Chemistry 212

Organic Chemistry II

Bilal R. Kaafarani
[Link]
[Link]@[Link]
Office: 416 Chemistry
Phone: 3986
O.H.: 12 M; 11 T; 10 Th

1
 Course Grading
Exam I 20%
Exam II 20%
Exam III 20%
Final 40%
100%
• Exam I: Wed, Nov 1st, 2006; 5:00 PM in 500 Nicely.
• Exam II: Wed, Dec 6th, 2006; 5:00 PM in 500 Nicely.
• Exam III: Tues, Jan 9th, 2007; 5:00 PM in 500 Nicely.
• Final Exam: to be determined.

¾This course is a WebCT course. Lectures, Syllabus, and

other related material will be regularly posted.
¾ Text: Carey, F. A. in Organic Chemistry, 6th Edition, 2006.2
 Lectures
Chapter Material covered
13 Spectroscopy
14 Organomettalic Compounds
15 Alcohols, diols, and thiols
16 Ethers, Epoxides, and sulfides
17 Aldehydes and ketones
18 Enols and enolates
19 Carboxylic acids
20 Carboxylic acid and derivatives
21 Ester enolates
22 Amines
23 Aryl halides
24 Phenols
25 Carbohydrates
27 Amino acids 3
 General Policy
• No make-up Final will be given except in prearranged,
extraordinary circumstances.
• NO make-up exams. If you miss an exam, you get zero
on it.
• ALL cell phones, pagers, and beepers are to BE SHUT
OFF during lecture; otherwise, you’ll be asked to leave
the room.
• Classes start on time.
• This course requires a lot of serious preparation and
time dedication.
• Extra lectures might be arranged on SATURDAYS to
cover any necessary additional materials.
4
¾ Keep questions to minimum during
lecture. We need to cover a lot of material.
¾ You can ask questions during O.H.’s
¾ Attendance in lectures and recitations is
a MUST.

5
 Chapter 13
Spectroscopy

Nuclear magnetic resonance spectroscopy (NMR)

Infrared spectroscopy (IR)

Ultraviolet-Visible spectroscopy (UV-vis)

Mass Spectrometry (MS)

6
 Structure Determination

NMR: Carbon skeleton & environment of the

hydrogens attached to it.
IR: Presence or absence of key functional
groups.
UV-vis: Electron distribution specially in molecules
with π-conjugated systems.
MS: Molecular weight and formula of the
compound & its fragments.

7
 13.1 Principles of Molecular
Spectroscopy: Electromagnetic Radiation

¾ Is propagated at the speed of light.

¾ Has properties of particles and waves.

¾ The energy of a photon is proportional to its frequency

(E=hν).

8
Figure 13.1: The Electromagnetic
Spectrum

Shorter Wavelength (λ) Longer Wavelength (λ)

400
400nm
nm 750 nm
750 nm

Visible Light
7.5×1014 s-1 4.0×1014 s-1

Higher Frequency (ν) Lower Frequency (ν)

Higher Energy (E) Lower Energy (E)

9
Figure 13.1: The Electromagnetic
Spectrum

Shorter Wavelength (λ) Longer Wavelength (λ)

Ultraviolet Infrared

Higher Frequency (ν) Lower Frequency (ν)

Higher Energy (E) Lower Energy (E)

10
 Figure 13.1: The Electromagnetic
Spectrum

Cosmic rays
γ Rays
X-rays
Energy
Ultraviolet light
Visible light
Infrared radiation
Microwaves
Radio waves 11
13.2. Principles of Molecular Spectroscopy:
Quantized Energy States

E2

ΔE = hν
E1

Electromagnetic radiation is absorbed when the energy of

photon corresponds to difference in energy between two states.
12
 What Kind of States?

Electronic UV-Vis

Vibrational infrared

Rotational microwave

Nuclear spin radiofrequency

13
13.3. Introduction to 1H NMR Spectroscopy

The nuclei that are most useful to

organic chemists are:

¾ 1H and 13C.

¾ Both have spin = ±1/2.

¾ 1H is 99% at natural abundance.

¾ 13C is 1.1% at natural abundance.

14
 Nuclear Spin

+ +

¾ A spinning charge, such as the nucleus of 1H or 13C,

generates a magnetic field. The magnetic field
generated by a nucleus of spin +1/2 is opposite in
direction from that generated by a nucleus of spin –1/2.
15
¾ The distribution
of nuclear spins is
random in the
+
absence of an
external magnetic
field. +

+
+
16
¾ An external magnetic
field causes nuclear
magnetic moments to
+
align parallel and
antiparallel to applied
field. +

+
H0

+
+
17
¾ There is a slight
excess of nuclear
magnetic moments
+
aligned parallel to the
applied field.
+

+
H0

+
+
18
Energy Differences Between Nuclear Spin States

ΔE ΔE '

Increasing field strength

¾ No difference in absence of magnetic field.

¾ Proportional to strength of external magnetic field. 19
Some important relationships in NMR

Units
¾ The frequency of absorbed
electromagnetic radiation is Hz
proportional to:

- The energy difference between

kJ/mol
two nuclear spin states
(kcal/mol)
which is proportional to:

- The applied magnetic field tesla (T)

20
 Some important relationships in NMR
¾ The frequency of absorbed electromagnetic radiation
is different for different elements, and for different
isotopes of the same element.

For a field strength of 4.7 T:

1H absorbs radiation having a frequency of 200

MHz (200 x 106 s-1)

13C absorbs radiation having a frequency of 50.4

MHz (50.4 x 106 s-1)

21
Some important relationships in NMR

¾ The frequency of absorbed electromagnetic

radiation for a particular nucleus (such as 1H)
depends on its molecular environment.

¾ This is why NMR is such a useful tool

for structure determination.

22
 13.4
Nuclear Shielding
and
1H Chemical Shifts

What do we mean by "shielding?"

What do we mean by "chemical shift?"

23
 Shielding

¾ An external magnetic field

affects the motion of the
electrons in a molecule,
inducing a magnetic field C H
within the molecule.

¾ The direction of the

induced magnetic field is
opposite to that of the applied
H0
field.
24
 Shielding

¾ The induced field shields

the nuclei (in this case, C and
H) from the applied field.

¾ A stronger external field is C H

needed in order for energy
difference between spin
states to match energy of rf
(radiofrequency) radiation.
H0
25
 Chemical Shift

¾ Chemical shift is a measure

of the degree to which a
nucleus in a molecule is
shielded. C H

¾ Protons in different
environments are shielded to
greater or lesser degrees;
they have different chemical H0
shifts.
26
 Chemical Shift

¾ Chemical shifts (δ) are

CH3
measured relative to the
protons in tetramethylsilane H3C Si CH3
(TMS) as a standard.
CH3

position of signal - position of TMS peak

δ = x 106
spectrometer frequency

27
 Downfield Upfield
Decreased shielding Increased shielding

(CH3)4Si (TMS)

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ, ppm)

measured relative to TMS 28
 Chemical Shift
¾ Example: The signal for the proton in chloroform
(CHCl3) appears 1456 Hz downfield from TMS at a
spectrometer frequency of 200 MHz.

position of signal - position of TMS peak

δ = x 106
spectrometer frequency

1456 Hz - 0 Hz
δ = x 106
200 x 106 Hz

δ = 7.28 ppm
29
 Cl
δ 7.28 ppm
H C Cl

Cl

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ, ppm)

30
 13.5
Effects of Molecular Structure
on
1H Chemical Shifts

Protons in different environments experience

different degrees of shielding and have different
chemical shifts.

31
 Electronegative substituents decrease
the shielding of methyl groups

least shielded H most shielded H

CH3F CH3OCH3 (CH3)3N CH3CH3 (CH3)4Si

δ 4.3 δ 3.2 δ 2.2 δ 0.9 δ 0.0

32
Electronegative substituents
decrease shielding

δ 0.9 δ 1.3 δ 0.9

H3C—CH2—CH3

δ 4.3 δ 2.0 δ 1.0

O2N—CH2—CH2—CH3

33
Effect is cumulative

– CHCl3 δ 7.3
– CH2Cl2 δ 5.3
– CH3Cl δ 3.1

34
 Methyl, Methylene, and Methine

CH3 more shielded than CH2 ;

CH2 more shielded than CH

δ 0.9 δ 0.9
CH3 CH3
δ 1.2 δ 0.8
H3C C H δ 1.6 H3C C CH2 CH3

CH3 CH3
35
 Protons attached to sp2 hybridized carbon
are less shielded than those attached
to sp3 hybridized carbon

H
H H H H
C C CH3CH3
H H H H

H
δ 7.3 δ 5.3 δ 0.9
π-electrons induce magnetic field reinforces the
applied field. 36
But protons attached to sp hybridized carbon
are more shielded than those attached
to sp2 hybridized carbon

δ 5.3
H H
δ 2.4
C C H C C CH2OCH3
H H Induced magnetic field is parallel to
long axis of the triple bond and shields
the acetylenic proton
37
 Protons attached to benzylic and allylic
carbons are somewhat less shielded than usual

H3C CH3
δ 1.5 δ 0.8
δ 0.9 δ 1.3 δ 0.9
H3C—CH2—CH3
δ 1.2 δ 2.6
H3C CH2

38
Proton attached to C=O of aldehyde
is most deshielded C—H

δ 2.4
H O

H3C C C H δ 9.7

CH3
δ 1.1

39
Type of proton Chemical shift (δ), Type of proton Chemical shift (δ),
ppm ppm

H C R 0.9-1.8 H C C N 2.1-2.3

H C C C 1.5-2.6 H C C C 2.5

H C C 2.0-2.5 H C Ar 2.3-2.8
40
Type of proton Chemical shift (δ), Type of proton Chemical shift (δ),
ppm ppm

H C NR 2.2-2.9
H
C C 4.5-6.5
H C Cl 3.1-4.1

H Ar 6.5-8.5
H C Br 2.7-4.1
O

3.3-3.7 H C 9-10
H C O 41
Type of proton Chemical shift (δ),
ppm

H NR 1-3

H OR 0.5-5

H OAr 6-8

HO C 10-13
42
13.6. Interpreting Proton NMR Spectra

Information contained in an NMR

spectrum includes:

1. Number of signals.

2. Their intensity (as measured by area under peak).

3. Splitting pattern (multiplicity).

43
 Number of Signals

¾ Protons that have different chemical shifts are

chemically nonequivalent.

¾ Exist in different molecular environment.

44
 N CCH2OCH3

OCH3

NCCH2O

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ, ppm) 45

 Chemically equivalent protons

- Are in identical environments.

- Have same chemical shift.

- Replacement test: replacement by some

arbitrary "test group" generates same compound.

H3CCH2CH3

chemically equivalent
46
 Chemically equivalent protons
¾ Replacing protons at C-1 and C-3 gives same
compound (1-chloropropane).
¾ C-1 and C-3 protons are chemically equivalent
and have the same chemical shift.

ClCH2CH2CH3 CH3CH2CH2Cl

H3CCH2CH3

chemically equivalent 47
 Diastereotopic protons
¾ Replacement by some arbitrary test group generates
diastereomers.

¾ Diastereotopic protons can have different chemical

shifts.

Br H δ 5.3 ppm

C C

H3C H δ 5.5 ppm

48
 Enantiotopic protons

- Are in mirror-image environments.

- Replacement by some arbitrary test group generates
enantiomers.
- Enantiotopic protons have the same chemical shift.

49
Enantiotopic
protons
H
H
C CH2OH

H3C

H Cl
Cl H
C CH2OH C CH2OH
R
R SS 50
H3C H3C
 13.7
Spin-Spin Splitting
in
NMR Spectroscopy

Not all peaks are singlets.

Signals can be split by coupling of
nuclear spins.

51
Figure 13.12 (page 536) Cl2CHCH3

4 lines; 2 lines;
quartet doublet

CH CH3

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ, ppm) 52

 Two-bond and three-bond coupling
H
C C H C C H
H
protons separated by protons separated by
two bonds three bonds
(geminal relationship) (vicinal relationship)

- In order to observe splitting, protons cannot have same

chemical shift.
- Coupling constant (2J or 3J) is independent of field strength.
53
Figure 13.12 (page 536) Cl2CHCH3

4 lines; 2 lines;
quartet doublet

CH CH3

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

¾ Coupled protons are vicinal (three-bond coupling).

¾ CH splits CH3 into a doublet, CH3 splits CH into
54
a quartet.
 Why do the methyl protons of
1,1-dichloroethane appear as a doublet?
Cl H
signal for methyl protons is
H C C H split into a doublet

Cl H

¾ To explain the splitting of the protons at C-2, we first focus on the

two possible spin orientations of the proton at C-1.
¾ There are two orientations of the nuclear spin for the proton at C-
1. One orientation shields the protons at C-2; the other deshields the
C-2 protons.
¾ The protons at C-2 "feel" the effect of both the applied magnetic
field and the local field resulting from the spin of the C-1 proton. 55
 Why do the methyl protons of
1,1-dichloroethane appear as a doublet?
Cl H
"true" chemical
H C C H shift of methyl
protons (no coupling)
Cl H
This line corresponds This line corresponds
to molecules in which to molecules in which
the nuclear spin of the nuclear spin of
the proton at C-1 the proton at C-1
reinforces the applied opposes the applied
field. field. 56
 Why do the methyl protons of
1,1-dichloroethane appear as a doublet?

Cl H
signal for methine H C C H
proton is split into a
quartet Cl H

¾ The proton at C-1 "feels" the effect of the applied

magnetic field and the local fields resulting from the
spin states of the three methyl protons. The possible
combinations are shown on the next slide.
57
 Why does the methine proton of
1,1-dichloroethane appear as a quartet?

Cl H ¾ There are eight combinations of

nuclear spins for the three methyl
protons.
H C C H
¾ These 8 combinations split the signal
into a 1:3:3:1 quartet.
Cl H

58
 The splitting rule for 1H NMR
¾ For simple cases, the multiplicity of a signal for a
particular proton is equal to the number of equivalent
vicinal protons + 1.

13.8. Splitting Patterns:

The Ethyl Group
¾ CH3CH2X is characterized by a triplet-quartet pattern
(quartet at lower field than the triplet)

59
 BrCH2CH3

4 lines; 3 lines;
quartet triplet
CH3

CH2

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ, ppm) 60

 Table 13.2 (page 540)
Splitting Patterns of Common Multiplets
Number of equivalent Appearance Intensities of lines
protons to which H of multiplet in multiplet
is coupled

1 Doublet 1:1
2 Triplet 1:2:1
3 Quartet 1:3:3:1
4 Pentet 1:4:6:4:1
5 Sextet 1:5:10:10:5:1
6 Septet 1:6:15:20:15:6:1 61
 13.9. Splitting Patterns:
The Isopropyl Group

¾ (CH3)2CHX is characterized by a doublet-septet

pattern (septet at lower field than the doublet).

62
 BrCH(CH3)2

2 lines;
7 lines; doublet
septet
CH3

CH

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Chemical shift (δ, ppm)

63
13.10. Splitting Patterns: Pairs of Doublets
¾ Splitting patterns are not always symmetrical, but
lean in one direction or the other.

H C C H

¾ Consider coupling between two vicinal protons.

¾ If the protons have different chemical shifts, each
will split the signal of the other into a doublet.
64
 Pairs of Doublets

H C C H

- Let Δν be the difference in chemical shift in Hz

between the two hydrogens.

- Let J be the coupling constant between them in Hz.

65
 AX H C C H

J J
Δν

¾ When Δν is much larger than J the signal for

each proton is a doublet, the doublet is
symmetrical, and the spin system is called AX.
66
 AM H C C H

J J

Δν

¾ As Δν/J decreases the signal for each proton

remains a doublet, but becomes skewed. The outer
lines decrease while the inner lines increase, causing
the doublets to "lean" toward each other.
67
 AB H C C H

J J

Δν

¾ When Δν and J are similar, the spin system is

called AB. Skewing is quite pronounced. It is
easy to mistake an AB system of two doublets for
a quartet.
68
 A2 H C C H

¾ When Δν = 0, the two protons have the same

chemical shift and don't split each other. A single
line is observed. The two doublets have
collapsed to a singlet.
69
 H H

skewed doublets Cl OCH3

H H

OCH3

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
Chemical shift (δ, ppm)
70
 13.11. Complex Splitting Patterns
Multiplets of multiplets
H

m-Nitrostyrene
H
H
O2N
¾ Consider the proton shown in red.
¾ It is unequally coupled to the protons shown in
green and brown.
¾ Jcis = 12 Hz; Jtrans = 16 Hz 71
 m-Nitrostyrene H

H
H
O2N

¾ The signal for the

16 Hz
proton shown in red
appears as a doublet
of doublets.

12 Hz 12 Hz
72
 H

H
doublet doublet
H
O2N

doublet of doublets

73
 “n+1 rule”

When a proton Ha is coupled to Hb, Hc, Hd, etc., and

Jab ≠ Jac ≠ Jad, etc., the original signal for Ha is split
into n+1 peaks by n Hb protons, and each of these
into n+1 lines by n Hc, and each of these into n+1
lines by n Hd, and so on…

74
13.12. 1H NMR Spectra of Alcohols (O—H)
What about H bonded to O?

H C O H

¾ The chemical shift for O—H is variable (δ 0.5-5 ppm)

and depends on temperature and concentration.
¾ Splitting of the O—H proton is sometimes observed,
but often is not. It usually appears as a broad peak.
¾ Adding D2O converts O—H to O—D. The O—H peak
disappears.
75
 13.13. NMR and Conformations
NMR is "slow“!
¾ Most conformational changes occur faster than NMR can
detect them.
¾ An NMR spectrum is the weighted average of the
conformations.
¾ For example: Cyclohexane gives a single peak for its H
atoms in NMR. Half of the time a single proton is axial and
half of the time it is equatorial. The observed chemical shift is
half way between the axial chemical shift and the equatorial
chemical shift. Rate of flipping can be slowed by lowering
temperature. At -100 °C, separate signals for ax and eq are
observed. 76
 13.14. 13C NMR Spectroscopy
1H and 13C NMR compared:

¾ Both give us information about the number of

chemically nonequivalent nuclei (nonequivalent
hydrogens or nonequivalent carbons).
¾ Both give us information about the environment of
the nuclei (hybridization state, attached atoms, etc.).
¾ It is convenient to use FT-NMR techniques for 1H; it
is standard practice for 13C NMR.
¾13C requires FT-NMR because the signal for a
carbon atom is 10-4 times weaker than the signal for a
hydrogen atom.
77
 1H and 13C NMR compared:
¾ A signal for a 13C nucleus is only about 1% as intense as
that for 1H because of the magnetic properties of the nuclei,
and at the "natural abundance" level only 1.1% of all the C
atoms in a sample are 13C (most are 12C).
¾ 13C signals are spread over a much wider range than 1H
signals making it easier to identify and count individual
nuclei.
¾ Figure 13.23 (a) shows the 1H NMR spectrum of 1
chloropentane; Figure 13.23 (b) shows the 13C spectrum. It is
much easier to identify the compound as 1-chloropentane by
its 13C spectrum than by its 1H spectrum.
78
 1H Spectrum

ClCH2CH2CH2CH2CH3 ClCH2 CH3

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
Chemical shift (δ, ppm) 79
 13C Spectrum

ClCH2CH2CH2CH2CH3

¾ A separate, distinct
peak appears for
each of the 5
carbons.
CDCl3

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (δ, ppm)

80
13.15. 13C Chemical Shifts are measured
in ppm (δ) from the carbons of TMS

13C Chemical shifts are most affected by:

1. Electronegativity of groups attached to carbon.

Electronegativity has an even greater effect on 13C
chemical shifts than it does on 1H chemical shifts.

2. Hybridization state of carbon.

81
Electronegativity Effect: Types of Carbons
Classification Chemical shift, δ
1H 13C

CH4 0.2 -2

CH3CH3 primary 0.9 8

CH3CH2CH3 secondary 1.3 16

(CH3)3CH tertiary 1.7 25

(CH3)4C quaternary 28

¾ Replacing H by C (more electronegative) deshields

82
C to which it is attached.
Electronegativity effects on CH3
Chemical shift, δ
1H 13C

CH4 0.2 -2
CH3NH2 2.5 27
CH3OH 3.4 50
CH3F 4.3 75

83
Electronegativity effects and chain length

Cl CH2 CH2 CH2 CH2 CH3

Chemical 45 33 29 22 14
shift, δ

¾ Deshielding effect of Cl decreases as number of

bonds between Cl and C increases.

84
 Hybridization effects
¾ sp3 hybridized
carbon is more
shielded than sp2.
114 36
138 36 126-142
¾ sp hybridized
carbon is
more shielded H C C CH2 CH2 CH3
than sp2, but
less shielded 68 84 22 20 13
than sp3.

85
Carbonyl carbons are especially
deshielded

CH2 C O CH2 CH3

41 171 61 14
127-134

86
 Table 13.3 (p 549)
Type of carbon Chemical shift (δ), Type of carbon Chemical shift (δ),
ppm ppm

RCH3 0-35 RC CR 65-90

R2CH2 15-40 R2C CR2 100-150

R3CH 25-50
110-175
R4C 30-40

87
 Table 13.3 (p 549)
Type of carbon Chemical shift (δ), Type of carbon Chemical shift (δ),
ppm ppm

RCH2Br 20-40 RC N 110-125

O
RCH2Cl 25-50
RCOR 160-185
RCH2NH2 35-50

RCH2OH 50-65 O

RCH2OR 50-65 RCR 190-220

88
 13.16. 13C NMR and Peak Intensities

¾ Pulse-FT NMR distorts intensities of signals.

Therefore, peak heights and areas can be
deceptive.

89
 Figure 13.24 (page 551)

CH3 ¾ 7 carbons give 7

signals, but intensities
are not equal.

OH

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (δ, ppm) 90

 13.17. 13C—H Coupling

Peaks in a 13C NMR spectrum are typically

singlets

¾ 13C—13C splitting is not seen because the

probability of two 13C nuclei being in the same
molecule is very small.
¾ 13C—1H splitting is not seen because spectrum
is measured under conditions that suppress
this splitting (broadband decoupling).

91
 13.18
Using DEPT to Count the Hydrogens
Attached to 13C

Distortionless
Enhancement of
Polarization Transfer

92
 Measuring a 13C NMR spectrum involves
4 things:

1. Equilibration of the nuclei between the lower

and higher spin states under the influence of
a magnetic field.
2. Application of a radiofrequency pulse to give
an excess of nuclei in the higher spin state.
3. Acquisition of free-induction decay data during
the time interval in which the equilibrium
distribution of nuclear spins is restored.
4. Mathematical manipulation (Fourier transform)
of the data to plot a spectrum.
93
Measuring a 13C NMR spectrum involves

Steps 2 and 3 can be repeated hundreds of times to

enhance the signal-noise ratio.

2. Application of a radiofrequency pulse to give

an excess of nuclei in the higher spin state.
3. Acquisition of free-induction decay data during
the time interval in which the equilibrium distribution
of nuclear spins is restored.

94
Measuring a 13C NMR spectrum involves

¾ In DEPT, a second transmitter irradiates 1H

during the sequence, which affects the appearance
of the 13C spectrum.
• some 13C signals stay the same.
• some 13C signals disappear.
• some 13C signals are inverted.

95
Figure 13.26 (a); 13C spectrum (page 576)
O

CCH2CH2CH2CH3

CH CH
CH2
CH CH2
O
CH2 CH3
C
C

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (δ, ppm) 96

Figure 13.26 (b) DEPT Spectrum (page 576)
O

CCH2CH2CH2CH3

CH CH
CH3
CH

CH and CH3 unaffected

C and C=O nulled
CH2 CH2
CH2 inverted CH2

200 180 160 140 120 100 80 60 40 20 0

Chemical shift (δ, ppm) 97
13.19. 2D NMR: COSY AND HETCOR
2D NMR Terminology

1D NMR = 1 frequency axis

2D NMR = 2 frequency axes

COSY = Correlated Spectroscopy

HETCOR = heteronuclear chemical shift correlation

1H-1H COSY provides connectivity information by

allowing one to identify spin-coupled protons.

x,y-coordinates of cross peaks are spin-coupled

98
protons
 1H-1H COSY

1H
O

CH3CCH2CH2CH2CH3

- Diagonal 1H

- Cross-peaks

99
 HETCOR

¾1H and 13C spectra plotted separately on two

frequency axes.

¾ Coordinates of cross peak connect signal of

carbon to protons that are bonded to it.

100
1H-13C HETCOR O

CH3CCH2CH2CH2CH3

13C

1H

101
 13.20. Infrared Spectroscopy (IR)

IR gives information about the functional groups in

a molecule.

¾ Region of infrared that is most useful lies between

2.5-16 μm (4000-625 cm-1).

¾ Depends on transitions between vibrational energy

states:

–- Stretching
Functional Group : 4000-1600 cm-1
–- Bending Fingerprint region: 1300-625 cm-1
102
Stretching Vibrations of a CH2 Group

Symmetric Antisymmetric

103
Bending Vibrations of a CH2 Group

In plane In plane

Out of plane Out of plane 104

Figure 13.31: Infrared Spectrum of Hexane

bending

C—H stretching bending bending

CH3CH2CH2CH2CH2CH3

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1

105
Figure 13.32: Infrared Spectrum of 1-Hexene

C=C
1640 cm-1
C=C—H H— C H2C=C
3095 cm-1 1000, 900
cm-1
H2C=CHCH2CH2CH2CH3

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
106
Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Stretching vibrations (single bonds)
sp C—H 3310-3320
sp2 C—H 3000-3100
sp3 C—H 2850-2950
sp2 C—O 1200
sp3 C—O 1025-1200

107
 Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Stretching vibrations (multiple bonds)

C C 1620-1680

—C C— 2100-2200

—C N 2240-2280
108
 Infrared Absorption Frequencies

Structural unit Frequency, cm-1 C O

Stretching vibrations (carbonyl groups)
Aldehydes and ketones 1710-1750
Carboxylic acids 1700-1725
Acid anhydrides 1800-1850 and 1740-1790
Esters 1730-1750
Amides 1680-1700
109
 Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Bending vibrations of alkenes

RCH CH2 910-990

R2C CH2 890

cis-RCH CHR' 665-730

trans-RCH CHR' 960-980

R2C CHR' 790-840 110

 Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Bending vibrations of derivatives of benzene
Monosubstituted 730-770 and 690-710
Ortho-disubstituted 735-770
Meta-disubstituted 750-810 and 680-730
Para-disubstituted 790-840

111
Figure 13.33: Infrared Spectrum of tert-butylbenzene

Ar—H
C6H5C(CH3)3

H— C Monsubstituted
benzene

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
112
 Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Stretching vibrations (single bonds)
O—H (alcohols) 3200-3600
O—H (carboxylic acids) 3000-3100
N—H 3350-3500

113
 Figure 13.34: Infrared Spectrum of 2-Hexanol

H— C

O—H
CH3CH2CH2CH2CHCH3

OH

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
114
Figure 13.35: Infrared Spectrum of 2-Hexanone

CH3CH2CH2CH2CCH3

O
H— C

C=O

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
115
 13.21
Ultraviolet-Visible (UV-VIS)
Spectroscopy

¾ Gives information about conjugated π−electron

systems.

116
Transitions between electron energy states

¾ Gaps between electron

energy levels are greater than
those between vibrational
Δ E = hν levels.
¾ Gap corresponds to
wavelengths between 200 and
800 nm.

117
 Conventions in UV-VIS

¾ X-axis is wavelength in nm (high energy at left, low

energy at right).

¾ λmax is the wavelength of maximum absorption and is

related to electronic makeup of molecule— especially π
electron system.

¾ Y axis is a measure of absorption of electromagnetic

radiation expressed as molar absorptivity (ε).

118
 UV Spectrum of cis,trans-1,3-
cyclooctadiene

2000
Molar λmax 230 nm
absorptivity (ε)
εmax 2630
1000

200 220 240 260 280

Wavelength, nm
119
 π→π* Transition in cis,trans-1,3-
cyclooctadiene
ψ4∗ ψ4∗

LUMO ψ3∗ ψ3∗

Δ E = hν
HOMO ψ2 ψ2

ψ1 ψ1

Most stable π-Electron

π-electron configuration of
configuration excited state
120
 π→π* Transition in Alkenes

¾ HOMO-LUMO energy gap is affected by

substituents on double bond.

¾ As HOMO-LUMO energy difference decreases

(smaller ΔE), λmax shifts to longer wavelengths.

121
¾ Methyl groups on double bond cause λmax to
shift to longer wavelengths.

H H H CH3
C C C C
H H H CH3

λmax 170 nm λmax 188 nm

122
¾ Extending conjugation has a larger effect on
λmax; shift is again to longer wavelengths.

H H H H
C C C C H
H H H C C
H H
λmax 170 nm
λmax 217 nm

123
 H H
C C H
H λmax 217 nm
C C
(conjugated diene)
H H
H3C H
C C H λmax 263 nm
H C C H conjugated triene plus
two methyl groups
H C C
H CH3 124
 Lycopene

orange-red pigment in tomatoes

λmax 505 nm

125
 13.22
Mass Spectrometry

126
Principles of Electron-Impact Mass Spectrometry

e–

e–
Atom or molecule is hit Electron is deflected
by high-energy electron. but transfers much of
its energy to the
molecule.

e– Electron is deflected but

transfers much of its energy to
the molecule. 127
Principles of Electron-Impact Mass Spectrometry

This energy-rich species ejects an electron.

+ e–
•

Forming a positively charged, odd-electron

species called the molecular ion.
128
Principles of Electron-Impact Mass Spectrometry

Molecular ion passes between poles of a

magnet and is deflected by magnetic field

- Amount of deflection
depends on mass-to-
charge ratio.
+
- Highest m/z •
deflected least.

- Lowest m/z
deflected most.
129
Principles of Electron-Impact Mass Spectrometry

¾ If the only ion that is present is the molecular

ion, mass spectrometry provides a way to
measure the molecular weight of a compound
and is often used for this purpose.

¾ However, the molecular ion often fragments to

a mixture of species of lower m/z.

130
Principles of Electron-Impact Mass Spectrometry

The molecular ion dissociates to a cation

and a radical.

+ + •
•

Usually several fragmentation pathways are available

and a mixture of ions is produced.
131
 Principles of Electron-Impact Mass Spectrometry

¾ Mixture of ions of different

mass gives separate peak
for each m/z.

¾ Intensity of peak
+ +
proportional to percentage of
each ion of different mass in + +
mixture.
+
+
¾ Separation of peaks
depends on relative mass.
132
 Principles of Electron-Impact Mass Spectrometry

¾ Mixture of ions of different

mass gives separate peak
+ + + +
for each m/z.

¾ Intensity of peak + +
proportional to percentage
of each ion of different mass
in mixture.

¾ Separation of peaks
depends on relative mass. 133
Some molecules undergo very little fragmentation

Benzene is an example. The major peak

corresponds to the molecular ion.
Relative
intensity

100
80 m/z = 78

60
40
20
0
20 40 60 80 100 120
m/z 134
 Isotopic Clusters

H H H

H H H H H H

78 79 79
H H H H H H

H H H

93.4% 6.5% 0.1%

all H are one C is 13C one H is 2H

1H and all
135
C are 12C
 Isotopic Clusters 35Cl 37Cl

in Chlorobenzene
Visible in peaks
Relative
intensity for molecular ion

100
80 112

60
40 114
m/z
20
0 20 40 60 80 100 120
136
 Isotopes

¾ A compound with one Cl present will show 1:3

peaks for M:M+2.

¾ A compound with one Br present will show 1:1

peaks for M:M+2.

137
 Isotopic Clusters
in Chlorobenzene +
H H
No m/z 77, 79
pair; therefore ion
Relative responsible for H H
intensity m/z 77 peak does not
contain Cl. H
100
80
60 77

40 m/z
20
0 20 40 60 80 100 120
138
 Alkanes undergo extensive fragmentation

CH3—CH2—CH2—CH2—CH2—CH2—CH2—CH2—CH2—CH3
Relative 43
intensity
57
100
80 Decane
60
71
40
85
20 99 142

0 20 40 60 80 100 120

m/z
139
 Propylbenzene fragments mostly
at the benzylic position
Relative
intensity

100
91
80
CH2—CH2CH3
60
40
120
20
0 20 40 60 80 100 120

m/z 140
 13.23. Molecular Formula as a Clue
to Structure

¾ One of the first pieces of information we try to

obtain when determining a molecular structure is
the molecular formula.

¾ However, we can gain some information even

from the molecular weight. Mass spectrometry
makes it relatively easy to determine molecular
weights.

141
 The Nitrogen Rule

¾ A molecule with an
NH2 93
odd number of nitrogens
has an odd molecular
weight.
O2N NH2 138
¾ A molecule that
contains only C, H, and NO2
O or which has an even
number of nitrogens has O2N NH2 183
an even molecular
weight. 142
 Exact Molecular Weights
O

CH3(CH2)5CH3 CH3CO
Heptane Cyclopropyl acetate

Molecular formula C7H16 C5H8O2

Molecular weight 100 100

Exact mass 100.1253 100.0524

¾ Mass spectrometry can measure exact masses.

Therefore, mass spectrometry can give molecular
143
formulas.
 Molecular Formulas

¾ Knowing that the molecular formula of a

substance is C7H16 tells us immediately that is an
alkane because it corresponds to CnH2n+2.

¾ C7H14 lacks two hydrogens of an alkane, therefore

contains either a ring or a double bond.

144
 Index of Hydrogen Deficiency

Relates molecular formulas to multiple bonds

and rings.

Index of hydrogen deficiency =

1 (molecular formula of alkane –

2 molecular formula of compound)

145
 Example 1
C7H14
Index of hydrogen deficiency
1
= (molecular formula of alkane –
2
molecular formula of compound)

= 1 (C7H16 – C7H14)
2

= 1 (2) = 1
2
Therefore, one ring or one double bond. 146
 Example 2
C7H12

1
= (C7H16 – C7H12)
2

1
= (4) = 2
2
Therefore, two rings, one triple bond, two double bonds, or
one double bond + one ring.

147
 Oxygen has no effect

CH3(CH2)5CH2OH (1-heptanol, C7H16O) has

same number of H atoms as heptane.

Index of hydrogen deficiency =

1 (C7H16 – C7H16O) = 0
2

no rings or double bonds

148
 Oxygen has no effect
O

CH3CO
Cyclopropyl acetate

Index of hydrogen deficiency =

1 (C H – C H O ) = 2
5 12 5 8 2
2

one ring plus one double bond

149
 If halogen is present

Treat a halogen as if it were hydrogen.

H Cl
C3H5Cl
C C
same index of hydrogen
H CH3
deficiency as for C3H6

150
 If N is present

Treat Nitrogen as CH.

H NH2
C3H7N
C C
same index of hydrogen
H CH3
deficiency as for C4H8

151
 Rings versus Multiple Bonds

¾ Index of hydrogen deficiency tells us the sum of

rings plus multiple bonds.

¾ Catalytic hydrogenation tells us how many multiple

bonds there are.

152