1,4,6,9-tetraoxa-5λ₅-phosphaspiro[4,4]nonane | 673460-28-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧磷杂环戊烷
• 英文名称: 1,4,6,9-tetraoxa-5λ₅-phosphaspiro[4,4]nonane
• 英文别名: 1,4,6,9-tetraoxa-5-phosphaspiro<4.4>nonane；1,4,6,9-tetraoxa-5λ⁵-phosphaspiro<4,4>nonane；Bis-aethylendioxy-phosphoran；1,4,6,9-tetraoxa-5-phosphaspiro[4.4]nonane；1,4,6,9-tetraoxa-5λ5-phosphaspiro[4.4]nonane
• CAS: 673460-28-1
• 化学式: C₄H₉O₄P
• 分子量: 152.087
• InChiKey: LAYXLQXTGGOAIR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.49
• 重原子数：
  9.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1,4,6,9-tetraoxa-5λ₅-phosphaspiro[4,4]nonane 生成 2-(1,3,2-二氧杂磷杂环戊烷-2-基氧基)乙醇
  参考文献：
  名称：

  Germa,H. et al., Comptes Rendus des Seances de l'Academie des Sciences, Serie C: Sciences Chimiques, 1970, vol. 270, p. 1426 - 1429

  摘要：

  DOI：
• 作为产物：
  描述：

  二氯(三氯甲基)膦 、 乙二醇 在 三乙胺 作用下， 以80%的产率得到1,4,6,9-tetraoxa-5λ₅-phosphaspiro[4,4]nonane
  参考文献：
  名称：

  Prishchenko, A. A.; Gromov, A. V.; Lutsenko, I. F., Journal of general chemistry of the USSR, 1984, vol. 54, # 3, p. 631 - 632

  摘要：

  DOI：

文献信息

• Synthesis of bis- and tris-organophosphorus substituted amines and amino acids with PCH2N Fragments
  作者：Andrey A. Prishchenko、Mikhail V. Livantsov、Olga P. Novikova、Ludmila I. Livantsova、Valery S. Petrosyan

  DOI：10.1002/hc.20616

  日期：——

  derivatives of trivalent organophosphorus acids, containing PH and POSiMe3 fragments with various bis- and tris(alkoxymethyl)amines and bis(alkoxymethyl)amino acids, is proposed as a convenient method for the synthesis of new bis- and trisphosphorylated amines and amino acids as well as their derivatives with four and five coordinated phosphorus. Also the three-components systems of phosphorous acid, paraformaldehyde

  三价有机磷酸衍生物（含有 PH 和 POSiMe3 片段与各种双和三（烷氧基甲基）胺和双（烷氧基甲基）氨基酸）的氨基甲基化被提议作为合成新的双和三磷酸化胺的便捷方法和氨基酸以及它们与四和五配位磷的衍生物。此外，通过用双（三甲基甲硅烷基）胺处理反应混合物，对亚磷酸、多聚甲醛和胺的三组分体系进行了彻底研究。© 2010 Wiley Periodicals, Inc. 杂原子化学 21:430–440, 2010; 在 wileyonlinelibrary.com 上在线查看这篇文章。DOI 10.1002/hc.20616
• Structure et acidite de composes a atome de bore et de phosphore hypercoordonnes
  作者：L. Lamandé、D. Boyer、A. Munoz

  DOI：10.1016/s0022-328x(00)98891-0

  日期：1980.7

  La réaction de l'acide borique, en solution dans le DMF, avec des α-hydroxyacides, acides, le méthyl-3-pyrocatechol, les acides oxalique, phénylhydroxamique, citrique et tartrique, conduit à des spirannes. Les borates de l'acide tartrique sont des dérivés dimères comparables aux émétiques de l'antimoine. La structure spirannique a étéétablie au moyen de la RMN (11B, 13C, 1H). Dans le cas de l'acide

  硼化物，DMF溶液，α-羟基酸，酸，3-邻甲基邻苯二酚，酸，草酸，邻苯二甲酰氧基苯胺，柠檬酸和焦油，螺旋藻类导管。Les borate de l'acide tartrique sont desdérivésdimères可与auxémétiquesde l'antimoine媲美。SPIN的结构气息（11 B，13 C，1 H）。确认使用抗坏血酸，不使用香精的基础溶液，无溶剂的硼烷溶液（THF，CH 3 CN），硼烷⇌硼酸酯和螺线虫灵。Le p K a de cescompsés，determinépar滴定法，三乙胺，suuivie parpotentiométrie，对应于des酸堡垒（1.5
• Synthesis of new mono- and bisorganophosphorus proline derivatives with P-C-N moieties
  作者：Andrey A. Prishchenko、Mikhail V. Livantsov、Olga P. Novikova、Ludmila I. Livantsova、Valery S. Petrosyan

  DOI：10.1002/hc.21358

  日期：2017.1

  The various methods of aminomethylation of some PH-acids with proline and their derivatives are investigated. The numerous derivatives of proline and corresponding phosphonates, phosphonites, phosphinates, and phosphorane with proline moieties are presented.

  研究了用脯氨酸及其衍生物氨甲基化某些 PH 酸的各种方法。介绍了脯氨酸和相应的膦酸盐、亚膦酸盐、次膦酸盐和具有脯氨酸部分的正膦的众多衍生物。
• Highly Selective Markovnikov Addition of Hypervalent<i>H</i>-Spirophosphoranes to Alkynes Mediated by Palladium Acetate: Generality and Mechanism
  作者：Li-Biao Han、Yutaka Ono、Qing Xu、Shigeru Shimada

  DOI：10.1246/bcsj.20100141

  日期：2010.9.15

  Palladium acetate efficiently catalyzes the addition of an H-spirophosphorane (pinacolato)2PH to alkynes to give Markovnikov addition products highly selectively. The addition products can be easily converted to the corresponding alkenylphosphonates and phosphonic acids via simple hydrolysis or thermal decomposition. This new reaction is a general method for the introduction of phosphorus functionality to the internal carbons of terminal alkynes, resolving the problem of the regioselectivity associated with hydrophosphorylation reactions so far reported. Mechanistic studies confirmed that (a) palladium acetate was reduced to metallic palladium by H-spirophosphorane, (b) the P–H bond of H-spirophosphorane could be activated by zero-valent platinum complexes to give the corresponding hydridoplatinum complexes, and (c) an alkenylpalladium species was identified from the reaction of palladium acetate with H-spirophosphorane and diphenylacetylene. These results support a reaction mechanism that palladium acetate was first reduced by H-spirophosphorane to give zero-valent palladium. This zero-valent palladium might insert into the P–H bond of the H-spirophosphorane to give a hydridopalladium species which then added to alkyne via the addition of H–Pd bond to form an alkenylpalladium species with the hydrogen atom added to the terminal carbon of alkynes. Reductive elimination of the alkenylpalladium affords the addition product.

  乙酸钯能高效催化H-螺磷烷（pinacolato）2PH与炔烃反应,高选择性地得到马氏加成产物。该加成产物通过简单的水解或热分解即可转化为相应的烯基膦酸盐和膦酸。这一新反应为解决端炔的内碳原子亲核膦化反应的区域选择性问题提供了一般性的方法。机理研究表明：（a）乙酸钯被H-螺磷烷还原为金属钯;（b）零价铂配合物可活化H-螺磷烷的P-H键,生成相应的氢铂配合物;（c）乙酸钯与H-螺磷烷和二苯基乙炔反应生成了烯基钯物种。这些结果支持下列反应机理：乙酸钯首先被H-螺磷烷还原为零价钯,后者插入H-螺磷烷的P-H键生成氢钯物种,该氢钯物种与炔烃反应时, H-Pd键加成形成烯基钯物种,其中的氢原子加成到炔烃的末端碳原子上,最后经还原消除生成加成产物。
• Mecanisme de formation et de transformation des spirophosphoranes—VIII
  作者：C. Laurenço、R. Burgada

  DOI：10.1016/0040-4020(76)85114-9

  日期：1976.1

  The reactions of spirophosphoranes containing a PH bond with aldehydes, imines, and animals lead to spirophosphoranes (10–10) containing a PC bond, while with acid chlorides, β-functional phosphiates are formed (compounds 35–38). Dependeing on the nature of the heteroatom attached to phosphorus, the reaction of spirophosphoranes with phenyl isocyanate gives a spirophosphorane (YHOH, compounds 31

  含有PH键的螺磷ora与醛，亚胺和动物的反应会导致含有P containingC键的螺磷phosph（10-10），而与酰氯形成β-官能的膦酸酯（化合物35-38）。取决于附接到磷的杂原子的性质，螺磷杂环戊烷与苯基异氰酸酯的反应得到螺磷杂环烷（YH ＝ OH，化合物31和32）或亚磷酸酯（YH ＝ NHR，化合物33和34）。