[Link].
UK
NMR
SPECTROSCOPY
© [Link] A2 1071 02-May-2024
• Sample usually dissolved in solvent
• Placed in long, narrow tube
• Uses radio-waves
• In a very strong magnetic field (uses
superconducting electromagnets)
• Compound absorbs radio-waves
to change the direction of ’spin’
of the nucleus
• Used by organic chemists to
look at 1H and 13C atoms
• Sample usually dissolved in solvent
• Placed in long, narrow tube
1
H NMR of ethanol
• Sample usually dissolved in solvent
• Place in long, narrow tube
• Samples are dissolved in solvents free of 1H atoms
• e.g. CCl4, CDCl3
© [Link] A2 1071 02-May-2024
• Radio-wave absorptions are measured relative to those for TMS CH3
(tetramethylsilane) in ppm – this is called the chemical shift (d) CH3 Si CH3
CH3
• TMS is used because: • its signal is away from all the others
• it only gives one signal
• it is non-toxic
• it is inert
© [Link] A2 1071 02-May-2024
Chemical shift (d) – the
closer the H/C is to
electronegative atoms and/or
double bonds – the bigger the
chemical shift
Similar or 1
H NMR 13
C NMR
different
Number of similar One signal for each set of equivalent 1H or 13C atoms
signals
Position of similar The closer the atom to a very electronegative atom and/or double bond, the greater
signal the chemical shift
Relative size different Relative area of signals related to relative No link between area of signal to number
of signals number of 1H atoms of 13C atoms
Splitting of different Signal split by 1H atoms on adjacent atom No splitting
signals (into doublets, triplets, etc)
© [Link] A2 1071 02-May-2024
© [Link] A2 1071 02-May-2024
TASK 1
5-40 C H 3 5-40
CH3 CH2 C CH3
5-40
Br
10-70 4 signals
90-150
C H 3 5-40
CH2 C CH3
90-150
3 signals
TASK 1
90-150 3 signals
CH2 CH CH3
90-150 5-40
Cl
5-40
C H 3 C H CH 3
10-70 2 signals
TASK 1
2 signals
O
20-50
CH3 C CH 3
190-220
25-60
1 signal
C H 3 NH 2
TASK 1
5 signals
20-50 O 50-90
CH3 CH2 C O CH2 CH3
5-40 160-185 5-40
3 signals
Br Br 5-40
10-70
CH 2 CH C H 3
10-70
TASK 1
5 signals
50-90
20-50 O CH 3
CH3 CH 2 C O C CH 3
5-40 160-185 CH 3 5-40
90-150
5-40
CH3 CH CH CH3
2 signals
TASK 2 propanoic acid pentane 2-chlorpropane
propanone 2,2-dichloropropane 2,3-dimethylbut-2-ene
A C E
B D F
TASK 2
A C E
B D F
© [Link] A2 1071 02-May-2024
Similar or 1
H NMR 13
C NMR
different
Number of similar One signal for each set of equivalent 1H or 13C atoms
signals
Position of similar The closer the atom to a very electronegative atom and/or double bond, the greater
signal the chemical shift
Relative size different Relative area of signals related to relative No link between area of signal to number
of signals number of 1H atoms of 13C atoms
Splitting of different Signal split by 1H atoms on adjacent atom No splitting
signals (into doublets, triplets, etc)
© [Link] A2 1071 02-May-2024
CH3 CH2 CH3 2 sets of equivalent H’s: ratio 6:2 (3:1)
Br
CH3 CH CH2 CH3 4 sets of equivalent H’s: ratio [Link]
Br
CH3 CH CH2 CH2 CH3 5 sets of equivalent H’s: ratio [Link]
CH3
CH3 C CH2 CH3 4 sets of equivalent H’s: ratio [Link]
OH
© [Link] A2 1071 12-Jun-2016
TASK 3a
CH3
CH3 CH2 C CH3 CH2 CH CH3
Br 3 signals: ratio [Link]
3 signals: ratio [Link]
CH3 Cl
CH2 C CH3 C H 3 C H CH 3
2 signals: ratio 6:2 (3:1) 2 signals: ratio 6:1
© [Link] A2 1071 02-May-2024
TASK 3a
O O
CH3 C CH 3 CH3 CH2 C O CH2 CH3
1 signal 4 signals: ratio [Link]
Br Br
C H 3 NH 2 CH 2 CH C H 3
2 signals: ratio 3:2 3 signals: ratio [Link]
© [Link] A2 1071 02-May-2024
TASK 3a
O CH 3
CH3 CH 2 C O C CH 3 CH3 CH CH CH3
CH 3
3 signals: ratio [Link] 2 signals: ratio 6:2 (3:1)
© [Link] A2 1071 02-May-2024
These four signals have the same overall area and
represent the same number of H atoms
© [Link] A2 1071 02-May-2024
H atoms couple together splitting signals
Lines = number of H next door + 1
n+1 rule
8 7 6 5 4 3 2 1 0
chemical shift
© [Link] A2 1071 02-May-2024
signal singlet doublet triplet quartet
appearance
number of lines 1 2 3 4
number of H’s next
0 1 2 3
door
relative size 1:1 [Link] [Link]
© [Link] A2 1071 02-May-2024
Lines = number of H next door + 1
n+1 rule
But H atoms do not couple to
• H’s that are equivalent
• H’s on O/N
© [Link] A2 1071 02-May-2024
© [Link] A2 1071 02-May-2024
© [Link] A2 1071 02-May-2024
© [Link] A2 1071 02-May-2024
© [Link] A2 1071 02-May-2024
Two identical sets of 1H atoms
produce one signal that is twice
the size that one set would
produce (not two signals!)
© [Link] A2 1071 02-May-2024
TASK 3b
CH3
CH3 CH2 C CH3 CH2 CH CH3
Br 3 signals: ratio [Link]
dmd
3 signals: ratio [Link]
tqs
CH3 Cl
CH2 C CH3 C H 3 C H CH 3
2 signals: ratio 6:2 (3:1) 2 signals: ratio 6:1
ss dm
© [Link] A2 1071 02-May-2024
TASK 3b
O O
CH3 C CH 3 CH3 CH2 C O CH2 CH3
1 signal 4 signals: ratio [Link]
s tqqt
Br Br
C H 3 NH 2 CH 2 CH C H 3
2 signals: ratio 3:2 3 signals: ratio [Link]
tq dmd
© [Link] A2 1071 02-May-2024
TASK 3b
O CH 3
CH3 CH 2 C O C CH 3 CH3 CH CH CH3
CH 3
3 signals: ratio [Link] 2 signals: ratio 6:2 (3:1)
tqs dq
© [Link] A2 1071 02-May-2024
[Link]
© [Link] A2 1071 02-May-2024
[Link]
© [Link] A2 1071 02-May-2024
TASK 4
[Link] [Link]
1:2
2:3
© [Link] A2 1071 02-May-2024
TASK 5
q s q d t q
© [Link] A2 1071 02-May-2024
TASK 5
d t m q m
© [Link] A2 1071 02-May-2024
2.1–2.6
H on C next
to C=O 0.7–1.2
CH3 next to 0.7–1.2
normal C CH3 next to
normal C
O CH3
1.2–1.4
CH 3 C O C H CH 2 C H 3 H on C with normal
C each side
3.7–4.1
H on C next to
O next to C=O
3
quartet & triplet triplet & triplet singlet singlet 9
quartet & doublet
2:3 2:2 1 1:3
© [Link] A2 1071 02-May-2024
O O
CH3 C CH2 CH2 C O CH2 CH3 3
2 2
2
© [Link] A2 1071 02-May-2024
