Carbon Nuclear Magnetic Resonance (13C-NMR) Spectroscopy

Nuclear Magnetic Resonance (NMR) Spectroscopy is not limited to the study of protons. Any
element with a nuclear spin (13C, 17O, 19F, 31P and many others) will give rise to an NMR signal.

Carbon-13 has a nuclear spin (I = ½) and makes up 1.1% of all naturally occurring carbon, a high
enough abundance along with modern technology to make carbon nuclear magnetic resonance
spectroscopy (13C-NMR) a useful technique. Since carbon is the element central to organic
chemistry, 13C-NMR plays an important role in determining the structure of unknown organic
molecules and the study of organic reactions and processes.

The idea and theory behind 13C-NMR is the same as with 1H-NMR, just a different nucleus, so
you really do not have to learn anything new to understand and interpret 13C-NMR's to help you
solve structures of unknown organic compounds.

In particular, the13C-NMR spectrum of an organic compound provides information

concerning:

 the # of different types of carbon atoms present in the molecule

 the electronic environment of the different types of carbons
 the number of "neighbors" a carbon has (splitting)

The major differences that you will notice in 13C-NMR in comparison to 1H-NMR spectra
include:

 No integration of carbon spectra

 Wide range (0-200 ppm) of resonances for common carbon atoms (typical range for
protons 1-10 ppm)

Use the index on the left to choose which topic you want to go.
If you are pretty good at interpreting 13C-NMR, you may want to go straight to the exercises. If
not, maybe you could visit the tutorial pages and take the included quizzes.

Number of Different Carbons

4-Methyl-2-pentanone contains 6 carbons and some of them are different from each other.

For example, the carbon labeled A is attached to a carbonyl group and no other
carbons. Carbon B is the carbon of a ketone carbonyl group. Carbon C is a carbon
attached to both a carbonyl carbon and a methine (-CH-) carbon. Carbon D is attached
to three other sp3 carbons. The carbons labeled E are both attached to carbon D.
Just like in 1H-NMR, every chemically distinct carbon or group of carbons
will give a unique resonance in the NMR spectra. You may want to use To start animation, right-
the model to the right to help you figure out which carbons are the same or click on the above
different. As mentioned, since common carbons resonate over such a wide molecular model and select
range (0-200 ppm) as compared to protons, it is unlikely that two carbons Animation, Start.
will resonante exactly at the same place (which is not very true of Highlight the carbon
protons). Therefore, one can tell how many different carbons or groups of labeled A
identical carbons exist in a molecule simply by counting the number of Highlight the carbon
resonances in the 13C NMR spectra. labeled B
Highlight the carbon
labeled C
Highlight the carbon
labeled D
Highlight the carbon
labeled E

Chemical Shift

Chemically different carbons in an organic molecule do not experiencethe same magnetic field.
Just like protons, electrons shield the nucleusthereby reducing the effective magnetic field and
requiring energy of alower frequency to cause resonance. On the other hand, when electrons
arewithdrawn from a nucleus, the nucleus is deshielded and feels a strongermagnetic field
requiring more energy (higher frequency) to cause resonance.Thus, NMR provides information
about a carbon’s electronic environment.

Generally, carbons attached to electron withdrawing groups tend to resonateat higher frequencies
(more downfield (to the left) from TMS, tetramethylsilane,a common NMR standard). The
position of where a particular carbon atomresonates relative to TMS is called its chemical shift.
Again, since carbonatoms resonate over such a wide range, learning some common chemical
shiftswill provide you with a tremendous advantage at solving structural problemsusing NMR.

For example carbonyl carbons resonate furthest downfield (typically160-200 ppm), aromatic
carbons (115-145 ppm) and saturated aliphatic carbons(5-40 ppm).

Click here to see a list of chemicalshifts of some typical carbon atoms.

Typical Chemical Shifts in Carbon NMR Spectra

Structure Chemical Shift (ppm)

Carbonyl (ketone) 205-220
Carbonyl (aldehyde) 190-200
Carbonyl (ester, acid) 170-185
Aromatic 125-150
Alkenes 115-140
Alkynes 67-85
 RCH2OH 50-65
RCH2Cl 40-45
RCH2NH2 37-45
R3CH 25-35
CH3CO- 20-30
R2CH2 16-25
RCH3 10-15

Splitting

Carbons couple with the hydrogen atoms that are directly attached to them.

Thus, a methyl group (-CH3) appears as a quartet in the 13C-NMR spectra.

A methylene group with two attached hydrogens appears as a triplet, a methine group (-CH)
appears as a doublet, and a quaternary carbon, with no hydrogens attached, appears as a singlet.

Carbon-13 will also couple with another directly bonded carbon-13 atom but the odds of this are
very low (.01%) in naturally occurring samples and this generally is not seen. With this coupling
to bound hydrogens, a 13C-NMR spectra can appear as a real jungle of lines.

To improve the spectra allowing easy counting of the number of carbons, the protons are often
"decoupled" from the carbons by irradiating them at a frequency that excites them and interrupts
their normal coupling. In the absence of coupling from the protons, the carbon resonances
all appear as singlets and such a spectrum is said to be "Proton Decoupled".

Proton decoupled 13C-NMR is probably the most widely used technique because it clarifies the
13
C-NMR spectrum making it easier to determine the number of carbon atoms. The student
should be aware that the proton coupled experiment does exist and can provide useful
information on how many hydrogen atoms are bound to a particular carbon.