2-(di-(2,4-dimethoxy-phenyl)phoshine)benzenesulfonic acid

• 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-(di-(2,4-dimethoxy-phenyl)phoshine)benzenesulfonic acid
• 英文别名: 2-(bis(2,4-dimethoxyphenyl)phosphino)benzenesulfonic acid；2-Bis(2,4-dimethoxyphenyl)phosphanylbenzenesulfonic acid
• 化学式: C₂₂H₂₃O₇PS
• 分子量: 462.46
• InChiKey: HPCAPDDOWCZRDI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  99.7
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (N,N,N',N'-tetramethylethylenediamine)dimethylpalladium(II) 、 2-(di-(2,4-dimethoxy-phenyl)phoshine)benzenesulfonic acid 以 二氯甲烷 为溶剂， 反应 1.0h， 以82%的产率得到bis{N,N’-{(κ2-P,O)-2-[di-(2,4-dimethoxy-phenyl)-phosphine]benzenesulfonate} palladium(II)-methyl}-N,N,N’,N’-tetramethylethylenediamine
  参考文献：
  名称：

  Electronic Influences in Phosphinesulfonato Palladium(II) Polymerization Catalysts

  摘要：

  To study the influence of electronics on catalytic polymerization properties independent from sterics, phosphinesulfonato Pd(II) complexes bearing remotely located substituents on the nonchelating P-bound aryls [kappa(2)-(P,O)-(4-R-2-anisyl)(2)PC6H4SO2O]Pd(Me)(dmso) (1ae-dmso: 1a, R = CF3; 1b, R = Cl; 1c, R = H; 1d, R = CH3; 1e, R = OCH3) were prepared. The electron-poor complex 1a-dmso (4-CF3) undergoes the fastest insertion of methyl acrylate (MA) and is the most active for ethylene polymerization. The polyethylene molecular weight increases by a factor of 2 for the more electron rich complex 1e-dmso (4-OCH3) (Mn = 17 x 10 (3) vs 8 x 10 (3) for 1a-dmso (4-CF3)). MA/ethylene copolymerization experiments revealed that the MA incorporation ratio and copolymer molecular weights are largely independent of the electronic nature of the remote substituents. These trends were further confirmed by studies of two mixed P-aryl/-alkyl complexes 1f-dmso ([kappa(2)-(2,4,6-(OMe)(3)C6H2)(tBu)PC6H4SO2O]Pd(Me)(dmso)) and 1g-dmso ([?2-(C6H5)(tBu)PC6H4SO2O]Pd(Me)(dmso)). In ethylene/MA copolymerization, 1f-dmso affords a significantly higher molecular weight polymer with reasonable MA incorporation (Mn = 12 x 10 (3) and 7.7 mol % MA) and activities similar to those observed for complexes 1ae-dmso.

  DOI：

  10.1021/om400297x
• 作为产物：
  描述：

  苯磺酸 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 生成 2-(di-(2,4-dimethoxy-phenyl)phoshine)benzenesulfonic acid
  参考文献：
  名称：

  Electronic Influences in Phosphinesulfonato Palladium(II) Polymerization Catalysts

  摘要：

  To study the influence of electronics on catalytic polymerization properties independent from sterics, phosphinesulfonato Pd(II) complexes bearing remotely located substituents on the nonchelating P-bound aryls [kappa(2)-(P,O)-(4-R-2-anisyl)(2)PC6H4SO2O]Pd(Me)(dmso) (1ae-dmso: 1a, R = CF3; 1b, R = Cl; 1c, R = H; 1d, R = CH3; 1e, R = OCH3) were prepared. The electron-poor complex 1a-dmso (4-CF3) undergoes the fastest insertion of methyl acrylate (MA) and is the most active for ethylene polymerization. The polyethylene molecular weight increases by a factor of 2 for the more electron rich complex 1e-dmso (4-OCH3) (Mn = 17 x 10 (3) vs 8 x 10 (3) for 1a-dmso (4-CF3)). MA/ethylene copolymerization experiments revealed that the MA incorporation ratio and copolymer molecular weights are largely independent of the electronic nature of the remote substituents. These trends were further confirmed by studies of two mixed P-aryl/-alkyl complexes 1f-dmso ([kappa(2)-(2,4,6-(OMe)(3)C6H2)(tBu)PC6H4SO2O]Pd(Me)(dmso)) and 1g-dmso ([?2-(C6H5)(tBu)PC6H4SO2O]Pd(Me)(dmso)). In ethylene/MA copolymerization, 1f-dmso affords a significantly higher molecular weight polymer with reasonable MA incorporation (Mn = 12 x 10 (3) and 7.7 mol % MA) and activities similar to those observed for complexes 1ae-dmso.

  DOI：

  10.1021/om400297x

文献信息

• Single site palladium catalyst complexes
  申请人：Rohm and Haas Company

  公开号：EP1760086A2

  公开（公告）日：2007-03-07

  Catalyst structures comprising a single palladium metal center and a substituted tri-arylphosphine ligand. Also disclosed are methods of making and using the catalyst structures to facilitate polymerization reactions and Heck coupling reactions.

  催化剂结构包括单个钯金属中心和取代的三芳基膦配体。还公开了制备和使用这种催化剂结构以促进聚合反应和Heck偶联反应的方法。
• Process for preparing ortho-substituted phenylphosphine ligands
  申请人：Rohm and Haas Company

  公开号：EP1762572A1

  公开（公告）日：2007-03-14

  Ligand synthesis methods for the preparation of ligands having the formula wherein Q is selected from phosphorus, arsenic and antimony; wherein X1, X2 and X3 are carbon anions; and, wherein R15 is selected from -SO3, -SO2N(R18), -CO2, -PO3, -AsO3, -SiO2, -C(CF3)2O; where R18 is selected from a hydrogen, a halogen, a hydrocarbyl group and a substituted hydrocarbyl group, are disclosed. Also disclosed are methods of complexing the ligands with late transition metals to form catalyst complexes that catalyze polymerization reactions and/or Heck coupling reactions.

  揭示了用于制备具有以下式的配体的配体合成方法：其中Q从磷、砷和锑中选择；其中X1、X2和X3是碳阴离子；其中R15从-SO3、-SO2N（R18）、-CO2、-PO3、-AsO3、-SiO2、-C（CF3）2O中选择；其中R18从氢、卤素、烃基和取代烃基中选择。还揭示了将这些配体与后期过渡金属配合形成催化剂复合物的方法，该复合物催化聚合反应和/或Heck偶联反应。
• Substantially linear copolymers of olefin and polar monomers. Methods of making the same.
  申请人：Rohm and Haas Company

  公开号：EP1760097A2

  公开（公告）日：2007-03-07

  Copolymers and terpolymers containing acyclic aliphatic olefin derived units and polar monomer derived units are disclosed. Also disclosed are methods of making such copolymers and terpolymers using late transition metal catalyst complexes.

  公开了含有无环脂肪族烯烃衍生单元和极性单体衍生单元的共聚物和三元共聚物。还公开了使用后期过渡金属催化剂复合物制造此类共聚物和三元共聚物的方法。
• Polymerization of acyclic aliphatic olefins
  申请人：Rohm and Haas Company

  公开号：EP1964857A1

  公开（公告）日：2008-09-03

  A polymerization process for preparing a polymer, comprising contacting at least one acyclic aliphatic olefin monomer and a catalyst composition comprising a palladium metal center complexed with at least one ligand, wherein the at least one ligand has a structure according to Formula I wherein R1-R14 are independently selected from a hydrogen; a halogen; and, a substituent selected from C1-C20 alkyl, C3-C20 cycloalkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, arylalkyl, alkylaryl, phenyl, biphenyl, C1-C20 carboxylate, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, C1-C20 alkylsulfinyl, silyl and derivatives thereof; wherein Q is selected from phosphorus and arsenic; wherein R15 is selected from -SO3, -PO3, -AsO3, and -C(CF3)2O; wherein the polymer prepared exhibits a branch content of ≤ 15 branched/1,000 carbon atoms, wherein the branch content is determined by Carbon 13 NMR and the melting point of the polymer prepared; with the proviso that R1-R10 are not all hydrogen; with the proviso that when R2, R4, R7 and R9 are each a hydrogen, none of R1, R5, R6 and R10 are CH3, CF3, F, SMe2, biphenyl or phenoxy; and, with the proviso that when R15 is -SO3, -PO3, or -AsO3, none of R1, R5, R6 and R10 is a polar group.

  一种制备聚合物的聚合工艺，包括将至少一种无环脂肪族烯烃单体与催化剂组合物接触，催化剂组合物包括与至少一种配体络合的钯金属中心，其中至少一种配体具有符合式 I 的结构 其中 R1-R14 独立选自氢、卤素和取代基，取代基选自 C1-C20 烷基、C3-C20 环烷基、C2-C20 烯基、C2-C20 炔基、芳基、芳烷基、烷芳基、苯基、联苯基、C1-C20 羧基、C1-C20 烷氧基、C2-C20 烯氧基、C2-C20 炔氧基、芳氧基、C2-C20 烷氧羰基、C1-C20 烷硫基、C1-C20 烷磺酰基、C1-C20 烷基亚磺酰基、硅烷基及其衍生物； 其中 Q 选自磷和砷； 其中 R15 选自-SO3、-PO3、-AsO3 和-C(CF3)2O； 其中制备的聚合物的支链含量≤15 个支链/1,000 个碳原子，其中支链含量由碳 13 NMR 和制备的聚合物的熔点确定； 但 R1-R10 不全是氢； 附带条件：当 R2、R4、R7 和 R9 均为氢时，R1、R5、R6 和 R10 均不是 CH3、 、F、SMe2、联苯或苯氧基；以及 但 R15 为-SO3、-PO3 或- 时，R1、R5、R6 和 R10 都不是极性基团。
• Substantially linear polymers and methods of making the same
  申请人：Rohm and Haas Company

  公开号：EP1964863A1

  公开（公告）日：2008-09-03

  Substantially linear copolymers derived from at least one acyclic aliphatic olefin monomer and at least one nitrogen containing vinyl monomer, wherein the at least one nitrogen containing vinyl monomer is according to Formula (I) wherein R19 is selected from -C=C, and -C(O)-C=C; wherein R20 and R21 are independently selected from H, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a biphenyl group, a carboxylate group, a carboxyalkyl group, a carboxyarylalkyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, and derivatives thereof. Also disclosed are methods of making such copolymers using late transition metal catalyst complexes.

  由至少一种无环脂肪族烯烃单体和至少一种含氮乙烯基单体衍生的基本线性共聚物，其中至少一种含氮乙烯基单体符合式 (I) 其中 R19 选自-C=C 和-C(O)-C=C；其中 R20 和 R21 独立选自 H、烷基、烯基、炔基、芳基、联苯基、羧酸基、羧基烷基、羧基芳烷基、烷氧基、烯氧基、炔氧基、芳氧基、烷氧羰基及其衍生物。还公开了使用后期过渡金属催化剂复合物制造此类共聚物的方法。