Organic Spectroscopy UV - Ultraviolet-Visible Spectroscopy

Methods for structure determination of organic compounds: Conjugated compounds absorb energy in the ultraviolet (UV) and
visible (Vis) regions on the electromagnetic spectrum
X-ray Crystallography Crystall structures
Mass spectroscopy Molecular formula ! ! 200- 800 nm
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UV UltraViolet radiation Electron exitation
Lambert-Beer's law : A = " · C · l
IR InfraRed Vibration excitation
NMR Nuclear Magnetic Resonance Nuclear spin excitation
A is the observed absorbance,
Etot = Eelec + Evib + Erot + Ekin " Molar absorptivity Is the intensity of the absorption
E2
C is the molar concentration of the sample and
h" E = h" l is length of the sample cell in centimeters
!E
v=c/ #
E1 E=hc/# The wavelength of maximum absorption (! max) is reported in units of
nanometers (nm).

Example: UV absorption spectrum of 2,5-dimethyl-2,4-hexadiene

Overview of methods: Ethyl propenoat

Use of UV

• Absorbance above 210 gives indication of conjugated systems

• Concentration measurements through calibration curve
Absorption Maxima for Nonconjugated and Conjugated Dienes
MS - Mass Spectroscopy
In UV-Vis spectroscopy the electrons are excited from lower energy levels to
higher ones In mass spectroscopy (MS) a small quantity of a sample is vaporized and
The electron is generally excited from the highest occupied molecular orbital
ionized to form charged particles – usually an electron is removed from
(HOMO) to the lowest unoccupied molecular orbital (LUMO) each molecule to form charge ions. The charged particles are sorted
according to their mass-to-charge ratio (m/z) and detected. All this is taken
Alkenes and nonconjugated dienes have absorptions below 200 nm because place in an instrument called a mass spectrometer.
the energy difference between the HOMO and LUMO is large
Scheme:
In conjugated dienes these energy levels are much closer together and the
wavelengths of absorption are longer than 200 nm

Example: Butanone

Ethene has lmax at 171 nm and 1,3-butadiene has lmax at 217 nm

The longer the conjugated system, the smaller the energy difference
between the HOMO and the LUMO

A smaller energy gap results in longer !max in the ultraviolet -visible spectrum

#-Carotene has 11 conjugated double bonds and an absorbance maximum at 497

nm which is in the blue-green region of the visible spectrum

#-Carotene is perceived as red-orange, the complementary color of blue-green

See more examples in Tab 13-2 (p. 412)

The molecule is commonly fragmentated into “stable” carbocations at
branching points.
IR - Infrared spectroscopy

Vibration
transitions:

Streching

Each Isotope of an atom gives a specific peak according to its abundance. and

Common example with different isotope distrubution from unity:

79
Br / 81Br is 1:1 Mw = 80 g/mole and 35Cl / 37Cl is 3:1 Mw= 35.45 g/mole
Bending

IR can be used for determination of functional groups in organic

compounds.

Important IR absorptions of fundamental bonding groups

E
4000 cm-1 3000 2000 1600 1000 650 cm-1

O-H C H C H C C C O C C C O
C N
N-H C HBend Ar-HBend
O
C H C O H Fingerprint area
All vibrations streching unless noted. Bending vibrations

Similar summary is presented in Fig 13,7

For more specified values see Table 13,3 (p. 416)

Stretching vibrations:1000 - 4000 cm-1 Bendning vibrations: 600 - 1600 cm-1

The fingerprint area gives specified pattern of many peaks (bending vibrations) in
the spectra for each organic molecule

Strong dipoles gives generally strong absorbance, e.g. Carbonyl, C=O

Dipole moment must be changed if IR-radiation should be absorbed.

CH3 C C CH3 CH3 C C H
No absorbance Absorbance
Interpreting IR Spectra Example: 1-hexene

Example: 1- hexyne

Generally only certain peaks are interpreted in the IR

-Those peaks that are large and above 1400 cm-1 are most valuable

Hydrocarbons
C-H bonds where the carbon has more s character are shorter, stronger and stiffer
and thus vibrate at higher frequency
! C-H bonds at sp centers appear at 3000-3100 cm-1
! C-H bonds at sp2 centers appear at about 3080 cm-1
! C-H bonds at sp3 centers appear at about 2800-3000 cm-1
! Aromatic Compounds
- C-C bond stretching frequencies are only useful for multiple bonds - The C-C bond stretching gives a set of characteristic sharp peaks between 1450-
! C-C double bonds give peaks at 1620-1680 cm-1 1600 cm -1. Substitution pattern can be analyzed by peaks at 600-800 cm -1
! C-C triple bonds give peaks at 2100-2260 cm-1 Example: Methyl benzene

Example: octane
 Amines

Functional Groups: Very dilute solution of 1o and 2o amines give sharp peaks at 3300-3500 cm-1
for the N-H stretching
! 1o amines give two peaks and 2o amines give one peak
The carbonyl group gives
! 3o have no N-H bonds and do not absorb in this region
a strong peak which
More concentrated solutions of amines have broader peaks
occurs round 1700 cm-1
Amides have amine N-H stretching peaks and a carbonyl peak

Example: p-Methylaniline

Alcohols and Phenols

The O-H stretching absorption is very characteristic
In concentrated solutions, the hydroxyl groups hydrogen bond to each other and
a very broad and large peak occurs at 3200-3550 cm-1. See the spectra above of
ethanol as an example..

Carboxylic Acids
The carbonyl peak at 1710-1780 cm-1 is very characteristic
The presence of both carbonyl and O-H stretching peaks (2500-3500 cm-1,
very broad due to extensive hydrogen bonding) is a good proof of the
presence of a carboxylic acid

Example: propanic acid

Övning: Identifiera IR-spektra med rätt förening: Table IR
A