有機光譜學
(Ch 10)
授課教師：呂彥禮
鑑定結構所需之光譜
• 顏色，晶形
• 分子式，分子量
• 熔點 mp
• 光學活性 []
• IR
• UV
• MS
• HR-MS
• 1
H-NMR
• 13
C-NMR
• X-ray
Introduction
Modern techniques for structure determination
of organic compounds include:
• Mass spectrometry
– Size and formula of the compound
• Infrared spectroscopy
– Functional groups present in the compound
• Ultraviolet spectroscopy
– Conjugated electron system present in the compound
• Nuclear magnetic resonance spectroscopy
– Carbon-hydrogen framework of the compound
10.1 Mass Spectrometry of Small Molecules:
Magnetic-Sector Instruments
Mass spectrometry (MS) measures the mass and molecular
weight (MW) of a molecule
• Provides structural information by finding the masses of
fragments produced when molecules break apart
• Three basic parts of mass spectrometers:
Mass Spectrometry of Small Molecules:
Magnetic-Sector Instruments
Electron-impact, magnetic-
sector instrument
• Sample is vaporized into
ionization source
• Bombarded by electron beam
(70 eV) dislodging valence
electron of sample producing
cation-radical
• Most cation-radicals fragment
and are separated in magnetic
field according to their mass-to-
charge ratio (m/z)
• Since z = 1 for most ions the
value of m/z is mass of ion
分子量
不含氮與含偶數氮 : 偶數
含奇數氮 : 奇數
Benzylic
Demethyl
Carbonyl
Allylic
Dehydrate
Rearrangement
Retro Diels-Alder
cleavage
Mass spectrum of propane (C3H8; MW = 44)
• Base peak
– Tallest peak
• Assigned intensity of 100%
– Base peak at m/z = 29 in propane mass spectrum
• Parent peak
– Unfragmented cation radical – molecular ion (M+)
– Parent peak only 30% of base peak for propane
EI-MS (rel. int.) m/z : 44 (M+, 30), 29 (100).
Interpreting Mass Spectra
Mass spectrum of hexane (C6H14; MW = 86)
• All carbon-carbon bonds of hexane are electronically
similar and break to a similar extent
• Mass spectrum contains mixture of ions
Interpreting Mass Spectra
M+ = 86 for hexane
• m/z = 71 arises from loss of
methyl radical from hexane
cation radical
• m/z = 57 arises from loss of
ethyl radical from hexane
cation radical
• m/z = 43 arises from loss of
propyl radical from hexane
cation radical
• m/z = 29 arises from loss of
butyl radical from hexane
cation radical
Worked Example 10.1
Using Mass Spectra to Identify Compounds
Assume that you have two unlabeled samples, one of methylcyclohexane
and the other of ethylcyclopentane.
How could you use mass spectrometry to identify them?
Worked Example 10.2
Identifying Fragmentation Patterns in a Mass
Spectrum
The mass spectrum of 2-methylpentan-3-ol is shown below.
What fragments can you identify?
10.6 Infrared Spectroscopy
Infrared (IR) region
• Ranges from 7.8 x 10-7 m to 10-4 m
– 2.5 x 10-6 m to 2.5 x 10-5 m used by organic chemists
• Wavelengths given in micrometers (1 m = 10-6 m)
• Frequencies given in wavenumbers
• Wavenumber
– Reciprocal of wavelength in centimeters
– Expressed in units of cm-1
Infrared Spectroscopy
Molecules stretch or bend at specific
frequencies
• Energy is absorbed if the frequency of the radiation matches the
frequency of the vibration
IR spectrum → What molecular motions? → What functional
groups?
Vibrations – change in dipole monent
1. Fundamental vibration
(no change in the center of gravity of the molecule)
a. stretching
b. bending (scissoring)
c. wagging
d. rocking
2. Overtones (multiples of a given frequency)
3. Combinations (sum of two other vibrations)
4. Fermi resonance (1 + 2 or 3)
5. Coupling of two fundamental vibrations
Material Transparent region (cm-1)
NaCl 625 - 50000
Glass 5000 – 29000
Quartz 2500 – 50000
Fluorite 1000 – 50000
KCl 500 – 30000
KBr 400 – 50000
AgCl 400 – 17000
CsBr 250 – 30000
CsI 200 – 30000
10.7 Interpreting Infrared Spectra
Most functional groups have characteristic IR absorption
bands that don’t change from one compound to another
Interpreting Infrared Spectra
Interpreting Infrared Spectra
IR spectra of hexane, hex-1-ene and hex-1-yne
Infrared Spectra of Some Common Functional
Groups
Characteristic aromatic IR absorptions
Infrared Spectra of Some Common Functional
Groups
IR spectrum of toluene
Worked Example 10.5
Predicting IR Absorptions of Compounds
Where might the following compounds have IR absorptions?
Worked Example 10.5
Predicting IR Absorptions of Compounds
Solution
(a) This molecule has an alcohol O-H group and an alkene double bond.
Absorptions: 3400 – 3650 cm-1 (O-H)
3020 – 3100 cm-1 (=C-H)
1640 – 1680 cm-1 (C=C)
(b) This molecule has a terminal alkyne triple bond and a saturated ester
group.
Absorptions: 3300 cm-1 (≡C-H)
2100 – 2260 cm-1 (C≡C)
1735 cm-1 (C=O)
Worked Example 10.6
Identifying Functional Groups from an IR
Spectrum
The IR spectrum of an unknown compound is shown below.
What functional groups does the compound contain?
Worked Example 10.6
Identifying Functional Groups from an IR
Strategy Spectrum
• All IR spectra have many absorptions, but those useful
for identifying specific functional groups are usually
found in the region from 1500 cm-1 to 3300 cm-1. Pay
particular attention to the carbonyl region (1670 – 1780
cm-1), the aromatic region (1660 – 2000 cm -1), the triple-
bond region (2000 – 2500 cm-1), and the C-H region
(2500 – 3500 cm-1)
Worked Example 10.6
Identifying Functional Groups from an IR
Spectrum
Solution
• The spectrum shows an intense absorption at 1725 cm -1 due to a
carbonyl group (perhaps an aldehyde, -CHO), a series of weak
absorptions from 1800 to 2000 cm-1 characteristic of aromatic
compounds, and a C-H absorption near 3030 cm-1, also
characteristic of aromatic compounds. In fact, the compound is
phenylacetaldehyde.
IR max cm-1 : 3337 (OH), 2967, 2928, 2882 (CH), 1463 (CH2),
1385 (CH3), 1054 (C-O)
10.9 Ultraviolet Spectroscopy
Ultraviolet (UV) region
• 4 x 10-7 m to 10-8 m
• Region of greatest interest to organic chemists from 2 x 10 -7 m to 4 x
10-7 meters
Ultraviolet Spectroscopy
Absorption usually measured in nanometers (nm), where 1 nm
= 10-9 m
• Energy absorbed from UV radiation promotes an electron from highest
occupied molecular orbital (HOMO) to the lowest unoccupied molecular
orbital (LUMO)
MO diagram for buta-1,3-diene
Ultraviolet Spectroscopy
Absorption detected and displayed on a chart
plotting wavelength versus absorbance (A)
Io
A = log
I
I o = intensity of the incident light
I = intensity of light transmitted through the sample
Ultraviolet Spectroscopy
Ultraviolet spectrum of buta-1,3-diene
Ultraviolet Spectroscopy
Amount of UV light absorbed is expressed as
the sample’s molar absorptivity (), defined
by the equation
A
A = bc =
c l
where A = Absorbance
c = Concentration in mol/L
l = Sample pathlength in cm
10.10 Interpreting Ultraviolet Spectra: The
Effect of Conjugation
Wavelength necessary to effect → *
transition in a conjugated molecule depends
on the energy gap between HOMO and
LUMO, which in turn depends on the nature
of the conjugated system
• Energy difference between HOMO and LUMO decreases as
conjugation increases
Interpreting Ultraviolet Spectra: The Effect of
Conjugation
10.11 Conjugation, Color, and the Chemistry
of Vision
Colored organic compounds have extended
conjugated systems
• “UV” absorptions extend into the visible region
-Carotene has max = 455 nm
– When white light strikes -carotene wavelengths in the blue
region are absorbed while the yellow-orange colors are
transmitted to our eyes
Conjugation, Color, and the Chemistry of Vision
Ultraviolet spectrum of -carotene, a conjugated molecule with 11
double bonds
• Absorption occurs in the visible region
UV max nm: 490, 455, 430, 415 (sh), 385, (sh), 345, 270.
