α,α'-bis(3,5-dimethylpyrazolyl)-m-xylene | 81028-65-1

• 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: α,α'-bis(3,5-dimethylpyrazolyl)-m-xylene
• 英文别名: α,α'-bis(3,5-dimethylpyrazoyl)-m-xylene；1,3-bis[(3,5-dimethylpyrazol-1-yl)methyl]benzene；1,3-bis(3,5-dimethylpyrazol-1-ylmethyl)benzene；1-[[3-[(3,5-Dimethylpyrazol-1-yl)methyl]phenyl]methyl]-3,5-dimethylpyrazole
• CAS: 81028-65-1
• 化学式: C₁₈H₂₂N₄
• 分子量: 294.399
• InChiKey: KQLAWIVLOFXKJJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  35.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α,α'-bis(3,5-dimethylpyrazolyl)-m-xylene 以 水 、 溶剂黄146 、 丙酮 为溶剂， 生成 1-(aquapalladium)-2,6-bis[(3,5-dimethylpyrazol-1-yl)methyl]benzene tetrafluoroborate
  参考文献：
  名称：

  Design and Performance of Rigid Nanosize Multimetallic Cartwheel Pincer Compounds as Lewis-Acid Catalysts

  摘要：

  Novel strategies for the preparation of rigid cartwheel pincer metal complexes have been developed. The aromatic backbone of these materials ensures a high rigidity, which is expected to be important for a high retention when these multimetallic nanosize complexes are applied as homogeneous catalysts in a nanomembrane reactor. The ligand precursors C-6[C6H3(CH2Y)(2)-3,5](6) (10, Y= NMe2; 11, Y = SPh; 12, Y = PPh2; 13, Y = pz = pyrazol-1-yl) have been prepared in high yields from the key intermediate C-6[C6H3(CH2Br)(2)-3,5](6) (9). The hexakis(pincer) palladium(II) complexes C-6[(PdX)-4-C2H2(CH2Y)(2)-3,5](6) (14, Y = SPh, L = Cl; 15, Y = PPh2, L = Cl; 16, Y = pyrazol-1-yl, L = OAc; 17, Y = pyrazol-1-yl, L = Cl) have been prepared via direct electrophilic palladation of the corresponding ligands. The (tris)pincer ligand C6H3 [Br-4-C6H3(CH2NMe2)(2)-3,5](3)-1,3,5 (20) was prepared via a triple-condensation reaction of 4-bromo-3,5-bis [(dimethylamino)methyl] acetophenone (19). Reaction of 20 with Pd(dba)(2) yielded the tripalladium complex C6H3[(PdBr)-4-C6H3(CH2NMe2)(2)-3,5](3)-1,3,5 (21). The crystal structure of 21 shows a propeller-like structure with D-3 symmetry and a fixed bromine-bromine distance of 17.4573(4) Angstrom, approximately forming a triangle with a height of 15.2 Angstrom. These nanosize cartwheel pincer metal complexes based on tridentate Y,C,Y ' pincer ligands have been used as homogeneous Lewis-acid catalysts. Moreover, the influence of the donor substituent Y on the catalytic activity of cationic mono-Y,C,Y ' Pd-II complexes as Lewis-acid catalysts in the double Michael reaction between methyl vinyl ketone and ethyl a-cyanoacetate, as a model reaction, has been investigated. It was found that cationic N,C,N ' -type pincer complexes (1a, Y = NMe2; 1b, Y = pz; 1c, Y = pz* = 3,5-dimethylpyrazol-1-yl; 23) were superior to the P,C,P '- and S,C,S'-pincer complexes (Id, Y = PPh2; le, Y = SPh). The nanosize cationic tri-N, C,N ' Pd-II complex 23 was found to have a catalytic activity per catalytic site in the double Michael reaction of the same order of magnitude as the monopincer analogue 1a (k = 279 x 10(-6) s(-1) for 1a vs k = 232 x 10(-6) s(-1) for 23). The combination of the nanosize dimensions, the catalytic activity, and the high thermal and air stability makes these complexes excellent candidates for application in a continuous process in a nanomembrane reactor.

  DOI：

  10.1021/om0101689
• 作为产物：
  描述：

  3,5-二甲基吡唑 、 间二溴苄 以 四氢呋喃 为溶剂， 生成 α,α'-bis(3,5-dimethylpyrazolyl)-m-xylene
  参考文献：
  名称：

  An explanation for the observed stoichiometry of carbon monoxide binding to hemocyanin

  摘要：

  DOI：

  10.1021/ja00371a057

文献信息

• Tandem ethylene oligomerisation and Friedel–Crafts alkylation of toluene catalysed by bis-(3,5-dimethylpyrazol-1-ylmethyl)benzene nickel(ii) complexes and ethylaluminium dichloride
  作者：Asheena Budhai、Bernard Omondi、Stephen O. Ojwach、Collins Obuah、Emmanuel Y. Osei-Twum、James Darkwa

  DOI：10.1039/c3cy00334e

  日期：——

  Three ligands, 1,2-bis(3,5-dimethylpyrazol-1-ylmethyl)benzene (L1), 1,3-bis(3,5-dimethylpyrazol-1-ylmethyl)benzene (L2) and 1,4-bis(3,5-dimethylpyrazol-1-ylmethyl)benzene (L3), were reacted with either nickel(II) chloride or nickel(II) bromide to produce four nickel complexes, Ni(L1)Br2 (1), Ni(L1)Cl2 (2), Ni(L2)Br2 (3), and Ni(L1)Br2 (4). The complexes were either mononuclear, 1 and 2, or polymeric

  三种配体，1,2-双（3,5-二甲基吡唑-1-基甲基）苯（L1），1,3-双（3,5-二甲基吡唑-1-基甲基）苯（L2）和1,4-双（3,5-二甲基吡唑-1-基甲基）苯（L3）与以下任何一种反应镍（II），氯化 或者 溴化镍（II）产生四个镍配合物，Ni（L1）Br 2（1），Ni（L1）Cl 2（2），Ni（L2）Br 2（3）和Ni（L1）Br 2（4）。取决于配体中苯连接基上吡唑基单元的位置，复合物可以是单核的1和2，也可以是聚合的3和4。这是从的晶体结构建立1，2和3。激活后所有四个复合物乙基氯化铝 产生了串联催化剂体系，该体系将乙烯低聚为主要成分 1-丁烯 和 1-己烯然后使用存在于反应介质中的烯烃将甲苯烷基化，该甲苯在反应中用作溶剂。这导致单，二和三烷基甲苯与乙烯，丁烯 和 己烯。
• Poly(pyrazol-1-ylmethyl)benzene Palladium Complexes: Synthesis, Characterisation and Evaluation as Heck Coupling Catalysts
  作者：Nthabiseng M. Motsoane、Ilia A. Guzei、James Darkwa

  DOI：10.1515/znb-2007-0304

  日期：2007.3.1

  The poly(pyrazol-1-ylmethyl)benzenes L1 - L5 react with [PdCl₂(NCMe)₂] or [PdClMe(COD)] to form dinuclear palladium complexes [PdClX(3,5-Me₂pzCH₂)₂-1,2-C₆H₄}₂] (X = Cl (1), Me (2)), [PdCl₂(3,5-Me₂pzCH₂)2-1,3-C₆H₄}₂] (3), palladium complexes [Pd₂(μ-Cl)₂Me₂(3,5- Me₂pzCH₂)₂-1,3-C₆H₄}] (4), [Pd₂(μ-Cl)₂X₂(3,5-Me₂pzCH₂)₂-1,4-C₆H₄}] (X = Cl (5), Me (6)), [Pd₂(μ-Cl)₂Cl₂(3,5-^tBu₂pzCH₂)₂-1,4-C₆H₄}] (7), and tetranuclear [Pd₂(μ-Cl)₂Cl₂(3,5- Me₂pzCH₂)₂}₂-1,4-C₆H₄] (8). The structures of 1, 2 and 8 were confirmed by X-ray structure analysis. The complexes efficiently catalyse the coupling reaction of iodobenzene and butylacrylate at 80 °C.

  聚(pyrazol-1-甲基)苯L1-L5与[PdCl₂(NCMe)₂]或[PdClMe(COD)]反应，形成二核钯配合物[ PdClX(3,5-Me₂pzCH₂)₂-1,2-C₆H₄}₂] (X = Cl (1), Me (2)), [PdCl₂(3,5-Me₂pzCH₂)2-1,3-C₆H₄}₂] (3), 钯配合物 [Pd₂(μ-Cl)₂Me₂(3,5-Me₂pzCH₂)₂-1,3-C₆H₄}] (4), [Pd₂(μ-Cl)₂X₂(3,5-Me₂pzCH₂)₂-1,4-C₆H₄}] (X = Cl (5), Me (6)), [Pd₂(μ-Cl)₂Cl₂(3,5-^tBu₂pzCH₂)₂-1,4-C₆H₄}] (7), 和四核[Pd₂(μ-Cl)₂Cl₂(3,5-Me₂pzCH₂)₂}₂-1,4-C₆H₄] (8)。1、2和8的结构经过X射线结构分析证实。这些配合物能有效催化碘苯和丁基丙烯酸酯的偶联反应，在80℃下进行。
• Design and Performance of Rigid Nanosize Multimetallic Cartwheel Pincer Compounds as Lewis-Acid Catalysts
  作者：Harm P. Dijkstra、Michel D. Meijer、Jim Patel、Rob Kreiter、Gerard P. M. van Klink、Martin Lutz、Anthony L. Spek、Allan J. Canty、Gerard van Koten

  DOI：10.1021/om0101689

  日期：2001.7.1

  Novel strategies for the preparation of rigid cartwheel pincer metal complexes have been developed. The aromatic backbone of these materials ensures a high rigidity, which is expected to be important for a high retention when these multimetallic nanosize complexes are applied as homogeneous catalysts in a nanomembrane reactor. The ligand precursors C-6[C6H3(CH2Y)(2)-3,5](6) (10, Y= NMe2; 11, Y = SPh; 12, Y = PPh2; 13, Y = pz = pyrazol-1-yl) have been prepared in high yields from the key intermediate C-6[C6H3(CH2Br)(2)-3,5](6) (9). The hexakis(pincer) palladium(II) complexes C-6[(PdX)-4-C2H2(CH2Y)(2)-3,5](6) (14, Y = SPh, L = Cl; 15, Y = PPh2, L = Cl; 16, Y = pyrazol-1-yl, L = OAc; 17, Y = pyrazol-1-yl, L = Cl) have been prepared via direct electrophilic palladation of the corresponding ligands. The (tris)pincer ligand C6H3 [Br-4-C6H3(CH2NMe2)(2)-3,5](3)-1,3,5 (20) was prepared via a triple-condensation reaction of 4-bromo-3,5-bis [(dimethylamino)methyl] acetophenone (19). Reaction of 20 with Pd(dba)(2) yielded the tripalladium complex C6H3[(PdBr)-4-C6H3(CH2NMe2)(2)-3,5](3)-1,3,5 (21). The crystal structure of 21 shows a propeller-like structure with D-3 symmetry and a fixed bromine-bromine distance of 17.4573(4) Angstrom, approximately forming a triangle with a height of 15.2 Angstrom. These nanosize cartwheel pincer metal complexes based on tridentate Y,C,Y ' pincer ligands have been used as homogeneous Lewis-acid catalysts. Moreover, the influence of the donor substituent Y on the catalytic activity of cationic mono-Y,C,Y ' Pd-II complexes as Lewis-acid catalysts in the double Michael reaction between methyl vinyl ketone and ethyl a-cyanoacetate, as a model reaction, has been investigated. It was found that cationic N,C,N ' -type pincer complexes (1a, Y = NMe2; 1b, Y = pz; 1c, Y = pz* = 3,5-dimethylpyrazol-1-yl; 23) were superior to the P,C,P '- and S,C,S'-pincer complexes (Id, Y = PPh2; le, Y = SPh). The nanosize cationic tri-N, C,N ' Pd-II complex 23 was found to have a catalytic activity per catalytic site in the double Michael reaction of the same order of magnitude as the monopincer analogue 1a (k = 279 x 10(-6) s(-1) for 1a vs k = 232 x 10(-6) s(-1) for 23). The combination of the nanosize dimensions, the catalytic activity, and the high thermal and air stability makes these complexes excellent candidates for application in a continuous process in a nanomembrane reactor.
• An explanation for the observed stoichiometry of carbon monoxide binding to hemocyanin
  作者：Thomas N. Sorrell、Donald L. Jameson

  DOI：10.1021/ja00371a057

  日期：1982.4