Chapter 14 Lecture Notes

For a detailed discussion of NMR spectroscopy, go to this link.

Proton NMR Spectra

In nuclear magnetic resonance spectroscopy (or spectrometry), nuclei that interact with
an external magnetic field are detected based on the frequency of radio waves that they
absorb. The property that allows a nucleus to interact with an external magnetic field is
nuclear spin. For both protons (1H) and carbon-13 (13C), spins are either + or -1/2
(arbitrarily ↑ or ↓ ). In the presence of an external magnetic field, spin aligned with the
direction of the field is low energy and spin opposed is higher in energy. The ΔE
between the two spin states allows the nucleus to absorb radio energy of a certain
frequency:

The radio frequency absorbed by the nucleus is represented as a chemical shift.

Chemical Shift
The position of a peak in NMR spectroscopy is called the chemical shift. What
“shift” are we talking about? Well, it’s relative to a zero reference, usually
tetramethylsilane (TMS), (CH3)4Si. Since TMS is a zero reference, we arbitrarily set its
chemical shift position to 0 ppm. The typical proton NMR spectral range is between 0 to
20 ppm or δ (delta). Chemical shift values determine the nature of the electronic
environment associate with an attached proton; the more electronegative the
environment, the bigger the chemical shift. As an example, here is the 1H-NMR
spectrum of acetic acid, CH3CO2H:
H attached to C(sp3)-(C=O)R has a chemical shift range of 2.1-2.7 ppm, but H attached to
O-(C=O)R has a chemical shift range of 10-12 ppm because of the higher
electronegativity of O vs. C. Increased partial positive charge on the atom to which the
proton is attached also causes the chemical shift to increase (go downfield or to the left).
In the case of TMS, the C-Si bond gives each carbon a partial negative charge, which
causes a decrease in chemical shift (upfield shift, to the right) for the protons, that is,
compared to most protons you would normally encounter. Since the peak for TMS is so
far upfield, we just call its position zero.

Below in Table 1 are typical chemical shifts in proton NMR spectroscopy. Note
that there are other factors that lead to higher chemical shifts. One of these is circulating
pi electrons in benzene (deshielding, chemical shifts move to higher values). You will
not be required to memorize this NMR chemical shift chart, but you will need to
understand how to use it to solve problems figuring out molecular structure using NMR
spectra. The first column shows the proton (the bold H) attached to its functional group.
R represent sp3-hybridized carbon and Ar represents aryl, which for now means a
benzene ring. Unless specified, a carbon shown in the table can have 1, 2, or 3
hydrogens attached to it. The chemical shift range for the proton is shown on the second
column.
Table 1. Approximate Chemical Shift Values in 1H-NMR Spectroscopy

Structure Chemical Shift Range

(ppm)
H-C-R 0.9 - 1.5
H-C-C=C 1.6 - 2.1
H-C-C≡C 1.7 - 2.8
H-C-(C=O)OR (or H) 2.0 - 2.5
H-C-(C=O)NR2(or H) 2.0 - 2.4
H-C-SR 2.1 - 3.0
H-C-(C=O)R(or H) 2.1 - 2.7
H-C-C≡N 2.1 - 2.9
H-C-Ar 2.2 - 2.9
H-C-NR2 2.2 - 2.9
H-C≡C-R 2-3
H-C-Br 2.7 - 4.1
H-C-NH(C=O)R 2.9 - 3.9
H-C-Cl 3.0 - 4.1
H-C-OH (or OR) 3.2 - 3.6
H-C-NH2 3.5 - 4.1
H-C-O(C=O)R 3.6 - 5.0
H-C-F 4.2 - 4.8
H-C=C 4.6 - 5.9
H-Ar 6.0 - 8.5
H-(C=O)R 9.4 - 10.0
H-O-(C=O)R 10 - 12
H-OR 0.5 - 4.5
H-N 0.5 - 6 (broad peak)
H-OAr 4.5 - 6.5

If you have multiple functional groups attached to a carbon with hydrogens, each
functional group will contribute to the chemical shift to a different extent. There are
programs that can calculate these additive chemical shifts.

Spin-Spin Splitting

OK, so now we can figure out if the proton is attached to a specific functional
group or to
multiple functional groups. But in order to put all the pieces of the molecule together
properly, we still need to know how the different pieces are put together. To figure this
out, we need to understand spin-spin splitting. Spin-spin splitting occurs when the
magnetic spins of different protons interact. Then a single (singlet) peak signal for a set
of protons gets split into several peaks because of the spin “disturbance” of the neighbors.
In most cases, a proton has to be within three bonds of a different proton to have spin-
spin splitting, but H on C≡C and H attached to a benzene ring can be within 4 bonds of a
different proton and produce measurable splitting. Note that a proton on a carbon could
have as many as three different sets of neighbors, A, B, and C. The equation for the # of
peaks caused by spin-spin splitting (split peaks) = (# of neighbor protons (different from
you) + 1)A x (# of neighbor protons (different from you) + 1)B x (# of neighbor protons
(different from you) + 1)C. If the neighbor protons are identical to each other because of
symmetry, it’s just # of neighbor protons (different from you) + 1.
Consider propanoic anhydride:

Each CH3 would “see” two neighboring protons (different from itself), so each CH3
would become 2+1 or three peaks, a triplet. The ratio of the areas of these peaks would
be 1:2:1. The CH2 next to CH3 would “see” three neighbors (different from itself) and
become 3 + 1 peaks, a quartet (area ratio: 1:3:3:1). In cases where there is only 1
neighbor proton, we get 1+1 = 2 peaks, a doublet (area ratio: 1:1). More than four split
peaks is called a multiplet.
Consider 2-propanol:

Both CH3s “see” CH, and so both become 1+1 peaks, a doublet. The methyls are
identical because of symmetry, so there is only one doublet corresponding to both
methyls. The CH “sees” two identical methyls, so it becomes 6 + 1 = 7 peaks, a
multiplet. Interestingly, the OH doesn’t affect the CH. OH and NH (in amines) don’t
cause spin-spin splitting. The OH doesn’t “see” the CH and would be 1 peak, a singlet.
So now we come to the complete spectrum, which includes the ratio of protons:
integration.
Integration

Below is the 1H-NMR spectrum for dipropyl ether, CH3CH2CH2OCH2CH2CH3:

The ratio of the areas under the peaks corresponds to the simplest whole number ratio of
different protons. A process called integration obtains this area ratio. Without the
integration, you have to guess how many protons are found at each chemical shift value,
which would be foolish. The results of the integration will be given to you in this lab.
As you can see in the NMR spectrum, they are 2:2:3 (left to right). But there are a total
of 10 hydrogens in the molecular formula. What happened? The 2:2:3 ratio is the
simplest whole number ratio of protons. Actually, the real ratio is 4:4:6 since, because of
symmetry, the two CH2’s next to O are identical to each other, the two CH2’s next to the
CH3’s are identical to each other, and the CH3’s are identical. Identical protons show up
at exactly the same chemical shift and just create a bigger (larger area) peak or set of split
peaks. Always look for symmetry when the integration doesn’t equal the actual number
of protons. The chemical shifts and spin-spin splitting also make sense:
for the two CH2’s next to O, δ3.4 (triplet, adjacent to CH2 ); for the middle two CH2’s
next to the CH3’s, δ1.6 (multiplet, adjacent to CH2 and CH3); for the CH3’s, δ0.9 (triplet,
adjacent to CH2 ).
Carbon-13 NMR Spectra
Just as 1H-NMR tells us about the hydrogens in a molecule, 13C-NMR gives information
about the carbons present. When analyzing a 13C-NMR spectrum, you will be primarily
concerned with number of peaks, chemical shift (where the peaks are), and peak
splitting (sometimes listed separately). Taken alone, a 13C-NMR spectrum rarely can
definitively identify a compound, but used along with 1H-NMR and IR you have
immense problem solving potential.

The resonances of 13C atoms in molecules are coupled to any hydrogens atoms that are
attached to them. There are two main types of 13C-NMR spectra: proton-decoupled and
off-resonance decoupled (or proton-coupled). The proton-decoupled spectra are
simplest. They show only the "un-split" signals. By counting up the number of signals in
a decoupled spectrum, you can quickly ascertain the number of different types of carbon
atoms in the molecule. When there is no symmetry in the molecule, the number of
signals should equal the number of carbons in the molecular formula. If the number of
signals is less than the number of carbons in the molecular formula, then some symmetry
exists in the molecule. The area or “size” of the signal peaks has very little relation to the
number of related carbons; therefore integration of peak areas is not usually used in 13C-
NMR.

In a proton-coupled spectrum each signal will be split into n+1 peaks, where n is the
number of hydrogens attached to the carbon, as shown in Figure 1. Sometimes you will
see a proton-coupled spectrum, but most of the time the splitting information will be
given as an inset, using the q-t-d-s coding. Contrary to 1H-NMR, in 13 C-NMR the
splitting gives information about substitution at the carbon itself, not on its neighbors.
As in 1H-NMR spectra, the position, or chemical shift, of a signal gives information about
the molecular environment of the carbon. The scale of a 13C-NMR spectrum is much
wider than that of a proton spectrum. Common shifts range from 0 to about 230 ppm.
The correlation table below shows some typical chemical shifts. The reference standard,
tetramethylsilane (TMS), used in carbon NMR gives a signal at 0 ppm. This is the same
standard used in proton NMR.

Typical Chemical Shift Ranges for 13C-NMR

1o alkane -CH3 10 - 30 ppm
2o alkane CH2 15 - 55
3o alkane CH 25 - 60
quaternary carbons (no hydrogens) 30 - 40
alcohols and ethers –C-O- 45 - 85
Alkynes -C≡C- 60 - 90
alkene and aromatic carbons –C≡C- 100 - 150
nitriles -C≡N 120 - 130
carbonyl of amides and imides 150 - 175
carbonyl of acids and esters 160 - 190
carbonyl of aldehyde or ketone 180 - 230

The presence of electron withdrawing groups will cause a resonance to shift downfield
(to the left, or toward higher chemical shift values). These effects are additive and, in
general, diminish with distance.