N
X
C
O
N
S
Hal
Solvents
Natural
Products
P Si
C
C
C C
C
C
410
8 Mass Spectrometry
Aromatic Isothiocyanates (Ar-NCS) [8]
Fragmentation: Dominant loss of NCS · (Δm 58). In contrast to aromatic
thiocyanates, the loss of HCN (Δm 27) or CS (Δm 44) leads to very weak fragments only.
Ion series: Aromatic fragments corresponding to C n H n and C n H n±1 (m/z 39, 51–53,
63–65, 75–77, …). Weak signal at m/z 45 (CHS + ) indicates sulfur.
Intensities: Intensive peaks in the higher mass range.
Molecular ion: Dominant; base peak in phenyl isothiocyanate. Characteristic 34 S
isotope peak at [M+2] +· and [frag+2] for S-containing fragments (4.5% per S atom).
8.9.7 References
[1] H. Schwarz, K. Levsen, The chemistry of ionized amino, nitroso and nitro compounds in the gas phase. In: Suppl. F, The Chemistry of the Amino, Nitroso and
Nitro Compounds and Their Derivatives, Part 1; S. Patai, Ed.; Wiley: Chichester, 1982; p 85.
[2] D.G.I. Kingston, B.W. Hobrock, M.M. Bursey, J.T. Bursey, Intramolecular
hydrogen transfer in mass spectra. III. Rearrangements involving the loss of
small neutral molecules, Chem. Rev. 1975, 75, 693.
[3] R.D. Bowen, The chemistry of C n H 2n+2 N + ions. Mass Spectrom. Rev. 1991, 10,
225.
[4] K.-P. Zeller, Mass spectra of cyano, isocyano and diazo compounds. In: Suppl.
C, The Chemistry of Triple-Bonded Functional Groups, Part 1; S. Patai, Z.
Rappoport, Eds.; Wiley: Chichester, 1983; p 57.
[5] C.W. Thomas, L.L. Levsen, Electron-impact spectra of 2-diazoacetophenones,
Org. Mass Spectrom. 1978, 13, 39.
[6] J.M. Miller, T.R.B. Jones, The mass spectra of azides and halides. In: Suppl.
D, The Chemistry of Halides, Pseudo-Halides and Azides, Part 1; S. Patai, Z.
Rappoport, Eds.; Wiley: Chichester, 1983; p 75.
[7] R.A. Abramovitch, E.P. Kyba, E.F. Scriven, Mass spectrometry of aryl azides,
J. Org. Chem. 1971, 36, 3796.
[8] K.A. Jensen, G. Schroll, Mass spectra of cyanates, isocyanates, and related
compounds. In: The Chemistry of Cyanates and Their Thio Derivatives, Part 1;
S. Patai, Ed.; Wiley: Chichester, 1977, p 273.
[9] W.M.A. Niessen, R.A. Correa C., Interpretation of MS-MS Mass Spectra of
Drugs and Pesticides, Wiley, Hoboken, 2017.
[10] M. Holcapek, R. Jirásko, M. Lisa, Basic rules for the interpretation of
atmospheric pressure ionisation mass spectra of small molecules, J.
Chromatogr. A, 2010, 1217, 3908.
[11] K. Levsen, H.-M. Schiebel, J.K. Terlouw, K.J. Jobst, M. Elend, A. Preiss, H.
Thiele, A. Ingendoh, Even-electron ions: a systematic study of the neutral
species lost in the dissociation of quasi-molecular ions, J. Mass Spectrom.
2007, 42, 1024.
X
C
O
N
S
Hal
Solvents
Natural
Products
P Si
C
C
C C
C
C
410
8 Mass Spectrometry
Aromatic Isothiocyanates (Ar-NCS) [8]
Fragmentation: Dominant loss of NCS · (Δm 58). In contrast to aromatic
thiocyanates, the loss of HCN (Δm 27) or CS (Δm 44) leads to very weak fragments only.
Ion series: Aromatic fragments corresponding to C n H n and C n H n±1 (m/z 39, 51–53,
63–65, 75–77, …). Weak signal at m/z 45 (CHS + ) indicates sulfur.
Intensities: Intensive peaks in the higher mass range.
Molecular ion: Dominant; base peak in phenyl isothiocyanate. Characteristic 34 S
isotope peak at [M+2] +· and [frag+2] for S-containing fragments (4.5% per S atom).
8.9.7 References
[1] H. Schwarz, K. Levsen, The chemistry of ionized amino, nitroso and nitro compounds in the gas phase. In: Suppl. F, The Chemistry of the Amino, Nitroso and
Nitro Compounds and Their Derivatives, Part 1; S. Patai, Ed.; Wiley: Chichester, 1982; p 85.
[2] D.G.I. Kingston, B.W. Hobrock, M.M. Bursey, J.T. Bursey, Intramolecular
hydrogen transfer in mass spectra. III. Rearrangements involving the loss of
small neutral molecules, Chem. Rev. 1975, 75, 693.
[3] R.D. Bowen, The chemistry of C n H 2n+2 N + ions. Mass Spectrom. Rev. 1991, 10,
225.
[4] K.-P. Zeller, Mass spectra of cyano, isocyano and diazo compounds. In: Suppl.
C, The Chemistry of Triple-Bonded Functional Groups, Part 1; S. Patai, Z.
Rappoport, Eds.; Wiley: Chichester, 1983; p 57.
[5] C.W. Thomas, L.L. Levsen, Electron-impact spectra of 2-diazoacetophenones,
Org. Mass Spectrom. 1978, 13, 39.
[6] J.M. Miller, T.R.B. Jones, The mass spectra of azides and halides. In: Suppl.
D, The Chemistry of Halides, Pseudo-Halides and Azides, Part 1; S. Patai, Z.
Rappoport, Eds.; Wiley: Chichester, 1983; p 75.
[7] R.A. Abramovitch, E.P. Kyba, E.F. Scriven, Mass spectrometry of aryl azides,
J. Org. Chem. 1971, 36, 3796.
[8] K.A. Jensen, G. Schroll, Mass spectra of cyanates, isocyanates, and related
compounds. In: The Chemistry of Cyanates and Their Thio Derivatives, Part 1;
S. Patai, Ed.; Wiley: Chichester, 1977, p 273.
[9] W.M.A. Niessen, R.A. Correa C., Interpretation of MS-MS Mass Spectra of
Drugs and Pesticides, Wiley, Hoboken, 2017.
[10] M. Holcapek, R. Jirásko, M. Lisa, Basic rules for the interpretation of
atmospheric pressure ionisation mass spectra of small molecules, J.
Chromatogr. A, 2010, 1217, 3908.
[11] K. Levsen, H.-M. Schiebel, J.K. Terlouw, K.J. Jobst, M. Elend, A. Preiss, H.
Thiele, A. Ingendoh, Even-electron ions: a systematic study of the neutral
species lost in the dissociation of quasi-molecular ions, J. Mass Spectrom.
2007, 42, 1024.