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Carbon nuclei have two options in the presence of external magnetic field (B0):
Energy difference (∆E) depends on
i) type of nucleus (1H, 13C, 19F, etc.)
∆E
ii) molecular environment around nucleus
B0 iii) strength of B0 ∆E ∆E
Carbon spins aligned with B0 Carbon spins aligned against B0
α state β state
(a lower energy state) (a higher energy state)
Chemical shift (δ )
As noted earlier, resonance frequency of ∆E ∆E ∆E
spin flip depends on strength of applied
outside magnetic field (B0). INSTRUMENTATION
Since different magnetic field strength NMR magnets are used in labs,
comparison of spin flip in Hertz from these different magnetic field
strengths magnets would be cumbersome (e.g., the methyl carbon in
CH3Br measures 1475 Hz in one field strength magnet versus 738.6 Hz in
another).
PULSED FOURIER TRANSFORM
However, if frequencies of each spin flip are divided by the operating TECHNOLOGY
frequency of the instrument, a number that is independent of the strength
of magnet used is obtained. That number is called chemical shift.
FT-NMR
frequency of carbons from reference cpd (in Hz)
δ = = parts per million
operating frequency of NMR spectrometer (in MHz) requires a computer
11 12
(or ppm in short)
H2
PULSED EXCITATION Let’s consider ethyl bromide C
N H3C Br
Number of chemically different set of carbons: 2
Each carbon releases a different amount of energy
ν2 (frequency) as it relaxes (free-induction decay or FID)
ν1
Carbon next to bromine atom Carbon beta to bromine atom
O
BROADBAND
RF PULSE
O
contains a range
of frequencies
ν3
FT
13C NMR SPECTROSCOPY
Fortunately for organic chemists, both carbon and
hydrogen nuclei are “NMR active”!
15 16
# of signals: 3 3
# of signals: 1 1 1 O
H3C O CH 3
2 2 H3 C CH 3 # of 4
# of signals: signals: 4
H3C CH3
O O
2 2 4
19 20
O O O Cl
3)
a b c d
CH 3CH 2O
4) (CH 3)3C O CH 2CH 3 CH 3O CH 2 N(CH 3)2 CHCH 3
CH 3CH 2O
a b c
21 22
CH4 -2 CH4 -2
CH3CH3 primary 8 CH3NH2 27
CH3CH2CH3 secondary 16 CH3OH 50
(CH3)3CH tertiary 25 CH3F 75
(CH3)4C quaternary 28
Replacing H by C (more electronegative) deshields
C to which it is attached. 23 24
Electronegativity effects and chain length 13C Chemical shifts are most affected by:
25 26
27 28
O
CH 3C O CH 3
derivative.
2 peaks
31 32
• Assign each structure to its 13C NMR spectrum. Briefly justify Match each of the following compounds with its 13C NMR spectrum.
your answers. O O H O Hint: how many 13C
OH
H signals expected
Hint: how many 13C O
OH P Q R S T for each cpd?
O O signals expected
X Y Z for each cpd? a b
a
c 2 peaks d
b 1 peak
1 peak
e
c
1 peak
33 34