IntroductoryOrganicChemistry

Chem 222&Chem 234

Summer2015
CHAPTER9:TOOLSFORSTRUCTUREDETERMINATION
Dr.LauraPavelka
DepartmentofChemistry
Pulp&Paper104
laura.pavelka@mcgill.ca

NOWTHATWEHAVEAHANDLEON
13C&1HNMRSPECTROSCOPY
TIMETOMOVEONTOMASSSPEC!

CHEM222/234

LectureChapter9

LETS SEEWHATELSEWECANDO...
Section2 NMRSpectroscopyandMassSpectrometry
Chapter9 ToolsforStructureDetermination(Part2)
IntrotoMassSpectrometry(MS)
IonizationandFragmentation
IsotopesinMS
IntegratedStructureDetermination

CHEM222/234

LectureChapter9

MassSpectrometry
Spectroscopy studying/plottingtheinteractionofmoleculeswith
electromagneticradiation

MassSpectrometry electromagneticradiationNOTinvolved

CHEM222/234

LectureChapter9

MassSpectrometry
Spectroscopy studying/plottingtheinteractionofmoleculeswith
electromagneticradiation

MassSpectrometry electromagneticradiationNOTinvolved
UsesofMassSpectrometry:
1. MolecularWeightand/orFormulaDetermination
2. StructuralAnalysis fragmentationpatterns
3. IsotopeAnalysis

CHEM222/234

LectureChapter9

TypicalMassSpectrum

KeyFeaturesofaMassSpectrum
A.
B.
C.
D.
E.

Mass/ChargeRatio formulaweightofeachionfragmentproduced
IonAbundance amountofeachionfragmentproduced(%)
BasePeak mostabundantionfragment(tallestpeak)
MolecularIon unfragmented ion(originalformulaweight)
IsotopePeaks molecularionscontainingheavierisolopes (ex.13C)

CHEM222/234

LectureChapter9

LETS SEEWHATELSEWECANDO...
Section2 NMRSpectroscopyandMassSpectrometry
Chapter9 ToolsforStructureDetermination(Part2)
IntrotoMassSpectrometry(MS)
IonizationandFragmentation
IsotopesinMS
IntegratedStructureDetermination

CHEM222/234

LectureChapter9

MassSpectrometry
CollectinganMassSpectrum:
ionizecompound(electronbeamcommon ElectronImpactMS)
sendthroughmassanalyzer(magnetortimeofflightToF)

sample
inlet

CHEM222/234

ionization
chamber

LectureChapter9

mass
analyzer

detector

EIMS:Ionization

ex.IonizationofPropane

*electronremovedfromnonbondingandelectronseasiest*

CHEM222/234

LectureChapter9

Fragmentation:BondCleavage
TwoPossibleCleavageOptions:
Cation +Radical

RadicalCation

Radical+Cation

*stabilityofcation determinesrelativeabundanceoffragments*
(highlysubstituted/resonancestabilizedR+ formedmore!)
CHEM222/234

LectureChapter9

10

Practice:Ionization/Fragmentation

CHEM222/234

LectureChapter9

11

Fragmentation:BondCleavage
ex.Hexane

CHEM222/234

LectureChapter9

12

Fragmentation:BondCleavage
ex.CH3F

CHEM222/234

LectureChapter9

13

Practice:Fragmentation
IdentifytheM+peakandbasepeakintheMSofethylbenzene.
Whatfragmentgivesrisetothebasepeak?

CHEM222/234

LectureChapter9

14

Fragmentation:BondCleavage
Ethers

CHEM222/234

LectureChapter9

15

Fragmentation:BondCleavage
Aldehydes

CHEM222/234

LectureChapter9

16

Fragmentation:BondCleavage
CarboxylicAcids

CHEM222/234

LectureChapter9

17

Fragmentation:BondCleavage
Alcohols

CHEM222/234

OftenNO
Molecularion

LectureChapter9

18

Fragmentation:BondCleavage
Halides

CHEM222/234

LectureChapter9

19

Practice:AlcoholFragmentation

MW:88.15g/mol

CHEM222/234

LectureChapter9

20

Practice:AlkeneFragmentation

MW:84.16g/mol

CHEM222/234

LectureChapter9

21

LETS SEEWHATELSEWECANDO...
Section2 NMRSpectroscopyandMassSpectrometry
Chapter9 ToolsforStructureDetermination(Part2)
IntrotoMassSpectrometry(MS)
IonizationandFragmentation
IsotopesinMS
IntegratedStructureDetermination

CHEM222/234

LectureChapter9

22

IsotopePeaksandMolecularIon

m+1

m+2

CHEM222/234

LectureChapter9

23

IsotopePeaksandMolecularIon
m+1:13C(and15N)IsotopePeaks
OneCarbon:Methane(CH4)
12CH

Ratio
MW

CHEM222/234

13CH

98.9
16

1.1
17

LectureChapter9

24

IsotopePeaksandMolecularIon
m+1:13C(and15N)IsotopePeaks
OneCarbon:Methane(CH4)

13C~1.1%naturalabundance

CHEM222/234

LectureChapter9

25

IsotopePeaksandMolecularIon
m+1:13C(and15N)IsotopePeaks
LargerMolecules(>1carbon)

1.1%x3(possible13Clocations)+0.37%x2(possible15Nlocations)
1.1%x5(possible13Clocations)
CHEM222/234

LectureChapter9

26

IsotopePeaksandMolecularIon
m+1:13C(and15N)IsotopePeaks
DeterminingMolecularFormulas(#ofCarbons)

Intensity[M+ +1]peak x100=max#carbons

Intensity[M+]peak

13C~1.1%naturalabundance

CHEM222/234

LectureChapter9

27

Practice:Determining#Carbons
Estimatethenumberofcarbonspresentinthecompoundthat
producedthefollowingMS.

CHEM222/234

LectureChapter9

28

IsotopePeaksandMolecularIon
m+2:34S,37Cl,or81BrIsotopePeaks
OneSulfur:Methanethiol (CH3SH)

CH332SH
Ratio
MW

CHEM222/234

95
48

CH334SH
4
50

LectureChapter9

29

IsotopePeaksandMolecularIon
m+2:34S,37Cl,or81BrIsotopePeaks
OneChlorine:Chloromethane(CH3Cl)

Ratio
MW

CHEM222/234

CH335Cl

CH337Cl

75
50

25
52

LectureChapter9

30

IsotopePeaksandMolecularIon
m+2:34S,37Cl,or81BrIsotopePeaks
OneBromine:Bromomethane (CH3Br)

CH379Br
Ratio
MW

CHEM222/234

50
94

CH381Br
50
96

LectureChapter9

31

IsotopePeaksandMolecularIon

CHEM222/234

LectureChapter9

32

IsotopePeaksandMolecularIon
m+4:Twoof34S,37Cl,or81BrIsotopePeaks
TwoBromines:Dibromomethane (CH2Br2)

CH279Br2

CH279Br81Br

CH281Br2

Ratio

25

50

25

MW

172

174

176

CHEM222/234

LectureChapter9

33

IsotopePeaksandMolecularIon

CHEM222/234

LectureChapter9

34

Nitrogen (Even Electron)Rule

Nitrogen Rule even mass(M+)=even number ofnitrogens (including zero)
odd mass(M+)=odd number ofnitrogens

*mostly odd massfragmentsforeven massM+ *

*mostly even massfragmentsforodd massM+ *

M+

F1+

even

even

odd

odd

odd

even

CHEM222/234

LectureChapter9

F2

35

Nitrogen (Even Electron)Rule

Nitrogen Rule even mass(M+)=even number ofnitrogens (including zero)
odd mass(M+)=odd number ofnitrogens

*mostly odd massfragmentsforeven massM+ *

*mostly even massfragmentsforodd massM+ *

CHEM222/234

LectureChapter9

36

Practice:DeterminingMolecularFormula
Whatisapossibleformulaforthiscompound?

CHEM222/234

LectureChapter9

37

NOWTHATWEKNOWABOUTIR,
13C&1HNMRSPECTROSCOPY
ANDMASSSPECTROMETRY
YOURCANTRYSOMEINTEGRATED
EXAMPLESANDSOLVEUNKNOWNS!

CHEM222/234

LectureChapter9

38

LETS SEEWHATELSEWECANDO...
Section2 NMRSpectroscopyandMassSpectrometry
Chapter9 ToolsforStructureDetermination(Part2)
IntrotoMassSpectrometry(MS)
IonizationandFragmentation
IsotopesinMS
IntegratedStructureDetermination

CHEM222/234

LectureChapter9

39

StructureDetermination
ISOLATIONOF
NATURAL
PRODUCTS

ORGANIC
SYNTHESIS

STRUCTURE
DETERMINATION&
ANALYSIS
(MS,IR,NMR)

CHEM222/234

LectureChapter9

40

StructureDetermination
1.
2.
3.
4.

MS molecular weight/formulaandunits ofunsaturation

IR identificationofpolarfunctional groups(OH,NH,C=O,etc)
13CNMR #typesofcarbons,possiblechemical environments
1HNMR #typesofhydrogens,possiblechemical environments,number
ofeach typeofhydrogen,number ofneighbouring hydrogens

MS

IR

13C

1H

NMR

NMR

STRUCTURE!

EXTRAPRACTICE
http://www.chem.ucla.edu/~webspectra/
CHEM222/234

LectureChapter9

41

Practice:IntegratedExample
SupposetheIRspectrumofthecompoundthatgaverisetotheMSbelow
containsastrongabsorptionat1670cm1 andnoabsorptionsabove3000
cm1.Drawthreepossiblestructures.

CHEM222/234

LectureChapter9

42

Practice:IntegratedExample
AnunknownhastheMSbelow.Thiscompoundalsohasa13CNMR
spectrumthatcontainsfoursignalsandanIRspectrumwithanintense
peakat1720cm1.Proposeastructure.

CHEM222/234

LectureChapter9

43

Practice:IntegratedExample
AcompoundhastheformulaC8H9NO2.Labelallpeaksandproposeastructure.

1HNMRZOOM

(6.0 7.3ppm)

CHEM222/234

LectureChapter9

44

Practice:IntegratedExample
AcompoundhastheformulaC8H9NO2.Labelallpeaksandproposeastructure.

CHEM222/234

LectureChapter9

45

Practice:IntegratedExample
AcompoundhastheformulaC8H9NO2.Labelallpeaksandproposeastructure.

CHEM222/234

LectureChapter9

46

Practice:IntegratedExample
AcompoundhastheformulaC8H9NO2.Labelallpeaksandproposeastructure.

1HNMRZOOM

(6.0 7.3ppm)

CHEM222/234

LectureChapter9

47

Practice:IntegratedExample
AcompoundhastheformulaC9H10O3.Labelallpeaksandproposeastructure.

CHEM222/234

LectureChapter9

48

Chapter9(MS):MainObjectives
1. UnderstandbasicsofMStheory(ionizationand
fragmentationofcommonfunctionalgroups).
2. Useamassspectratohelpelucidatethestructureofan
unknown(findmolecularweight/formula).
3. Recognizebasepeakandmolecularion.
4. RecognizeisotopepatternsforC,S,Cl,Br.
5. UseNitrogen/EvenElectronRuletodifferentiate
fragmentsfromM+ anddetermineeven/odd#Ns.

CHEM222/234

LectureChapter9

49

Chapter9:MSSummary
Section2 NMRSpectroscopyandMassSpectrometry
Chapter9 ToolsforStructureDetermination(Part2)
IntrotoMassSpectrometry(9.13)
IonizationandFragmentation(9.149.16)
IsotopesinMS(9.17)
IntegratedStructureDetermination

CHEM222/234

LectureChapter9

50

Chapter9:MSPractice
Section2 NMRSpectroscopyandMassSpectrometry
Chapter9 ToolsforStructureDetermination(Part2)
AssignedProblems(Solomons,10th Edition):
9.16 9.19,9.21,9.22,9.32,9.33,9.37
9.39 9.47
14.14,14.30 14.39

(MS)
(Integrated)
(Integrated Aromatic)

AssignedProblems(Solomons,11th Edition):
9.17 9.21,9.31,9.32,9.36
9.38 9.46
14.14,14.30 14.39

(MS)
(Integrated)
(Integrated Aromatic)

Sapling(ExtraPractice):Ch 9Assignment
CHEM222/234

LectureChapter9

51