Ultraviolet – Visible Spectroscopy
Lecture 2
Woodward-Fieser Rules
Structure Determination
What are the Woodward-Fieser Rules?
These are a set of rules which allow the absorption
maximum of a given compound to be calculated
from the chromophores present, the substituents on
the chromophores, and shifts due to the solvent.
Woodward-Fieser Rules
This quantification is referred to as the Woodward-Fieser Rules which we will
apply to three specific chromophores:
1. Conjugated dienes
2. Conjugated dienones
3. Aromatic systems
O
Empirical Rules for Calculating max Values
Parent Chromophore
Auxochromes
max = max(parent chromophore) + (auxochrome values)
Chromophores
Acyclic dienes
For acyclic butadiene, two conformers are possible – s-cis and s-trans
s-trans s-cis
The s-cis conformer is at an overall higher potential energy
than the s-trans; therefore the HOMO electrons of the
conjugated system have less of a jump to the LUMO – lower
energy, longer wavelength
Woodward-Fieser Rules - Dienes
The rules begin with a base value for max of the chromophore being
observed:
acyclic butadiene = 217 nm
The incremental contribution of substituents is added to this base value
from the group tables:
Group Increment
Extended conjugation +30
Each exo-cyclic C=C +5
Alkyl +5
-OCOCH3 +0
-OR +6
-SR +30
-Cl, -Br +5
-NR2 +60
Woodward-Fieser Rules – Dienes
Worked example:
Isoprene - acyclic butadiene =
217 nm
one alkyl subs.
+ 5 nm
222 nm
Experimental value
220 nm
Allylidenecyclohexane
- acyclic butadiene =
217 nm
one exocyclic C=C
+ 5 nm
2 alkyl subs.
Woodward-Fieser Rules – Cyclic Dienes
There are two major types of cyclic dienes, with two different base values
Heteroannular (transoid): Homoannular (cisoid):
= 5,000 – 15,000 = 12,000-28,000
base max = 214 base max = 253
The increment table is the same as for acyclic butadienes with a couple
additions:
Group Increment
Additional homoannular +39
Where both types of diene
are present, the one with
the longer becomes the
base
Woodward-Fieser Rules – Cyclic Dienes
For example: 1,2,3,7,8,8a-hexahydro-8a-methylnaphthalene
heteroannular diene =
214 nm
3 alkyl subs. (3 x 5)
+15 nm
1 exo C=C
+ 5 nm
234 nm
Experimental value
235 nm
Woodward-Fieser Rules – Cyclic Dienes
In the pre-NMR era of organic spectral determination, the power of the
method for discerning isomers is readily apparent
Consider abietic vs. levopimaric acid:
C OH C OH
O O
abietic acid levopimaric acid
Woodward-Fieser Rules – Cyclic Dienes
For example: heteroannular diene = 214 nm
4 alkyl subs. (4 x 5) +20 nm
1 exo C=C + 5 nm
C OH
O
239 nm
homoannular diene = 253 nm
4 alkyl subs. (4 x 5) +20 nm
1 exo C=C + 5 nm
C OH
O
278 nm
Woodward-Fieser Rules – Cyclic Dienes
Be careful with your assignments – three common errors:
This compound has three exocyclic
double bonds; the indicated bond is
exocyclic to two rings
This is not a heteroannular diene; you would
use the base value for an acyclic diene
Likewise, this is not a homooannular diene;
you would use the base value for an acyclic
diene
Woodward-Fieser Rules - Conjugated
Carbonyl Compounds
C C C C C C C C
O O
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
Alkyl group or ring residue and higher 10, 12, 18
-OH and higher 35, 30, 50
-OR 35, 30, 17, 31
-O(C=O)R 6
-Cl 15, 12
-Br 25, 30
-NR2 95
Exocyclic double bond 5
Homocyclic diene component 39
Woodward-Fieser Rules - Enones
Aldehydes, esters and carboxylic acids have different base values than
ketones
Unsaturated system Base Value
Aldehyde 208
With or alkyl groups 220
With or alkyl groups 230
With alkyl groups 242
Acid or ester
With or alkyl groups 208
With or alkyl groups 217
Group value – exocyclic double bond +5
Group value – endocyclic bond in 5 +5
or 7 membered ring
Woodward-Fieser Rules - Enones
Unlike conjugated alkenes, solvent does have an effect on max
These effects are also described by the Woodward-Fieser rules
Solvent correction Increment
Water +8
Ethanol, methanol 0
Chloroform -1
Dioxane -5
Ether -7
Hydrocarbon -11
Woodward-Fieser Rules - Enones
Some examples – keep in mind these are more complex than dienes
cyclic enone =
O
215 nm 2 x - alkyl subs.
(2 x 12) +24 nm
239 nm
Experimental value
238 nm
R
cyclic enone =
215 nm
O extended conj.
+30 nm
-ring residue
+12 nm -ring residue
+18 nm exocyclic
Calculations for conjugated ketone
Five-membered ring parent enone: 202 nm
-Br: 25 nm
-Alkyl groups or ring residues: 2 x 12 = 24 nm
Calculated: 251 nm
Observed: 251 nm
http://www.chemistry.ccsu.edu/glagovich/teaching/472/uvvis/conjugated.html
Aromatic Compounds
General Features that cause shift in wavelength and intensity of aromatic
systems
1. Substitution
2. Auxochromes
3. Conjugation
4. Choice of solvent
However, these shifts are difficult to predict – the formulation of
empirical rules is for the most part is not efficient (there are more
exceptions than rules)
There are some general qualitative observations that can be made by
classifying substituent groups
Aromatic Compounds
Substituents with Unshared Electrons
• pH can change the nature of the substituent group
• deprotonation of oxygen gives more available n-pairs, lowering transition
energy
• protonation of nitrogen eliminates the n-pair,
raising transition energy
Primary Secondary
Substituent max max
-H 203.5 7,400 254 204
-OH 211 6,200 270 1,450
-O- 235 9,400 287 2,600
-NH2 230 8,600 280 1,430
-NH3+ 203 7,500 254 169
-C(O)OH 230 11,600 273 970
-C(O)O- 224 8,700 268 560
Aromatic Compounds
Substituents capable of -conjugation
• When the substituent is a -chromophore, it can interact with the
benzene -system
• With benzoic acids, this causes an appreciable shift in the primary and
secondary bands
• For the benzoate ion, the effect of extra n-electrons from the anion
reduces the effect slightly
Primary Secondary
Substituent max max
-C(O)OH 230 11,600 273 970
-C(O)O- 224 8,700 268 560
Aromatic Compounds
Substituent Effects - Electron-donating and electron-withdrawing effects
Primary Secondary
Substituent max max
-H 203.5 7,400 254 204
-CH3 207 7,000 261 225
Electron donating
-Cl 210 7,400 264 190
-Br 210 7,900 261 192
-OH 211 6,200 270 1,450
-OCH3 217 6,400 269 1,480
-NH2 230 8,600 280 1,430
Electron withdrawing
-CN 224 13,000 271 1,000
C(O)OH 230 11,600 273 970
-C(O)H 250 11,400
-C(O)CH3 224 9,800
-NO2 269 7,800
Aromatic Compounds
Substituent Effects - Di-substituted and multiple group effects
Parent Chromophore max
R = alkyl or ring residue 246
R=H 250
O R R = OH or O-Alkyl 230
Substituent increment
G o m p
Alkyl or ring residue 3 3 10
-O-Alkyl, -OH, -O-Ring 7 7 25
G
-O- 11 20 78
-Cl 0 0 10
-Br 2 2 15
-NH2 13 13 58
-NHC(O)CH3 20 20 45
-NHCH3 73
-N(CH3)2 20 20 85
Calculations for a aryl conjugated ketone
Parent chromophore: 246 nm
o-Ring residue: 3 nm
m-Br: 2 nm
Calculated: 251 nm
Observed: 253 nm
http://www.chemistry.ccsu.edu/glagovich/teaching/472/uvvis/benzoyl.html
Calculations for a substituted benzoic acid
Parent chromophore: 230 nm
p-OH: 25 nm
m-OH: 2x7= 14 nm
Calculated: 269 nm
Observed: 270 nm
http://www.chemistry.ccsu.edu/glagovich/teaching/472/uvvis/benzoyl.html
Aromatic Compounds
Polynuclear aromatics
• When the number of fused aromatic rings increases, the for
the primary and secondary bands also increase
• For heteroaromatic systems spectra become complex with the
addition of the n * transition and ring size effects and are
unique to each case
Worked Problems 1
Can these two isomers be differentiated by UV-spec
O
O
Eremophilone allo-Eremophilone
Worked Problems 2
Example of cis diene calculation
Cisoid: 253 nm
Alkyl groups or ring residues: 2x5= 10 nm
Calculated: 263 nm
Observed: 256 nm
http://www.chemistry.ccsu.edu/glagovich/teaching/472/uvvis/diene.html
Worked Problems 3
Worked Problems 4
Calculations for conjugated ketone
Acyclic enone: 215 nm
-Alkyl groups or ring residues: 10 nm
-Alkyl groups or ring residues: 2 x 12 = 24 nm
Calculated: 249 nm
Observed: 249 nm
http://www.chemistry.ccsu.edu/glagovich/teaching/472/uvvis/conjugated.html
Worked Problems 5
Example of conjugate aldehyde calculation
Aldehyde: 208 nm
-Alkyl groups
or ring 10 nm
residues:
-Alkyl groups
or ring 2 x 12 = 24 nm
residues:
Calculated: 242 nm
Observed: 242 nm
http://www.chemistry.ccsu.edu/glagovich/teaching/472/uvvis/conjugated.html
Worked Problems 6
Calculations for a aryl conjugated ketone
Parent chromophore: 246 nm
o-Ring residue: 3 nm
m-Br: 2 nm
Calculated: 251 nm
Observed: 253 nm
http://www.chemistry.ccsu.edu/glagovich/teaching/472/uvvis/benzoyl.html
Visible Spectroscopy
• The portion of the EM spectrum from 400-800 is observable to
humans- we (and some other mammals) have the adaptation of
seeing color at the expense of greater detail
400 500 600 700 800
, nm
Violet 400-420
Indigo 420-440
Blue 440-490
Green 490-570
Yellow 570-585
Orange 585-620
Red 620-780
Visible Spectroscopy
• When white (continuum of ) light passes through, or is reflected
by a surface, those that are absorbed are removed from the
transmitted or reflected light respectively
• What is “seen” is the complimentary colors (those that are not
absorbed)
• This is the origin of the “color wheel”
Visible Spectroscopy
• Organic compounds that are “colored” are typically those with
extensively conjugated systems (typically more than five)
• Consider -carotene
-carotene, max = 455 nm
max is at 455 – in the far blue region of the
spectrum – this is absorbed
The remaining light has the complementary
color of orange
Visible Spectroscopy
• Likewise:
lycopene, max = 474 nm
O
H
N
N
H
O
indigo
max for lycopene is at 474 – in the near blue region of the
spectrum – this is absorbed, the compliment is now red
max for indigo is at 602 – in the orange region of the
spectrum – this is absorbed, the compliment is now indigo!
The colors of M&M’s
Bright Blue Royal Blue
Common Food Uses Common Food Uses
Beverages, dairy products, powders, jellies, confections, Baked goods, cereals, snack foods, ice-cream, confections,
condiments, icing. cherries.
Orange-red Lemon-yellow
Common Food Uses Common Food Uses
Gelatins, puddings, dairy products, confections, beverages, Custards, beverages, ice-cream, confections, preserves,
condiments. cereals.
Orange
Common Food Uses
Cereals, baked goods, snack foods, ice-cream, beverages,
dessert powders, confections
Visible Spectroscopy
• In the biological sciences these compounds are used as dyes to
selectively stain different tissues or cell structures
• Biebrich Scarlet - Used with picric acid/aniline blue for staining
collagen, recticulum, muscle, and plasma. Luna's method for
erythrocytes & eosinophil granules. Guard's method for sex
chromatin and nuclear chromatin.
HO
O3S N N N N
SO3
Visible Spectroscopy
• In the chemical sciences these are the acid-base indicators used for
the various pH ranges:
• Remember the effects of pH on aromatic substituents
Methyl Orange
CH3 CH3
H
O3 S N N N O3 S N N N
CH3 CH3
Yellow, pH > 4.4 Red, pH < 3.2
