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Structure

Determination

• Mass Spectrometry
• Infrared Spectroscopy
• NMR Spectroscopy

Chem 342 Final Exam Review May 10, 2003
+ CH3
m/z = 71
( -15 )

m/z = 86 CH2CH3 m/z = 57 will be more
abundant in the mass
m/z = 57 more likely spectrum of hexane
( -29 )

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

C H 2850-2960 medium-strong below 3000

3020-3100 medium above 3000
C H
C H 3300 strong above 3000

O H 3400-3650 broad-strong

N H 3300-3500 medium #H's = #peaks

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

Alkene out of plane bending
H H H H
C C 910 and 990 strong C C 700 strong
R H R R

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

The magnetic field that a particular
nuclei are nucleus feels is less than Bo
surrounded by because of the eletron shielding.
electron clouds
which shield the This makes every H or C in the
nucleus from the molecule that have different electron
magnetic field densities around them resonate at
different frequencies.
Bo

Chem 342 Final Exam Review May 10, 2003
13
C NMR
O

C C
R OR
C C
O
O
C
C R NR2
R R C O C N C X

d 200 150 100 50 0 ppm

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

Chem 342 Final Exam Review May 10, 2003
Strategies for using Spectroscopy to identify
structures.
Find the molecular formula (MS)
Determine degrees of unsaturation
Identify functional groups (IR, NMR)
Try to find pieces of the structure (NMR #H’s, coupling,
number of carbons, etc.)
Try to put the pieces together in a reasonable way
Double check that your structure matches all the data given

Chem 342 Final Exam Review May 10, 2003
A molecule with the formula C6H12O2 shows a characteristic Infrared

absorption at 1735 cm-1 and the following NMR spectra.

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

Chem 342 Final Exam Review May 10, 2003
C10H12O

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

O

O

O

Chem 342 Final Exam Review May 10, 2003
HBr
H H

Br
H H
Br 1,2-addition 1,4-addition

H
not formed

Chem 342 Final Exam Review May 10, 2003
cyclic transition state
with secondary orbital interaction

CH3 CH3
+
H3C
CO2CH3 H3CO CO2CH3

diene dieneophile O

H3C CH3
+ CH3
H3CO
CO2CH3 CO2CH3
O
diene dieneophile

Chem 342 Final Exam Review May 10, 2003
O O O
O
= + = O
+ O O O O
O
O O O O
O
dieneophile endo product exo product
major minor

exo product secondary orbital O endo product
O
interaction with the O
carbonyl pi-bond
O
lowers the energy for
this transition state O
O

Chem 342 Final Exam Review May 10, 2003
H H
H H
H H
bonds identical
1.39 Å

• Aromatic Compounds
• Planar Ring
• Fully Conjugated
• 4n+2 number of pi electrons

Chem 342 Final Exam Review May 10, 2003
AROMATIC 4 pi electrons 4 pi electrons AROMATIC AROMATIC AROMATIC 8 pi electrons
2 pi electrons 6 pi electrons 6 pi electrons 6 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

Chem 342 Final Exam Review May 10, 2003
Br

H H H Br
Br Br Br -HBr
Br

Electron Donating Groups Electron Withdrawing Groups

alkyl OR NR2 acyl CN NO2 SO3H

SR meta directors

ortho-para directors X ortho-para director

Chem 342 Final Exam Review May 10, 2003
OH OH
Br2, FeBr3 Br
OH is the stronger director (resonance) so it will be the
important director for the substitution with bromine.

CH3 CH3

CH3 CH3 CH3
NO2 Br2, FeBr3 Br NO2 NO2 CH3 and NO2 are both directing to
+ the same positions and are thus
working together

Br

Chem 342 Final Exam Review May 10, 2003
Br2
FeBr3 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

Chem 342 Final Exam Review May 10, 2003
O O O
O O O
OH F OH OH
OH OH F3C OH
pKa 4.75 4.19 2.59 0.23 O2N 3.41 H3CO 4.46

O O O O O
pKa = 20 pKa = 9 pKa =13
EtO OEt

Chem 342 Final Exam Review May 10, 2003
R O H weakly acidic R O H + H2O R O + H3O

weakly basic alkoxide

[RO-] [H3O+]
Ka =
[ROH]

pKa = -logKa

18.0 CH3OH 15.5 OH 10.5
OH

CF3CH2OH 12.4 H2N
OH 16.0
OH 9.9 OH
HOH 15.7 7.2
O2N

Chem 342 Final Exam Review May 10, 2003
CH3 CH3 H2O2, OH- CH3
BH3
H H Hydroboration
BH2 OH

CH3 Hg(OAc) CH3 CH3
2 NaBH4
OH OH Oxymercuration
H2O HgOAc
CH3
CH3 OsO CH3
4
O O NaHSO3
Os OH Dihydroxylation
O O OH

O
O
O H
MCPBA CH3 CH3
CH3
Cl H3O+
O OH
epoxide OH

Br2, H2O NaH
CH3
OH
halohydrin
Br
Chem 342 Final Exam Review May 10, 2003
POBr3 Promoted Dehydration - E2 elimination

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

2° alcohol Good Leaving Inversion of
Group Configuration

Br Br
P H P
OH Br Br O Br Br Br

2° alcohol Good Leaving Inversion of
Group Configuration

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

Chem 342 Final Exam Review May 10, 2003
H SN2 OH
O HCl O Cl
Cl

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

Chem 342 Final Exam Review May 10, 2003
1) NaBH4 or LiAlH4
O 2) H3O+ 1) BH3
O 2) H3O+
R Y R OH
R OH R OH

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

Chem 342 Final Exam Review May 10, 2003
O
O HA catalyst
HO O + CH3OH
OCH3

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

Chem 342 Final Exam Review May 10, 2003
O OH

CH3

Br2 1) LiAlH4 or NaBH4
CH3CO2H 2) H2O

O O
O
pyridine (CH3)2CuLi
Br

(or other base)
CH3

Chem 342 Final Exam Review May 10, 2003
O
O O
CH3
and OH
EtO OEt
Br

NBS
peroxides 1) PBr3, Br2
2) H2O

O O O O
H3O+
EtO OEt OEt
Heat OH
Br
NaOEt
EtOH O OEt

Chem 342 Final Exam Review May 10, 2003
O

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

O

NO2 CH3

Chem 342 Final Exam Review May 10, 2003
MCPBA
1) Hg(OAc)2 or
CH3OH 1) Br2, H2O
2) NaBH4 2) NaH
OCH3 O

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

Chem 342 Final Exam Review May 10, 2003
1) NaOH, H2O
O O 1) BH3
2) H3O+ or LiAlH4
2) H3O+ Ph OH
Ph OCH3
Ph OH

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

Chem 342 Final Exam Review May 10, 2003