Organic Spectroscopy 1 Lecture 6 Dr Rob Paton robert.paton@chem.ox.ac.uk http://paton.chem.ox.ac.

uk

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

Infrared (IR) Spectroscopy

Measures molecular vibrational energy levels Molecules vibrate in many ways simultaneously, however, fundamental normal modes give rise to characteristic IR absorptions. The strength of absorption depends on the change in dipole-moment of the vibrating group.

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

alkene CH bond: 3040

terminal alkyne CH bond: 3300

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

N-H bonds: Slightly higher than C-H stretches (3330-3450 cm-1):

H N H H N Me

symmetric 3400 cm-1

H H NH Me

antisymme 3500 cm

H HN

symmetric 3400 cm-1

N-methylaniline & aniline

antisymmetric 3500 cm-1

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

Carboxylic acids display a characteristic V-shape in the O-H absoprtion

O O H

O R

H O R O
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O H
1-cyclopentene-1-carboxylic acid

IR Spectroscopy
Hydrogen bonding affects the strength of an O-H bond:

pka: Steric factors inhibit H-bonding:

-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

allene C=C 2160 cm-1

3-methyl-1,2-butadiene (an allene)

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

Nitro groups are also diagnostic:

100 90

NICOLET 20SX FT-IR

0.0

.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

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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

(stronger C=O bond)

R O R' anhydrides

1.18

O R Cl acid chlorides 1800 cm-1 R

O Cl

O Cl R

increasing stretching frequency

O R O esters R' 1740 cm-1

1.20

O R H aldehydes 1730 cm-1 H O H 1715 cm-1 H

1.21

O R R' ketones

12
ond)
O

increasing str

O aldehydes 1730 cm-1 H O H 1715 cm-1 H

1.21

IR Spectroscopy R H
O R R' ketones

(weaker C=O bond)

O R OH acids 1710 cm-1

1.22

O R NR'2 amides 1660 cm-1 R

O NR'2 R

O NR'2

decreasing stretching frequency

O R SiR'3 acylsilanes 1640 cm-1

1.25

O O carboxylates 1580 cm-1 R

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

Conjugated ketones C=O stretch ca. 1690 cm-1

Non-conjugated ketones C=O stretch ca. 1715 cm-1

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

1790 cm-1 1841 cm-1 1750 cm-1

1815 cm-1

X=O 1727 cm-1 X = NH2 1669 cm-1

1750 cm-1 1673 cm-1

1774 cm-1 1717 cm-1

Conjugation weakens C=O and C=C

14

IR Spectroscopy
Me O N Me Me Me N O

Stable to hydrolysis

pka = -0.5

Hydrolyses in H2O/H+ in 45s C=O stretch 1732 cm-1

CN 1.352 CO 1.233 CN 1.475 CO 1.196

pka = 5.3

C=O stretch 1650 cm-1

Kirby et al. Angewandte Chemie International Edition 1998, 37, 785.

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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

Selected IR absorptions (s=strong, w=weak):

Spectrum 1 2 3 (cm-1) 1715 (s) 1724 (s), 1712 (s) 1730 (s), 1695 (s), 1642 (w) Spectrum 4 5 6 (cm-1) 1695 (s), 1686 (s), 1608 (w) 1653 (s), 1626 1730 (s), 1658 (w), 1626
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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

4 x 12.0000 + 1 x 15.9949 + 4 x 1.0078 = 68.0261

O 1700 2100 conjugated strength suggests conjugated

C4H4O

O CH3 or H3C

O H 3300 strong terminal acetylene C-H

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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

O 1730 (s) O 1685 (s) 1620 (w) conjugated conjugated

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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

C=O 1690 C=C 1630 C(sp2)-H 3100

Reactant IR spectrum

C=O 1710 C=C gone C(sp2)-H gone no broad OH!

Product IR spectrum

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IR Spectroscopy
Example: Use the following IR and 1H NMR spectra to assign the structures of two isomers of C6H12

both: C=C 1650 C(sp2)-H 3090

Overlay of X & Y IR spectra

H NMR spectrum of X (ppm)

H NMR spectrum of Y (ppm)

1.8 s
CH3

5.8 m 1.6 sextet

H2 C H

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
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4.7 d

5.0 dd