tris(2,6-difluorophenyl)phosphine | 21041-54-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tris(2,6-difluorophenyl)phosphine
• 英文别名: tris(2,6-difluorophenyl)phosphane
• CAS: 21041-54-3
• 化学式: C₁₈H₉F₆P
• 分子量: 370.234
• InChiKey: CTXPXQLWCUNCNP-UHFFFAOYSA-N

物化性质

• 沸点：
  357.5±42.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  tris(2,6-difluorophenyl)phosphine 在 双氧水 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 2.0h， 生成
  参考文献：
  名称：

  使用氧化膦和受阻路易斯对催化氢化仲酰胺

  摘要：

  开发了仲羧酸酰胺的无金属催化加氢。还原是通过两个新的催化反应实现的。首先，使用新型磷 (V) 催化剂，通过三光气 (CO(OCCl 3 ) 2 )将酰胺转化为亚氨酰氯。其次，原位生成的亚氨酰氯被 FLP 催化剂以高产率氢化。机械和量子力学计算支持氢化的自诱导催化循环，其中氯化物充当不寻常的路易斯碱，用于 FLP 介导的 H 2活化。

  DOI：

  10.1002/chem.202100041
• 作为产物：
  描述：

  1,3-二氟苯 在 正丁基锂 、 三氯化磷 作用下， 以 四氢呋喃 为溶剂， 反应 14.33h， 以31%的产率得到tris(2,6-difluorophenyl)phosphine
  参考文献：
  名称：

  Aryne-Induced S_NAr/Dearylation Strategy for the Synthesis of Fluorinated Dibenzophospholes from Triarylphosphines via a P(V) Intermediate

  摘要：

  We report on a method for the synthesis of fluorinated dibenzophospholes using triarylphosphine via dearylative annulation with an aryne. This intermolecular annulation allows the preparation of a variety of fluorinated dibenzophospholes from simple building blocks. The key to the success of this dearylative annulation is the formation of a five-coordinated tetraarylfluorophosphorane. In this work, we successfully synthesized stable tetraarylfluorophosphorane, the structure of which was unambiguously determined by X-ray crystallography.

  DOI：

  10.1021/acs.orglett.0c00489

文献信息

• Structural and electronic impact of fluorine in the ortho positions of triphenylphosphine and 1,2-bis(diphenylphosphino)ethane; a comparison of 2,6-difluorophenyl- with pentafluorophenyl-phosphines
  作者：Christopher Corcoran、John Fawcett、Steffi Friedrichs、John H. Holloway、Eric G. Hope、David R. Russell、Graham C. Saunders、Alison M. Stuart

  DOI：10.1039/a907759f

  日期：——

  The new fluorine-containing phosphines PPh2(C6H3F2-2,6) I and PPh(C6H3F2-2,6)2 II were synthesized in high yield from C6H3BrF2-2,6 and PPh2Cl or PPhCl2. Phosphines I, II and the previously reported P(C6H3F2-2,6)3 III have been structurally characterized by single-crystal X-ray diffraction. A range of transition metal complexes of IIII and the diphosphine (C6H3F2-2,6)2PCH2CH2P(C6H3F2-2,6)2 have been prepared and their spectroscopic properties compared with those of the analogous complexes of the pentafluorophenylphosphines PPhx(C6F5)3  x (x = 02) and the diphosphine (C6F5)2PCH2CH2P(C6F5)2. The structures of trans-[PtCl2(PEt3)PPhx(C6H3F2-2,6)3  x}] (x = 2, 1 or 0), trans-[MCl(CO)PPh(C6H3F2-2,6)2}2] (M = Rh or Ir), trans-[IrCl(CO)P(C6H3F2-2,6)3}2] and trans-[PtCl2PPh(C6H3F2-2,6)2}2] have been determined by single-crystal X-ray diffraction. The spectroscopic and structural data indicate that the 2,6-difluorophenylphosphines are more basic than the analogous pentafluorophenylphosphines and exert a similar or slightly smaller steric influence.

  以 C6H3BrF2-2,6 和 PPh2Cl 或 PPhCl2 为原料，高产合成了新的含氟膦 PPh2(C6H3F2-2,6) I 和 PPh(C6H3F2-2,6)2 II。膦 I、膦 II 和之前报道的 P(C6H3F2-2,6)3 III 已通过单晶 X 射线衍射获得了结构特征。制备了 IIII 和二膦 (C6H3F2-2,6)2PCH2CH2P(C6H3F2-2,6)2 的一系列过渡金属配合物，并将它们的光谱特性与五氟苯基膦 PPhx(C6F5)3 x (x = 02) 和二膦 (C6F5)2PCH2CH2P(C6F5)2 的类似配合物的光谱特性进行了比较。反式-[PtCl2(PEt3)PPhx(C6H3F2-2,6)3 x}]（x = 2、1 或 0）、反式-[MCl(CO)PPh(C6H3F2-2,6)2}2]（M = Rh 或 Ir）的结构、通过单晶 X 射线衍射测定了反式[IrCl(CO)P(C6H3F2-2,6)3}2]和反式[PtCl2PPh(C6H3F2-2,6)2}2]。光谱和结构数据表明，2,6-二氟苯基膦比类似的五氟苯基膦碱性更强，并且具有类似或稍小的立体影响。
• Hydrogenation of Secondary Amides using Phosphane Oxide and Frustrated Lewis Pair Catalysis
  作者：Laura Köring、Nikolai A. Sitte、Markus Bursch、Stefan Grimme、Jan Paradies

  DOI：10.1002/chem.202100041

  日期：2021.10.13

  The metal-free catalytic hydrogenation of secondary carboxylic acid amides is developed. The reduction is realized by two new catalytic reactions. First, the amide is converted into the imidoyl chloride by triphosgene (CO(OCCl3)2) using novel phosphorus(V) catalysts. Second, the in situ generated imidoyl chlorides are hydrogenated in high yields by an FLP-catalyst. Mechanistic and quantum mechanical

  开发了仲羧酸酰胺的无金属催化加氢。还原是通过两个新的催化反应实现的。首先，使用新型磷 (V) 催化剂，通过三光气 (CO(OCCl 3 ) 2 )将酰胺转化为亚氨酰氯。其次，原位生成的亚氨酰氯被 FLP 催化剂以高产率氢化。机械和量子力学计算支持氢化的自诱导催化循环，其中氯化物充当不寻常的路易斯碱，用于 FLP 介导的 H 2活化。
• Aryne-Induced S_NAr/Dearylation Strategy for the Synthesis of Fluorinated Dibenzophospholes from Triarylphosphines via a P(V) Intermediate
  作者：Hayato Fujimoto、Momoka Kusano、Takuya Kodama、Mamoru Tobisu

  DOI：10.1021/acs.orglett.0c00489

  日期：2020.3.20

  We report on a method for the synthesis of fluorinated dibenzophospholes using triarylphosphine via dearylative annulation with an aryne. This intermolecular annulation allows the preparation of a variety of fluorinated dibenzophospholes from simple building blocks. The key to the success of this dearylative annulation is the formation of a five-coordinated tetraarylfluorophosphorane. In this work, we successfully synthesized stable tetraarylfluorophosphorane, the structure of which was unambiguously determined by X-ray crystallography.