The interpretation of 13C NMR spectra does not form a part of Chemistry 350; hence, you may omit Section 13.7. Interested students may wish to read this section for enrichment purposes.
Butane shows two different peaks in the 13C NMR spectrum, below. Note that: the chemical shifts of these peaks are not very different from methane. The carbons in butane are in a similar environment to the one in methane.
- there are two distinct carbons in butane: the methyl, or CH3, carbon, and the methylene, or CH2, carbon.
- the methyl carbon absorbs slightly upfield, or at lower shift, around 10 ppm.
- the methylene carbon absorbs at slightly downfield, or at higher shift, around 20 ppm.
- other factors being equal, methylene carbons show up at slightly higher shift than methyl carbons.
Figure NMR2. Simulated 13C NMR spectrum of butane (showing only the upfield portion of the spectrum).
In the 13C NMR spectrum of pentane (below), you can see three different peaks, even though pentane just contains methyl carbons and methylene carbons like butane. As far as the NMR spectrometer is concerned, pentane contains three different kinds of carbon, in three different environments. That result comes from symmetry.
Figure NMR3.13C NMR spectrum of pentane. Source: SDBSWeb : http://riodb01.ibase.aist.go.jp/sdbs/ (National Institute of Advanced Industrial Science and Technology of Japan, 15 August 2008)
Symmetry is an important factor in spectroscopy. Nature says:
- atoms that are symmetry-inequivalent can absorb at different shifts.
- atoms that are symmetry-equivalent must absorb at the same shift.
To learn about symmetry, take a model of pentane and do the following:
- make sure the model is twisted into the most symmetric shape possible: a nice "W".
- choose one of the methyl carbons to focus on.
- rotate the model 180 degrees so that you are looking at the same "W" but from the other side.
- note that the methyl you were focusing on has simply switched places with the other methyl group. These two carbons are symmetry-equivalent via two-fold rotation.
Animation NMR1. A three-dimensional model of pentane. Grab the model with the mouse and rotate it so that you are convinced that the second and fourth carbons are symmetry-equivalent, but the third carbon is not.
By the same process, you can see that the second and fourth carbons along the chain are also symmetry-equivalent. However, the middle carbon is not; it never switches places with the other carbons if you rotate the model. There are three different sets of inequivalent carbons; these three groups are not the same as each other according to symmetry.
Determine how many inequivalent carbons there are in each of the following compounds. How many peaks do you expect in each 13C NMR spectrum?
Practically speaking, there is only so much room in the spectrum from one end to the other. At some point, peaks can get so crowded together that you can't distinguish one from another. You might expect to see ten different peaks in eicosane, a twenty-carbon alkane chain, but when you look at the spectrum you can only see seven different peaks. That may be frustrating, because the experiment does not seem to agree with your expectation. However, you will be using a number of methods together to minimize the problem of misleading data.
This is a simple example of a C-13 NMR spectrum. Don't worry about the scale for now - we'll look at that in a minute.
Note: The NMR spectra on this page have been produced from graphs taken from the Spectral Data Base System for Organic Compounds (SDBS) at the National Institute of Materials and Chemical Research in Japan.
There are two peaks because there are two different environments for the carbons. The carbon in the CH3 group is attached to 3 hydrogens and a carbon. The carbon in the CH2 group is attached to 2 hydrogens, a carbon and an oxygen. The two lines are in different places in the NMR spectrum because they need different external magnetic fields to bring them in to resonance at a particular radio frequency.
The C-13 NMR spectrum for a more complicated compound
This is the C-13 NMR spectrum for 1-methylethyl propanoate (also known as isopropyl propanoate or isopropyl propionate).
This time there are 5 lines in the spectrum. That means that there must be 5 different environments for the carbon atoms in the compound. Is that reasonable from the structure?
Well - if you count the carbon atoms, there are 6 of them. So why only 5 lines? In this case, two of the carbons are in exactly the same environment. They are attached to exactly the same things. Look at the two CH3 groups on the right-hand side of the molecule.
You might reasonably ask why the carbon in the CH3 on the left is not also in the same environment. Just like the ones on the right, the carbon is attached to 3 hydrogens and another carbon. But the similarity is not exact - you have to chase the similarity along the rest of the molecule as well to be sure.
The carbon in the left-hand CH3 group is attached to a carbon atom which in turn is attached to a carbon with two oxygens on it - and so on down the molecule. That's not exactly the same environment as the carbons in the right-hand CH3 groups. They are attached to a carbon which is attached to a single oxygen - and so on down the molecule. We'll look at this spectrum again in detail on the next page - and look at some more similar examples as well. This all gets easier the more examples you look at.
For now, all you need to realize is that each line in a C-13 NMR spectrum recognizes a carbon atom in one particular environment in the compound. If two (or more) carbon atoms in a compound have exactly the same environment, they will be represented by a single line.
You might wonder why all this works, since only about 1% of carbon atoms are C-13. These are the only ones picked up by this form of NMR. If you had a single molecule of ethanol, then the chances are only about 1 in 50 of there being one C-13 atom in it, and only about 1 in 10,000 of both being C-13.
But you have got to remember that you will be working with a sample containing huge numbers of molecules. The instrument can pick up the magnetic effect of the C-13 nuclei in the carbon of the CH3 group and the carbon of the CH2 group even if they are in separate molecules. There's no need for them to be in the same one.