NMR

13C-NMR
Learning outcome
• Capable to interpreted the 13C-NMR spectra
SALIENT FACTS ABOUT 13C-NMR
12C is not NMR-active I = 0

however…. 13C does have spin, I = 1/2 (odd mass)

13C signals are 6000 times weaker than 1H because:

1. Natural abundance of 13C is small (1.08% of all C)

2. Magnetic moment of 13C is small

PULSED FT-NMR IS REQUIRED

The chemical shift range is larger than for protons

0 - 200 ppm
SALIENT FACTS ABOUT 13C-NMR
For a given field strength 13C has its resonance at a
different (lower) frequency than 1H.

Divide the hydrogen

1H frequency by 4 (approximately)
for carbon-13
1.41 T 60 MHz
2.35 T 100 MHz
7.05 T 300 MHz 13C
1.41 T 15.1 MHz
2.35 T 25.0 MHz
7.05 T 75.0 MHz
SALIENT FACTS ABOUT 13C NMR(cont)
Because of its low natural abundance (0.0108) there
is a low probability of finding two 13C atoms next to
each other in a single molecule.

not probable
13C - 13C coupling NO!

Spectra are determined by many molecules contributing

to the spectrum, each having only one 13C atom.

However, 13C does couple to hydrogen atoms (I = 1/2)

very common
13C - 1H coupling YES!
COUPLING TO ATTACHED PROTONS
3 protons 2 protons 1 proton 0 protons

H H
13 13 13 13
C H C H C H C

H
n+1 = 4 n+1 = 3 n+1 = 2 n+1 = 1

Methyl Methylene Methine Quaternary

carbon carbon carbon carbon

The effect of attached protons on 13C resonances

( n+1 rule applies ) (J’s are large ~ 100 - 200 Hz)
 ETHYL PHENYLACETATE

13C coupled
to the hydrogens
DECOUPLING THE PROTON SPINS
PROTON-DECOUPLED SPECTRA
A common method used in determining a carbon-13
NMR spectrum is to irradiate all of the hydrogen
nuclei in the molecule at the same time the carbon
resonances are being measured.

This requires a second radiofrequency (RF) source

(the decoupler) tuned to the frequency of the hydrogen
nuclei, while the primary RF source is tuned to the 13C
frequency.

RF source 1
RF source 2 1H-13C
“the decoupler” pulse tuned to
carbon-13
continuously
saturates
hydrogens
13C signal (FID) measured
 In this method the hydrogen nuclei are “saturated”,
a situation where there are as many downward as
there are upward transitions, all occurring rapidly.

During the time the carbon-13 spectrum is being

determined, the hydrogen nuclei cycle rapidly between
their two spin states (+1/2 and -1/2) and the carbon nuclei
see an average coupling (i.e., zero) to the hydrogens.

The hydrogens are said to be decoupled from the

carbon-13 nuclei.

You no longer see multiplets for the 13C resonances.

Each carbon gives a singlet, and the spectrum is
easier to interpret.
ETHYL PHENYLACETATE in some cases
the peaks of the
multiplets will
overlap
13C coupled
to the hydrogens

this is an
13C
easier spectrum
decoupled to interpret
from the hydrogens
SOME INSTRUMENTS SHOW THE MULTIPLICITIES
OF THE PEAKS ON THE DECOUPLED SPECTRA
s = singlet t = triplet
CODE : d = doublet q = quartet

d d
q
s s t
t
d

This method gives the best of both worlds.

CORRELATION CHARTS
APPROXIMATE 13C CHEMICAL SHIFT RANGES FOR
SELECTED TYPES OF CARBON (ppm)

R-CH3 8 - 30 C C 65 - 90
R2CH2 15 – 55 C=C 100 - 150
R3CH 20 - 60 C N 110 - 140

110 - 175
C-I 0 - 40
C-Br 25 - 65 O O
C-Cl 35 - 80 R-C-OR R-C-OH 155 - 185
O
C-N 30 - 65 R-C-NH2 155 - 185
O O
C-O 40 - 80 R-C-H R-C-R 185 - 220
 200 150 100 50 0 RANGE

R-CH3 8 - 30

Saturated carbon - sp3 R-CH2-R 15 - 55

no electronegativity effects 20 - 60
R3CH / R4C

C-O 40 - 80
Saturated carbon - sp3
electronegativity effects C-Cl 35 - 80
C-Br 25 - 65

C C Alkyne 65 - 90
Unsaturated carbons - sp
carbon - sp2 C=C 100 - 150
Aromatic ring 110 - 175
carbons
Acids Amides 155 - 185
C=O
Esters Anhydrides
C=O Aldehydes 185 - 220
Ketones

200 150 100 50 0

Correlation chart for 13C Chemical Shifts (ppm)

 nitriles
acid anhydrides
acid chlorides
amides
esters

carboxylic acids
aldehydes
a,b-unsaturated ketones
ketones

220 200 180 160 140 120 100 ppm

13C Correlation Chart for Carbonyl and Nitrile Functional Groups

DEPT 13C in NMR spectroscopy
• DEPT –NMR- distortion-less enhancement by polarization
transfer

Function: to determine the number of hydrogens

attached to each carbon in a molecule (or types of
carbons: CH, CH2, CH3)
3 stages involved:

1. Broadband-decoupled spectrum – to locate the

chemical shifts of all carbons

2. DEPT-90 – only signals due to CH carbons will appear.

Signals due to CH3, CH2 and quartenary carbons are
absent.

3. DEPT-135 – signals CH and CH3 will appear as positive

signals and CH2 resonances as negative signals (peaks
below the baseline). Quartenary carbons are absent.

If put together all informations from all

three spectra, the number of hydrogens
attached to each carbon can be
determined.
Summary of DEPT-NMR:
• Broadband-decoupled : C, CH, CH2, CH3
• DEPT-90 : CH
• DEPT-135 : CH3, CH are positive peaks
CH2 is negative peak

• C : substract DEPT-135 from broadband-decoupled spectrum

• CH: DEPT-90
• CH2: Negative DEPT-135
• CH3: substract DEPT-90 from positive DEPT-135
• Example: DEPT-NMR spectrum for 6-methyl-5-en-2-ol.
• a. broadband-decoupled
b. DEPT-90

• C. DEPT-135
SPECTRA
1-PROPANOL

HO-CH2-CH2-CH3
c b a
PROTON
DECOUPLED

200 150 100 50 0

Proton-decoupled 13C spectrum of 1-propanol (22.5 MHz)
2,2-DIMETHYLBUTANE
BROMOCYCLOHEXANE
CYCLOHEXANOL
CYCLOHEXANONE
TOLUENE
1,2-DICHLOROBENZENE

b
c Cl
a
a
c Cl
b
 1,3-DICHLOROBENZENE

solvent
Cl
d b
a

Cl
c d
a
PROBLEMS
1. C3H6O2
4. C5H8O2 (ester)
Isomers of
C7H14O
(ketones)