2,2-ethylenedioxy-4,4,6,6-tetrachlorocyclotriphosphazatriene | 53943-77-4

• 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: 2,2-ethylenedioxy-4,4,6,6-tetrachlorocyclotriphosphazatriene
• 英文别名: 2.2-Ethylendioxy-tetrachlor-cyclotriphosphazatrien；7,7,9,9-tetrachloro-1,4-dioxa-6,8,10-triaza-5λ⁵,7λ⁵,9λ⁵-triphospha-spiro[4.5]deca-5,7,9-triene；2,2,4,4-tetrachloro-6,6-ethane-1,2-diyldioxy-2λ⁵,4λ⁵,6λ⁵-cyclotriphosphazene；7,7,9,9-Tetrachloro-1,4-dioxa-6,8,10-triaza-5lambda5,7lambda5,9lambda5-triphosphaspiro[4.5]deca-5(10),6,8-triene；7,7,9,9-tetrachloro-1,4-dioxa-6,8,10-triaza-5λ5,7λ5,9λ5-triphosphaspiro[4.5]deca-5(10),6,8-triene
• CAS: 53943-77-4
• 化学式: C₂H₄Cl₄N₃O₂P₃
• 分子量: 336.806
• InChiKey: RCURRFNPNOOMDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  四氟丁二醇 、 2,2-ethylenedioxy-4,4,6,6-tetrachlorocyclotriphosphazatriene 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 24.0h， 以85%的产率得到1,1-(ethane-1',2'-dioxy)-3,3-(2',2',3',3'-tetrafluorobutane-1',4'-dioxy)-5,5-dichlorocyclotriphosphazene
  参考文献：
  名称：

  环三磷腈衍生物中双官能团的螺旋到ansa重排的研究

  摘要：

  通过具有五元螺环，N 3 P 3 Cl 4 [O（CH 2）2 NH]，（1）和N 3 P 3 Cl 4 [O（ CH 2）2 O]，（2）与1，3-丙二醇和2，2，3，3-四氟-1，4-丁二醇的二钠盐。具有强亲核体1,3-丙二醇的化合物1和2进行重排反应，形成稳定的ansa–ansa化合物，而化合物1和2的反应用氟化的醇盐进行的亲核取代在PCl 2基团处发生，并且较弱的亲核试剂不会发生重排。合成的化合物（3a，3b，4b，5a - d，6c和6d）已通过元素和质量（MS）分析以及1 H和31 P NMR光谱进行了全面表征。3b，4b，5b - d和6c的晶体结构已经通过X射线晶体学表征。发现，1,3-丙二醇是足够强的亲核试剂，即使单晶环证据表明七元和八元ansa-ansa的形成，也能引起单螺环三磷腈化合物1和2中螺线的ansa重排。化合物3b中的环导致环磷腈环的变形和压缩。一种可能的机制

  DOI：

  10.1016/j.poly.2012.06.014
• 作为产物：
  描述：

  乙二醇 在 吡啶 、 六氯环三磷腈 作用下， 以 苯 为溶剂， 生成 2,2-ethylenedioxy-4,4,6,6-tetrachlorocyclotriphosphazatriene
  参考文献：
  名称：

  Wende,A.; Joel,D., Zeitschrift fur Chemie, 1963, vol. 3, p. 467

  摘要：

  DOI：

文献信息

• Preparation of urethane and urea derivatives of (NPCl2)3. Crystal structure of a spirocyclic phosphazene with a phosphacyanuric loop
  作者：Adri A. van der Huizen、Pieter L. Buwalda、Theo Wilting、Harm Pol、Andries P. Jekel、Auke Meetsma、Johan C. van de Grampel

  DOI：10.1039/dt9940000577

  日期：——

  gem-N3P3Cl4(NHCO2R)2, and a spiro derivative (NPCl2)2NP[N(CO2R)C(O)NHC(CH3)N]. The crystal structure of the last compound (R = CH3) has been determined. The difference between the reaction pathways observed for NaNCO and AgNCO is discussed in terms of SN2 and SN1 mechanisms, respectively. An improved synthesis of (NPCl2)2NP(NH2)(NCO) and its reactions with alcohols and amines are described.

  已经研究了（NPCl 2）3与NaNCO在脂肪醇存在下的反应。在回流乙腈中使用等摩尔量的NaNCO，可获得高产率的单（氨基甲酸酯）衍生物N 3 P 3 Cl 5（NHCO 2 R）。替代主要是非双基因的。（NPCl 2）3与AgNCO和甲醇在乙腈中的反应遵循完全不同的模式，并导致形成基本具有宝石结构的三种产物，例如，宝石-N 3 P 3 Cl 4（OR）（NHCO 2 R），宝石-N3 P 3 Cl 4（NHCO 2 R） 2和螺衍生物（NPCl 2） 2 NP [N（CO 2 R）C（O）NHC（CH 3）N]。已确定最后一种化合物的晶体结构（R = CH 3）。分别根据S N 2和S N 1机制讨论了NaNCO和AgNCO观察到的反应途径之间的差异。描述了一种改进的（NPCl 2） 2 NP（NH 2）（NCO）的合成及其与醇和胺的反应。
• A spiro to ansa rearrangement in cyclotriphosphazene derivatives
  作者：Serap Beşli、Simon J. Coles、David B. Davies、Michael B. Hursthouse、Adem Kılıç、Robert A. Shaw

  DOI：10.1039/b703541a

  日期：——

  cyclotriphosphazene derivatives having five-membered spiro rings, N(3)P(3)Cl(4)[O(CH(2))(2)X] (X = NH or O) with alkoxides (of tetraethylene glycol and some mono-functional alcohols) give unexpected rearrangements to form stable seven-membered ring ansa compounds, even though crystallographic evidence shows ring distortion and compression of the cyclophosphazene ring. With weaker nucleophiles such as sodium phenoxide

  具有五元螺环，N（3）P（3）Cl（4）[O（CH（2））（2）X]（X = NH或O）（X = NH或O）的醇盐（四亚乙基的）的亲核取代反应乙二醇和某些单官能醇）会产生意想不到的重排，以形成稳定的七元环ansa化合物，即使晶体学证据表明环畸变和环磷腈环的压缩也是如此。对于较弱的亲核试剂，例如苯酚钠和吡咯烷，优选在PCl2基团上进行取代，并且不会发生重排。相反，含有六元螺环，N（3）P（3）Cl（4）[O（CH（2））（3）X]的类似磷腈与上述所有试剂的反应仅给出正常反应。在PCl2部分的取代反应并且没有重排产物。
• Effect of chain length on the formation of intramolecular and intermolecular products: Reaction of diols with cyclotriphosphazene
  作者：Serap Beşli、Simon J. Coles、Derya Davarcı、David B. Davies、Fatma Yuksel

  DOI：10.1016/j.poly.2010.10.020

  日期：2011.2

  The reactions of cyclotriphosphazene, N(3)P(3)Cl(6) (1), in a 1:1.2 stoichiometry with the sodium derivative of seven diols [ethane- (2a), 1,3-propane- (2b), 1,4-butane- (2c), 1,5-pentane- (2d.), 1,6-hexane- (2e), 1,8-octane- (2f) and 1,10-decane- (2g) diol] in THF solution at room temperature have been used to investigate the effect of chain length on the formation of reaction products. Although no new products were found for the reaction of 1 with diols 2a-c compared to those in the literature using other bases and solution conditions, the reactions of 1 with the diols 2d-g gave six different types of products, whose structures have been characterized by elemental analysis, mass spectrometry, I H and (31)P NMR spectroscopy; ansa compounds N(3)P(3)Cl(4)[O(CH(2))(n)O], (5d-5g): single-bridged compounds N(3)P(3)Cl(5)[O(CH(2))(n)O]N(3)P(3)Cl(5) (6d-6f); double-bridged compounds N(3)P(3)Cl(4)[O(CH(2))(n)O](2)N(3)P(3)Cl(4) (7d-7g, syn and anti) and triple-bridged compounds, N(3)P(3)Cl(3)[O(CH(2))(n)O](3)N(3)P(3)Cl(3) (8d-f). Where suitable single crystals were obtained, X-ray crystallographic studies confirmed the structures of two ansa compounds (5d and 5f), one single-bridged compound (6e), and five double-bridged compounds (meso-anti for 7d, 7e, 7f and meso-syn for 7d and 7f). (31)P NMR measurements of the reaction mixtures were used to quantify the formation of products for the reactions 1 with all the diols, 2a-g; it is found that, with increasing chain length of the diol, there is a decrease in the products formed by intramolecular reactions (spiro and ansa derivatives) and a concomitant increase in the amounts of products formed by intermolecular reactions (single-, double- and triple-bridged derivatives) of cyclophosphazene. (C) 2010 Elsevier Ltd. All rights reserved.
• Al-Madfa, Homaid A.; Shaw, Robert A., Phosphorus, Sulfur and Silicon and the Related Elements, 1989, vol. 45, p. 1 - 6
  作者：Al-Madfa, Homaid A.、Shaw, Robert A.

  DOI：——

  日期：——
• Alkubaisi, Abdulla H.; Parkes, Harold G.; Shaw, Robert A., Heterocycles, 1989, vol. 28, # 1, p. 347 - 358
  作者：Alkubaisi, Abdulla H.、Parkes, Harold G.、Shaw, Robert A.

  DOI：——

  日期：——