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Michaelmas 2011
Recap of Lecture 5
UV-vis Spectroscopy
Measures the gaps between electronic energy levels Most useful for conjugated double bonds since the HOMO-LUMO energy gap is small enough to promote an electron in this spectral region Increasing conjugation leads to greater absorption, and a shift to absorption at longer wavelengths (max) Characteristic absorption for certain classes of organic compounds may be predicted (albeit relatively crudely) using Woodwards rules Steric effects and geometric strain may prevent efficient conjugation, and therefore will affect UV-vis absorption wavelengths
IR Spectroscopy
The X-H region: 2500-4000 cm-1 For example: C-H bonds:
H H
H H
HH H
ring CH single bond: 2800-300 cm-1 ring CH bond: alkene CH single2800-3000 bond: 3040 cm-1 alkyne CN triple bond: 3300 cm-1
1-ethynyl-1-cyclohexene
Typical C-H stretching frequencies: sp3 C-H sp2 C-H sp C-H 2800-3000 cm-1 usually CH3 and CH2 symmetric and antisymmetric stretches are seen 3040-3125 cm-1 exact form depends on the number of alkene substituents 3270-3340 cm-1 usually appears as a single sharp peak
IR Spectroscopy
Some C-H stretches are diagnostically useful (Bohlmann bands):
R O H
antisymme 3500 cm
H HN
IR Spectroscopy
O-H bonds: Very broad absorption around 3300 cm-1 is characterstic
O F
4-fluorophenol
R H OH O O R H H R O R
O O H
O R
H O R O
5
O H
1-cyclopentene-1-carboxylic acid
IR Spectroscopy
Hydrogen bonding affects the strength of an O-H bond:
-2.1
5.2
10.8
tBu O H
Me
2-tbutyl-6-methylphenol
IR Spectroscopy
Example Problem Using NMR, UV-vis and IR:
C6H6O CHCl3/OH-/H2O A + B (C7H6O2) B max 255 ( 10,000) 7.0-7.4 (m, 4H), 9.8 (s, 1H), 10.9 (s, 1H)* 3500-3000 (no change on dilution.), 1660 *exchanges in D2O
A max 285 ( 16,000) 7.0 (d, 2H), 7.8 (d, 2H), 9.8 (s, 1H), 10.4 (brs, 1H)* 3600 (dil. sol.) 3100-3400 (conc. sol.), 1690
IR Spectroscopy
The triple bond region: 2000-2500 cm-1 CN and CC bonds:
1-Pentyne IR Spectrum
propionitrile
IR Spectroscopy
ethylisocyanoacetate
Cumulenes
IR Spectroscopy
The double bond region: 1500-2000 cm-1 C=C bonds: Alkenes, aromatics
oleyl alcohol
E-4-nonene
10
IR Spectroscopy
methyl crotonate
.05
80
0.1
70
% T R A N S M I T T A N C E 0.2
60
50
40
A B S O R B A N C E
0.3
0.4
30
0.5 0.6
20
0.7 0.8
10
0.9 1.0
0 4000
2.0
3800
3600
3400
3200
3000
2800
2600
2400
2200
2000
1800
1600 WAVENUMBERS
1400
1200
1000
800
600
450
Nitrocyclohexane
11
IR Spectroscopy
Carbonyl Groups Learn these numbers! IR spectroscopy is particularly useful in identifying which of the several different kinds of carbonyl group is present in a molecule. C=O double bonds show a strong absorption band since they have a large dipole moment. The position of the absorption is governed by the electronic structure.
carbonyl group O O stretching frequency (approx.) 1820 & 1760 cm-1
R O R' anhydrides
1.18
O Cl
O Cl R
O R R' ketones
12
ond)
O
increasing str
IR Spectroscopy R H
O R R' ketones
O NR'2 R
O NR'2
O O R
O O
Electron Donating Groups weaken the C=O bond shifting IR frequency down Electron Withdrawing Groups strengthen the C=O bond shifting the IR frequency up
13
IR Spectroscopy
Conjugation:
O O O O
Conjugation lowers the stretching frequency, typically by around 30 cm-1. Ring Strain: When a carbonyl is part of a ring, the C=O stretching frequency depends on ring size: as ring size decreases, the carbonyl stretching frequency increases.
O O X X O
+40
cm-1 1750
+40
cm-1
X
+25
cm-1
X = CH2 1710
cm-1
1715
cm-1
cm-1
1815 cm-1
14
IR Spectroscopy
Me O N Me Me Me N O
Stable to hydrolysis
pka = -0.5
pka = 5.3
15
IR Spectroscopy
Example: Six derivatives of the steroid cholestane: match up the structures with the IR data
A O O O 2 x C=O (conjugated): 1715 - 30 = 1685 cm-1 (s) 4 1 x C=C (conjugated): 1650 - 30 = 1620 cm-1 (w) O O 1 x C=O (ketone): 2 1715 cm-1 (s) 1 x C=O (ester): 1730 cm-1 (s) B O O O 1 x C=O (ester): 3 1730 cm-1 (s) 1 x C=O (conjugated ketone): 1715 - 30 = 1685 cm-1 (s) 1 x C=C (conjugated): 1650 - 30 = 1620 cm-1 (w) F O O OEt 1 x C=O (conj. ketone): 1730 - 60 = 1670 cm-1 (s) 5 1 x C=C (enol ether): 1630 cm-1 O O 1 x C=O (ketone): 1 1730 cm-1 (s) O OEt 1 x C=O (ester): 1730 cm-1 (s) 1 x C=C: 1650 cm-1 (w) 1 x C=C (enol ether): 1630 cm-1 6 C
IR Spectroscopy
Example: The molecular mass of X has been determined by high-resolution mass spectrometry as 68.02621. What is the formula and structure of X? (masses H: 1.0078 C: 12.0000 O: 15.9949)
IR spectrum of X
C4H4O
O CH3 or H3C
17
IR Spectroscopy
Example: It was envisaged that the condensation of two equivalents of ethyl acetoacetate with formaldehyde would produce Hagemanns ester. Is the products IR spectrum consistent with this proposal?
O O H H EtO (2 equiv) O O piperidine (cat.) then heat CO2Et "Hagemann's ester"
Product IR spectrum
OR
IR Spectroscopy
Example: Identify the product from the reaction of cyclohexenone and dimethylcopper lithium
O i) Me2CuLi ii) H+ C7H12O
Nuc Me O O O Nuc HO Me
Reactant IR spectrum
Product IR spectrum
19
IR Spectroscopy
Example: Use the following IR and 1H NMR spectra to assign the structures of two isomers of C6H12
1.8 s
CH3
1.7 nonet
H CH3 C C H2
4.7 d
H C H2 H
5.0 dd
H
0.9 d
CH3
CH3
2.0 t
0.9 t
H
1.95 dd
20
4.7 d
5.0 dd