215-216 HH W13 Notes - Dr.

Masato Koreeda Date: January 9, 2013

Topic: _NMR-III (C-13 NMR)_ page 1 of 2.
13
C NMR Spectroscopy
(1) 13C Isotope (I = 1/2; the same as 1H)
Natural abundance of 13C is only 1% [99% of carbon is 12C (I = 0)].
For example, for CH3CH2OH: A probability of finding 13C in the CH3 is 0.01 (1%) and
a probability of finding 13C in the CH2 is 0.01 (1%).
Thus, a probability of finding 13C in both the CH3 and CH2 at the same time is 0.001 (1% of 1%).
Therefore, the contribution of 13C-13C coupling in natural abundance 13C NMR may be ignored.
However, 13C found at any 1H-attached carbon exhibits spin-spin coupling with the 1H(s) (one-bond
coupling; 1J13C,1H). In order to avoid complications due to these 13C-1H couplings, 13C NMR spectra are
usually obtained by eliminating these couplings by irradiating the entire 1H NMR absorption range
(called decoupling). Consequently, all 13C NMR peaks are observed as singlets. This mode of
obtaining 13C NMR spectra is called a proton-decoupled (or broad-band decoupled) method.
(2) Proton-decoupled 13C NMR Spectra
As in the case of 1H NMR, 13C NMR spectra are obtained typically in CDCl3 with tetramethylsilane
(TMS) as internal reference, i.e., δ = 0 ppm for TMS methyl carbons. Most of the 13C NMR chemical
shift values fall in the range between 0 and 220 ppm. For representative 13C NMR chemical shifts, see
Table 11.2, p. 403 of Ege’s book.

aromatic C's
O D: I = 1
O on the basis of 2 I + 1,
H3C H becomes a triplet 1
i.e., J13C-D
6-chemically different C groups -O-CH3
CDCl3 TMS
H
C
O

191 165 114 78 56 0 ppm (δ)

132 130
(a) Unlike 1H NMR, the intensity of each of the 13C peaks is not proportional to the number of 13C
nuclei belonging to each peak.
(b) 13C NMR chemical shifts are predictable primarily based upon the electron density on each C.
H CH3
e.g., -CH2-CH3 10-15 ppm -O-CH2-CH3 | |
-O-C-CH3 -O-C-CH3
60-65 ppm | |
-O-CH3 55 ppm 75-80 ppm CH 90-100 ppm CH
3 3
(c) The chemical shifts of alkynic sp carbons are unusual as in the case of alkynic Hs in 1H NMR.
However, allenic sp carbons have expected chemical shifts (~ 200 ppm).
sp2
67-70 ppm sp cf.
H3C
R-C C-H C=C=CH2 72 ppm CH3
H3C CH3 143.7 ppm
H3C
74-85 ppm C C
93.4 ppm 207 ppm H3C C CH2
H2
R-C N 114.4 ppm
These are quite high-field shifted
117-125 ppm for sp2 carbons!
215-216 HH W13 Notes - Dr. Masato Koreeda Date: January 9, 2013
Topic: _NMR-III (C-13 NMR)_ page 2 of 2.

(d) Unlike 1H NMR, alkenic and aromatic carbons have similar chemical shifts (δ 110 – 140 ppm)
(i.e., no significant ring current effect observed in C-13 NMR).
(e) Chemical shifts of aromatic carbons: predictable on the basis of the resonance and inductive
effects of the substituents on the ring.

155.4 ppm! - due to the inductive

effect of the oxygen atom.

OH O O O O
H H H H

115.8 ppm

129.9 ppm increased p-electron

up-field shifted density due to the resonance
121.2 ppm from 128.5 ppm
effects caused by the OH.

(3) Proton-coupled 13C NMR Spectra

By irradiating slightly off the 1H NMR region, each of the 13C NMR peaks can be designed to exhibit
couplings with the 1H nuclei attached to the C, i.e., one-bond 13C-1H coupling(s).
Under such conditions: a CH3 (methyl) carbon appears as a quartet.
a CH2 (methylene) carbon appears as a triplet.
a CH (methine) carbon appears as a doublet.
a quaternary carbon appears as a singlet.

O aromatic C's Proton-decoupled

C-13 spectrum D: I = 1
O on the basis of 2 I + 1,
H3C H in CDCl3
becomes a triplet 1
i.e., J13C-D
6-chemically different C groups -O-CH3
CDCl3 TMS
H
C
O

191 165 114 78 56 0 ppm (δ)

132 130
Proton-coupled
C-13 spectrum
doublet in CDCl3
doublet
quartet CH3
doublet CH3 quartet
singlet singlet CDCl3 TMS [=Si(CH3)4]
H °
C °
O

191 165 132 114 H 78 56 0 ppm (δ)

130