Chapter 13: Spectroscopy

Methods of structure determination

Nuclear Magnetic Resonances (NMR) Spectroscopy
(Sections 13.3-13.19)
Infrared (IR) Spectroscopy (Sections 13.20-13.22)
Ultraviolet-visible (UV-Vis) Spectroscopy (Section 13.23)
Mass (MS) spectrometry (not really spectroscopy)
(Section 13.24)
Molecular Spectroscopy: the interaction of electromagnetic
radiation (light) with matter (organic compounds). This
interaction gives specific structural information.

13.24: Mass Spectrometry:

molecular weight of the sample

formula

The mass spectrometer gives the mass to charge ratio (m/z),

therefore the sample (analyte) must be an ion.
Mass spectrometry is a gas phase technique- the sample must
be vaporized.
Electron-impact
ionization
Sample Inlet
10-7 - 10-8 torr

ionization
chamber
R-H

e_
R-H

(M+)

electron beam
70 eV
(6700 KJ/mol)

proton
neutron
electron

mass
analyzer
m/z

1.00728 u
1.00866 u
0.00055 u
2

mass
m
=
=
charge
z

B2 r2
2V

B= magnetic field strength

r = radius of the analyzer tube
V= voltage (accelerator plate)
Magnetic
Field, Bo

Ions of selected
mass/charge ratio
are detected

Ions of non-selected
mass/charge ratio
are not detected

Ionization
chamber
3

The Mass Spectrometer

Exact Masses of Common Natural Isotopes

Isotope
1H
2H
12C
13C
14N
15N
16O
17O
18O

mass

natural abundance

Isotope

mass

natural abundance

1.00782
2.01410

99.985
0.015

19F

18.99840

35Cl

12.0000
13.0033

98.892
1.108 (1.11%)

37Cl

34.96885
36.96590

75.77
24.23 (32.5%)

14.00307
15.00010

99.634
0.366 (0.38%)

81Br

78.91839
80.91642

50.69
49.31 (98%)

15.99491
16.99913
17.99916

99.763
0.037 (0.04%)
0.200 (0.20%)

79Br

127I

126.90447

100.00

100.00

Molecular Ion (parent ion, M) = molecular mass of the analyte;

sample minus an electron
Base peak- largest (most abundant) peak in a mass spectrum;
arbitrarily assigned a relative abundance of 100%.

m/z=78 (M+)

(100%)

C6H6
m/z = 78.04695

m/z=79 (M+1)

(~ 6.6% of M+)

The radical cation (M+) is unstable and will fragment into

smaller ions
m/z=15

Relative abundance (%)

m/z=16 (M+)

H C H

H
H C+

charge neutral
m/z = 15 not detected

m/z = 16

m/z=17

(M+1)

m/z=14

H C H

H H H
H C C C H

m/z=29

-e

-e

m/z=43

m/z=44

(M)

H H H
H C C C

H H H
_

H H H

H H
H H

m/z

charge neutral
not detected

charge
neutral not
detected

H
+

H H

m/z = 29

H C C

m/z = 43

H H
H C C

H H H

m/z = 44

H C C C H

m/z=45

(M+1)

H H H
H C C C

H H H

H H H

m/z=15

charge neutral
not detected

m/z = 14

m/z
Relative abundance (%)

-e

H C H

C H
H

charge neutral
not detected

+C H
H

m/z = 15

35Cl

m/z=112

(M+)

Cl

37Cl

34.96885
36.96590

75.77
24.23 (32.5%)

m/z=114

(M+ +2)

m/z=77

m/z=113

(M+ +1)

m/z=115

(M+ +3)

m/z
Br

m/z=77

79Br

m/z=156

(M+)

m/z=157

(M+ +1)

m/z=158

(M+ +2)

81Br

78.91839
80.91642

50.69
49.31 (98%)

m/z=159

(M+ +3)

m/z

Mass spectra can be quite complicated and interpretation difficult.

Some functional groups have characteristic fragmentation
It is difficult to assign an entire structure based only on the mass
spectrum. However, the mass spectrum gives the mass and
formula of the sample, which is very important information.
To obtain the formula, the molecular ion must be observed.
Soft ionization techniques
Methods have been developed to get large molecules such as
polymers and biological macromolecules (proteins,
peptides, nucleic acids) into the vapor phase

13.25: Molecular Formula as a Clue to Structure

Nitrogen rule: In general, small organic molecules with an
odd mass must have an odd number of nitrogens.
Organic molecules with an even mass have zero or an
even number of nitrogens
If the mass can be determined accurately enough, then the
molecular formula can be determined (high-resolution
mass spectrometry)
Information can be obtained from the molecular formula:
Degrees of unsaturation: the number of rings and/or
-bonds in a molecule (Index of Hydrogen
Deficiency)
9

Degrees of unsaturation


saturated hydrocarbon


CnH2n+2


cycloalkane (1 ring)


CnH2n


alkene (1 -bond)



CnH2n


alkyne (2 -bonds)


CnH2n-2



For each ring or -bond, -2H from the formula of the saturated alkane

H H

H
H

H
H
H

H H

C6H14
- C6H12
H2
1
2

2=1

Hydrogen Deficiency

Degrees of Unsaturation

C6H14
- C6H6
H8
1
2

H
H

H
H

8=4

10

Correction for other elements:

For Group VII elements (halogens): subtract 1H from the
H-deficiency for each halogen,
For Group VI elements (O and S): No correction is needed
For Group V elements (N and P): add 1H to the H-deficiency
for each N or P
C10H14N2

C12H4O2Cl4

11

13.1: Principles of molecular spectroscopy:

Electromagnetic radiation
organic
molecule
(ground state)

light
h

organic
relaxation organic
+ h

molecule
molecule
(excited state)
(ground state)

Electromagnetic radiation has the properties of a particle

(photon) and a wave.

= distance of one wave

= frequency: waves per unit time (sec-1, Hz)
c = speed of light (3.0 x 108 m sec-1)
h = Plank s constant (6.63 x 10-34 J sec)

12

Quantum: the energy of a photon

E = h

=
E=

E
x-rays

!-rays

10-10

10-8

short
high
high

hc

E -1
Vis

UV

10-6

10-5

-1

IR

10-4

microwaves

10-2

Wavelength ()
Frequency ()
Energy (E)

radiowaves

108

(cm)

long
low
low
13

13.2: Principles of molecular spectroscopy:

Quantized Energy Levels
molecules have discrete energy levels
(no continuum between levels)

A molecule absorbs electromagnetic radiation when

the energy of photon corresponds to the difference in
energy between two states
14

organic
molecule
(ground state)

light
h

organic
relaxation organic
+ h

molecule
molecule
(excited state)
(ground state)

UV-Vis: valance electron transitions

- gives information about -bonds and conjugated systems



Infrared: molecular vibrations (stretches, bends)


- identify functional groups



Radiowaves: nuclear spin in a magnetic field (NMR)


- gives a map of the H and C framework



15

13.23 Ultraviolet-Visible (UV-Vis) Spectroscopy

UV

Vis

400
200
Recall bonding of a -bond from Chapter 10.16

800 nm

16

-molecular orbitals of butadiene

4: 3 Nodes

0 bonding interactions

3 antibonding interactions

ANTIBONDING MO

3: 2 Nodes

1 bonding interactions

2 antibonding interactions

ANTIBONDING MO

2: 1 Nodes

2 bonding interactions

1 antibonding interactions

BONDING MO

1: 0 Nodes

3 bonding interactions

0 antibonding interactions

BONDING MO

2 is the Highest Occupied Molecular Orbital (HOMO)

17
3 is the Lowest Unoccupied Molecular Orbital (LUMO)

UV-Vis light causes electrons in lower energy molecular orbitals

to be promoted to higher energy molecular orbitals.
HOMO
LUMO

Chromophore: light absorbing portion of a molecule

Butadiene

Butadiene

18

Bonding

Energy

Antibonding

Molecular orbitals of conjugated polyenes

H2C CH2
180 nm

258 nm

217 nm

290 nm

19

Molecules with extended conjugation move toward the visible

region

380 nm

400 nm

violet-indigo

450 nm
blue

500 nm

550 nm

green

yellow

Color of
absorbed light
violet
blue
blue-green
yellow-green
yellow
orange
red

600 nm
orange

400 nm
450
500
530
550
600
700

700 nm

780 nm

red

Color
observed
yellow
orange
red
red-violet
violet
blue-green
green

20

10

Many natural pigments have conjugated systems

OH
OH
N

+
O

HO

N Mg N

OH

OH
HO

CO2CH3
O

OH
O

OH
OH

Chlorophyll

anthocyanin

-carotene

lycopene

21

Chromophore: light absorbing portion of a molecule

Beer s Law: There is a linear relationship between
absorbance and concentration

A = c l

A = absorbance
c = concentration (M, mol/L)
l = sample path length (cm)
= molar absorptivity (extinction coefficient)
a proportionality constant for a specific
absorbance of a substance

22

11

13.20: Introduction to Infrared Spectroscopy

Near
IR

Vis

10-4

Far
IR

Infrared (IR)

2.5 x 10-4 cm
2.5 m
_
4000 !

1.6 x 10-3 cm
16 m
_
600 !

microwave

10-2

(cm)

1

E



_

is expressed as (wavenumber), reciprocal cm (cm-1)

_

_

=
1

therefore

E



IR radiation causes changes in a molecular vibrations
23

Stretch: change in bond length

http://www2.chem.ucalgary.ca/Flash/photon.html

Symmetric stretch

Antisymmetric stretch

Bend: change in bond angle

>

>

>

>

>

>

>

>

>

>

>

>

>
>

>

>

scissoring
rocking
in-plane bend

wagging
twisting
out-of-plane bend

Animation of bond streches and bends:

http://wetche.cmbi.ru.nl//organic/vibr/methamjm.html

24

12

Bond Stretch:
Hooke s Law

f
_
!=

1
2"c

mx my

1
2

_
! = vibrational frequency
c = speed of light
mx = mass of X
my = mass of Y

mx + my

mx my

= reduced mass ()

mx + my

_

E f

f = spring constant; type of

bond between X and Y
(single, double or triple)

Hooke s law simulation:

http://www2.chem.ucalgary.ca/Flash/hooke.html

25

13.21 Infrared Spectra

Interpretation of an Infrared Spectra:
Organic molecules contain many atoms. As a result,
there are many stretching and bending modesIR spectra have many absorption bands
Four distinct regions of an IR spectra
X-H
single bond
region

4000 cm-1

triple
bond
region

2500 cm-1

C-H
O-H
N-H

CC
CN

double
bond
region

fingerprint
region

2000 cm-1 1500 cm-1

600 cm-1

C=C
C=O

26

13

Fingerprint region (600 - 1500 cm-1)- low energy single bond

stretching and bending modes. The fingerprint region is




unique for any given organic compound. However, there are


few diagnostic absorptions.



Double-bond regions (1500 - 2000 cm-1)


C=C
1620 - 1680 cm-1


C=O
1680 - 1790 cm-1



Triple-bond region: (2000 - 2500 cm-1)


CC
2100 - 2200 cm-1 (weak, often not observed)


CN
2240 - 2280 cm-1



X-H Single-bond region (2500 - 4000 cm-1)


O-H
3200 - 3600 cm-1 (broad)


CO-OH 2500-3600 cm-1 (very broad)


N-H
3350 - 3500 cm-1


C-H
2800 - 3300 cm-1




sp3 -C-H

2850 - 2950 cm-1

2



sp =C-H

3000 - 3100 cm-1

27



sp C-H

3310 - 3320 cm-1

13.22 Characteristic Absorption Frequencies

Table 13.4, p. 578
Alkenes

=C-H
C=C
Aromatic
=C-H
C=C
Alkynes
C-H
CC
Alcohols
C-O
O-H
Amines
C-N
N-H
Carbonyl
C=O
Carboxylic acids
O-H
Nitrile
CN

3020 - 3100 cm-1

1640 - 1680 cm-1

medium - strong
medium

3030 cm-1
1450 - 1600 cm-1

strong
strong

3300 cm-1
2100-2260 cm-1

strong
weak - medium

1050 - 1150 cm-1

3400 - 3600 cm-1

strong
strong and broad

1030 - 1230 cm-1

3300 - 3500 cm-1

medium
medium

1670 - 1780 cm-1

strong

2500 - 3500 cm-1

strong and very broad

2240 - 2280 cm-1

weak-medium
28

14

C-H

hexane

% transmittance

% transmittance

H3CH2CH2CH2C

C-H

H3CH2CH2CH2C C C H

C=C
C-H
cm-1

% transmittance

% transmittance

C-H

C
H

=C-H

cm-1

CC

H
C

CC

C-H

H3CH2CH2C C C CH3

cm-1

cm-1

29

CH3(CH2)4CH2OH

CN
C-H

H3C(H2C)4CH2CN

O-H

C-H

C-O

CH3(CH2)4CH2NH-CH3

CH3(CH2)4CH2NH2
N-H
N-H

C-H
C-H
30

15

(H3C)3CH2C

O
C

OH

H3C(H2C)3H2C

O
C

OCH2CH3

O-H
C=O
1705 cm-1

H3C(H2C)3H2C

C-H

O
C

C=O
1710 cm-1

H3C(H2C)2H2C

O
C

CH3

O
C

C=O
1730 cm-1

C=O
1715 cm-1

C-H

31

Typical IR Absorptions for Funtional Groups

4000

3000

X-H Regon
(2500-4000 cm-1)
C-H
O-H
N-H

4000

Functional Group
Alkanes, Alkyl groups
C-H
Alkenes
=C-H
C=C

C
C

3000

1000

C
N

C
C

C
O

cm-1
2850-2960

3020-3150
1600-1700

3300
2100-2200

Alkyl Halides
C-Cl
C-Br
C-I

600-800
500-600
500

Alcohols
O-H
C-O

3400-3650
1050-1150

600

Fingerprint Region
(600-1500 cm-1)
difficult to interpret

2000

Alkynes
!C-H
C!C

Aromatics
=C-H

2000
Triple Bond Double Bond
Region
Region
(2000-2500) (1500-2000)

Functional Group

1000

600

cm-1

Amines
N-H

3300-3500

Amide
N-H

3180-3350

Carbonyl Group
C=O

1650-1780

Carboxylic Acids
O-H

2500-3100

Nitriles
C!N

2210-2260

Nitro Group
-NO2

1540

3030

32
1600, 1500

16

13.3: Introduction to 1H NMR

direct observation of the H s of a molecules
Nuclei are positively charged and spin on an axis; they create
a tiny magnetic field

Not all nuclei are suitable for NMR.

1H and 13C are the most important NMR active nuclei in
organic chemistry
Natural Abundance
1H 99.9%
13C 1.1%
12C 98.9% (not NMR active)
33

(a) Normally the nuclear magnetic fields are randomly oriented

(b) When placed in an external magnetic field (Bo), the nuclear
magnetic field will either aligned with (lower energy) or
oppose (higher energy) the external magnetic field

Fig 13.3, p. 520

34

17

The energy difference between aligned and opposed to the external

magnetic field (Bo) is generally small and is dependant upon Bo
Applied EM radiation (radio waves) causes the spin to flip and the
nuclei are said to be in resonance with Bo
+

E = h
Note that h

2

Bo = external magnetic field strength

= gyromagnetic ratio

1H= 26,752

13C= 6.7

is a constant and is sometimes denoted as h
35

B h

E =
2 o

NMR Active Nuclei: nuclear spin quantum number (I)

atomic mass and atomic number
Number of spin states = 2I + 1 (number of possible energy levels)
Even mass nuclei that have even number of neutron have I = 0
(NMR inactive)
Even mass nuclei that have odd number of neutrons have an
integer spin quantum number (I = 1, 2, 3, etc)
Odd mass nuclei have half-integer spin quantum number
(I = 1/2, 3/2, 5/2, etc)
I= 1/2: 1H, 13C, 19F, 31P
I= 1: 2H, 14N
I= 3/2: 15N
I= 0: 12C, 16O

36

18

Continuous wave


(CW) NMR

Pulsed (FT) NMR

37

13.4: Nuclear Shielding and 1H Chemical Shift

Different nuclei absorb EM radiation at different wavelength
(energy required to bring about resonance)
Nuclei of a given type, will resonate at different energies
depending on their chemical and electronic environment.
The position (chemical shift, ) and pattern (splitting or multiplicity)
of the NMR signals gives important information about the
chemical environment of the nuclei. The integration of the
signal is proportional to the number of nuclei giving rise to
that signal
H O

H H

H C C O C C H
H

H H

38

19

Chemical shift: the exact field strength (in ppm) that a nuclei comes
into resonance relative to a reference standard (TMS)
Electron clouds shield nuclei from the external magnetic field causing
them to resonate at slightly higher energy
Shielding: influence of neighboring functional groups on the electronic
structure around a nuclei and consequently the chemical shift
of their resonance.
CH3

Cl
H

H3C Si CH3

Cl

CH3

Cl

downfield

lower magnetic field

less shielded

(deshielded)

Tetramethylsilane (TMS);
Reference standard = 0

for 1H NMR

HCCl3

upfield

higher magnetic field

more shielded

= 7.28 ppm

TMS

39
Chemical shift (, ppm)

downfield

lower magnetic field

less shielded

(deshielded)

NCCH2OCH3

= 4.20 ppm

2H

= 3.50 ppm

3H

upfield

higher magnetic field

more shielded

TMS

Chemical shift (, ppm)

Vertical scale= intensity of the signal

Horizontal scale= chemical shift (), dependent upon the field strength
of the external magnetic field; for 1H, d is usually from 1-10 ppm













chemical shift in Hz





= - TMS =

n
operating
frequency in MHz


o
1

14,100 gauss: 60 MHz for H (60 million hertz) ppm= 60 Hz
15 MHz for 13C
140,000 gauss: 600 MHz for 1H
ppm = 600 Hz
150 MHz for 13C
40

20

13.5: Effect of Molecular Structure on 1H Chemical Shift

Electronegative substituents deshield nearby protons

less shielded

more shielded

H3C-F H3C-O-CH3 (H3C)3-N H3C-CH3 (H3C)4-Si

4.3

3.2

0.9

2.2

0.0

The deshielding effect of a group drops off quickly with distance

(number of bonds between the substituent and the proton)

H3C-H2C-H2C-H2C-O-CH2-CH2-CH2-CH3
=

1.37

3.40

0.92

1.55

41

The influence of neighboring groups (deshielding) on 1H

chemical shifts is cumulative

Cl

Cl

Cl

7.3
O

O
H

2.1

5.3

CH3CH2O

Cl

Cl

Cl
C
H

3.1 ppm
O

Cl
H

CH3CH2O
H

4.06

Cl
Cl

CH3CH2O
H

5.96 ppm

42

21

Typical 1H NMR chemical shifts ranges; additional substitution

can move the resonances out of the range
12

11

10

H
1H

R2N

NMR Shift Ranges

O

RCO CR2

CR2
N

RC!C-H

aromatics

H
RCHO

PhOH

O
C C

vinyl

10

R2N-H

H
X CR2 X= F, Cl, Br, I

RCO2H

11

H
C-CR2

RO CR2
N

12

RC CR2
X=O, CR2

H
Ar

CR2
X

ROH
sat. alkanes
R-H

" (ppm)

also see Table 13.1 (p. 548)

43

Protons attached to sp2 and sp hybridize carbons are deshielded

relative to protons attached to sp3 hybridized carbons
H
H

H
C

C
H

H C C H

H3C CH3

= 9.7

7.3

5.3

2.1

0.9-1.5 ppm

Please read about ring current effects of -bonds

(Figs. 13.8-13.10, p. 548-9 & 551)
CH3
C

CH3
C

O
CH3

= 2.3 - 2.8

1.5 - 2.6

2.1-2.5 ppm
44

22

13.6: Interpreting 1H NMR Spectra

Equivalence (chemical-shift equivalence): chemically and
magnetically equivalent nuclei resonate at the same
energy and give a single signal or pattern
H
H
N C C O C H
H
H
= 4.20 ppm

2H

= 3.50 ppm

3H

TMS

45

H3C

H
C C

H3C

CH3

46

23

Test of Equivalence:

1. Do a mental substitution of the nuclei you are testing with an
arbitrary label
2. Ask what is the relationship of the compounds with the
arbitrary label
3. If the labeled compounds are identical (or enantiomers), then the
original nuclei are chemically equivalent and do not normally
give rise to separate resonances in the NMR spectra
If the labeled compounds are not identical (and not enantiomers),
then the original nuclei are not chemically equivalent and can
give rise to different resonances in the NMR spectra
H H
H C
CH3
C C
H3C
CH3

H H
H C
CH3
C C
H3C
CH3

H H
H C
CH3
C C
H3C
CH3

H H
H C
CH3
C C
H3C
CH3

Identical, so the protons are equivalent

H3C

CH3

H3C

CH3

H3C

C C

H3C

C C
CH3

H3C

CH3

H3C

C C
CH3

H3C

CH3

H3C

C C
CH3

H3C

CH3
C C

CH3

H3C

CH3

Identical, so the methyl groups are equivalent

47

H3C

H3C

C C
H3C
H3C

H3C

CH3

H3C

H3C

H3C

C C

H
C C

C C
CH3

H3C

CH3
H
C C

CH3

H3C

H3C

H3C
C C
H3C

H3C

CH3

H
C C

CH3

H3C

These are geometric

isomers (not identical and
not enantiomers). The three
methyl groups are therefore
not chemically equivalent
and can give rise to different
resonances

CH3

H
C C

H3C

CH3

48

24

H
H

CH2CH3

H
H

49

H Cl
H3C C C CH3
H H

Homotopic: equivalent

Enantiotopic: equivalent

Diastereotopic: non-equivalent

50

25

Integration of 1H NMR resonances: The area under an NMR

resonance is proportional to the number of equivalent
nuclei that give rise to that resonance.
H
H
N C C O C H
H
H

= 4.20,

2H

= 3.50,

3H

TMS

The relative area under the resonances at = 4.20 and 3.50

is 2:3
51

13.7: Spin-spin splitting in 1H NMR spectroscopy

protons on adjacent carbons will interact and split each others
resonances into multiple peaks (multiplets)
n + 1 rule: equivalent protons that have n equivalent protons
on the adjacent carbon will be split into n + 1 peaks.
H O

= 2.0

3H

H H

H C C O C C H
H

H H

= 1.2

3H

= 4.1

2H

Resonances always split each other. The resonance at = 4.1

splits the resonance at = 1.2; therefore, the resonance at
= 1.2 must split the resonance at = 4.2.
52

26

The multiplicity is defined by the number of peaks and the pattern

(see Table 13.2 for common multiplicities patterns and relative
intensities)
H O

= 2.0

s, 3H

H H

H C C O C C H
H

= 1.2

t, 3H

H H

= 4.1

q, 2H

-CH3-

-CH2-

1 : 2 : 1

53

1 : 3 : 3 : 1

The resonance of a proton with n equivalent protons on the adjacent

carbon will be split into n + 1 peaks with a coupling constant J.

Coupling constant: distance between peaks of a split pattern; J is

expressed in Hz. Protons coupled to each other have the same

coupling constant J.

H O

= 2.0

s, 3H

H H

H C C O C C H
H

H H

= 1.2

t, J=7.2 Hz, 3H

= 4.1

q, J=7.2 Hz, 2H

3J

ab

3J

ab

3J

ab

3J

ab

3J

ab

54

27

13.8: Splitting Patterns: The Ethyl Group

Two equivalent protons on an adjacent carbon will split a proton
a triplet (t), three peaks of 1:2:1 relative intensity
Three equivalent protons on an adjacent carbon will split a proton
into a quartet (q), four peaks of 1:3:3:1 relative intensity
H

H
O H H

H H
H H
H

= 7.4-7.1,
m, 5H

C C C H

C C H

= 1.2, t
J= 7.0, 3H

= 2.6, q,
J= 7.0, 2H

H H
H

= 3.0, q
J= 7.2, 2H

= 1.2, t
J= 7.2, 3H

= 8.0,
2H
= 7.6-7.3,
m, 3H

55

13.8: Splitting Patterns: The Isopropyl Group

One proton on an adjacent carbon will split a proton into a
doublet (d), two peaks of 1:1 relative intensity
Six equivalent protons on an adjacent carbon will split a proton
into a septet (s), seven peaks of 1:6:15:20:15:6:1 relative
intensity
H

H
C CH3

CH3
H

= 1.2, d
J= 6.9, 6H

H
C CH3

O2N

= 1.2, d
J= 6.9, 6H

CH3

= 7.4-7.1,
m, 5H

= 2.9, s,
J= 6.9, 1H
= 8.1, d,
J= 6.1 Hz,
2H

= 7.4, d
J= 6.1 Hz,
2H

= 3.0, s,
J= 6.9, 1H

56

28

13.10: Splitting Patterns: Pairs of Doublets

H
H
H3C

C
H3C CH H
3

O
C
H

OCH3

= 1.2, s, 9H
= 8.0, d,
J= 9.0 2H

= 7.4, d,
J= 9.0 2H

= 3.9,
s, 3H

fig 13.20,

p. 560

57

13.11: Complex Splitting Patterns: when a protons is adjacent

to more than one set of non-equivalent protons, they
will split independently
J1-2 = 7.0

J2-3 = 16.0

J1-2 = 7.0

J2-3 = 16.0

H2 splits H3 into a doublet with coupling constant J2-3 = 16.0

H2 splits H1 into a doublet with coupling constant J1-2 = 7.0

H1 splits H2 into a doublet with a coupling constants J1-2 =7.0; H3 further splits H2


into a doublet (doublet of doublets) with coupling constants J2-3 = 16.0

H
C

C
H

O
C

58

29

J1,2 = J2,3

J1,2

H H H
C C C H
H H H

= 7.1-7.3,
m, 5H

= 0.9, t,
J = 7.4, 3H

= 2.6, t
J = 7.4, 2H

= 1.6, sextet
J=7.4, 2H

J2,3

1 : 5 : 10:10 : 5 : 1

59

13.12: 1H NMR Spectra of Alcohols

Usually no spin-spin coupling between the OH proton and
neighboring protons on carbon due to exchange reaction
C O H
H

H A
C O H

H A

The chemical shift of the -OH proton occurs over a large

range (2.0 - 5.5 ppm). This proton usually appears as
a broad singlet. It is not uncommon for this proton
not to be observed.
13.13: NMR and Conformation (please read)
NMR is like a camera with a slow shutter speed. What is
observed is a weighted time average of all conformations
60
present.

30

Summary of 1H-1H spin-spin coupling

chemically equivalent protons do not exhibit spin-spin
coupling to each other.
the resonance of a proton that has n equivalent protons on
the adjacent carbon is split into n+1 peaks (multiplicity)
with a coupling constant J.
protons that are coupled to each other have the same
coupling constant
non-equivalent protons will split a common proton
independently: complex coupling.
Spin-spin coupling is normally observed between nuclei that
are one, two and three bonds away. Four-bond
coupling can be observed in certain situations
(i.e., aromatic rings), but is not common.
61

Summary of 1H-NMR Spectroscopy

the number of proton resonances equals the number of
non-equivalent protons
the chemical shift (, ppm) of a proton is diagnostic of the
chemical environment (shielding and deshielding)
Integration: number of equivalent protons giving rise to a
resonance
spin-spin coupling is dependent upon the number of equivalent
protons on the adjacent carbon(s)

62

31

13.14: 13C NMR Spectroscopy:

Natural Abundance
1H 99.9% (I= 1/2)
12C 98.9% (I= 0)
13C 1.1% (I= 1/2)
E=
Bo h

2

13C

O
H3C C OCH3

1.1 %

1.1 %

1.1 %

Bo = external magnetic field strength

= magnetogyric ratio
1H= 26,752
13C= 6.7

is a much less sensitive nuclei than 1H for NMR spectroscopy

New techniques (hardware and software) has made 13C NMR

routine
Pulsed NMR techniques (FT or time domain NMR)
Signal averaging (improved signal to noise)
Animation: http://mutuslab.cs.uwindsor.ca/schurko/nmrcourse/animations/eth_anim/puls_evol.gif

63

Fourier Transform (FT) deconvolutes all of the FID s and gives

an NMR spectra.

time

Signal-averaging: pulsed NMR allows for many FID s (NMR

spectra) to be accumulated over time. These FID s are added
together and averaged. Signals (resonances) build up while the
noise is random and cancels out during the averaging.
Enhanced signal to noise ratio and allows for NMR spectra to
be collected on insensitive nuclei such as 13C and small samples.
13C-spectra

of CH3CH2CH2CH2CH2OH

after one scan

average of 200 scans

64

32

Chemical shifts give an idea of the chemical and electronic

environment of the 13C nuclei due to shielding and
deshielding effects range: 0 - 220 ppm from TMS
13C

NMR spectra will give a map of the carbon framework. The

number of resonances equals the number of
non-equivalent carbons.
132.8

128.5

O
C CH2CH2CH3

128.0
128.0

137.1

128.5
132.8

17.8 13.9
40.5

200.3

TMS

CDCl3

137.1

65

13.15: 13C Chemical Shifts

Chemical Shift Range of 13C see Table 13.13 (page 567)
220

200

180

160

140

120

100

80

60

40

20

-20

R3C-Br

Typical 13C NMR Shift Ranges

R3C-F

R3C-Cl

R3C-I

R2N-CR3
R3C OH

nitriles

O
RC

aromatics

RO CR3

vinyl

carbonyls

200

180

160

Ar-CR3

alkyne
saturated
alkanes

ketones & esters, amides

aldehydes & acids
220

CR3

140

120

100

80

60

40

20

-20

! (PPM)

Note the carbonyl range

66

33

13.16: 13C NMR and Peak Intensities (please read) - 13C NMR
peak integration are not generally useful
13.17: 13C-1H Coupling
1H-13C spin-spin coupling are usually turned off in the 13C
spectra (broadband decoupled). However, spin-spin
coupling tells how many protons are attached to the
13C nuclei. (i.e., primary, secondary tertiary, or quaternary
carbon)
13.18: Using DEPT to Count Hydrogens Attached to 13C
13C spectra are usually collected with the 1H-13C coupling
turned off (broad band decoupled). In this mode all
13C resonances appear as singlets.
DEPT spectra (Distortionless Enhancement by Polarization
Transfer) a modern 13C NMR spectra that allows you to
67
determine the number of attached hydrogens.

8
7

Broad-band decoupled

OH

8
7

1

DEPT

CH

CH3

CH

CH3

CH2

CH3

CH2

CH2 s give negative resonances

CH s and CH3 s give positive resonances
Quaternary carbon (no attached H s) are not observed
13.19: 2D NMR: COSY and HETCOR (please read)

68

34

Solving Combined Spectra Problems:

Mass Spectra:
Molecular Formula
Nitrogen Rule # of nitrogen atoms in the molecule
M+1 peak # of carbons
Degrees of Unsaturation: # of rings and/or -bonds
Infrared Spectra:
Functional Groups




C=O
O-H




C=C
N-H




CC
CO-OH



CN

1H NMR:


Chemical Shift () chemical environment of the H's
Integration # of H's giving rise to the resonance
Spin-Spin Coupling (multiplicity) # of non-equivalent H's on the
adjacent carbons (vicinal coupling).
13C NMR:

# of resonances symmetry of carbon framework
Type of Carbonyl

Each piece of evidence gives a fragment (puzzle piece) of the structure.

Piece the puzzle together to give a proposed structure. The proposed
structure should be consistent with all the evidence.
69

Problem 13.43

70

35

Problem 13.44

71

Problem 13.46: C5H10O

13C

NMR:

7.9
35.5

212.1

72

36

C10H14

127.0
128.2

125.7

31.2
41.7

21.8
12.3

147.6

= 2.61
= 2.61
(d, J=7.0, 3H) (t, J=7.0, 3H)
= 2.61
(sextet,
J=7.0, 1H)

= 2.61
(pentet,
J=7.0, 2H)

= 7.4-7.1
(m, 5H)

73

37