C NMR Spectroscopy

13
 1
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 NMR techniques for 1H;
it is standard practice for 13C NMR
 Chemical Shift Equivalence

CSE = Interchangeability by a symmetry operation or by rapid mechanism.

Eg. The CH3 groups of t-Butyl alcohol are CSE due to rapid rotation
Thus will give one signal
 CSE continued

75.5 MHz
C/C’ coincident

150.9 MHz
C/C’ are resolved

At higher magnetic field CSE can be resolved

 1
H and 13C NMR
• In13C NMR, the signal for a C atom is 10-4 times weaker
than the signal for a H atom
• a signal for a 13C nucleus is only about 1% as intense as
that for 1H due to the magnetic properties of the nuclei
• at the "natural abundance" level only 1.1% of all the C
atoms in a sample are 13C (most are 12C)
• 13
C signals are spread over a much wider range than 1H
signals making it easier to identify and count individual
nuclei

• Lets compare 1H NMR spectrum of 1-chloropentane

and13C spectrum.
 Proton Spectrum 1
H

ClCH2 CH3
ClCH2CH2CH2CH2CH3

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (, ppm)

 Carbon Spectrum 13
C

ClCH2CH2CH2CH2CH3
a separate, distinct
peak appears for each
of the 5 carbons
CDCl3

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (, ppm)

 Chemical Shift Scale and Range
Chemical shift range for 13C is larger than for 1H

Δ thus overlap of signals is less frequently encountered.

 C Chemical Shifts
13

• Measured in ppm () from the carbons of TMS

• Affected by:
- electronegativity of groups or atoms attached to
carbon
- hybridization state of carbon

Electronegativity Effect:
has a even greater effect on 13C chemical shifts than it
does on 1H chemical shifts.
 Types of Carbons

Classification Chemical shift, 

1
H 13
C
CH4 0.2 -2

CH3CH3 primary 0.9 8

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 C
13

CH4 0.2 -2

CH3NH2 2.5 27
CH3OH 3.4 50

CH3F 4.3 75
 Electronegativity effects and chain length

Cl CH2 CH2 CH2 CH2 CH3

Chemical 45 33 29 22 14
shift, 

Deshielding effect of Cl decreases as

number of bonds between Cl and C increases.
 Hybridization effects

sp3 hybridized
carbon is more
shielded than sp2 114 36

138 36 126-142
sp hybridized
carbon is more
shielded than
H C C CH2 CH2 CH3
sp2, but less
shielded than 68 84 22 20 13
sp3
Carbonyl carbons are especially deshielded

CH2 C O CH2 CH3

41 171 61 14
127-134
 Table of Chemical Shifts

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

RCH3 0-35 RC CR 65-90

R2CH2 15-40 R2C CR2 100-150

R3CH 25-50
110-175
R4C 30-40
 Table of Chemical Shifts

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

RCH2Br 20-40 RC N 110-125

RCH2Cl O
25-50
RCOR 160-185
RCH2NH2 35-50

RCH2OH 50-65 O

RCH2OR 50-65 RCR 190-220

 13
C NMR and Peak
Intensities

Pulse-NMR distorts intensities of signals.

Therefore, peak heights and areas can be
deceptive.
 Attached Protons and Signal Intensity

CH3
7 carbons give 7
signals, but intensities
are not equal

OH

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (, ppm)

 13
C—1H Coupling

• Peaks in a 13C NMR spectrum are typically singlets

• 13
C—13C splitting is not seen because the
probability of two 13C nuclei being in the same
molecule is very small.
• 13
C—1H splitting is not seen because spectrum
is measured under conditions that suppress
this splitting (broadband decoupling).
 1
H Decoupling Techniques
J values for C-H are typically 110-300 Hz (C-C-H and C-C-C-H are 0-60Hz)

In Proton coupling: CH3 group would appear as a quartet, CH2-triplet CH-doublet

etc. (split according to the number of hydrogen atoms on the Carbon)

In decoupling: 1H nuclei are irradiated with a broadband radio frequency to

remove coupling to Carbon.
Interpretation of a Simple
C13 Spectrum
Diethyl Phthalate

decoupled

coupled

Expansions:
Additional splitting
Is due to J2 and J3
couplings
Using DEPT to Count the
Hydrogens
Attached to 13C
Distortionless Enhancement
of Polarization Transfer
 Measuring a 13C NMR spectrum involves

1. Equilibration of the nuclei between the lower

and higher spin states under the influence of
a magnetic field
2. Application of a radiofrequency pulse to give
an excess of nuclei in the higher spin state
3. Acquisition of free-induction decay data
during the time interval in which the equilibrium
distribution of nuclear spins is restored
4. Mathematical manipulation (Fourier transform)
of the data to plot a spectrum
 Measuring a 13C NMR spectrum involves

Steps 2 and 3 can be repeated hundreds of times

to enhance the signal-noise ratio

2. Application of a radiofrequency pulse to give

an excess of nuclei in the higher spin state

3. Acquisition of free-induction decay data

during the time interval in which the equilibrium
distribution of nuclear spins is restored
 Measuring a 13C NMR spectrum involves

In DEPT, a second transmitter irradiates 1H

during the sequence, which affects the
Appearance of the 13C spectrum.

some 13C signals stay the same

some 13C signals disappear
some 13C signals are inverted
 Proton Decoupled Spectrum
O

CCH2CH2CH2CH3

CH CH
CH2
CH CH2
O
CH2 CH3
C
C

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (, ppm)

 DEPT Spectrum
O

CCH2CH2CH2CH3

CH CH
CH3
CH

CH and CH3 unaffected

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

Chemical shift (, ppm)

Distortionless Enhancement by Polarization Transfer
(DEPT)
Pulse sequence developed to determine the number of protons
Directly attached to a carbon.

DEPT 90 deg.
CH only

DEPT 135 deg.

CH &CH3 up,
CH2 down

Std 1H decoupled
spectrum

DEPT is a helpful to determine proton inventory, but it does not

Record H’s on heteroatoms; must correlate with 1H spectrum.