2-(2,4,5-Trimethylcyclopenta-1,4-dien-1-yl)aniline | 912675-97-9

• 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: 2-(2,4,5-Trimethylcyclopenta-1,4-dien-1-yl)aniline
• 英文别名: 2-(2,4,5-trimethylcyclopenta-1,4-dien-1-yl)aniline
• CAS: 912675-97-9
• 化学式: C₁₄H₁₇N
• 分子量: 199.296
• InChiKey: TVEKTTAKSMRXEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(2,4,5-Trimethylcyclopenta-1,4-dien-1-yl)aniline 、 二环己基氯化膦 在 吡啶 作用下， 以 苯 为溶剂， 反应 3.0h， 生成 1,1-dicyclohexyl-N-(2-(2,4,5-trimethylcyclopenta-1,4-dien-1-yl)phenyl)phosphanamine
  参考文献：
  名称：

  Synthesis and structures of o-phenylene-bridged Cp/phosphinoamide titanium complexes

  摘要：

  Addition of (R2PCI)-P-' to anilines substituted with di- or trimethylcyclopentadienyl unit at ortho-position affords ortho-phenylenebridged Me2Cp or Me3Cp/phosophinoamide ligands, 2-(RMe2C5H2)C6H4NHPR'(2) (R=Me or H; R'=Ph, iPr, or Cyclohexyl). Successive addition of Ti(NMe2)(4) and Me2SiCl2 to the ligands affords the desired dichlorotitanium complexes, [2-(eta(5)-RMe2C5H)C6H4NPR'(2)-kappa N-2,P]TiC1(2) (R=H, R'=Ph, 9; R=Me, R'=Ph, 10; R=H, R'=iPr, 11; R=Me, R'=iPr, 12; R=H, R'=Cy, 13; R=Me, R'=Cy, 14). By using Zr(NMe2)(4) instead of Ti(NMe2)(4), a zirconium complex, [2-(eta(5)-Me3C5H)C6H4NP(iPr)(2)-kappa N-2,P]ZrC1(2) (15) is prepared. Molecular structures of 10, 14 and [2-(eta(5)-Me2C5H2)C6H4NPPh2-kappa N]Ti(NMe2)(2) (16) were determined. The metric parameters determined on the X-ray crystallographic studies and the chemical shifts of the P-31 NMR signal indicate that the phosphorous atom coordinates to the titanium in the dichloro-complexes 9-15. The titanium and zirconium complexes show negligible activity in ethylene and ethylene/l-hexene (co)polymerization when activated with MAO or iBu(3)Al/[Ph3C][B(C6F5)(4)]. (c) 2006 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2006.09.010
• 作为产物：
  描述：

  (2,3-二甲基-5-氧代环戊烯-1-基)硼酸 在 四(三苯基膦)钯 cerium(III) chloride 、 sodium carbonate 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 乙醚 、 水 为溶剂， 反应 14.0h， 生成 2-(2,4,5-Trimethylcyclopenta-1,4-dien-1-yl)aniline
  参考文献：
  名称：

  o-Phenylene-bridged Cp/sulfonamido titanium complexes for ethylene/1-octene copolymerization

  摘要：

  2-(二羟基硼基)-3,4-二甲基-2-环戊烯-1-酮(1)和2-(二羟基硼基)-3-甲基-2-环戊烯-1-酮(2)的Suzuki偶联反应2-溴苯胺衍生物提供环戊烯酮化合物 (3–8)，由环戊二烯化合物 4,6-R'2-2-(2,5-Me2C5H3)C6H2NH2 (9–11) 和 4,6-R'2-2制备-(2,3,5-Me3C5H2)C6H2NH2 (12–14)。用 p-TsCl 磺化 –NH2 基团后，通过连续添加 Ti(NMe2)4 和 Me2SiCl2 进行金属化，得到邻亚苯基桥联的 Cp/磺酰胺二氯化钛络合物，[4,6-R'2-2 -(2,5-Me2C5H2)C6H2NSO2C6H4CH3)]TiCl2 (R' = H, 21;R' = Me, 22;R' = F, 23) 和 [4,6-R'2-2-(2,3 ,5-Me3C5H)C6H2NSO2C6H4CH3)]TiCl2 (R' = H, 24;R' = Me, 25;R' = F, 26)。 24 和 [2-(2,5-Me2C5H2)C6H4NSO2C6H4CH3)]Ti(NMe2)2 (27) 的分子结构通过 X 射线晶体学测定。 24 中的 Cp(质心)-Ti-N 角 (100.90°) 比 CGC（约束几何催化剂）[Me2Si(η5-Me4Cp)(NtBu)]TiCl2 (107.6°) 观察到的更小，表明24 中的“受限特征”比 CGC 中的“受限特征”要多。在新制备的配合物中，配合物24在乙烯/1-辛烯共聚中表现出最高的活性，但在活性、共聚单体掺入能力和所得聚合物的分子量方面略逊于CGC。

  DOI：

  10.1039/b605345a

文献信息

• o-Phenylene-bridged Cp/sulfonamido titanium complexes for ethylene/1-octene copolymerization
  作者：Dae June Joe、Chun Ji Wu、Taekki Bok、Eun Jung Lee、Choong Hoon Lee、Won-Sik Han、Sang Ook Kang、Bun Yeoul Lee

  DOI：10.1039/b605345a

  日期：——

  The Suzuki-coupling reaction of 2-(dihydroxyboryl)-3,4-dimethyl-2-cyclopenten-1-one (1) and 2-(dihydroxyboryl)-3-methyl-2-cyclopenten-1-one (2) with 2-bromoaniline derivatives affords cyclopentenone compounds (3–8) from which cyclopentadiene compounds, 4,6-R′2-2-(2,5-Me2C5H3)C6H2NH2 (9–11) and 4,6-R′2-2-(2,3,5-Me3C5H2)C6H2NH2 (12–14) are prepared. After sulfonation of the –NH2 group with p-TsCl, metallation is carried out by successive addition of Ti(NMe2)4 and Me2SiCl2 affording o-phenylene-bridged Cp/sulfonamido titanium dichloride complexes, [4,6-R′2-2-(2,5-Me2C5H2)C6H2NSO2C6H4CH3)]TiCl2 (R′ = H, 21; R′ = Me, 22; R′ = F, 23) and [4,6-R′2-2-(2,3,5-Me3C5H)C6H2NSO2C6H4CH3)]TiCl2 (R′ = H, 24; R′ = Me, 25; R′ = F, 26). The molecular structures of 24 and [2-(2,5-Me2C5H2)C6H4NSO2C6H4CH3)]Ti(NMe2)2 (27) are determined by X-ray crystallography. The Cp(centroid)–Ti–N angle in 24 is smaller (100.90°) than that observed for the CGC (constrained-geometry catalyst), [Me2Si(η5-Me4Cp)(NtBu)]TiCl2 (107.6°) indicating a more “constrained feature” in 24 than in the CGC. Complex 24 shows the highest activity among the newly prepared complexes in ethylene/1-octene copolymerization but it is slightly inferior to the CGC in terms of activity, comonomer-incorporation ability, and molecular weight of the obtained polymers.

  2-(二羟基硼基)-3,4-二甲基-2-环戊烯-1-酮(1)和2-(二羟基硼基)-3-甲基-2-环戊烯-1-酮(2)的Suzuki偶联反应2-溴苯胺衍生物提供环戊烯酮化合物 (3–8)，由环戊二烯化合物 4,6-R'2-2-(2,5-Me2C5H3)C6H2NH2 (9–11) 和 4,6-R'2-2制备-(2,3,5-Me3C5H2)C6H2NH2 (12–14)。用 p-TsCl 磺化 –NH2 基团后，通过连续添加 Ti(NMe2)4 和 Me2SiCl2 进行金属化，得到邻亚苯基桥联的 Cp/磺酰胺二氯化钛络合物，[4,6-R'2-2 -(2,5-Me2C5H2)C6H2NSO2C6H4CH3)]TiCl2 (R' = H, 21;R' = Me, 22;R' = F, 23) 和 [4,6-R'2-2-(2,3 ,5-Me3C5H)C6H2NSO2C6H4CH3)]TiCl2 (R' = H, 24;R' = Me, 25;R' = F, 26)。 24 和 [2-(2,5-Me2C5H2)C6H4NSO2C6H4CH3)]Ti(NMe2)2 (27) 的分子结构通过 X 射线晶体学测定。 24 中的 Cp(质心)-Ti-N 角 (100.90°) 比 CGC（约束几何催化剂）[Me2Si(η5-Me4Cp)(NtBu)]TiCl2 (107.6°) 观察到的更小，表明24 中的“受限特征”比 CGC 中的“受限特征”要多。在新制备的配合物中，配合物24在乙烯/1-辛烯共聚中表现出最高的活性，但在活性、共聚单体掺入能力和所得聚合物的分子量方面略逊于CGC。
• Synthesis and structures of o-phenylene-bridged Cp/phosphinoamide titanium complexes
  作者：Chun Ji Wu、Sang Hoon Lee、Hoseop Yun、Bun Yeoul Lee

  DOI：10.1016/j.jorganchem.2006.09.010

  日期：2006.12

  Addition of (R2PCI)-P-' to anilines substituted with di- or trimethylcyclopentadienyl unit at ortho-position affords ortho-phenylenebridged Me2Cp or Me3Cp/phosophinoamide ligands, 2-(RMe2C5H2)C6H4NHPR'(2) (R=Me or H; R'=Ph, iPr, or Cyclohexyl). Successive addition of Ti(NMe2)(4) and Me2SiCl2 to the ligands affords the desired dichlorotitanium complexes, [2-(eta(5)-RMe2C5H)C6H4NPR'(2)-kappa N-2,P]TiC1(2) (R=H, R'=Ph, 9; R=Me, R'=Ph, 10; R=H, R'=iPr, 11; R=Me, R'=iPr, 12; R=H, R'=Cy, 13; R=Me, R'=Cy, 14). By using Zr(NMe2)(4) instead of Ti(NMe2)(4), a zirconium complex, [2-(eta(5)-Me3C5H)C6H4NP(iPr)(2)-kappa N-2,P]ZrC1(2) (15) is prepared. Molecular structures of 10, 14 and [2-(eta(5)-Me2C5H2)C6H4NPPh2-kappa N]Ti(NMe2)(2) (16) were determined. The metric parameters determined on the X-ray crystallographic studies and the chemical shifts of the P-31 NMR signal indicate that the phosphorous atom coordinates to the titanium in the dichloro-complexes 9-15. The titanium and zirconium complexes show negligible activity in ethylene and ethylene/l-hexene (co)polymerization when activated with MAO or iBu(3)Al/[Ph3C][B(C6F5)(4)]. (c) 2006 Elsevier B.V. All rights reserved.