Welcome to Scribd, the world's digital library. Read, publish, and share books and documents. See more
Download
Standard view
Full view
of .
Look up keyword
Like this
2Activity
0 of .
Results for:
No results containing your search query
P. 1
113 HIGH RESOLOUTION NMR SPECTROSCOPY

113 HIGH RESOLOUTION NMR SPECTROSCOPY

Ratings: (0)|Views: 98 |Likes:
Published by Zara
Uploaded from Google Docs
Uploaded from Google Docs

More info:

Categories:Types, School Work
Published by: Zara on May 13, 2012
Copyright:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

12/17/2013

pdf

text

original

 
High Resolution NMR Spectroscopy
Number 113
1
C
 hem
 F
 actsheet
www.curriculum-press.co.uk
To succeed in this topic you need to understand:
the structure of atoms
the functional groups of the organic compounds studied at ASand A2
that chemists need to analyse compounds (for example throughmass spectrometry and infra-red)
After working through this Factsheet you will be able to:
understand the importance of NMR as an analytical technique
predict and interpret high resolution proton NMR spectra
What is NMR?
NMR stands for
nuclear magnetic resonance
. It is a powerfultechnique which gives us detailed information about the structureof compounds. NMR can be used to analyse a number of elementsin compounds provided they have an odd mass number; theseinclude
13
C,
19
F and
31
P, but is most commonly used to studyhydrogen atoms,
1
H. Remember that the nucleus of a hydrogenatom contains a single proton, so we often refer to hydrogen NMRas proton NMR. NMR is always used in conjunction with othertechniques, like mass spectrometry and infra-red, but is arguablythe most powerful method of analysis available to organic chemists.
How does NMR work?
Hydrogen nuclei have a property called spin, which makes thembehave like tiny magnets. When you hold the nuclei in a magneticfield, they align themselves with the field, like compass needles allpointing north (Fig 1).
Fig 1 Hydrogen nuclei without and with a magnetic field applied
No magnetic field applied
   D   i  r  e  c   t   i  o  n  o   f  a  p  p   l   i  e   d  m  a  g  n  e   t   i  c   f   i  e   l   d
If exactly the right amount of energy is absorbed by the nuclei, theywill flip and point in the other direction (Fig 2). This is called nuclearmagnetic resonance.
Fig 2 Hydrogen nuclei absorb energy and their spin flips
   D   i  r  e  c   t   i  o  n  o   f  a  p  p   l   i  e   d  m  a  g  n  e   t   i  c   f   i  e   l   d
The exact amount of energy required depends on the chemicalenvironment of the hydrogen nuclei. Nuclei with a high electrondensity surrounding them are shielded from the effects of themagnetic field, so require more energy, while nuclei near to anelectron-withdrawing group like chlorine or oxygen are deshieldedand need less energy. The NMR machine detects the amount of energy needed and scans through a range of energies until all thehydrogen nuclei have flipped.
How is an NMR carried out?
To carry out an NMR spectrum, the sample is first dissolved in asolvent. The solvent must not contain any hydrogen atoms, sincethese would interfere with the resonance of the sample. The solventsnormally used are tetrachloromethane (CCl
4
), or deuterated solventslike CDCl
3
, where the hydrogen atoms have been replaced bydeuterium atoms (the
2
H isotope of hydrogen), which do notinterfere with the magnetic resonance.Spectra are calibrated usingtetramethylsilane (TMS) (Fig 3).
Fig 3 Tetramethylsilane
CH
3
SiCH
3
CH
3
H
3
C
All the hydrogen atoms in TMS are in the same, highly shielded,environment and so will produce a single peak in the NMR spectrum.The horizontal axis of the spectrum is called the chemical shift (
δ
),which is measured in parts per million (ppm). It indicates thedifference in absorbed energy between the TMS protons and thesample protons. The peak for TMS at 0 ppm does not always appearin the spectra, since machines are often internally calibrated, but if there is a peak at 0 ppm, it will be due to the TMS protons.
What does an NMR spectrum tell us?
Fig 4 shows the proton NMR spectrum of 1,2-dichloro-2-methylpropane. In the spectrum there are two peaks, at 1.6 and 3.7ppm. There are four pieces of information we can gather from thesepeaks.
Fig 4 The proton NMR spectrum of 1,2-dichloro-2-methylpropane
δ
(ppm)CHHHCCCHHHHHClCl109876543210
 
Chem Factsheet
2
113 High Resolution NMR Spectroscopy
1.The number of different chemical environments in the compound
Firstly, the NMR shows us that there are two different chemicalenvironments for hydrogen atoms in this compound (Figure 5).The six hydrogens in the methyl (CH
3
) groups are in the sameenvironment since they are the same distance from the chlorineatoms and from the central carbon atom. The two hydrogens inEnvironment 2 are closer to one of the chlorine atoms andtherefore chemically different from Environment 1.
Fig 5 The two hydrogen environments in 1,2-dichloro-2-methylpropane
2.The relative number of hydrogens in each environment
The second piece of information comes from the integrationcurve, the line above each peak. The height of this linecorresponds to the area under the curve and therefore tells usthe relative numbers of hydrogen atoms in the differentenvironments. If you measure the height of the two integrationcurves in Fig 4 you will find that they are in a ratio of 1:3. Thismatches the structure of the compound, with two hydrogennuclei in Environment 2 and six in Environment 1.
3.The electron density around the hydrogen atoms
The third piece of information is about the nature of eachenvironment. This information is given by the chemical shifts(Table 1). In the exam, you will be given the chemical shifts thatyou need, so don’t try to memorise them.Looking at Fig 4 again, the peaks at 1.6 and 3.7 ppm correspondrespectively to the methyl hydrogens (Environment 1) and theCH
2
Cl hydrogens (Environment 2), which are deshielded by thecloser electron-withdrawing chlorine atom.
Table 1 Typical chemical shifts of a range of hydrogen nuclei
Chemical shift (ppm)Proton
R-C
H
3
0.8-1.2R
2
-C
H
2
1.1-1.5R
3
-C
H
1.5R
3
-O
H
1.0-6.0Note that the OH hydrogenatom can appear almostanywhere along the chemicalshift scaleCOC
H
2
RR1.0-6.0R-C
H
2
-Cl2.5-4.3R-C
H
2
-OH3.3-4.04.4-6.9CC
H
RRR9.2-9.8COO
H
RCHHHCCCHHHHHClClenvironment 1environment 2CO
H
R10.0-12.0
4.How many neighbours each hydrogen atom has
Finally, the spectrum gives us information about theneighbouring hydrogen atoms of the nuclei. This comes fromthe splitting pattern, where the peaks in the spectrum are splitinto groups of sub-peaks (Table 2). The splitting pattern dependson how many non-equivalent hydrogen nuclei are on theadjacent carbon atoms. Splitting occurs because the magneticfields of different hydrogen nuclei interact with each other, andthe number of sub-peaks is always one more (n+1) than thenumber of hydrogens (n) on the adjacent carbon atom. Youwon’t need to explain how this happens, but you do need tounderstand its effects.
Table 2 Splitting patterns
0SingletR
3
CC
H
1DoubletR
2
CH-C
H
2TripletRCH
2
-C
H
3QuartetCH
3
-C
HNumber of hydrogen atomson the adjacentcarbon atom (n)Splittingpattern(n+1)How it looksTypicalstructure
In the NMR of 1,2-dichloro-2-methylpropane (Fig 4), both peaks aresinglets. This means that none of the hydrogens are adjacent tonon-equivalent hydrogen nuclei (Fig 6).
Fig 6 No adjacent hydrogen atoms to either environment
 
CHHHCCCHHHHHClClenvironment 1environment 2This carbon atom is adjacent to both environments. It has no hydrogenatoms so both peaks are singlets
 
Chem Factsheet
3
113 High Resolution NMR Spectroscopy
Fig 7 shows the proton NMR spectrum of ethyl ethanoate. Thethree peaks show that there are three different environments for thehydrogen atoms. The integration curves give us a ratio of 2:1:3,and analysis of the splitting patterns (Table 3) leads to a fullassignment of peaks (Fig 8).
Fig 7 The proton NMR spectrum of ethyl ethanoate
11109876543210
 
H
δ
(ppm)
Table 3 Assigning the peaks in the NMR of ethyl ethanoate
ChemicalRelativeSplittingNumber ofAssignedshift numberpatternadjacentto protonof hydrogenhydrogensgroupatoms
4.12Quartet3b2.03Singlet0a1.23Triplet2c
CHHHCOOCCHHHHHCHHHCOOCCHHHHH
Fig 8 Assigned peaks in ethyl ethanoate
cba
Worked example
1.Draw the displayed formula of chloroethane.2.State the number of different hydrogen environments foundin chloroethane.3.Predict approximate chemical shifts for the differentenvironments.4.Predict the splitting pattern of the NMR peaks.5.Sketch the NMR spectrum of chloroethane, includingintegration curves to show the relative numbers of hydrogenatoms in each environment.
Answer
The displayed formula and NMR spectrum of chloroethane areshown in Fig 9. There are two hydrogen environments: the methylhydrogens (a) and the CH
2
Cl hydrogens (b). Using Table 1 theapproximate chemical shifts are 1.1-1.5 and 2.5-4.3 ppm respectively.The peak at about 1.4 ppm (corresponding to the CH
3
) is split into atriplet by the neighbouring CH
2
Cl hydrogens, while the peak at 3.5ppm (corresponding to the CH
2
Cl) is split into a quartet by themethyl group.
Fig 9 Chloroethane and its NMR spectrum
δ
(ppm)109876543210HCHHHCClHHba-CH
2
Cl(b)-CH
3
(a)
An unusual case: Alcohol OH groups
The hydrogen atom in alcohol OH groups is unusual in two ways.Firstly, as it says in Table 1, this proton can have almost any chemicalshift. The actual shift depends on, among other things, the solventthat the compound is dissolved in. Secondly, at room temperatureOH proton peaks do not get split like others, no matter how manyadjacent hydrogen nuclei there are. This helps you, therefore, toidentify them in the spectra since they are always singlet peaks.
Practice Questions
1.For each of the following compounds, draw the displayedformula, label the different hydrogen environments and predictapproximate chemical shifts for each peak in the proton NMRspectrum:(a)2-chloropropane(b)1-chloropropane(c)ethanol(d)ethanoic acid(e)2-chloropentane(f)3-chloropentane2.Sketch the proton NMR spectra you would expect for thefollowing compounds:(a)ethanoic acid(b)propanone(c)ethanal(d)ethanol

You're Reading a Free Preview

Download
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->