(2-allyloxy-3-tert-butyl-5-methylphenyl)(2,7-di-tert-butylfluoren-9-yl)dimethylsilane | 903512-51-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: (2-allyloxy-3-tert-butyl-5-methylphenyl)(2,7-di-tert-butylfluoren-9-yl)dimethylsilane
• 英文别名: (3-tert-butyl-5-methyl-2-prop-2-enoxyphenyl)-(2,7-ditert-butyl-9H-fluoren-9-yl)-dimethylsilane
• CAS: 903512-51-6
• 化学式: C₃₇H₅₀OSi
• 分子量: 538.889
• InChiKey: XNYFDBWJIGXCQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.72
• 重原子数：
  39
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2-allyloxy-3-tert-butyl-5-methylphenyl)(2,7-di-tert-butylfluoren-9-yl)dimethylsilane 在 正丁基锂 、 四氯化钛 、 三乙胺 作用下， 以 正己烷 、 甲苯 为溶剂， 以0.371 g的产率得到2',7,7'-Tritert-butyl-3,3,5-trimethylspiro[1,3-benzoxasilole-2,9'-fluorene]
  参考文献：
  名称：

  Rational Design of Silicon-Bridged Fluorenyl−Phenoxy Group 4 Metal Complexes as Catalysts for Producing High Molecular Weight Copolymers of Ethylene and 1-Hexene at Elevated Temperature

  摘要：

  For producing high molecular weight copolymers of ethylene and I-hexene, a series of silicon-bridged fluorenyl-phenoxy group 4 complexes R2Si(Flu)(3-'Bu-5-Me-2-C6H2O)MCl2 (4a: M = Ti; R = Me; Flu = fluoren-9-yl; 4b: M = Ti; R = Et; Flu = fluoren-9-yl; 4c: M = Ti; R Me; Flu = 2,7-'Bu-2-fluoren-9-yl; 4d: M = Ti; R = Et; Flu = 2,7-'Bu-2-fluoren-9-yl; 8: M = Zr; R Me; Flu 2,7-'Bu-2-fluoren-9-yl; 9: M = Hf; R = Me; Flu = 2,7-'Bu-2-fluoren-9-yl) were prepared by two methods. One was a reaction of MCl4 (M = Ti, Zr, and Ho with the dilithium salts generated by treating corresponding ligands 1a-d with "BuLi in the presence of Et3N in toluene and the other used MCl2(NR'(2))(2) (6a: M = Ti; R' = Me, 6b: M = Zr; R' = Et, 6c: M = Hf, R' = Me) instead of MCl4 followed by successive chlorination with Me3SiCl. X-ray crystallographic study of 4d indicated that the cyclopentadienyl moiety of the fluorenyl ligand is bound to the titanium atom in a fashion between eta(3) and eta(5). The newly prepared titanium Complexes 4a-d exhibited high catalytic activities for copolymerization of ethylene and 1-hexene in the presence of 'Bu3Al/[Me3NHPh][B(C6F5)(4)] and afforded higher molecular weight copolymers than the parent tetramethyl-substituted cyclopentadienyl titanium complex Me2Si(eta(5)-C5Me4)(3-'Bu-5-Me-2-C6H2O)TiCl2 (10). In particular, the active species generated from complex 4d was thermally stable and exhibited high polymerization activities even at 210 degrees C and produced high molecular weight copolymers with good 1-hexene content.

  DOI：

  10.1021/ma902700v
• 作为产物：
  描述：

  [2-(allyloxy)-3-tert-butyl-5-methylphenyl](chloro)dimethylsilane 、 2,7-二叔丁基芴 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 生成 (2-allyloxy-3-tert-butyl-5-methylphenyl)(2,7-di-tert-butylfluoren-9-yl)dimethylsilane
  参考文献：
  名称：

  Rational Design of Silicon-Bridged Fluorenyl−Phenoxy Group 4 Metal Complexes as Catalysts for Producing High Molecular Weight Copolymers of Ethylene and 1-Hexene at Elevated Temperature

  摘要：

  For producing high molecular weight copolymers of ethylene and I-hexene, a series of silicon-bridged fluorenyl-phenoxy group 4 complexes R2Si(Flu)(3-'Bu-5-Me-2-C6H2O)MCl2 (4a: M = Ti; R = Me; Flu = fluoren-9-yl; 4b: M = Ti; R = Et; Flu = fluoren-9-yl; 4c: M = Ti; R Me; Flu = 2,7-'Bu-2-fluoren-9-yl; 4d: M = Ti; R = Et; Flu = 2,7-'Bu-2-fluoren-9-yl; 8: M = Zr; R Me; Flu 2,7-'Bu-2-fluoren-9-yl; 9: M = Hf; R = Me; Flu = 2,7-'Bu-2-fluoren-9-yl) were prepared by two methods. One was a reaction of MCl4 (M = Ti, Zr, and Ho with the dilithium salts generated by treating corresponding ligands 1a-d with "BuLi in the presence of Et3N in toluene and the other used MCl2(NR'(2))(2) (6a: M = Ti; R' = Me, 6b: M = Zr; R' = Et, 6c: M = Hf, R' = Me) instead of MCl4 followed by successive chlorination with Me3SiCl. X-ray crystallographic study of 4d indicated that the cyclopentadienyl moiety of the fluorenyl ligand is bound to the titanium atom in a fashion between eta(3) and eta(5). The newly prepared titanium Complexes 4a-d exhibited high catalytic activities for copolymerization of ethylene and 1-hexene in the presence of 'Bu3Al/[Me3NHPh][B(C6F5)(4)] and afforded higher molecular weight copolymers than the parent tetramethyl-substituted cyclopentadienyl titanium complex Me2Si(eta(5)-C5Me4)(3-'Bu-5-Me-2-C6H2O)TiCl2 (10). In particular, the active species generated from complex 4d was thermally stable and exhibited high polymerization activities even at 210 degrees C and produced high molecular weight copolymers with good 1-hexene content.

  DOI：

  10.1021/ma902700v

文献信息

• Transition Metal Complex, Process For Producing Said Transition Metal Complex, Substituent-Carrying Fluorene Compound, Process For Producing Said Fluorene Compound, Catalyst Component For Olefin Polymerization, Catalyst For Olefin Polymerization, and Process For Producing Olefin Polymer
  申请人：Senda Taichi

  公开号：US20080161514A1

  公开（公告）日：2008-07-03

  A transition metal complex represented by the general formula [1]; a catalyst component for olefin polymerization comprising said transition metal complex; a catalyst for olefin polymerization using said transition metal complex as a catalyst component for olefin polymerization; a process for producing an olefin polymer comprising the step of polymerizing an olefin in the presence of said catalyst for olefin polymerization; a substituent-carrying fluorene compound; a process for producing said substituent-carrying fluorene compound; and a process for producing said transition metal complex using said substituent-carrying fluorene compound: wherein M is the group 4 transition metal atom in the periodic table of elements; A is the group 16 atom therein; J is the group 14 atom therein; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X 1 and X 2 are independently of one another (1) a substituent selected from the group consisting of (1-1) an alkyl group having 1 to 20 carbon atoms, which may be substituted by a halogen atom, (1-2) an aralkyl group having 7 to 20 carbon atoms, which may be substituted by a halogen atom, (1-3) an aryl group having 6 to 20 carbon atoms, which may be substituted by a halogen atom, (1-4) a substituent-carrying silyl group having 1 to 20 carbon atoms, which substituent is a hydrocarbyl group, and said hydrocarbyl group may be substituted by a halogen atom, (1-5) a disubstituent-carrying amino group having 2 to 20 carbon atoms, which substituent is a hydrocarbyl group, and said hydrocarbyl group may be substituted by a halogen atom, (1-6) an alkoxy group having 1 to 20 carbon atoms, which may be substituted by a halogen atom, (1-7) an aralkyloxy group having 7 to 20 carbon atoms, which may be substituted by a halogen atom, and (1-8) an aryloxy group having 6 to 20 carbon atoms, which may be substituted by a halogen atom, (2) a halogen atom or (3) a hydrogen atom; R 1 and R 2 , R 2 and R 3 , and R 3 and R 4 may be linked to each other, respectively, to form respective rings; R 5 and R 6 may be linked to each other to form a ring; R 7 , R 8 , R 9 and R 10 are independently of one another (1) a substituent selected from the group consisting of (1-1) an alkyl group having 1 to 20 carbon atoms, which may be substituted by a halogen atom, (1-2) an aralkyl group having 7 to 20 carbon atoms, which may be substituted by a halogen atom, (1-3) an aryl group having 6 to 20 carbon atoms, which may be substituted by a halogen atom, (1-4) a substituent-carrying silyl group having 1 to 20 carbon atoms, which substituent is a hydrocarbyl group, and said hydrocarbyl group may be substituted by a halogen atom, (1-5) a disubstituent-carrying amino group having 2 to 20 carbon atoms, which substituent is a hydrocarbyl group, and said hydrocarbyl group may be substituted by a halogen atom, (1-6) an alkoxy group having 1 to 20 carbon atoms, which may be substituted by a halogen atom, (1-7) an aralkyloxy group having 7 to 20 carbon atoms, which may be substituted by a halogen atom, and (1-8) an aryloxy group having 6 to 20 carbon atoms, which may be substituted by a halogen atom, (2) a halogen atom or (3) a hydrogen atom; at least two of R 7 , R 8 , R 9 and R 10 are the substituent selected from the above-mentioned group or a halogen atom; R 7 and R 8 may be linked to each other to form a ring; and R 9 and R 10 may be linked to each other to form a ring.

  一种以通式[1]表示的过渡金属配合物；一种包括该过渡金属配合物的烯烃聚合催化剂组分；一种使用该过渡金属配合物作为烯烃聚合催化剂组分的烯烃聚合催化剂；一种在该烯烃聚合催化剂存在下聚合烯烃的方法；一种携带取代基的芴化合物；一种制备该携带取代基的芴化合物的方法；以及一种使用该携带取代基的芴化合物制备该过渡金属配合物的方法：其中，M是元素周期表中的第4族过渡金属原子；A是其中的第16族原子；J是其中的第14族原子；R1、R2、R3、R4、R5、R6、X1和X2各自独立地是（1）选自以下组中的取代基：（1-1）具有1至20个碳原子的烷基取代基，其可以被卤素原子取代，（1-2）具有7至20个碳原子的芳基烷基取代基，其可以被卤素原子取代，（1-3）具有6至20个碳原子的芳基取代基，其可以被卤素原子取代，（1-4）携带取代基的具有1至20个碳原子的硅烷基，其取代基是烃基，且该烃基可以被卤素原子取代，（1-5）携带二个取代基的具有2至20个碳原子的氨基取代基，其取代基是烃基，且该烃基可以被卤素原子取代，（1-6）具有1至20个碳原子的烷氧基，其可以被卤素原子取代，（1-7）具有7至20个碳原子的芳基烷氧基，其可以被卤素原子取代，以及（1-8）具有6至20个碳原子的芳氧基，其可以被卤素原子取代，（2）卤素原子或（3）氢原子；R1和R2、R2和R3以及R3和R4可以分别相互连接以形成相应的环；R5和R6可以连接以形成环；R7、R8、R9和R10各自独立地是（1）选自上述组中的取代基：（1-1）具有1至20个碳原子的烷基取代基，其可以被卤素原子取代，（1-2）具有7至20个碳原子的芳基烷基取代基，其可以被卤素原子取代，（1-3）具有6至20个碳原子的芳基取代基，其可以被卤素原子取代，（1-4）携带取代基的具有1至20个碳原子的硅烷基，其取代基是烃基，且该烃基可以被卤素原子取代，（1-5）携带二个取代基的具有2至20个碳原子的氨基取代基，其取代基是烃基，且该烃基可以被卤素原子取代，（1-6）具有1至20个碳原子的烷氧基，其可以被卤素原子取代，（1-7）具有7至20个碳原子的芳基烷氧基，其可以被卤素原子取代，以及（1-8）具有6至20个碳原子的芳氧基，其可以被卤素原子取代，（2）卤素原子或（3）氢原子；R7、R8、R9和R10中至少有两个是上述组中的取代基或卤素原子；R7和R8可以连接以形成环；R9和R10可以连接以形成环。
• Transition metal complex, process for producing said transition metal complex, substituent-carrying fluorene compound, process for producing said fluorene compound, catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin polymer
  申请人：Sumitomo Chemical Company, Limited

  公开号：US08084559B2

  公开（公告）日：2011-12-27

  A transition metal complex represented by formula [1], and its production process; a substituent-carrying fluorene compound represented by formula [2], and its production process; an olefin polymerization catalyst component comprising the complex; an olefin polymerization catalyst obtained by contacting the catalyst component with a defined aluminum compound and/or a defined boron compound; and a production process of an olefin polymer using the catalyst:

  一种由公式[1]表示的过渡金属配合物及其制备方法；一种由公式[2]表示的含有取代基的芴化合物及其制备方法；一种包含该配合物的烯烃聚合催化剂组分；通过将催化剂组分与定义的铝化合物和/或定义的硼化合物接触而得到的烯烃聚合催化剂；以及使用该催化剂的烯烃聚合物的制备方法。
• Rational Design of Silicon-Bridged Fluorenyl−Phenoxy Group 4 Metal Complexes as Catalysts for Producing High Molecular Weight Copolymers of Ethylene and 1-Hexene at Elevated Temperature
  作者：Taichi Senda、Hidenori Hanaoka、Shinya Nakahara、Yoshiaki Oda、Hayato Tsurugi、Kazushi Mashima

  DOI：10.1021/ma902700v

  日期：2010.3.9

  For producing high molecular weight copolymers of ethylene and I-hexene, a series of silicon-bridged fluorenyl-phenoxy group 4 complexes R2Si(Flu)(3-'Bu-5-Me-2-C6H2O)MCl2 (4a: M = Ti; R = Me; Flu = fluoren-9-yl; 4b: M = Ti; R = Et; Flu = fluoren-9-yl; 4c: M = Ti; R Me; Flu = 2,7-'Bu-2-fluoren-9-yl; 4d: M = Ti; R = Et; Flu = 2,7-'Bu-2-fluoren-9-yl; 8: M = Zr; R Me; Flu 2,7-'Bu-2-fluoren-9-yl; 9: M = Hf; R = Me; Flu = 2,7-'Bu-2-fluoren-9-yl) were prepared by two methods. One was a reaction of MCl4 (M = Ti, Zr, and Ho with the dilithium salts generated by treating corresponding ligands 1a-d with "BuLi in the presence of Et3N in toluene and the other used MCl2(NR'(2))(2) (6a: M = Ti; R' = Me, 6b: M = Zr; R' = Et, 6c: M = Hf, R' = Me) instead of MCl4 followed by successive chlorination with Me3SiCl. X-ray crystallographic study of 4d indicated that the cyclopentadienyl moiety of the fluorenyl ligand is bound to the titanium atom in a fashion between eta(3) and eta(5). The newly prepared titanium Complexes 4a-d exhibited high catalytic activities for copolymerization of ethylene and 1-hexene in the presence of 'Bu3Al/[Me3NHPh][B(C6F5)(4)] and afforded higher molecular weight copolymers than the parent tetramethyl-substituted cyclopentadienyl titanium complex Me2Si(eta(5)-C5Me4)(3-'Bu-5-Me-2-C6H2O)TiCl2 (10). In particular, the active species generated from complex 4d was thermally stable and exhibited high polymerization activities even at 210 degrees C and produced high molecular weight copolymers with good 1-hexene content.