NUCLEAR MAGNETIC RESONANCE MENU

The sections on C-13 NMR and proton NMR are written so that they are entirely independent of each other. Obviously I have no way of telling whether you need one of these or both - and if both, what order you need to do them in. That means that you will find quite a lot of duplication in the "Background" pages for both techniques. If you have a choice, start with C-13 NMR. The spectra are a lot easier to interpret!

C-13 NMR Background to C-13 NMR. . . An explanation of how a C-13 NMR spectrum arises, and the meaning of the term "chemical shift". Interpreting C-13 NMR spectra . . . How a C-13 NMR spectrum gives you information about the structure of a molecule.

Proton NMR Background to proton NMR. . . An explanation of how a proton (1H) NMR spectrum arises, and the meaning of the term "chemical shift". Low resolution NMR spectra . . . How a low resolution NMR spectrum is used to identify where the hydrogen atoms in a molecule are. Read this before you go on to high resolution spectra. High resolution NMR spectra . . . Looks at the additional information which you can get from a high resolution NMR spectrum. Integrator traces . . . How to find the ratio of the numbers of differently placed hydrogen atoms from an integrator trace.

WHAT IS NUCLEAR MAGNETIC RESONANCE (NMR)?

This page describes what a proton NMR spectrum is and how it tells you useful things about the hydrogen atoms in organic molecules.

The background to NMR spectroscopy Nuclear magnetic resonance is concerned with the magnetic properties of certain nuclei. On this page we are focussing on the magnetic behaviour of hydrogen nuclei - hence the term proton NMR or 1HNMR. Hydrogen atoms as little magnets If you have a compass needle, it normally lines up with the Earth's magnetic field with the north-seeking end pointing north. Provided it isn't sealed in some sort of container, you could twist the needle around with your fingers so that it pointed south - lining it up opposed to the Earth's magnetic field. It is very unstable opposed to the Earth's field, and as soon as you let it go again, it will flip back to its more stable state.

Hydrogen nuclei also behave as little magnets and a hydrogen nucleus can also be aligned with an external magnetic field or opposed to it. Again, the alignment where it is opposed to the field is less stable (at a higher energy). It is possible to make it flip from the more stable alignment to the less stable one by supplying exactly the right amount of energy.

The energy needed to make this flip depends on the strength of the external magnetic field used, but is usually in the range of energies found in radio waves - at frequencies of about 60 - 100 MHz. (BBC Radio 4 is found between 92 - 95 MHz!) It's possible to detect this interaction between the radio waves of just the right frequency and the proton as it flips from one orientation to the other as a peak on a graph. This flipping of the proton from one magnetic alignment to the other by the radio waves is known as the resonance condition.

The importance of the hydrogen atom's environment What we've said so far would apply to an isolated proton, but real protons have other things around them - especially electrons. The effect of the electrons is to cut down the size of the external magnetic field felt by the hydrogen nucleus.

Suppose you were using a radio frequency of 90 MHz, and you adjusted the size of the magnetic field so that an isolated proton was in the resonance condition. If you replaced the isolated proton with one that was attached to something, it wouldn't be feeling the full effect of the external field any more and so would stop resonating (flipping from one magnetic alignment to the other). The resonance condition depends on having exactly the right combination of external magnetic field and radio frequency.

How would you bring it back into the resonance condition again? You would have to increase the external magnetic field slightly to compensate for the effect of the electrons. Now suppose that you attached the hydrogen to something more electronegative. The electrons in the bond would be further away from the hydrogen nucleus, and so would have less effect on the magnetic field around the hydrogen.

Note: Electronegativity is a measure of the ability of an atom to attract a bonding pair of electrons. If you aren't happy about electronegativity, you could follow this link at some point in the future, but it probably isn't worth doing it now!

The external magnetic field needed to bring the hydrogen into resonance will be smaller if it is attached to a more electronegative element, because the hydrogen nucleus feels more of the field. Even small differences in the electronegativities of the attached atom or groups of atoms will make a difference to the magnetic field needed to achieve resonance.

Summary For a given radio frequency (say, 90 MHz) each hydrogen atom will need a slightly different magnetic field applied to it to bring it into the resonance condition depending on what exactly it is attached to - in other words the magnetic field needed is a useful guide to the hydrogen atom's environment in the molecule.

Features of an NMR spectrum A simple NMR spectrum looks like this:

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. It is possible that small errors may have been introduced during the process of converting them for use on this site, but these won't affect the argument in any way.

The peaks There are two peaks because there are two different environments for the hydrogens - in the CH3 group and attached to the oxygen in the COOH group. They are in different places in the spectrum because they need slightly different external magnetic fields to bring them in to resonance at a particular radio frequency. The sizes of the two peaks gives important information about the numbers of hydrogen atoms in each environment. It isn't the height of the peaks that matters, but the ratio of the areas under the peaks. If you could measure the areas under the peaks in the diagram above, you would find that they were in the ratio of 3 (for the larger peak) to 1 (for the smaller one). That shows a ratio of 3:1 in the number of hydrogen atoms in the two environments - which is exactly what you would expect for CH3COOH.

The need for a standard for comparison - TMS Before we can explain what the horizontal scale means, we need to explain

the fact that it has a zero point - at the right-hand end of the scale. The zero is where you would find a peak due to the hydrogen atoms in tetramethylsilane - usually called TMS.Everything else is compared with this.

You will find that some NMR spectra show the peak due to TMS (at zero), and others leave it out. Essentially, if you have to analyse a spectrum which has a peak at zero, you can ignore it because that's the TMS peak. TMS is chosen as the standard for several reasons. The most important are:

It has 12 hydrogen atoms all of which are in exactly the same environment. They are joined to exactly the same things in exactly the same way. That produces a single peak, but it's also a strong peak (because there are lots of hydrogen atoms). The electrons in the C-H bonds are closer to the hydrogens in this compound than in almost any other one. That means that these hydrogen nuclei are the most shielded from the external magnetic field, and so you would have to increase the magnetic field by the greatest amount to bring the hydrogens back into resonance. The net effect of this is that TMS produces a peak on the spectrum at the extreme right-hand side. Almost everything else produces peaks to the left of it.

The chemical shift The horizontal scale is shown as (ppm). is measured in parts per million - ppm. is called the chemical shift and

A peak at a chemical shift of, say, 2.0 means that the hydrogen atoms which caused that peak need a magnetic field two millionths less than the field needed by TMS to produce resonance. A peak at a chemical shift of 2.0 is said to be downfield of TMS. The further to the left a peak is, the more downfield it is.

Solvents for NMR spectroscopy NMR spectra are usually measured using solutions of the substance being investigated. It is important that the solvent itself doesn't contain any simple

hydrogen atoms, because they would produce confusing peaks in the spectrum. There are two ways of avoiding this. You can use a solvent such as tetrachloromethane, CCl4, which doesn't contain any hydrogen, or you can use a solvent in which any ordinary hydrogen atoms are replaced by its isotope, deuterium - for example, CDCl3 instead of CHCl3. All the NMR spectra used on this site involve CDCl3 as the solvent. Deuterium atoms have sufficiently different magnetic properties from ordinary hydrogen that they don't produce peaks in the area of the spectrum that we are looking at. LOW RESOLUTION NMR SPECTRA

This page describes how you interpret simple low resolution nuclear magnetic resonance (NMR) spectra. It assumes that you have already read the background page on NMR so that you understand what an NMR spectrum looks like and the use of the term "chemical shift". Note: If you haven't read the background page on NMR, you really ought to do that before you go on.

The difference between high and low resolution spectra

Note: This high resolution nmr spectrum has been produced from a graph taken from the Spectral Data Base System for

Organic Compounds (SDBS) at the National Institute of Materials and Chemical Research in Japan. A low resolution spectrum looks much simpler because it can't distinguish between the individual peaks in the various groups of peaks.

Note: I haven't been able to find a reliable source of low resolution NMR spectra. The low resolution spectra on this page are my best guess at what the low resolution spectra would look like, based on the high resolution ones. The numbers against the peaks represent the relative areas under each peak. That information is extremely important in interpreting the spectra.

Interpreting a low resolution spectrum Using the total number of peaks Each peak represents a different environment for hydrogen atoms in the molecule. In the methyl propanoate spectrum above, there are three peaks because there are three different environments for the hydrogens. Remember that methyl propanoate is CH3CH2COOCH3. The hydrogens in the CH2 group are obviously in a different environment from those in the CH3 groups. The two CH3 groups aren't in the same environment either. One is attached to a CH2group, the other to an oxygen.

Using the areas under the peaks The ratio of the areas under the peaks tell you the ratio of the numbers of hydrogens in the various environments. In the methyl propanoate case, the areas were in the ratio of 3:2:3, which is exactly what you want for the two differently placed CH3 groups and the CH2 group. You will probably be told the relative areas under the peaks especially if you are only looking at low resolution spectra, but it is just possible that you might have to work them out. NMR spectrometers have a device which draws another line on the spectrum called an integrator trace (or integration trace). You can measure the relative areas from this trace. Note: You need to find out whether your examiners expect you to know how to interpret an integrator trace. Check your syllabus and, particularly, past papers to see whether they ask it. If you are doing a UK-based exam and haven't got copies of your syllabus and past papers, follow this link to find out how to get them.

If you do need to be able to interpret integrator traces, you can find out how by following this link. You can also find it from the NMR menu.

Using chemical shifts The position of the peaks tells you useful things about what groups the various hydrogen atoms are in. In any exam, you will be given a table of chemical shifts if you need them. The important shifts for the groups present in methyl propanoate are:

Notes: "R" represents an alkyl group (like methyl, ethyl, etc) which in this case may have other things substituted in it. The shifts are shown as ranges of values. The exact position varies depending on what else is near that particular group in

the molecule.

Showing these groups on the low resolution spectrum gives:

Some sample questions Example 1 An organic compound was known to be one of the following. Use its low resolution NMR spectrum to decide which it is.

Notice that there are three peaks showing three different environments for the hydrogens. That eliminates methyl ethanoate as a possibility because that would only give two peaks - due to the two differently situated CH3 group hydrogens. Does the ratio of the areas under the peaks help? Not in this case -

both the other compounds would have three peaks in the ratio of 1:2:3. Now you need to look at the chemical shifts:

Checking the positions of the various hydrogens in the two possible compounds against the chemical shift table gives you this pattern of shifts:

Comparing these with the actual spectrum means that the substance was propanoic acid, CH3CH2COOH.

Example 2 How would you use low resolution NMR to distinguish between the isomers propanone and propanal?

The propanone would only give one peak in its NMR spectrum because both CH3 groups are in an identical environment - both are attached to -COCH3. The propanal would give three peaks with the areas underneath in the ratio 3:2:1. You could refer to the chemical shift table above to decide where the peaks are likely to be found, but it isn't really necessary.

Example 3 How many peaks would there be in the low resolution NMR spectrum of the following compound, and what would be the ratio of the areas under the peaks?

All the CH3 groups are exactly equivalent so would only produce 1 peak. There would also be peaks for the hydrogens in the CH2group and the COOH group. There would be three peaks in total with areas in the ratio 9:2:1 HIGH RESOLUTION NMR SPECTRA

This page describes how you interpret simple high resolution nuclear magnetic resonance (NMR) spectra. It assumes that you have already read the background page on NMR so that you understand what an NMR spectrum looks like and the use of the term "chemical shift". It also assumes that you know how to interpret simple low resolution spectra. Note: If you haven't read the background page on NMR or the page on low resolution NMR, you really ought to read them before you go on.

The difference between high and low resolution spectra What a low resolution NMR spectrum tells you Remember:

The number of peaks tells you the number of different environments the hydrogen atoms are in. The ratio of the areas under the peaks tells you the ratio of the numbers of hydrogen atoms in each of these environments. The chemical shifts give you important information about the sort of environment the hydrogen atoms are in.

High resolution NMR spectra In a high resolution spectrum, you find that many of what looked like single peaks in the low resolution spectrum are split into clusters of peaks. For A'level purposes, you will only need to consider these possibilities: 1 peak 2 peaks in the cluster 3 peaks in the cluster 4 peaks in the cluster a singlet a doublet a triplet a quartet

You can get exactly the same information from a high resolution spectrum as from a low resolution one - you simply treat eachcluster of peaks as if it were a single one in a low resolution spectrum. But in addition, the amount of splitting of the peaks gives you important extra information.

Interpreting a high resolution spectrum The n+1 rule The amount of splitting tells you about the number of hydrogens attached to the carbon atom or atoms next door to the one you are currently interested in. The number of sub-peaks in a cluster is one more than the number

of hydrogens attached to the next door carbon(s). So - on the assumption that there is only one carbon atom with hydrogens on next door to the carbon we're interested in (usually true at A'level!): singlet doublet triplet quartet next door to carbon with no hydrogens attached next door to a CH group next door to a CH2 group next door to a CH3 group

Note: You probably won't need to know the origin of the n+1 rule, but if you are interested there is a page on the reasons for splitting which you could look at. Using the n+1 rule What information can you get from this NMR spectrum?

Note: The nmr spectra on this page have been produced from data taken from the Spectral Data Base System for Organic Compounds (SDBS) at the National Institute of Materials and Chemical Research in Japan. Any small errors that I've introduced during the process of converting them for use on this site won't affect the argument in any way. Assume that you know that the compound above has the molecular formula C4H8O2. Treating this as a low resolution spectrum to start with, there are

three clusters of peaks and so three different environments for the hydrogens. The hydrogens in those three environments are in the ratio 2:3:3. Since there are 8 hydrogens altogether, this represents a CH2 group and two CH3 groups. What about the splitting? The CH2 group at about 4.1 ppm is a quartet. That tells you that it is next door to a carbon with three hydrogens attached - a CH3group. The CH3 group at about 1.3 ppm is a triplet. That must be next door to a CH2 group. This combination of these two clusters of peaks - one a quartet and the other a triplet - is typical of an ethyl group, CH3CH2. It is very common. Get to recognise it! Finally, the CH3 group at about 2.0 ppm is a singlet. That means that the carbon next door doesn't have any hydrogens attached. So what is this compound? You would also use chemical shift data to help to identify the environment each group was in, and eventually you would come up with:

Note: You now know how to get the information you need from NMR spectra, but it often isn't easy to fit all that information together into a final formula. You simply need to practise! Go through all the examples in past papers from your Exam Board. How complicated they are will vary markedly from Board to Board. Some of the compounds you will come across may be very unfamiliar. Don't forget to use the information in chemical shift tables - if your examiners include some obscure group, it's almost certain you will need to use it. Take all the hints that are going!

Two special cases Alcohols Where is the -O-H peak? This is very confusing! Different sources quote totally different chemical shifts for the hydrogen atom in the -OH group in alcohols - often inconsistently. For example:

The Nuffield Data Book quotes 2.0 - 4.0, but the Nuffield text book shows a peak at about 5.4. The OCR Data Sheet for use in their exams quotes 3.5 - 5.5. A reliable degree level organic chemistry text book quotes1.0 - 5.0, but then shows an NMR spectrum for ethanol with a peak at about 6.1. The SDBS database (used throughout this site) gives the OH peak in ethanol at about 2.6.

The problem seems to be that the position of the -OH peak varies dramatically depending on the conditions - for example, what solvent is used, the concentration, and the purity of the alcohol especially on whether or not it is totally dry. Help! Do you need to worry about this? Not really you can assume that in an exam question, any NMR spectrum will be consistent with the chemical shift data you are given. A clever way of picking out the -OH peak If you measure an NMR spectrum for an alcohol like ethanol, and then add a few drops of deuterium oxide, D2O, to the solution,

allow it to settle and then re-measure the spectrum, the -OH peak disappears! By comparing the two spectra, you can tell immediately which peak was due to the -OH group. Note: Deuterium oxide (sometimes called "heavy water") is simply water in which all the normal hydrogen-1 atoms are replaced by its isotope, hydrogen-2 (or deuterium). The reason for the loss of the peak lies in the interaction between the deuterium oxide and the alcohol. All alcohols, such as ethanol, are very, very slightly acidic. The hydrogen on the -OH group transfers to one of the lone pairs on the oxygen of the water molecule. The fact that here we've got "heavy water" makes no difference to that.

The negative ion formed is most likely to bump into a simple deuterium oxide molecule to regenerate the alcohol - except that now the -OH group has turned into an -OD group.

Deuterium atoms don't produce peaks in the same region of an NMR spectrum as ordinary hydrogen atoms, and so the peak disappears. You might wonder what happens to the positive ion in the first equation and the OD- in the second one. These get lost into the normal equilibrium which exists wherever you have water molecules - heavy or otherwise.

The lack of splitting with -OH groups Unless the alcohol is absolutely free of any water, the hydrogen on the -OH group and any hydrogens on the next door carbon don't interact to produce any splitting. The -OH peak is a singlet and you don't have to worry about its effect on the next door hydrogens.

The left-hand cluster of peaks is due to the CH2 group. It is a quartet because of the 3 hydrogens on the next door CH3 group. You can ignore the effect of the -OH hydrogen. Similarly, the -OH peak in the middle of the spectrum is a singlet. It hasn't turned into a triplet because of the influence of the CH2group. Note: The reason for this is quite complex, and certainly goes beyond A'level. It lies in the very rapid interchange that occurs between the hydrogen atoms on the -OH group and either water molecules or other alcohol molecules. To find out about it you will have to read either a degree level organic chemistry book or one specifically about NMR. For A'level purposes just accept the fact that -OH produces a singlet and has no effect on neighbouring groups!

Equivalent hydrogen atoms Hydrogen atoms attached to the same carbon atom are said to beequivalent. Equivalent hydrogen atoms have no effect on each other - so that one hydrogen atom in a CH2 group doesn't cause any splitting in the spectrum of the other one. But hydrogen atoms on neighbouring carbon atoms can also be equivalent if they are in exactly the same environment. For example:

These four hydrogens are all exactly equivalent. You would get a single peak with no splitting at all. You only have to change the molecule very slightly for this no longer to be true.

Because the molecule now contains different atoms at each end, the hydrogens are no longer all in the same environment. This compound would give two separate peaks on a low resolution NMR spectrum. The high resolution spectrum would show that both peaks subdivided into triplets - because each is next door to a differently placed CH2 group. NMR SPECTRA - THE INTEGRATOR TRACE

This page describes how you use an integrator trace (or integration trace) to find the ratio of the numbers of hydrogen atoms in different environments in an organic compound. Note: If you have come straight to this page via a search engine, it might pay you to explore the NMR menu before you go on. What an integrator trace looks like An integrator trace is a computer generated line which is superimposed on an NMR spectrum. In the diagram, the integrator trace is shown in red.

Note: This high resolution nmr spectrum has been produced from a graph taken from the Spectral Data Base System for Organic Compounds (SDBS) at the National Institute of Materials and Chemical Research in Japan. The integrator trace isn't a real one! I haven't been able to find a source of NMR spectra which include the trace, and so this is a simulation. That doesn't affect the argument in any way.

What an integrator trace shows An integrator trace measures the relative areas under the various peaks in the spectrum. When the integrator trace crosses a peak or group of peaks, it gains height. The height gained is proportional to the area under the peak or group of peaks. You measure the height gained at each peak or group of peaks by measuring the distances shown in green in the diagram above - and then find their ratio. For example, if the heights were 0.7 cm, 1.4 cm and 2.1 cm, the ratio of the peak areas would be 1:2:3. That in turn shows that the ratio of the hydrogen atoms in the three different environments is 1:2:3. Note: Where the integrator trace crosses a group of peaks, it gains height in a series of steps - one step for each of the sub-peaks. When you measure the height gained, you measure the total for that group of peaks, ignoring the individual steps.

WHAT IS C-13 NMR?

This page describes what a C-13 NMR spectrum is and how it tells you useful things about the carbon atoms in organic molecules.

The background to C-13 NMR spectroscopy Nuclear magnetic resonance is concerned with the magnetic properties of certain nuclei. On this page we are focussing on the magnetic behaviour of carbon-13 nuclei.

Carbon-13 nuclei as little magnets About 1% of all carbon atoms are the C-13 isotope; the rest (apart from tiny amounts of the radioactive C-14) is C-12. C-13 NMR relies on the magnetic properties of the C-13 nuclei. Carbon-13 nuclei fall into a class known as "spin " nuclei for reasons which don't really need to concern us at the introductory level this page is aimed at (UK A level and its equivalents). The effect of this is that a C-13 nucleus can behave as a little magnet. C-12 nuclei don't have this property. If you have a compass needle, it normally lines up with the Earth's magnetic field with the north-seeking end pointing north. Provided it isn't sealed in some sort of container, you could twist the needle around with your fingers so that it pointed south - lining it up opposed to the Earth's magnetic field. It is very unstable opposed to the Earth's field, and as soon as you let it go again, it will flip back to its more stable state.

Because a C-13 nucleus behaves like a little magnet, it means that it can also be aligned with an external magnetic field or opposed to it. Again, the alignment where it is opposed to the field is less stable (at a higher energy). It is possible to make it flip from the more stable alignment to the less stable one by supplying exactly the right amount of energy.

The energy needed to make this flip depends on the strength of the external magnetic field used, but is usually in the range of energies found in radio waves - at frequencies of about 25 - 100 MHz. (BBC Radio 4 is found between 92 - 95 MHz!) If you have also looked at proton-NMR, the frequency is about a quarter of that used to flip a hydrogen nucleus for a given magnetic field strength. It's possible to detect this interaction between the radio waves of just the right frequency and the carbon-13 nucleus as it flips from one orientation to the other as a peak on a graph. This flipping of the carbon-13 nucleus from one magnetic alignment to the other by the radio waves is known as the resonance condition.

The importance of the carbon's environment What we've said so far would apply to an isolated carbon-13 nucleus, but real carbon atoms in real bonds have other things around them - especially electrons. The effect of the electrons is to cut down the size of the external magnetic field felt by the carbon-13 nucleus.

Suppose you were using a radio frequency of 25 MHz, and you adjusted the size of the magnetic field so that an isolated carbon-13 atom was in the

resonance condition. If you replaced the isolated carbon with the more realistic case of it being surrounded by bonding electrons, it wouldn't be feeling the full effect of the external field any more and so would stop resonating (flipping from one magnetic alignment to the other). The resonance condition depends on having exactly the right combination of external magnetic field and radio frequency. How would you bring it back into the resonance condition again? You would have to increase the external magnetic field slightly to compensate for the shielding effect of the electrons. Now suppose that you attached the carbon to something more electronegative. The electrons in the bond would be further away from the carbon nucleus, and so would have less of a lowering effect on the magnetic field around the carbon nucleus.

Note: Electronegativity is a measure of the ability of an atom to attract a bonding pair of electrons. If you aren't happy about electronegativity, you could follow this link at some point in the future, but it probably isn't worth doing it now!

The external magnetic field needed to bring the carbon into resonance will be smaller if it is attached to a more electronegative element, because the C-13 nucleus feels more of the field. Even small differences in the electronegativities of the attached atoms will make a difference to the magnetic field needed to achieve resonance.

Summary For a given radio frequency (say, 25 MHz) each carbon-13 atom will need a slightly different magnetic field applied to it to bring it into the resonance condition depending on what exactly it is attached to - in other words the magnetic field needed is a useful guide to the carbon atom's environment in the molecule.

Features of a C-13 NMR spectrum The C-13 NMR spectrum for ethanol 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. It is possible that small errors may have been introduced during the process of converting them for use on this site, but these won't affect the argument in any way.

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 isn't 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 isn't 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 realise is that each line in a C-13 NMR spectrum recognises 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. Note: If you are fairly wide-awake, 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 CH2group even if they are in separate molecules. There's no need for them to be in the same one.

The need for a standard for comparison - TMS Before we can explain what the horizontal scale means, we need to explain the fact that it has a zero point - at the right-hand end of the scale. The zero is where you would find a peak due to the carbon-13 atoms in tetramethylsilane - usually called TMS.Everything else is compared with this.

You will find that some NMR spectra show the peak due to TMS (at zero), and others leave it out. Essentially, if you have to analyse a spectrum which has a peak at zero, you can ignore it because that's the TMS peak. TMS is chosen as the standard for several reasons. The most important are:

It has 4 carbon atoms all of which are in exactly the same environment. They are joined to exactly the same things in exactly the same way. That produces a single peak, but it's also a strong peak (because there are lots of carbon atoms all doing the same thing). The electrons in the C-Si bonds are closer to the carbons in this

compound than in almost any other one. That means that these carbon nuclei are the most shielded from the external magnetic field, and so you would have to increase the magnetic field by the greatest amount to bring the carbons back into resonance. The net effect of this is that TMS produces a peak on the spectrum at the extreme right-hand side. Almost everything else produces peaks to the left of it.

The chemical shift The horizontal scale is shown as (ppm). is measured in parts per million - ppm. is called the chemical shift and

A peak at a chemical shift of, say, 60 means that the carbon atoms which caused that peak need a magnetic field 60 millionths lessthan the field needed by TMS to produce resonance. A peak at a chemical shift of 60 is said to be downfield of TMS. The further to the left a peak is, the more downfield it is. Note: If you are familiar with proton-NMR, you will notice that the chemical shifts for C-13 NMR are much bigger than for proton-NMR. In C-13 NMR, they range up to about 200 ppm. In proton-NMR they only go up to about 12 ppm. You don't need to worry about the reasons for this at this level.

Solvents for NMR spectroscopy NMR spectra are usually measured using solutions of the substance being investigated. A commonly used solvent is CDCl3. This is a trichloromethane (chloroform) molecule in which the hydrogen has been replaced by its isotope, deuterium. CDCl3 is also commonly used as the solvent in proton-NMR because it doesn't have any ordinary hydrogen nuclei (protons) which would give a line in a proton-NMR spectrum. It does, of course, have a carbon atom - so why doesn't it give a potentially confusing line in a C-13 NMR spectrum? In fact it does give a line, but the line has an easily recognisable chemical shift and so can be removed from the final spectrum. All of the spectra from the SDBS have this line removed to avoid any confusion.

INTERPRETING C-13 NMR SPECTRA? This page takes an introductory look at how you can get useful information from a C-13 NMR spectrum. Important: If you have come straight to this page via a search engine, you should be aware that this is the second of two pages about C-13 NMR. Unless you are familiar with C-13 NMR, you should read the introduction to C-13 NMR first by following this link.

Taking a close look at three C-13 NMR spectra The C-13 NMR spectrum for ethanol

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. It is possible that small errors may have been introduced during the process of converting them for use on this site, but these won't affect the argument in any way.

Remember that each peak identifies a carbon atom in a different environment within the molecule. In this case 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.

So which peak is which? You might remember from the introductory page that the external magnetic field experienced by the carbon nuclei is affected by the electronegativity of the atoms attached to them. The effect of this is that the chemical shift of the carbon increases if you attach an atom like oxygen to it. That means that the peak at about 60 (the larger chemical shift) is due to the CH2 group because it has a more electronegative atom attached. Note: In principle, you should be able to work out the fact that the carbon attached to the oxygen will have the larger chemical shift. In practice, given the level I am aiming at (16 - 18 year old chemistry students), you always work from tables of chemical shift values for different groups (see below). What if you needed to work it out? The electronegative oxygen pulls electrons away from the carbon nucleus leaving it more exposed to any external magnetic field. That means that you will need a smaller external magnetic field to bring the nucleus into the resonance condition than if it was attached to less electronegative things. The smaller the magnetic field needed, the higher the chemical shift. All this is covered in more detail on the introduction to C-13 NMR page mentioned above.

A table of typical chemical shifts in C-13 NMR spectra carbon environment C=O (in ketones) C=O (in aldehydes) chemical shift (ppm) 205 - 220 190 - 200

C=O (in acids and esters) 170 - 185 C in aromatic rings C=C (in alkenes) RCH2OH RCH2Cl RCH2NH2 R3CH CH3CO125 - 150 115 - 140 50 - 65 40 - 45 37 - 45 25 - 35 20 - 30

R2CH2 RCH3

16 - 25 10 - 15

In the table, the "R" groups won't necessarily be simple alkyl groups. In each case there will be a carbon atom attached to the one shown in red, but there may well be other things substituted into the "R" group. If a substituent is very close to the carbon in question, and very electronegative, that might affect the values given in the table slightly. For example, ethanol has a peak at about 60 because of theCH2OH group. No problem! It also has a peak due to the RCH3 group. The "R" group this time is CH2OH. The electron pulling effect of the oxygen atom increases the chemical shift slightly from the one shown in the table to a value of about 18.

A simplification of the table At the time of writing, a draft UK syllabus (Cambridge pre-U) was expecting their students to learn the following simplification: carbon environment chemical shift (ppm) C-C C-O C=C C=O 0 - 50 50 - 100 100 - 150 150 - 200

This may, of course, change and other syllabuses might want something similar. The only way to find out is to check your syllabus, and recent question papers to see whether you are given tables of chemical shifts or not. Note: If you are following a UK-based syllabus, and haven't got a copies of your syllabus and past papers, follow this link to find out how to get hold of them.

The C-13 NMR spectrum for but-3-en-2-one

This is also known as 3-buten-2-one (amongst many other things!)

Here is the structure for the compound:

You can pick out all the peaks in this compound using the simplified table above. The peak at just under 200 is due to a carbon-oxygen double bond. The two peaks at 137 and 129 are due to the carbons at either end of the carboncarbon double bond. And the peak at 26 is the methyl group which, of course, is joined to the rest of the molecule by a carbon-carbon single bond. If you want to use the more accurate table, you have to put a bit more thought into it - and, in particular, worry about the values which don't always exactly match those in the table! The carbon-oxygen double bond in the peak for the ketone group has a slightly lower value than the table suggests for a ketone. There is an interaction between the carbon-oxygen and carbon-carbon double bonds in the molecule which affects the value slightly. This isn't something which we need to look at in detail for the purposes of this topic. You must be prepared to find small discrepancies of this sort in more complicated molecules - but don't worry about this for exam purposes at this level. Your examiners should give you shift values which exactly match the compound you are given. The two peaks for the carbons in the carbon-carbon double bond are exactly where they would be expected to be. Notice that they aren't in exactly the same environment, and so don't have the same shift values. The one closer to the carbon-oxygen double bond has the larger value. And the methyl group on the end has exactly the sort of value you would

expect for one attached to C=O. The table gives a range of 20 - 30, and that's where it is. One final important thing to notice. There are four carbons in the molecule and four peaks because they are all in different environments. But they aren't all the same height. In C-13 NMR, you can't draw any simple conclusions from the heights of the various peaks.

The C-13 NMR spectrum for 1-methylethyl propanoate 1-methylethyl propanoate is also known as isopropyl propanoate or isopropyl propionate.

Here is the structure for 1-methylethyl propanoate:

Two simple peaks There are two very simple peaks in the spectrum which could be identified easily from the second table above. The peak at 174 is due to a carbon in a carbon-oxygen double bond. (Looking at the more detailed table, this peak is due to the carbon in a carbon-oxygen double bond in an acid or ester.) The peak at 67 is due to a different carbon singly bonded to an oxygen. Those two peaks are therefore due to:

If you look back at the more detailed table of chemical shifts, you will find that a carbon singly bonded to an oxygen has a range of 50 - 65. 67 is, of course, a little bit higher than that. As before, you must expect these small differences. No table can account for all the fine differences in environment of a carbon in a molecule. Different tables will quote slightly different ranges. At this level, you can just ignore that problem! Before we go on to look at the other peaks, notice the heights of these two peaks we've been talking about. They are both due to a single carbon atom in the molecule, and yet they have different heights. Again, you can't read any reliable information directly from peak heights in these spectra.

The three right-hand peaks From the simplified table, all you can say is that these are due to carbons attached to other carbon atoms by single bonds. But because there are three peaks, the carbons must be in three different environments. The more detailed table is more helpful. Here are the structure and the spectrum again:

The easiest peak to sort out is the one at 28. If you look back at the table, that could well be a carbon attached to a carbon-oxygen double bond. The table quotes the group as CH3CO-, but replacing one of the hydrogens by a simple CH3 group won't make much difference to the shift value. The right-hand peak is also fairly easy. This is the left-hand methyl group in the molecule. It is attached to an admittedly complicated R group (the rest of the molecule). It is the bottom value given in the detailed table. The tall peak at 22 must be due to the two methyl groups at the right-hand end of the molecule - because that's all that's left. These combine to give a single peak because they are both in exactlythe same environment. If you are looking at the detailed table, you need to think very carefully which of the environments you should be looking at. Without thinking, it is tempting to go for the R2CH2 with peaks in the 16 - 25 region. But you would be wrong! The carbons we are interested in are the ones in the methyl group, not in the R groups. These carbons are again in the environment: RCH3. The R is the rest of the molecule. The table says that these should have peaks in the range 10 - 15, but our peak is a bit higher. This is because of the presence of the nearby oxygen atom. Its electronegativity is pulling electrons away from the methyl groups - and, as we've seen above, this tends to increase the chemical shift slightly. Once again, don't worry about the discrepancies. In an exam, perhaps your examiners will just want you to have learnt the simple table above - in which case, they can't expect you to work out which peak is which in a complicated spectrum of this sort. Or they will give you tables of chemical shifts - in which case, they will give you values which match the peaks in the spectra. Remember that you are only doing an introduction to C-13 NMR at this level. It isn't going to be that hard in an exam!

Working out structures from C-13 NMR spectra So far, we've just been trying to see the relationship between carbons in particular environments in a molecule and the spectrum produced. We've had all the information necessary. Now let's make it a little more difficult - but we'll work from much easier examples! In each example, try to work it out for yourself before you read the explanation.

Example 1 How could you tell from just a quick look at a C-13 NMR spectrum (and without worrying about chemical shifts) whether you had propanone or propanal (assuming those were the only options)?

Because these are isomers, each has the same number of carbon atoms, but there is a difference between the environments of the carbons which will make a big impact on the spectra. In propanone, the two carbons in the methyl groups are in exactly the same environment, and so will produce only a single peak. That means that the propanone spectrum will have only 2 peaks - one for the methyl groups and one for the carbon in the C=O group. However, in propanal, all the carbons are in completely different environments, and the spectrum will have three peaks.

Example 2 Thare are four alcohols with the molecular formula C4H10O.

Which one produced the C-13 NMR spectrum below?

You can do this perfectly well without referring to chemical shift tables at all. In the spectrum there are a total of three peaks - that means that there are only three different environments for the carbons, despite there being four carbon atoms. In A and B, there are four totally different environments. Both of these would produce four peaks. In D, there are only two different environments - all the methyl groups are exactly equivalent. D would only produce two peaks. That leaves C. Two of the methyl groups are in exactly the same environment - attached to the rest of the molecule in exactly the same way. They would only produce one peak. With the other two carbon atoms, that would make a total of three. The alcohol is C.

Example 3 This follows on from Example 2, and also involves an isomer of C4H10O but which isn't an alcohol. Its C-13 NMR spectrum is below. Work out what its structure is.

Because we don't know what sort of structure we are looking at, this time it would be a good idea to look at the shift values. The approximations are perfectly good, and we will work from this table: carbon environment chemical shift (ppm) C-C C-O C=C C=O 0 - 50 50 - 100 100 - 150 150 - 200

There is a peak for carbon(s) in a carbon-oxygen single bond and one for carbon(s) in a carbon-carbon single bond. That would be consistent with CC-O in the structure. It isn't an alcohol (you are told that in the question), and so there must be another carbon on the right-hand side of the oxygen in the structure in the last paragraph. The molecular formula is C4H10O, and there are only two peaks. The only solution to that is to have two identical ethyl groups either side of the oxygen. The compound is ethoxyethane (diethyl ether), CH3CH2OCH2CH3.

Example 4 Using the simplified table of chemical shifts above, work out the structure of the compound with the following C-13 NMR spectrum. Its molecular formula is C4H6O2.

Let's sort out what we've got.

There are four peaks and four carbons. No two carbons are in exactly the same environment. The peak at just over 50 must be a carbon attached to an oxygen by a single bond. The two peaks around 130 must be the two carbons at either end of a carbon-carbon double bond. The peak at just less than 170 is the carbon in a carbon-oxygen double bond.

Putting this together is a matter of playing around with the structures until you have come up with something reasonable. But you can't be sure that you have got the right structure using this simplified table. In this particular case, the spectrum was for the compound:

If you refer back to the more accurate table of chemical shifts towards the top of the page, you will get some better confirmation of this. The relatively low value of the carbon-oxygen double bond peak suggests an ester or acid rather than an aldehyde or ketone. It can't be an acid because there has to be a carbon attached to an oxygen by a single bond somewhere - apart from the one in the -COOH group. We've already accounted for that carbon atom from the peak at about 170. If it was an acid, you would already have used up both oxygens in the structure in the -COOH group. Without this information, though, you could probably come up with reasonable alternative structures. If you were working from the simplified table in an exam, your examiners would have to allow any valid alternatives.

Note: It is worth explaining again why I am using this simplified table of chemical shifts. This site is aimed primarily at students doing UKbased chemistry exams for 16 - 18 year olds. I know it is widely used beyond that, but I can't risk making life more difficult than it need be for my target audience by, for example, approaching C-13 NMR in the sort of detail needed by university students. At the time of writing, no current UK-based syllabuses even mentioned C-13 NMR, but two draft syllabuses for teaching from September 2008 do mention it. The one going into most detail is the Cambridge pre-U syllabus, and they use the simplified shift table. When things become clearer when the syllabus is finalised and specimen exam papers are produced, I may need to rewrite some of this page if it turns out that they (or AQA - the other syllabus mentioning it) are looking for something more sophisticated. I doubt that they will be though!