH
3
OH
CH
3
CH
2
OH +
HCl or H
2
SO
4
H
+
(catalyst)
O
CH
3
O CH
2
CH
3
Acetic acid
(ethanoic acid)
Ethyl acetate
O
Ph OH
H
3
C OH
+
H
+
(catalyst)
O
Ph O CH
3
Benzoic acid
Methyl benzoate
O
O
O
O
Ethyl propanoate
vinyl acetate
O
H O
Methyl formate
373 DEDE KIM-UA
Ester molecules cannot H-bond to each
other, because they do not have an OH
Consequently, B.pt is much lower than that
of alcohols and acids of comparable mass
H-bonding to water is possible
-low mw esters are soluble in water
Solubility rapidly decreases with carbon
chain length.

O
H
O
H
H
O
H
O R
R
374 DEDE KIM-UA
O
C R
O H
O
C R
O H
........
........
Two hydrogen bonds
O
C R
O R
cannot H-bond to another ester molecule
Highest Boiling points and exceedingly water soluble
Hexane = 69 C
Diethyl ether = 56 C
Ethanol = 78 C
Ethanoic acid = 118 C
Ethyl acetate = 77 C
Boiling points
375 DEDE KIM-UA
Redox Reactions
Addition of Oxygen or Removal of Hydrogen is OXIDATION
Removal of Oxygen or Addition of Hydrogen is REDUCTION
CH
4
+ O
CH
3
OH
- 2H
C O
H
H
C O
HO
H
+ O - 2H
O
C
O
C O
H
R
H
C R
H
O
H
Reduction
Oxidation
C O
R
R
H
C R
R
O
H
Reduction
Oxidation
Aldehydes
Primary Alcohols
Secondary Alcohols Ketones
376 DEDE KIM-UA
Examples of Reduction Reactions
O
H
2
, Pt
O
H
H
Cyclohexanone Cyclohexanol
CH
3
H
3
C
O
H
3-Methylbutanal
H
2
, Pd-C
CH
3
H
3
C
O
H
H
H
3-Methylbutanol
Examples of Oxidation Reactions
OH
H
O
K
2
Cr
2
O
7
, H
2
SO
4
, H
2
O
Overoxidation
OH
O
377 DEDE KIM-UA
H N H
H
R N H
H
R N H
R
R N R
R
Ammonia
Primary (1
o
) Amine
Secondary (2
o
) Amine
Tertiary (3
o
) Amine
Organic bases are amines
Amines are derivatives of ammonia
N 1s
2
, 2s
2
2p
1
2p
1
2p
1
----------- lone pair
occupies an sp
3
orbital

378 DEDE KIM-UA
AMINES, AMIDES and ANILINE
379 DEDE KIM-UA
Ammonia
3
o
Amine
Unshared lone pair of electrons in the fourth sp
3
hybrid occupies
slightly more space than the electrons in the obonds
N
H
H
H
N
R
R
R
..
107
O
..
107
O
380 DEDE KIM-UA
H
2
NEt HNEt
2
NEt
3
H
2
NMe
HNMe
2
NMe
3
where Et = CH
2
CH
3
ethylamine diethylamine
triethylamine
primary
secondary
tertiary
where Me = CH
3
methylamine
dimethylamine
trimethylamine
primary
secondary
tertiary
Naming amines
N
H
methylpropyl amine
381 DEDE KIM-UA
H
2
N
NH
2
Putrescine
(found in decaying meat)
NH
2
Amphetamine
(dangerous stimulant)
N
H
Piperidine
N
Triethylamine
NH
2
Isopropylamine
1,4-butanediamine
Some Common Amines
Both upper amines are 1
o
This amine is are 2
o

This amine is 3
o
This amine is 1
o
382 DEDE KIM-UA
NH
2
H
Cl
N
H
H
H Cl
Base + Acid = Ammonium Salt
Amines are bases because of the lone pair on the
nitrogen atom - red litmus paper to blue
O
O H
O
O H
N(CH
2
CH
3
)
3
O
O
O
O
HN(CH
2
CH
3
)
3
+ 2
+
2
oxalic acid
triethylamine
triethylaminium oxalate
383 DEDE KIM-UA
= aniline
Aniline is useful in the synthesis of many other aromatic compounds
NO
2
NO
2
NH
2
HNO
3
, H
2
SO
4
Sn, HCl
phenylamine
384 DEDE KIM-UA
NH
2
N N
NaNO
2
, HCl
benzenediazonium chloride
+
Cl
-
0 C
Aniline can be converted into useful diazonium salt
N N
N N
Nuc
+
Cl
-
Nuc
-
-
385 DEDE KIM-UA
N N
N N
CN
+
Cl
-
CuCN
-
+
KCN
N N
N N
I
+
Cl
-
NaI
-
Benzene nitrile
N N
N N
Br
+
Cl
-
HBr, CuBr
-
iodobenzene
bromobenzene
386 DEDE KIM-UA
N
C R
R'
O
N
C R
R'
O
Amides
Features of a Peptide Bond;
1. Usually inert
2. Planar to allow delocalisation
3. Restricted Rotation about the amide bond
4. Rotation of Groups (R and R) attached to the amide
bond is relatively free
------------- Not acids or bases
387 DEDE KIM-UA
O
C
C H
3
NH
2
O
C
H NH
2
NH
2
O
O
C
N H
2
NH
2
R
C N H
2
H
COOH
acetamide
benzamide
urea
AMINO ACIDS
formamide
All are high melting point solids, only
benzamide not soluble in water
388 DEDE KIM-UA

389 DEDE KIM-UA

390 DEDE KIM-UA

391 DEDE KIM-UA

392 DEDE KIM-UA

393 DEDE KIM-UA

394 DEDE KIM-UA

395 DEDE KIM-UA

396 DEDE KIM-UA

397 DEDE KIM-UA

398 DEDE KIM-UA

399 DEDE KIM-UA

400 DEDE KIM-UA

401 DEDE KIM-UA

402 DEDE KIM-UA
403 DEDE KIM-UA
Solubility in Water
Water has been referred to as the "universal solvent", and its widespread distribution on this planet
and essential role in life make it the benchmark for discussions of solubility. Water dissolves many
ionic salts thanks to its high dielectric constant and ability to solvate ions. The former reduces the
attraction between oppositely charged ions and the latter stabilizes the ions by binding to them and
delocalizing charge density.
when hexane or other nonpolar compounds are mixed with water, the strong association forces of
the water network exclude the nonpolar molecules, which must then exist in a separate phase.
This is shown in the following illustration, and since hexane is less dense than water, the hexane
phase floats on the water phase.
404 DEDE KIM-UA
Water Solubility of Characteristic Compounds
Compound
Type
Specific
Compound
s
Grams/100
mL
Moles/Liter
Specific
Compound
s
Grams/100
mL
Moles/Liter
Hydrocarb
ons &
Alkyl
Halides
butane
hexane
cyclohexan
e
0.007
0.0009
0.006
0.0012
0.0001
0.0007
benzene
methylene
chloride
chloroform
0.07
1.50
0.8
0.009
0.180
0.07</TD<
TR>
Compound
s
Having
One
Oxygen
1-butanol
tert-butanol
cyclohexan
ol
phenol
9.0
complete
3.6
8.7
1.2
complete
0.36
0.90
ethyl ether
THF
furan
anisole
6.0
complete
1.0
1.0
0.80
complete
0.15
0.09</TD<
TR>
Compound
s
Having
Two
Oxygens
1,3-
propanediol
2-
butoxyethan
ol
butanoic
acid
benzoic
acid
complete
complete
complete
complete
complete
complete
complete
complete
1,2-
dimethoxyet
hane
1,4-dioxane
ethyl
acetate
-
butyrolacton
e
complete
complete
8.0
complete
complete
complete
0.91
complete</T
D< TR>
Nitrogen
Containing
Compound
s
1-
aminobutan
e
cyclohexyla
mine
aniline
pyrrolidine
pyrrole
complete
complete
3.4
complete
6.0
complete
complete
0.37
complete
0.9
triethylamin
e
pyridine
propionitrile
1-
nitropropan
e
DMF
5.5
complete
10.3
1.5
complete
0.54
complete
2.0
0.17
complete</T
D< TR>
405 DEDE KIM-UA
* Meerwein-Pondorf-Verley Reduction
Redox Reactions
Hydrogen Transfer
The MVP reduction is also an oxidation, as evidenced by the conversion of
isopropoxide to acetone. Consequently, the reaction can be converted into
an oxidation of alcohols to ketones or aldehydes. This procedure is called
the Oppenauer oxidation.
406 DEDE KIM-UA
The Cannizzaro Reaction
407 DEDE KIM-UA
The Haloform Reaction
base-catalyzed halogenation of methyl ketones is accompanied by CC bond cleavage, yielding
a carboxylate salt and haloform ( X3CH )
408 DEDE KIM-UA
Alkane Reactions
The alkanes and cycloalkanes, with the exception of cyclopropane, are probably the least chemically
reactive class of organic compounds. Despite their relative inertness, alkanes undergo several important
reactions that are discussed in the following section.
1. Combustion
The combustion of carbon compounds, especially hydrocarbons, has been the most important
source of heat energy for human
Every covalent bond in the reactants has been broken and an entirely new set of covalent bonds
have formed in the products
CH3-CH2-CH3 + 5 O2 > 3 CO2 + 4 H2O + heat
Two points concerning this reaction are important:
1. Since all the covalent bonds in the reactant molecules are broken, the quantity of heat evolved
in this reaction is related to the strength of these bonds (and, of course, the strength of the bonds
formed in the products). Precise heats of combustion measurements can provide useful iinformation
about the structure of molecules.
2. The stoichiometry of the reactants is important. If insufficient oxygen is supplied some of the products
will consist of carbon monoxide, a highly toxic gas.

CH3-CH2-CH3 + 4 O2 > CO2 + 2 CO + 4 H2O + heat

409 DEDE KIM-UA
Cycloalkane
(CH
2
)
n

CH
2
Units
n
H
25

kcal/mole
H
25

per CH
2
Unit
Ring Strain
kcal/mole
Cyclopropane n = 3 468.7 156.2 27.6
Cyclobutane n = 4 614.3 153.6 26.4
Cyclopentane n = 5 741.5 148.3 6.5
Cyclohexane n = 6 882.1 147.0 0.0
Cycloheptane n = 7 1035.4 147.9 6.3
Cyclooctane n = 8 1186.0 148.2 9.6
Cyclononane n = 9 1335.0 148.3 11.7
Cyclodecane n = 10 1481 148.1 11.0
CH
3
(CH
2
)
m
CH
3
m = large 147.0 0.0
Heat of Combustion
The chief source of ring strain in smaller rings is angle strain and eclipsing strain. As noted elsewhere, cyclopropane
and cyclobutane have large contributions of both strains, with angle strain being especially severe.
410 DEDE KIM-UA
2. Halogenation
Halogenation is the replacement of one or more hydrogen atoms in an organic compound by a halogen
(fluorine, chlorine, bromine or iodine).
Simple substitution reaction in which a C-H bond is broken and a new C-X bond is formed
CH4 + Cl2 + energy > CH3Cl + HCl
only two covalent bonds are broken (C-H & Cl-Cl) and two covalent bonds are formed (C-Cl & H-Cl), this reaction
seems to be an ideal case for mechanistic investigation and speculation
The relative amounts of the various products depend on the proportion of the two reactants used. In the case of
methane, a large excess of the hydrocarbon favors formation of methyl chloride as the chief product; whereas, an
excess of chlorine favors formation of chloroform and carbon tetrachloride.
CH4 + Cl2 + energy > CH3Cl + CH2Cl2 + CHCl3 + CCl4 + HCl
The following facts must be accomodated by any reasonable mechanism for the halogenation reaction.

1. The reactivity of the halogens decreases in the following order: F2 > Cl2 > Br2 > I2.
2. We shall confine our attention to chlorine and bromine, since fluorine is so explosively reactive it is difficult to
control, and iodine is generally unreactive.
3. Chlorinations and brominations are normally exothermic.
4. Energy input in the form of heat or light is necessary to initiate these halogenations.
5. If light is used to initiate halogenation, thousands of molecules react for each photon of light absorbed.
6. Halogenation reactions may be conducted in either the gaseous or liquid phase.
7. In gas phase chlorinations the presence of oxygen (a radical trap) inhibits the reaction.
8. In liquid phase halogenations radical initiators such as peroxides facilitate the reaction.
411 DEDE KIM-UA
The most plausible mechanism for halogenation is a chain reaction involving neutral intermediates such as free radicals
or atoms. The weakest covalent bond in the reactants is the halogen-halogen bond
(Cl-Cl = 58 kcal/mole;
Br-Br = 46 kcal/mole)
so the initiating step is the homolytic cleavage of this bond by heat or light, note that chlorine andbromine both absorb
visible light (they are colored).
. All the hydrogens in a complex alkane do not exhibit equal reactivity. For example, propane has eight hydrogens,
six of them being structurally equivalent primary, and the other two being secondary. If all these hydrogen atoms were
equally reactive, halogenation should give a 3:1 ratio of 1-halopropane to 2-halopropane mono-halogenated products,
reflecting the primary/secondary numbers. This is not what we observe. Light-induced gas phase chlorination at 25 C
gives 45% 1-chloropropane and 55% 2-chloropropane.
CH3-CH2-CH3 + Cl2 > 45% CH3-CH2-CH2Cl + 55% CH3-CHCl-CH3
The results of bromination ( light-induced at 25 C ) are even more suprising, with 2-bromopropane accounting for 97%
of the mono-bromo product.
CH3-CH2-CH3 + Br2 > 3% CH3-CH2-CH2Br + 97% CH3-CHBr-CH3
412 DEDE KIM-UA
These results suggest strongly that 2-hydrogens are inherently more reactive than 1-hydrogens, by a factor of about 3:1.
Further experiments showed that 3-hydrogens are even more reactive toward halogen atoms. Thus, light-induced chlorination
of 2-methylpropane gave predominantly (65%) 2-chloro-2-methylpropane, the substitution product of the sole 3-hydrogen,
despite the presence of nine 1-hydrogens in the molecule.

(CH3)3CH + Cl2 > 65% (CH3)3CCl + 35% (CH3)2CHCH2Cl
Producing radical

First Step: R3CH + X > R3C + H-X
Second Step: R3C + X2 > R3CX + X
. In the case of carbon-hydrogen bonds, there are significant differences, and the specific dissociation energies
(energy required to break a bond homolytically) for various kinds of C-H bonds have been measured
R (in RH) methyl ethyl i-propyl t-butyl phenyl benzyl allyl vinyl
Bond Dissociation Energy
(kcal/mole)
103 98 95 93 110 85 88 112
The difference in C-H bond dissociation energy reported for primary (1), secondary (2) and tertiary (3) sites agrees with
the halogenation observations reported above, in that we would expect weaker bonds to be broken more easily than are
strong bonds. By this reasoning we would expect benzylic and allylic sites to be exceptionally reactive in free radical
halogenation, as experiments have shown. The methyl group of toluene, C6H5CH3, is readily chlorinated or brominated in
the presence of free radical initiators (usually peroxides), and ethylbenzene is similarly chlorinated at the benzylic location
exclusively. The hydrogens bonded to the aromatic ring (referred to as phenyl hydrogens above) have relatively high bond
dissociation energies and are not substituted.
413 DEDE KIM-UA
Free Radical Reactions of Alkenes
1. Addition of Radicals to Alkenes
Protons and other electrophiles are not the only reactive species that initiate addition reactions to carbon-carbon
double bonds
Further study showed that an alternative radical chain-reaction, initiated by peroxides, was responsible for the
anti-Markovnikov product. This is shown by the following equations.
The weak OO bond of a peroxide initiator is broken homolytically by thermal or hight energy
414 DEDE KIM-UA
Other radical addition reactions to alkenes have been observed, one example being the peroxide induced addition of carbon tetrachloride shown in the following equation
RCH=CH
2
+ CCl
4
(peroxide initiator) > RCHClCH
2
CCl
3

Since the addition of carbon radicals to double bonds is energetically favorable, concentrated solutions of alkenes are prone to
radical-initiated polymerization, as illustrated for propene by the following equation. The blue colored R-group represents an
initiating radical species or a growing polymer chain; the propene monomers are colored maroon. The addition always occurs
so that the more stable radical intermediate is formed.
RCH
2
(CH
3
)CH + CH
3
CH=CH
2
> RCH
2
(CH
3
)CH-CH
2
(CH
3
)CH + CH
3
CH=CH
2
> RCH
2
(CH
3
)CHCH
2
(CH
3
)CH-CH
2
(CH
3
)CH >
etc.
415 DEDE KIM-UA
C6H5CH2CH3 + Cl2 > C6H5CHClCH3 + HCl
Since carbon-carbon double bonds add chlorine and bromine rapidly in liquid phase solutions, free radical substitution reactions
of alkenes by these halogens must be carried out in the gas phase, or by other halogenating reagents. One such reagent is
N-bromosuccinimide (NBS), shown in the second equation below. By using NBS as a brominating agent, allylic brominations
are readily achieved in the liquid phase.
The covalent bond homolyses that define the bond dissociation energies listed above may are described by the general equation:
R3C-H + energy > R3C + H
416 DEDE KIM-UA
that alkyl radical stability increases in the order: phenyl < primary (1) < secondary (2) < tertiary (3) < allyl benzyl.
Because alkyl radicals are important intermediates in many reactions, this stability relationship will prove to be very useful in
future discussions. The enhanced stability of allyl and benzyl radicals may be attributed to resonance stabilization
The poor stability of phenyl radicals, C6H5, may in turn be attributed to the different hybridization state of the carbon
bearing the unpaired electron (sp2 vs. sp3).
3. Addition Reactions Involving Other Cyclic Onium Intermediates
Hydroboration
417 DEDE KIM-UA
4. Hydrogenation
Addition of hydrogen to a carbon-carbon double bond is called hydrogenation.
hydrogenation reaction is exothermic, a high activation energy prevents it from taking place under normal conditions.
This restriction may be circumvented by the use of a catalyst, as shown in the following diagram.
Catalysts act by lowering the activation energy of reactions, but they do not change the relative potential energy
of the reactants and products. Finely divided metals, such as platinum, palladium and nickel, are among the most
widely used hydrogenation catalysts. Catalytic hydrogenation takes place in at least two stages, as depicted in the
diagram. First, the alkene must be adsorbed on the surface of the catalyst along with some of the hydrogen.
Next, two hydrogens shift from the metal surface to the carbons of the double bond, and the resulting saturated
hydrocarbon, which is more weakly adsorbed, leaves the catalyst surface. The exact nature and timing of the last
events is not well understood
418 DEDE KIM-UA
Alkene Isomer (CH
3
)
2
CHCH=C
H
2

3-methyl-1-
butene
CH
2
=C(CH
3
)CH
2
C
H
3

2-methyl-1-butene
(CH
3
)
2
C=CHCH
3

2-methyl-2-
butene
Heat of
Reaction
( H )
30.3 kcal/mole 28.5 kcal/mole 26.9 kcal/mole
From the mechanism shown here we would expect the addition of hydrogen to occur with syn-stereoselectivity. This is often
true, but the hydrogenation catalysts may also cause isomerization of the double bond prior to hydrogen addition, in which
case stereoselectivity may be uncertain.
A non-catalytic procedure for the syn-addition of hydrogen makes use of the unstable compound diimide, N2H2. This
reagent mustbe freshly generated in the reaction system, usually by oxidation of hydrazine, and the strongly exothermic
reaction is favored by the elimination of nitrogen gas (a very stable compound). Diimide may exist as cis-trans isomers; only
the cis-isomer serves as a reducing agent. Examples of alkene reductions by both procedures are shown on the right.
419 DEDE KIM-UA
5. Oxidations
(i) Hydroxylation
Dihydroxylated products (glycols) are obtained by reaction with aqueous potassium permanganate (pH > 8)
the metallocyclic intermediate may be isolated in the osmium reaction.
420 DEDE KIM-UA
(ii) Epoxidation
oxidation reactions of alkenes give cyclic ethers in which both carbons of a double bond become bonded to the same
oxygen atom. These products are called epoxides or oxiranes. An important method for preparing epoxides is by reaction
with peracids, RCO

been classified as reductions or oxidations, depending on the change in oxidation state of the functional carbons.
It is important to remember that whenever an atom or group is reduced, some other atom or group is oxidized, and
a balanced equation must balance the electron gain in the reduced species with the electron loss in the oxidized
moiety, as well as numbers and kinds of atoms
421 DEDE KIM-UA
The previous few reactions have been classified as reductions or oxidations, depending on the change in oxidation
state of the functional carbons
422 DEDE KIM-UA
The Variables of Organic Reactions
In an effort to understand how and why reactions of functional groups take place in the way they do, chemists try to discover
just how different molecules and ions interact with each other as they come together. To this end, it is important to consider
the various properties and characteristics of a reaction that may be observed and/or measured as the reaction
proceeds .
1. Reactants and Reagents
A. Reactant Structure:
Variations in the structure of the reactant may have a marked influence on the course of a reaction, even though the
functional group is unchanged. Thus, reaction of 1-bromopropane with sodium cyanide proceeds smoothly to yield
butanenitrile, whereas 1-bromo-2,2-dimethylpropane fails to give any product and is recovered unchanged. In contrast,
both alkyl bromides form Grignard reagents (RMgBr) on reaction with magnesium.

B. Reagent Characteristics: Apparently minor changes in a reagent may lead to a significant change in the course of a reaction.
For example, 2-bromopropane gives a substitution reaction with sodium methylthiolate but undergoes predominant elimination on treatment
with sodium methoxide.
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2. Product Selectivity
A. Regioselectivity: It is often the case that addition and elimination reactions may, in principle, proceed to more than one
product. Thus 1-butene might add HBr to give either 1-bromobutane or 2-bromobutane, depending on which carbon of the
double bond receives the hydrogen and which the bromine. If one possible product out of two or more is formed preferentially,
the reaction is said to be regioselective.
B. Stereoselectivity: If the reaction products are such that stereoisomers may be formed, a reaction that yields one
stereoisomer preferentially is said to be stereoselective. In the addition of bromine to cyclohexene, for example, cis and
trans-1,2-dibromocyclohexane are both possible products of the addition. Since the trans-isomer is the only isolated product,
this reaction is stereoselective
C. Stereospecificity: This term is applied to cases in which stereoisomeric reactants behave differently in a given reaction.
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(i) Formation of different stereoisomeric products, as in the reaction of enantiomeric 2-bromobutane isomers with sodium methylthiolate,
shown in the following diagram.

Here, the (R)-reactant gives the configurationally inverted (S)-product, and (S)-reactant produces (R)-product.
(ii) Different rates of reaction, as in the base-induced eleimination of cis & trans-4-tert-butylcyclohexyl bromide

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Chemical reactions involve breaking and making some (or even all) of the bonds that hold together the atoms
of reactant and product molecules. Energy is required to break bonds, and since the strengths of different
kinds of bonds differ, there is often a significant overall energy change in the course of a reaction. In the
combustion of methane, for example, all six bonds in the reactant molecules are broken, and six new bonds
are formed in the product molecules (equation 1).
Reaction Energetics
The sum of the product bond strengths in this case is greater than the sum of reactant bond strengths;
Reactants Products
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the products are energetically (or thermodynamically) more stable than the reactants, and energy is released in the form
of heat. Such reactions are called exothermic It is helpful to think of exothermic reactions as proceeding from a higher
energy (less stable) reactant state to a lower energy (more stable) product state
Photosynthesis (equation 2) is an important example of an endothermic process. Energy in the form of
photons (sunlight) drives the reaction, which requires chlorophyll as a catalyst
Reactants Products
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Atomic Structure & Chemistry
Anyone who is not shocked about
quantum theory has not understood it.
- Niels Bohr
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The Atom
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Nomenclature
Carbon-14 has:
6 Protons
8 Neutrons
14 Nucleons
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The Bohr Hydrogen Atom
What is it about an atom that allows it to absorb or
emit radiation at only specific wavelengths? Do the
wavelengths tell us anything about the structure of
the atoms?
Niels Bohr suggested that emitted or absorbed
radiation corresponds to changes in the orbits of
electrons about the nucleus. Moreover, the electrons
can not orbit at any distance from the nucleus, but
exist only in specific allowed orbits.
To explain the allowed orbits, Bohr postulated that
electrons had both wave and particle properties.
The allowed orbits were those for which a
wavelength fit perfectly inside the orbit, just as only
certain wavelengths are allowed on a vibrating string.
Niels Bohr (1885-1962) was a
Danish Physicist. His model for
the hydrogen atom was the
beginning of quantum theory.
Atomic Structure
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Atomic Structure
According to Bohr, an atom arranges
its electrons into discrete orbits.
These orbits have discrete energy
levels that are specific to the
element.
For hydrogen, the energy of level n
is: E
n
= -10.97 h c /(n
2
)

When a transition is made between
two levels, a photon is emitted with
an energy equal to the change in the
energy of the two levels: E = h c/
The atom loses energy and that
energy goes into the emitted photon.
Energy is conserved.
lower energy orbit

higher energy orbit

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Quantum
Leaps and
Photons
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Spectroscopy
Gases emit and absorb light at only specific wavelengths, called spectral
lines. For example, in the visible region of the spectrum, hydrogen will absorb
or emit only at 0.656, 0.481, 0.434, and 0.410 microns. Chemicals can be
easily identified by measuring the wavelength of absorbed or emitted light.
The spectrum of atomic
hydrogen
Spectral Lines
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Solar Spectrum
Absorption lines appear as hydrogen atoms in the Suns atmosphere capture
photons and jump to more excited atomic levels.
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The Riddle of the Hydrogen
Spectrum
microns
1 1
97 . 10
1
2 2
|
.
|
\
|
=
m n
Spectroscopists discovered some simple formulas relating the wavelengths of
the spectral lines of atomic hydrogen.
Where is the wavelength of the emitted light and n and m are integers.

Pick any two integers n and m (n must be less than m), calculate the
wavelength and hydrogen will have a spectral line at that wavelength.
There are no spectral lines at any wavelengths not given by this equation.

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First 4 shells of a
Hydrogen atom.
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Atomic Shells
The discrete electron levels are arranged in
shells. Each shell has a maximum
occupancy.
The first electronic shell can have at most 2
electrons, the second shell has room for 8
electrons and so on.
The 1
st
shell has the lowest energy. Thus,
elements, in their lowest energy state fill the
1
st
level first, and then fill the 2
nd
level next.
These elements are listed in the 1
st
and 2
nd

rows of the periodic table.
Atoms are most stable if their outer shell is
full.
The electrons in outer shells are shielded by
the inner shells from the full attraction of the
nucleus. These electrons participate most
readily in chemical reactions.
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The Periodic Table
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Molecular
Sizes
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Periodic Table
Li: solid, Cs: liquid, Ar: gas, Tc: synthetic
# protons
1 e- in outer shell (Alkali Metals)
Full outer shell (Noble Gases)
1 e- missing to fill shell (Halogens)
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Ionic Bonds
Atoms with one electron in the
outer shell, and atoms with
one electron missing are, on
the other hand, highly
reactive. These atoms form
ionic bonds. The alkali gives
up an electron. The halogen
takes the electron. Elements
are bonded by the electric
force between the ions.
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Example of ionic bonds
Ruby
Sapphire
Aluminum oxide, Al
2
O
3
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Metallic Bonds
Atoms in a metals also
give up electrons,
however the electrons
are not transferred to
the other atom.
Instead, the electrons
are shared by all the
atoms.
The sea of electrons
allow current to flow
through metal. Metals
thus make good
conductors.

In sodium, for example, 1 out of the 11 electrons is
released so that Na has two filled shells. The extra
electrons move around the metal in a sea of negative
charge. This negatively charged sea moves around a
regular structure of positive Na ions.
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Covalent Bonds
Certain molecules are formed by sharing
electrons. The covalent bond that forms
resembles metallic bonds in that electrons are
shared. Yet, like ionic bonds the electrons are
shared in discrete shells of the atoms and dont
run willy nilly throughout the material.
The main constituents of our atmosphere are
covalently bonded molecules.
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Multiple Covalent
Bonds
N
2
78%
O
2
21%
H
2
O 0-4%
Ar 0.9%
CO
2
0.035%
Ne 0.0018%
He 0.0005%
CH
4
0.0001%
H
2
0.00005%
O
3
0.000004
%
Earths Atmosphere
Gases in Earths atmosphere are
mainly covalently bonded
molecules or noble gases.
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Bonding
There are three major ways that elements bond to form molecules.
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Molecular
attractions
Polar molecules are more
positively charged on one
side and more negative
on the other. This
provides a cohesion.
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TAUTOMERI
Greek tauto, meaning the same,
and meros, meaning part
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Keto-Enol Tautomerism
Carbonyl compounds with o-hydrogens rapidly
equilibrate with corresponding enol (ene + alcohol)
Interconversion known as keto-enol tautomerism
Individual isomers called tautomers

Tautomers are constitutional isomers
Isomers are different compounds with different structures
Atoms arranged differently
Different from resonance structures that differ only in the
position of their electrons
Most carbonyl compounds exist almost exclusively in the keto
form at equilibrium

Mechanism of acid-catalyzed enol formation
Protonated intermediate can lose H
+
, either from the oxygen atom to regenerate
the keto tautomer or from the o carbon atom to yield an enol tautomer
Mechanism of base-catalyzed enol formation
The intermediate enolate ion, a resonance hybrid of two forms, can be
protonated either on carbon to generate the starting keto tautomer
or on oxygen to give an enol tautomer
Only o-hydrogens are acidic
o-Hydrogens are acidic because the enolate ion that
results from deprotonation is resonance stabilized
with the electronegative oxygen of the carbonyl
|-, -, o-Hydrogens (and so on) are not acidic
because the ion that results from deprotonation is
not resonance stabilized
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o-Substitution and Carbonyl
Condensation Reactions
Alpha-substitution reactions occur
at the carbon next to the
carbonyl carbon the o
position
Involve substitution of o-
hydrogen by electrophile
Proceed through enol or
enolate ion intermediate
Carbonyl condensation reactions
occur between two carbonyl
partners
Combination of o-substitution
and nucleophilic addition steps
Gives |-hydroxy carbonyl
compound

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Reactivity of Enols: o-Substitution Reactions
Enols are nucleophiles that react with electrophiles
There is a substantial build-up of electron density on
the o carbon of the enol

Mechanism of carbonyl o-substitution reaction on an enol
Enol is formed with acid catalysis
Electron pair from C=C
bond of enol attacks an
electrophile (E
+
), forming
new C-E bond and a
resonance stabilized
intermediate
Loss of H
+
from oxygen
yields the neutral alpha-
substitution product and
restores the C=O bond
Acid-catalyzed o-halogenation (Cl
2
, Br
2
, and I
2
) of aldehydes and
ketones is a common laboratory reaction o-Halogenation
occurs in biological systems
o-Halogenation of ketones in marine alga
Mechanism of acid-catalyzed bromination of acetone
Isotopic labeling experiments support reaction mechanism of
acid-catalyzed halogenation
For a given ketone, the rate of deuterium exchange is
identical to the rate of halogenation
Enol intermediate involved in both processes
Reactivity of Enols: o-Substitution Reactions
o-Bromoketones are dehydrobrominated by base to yield
o,|-unsaturated ketones
E2 reaction mechanism
2-Methylcyclohexanone gives 2-methylcyclohex-2-enone
on heating in pyridine

Acidity of o Hydrogen Atoms: Enolate Ion Formation
Presence of neighboring carbonyl
group increases the acidity of the
ketone over the alkane by a factor
of 10
40

Proton abstraction from carbonyl occurs when the o C-H bond is
oriented parallel to the p orbitals of the carbonyl group
A carbon of the enolate ion has a p orbital that overlaps neighboring
p orbitals of the carbonyl group
Negative charge shared with oxygen atom by resonance
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Acidity of o Hydrogen Atoms:
Enolate Ion Formation
Strong base required for enolate formation
If NaOCH
2
CH
3
is used the extent of enolate formation is only
about 0.1%
If sodium hydride, NaH, or lithium diisopropylamide (LDA),
[LiN(i-C
3
H
7
)
2
], is used the carbonyl is completely converted to its
enolate conjugate base
LDA is prepared by reaction of butyllithium with
diisopropylamine
A C-H bond flanked by two carbonyl groups is even
more acidic
Enolate ion is stabilized by delocalization of negative
charge over both carbonyl groups
Pentane-2,4-dione has three resonance forms
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Identifying Acidic Hydrogens in a Compound
Identify the most acidic hydrogens in each of the
following compounds, and rank the compounds in
order of increasing acidity:

Strategy
Hydrogens on carbon next to a carbonyl
group are acidic.
In general, a |-dicarbonyl compound is
most acidic, a ketone or aldehyde is next
most acidic, and a carboxylic acid
derivative is least acidic.
Remember that alcohols, phenols, and
carboxylic acids are also acidic because
of their OH hydrogens
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Solution
The acidity order is (a) > (c) > (b). Acidic hydrogens
are shown in red:
Alkylation of Enolate Ions
Enolate ions are resonance
hybrides of two
nonequivalent
contributors
Enolate ions are vinylic
alkoxides (C=CO
-
)
Reaction on the
oxygen yields an
enol derivative
Enolate ions are a-keto
carbanions (
-
CC=O)
Reaction on the
carbon yields an
a-substituted
carbonyl
compound
Enolate ions undergo alkylation by treatment with an
alkyl halide or tosylate
Nucleophilic enolate ion reacts with the electrophilic
alkyl halide in an S
N
2 reaction
Leaving group displaced by backside attack
Alkylations are subject to all constraints that affect all
S
N
2 reactions
Alkyl group R should be primary or methyl and preferably
allylic or benzylic
Secondary alkyl halides react poorly and tertiary are
unreactive due to competing E2 reaction
The Malonic Ester Synthesis
Preparation of carboxylic acids from alkyl halides
while lengthening the carbon chain by two atoms

Diethyl propanedioate, commonly known as diethyl
malonate, or malonic ester is more acidic than
monocarbonyl compounds (pK
a
= 13) because its o
hydrogens are flanked by two carbonyl groups
Easily converted to enolate ion by sodium ethoxide in
ethanol
Et is used as an abbreviation for CH
2
CH
3

Malonic ester contains two a hydrogens
Product of o-alkylation can itself undergo alkylation
Alkylated of dialkylated malonic ester undergoes
hydrolysis to yield the diacid followed by
decarboxylation (loss of CO
2
) to yield the monoacid

Decarboxylation is unique to carboxylic acids with a
second carbonyl group located at the | position
Decarboxylation occurs via a cyclic mechanism
Involves initial formation of an enol

Overall result of malonic ester synthesis is the
conversion of an alkyl halide into a carboxylic acid
while lengthening the carbon chain by two carbons
Malonic ester synthesis can be used to prepare
cycloalkane-carboxylic acids
Three-, four-, five-, and six-membered rings can all
be prepared in this way

Using the Malonic Ester Synthesis to Prepare a
Carboxylic Acid
How would you prepare heptanoic acid
using a malonic ester systhesis?
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Carboxylic Acid
Strategy
The malonic ester synthesis converts an
alkyl halide into a carboxylic acid having
two more carbons.
Thus, a seven-carbon acid chain must be
derived from the five-carbon alkyl halide 1-
bromopentane
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Carboxylic Acid
Solution

The Acetoacetic Ester Synthesis
The acetoacetic ester synthesis converts an alkyl
halide into a methyl ketone having three more
carbons

Ethyl-3-oxobutanoate, commonly called ethyl acetoacetate
or acetoacetic ester, contains o hydrogens flanked by
two carbonyl groups
Enolate ion is readily formed and alkylated under S
N
2 reaction
conditions
A second alkylation product can be derived from
monoalkylated product
Alkylated or dialkylated acetoacetic ester is hydrolyzed
in aqueous acid to a |-keto acid
|-Keto acid undergoes decarboxylation to yield ketone
product
Ketone product formed in three-step sequence:
1. Enolate formation
2. Alkylation
3. Hydrolysis/decarboxylation
Sequence applicable to all |-keto esters with acidic o
hydrogens

Cyclic |-keto esters such as ethyl 2-
oxocyclohexanecarboxylate can be alkylated and
decarboxylated to give 2-substituted cyclohexanones

Using the Acetoacetic Ester Synthesis to Prepare a
Ketone
How would you prepare pentan-2-one by an
acetoacetic ester synthesis?
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Ketone
Strategy
The acetoacetic ester synthesis yields a methyl
ketone by adding three carbons to an alkyl halide:

Thus, the acetoacetic ester synthesis of pentan-2-
one must involve reaction of bromoethane

Ketone
Solution

Direct Alkylation of Ketones, Esters, and
Nitriles
A strong, sterically hindered base such as
LDA converts a ketone, ester, or nitrile to
its enolate ion
Use of a sterically hindered base avoids
nucleophilic addition
A nonprotic solvent such as THF is required
Aldehydes rarely give high yields of
alkylation products because their enolate
ions undergo carbonyl condensation
reactions

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Example alkylations
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Example alkylations
Example alkylations

Using an Alkylation Reaction to Prepare a
Substituted Ester
How might you use an alkylation reaction to prepare
ethyl 1-methylcyclohexanecarboxylate?

Substituted Ester
Strategy
An alkylation reaction is used to introduce a methyl or
primary alkyl group onto the o position of a ketone, ester,
or nitrile by S
N
2 reaction of an enolate ion with an alkyl
halide.
Look at the target molecule and identify any methyl or
primary alkyl groups attached to an o carbon.
The target has an o methyl group, which might be
introduced by alkylation of an ester enolate ion with
iodomethane
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Substituted Ester
Solution

Biological
Alkylations
Alkylations are
not common in
biological
systems
o-Methylation
occurs in the
biosynthesis of
the antibiotic
indolmycin from
indolylpyruvate
Carbonyl Condensations:
The Aldol Reaction
Carbonyl condensation
reactions occur
between an
electrophilic
carbonyl group of
one partner and the
nucleophilic enolate
ion of the other
partner
Combination of o-
substitution and
nucleophilic addition
steps
The Aldol Reaction
Aldehydes and ketones with an o hydrogen atom
undergo a base-catalyzed carbonyl condensation
reaction called the aldol reaction
Treatment of acetaldehyde with sodium ethoxide
yields 3-hydroxybutanal (an aldol)
The Aldol Reaction
Position of the aldol equilibrium depends both on
reaction condition and substrate structure
Equilibrium favors condensation product in the case
of aldehydes with no o substituent (RCH
2
CHO)
The Aldol Reaction
Equilibrium favors reactant for disubstituted aldehydes
(R
2
CHCHO) and most ketones

The Aldol Reaction
Aldol reactions occur by
nucleophilic addition of
the enolate ion of the
donor molecule to the
carbonyl group of the
acceptor molecule
Resultant tetrahedral
intermediate is
protonated to give an
alcohol product
The reverse process occurs
when base abstracts the
OH hydrogen from the
aldol to yield a |-keto
alkoxide ion, which
cleaves to give one
molecule of enolate ion
and one molecule of
neutral carbonyl
compound

Predicting the Product of an Aldol Reaction
What is the structure of the aldol product
from propanal?
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Worked Example 17.5
Strategy
An aldol reaction combines two molecules
of reactant, forming a bond between the o
carbon of one partner and the carbonyl
carbon of the second partner
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Solution

The Aldol Reaction
Carbonyl Condensations versus o-Substitutions
Carbonyl condensation reactions and o substitutions take place
under basic conditions and involve enolate-ion intermediates
Alpha-substitution reactions require a full equivalent of strong
base and are carried out so that the carbonyl compound is
rapidly and completely converted into its enolate ion at low
temperature before addition of the electrophile
The Aldol Reaction
Carbonyl condensation reactions require only a
catalytic amount of a relatively weak base
Enolate ion is generated in the presence of unreacted
carbonyl compound
17.6 Dehydration of Aldol
Products
|-Hydroxy aldehydes or ketones formed in aldol
reactions can be easily dehydrated to yield a,b-
unsaturated products, or conjugated enones
Aldol reactions were named condensation reactions
due to the loss of water
Dehydration of Aldol Products
Aldol products dehydrate easily because of carbonyl group
Under basic conditions, an acidic o hydrogen is removed,
yielding an enolate ion that expels the OH leaving group in an
E1cB reaction
Under acidic conditions an enol is formed, the OH group is
protonated, and water is expelled in an E1 or E2 reaction

Reaction condition needed for aldol dehydration are often
only slightly more vigorous than conditions for aldol
formation
Conjugated enones are often obtained directly from aldol
reactions without isolating the intermediate |-hydroxy carbonyl
compounds
Conjugated enones are more stable than nonconjugated enones
Interaction between t electrons of C=C bond and the t
electrons of the C=O bond
Removal of water from reaction mixture drives the aldol
equilibrium toward product
Worked Example 17.6
What is the structure of the enone obtained
from aldol condensation of acetaldehyde?
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Worked Example 17.6
Strategy
In the aldol reaction, H
2
O is eliminated and
a double bond is formed by removing two
hydrogens from the acidic o position of
one partner and the carbonyl oxygen from
the second partner.

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Worked Example 17.6
Solution

Intramolecular Aldol Reactions
Some dicarbonyl compounds react when treated
with base in an intramolecular aldol reaction
Leads to formation of cyclic product
Intramolecular Aldol Reactions
Intramolecular aldol reactions may lead to product mixtures
Most thermodynamically stable product formed selectively
All reaction steps are reversible
Most thermodynamically stable product predominates at
equilibrium
17.8 The Claisen
Condensation Reaction
Reversible condensation reaction between two esters is
called the Claisen condensation reaction
Esters have weakly acidic o hydrogens
When an ester with an o hydrogen is treated with 1
equivalent of a base a |-keto ester is formed

The Claisen Condensation
Reaction
Claisen condensation
mechanism proceeds
through a tetrahedral
intermediate
The tetrahedral intermediate
expels an alkoxide leaving
group to yield an acyl
substitution product
If the product |-keto ester has
another acidic o proton, 1 full
equivalent of base is used for
deprotonation
Deprotonation of |-keto ester
drives reaction to the product
side giving high yields of
Claisen product

Worked Example 17.7
Predicting the Product of a Claisen
What product would you obtain from Claisen
condensation of ethyl propanoate?
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Worked Example 17.7
Strategy
The Claisen condensation of an ester
results in loss of one molecule of alcohol
and formation of a product in which an
acyl group of one reactant bonds to the o
carbon of the second reactant.
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Worked Example 17.7
Solution

17.9 Intramolecular Claisen
Condensations
Intramolecular Claisen condensations are called Deickman
cyclizations
Reaction works best for 1,6 and 1,7 diesters
1,6 Diester gives a five-membered cyclic |-keto ester
1,7 Diester gives a six-membered cyclic |-keto ester
Intramolecular Claisen Condensations
Mechanism of Dieckmann
cyclization
Same as Claisen reaction
mechanism

Intramolecular Claisen Condensations
The cyclic |-keto ester produced in an intramolecular Claisen
cyclization can be further alkylated and decarboxylated
2-cyclohexanones and 2-cyclopentanones are prepared by the
following sequence:
1. Intramolecular Claisen cyclization
2. |-Keto ester alkylation
3. Decarboxylation
17.10 Conjugate Carbonyl Additions:
The Michael Reaction
The conjugate addition of a nucleophilic enolate ion to an o.|-
unsaturated carbonyl compound is known as the Michael
reaction
Best reactions are derived from addition of a b-keto ester or
other 1,3-dicarbonyl compound to an unhindered o.|-
unsaturated ketone
Ethyl acetoacetate reacts with but-3-en-2-one in the presence of
sodium ethoxide to yield the Michael addition product
Conjugate Carbonyl Additions:
The Michael reaction
Conjugate addition of a
nucleophilic enolate
ion to | carbon of an
o.|-unsaturated
carbonyl compound
Best Michael
reactions between
stable enolate ions
and unhindered o.|-
unsaturated ketones

Conjugate Carbonyl Additions:
Michael reaction occurs with a variety of o.|-unsaturated
carbonyl compounds
Worked Example 17.8
Using the Michael Reaction
How might you obtain the following compound using a
Michael reaction?
Worked Example 17.8
Strategy
A Michael reaction involves the conjugate
addition of a stable enolate ion donor to an
o.|-unsaturated carbonyl acceptor,
yielding a 1,5-dicarbonyl product
Usually the stable enolate ion is derived
from a |-diketone, |-keto ester, malonic
ester or similar compound
The C-C bond made in the conjugate
addition step is the one between the o
carbon of the acidic donor and the |
carbon of the unsaturated acceptor
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Worked Example 17.8
Solution
17.11 Carbonyl Condensations with
Enamines: The Stork Reaction
Enamine nucleophiles add to o.|-unsaturated acceptors
in Michael-like reactions
Reactions are particularly important in biological
chemistry
Enamines are prepared by reaction between a
ketone and a secondary amine

Carbonyl Condensations with
Enamines are electronically similar to enolate ions
Overlap of the nitrogen lone-pair orbital with the
double-bond p orbitals leads to an increase in
electron density on the o carbon atom
Stork reaction
Enamine adds to an o.|-unsaturated
carbonyl acceptor in a Michael-like
reaction
Initial product is hydrolyzed by aqueous
acid to yield a 1,5-dicarbonyl compound
Overall reaction is a three-step sequence:
1. Enamine formation from a ketone
2. Michael addition to an o.|-unsaturated
carbonyl compound
3. Enamine hydrolysis back to ketone
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The net effect of the Stork reaction is a Michael addition
of a ketone to an a,b-unsaturated carbonyl compound
Two advantages to the enamine-Michael
reaction that make the pathway useful in
biological systems
1. Enamine is neutral and easily prepared
and handled
Enolate is charged and difficult to prepare
and handle
2. Enamine from a monoketone can be
used in the Michael addition
Only enolate ions from |-dicarbonyl
compounds can be used
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Worked Example 17.9
Using the Stork Enamine Reaction
How might you use an enamine reaction to prepare the
following compound?
Worked Example 17.9
Strategy
The overall result of an enamine reaction
is the Michael addition of a ketone as
donor to an o.|-unsaturated carbonyl
compound as acceptor, yielding a 1,5-
dicarbonyl product
The C-C bond made in the Michael
addition step is the one between the o
carbon of the ketone donor and the |
carbon of the unsaturated acceptor
541 DEDE KIM-UA
Worked Example 17.9
Solution

17.12 Some Biological
Carbonyl Condensation
Reactions
Biological Aldol Reactions
Aldol reactions are particularly important in
carbohydrate metabolism
Enzymes called aldolases catalyze
addition of a ketone enolate ion to an
aldehyde
Type I aldolases occur primarily in animals
and higher plants
Operate through an enolate ion
Type II aldolases occur primarily in fungi and
bacteria
543 DEDE KIM-UA
Some Biological Carbonyl
Mechanism of Type I aldolase in glucose biosynthesis
Dihydroxyacetone phosphate is first converted into an enamine
by reaction with the NH
2
group on a lysine amino acid in the
enzyme
Enamine adds to glyceraldehyde 3-phosphate
Resultant iminium ion is hydrolyzed
Mechanism of Type II aldolase in glucose biosynthesis
Aldol reaction occurs directly
Ketone carbonyl group of glyceraldegyde 3-phosphate
complexed to a Zn
2+
ion to make it a better acceptor
Biological Claisen Condensations
Claisen condensations occur in a large number of biological
pathways
In fatty acid biosynthesis an enolate ion generated by
decarboxylation of malonyl ACP adds to the carbonyl group of
another acyl group bonded through a thioester linkage to a
synthase enzyme
The tetrahedral intermediate expels the synthase, giving
acetoacetyl ACP
Mixed Claisen consensations occur frequently in living
organisms
Butyryl synthase, in the fatty-acid biosynthesis
pathway, reacts with malonyl ACP in a mixed Claisen
condensation to give 3-ketohexanoyl ACP
Functional Groups with Single Bonds to Heteroatoms

Group Formula

Class Name

Specific Example

IUPAC Name

Common Name

Halide H
3
C-I Iodomethane Methyl iodide
Alcohol CH
3
CH
2
OH Ethanol Ethyl alcohol
Ether CH
3
CH
2
OCH
2
CH
3
Diethyl ether Ether
Amine H
3
C-NH
2
Aminomethane Methylamine
Nitro Compound H
3
C-NO
2
Nitromethane
Thiol H
3
C-SH Methanethiol Methyl mercaptan
Sulfide H
3
C-S-CH
3
Dimethyl sulfide
548 DEDE KIM-UA
Functional Groups with Multiple Bonds to Heteroatoms

Group Formula

Class Name

Specific Example

IUPAC Name

Common Name

Nitrile H
3
C-CN Ethanenitrile Acetonitrile
Aldehyde H
3
CCHO Ethanal Acetaldehyde
Ketone H
3
CCOCH
3
Propanone Acetone
Carboxylic Acid H
3
CCO
2
H Ethanoic Acid Acetic acid
Ester H
3
CCO
2
CH
2
CH
3
Ethyl ethanoate Ethyl acetate
Acid Halide H
3
CCOCl Ethanoyl chloride Acetyl chloride
Amide H
3
CCON(CH
3
)
2
N,N-Dimethylethanamide N,N-Dimethylacetamide
Acid Anhydride (H
3
CCO)
2
O Ethanoic anhydride Acetic anhydride
549 DEDE KIM-UA
Boiling Points (C) of Selected Elements and Compounds
Increasing Size
Atomic Ar (40) -186 Kr (83) -153 Xe (131) -109
Molecular CH
4
(16) -161 (CH
3
)
4
C (72) 9.5 (CH
3
)
4
Si (88) 27 CCl
4
(154) 77
Molecular Shape
Spherical: (CH
3
)
4
C (72) 9.5 (CH
3
)
2
CCl
2
(113) 69 (CH
3
)
3
CC(CH
3
)
3
(114) 106
Linear: CH
3
(CH
2
)
3
CH
3
(72) 36 Cl(CH
2
)
3
Cl (113) 121 CH
3
(CH
2
)
6
CH
3
(114) 126
Molecular Polarity
Non-polar: H
2
C=CH
2
(28) -104 F
2
(38) -188 CH
3
CCCH
3
(54) -32 CF
4
(88) -130
Polar:
H
2
C=O (30) -21 CH
3
CH=O (44) 20 (CH
3
)
3
N (59) 3.5 (CH
3
)
2
C=O (58) 56
HCN (27) 26 CH
3
CN (41) 82 (CH
2
)
3
O (58) 50 CH
3
NO
2
(61) 101
550 DEDE KIM-UA
Compound Formula
Boiling
Point
Melting
Point
pentane CH
3
(CH
2
)
3
CH
3
36C 130C
hexane CH
3
(CH
2
)
4
CH
3
69C 95C
heptane CH
3
(CH
2
)
5
CH
3
98C 91C
octane CH
3
(CH
2
)
6
CH
3
126C 57C
nonane CH
3
(CH
2
)
7
CH
3
151C 54C
decane CH
3
(CH
2
)
8
CH
3
174C 30C
tetramethylbuta
ne
(CH
3
)
3
C-
C(CH
3
)
3

106C +100C
551 DEDE KIM-UA
Exclusively Carbon Functional Groups

Group
Formula
Class Name
Specific
Example
IUPAC Name
Common
Name

Alkene H
2
C=CH
2
Ethene Ethylene
Alkyne HCCH Ethyne Acetylene
Arene C
6
H
6
Benzene Benzene
552 DEDE KIM-UA

Configurat
ion
Bonding
Partners
Bond
Angles
Example
Tetrahedral 4 109.5
Trigonal 3 120
Linear 2 180
553 DEDE KIM-UA
554 DEDE KIM-UA
Group Molecules & boiling points C
VII HF 19 ; HCl 85 ; HBr 67 ; HI 36
VI H
2
O 100 ; H
2
S 60 ; H
2
Se 41 ; H
2
Te 2
V NH
3
33 ; PH
3
88 ; AsH
3
62 ; SbH
3
18
Class Molecules & boiling points C
Oxygen
Compounds
C
2
H
5
OH 78 ; (CH
3
)
2
O 24 ; (CH
2
)
2
O 11
ethanol dimethyl ether ethylene oxide
(CH
2
)
3
CHOH 124 & (CH
2
)
4
O 66
cyclobutanol tetrahydrofuran
Nitrogen
Compounds
C
3
H
7
NH
2
50 ; C
2
H
5
NH(CH
3
) 37 ; (CH
3
)
3
N 3
propyl amine ethyl methyl amine trimethyl amine
(CH
2
)
4
CHNH
2
107 & (CH
2
)
4
NCH
3
80
cyclopentyl amine N-methylpyrrolidine
Complex
Functions
C
2
H
5
CO
2
H 141 & CH
3
CO
2
CH
3
57
propanoic acid methyl acetate
C
3
H
7
CONH
2
218 & CH
3
CON(CH
3
)
2
165
butyramide N,N-dimethylacetamide
555 DEDE KIM-UA
Compound Formula Mol. Wt. Boiling Point Melting Point
dimethyl ether CH
3
OCH
3
46 24C 138C
ethanol CH
3
CH
2
OH 46 78C 130C
propanol CH
3
(CH
2
)
2
OH 60 98C 127C
diethyl ether (CH
3
CH
2
)
2
O 74 34C 116C
propyl amine CH
3
(CH
2
)
2
NH
2
59 48C 83C
methylaminoethane CH
3
CH
2
NHCH
3
59 37C
trimethylamine (CH
3
)
3
N 59 3C 117C
ethylene glycol HOCH
2
CH
2
OH 62 197C 13C
acetic acid CH
3
CO
2
H 60 118C 17C
ethylene diamine H
2
NCH
2
CH
2
NH
2
60 118C 8.5C
556 DEDE KIM-UA
557 DEDE KIM-UA

558 DEDE KIM-UA

559 DEDE KIM-UA

560 DEDE KIM-UA

561 DEDE KIM-UA

562 DEDE KIM-UA

563 DEDE KIM-UA

564 DEDE KIM-UA

565 DEDE KIM-UA
REAKSI UTAMA DARI ATOM-ATOM ADALAH :
PUTUSNYA IKATAN carbon-hydrogen and carbon-halogen DALAM WAKTU
BERSAMAAN.
PEMBENTUKAN carbon = carbon SEBAGAI IKATAN
An example of this type of reaction in scheme 1 is the reaction of
isopropylbromide with potassium ethoxide in ethanol. The reaction products are
isobutylene, ethanol and potassium bromide.
566 DEDE KIM-UA

567 DEDE KIM-UA
568 DEDE KIM-UA
An example in scheme 2 is the reaction of tert-butylbromide with potassium
ethoxide in ethanol.
E1 eliminations happen with highly substituted alkyl halides due to 2 main reasons.
569 DEDE KIM-UA

570 DEDE KIM-UA
Organic Chemistry

The Complete Lecture
571 DEDE KIM-UA
Has Four Bonding Electrons

Unique Strong Covalent Bonds

Strong Single, Double and Triple Bonds
Average Bond Energies (KJ mol
-1
)
C-C 607 Si-Si 230 C-H 416 Si-H 323
C-N 754 Si-N 470 C-O 336 Si-O 368
O-Si-O = Sand and Rocks
Carbon
572 DEDE KIM-UA
573 DEDE KIM-UA

H
C H H
H
methane
Carbon has 4 valence electrons
C
H
H
H
H
H C
Ne
Neon
Stable Octet required
Simplest Organic molecule
Covalent Bonding Atoms Share Electrons
574 DEDE KIM-UA
IKATAN KOVALEN
BANYAKNYA ELEKTRON TAMBAHAN
YANG DIPERLUKAN UNTUK MENCAPAI
KONFIGURASI GAS MULIA .

MUATAN FORMAL = (banyak elektron
valensi dlm sbh atm netral) (banyak
elektron terbagi) (banyak elektron valensi
menyendiri)

ATOM NUMBER OF
COV. BOND
IDENTIFICATI
ON Priod Tab
H 1 IA
C 4 IVA
N 3 VA
O 2 VIA
CL 1 VIIA
I 1 VII
Br 1 VIIA
575 DEDE KIM-UA
Electron promotion
576 DEDE KIM-UA
Electronegatifity
577 DEDE KIM-UA
C(6) - 1s
2
, 2s
2
, 2p
x
1
, 2p
y
1
, 2p
z
0
lowest energy
state
Hybridization
C(6) - 1s
2
, 2s
1
, 2p
x
1
, 2p
y
1
, 2p
z
1
Excited state

4 sp
3
2s
2p
x
2p
y
2p
z
+
+ +
4 X sp
3
578 DEDE KIM-UA
Methane is Tetrahedral
109.5
0
Sp
3
hybridized carbon
4 equivalent C-H bonds (obonds)
All purely single bonds are called obonds
H
C
H
H
H
579 DEDE KIM-UA
ALKANES
580 DEDE KIM-UA
Alkanes
C
n
H
2n+2
consist of only carbon and hydrogen bonded by single covalent bonds single
H
C H H
H
H
C H C
H
H
H
H
H
C H C
H
H
C
H
H
H
H
H
C H C
H
H
C
H
H
C
H
H
H
H
CH
3
H
C H C
H
H
C
H
H
C
H
H
C
H
H
H
H
methane ethane propane butane
CH
3
CH
3
CH
3
CH
2
CH
3
CH
3
CH
2
CH
2
CH
3
pentane
CH
3
CH
2
CH
2
CH
2
CH
3
Skeletal structure of only carbon atoms
propane
butane
pentane
C1 C4 n-alkanes are all gases
Methane main component of natural gas
Propane and butane often stored as compressed gases

581 DEDE KIM-UA
Name the following compound
CH
3
CH
2
CH
2
CH
2
CH
C
H
CH
3
C
H
CH
2
CH
2
C
H
CH
3
CH
3
CH
3
CH
3
longest chain = 9 carbons = nonane
1,2-dimethyl propyl substituent
methyl
need to be in alphabetical order
5-(1,2-dimethylpropyl)-2-methylnonane
C C
H
H
H
H H
H
Ethane
Rotation about single covalent bonds
occurs freely. The energy barrier is
small. The position of hydrogen
atoms relative to one is thus
constantly changing
3D models show that because of
the tetrahedral carbon atoms the
chains are zig-zagged and not at all
straight
582 DEDE KIM-UA
Physical Properties of Alkanes
Non-polar molecules, which are less dense than water.
Alkanes are immiscible with water making two layers.
Van-der Waals or dipole-dipole attractive forces, and not H-bonding
(as in polar molecules) are the main intermolecular forces
Alkanes show regular increases in bpt and mpt as molecular weight
increases down the homolgous series
These weak intermolecular forces operate over small distances, arising
because the electron distribution within molecules at any given
instance is not uniform. Resulting in tiny electrical attractions between
molecules.
These temporary dipoles hold alkanes as liquids or solids,
and must be overcome in order to vaporize a liquid or melt a
solid (wax)
583 DEDE KIM-UA
Isomers the have the same molecular formula, but a different structures
Structural Isomers same molecular formula, but atoms are bonded in different
orders.
H
3
C C
CH
3
CH
3
H
Isobutane
H
3
C CH
CH
3
CH
2
CH
3
Isopentane
H
3
C C
CH
3
CH
3
CH
3
Neopentane
Has the same molecular
formula as n-pentane, C
5
H
12

Have different Physical
Properties, Mpt, Bpt, densities,
C
4
H
10
has two isomers, n-butane and isobutane (2-
methylpropane)
(2,2-dimethylpropane)
(2-methylbutane)
584 DEDE KIM-UA
585 DEDE KIM-UA
Fractional distillation of crude oil
Petroleum
Kerosene (C
12
-C
16
)
Bpt (200-250 C)
Heating oil (C
15
-C
18
)
Bpt (250-300 C)
Natural Gas (C
1
-C
4
) < 20
o
C
Gasoline (C
4
-C
12
)
Bpt (40-200 C)
Straight-chain alkanes are a pure fuel, because of engine knock.
n-Heptane has an octane rating = 0
2,2,4-trimethylpentane has an octane rating = 100
Catalytic cracking
INDUSTRIAL SOURCE
bensin
minyak tanah
Pelumas, bahan bakar diesel,
586 DEDE KIM-UA
Petroleum
587 DEDE KIM-UA
CH
3
CCH
2
CHCH
3
CH
3
CH
3
CH
3
2,2,4-trimetilpentana
isooktana )
(
CH
3
( CH
2
)
5
CH
3
heptana
Anti kertakan pada mesin mobil
Angka oktan ditentukan oleh perbandingan
isooktana heptana
a.o 75 ; 75% -i o 25% -h
ANGKA OKTAN ~ 100 ANGKA OKTAN ~ 0
Mpt~ -107 : bpt~ 98 - 99
o
C Mpt~ -91 : bpt~ 98
o
C
Flamable Flamable
588 DEDE KIM-UA
CYCLOALKANES and
Conformational Analysis
589 DEDE KIM-UA
Cycloalkanes
H
2
C
C
H
2
CH
2
Cyclopropane
C
n
H
2n
C
C
C
H
H
H H
H
H
H
2
C
H
2
C CH
2
CH
2
Cyclobutane
C
H
2
CH
2
CH
2
H
2
C
H
2
C
Cyclopentane
590 DEDE KIM-UA

Angle Strain in Cyclopropane and Cyclobutane
weaker Bent C-C bonds C-C Bond angles 60
and 88
o
respectively

Eclipsed hydrogens Torsional Angle
Reduced in Cyclobutane by folding or bending
Pentane has C-C bond angles of 108
o
C-C bonds slightly bent out of planarity in order
to reduce torsional strain
The most stable cycloalkane with
109.5
o
C-C bond angles
Cycloalkanes have higher bpt/mpt than straight chain
alkanes with the same number of carbon atoms
591 DEDE KIM-UA
Sir D.H.R. Barton, Nobel Prize 1969
592 DEDE KIM-UA
How to draw Cyclohexane ?
H
H
H
H
H
H
put in axial Hs
put in equitorial Hs
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H H
H
H
H
593 DEDE KIM-UA

Preparations of Alkanes

Alkanes can be prepared by catalytic
hydrogenation of alkenes or alkynes.
Pt
CH2=CH2 + H2 -----------> CH3-CH3

Alkanes can be prepared by a coupling
reaction known as the Wurtz Reaction:

2CH3-Br + 2Na ---------> CH3-CH3 + 2NaBr

594 DEDE KIM-UA
Alkanes can be prepared by forming an organo-metallic
reagent known as a Grignard from an alkyl halide and then
hydrolyzing it (react it with water):
anhyd ether
CH3-Br + Mg ----------------> CH3- + MgBr

CH3- +MgBr + H2O ----->CH4 + MgBrOH

Thermal Decarboxylation of a Carboxylate Salt

CH3-CH2-COOH + NaOH ----> CH3-CH3 + CO2

595 DEDE KIM-UA
CH
4
O
2
CO
2
H
2
O energy
+
2 2
+
+
RCH
2
CH
2
R RHC CHR H H
+
alkene
High Temp.
catalyst
Reactions of Alkanes
Combustion
Dehydrogenation
Halogenation radical substitution reactions
Br
2
Br
+
+
HBr
light or heat
596 DEDE KIM-UA
H Cl
H
Cl +
1 electron
7 electrons in outer shell
Less Energy Demand
Gaseous phase
Monoatomic - Radicals
H Cl
H Cl +
0 electrons 8 electrons in outer shell
water
H
2
O
H
3
O Cl
Only possible in solution
597 DEDE KIM-UA
When bonds break ions are created driven by
the energy of solvation
Each atom gets one electron each results in
the formation of radicals
Radical neutral species with one unpaired
electron
Using Curly Arrows
598 DEDE KIM-UA

Sir Robert Robinson, Nobel Prize 1947
Introduced curly arrows in 1922, numerous
brilliant syntheses of complex natural products

599 DEDE KIM-UA
Halogenation
Substitution Reaction a reaction in which part
of a small reacting molecule replaces an atom or a
group of atoms on the organic molecule
H
C H
H
C
H
H
H
+
Br
2
H
C H
H
C
H
H
Br
Heat or Light
A or hv
Ethane Bromoethane
HBr
+
C
H
H
H
+
Cl
2
Heat or Light
A or hv
Methane
chloromethane
HCl
+
H C
H
H
Cl H
CH
2
Cl
2
and CHCl
3
may be observed
600 DEDE KIM-UA
Mechanisms are widely used by organic chemists to explain reaction
pathways to observed reaction products
Initiation
Two highly reactive Chlorine radicals formed
Cl Cl
Cl +
Cl
hv or A
+
Cl
H
C H
H
H
H
C H
H
H Cl
Hydrogen abstraction to form a methyl radical
Propagation
Cl Cl
Cl +
H
C Cl
H
H
H
C H
H
Chlorine atom is abstracted to form a chlorine radical
Propagation are the product forming steps
Chain Reaction thousands of radical forming cycles
601 DEDE KIM-UA
Cl Cl Cl
CH
3
H
3
C CH
3
CH
3
Cl
Cl CH
3
CH
3
Cl
Termination
Radicals Couple
Product forming Chains
are broken
Fluorine is the most reactive halogen mixtures of fluorine and methane can
be explosive. Fluorine radical is very reactive. The reaction is controlled with
the addition of an inert gas to dilute the reaction.
Chlorine is next most reactive, followed by bromine.
Cl
2
and Br
2
require heat or light. Iodine does not react with methane
easily. Iodine radical is disperse and large - unreactive

As the reaction progresses chloromethane
accumulates and its hydrogen atoms can be
abstracted.
Cl
Cl Cl
Cl
C
H
H
H
C H
Cl
Cl
Dichloromethane (DCM)
+
602 DEDE KIM-UA
Alkyl Halides or Haloalkanes
603 DEDE KIM-UA
CH
3
CH
Cl
CH CH
3
CH
3
Cl
C Cl Cl
Cl
CH
3
CH
Br
CH
2
CH
2
Cl
F
CH
2
CH
3
Br
Cl
Cl
C Cl F
Cl
F
C Cl F
Cl
F
C F
F
C
F
H
H
Naming them
Tetrachloromethane
or carbon tetrachloride
2-Chloro-3-methylbutane 3-Bromo-1-chlorobutane
1-Ethyl-2-fluorocyclohexane
1-Bromobutane
2-Chloropropane or
Isopropyl chloride
Tend to be Heavier than water
More Toxic than Alkanes
Trichlorofluoromethane
(Freon-11)
Dichlorodifluoromethane
(Freon-12)
1,1,1, 2-Tetrafluoroethane
Chlorofluorocarbons (CFCs)
Refrigerant Gases, Ozone Depletion, More Hs more degradable
604 DEDE KIM-UA
PROPERTIES OF ALKANES HALOGENIDA
structure name bpt

CH3CH2Cl ethyl chlorida 13
o
C

CH3CH2CH2Cl n-propil chlorida 47
o
C

CH3CHClCH3 isopropyl chlorida 36
o
C

CH3CH2CH2CH2Cl n-butyl chlorida 78,5
o
C

CH3CH2CHClCH3 sec-butyl chlorida 68
O
C

CH3CClCH3CH3 t-butyl chlorida 51
o
C

605 DEDE KIM-UA
X
C
X = F, Cl, Br
o+
o-
Nu
-
Electronegativity is defined as the ability of atoms to attract shared
electrons in a covalennt bond ------------ leads to nucleophilic
substitution in alkyl halides
X is readily displaced by nucleophiles
Cl
C Cl Cl
Cl
Symmetrical molecules have no dipole
moment or have equal distribution of
electrons within covalent bonds
Therefore, they are unreactive! 606 DEDE KIM-UA
The C-Cl bond in the halogenoalkane starts to lengthen and
weaken
The chloride ion is eventually detached from the carbon atom
and a flat carbocation forms. This is the rate determining step.
The hydroxide ion could attack from the left-hand side, lead
ing to inversion of the configuration of the carbon skeleton; or
attack could come from the right, leading to retention of con
figuration.
* The use of a chiral halogenoalkane in this reaction leads
to production of a racemic mixture if the amount of attack from
each side is equal. The hindrance caused by the departing
cloride ion gives about 40% attack from the right and 60% from
the left, however.
607 DEDE KIM-UA
The general form of the S
N
1 mechanism is as follows:

Because the mechanism goes through a carbocation, the leaving group must be attached to either
a tertiary or secondary carbon to stabilize the intermediate. A methyl or primary leaving group will
not form a carbocation

. Since it goes through a carbocation intermediate, there are possibilities for alkyl and hydrogen
rearrangements(HINT: In mechanism problems if you see a change in the carbon skeleton
between the reactant and the product, automatically
suspect a carbocation intermediate (ie, E1, Sn1) stabilized by an alkyl or hydrogen rearangement). .
An example ofthe Sn1 Mechanism

608 DEDE KIM-UA
Base Strength: Base strength is unimportant, since the base is not involved in the rate determining
step (the formation of the carbocation). .
Leaving groups: A good leaving group is required, such as a halide or a tosylate, since the leaving
group is involved in the rate-determining step.
Notes: Be wary of rearangements that can occur with the S
N
1 reaction. Because it goes through a carbocation
intermediate, both hydrogen shifts and alkyl shifts can occur!
609 DEDE KIM-UA
ALKENES
610 DEDE KIM-UA
Unsaturated Compounds contain DB and or TB
ALKENES
C
n
H
2n
End in ene
CH
2
H
2
C
H
3
C CH CH
2
Ethene
Propene
1-Butene
1-Pentene
1-Hexene
1,3-Butadiene
3-methyl-1,4-pentadiene
611 DEDE KIM-UA
C
C
H
H
H
H
120
o
Flat molecule Planar
C(6) - 1s
2
, 2s
2
, 2p
x
1
, 2p
y
1
, 2p
z
0
C(6) - 1s
2
, 2s
1
, 2p
x
1
, 2p
y
1
, 2p
z
1
Hybridization
3 sp
2
Three o-bonds
t-bond
C C
H H
H H
o-bonds One C-C, two C-H bonds per carbon atom
t-bond
612 DEDE KIM-UA
s-orbital
p-orbitals
When a single bond is
present between atoms, that
bond is always obond
DB contains one obond and
one tbond
end to end overlap of orbitals leads to o-bond
Spherical Symmetry
tbond
side ways overlap
Groups or atoms can be rotated about a single bond, but DB
is rigid No rotation about a DB is possible without breaking
the tbond
This leads to cis-trans Isomerism
o-bond
The t-bond lies perpendicular to the o-bond
overlapping lobes above and below the plane of o-
bond
613 DEDE KIM-UA
cis- trans-
If each of the two carbons has two different groups attached to it
H
R R
H R
R H
H
H
H
3
C CH
3
H CH
3
H
3
C H
H
cis-(Z)-2-butene
trans-(E)-2-butene
Z-E system, we take the group with higher priority (here
higher molecular weight), and compare it with the group
with higher priority on the other carbon
Geometric isomers have
different chemical &
physical properties
614 DEDE KIM-UA
Cl Br
H F
Cl > F
Br > H
(Z)-2-Bromo-1-chloro-1-fluoroethene
Cl H
Br F
Cl > F
Br > H
(E)-2-Bromo-1-chloro-1-fluoroethene
C H
3
H
CH
3
F
F > CH
3
CH
3
> H
(Z)-2-fluorobutene
1. no.atom, no atom bsr prioritas
2. no. massa kel atom substituen

615 DEDE KIM-UA
tbond lobes represent areas of high electron density
E
+
Therefore, the tbond is susceptible to attack by
electron deficient molecules, called electrophiles, E
+
WHAT ARE ADDITION REACTIONS ?
C C
+
A B C A C B
C C
H X
C H C X
X X
C X C X
C H C OSO
3
H
H OSO
3
H
C H C OH
H OH
H
+
Alkyl Halides
Alkyl hydrogen Sulfate
Alcohols
Dihaloalkanes
616 DEDE KIM-UA
Mechanism
The electrophile is a Lewis acid, its accepted a pair of electrons,
the simplest Lewis acid is H
+

The nucleophile is a Lewis base, its donated a pair of electrons

X
-
is the nucleophile, and the carbocation is the electrophile
C C
H X
C C
H
X +
Slow
C C
H X
C C
H
X
fast
617 DEDE KIM-UA
C C
H OSO
2
OH
C C
H
C C
H
O
S
O
O O H
OSO
3
H
Slow
Fast
Markovnikovs Rule
H atom adds to the carbon atom
which already has the most H
atoms
H
2
C
H
C CH
3
H
2
C
H
C CH
3
H Br
Markovnikov addition
Product
H Br
Unsymmetrical Alkene
618 DEDE KIM-UA
H
C H
H
CH
3
C H
H
CH
3
C CH
3
H
CH
3
C CH
3
CH
3
+ + + +
INCREASING STABILITY OF CARBOCATIONS
This determines the selectivity
of addition of HX onto an
unsymmetrical alkene
619 DEDE KIM-UA
C C
H
H
H
CH
3
H Br
C C
H
H
H
CH
3
H
Slow
Br
C C
H
H
H
CH
3
H Br
C C
Slow
CH
3
H
H
H
H
2
o
Carbocation prefered
1
o
Carbocation
3
o
> 2
o
> 1
o
Carbocation stability
2-Bromopropane
is the main product
1-Bromopropane little formed
The Slow Step is the Rate Determining Step
CH
3
CHBr CH
3
CH
3
H
2
C BrH
2
C
620 DEDE KIM-UA
Bromination of DB This is an Ionic Mechanism
1. Bromine molecule becomes polarised
3. Formation of Bromonium cation and Bromide anion
2. Bromine bond breaks heterolytically
4. Back-side nucleophilic attack opening of three membered ring
5. Stereospecific Product
Test for DB or TB
Decloroization of Br
2
/CCl
4
colourless
Contrast with reaction
between Bromine and
Alkanes
C C
Br
Br
o+
o
C C
Br
Br
+
Br
C C
Br
C C
Br
Br
621 DEDE KIM-UA
C
C
H
H
C H
C H
Pt or Pd - catalyst
solvent, pressure
C
C
H
H
2 X
C H H
C H H
Pt - catalyst
solvent, pressure
Example
Pt
ethanol, 1 atm
cyclohexene
cyclohexane
Hydrogenation Reduction
622 DEDE KIM-UA
623 DEDE KIM-UA
H
2
C CH
2
KMnO
4
,
-
OH, H
2
O
OHOH
H
2
C CH
2
+
MnO
2
Oxidation of Alkenes
LEO Says GER
1,2-Ethanediol
Reduction =
Gain of electrons
Gain of Hydrogen
Loss of Oxygen
Oxidation =
Loss of electrons
Loss of Hydrogen
Gain of Oxygen
An oxidizing agent gets reduced
A reducing agent gets oxidized
624 DEDE KIM-UA
C C
H
H
H
H
H
C C
H
H H
C C
H
H
H
CH
3
H
C C
CH
3
H H
C C
H
H
H
Cl
C C
F
F
F
F
C C
H H
C C
H
H H
H
C C
H
H
Cl H
C C
F F
F F
n
Polyethylene
n
Polypropylene
propylene
ethylene
vinyl chloride
n
n
n
n
Poly(vinylchloride), PVC
n
n
n
n
Teflon Tetrafluoroethene
Styrene
Polystyrene
Polymers are large
molecules containing
many identical repeating
units (100-1000000)
Polymerisation reaction is a repetition
reaction which combines many small
molecules of monomer (alkene) to
form a polymer
Addition polymer is a
polymer in which the
monomer simply add
together with no other
products formed besides
polymer
625 DEDE KIM-UA
ALKYNES
626 DEDE KIM-UA
Alkynes
H C C H
H
3
C C C H
Ethyne
(acetylene)
Propyne
180
o
Sp
3
hybridisation in Saturated Bonds (e.g. alkanes)
Sp
2
hybridisation in DB (e.g. alkenes)
Sp hybridisation in TB (e.g. alkynes)
C(6) - 1s
2
, 2s
2
, 2p
x
1
, 2p
y
1
, 2p
z
0
C(6) - 1s
2
, 2s
1
, 2p
x
1
, 2p
y
1
, 2p
z
1
Hybridization
2sp

2tbonds
Two o-bonds (C-H) and (C-C)
And Two t-bonds between C-C
per C atom
Linear Molecule
627 DEDE KIM-UA
Therefore, a Triple bond consists of one o-bond and two t-
bonds
The two t-bonds are perpendicular to each other and
form a cylinder of negative charge about the axis of the
bond ---------- No bond rotation about TB
sp-orbitals contain 50% s- and 50% p-character
Far less disperse than sp
2
, which is less disperse than sp
3
The Carbon-Carbon bond is 1.2A
o
shorter than C=C, which is
1.3A
o
. C-H bond is also shorter than ethene, which is shorter
than ethane, because in ethyne it is overlap between an sp
orbital and a s-orbital of H to give the o-bond.
The bonding electrons reside closer to the C-nucleus, and so
are held more tightly.

628 DEDE KIM-UA
Alkynes are high energy compounds
C C H H +
2.5 O
2
2 CO
2
+ H
2
O
Welding gas
Combustion
Alkynes are more reactive in halogenation reactions than
alkenes (no longer in this course) and --------
629 DEDE KIM-UA
Benzenes & AROMATICS
630 DEDE KIM-UA
Benzene
C
C
C
C
C
C
H
H
H
H
H H
An Aromatic Hydrocarbon is a cyclic compound that does not
readily undergo addition reactions
Reactivity is different to other unsaturated compounds-
Substitution rather than Addition is favoured.
C
6
H
6
Resonance Structure
- Rearrange the bonding electrons
Delocalised or Conjugated System t-bonding
electrons can move within the molecule
Delocalisation, Resonance
-Stabilise molecules, so make
them less reactive
High Carbon content
burn with a smoky flame
631 DEDE KIM-UA
In aromatic compounds the C atoms are sp
2
hybrids, so that each
C atom has one remaining p-electron involved in t-bonding
C
C
C
C
C
C
H
H
H
H
H H
Kekul said that he dreamt
the structure of benzene
so called Kekul structure
of benzene
Three sp
2
hybrid orbitals arrange themselves as far apart as possible -
which is at 120 to each other in a plane. The remaining p orbital is at
right angles to them.

Each carbon atom uses the sp
2
hybrids to form sigma bonds with two other carbons and one hydrogen atom.

Each carbon atom uses the sp
2
hybrids to form o-bonds with two other
carbons and one hydrogen atom.

This extensive sideways overlap produces a system of t-bonds which are
spread out over the whole carbon ring. Because the electrons are no longer
held between just two carbon atoms, but are spread over the whole ring, the
electrons are said to be delocalised.
632 DEDE KIM-UA
=
Flat (Planar) Molecule
Regular Hexagon
t-Electron Density Rings above and below
the plane of the ring Susceptible to
electrophilic attack
Benzene is a colourless odourless liquid
that is a suspected carcinogen
Benzene and its derivatives are said
to be aromatic - a term coined
because of the strong fragrance of
some of the derivatives of benzene
Non-aromatic compounds are
said to be aliphatic
Michael Faraday first
isolated benzene in 1825
633 DEDE KIM-UA
=
Flat (Planar) Molecule
Regular Hexagon
Delocalised or Conjugated System
t-bonding electrons can move within the
molecule
634 DEDE KIM-UA
1. Must be cyclic
2. Must be planar
3. Each atom of the ring must have a p orbital and these p orbitals must be perpendicular
to the plane of the ring
4. Must contain 4n+2 = telectrons (where n = 0, 1, 2, ...) Hckel Rule
n = 1 , 6t electrons
Naphthalene
Anthracene Phenanthrene
10
14
Rules for Aromaticity
635 DEDE KIM-UA
Br
OH
O O H
N
+
O O
N
H H
CH
3
1
2
3
4
O
m
p
Vinyl group
636 DEDE KIM-UA
Naming Aromatic Hydrocarbons
F CH
2
CH
3 CH
3
NH
2
OH
C
OH
O
Cl
Cl
Cl
Cl
Cl
Cl
CH
3
NO
2
NO
2
CH
3
CH
3
O
2
N
Br
Fluorobenzene Ethylbenzene
Toluene Aniline
Phenol
Benzoic Acid 1,2-Dichlorobenzene 1,3-Dichlorobenzene
-meta
-ortho
-para
1,4-Dichlorobenzene 2,4,6-Trinitrotoluene (TNT)
o-Xylene
m-Bromostyrene
637 DEDE KIM-UA
Electrophilic Aromatic Substitution
H
H
H
H
H
H
E
H
H
H
H
H
E X
+
H X
E
E
H
E
H
E
H
Electrophilic attack Slow Rate Determining Step
E
H
sp
3
Delocalised Cyclohexadienyl cation
Transition State or Wheland Intermediate
638 DEDE KIM-UA
H
E
E
+ - H
+
Fast Step is the loss of a proton
Sir Christopher Ingold's ideas (1930s), terminology and
nomenclature for reaction mechanisms (e.g. electrophilic,
nucleophilic, inductive, mesomeric, S
N
1, S
N
2 etc) were
generally accepted and employed everywhere.

HNO
3(c),
H
2
SO
4(c)
NO
2
E.g. Nitration of benzene
---rapid re-aromatization
639 DEDE KIM-UA
The Nitration of Benzene
O
N
O
N
O O
O
2
N
H
N
O
O
NO
2
N
O O
+
electrophile
+
_
electrophilic attack
+
slow
+
- H
+
fast
=
=
+
_
+
+
640 DEDE KIM-UA
Generating NO
2
+
Sulfuric acid is a stronger acid than nitric acid
NO
2
H
NO
2
NO
2
Nitrobenzene
S
O
O
O O H H S
O
O
O O
O H NO
2
O
H
H
NO
2
_
_
+
H
+
+
NO
2
+
+
H
2
O
2 H
+
- [H
+
]
641 DEDE KIM-UA
Friedel-Crafts Alkylation
RX +
AlCl
3
or FeCl
3
R
+
HX
Lewis Acid Catalyst is used to activate the alkyl halide
CH
3
CH
2
Cl
+
AlCl
3
CH
2
CH
3
AlCl
4
H
CH
2
CH
3
H
Al Cl
Cl
Cl
Cl
CH
2
CH
3
+
HCl
+
AlCl
3
+o
o
slow
fast
642 DEDE KIM-UA
Professor Charles Friedel
and Professor James Crafts
Cl
Br
Br
2
, FeBr
3
Cl
2
, AlCl
3
HALOGENATION
Br
FeBr
4
Br Br FeBr
3
H
+
The Halogen is polarised
643 DEDE KIM-UA
Conclusions
Aromatic Compounds are resonance stabilized
This gives them added stability
They undergo Electrophilic Substitution Reactions
Upon substitution, the fast step is the loss of a proton to regenerate aromaticity
H
Br
H
Br
H
Br
+
+
+
Br
+ HBr
FeBr
4
FeBr
3
Regenerate the catalyst so only a small amount is required
double-headed arrows
644 DEDE KIM-UA
William Perkin
mauve
Write the mechanism for the formation of mauve from the
diazonium salt of aniline
Diazonium Coupling Reactions
Azo Dyes
645 DEDE KIM-UA
ALCOHOLS, PHENOL and
ETHERS
646 DEDE KIM-UA
Alcohols and Ethers
Alcohols and Ethers can be regarded as derivatives of water
in which one or two of the H atoms has been replaced by an
alkyl group
Electronegativity of oxygen causes an
unsymmetrical distribution of charge
Saturated molecules
are sp
3
hybridized
O
H H
104.5
o
0.96 A
o
Water, H
2
O
O
C H
108.5
o
0.96 A
o
Methanol, CH
3
OH
H
H
H
1.43 A
o
O
C C
111.7
o
Methoxymethane, CH
3
OCH
3
H
H
H
1.43 A
o
H
H
H
109.5
o
1.10 A
o
O
H
3
C H
- I (net dipole)
o +
o
647 DEDE KIM-UA
Alcohols are found to have much higher bpt than those of alkanes or
haloalkanes of comparable size, e.g. Methanol (65
o
C),
Chloromethane and Methane are gases ; Ethanol (78.5
o
C),
Chloroethane (12
o
C) and Ethane is a gas
Methanol and Ethanol are classed as Polar Molecules (Hydrophilic)
They are Infinitely Soluble in Water
Why? Answer Hydrogen Bonding
H-bonds weaker than covalent bonds, although these bonds can be
continually broken and reformed a highly ordered structure
results H-Bonding to water can also occur
Water (mw = 18) is a liquid, bpt 100
o
C otherwise a gas
R
O
H
H
O
R
o
o+
R
O
H
H
O
H
H
O
H
o
o+
H
O
H
648 DEDE KIM-UA
As R-group increases in size,
so does the solubility in non-
polar solvents
As the number OHs increases so does solubility in water
Bpt increase with chain length and number of OHs

Methanol, CH
3
OH
- Solvent in varnishes, paint
- Racing Car Fuel (easy to put
out flames)
- Highly Toxic Blindness -
Formaldehyde
Ethanol, CH
3
OH
-Drinking Alcohol
- 50% Ethanol is
flammable
C O
H
H
H
C
H
H
H C O
H
H
H
C
H
H
C
H
H
C
H
H
C
H
H
H
Hydrophobic end
Hydrophilic end
1-Pentanol
Ethanol
H
3
C OH
Alcohol Dehydrogenase
O
C
H H
O
C
H OH
[O]
In the Liver
Alcohol Dehydrogenase
O
C
H
3
C H
O
C
H
3
C OH
[O]
In the Liver
CH
3
CH
2
OH
Acetaldehyde
Acetic Acid
Odour on your breath
Symptoms - Hang-over
649 DEDE KIM-UA
Preparation of Ethanol
- Fermentation of Sugar Break down of sugar to CO
2

and Ethanol by Yeast Enzymes
- Industrial Process Hydration of Ethene
CH
3
CH
2
OH
H
H
H
H
H
3
PO
4
, 300C
H
2
O
Ethanol content; Beer, 3-9% ; Wine, 11-13% ; Whisky, 40-45% ; Vanilla Extracts, 35% ;
Night Nurse, 25% ; Listerine, 25%
CH
3
OH
hydroxy or alcohol group
CH
2
OH CH
3
CH
2
OH CH
2
CH
3
CH
3
CH OH
CH
3
CH
2
CH CH
2
CH
2
OH
CH
3
CH
3
Naming Alcohols
Methyl alcohol
(methanol)
Ethyl alcohol (ethanol) Propyl alcohol (propanol)
Isopropyl alcohol 2-Ethyl-1-butanol
650 DEDE KIM-UA
Naming Alcohols
Polyhydroxy alcohols are alcohols that possess more than one
hydroxyl group
CH
2
CH
2
HO OH
1,2-Ethanediol (ethylene glycol)
1,2-Propanediol (propylene glycol)
1,2,3-Propanetriol (glycerol)
CH CH
2
OH
CH
3
HO
CH CH
2
OH
CH
2
HO HO
Extremely Toxic
Calcium Oxalate
crystallises in the kidney
leading to renal problems
Harmless
C OH C
O O
HO
Liver Enzymes Oxalic acid
CH
2
CH
2
OH HO
CH CH
2
OH
CH
3
C OH C
O O
H
3
C
Liver Enzymes Pyruvic acid
HO
651 DEDE KIM-UA
Alcohols are very weak Acids
H
C OH H
3
C
H
CH
3
C OH H
3
C
H
CH
3
C OH H
3
C
CH
3
Primary (1
o
) Alcohol
Secondary (2
o
) Alcohol
Tertiary (3
o
) Alcohol
R O H
H
O H R O
+
H
O H H
Alcohol
Alkoxide
o +
o +
o
Relative Acidity ; H
2
O > ROH >
C C R H > RH
CH
3
CH
2
OH
+ Na
CH
3
CH
2
O
Na
+ H
2
Vigorous Reaction
2
2
2
652 DEDE KIM-UA
OH groups are poor leaving groups
Weak acids make Poor Leaving Groups in Organic Reactions
Strong Acids have Conjugate Bases that are Good Leaving
Groups in Organic Reactions
R-I > R-Br > R-Cl > R-F ..Order of leaving group ability
H-I < H-Br < H-Cl < H-F -------- reverse of bond strength
C O H H A +
C O H
H
+
A
Strong Acid
Protonated Alcohol
C O H
H
Nu
C Nu H
2
O +
653 DEDE KIM-UA
OMs and OTs are excellent leaving groups in Nucleophilic
Substitution Reactions- Derivatives of Sulfuric Acid
C O H
Base
C O
Na
C O
O
S CH
3
O
Cl
C O SO
2
CH
3
Cl Ms
C OMs
Methanesulfonyl chloride
Alkanesulfonate(Alkane Mesylate)
Similiarly,
S
O
O
Cl
CH
3
CH
2
O H
+
CH
3
CH
2
O S
O
O
CH
3
NaOH , - HCl
CH
3
p-Toluenesulfonyl chloride
(Tosyl Chloride)
CH
3
CH
2
-OTs
Ethyl-p-toluenesulfonate
(Ethyltosylate)
O
S OH
O
HO
Sulfuric Acid
654 DEDE KIM-UA
S
N
2 Substitution, Nucleophilic, Bimolecular
Rate = k [CH
3
CH
2
OTs] [ Nu
-
] ---------Bimolecular
Backside Nucleophilic Attack Inversion in Configuration
Concerted Mechanism
Optically Active
Enantiomericaly Pure
C Br
H
3
C
H
C
6
H
13
HO
C HO
CH
3
H C
6
H
13
Br
CH
3
HO
C
6
H
13
H
Transition State
R-(-)-2-Bromooctane
S-(+)-2-Octanol
Inversion of Stereochemistry
C OTs
H
3
C
H
H
Nu
C Nu
CH
3
H H
OTs
CH
3
Nu
H
H
Transition State
655 DEDE KIM-UA
S
N
1 Substitution, Nucleophilic, Unimolecular
(CH
3
)
3
CCl + 2 H
2
O
(CH
3
)
3
COH + 2 H
3
O
+
+ Cl
-

Professor George Olah
Nobel Prize 1994
Carbocation is sp
2
-planar
CH
3
C H
3
C
CH
3
Cl
CH
2
CH
3
H
3
C
+
Cl
Slow Step (RDS)
Aided by polar Solvent Stable 3
o
Carbocation
ions are stabilized via solvation
CH
2
CH
3
H
3
C
Fast Step
H
O
H
Front or Backside Attack
CH
3
C H
3
C
CH
3
O
tert-Butyl alcohol
H
H
CH
3
C H
3
C
CH
3
O H
- H
+
C R
R
R
C R
R
H
C R
H
H
>
>
R groups are electron releasing
- delocalise the positive charge
more stable
656 DEDE KIM-UA
H
3
CH
2
CH
2
C
C Br
H
3
CH
2
C
H
3
C
CH
2
CH
2
CH
3
C HO
CH
2
CH
3
CH
3
H
3
CH
2
CH
2
C
C OH
H
3
CH
2
C
H
3
C
+
- HBr
S-3-Bromo-3-methylhexane
1:1 Mixture of R- and S-3-Methyl-3-hexanol
The Carbocation intermediate is
attacked by water from either side by
the same rate
657 DEDE KIM-UA
Phenols are stronger acids than alcohols
O
CH
3
H
3
C
CH
3
cyclohexene
phenol
cyclic ether
Tetrahydrocannabinol
OH
OH OH
pKa = 18
pKa = 10
O H
O
O
O
Resonance Stabilised Phenoxide anion
658 DEDE KIM-UA
ETHERS, RO-OR CH
3
CH
2
O CH
2
CH
3
CH
3
CH
2
O
H
3
C O
Ethoxy group
Methoxy group
Diethyl Ether
1-Propoxypropane
Methoxybenzene
anisole
Methoxycyclohexane
Bpt are similar to alkanes No H-bonding to one another
But are soluble in water- H-bonding to water - Polar
Flammable Ether can cause flash fires
Low Reactivity Make Good Reaction Solvents
O
Tetrahydrofuran (THF)
O
O
Furan
Pyran
Cyclic Ethers
Non-Flammable Anaesthetics
Cl
C H
F
C
F
F
O C
H
F
F
Enflurane
F
C F
F
C
H
Cl
O C
H
F
F
Isoflurane
H
3
CO
O
OCH
3
659 DEDE KIM-UA
STEREOCHEMISTRY
660 DEDE KIM-UA
Isomers are different compounds that have the same molecular formula
Structural isomers are isomers that differ because their atoms are
connected in a different order
Stereoisomers differ only in the arrangement of
their atoms in space
Cl H
Cl H
Cl H
H Cl
cis-1,2-Dichloroethene trans-1,2-Dichloroethene
C
2
H
2
Cl
2
Geometric Isomers
CH
3
OCH
3
---- dimethyl ether and
CH
3
CH
2
OH ---- ethanol

661 DEDE KIM-UA
Enantiomers are stereoisomers whose molecules are
nonsuperimposable mirror images of one another
Objects that are superimposable on their
mirror images are said to be achiral
CH
3
CH
2
C
H HO
CH
3
CH
2
C
H
CH
3
CH
3
OH
Interchanging any two groups at a chiral
centre (stereocentre) that bears four
different groups converts one enantiomer
into another
Involves a tetrahedral sp
3
atom
CH
3
C
OH
CH
2
CH
3
2-Butanol
H
Chiral Centre
662 DEDE KIM-UA

Nobel Prize 2001
For synthesis of optically active compounds asymmetric synthesis
Professor William Knowles
Professor Ryoji Noyori
Professor K. Barry Sharpless
C Br
H
3
C
H
C
6
H
13
HO
C HO
CH
3
H C
6
H
13
Br
CH
3
HO
C
6
H
13
H
Transition State
R-(-)-2-Bromooctane
S-(+)-2-Octanol
Inversion of Stereochemistry
S
N
2
663 DEDE KIM-UA
One structure can be superimposed on another
If any of the groups
attached to the
tetrahedral atom are
the same, the centre
is achiral.
The ultimate way to test for
molecular chirality is to construct
models of the molecule and its
mirror image and then determine
whether they are superimposable
A molecule will not be chiral if it possess a
centre or plane of Symmetry
2-Propanol
CH
3
C
OH H
CH
3
C
CH
3
H HO
CH
3
Screwdriver is achiral
Socks are achiral
Golf club is chiral
Gloves are chiral
664 DEDE KIM-UA
Properties of Enantiomers
Enantiomers have identical melting points and boiling points
Enantiomers have identical solubilities in solvents
Enantiomers have identical spectra and refractive index
Enantiomers interact, and react with achiral molecules in the
same manner
Enantiomers interact and react with other
chiral molecules at different rates
Enantiomers rotate plane-polarised light by
equal amounts but in opposite directions
Plane-polarised light
Oscillation of electrical field of ordinary light
occurs in all possible directions
Polarimeter is a devise used to measure the effect of plane-
polarised light on an optically active compound
Chiral molecules are
optically active
665 DEDE KIM-UA
No Correlation between the direction of rotation of plane
polarised light and the absolute configuration of a molecule
Clockwise Rotation (+) dextrorotatory
Anti-Clockwise Rotation (-) levorotatory

C
CH
2
CH
3
H
2
C
CH
3
H
HO
C
CH
2
CH
3
H
2
C
CH
3
H
Cl
(R)-(+)-2-Methyl-1-butanol
(R)-(-)-1-Chloro-2-methylbutanol
Same Configuration
An equimolar mixture of two enantiomers is called a Racemic
Mixture
It is Optically Inactive
666 DEDE KIM-UA
H
O
S-(+)-Carvone
O
R-(-)-Carvone
H
Principle component of
Caraway seed oil and
responsible for the
characteristic odour
Principle component
of Spearmint oil and
responsible for the
characteristic odour
Receptor Sites in the Nose are Chiral
667 DEDE KIM-UA
668 DEDE KIM-UA
669 DEDE KIM-UA

670 DEDE KIM-UA

671 DEDE KIM-UA

672 DEDE KIM-UA
ALDEHYDES AND KETONES
673 DEDE KIM-UA
Aldehydes and Ketones
O 1s
2
, 2s
2
2p
2
2p
1
2p
1
3 sp
2
orbitals
C
H
R
O C
R
R
O
Aldehyde
Ketone
C
H
H
O
lone Pairs
tbond - two overlapping 2p orbitals
obond
obond- overlapping 1s
H-orbital and sp
2
C-orbital
674 DEDE KIM-UA
C O
H
3
C
H
118
o
121
o
C C
H
H
H
H
118
o
121
o
o
o+
C O
H
3
C
H
C O
H
3
C
H
Resonance Structures
Most Reactive Group
telectrons + polarisation
Useful in Synthesis
Names
al aldehydes, one - ketones
C O
H
H
C O
H
3
C
H
C O
CH
3
CH
2
H
C O
CH
3
CH
2
CH
2
CH
2
H
Methanal
(formaldehyde)
Ethanal
(acetaldehyde)
Propanal
Pentanal
675 DEDE KIM-UA
O
H
H O
H
H
Benzaldehyde
trans-Cinnamaldehyde
Formalin, 35-40% formadehyde in water
Preservative that reacts with
proteins causing them to resist decay
Coelacanth, prehistoric fish
O
H
Acrolein (2-propenal)
S
H
Thiopropionaldehyde
(propanethiol)
- lachrymator from chopped onion
- lachrymator and pleasant "odour"
from barbacuing meat
676 DEDE KIM-UA
Propanone
(ACETONE)
Butanone
Acetophenone
Benzophenone

O
H
3
C
CH
CH
2
CH
3
CH
3
3-Methyl-2-pentanone
O
H
OCH
3
OH
Vanillin
CH
3
O
Carvone
(spearmint flavour)
O O
H
3
C CH
3
Butadione
(butter flavour)
O
H
3
C CH
3
O
CH
3
O
O
H
3
C C
H
2
CH
3
677 DEDE KIM-UA
Carbonyls readily undergo Nucleophilic Attack
ANHYDROUS
Conditions are required for
imine formation
O
C
RNH
2
o
o+
O
C
N H
H
R
O
C
N H R
H
O
C
N H R
H
C
N
R
- H
2
O
Imine
Reaction between an amine and a carbonyl compound
678 DEDE KIM-UA
Condensation Reaction Elimination of water
C O
C H
3
C H
3
N N
H
H H
H
C N
C H
3
C H
3
N
H
H
+
hydrazine
acetone
Emil Fischer, Nobel Prize 1902
C O
C H
3
C H
3
N N
H H
H
O
2
N
O
2
N
C N
C H
3
C H
3
N
H
NO
2
NO
2
+
2,4-diphenylhydrazine
acetone
DNP test for aldehydes & ketones gives crystalline hydrazones
- H
2
O
- H
2
O
679 DEDE KIM-UA
Professor Victor Grignard (1912 Nobel Prize)
Developed this chemistry with Professor P. A. Barbier
C R O
H
Protonation
H
H
2
O
Alcohol
C R
X
H
H
X = I or Br
o+
o
C
H
H
MgX R
o
o+
RCH
2
MgX
Grignard Reagent
Mg
Ether
C R
X
H
H
X = I or Br
o+
o
C
H
H
Li R
o
o+
RCH
2
Li
Organolithium Reagent
Li
Ether
C O
R Li
o+
o
o
o+
C R O
Li
ADDITION
680 DEDE KIM-UA
MgBr
C O
H
H
Ether
C
H
H
O MgBr
H
3
O
+
C
H
H
O H
Benzylalcohol
C O
MgBr
+
Ether
C OH
Triphenylmethanol
Benzyl Group
Phenyl, Ph Group
Ph
2. H
3
O
+
Organometallics add to carbonyls to give alcohols
681 DEDE KIM-UA
O
C
H H
O
C
R H
O
C
R R
MgI Ph MgI Ph MgI Ph
O
C H H
H
Ph
O
C R H
H
Ph
O
C R R
H
Ph
+
+
+
Primary alcohols
Secondary alcohols tertiary alcohols
Ketone
Aldehydes
Formaldehyde
Nucleophilic Addition Reactions
your adding Ph

_
682 DEDE KIM-UA
Mg
Br
O
CH
2
CH
3
CH
3
CH
2
O
CH
2
CH
3 CH
3
CH
2
.. ..
.. ..
Ethers (Lewis base) stabilize the
Grignard Reagent making it
more reactive
Organometallic Reactions must always be done under anhydrous conditions
Mg Br
H
O
H
H
+o
o
OH
_
+
Grignards are powerful bases and
will deprotonate water
683 DEDE KIM-UA
CARBOXYLIC ACIDS and
ESTERS
684 DEDE KIM-UA
Carboxylic Acids
O
C
O H H
2
O +
O
C
O
H
3
O +
pKa = 4 - 5 , water = 16
We can distinguish a water-insoluble carboxylic acid and phenol from
an alcohol
O
C
O H NaOH +
O
C
O
H
2
O
Na
Benzoic acid
Sodium Benzoate
685 DEDE KIM-UA
Highly Polar
Low molecular weight acids show Appreciable Solubility in Water
High Bpt Extensive H-bonds to themselves and water
Carboxylic Acids
NAMES
Methanoic acid
Ethanoic acid
Propanoic acid
4-Bromo-2-ethylpentanoic acid
O
H OH
O
CH
3
OH
O
CH
3
CH
2
OH
O
OH
Br
O
C
C OH
HO
O
Ethanedioic acid (oxalic acid)
rhubarb
Red ants
O
OH
O
HO ( )
n
n = 1 = malonic acid
n = 2 = succinic acid
n = 3 = glutaric acid
HO
2
C CO
2
H
CO
2
H
CO
2
H
Terephthalic acid
Phthalic acid
686 DEDE KIM-UA
Esterification condensation reaction, where H
2
O is lost
Alcohol part appears first in the name
O
CH
3
OH
CH
3
CH
2
OH +
HCl or H
2
SO
4
H
+
(catalyst)
O
CH
3
O CH
2
CH
3
Acetic acid
(ethanoic acid)
Ethyl acetate
O
Ph OH
H
3
C OH
+
H
+
(catalyst)
O
Ph O CH
3
Benzoic acid
Methyl benzoate
O
O
O
O
Ethyl propanoate
vinyl acetate
O
H O
Methyl formate
687 DEDE KIM-UA
Ester molecules cannot H-bond to each
other, because they do not have an OH
Consequently, B.pt is much lower than that
of alcohols and acids of comparable mass
H-bonding to water is possible
-low mw esters are soluble in water
Solubility rapidly decreases with carbon
chain length.

O
H
O
H
H
O
H
O R
R
688 DEDE KIM-UA
O
C R
O H
O
C R
O H
........
........
Two hydrogen bonds
O
C R
O R
cannot H-bond to another ester molecule
Highest Boiling points and exceedingly water soluble
Hexane = 69 C
Diethyl ether = 56 C
Ethanol = 78 C
Ethanoic acid = 118 C
Ethyl acetate = 77 C
Boiling points
689 DEDE KIM-UA
Redox Reactions
Addition of Oxygen or Removal of Hydrogen is OXIDATION
Removal of Oxygen or Addition of Hydrogen is REDUCTION
CH
4
+ O
CH
3
OH
- 2H
C O
H
H
C O
HO
H
+ O - 2H
O
C
O
C O
H
R
H
C R
H
O
H
Reduction
Oxidation
C O
R
R
H
C R
R
O
H
Reduction
Oxidation
Aldehydes
Primary Alcohols
Secondary Alcohols Ketones
690 DEDE KIM-UA
Examples of Reduction Reactions
O
H
2
, Pt
O
H
H
Cyclohexanone Cyclohexanol
CH
3
H
3
C
O
H
3-Methylbutanal
H
2
, Pd-C
CH
3
H
3
C
O
H
H
H
3-Methylbutanol
Examples of Oxidation Reactions
OH
H
O
K
2
Cr
2
O
7
, H
2
SO
4
, H
2
O
Overoxidation
OH
O
691 DEDE KIM-UA
H N H
H
R N H
H
R N H
R
R N R
R
Ammonia
Primary (1
o
) Amine
Secondary (2
o
) Amine
Tertiary (3
o
) Amine
Organic bases are amines
Amines are derivatives of ammonia
N 1s
2
, 2s
2
2p
1
2p
1
2p
1
----------- lone pair
occupies an sp
3
orbital

692 DEDE KIM-UA
AMINES, AMIDES and ANILINE
693 DEDE KIM-UA
Ammonia
3
o
Amine
Unshared lone pair of electrons in the fourth sp
3
hybrid occupies
slightly more space than the electrons in the obonds
N
H
H
H
N
R
R
R
..
107
O
..
107
O
694 DEDE KIM-UA
H
2
NEt HNEt
2
NEt
3
H
2
NMe
HNMe
2
NMe
3
where Et = CH
2
CH
3
ethylamine diethylamine
triethylamine
primary
secondary
tertiary
where Me = CH
3
methylamine
dimethylamine
trimethylamine
primary
secondary
tertiary
Naming amines
N
H
methylpropyl amine
695 DEDE KIM-UA
H
2
N
NH
2
Putrescine
(found in decaying meat)
NH
2
Amphetamine
(dangerous stimulant)
N
H
Piperidine
N
Triethylamine
NH
2
Isopropylamine
1,4-butanediamine
Some Common Amines
Both upper amines are 1
o
This amine is are 2
o

This amine is 3
o
This amine is 1
o
696 DEDE KIM-UA
NH
2
H
Cl
N
H
H
H Cl
Base + Acid = Ammonium Salt
Amines are bases because of the lone pair on the
nitrogen atom - red litmus paper to blue
O
O H
O
O H
N(CH
2
CH
3
)
3
O
O
O
O
HN(CH
2
CH
3
)
3
+ 2
+
2
oxalic acid
triethylamine
triethylaminium oxalate
697 DEDE KIM-UA
= aniline
Aniline is useful in the synthesis of many other aromatic compounds
NO
2
NO
2
NH
2
HNO
3
, H
2
SO
4
Sn, HCl
phenylamine
698 DEDE KIM-UA
NH
2
N N
NaNO
2
, HCl
benzenediazonium chloride
+
Cl
-
0 C
Aniline can be converted into useful diazonium salt
N N
N N
Nuc
+
Cl
-
Nuc
-
-
699 DEDE KIM-UA
N N
N N
CN
+
Cl
-
CuCN
-
+
KCN
N N
N N
I
+
Cl
-
NaI
-
Benzene nitrile
N N
N N
Br
+
Cl
-
HBr, CuBr
-
iodobenzene
bromobenzene
700 DEDE KIM-UA
N
C R
R'
O
N
C R
R'
O
Amides
Features of a Peptide Bond;
1. Usually inert
2. Planar to allow delocalisation
3. Restricted Rotation about the amide bond
4. Rotation of Groups (R and R) attached to the amide
bond is relatively free
------------- Not acids or bases
701 DEDE KIM-UA
O
C
C H
3
NH
2
O
C
H NH
2
NH
2
O
O
C
N H
2
NH
2
R
C N H
2
H
COOH
acetamide
benzamide
urea
AMINO ACIDS
formamide
All are high melting point solids, only
benzamide not soluble in water
702 DEDE KIM-UA
Chemicals : maleic acid ; bromine
Apparatus and glass wares : 500 watt day light bulb ;
3 volumetric flasks 100 mL
volumetric pipet 20 mL
2 measuring pipets10 mL
2 erlenmeyer flasks 50 mL
Safety precautions:
Bromine is highly toxic if inhaled, ingested or comes in contact
with the skin.
STEREOKIMIA
703 DEDE KIM-UA
Safety goggles and gloves must be worn when handling bromine. The experiment
should be performed under a laboratory fume.

Preparation:
Saturated solution of maleic acid: 94.8 g of maleic acid dissolved in 120 mL of
dist. H2O
Saturated bromine water: 3.5 g of bromine in 100 mL of dist. H2O
Flask A and B: 40 mL of aqueous maleic acid solution are mixed with 10 mL of
saturated bromine water.
Flask C: 40 mL of aqueous maleic acid solution are diluted with 10 mL of dist.
H2O.

The volumetric flask A is covered by a black paperboard cylinder. The solutions B
and C are simultaneously exposed to the light of a 500 watt day light bulb until a
precipitate is formed in flask B.

After the light is turned off the paperboard cylinder is removed.

704 DEDE KIM-UA
Light initiates the reaction by generating bromine atoms (free radicals)
from bromine molecules. (1).

The bromine radical is added to maleic acid. In the addition compound
the partial single bond character allows rotation around the central CC
bond (2).

After rotation around the CC-bond and the elimination of the bromine
radical fumaric acid is formed (3).
705 DEDE KIM-UA

706 DEDE KIM-UA
707 DEDE KIM-UA

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KIMIA ORGANIK LANJUT

(ADVANCED ORGANIC CHEMISTRY)

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