Appendices 1253
APPENDIX 2B (continued)
Range Range
G roup Intensitya (cm - ' ) Group I ntensitya (cm - ' )
and s1 370- 1 300 b. C = S stretching vibrations s 1 200- 1 050
Aliphatic 1 570- 1 550 c. S = 0 stretching vibrations:
and s 1 380-1 370 Sulfoxides s 1 070- 1 030
g. O - NOb nitrates s 1 650-1 600 Sulfones 1 1 60- 1 1 40
and s 1 300- 1 250 and s 1 350-1 300
h . C - NO, nitroso compound 1 600- 1 500 Sulfites 1 230- 1 1 50
I . 0 - NO, nitrites s 1 680- 1 650 and s 1 430- 1 350
and s 1 625- 1 6 1 0 Sulfonyl chlorides s 1 1 85-1 1 65
4. Halogen compounds, C - X stretching vibrations and s [ 370-1 340
a. C - F s 1 400-1000 Sulfonamides s 1 1 80- 1 1 40
b. C - CI 800-600 and s 1 350-1 300
c. C - Br s 600-500 Sulfonic acids 1 2 1 0- 1 1 50
d. C - I s � 500 s 1 060- [ 030
5. Sulfur compounds and s �650
a. S - H stretching vibrations w 2600-2550 Thioesters (C = O)S � 1 690
a Abbreviations: s =
strong, m = medium, w = weak, v = =
variable, b broad, sh = sharp, - = approximately
b I
Substituted benzenes also show weak bands in the 2000 - 1 670 em- region.
To use UV -visible spectroscopy for structure determination, we need to know what Appendix 3
types of spectra correspond to the most common types of conjugated systems. The most
useful correlations between structures and UV spectra were developed in the early 1 940s UV: T h e Wood wa rd
by R. B . Woodward and L. F. Fieser. These correlations are called the Woodward-Fieser Fieser Rules for
rules. The rules presented here predict only the lowest-energy 1T � 1T * transition from
Predicting UV-Visible
the HOMO to the LUMO. Values of "- max measured in different solvents can be differ
ent, so we generally assume that ethanol is the solvent. Spectra
In discussing these rules, we use the following specialized terms:
CHROMOPHORE: Any functional group (or collection of groups) responsible
for absorption.
AUXOCHROME: A substituent that is not a chromophore by itself, but
which alters the wavelength or the molar absorbtivity when it is attached to a
chromophore.
BATHOCHROMIC SHIFT: A shift toward lower frequency and longer wave
length (longer "-max ) .
HYPSOCHROMIC SHIFT: A shift toward higher frequency and shorter wave
length (shorter "-max ) .
UV S pect ra of D ie n es a nd Polyenes
Bathochromic Effects of A lkyl Groups A molecule's system o f conjugated
double bonds (the chromophore) is the largest factor in determining its UV spec
trum, but the absorption is also affected by alkyl substituen ts . Each alkyl group
attached to the chromophore s erves as an auxochrome, producing a small
bathochromic s hift of about 5 nm. Tabl e A 3 - 1 shows the effects of adding alkyl
groups to 1 ,3-butadiene.
1254 Appendices
APPENDIX A3-1 Values of Amax for Some Substituted 1 .[Link]
Num be r of Alkyl Groups Compound Amax (nm)
o H2C= C H - C H=CH2 217
CH3-CH = CH -CH =CH2 224
CH3
I
H2C=C-CH= CH2 220
H3C CH3
I I
2 H2C = C -C= CH2 226
2 CH3-CH=CH-CH=CH -CH3 227
CH3 CH3
I I
3 CH3 - C = C H -C=CH2 232
CH3 CH3
I I
4 CH3 -C=CH-C=CH - CH3 24 1
Conformation Effects
For dienes that are predominantly in the s-trans conformation (either free to rotate or
held in the s-trans conformation), Woodward and Fieser used a base value of 2 1 7 nm,
the Amax for unsubstituted 1 ,3-butadiene. To this value, add 5 nm for each alkyl sub
stituent. For dienes that are held in the s-cis conformation by a six-membered ring, the
base value is 253 nm for the diene, plus 5 nm for each alkyl substituent.
+5
+5 £0 :: �
acyclic (s-trans) diene transoid cyclic diene cisoid cyclic diene
base 2 1 7 nm base 2 1 7 nm base 253 nm
+ 2 alkyl X (5 nm) + 2 alkyl X (5 nm)
Additional Conjugated Double Bonds For trienes and l arger conjugated
systems, add 30 nm to the base value for each additional double bond. The additional
double bond must be attached at the end of the conjugated system to extend the length
of the polyene system, however, in order to have this large 30-nm contribution.
+5
0
�
+5
acyclic (s-trans) triene cisoid cyclic triene
2 1 7 n m + 30 nm = base 247 nm 253 nm + 30 nm = base 283 nm
+ 2 alky l X (5 nm)
Contributions of auxochromic groups are added to the base values of the polyene
chromophore. Add 5 nm for each alkyl group and 5 nm if one of the double bonds in
the conjugated system is exocyclic to a ring. An exocyclic double bond is one that is
attached to a ring at one end.
exocyclic double bonds
Appendices 1 255
Table A3-2 summarizes the shifts associated with common auxochromic groups.
TABLE A3-2 The Woodward-Fieser Rules for Conjugated Dienes: Values
for Auxochromic Groups
Grouping Substituent Correction (nm)
another conjugated C C
= + 30
alkyl group +S
alkoxy ( - OR) group 0
If one of the double bonds in the chromophore is exocyclic, add another S nm:
� exocycli c
� +S (in adclition to 30 nm if it lengthens the system)
exocyclic double bond
NOle: These values are added to the base value for the diene system.
Examples The best way to learn to use the rules for predicting UV absorptions is to
work through some examples. The following examples show several structures that fol
low the rules closely and one that does not.
base: 2 1 7 nm
three alkyl groups: 15
1. predicted A max : 232 nm; observed: 232 nm
2,4-dimethyl- l ,3-pentadiene
base: 2 1 7 nm
two alkyl groups: 10
exocyclic C = C : 5
3. ( ��ChC
predicted A max: 232 n m ; observed: 230 nm
base: 2 1 7 nm
two alkyl groups: to
exocyclic C = C : 5
predicted Amax: 232 nm; observed: 236 nm
4·CP
base: 2 1 7 nm
three alkyl groups: 15
exocyclic C = C : 5
predicted Amax : 237 nm; observed: 235 nm
exocyclic
base: 253 nm
conj ugated C = C : 30
5. three alkyl groups: 15
exocyclic C = C : 5
predicted A max: 303 nm; observed: 304 11m
6. � base: 2 1 7 11m
1 ,3,S-hexatriene conjugated C = C : 30
predicted A max: 247 11m; observed : 258 11m
1 2 56 Appendices
UV Spect ra of Conj ugated Ketones and Aldehydes
7T � 7T * Transitions As with dienes and polyenes, the strongest absorptions in the
UV spectra of aldehydes and ketones result from 11" � 11"* electronic transitions. These
absorptions are observable (Amax > 200 nm) only if the carbonyl double bond is con
jugated with another double bond.
The Woodward-Fieser rules for conjugated ketones and aldehydes appear in Table
A3-3 . Note that bathochromic effects of alkyl groups depend on their location: 1 0 nm
for groups 0' to the carbonyl and 12 nm for groups in f3 positions. Contributions from
additional conjugated double bonds (30 nm) and exocyclic positions of double bonds
(5 nm) are sirrular to those in dienes and polyenes.
TABLE A3-3 The Woodward-Fieser Rules for Conjugated Ketones
and Aldehydes
f3" /'
c=c R
/ " /
Base values: 2 1 0 11m if R = H (aldehyde)
f3
�
o
2 1 5 nm i f R = alkyl (ketone)
general structure
Grouping Position Correction
alkyl group, a + lO nm
alkyl group, f3 + 1 2 nm
exocyclic position of a C = C bond + 5 nm
additional conjugated double bond + 3 0 nm
The following examples show how the Woodward-Fieser rules predict values of
Amax for a variety of conjugated ketones and aldehydes. Notice that the molar absorp
tivities (e) for these transitions are quite large (>5000), as we also observed for 11" � 11" *
transitions in conjugated dienes and polyenes.
H" /H Base value 2 1 0 nm
1. /C=C" /H (no corrections)
H C Predicted A max 2 1 0 nm
II Experimental: A max = 2 1 0 nm, e = 1 1 ,000
0
f3 �
2. �
f3 CH3
_
/H
C - C " / CH3
C
Base value
2 X f3 substituent
215
24
nm
nm
Predicted A max 239 nm
II Experimental: \nax = 237 nm, e = 1 2,000
0
Appendices 1 2 57
3. ifCH' 0 B ase value
a substituent
{3 substituent
Predicted A max
Experimental: A max =
215
10
12
237
233
nm
nm
nm
nm
nm, 8 = 1 2,500
(3
B ase value 215 nm
4. c;p.
a substituent 10 nm
{3 substituent 12 nm
Exocyclic double bond 5 nm
Predicted A max 242 nm
8 =
�
exocyclic Experimental: A max 24 1 = nm, 5 200
�
double bond
*
n n
�
Transitions As discussed in Section 1 8-5E, ketones and aldehydes also
show weak UV absorptions (8 == 1 0 to 200) from "forbidden" n 7T * transitions.
Because the promoted electron leaves a nonbonding (n) orbital that is higher in energy
than the pi bonding orbital, this transition involves a smaller amount of energy and
results in a longer-wavelength (lower-frequency) absorption. n 7T* transitions of sim
ple, unconjugated ketones and aldehydes give absorptions with values of Amax between
280 and 300 nm. Each double bond added in conjugation with the carbonyl group
increases the value of Amax by about 30 nm.
In this appendix, we consider how an organic chemist systematically approaches a Appendix 4A
mechanism problem. Although there is no "formula" for solving all mechanism prob
lems, this stepwise method should provide a starting point for you to begin building M ethods a nd
experience and confidence. Solved problems that apply this approach appear on pages Suggestions
1 5 1 , 3 1 0, 484, 848, 1 004, 1 062, and 1 086.
for Pro posi ng
M echan isms
Determ i n i ng the Type of M echan ism
First, determine what conditions o r catalysts are involved. I n general, reactions may be
classified as (a) involving strong electrophiles (includes acid-catalyzed reactions),
(b) involving strong nucleophiles (includes base-catalyzed reactions), or (c) involving
free radicals. These three types of mechanisms are quite distinct, and you should first
try to determine which type is involved. If uncertain, you can develop more than one
type of mechanism and see which one fits the facts better.
(a) In the presence of a strong acid or a reactant that can give a strong electrophile,
the mechanism probably involves strong electrophiles as intermediates. Acid
catalyzed reactions and reactions involving carbocations (such as the S N 1 , E l , and
most alcohol dehydrations) generally fall in this category.
(b) In the presence of a strong base or strong nucleophile, the mechanism probably
involves strong nucleophiles as intermediates. B ase-catalyzed reactions and
those whose rates depend on base strength (such as SN2 and E2) generally fall
in thi s category.
(c) Free-radical reactions usually require a free-radical initiator such as chlorine,
bromine, NBS , AIBN, or a peroxide. In most free-radical reactions, there is no need
for a strong acid or base.