C H A P T E R 2 4

NITRILES

24.1. GC SEPARATION OF NITRILES

A. General
1. Capillary columns
a. Ethyl succinonitrile, 1,1-cyanophenylethane, 1,2-cyano­
phenylethane, methylglutaronitrile, and adiponitrile: 30-m
DB-210 column, 50–225 °C at 10 °C min�1.
b. Dicyanobutenes: 30-m DB-210 column, 50–225 °C at 6 °C min�1.
c. Isoxazole, fumaronitrile, propanedinitrile, and ethylene nitrile:
30-m DB-WAX column, 100–225 °C at 8 °C min�1.

24.2. MASS SPECTRA

A. Aliphatic mononitriles
1. General formula: RCN.
2. Molecular ion: The aliphatic mononitriles may not show molecular
ions when R is greater than C2.
3. Fragmentation: The saturated aliphatic mononitriles with molecular
weights greater than 69 are characterized by intense peaks at m/z 41,
54, 68, 82, 96, 110, 124, 138, 152, 166, and so forth. Aliphatic
nitriles undergo the McLafferty rearrangement producing an ion
with m/z 41.
The aliphatic mononitriles may not show M+• peaks, but [M – 1]+,
[M – 27]+, or [M – 28]+ peaks are usually observed. Sometimes a loss
of 15 Da may also be observed. If CH3 is replaced by CF3, as in the
case of CF3CH2CH2CN, a fluorine is first lost from the molecular ion
followed by the loss of HCN (from the [M – F]+ ion). This influence
of the CF3 group diminishes as the alkyl chain length increases.
B. Sample mass spectrum of an aliphatic mononitrile
The mass spectrum in Figure 24.1 has intense peaks at m/z 41, 54, 68,
and so forth, which suggests an alkyl nitrile. The highest m/z value peak
at m/z 96 represents the [M – 1]+ ion. Also observed are peaks
representing [M – 15]+, [M – 27]+, and/or [M – 28]+ ions.
Gas Chromatography and Mass Spectrometry � 2010 by Academic Press. Inc.
DOI: 10.1016/B978-0-12-373628-4.00024-1 All rights reserved.

351
352 Chapter 24

41
100

54
N

50
29 55
27 57 68
43
39 82

96
15 44 58 61 66 70 79 83 97
0
10 20 30 40 50 60 70 80 90 100 110

Figure 24.1 EI mass spectrum of hexanenitrile.

C. Aliphatic dinitriles
1. General formula: NC(CH2) � CN.
2. Molecular ion: The M+• peaks of aliphatic dinitriles with molecular
weights greater than 80 are usually not observed, but their molecular
weights can be deduced by adding 40 Da (CH2CN) to the highest m/z
value peak of reasonable intensity.
3. Fragmentation: The highest two m/z value peaks usually represent
the [M – 40]+ ion and a less-abundant [M – 28]+ ion. Intense peaks at
m/z 41, 54, and 55 also should be present (see Figure 24.2). Dinitriles
also may have peaks representing ions with m/z 82, 96, 110, 124,
138, 152, and so forth. Except for adiponitrile and
methylglutaronitrile, the peak at m/z 68 has a very low intensity in
the mass spectra of aliphatic dinitriles. Adiponitrile may be
distinguished from methylglutaronitrile by the relative intensities of

41
100

N
68
50
54
N

39
27
52 66
15 75 80 109
0
10 20 30 40 50 60 70 80 90 100 110 120

Figure 24.2 EI mass spectrum of hexanedinitrile.

Nitriles 353

peaks at m/z 41 and 68. If the peak at m/z 41 is of greater intensity

than the peak at m/z 68, the mass spectrum suggests adiponitrile.
Conversely, if the intensity of the peak at m/z 68 is greater than
that of the peak at m/z 41, the mass spectrum represents
methylglutaronitrile.
D. Aromatic nitriles and dinitriles
1. General formula: ArCN and Ar(CN)2.
2. Molecular ion: The mass spectra of aromatic nitriles and dinitriles
show intense M+• peaks, consistent with the mass spectra of aromatic
compounds.
3. Fragmentation: The loss of 27 Da (HCN) from the molecular ion of
aromatic and dinitriles is characteristic. The tolunitriles show a loss of
hydrogen as well as the loss of HCN and H2CN. If the methyl group
is replaced by a CF3 group, the loss of 19 (F) and 50 (CF2) Da is
represented by a very intense peak, whereas the intensity of the peak
representing the loss of 27 Da is practically nonexistent. If the nitrile
group is on the side chain rather than on the aromatic ring, the loss of
27 Da (HCN) will occur (Figure 24.3).

103
100

N
50
76

50
51 75
77
26 37 39 43 49 53 63
65 78 8486 88 99
0
20 30 40 50 60 70 80 90 100 110

Figure 24.3 EI mass spectrum of benzonitrile.