16-10-2023

Theory and application of 13C NMR

spectroscopy in structure assignment
to organic compounds

Dr D. I. Brahmbhatt
Ex.Head & Professor of Organic Chemistry (Retired)
Department of chemistry
Sardar Patel University
Vallabh Vidyanagar – 388 120
Gujarat
Email: drdibrahmbhatt@gmail.com
Mob: 9427547665

NMR spectroscopy
• NMR spectroscopy is a very powerful tool in the
structure assignment of organic compounds.

• Nuclei with spin ½ can be nicely studied by NMR. Thus

1H, 13C, 15N, 19F, 31P etc. can be studied by NMR.

• 1H and 13C are studied very widely and routinely.

• The structure assignment of a unknown compound

becomes easy and convenient if one has both 1H and 13C
spectral information.
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Difficulties in production of 13C spectra

• 13C has very poor relative abundance 1.1% that of 12C.
i.e. roughly 1 atom of 13C per 100 atoms of 12C.
• 13C nucleus has very poor sensitivity 1.6% that of 1H.
Thus overall sensitivity of 13C compared with 1H is about
1/5700.
• Due to this poor sensitivity 13C spectrum can not be
recorded by single scanning.
• Large number of scannings must be done and then their
combination can produce the spectrum.
• The conventional continuous wave method for scanning
NMR is a slow scan procedure and requires large time and
large quantity of sample.
• Thus by continuous wave method it is impossible to
record 13C spectra.

Solution of difficulties : Use of FT and

Computer
• Use of Fourier Transform technique.

• In Fourier Transform procedure, a FID (time domain)

spectrum is obtained and it is then converted into
frequency domain spectrum.

• Large number of such spectra are scanned(100 or so)

and then by the help of computer their addition (sum)
is obtained and recorded.

• Thus within a short time and with a small quantity of

sample one can record 13C spectra.
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Principle of Fourier Transform

• Fourier – a French mathematician gave equation to solve
combined waves.
• Two combined waves – four answers
2 – frequencies
2 – amplitudes
• Five combined waves – ten answers
5 – frequencies
5 - amplitudes

• FID – Free Induction Decay.

• Time domain spectrum
• FID FT Frequency Domain Spectrum.

• Length of FID – more sharp signal

• Length of FID short - broad signal
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Fourier transform of FID

Recording of 13C spectra

• A solution of sample in deuterated solvent is made.
• A sample is put in magnetic field.
• A radio frequency pulse is applied(90º)
• Acquisition time is given. FID is produced. This is one
scan.
• Thus repeated scannings are done.
• A combined FID is obtained.
• FT converts it into a frequency domain spectrum.
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FID spectrum of Methanol and Ethanol

CH3
49.0 CH2 CH3
57.0 17.0

Methanol Ethanol

13C spectra : Scale, Solvent and Signals

• 13C spectrum has normal scale range from 0 - 200.
• For 2.3T field 1H needs 100 MHz frequency, but for 13C, as carbon
has γ = 6728 (1/4 of 1H, 1H γ = 26753) it needs 25.2 MHz
frequency for resonance.
• Normally deuterated solvents like Acetone–d6, Chloroform – d,
DMSO – d6 , Benzene – d6 , Acetonitrile –d3 are used
• The multiplicity and position of above solvents signal in 13C
spectrum is
Acetone – d6 : 29.8(septet),
206.5(unresolved septet)
Chloroform-d(CDCl3) : 77.0(triplet)
DMSO – d6 : 39.7(septet)
Benzene – d6 : 128.0(triplet)
Acetonitrile – d3 : 13.0(methyl,septet)
118.3(CN,unresolved septet)
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13C proton coupled and decoupled spectra

• 13C proton coupled spectra show multiplicity of signal i.e
splitting of the signal if proton is attached to a carbon.
• The splitting is governed by rules identical for 1H (simple
rule : n + 1).
• As 13C-1H coupling constant is very high(110 – 320Hz), a
splitted signal covers a big area. This causes overlapping
and crowding of signals. This creates confusion and
problem in the interpretation of spectra.
• The proton decoupled spectra are recorded. A broadband
decoupled spectra are recorded.
• Proton decoupled spectra show only single line for 13C
signal.
• 13C spectra do not have integration and hence do not give

information about number of carbons for each signal.

2 1
COO CH2CH3
3 124-136
4 COO CH2CH3
5 6
60
14

168
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2 1
COO
124-136
CH2CH3
3 60 14
4 COO CH2CH3
5 6

168

Chemical shift equivalence and chemical shifts

• The rules for the chemical shift equivalence for 13C are
same as those for 1H.
• The equivalent carbons give only one signal
e.g. Benzene – all carbons are equivalent, hence only
one signal.
• Chemical shifts of 13C are somewhat parallel to those
of 1H.
• The concept of additivity of substituent effects is useful
for 13C spectral chemical shifts.
• 13C chemical shifts are mainly related to hybridization
and substituent electronegativity.
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Chemical shift calculation

Chemical shift calculation

6 CH3
H3C CH2 CH CH2 CH3 3-methyl pentane
1 2 3

δ = -2.5 + Σ nA , δ = chemical shift

n = no of carbon atoms for
each shift parameter
A = shift parameter
• Calculation
δC1 = -2.5 + (9.1×1) + (9.4×1) + (-2.5×2) + (0.3×1)
= + 11.3
δC2 = -2.5 + (9.1×2) + (9.4×2) + (-2.5×1) +(-2.5×1)
= + 29.5
δC3 = -2.5 + (9.1×3) + (9.4×2) + (-3.7×2) = + 36.2
δC6 = -2.5 + (9.1×1) + (9.4×2) + (-2.5×2) +(-1.1×1)
= + 19.3
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For branched compounds

OH

H3C CH2 CH CH2 CH3

γ β α
3 – hydroxy pentane
Cα = 34.7 + 41
= 75.8 (observed 73.8)
Cβ = 22.8 + 8
= 30.8 (observed 29.7)
Cγ = 13.9 – 5
= 8.9 (observed 9.8)

For terminal compounds

5 4 3 2 1
H3C CH2 CH2 CH2 CH2 OH
1 - pentanol
H3C CH2 CH2 CH2 CH3
13.9 22.8 34.7
δc1 = 13.9 + 48.0 = 61.9 (observed 62.1)
δc2 = 22.8 + 10.0 = 32.8 (observed 32.8)
δc3 = 34.7 - 5.0 = 29.7 (observed 28.5)
δc4 = 22.8 (observed 22.9)
δc5 = 13.9 (observed 14.1)
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13C spectrum of n - pentanol

32.8
C2
28.5
22.9
C3
C4
62.1 14.1
C1 C5

For Aromatic compounds

Benzene δC = 128.5 only one signal

1

Naphthalene
2 δC1 = 128.1, δC2 = 125.9
3
4a
4 δC4a = 133.7
9 1

Anthracene
2 δC1 = 130.1 , δC2 = 125.4
4a 4
3
δC4a = 132.2 , δC9 = 132.6
2
3 1 δC1 = 128.3 , δC2 = 126.3
Phenanthrene
4 10 δC3 = 126.3 , δC4 = 122.2
9
5
δC4a = 131.9 , δC9 = 126.6
6 8
7 δC10a = 130.1
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Aromatic chemical shifts calculation

Calculation of chemical shift for

aromatic compounds

OH δc1 = 128.5 + 26.6 = 155.1

1 δc2 = 128.5 +(-12.7) = 115.8
2
3
δc3 = 128.5 + 1.6 = 130.1
4 δc4 = 128.5 + (-7.3) = 121.1

C H3 δc1 = 128.5 + 9.3 = 137.8

1
2 δc2 = 128.5 + 0.7 = 129.2
3 δc3 = 128.5 + (-0.1) = 128.4
4 δc4 = 128.5 + (-2.9) = 125.6
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C HO C HO
1 4
1
2 2 3
+ 2
3 3
4 4 1
OMe OMe

p - Anisaldehyde II III
II III Combined effect
C1 + 8.2 C4 – 7.7 + 0.5
C2 + 1.2 C3 + 1.0 + 2.2
C3 + 0.6 C2 – 14.4 - 13.8
C4 + 5.8 C1 + 31.4 + 37.2
Calculated Observed
C1 = 128.5 + 0.5 = 129.0 130.2
C2 = 128.5 + 2.2 = 130.7 132.1
C3 = 128.5 – 13.8 = 114.7 114.5
C4 = 128.5 + 37.2 = 165.7 164.9

CHO
1
2 6
55.0
132.0 115.0 3 5
C2& C6 C3& C5 4
192.0
OMe OMe
165.0
CHO 130.0
C4 C1

CHO
1
2 6

3 5
4
OMe
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CN CN
1 4
2 3
is equivalent to
3
+ 2
4 1
Cl Cl
I II III
For I For II For III II + III
C1 C1 = - 1.6 C4 = - 2.0 - 18.0
C2 C2 = + 3.6 C3 = + 1.0 + 4.6
C3 C3 = + 0.6 C2 = + 0.2 + 0.8
C4 C4 = + 4.3 C1 = + 6.4 + 10.7

δC1 = 128.5 + (- 18.0) = 110.5

δC2 = 128.5 + 4.6 = 133.1
δC3 = 128.5 + 0.8 = 129.3
δC4 = 128.5 + 10.7 = 139.2

CH 3 CH 3
1
6 2
equivalent to +
5
3 OH OH
4
I II III
II III Combined
C1 + 9.3 + 1.6 + 10.9 + 128.5 = 139.4
C2 + 0.7 - 12.7 - 12.0 + 128.5 = 116.5
C3 - 0.1 + 26.6 + 26.5 + 128.5 = 155.0
C4 - 2.9 - 12.7 - 15.6 + 128.5 = 112.9
C5 - 0.1 + 1.6 + 1.5 + 128.5 = 130.0
C6 + 0.7 - 7.3 - 6.6 + 128.5 = 121.9
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C4
C2
C6
C5 1
6 2
5 3
4

CH3 22.0
C3
C1

Chemical shift calculation for

Some selected compounds

1 2 3 4 5 6
HO-CH2-CH2-CH2-CH2-CH2-CH2-NH2

δC1 = 14.1 + 48 = 62.1

δC2 = 23.1 + 10 = 33.1
δC3 = 32.2 + (-5) = 27.1
δC4 = 32.2 + (-5) = 27.1
δC5 = 23.1 + 11 = 34.1
δC6 = 14.1 + 29 = 43.1
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=
CH3-C-CH2-CH3 δC1 = -2.3 + 30 = 27.7
1 2 3 4 δC3 = 5.7 + 24 = 29.7
δC4 = 5.7 + 2 = 7.7
δC2 = 207.78

4 3 2 1
CH3-CH2-CH-CH3 δC1 = 13.4 + 7 = 20.4
δC2 = 25.2 + 50 = 75.2
O-C-CH3
δC3 = 25.2 + 7 = 32.2
=

O
δC2 = 13.4 +(-6) = 7.4

Cl
1 δC2 = 5.7 + 16 + 35 = 56.7
CH3-CH-C-OH
3 2 δC3 = 5.7 + 2 + 10 = 17.7
=

5
CH3 2 δC3 = 24.5 + 52 = 76.5
CH3-CH-CH2-O-C-CH3 δC = 25.4 + 7 = 32.4
=

4
6 4 3 O 1 δC5 & δC6 = 24.5 + (-6) = 18.4
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CH3-CH2-CH2-CH2-O-CH=CH2
4 3 2 1 5 6

δC1 = 13.4 + 50.0 = 63.4

δC2 = 25.2 + 10.0 = 35.2
δC3 = 25.2 + (-6.0) = 19.2
δC4 = 13.4
δC5 = 123.0 + 29.0 = 152.0
δC6 = 123.0 + (-39.0) = 84.0

CH3-CH2-CH2-CH2-O-C-CH=CH2
=

4 3 2 1 O 1 2

δC1 = 13.4 + 52.0 = 65.4

δC2 = 25.2 + 7.0 = 32.2
δC3 = 25.2+ (-6.0) = 19.2
δC4 = 13.4 + 0 = 13.4

δC1 = 123.0 + 4.0 = 127.0

δC2 = 123.0 + 9.0 = 132.0
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_
CH=C-CH2-CH2-CH2-CH3
1 2 3 4 5 6

Chemical shift (δ) = 72 + Σ (Incriments for carbon atom)

δC1 = 72.0 + (-6.0) + 2.0 + (-1.0) + 0.5 = 67.5

δC2 = 72.0 + 7.0 + 5.0 + 0.0 + 0.5 = 84.5
δC3 = 13.4 + 4.0 = 17.4
δC4 = 25.2 + 3.0 = 28.2
δC5 = 25.2- 3.0 = 22.2
δC6 = 13.4

HO-CH2-CH-CH2-CH2-CH2-CH3
_

CH2-CH3
1 2 3 4 5 6
Parent : CH3-CH-CH2-CH2-CH2-CH3
_

CH2-CH3
7 8
δC1 = 6.80 + 17.83 + (2X-2.99) + 0.49 = 19.14
δC2 = 23.46 + (2X6.60) + (-2.07) = 34.59
δC3 = 15.34 + (2X9.75) + (2X-2.69) = 35.25
δC4 = 15.34 + (2X9.75) + (2X-2.69) + 0.25 = 29.71
δC5 = 15.34 + 9.75 + (2X-2.69) + (2X0.25) = 22.90
δC6 = 6.80 + 9.56 + (-2.99) + 0.49 = 13.86
δC7 = 15.34 + 16.70 + (-2.69) +0.49 = 29.84
δC8 = 6.80 + 9.56 + (2X2.99) + 0.49 = 10.87
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1 2 3 4 5 6
HO-CH2-CH-CH2-CH2-CH2-CH3

_
CH2-CH3
7 8
δC1 = 19.14 + 50.0 = 69.14
δC2 = 34.59 + 9.0 = 43.59
δC3 = 35.25 – 3.0 = 32.25
δC4 = 29.71
δC5 = 22.90
δC6 = 13.86
δC7 = 29.84 – 3.0 = 26.84
δC8 = 10.87

1 2 3 4
CH2=CH-C-O-CH2-CH3
=

δC1 = 123.3 + 7.0 = 130.3

δC2 = 123.3 + 6.0 = 129.3
δC3 = 5.7 + 52.0 = 57.7
δC4 = 5.7 + 7.0 = 12.7
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Differentiation of stereoisomers by 13C spectra

Differentiation of primary, secondary and

tertiary carbons
• Broad band decoupled 13C spectra do not give
information about proton attached to carbon.
• Though a off-resonance spectral technique provides
splitting of the 13C signal by attached protons, it does not
give correct coupling constant and here also problem of
overlapping of signals still remains.
• The DEPT technique (Distortionless Enhancement by
Polarization Transfer) is important for differentiating
primary, secondary, tertiary etc. carbons.
• Variable proton pulse is set at 45°, 90° or 135° in three
separate experiments and thus DEPT – 45 , DEPT – 90,
DEPT – 135 spectra are obtained.
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13C DEPT spectra

• Normal 13C spectrum shows all carbon signals.
• DEPT - 45° - no quaternary
• DEPT - 90° - only C – H signals seen.
• DEPT - 135° - no quaternary carbons.
- CH and CH3 signals are shown
normal.
- CH2 signals are inverted.

DEPT spectra of ipsenol

9
C2
C4
C7
CH up
1a DEPT - 90°

C 1 C2
C4 C1a
CH3 & CH up C7
DEPT- 135°

CH2 down C3&C5

C8 &C9

Normal13C spectrum
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DEPT spectrum of 1 – phenyl – 1 - pentanone

Normal13C spectrum

DEPT- 135°

DEPT spectra of Limonene

2 Signals

C2
C4
CH up

C7 & C10
C2 C4
CH3 & CH up
CH2 down
C9 C3,C5 & C6
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