Enrichment of H(2)(17)O from tap water, characterization of the enriched water, and properties of several (17)O-labeled compounds.
A low-abundance form of water, H(2)(17)O, was enriched from 0.04% to ∼90% by slow evaporation and fractional distillation of tap water. The density and refractive index for H(2)(17)O are reported. Gas chromatography-mass spectrometry (GC-MS) of (16)O- and (17)O-1-hexanols and their trimethyl silyl ethers and of (16)O- and (17)O-hexamethyl disiloxanes was used to determine the percentage of (17)O enrichment in the H(2)(17)O. Furthermore, the chemical shifts of labeled and nonlabeled water dissolved in CDCl(3) differed sufficiently that we could verify the enrichment of H(2)(17)O. (17)O hexanol was synthesized by the reaction of iodohexane with Na(17)OH. (17)O-Labeled trimethylsilanol and (17)O-labeled hexamethyldisiloxane were prepared by the reaction of H(2)(17)O with bis(trimethylsilyl)trifluoroacetamide (BSTFA). To generate standards for (17)O NMR, H(2)(17)O(2), and (17)O camphor were prepared. H(2)(17)O was electrolyzed to form (17)O-labeled hydrogen peroxide which was quantified using two colorimetric assays. (17)O-Labeled camphor was prepared by exchanging the ketone oxygen of camphor using H(2)(17)O. The (17)O-labeled compounds were characterized using (17)O, (1)H, and (13)C NMR and GC-MS. While we were characterizing the labeled camphor, we also detected an unexpected oxygen exchange reaction of primary alcohols, catalyzed by electrophilic ketones such as camphor. The reaction is a displacement of the alcohol OH group by water. This is an example of the usefulness of (17)O NMR in the study of a reaction mechanism that has not been noticed previously.
Department of Chemistry, Simon Fraser University, 8888 University Drive, Burnaby, BC, Canada - V5A 1S6.
Brinda
B
Prasad
Andrew R
AR
Lewis
Erika
E
Plettner
D002164:Camphor / Q000737:chemistry; D019475:Camphor 5-Monooxygenase / Q000378:metabolism; D057168:Distillation; D004572:Electrolysis; D008401:Gas Chromatography-Mass Spectrometry; D000441:Hexanols / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry / Q000378:metabolism; D007553:Isotope Labeling / Q000379:methods*; D009682:Magnetic Resonance Spectroscopy; D010103:Oxygen Isotopes / Q000737:chemistry; D012833:Siloxanes / Q000737:chemistry; D014297:Trimethylsilyl Compounds / Q000737:chemistry; D014867:Water / Q000737:chemistry*
D000441:Hexanols; D010103:Oxygen Isotopes; D012833:Siloxanes; D014297:Trimethylsilyl Compounds; D014867:Water; D002164:Camphor; D006861:Hydrogen Peroxide; C015917:hexamethyldisiloxane; D019475:Camphor 5-Monooxygenase; C055926:trimethylsilanol