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NUCLEAR MAGNETIC RESONANCE SPECTROSCPY A guide for A level students. 2008 SPECIFICATIONS. KNOCKHARDY PUBLISHING. KNOCKHARDY PUBLISHING. NMR SPECTROSCOPY. INTRODUCTION

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slide1

NUCLEAR MAGNETIC RESONANCE SPECTROSCPY

A guide for A level students

2008 SPECIFICATIONS

KNOCKHARDY PUBLISHING

slide2

KNOCKHARDY PUBLISHING

NMR SPECTROSCOPY

INTRODUCTION

This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards.

Individual students may use the material at home for revision purposes or it may be used for classroom teaching if an interactive white board is available.

Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at...

www.knockhardy.org.uk/sci.htm

Navigation is achieved by...

either clicking on the grey arrows at the foot of each page

or using the left and right arrow keys on the keyboard

slide3

NMR SPECTROSCOPY

  • CONTENTS
  • Prior knowledge
  • What is nmr?
  • Origin of spectra
  • Tetramethylsilane
  • Chemical shift
  • Resolution
  • Multiplicity - splitting patterns
  • Integration
  • OH signals and the use of D2O
  • Working out spectra
  • Questions on proton nmr
  • Carbon-13 nmr
slide4

NMR SPECTROSCOPY

  • Before you start it would be helpful to…
  • know the names and structures of organic functional groups
  • find the structures of isomers given the molecular formula
slide5

PREVIEW

  • WHAT IS NMR AND WHAT DOES AN NMR SPECTRUM TELL YOU?
  • Proton nuclear magnetic resonance spectroscopy provides...
  • information about the hydrogenatoms in molecules
  • How does it work?
  • involves the interaction of materials with theLOW ENERGY RADIO WAVES
  • It provides the information by...
  • spinning a sample of the compound in a magnetic field
  • hydrogen atoms in different environments respond differently to the field
  • each different environment of hydrogen produces a signal in a different position
  • the area under each peak / signal is proportional to the number of hydrogens
  • signal can be split according to how many H’s are on adjacent atoms
slide6

b

aligned against the field

DE = h

ENERGY

a

aligned with the field

NMR SPECTROSCOPY – ORIGIN OF SPECTRA

All nuclei possess charge and mass. Those with either an odd mass number or an odd atomic number also possess spin. This means they have angular momentum.

POSSESS SPIN1 2 13 19 31

H H C F P

1 1 6 9 15

DON’ T POSSESS SPIN 12

C

6

A nucleus without spin cannot be detected by nuclear magnetic resonance spectroscopy.

A spinning nucleus such as 1H behaves as a spinning charge and generates a magnetic field. It can be likened to a bar magnet. When it is placed in an externally applied field it can align with, or against, the field. The energy difference between the two states (DE) depends on the applied field.

slide7

RADIOFREQUENCY

OSCILLATOR

NMR SPECTROMETERS

The sample is spun round in the field of a large electromagnet and a radio-frequency (RF) field is applied. The magnetic field is increased and the excitation or “flipping” of nuclei from one orientation to another is detected as an induced voltage resulting from the absorption of energy from the RF field.

An nmr spectrum is the plot of the induced voltage against the sweep of the field. The area under a peak is proportional to the number of nuclei “flipping”

Not all hydrogen nuclei absorb energy at the same field strength at a given frequency; the field strength required depends on the environment of the hydrogen.

By observing the field strength at which protons absorb energy, one can deduce something about the structure of a molecule.

THE BASIC ELEMENTS OF AN NMR SPECTROMETER

slide8

NMR SPECTROSCOPY

  • INTERPRETATION OF SPECTRA
  • NMR spectra provide information about the structure of organic molecules from the ...
  • number of different signals in the spectrum
  • position of the signals (chemical shift)
  • intensity of the signals
  • splitting pattern of the signals
slide9

NMR SPECTROSCOPY

  • INTERPRETATION OF SPECTRA
  • NMR spectra provide information about the structure of organic molecules from the ...
  • number of different signals in the spectrum
  • position of the signals (chemical shift)
  • intensity of the signals
  • splitting pattern of the signals
slide10

NMR SPECTROSCOPY

  • INTERPRETATION OF SPECTRA
  • NMR spectra provide information about the structure of organic molecules from the ...
  • number of different signals in the spectrum
  • position of the signals (chemical shift)
  • intensity of the signals
  • splitting pattern of the signals
  • OBTAINING SPECTRA
  • a liquid sample is placed in a tube which spins in a magnetic field
  • solids are dissolved in deuterated solvents (CDCl3) or solvents without H’s (CCl4 )
  • [solvents with hydrogen atoms in them will produce peaks in the spectrum]
  • TMS, tetramethylsilane, (CH3)4Si, is added to provide a reference signal
  • when the spectrum is run, it can be integrated to find the relative peak areas
  • spectrometers are now linked to computers to analyse data and store information
slide11

TETRAMETHYLSILANE - TMS

PROVIDES THE REFERENCE SIGNAL

  • non-toxic liquid - SAFE TO USE
  • inert - DOESN’T REACT WITH COMPOUND BEING ANALYSED
  • has a low boiling point - CAN BE DISTILLED OFF AND USED AGAIN
  • all the hydrogen atoms are chemically equivalent - PRODUCES A SINGLE PEAK
  • twelve hydrogens so it produces an intense peak - DON’T NEED TO USE MUCH
  • signal is outside the range shown by most protons - WON’T OBSCURE MAIN SIGNALS
  • given the chemical shift of d = 0
  • the position of all other signals is measured relative to TMS

The molecule contains four methyl groups attached to a silicon atom in a tetrahedral arrangement. All the hydrogen atoms are chemically equivalent.

slide12

H

- C - X

- C - H

CHEMICAL SHIFT

  • each proton type is said to be chemically shifted relative to a standard (usually TMS)
  • the chemical shift is the difference between the field strength at which it absorbs and
  • the field strength at which TMS protons absorb
  • the delta (d) scale is widely used as a means of reporting chemical shifts
  • Observed chemical shift (Hz) x 106
  • d = ppm (parts per million)
  • Spectrometer frequency (Hz)
  • the chemical shift of a proton is constant under the same conditions (solvent, temperature)
  • the TMS peak is assigned a value of ZERO (d = 0.00)
  • all peaks of a sample under study are related to it and reported in parts per million
  • H’s near to an electronegative species are shifted “downfield” to higher d values

Approximate

chemical shifts

The actual values depend on the environment

ROH

-CHO

-COOH

-C=CH-

TMS

13 12 11 10 9 8 7 6 5 4 3 2 1 0 d

DOWNFIELD - ‘deshielding’

slide13

LOW RESOLUTION - HIGH RESOLUTION

  • low resolution nmr gives 1 peak for each environmentally different group of protons
  • high resolution gives more complex signals - doublets, triplets, quartets, multiplets
  • the signal produced indicates the number of protons on adjacent carbon atoms

LOW RESOLUTION SPECTRUM OF 1-BROMOPROPANE

slide14

LOW RESOLUTION - HIGH RESOLUTION

  • low resolution nmr gives 1 peak for each environmentally different group of protons
  • high resolution gives more complex signals - doublets, triplets, quartets, multiplets
  • the signal produced indicates the number of protons on adjacent carbon atoms

HIGH RESOLUTION SPECTRUM OF 1-BROMOPROPANE

The broad peaks are split into sharper signals

The splitting pattern depends on the number of hydrogen atoms on adjacent atoms

slide15

MULTIPLICITY (Spin-spin splitting)

  • low resolution nmr gives 1 peak for each environmentally different group of protons
  • high resolution gives more complex signals - doublets, triplets, quartets, multiplets
  • the signal produced indicates the number of protons on adjacent carbon atoms

Number of peaks = number of chemically different H’s on adjacent atoms + 1

1 neighbouring H 2 peaks “doublet” 1:1

2 neighbouring H’s 3 peaks “triplet” 1:2:1

3 neighbouring H’s 4 peaks “quartet” 1:3:3:1

4 neighbouring H’s 5 peaks “quintet” 1:4:6:4:1

Signals for the H in an O-H bond are unaffected by hydrogens on adjacent atoms - get a singlet

slide16

MULTIPLICITY (Spin-spin splitting)

  • low resolution nmr gives 1 peak for each environmentally different group of protons
  • high resolution gives more complex signals - doublets, triplets, quartets, multiplets
  • the signal produced indicates the number of protons on adjacent carbon atoms

Number of peaks = number of chemically different H’s on adjacent atoms + 1

0 neighbouring H’s signal isn’t split 1 peak “singlet”

1 neighbouring H signal split into 2 peaks “doublet” ratio = 1:1

2 neighbouring H’s 3 peaks “triplet” 1:2:1

3 neighbouring H’s 4 peaks “quartet” 1:3:3:1

4 neighbouring H’s 5 peaks “quintet” 1:4:6:4:1

slide17

MULTIPLICITY (Spin-spin splitting)

  • low resolution nmr gives 1 peak for each environmentally different group of protons
  • high resolution gives more complex signals - doublets, triplets, quartets, multiplets
  • the signal produced indicates the number of protons on adjacent carbon atoms

Number of peaks = number of chemically different H’s on adjacent atoms + 1

0 neighbouring H’s signal isn’t split 1 peak “singlet”

1 neighbouring H signal split into 2 peaks “doublet” ratio = 1:1

2 neighbouring H’s 3 peaks “triplet” 1:2:1

3 neighbouring H’s 4 peaks “quartet” 1:3:3:1

4 neighbouring H’s 5 peaks “quintet” 1:4:6:4:1

PASCAL’S TRIANGLE

1

1 1

1 2 1

1 3 3 1

1 4 6 4 1

1 5 10 10 5 1

It is interesting to note the relationship between the successive peak ratios. It follows the pattern found in Pascal’s triangle.

Each number in the series is the sum of the two numbers above it in the triangle

What would be the pattern for 6 neighbouring hydrogens?

1 6 15 20 15 6 1

PRESS THE SPACE BAR FOR THE ANSWER

slide18

MULTIPLICITY (Spin-spin splitting)

Splitting patterns are worked out by considering the effect adjacent, chemically different protons have on another signal in a given environment.

The spin of the proton producing the signal is affected by each of the two forms of the adjacent proton.

One orientation augments/enhances its field and the other opposes/reduces it. This is done by calculating the various possible combinations of alignment of adjacent protons.

HOWEVER Signals for the H in an O-H bond are not affected

by hydrogens on adjacent atoms so are not split

slide19

MULTIPLICITY (Spin-spin splitting)

ANALOGY

Imagine you had an opinion on something. If nobody influenced you, your opinion would be the same. However if another person had a view on the topic, they would either agree or disagree with you. Their ideas would either enhance what you thought or diminish it. There would be two possibilities of equal chance.

If there were two people offering views they could either be both for it (1 possibility) , both against (1 possibility) or one could be in favour and the other against (2 possibilities). There would be three possibilities of relative chance1:2:1

FOR AGAINST

CONTENTS

slide20

MULTIPLICITY (Spin-spin splitting)

O adjacent H’s

There is no effect

slide21

MULTIPLICITY (Spin-spin splitting)

O adjacent H’s

There is no effect

1 adjacent H

can be aligned either with a or against b the field

there are only two equally probable possibilities

the signal is split into 2 peaks of equal intensity

slide22

MULTIPLICITY (Spin-spin splitting)

O adjacent H’s

There is no effect

1 adjacent H

can be aligned either with a or against b the field

there are only two equally probable possibilities

the signal is split into 2 peaks of equal intensity

2 adjacent H’s

more possible combinations

get 3 peaks in the ratio 1 : 2 : 1

slide23

MULTIPLICITY (Spin-spin splitting)

O adjacent H’s

There is no effect

1 adjacent H

can be aligned either with a or against b the field

there are only two equally probable possibilities

the signal is split into 2 peaks of equal intensity

2 adjacent H’s

more possible combinations

get 3 peaks in the ratio 1 : 2 : 1

3 adjacent H’s

even more possible combinations

get 4 peaks in the ratio 1 : 3 : 3 : 1

EXPLAIN THE THEORY BEHIND THE SPLITTING PATTERN FOR 4 ADJACENT H’s

slide24

MULTIPLICITY (Spin-spin splitting)

4 adjacent H’s

gives 5 peaks in the ratio 1 : 4 : 6 : 4 : 1

slide25

INTEGRATION

  • the area under a signal is proportional to the number of hydrogen atoms present
  • an integration device scans the area under the peaks
  • lines on the spectrum show the relative abundance of each hydrogen type (old method)
  • computers now display the information as numerical data
  • By measuring the distances between the integration lines one can
  • work out the simple ratio between the various types of hydrogen.
  • before integration after integration

NOTICE THAT THE O-H SIGNAL IS ONLY A SINGLET

(see later for an explanation of this)

slide26

INTEGRATION

Measure the distance between the top and bottom lines.

Compare the heights from each signal and make them into a simple ratio.

Computers now do the integration automatically

  • HOW TO WORK OUT THE SIMPLE RATIOS (OLD METHOD)
  • Measure how much each integration line rises as it goes of a set of signals
  • Compare the relative values and work out the simple ratio between them
  • In the above spectrum the rises are in the ratio... 1:2:3

IMPORTANT: It doesn’t provide the actual number of H’s in each environment, just the ratio

slide27

O-H bonds and splitting patterns

  • The signal due to the hydroxyl (OH) hydrogen is a singlet ... there is no splitting
  • H’s on OH groups do not couple with adjacent hydrogen atoms
  • Arises because the H on the OH, rapidly exchanges with protons on other molecules (such as water or acids) and is not attached to any particular oxygen long enough to register a splitting signal.
slide28

O-H bonds and splitting patterns

  • The signal due to the hydroxyl (OH) hydrogen is a singlet ... there is no splitting
  • H’s on OH groups do not couple with adjacent hydrogen atoms
  • Arises because the H on the OH, rapidly exchanges with protons on other molecules (such as water or acids) and is not attached to any particular oxygen long enough to register a splitting signal.

OH hydrogens are always seen as a singlet ... there is no splitting

This is a quartet despite the fact that there are 4 H’s on adjacent atoms - the H on the OH doesn’t couple

slide29

O-H bonds and the D2O shake

As has been pointed out, the signal due to the hydroxyl (OH) hydrogen is a singlet.

It is possible to identify which signal is caused by the H of an O-H group by doing a ‘D2O shake’. A small amount of deuterium oxide D2O, a form of water, is added to the sample and the spectrum is re-run. Any signal due to O-H proton disappears.

The H in the O-H bond changes places with a deuterium atom, 2H or D, from D2O

Deuterium doesn’t exhibit nuclear magnetic resonance under the conditions used for proton nmr so the signal is removed to another part of the spectrum.

.

slide30

O-H bonds and the D2O shake

As has been pointed out, the signal due to the hydroxyl (OH) hydrogen is a singlet.

It is possible to identify which signal is caused by the H of an O-H group by doing a ‘D2O shake’. A small amount of deuterium oxide D2O, a form of water, is added to the sample and the spectrum is re-run. Any signal due to O-H proton disappears.

The H in the O-H bond changes places with a deuterium atom, 2H or D, from D2O

Deuterium doesn’t exhibit nuclear magnetic resonance under the conditions used for proton nmr so the signal is removed to another part of the spectrum.

before shaking with D2O

slide31

O-H bonds and the D2O shake

As has been pointed out, the signal due to the hydroxyl (OH) hydrogen is a singlet.

It is possible to identify which signal is caused by the H of an O-H group by doing a ‘D2O shake’. A small amount of deuterium oxide D2O, a form of water, is added to the sample and the spectrum is re-run. Any signal due to O-H proton disappears.

The H in the O-H bond changes places with a deuterium atom, 2H or D, from D2O

Deuterium doesn’t exhibit nuclear magnetic resonance under the conditions used for proton nmr so the signal is removed to another part of the spectrum.

.

before shaking with D2O after shaking with D2O

H atoms attached to the N in amines also interchange with deuterium

slide32

1

2

3

4

NMR SPECTROSCOPY

When is a hydrogen chemically different?

TWO SIGNALS

Quartet and triplet :- ratio of peak areas = 3 : 2

Carbons 1 & 4 are the similar and so are carbons 2 & 3 so there are only two different chemical environments.

The signal for H’s on carbon 2 is a quartet - you ignore the two neighbours on carbon 3 because they are chemically identical.

BUTANE

slide33

1

2

3

4

NMR SPECTROSCOPY

When is a hydrogen chemically different?

TWO SIGNALS

Quartet and triplet :- ratio of peak areas = 3 : 2

Carbons 1 & 4 are the similar and so are carbons 2 & 3 so there are only two different chemical environments.

The signal for H’s on carbon 2 is a quartet - you ignore the two neighbours on carbon 3 because they are chemically identical.

TWO SIGNALS

both singlets :- ratio of peak areas = 2 : 1

Hydrogens on OH groups only give singlets. The signal for H’s on each carbon are not split, because

- H’s on the neighbouring carbon are chemically

identical... and

- H’s on adjacent OH groups do not couple.

BUTANE

ETHANE-1,2-DIOL

slide34

NMR SPECTROSCOPY - SUMMARY

An nmr spectrum provides several types of information :-

number of signal groups tells youthe number of different proton environments

chemical shift the general environment of the protons

peak area (integration) the number of protons in each environment

multiplicity how many protons are on adjacent atoms

In many cases this information is sufficient to deduce the structure of an organic molecule but other forms of spectroscopy are used in conjunction with nmr.

slide35

NMR SPECTROSCOPY

HOW TO WORK OUT AN NMR SPECTRUM

1. Get the formula of the compound

2. Draw out the structure

3. Go to each atom in turn and ask the ‘census’ questions

4. Work out what the spectrum would look like ... signals due to H’s nearer

electronegative atoms (Cl,Br,O) are shifted downfield to higher d values

THE BASIC “CENSUS”

Ask each hydrogen atom to...

- describe the position of the atom on which it lives

- say how many hydrogen atoms live on that atom

- say how many chemically different hydrogen atoms live

on adjacent atoms

BUT, REMEMBER THAT

H atoms on OH groups - ONLY PRODUCE ONE PEAK

- DON’T COUNT AS A NEIGHBOUR

slide36

ATOM

UNIQUE DESCRIPTION OF THE POSITION OF THE HYDROGEN ATOMS

H’S ON THE ATOM

CHEMICALLY DIFFERENT H’S ON ADJACENT ATOMS

SIGNAL SPLIT INTO

1

2

3

1

On an end carbon, two away from the carbon with the bromine atom on it

3

2

2+1 = 3

2

On a carbon atom second from the end and one away from the carbon with the bromine atom

2

3+2 = 5

5+1 = 6

3

On an end carbon atom which also has the bromine atom on it

2

2

2+1 = 3

NMR SPECTROSCOPY

“CENSUS” QUESTIONS

- describe where each hydrogen lives

- say how many hydrogens live on that atom

- say how many chemically different hydrogen

atoms live on adjacent atoms

1-BROMOPROPANE

slide37

Spectrum of 1-bromopropane

CHEMICAL SHIFTS

3 environments = 3 signals

Triplet d = 3.4

Sextet d = 1.9

Triplet d = 1.0

Signal for H’s on carbon 3 is shifted furthest downfield from TMS due to proximity of the electronegative halogen

1

2

3

TMS

5 4 3 2 1 0 d

slide38

Spectrum of 1-bromopropane

INTEGRATION

Area ratio from relative heights of integration lines = 2 : 2 : 3

Carbon 1 3

Carbon 2 2

Carbon 3 2

1

2

3

2

3

TMS

2

5 4 3 2 1 0 d

slide39

Spectrum of 1-bromopropane

SPLITTING

SPLITTING PATTERN

Carbon 1

Chemically different hydrogen atoms on adjacent atoms = 2

2 + 1 = 3

The signal will be a

TRIPLET

1

1

2

3

TMS

5 4 3 2 1 0 d

slide40

Spectrum of 1-bromopropane

SPLITTING

SPLITTING PATTERN

Carbon 2

Chemically different hydrogen atoms on adjacent atoms = 5

5 + 1 = 6

The signal will be a

SEXTET

2

1

2

3

TMS

5 4 3 2 1 0 d

slide41

Spectrum of 1-bromopropane

SPLITTING

SPLITTING PATTERN

Carbon 3

Chemically different hydrogen atoms on adjacent atoms = 2

2 + 1 = 3

The signal will be a

TRIPLET

3

1

2

3

TMS

5 4 3 2 1 0 d

The signal is shifted furthest away (downfield) from TMS as the hydrogen atoms are nearest the electronegative bromine atom.

slide42

Spectrum of 1-bromopropane

SPLITTING

3 environments = 3 signals

1 Triplet d = 1.0 3 H’s

2 Sextet d = 1.9 2 H’s

3 Triplet d = 3.4 2 H’s

Signal for H’s on carbon 3 is shifted furthest downfield from TMS due to proximity of the electronegative halogen

3

2

1

1

2

3

TMS

5 4 3 2 1 0 d

slide43

Spectrum of 1-bromopropane

1

2

3

TMS

SUMMARY

4 3 2 1 0 d

Peaks Three different signals as there are three chemically different protons.

Shift Signals are shifted away from TMS signal, are nearer to the halogen.

Splitting Signals include a triplet (d = 1.0) sextet (d = 1.8) triplet (d = 3.4)

Integration The integration lines show that the ratio of protons is 2:2:3

The signals due to the protons attached to carbon ...

C1 triplet (d = 1.0) coupled to the two protons on carbon C2 ( 2+1 = 3 )

C2 sextet (d = 1.8) coupled to five protons on carbons C1 and C3 ( 5+1 = 6 )

C3 triplet (d = 3.4) coupled to the two protons on carbon C2 ( 2+1 = 3 )

slide44

NMR SPECTROSCOPY

SUPPLEMENTARY QUESTIONS

1. Why is proton nmr more useful for the investigation of organic compounds ?

2. What other nucleus found in organic compounds is investigated using nmr ?

3. What compound is used as the internal reference for proton nmr chemical shifts ?

How many peaks does it produce and at what delta (d) value does it appear ?

4. What uses have been made of nuclear magnetic resonance in other scientific areas ?

Supplementary Questions - Answers

1. Because organic compounds tend to contain hydrogen atoms.

2. Carbon 13

3. Tetramethylsilane (TMS) gives a strong single peak at d = 0

4. Magnetic resonance imaging in body scanners

SEE NEXT PAGE FOR ANSWERS

slide45

NMR SPECTROSCOPY

SUPPLEMENTARY QUESTIONS

1. Why is proton nmr more useful for the investigation of organic compounds ?

2. What other nucleus found in organic compounds is investigated using nmr ?

3. What compound is used as the internal reference for proton nmr chemical shifts ?

How many peaks does it produce and at what delta (d) value does it appear ?

4. What uses have been made of nuclear magnetic resonance in other scientific areas ?

Supplementary Questions - Answers

1. Because organic compounds tend to contain hydrogen atoms.

2. Carbon 13

3. Tetramethylsilane (TMS) gives a strong single peak at d = 0

4. Magnetic resonance imaging in body scanners

slide62

CARBON-13

NMR SPECTROSCOPY

slide63

CARBON-13 NMR SPECTROSCOPY

After hydrogen, the most useful atom providing information is carbon-13.

Natural carbon contains about 1% of this isotope so the instruments for its detection need to be sensitive and spectra will take longer to record.

Only the chemical shift is important as each spectrum gives only single lines for each chemically equivalent carbon.

slide64

CARBON-13 NMR SPECTROSCOPY

After hydrogen, the most useful atom providing information is carbon-13.

Natural carbon contains about 1% of this isotope so the instruments for its detection need to be sensitive and spectra will take longer to record.

Only the chemical shift is important as each spectrum gives only single lines for each chemically equivalent carbon.

Environment Chemical shift / d

C - C (alkanes) 10 - 35

C - C=O 10 - 35

C - Cl or C - Br 30 - 70

C - N (amines) 35 - 65

C - OH 50 - 65

C = C (alkenes) 115 - 140

aromatic C’s (benzene rings) 125 - 150

C=O (esters, acids, amides) 160 - 185

C=O (aldehydes, ketones) 190 – 220

Carbon-13 nmr has wide applications in the study of natural

products, biological molecules and polymers.

slide65

H

H

H

HCCCBr

H

H

H

CARBON-13 NMR SPECTRA

Isomers

of C3H7Br

3 peaks 2 peaks

all three carbons are different the two outer carbons are similar

Br

H

H

HCCCH

H

H

H

slide66

H

H

H

HCCCBr

H

H

H

CARBON-13 NMR SPECTRA

Isomers

of C3H7Br

3 peaks 2 peaks

all three carbons are different the two outer carbons are similar

Ethanol

C2H5OH

Br

H

H

HCCCH

H

H

H

H

H

HC

COH

H

H

This is where the proton nmr spectrum of ethanol would be on the same scale.

H

H

H  C C  OH

H

H

slide67

CH3

H

H

H

H  C C  C  C H

H

H

H

H

CARBON-13 NMR SPECTRA

The carbon-13 spectrum of 2-methylbutane (CH3)2CHCH2CH3

Other isomers of C5H12

pentane CH3CH2CH2CH2CH3 3 peaks

2,3-dimethylpropane (CH3)4C 2 peaks

chemically equivalent carbon atoms

There are four chemically different carbon atoms in the molecule so there are four peaks in the C-13 nmr spectrum.

NO SPLITTING WITH C-13

ONLY ONE PEAK FOR EACH CARBON

slide68

CARBON-13 NMR SPECTRA - QUESTIONS

  • How many peaks would you expect there to be in the carbon-13 spectrum of…
  • butane CH3CH2CH2CH3
  • 2-methylpropane CH3CH(CH3)CH3
  • butanal CH3CH2CH2CHO
  • butanone CH3COCH2CH3
  • pentan-2-one CH3COCH2CH2CH3
  • pentan-3-one CH3CH2COCH2CH3
  • cyclohexane C6H12
slide69

CARBON-13 NMR SPECTRA - QUESTIONS

  • How many peaks would you expect there to be in the carbon-13 spectrum of…
  • butane CH3CH2CH2CH3 2
  • 2-methylpropane CH3CH(CH3)CH3 2
  • butanal CH3CH2CH2CHO 4
  • butanone CH3COCH2CH3 4
  • pentan-2-one CH3COCH2CH2CH3 5
  • pentan-3-one CH3CH2COCH2CH3 3
  • cyclohexane C6H12 1

19

slide70

CARBON-13 NMR SPECTRA - QUESTIONS

Identify the isomers of C4H8O

slide71

CARBON-13 NMR SPECTRA - QUESTIONS

Identify the isomers of C4H8O

A butanal

B butanone

C 2-methylpropanal

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CARBON-13 NMR SPECTRA - QUESTIONS

Identify the isomers of C6H12

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CARBON-13 NMR SPECTRA - QUESTIONS

Identify the isomers of C6H12

X hex-1-ene or hex-2-ene or

2-methylpent-1-ene or

3-methylpent-1-ene or

2-methylpent-2-ene or

3-methylpent-2-ene or

Y cyclohexane

Z 2,3-dimethylbut-2-ene

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REVISION CHECK

What should you be able to do?

Recall the how an nmr spectrum is produced

Explain and understand the origin of chemical shift

Explain and understand the purpose of integration

Explain and understand the purpose of shaking with D2O

Recall the differences between high and low resolution spectra

Explain and understand the origin of splitting patterns

Interpret and explain a simple proton or carbon-13 nmr spectrum

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NUCLEAR MAGNETIC RESONANCE SPECTROSCPY

THE END

KNOCKHARDY PUBLISHING