Restricted accessResearch articleFirst published online 2009-8
Differentiation of the Isomeric o -( m - and p -) Nitro-(Chloro- and Bromo-)Benzyl-2,4-(and 2,1-) Disubstituted 2-Thiocytosinium Halides by Electron Impact Ionisation and Fast Atom Bombardment Mass Spectrometry
Electron ionisation (EI) and fast atom bombardment (FAB) mass spectral fragmentations of nine 2,4-(and 2,1-) disubstituted o-(m- and p-)nitro-(chloro- and bromo-)-2-thiocytosinium halides are investigated. Fragmentation pathways, whose elucidation is assisted by accurate mass measurements and metastable transitions [EI-mass spectrometry (MS)], as well as FAB/collision-induced dissociation (CID) mass spectra measurements are discussed. The correlations between the abundances of the (C11H10N4SO2)+1–3; (C11H10N3SCl)+4–6 and (C11H10N3SBr)+7–9 ions and the selected fragment ions (EI-MS), as well as (C18H16N5SO4)+1–3; (C18H16N3SCl2)+4–6 and (C18H16N3SBr2) + 7–9 ions and the selected ions (C7H6NO2)+1–3; (C7H6Cl)+ 4–6; (C7H6Br)+ 7–9 (FAB-MS) are discussed. The data obtained can be used for distinguishing isomers.
ShigetaS.MoriS.KiraT.TakahashiK.KodamaE.KonnoK.NagataT.KatoH.WakayamaT.KoikeN.SaneyoshiM., “Anti-herpesvirus activities and cytotoxicities of 2-thiopyrimidine nucleoside analogues in vitro”, Antivir. Chem. Chemoth.10, 195–209 (1999).
2.
BretnerM.BalinskaM.KrawiecK.KierdaszukB.ShugarD.KulikowskiT., “Synthesis and biological activity of 5-fluoro-2-thiocytosine nucleosides”, Nucleos. Nucleot.32, 657–660 (1995). doi: 10.1080/15257779508012445
3.
ShigetaS.MoriS.WatanableF.TakahashiK.NagataT.KoikeN.WakayamaT.SaneyoshiM., “Synthesis and antiherpesvirus activities of 5-alkyl-2-thiopyrimidine nucleoside analogues”, Antivir. Chem. Chemoth.13(2), 67–82 (2002).
4.
KawaguchiT.YchikawaT.HasegawaT.SaneyoshiM.WakayamaT.KatoH.YukitaA.NagataT., “Enzymatic reactivity and antitumor activity of 1-(beta-D-arabinofuranosyl)-2-thiocytosine derivatives”, Chem. Pharm. Bull.48(4), 454–457 (2000).
5.
KawaguchiT.IchikawaT.HasegawaT.SaneyoshiM.YukitaA.AsanoM.WakayamaT.KatoH.NagataT., “Cytotoxicity and pharmacokinetics of 1-β-D-arabinofuranosyl-2-thiocytosine, a 2-sulphur substituted derivative of cytarabine”, Biol. Pharm. Bull.22(1), 100–102 (1999).
6.
YupC.L.ShahR.DayA.R., “Metabolic control of penicillinase biosynthesis in Bacillus cerens”, J. Bacteriol. Jan, (2004).
7.
SaneyoshiM.NagataT.WakayamaT., N. Koike (Toagosi Co Ltd.), “5-alkyl-2-thiocytosine nucleoside its salt, and antiviral agent containing the compound,” Patent No. JP2001097993, Patent Abstracts of Japan, April (2001).
8.
TurnerC.AlexanderJ.MathurB.FriddleC.J., (Lexicon Genetics Incorporated) Novel Human Kinases and uses thereof, Patent No. EP1676917, European Patent Application, July (2006).
9.
M. Saneyoshi, T. Wakayama, A. Koda, T. Nagata and M. Yoshida (Joagosei Co Ltd.), “1-(5′-O-acyl-Beta-D-arabinofurosyl)-2-thiocytosine and anticancer agent containing the compound as active component”, Patent No. JP10101692, Patent Abstracts of Japan, April (1998).
10.
SaneyoshiM.KatoH.KodaA.NagataT.YoshidaM.(Joagosei Co Ltd.), “4-Nacyl-2-thiocytosine arabinoside and anticancer agent containing the compound as active ingredient”, Patent No. JP10036383, Patent Abstracts of Japan, February (1988).
11.
RajC. RetnaBeheraS., “Mediatorless voltam-metric oxidation of NADH and sensing of ethanol”, Biosens. Bioelectron.21(6), 949–956 (2005). doi: 10.1016/j.bios.2005.03.001
12.
ChuX.DuanD.ShenG.YuR., “Amperometric glucose biosensor based on electrodeposition nanoparticles onto covalently immobilized carbon nanotube electrode of platinum”, Talanta71, 2040–2047 (2007). doi: 10.1016/j.talanta.2006.09.013
13.
HerakJ.N.SankovicK.HuttermannJ., “Thiocytosine as radiation energy trap in a single crystal of cytosine hydrochloride”, Int. J. Radiat. Biol.66, 3 (1994). doi: 10.1080/09553009414550891
14.
WyrzykiewiczE.PospiesznyT.MielcarekS., “Syntheses, EIMS, 1H NMR and 13C NMR study of 2-mono, 1,2-di, and 2,4-di substituted derivatives of 2-thiocytosine”, Phosphorus, Sulfur180(9), 2051–2070 (2005). doi: 10.1080/104265090902840
15.
WyrzykiewiczE.NowakowskaZ., “Mass spectrometry of thio analogues of pyrimidine bases: Correlation of the intensities of the M+• and selected fragment ions of o-(m- and p-)substituted benzylthiouracils”, J. Mass Spectrom.30(2), 269–274 (1995). doi: 10.1002/jms.1190300207
16.
WyrzykiewiczE.BartkowiakG., “Mass spectrometry of thio analogues of pyrimidine bases: Correlation of the intensities of the M+• and the [M–•SH] ions of 2-alkylthiouracils”, J. Mass Spectrom.27, 1377–1380 (1992). doi: 10.1002/oms.1210271208
17.
WyrzykiewiczE.PospiesznyT.SobolewskaM., “Electron ionization induced mass spectral study of new isomeric 2-o-(m- and p-)nitrobenzylthio-5-piperidinomethyl-(morpholinomethyl-) uracils and 1,2-di-o-(m- and p-)nitrobenzyl-5-piperidinomethyl-(morpholinomethyl-)-2-thiouracils”, Rapid Commun. Mass Spectrom.20(40), 713–718 (2006). doi: 10.1002/rcm.2338
18.
WyrzykiewiczE.WendzonkaM., “Electrononization induced mass spectral study of new metameric N-(E)-stilbenyloxyalkylpiperidines, N-(E)-stilbenyloxyalkyl-4-methylpiperidines and N-(E)-stilbenyloxyalkylmorpholines”, Rapid Commun. Mass Spectrom.19(3), 1911–1914 (2005). doi: 10.1002/rcm.2001
19.
WyrzykiewiczE.PospiesznyT.BarłógA., “Electron-impact mass spectral study of 1,2-di-o-(m- and p-) nitro-(bromo-)benzyl-2-thio-6-methyluracils and 1,2-di-o-(m- and p-)nitro-(bromo-)benzyl-2-thio-5-bromo-6-methyluracils”, Rapid Commun. Mass Spectrom.19(4), 580–584 (2005). doi: 10.1002/rcm.1801
20.
BartkowiakG., “Differentiation of 2-alkylthioorotic acids methyl- and ethyl-2-alkylthioorotates and hydrazides of 2-alkylthioorotic acids by using electron ionization mass spectra”, Eur. J. Mass Spectrom.14, 27–35 (2008), doi: 10.1255/ejms.906
21.
JasiewiczB.WyrzykiewiczE.BoczońW., “Mass spectrometry of bisquinolizidine alkaloids: 2-and 17-cyano-substituted derivatives of sparteine and lupanine”, J. Mass Spectrom.39(5), 541–547 (2004). doi: 10.1002/jms.620
22.
WyrzykiewiczE.BoczońW.KoziołB., “Mass spectrometry of bisquinolizidine alkaloids: 2- and 15-substituted derivatives of sparteine and 2- (or 14)-dehydrosparteine”, J. Mass Spectrom.33(10), 971–975 (1998). doi: 10.1002/(SICI)1096-9888(1998100)33:10<971::AID-JMS709>3.0.CO;2-X
23.
WyrzykiewiczE.BoczońW.KoziołB., “Mass spectrometry of bis-quinolizidine alkaloids: 2- And 17-alkyl-substituted derivatives of sparteine and lupanine”, J. Mass Spectrom.35(11), 1271–1277 (2000). doi:
24.
WyrzykiewiczE.PrukałaD., “Electron impact-induced mass spectral study of new isomeric N-substituted hydrazones of ortho-, meta- and para-hydroxybenzaldehydes”, Eur. J. Mass Spectrom.5(3), 183–190 (1999). doi: 10.1255/ejms.274
25.
NowakowskaZ., “Structural characterization and differentiation of isomeric ω-bromoalkoxy derivatives of (E)-chalcone by means of mass spectrometry”, Eur. J. Mass Spectrom.14(1), 37–47 (2008), doi: 10.1255/ejms.905
26.
NowakowskaZ., “Electron ionization-induced fragmentation of new thiochalcone derivatives”, Eur. J. Mass Spectrom.12(5), 339–343 (2006), doi: 10.1255/ejms.826
