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Finalreview 03
Finalreview 03
Finalreview 03
Determination
• Mass Spectrometry
• Infrared Spectroscopy
• NMR Spectroscopy
R + R
m/z = 91
base peak
benzylic cation
OH OH
+
a-cleavage will occur
OH very stable
on the more
substituted side more
readily (more stable
radical)
+ H2O
Chem 342 Final Exam Review May 10, 2003
Functional Wavenumber Absorption
Group Range (cm-1) Strength notes
O H 3400-3650 broad-strong
C C
C N 2100-2260 medium
O C O
C O 1680-1750 strong
C C 1640-1750 medium
C C 800-1300 medium
C O 1050-1150 medium
C X <1000 strong
R H R H
C C 890 strong C C 815 strong
R H R R
H R
C C 970 strong
R H
Chem 342 Final Exam Review May 10, 2003
A spinning nucleus When a molecule is
(which is charged) placed in an external
generates a magnetic field, the
magnetic field nuclear spins will align
with or against this field
Bo
C C
R OR
C C
O
O
C
C R NR2
R R C O C N C X
1
H NMR
H
H H
H H
C
H H C C
H H
OH
H
C O
C O H H
H
H
C X
d 10 9 8 7 6 5 4 3 2 1 0 ppm
Chem 342 Final Exam Review May 10, 2003
Ha Hb
Ha Hb
C C
J J
Ha Hb
Ha Hb
C C Hb
J J J
1 2 1
6H
1
H NMR
J = 7 HZ 3H O
J = 8 HZ
2H
1H
J = 7 HZ
J = 8 HZ O
ppm 4 3 2 1 0
H H
H 13
C NMR
C
H C ?
H
H3C
?
H3C H ppm 200 175 150 125 100 75 50 25 0
IR 1680 cm-1
Answer the following questions about an unknown molecule with a molecular formula of C10H12O. The IR spectra shows a strong absorbance at 1680 cm-1
Br
H H
Br 1,2-addition 1,4-addition
H
not formed
CH3 CH3
+
H3C
CO2CH3 H3CO CO2CH3
diene dieneophile O
H3C CH3
+ CH3
H3CO
CO2CH3 CO2CH3
O
diene dieneophile
• Aromatic Compounds
• Planar Ring
• Fully Conjugated
• 4n+2 number of pi electrons
N
lone pair lone pair lone pair
N in resonance O in resonance in resonance
N with aromatic with aromatic N with aromatic
H H
pi system pi system pi system
N N H O N H
N
H H H Br
Br Br Br -HBr
Br
SR meta directors
CH3 CH3
Br
Cl2 NaOH
FeCl3 Cl high heat OH
I2
CuI2 I
H2 Pd/C
HNO3 or
H2SO4 NO2 NH2
SnCl2, H3O +
SO3
H2SO4 SO3H
R-Cl
AlCl3 R KMnO4
CO2H
O
O
R Cl
AlCl3 H2, Pd/C
R
R
O O O O O
pKa = 20 pKa = 9 pKa =13
EtO OEt
[RO-] [H3O+]
Ka =
[ROH]
pKa = -logKa
O
O
O H
MCPBA CH3 CH3
CH3
Cl H3O+
O OH
epoxide OH
O N
pyridine
H O O
P mild base
OH Br Br O P Br O P Br
Br Br Br
H
2° alcohol Good Leaving pyridine
Group
O O
S H S
OH Cl Cl O Cl Cl Cl
Br Br
P H P
OH Br Br O Br Br Br
O Tos-Cl
S
Cl Tos
OH O CH3ONa OCH3
Ph pyridine Ph Ph
2° alcohol Retention of Inversion of
Configuration Configuration
Chem 342 Final Exam Review May 10, 2003
NaH CH3I + CH O
OH O O CH3 I 3
SN2
HO Br NaH Br
O O
HI H I H
O O O
+ I
CH3
CH3 CH3 Cl Cl
O HCl
O H
SN2 but more + OH
charge at more
substituted carbon
O H2O OH
O PhMgBr
Ph Ph
1) DIBAH 1) LiAlH4
O 2) H3O+ O 2) H2O
O
R OCH3 R H R NH2
R NH2
1) DIBAH
2) H3O+ O
C N R H
R O CH2
+ Ph3P CH2
phosphonium
ylide
1) PhMgBr
O 2) H3O+ OH
R Y R Ph
Ph
O C O O O
O +
H3O
1) CH3MgBr MgBr
C N O MgBr OH
2) H2O CH3
NH2
O H2N NH2 N H H
KOH
a hydrazone
HA
A
H H
O O H H
HO HO O O
OCH3 OCH3
O O
H
A HO OCH3 HA HO OCH3
HO OCH3
O H O O
CH3
O O
O
pyridine (CH3)2CuLi
Br
NBS
peroxides 1) PBr3, Br2
2) H2O
O O O O
H3O+
EtO OEt OEt
Heat OH
Br
NaOEt
EtOH O OEt
Ph Cl CH3
CH3 H2, Rh/C CH3 AlCl3
HNO3 O Ph
H2SO4 NBS
peroxides
CH3 Cl2
Br CH
AlCl3 2
NO2 CH3
O
KMNO4
Cl SNa
CO2H NaNH2 S CH
Heat 2
NO2 CH3
1) CH3MgBr HBr
HI
2) H3O+
1) BH3
2) NaOH OH
H2O2 Br
OH
CH3 OH
OH
1) Tos-Cl O O
pyridine
2) NaSPh O
1) PBr3 pyridine
PCC
2) NaSPh
O
SPh SPh O O
1) DIBAH 1) SOCl2
2) H2O 2) CH3NH2
1) LiAlH4
O O 2) H2O
Ph N CH3
Ph N CH3 H
Ph H H
CH3NH2
Ph3P CH3 HA catalyst
CH3
H3C N
Ph H
Ph