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Organic chemistry
Course: Organic chemistry > Unit 14
Lesson 3: Proton NMR- Introduction to proton NMR
- Nuclear shielding
- Chemical equivalence
- Chemical shift
- Electronegativity and chemical shift
- Diamagnetic anisotropy
- Integration
- Spin-spin splitting (coupling)
- Multiplicity: n + 1 rule
- Coupling constant
- Complex splitting
- Hydrogen deficiency index
- Proton NMR practice 1
- Proton NMR practice 2
- Proton NMR practice 3
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Chemical equivalence
How to predict the number of signals in a proton NMR spectrum based on the number of non-equivalent hydrogens in a compound. Created by Jay.
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- I don't really understand what you mean by "same environment." I understand your examples, but for more complicated structures, that intuition of two molecules having the same environment starts to fall apart...(24 votes)
- If two protons are in the same environment it just means that they have the exact same kinds of forces affecting them. So they must be surrounded by all of the same atoms in the same respective positions, charges, ect because if anything was changed they would be in a different environment.(58 votes)
- why don't we see the same affect from Chirality in the three Hydrogen attached to the first Carbon? They are still adjacent to the Chiral Carbon the same way the two Hydrogen on the third Carbon is(22 votes)
- The carbon to the left of the chiral center in that example aroundcan rotate freely, so each of those hydrogen molecules can be found in any of those positions, therefore they are in the same environment. Each hydrogen is feeling the exact same amount of force from the chiral carbon due to their ability to rotate and be in any of those positions at any given time. 6:30(10 votes)
- My textbook says that there's something called the replacement test. You mentioned it briefly in the video with Deuterium, but I still don't fully understand how that works. How would you differ the structures of an enantiotopic, diasteriotopic and not chemically equivalent compounds using this test? Would you use it after you realized it's not homotopic or afterwards in the process? Thanks.(8 votes)
- There is a clear explanation here:
http://www.masterorganicchemistry.com/2012/04/17/homotopic-enantiotopic-diastereotopic/
Essentially, you imagine that you replace the hydrogens with a heavier atom.
If the resulting molecules are identical, then the hydrogens are homotopic.
If the resulting molecules are enantiomers, then the hydrogens are enantiotopic.
If the resulting molecules are diastereomers, then the hydrogens are diastereotopic.
The way this relates to proton NMR, is that:
diastereotopic hydrogens are always in unique environments and thus have separate signals,
enantiotopic hydrogens only have separate signals in an enantiomeric solvent, and
homotopic hydrogens never have separate signals.(5 votes)
- At, it was mentioned that the two protons are chemically different. Now, this would arise due to the differences in OH and H on the adjacent carbon (C2 from the left), like say the electronegativity of Oxygen. But around the C2-C3 sigma bond, I can rotate the molecule such that the OH is now closer to the other H atom. So, because this rotation would be there in the molecule, shouldn't it be that both of them are chemically equivalent? 6:20(7 votes)
- The two hydrogens on C3 are diastereotopic, meaning that if one of them were substituted with another element (Cl, for example), you would create different compounds depending on which H you substituted. The two options would be diastereomers because of the two chiral centers you have next to each other (one already existing on C2, and one you just created by substituting a hydrogen on C3). I used this powerpoint to discover this information, under the part about Stereochemistry and Topicity: http://disciplinas.stoa.usp.br/pluginfile.php/258043/mod_resource/content/1/FBF5704AULA3.pdf(6 votes)
- Are Signals the same as peaks?(4 votes)
- Signals are sometimes a set of peaks. A doublet is 1 signal made up of 2 peaks, a triplet is 1 signal made up of 3 peaks, etc.
Each signal in the spectrum comes from a unique proton environment in the molecue.(7 votes)
- How would you apply the equivalency to a fused bridge system like bicyclo [2:2:2]octane? Is it two signals, or are each side different? I have a hard time visualizing it.(3 votes)
- I think 2 signals
One signal of 12 H intensity by 6 methylene and one signal of 2- H intensity by 2 methine grps(2 votes)
- in6:49
you said that the adjacent carbon that attached to two Hydrogen ..
one of two hyddrogen is slightly different .. why ?
they are attached to the same carbon ..
thanking you about your efforts :)(4 votes)- He mentions the fact that because there is a chiral center close to those two hydrogens, they are no longer chemically equivalent. So chirality has the effect of changing the chemical equivalence.(2 votes)
- on, I do not understand why the red and purple protons aren't in the same environment. Thank you! 6:57(2 votes)
- I think the material on conformations of alkanes is relevant to this:
https://www.khanacademy.org/science/organic-chemistry/bond-line-structures-alkanes-cycloalkanes#conformations-alkanes-cycloalkanes
The short version:
The methyl groups prefer to be anti to each other – atwe can see that Jay has drawn butan-2-ol in this conformation. This constraint on the rotation between C2 and C3 means that the two hydrogens on C3 will tend to be in different environments – one will usually be near to the hydroxyl group, while the other is usually on the opposite side of the molecule (anti). 6:40(2 votes)
- How many types of nmr protons are there in butanoic acid? Please explain with structure!(1 vote)
- The structure of butanoic acid is CH₃CH₂CH₂COOH.
There are four different types of protons:
The H of the OH group
The two H atoms on C-2
The two H atoms on C-3
The three H atoms on C-4
An easy way to figure this out is to replace each H atom in turn with an X atom (Cl?)
With butanoic acid, the four possibilities are:
butanoyl chloride
2-chlorobutanoic acid
3-chlorobutanoic acid
4-chlorobutanoic acid(4 votes)
- Why don't the protons that make up the carbon, oxygen, or any other grouped protons affect NMR? Is it because they are far outside the normal spectrum given that there are several protons/neutrons grouped together at once?(1 vote)
- By proton here we are referring to the hydrogen atoms, seeing as they are essentially a proton and an electron.
1H NMR specifically looks at hydrogen atoms.
There is such a technique as 13C NMR and that is quite common, 17O NMR is also a thing but less common.
In order for a nucleus to be "seen" it needs to have a nonzero nuclear spin. The common isotopes of carbon (C-12) and oxygen (O-16) do not have this property.(3 votes)
Video transcript
- Let's see how to determine the number of expected signals in an NMR spectrum. And the best way to do this is just to do a lot of practice problems, and we'll start with methane. Methane has four protons
in the same environment. Therefore, we say those four protons are chemically equivalent,
and we would expect to see only one signal on our NMR spectrum. So, for methane, we would
expect to see one signal, because all four protons
are chemically equivalent. If we move on to propane,
this carbon right here has two protons on it,
and these two protons are in the same environment. Therefore, they are chemically equivalent, and we would expect to see only one signal for these two protons. If we look at these protons over here, so let me go ahead and draw them in, so these methyl protons. These methyl protons are in
their own environment here, so we would expect one signal
for these methyl protons. But for a molecule like this, you need to think about symmetry. So, if I draw a line right
here, it's easy to see that these three protons are in the same environment as these. So really, really we have six protons in the same environment. So these six protons are
chemically equivalent, and we would expect to see
one signal for all six. So, for propane, we would expect to see a total of two signals. Alright, let's move on to this one. So let's draw in our protons here. Let's just go ahead and
draw in all of them, first. So we're drawing in all
of the protons, alright? So we have these methyl protons here, and then right here, we have
a proton on this carbon, and then we have all of these protons. So, a lot of them. Let's focus in on the
methyl protons first. These methyl protons here
are in their own environment, and that environment is the same as all of these methyl protons. They're all in the exact same environment. They're all right next to a
carbon with a hydrogen on it. And so, we would expect to see only one signal for all these protons. So one signal for the magenta protons. Alright, so again, think about symmetry. Think about the symmetry of this. And then, if I look at
this proton right here, right, this is in a different environment from the magenta protons, but it's in the same
environment as this proton. So we would expect one signal
for these red protons, here. So, one signal for the red protons. So a total of two
signals for the molecule. Alright, let's do some more examples. Let's look at this one next, alright? We have a carbon right here
with two protons on it. And these two protons are
in the same environment. They're chemically equivalent. These two protons are
next to this oxygen here. We know oxygen is more
electronegative than carbon, so oxygen is going to withdraw
some electron density. And so, these two protons are
in a different environment from these two protons. These two protons right here, let me go ahead and change
colors, these two protons in red are further away from the oxygen, so they're in a different environment. So we'd expect one signal
from the protons in red, and we would expect one signal
from the protons in yellow. Alright, we still have our methyl protons. Let me go ahead and draw those in. So we have three protons
over here on this carbon. They're further away from the oxygen. They're in their own environment, right? They're chemically equivalent. So, one signal expected for these protons. Finally, don't forget about
the proton right here, the proton on the oxygen. So, that's in its own environment, so we would expect one
signal for that proton. So, really, a total, if
you count them all up, a total of four signals. So, we would expect four signals. Not sure why I put an S
on here, only one signal. So, a total of four for this alcohol. Let's look at this alcohol down here. So, we have these two protons, right? And these protons over here, and these protons over here. So let's think about that. Symmetry helps for an example like this. These two protons are
in the same environment. They're between two CH2's,
so we would expect one signal for these protons, so they're
chemically equivalent. Let's look at these protons
next, so these, right here, are next to a CH2. They're also next to an OH. That's the exact same environment
as these protons, right? They're next to a CH2 and next to an OH. So, if you think about
symmetry right here, we'd expect only one signal, only one signal for these four protons. And then, finally, we still
have the proton on the oxygen, and once again, symmetry
helps us think about the fact that this proton is in the same
environment as this proton, so we would expect one signal there. So a total of three expected
signals for this molecule. Alright, let's move on to this compound over here on the right. And we can see there's a
chiral center right here on this carbon, and there
therefore must be a hydrogen, a proton, on that carbon. So, let's go ahead and
draw in all our protons and then let's analyze them, here. So we have three protons on this carbon. On this carbon right
here, we have two protons. And I'm drawing them in
with a wedge and a dash because we're gonna need to
think about those two protons. And then over here, we
have three, like that. Alright, so let's think about how many different signals
we're going to get. In the past, let me go back and
use a different color, here, we talked about a CH2 group, right? And we didn't have any chiral centers, like these two protons right here. We didn't have any chiral
centers in this molecule. These two protons are,
generally, equivalent. But if I think about over
here, I have a chiral center at this carbon, and that's going to affect these two protons. These two protons are no
longer chemically equivalent, alright, because a
chiral center is present. So in general, if a
chiral center is present, the two protons on a methylene
group, on a CH2 group, are generally not equivalent. So, we would expect two different signals. So this one might give us one signal, and I'll put that in magenta. So, one signal here. And this one, we would
expect a different signal. They're in slightly
different environments, because of this chiral
center that is present. Alright, so let's keep on
going, and let's figure out how many more signals we would expect. So, over here, we have these three protons are chemically equivalent,
and they're in their own unique environment, so we would expect one signal for those
three protons, alright? And those are in a different environment from these over here, so we would expect one signal for these. So for a methyl group,
methyl protons are always in the same environment, so
they're chemically equivalent. So you don't have to worry about them. And then let's see, what
else do we have here? We have the proton on the oxygen, so we would expect one signal for that. And then, finally, we're going to have, let's see, what color
should I choose here, let's go with orange. We still have a proton right here in its own unique environment, so we would expect one
signal for that proton. So, how many total signals do we expect? Let's count them up. One, two, three, four, five, and six, so a total of six expected
signals for this alcohol. Alright, let's move on
to a benzene ring, here. Let's look at benzene. And we know that benzene
has six protons, right? So I could draw in the six protons, here. And those six protons are all
in the exact same environment. They're all chemically equivalent. And sometimes it's easier to just go ahead and draw your circle in here, and that just helps you to see that these protons are equivalent. It allows you to see the
symmetry a little bit better. So, again, thinking about symmetry, all six protons are in
the same environment. Therefore, we would expect only one signal for benzene on an NMR spectrum. Let me go ahead and write that here. So only one signal for benzene, because all six protons
are chemically equivalent. Move over here to this
molecule down here, alright? So, let's think about what we have. We have a methyl group
here, a methyl group here, so that's three protons, three protons for each methyl group. And those protons are in the
same environment, alright? So, these three protons
on this methyl group are in the same environment
as these three protons. They're right next to an oxygen, which is right next to this benzene ring. So, next to an oxygen
next to a benzene ring. And so, we'd expect
only one signal, right? Only one signal for these
six protons right here. If you look at our ring, we
know that there's a proton here. We know that there's a
proton here, a proton here, and a proton here. And, if we think about those protons, they're all in the exact same environment. So if I think about,
let's say, this proton. This proton is next to
CH with a double bond. It's next to a carbon
right here with an oxygen. This is in the same
environment as this one, right? This one's in the exact same
environment this one is, this one is, so again,
symmetry helps you realize that all four protons are
in the same environment. They're chemically equivalent. Therefore, one signal. So, we would expect to see two signals. We would expect to see two signals for this molecule on an NMR spectrum. Finally, let's just, for fun, let's just look at cubane, here. So one of the most interesting
molecules, in my opinion. There are eight protons on cubane. Cubane is just this cube here. And these eight protons
are all equivalent, right? So if you think about it, if
you just rotated this cube, you wouldn't be able to
tell the difference, here. So we have eight protons, all equivalent, therefore only one signal. So, cubane's NMR should
have only one signal on it. So that's hopefully some
insight into how to look at a dot structure, and how to figure out how many signals you would expect to see on your NMR spectrum.