Interpretation of Mass Spectra

Choose a reasonable structure

NO

Do the expected fragments agree w/ chosen structure

YES NO

Is the structure unique?

YES

Make assignment

General approach for acquiring information about a sample:

Molecular weight, elemental composition, degree of unsaturation (DBE) Substructures and functional groups Connectivity of substructures Reference spectra and comparison to possible structures where unique identification is not possible

From: Interpretation of Mass Spectra, 4 ed., FW McLafferty and Frantiek Tureek, 1993, University Science Books, Sausalito, Ca, USA

General approach for acquiring information about a sample:

Molecular weight, elemental composition, M+ degree of unsaturation (DBE) Substructures and functional groups Neutral losses and rearrangements Connectivity of substructures Reference spectra and comparison to possible structures where unique identification is not possible Purchase of standards and
automated identification

From: Interpretation of Mass Spectra, 4 ed., FW McLafferty and Frantiek Tureek, 1993, University Science Books, Sausalito, Ca, USA

Toolbox 1: M+ The (quasi-) molecular ion:

Elemental information from natural abundance of isotopes and appearance of the molecular ion cluster (e.g. N-rule, A+1 and A+2 elements) #C = (11.2/1.1) = 10.2 162
#Cl = (32.5/0.32) = 1.0 162 -Mw (C10Cl)= 7 Formula=C10H7Cl
50 Cl 164 163 165 153 154 155 156 157 158 (nistdemo) Naphthalene, 2-chloro0 159 160 161

100

#DBE= 7 M M+1 M+2

166 167

2-chloronaphthalene
162

RA(%) 100 11.2 32.5

168 169 170

m/z

163

164

165

For Formula CxHyNzOn DBE= x y + z +1

Toolbox 1: M+
Requirements for the molecular ion:
Highest mass in spectrum (smallest mass in molecular ion cluster) OE (M+) Must yield important high mass fragments by loss of logical neutral species
100 61

Cl (A+2)
96 50 63 98

10 20 30 (nistdemo) Ethene, 1,1-dichloro-

14

26 28

35 32 40

47 50 60

100

m/z

70

80

90

100

110

Toolbox 1: M+
Requirements for the molecular ion:
Highest mass in spectrum (smallest mass in molecular ion cluster) OE (M+) Must yield important high mass fragments by loss of logical neutral species
100 30

50 28 15 0 27 29 26 22 26 44 31 34 38 40 42 42 46 50 54 58

16 18

10 14 18 (nistdemo) Ethylamine

30

m/z

Toolbox 2: Neutral losses and Rearrangements

4 Ways to fragment ions: Homolytic cleaveage
(radical site-driven)
H H C CH H3C CH NH2 H O C OH H3C H C CH CH NH2 H H O C

OH

Heterolytic cleavage
(charge site-driven)

-Bond cleavage Rearrangements

( 2 e- pairs)

Toolbox 2: M+ A+ + B
Some Rules that are useful: Even electron rule
(EE+ ions generally do not form OE+ ions)

Stevensons Rule
(charge retained on fragment w/ lowest IE)

Nitrogen rule
M+ = even (N=0,2,..) ; M+ = odd (N=1,3,..) A+ + B
N = even N = odd odd even

A+ + B
even odd

Toolbox 2: M+ A+ + B

Common losses

n-propyl benzoate: MCL (r2H),-cleavage M M+1 RA (%) 4.10 0.40

Some important ions for n-propyl benzoate

Alternate path via initial charge on alkoxide O also possible

Cyclohexene: RDA, Rearrangements Problem set 3work on your own but some hints below
100 67

CH3 loss (rH)

Formed by RDA Common losses Dominant in butadiene

54

50 39

Seen in cyclopentene
82 41

27 53 65 63 60 65 70 68 74 75 79 81 77 78 83 80 80 85 90

51 14 0 26 16 25 29 30 35 38 40 42 40 45 49 50

52

55 55

10 15 20 (nistdemo) Cyclohexene

Interpretation of Mass Spectra

Choose a reasonable structure
NO

Do the expected fragments agree w/ chosen structure Run Alternate Experiments

YES NO

Is the structure unique?

YES

Make assignment

Experiments that are useful when proposed structures are not unique:
Generating the molecular ion: Soft ionization methods Run EI at lower energies

Information on structure: Run EI at lower energies (appearance of lower IE fragments to determine paths) Derivatize functional groups Compare w/ similar molecules or isotope-labeled analogues

When all else fails: Automated ID w/ libraries.

100 162

50 63 60 75

127 164 39 50 68 70 81 80 87 90 101 100 110 120 130 140 150 Cl 160 170

20 30 40 50 (nistdemo) Naphthalene, 2-chloro-

31 0 31 20 30 40 50 60 70 80 90 Difference 100 110 120 50 62 74 77 87 98

127

163

130

140

150

160

170

Naphthalene, 2-chloro-

Naphthalene, 1-chloro-

100

162

50 50 60 63 68 70 75 81 80 87 90 101 100 110 120

127 Cl 130 140 150 160 39

164

20 30 40 50 (nistdemo) Naphthalene, 1-chloro-

170