(2-甲基-5-氧代环戊烯-1-基)硼酸 | 912675-87-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 硼酸衍生物
• 中文名称: (2-甲基-5-氧代环戊烯-1-基)硼酸
• 英文名称: 2-(dihydroxyboryl)-3-methyl-2-cyclopenten-1-one
• 英文别名: 2-dihydroxyboryl-3-methyl-2-cyclopenten-1-one；2-dihydroxyboryl-3-methyl-2-cyclopentene-1-one；(2-Methyl-5-oxocyclopent-1-en-1-yl)boronic acid；(2-methyl-5-oxocyclopenten-1-yl)boronic acid
• CAS: 912675-87-7
• 化学式: C₆H₉BO₃
• 分子量: 139.947
• InChiKey: JIJQAHZWDVEJJR-UHFFFAOYSA-N

物化性质

• 沸点：
  339.4±52.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.32
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2-甲基-5-氧代环戊烯-1-基)硼酸 在 四(三苯基膦)钯 吡啶 、 cerium(III) chloride 、 sodium carbonate 作用下， 以 苯 为溶剂， 反应 3.0h， 生成 N-(2-(2,5-dimethylcyclopenta-1,4-dien-1-yl)phenyl)-1,1-diphenylphosphanamine
  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：

  9-溴-8-甲基-1,4-二氧杂螺[4.4]壬-8-烯 在 正丁基锂 、 硼酸三异丙酯 、 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以94%的产率得到(2-甲基-5-氧代环戊烯-1-基)硼酸
  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

• Transition metal complexes, catalyst compositions containing the same, and olefin polymerization using the catalyst compositions
  申请人：LG Chem, Ltd.

  公开号：US07538239B2

  公开（公告）日：2009-05-26

  Provided are a novel transition metal complex where a monocyclopentadienyl ligand to which an amido or alcoxy group is introduced is coordinated, a method of synthesizing the same, and olefin polymerization using the transition metal complex. Compared to a conventional transition metal complex having a silicon bridge and an oxido ligand, the transition metal complex has a phenylene bridge, so that a monomer easily approaches the transition metal complex in terms of structure and a pentagon ring structure of the transition metal complex is stably maintained. The catalyst composition including the transition metal complex is used to synthesize a polyolefin copolymer having a very low density less than 0.910 g/cc.

  提供了一种新型过渡金属配合物，其中配位了一个含有氨基或烷氧基团的单环戊二烯基配体，还提供了一种合成该配合物的方法，以及使用该过渡金属配合物进行烯烃聚合的方法。与具有硅桥和氧化物配体的传统过渡金属配合物相比，该过渡金属配合物具有苯桥，使得单体在结构上更容易接近该过渡金属配合物，并且过渡金属配合物的五边形环结构得到稳定维持。包括该过渡金属配合物的催化剂组合物用于合成具有非常低密度小于0.910克/立方厘米的聚烯烃共聚物。
• Bimetallic phenylene-bridged Cp/amide titanium complexes and their olefin polymerization
  作者：Sang Hoon Lee、Chun Ji Wu、Ui Gab Joung、Bun Yeoul Lee、Jinil Park

  DOI：10.1039/b710017e

  日期：——

  Bimetallic dichlorotitanium complexes, 2,6-[η5-2,5-Me2C5H2]2-4-R-C6H2N-µN}Ti(IV)Cl2}2 (7, R = Me; 8, R = F) and 4,4′-A[2-(η5-2,3,5-Me3C5H)C6H3NC6H11-κN}Ti(IV)Cl2]2 (18, A = CH2; 19, A = O; 20, A = ortho-C6H4) are prepared via a key step of the Suzuki-coupling reaction of 2-dihydroxyboryl-3-methyl-2-cyclopenten-1-one (1) with dibromo-compounds. The solid state structure of 7 was determined by X-ray crystallography. Complexes 7 and 8 are not active for ethylene/1-hexene copolymerization. Meanwhile, the complexes 18–20 are highly active and their activities are higher than that of the mononuclear analogue, 2-(η5-2,3,5-Me3C5H)C6H3NC6H11-κN}Ti(IV)Cl2 (21). The molecular weights of the polymers obtained with the bimetallic complexes 18–20 are higher than that of the polymer obtained using 21. Slightly higher contents of long-chain-branching are observed for the copolymers obtained using the bimetallic system.

  双金属二氯钛配合物2,6-[η5-2,5-Me2C5H2]2-4-R-C6H2N-µN}Ti(IV)Cl2}2 (7, R = Me; 8, R = F)和4,4′-A[2-(η5-2,3,5-Me3C5H)C6H3NC6H11-κN}Ti(IV)Cl2]2 (18, A = CH2; 19, A = O; 20, A = ortho-C6H4)是通过2-二羟基硼酰基-3-甲基-2-环戊烯-1-酮(1)与二溴化合物进行铃木偶联反应的关键步骤制备的。7的固态结构通过X射线晶体学测定。配合物7和8对乙烯/1-己烯共聚反应不活跃。同时，配合物18-20具有高度活性，其活性高于单核类似物2-(η5-2,3,5-Me3C5H)C6H3NC6H11-κN}Ti(IV)Cl2 (21)。用双金属配合物18-20制备的聚合物的分子量高于用21制备的聚合
• 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.