Solution Manual for Organic Structural

Spectroscopy, 2/E 2nd Edition Joseph B. Lambert,

Scott Gronert, Herbert F. Shurvell, David Lightner,
Robert Graham Cooks

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Solution Manual for Organic Structural Spectroscopy, 2/E 2nd Edition Joseph B. Lambert, Scot

Chapter 8

Fragmentation and Ion Activation Methods

8-1 (a) For 1-phenyl-3-heptanone, only a single McLafferty is possible, which
involves the loss of carbons 5-7 as propene. The product has m/z 148.
(b) For ethyl 2-methylpentanoic acid, there are two possible single McLaffertys.
Loss of ethene from the ethyl ester gives m/z 116, and loss of propene from
the acid component gives m/z 102. The double McLafferty gives m/z 74.
(c) For 2,2-dimethyl-6-phenylhexanoic acid, only a single McLafferty is possible.
Loss of 4-phenyl-1-butene gives m/z 88.
(d) For 4,6-dimethyl-5-decanone, loss of propene or butene is possible to give m/z
142 or 128. A double McLafferty would give m/z 86.
8-2 (a) The ion at m/z 44 is the typical aldehyde McLafferty ion. The ion at m/z 56 is
the radical cation of butene. These are complementary ions (the sum of their
masses is the molecular weight of hexanal).

OH

H
m/z 44 m/z 56
(b) In this case, the ionization potential of butene is close to that of the enol of
acetaldehyde (this observation indicates that the EAs of the cations are
similar).

8-3 (a)

100
88 Ethyl 4-Methylpentanoate EI
(a) 43 MW = 144 O

80
O
101
99
60

40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170
m/z

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64 Chapter 8

m/z 144
m/z 99 O
O
α-cleavage
m/z 43
O
γ-cleavage O
products
O m/z 88
McLafferty
OH
(potentially cyclized)
m/z 101 O

(b)

100
57 115
(b) t-Butyl Ether EI
MW = 130
80 59
O

60

40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
m/z

O
3° cation
m/z 115 α-cleavage
m / z 57

m/z 130
H
O m/z 59

β-elimination

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Fragmentation and Ion Activation Methods 65

(c)

100
162
(C) N,N-Dibutylaniline EI
MW = 205
80
N

60

106
120
40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210

m/z

N α-cleavage

m/z 162
N

m/z 205 N ene reaction

NH

m/z 106 m/z 120

(d)

100
43 72 3,5-Dimethyl-2-octanone EI
(d)
MW = 156
80

O
60

40

20 85

113
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160

m/z

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66 Chapter 8

m/z 72

McLafferty m/z 113

OH α-cleavage
products

γ-cleavage O m/z 43
(potentially cyclized) O
m/z 156

m/z 85 O

(e)

100
43 71 2,3-Dimethyl-1-butanol EI
(e) MW = 102

80 OH

60
69

84
40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150

m/z

d e h y d ra t i o n

m/z 84
OH
m/ z 4 3

2° cation m/z 102

m/z 71
m/z 69
α-cleavage
(charge stays with alkyl group) allylic cation

8-4 (a) For 2-hexanone and 3-methyl-2-pentanone, there would be a difference in the
McLafferty ions. 2-Hexanone gives m/z 58 and 3-methyl-2-pentanone gives
m/z 72. In the α-cleavages to give acyl and alkyl cations, one expects 3-
methyl-2-pentanone to give a greater yield of the alkyl cation component (sec-

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Fragmentation and Ion Activation Methods 67

butyl, m/z 57) than 2-hexanone, which yields a 1˚ cation (butyl). The former
difference is the most useful.
(b) For ethyl heptanoate and propyl hexanoate, the McLaffertys are a key. Ethyl
heptanoate has McLaffertys potentially at m/z 88 (single on alkyl), 130 (single
on ethoxy), and 60 (double). Propyl hexanoate has McLaffertys potentially at
m/z 102 (single on alkyl), 116 (single on propoxy), and 60 (double). In the
observed spectrum, propyl hexanoate gives a significant signal at m/z 117,
which corresponds to a hydrogen atom transfer to the McLafferty ion. α-
cleavages are the other key. One expects loss of ethoxy from ethyl heptanoate
to give m/z 113 and loss of propoxy from propyl pentanoate to give m/z 99.
(c) For ethyl benzoate and methyl 4-methylbenzoate, α-cleavages also are
important. Ethyl benzoate loses ethoxy to give m/z 105 and methyl 4-
methylbenzoate loses 31 to give m/z 119. Ethyl benzoate is capable of β-
elimination with loss of ethene to give m/z 122. Both can give α-cleavages to
produce different phenyl cations (m/z 77 for ethyl benzoate and m/z 91 for
methyl 4-methylbenzoate).
(d) For N-propylbutanamine and N,N-diethylpropanamine, the α-cleavages are
important. A key difference is that N-propylbutanamine can lose propyl in an
α-cleavage (from the butyl group) to give m/z 72. This mass is not likely in
N,N-diethylpropanamine. The other difference is that N,N-diethylpropan-
amine can give an α-cleavage via methyl loss, so m/z 100 is likely with it.
Both give loss of ethyl to give m/z 86.
8-5 (a) In the radical cation of tributylamine, loss of propyl via α-cleavage is likely.
In the protonated amine, loss of butene and potentially of butane are likely.
(b) In the radical cation of dibutyl ether, loss of propyl via α-cleavage is likely. In
the protonated ether, loss of butene and potentially of butane are likely.
(c) In the radical cation of butyl benzoate, loss of propyl via α-cleavage on the
butoxy group, loss of butoxy, or formation of the phenyl cation are likely. In
the protonated ester, loss of butanol is likely, and loss of butene is a
possibility.

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Solution Manual for Organic Structural Spectroscopy, 2/E 2nd Edition Joseph B. Lambert, Scot

68 Chapter 8

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