NMR Spectroscopy
13C NMR spectroscopy
Dr. Mohammed Fanokh Al-Jubouri
Nuclear Magnetic Resonance Spectroscopy
2 13C NMR
After hydrogen, the most useful atom providing information is carbon-13.
The overall intensity of a 13C signal is about 6400 times less than the
intensity of an 1H signal.
The chemical shift ranges over 220 ppm.
The reference compound is TMS.
Natural carbon contains about 1% of this isotope so the instruments for its
detection need to be sensitive and spectra will take longer to record.
Only the chemical shift is important as each spectrum gives only single lines
for each chemically equivalent carbon.
Carbon-13 nmr has wide applications in the study of natural products,
biological molecules and polymers.
Nuclear Magnetic Resonance Spectroscopy
3 13C NMR
a
d (˚2) higher δ than (˚1)
˚2
b c a˚1
b c
d
Nuclear Magnetic Resonance Spectroscopy
7 13C NMR
A score value depends on the type
˚1 a a
of C atom attached to the analysed
carbon atom. d ˚1
b
˚1 a c cb d
It can help to know which signal ˚3 2
matches with its respective shift. 3 4 ˚2
4
For example:
A score value of a is 3 because it
attaches to b (tertiary carbon ˚3)
A score value of b is 4 because it
attaches to (two primary carbon ˚1
for a) and a secondary carbon ˚2
for c….etc.
Nuclear Magnetic Resonance Spectroscopy
8 13C NMR
A score value depends on the type 3 4 5 3 2
a
of C atom attached to the analysed a b c d e
C. ˚3 ˚2 ˚2 ˚1
˚1
It can help to know which signal a c bd
matches with its respective shift. e
For example:
A score value of a is 3 because it
attaches to b (tertiary carbon ˚3)
A score value of b is 4 because it
attaches to (two primary carbon ˚1 Sometimes :
for a) and a secondary carbon ˚2 ˚1 > ˚2 > ˚3
Increase δ
for c….etc.
Nuclear Magnetic Resonance Spectroscopy
9 13C NMR
The C-13 NMR spectrum of pentane shows 3 signals with chemical shifts 14, 23,
and 34 ppm. Match the carbon atoms with their respective shifts.
a
˚2 ˚2 b
˚1
b
˚2 c b
˚1
a a
c
C atom Score value
a 2
b 3
c 4
Nuclear Magnetic Resonance Spectroscopy
10 13C NMR
The C-13 NMR spectrum of 3-methylpentane shows 4 signals with chemical shifts
11, 19, 29 and 36 ppm. Match the carbon atoms with their respective shifts.
a b b a b
˚2
˚3 c ˚2
˚1 ˚1
d a
˚1
c
C atom Score value d
a 2
b 4
c 5
d 3
Nuclear Magnetic Resonance Spectroscopy
11 13C NMR: Effect of electronegativity of attached atoms
Environment Chemical shift (ppm)
C - OH 50 - 65
C-N 35 - 65
C - Cl or C - Br 30 - 70
EN
63 3.44
42 3.04
45 3.16
2.96
34
7 2.66
(High δ ) C-O > C-N > C-Cl > C-Br > C-I (low δ)
Nuclear Magnetic Resonance Spectroscopy
12 13C NMR
Which carbon atom will have a higher chemical shift, a or b?
45
11 a
c Score value 26
3
bb
35 60
2 3
I II
When C atom is in the interior of a chain, it usually has a higher δ than an atom at the end
of a chain
CH3 in (II) is closest to Cl atom, so it will be deshielded (26 ppm)
CH3 in (I) is too far from Cl, so it will be shielded (11 ppm)
The score value of c (C atom next to a ) is 3 BUT Cl atom has the powerful EN effect on
a which makes appear at 45 ppm while c at 35 ppm.
So, we depended on the proximity to identify the signals.
Nuclear Magnetic Resonance Spectroscopy
13 13C NMR
Which carbon atom will have a higher chemical shift, a or b?
d c a
35
33
b
Score value 2 3 3 2
Carbon a will have a lower δ value than b although it attaches to Br atom because
of the EN value of Br is less than of Cl atom
NOTE: we have to be aware when we deal with any alkyl halide, and notice if we
have a powerful halogen like Cl, the proximity effect will dominate.
While, if we have Br atom in the compound, the score value will dominate.
Nuclear Magnetic Resonance Spectroscopy
14 13C NMR
Which carbon atom will have a higher chemical shift, a or b?
b a
Score value 3 3
Both a and b have the same score value, BUT b will be higher δ than a because of the EN
values of (C = 2.55) and (I = 2.66), so I will not affect too much on C atom.
14 7
Iodine has the effect to lower the δ value for the attached carbon.
Nuclear Magnetic Resonance Spectroscopy
15 13C NMR: (C-O)
58 a b 63
˚1 ˚2
1 2
69 ˚3 d ˚3
c ˚2 82
˚1 3 6
71
˚2 ˚2
e f
˚3 ˚2
73
˚1 ˚1 ˚1
4 5 Score value
Chemical shift
Chemical shift (C-O) = (50-100) ppm
Nuclear Magnetic Resonance Spectroscopy
16 13C NMR: (C-O)
The C-13 NMR spectrum is shown below for a compound with a molecular formula
C6H14O, propose a structure for the molecule.
1. Look at the possible functional C6H14O
groups locations.
2. (C-O) alcohol or ether (50-100) ppm
3. It can not be an ester because it
should has two oxygen atoms
4. It can not be an aldehyde or ketone
because there is no a significant
signal at (150-200) ppm.
5. It is impossible to have a (C=C) or a
ring because they appear at (100-
150) ppm.
Nuclear Magnetic Resonance Spectroscopy
17 13C NMR: (C-O)
The C-13 NMR spectrum is shown below for a compound with a molecular formula
C6H14O, propose a structure for the molecule.
Calculate index of hydrogen C6H14O
deficiency (IHD).
2 𝑛 +2 − #𝐻
𝐼𝐷𝐻 =
2
2 6 +2 − 14
𝐼𝐷𝐻 =
2
𝐼𝐷𝐻 =0
IDH = 0 means NO (=), (≡), or ring
IDH = 1 means (=), or ring
IDH = 2 means (≡)
Nuclear Magnetic Resonance Spectroscopy
18 13C NMR: (C-O)
The C-13 NMR spectrum is shown below for a compound with a molecular formula
C6H14O, propose a structure for the molecule.
In alcohols, only one signal will appear C6H14O
between (50-100) ppm, while in ethers
we will find two.
So, we have an ether.
Now, focus on the number of signals,
as we have six carbon atoms and four
signals, that means we have an
equivalent atoms which give one signal.
Nuclear Magnetic Resonance Spectroscopy
19 13C NMR: C6H14O
X 6
X 6
X 2 5
X
√ 4 Number of signals
Nuclear Magnetic Resonance Spectroscopy
20 13C NMR: (C-O)
The C-13 NMR spectrum is shown below for a compound with a molecular formula
C6H14O, propose a structure for the molecule.
Equivalent atoms give a one high peak, a a
C6H14O
so a appears at 23 ppm, d will be the a
b
lower δ (16 ppm) according to the d c
score values. a
Both b and c are attached to O, and Atom Score value
that gives the possibilities to find a 3
c d
b 5
absorbance between 50 and 100 ppm.
c 4 b
According to the score values, b is d 2
the highest δ (74 ppm) than c (55
ppm).
Nuclear Magnetic Resonance Spectroscopy
21 13C NMR: (C≡C) (50-100) ppm
(70-100) ppm
b a a b
Two signals
3 75 75 3
Normally, all methyl groups appear at (10-20)ppm, BUT the (≡) has a strong
effect on the δ values of C atoms attached (alpha carbon).
It reduces δ of methyl group to 3 ppm.
Nuclear Magnetic Resonance Spectroscopy
22 13C NMR: (C≡C) (50-100) ppm
(70-100) ppm
Calculate the score value.
d d
We can differentiate between b and c by c e e
3
the score values, where c is higher in δ b
a 4 2
value (4) than b (3). 3
2
Both a and d are attached to the (≡C), c
BUT they have different score values, a b a
(2) and d (3).
According to the score values, d should be
higher in δ value than e, BUT because of
the closeness of d to (≡C), the triple bond
will decrease the chemical shift of d to be
13 ppm. While e will appear at 14 ppm.
Nuclear Magnetic Resonance Spectroscopy
23 13C NMR: (C≡C) (50-100) ppm
(70-100) ppm c e
Determine the number of signals f
b d
Compare between a and b by score value a
NOTE : chemical shifts (δ) of 2 3 4 4 3 2
internal alkynes are fairly close, Chemical shift 68 85 18 31 22 14
while they are not so close in d ec f
terminal alkynes, by this way, we a
can differentiate between terminal
and internal alkynes.
b
Calculate the score values for c, d, e, and f
Carbon c and d have the same score value,
BUT c will be lower in (δ) than d because it
is closer to the (≡C).
The two C-13 NMR spectra are shown below corresponded to different
constitutional isomers of C6H10, propose a structure for each spectrum.
24
I II
Calculate index of hydrogen deficiency (IHD).
2 6 +2 − 10
𝐼𝐷𝐻 =
2
𝐼𝐷𝐻 =2 That means we have either (≡) or 2(=)
Because the(C=C) appears at (100-150)ppm, it is impossible to have an alkene here
SO, we have an alkyne
The two C-13 NMR spectra are shown below corresponded to different
constitutional isomers of C6H10, propose a structure for each spectrum.
25
I II
1. Number of signals is 6 (no equivalent C) 1. Number of signals is 4 (equivalent C)
2. The last two signals are too close 2. The last two signals are not close
(INTERNAL) alkyne (TERMINAL) alkyne
The two C-13 NMR spectra are shown below corresponded to different
constitutional isomers of C6H10, propose a structure for each spectrum.
26
I
Six signals
Six signals Three signals
Five signals
27 The two C-13 NMR spectra are shown below corresponded to different
constitutional isomers of C6H10, propose a structure for each spectrum.
1. Carbon a will be the lowest δ value (3) e
d f
because it attaches to (≡C) directly. c e d f
b 4
2. According to the score value, c will a 3 2
4
appear at higher chemical shift (79 3
2 a
ppm) than b (75 ppm).
cb
3. Although d has a higher a score value
than e, it will appear at low δ value (21
ppm), while e (23 ppm) because of the
(≡) effect.
4. Carbon f is too far than (≡C), so it will
appear at normal δ value (14 ppm).
28 The two C-13 NMR spectra are shown below corresponded to different
constitutional isomers of C6H10, propose a structure for each spectrum.
II
Four signals
Five signals
Four signals
29 The two C-13 NMR spectra are shown below corresponded to different
constitutional isomers of C6H10, propose a structure for each spectrum.
1. Calculate the score values
d d
2. Carbon b will appear at (93) ppm, while
a b c d
a will appear at (67) ppm.
3. Carbon c will be lower in δ value than d
although it has high score value d
Atom Score value
because of the (≡) effect.
a 2
4. Also, we can detect d in the chart a
b 5
because it contain three equivalent c 5 c
b
d 4
carbons which give a big single signal.
Nuclear Magnetic Resonance Spectroscopy
30 13C NMR: (C=C) (100-150) ppm
d
c
b d
e
c b a
a e
Score value 2 3 4 3 2
Double bond does not have the same effect
of triple bond, that means it does not lower
the chemical shift value at (alpha carbon)
Nuclear Magnetic Resonance Spectroscopy
31 13C NMR: (C=C) (100-150) ppm
2 methyl-1-butane has five signals with chemical shifts 12, 22, 31, 109, and 148
ppm. Assign a chemical shift to each carbon atom.
Carbon a will have a lower chemical shift e
22
(109 ppm) than b (148 ppm) because it is
d
terminal b
a c
148 12
according the score values, we can detect 31
109
the other carbon atoms, c, d, and e
C atom Score value
c 4
d 2
e 3
Nuclear Magnetic Resonance Spectroscopy
32 13C NMR: (C=C) (100-150) ppm
The C-13 NMR spectrum for C8H10 is shown below, propose a structure for this
molecule.
Calculate index of hydrogen deficiency (IHD).
2 8 +2 − 10
𝐼𝐷𝐻 =
2
𝐼𝐷𝐻 =4
IDH value means that we have either 4(=) or a ring which they are appear at (100-
150)ppm.
So we need to propose some structures which may fit with our outcomes.
Nuclear Magnetic Resonance Spectroscopy
33 13C NMR: (C=C) (100-150) ppm
The C-13 NMR spectrum for C8H10 is shown below, propose a structure for this
molecule.
Four signals Three signals
Three signals
Five signals
Nuclear Magnetic Resonance Spectroscopy
34 13C NMR: (C=C) (100-150) ppm
The C-13 NMR spectrum for C8H10 is shown below, propose a structure for this
molecule. c
1. It is clearly to find a at (21) ppm c a
c
2. There is four signals that b
a b c
corresponds to c, and two for b. c
3. So c has to appear at (129) ppm, and
b at (135) ppm.
4. SO, height plays an important role b a
to determine benzene rings and its
substitutions.
5. NOTE: The more carbon atoms are
chemically equivalent will appear in a
taller peak than the other ones.
Nuclear Magnetic Resonance Spectroscopy
35 13C NMR: (C=O) (150-220) ppm
Chemical shifts (205-220) (190-205) (175-185) (165-175)
Chemical shifts (209) (203) (181) (170)
Chemical shifts (198) (192) (172) (167)
Nuclear Magnetic Resonance Spectroscopy
36 13C NMR: (C=O) (150-220) ppm
The C-13 NMR spectra for two constitutional isomers of C4H8O2 are shown below,
identify the functional groups corresponded for each spectrum.
I II
Calculate index of hydrogen deficiency (IHD).
2 4 +2 − 8
𝐼𝐷𝐻 = 𝐼𝐷𝐻 =1 means we have (=) bond or a ring
2
Both charts include a signal in the range (150-220) ppm, which indicates the existence of
(C=O). So we do not have an alkene or a ring.
Nuclear Magnetic Resonance Spectroscopy
37 13C NMR: (C=O) (150-220) ppm
The C-13 NMR spectra for two constitutional isomers of C4H8O2 are shown below,
identify the functional groups corresponded for each spectrum.
I II
(C=O) means: In esters, a signal should appear around 60 ppm,
A ketone (205-220) ppm that is clearly noticed in (II) only, which gives
An aldehyde (190-205) ppm an indication that (II) is an ester.
A carboxylic acid (175-185) ppm Compound (I) is a carboxylic acid as its
An ester (165-175) ppm spectrum does not include a signal at 60 ppm.
Nuclear Magnetic Resonance Spectroscopy
38 13C NMR: Proton coupled mode N+1 (splitting)
All the spectra that we have considered were based on (broadband decoupled mode), where
all the signals appeared as singlets.
Another mode we have to be familiar with is (proton coupled mode (N+1)), which shows
splitting not from adjacent hydrogens BUT from the hydrogens that directly attached to
the carbon atom that will split (+1).
Example: What type of splitting in the following compound?
Carbon a attached to 3H (n=3), so (n+1) = 4 (quartet)
Carbon b attached to 1H (n=1), so (n+1) = 2 (doublet) d
Carbon c attached to 2H (n=2), so (n+1) = 3 (triplet) a c
b
Carbon d attached to 3H (n=3), so (n+1) = 4 (quartet)
Nuclear Magnetic Resonance Spectroscopy
39 13C NMR: Proton coupled mode N+1 (splitting)
All the spectra that we have considered were based on (broadband decoupled mode), where
all the signals appeared as singlets.
Another mode we have to be familiar with is (proton coupled mode (N+1)), which shows
splitting not from adjacent hydrogens BUT from the hydrogens that directly attached to
the carbon atom that will split (+1).
Example: What type of splitting in the following compound?
a
c d
d
a c
b b
