fluoren-9-ylphosphonic dichloride | 169053-46-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: fluoren-9-ylphosphonic dichloride
• 英文别名: 9-fluorenylphosphonic dichloride；9-dichlorophosphoryl-9H-fluorene
• CAS: 169053-46-7
• 化学式: C₁₃H₉Cl₂OP
• 分子量: 283.094
• InChiKey: GQHJRUHFCQZZNX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  fluoren-9-ylphosphonic dichloride 在 tetraphosphorus decasulfide 、 N,N-二甲基甲酰胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 N-[diethylamino(9H-fluoren-9-yl)phosphinothioyl]-N-ethylethanamine
  参考文献：
  名称：

  Relative Ease of Formation of Alkylidine(oxo and thioxo)phosphorane Intermediates in Nucleophilic Substitution at Phosphonyl and Thiophosphonyl Centres

  摘要：

  R2CHP(X)(NEt2)Cl（R2CH=9-荧蒽基）通过中间体R2CP(X)NEt2（消除-加成机制）转化为R2CHP(X)(NEt2)2时，当X=S时，反应速度远快于X=O的情况。

  DOI：

  10.1039/a802407c
• 作为产物：
  描述：

  9-溴芴 在 三氯化铝 、 三氯化磷 作用下， 以 二氯甲烷 为溶剂， 生成 fluoren-9-ylphosphonic dichloride
  参考文献：
  名称：

  烷基膦酰基亲核取代反应，通过消除加成机理与亚烷基氧代膦基膦（膦）中间体进行

  摘要：

  对于具有R 2 CH = 9-芴基的膦酰氯氯化物R 2 CHP（O）（NEt 2）Cl，用Et 2 NH作为亲核试剂，磷的取代出乎意料地快，并且与竞争的Me 2 NH和Et 2 NH亲核试剂；这样的行为与消除加成机理和芴基氧代次膦酸酯中间体8是一致的。

  DOI：

  10.1039/c39950001701

文献信息

• An alkylphosphonyl nucleophilic substitution reaction that proceeds by an elimination–addition mechanism with an alkylidineoxophosphorane (phosphene) intermediate
  作者：Martin J. P. Harger、Barbara T. Hurman

  DOI：10.1039/c39950001701

  日期：——

  For the phosphonamidic chloride R2CHP(O)(NEt2) Cl having R2CH = 9-fluorenyl, substitution at phosphorus is unexpectedly fast with Et2NH as the nucleophile, and discriminates less than is usual between competing Me2NH and Et2NH nucleophiles; such behaviour is consistent with an elimination-addition mechanism and a fluorenylidineoxophosphorane intermediate 8.

  对于具有R 2 CH = 9-芴基的膦酰氯氯化物R 2 CHP（O）（NEt 2）Cl，用Et 2 NH作为亲核试剂，磷的取代出乎意料地快，并且与竞争的Me 2 NH和Et 2 NH亲核试剂；这样的行为与消除加成机理和芴基氧代次膦酸酯中间体8是一致的。
• The elimination–addition mechanism of nucleophilic substitution at an alkylphosphonyl centre: stereospecificity, non-stereospecificity and the alkylidineoxophosphorane (phosphene) intermediate
  作者：Martin J. P. Harger、Deborah K. Jones

  DOI：10.1039/a809407a

  日期：——

  The substitution reactions of R′2CHP(O)(NMeR*)Cl (R′2CH = fluoren-9-yl; R* = CHMePh) with secondary amines (Me2NH, Et2NH, PriNHEt) are largely stereospecific or non-stereospecific depending on the bulk of the amine and its concentration; two elimination–additon pathways, differing in whether or not the phosphene intermediate R′2CP(O)NMeR* becomes liberated, may be responsible.

  R²2CHP(O)(NMeR*)Cl（R²2CH = 芴-9-基；R* = CHMePh）与仲胺（Me2NH、Et2NH、PriNHEt）的取代反应主要是立体特异性或非立体特异性的，这取决于胺的主体及其浓度；可能有两种消除和加成途径，这两种途径的区别在于是否会释放出磷烯中间体 R²2CP(O)NMeR*。
• Relative Ease of Formation of Alkylidine(oxo and thioxo)phosphorane Intermediates in Nucleophilic Substitution at Phosphonyl and Thiophosphonyl Centres
  作者：Caroline D. Cox、Martin J. P. Harger

  DOI：10.1039/a802407c

  日期：——

  The conversion of R2CHP(X)(NEt2)Cl (R2CH=9-fluorenyl) into R2CHP(X)(NEt2)2via the intermediate R2CP(X)NEt2 (elimination–addition mechanism) is much faster when X=S than when X=O.

  R2CHP(X)(NEt2)Cl（R2CH=9-荧蒽基）通过中间体R2CP(X)NEt2（消除-加成机制）转化为R2CHP(X)(NEt2)2时，当X=S时，反应速度远快于X=O的情况。
• Elimination–addition with alkylidineoxophosphorane (phosphene) intermediates in nucleophilic substitution at PO centres: fluoren-9-ylphosphonamidic chlorides with amine nucleophiles 1
  作者：Martin J. P. Harger、Barbara T. Hurman

  DOI：10.1039/a800683k

  日期：——

  Compared with Me2CHP(O)(NEt2)Cl, the fluorenyl compound R2CHP(O)(NEt2)Cl (R2CH = fluoren-9-yl) shows remarkably high reactivity in nucleophilic substitution with Et2NH. Substitution is catalysed by base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)} and shows little discrimination between competing Me2NH and Et2NH. These characteristics point to an elimination–addition (EA) mechanism with a reactive phosphene intermediate [R2CP(O)NEt2]. When Et2ND is the nucleophile, H–D exchange at the α carbon atom occurs much more quickly than substitution. This suggests that the elimination stage of the EA mechanism is reversible E1cB.

  与 Me2CHP(O)(NEt2)Cl 相比，芴基化合物 R2CHP(O)(NEt2)Cl （R2CHÂ =Â fluoren-9-yl）在与 Et2NH 的亲核取代中显示出极高的反应活性。在碱 1,8-二氮杂双环[5.4.0]十一-7-烯（DBU）} 的催化下进行置换，在竞争的 Me2NH 和 Et2NH 之间几乎没有区别。这些特征表明，这种消去加成（EA）机理带有一个活性磷烯中间体[R2CP(O)NEt2]。当 Et2ND 为亲核体时，δ 碳原子上的 HâD 交换发生得比取代快得多。这表明 EA 机制的消去阶段是可逆的 E1cB。