NMR Lecture
NMR Lecture
NMR Lecture
Building A Toolset
For
The Identification of Organic Compounds
Physical Properties
Melting Point
Boiling Point
Density
Solubility
Refractive Index
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4
Chemical Tests
Hydrocarbons
Alkanes
Alkenes
Alkynes
Halides
Alcohols
Aldehydes
Ketones
Spectroscopy
Mass
(Molecular Weight)
Ultraviolet
(Conjugation, Carbonyl)
Infrared
Functional Groups
NMR
(Number, Type, Location
of protons)
Gas Chromatography
(Identity, Mole %)
1
Spectroscopy
The Absorption of Electromagnetic
Radiation and the use of the Resulting
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Spectroscopy
Spectroscopy Types:
Bombardment
Movements
of Nuclei
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Frequency ()
Low
High
Energy (E)
Low
Short
Wavelength ()
Long
1.2 x 1014 Hz
Frequency
3 x 1019 Hz
3 x 1016 Hz
1.5 x 1015 Hz
3 x 108 Hz
2 x 1013 Hz
3 x 1011 Hz
1 x 109 Hz
6 x 107 Hz
4 x103cm-1
1.25 x104cm-1
Wave Number
2.5 x104cm-1
1 x109cm-1 1 x107cm-1
Cosmic
&
Ray
X-Ray
0.01 nm
Wavelength
5 x104cm-1
667cm-1
Vacuum
UV
10 cm-1
Infrared
200 nm
400 nm
800 nm
Visible
Blue
Red
2.5
3 cm-1
Microwave
1 mm
10 nm
Near
Ultraviolet
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0.002 cm-1
0.01 cm-1
Radio
30 cm
1m
Frequency
5m
15
Vibrational
Infrared
Nuclear
Magnetic
Resonance
NMR
NMR
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NMR
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Nuclear Spin
Magnetic Moments
Resonance
Chemical Shift
Chemical Equivalence
Spin-Spin Splitting
6
NMR
NMR
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NMR
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NMR
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NMR
The
2I + 1 = 2 * 5/2 + 1 = 5 + 1 = 6
Thus, Spin State Values = 5/2, 3/2, 1/2, -1/2, -3/2, -5/2
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NMR
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NMR
Spin +1/2
Aligned
Spin -1/2
Opposed
Ho
Direction of an
Externally Applied
Magnetic Field (Ho)
+1/2 Aligned
Externally Applied
Magnetic Field Ho
Eabsorbed
-1/2 Opposed
Ho
Alignments
= h
E = f(Ho)
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12
NMR
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NMR
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NMR Spectrometers
NMR
Typically, Continuous Wave (CV) Spectrometers are used in
which the externally applied magnetic field is held constant
and RF Radio Oscillator applies a full range of frequencies
at which protons or C-13 nuclei resonate
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15
NMR
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NMR
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NMR
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NMR
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Fourier Transform
19
NMR
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20
NMR
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Continuous Wave
NMR
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22
NMR
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NMR
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NMR
Signal
TMS
13
PPM
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NMR
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26
NMR
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27
NMR
Chemical Shift =
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28
NMR
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NMR
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30
NMR
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31
NMR
Ethane
Signal
(singlet)
TMS
13 12 11 10 9 8 7 6 5 4 3 2 1 0
Chemical Shift (PPM)
Typical location (1 ppm) of resonance signal for Methyl group
protons not under the influence of an electronegative group
(see slide )
Note the 6 at the top of the signal
This is the peak integration value and represents the electronically
integrated area under the signal curve and is proportional to the
number of Protons generating the signal, i.e., Ethane has 6 chemically
and magnetically equivalent protons
32
NMR
Propane
13
12
11
(2)
10
9
8
7
6
5
Chemical Shift (PPM)
TMS
13
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12
5 unsubstituted Protons
on Benzene ring are not
equivalent, producing
complex spitting
patterns typical of the
resonance structures in
aromatic rings.
See slides 60-65.
11
10
(3)
(5)
Toluene
(6)
3 equivalent Protons on
Methyl Group Carbon
attached to a Benzene
ring Carbon that has no
attached protons.
Therefore, the signal is a
singlet with no splitting.
0
33
NMR
Chemical Equivalence
Protons in a molecule that are in chemically identical
environments will often show the same chemical shift
Protons with the same chemical shift are chemically equivalent
Chemical equivalence can be evaluated through symmetry
Protons in different chemical environments have different
chemical shifts, i.e. a signal is produced for each.
Chemicals giving rise to 1 NMR signal
CH3
O
H
CH3 C O CH3
Benzene
Cyclopentane
Methyl Acetate
O
C
CH3
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CH3
CH3 O CH2Cl
CH3
Acetone
34
NMR
CH3
(a)
CH3
(b)
Signals
Value
Rel Area
of Signal
~1
b
c
>2
~2
2
1
(c)
C CH2OH
(a) CH3
2-Dimethyl Propanol
a
9
b
2
c
1
tms
0.9
9 protons on 3 Methyl groups are equivalent and are not under the influence of the
electronegative OH group.
2 protons on Methylene group are equivalent and are influenced by electronegative OH group.
The proton on OH group is concentration and hydrogen bonding dependent. Location on
spectrum variable.
Note: All signals are singlets, i.e., no adjacent protons to produce spin-spine asplitting.
Signals
(a)
CH3
(a)
CH3 C
(b)
CH3
(a)CH3
Value
Rel Area
of Signal
~1
>>1
b
3
tms
9 protons on 3 Methyl groups are equivalent and not under the influence of electronegative group.
3 protons on single Methyl groups are equivalent and are under influence of electronegative oxygen.
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35
NMR
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3.6 ppm
(2 protons)
2.1 ppm
(3 protons)
36
NMR
Ring
5 Protons
Methyl
3 Protons
Methylene
2 Protons
C9H10O
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37
NMR
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NMR
(c)
(b)
h3
h2
55.5 div
= 2.52
22.0 div
22.0 div = 1.00
22.0 div
h1
32.5 div
= 1.48
22.0 div
2.52 : 1.00 : 1.48
5 : 2 : 3
c : b :
a
Each value multiplied by 2
to obtain integral values
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39
NMR
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Valence Electrons
40
NMR
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NMR
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NMR
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NMR
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NMR
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NMR
Chemical Shift Impact of Electronegative Elements
(Cont)
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NMR
Compound CH3X
CH3F CH3OH CH3Cl CH3Br
Element X
F
O
Cl
Br
Electronegativity of X 4.0
3.5
3.1
2.8
Chemical Shift (ppm) 4.26
3.40
3.05 2.68
3.59 ppm
CH4
0.23 ppm
CH3OH
3.39 ppm
CH3CH2OH
1.18 ppm
CH3I
I
2.5
2.16
CH4 (CH3)4Si
H
Si
2.1
1.8
0.23
0
1.53 ppm
CH3CH2CH2OH
0.93 ppm
3.49 ppm
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47
NMR
Chemical Shift values of typical
Proton environments and the effects
of Electronegative Elements on the
Chemical Shift.
-OH, -NH
TMS
12
11
10
CHCl3
Groups with variable chemical shifts
(Protons attached to elements other than Carbon)
Acids
Aldehydes
Phenols
Alcohols
Amines
Amides
Enols
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RCOOH
RCOH
ArOH
ROH
RNH2
RCONH2
CH=CH-OH
11.0
9.0
4.0
0.5
0.5
5.0
15.0
- 12.0 ppm
- 10.0
- 7.0
- 5.0
- 5.0
- 8.0
4
CH2F
CH2Cl
CH2Br
CH2I
CH2O
CH2NO3
CH2Ar
CH2NR2
CH2S
C C H
CH2 C
0 (ppm)
C CH C Methine (1H)
C
C CH2 C Methylene (2H)
C CH3
Methyl (3H)
O
CH2
Effects of Electronegativity
F > O > Cl = N > Br > S > I
NMR
-Substituted Aliphatic
Alkyne
-Monosubstituted Aliphatic
-Disubstituted Aliphatic
Alkene
Aromatic & Heteroaromatic
Carboxylic
12
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11
Aldehydic
TMS
10
0 (ppm)
49
NMR
Approximate Chemical Shifts
Protons (1H1)
Type of Proton
1o Alkyl, RCH3
2o Alkyl, RCH2R
3o Alkyl, R3CH
Allylic, R2C C CH3
R
Ketone, RCCH3
O
Benzylic, ArCH2-R
Acetylenic, RC CH
Alkyl Iodide, RCH2I
Ether, ROCH2R
Alcohol, HOCH2R
Alkyl Bromide, RCH2Br
Alkyl Chloride, RCH2Cl
Vinylic, RC2 CH2
Vinylic, RC2 CH2-R
Aromatic, ArH
Aldehyde, RCH
O
Alcohol hydroxyl, ROH
Amino, R NH2
Phenolic, ArOH
Carboxylic, RCOOH
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1o Alkyl, RCH3
2o Alkyl, RCH2R
3o Alkyl, RCHR2
Alkyl Halide or Amine, C-X
Alcohol or Ether, C-O
Alkyne, C
Alkene, C =
0.8 - 1.0
1.2 - 1.4
1.4 - 1.7
1.6 - 1.9
2.1 - 2.6
2.2 - 2.5
2.5 - 3.1
3.1 - 3.3
3.3 - 3.9
3.3 - 4.0
3.4 - 3.6
3.6 - 3.8
4.6 - 5.0
5.2 - 5.7
6.0 - 9.5
9.0 - 10.0
0.5 - 6.0a
1.0 - 5.0a
4.5 - 7.7a
11 - 12a
Carbon (13C6)
Aryl,
Ar-
C-
Nitriles, -C N O
Amides, -C - N O
Carboxylic Acids, Esters, C O
O
Aldehydes, Ketones, -C -
0 - 40
10 - 50
15 - 50
10 - 65
50 - 90
60 - 90
100 - 170
100 - 170
120 - 130
150 - 180
160 - 185
182 - 215
NMR
Functional
Group
Chemical
Shift, ppm
TMS (CH3)4Si
Cyclopropane
0 - 1.0
Alkanes
RCH3
R2CH2
R3CH
0.9
1.3
1.5
Alkenes
C=CH
C = C CH3
4.6 5.9
1.5 2.5
Alkynes
CCH
C C CH3
1.7 2.7
1.6 2.6
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Functional
Group
Aromatic
AR H
AR C H (benzyl)
Fluorides
FCH
Chlorides
Cl C H
Cl
Cl C H
Chemical
Shift, ppm
6.5 8.0
2.3 2.7
4.2 4.8
3.1 4.1
5.8
Bromides
Br C H
2.5 4.0
Iodides
ICH
2.0 4.0
Nitroalkanes
O2N C H
4.2 4.6
51
NMR
Functional
Group
Chemical
Shift, ppm
Alcohols
Functional
Group
Chemical
Shift, ppm
Carboxylic Acids
HCOH
3.4 4
ROH
0.5 5.0
Phenols
O
HOCCH
2.1 2.6
Ar O H
4.0 7.0
Amines
R NH2
0.5 4.0
Ethers
R COH
11.0 12.0
Ketones
O
ROC-H
3.2 3.8
RCCH
2.1 2.4
Acetals
RO
R
C
RO
Aldehydes
5.3
RCH
Esters
9.0 10.0
Amides
O
ROCCH
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3.5 4.8
RCNH
5.0 9.0
52
NMR
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NMR
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54
NMR
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55
NMR
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56
NMR
(a)
(b)
(a)
All protons chemically equivalent
(a) protons & (b) protons are separated by more than
three (3) bonds
No signal splitting - 2 signals (a) & (b)
Possible spin
combinations of
adjacent protons
b
3H
a
9H
TMS
0
+1
1
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0
2
-1
1
+1/2
1
-1/2
1
Net Spin
Signal Intensity
57
NMR
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58
NMR
(a)
CH3
(b)
CH2
(b)
3.20
No.
Adjacent
Protons
(a)
1.83
= spin +1/2
= spin -1/2
Net Spin
Intensity
Pascals Triangle
No.
Peaks
Seen
Singlet
Doublet
Triplet
Quartet
Quintet
Sextet
Septet1
Relative
Intensity
1
1
1
1
1
1
2
3
4
5
3
6
10
15
1
1
4
10
20
1
5
15
1
6
NMR
Doublet
2 signals
(see 1)
Triplet
Quartet
Sextet
Septet
2 signals
(see 1)
3 signals
(see 2)
Quintet
CH2 CH2
(X Y)
CH3
3 signals
(see 2)
CH3
CH2
CH3
CH3
2 signal
(see 1)
3 signals
(see 2)
CH
2 signals
(see 1)
2 signals
(see 1)
CH
3 signals
(see 2)
4 signals
(see 3)
4 signals
(see 3)
7 signals
(see 6)
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60
NMR
1-Chloropropane
3 signals
Signal
a
a
b
c
Rel Chem
Shift
lowest
middle
highest
0 ppm
(a)
2-Chloropropane
CH3
Cl
CH
(a)
2 signals
CH3
(b)
a
Signal
a
b
Rel Chem
Shift
lowest
highest
Rel Signal
Area
6
1
Neighbors
Multiplicity
1
6
2 (Doublet)
7 (Septet)
0 ppm
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61
NMR
H
C
6-8 Hz
H
11-18 Hz
6-15 Hz
H
4-10 Hz
CH
H C
meta
0-2 Hz
O
H
H
8-10 Hz
H
CH 0-3 Hz
cis 6-12 Hz
trans 4-8 Hz
0-5 Hz
H
a,a 8-14 Hz
a,e 0-7 Hz
e,e 0-5 Hz
H
para
1-4
Hz
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H
H
Ortho
6-10 Hz
cis 2-5 Hz
trans 1-3 Hz
5-7 Hz
H
62
NMR
Magnetic Equivalence
In the spin-spin example of 1,1,2-Trichloroethane, the two
(geminal) protons attached to the same carbon atom (HB & HC),
do not split each other
Cl
HA
HB
Cl
HC
HA HB
Cl
Cl
Cl
HC
Cl
63
NMR
Br
CH3
CH3
HA
HB
Cyclopropane Compound
Two geminal protons (HA & HB) are chemically equivalent, but
not magnetically equivalent
Proton HA is on same side of ring as two halogens
Proton HB is on same side of ring as the two methyls
64
NMR
HC
C=C
HB
Vinyl Compound
Geminal protons (HA & HB) are chemically equivalent, but not magnetically
equivalent
Protons HA & HB have different chemical shifts
Each has different coupling constant with HC
Constant JAC is a cis coupling constant
Constant JBC is a trans coupling constant
Therefore, HA & HB are not magnetically equivalent
They do not act as group to split proton HC
HB splits HC with constant JBC into a doublet
HA splits each component of doublet into doublets with coupling constant
JAC
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65
NMR
66
NMR
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NMR
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68
NMR
When a single substituted group is neither strongly electronwithdrawing (deactivates ring by decreasing electron density
about the ring protons) nor strongly electron-donating
(activates ring by increasing the electron density) Methyl &
Alkyl groups , all ring protons (ortho, meta, para) have near
identical chemical shifts resulting in a slightly broad singlet
(the protons are not quite chemically equivalent).
See pattern A on slide 73
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69
NMR
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NMR
71
NMR
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4
NMR
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73
NMR
o
m
p
o
m
3 Methyl Protons
m o, p
Anisole (C7H8O)
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74
NMR
o
m
p
o
m
o/p
Aniline (C6H7N)
2 Amino
Protons
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75
NMR
o
m
p
Nitrobenzene (C6H5NO2)
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76
NMR
P-Chloroaniline (C6H6ClN)
Hb&Hb
Ha
Ha
Hb
Hb
Ha&Ha
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77
NMR
c
b
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78
NMR
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79
NMR
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80
NMR
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81
NMR
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82
NMR
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NMR
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NMR
Suggestions
For
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85
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87
88
Doublet
Triplet
3H
Mono-substituted
Benzene Ring
Quintet
Sextet
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89
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90
The Solution:
2-Phenylbutane (C10H14)
3H
3 protons on a
Methyl group
see 2 adjacent
protons
triplet
5 protons on a
mono-substituted
Benzene Ring
3 + 2 +1 = 6
Spin-Spin Splitting
No. of peaks in a signal is equal
to the number of protons on all
adjacent carbon atoms plus 1
(N+1 rule)
Integration value (Area under signal)
is proportional to No. of Protons
generating the signal
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doublet
sextet
quintet
3 protons on a
Methyl group
see 1 adjacent
proton
2 protons on a
Methylene group
see 4 adjacen
protons
1 proton on
Methine group
sees 5 adjacen
protons
91
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4
92
a
b
4H a
The a protons have a
smaller Chemical Shift
than the b protons
because of their
4H b
relative position to the
electron rich bond.
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93
n+1=0+1=1
(singlet)
2 Sets Methylene Protons
Chemical & Magnetically Equivalent
They do not split each other
4H
n+1=0+1=1
(singlet)
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94
Cis-Stilbene (C14H12)
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95
Note: 2 Overlapping
Absorptions!! Electronegative
Carboxyl Oxygen forces shift
of Methyl Proton absorptions
downfield to about same
location as shift of Methylene
Protons forced downfield by
effects of electronegative
Carbonyl group.
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96
n+1 = 2+1=3
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n+1 = 5+1=6
n+1 = 2+1=3
97
6 protons see 6H
1 proton
producing
Doublet
n+1=1+1=2
5H
1H
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98
3H
P- Dibsubstitution
4H
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99
n+1=0+1=1
(singlet)
3H
n+1=2+1=3
(triplet)
P-Disubstitution
4H
2H
1H
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n+1=3+1=4
(quartet)
100
6H
Carboxylic
Proton
1H
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n+1=6+1=7
(septet)
1H
101
Donating
3
3 Methyl protons see
0 adjacent protons
producing singlet
n+1=0+1=1
Chemical Shift moved
downfield because
of proximity to
Electronegative
Carbonyl group (C=O)
P-Disubstitution
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102
3
Propoxyl group is moderately
deactivating, deshielding o
ring protons more so than p
protons (aniostropic effect)
m protons are deshielded least
ortho
(2)
para, meta
(3)
2
2
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103
4
b
b
c
Two quintets
overlappiing
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104
6
3 protons see 0 protons on
Carbonyl carbon producing a singlet
1 proton sees
8 adjacent protons
producing (8+1) 9 peaks
Singlet
2
2 protons see
1 adjacent proton
produces doublet
Triplet
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2
Nonet
Doublet
105
NMR (Carbon13)
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NMR (Carbon13)
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107
NMR (Carbon13)
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108
NMR (Carbon13)
CH2
CH3
1
1
1
1
1
Carbons
Aromatic Ar
Benzyl
CH2
Methylene CH2
Methyl
CH3
Carboxyl O=C-O
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109
NMR (Carbon13)
O
CH2
CH2
CH3
1
1
1
1
1
Carbons
Aromatic Ar
Benzyl
CH2
Methylene CH2
Methyl
CH3
Carboxyl O=C-O
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NMR (Carbon13)
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Broad-Band Decoupled
13C
6
Spectra
111
NMR (Carbon13)
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Broad-Band Decoupled
13C
6
Spectra (Cont)
112
NMR (Carbon13)
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113
NMR (Carbon13)
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114
NMR (Carbon13)
2,2-Dimethylbutane
115
NMR (Carbon13)
2,2-Dimethylbutane (Cont)
2,2-Dimethylbutane
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116
NMR (Carbon13)
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
5 Carbon Types
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3 Carbon Types
9 Carbon Types
6 Carbon Types
117
NMR (Carbon13)
Cyclohexanol
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118
NMR (Carbon13)
Cyclohexene
Chemical Shift
(c) > (b) > (a)
Cyclohexene
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119
NMR (Carbon13)
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120
NMR (Carbon13)
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Cyclohexanone
121
NMR (Carbon13)
1,3-Dichlorobenzene
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122
NMR Summary
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NMR Summary
1H1
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and
13C
124
NMR Summary
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125
NMR Summary
Chemical Shift () =
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60 MHz
Hz
=
MHz
= PPM
NMR Summary
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NMR Summary
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128
NMR Summary
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129
NMR Summary
11/10/201
4
130
NMR Summary
11/10/201
4
NMR Summary
11/10/201
4
13C
6
132
NMR Summary
11/10/201
4
133