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).
Use of UV
Example: Butanone
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
Vibration
transitions:
Streching
Each Isotope of an atom gives a specific peak according to its abundance. and
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
The fingerprint area gives specified pattern of many peaks (bending vibrations) in
the spectra for each organic molecule
Example: 1- hexyne
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
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