C NMR Spectroscopy

13

H and 13C NMR compared:

both give us information about the number of

chemically nonequivalent nuclei
(nonequivalent hydrogens or nonequivalent
carbons)
both give us information about the
environment of the nuclei (hybridization state,
attached atoms, etc.)
it is convenient to use FT-NMR techniques for
1H; it is standard practice for 13C NMR

H and 13C NMR compared:

C requires FT-NMR because the signal for a

carbon atom is 10-4 times weaker than the
signal for a hydrogen atom
13

a signal for a 13C nucleus is only about 1% as

intense as that for 1H because of the magnetic
properties of the nuclei, and
at the "natural abundance" level only 1.1% of
all the C atoms in a sample are 13C (most are
12C)

H and 13C NMR compared:

C signals are spread over a much wider

range than 1H signals making it easier to
identify and count individual nuclei
13

Figure 1 (a) shows the 1H NMR spectrum of

1-chloropentane; Figure 2 (b) shows the 13C
spectrum. It is much easier to identify the
compound as 1-chloropentane by its 13C
spectrum than by its 1H spectrum.

Figure 1 Proton NMR

9.0

8.0

7.0

6.0

CH3

ClCH2

ClCH2CH2CH2CH2CH3

10.0

5.0

4.0

3.0

Chemical shift (, ppm)

2.0

1.0

Figure 2 Carbon NMR

13

ClCH2CH2CH2CH2CH3
a separate, distinct
peak appears for
each of the 5
carbons
200

180

160

140

120

CDCl3

100

80

60

Chemical shift (, ppm)

40

20

C Chemical Shifts

13

are measured in ppm ()

from the carbons of TMS

C Chemical shifts are most affected by:

13

electronegativity of groups attached to carbon

hybridization state of carbon

Electronegativity Effects
Electronegativity has an even greater effect
on 13C chemical shifts than it does on 1H
chemical shifts.

Types of Carbons
Classification

Chemical shift,
1
H

CH4

13
C

0.2

-2

CH3CH3

primary

0.9

CH3CH2CH3

secondary

1.3

16

(CH3)3CH

tertiary

1.7

25

(CH3)4C

quaternary

28

Replacing H by C (more electronegative) deshields

C to which it is attached.

Electronegativity effects on CH3

Chemical shift,
1
H

13
C

CH4

0.2

-2

CH3NH2

2.5

27

CH3OH

3.4

50

CH3F

4.3

75

Electronegativity effects and chain length

Cl
Chemical
shift,

CH2

CH2

CH2

CH2

CH3

45

33

29

22

14

Deshielding effect of Cl decreases as

number of bonds between Cl and C increases.

C Chemical shifts are most affected by:

13

electronegativity of groups attached to carbon

hybridization state of carbon

Hybridization effects
sp hybridized
carbon is more
shielded than sp2

sp hybridized
carbon is
more
H
shielded than
sp2, but less
shielded than
sp3

114

36
138 36 126-142

C
68

C CH2
84 22

CH2

CH3

20

13

Carbonyl carbons are especially deshielded

127-134

CH2

41

171

CH2

CH3

61

14

Table 1 Type Of Carbon vs Chemical shift

Type of carbon Chemical shift (), Type of carbon
ppm

Chemical shift (),

ppm

RCH3

0-35

RC

CR

65-90

R2CH2

15-40

R2C

CR2

100-150

R3CH
R4C

25-50
30-40

110-175

Type of carbon Chemical shift (), Type of carbon

ppm

RCH2Br
RCH2Cl

20-40
25-50

RC

Chemical shift (),

ppm

110-125

RCOR

160-185

RCH2NH2

35-50

RCH2OH

50-65

RCH2OR

50-65

RCR

190-220

C NMR and Peak Intensities

13

Pulse-FT NMR distorts intensities of signals.

Therefore, peak heights and areas can be
deceptive.

CH3

7 carbons give 7
signals, but
intensities are not
equal
OH

200

180

160

140

120

100

80

60

Chemical shift (, ppm)

40

20

CH Coupling

13

Peaks in a 13C NMR spectrum are typically

singlets
C13C splitting is not seen because the
probability of two 13C nuclei being in the same
molecule is very small.
13

C1H splitting is not seen because spectrum

is measured under conditions that suppress
this splitting (broadband decoupling).
13

Proton Decoupled
Proton coupling can
provide information about
number of protons.
Often useful to decouple
protons.
Irradiate sample with
broad spectrum of
frequencies.
Substituents on C can
enhance of reduce
signal.
Protons enhance the 13C
signal.

O
H2C

Undecoupled

H2
C

CH3

Decoupled from protons

2,6

TMS

3,5
1

6
5

180

O
H2
C C

2
3

O CH2

CH3

160

140

120

100

80

60

40

20

0 ,ppm

Summary Carbon-13 NMR

~1.08% of C atoms are the 13C isotope.

Do not usually see C-C spin-spin interactions.
Can see coupling between C and attached Hs.
Magnetic moment of 13C is low.
Resonances of 13C nuclei are ~6000 fold weaker
than 1H resonances.
Therefore most useful information is chemical shift.
Covers a range of 0-200ppm.
Influence chemical shift in proton spectra also
influence in carbon spectra

Rumus Molekul C5H7O2N

Rumus Molekul C6H8O

Rumus Molekul C8H8O