(C6F5)BCl(C6F4P(tBu)2CH2) | 1254122-18-3

• 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: (C6F5)BCl(C6F4P(tBu)2CH2)
• CAS: 1254122-18-3
• 化学式: C₂₁H₂₀BClF₉P
• 分子量: 520.613
• InChiKey: RQDKFXVIYMDMOT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.03
• 重原子数：
  33.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (C6F5)BCl(C6F4P(tBu)2CH2) 在 thallium(I) hexafluorophosphate 作用下， 以 苯 为溶剂， 反应 48.0h， 以45%的产率得到(C6F5)BF(C6F4P(tBu)2CH2)
  参考文献：
  名称：

  Rigid, Fluoroarene-Containing Phosphonium Borates and Boranes: Syntheses and Reactivity Studies

  摘要：

  The reaction of (C6F5)(2)B(OEt) with (Bu2P)-Bu-t(CH2Li) yields the cyclic phosphonium ethoxyborate (C6F5)(OEt)B(CH2)(C6F4)(PBu2)-Bu-t ([1]OEt) via B-C adduct formation and ortho-fluoride substitution. Treatment of [1]OEt with HCl in Et2O gives the chloroborate [1]Cl in almost quantitative yield. The reaction of [1]Cl with Li[AlH4] leads not only to the reduction of the B-Cl bond but also to the selective substitution of one fluorine atom on the tetrafluorophenylene bridge ([4]H). [1]Cl is readily transformed into [1]F, [1]OAc, and [1]OTf upon reaction with Tl[PF6], AgOAc, and AgOTf, respectively (OAc = acetate; OTf = triflate). [1]OTf represents a convenient storage form of [1](+), because its B-O bond is highly labile. The free Lewis acid [1](+) was prepared in the form of its aluminate salt [1](+)[Al((OBuF)-Bu-t)4](-). The phenyl derivative of [1]OEt, (C6H5)(OEt)B(CH2)(C6F4)1)(PBu2)-Bu-t ([5]OEt), is also accessible and serves as starting material for the preparation of [5]Cl and [5](+)[Al((OBuF)-Bu-t)(4)](-).

  DOI：

  10.1021/om100776k
• 作为产物：
  描述：

  (lithiomethyl)bis(tert-butyl)phosphane 在 盐酸 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 48.0h， 生成 (C6F5)BCl(C6F4P(tBu)2CH2)
  参考文献：
  名称：

  Rigid, Fluoroarene-Containing Phosphonium Borates and Boranes: Syntheses and Reactivity Studies

  摘要：

  The reaction of (C6F5)(2)B(OEt) with (Bu2P)-Bu-t(CH2Li) yields the cyclic phosphonium ethoxyborate (C6F5)(OEt)B(CH2)(C6F4)(PBu2)-Bu-t ([1]OEt) via B-C adduct formation and ortho-fluoride substitution. Treatment of [1]OEt with HCl in Et2O gives the chloroborate [1]Cl in almost quantitative yield. The reaction of [1]Cl with Li[AlH4] leads not only to the reduction of the B-Cl bond but also to the selective substitution of one fluorine atom on the tetrafluorophenylene bridge ([4]H). [1]Cl is readily transformed into [1]F, [1]OAc, and [1]OTf upon reaction with Tl[PF6], AgOAc, and AgOTf, respectively (OAc = acetate; OTf = triflate). [1]OTf represents a convenient storage form of [1](+), because its B-O bond is highly labile. The free Lewis acid [1](+) was prepared in the form of its aluminate salt [1](+)[Al((OBuF)-Bu-t)4](-). The phenyl derivative of [1]OEt, (C6H5)(OEt)B(CH2)(C6F4)1)(PBu2)-Bu-t ([5]OEt), is also accessible and serves as starting material for the preparation of [5]Cl and [5](+)[Al((OBuF)-Bu-t)(4)](-).

  DOI：

  10.1021/om100776k

文献信息

• Cyclic Phosphonium Bis(fluoroaryl)boranes – Trends in Lewis Acidities and Application in Diels–Alder Catalysis
  作者：Anna Schnurr、Michael Bolte、Hans‐Wolfram Lerner、Matthias Wagner

  DOI：10.1002/ejic.201101098

  日期：2012.1

  lengths than those in the corresponding adducts (C6F5)3B·Do. Both the free Lewis acid [1][Al(O(tBuF))4] and its triflate adduct (1)OTf have successfully been employed as catalysts for the [4+2] cycloaddition reaction between 2,5-dimethyl-1,4-benzoquinone and cyclopentadiene. Moreover, we have shown that chiral phosphonium boranes are accessible by replacement of one tBu group in [1]+ by a Me substituent

  刚性环状路易斯酸 [(C6F5)B(CH2)(C6F4)P(tBu)2]+ ([1]+), [( )B( )(C6F3H)P(tBu)2]+ ([ 2]+) 和 [(C6H5)B( )( )P(tBu)2]+ ([3]+) 的古特曼受体数分别为 AN = 87.3、85.7 和 85.7，其中有机硼烷最高。从 (1)OTf 开始，加合物 [(1)Do][OTf]（Do = OPEt3，吡啶，H2O）已被制备并充分表征。在所有三种情况下，X 射线晶体学显示 B-O/N 键长明显短于相应的加合物 ( )3B·Do。游离路易斯酸 [1][Al(O(tBuF))4] 及其三氟甲磺酸酯加合物 (1)OTf 已成功用作 2,5-二甲基-1 之间 [4+2] 环加成反应的催化剂， 4-苯醌和环戊二烯。而且，我们已经证明手性鏻硼烷可以通过用 Me 取代基替换 [1]+ 中的一个 tBu
• CC Coupling by Thermolysis of Alkynyl Phosphonium Borates
  作者：Xiaoxi Zhao、Thomas M. Gilbert、Douglas W. Stephan

  DOI：10.1002/chem.201001575

  日期：2010.9.10

  When the heat is on, alkynyl phosphonium borates, tBu2PHCCBH(C6F5)2 and (tBu2PCCB(C6F5)2)(BuCH2CH)(tBu2PCCB(C6F5)2), undergo CC coupling reactions leading to a C4 alkene derivative, (tBu2PCHBF(C6F4)(C6F5)CH)2, and a cumulene derivative, (tBu2P)C6F4BF(C6F5)C4B(C6F5)2(BuCH2CH)(PtBu2), respectively (see figure).

  当热是上，炔基鏻硼酸盐，吨卜2 PHCCBH（C 6 ˚F 5）2和（吨卜2 PCCB（C 6 ˚F 5）2）（布赫2 CH）（吨卜2 PC CB（C 6 F 5）2），经历CC偶联反应，生成C 4烯烃衍生物，（t Bu 2 PCHBF（C 6 F 4）（C 6 F 5）CH）2和异丙苯衍生物（t Bu 2 P）C 6 F 4 BF（C 6 F 5）C 4 B（C 6 F 5）2（BuCH 2 CH）（P t Bu 2）分别（见图）。