International E-publication: Publish Projects, Dissertation, Theses, Books, Souvenir, Conference Proceeding with ISBN.  International E-Bulletin: Information/News regarding: Academics and Research

Structural Identification of C2H5O+ and C5H7O+ ions obtained from Polyethylene Glycols and Polyethylene Glycol Dialkyl Ethers and other Sources using Chemical ionization and Fourier Transformation ion Cyclotron Mass Spectrometry

Author Affiliations

  • 1Basic Sciences Department, Chemistry Unit, Babcock University, Ilishan, Remo, Ogun State, NIGERIA
  • 2 Department of Chemistry and Biochemistry, University of Delaware Newark DE, 19716, USA
  • 3 Department of Chemistry, Niger-Delta University, Bayelsa State, NIGERIA

Res.J.chem.sci., Volume 3, Issue (6), Pages 3-9, June,18 (2013)

Abstract

Sample ion/sample molecule reactions often occur under high pressure CI and low pressure FT/ICR conditions with large sample size of polar compounds, and are useful in obtaining molecular weight information. In this paper, FT/ICR/MS was used to study ion-molecule reactions of C2H5O+ ions made from three different sources. The ions were reacted with PEG oligomers so as to differentiate among the structures of the m/z 45 ions. Time dependence studies of product ions from these reactions were also made. C2H5O+ ions produced from ethylene oxide and from PEG oligomers reacted essentially by proton transfer and gave similar spectra which are different from those of C2H5O+ ions made from dimethyl ether. The suggested structure could be any of II –IV. The reactions of the isomeric C2H5+ ions from dimethyl ether with PEG oligomers show a methyl cation transfer as a product ion, (M+13)+ ions, suggesting a CH3--O=CH2+ structure as shown in structure I. The two isomers reacted mostly by proton transfer with minor amounts of methyl cation transfer which points to structure IX. The C3H7O+ ions from the ion-molecule reaction of acetone and vinyl methyl ether react mostly by proton transfer could have the structure of X or XI.

References

  1. Harrison A.G., Chemical Ionization Mass Spectrometry, 2ndEdn., CRC Press, BOCA Raton, FL., (1992)
  2. Eitchmann E.S and Broadbelt J.S, Functional Group-Selective Ion-Molecule Reactions of Ethylene Glycol and Its Monomethyl and Dimethyl ethers, J. Am. Soc. Mass Spectrom,28, 738 (1993)
  3. Orlando R., Ridge D.P. and Munson B., Selective Reagents in Chemica Ionization Mass spectrometry: Tetramethylsilane with ethers, Org. Mass Spectrom,23, 527 (1988)
  4. Rudewicz P. and Munson B., Analysis of Complex Mixtures of Ethoxylated Alcohols by Probe Distillation/Chemical Ionization Mass Spectrometry, Anal. Chem., 54, 674-79 (1986)
  5. Stephanou E., Ionization Mass Spectra of Alkylphenol and Linear Alcohol Polyethoxylates, Org. Mass Spectrom, 19, 510-13 (1984)
  6. Lin Hung-Yu, Rockwood A., Munson M.S.B. and Ridge D.P., Proton Affinity and Collision-Induced Decomposition of Ethoxylated Alcohols: Effects of Intra-molecular Hydrogen Bonding on Polymer Ion Collision-Induced Decomposition, Anal. Chem., 68, 2119-24 (1993)
  7. Lee Y.C., Popov A.I. and Allison J., The Mass Spectra of Crown Ethers: The Effects of Preferred Secondary Structures on Fragmentation Patterns, Int. J. Mass Spectrom. Ion Process,51, 267-77 (1983)
  8. Blair I.A., Trenerry V.C. and Bowie J.H., Ion Cyclotron Resonance Studies of Alkylsilyl Ions: V—The Reactions of Alcohols and Ethers with the Allyldimethylsilyl Cation, Org. Mass Spectrom., 15, 15 (1980)
  9. Clemens D. and Munson B., Selective Reagents in Chemical Ionization Mass Spectrometry: Tetramethylsilane, Org. Mass Spectrom,20, 368 (1985)
  10. Trenerry V.C., Bowie J.H. and Blair I.A., Electron Impact Studies: CXXXI—Ion Cyclotron Resonance Studies of Ambident Nucleophiles, The Reaction between the Thioacetate Anion and Thioacetic Anhydride, A further example of a negative ion McLafferty rearrangement, J. Chem. Soc., Perkin Trans, , 1640 (1979)
  11. Orlando R. and Munson B., Trimethylsilyl Ions for Selective Detection ofOxygenated Compounds in Gasoline by Gas Chromatography Chemical Ionization, Anal. Chem., 58, 2788 (1986)
  12. Onigbinde A.O., Munson B.G., Amos-Tautua B.M.W., Gas Chromatography/Chemical Ionization of Polyethylene Glycol Mono Alkyl and Dialkyl Ethers, Res. J. Chem. Sci.,3(2), 4- 9 (2013)
  13. Onigbinde A.O., Munson B. and Amos-Tautua B.M.W., Ion/Molecule Reactions of Polyethylene Glycols and Polyethylene Glycol Dialkyl Ethers with Fourier Transformation/Ion Cyclotron Resonance Mass Spectrometry, Submitted for publication in J. Emerg. Trend. Eng. Appl. Sci. April (2013)
  14. Beauchamp J.L. and Dunbar R.C., Identification of C2H5O + Structural Isomers by Ion Cyclotron Resonance Spectroscopy, J. Am. Chem. Soc., 92, 1477- 1485 (1970)
  15. Blair A.S. and Harrison A.G., Bimolecular Reactions of Trapped Ions, V: Ionic Chemistry of Simple Oxygen-Containing Molecules, Can. J. Chem., 51, 703-70, 8 (1973)
  16. Shannon T.W. and McLafferty F.W., Identification of gaseous organic ions by the use of “metastable peaks”, J. Am. Chem. Soc., 88, 5021–22 (1966)
  17. Tsang C.W. and Harrison A.G., Internal energy effects on metastable characteristics, The structure of [CO] ions, J. Mass Spectrometry, 5(7), 877- 884 (1973)
  18. Tsang C.W. and Harrison A.G., Concerning the structure and fragmentation of [CO] ions derived from alcohols, J. Mass Spectrometry, 5(7), 877- 884 (1971)
  19. McLafferty F.W. and Sakai I., Collisional Activation Spectra, Behavior of C3H7O+ and Other C2n+1 Ion, Org. Mass Spectrom, , 971 (1973)
  20. Sekiguchi O., Aoyagi K., Tajima S. and Nibering N.M., J. Mass Spectro., 32, 755 (1997)
  21. Beauchamp J.L. and David Holtz, Relative Basicity of Phosphine and Ammonia in the Gas Phase, J. Am. Chem. Soc., 91, 5925, 22 (1969)
  22. Beauchamp J.L., Caserio M.C. and McMahon T.B., Ion Molecule Reactions of tert-butyl Alcohol by Ion Cyclotron Mass Spectrometry, J. Am. Chem. Soc., 96, 6243 (1974)
  23. Munson M.S.B., Chemical Ionization, J. Am. Chem. Soc., 88(12), 2621-2730 (1965)
  24. MacNeil K.A.G. and Futrell J.H., Ion-molecule reactions in gaseous acetone, J. Phys. Chem.,76, 409 (1972)