Organic Spectroscopy 1 Lecture 5 Dr Rob Paton robert.paton@chem.ox.ac.uk http://paton.chem.ox.ac.

uk

Michaelmas 2011

Organic Spectroscopy 1: Outline of Lectures 5-8

In lectures 5-6 of this course, aspects of Ultraviolet-visible and Infra red techniques will be introduced that are important in assigning organic structures. Coverage of the underlying theory and instrumentation associated with each method will be kept to a bare minimum since these aspects are covered elsewhere. We will look at a variety of real spectra and learn to correlate distinguishing features in these spectra with functional groups. UV-vis and IR spectroscopy provide direct experimental data to support of a number of the underlying concepts in organic chemistry introduced last year, such as conjugation and the mesomeric effect. We will also take a moment to consider these points.
O O O N O N

In lectures 7-8 we will go through worked examples to illustrate how to combine 13C and 1H NMR with UV-vis and IR spectra to assign structures. Digital copies of all handouts, problems and slides are available through the web: http://paton.chem.ox.ac.uk

Organic Spectroscopy 1: Outline of Lectures 5-8

Further Reading: Chemical Structure and Reactivity: an Integrated Approach J. Keeler and P. D. Wothers, OUP (Chapter 11) Introduction to Organic Spectroscopy - L. M. Harwood and T. D.W. Claridge, Oxford Chemistry Primers Organic Chemistry Clayden, Greeves, Warren and Wothers, OUP (Chapter 3) Organic Spectroscopic Analysis R. J. Anderson. D. J. Bendell and P. W. Groundwater, RSC For more complete coverage including many more real examples of spectra, tables of spectroscopic data that will be useful in structural elucidation, and worked examples consult the following: Organic Structure Analysis P. Crews, J. Rodriguez and M. Jaspers, OUP Spectroscopic Methods in Organic Chemistry (6th edition) D. H. Williams and I. Fleming, Mcgraw-Hill A wealth of experimental spectra may be found on the internet, in openly accessible repositories. The following may be of interest: NMRshift DB - NMR database for organic structures: http://www.ebi.ac.uk/nmrshiftdb/ The Japanese Spectral Database for Organic Compounds (SDBS) has free access to IR, Raman, 1H and 13C NMR and MS data: http://riodb01.ibase.aist.go.jp/sdbs/cgi-bin/cre_index.cgi?lang=eng Sigma-Aldrich has IR, Raman and 1H and 13C NMR spectra for many of their commericially available compounds: http://www.sigmaaldrich.com Problems in structure, combining IR with 1H and 13C NMR courtesy of Prof Craig Merlic, UCLA: http://www.chem.ucla.edu/~webspectra/ Past Paper Questions containing to NMR/IR/UV-vis spectroscopy: NB Since 2011 Mass Spectrometry has been shifted to 1B Part IA: 2004 (Q7), 2005 (Q2), 2006 (Q1), 2007 (Q8), 2008 (Q9), 2009 (Q1), 2010 (Q1), 2011 (Q7). General Paper I: 1993 Q6, 2000 (Q1), 2001 (Q5) and 2004 (Q8) General Paper II: 1991 (Q3, Q5), 1992 (Q8), 1993 (Q3), 1994 (Q1), 1995 (Q3), 1996 (Q7), 1997 (Q5), 1998, Q3), 1999 (Q6), 2000 (Q9), 2002 (Q1) and 2003 (Q3)
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The Electromagnetic Spectrum

By irradiating molecules at different frequencies, it is possible to gain different types of information about their structure, since these frequencies bring into resonance various modes of molecular motion, or electronic or nuclear excitation. In modern laboratories, NMR spectroscopy is the first choice method for gaining structural information, with Infrared (IR) and mass spectroscopy (MS) techniques acting in a supporting capacity and UV spectra only being required in specialized circumstances (e.g. analysis of specific compound classes such as polymers or porphyrins).

The Electromagnetic Spectrum

Electronic States
100000 -

Vibrational energy levels

25000 -

Rotational energy levels

2500 -

Nuclear spin states

80000 -

20000 -

2000 -

60000 -

15000 -

1500 -

0.01 cm-1 (400 MHz)

40000 -

10000 -

1000 -

20000 -

5000 -

500 -

(energies in wavenumbers, cm-1)

UV-vis Spectroscopy
UV-vis is a form of absorption spectroscopy. Radiation in the UV-visible region of the EM spectrum is absorbed, causing an electron to be excited to a higher energy level.

ground state

excited state

UV and visible spectra of organic compounds are associated with excitations of electrons from the ground state to an excited state higher in energy. The transition occurs from a filled bonding or non-bonding orbital to a formerly empty antibonding orbital. The energy gap is proportional to the frequency of absorption, and so UV-vis spectroscopy is a source of bonding information UV spectroscopy is most important in the structural analysis of compounds containing -bonds, in particular conjugated systems.
4 2 3 (750 kJ/mol) (500 kJ/mol) 2 1 1

(900 kJ/mol)

UV-vis Spectroscopy

hypsos = height

molar extinction coefficient,

bathos = depth hyper = above hypo = below

200

400 600 wavelength, (nm)

800

600

300

200 Energy gap (kJ/mol)

150

Recording UV-vis spectra The ultraviolet or visible spectrum is usually taken using a dilute solution of the sample in a glass or quartz tube, or cuvette. Typically the sides of the cuvette are 1 cm, and the total volume is 2-3 cm3. UV or visible light is passed through the sample and the intensity of the transmitted beam is recorded across the wavelength range of the instrument (I). First the intensity of the light is recorded with pure solvent in the cuvette (I0) the absorbance due to the sample can then be computed as log10 (I0/I).
I0 I

light source *

detector

UV-vis Spectroscopy
The Beer-Lambert law states that the absorption of light by a given sample is proportional to the number of absorbing molecules, and independent of the source intensity.

I0 and I are the intensities of the incident and transmitted light, respectively, l is the path length of the absorbing solution in cm and c is the concentration in moles/litre. is the molar extinction coefficient in 1000 cm2 mol-1. log10 (I0/I) is called the absorbance.

Example: A 1.12 x 10-4 M solution of paranitroaniline, in a cuvette of path length 1cm, has a measured absorbance maximum of 1.55 at 227 nm. This means the intensity of the transmitted light is 101.55 = 35 times the intensity of the incident light. The value for this absorption is: This would be quoted as:

UV-vis Spectroscopy
The solvent and vessels must be transparent in the range of interest.
cyclohexane chloroform 95% ethanol water quartz glass
150 170 190 210 230 wavelength (nm) 290 310 330 350

UV-vis absorptions of common functional groups:

*
n* conjugated * double bonds isolated * lone pairs (O, N, S) n* single bonds * 150 170 Vacuum UV 190 210 UV 230 wavelength (nm) 290 310 330 350

* n (LP)

Functional groups such as polyenes and poly-ynes that give rise to diagnostic absorptions in the UV-vis region of the EM spectrum are referred to as chromophores
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UV-vis Spectroscopy
Selection Rules and Intensity Irradiation of organic compounds does not always give rise to excitations of electrons from any filled to unfilled orbital, because there are rules based on symmetry governing which transitions are allowed. The intensity of absorption is related to the allowedness of a particular transition A chromophore with two double bonds conjugated together possesses a fully allowed transition, and has associated values of about 10,000 Forbidden absorptions are in practice observed with weak absorptions, as the symmetry may be broken by a molecular vibration or by unsymmetrical substitution.
allowed O - * > 10,000 n - * = 10 - 100 - * = 100 - 1000 "forbidden"

The most important point to be made is that, in general:

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UV-vis Spectroscopy
Example: conjugated dienes:
Me Me
n

Ph

Ph
n

n 3 4 5 6 7 8

max (nm)
275 310 342 380 401 411

30,000 76,500 122,000 146,000 -

max (nm)
358 384 403 420 435 -

75,000 86,500 94,000 113,000 135,000

The most important point to be made is that, in general:

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UV-vis Spectroscopy
Absorption maxima for substituted benzene rings (Ph-R)
R H NH3 Me I Cl Br OH OMe SO2NH2 CN CO2 CO2H NH2 O NHAc COMe CH=CH2 CHO Ph OPh NO2 CH=CHCO2H CH=CHPh

max (nm)
203.5 203 206.5 207 209.5 210 210.5 217 217.5 224 224 230 230 235 238 245.5 248 249.5 251.5 255 268.5 273 295.5

7,400 7,500 7,000 7,000 7,400 7,900 6,200 6,400 9,700 13,000 8,700 11,600 8,600 9,400 10,500 9,800 14,000 11,400 18,300 11,000 7,800 21,000 29,000

max (nm)
254 254 261 257 263.5 261 270 269 264.5 271 268 273 280 287 282 272

204 160 225 700 190 192 1450 1480 740 1000 560 970 1430 2600 750 2000

max (nm)
254 254 261 257 263.5 261 270 269 264.5 271 268 273 280 287 291 278

204 160 225 700 190 192 1450 1480 740 1000 560 970 1430 2600 500 1800

pH induced shifts: an acid induced blue (i.e. hypsochromic) shift

NH2
max 230 nm

NH3
max 203 nm

NH2

NH2

NH2 H N H
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UV-vis Spectroscopy
pH induced shifts: a base induced red (i.e. bathochromic) shift
OH -H
max 210.5 nm max 235 nm

Effects of complementary EWG/EDG substituents

NH2 NO2

max 230 nm

max 269 nm

7800
NO2
NO2 NH2 NH2

8600
NH2 NH2 O2N O2N

H2N

H2N

NO2

NO2

NO2 O2N
max 260 nm

max 229 nm max 229 nm

max 235 nm max 235 nm

max 375 nm max 375 nm

14800 14800

16000 16000

16000 16000

1300

Acid base indicators: e.g phenolphthalein

max 231 nm (25,800) max 275 nm (4,200) max 230 nm (25,800) max 553 nm (26,000)

HO OH HO O pKa 9.4 O HO

O
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UV-vis Spectroscopy
Carbonyls:
4 2 2 3 2pO 2 1 1 1 2pO

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UV-vis Spectroscopy
Predicting UV absorptions of conjugated dienes: Alkyl substitution of a diene extends the chromophore through hyperconjugative interactions, causing a small red shift to longer values for max.

The effect of alkyl substitution on open chain dienes and dienes in six-membered rings is approximately additive, so a few rules (first formulated by R. B. Woodward in 1941) can be used to predict absorption. Woodwards rules have since been refined as a result of experience by Fieser. Woodwards rules may be applied to predict the absoroption of a diene that is either homoannular with both double bonds contained in one ring or heteroannular with two double bonds distributed between two rings.
Woodward's rules for diene and triene absorption Base value for parent s-trans diene (heteroannular) Base value for parent s-cis diene (homoannular) Increments for: (a) each alkyl substituent or ring residue (b) exocyclic nature of any double bond (c) additional double bond extending conjugation (d) auxochrome: -OAcyl -OAlkyl -SAlkyl -Cl or -Br -NAlkyl 214 nm 253 nm +5 nm +5 nm +30 nm +0 nm -OAcyl +6 nm -OAlkyl +30 nm - -SAlkyl +5 nm -Cl or -Br +60 nm -NAlkyl
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UV-vis Spectroscopy
Example of applying the Woodward-Fieser rules:

Less empirical treatment particle in a box: En = n2h2/8mL2

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UV-vis Spectroscopy
Rules for the principal band of substituted benzenes RC6H4OX Parent chromophore: X alkyl or ring residue H OH or Oalkyl Increment for each substituent: -alkyl/ring residue -OH, OMe, OAlkyl o, m -O o m -Cl o, m p o, m p o, m p o m p o, m p +3 +10 +7 +25 +11 +20 +78 0 +10 -Br -OH, OMe, OAlkyl -NH2 om -NHAc o, m -NHMe -NMe2 o, m p o, m p o, m p p o, m p +2 +15 +13 +58 +20 +45 +73 +20 +85 246 nm 250 nm 230 nm O R X

Example:
O

MeO

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UV-vis Spectroscopy
trans-stilbene and cis-stilbene

max 296 nm ( 29,000)

max 280 nm ( 10,500)

2,4,6-trimethylacetophenone and para-methylacetophenone

max 242 nm ( 3,200)

max 252 nm ( 15,000)

Strain release in the hydrolysis of a dilactone produced from shelloic acid.

O H O H O H OH O H O H2O H O H OH O

no strong absoprtion >210 nm

max 227 nm ( 5,500)

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UV-vis Spectroscopy
Tomatoes are a deeper red than carrots. Given that the conjugated systems of -carotene and lycopene are both eleven double bonds conjugated together with a similar number of alkyl substituents, why might lycopene absorb at a longer wavelength and with greater intensity?

-carotene

lycopene

Dehydration of graphene oxide to grapheme (Chem. Mater. 2009, 21, 2950)

H+

OH

Expanding a porphyrin -system (Org. Lett. 2008, 10, 3945)

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IR Spectroscopy

O Me Me H O H H

O O O H

cortisone acetate

Electronic States
100000 -

Vibrational energy levels

25000 -

Rotational energy levels

2500 -

E = h c / i.e. C-H bonds absorb at around 3000 cm -1 : 6.63x10 -34 x 3x10 8 x 3000x10 2 x N a = 36 kJ/mol

80000 -

20000 -

2000 -

60000 -

15000 -

1500 -

40000 -

10000 -

1000 -

20000 -

5000 -

500 -

(energies in wavenumbers, cm-1)

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IR Spectroscopy
High-resolution IR spectrum of CO in the gas phase:

Transmission
2000

2050

2100 2150 wavenumber (cm-1)

2200

2250

Modelling a vibration: Hookes law (as the extension, so the force)

kf m1 m2

oscillation about COM

The frequency depends on the mass and the stiffness of the spring

When applying this model to a pair of bonded atoms, the force constant corresponds to the strength of the covalent bond. Stronger bonds are harder to stretch.

21

IR Spectroscopy
Unlike a mass hanging from a spring, when a diatomic molecule vibrates, both of the atoms move. We take this into account by using the reduced mass for the system to compute the frequency of oscillation:

For a vibrating diatomic molecule, the frequency of vibration (expressed as a wavenumber, in cm-1) is given by:

When one of the two masses is considerably larger than the other, as in a X-H bond, this expression approximates to the lighter of the two masses:

Due to the inverse relationship between reduced mass and frequency, the stretching frequencies for X-H bonds are considerably greater than those for other bonds.

For atoms with similar masses, the stretching frequencies of triple bonds are greater than double bonds, which in turn are greater than for single bonds. This is a consequence of force constants following the bond strengths.

22

IR Spectroscopy
Compare the C-H region of the IR spectra of fluorobenzene and d5-fluorobenzene.
1H 1H 1H 2D 2D 2D 2D 1H

F
1H

F
2D

C-H - 3050 cm-1 C-H/ C-D = 1.34

C-D - 2280 cm-1

reduced mass C-H: 1 x 12 / (1+ 12) 1 reduced mass C-D: 2 x 12 / (2+ 12) 2 ratio of C-H to C-D stretching frequency = = 1.4

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IR Spectroscopy
The complex vibrational motion of polyatomic molecules can be resolved into a series of simpler normal modes. There are 3N 6 (non-linear molecule) or 3N 5 (linear molecule) normal modes. Normal modes of sulfur dioxide, SO2:
bending mode 519 cm-1 symmetric stretching mode 1151 cm-1 antisymmetric mode 1361 cm-1

Different bends of a methylene group:

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IR Spectroscopy
Normal modes of carbon dioxide:
symmetric stretching mode antisymmetric mode

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IR Spectroscopy
It is helpful to divide the IR spectrum into regions:

Example: cyanoacetamide

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