6-ethoxy-6H-dibenzo[c,e][1,2]oxaphosphinine | 194091-96-8

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 6-ethoxy-6H-dibenzo[c,e][1,2]oxaphosphinine
• 英文别名: 6-ethoxy-(6H)-dibenzo[c,e][1,2]oxaphosphorine；6-ethoxybenzo[c][2,1]benzoxaphosphinine
• CAS: 194091-96-8
• 化学式: C₁₄H₁₃O₂P
• 分子量: 244.23
• InChiKey: CFEIEZNFRVWPLE-UHFFFAOYSA-N

物化性质

• 熔点：
  42 °C
• 沸点：
  135-142 °C(Press: 0.08 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  6-ethoxy-6H-dibenzo[c,e][1,2]oxaphosphinine 在 对甲苯磺酸甲酯 作用下， 120.0~175.0 ℃ 、999.92 Pa 条件下， 反应 24.0h， 生成 10-octadecyl-9-oxa-10-phosphaphenanthrene-10-oxide
  参考文献：
  名称：

  A Novel and Effective Synthetic Approach to 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) Derivatives

  摘要：

  DOPO and its derivatives generally exhibit an outstanding performance as flame retardants in various polymers. Starting from trivalent 10-alkoxy-10H-9-oxa-10-phosphaphenanthrenes, a broad range of DOPO derivatives was synthesized via transesterification with aliphatic alcohols and subsequent Michaelis-Arbuzou rearrangement using catalytic amounts of p-toluenesulfonic acid methylester. Due to the considerable differences in the nature of the alcohols employed, several procedures for processing them are presented.

  DOI：

  10.1080/10426500701407417
• 作为产物：
  描述：

  10-氯-9,10-二氢-9-氧杂-10-磷杂菲 以 乙醇 、 氨 、 甲苯 为溶剂， 生成 6-ethoxy-6H-dibenzo[c,e][1,2]oxaphosphinine
  参考文献：
  名称：

  Process for preparing 6-alkoxy-(6H)-dibenzo\x9bC,E!\x9b1,2!-oxaphosphorines

  摘要：

  该发明涉及一种制备式(I)的6-烷氧基-(6H)-二苯并[b,c,e][1,2]-氧代磷杂环戊烷的方法，其中R^1至R^6独立地为卤素、(C1-C6)烷基或(C1-C6)烷氧基，R^7为(C1-C8)烷基，包括将式(II)的6-卤代-(6H)-二苯并[b,c,e][1,2]-氧代磷杂环戊烷加入醇R^7 OH，其中R^7具有上述给定的含义，温度为-30°C至+5°C，然后在此温度下引入氨。

  公开号：

  US05698729A1

文献信息

• Multinuclear NMR Studies and Spin System Analyses on Dibenzo[c.e][1,2]Oxaphosphorine 2-Oxides
  作者：Zoltán Szakács、Gerhard Hägele、Miklós Dékány、Péter Ábrányi-Balogh、György Keglevich

  DOI：10.1002/hc.21313

  日期：2016.5

  characterized in CDCl3 by 1H, 13C, 31P, and 15N NMR spectroscopy on 800- and 500-MHz instruments. A strategy enabling their unambiguous signal assignment is presented, with special emphasis on 2D 1H,13C HMBC spectra. Additional line-shape iterations of the aromatic 1H multiplets (ABCDX and ABCDEX spin systems) provided all long-range nJH,H and nJP,H coupling constants with utmost precision. The experimental

  2H-二苯并[ce][1,2]氧杂磷2-氧化物(HDOPO)、2-(N,N-二乙氨基)-二苯并[ce][1,2]氧杂磷2-氧化物(DEADOPO)和2-乙氧基-dibenzo[ce][1,2]oxaphosphorine 2-oxide (EtODOPO) 在 CDCl3 中通过 1H、13C、31P 和 15N NMR 光谱在 800-和 500-MHz 仪器上得到充分表征。提出了一种能够明确信号分配的策略，特别强调 2D 1H,13C HMBC 光谱。芳香族 1H 多重峰（ABCDX 和 ABCDEX 自旋系统）的附加线形迭代提供了所有长程 nJH,H 和 nJP,H 耦合常数，精度最高。用模型化合物苯基亚膦酸的实验结果增强的实验结果清楚地表明，PH 质子和 nJP 的 nJH,H 耦合，C 值不会随着来自磷原子的中间键的数量而单调下降。如果分析从耦合常数开始，这一事实可能会导致信号错误分配，正如
• Silver-Catalyzed Regioselective Phosphorylation of <i>para</i>-Quinone Methides with P(III)-Nucleophiles
  作者：Shipan Xu、Jun Xie、Yu Liu、Weifeng Xu、Ke-Wen Tang、Biquan Xiong、Wai-Yeung Wong

  DOI：10.1021/acs.joc.1c01703

  日期：2021.11.5

  Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)–P bonds in Michaelis–Arbuzov-type reactions.

  P(III)-亲核试剂 (P(OR) 3 , ArP(OR) 2 , Ar 2 P-OR)银催化对醌甲基化物 ( p -QMs )区域选择性磷酸化的简单有效方法通过 Michaelis-Arbuzov 型反应建立。在温和条件下，广泛的 P(III)-亲核试剂和对-醌甲基化物具有良好的耐受性，从而得到预期的二芳基甲基取代的有机磷化合物，具有良好的产率。此外，以二烷基芳基亚膦酸酯(ArP(OR) 2 )为底物，可以得到一系列相应的对映异构体。对照实验和31还进行了 P NMR 跟踪实验以深入了解可能的反应机制。该协议可能对Michaelis-Arbuzov 型反应中 C( sp 3 )-P 键的形成具有重要意义。
• Novel N-phosphorylated iminophosphoranes based on 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  作者：Michael Weinert、Olaf Fuhr、Manfred Döring

  DOI：10.24820/ark.5550190.p010.704

  日期：——

  A series of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-based N-phosphorylated iminophosphoranes was synthesized utilizing Atherton-Todd and subsequently Staudinger reactions. The structures of these iminophosphoranes were revealed by nuclear magnetic resonance spectroscopy and X-ray crystallography. The decomposition properties were determined by thermogravimetric analysis and indicate a relationship

  利用 Atherton-Todd 和随后的 Staudinger 反应合成了一系列基于 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 的 N-磷酸化亚氨基膦。这些亚氨基膦的结构通过核磁共振光谱和 X 射线晶体学揭示。分解特性通过热重分析确定，表明磷原子周围的化学环境与相应化合物的热稳定性之间存在关系。
• Proces for the preparation of 9, 10-dihydro-9-oxa-10-organylphosphaphenanthrene-10-oxide and derivatives of the same substituted on the phenyl groups
  申请人：Dittrich Uwe

  公开号：US20050038279A1

  公开（公告）日：2005-02-17

  A process is provided for the preparation of 9,10-dihydro-9-oxa-10-organylphosphaphenanthrene-10-oxide and derivatives of same substituted on the phenyl groups, in which: (a) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOP) or a derivative of same is reacted in the presence of at least one mono- or polyhydric alcohol with at least one ortho ester with formation of a first intermediate product, (b) the intermediate product from step (a) is optionally reacted with at least one further mono- or polyhydric alcohol with formation of a further intermediate product and (c) the intermediate product from steps (a) or (b) is transformed by addition of catalytic quantities of alkylation agent into 9,10-dihydro-9-oxa-10-organylphosphaphenanthrene-10-oxide or a derivative of same substituted on the phenyl groups.

  提供了一种制备9,10-二氢-9-氧-10-有机磷酚蒽-10-氧化物及其苯基取代物的方法，其中：(a) 在至少一种单醇或多元醇的存在下，将9,10-二氢-9-氧-10-磷酚蒽-10-氧化物（DOP）或其衍生物与至少一种正酯反应，形成第一中间产物，(b) 可选地将步骤(a)中的中间产物与至少一种进一步的单醇或多元醇反应，形成进一步的中间产物，(c) 通过添加催化剂量的烷基化剂将步骤(a)或(b)中的中间产物转化为9,10-二氢-9-氧-10-有机磷酚蒽-10-氧化物或其苯基取代物。
• Copper-Catalyzed Aerobic Oxidative/Decarboxylative Phosphorylation of Aryl Acrylic Acids with P(III)-Nucleophiles
  作者：Biquan Xiong、Lulu Si、Longzhi Zhu、Yu Liu、Weifeng Xu、Ke-Wen Tang、Shuang-Feng Yin、Peng-Cheng Qian、Wai-Yeung Wong

  DOI：10.1021/acs.joc.3c01238

  日期：2023.9.1

  A copper-catalyzed aerobic oxidative/decarboxylative phosphorylation of aryl acrylic acids with P(III)-nucleophiles via the Michaelis–Arbuzov rearrangement for the synthesis of β-ketophosphine oxides, β-ketophosphinates, and β-ketophosphonates is reported. The present reaction could be conducted effectively without the use of a ligand and a base. Various kinds of aryl acrylic acids and P(III)-nucleophiles

  据报道，通过Michaelis-Arbuzov 重排，铜催化芳基丙烯酸与 P(III)-亲核试剂发生有氧氧化/脱羧磷酸化，合成β-酮膦氧化物、β-酮次膦酸盐和 β-酮膦酸盐。本反应可以在不使用配体和碱的情况下有效地进行。各种芳基丙烯酸和 P(III)-亲核试剂在转化过程中均可耐受，生成所需的 β-酮基有机磷化合物，作为一类有价值的含磷中间体，且收率良好至优异。此外，通过逐步控制实验和竞争实验探索了该反应可能的机理和动力学研究，结果证明该转变可能遵循二级化学动力学，并且涉及自由基过程。