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NMR = Nuclear Magnetic Resonance
                                              Physical Principles:
Some (but not all) nuclei, such as 1H, 13C, 19F, 31P have nuclear spin.
A spinning charge creates a magnetic moment, so these nuclei can be
thought of as tiny magnets.
If we place these nuclei in a magnetic field, they can line up with or against
the field by spinning clockwise or counter clockwise.
                           N                                                        N

                           N           - sp in state,                                S        - spin state,
                                     favorab le,                                             unfav orable,
                                     low er energy                                           high er en erg y
                           S                                                         N

                           S                                                        S


A spin ning n ucleus w ith it's m agnetic field           A spin ning n ucleus w ith it's m agnetic field
align ed w ith the m agnetic field of a m ag net        aligned a gain st the m agnetic field of a m ag net

Alignment with the magnetic field (called ) is lower energy than against the
magnetic field (called ). How much lower it is depends on the strength of
the magnetic field
Note that for nuclei that don’t have spin, such as 12C, there is no difference
in energy between alignments in a magnetic field since they are not
magnets. As such, we can’t do NMR spectroscopy on 12C.
NMR: Basic Experimental Principles
Imagine placing a molecule, for example, CH4, in a magnetic field.
We can probe the energy difference of the - and - state of the protons by
irradiating them with EM radiation of just the right energy.
In a magnet of 7.05 Tesla, it takes EM radiation of about 300 MHz (radio
waves).
So, if we bombard the molecule with 300 MHz radio waves, the protons will
absorb that energy and we can measure that absorbance.
In a magnet of 11.75 Tesla, it takes EM radiation of about 500 MHz (stronger
magnet means greater energy difference between the - and - state of the
                                     at no magnetic field,
                                                                    proton spin state
protons)                             there is no difference beteen (higher energy)
                                                     - and   - states.
 Graphical relationship between
 magnetic field (B   o)   and frequency (   E                     E = h x 300 MHz       E = h x 500 MHz

     1
 for H NMR absorptions
                                                                                                      proton spin state
                                                                                                     (lower energy)

                                                0T                       7.05 T     11.75 T

                                                                         Bo

But there’s a problem. If two researchers want to compare their data using
magnets of different strengths, they have to adjust for that difference. That’s
a pain, so, data is instead reported using the “chemical shift” scale as
The Chemical Shift (Also Called ) Scale
Here’s how it works. We decide on a sample we’ll use to standardize our
instruments. We take an NMR of that standard and measure its absorbance
frequency. We then measure the frequency of our sample and subtract its
frequency from that of the standard. We then then divide by the frequency
of the standard. This gives a number called the “chemical shift,” also called
  , which does not depend on the magnetic field strength. Why not? Let’s
look at two examples.
Imagine that we have a magnet where our standard absorbs at 300,000,000
Hz (300 megahertz), and our sample absorbs at 300,000,300 Hz. The
difference is 300 Hz, so we take 300/300,000,000 = 1/1,000,000 and call
that 1 part per million (or 1 PPM). Now lets examine the same sample in a
stronger magnetic field where the reference comes at 500,000,000 Hz, or
500 megahertz. The frequency of our sample will increase proportionally,
and will come at 500,000,500 Hz. The difference is now 500 Hz, but we
divide by 500,000,000 (500/500,000,000 = 1/1,000,000, = 1 PPM).
It’s brilliant.
Of course, we don’t do any of this, it’s all done automatically by the NMR
machine.
Even more brilliant.
NMR
The Chemical Shift of Different Protons
NMR would not be very valuable if all protons absorbed at the same
frequency. You’d see a signal that indicates the presence of hydrogens in
your sample, but any fool knows there’s hydrogen in organic molecules.
What makes it useful is that different protons usually appear at different
chemical shifts ( . So, we can distinguish one kind of proton from another.
Why do different protons appear at different ? There are several reasons,
one of which is shielding. The electrons in a bond shield the nuclei from the
magnetic field. So, if there is more electron density around a proton, it sees
a slightly lower magnetic field, less electron density means it sees a higher
magnetic field:
                This represents the electron density of a C-H bond. How much electron
Z               density is on the proton depends on what else is attached to the carbon. If Z
    C   H       is an elelctronegative atom, the carbon becomes electron deficient and pulls
                some of the electron density away from the H. if Z is an electron donating
                group, more electron density ends up on the H.


How do the electrons shield the magnetic field? By moving. A moving
charge creates a magnetic field, and the field created by the moving
electrons opposes the magnetic field of our NMR machine. It’s not a huge
effect, but it’s enough to enable us to distinguish between different protons
in our sample.
The Hard Part - Interpreting Spectra
Learning how an NMR machine works is straightforward. What is less
straightforward is learning how to use the data we get from an NMR machine
(the spectrum of ethyl acetate is shown below). That’s because each NMR
spectrum is a puzzle, and there’s no single fact that you simply have to
memorize to solve these spectra. You have to consider lots of pieces of data
and come up with a structure that fits all the data. What kinds of data do we
get from NMR spectra? For 1H NMR, there are three kinds each of which we
will consider each of these separately:what kinds of protons we have.
      1) Chemical shift data - tells us
     2) Integrals - tells us the ratio of each kind of proton in our sample.
     3) 1H - 1H coupling - tells us about protons that are near other protons.
Chemical Shift Data
As previously mentioned, different kinds of protons typically come at different
chemical shifts. Shown below is a chart of where some common kinds of
protons appear in the scale. Note that most protons appear between 0 and
10 ppm. The reference, tetramethylsilane (TMS) appears at 0 ppm, and
aldehydes appear near 10 ppm. There is a page in your lab handout with
more precise values for this chart.
Note that these are typical values and that there are lots of exceptions!
                                                                                                      R

                                                                                                      NH
                                                                                                  R

                                                        OH



                          Ph                                                  R              H
                                                                                                                         Me
                          OH
                                                            (R)                                            TMS =   Me       Si Me
                                                             HO      C H3
                                                                                  P h C H3                               Me
                                          R   R
              R                                         O     R                              R
      O                                                                           N R2 O
                                                                       Cl
          H               H                                 OC H 3                C H3     C H3             C H3
                                          R   H                        C H3
                                                                                                                        TM S


 10               9   8        7      6           5           4               3              2                1              0
 Downfield region                                 ppm                                                     Upfield region
  of the spectrum                                                                                         of the spectrum
Integrals
Integrals tell us the ratio of each kind of proton. They are lines, the heights
of which are proportional to the intensity of the signal. Consider ethyl
acetate. There are three kinds of protons in this molecule, the CH3 next to
the carbonyl, the CH2 next to the O and the CH3 next to the CH2. The ratio of
the signals arising from each of these kinds of protons should be 3 to 2 to 3,
respectively. So, if we look at the height of the integrals they should be 3 to
2 to 3. With this information, we can know which is the CH2 signal (it’s the
smallest one), but to distinguish the other two, we have to be able to predict
their chemical shifts. The chart on the previous page allows us to make that
assignment (the CH3 next to the C=O should appear at ~ 2 PPM, while the
other CH3 should be at ~ 1 PPM).
                                                        3H'S
                                      O

                                  O       CH3                             O
              O

                  H                                            H 3C   O
          O   H
                                                3H'S




                      2 H'S
- 1H Coupling 1H

You’ll notice in the spectra that we’ve seen that the signals don’t appear as
single lines, sometimes they appear as multiple lines. This is due to 1H - 1H
coupling (also called spin-spin splitting or J-coupling). Here’s how it works:
Imagine we have a molecule which contains a proton (let’s call it HA)
attached to a carbon, and that this carbon is attached to another carbon
which also contains a proton (let’s call it HB). It turns out that HA feels the
presence of HB. Recall that these protons are tiny little magnets, that can be
oriented either with or against the magnetic field of the NMR machine. When
the field created by HB reinforces the magnetic field of the NMR machine (B0
) HA feels a slightly stronger field, but when the field created by HB opposes
B0, HA feels a slightly weaker field. So, we see two signals for HA depending
on the alignment of HB. The same is true for HB, it can feel either a slightly
stronger or weaker field due to HA’s presence. So, rather than see a single
line for each of these protons, we see two lines for each.
   For this line, H B is lined up                For this line, H B is lined up
     with the magnetic field                     aga inst the magnetic field
        ( adds to the overall                    (subtracts from the overall
    magnetic field, so the line                   magnetic field, so the line
   comes at higher frequency)                    comes at lower frequency)                                        HA   HB

                                                                                                                  C    C
                                          HA                                                HB
                      H A is split into two lines because              H B is split into two lines because
                      it feels the m agnetic field of H     B.         it feels the m agnetic field of H     A.
More 1H - 1H Coupling
What happens when there is more than one proton splitting a neighboring
proton? We get more lines. Consider the molecule below where we have
two protons on one carbon and one proton on another.



                             Note that the signal produced
                              by H A + H A' is twice the size
                                of that produced by H      B




                                                                                              HA   HB

                                                                                       HA '   C    C
                  H A + H A'                                          HB
  H A and H A' appear at the same                      H B is split into three lines
  chemical shift because they are                    because it feels the magnetic
      in identical environments                            field of H A and H A'
  They are also split into two lines
  (called a doublet) because they
    feel the magnetic field of H     B.
Why are There Three Lines for HB?

H        B feels the splitting of both HA and HA’. So, let’s imagine starting
with HB as a single line, then let’s “turn on” the coupling from HA and HA’ one
at a time:
              HB     If uncoupled, H       B would appear as a
                   singlet where the dashed line indicates
                         the chemic al shift of the sin glet.

                   Now, let's "turn on"        H B - H A coupling. This splits
                                 the single line into two lin es
                                                                                             HA   HB

                                 Now, let's "turn on"      H B - H A' coupling. This
                                                                                       HA'   C    C
                               splits each of the two new lines into two lines,
                                  but notice how the two lines in the middle
                                overlap. Overall, we then have three lines.




Because the two lines in the middle overlap, that line is twice as big as the
lines on the outside. More neighboring protons leads to more lines as shown
on the next slide.
Splitting Patterns with Multiple Neighboring
                                           Protons
If a proton has n neighboring protons that are equivalent, that proton will be
split into n+1 lines. So, if we have four equivalent neighbors, we will have
five lines, six equivalent neighbors… well, you can do the math. The lines
will not be of equal intensity, rather their intensity will be given by Pascal’s
triangle as shown below. intensities
              no. of neighbors   relative       pattern   example

                 0                  1                   singlet (s)


                                                                               H   H
                 1              1       1               doublet (d)
                                                                               C   C
                                                                                           H       H

                 2          1       2       1            triplet (t)                       C       C       H

                                                                               H   H

                 3         1    3 3             1       quartet (q)            C   C   H

                                                                                   H           H       H       H

                 4        1 4 6             4       1     pentet                               C       C       C   H

                                                                           H   H   H                           H


                 5       1 5 10 10 5 1                     sextet      H   C   C   C   H

                                                                                   H           H       H       H

                 6      1 6 15 20 15 6 1                   septet                          H   C       C       C   H

                                                                                               H               H




We keep emphasizing that this pattern only holds for when the neighboring
protons are equivalent. Why is that? The answer is two slides away.
More About Coupling
Earlier we said that protons couple to each other because they feel the
magnetic field of the neighboring protons. While this is true, the
mechanism by which they feel this field is complicated and is beyond the
scope of this class (they don’t just feel it through space, it’s transmitted
through the electrons in the bonds). It turns out that when two protons
appear at the same chemical shift, they do not split each other. So, in
EtBr, we have a CH3 next to a CH2, and each proton of the CH3 group is
only coupled to the protons of the CH2 group, not the other CH3 protons
because bluethe CH3 protons come at the same chemical shift. come
     The all protons all come          H H
                                                    The red protons both
    at the same chemical shift    H   C   C   Br   at the same chemical shift
    and do not split each other                    and do not split each other
                                      H   H




                                                            H   H
                 H   H                                  H   C   C   Br
             H   C   C   Br                                 H   H
                 H   H
Not all Couplings are Equal
When protons couple to each other, they do so with a certain intensity. This
is called the “coupling constant.” Coupling constants can vary from 0 Hz
(which means that the protons are not coupled, even though they are
neighbors) to 16 Hz. Typically, they are around 7 Hz, but many molecules
contain coupling constants that vary significantly from that. So, what
happens when a molecule contains a proton which is coupled to two
different protons with different coupling constants? We get a different
pattern as described in the diagram below.




So, if the protons are not equivalent, they can have different coupling
constants and the resulting pattern will not be a triplet, but a “doublet of
doublets.” Sometimes, nonequivalent protons can be on the same carbon
Coupling Constants in Alkenes

Coupling constants in alkenes can also differ depending on whether the
protons are cis or trans to each other. Note that in a terminal alkene (i.e., an
alkene at the end of a carbon chain), the cis and trans protons are NOT
equivalent. One is on the same side as the substituent, the other is on the
opposite side. The coupling of trans protons to each other is typically very
large, around 16 Hz, while the coupling of cis protons, while still large, is a
little smaller, around 12 Hz. This leads to the pattern shown below, and an
example of a molecule with this splitting pattern is shown on the next slide.
                                       H     If uncoupled, H would appear as a
                                                                A                          A
                                                                    single t where the dashed lin e indicates


12Hz coupling                                           16 Hz        Now, let's "turn on"        H A - H X coupling. This splits
                          HA
                                                                    the single line into two lines that are 16 Hz appart

                HM
                                                12 Hz
                                                                         12 Hz       Now, let's "turn on"      H A - H M coupling. This
                                                                                   splits each of the two new lines in to two lines
                          16 Hz coupling                                            that are 12 Hz appart for a total of four lines
                     HX




There are other times when protons on the same carbon are nonequivalent,
which we’ll see later.
H    HO
                                                                                            HO   CH3
A molecule with a terminal alkene
                                                H

                                                          H
                                                                                                 HO
                                                                                                                          HO
                                                                                                                               CH3
                                                                                                       H   H
        H HO

    H
          H                         H HO                                                    HO

                                H
                                      H




A molecule with a nine line splitting pattern


                                                                                                                    Me
                                                                            OH
                                                                                                                         OH
                                                                                                               Me




                                                               Nine lines, you just can't
                    Me
                                                              see two of them because
                          OH                                      they are so small.
               Me

                     H   H                      Me
                                                                                 Me
                                                         OH                  H
                                           Me                                          OH
                                                                            Me

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NMR

  • 1. NMR = Nuclear Magnetic Resonance Physical Principles: Some (but not all) nuclei, such as 1H, 13C, 19F, 31P have nuclear spin. A spinning charge creates a magnetic moment, so these nuclei can be thought of as tiny magnets. If we place these nuclei in a magnetic field, they can line up with or against the field by spinning clockwise or counter clockwise. N N N - sp in state, S - spin state, favorab le, unfav orable, low er energy high er en erg y S N S S A spin ning n ucleus w ith it's m agnetic field A spin ning n ucleus w ith it's m agnetic field align ed w ith the m agnetic field of a m ag net aligned a gain st the m agnetic field of a m ag net Alignment with the magnetic field (called ) is lower energy than against the magnetic field (called ). How much lower it is depends on the strength of the magnetic field Note that for nuclei that don’t have spin, such as 12C, there is no difference in energy between alignments in a magnetic field since they are not magnets. As such, we can’t do NMR spectroscopy on 12C.
  • 2. NMR: Basic Experimental Principles Imagine placing a molecule, for example, CH4, in a magnetic field. We can probe the energy difference of the - and - state of the protons by irradiating them with EM radiation of just the right energy. In a magnet of 7.05 Tesla, it takes EM radiation of about 300 MHz (radio waves). So, if we bombard the molecule with 300 MHz radio waves, the protons will absorb that energy and we can measure that absorbance. In a magnet of 11.75 Tesla, it takes EM radiation of about 500 MHz (stronger magnet means greater energy difference between the - and - state of the at no magnetic field, proton spin state protons) there is no difference beteen (higher energy) - and - states. Graphical relationship between magnetic field (B o) and frequency ( E E = h x 300 MHz E = h x 500 MHz 1 for H NMR absorptions proton spin state (lower energy) 0T 7.05 T 11.75 T Bo But there’s a problem. If two researchers want to compare their data using magnets of different strengths, they have to adjust for that difference. That’s a pain, so, data is instead reported using the “chemical shift” scale as
  • 3. The Chemical Shift (Also Called ) Scale Here’s how it works. We decide on a sample we’ll use to standardize our instruments. We take an NMR of that standard and measure its absorbance frequency. We then measure the frequency of our sample and subtract its frequency from that of the standard. We then then divide by the frequency of the standard. This gives a number called the “chemical shift,” also called , which does not depend on the magnetic field strength. Why not? Let’s look at two examples. Imagine that we have a magnet where our standard absorbs at 300,000,000 Hz (300 megahertz), and our sample absorbs at 300,000,300 Hz. The difference is 300 Hz, so we take 300/300,000,000 = 1/1,000,000 and call that 1 part per million (or 1 PPM). Now lets examine the same sample in a stronger magnetic field where the reference comes at 500,000,000 Hz, or 500 megahertz. The frequency of our sample will increase proportionally, and will come at 500,000,500 Hz. The difference is now 500 Hz, but we divide by 500,000,000 (500/500,000,000 = 1/1,000,000, = 1 PPM). It’s brilliant. Of course, we don’t do any of this, it’s all done automatically by the NMR machine. Even more brilliant.
  • 5. The Chemical Shift of Different Protons NMR would not be very valuable if all protons absorbed at the same frequency. You’d see a signal that indicates the presence of hydrogens in your sample, but any fool knows there’s hydrogen in organic molecules. What makes it useful is that different protons usually appear at different chemical shifts ( . So, we can distinguish one kind of proton from another. Why do different protons appear at different ? There are several reasons, one of which is shielding. The electrons in a bond shield the nuclei from the magnetic field. So, if there is more electron density around a proton, it sees a slightly lower magnetic field, less electron density means it sees a higher magnetic field: This represents the electron density of a C-H bond. How much electron Z density is on the proton depends on what else is attached to the carbon. If Z C H is an elelctronegative atom, the carbon becomes electron deficient and pulls some of the electron density away from the H. if Z is an electron donating group, more electron density ends up on the H. How do the electrons shield the magnetic field? By moving. A moving charge creates a magnetic field, and the field created by the moving electrons opposes the magnetic field of our NMR machine. It’s not a huge effect, but it’s enough to enable us to distinguish between different protons in our sample.
  • 6. The Hard Part - Interpreting Spectra Learning how an NMR machine works is straightforward. What is less straightforward is learning how to use the data we get from an NMR machine (the spectrum of ethyl acetate is shown below). That’s because each NMR spectrum is a puzzle, and there’s no single fact that you simply have to memorize to solve these spectra. You have to consider lots of pieces of data and come up with a structure that fits all the data. What kinds of data do we get from NMR spectra? For 1H NMR, there are three kinds each of which we will consider each of these separately:what kinds of protons we have. 1) Chemical shift data - tells us 2) Integrals - tells us the ratio of each kind of proton in our sample. 3) 1H - 1H coupling - tells us about protons that are near other protons.
  • 7. Chemical Shift Data As previously mentioned, different kinds of protons typically come at different chemical shifts. Shown below is a chart of where some common kinds of protons appear in the scale. Note that most protons appear between 0 and 10 ppm. The reference, tetramethylsilane (TMS) appears at 0 ppm, and aldehydes appear near 10 ppm. There is a page in your lab handout with more precise values for this chart. Note that these are typical values and that there are lots of exceptions! R NH R OH Ph R H Me OH (R) TMS = Me Si Me HO C H3 P h C H3 Me R R R O R R O N R2 O Cl H H OC H 3 C H3 C H3 C H3 R H C H3 TM S 10 9 8 7 6 5 4 3 2 1 0 Downfield region ppm Upfield region of the spectrum of the spectrum
  • 8. Integrals Integrals tell us the ratio of each kind of proton. They are lines, the heights of which are proportional to the intensity of the signal. Consider ethyl acetate. There are three kinds of protons in this molecule, the CH3 next to the carbonyl, the CH2 next to the O and the CH3 next to the CH2. The ratio of the signals arising from each of these kinds of protons should be 3 to 2 to 3, respectively. So, if we look at the height of the integrals they should be 3 to 2 to 3. With this information, we can know which is the CH2 signal (it’s the smallest one), but to distinguish the other two, we have to be able to predict their chemical shifts. The chart on the previous page allows us to make that assignment (the CH3 next to the C=O should appear at ~ 2 PPM, while the other CH3 should be at ~ 1 PPM). 3H'S O O CH3 O O H H 3C O O H 3H'S 2 H'S
  • 9. - 1H Coupling 1H You’ll notice in the spectra that we’ve seen that the signals don’t appear as single lines, sometimes they appear as multiple lines. This is due to 1H - 1H coupling (also called spin-spin splitting or J-coupling). Here’s how it works: Imagine we have a molecule which contains a proton (let’s call it HA) attached to a carbon, and that this carbon is attached to another carbon which also contains a proton (let’s call it HB). It turns out that HA feels the presence of HB. Recall that these protons are tiny little magnets, that can be oriented either with or against the magnetic field of the NMR machine. When the field created by HB reinforces the magnetic field of the NMR machine (B0 ) HA feels a slightly stronger field, but when the field created by HB opposes B0, HA feels a slightly weaker field. So, we see two signals for HA depending on the alignment of HB. The same is true for HB, it can feel either a slightly stronger or weaker field due to HA’s presence. So, rather than see a single line for each of these protons, we see two lines for each. For this line, H B is lined up For this line, H B is lined up with the magnetic field aga inst the magnetic field ( adds to the overall (subtracts from the overall magnetic field, so the line magnetic field, so the line comes at higher frequency) comes at lower frequency) HA HB C C HA HB H A is split into two lines because H B is split into two lines because it feels the m agnetic field of H B. it feels the m agnetic field of H A.
  • 10. More 1H - 1H Coupling What happens when there is more than one proton splitting a neighboring proton? We get more lines. Consider the molecule below where we have two protons on one carbon and one proton on another. Note that the signal produced by H A + H A' is twice the size of that produced by H B HA HB HA ' C C H A + H A' HB H A and H A' appear at the same H B is split into three lines chemical shift because they are because it feels the magnetic in identical environments field of H A and H A' They are also split into two lines (called a doublet) because they feel the magnetic field of H B.
  • 11. Why are There Three Lines for HB? H B feels the splitting of both HA and HA’. So, let’s imagine starting with HB as a single line, then let’s “turn on” the coupling from HA and HA’ one at a time: HB If uncoupled, H B would appear as a singlet where the dashed line indicates the chemic al shift of the sin glet. Now, let's "turn on" H B - H A coupling. This splits the single line into two lin es HA HB Now, let's "turn on" H B - H A' coupling. This HA' C C splits each of the two new lines into two lines, but notice how the two lines in the middle overlap. Overall, we then have three lines. Because the two lines in the middle overlap, that line is twice as big as the lines on the outside. More neighboring protons leads to more lines as shown on the next slide.
  • 12. Splitting Patterns with Multiple Neighboring Protons If a proton has n neighboring protons that are equivalent, that proton will be split into n+1 lines. So, if we have four equivalent neighbors, we will have five lines, six equivalent neighbors… well, you can do the math. The lines will not be of equal intensity, rather their intensity will be given by Pascal’s triangle as shown below. intensities no. of neighbors relative pattern example 0 1 singlet (s) H H 1 1 1 doublet (d) C C H H 2 1 2 1 triplet (t) C C H H H 3 1 3 3 1 quartet (q) C C H H H H H 4 1 4 6 4 1 pentet C C C H H H H H 5 1 5 10 10 5 1 sextet H C C C H H H H H 6 1 6 15 20 15 6 1 septet H C C C H H H We keep emphasizing that this pattern only holds for when the neighboring protons are equivalent. Why is that? The answer is two slides away.
  • 13. More About Coupling Earlier we said that protons couple to each other because they feel the magnetic field of the neighboring protons. While this is true, the mechanism by which they feel this field is complicated and is beyond the scope of this class (they don’t just feel it through space, it’s transmitted through the electrons in the bonds). It turns out that when two protons appear at the same chemical shift, they do not split each other. So, in EtBr, we have a CH3 next to a CH2, and each proton of the CH3 group is only coupled to the protons of the CH2 group, not the other CH3 protons because bluethe CH3 protons come at the same chemical shift. come The all protons all come H H The red protons both at the same chemical shift H C C Br at the same chemical shift and do not split each other and do not split each other H H H H H H H C C Br H C C Br H H H H
  • 14. Not all Couplings are Equal When protons couple to each other, they do so with a certain intensity. This is called the “coupling constant.” Coupling constants can vary from 0 Hz (which means that the protons are not coupled, even though they are neighbors) to 16 Hz. Typically, they are around 7 Hz, but many molecules contain coupling constants that vary significantly from that. So, what happens when a molecule contains a proton which is coupled to two different protons with different coupling constants? We get a different pattern as described in the diagram below. So, if the protons are not equivalent, they can have different coupling constants and the resulting pattern will not be a triplet, but a “doublet of doublets.” Sometimes, nonequivalent protons can be on the same carbon
  • 15. Coupling Constants in Alkenes Coupling constants in alkenes can also differ depending on whether the protons are cis or trans to each other. Note that in a terminal alkene (i.e., an alkene at the end of a carbon chain), the cis and trans protons are NOT equivalent. One is on the same side as the substituent, the other is on the opposite side. The coupling of trans protons to each other is typically very large, around 16 Hz, while the coupling of cis protons, while still large, is a little smaller, around 12 Hz. This leads to the pattern shown below, and an example of a molecule with this splitting pattern is shown on the next slide. H If uncoupled, H would appear as a A A single t where the dashed lin e indicates 12Hz coupling 16 Hz Now, let's "turn on" H A - H X coupling. This splits HA the single line into two lines that are 16 Hz appart HM 12 Hz 12 Hz Now, let's "turn on" H A - H M coupling. This splits each of the two new lines in to two lines 16 Hz coupling that are 12 Hz appart for a total of four lines HX There are other times when protons on the same carbon are nonequivalent, which we’ll see later.
  • 16. H HO HO CH3 A molecule with a terminal alkene H H HO HO CH3 H H H HO H H H HO HO H H A molecule with a nine line splitting pattern Me OH OH Me Nine lines, you just can't Me see two of them because OH they are so small. Me H H Me Me OH H Me OH Me