C H A P T E R 9

ALDEHYDES

9.1. GC SEPARATION OF UNDERIVATIZED ALDEHYDES

A. Capillary columns
1. Acetic acid, isobutyraldehyde, methylethyl ketone, isobutyl alcohol,
n-propyl acetate, and isobutyric acid: 30-m Poraplot Q column,
100–200 °C at 10 °C min�1.
2. Acetaldehyde, acetone, tetrahydrofuran, ethyl acetate, isopropyl
alcohol, ethyl alcohol, 4-methyl-1,3-dioxolane, n-propyl acetate,
methyl isobutyl ketone, n-propyl alcohol, toluene, n-butyl alcohol,
2-ethoxyethanol, and cyclohexane: 30-m DB-WAX column, 75 °C
(16 minutes)–150 °C at 6 °C min�1. Although the DB-FFAB column
is similar to the DB-WAX column, it should not be used to separate
aldehydes because it may remove them from the chromatogram.
3. Acetaldehyde, acetone, isopropyl alcohol, ethyl acetate, methyl
isobutyl ketone, toluene, butyl acetate, isobutyl alcohol, and acetic
acid: 30-m FFAP-DB column, 50–200 °C at 6 °C min�1.
4. Aromatic aldehydes
a. Benzyl alcohol, 1-octanol, benzaldehyde, octanoic acid,
benzophenone, benzoic acid, and benzhydrol: 30-m DB-WAX
column, 60 °C (1 minute)–230 °C at 10 °C min�1.
b. Tolualdehydes: Ortho- and meta-isomers do not separate very
well. Para-isomers elute last. 50-m DB-WAX column, 60–180 °C
at 6 °C min�1.

9.2. DERIVATIZATION OF FORMALDEHYDE

A. Formaldehyde is derivatized for trace analyses. React 2-hydroxyethyl­
piperidine with formaldehyde to form 2-oxaindolizidine (C7H13NO).
Selected ion monitoring of m/z 127 is used to determine the
concentration of formaldehyde.
Gas Chromatography and Mass Spectrometry � 2010 by Academic Press. Inc.
DOI: 10.1016/B978-0-12-373628-4.00009-5 All rights reserved.

239
240 Chapter 9

9.3. MASS SPECTRA OF ALDEHYDES

A. Aliphatic aldehydes
1. General formula: RCHO.
2. Molecular ion: Both straight-chain and branched aliphatic aldehydes
show molecular ion peaks up to a minimum of C14 aldehydes.
3. Fragmentation: Above C4, aliphatic aldehydes undergo the
McLafferty rearrangement, resulting in a peak at m/z 44, provided
the α- or β-carbon is not substituted. Substitution on the α- or β-carbon
results in a peak at a higher m/z value (see the preceding text).

R1 H
O Note: Subtract 43 from
H C the m/z value of the
C H rearrangement ion to
determine the mass of R2
H R2

When R2 = H, observe m/z 44.

When R2 = CH3, observe m/z 58.
When R2 = C2H5, observe m/z 72, etc.
Small peaks at m/z 31, 45, and 59 indicate the presence of oxygen in
the compound. Also, the mass spectra of aldehydes exhibit peaks at
m/z values representing the losses of 28 and 44 from the molecular
ion.
4. Characteristic fragment ions
The mass spectra of aliphatic aldehydes show m/z 29 (CHO) for C1–C3
aldehydes and m/z 44 for C4 and longer chain aldehydes.
Characteristic losses from the molecular ion: [M – 1]+ (loss of H),
[M – 18]+ (loss of H2O), [M – 28]+ (loss of CO), and [M – 44]+ (loss
of CH3CHO).
Aldehydes are distinguished from alcohols by the losses of 28 and 44
from the molecular ion. The [M – 44]+ ion results from the McLafferty
rearrangement with the charge remaining on the carbonyl oxygen.
B. Aromatic aldehydes
1. General formula: ArCHO.
2. Molecular ion: Aromatic aldehydes exhibit a very intense molecular
ion peak.
3. Fragmentation: The [M – 1]+ peak due to the loss of the aldehyde
hydrogen through the special case of homolytic cleavage (α cleavage)
is usually very intense. An [M – 29]+ peak is characteristic of an
aldehyde group attached to an aromatic moiety. Peaks at m/z 39, 50,
Aldehydes 241

51, 63, and 65, and the abundance of the molecular ion peak show
that the compound is aromatic. Accurate mass measurement data
indicate the presence of an oxygen atom.
4. Characteristic losses from the molecular ion: [M – 1]+ (loss of H) and
[M – 29]+ (loss of CHO).
C. Sample mass spectra
1. An intense peak at m/z 44 in the mass spectrum of hexanal suggests an
aliphatic aldehyde. [M – 18]+, [M – 28]+, and [M – 44]+ peaks (at
m/z 56, 72, and 82, respectively) suggest an aliphatic aldehyde
unbranched at the α-carbon (see Appendix Q: Ions for Determining
Unknown Structures). The molecular ion peak at m/z 100 confirms
that this is the spectrum of hexanal (see Figure 9.1).
2. The mass spectrum of 2-methylbenzaldehyde suggests an aromatic
compound because of the intensity of the molecular ion peak, the
peak at m/z 91, and the peaks at m/z 39, 51, and 65 (see Figure 9.2).
The peaks representing the loss of a hydrogen atom and loss of 29
(•CH=O radical) from the molecular ion indicate that this is an
aromatic aldehyde. The peak at m/z 91 suggests the following
structure:

CH3

44
100

56

41
O
43

50

27

39
55 72
82
58 67
15 18 26 31 53 60 73 77 81 84 87
46 63 66 69 99
0
10 20 30 40 50 60 70 80 90 100 110

Figure 9.1 EI mass spectrum of hexanal.

242 Chapter 9

91
100
119

50

65
39
63
51
89
27 41
15 18 31 45 56 71 74 77 86 98 103 107
0
10 20 30 40 50 60 70 80 90 100 110 120 130

Figure 9.2 EI mass spectrum of 2-methylbenzaldehyde (2-tolualdehyde).

From the m/z value of the molecular ion (m/z 120), the structure for
the aromatic aldehyde is

O H
C

CH3