Structure Determination in

Conjugated Systems
Ultraviolet Spectroscopy
Multiple bonds that alternate with single
bonds are said to be conjugated

CH2=CH-CH=CH2 CH2=CH-CH2-CH=CH2
1,3-Butadiene 1,4-Pentadiene
Conjugated diene Non-conjugated diene

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The UV region of electromagnetic spectrum
extends from the low  end of the visible
region (4 x 10-7 m) to 10-8 m, but the range
2 x 10-7 m to 4 x 10-7 m is the of greatest
interest to organic chemists

Absorptions in this region are measured in

nanometers (nm)

where 1 nm = 10-9 m
Thus, the ultraviolet range of interest is
from 200 to 400 nm

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when an organic molecule is irradiated with
electromagnetic energy, the radiation either
passes through the sample or is absorbed,
depending on its energy
With IR irradiation, the energy absorbed
corresponds to the amount necessary to
increase molecular bending and stretching
vibrations

With UV radiation, the energy absorbed

corresponds to the amount necessary to
promote electron from one orbital to another

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1,3-Butadiene has four  molecular orbitals
Two lower-energy, bonding MO's are
occupied in the ground state, and the two
higher-energy, antibonding MO's unoccupied,

CH2=CH-CH=CH2
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 On irradiation with ultraviolet light,
1,3-butadiene absorbs energy and  electron
is promoted from highest occupied molecular
orbital (HOMO) to the lowest unoccupied
molecular orbital (LUMO)
Since the electron is promoted from bonding
molecular orbital  to antibonding molecular
orbital *, we call this a  ―› * excitation
(read as "pi to pi star")

The energy gap between HOMO and LUMO of

1,3-butadiene is such that UV light of 217 nm
 is required to accomplish  ―› *
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Observed electronic transitions
From the molecular orbital diagram, there are
several possible electronic transitions that can
occur, each of a different relative energy:

s*

* s s* alkanes

 * unsaturated cmpds.
n
Energy
n s* O, N, S, halogens

n * carbonyls


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 s s* alkanes 150 nm

s * carbonyls 170 nm

 * unsaturated cmpds. 180 nm √ - if conjugated!

n s* O, N, S, halogens 190 nm

n * carbonyls 300 nm √

log(I0/I) = A
I0 I

sample
UV-VIS sources

200 700

detector
, nm

monochromator/
reference

beam splitter optics I0 I0

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 In practice, an ultraviolet spectrum is
recorded by irradiating the sample with UV
light of continuously changing wavelength
When the wavelength corresponds to energy
level required to excite an electron to higher
level, energy is absorbed
This absorption is detected and displayed on
a chart that plots wavelength () versus
absorbance (A)

where I is intensity of incident light , I is the

intensity
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 Note that UV spectra differ from IR spectra
in the way they are presented

IR spectra are usually displayed so that the

baseline corresponding to zero absorption
runs across the top of the chart and a valley
indicates an absorption

UV spectra are displayed with the baseline at

the bottom of the chart so that a peak
indicates an absorption

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The exact amount of UV light absorbed is
expressed as sample's molar absorptivity
(), defined by the equation:
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Where A = Absorbance; C = Concentration in
mol/L; I = Sample pathlength in cm

Molar absorptivity () is a physical constant,

characteristic of the particular substance
being observed and thus characteristic of the
particular it electron system in the molecule

Typical values for conjugated dienes are in

the rang of  = 10,000-25,000
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 Unlike IR and NMR spectra, which show
many absorptions for a give molecule, UV
spectra are usually quite simple - often
only a single peak

The peak is usually broad, however, and we

identify its position by noting the wavelength
at the very top of the peak
(max, read as "lambda max")

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 Interpreting Ultraviolet Spectra:
The Effect of Conjugation

The exact wavelength necessary to effect the

 ―› * transition in a conjugated molecule
depends on the energy gap between HOMO
and LUMO which in turn depends on the
nature of the conjugated system

Thus, by measuring UV spectrum of unknown,

we can derive structural information about
the nature of any conjugated  electron
system present
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One of the most important factors affecting
the  of UV absorption by a molecule is the
extent of conjugation

Molecular orbital calculations show that the

energy difference between HOMO and LUMO
decreases as extent of conjugation increases

Thus, 1,3-butadiene absorbs at max = 217 nm

while 1,3,5-hexatriene absorbs at max=258
and 1,3,5,7-octatetraene absorbs at max=290

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 The UV absorption maxima of some
representative conjugated molecules:

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 Structure Determination of Dienes
Woodward- Fieser Rules

Woodward and the Fieser performed

extensive studies of terpene and
steroidal alkenes and noted similar
substituents and structural features
would predictably lead to an empirical
prediction of the wavelength for the
lowest energy p → p*electronic
transition

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Dienes and cyclic dienes
Woodward-Fieser Rules
Dienes and Cyclic Dienes
The rules begin with a base value for
max of the chromophore being
observed: Acyclic butadiene = 214 nm

transoid, heteroannular = 214 nm

Cisoid, homoannular = 253 nm

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The incremental contribution of substituents
is added to this base value from tables:

Group Increment
Extended conjugation +30
Each exo -cyclic C=C +5
Alkyl or ring residue +5
-OCOCH3 +0
-OR +6
-SR +30
-Cl, -Br +5
-NR2 +60

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 For example:

acyclic butadiene = 214 nm

one alkyl subs. + 5 nm
219 nm
Experimental value 220 nm

acyclic butadiene = 214 nm

one exocyclic C=C + 5 nm
2 ring residues +10 nm
229 nm
Experimental value 233 nm

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 heteroannular diene = 214 nm

3 ring residues (3 x 5) +15 nm

1 exo C=C + 5 nm
234 nm
Experimental value 235 nm

heteroannular diene = 214 nm

4 alkyl subs. (4 x 5) +20 nm
1 exo C=C + 5 nm
C OH 239 nm
O
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 C OH
O

homoannular diene = 253 nm

4 alkyl subs. (4 x 5) +20 nm

1 exo C=C + 5 nm
278 nm

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 Group Increment
6-membered ring or acyclic enone Base 215 nm
5-membered ring parent enone Base 202 nm
Acyclic dienone Base 245 nm

Double bond extending conjugation 30 nm

Alkyl group or ring residue , ,  and 10, 12, 18 nm
higher
-OH 35, 30, 18 nm
-OR , ,  ,  35, 30, 17, 31 nm
-O(C=O)R , ,  6 nm
-Cl ,  15, 12 nm
-Br ,  25, 30 nm
-NR2  95 nm
Exocyclic double bond 5 nm
Homocyclic diene component 39 nm

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 Examples
cyclic enone = 215 nm

 O 2 x  - alkyl subs. (2 x 12) +24 nm
239 nm

Experimental value 238 nm

cyclic enone = 215 nm

extended conj. +30 nm
  -ring residue +12 nm
 O
  -ring residue +18 nm
exocyclic double bond + 5 nm
280 nm

Experimental 280 nm

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