Organic chemistry 4

Prof. Dr. Fakhri Elabbar

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INDEX OF HYDROGEN DEFICIENCY

and

THE BASIC THEORY OF

INFRARED SPECTROSCOPY
 What Can You Learn From a
Molecular Formula ?

you can determine the number of rings and or double

bonds.
Saturated Hydrocarbons
CnH2n+2 GENERAL FORMULA

CH4 CH4
CH3 CH3 C2H6
CH3 CH2 CH 3 C3H8
CH3 CH2 CH 2 CH3 C4H10
CH3 CH2 CH 2 CH2 CH3 C5H12

CH3 CH3
CH3 CH CH C CH 3 C9H20
CH3 CH3
branched compounds
also follow the formula
FORMATION OF RINGS AND DOUBLE BONDS

-2H
C C C C
H H

H H
-4H
C C C C
H H

CH2 CH2
H2 C -2H H2 C CH2
CH2 H
H2 C CH2 H H2 C CH2
CH2 CH2

Formation of each ring or double bond causes the loss of 2H.

 Index of Hydrogen Deficiency
CALCULATION METHOD

• Determine the expected formula for a noncyclic, saturated compound ( CnH2n+2 ) with
the same
number of carbon atoms as your compound.

• Correct the formula for heteroatoms

(explained later)
• Subtract the actual formula of your compound

• The difference in H’s divided by 2 is the

Index of Hydrogen-deficiency
 C5H8

C5H12 = ( CnH2n+2 )
C5H8
H4 Index = 4/2 = 2
Two Unsaturations
double bond and
ring in this example
 Index of Hydrogen Deficiency
CORRECTIONS FOR ATOMS OTHER THAN HYDROGEN
• O or S -- doesn’t change H in calculated formula

+0 C-H
+O
C-O-H

• N or P -- add one H to the calculated formula

+1 C-H
+N,+H
C-NH2

• F, Cl, Br, I -- subtract one H from calculated

formula

-1 C-H C-X
-H,+X
 H
N
C4H5N

C4H10 = ( CnH2n+2 )
C4H11N add one H for N

C4H5 N
H6 Index = 6/2 = 3
two double bonds and
ring in this example
 The index gives the number of
• double bonds or
• triple bonds or
• rings in a molecule

one ring and the

equivalent of three
Benzene
double bonds gives
an index of 4

If index = 4, or more,
expect a benzene ring
 Find the HDI for C9H8O4
C9H8O4 C9H20 CnH2n+2
C21H30O2 C9H8O4
C11H15NO2 ---------------------- N=+1
12/2= 6
C21H30O2
C11H15NO2
C21H44 CnH2n+2
C11H25 CnH2n+2
C21H30O2
C11H15NO2
----------------------
----------------------
14/2= 7
10/2= 5
Note
•When HDI is 4 or more think of benzene ring
•When Nitrogen is present +1 to CnH2n+2
•When halogen is present -1 from CnH2n+2
•When oxygen or sulfur is present +0 to CnH2n+2
PROBLEM A hydrocarbon has a molecular
formula of C6H8. It will react with
hydrogen and a palladium catalyst
to give a compound of formula
C6H12. Give a possible structure.

INDEX C6H14
-C6H8
H6 Index = 6/2 = 3

HYDROGENATION
Pd
C6H8 + 2 H2 C6H12
Hydrogenation shows only two double bonds.
Therefore, there must also be a ring.
 A FEW POSSIBLE ANSWERS
CH3
CH3

H3 C CH3

CH3

CH2 CH3

..... there is still work required to fully solve the problem

INFRARED SPECTROSCOPY
 THE ELECTROMAGNETIC SPECTRUM
high Frequency () low
high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational magnetic
Ultraviolet Visible infrared
resonance
2.5 m 15 m 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength () long

 Types of Energy Transitions in Each Region
of the Electromagnetic Spectrum

REGION ENERGY TRANSITIONS

X-ray Bond-breaking
UV/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radio Frequency Nuclear and
(NMR) Electronic Spin
 Simplified Infrared Spectrophotometer
NaCl
focusing plates
mirror
Detection Electronics
and Computer

Determines Frequencies
of Infrared Absorbed and
Infrared
plots them on a chart
Source

Infrared
Sample Spectrum

intensity of
Absorption absorption
“peaks”
frequency
(decreasing)
AN INFRARED SPECTRUM KETONE

4-Methyl-2-pentanone
C-H < 3000, C=O @ 1715 cm-1

100
100
%

T 80
80
R
A
N 60
S 60
M
I 40
T 40
T
A
N 20 CH3 O
20
C
E
0
CH3 CH CH2 C CH3
0

3500 3000 2500 2000 1500 1000 500

WAVELENGTH (cm-1)
THE UNIT USED ON AN IR SPECTRUM IS
WAVENUMBERS ( )
 = wavenumbers (cm-1)
1
=  (cm)
 = wavelength (cm)

c = speed of light
 = frequency = c c = 3 x 1010 cm/sec
or

 =( 1
) c = c cm/sec = 1
  cm sec

wavenumbers are directly proportional to frequency

 Molecular vibrations
Two major types :

STRETCHING
C C
BENDING C

C
C
both of these types are “infrared active”
( excited by infrared radiation )
Types of Molecular Vibrations
Bond Stretching Bond Bending

symmetric In-plane rocking

asymmetric In-plane scissoring

Out-of-plane wagging

Out-of-plane twisting
Typical Infrared Absorption Regions
(stretching vibrations)

WAVELENGTH (m)
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
* nitro has
two bands
 HARMONIC OSCILLATOR

MATHEMATICAL DESCRIPTION
OF THE
VIBRATION IN A BOND

…. assumes a bond is like a spring

 force
HOOKE’S LAW
constant
compress
K stretch

x

restoring x0 x1
force = -F = K(x)

Molecule
as a
m1 m2 Hooke’s
Law
K device
THE EQUATION OF A = frequency
SIMPLE HARMONIC in cm-1
OSCILLATOR
c = velocity of light
( 3 x 1010 cm/sec )
1 K
 = 2c 
K = force constant
in dynes/cm
where

m1 m 2 C C > C C >C C
 = multiple bonds have higher K’s
m 1 + m2
m = atomic masses
This equation describes the
vibrations of a bond. =reduced mass
 larger K,
higher frequency

1 K
 = 2c  larger atom masses,
lower frequency

constants increasing K

=
C=C > C=C > C-C
2150 1650 1200

increasing 

C-H > C-C > C-O > C-Cl > C-Br

3000 1200 1100 750 650
DIPOLE MOMENTS
Dipole Moment
 DIPOLE MOMENTS
Only bonds which have significant dipole moments will
absorb infrared radiation.

Bonds which do not absorb infrared include:

• Symmetrically substituted alkenes and alkynes
R R
R C C R
R R
• Many types of C-C Bonds

• Symmetric diatomic molecules

H-H Cl-Cl
 STRONG ABSORBERS
-
The carbonyl group is one O
of the strongest absorbers +
C

Also O-H and C-O bonds O H C O

infrared beam
C C
+ + O +
O
- - -

oscillating dipoles couple and

energy is transferred
RAMAN SPECTROSCOPY

Another kind of vibrational spectroscopy that

can detect symmetric bonds.

Infrared spectroscopy and Raman spectroscopy

complement each other.
 RAMAN SPECTROSCOPY
In this technique the molecule is irradiated with
strong ultraviolet light at the same time that the
infrared spectrum is determined.

Ultraviolet light promotes electrons from bonding

orbitals into antibonding orbitals. This causes
formation of a dipole in groups that were formerly
IR inactive and they will absorb infrared radiation.

* . induced
+ -
h .
C ..C
dipole
R R R C C R
UV
 * absorbs IR
transition
no dipole
symmetric
….. we will not talk further about this technique
• index of hydrogen deficiency
• the electromagnetic spectrum
• types of energy transitions in each region of the
electromagnetic spectrum
• simplified infrared spectrophotometer
• molecular vibrations and its types
• mathematical description of the vibration in a bond
• dipole moments and its effect on ir absorption
• Raman spectroscopy