Subject Chemistry

Paper No and Title 12 and Organic Spectroscopy

Module No and Title 22 and Applications of 13C NMR

Module Tag CHE_P12_M22

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction
3. Structural Determination
4. Factors affecting 13C NMR chemical shifts
5. 13C NMR of selected molecules
6. Summary

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 1. Learning Outcomes
After studying this module, you shall be able to

 Know about structural determination using 13C NMR

 Learn the factors affecting 13C NMR chemical shifts

2. Introduction

The first NMR signal for 1H was observed in 1945 but the first 13
C NMR signal
13
was detected in 1957 by Lauterbur. The first C NMR of some organic compound was
recorded in early 1960. This discovery made structural determination very simple and
interesting. This is more helpful to those molecules which have very few C-H bonds. This
is because, this type of molecules are not identified completely by 1H NMR. Also, the
complex molecules mainly biomolecules found this method of identification more
efficient. The study of biosynthetic pathways of natural products and brain metabolism can
easily be monitored with the help of 13C NMR spectroscopy.
13
The recording of C NMR spectrum is usually done as 1H decoupled for
simplicity. Each chemically unique carbon present in the molecule gives a single peak
whereas chemically equivalent carbons contribute to the same peak. The presence of
different signals or peaks indicates the number of different kinds of carbon present in
different chemically and magnetically different environment.
The following sections are going to discuss the pathway for structural determination
of different molecules.

3. Structural Determination

Similar to the 1H NMR spectroscopy; 13

C NMR spectroscopy also helps in the
determination of structure of the substances. This spectroscopy helps in finding the
presence of carbon skeleton in study of natural products, synthetic molecules, polymers
and other molecules. It is always difficult to find the complete structure of any compound
with any individual spectroscopic data.

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 13
The reference compound for C NMR is same as that of 1H NMR which is
Tetramethylsilane [TMS; (CH3)4Si). The chemical shifts are expressed in ppm. There is
large difference between the chemical shift of 13CNMR and 1HNMR, in 13C the range of
chemical shift is ranges from 0-250 ppm while in case of 1HNMR it ranges from 0-15 ppm.

CH3

H3C Si CH3

CH3
Tetramethylsilane

(1) Correlation Data for 13C NMR spectra

A 13C spectrum is typically recorded from 0-250 ppm with zero being the methyl
carbon in TMS. This range is about 20 times that of routine PMR spectra (~12 δ). Due to
13
this large spread of chemical shifts, relatively fewer peaks overlap in C NMR spectra.
These spectra are shielded or deshielded due to the same factors as for 1H NMR, such as:
 Electron withdrawing group
 Hybridization
 Electron current effects
Some functionality only appears in 13C NMR not in 1H NMR such as quaternary carbon,
ipso carbons, carbonyl carbons etc. Several cations absorb at ~335 δ downfield and CI4 has
been recorded at approximately -290 δ upfield from TMS.
A general  values for different types of carbon environment is given in figure 9. Some
general rules for the correlation data is important to know:

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 aromatic sp3 C-EWG sp3 carbon

240 220 200 180 160 140 120 100 80 60 40 20 0

carbonyl alkenes alkynes

 (ppm)

Figure 9.  (ppm) values for different carbon environments

sp3 hybridised carbons

The sp3hybridised carbons are either unsubstituted or substituted with electron
withdrawing groups (EWG). Overall range of resonance observed in between 0 to 50 ppm
for unsubstituted and between 60-90 ppm for EWG substituted carbons. The influence of
strong electronic and steric effect cannot be ruled out. For an extreme case like
tetraiodomethane (CI4) where, carbon has been observed at 300 ppm lower than the TMS
( = -300). The 13C NMR signal ranges for some substituted sp3 carbons are:
 CH2Br 28-35 ppm
 CH2NH2 37-45 ppm
 CH2OH 50-65 ppm

sp2 hybridised carbons

The sp2hybridised carbons include alkene and aromatic carbons. These carbons
give signals in overlapped regions. The range alkene and aromatic carbon signals are
between 90 to 150 and 100 to 170 respectively. In this case, a diversity of other functional
groups also falls. For example, >C=O, >C=N etc. The shift in ppm differs for these cases
depending upon the electronic and steric factors. The >C=N present in the Schiffs bases
are generally observed in the range 130-150 ppm. The 13C NMR signal ranges of important
>C=O groups are:
CHEMISTRY PAPER No.12 :Organic Spectroscopy
MODULE No.22: Applications of 13C NMR
  ester C=O  170-175 ppm
 acid C=O  177-185 ppm
 aldehyde C=O  190-200 ppm
 ketone C=O  200-220 ppm

sp hybridised carbons
The sp hybridised carbons include alkynes, nitriles and isonitriles. The signals for
these groups are generally present in very narrow range. The unsubstituted alkynes have
been observed in the range of 40-80 ppm.

(2) Chemical Shift Equivalence for 13C NMR spectra

The chemical shift equivalence for carbon atoms is similar to the one applied to protons.
The chemical equivalence or non-equivalence of carbon is mainly judged in the same way
as required for 1H NMR. It is important to recognize various kinds of carbon atoms present
in the molecule.

Some of the common molecules are discussed below:

t-Butyl alcohol [(CH3)3COH]

1 CH3

1
H3C C OH
2

1 CH3

t-Butyl alcohol
In t-butyl alcohol, the carbon atoms of all the three methyl groups are equivalent whereas
the carbon attached with –OH is in different environment. Hence, the 13
C NMR of this
molecule gives only two signals for carbons 1 and 2.
CHEMISTRY PAPER No.12 :Organic Spectroscopy
MODULE No.22: Applications of 13C NMR
 Diethyl ether
Diethyl ether has two kind of carbon atoms labeled as 1and 2. Hence, this molecule gives
two signals in 13C NMR spectra.
2 1 1 2
CH3CH2OCH2CH3

1,3-Dicholropropane
The 1,3-dichloropropane has two types of carbon atoms labeled as 1and 2. Hence this
molecule gives two signals in 13C NMR spectra.
1 2 1
ClCH2CH2CH2Cl

1-Chloro-4-methylbenzene
The 1-chloro-4-methylbenzene molecule has five types of carbon atoms labeled as 1-5.
Hence this molecule gives five signals in 13C NMR spectra.

4 3

2 1
Cl CH3
5

4 3

Butan-2-ol
The butan-2-ol molecule has four types of carbon atoms labeled as 1-4. Hence this
molecule gives four signals in 13C NMR spectra.
1 2 3 4
CH3CHCH2CH3

OH

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 4. Factor affecting 13C NMR chemical shifts

Some of the important factors that affect 13C NMR are discussed.

(a) α-, - and γ-Substituent Effects

13
The chemical shifts for C NMR spectra are affected by the presence and absence of
substituents at α-, - and γ-positions. The α-substituents results from the replacement of a
directly bonded H by an X group:
C-H → C-X
The -substituents results from the replacement of a H on an adjacent atom by an X group:
C-C-H → C-C-X
The -substituents results from the replacement of a H on an adjacent to adjacent atom by
an X group:
C-C-C-H → C-C-C-X
The chemical shift increases on going from primary to secondary to tertiary to quaternary
carbon atoms. The average increase per carbon atom lies in the range of 7-10 ppm. The
substituents at - and -position increases the  value. In other words, the 13C absorption
position is shifted downfield. The case with -subsitution is opposite. In this case, the 13C
absorption position is shifted upfield i.e. the  value is decreased.
Based on the observations, a formula for calculating 13C shifts is given as:
C = -2.5 + 9.1n + 9.4n - 2.5n + 0.3n
where, C is chemical shift for carbon with reference to TMS.
n is number of carbon atoms one bond away
n is number of carbon atoms two bond away
n is number of carbon atoms three bond away
n is number of carbon atoms four bond away from the carbon atom whose chemical shift
is calculated.

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 There is very good agreement has been observed between the calculated and observed
value.

The other important factor influencing the substituent effects is the electronegativity of the
attached atom. The attachment of electronegative atom shifts the  value towards higher
side.
13
For example, in the C NMR spectrum of ethanol (Figure 10), the signal for CH3 is
observed at higher  value in comparison to the CH2. This is due to the attachment of CH2
group with electron withdrawing group –OH.

(b) Hybridization Effect

The hybrid state of carbon also affects the chemical shift of carbon. The details of
this effect are discussed in correlation data section.

(c) Three-Membered Rings

The three-membered ring has significant effect on the chemical shifts in 13C NMR
spectra. The compounds such as cyclopropanes, cyclopropenes, epoxides, aziridines and
other 3-membered rings tend to show pronounced upfield shifts i.e. shift towards lower -
values.
For example, the C-2 carbon of propane is observed at 16 ppm in 13C NMR spectra whereas
the carbon in cyclopropane is observed at -3 ppm (Figure 11). Similar trend has also been
observed for propene and dimethyl ether with respect to their cyclic counterpart carbon
(Figure 11).

(d) Conjugation to carbonyl group

The conjugation to carbonyl carbon also affects the chemical shift. The conjugation
may be due to a double bond or aromatic ring. This causes upfield shifts i.e. towards lower

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
  value about 6-10 ppm for all types of carbonyl compounds. The effect is smaller for
nitriles also.
For example, the carbonyl carbon of 2-butanone appears at 206 ppm whereas,
corresponding conjugated carbonyl carbon for but-3-ene-2-one appears at 197 ppm and
acetophenone at 195 ppm (Figure 12).

(e) Hydrogen Bonding Effects

13
The intramolecular hydrogen bonding causes substantial downfield shifts in C
NMR spectra i.e. towards higher  value. It has been observed that most carbon signals are
resistant to solvent effects but the carbonyl groups are an exception. The chemical shifts
for carbonyl carbon move to downfield in protic solvents. This may be attributed to
hydrogen bonding.

Figure 10. 13C NMR spectrum of ethanol

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 16
O

59
18
-3 3
O

41
13
Figure 11. C NMR showing ring effect

5. Coupling and Decoupling in 13C NMR

13C NMR of selected molecules

The examples of proton decoupled 13C NMR of few compounds is given below (Figure
13,14). The solvent and TMS peaks has not been shown.
O O O

C CH3 C CH2 C
H3C 206 C H3C 197 C H3C 195
H2 H

O O O O

220 210 210 199

Figure 12. 13C NMR chemical shifts of conjugated carbonyl carbon

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 Figure 13. 13C NMR (proton decoupled) of conjugated carbonyl carbon, crotonaldehyde

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR
 Figure 14. 13C NMR (proton decoupled) of cyclohexene

6. Summary

 Chemical shift range is normally 0 to 220 ppm

 For recording the spectra about 10-20 mg of sample dissolved in 0.5 - 2 ml of
deuterated solvent are required, and a good spectrum would be obtained in 64 -
6400 scans.
 The 13
C–NMR spectrum gives us the carbon backbone of a molecule with
following informations:
 The number of signals gives information about the number of equivalent carbons.
 The position of chemical shift gives information about the environment of carbon
atom.
 The integration of peak gives the ratios of equivalent carbons.
 The 13
C-NMR splitting suggests that the presence of NMR active nuclei in
neighbourhood.
 In the spectrum, the horizontal scale is shown as (ppm). is called the chemical
shift and is measured in parts per million - ppm.
 The zero is where you would find a peak due to the carbon-13 atoms in
tetramethylsilane - usually called TMS.
 Factors affecting 13C NMR chemical shifts are:
o α-, - and γ-Substituent Effects
o Hybridization effects
o Ring effects
o Conjugation to carbonyl group
o Hydrogen bond effect

CHEMISTRY PAPER No.12 :Organic Spectroscopy

MODULE No.22: Applications of 13C NMR