13C NMR Spectroscopy

1H Vs 13C Technique
• 13C- NMR spectrum is obtained in a similar manner to
1H-NMR

• 12C has no magnetic spin.

• 13Chas a magnetic spin but only has about 1.1% natural

abundance of carbon atoms. Due to the low abundance,
we do not usually see 13C-13C coupling.

• Carbon atoms with more hydrogens absorb more

strongly.

• 13Cnucleus is about 400 times less sensitive than H

nucleus to the NMR phenomena.

• Chemical shifts are also measured with respect to

tetramethylsilane, (CH3)4Si (i.e. TMS).
 Differences in 13C Technique
• Chemical shift range is normally 0 to 220 ppm

• Number of peaks indicates the number of types of C

• 13C-NMR spectra take longer to acquire than H-NMR

• Similar factors affect the chemical shifts in 13C as seen for

H-NMR

• The most significant factors affecting the chemical shifts

are:
- Electronegativity of the groups attached to the C
- Hybridisation of C
Hydrogen and Carbon Chemical Shifts
Combined 13C and 1H Spectra
 Spin-Spin Splitting

• It is unlikely that a 13C would be adjacent to

another 13C, so splitting by carbon is
negligible.

• 13C will magnetically couple with attached

protons and adjacent protons.

• These complex splitting patterns are difficult

to interpret.
 Proton Spin Decoupling

• To simplify the spectrum, in a "normal" 13C

spectra, these couplings are "removed"

• This means that each C is seen as an unsplit

single line.
 Typical Values
Type of carbon Chemical shift (d), Type of carbon Chemical shift (d),
ppm ppm

RCH3 0-35 RC CR 65-90

R2CH2 15-40 R2C CR2 100-150

R3CH 25-50
110-175
R4C 30-40

Carey, Table 13.3 (p 513)

 Typical values
Type of carbon Chemical shift (d), Type of carbon Chemical shift (d),
ppm ppm

RCH2Br 20-40 O

RCH2Cl 25-50 RCOR 160-185

RCH2NH2 35-50 O

RCH2OH 50-65 RCR 190-220

RCH2OR 50-65
Carey Table 13.3 (p 513)
Typical 13C NMR Spectrum
Typical 13C NMR Spectrum
 Off-Resonance Decoupling

• 13C nuclei are split only by the protons

attached directly to them.

• The N + 1 rule applies: a carbon with N

number of protons gives a signal with N + 1
peaks.

• For example, a -CH3 shows as a quartet

a -CH2- as a triplet
a -CH- as a doublet
 Two 13C NMR Spectra
Off resonance and normal 13C
spectra
 DEPT
(distortionless enhancement of polarisation transfer)

In a DEPT experiment, a sequence of pulses with various delay

times and selection angles are used to create the DEPT spectra.

It differentiates between CH, CH2 and CH3 groups – where CH3

and CH peaks appear as normal and -CH2- peaks appear
inverted. Quaternary C are not usually seen.

• 135° angle gives all CH and CH3 in a phase opposite to CH2

• A ‘normal’ carbon spectrum gives all the chemical shifts of
all carbons
Example: DEPT spectrum of 2-butanol
13C NMR Spectrum of O
1-phenyl-1-pentanone
CCH2CH2CH2CH3
CH
CH
CH2
CH CH2
O
CH2
CH3
C
C

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (d, ppm)

Carey, Figure 13.23 (a) (page 516)

DEPT spectrum of O
1-phenyl-1-pentanone
CCH2CH2CH2CH3

CH CH
CH3
CH

CH and CH3 unaffected

C and C=O nulled
CH2 inverted CH2
CH2
CH2
200 180 160 140 120 100 80 60 40 20 0

Chemical shift (d, ppm)

Figure 13.23 (b) (page 516)

 Assign all peaks of α-Terpinene

135°

• Subtract all peaks in the DEPT-135 spectrum from the

‘normal’ C spectrum to find Cq.

• Use negative DEPT-135 peaks to identify CH2

 Interpreting 13C NMR
• The number of different signals indicates the number of
different kinds of carbons.

• The location (chemical shift) indicates the type of functional

group neighboring to the carbon.

• The splitting pattern of off-resonance coupled spectrum

indicates the number of protons attached to the carbon.

• In a DEPT experiment, CH3 and CH peaks appear as normal

and -CH2- peaks appear inverted. Quaternary C are not
usually seen.
 A Strategy for Handling Unknown
Structures
• Look at 1H NMR, 13C NMR, Mass Spec, UV--any
features stand out?
• Use the DBE (sites of unsaturation) rule
• Infrared - Functional groups present? Identify and
possibly subtract from formula
• List important 13C and 1H NMR peaks and classify
the C,H groups present.
• Tabulate fragments of structure. Reconcile MS
fragments.
• Assemble possible structures
NMR Spectral Problems
see handout