I.

1
H NMR
Chapter 4. Nuclear magnetic resonance spectroscopy
Reading:
Pavia
the rest of Chapter 3
Chapter 5
Chapter 6.1
1. Chemical equivalence
- protons in chemically identical environments - are chemically equivalent
- exhibit the same
C H
3
CH
3
CH
3
CH
3
C H
3
CH
3
O
CH
3
CH
3
H
H
H
H
O
O
O
O
1 signal for 12
1
H 1 signal for 6
1
H
- equivalence through symmetry considerations
- obvious non-equivalence
2 sets:
1 signal for 6
1
H in CH
3
1 signal for 4
1
H in CH
2 sets:
1 signal for 6
1
H in OCH
3
1 signal for 4
1
H in CH
2
C H
3
O
O
CH
3
2 sets:
1 signal for 3
1
H in CH
3
1 signal for 3
1
H in OCH
3
Example
Chemical and magnetic equivalence: Proton signal is a singlet
1. Chemical equivalence continued
- spectral regions
- chemical environment of the
1
H is important: - hybridization effects
- electronegativity effects
- magnetic anisotropy effects
deshielded shielded
variable
often given
as inset
see p. A-8 ff
Fig. 3.49
2. Integration
- determines the number of equivalent
1
H for a signal
- determined through the area under the signal
- given through a step trace (need a ruler!)
- provides first important label
digital information:
55.5 : 22 : 32.5
2.5 : 1 : 1.5
5 : 2 : 3 for a total of 10
1
H!
5 H 2 H 3 H
5 H 2 H 3 H
or mm
3. Simple (singlet) spectra
- signal is only one peak: singlet, s
C H
3
CH
3
O
C H
3
O
O
CH
3
4.0 3.0 2.0 1.0 0 ppm: -scale
-scale: 10 -
4.0 3.0 2.0 1.0 0 ppm
:2.0 ppm
reported:
2.1 s (6H)
s
(second important label)
work this way
reported:
2.0 s (3H)
3.65 s (3H)
C
3
H
6
O
C
3
H
6
O
2
s
3 H
-CH
3
s
3 H
-OCH
3
: multiplicity
: integration
: assignment
(third important label)
3. Simple spectra continued
4.0 3.0 2.0 1.0 0 ppm
4.0 3.0 2.0 1.0 0 ppm
7.0
C
6
H
10
O
4
C
6
H
8
O
4
reported:
2.55 s 4H
3.65 s 6H
reported:
3.8 s 6H
6.85 s 2H
for a total
of 10
1
H
for a total
of 8
1
H
s
2 H
-CH
2
-
s
3 H
-OCH
3
integration:
1.5 : 1 or
3 : 2 or revised
6 : 4
s
3 H
-OCH
3
s
1 H
C=C-H
thoughts:
- aromatic?
- U?
- empirical formula?
4. Estimation of
1
H
O
O
O
O
O
O
O
O
O
O
- from increment systems
- for X-CH
2
-Y (and X-CH
3
, where Y adds 0)

1
H (ppm) = 0.23 + increments for X and Y substituents
see p. A-17
- for

1
H (ppm) = 5.25 + increments for gem, trans and cis substituents
a
b
a
b
a
b
H
see p. A-18
gem
trans
cis

1
H
a
= 0.23 + 1.55 + 0 = 1.78 ppm (exp. 2.0 ppm) ok

1
H
b
= 0.23 + 3.13 + 0 = 3.36 ppm (exp. 3.65 ppm) ok

1
H
a
= 0.23 + 1.55 + 0.47 = 2.25 ppm (exp. 2.55 ppm) ok

1
H
b
= 0.23 + 3.13 + 0 = 3.36 ppm (exp. 3.65 ppm) ok
?

1
H
a
= 0.23 + 3.13 + 0 = 3.36 ppm (exp. 3.8 ppm) ok?

1
H
b
= 5.25 + 0.84 + 1.15 + 0 = 7.24 ppm (exp. 6.85 ppm) ok
?
gem cis
4. Estimation of
1
H continued
- from an increment system
- for
a
b
H

1
H (ppm) = 7.27 + increments for substituents
see p. A-19
O
O
OH
Cl
Cl Cl
c

1
H
a
= 0.23 + 1.55 + 3.23 = 5.01 ppm (exp. 4.6 ppm) ok
? ?

1
H
b
= 7.27 + 20.03 + (-0.09) + (-0.09) = 7.15 ppm (exp. 7.5 ppm) ok?
o-Cl p-Cl m-OR

1
H
c
= 11-12 ppm
O
O
OH
Cl
Cl Cl
7.0 4.0
inset;
problem:
no scale!
5. Magnetic anisotropy
- phenomenon observed for protons near -systems
- mobile -electrons create local magnetic fields
- shielding and deshielding regions
- unusual chemical shifts
2-3 ppm
5-7 ppm >7 ppm
-1.4 ppm
-0.5 ppm
-1.8 ppm
general shielding observations:
reasoning:
antiparallel:
shielded (+)
weaker apparent B
0
parallel:
deshielded (-)
stronger apparent B
0
6 18 10
9 ppm
6. Spin-spin coupling
- chemically equivalent protons do not always just give a singlet
- signal can be split into:
- 2 lines: doublet, d
- 3 lines: triplet, t
- 4 lines, quartet, q
- 5 lines, quintet, quint
- 6 lines, sextet, sext
- 7 lines, septet, sept
# of lines depends on the number of neighbouring
1
H:
n+1 rule:
n+1 lines in the signal for n equivalent neighbouring
1
H
- protons can couple over
- 2 bonds:
2
J coupling
- 3 bonds:
3
J coupling
- 4 bonds or more:
4
J,
5
J coupling or long-range coupling (mostly not observed)
H
C
H
H
C C
H
but across multiple bonds:
H H
H
H
X
Y
H
H
6. Spin-spin coupling continued
-
3
J coupling explained:
H
C C
H
H
C C
H
H
signal observed for this
1
H
1
H sees one
1
H on the next carbon atom:
- total of 2 different spin situations: and
- signal for
1
H splits into 2 lines: doublet

equal probability
same area/height
intensity ratio in signal 1:1
signal observed for this
1
H

1
H sees two
1
H on the next carbon atom:
- total of 3 different spin situations
- signal for
1
H splits into 3 lines: triplet

intensity ratio in signal 1:2:1

total spin observed by
1
H: + -
total spin observed by
1
H: +1 0 -1
6. Spin-spin coupling continued
- for I = , intensities of the lines within a signal follow the binomial distribution
- Pascals triangle
1
1 1
1 2 1
1 3 3 1
1 4 6 4 1
1 5 10 10 5 1
1 6 15 20 15 6 1 septet, outer lines
often tough to detect
OH
looks like only 5 lines
dont miss the outer lines!
now we can
predict
1
H spectra
Example
Predict (draw) the
1
H NMR spectrum for .
Consider , multiplicity and integration.
O
O
7. Spectra with simple multiplets
O
O
O
t
3 H
-CH
2
-CH
3
s
3 H
EW-CH
3
q
2 H
EW-CH
2
-CH
3
t
(3 H)
-CH
2
-CH
3
q
(2 H)
-O-CH
2
-CH
3
s
(3 H)
EW-CH
3
Table 3.8:
examples of
splitting patterns
7. Spectra with simple multiplets continued
- multiplet issues
I. Multiplicity
CH
3
CH
2
CH
2
CH
2
Cl CH
3
CH
2
CH
2
CH
2
OCH
3
Fig. 3.41 Fig. 3.43
sext quint
sext? quint?
Or both rather mult? Will discuss
later.
7. Spectra with simple multiplets continued
couples to a
1
H of a downfield signal
more complex
coupling
c
a
b
d
- multiplet issues
II. Skewing in multiplets
- first information on which protons are coupled
4
J
coupling
C C
Cl I
H H
Ph Ph
8. Coupling constant, J
- number assigned to the spread of the lines in a multiplet
- more reliable information on which protons are coupled than skewing
- for two multiplets from coupling protons, J is the same
X A
4 ppm 5
H
A
H
X
J, same! J
if this spectrum was taken at 60 MHz:
1 ppm or 60 Hz
0.1 ppm
3
J 6 Hz
AX spin system:
- Pople notation
- two chemically different protons, is (relatively) large
8. Coupling constant, J, continued
A
2
X
3
spin system:
- Pople notation
- two sets of chemically different protons, is (relatively) large
ICH
2
CH
3
all spacings are the same,
3
J 7.5 Hz
Table 3.9:
generalized J values
and
A-13 ff
Example
Assuming that
3
J is greater upon Br-substitution, which structure is correct?
2 ppm 4
Br O
O
NO
2
O
O
Br
O
2
N
8. Coupling constant, J, continued
- origin of the coupling: via the electrons in the bonds
: interaction between spins of nuclei and electrons
size of J depends on the geometry:
-
2
J depends on the HCH bond angle: larger J with smaller angle
(better interaction of -orbitals)
-
3
J depends on the HCCH torsion angle: minimum function at 90
(no interaction of -orbitals)
2
J
HH
[Hz]
Fig. 5.4
Fig. 5.7

H
C
H

3
J
HH
[Hz]
H
C
C
H
Karplus curve
H
H
H
H
H
H
H
H
109
2
J 12 Hz
118
2
J 5 Hz
180
3
J 12 Hz
60
3
J 4 Hz

9. First and second order spectra

- sets of protons in Table 3.8 are chemically and magnetically equivalent
give one show no J
Example for protons that are chemically, but not magnetically equivalent
Br
Br
H
A
H
A
H
X
H
X
H
X
and H
X
: chemically equivalent
but
H
A
sees H
X
trans
sees H
X
cis
: magnetically inequivalent
two different
3
J
not A
2
X
2
but AAXX system
gives rise to a second-order spectrum:
- splitting patterns, intensities and # of lines are wrong
- n+1 rule breaks down
Contrast:
9. First and second order spectra continued
- Second-order spectra are also found for sets of nuclei if /J < 10
A
2
B
2
A
2
X
2
60 MHz
300 MHz
both in Hz
Y Z
10. Non-equivalence within a group
- coupling within a group (CH
2
, e.g.) when protons are not chemically equivalent
O
H
H
H
Ph
B
A
C
all three
1
H are different (chemically and magnetically)
all will couple amongst each other
this is not , H
C
does not couple into a triplet!
C H
2
O
H
Ph
C
- observed coupling here:
3
J
AC

3
J
BC
,
2
J
AB
- we expect - three different coupling constants
- signals of different multiplicity than so far
- we can analyse coupling constants
- appearance of a signal
through tree-diagrams

10. Non-equivalence within a group continued

- analysis with a tree-diagram
simple system:
coupling to one type of
1
H
advanced system:
coupling to two types of
1
H
H
C C
H
H
C C
H
H
A X A X
X
doublet for H
A
triplet for H
A
H
A
H
A

undisturbed signal
signal split by H
X
H
C C
H
H
A M
X
AMX system
one doublet for H
A
with H
M
, one doublet for H
A
with H
X
doublet of doublets for H
A
, dd
doublet with H
X
doublet with H
M

H
A
3
J
AX
3
J
AM
1 signal, 4 lines
10. Non-equivalence within a group continued
- two uses of a tree-diagram
towards a spectrum: what does the signal look like?
from a spectrum: what are the coupling constants?
H
A
- use larger J first
- stay symmetrical
not like this:
H
A
: not like this, either!
- take distance within and between multiplets
H
A
between
within
1 2 3 4
for a dd, measure
within: distance of lines 1 and 2 or 3 and 4
between: distance of lines 1 and 3 or 2 and 4
10. Non-equivalence within a group continued
- appearance of the spectrum
O
H
H
H
Ph
B
A
C
in Hz: can use for J directly!
in ppm: can use for J
(300 MHz spectrum)
H
A
H
C
H
B
dd
1 H
dd
1 H
dd
1 H
tree-diagram
analysis
example:
J
AC
appears twice:
- in the signal for H
A
- in the signal for H
C
note:
3
J
AC
3
J
BC
but
2
J
AB
10. Non-equivalence within a group continued
- two practice patterns
CH CH
2
C
O
H
Br
Br
multiplicities:
spin system: spin system:
tree-diagram (assume J
1
> J
2
):
How do you determine which J is which?
multiplicities:
tree-diagram:
CH CH
2
CH
2
C(CH
3
)
3
10. Non-equivalence within a group continued
- the appearance of a dt as J changes
H
A
J
1
14 Hz
J
2
3 Hz
H
A
J
1
14 Hz
J
2
6 Hz
H
A
J
1
8 Hz
J
2
3 Hz
H
A
J
1
6 Hz
J
2
3 Hz
10. Non-equivalence within a group continued
- coupling examples in alkenes
R
H
H
R
R
H
H
R'
H
R
H
R'
R
R'
H
H
H
R
H
H
1
H are chemically and magnetically equivalent
s, no splitting
2 d,
3
J 16 Hz (large)
2 d,
3
J 8 Hz
2 d,
2
J 0-5 Hz
3 dd
H
H
C H
3
COOH
Table A6.2
5.25
+ 1.00
- 0.26
= 4.99
5.25
+ 1.35
+ 0.44
= 7.04
11. Non-equivalence for geminal groups
- two protons in CH
2
groups
- two CH
3
in i-propyl groups
can be homotopic, enantiotopic, diastereotopic
: which of the three is important for the appearance of the spectrum
- homotopic protons: replacement of either
1
H gives identical molecules
- enantiotopic protons: replacement of either
1
H gives enantiomers
H H
X X
H D
X X
D H
X X
and
H H
X Y
H D
X Y
D H
X Y
and
protons are equivalent, give a singlet
protons appear to be equivalent, give a singlet only in
achiral solvents
11. Non-equivalence for geminal groups continued
- diastereotopic protons: replacement of either
1
H gives diastereomers
protons are not equivalent, have different
H H
X Y
H D
X Y
D H
X Y
and
* * *
, often split with
2
J coupling
Y* contains a C*
Cl
Cl
Example
Cl
Cl
HH
not a regular CH
2
group,
H are diasterotopic
dd dd m
*
2
J
AB
11 Hz
3
J
AC
8 Hz
3
J
BC
5 Hz
CH
3
C H
3
OH
- diastereotopic protons: replacement of either
1
H gives diastereomers
Example
not a regular i-propyl group,
CH
3
are diasterotopic
*
OH
2 d,
not t!
(d)
11. Non-equivalence for geminal groups continued
Read by yourself: Chapter 6.1
12. Protons on oxygen
, so that you can explain why CH
3
CH
2
OH has these two different spectra
ordinary sample ultrapure sample