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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Nucleophilic substitution reactions of 10- and 11-membered fluorodioxy ansa cyclotriphosphazene derivatives
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Nucleophilic substitution reactions of 10- and 11-membered fluorodioxy ansa cyclotriphosphazene derivatives

机译：10和11元氟代二氧基ansa环三磷腈衍生物的亲核取代反应

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摘要

The reactions of cyclophosphazenes with 10-membered ansa-{N _3P_3Cl_4[OCH_2(CF_2) _3CH_2O] (1a)} and 11-membered ansa-{N3P 3Cl4[OCH2(CF2)4CH 2O] (1b)} rings with the sodium salts of methanol in a THF solution at different molar ratios were used to investigate the reaction pathways and mechanism of nucleophilic substitution at the PCl_2 and PCl(OR) phosphorus atoms. The reactions afforded eleven products, whose structures have been characterized by elemental analysis, mass spectrometry, ~1H, ~(19)F and ~(31)P NMR spectroscopy and X-ray crystallography; mono-methoxy derivatives (2a, 3a, 3b), di-methoxy derivatives (5a-7a, 5b), tri-methoxy derivatives (8a, 8b) and the tetra-methoxy derivatives (9a, 9b). The X-ray crystallographic studies of four compounds (6a-8a and 8b) demonstrated unambiguously that nucleophilic substitution reactions at the ansa-ring PCl(OR) phosphorus atoms of the cyclotriphosphazene compounds N_3P _3Cl_4[OCH_2(CF_2)_nCH _2O] _n = 3 (1a) and 4 (1b) occurred with a retention of configuration for both the 10- and 11-membered fluorodioxy ansa rings, respectively. The results confirmed that the reactions with 1a containing the 10-membered ansa-ring occurred competitively at both the PCl_2 and P(OR)Cl moieties with an approximate 8:1 preference at the PCl_2 group, whereas reactions with 1b containing the 11-membered ansa-ring occurred exclusively at the PCl2 group before the P(OR)Cl moiety. The results were mainly rationalized in terms of the P-Cl bond lengths of the reactants and the cation-assisted mechanism of reaction.
机译：环磷腈与10元ansa- {N _3P_3Cl_4 [OCH_2（CF_2）_3CH_2O]（1a）}和11元ansa- {N3P 3Cl4 [OCH2（CF2）4CH 2O]（1b）}环与钠盐的反应用不同摩尔比的THF溶液中的甲醇溶液研究PCl_2和PCl（OR）磷原子处的亲核取代反应的路径和机理。反应提供了十一种产物，其结构已通过元素分析，质谱，〜1H，〜（19）F和〜（31）P NMR光谱学和X射线晶体学表征。单甲氧基衍生物（2a，3a，3b），二甲氧基衍生物（5a-7a，5b），三甲氧基衍生物（8a，8b）和四甲氧基衍生物（9a，9b）。四种化合物（6a-8a和8b）的X射线晶体学研究清楚地表明，环三磷腈化合物N_3P _3Cl_4 [OCH_2（CF_2）_nCH _2O] _n = 3的ansa-ring PCl（OR）磷原子处的亲核取代反应（1a）和4（1b）分别保留了10元和11元氟代二氧基ansa环的构型。结果证实，与PCa_2组和PCl_2组的PCl_2和P（OR）Cl部分均具有竞争性地发生与包含10元ansaring的1a的反应，而与包含11元成员的1b的反应竞争性地发生。 ansa-ring仅在P（OR）Cl部分之前的PCl2组发生。主要根据反应物的P-Cl键长度和阳离子辅助反应机理对结果进行了合理化。

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