10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide | 32186-92-8

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
• 英文别名: 6-Chlorobenzo[c][2,1]benzoxaphosphinine 6-oxide
• CAS: 32186-92-8
• 化学式: C₁₂H₈ClO₂P
• 分子量: 250.621
• InChiKey: GCDRIRYINCSSIW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 以 乙醇 为溶剂， 生成 10-hydroxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  参考文献：
  名称：

  Chernyshev,E.A. et al., Journal of general chemistry of the USSR, 1971, vol. 41, p. 2214 - 2216

  摘要：

  DOI：
• 作为产物：
  描述：

  10-氯-9,10-二氢-9-氧杂-10-磷杂菲 在 臭氧 作用下， 生成 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  参考文献：
  名称：

  Method for preparing a biphenylphosphonate compound

  摘要：

  制备以下式（I）的二苯基膦酸酯化合物的方法：其中n为2或3；Ar为C6-C16芳香基团；包括以下步骤：（a）在锌氯化物催化剂存在下，将邻苯酚与三氯化磷反应，形成以下式（II）的6-氯-6H-二苯[c,e][1,2]氧磷杂环戊烷；（b）将式（III）的多羟基苯化合物（HO)n—Ar（III）（其中n和Ar的定义与上述相同）与式（II）的化合物反应，形成以下式（IV）的化合物；其中n和Ar的定义与上述相同；（c）在水和臭氧存在下氧化式（IV）的化合物，形成式（I）的化合物。

  公开号：

  US20050101793A1

文献信息

• Process for preparing 10-chloro-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound
  申请人：UFC Corporation

  公开号：US08703986B1

  公开（公告）日：2014-04-22

  Provided is a process for preparing 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-C) compound, the process having steps of: reacting a liquid chlorinating agent and 9,10-dihydro-10-hydroxy-9-oxa 10-phosphaphenanthrene 10-oxide compound represented by formula (B) to form a mixture, the mixture comprises DOPO-C compound represented by formula (A) and an unreacted liquid chlorinating agent, separating the DOPO-C compound and the unreacted liquid chlorinating agent from the mixture to obtain the DOPO-C compound; wherein X1, X2, and X3 are each independently selected from the group consisting of hydrogen atom, hydroxyl group, cyano group, sulfonic acid group, sulfonate ester group represented by —SO3R1, halogen atom, alkoxy group represented by —OR2, acyclic hydrocarbon group having 1 to 8 carbon atoms, cyclic alkyl group having 3 to 8 carbon atoms, aryl group, heteroaryl group, and arylalkyl group, wherein R1 and R2 are each an acyclic hydrocarbon group having 1 to 8 carbon atoms.

  提供了一种制备10-氯-9,10-二氢-9-氧-10-磷代菲-10-氧化物（DOPO-C）化合物的过程，该过程包括以下步骤：将液体氯化剂与由式（B）表示的9,10-二氢-10-羟基-9-氧-10-磷代菲-10-氧化物化合物反应，形成混合物，该混合物包含由式（A）表示的DOPO-C化合物和未反应的液体氯化剂，将DOPO-C化合物和未反应的液体氯化剂从混合物中分离出来，以获得DOPO-C化合物；其中X1、X2和X3分别独立地选自氢原子、羟基、氰基、磺酸基、由—SO3R1表示的磺酸酯基、卤素原子、由—OR2表示的烷氧基、具有1至8个碳原子的非环烃基、具有3至8个碳原子的环烷基、芳基、杂环芳基和芳基烷基的群，其中R1和R2分别是具有1至8个碳原子的非环烃基。
• Synthesis of Trispirocyclotriphosphazenes with Oxaphosphorine Rings and Their Crystal and Molecular Structures
  作者：Yuji Tada、Atsushi Sunada、Riki Watanabe、Makoto Kanazawa、Keiichiro Utsumi

  DOI：10.1021/acs.inorgchem.1c00054

  日期：2021.4.5

  were characterized by 1H, 13C1H}, and 31P1H} nuclear magnetic resonance spectroscopy and time-of-flight mass spectrometry and shown to consist of cis–trans isomers. Moreover, the crystal and molecular structures of the DOP-PZs were determined by X-ray diffraction; cis- and trans-DOP-PZs (C36H24N3O3P3, M = 639.49 g/mol) were refined to final R1 values of 0.0260 and 0.0463, respectively, with the SHELXL

  通过氨与10-氯-9,10-二氢-9-氧杂-10-膦菲10氧化物从9衍生而来的磷酰胺的Appel反应成功地合成了具有氧杂磷环（DOP-PZs）的新型三螺环三磷腈（DOP-PZs）。 ，10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide，通常缩写为DOPO。所得DOP-PZs的特征在于1 H，13 C 1 H}和31 P 1 H}核磁共振波谱和飞行时间质谱，并显示由顺-反异构体组成。此外，通过X射线衍射确定了DOP-PZ的晶体和分子结构。顺式和反式使用最小二乘最小化的SHELXL精制软件包，将-DOP-PZs（C 36 H 24 N 3 O 3 P 3，M = 639.49 g / mol）精制为最终R 1值0.0260和0.0463。的晶体顺-DOP-PZ是在空间群三角- [R 3 Ç和下面的晶胞常数：一个= 19.5984（5），C ^
• Phosphonamidate Compounds for Butyrylcholinesterase Selective Inhibitors
  作者：Jintaek Oh、Jung‐Youl Park、Kyoung Chan Park、Ji Hyun Hwang、Jeong Ho Park

  DOI：10.1002/bkcs.12126

  日期：2020.12

  To find a new type of cholinergic drug, phosphonamidate compounds 18–32 were synthesized using a click reaction between propargylated‐9,10‐Dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO, 2) and substituted benzyl azide. Their inhibitory activity against butyrylcholinesterase (BuChE) and acetylcholinesterase (AChE) was evaluated. Compound 31 was the most active of the 15 compounds (IC50 = 3.14 ± 0

  为了找到一种新型的胆碱能药物，使用炔丙基化的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO，2）和取代的叠氮化苄之间的点击反应合成了膦酰胺化合物18–32。评价了它们对丁酰胆碱酯酶（BuChE）和乙酰胆碱酯酶（AChE）的抑制活性。化合物31是15种化合物中活性最高的（马类BuChE的IC 50 = 3.14±0.02μM），其IC 50值略低于加兰他敏的IC 50值（马类BuChE的IC 50 = 9.4±2.50）。
• Industrial Upscaling of DOPO-Based Phosphonamidates and Phosphonates Derivatives Using Cl₂ Gas as a Chlorinating Agent
  作者：Khalifah A. Salmeia、Georg Baumgartner、Milijana Jovic、Angelo Gössi、Wolfgang Riedl、Thomas Zich、Sabyasachi Gaan

  DOI：10.1021/acs.oprd.8b00295

  日期：2018.11.16

  and used for this synthesis of DOPO-based phosphonamidates and phosphonates in relatively high yield by reaction with the corresponding amines and alcohols, respectively. The experimental results show that the chlorination reaction occurs in equimolar ratios of Cl2 gas to DOPO compound. Subsequently, the procedure developed in laboratory scale was industrially applied for synthesis of the 6,6′-(ethane-1

  在本文中，我们报告了通过Cl 2气体对9,10-dihydro-9-oxa-10-phosphaphenanthren-10-oxide（DOPO）进行有效而简单的氯化，从而合成了膦酰胺和膦酸酯衍生物的工业合成方法。合成中的关键步骤是通过使Cl 2流动将P–H键转变为DOPO的P–Cl。将其通入DOPO的二氯甲烷溶液中，得到关键的中间体9,10-二氢-9-氧杂-10-磷菲基-10-氯化物（DOPO-Cl）化合物，该化合物在工业上无法获得。分离，表征DOPO-Cl，并通过分别与相应的胺和醇反应，以相对高的产率用于基于DOPO的膦酸酯和膦酸酯的合成。实验结果表明，氯化反应以Cl 2气体与DOPO化合物的等摩尔比进行。随后，将实验室规模开发的方法工业化用于合成6,6'-（乙烷-1,2-二基双（氮杂二基））双（二苯并[ c，e] [1,2]氧杂膦-6-氧化物）（EDA-DOPO）化合物和6-（（1-氧化-2
• [EN] A PROCESS FOR PREPARATION OF DOPO DERIVATIVES<br/>[FR] PROCÉDÉ DE PRÉPARATION DE DÉRIVÉS DOPO
  申请人：METADYNEA AUSTRIA GMBH

  公开号：WO2019002201A1

  公开（公告）日：2019-01-03

  The present invention relates to a process for the preparation of a DOPO derivative DOPO-X comprising a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO moiety and a derivative group X according to formula 1, the process comprising the preparation of a DOPO derivative wherein X = CI comprising the steps; a) providing a solution of DOPO in a solvent, b) introducing chlorine into the DOPO solution whilst maintaining a maximum reaction temperature below 20°C forming DOPO-CI, c) optionally removing volatiles and/or crystallising DOPO-CI, d) optionally further derivatization reaction steps. The invention further relates to DOPO-CI obtainable by the process having high purity, to the use thereof in a process for preparation of further DOPO-derivatives and the high purity products obtained, in particular DOPO-EDA, DOPO-ETA or DOPO-PEPA and the use thereof in polymer composition as flame retardant.

  本发明涉及一种制备DOPO衍生物DOPO-X的方法，其中包括9,10-二氢-9-氧-10-磷杂蒽-10-氧化物DOPO基团和根据式1的衍生基团X的DOPO衍生物的制备过程，该过程包括制备一个DOPO衍生物，其中X = CI，包括以下步骤：a)提供DOPO在溶剂中的溶液，b)在保持最大反应温度低于20°C的情况下向DOPO溶液中引入氯，形成DOPO-CI，c)可选择性地去除挥发物和/或结晶DOPO-CI，d)可选择性地进一步进行衍生反应步骤。该发明还涉及通过该方法获得的高纯度DOPO-CI，以及其在制备进一步的DOPO衍生物和获得的高纯度产品中的用途，特别是DOPO-EDA、DOPO-ETA或DOPO-PEPA以及其在聚合物组合物中作为阻燃剂的用途。