1-(trimethylsilyl)-3,5-bis[(dimethylamino)methyl]benzene | 184651-95-4

• 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: 1-(trimethylsilyl)-3,5-bis[(dimethylamino)methyl]benzene
• 英文别名: 1-[3-[(dimethylamino)methyl]-5-trimethylsilylphenyl]-N,N-dimethylmethanamine
• CAS: 184651-95-4
• 化学式: C₁₅H₂₈N₂Si
• 分子量: 264.486
• InChiKey: JYEDMHWWATUDFA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.36
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  NiCl₂(PEt₃)₂ 、 1-(trimethylsilyl)-3,5-bis[(dimethylamino)methyl]benzene 在 t-C₄H₉Li 作用下， 以 正己烷 为溶剂， 以61%的产率得到
  参考文献：
  名称：

  A “Dendritic Effect” in Homogeneous Catalysis with Carbosilane-Supported Arylnickel(II) Catalysts:  Observation of Active-Site Proximity Effects in Atom-Transfer Radical Addition

  摘要：

  Transmetalation of polylithiated, carbosilane (CS) dendrimers functionalized with the potentially terdentate ligand [C6H2(CH2NMe2)(2)-2,6-R-4](-) ( NCN) with NiCl2(PEt3)(2) produced a series of nickel-containing dendrimers [GO]-N-4 (4), [G1]-Ni-12 (5), and [G2]-Ni-36 (7) in moderate to good yields. The metallodendrimers 4, 5, and 7 are catalytically active in the atom-transfer radical addition (ATRA) reaction (Kharasch addition reaction), viz. the 1:1 addition of CCl4 to methyl methacrylate (MMA). The catalytic data were compared to those obtained for the respective mononuclear compound [NiCl(C6H2{CH2NMe2}(2)-2,6-SiMe3-4)] (2). This comparison indicates a fast deactivation for the dendrimer catalysts beyond generation [GO]. The deactivation of [G1]-Ni-12 (5) and [G2]-Ni-36 (7) is caused by irreversible formation of catalytically inactive Ni(III) sites on the periphery of these dendrimers. This hypothesis is supported by results of model studies as well as ESR spectroscopic investigations. Interestingly, the use of two alternative nickelated [G1] dendrimers [G1]*-Ni-12 (11) and [G1]-Ni-8 (15), respectively, in which the distance between the Ni sites is increased, leads to significantly improved catalytic efficiencies which approximate those of the parent derivative 2 and [GO]-Ni-4 (4). Preliminary membrane catalysis experiments with [GO]-Ni-4 (4) and [G1]-Ni-12 (5) show that 5 can be efficiently retained in a membrane reactor system. The X-ray crystal structure of the Ni(III) complex [NiCl2(C6H2{CH2NMe2}(2)-2,6-SiMe3-4)] (16), obtained from the reaction of 2 with CCl4, is also reported.

  DOI：

  10.1021/ja0026612
• 作为产物：
  描述：

  三甲基氯硅烷 、 1-bromo-3,5-bis[(dimethylamino)methyl]benzene 在 叔丁基锂 作用下， 以 乙醚 为溶剂， 生成 1-(trimethylsilyl)-3,5-bis[(dimethylamino)methyl]benzene
  参考文献：
  名称：

  A “Dendritic Effect” in Homogeneous Catalysis with Carbosilane-Supported Arylnickel(II) Catalysts:  Observation of Active-Site Proximity Effects in Atom-Transfer Radical Addition

  摘要：

  Transmetalation of polylithiated, carbosilane (CS) dendrimers functionalized with the potentially terdentate ligand [C6H2(CH2NMe2)(2)-2,6-R-4](-) ( NCN) with NiCl2(PEt3)(2) produced a series of nickel-containing dendrimers [GO]-N-4 (4), [G1]-Ni-12 (5), and [G2]-Ni-36 (7) in moderate to good yields. The metallodendrimers 4, 5, and 7 are catalytically active in the atom-transfer radical addition (ATRA) reaction (Kharasch addition reaction), viz. the 1:1 addition of CCl4 to methyl methacrylate (MMA). The catalytic data were compared to those obtained for the respective mononuclear compound [NiCl(C6H2{CH2NMe2}(2)-2,6-SiMe3-4)] (2). This comparison indicates a fast deactivation for the dendrimer catalysts beyond generation [GO]. The deactivation of [G1]-Ni-12 (5) and [G2]-Ni-36 (7) is caused by irreversible formation of catalytically inactive Ni(III) sites on the periphery of these dendrimers. This hypothesis is supported by results of model studies as well as ESR spectroscopic investigations. Interestingly, the use of two alternative nickelated [G1] dendrimers [G1]*-Ni-12 (11) and [G1]-Ni-8 (15), respectively, in which the distance between the Ni sites is increased, leads to significantly improved catalytic efficiencies which approximate those of the parent derivative 2 and [GO]-Ni-4 (4). Preliminary membrane catalysis experiments with [GO]-Ni-4 (4) and [G1]-Ni-12 (5) show that 5 can be efficiently retained in a membrane reactor system. The X-ray crystal structure of the Ni(III) complex [NiCl2(C6H2{CH2NMe2}(2)-2,6-SiMe3-4)] (16), obtained from the reaction of 2 with CCl4, is also reported.

  DOI：

  10.1021/ja0026612

文献信息

• Carbosilane Molecules with Mono- and Bis(amino)arylmetal End Groups:  Structures of {NiI[C₆H₂(CH₂NMe₂)₂-2,6-SiMe₃-4]} and Tetranuclear {[CH₂Si(Me)₂C₆H₃(CH₂NMe₂)-4-(PdCl)-3]₂}₂
  作者：Arjan W. Kleij、Henk Kleijn、Johann T. B. H. Jastrzebski、Anthony L. Spek、Gerard van Koten

  DOI：10.1021/om980758f

  日期：1999.1.1

  synthetic approaches have also been applied to the (N)CN-substituted carbosilane ligand systems [CH2Si(Me)2C6H3(CH2NMe2)2-3,5]2 and [CH2Si(Me)2C6H4(CH2NMe2)-4]2 to give the bismetalated species [CH2Si(Me)2C6H2(CH2NMe2)2-3,5-(MX)-4]2 (MX = PdCl (9), PtCl (10), PdI (12)) and [CH2Si(Me)2C6H3(CH2NMe2)-4-(PdCl)-3]2 (13) in good yields. The molecular structures of 5 and bispalladated 13 have been determined

  设计了一组模型化合物，以开发有用的合成路线，以新颖的树状碳硅烷分子用衍生自单阴离子[C 6 H 3（CH 2 NMe 2）2 -2,6] -（= NCN）的有机金属配合物官能化和[C 6 H 4（CH 2 NMe 2）-2] -（= CN）配体。两者的[C 6 H 2（CH 2 NMe 2）2 -2,6-（SiMe 3）2 -1,4]的选择性亲电合（1）和[C 6 H 4（CH 2 NMe 2）-4-SiMe 3 -1]（6）和Pd（OAc）2使用，在加入LiCl之后，得到[PdCl（C 6 H 2 CH 2 NMe 2 } 2 -2,6-SiMe 3 -4）]（2）和二聚体[PdCl（C 6 H 3 CH 2 NMe 2 } -2-SiMe 3 -5）] 2（7），分别为98％和产率84％。[C 6 H 3（CH 2NMe 2）2 -3,5-SiMe 3 -1]，然后在室温下使用1当量的PtCl