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SYNTHESIS OF ORGANOARSENIC COMPOUNDS FOR ELEMENTAL SPECIATION

FRICKE, MICHAEL WILLIAM
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1078519638

Abstract Details

2004, PhD, University of Cincinnati, Arts and Sciences : Chemistry.
Ongoing toxicokinetic and biogenesis investigations require gram quantities of naturally occurring arsenobetaines and dimethylribofuranosides. The principal synthetic routes to these compounds are hazardous; at least one laboratory explosion has occurred. New routes to these compounds are now reported that eliminate dangerous procedures and materials inherent in these syntheses. Previously reported syntheses of arsenobetaines have all involved trimethylarsine as a synthetic precursor. Due to the high vapor pressure (BP 52C), extreme toxicity and pyrophoric nature of this compound it is both difficult and expensive to handle in a laboratory. In seeking to avoid this trimethylarsine as a precursor in the synthesis of arsenobetaines, the novel arsines ethoxycarbonylmethyldimethylarsine and 2-ethoxycarbonylethyl(dimethyl)arsine have been synthesized and isolated. The higher vapor pressure of these arsines permits purification by vacuum distillation and allows for safer handling. Subsequent conversion to arsenobetaines is simple and this route is preferred to those previously reported on the basis of material costs, operator time and safety. The synthesis of the desired dimethylribofuranoside has involved the hydrogen peroxide oxidation in ether of a parent arsine to provide the desired arsine oxide moiety. This reaction is hazardous. New routes to arsine oxides have been explored including the reduction of novel arsinoyl imidazolides and rearrangements involving Meyer chemistry that dates from the year 1883. Finally, the oxidation of arsines using the mild oxidant dimethyldioxirane was attempted. The dimethyldioxirane oxidation of triphenylarsine provided the desired triphenylarsine oxide quickly and quantitatively. After demonstrating this reaction on the small scale oxidation of triphenylarsine, the dimethyldioxirane oxidation was employed to replace the oxidation step in the synthesis of the required dimethylribofuranoside. This alternative oxidation worked well and the hazardous oxidation of arsines with hydrogen peroxide in ether can be abandoned.
Dr. John Thayer (Advisor)
135 p.
Chemistry, Organic
Arsenic; Synthesis; ICP-MS; Speciation

Recommended Citations

Citations

  • FRICKE, M. W. (2004). SYNTHESIS OF ORGANOARSENIC COMPOUNDS FOR ELEMENTAL SPECIATION [Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1078519638

    APA Style (7th edition)

  • FRICKE, MICHAEL. SYNTHESIS OF ORGANOARSENIC COMPOUNDS FOR ELEMENTAL SPECIATION. 2004. University of Cincinnati, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1078519638.

    MLA Style (8th edition)

  • FRICKE, MICHAEL. "SYNTHESIS OF ORGANOARSENIC COMPOUNDS FOR ELEMENTAL SPECIATION." Doctoral dissertation, University of Cincinnati, 2004. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1078519638

    Chicago Manual of Style (17th edition)

ucin1078519638
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© 2004, all rights reserved.
This open access ETD is published by University of Cincinnati and OhioLINK.