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Structure and reactivity of some o-iodosylbenzoate phosphorolytic reagents.

机译：一些邻碘基苯甲酸酯磷酸分解试剂的结构和反应性。

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摘要

This dissertation examines the structure of o-iodosylbenzoates and explores the reactivity of cetyltrimethylammonium iodosobenzoate , (CTA)IBA, with phosphates and phosphonoformates. Chapter 1 discusses experimental and theoretical studies that show that o-iodosobenzoic acid and its derivatives exist in a heterocyclic iodoxolone structure, and not the tautomeric carboxylic acid structure. The report of simultaneous isolation of the open and closed tautomeric forms of 4-pentyl-o-iodosobenzoic acid is reinvestigated.;Our results show that the compound X, reported to have the iodoxolone structure in the original paper, is actually 4-pentanoyl-2-iodobenzoic acid. Similar studies show that compound Y is actually a cyclic benziodoxolone.;Chapter 2 describes the reactivity of (CTA)IBA towards the pesticides paraoxon and parathion, and anionic phosphonoforlnate diesters. The widespread use of persistent pesticides poses a threat to public licalth and environmental safety. Thus their decontamination is important and necessary. (CTA)IBA, when used in excess, provides appreciable rate enhancements for paraoxon and parathion cleavages. Low half-lives for the cleavages, ease of preparation, and a relatively long shelf-life give promise for the use of (CTA)IBA for practical decontamination of the toxic pesticides.;A study of the kinetics of (CTA)IBA-mediated cleavages was carried out on a series of anionic phosphonoformate diesters that are of interest as potential antiviral prodrugs. The results show the remarkable propensity of IBA - to promote P-O scission of phosphonoformate diesters, when a reactive leaving group is present at the phosphoryl site. In the absence of IBA, only C-O scission is observed.;Chapter 2 also describes studies of metal-assisted hydrolysis of these phosphonoformates. Previous studies show the remarkable chemoselectivity of Zr(IV) and Hf(IV), which preferentially attack the P-O ester bond, when identical leaving groups are attached at both the carbonyl and phosphoryl sites. Th(IV), to the contrary, induces only C-O scission, regardless of the nature of leaving group. Results reported here show that these trends for diphenyl phosphonoformate and dimethyl phosphonoformate persist in aqueous acetonitrile.
机译：本文研究了邻碘基苯甲酸酯的结构，并探讨了十六烷基三甲基碘代苯甲酸酯（CTA）IBA与磷酸盐和膦酰基甲酸酯的反应性。第1章讨论了实验和理论研究，这些研究表明邻碘苯甲酸及其衍生物存在于杂环碘克龙的结构中，而不存在于互变异构的羧酸结构中。重新研究了同时分离4-戊基-邻-碘苯甲酸的开放和闭合互变异构形式的报告。;我们的结果表明，在原始论文中报道的具有碘代异龙酮结构的化合物X实际上是4-戊酰基- 2-碘苯甲酸。相似的研究表明，化合物Y实际上是环状苯并恶唑啉酮。第2章描述了（CTA）IBA对杀虫剂对氧磷和对硫磷以及阴离子膦酸酯的二酯的反应性。持久性杀虫剂的广泛使用对公共卫生和环境安全构成威胁。因此，它们的净化是重要和必要的。 （CTA）IBA过量使用时，可显着提高对氧磷和对硫磷裂解的速率。裂解的半衰期低，易于制备以及相对较长的保存期限，为使用（CTA）IBA进行有毒农药的实际净化提供了希望。;（CTA）IBA介导的动力学研究在一系列作为潜在抗病毒前药感兴趣的阴离子膦酸酯二酯上进行了裂解。结果表明，当磷酸基位上存在一个反应​​性离去基团时，IBA显着促进磷酸甲酸酯二酯的P-O断裂。在没有IBA的情况下，仅观察到C-O断裂。第二章还描述了这些膦酰基甲酸酯的金属辅助水解的研究。先前的研究表明Zr（IV）和Hf（IV）的出色的化学选择性，当相同的离去基团同时连接在羰基和磷酰基位点时，它们优先攻击P-O酯键。相反，无论离去基团的性质如何，Th（IV）仅引起C-O分裂。此处报道的结果表明，乙腈甲酸二苯酯和膦酸二甲酯的趋势在乙腈水溶液中仍然存在。

著录项

  • 作者

    Vijayaraghavan, Saketh.;

  • 作者单位

    Rutgers The State University of New Jersey - New Brunswick.;

  • 授予单位 Rutgers The State University of New Jersey - New Brunswick.;
  • 学科 Chemistry Organic.;Chemistry Physical.
  • 学位 Ph.D.
  • 年度 2002
  • 页码 129 p.
  • 总页数 129
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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