13

C NMR
The
13
C NMR is generated in the same fundamental was as proton NMR spectrum.
Only 1.1 % of naturally occurring carbon is
13
C and actually an advantage because
of less coupling.
Requirement for NMR: Spin quantum # (I) ! 0 Meaning ! must be an odd number
and/or neutrons. Ex.
1
H,
2
H,
13
C,
19
F, etc(Thinkbook)
How do we find this? Look at the atomic number.
The
13
C NMR is directly about the carbon skeleton not just the proton attached to it.
a. The number of signals tell us how many different carbons or set of equivalent
carbons
b. The splitting of a signal tells us how many hydrogens are attached to each
carbon. (N+1 rule)
c. The chemical shift tells us the hybridization (sp
3
, sp
2
, sp) of each carbon.
d. Integration: Not useful for
13
C NMR
Proton coupled spectrum shows splitting of the carbon signal only by protons
attached to that carbon itself.
13
C_H coupling not
13
C_
13
C_H or not
13
C_
13
C_
13
C_H or not
12
C_
13
C
coupling occurs but very low No coupling
due to low abundance 1.1 %x1.11%
12
C I=0
(Thinkbook) (Thinkbook)
Thus, for each carbon the multiplicity of the signal depends upon how many protons
are attached to it.
Note: Due to low natural abundance,
13
C NMR spectra do not ordinarily show
carbon-carbon splitting two
13
C being next to other is 1.1 %x 1.1%=0.012 %
(because
12
C does not have a magnetic moment, it cannot split the signal of an
adjacent
13
C), and are thus enormously simplified. (Thinkbook)
Proton-Decoupled Spectrum shows no splitting at all; it consists of a set of single
peaks, one for each carbon or each set of equivalent carbons in a molecule. Even for
very complicated molecules, such a spectrum is amazingly simple (because
overlapping multiplets very difficult to interpret)-most commonly run spectrum for
structural analysis; and will list the multiplicity of the peaks in the upper left-hand
corner. (Bruice)
Chemical Shift in
13
C NMR spectrum arises in the same way as in the proton NMR
spectrum. Each carbon nucleus has its own electronic environment, different from
the environment of other, non-equivalent nuclei; it feels a different magnetic field,
and absorbs at different applied fields strength.
" Electronegative atoms and pi bonds cause downfield shifts (Thinkbook)
"
13
C chemical shift range 0-250 ppm (Thinkbook)
In
13
C NMR spectrum, the more electronegative group bonded to carbon atom !
deshielding increases. This table demonstrates this effect.
I Br Cl F
Electronegativity
(Pauling Scale)
2.5 2.8 3.0 4.0
Sp
3
hydrid
carbon
CH
3
I CH
3
Br CH
3
Cl CH
3
F
Chemical shift
(ppm)
9.6 25.6 49.9 71.6
How many signals are in the
13
C NMR spectrum?
CH
3
_CH
2
_CH
2
_CH
2
_CH
2
_CH
2
_CH=CH
2
14.1 22.9 32.1 29.3 29.1 34.1 139 114 ( sp
2
! larger chemical shift.)
Eight signals,
no equivalent carbons
29.1 15.6
CH
2
_CH
3

144.2
127.9
128.4
125.7
Equivalent carbons
On benzene ring (6 signals)
Note: there are two methyl groups and one corresponding
to CH
2
downfield (60.6 ppm) is attached to O cause
deshielded
Benzyl CH
2
(41.1 ppm) . Aromatic ring carbons have
resonance over range from 126 ppm to 135 ppm.
Determine the structure from this formula C
4
H
8
O
2
in 13 spectrum # 179.9 ppm (triplet)
51.5 ppm (quartet), 27.5 ppm (triplet) and 9.2 ppm (quartet) (Thinkbook PP#12)
179.9 ppm corresponding to ester or ketone carbonyl group; 51.5 ppm is downfield must
be close to carbonyl or oxygen (OCH3) ; 27.5 ppm (CH2) and 9.2 ppm (quartet) CH3
group further away from carbonyl group in upfield region.
These are three structures possibilities:
O O O
_ _ _
CH
3
COCH
2
CH
3
CH
3
CH
2
COCH
3
CH
3
CCH
2
OCH
3
Methyl propionate a b c d
Note: b. this C must downfield and
probably over 200 ppm.
O
e _ f g
CH
2
_C_O_CH2_CH3
_a
b b g. 14.2 ppm b.129 ppm
c c e. 41.4 ppm c. 127 ppm
d f. 60.6 ppm d. 126 pm
a. 135.ppm
Actual structure = Methyl Propionate (
13
C spectrum above)
CH
3
_CH
2
_CH
2
_CH
2
_C_CH
13.7 22.1 30.9 18.3 84.5 68.4
Six signals (no equivalent carbons)
CH
3
_CH
2
_CH
2
_CH
2
_CH
2
_CH
3
(note: there are six carbons but
13
C
a a b b c c NMR showed only 3 signals
a. 14.16ppm b. 31.87 ppm c. 22.89 ppm due to molecular symmetry)
Cyclohexane has one signal because all carbons on the ring are equivalent carbons
Note: Enantiomers and resonance contributors have identical spectra but diastereomers
spectra are NOT identical.
Typical 13C NMR Chemical Shift ranges
ppm Hybridzation Kinds of compounds
0-70 Sp
3
Alkane (CH3)
70-100 Sp
3
and sp C-O and C-N
100-160 Sp
2
Aromatic C and C=C
160-210 Sp
2
Aldehydes and ketone
carbonyl (C=0)
Splitting Pattern (N+1 rule): for each carbon the multiplicity of the signal depends upon
how many protons are attached to it.
Ex. H
_ _ _ _
_C_ H _C_ H _C_ H H_C_H
_ _ _ _
no proton one proton two protons three protons
singlet doublet triplet quartet
_
2D- NMR: Interaction of nuclear spins plotted in two dimensions.
Correlation Spectroscopy (COSY)
" Two axes correspond to the single isotope Thinkbook)
" The interaction indicates with Hs are coupled! gives better
understanding of structure. (Thinkbook)
Heteronuclear Multiple-Quantum Coherence (HMQC)
" 2 axes correspond to 2 different isotopes (usually
13
C and
1
H)
" Interaction indicates Hs coupling to nuclei other than H
Magnetic Resonance Imaging (MRI)
"
1
H NMR spectroscopy has been applied to diagnostic medicine.
" The relaxation times of hydrogen atoms in different environments (ex. brain vs.
bone)
" The rate of relaxation is related to the extent of binding of water to the surface of
biological molecules.
Note: These
13
C spectra obtained from National Institute of Advanced Science
and Technology (AIST) website:http://www.aist.go.jp/