13C NMR

• much lower signal to noise (6000 x less sensitive than 1H NMR)

-due to a combination of lower inherent sensitivity and also lower
abundance of 13C isotope (~1%).

Noise

• improve signal to noise by:

-more sample (higher concentration)
-more scans (shorter time between scans)
-increase line broadening (LB = 2 - 10)
Line Broadening (LB)
 !"#$!%&#'()*+,-&.,/&13
!"#&01'./2.,/&
C NMR !"#$!%&#'()*+,-&.,/
345'()*+,-
!"#$!%&#'()*+,-&.,/&!"#&01'./2.,/&
• usually broad band decoupled (C-H coupling
bridge
100-250 Hz) 345'()
-each carbon is a singlet
345'()*+,- -CH - -CH 2
bridgehead
3
-CH2- -CH3 -CH3
bridge
1H decoupled
O bridgehead
-CH2- -CH3
-CH2- -CH3 -CH3 O
O
1H!C 13C NMR, 1H (broadband) decoupled
coupling not observed;
abundance of 13C too low. 1H!C
coupling not observed; 13C N
H!C coupling not observed; abundance of 13C too low.
13C NMR, 1H (broadband) decoupled

13abundance of 13is
C!H coupling C observed,
too low.
no decoupling
and complicates spectrum. 13C!H coupling is observed,
3C!H coupling is observed, and complicates spectrum.
Solution: Decoupling pulse.
and complicates spectrum.
Solution: Decoupling pulse.
13C NMR
Solution: Decoupling pulse.

13C NMR
• cannot integrate normal broadband decoupled spectra!
-due to NOE, decoupling, and incomplete FID
 13C NMR
• much wider frequency range (200 ppm) versus 1H NMR (12 ppm)

• much more sensitive

to subtle differences in
local environment
(less overlap of peaks)

http://chemwiki.ucdavis.edu/Organic_Chemistry/Organic_Chemistry_With_a_Biological_Emphasis/Chapter__5%3A_Structure_Determination_II/Section_5.6%3A_13C-NMR_spectroscopy
usually see one singlet per chemically equivalent Carbon
(coincidental overlap is rare compared to 1H NMR)

75 MHz

150 MHz
13C NMR chemical shifts
• chemical shifts similar to 1H NMR (spread out over 200 ppm)
- also referenced to TMS
 examples

-Much less structural information in 13C NMR

• only chemical shift (no integration, no coupling)
http://chemwiki.ucdavis.edu/Organic_Chemistry/Organic_Chemistry_With_a_Biological_Emphasis/Chapter__5%3A_Structure_Determination_II/Section_5.6%3A_13C-NMR_spectroscopy
Heights of peaks does provide some information

•C’s with protons have enhanced signal (due to NOE)

-carbons without protons will be shorter
-also explains why deuterated solvent peak is small

•Why is CDCl3 peak a “triplet”?

DEPT (number of attached H’s)

DEPT 90°
CH only

DEPT 135°
CH, CH3 up
CH2 down

normal
13C NMR
 DEPT (number of attached H’s)

DEPT 90°
CH only

DEPT 135°
CH, CH3 up
CH2 down
4 2, (9, 1)
7 (8, 10)
5 3
6

normal
13C NMR
 What information can we get from NMR?
(from 1D studies- that we have discuss so far)
1) proton environments and spin systems
1I) carbon environment and #’s of attached protons

Other 1D experiments can tell us:

a) confirm that two protons are really coupled to each other
b) 3-D shape (what protons are close to each other in space)
c) presence and chemical environments of other heteroatoms
d) estimate of molecular size
e) measure enantiomeric excess