Anderson University

ectromagnetic Spectrum
X-Ray Ultraviolet inIrared micro radio
wave wave
high
ultraviolet
visible
Irequency (4
energy
low
wavelength (2
short
long
WVioIet: - nm
WIndigo: - nm
WBIue: - nm
WGreen: - 57 nm
WYeIIow: 57 - 585 nm
WOrange: 585 - 6 nm
WRed: 6 - 78 nm
I a compound absorbs one color, we see its
complementary color.
!rincipes of UV-Visibe
Spectroscopy

(ground electronic state

(excited electronic state

Electronic transitions
Chromophores - groups oI atoms responsible Ior these transitions
UV Visibe Spectrum

avelength in nm (2
2
max
UV/visible bands are
broad due to overlap oI
rotational and
vibrational states oI a
molecule.
Sovents and Ces for UV
Spectroscopy
$olvent CutoII (nm
ethanol 20
ater 10
n-hexane 201
200 nm 400 nm 800 nm
uv visible
quartz
Glass or plastic
$ample cell
solvent
Common Chromophores
Aenes
6
6
6 6
16 nm
1 1,000
EE
Common Chromophores
Carbony Compounds
6
6
n
6
6
170 nm
n
6
20 nm
EE
!ossible transitions
Conjugation
lternate single and double bonds
overlap oI p-orbitals
Conjugation lowers energy oI 6 F 6 transition
-butadiene
bonding
antibonding
6
6
UV Absorption of Conjugated
Aenes
6
6
2
max
17 217 28
1
1,000 21,000 3,000

ncreasing conjugation gives:

longer wavelength absorption
more intense absorption
.arotene

C
C

11 double bonds
2
max
460 nm
ycopene
2
max
474 nm
conjugated doube bonds tota
I a compound absorbs one color, we see its
complementary color.
eme Metaboism
ilirubin is normally
metabolized in the liver
to a water soluble
derivative that is
eliminated in the bile.
$ome inIants or
individuals with a
genetic disorder lack
the enzyme that
produces this
derivative and develop
jaundice. uildup oI
bilirubin leads to brain
damage.
iirubin

O
2

O
2

O
O

O
O

O
O

-iIiru-in sta-iIized - hdrogen -onds

onpolar
not excreted
!hotoenoization

O
O

O
O

O
O

O
O

5hoto-iIiru-in
-iIir-uin
(PBR)
(BR)
Iight
R
!R
R-albumin
!R-albumin
R
!R
light
skin
blood liver
bile
nonpolar
polar
UV-Vis
W hich woud absorb a onger waveength of
ight -pentadiene or -pentadiene?
78 nm nm
soated
Conjugated
ies-Ader Reaction

CO

O
C

CO
O
C

CO
O
-
C

CO
O
C

hy?
The diene is not eectron rich enough because it has an
eectron withdrawing carbony on it.
CO

CO

O
O
N
C

(--morphine
$everal $teps
O
O
NC

CO

CO

raw the product () of the foowing ies-Ader reaction. is a ey

intermediate in the synthesis of the addicting pain reiever morphine
isoated form the opium poppy.
The Opium Poppy
hat is ?
O
O

CO

CO
NC
O
O
N
C

(--morphine
$everal $teps
O
O
NC

CO

CO

O
O
N
C

(--morphine
$everal $teps
O
O
NC

CO

CO

Opium continued. . .
hy is such a good dienophie?
t has a carbony adjacent to the doube bond to mae it eectron poor.
Cortisone (a hormone
responsibe for the contro
of infammation and the
reguation of carbohydrate
metaboism) can be
synthesized using a ies-
Ader reaction aong the
synthetic pathway. raw
the diene and dienophie
used to mae the
intermediate. An arrow
shows the 6-membered ring
made in the reaction.

iene ienophile
O
O
C

O
This ring Iormed
O

O
C

O
O

$everal $teps
Cortisone

CO
O
O
ou' thin 'm maing these compounds up but they're rea. The
foowing reactions have been used to synthesize diedrin and adrin
(named for ies and Ader) two pesticides having a simiar story to
T. dentify X and Z in the reaction scheme.

C
C
C
C
C
C
aldrin
MC!, 1 equivalent

dieldrin
C
C
C
C
C
C
or
C C
C
C
C
C
O
C
C
The compound shown beow is the product
formed in a ies-Ader reaction between methy
acryate (C

CCO

) and a diene. raw the

structure of the diene. (.5 pts)
CO

O
The hydrobromination of 5-hexatriene gives - -
and 6-addition products
raw these products and show the mechanism that
accounts for their formation.

r
1,2 1,4

1,6
r
H-r

r
-

r
-
r
-
Of the three products abe the inetic product(s) and the thermodynamic
product(s).
Thermodynamic Kinetic Kinetic
hat reaction conditions woud you empoy to mae a majority of the 6-addition
product? xpain why.
eat the reaction. oud get more
of the more stabe thermodynamic
product.
The foowing ies-Ader reaction comes to us from the Journa of
Organic Chemistry 8.
N !h
R
SO

!h
, 24 hours

Since the above reaction is a ies-Ader reaction we need a diene and a

dienophie. For this question redraw the reactant so that the diene is in
an s-cis conformation and the dienophie is in the proper orientation to
react with the diene.
N !h
R
!hO

S
N !h
R
SO

!h
, 24 hours

raw the mechanism of the reaction and show the product

. (on't worry about the ndo rue if it appies here).
N !h
R
!hO

S
N !h
R
!hO

S
n a ies-Ader reaction which tend to be eectron poor the
diene or the dienophie?
xpain in detai why in this reaction the answer to part d is quite
eectron poor.
N !h
R
SO

!h
, 24 hours

hat does the up/down arrow

indicate for the reaction conditions
for the above reaction?
ienophie
Can draw resonance forms into SO

!h.
Refux
n the journa 7anic Lette7s Thomas oye made the foowing
compound
O
O

C
C

le lourd lral lr|s corpourd d|rer|zed (reacled W|lr |lse|l) v|a a 0|e|s-A|der reacl|or lo
lorr:
O
O
O
O
a. Show the mechanism for this reaction.
O
O
O
O
O
O
O
O

abe the diene and the dienophie.
iene
ienophie
ry does lre d|ere sroWr oe|oW la|| lo urdergo a 0|e|s-A|der
reacl|or W|lr ever lre rosl reacl|ve d|eropr||es?
t cannot get into an s-cis conformation.