1,7,9,9-Tetrachloro-2,6-dioxa-8,10,11-triaza-1λ⁵,7λ⁵,9λ⁵-triphospha-bicyclo[5.3.1]undeca-1(10),7(11),8-triene | 123519-37-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环化合物
• 英文名称: 1,7,9,9-Tetrachloro-2,6-dioxa-8,10,11-triaza-1λ⁵,7λ⁵,9λ⁵-triphospha-bicyclo[5.3.1]undeca-1(10),7(11),8-triene
• 英文别名: 1,7,9,9-Tetrachloro-2,6-dioxa-10,11-diaza-8-azanida-1lambda5,9lambda5-diphospha-7-phosphoniabicyclo[5.3.1]undeca-1(11),9-diene；1,7,9,9-tetrachloro-2,6-dioxa-10,11-diaza-8-azanida-1λ5,9λ5-diphospha-7-phosphoniabicyclo[5.3.1]undeca-1(11),9-diene
• CAS: 123519-37-9
• 化学式: C₃H₆Cl₄N₃O₂P₃
• 分子量: 350.833
• InChiKey: RFPOLJOOTWHJGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 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：
  44.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  1,3-丙二醇 在 六氯环三磷腈 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以35%的产率得到3,3,5,5-Tetrachloro-1',3'-propanedioxycyclotriphosphazatriene
  参考文献：
  名称：

  pentaerythritoxy桥接环三磷腈衍生物的结构和立体异构属性：螺-螺，螺-安莎和柄型-袢异构体

  摘要：

  的反应 季戊四醇 和 六氯环三磷腈，N 3 P 3 Cl 6和宝石二取代的环三磷腈衍生物N 3 P 3 Cl 4 R 2 [R = Ph，NHBu t或（OCH 2 CF 2 CF 2 CH 2 O）0.5 ]得到一系列季戊四醇-桥接衍生工具链接了spiro – spiro，spiro – ansa和ansa – ansa。产品的结构和立体感特性通过X射线晶体学 和 31 P NMR光谱 加入手性溶剂后， （S）-（+）-2,2,2-三氟-1-（9-蒽基）乙醇。发现具有螺–螺和螺– ansa桥联的宝石-二取代的环磷腈[R = Ph，NHBu t或（OCH 2 CF 2 CF 2 CH 2 O）0.5 ]的分子是手性的，并且以队友。具有ansa – ansa桥联环磷腈[R = Cl或（OCH 2 CF 2 CF 2 CH 2 O）0.5 ]的分子首次得到表征，并显示具有内消旋构型。晶体分析结

  DOI：

  10.1039/b512854d

文献信息

• The structural and stereogenic properties of pentaerythritoxy-bridged cyclotriphosphazene derivatives: spiro–spiro, spiro–ansa and ansa–ansa isomers
  作者：Simon J. Coles、David B. Davies、Robert J. Eaton、Michael B. Hursthouse、Adem Kılıç、Robert A. Shaw、Aylin Uslu

  DOI：10.1039/b512854d

  日期：——

  derivatives linked spiro–spiro, spiro–ansa and ansa–ansa. The structures and stereogenic properties of the products were characterised by X-ray crystallography and 31P NMR spectroscopy on addition of the chiral solvating agent, (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol. Molecules with spiro–spiro and spiro–ansa bridged gem-disubstituted cyclophosphazenes [R = Ph, NHBut or (OCH2CF2CF2CH2O)0.5] are found to

  的反应 季戊四醇 和 六氯环三磷腈，N 3 P 3 Cl 6和宝石二取代的环三磷腈衍生物N 3 P 3 Cl 4 R 2 [R = Ph，NHBu t或（OCH 2 CF 2 CF 2 CH 2 O）0.5 ]得到一系列季戊四醇-桥接衍生工具链接了spiro – spiro，spiro – ansa和ansa – ansa。产品的结构和立体感特性通过X射线晶体学 和 31 P NMR光谱 加入手性溶剂后， （S）-（+）-2,2,2-三氟-1-（9-蒽基）乙醇。发现具有螺–螺和螺– ansa桥联的宝石-二取代的环磷腈[R = Ph，NHBu t或（OCH 2 CF 2 CF 2 CH 2 O）0.5 ]的分子是手性的，并且以队友。具有ansa – ansa桥联环磷腈[R = Cl或（OCH 2 CF 2 CF 2 CH 2 O）0.5 ]的分子首次得到表征，并显示具有内消旋构型。晶体分析结
• 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.
• 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：——
• Effect of gem 2,2′-disubstitution and base in the formation of spiro- and ansa-1,3-propandioxy derivatives of cyclotriphosphazenes
  作者：Aylin Uslu、Simon J. Coles、David B. Davies、Mükremin Esen、Michael B. Hursthouse、Adem Kılıç

  DOI：10.1016/j.ica.2010.07.005

  日期：2010.10

  The gem-dialkyl effect has been investigated in the reactions of cyclotriphosphazene, N3P3Cl6 1, with various 2,2'-derivatives of 1,3-propandiol, CXY(CH2OH)(2), in either THF or DCM to form spiro (6-membered) and ansa (8-membered ring) derivatives. The reactions were made with a number of symmetrically-substituted (X = Y, methyl, ethyl, n-butyl and a malonate ester) and unsymmetrically-substituted (X not equal Y, methyl/H, phenyl/H, methyl/n-propyl, ethyl/n-butyl and Br/NO2) 1,3-propandiols. The products were analysed by H-1 and P-31 NMR spectroscopy and some of the spiro and ansa derivatives were also characterized by X-ray crystallography. Reactions of 1 with unsymmetrically-substituted 1,3-propandiols results in the formation of two structural isomers of ansa-substituted compounds, both isomers (endo and exo) have been structurally-characterized by X-ray crystallography for the ethyl/n-butyl derivative. It is found that the regioselectivity of the reaction is changed when the base is changed. The relative proportions of spiro and ansa compounds formed under different reaction conditions were quantified by P-31 NMR measurements of the reaction mixtures. The results were rationalised mainly in terms of the electronic effect of the substituents, whereas the steric effect has a secondary role in the formation of both spiro and ansa compounds. (C) 2010 Elsevier B.V. All rights reserved.