2-(di-tert-butylphosphonium)benzenesulfonate | 1380204-84-1

• 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: 2-(di-tert-butylphosphonium)benzenesulfonate
• 英文别名: 2-(di-tert-butylphosphanyl)benzenesulfonic acid；2-(di-tert-butylphosphaneyl)benzenesulfonic acid；di-tert-butylphosphanobenzenesulfonic acid；2-(di-tert-butylphosphonio)benzenesulfonate；2-Ditert-butylphosphanylbenzenesulfonic acid；2-ditert-butylphosphanylbenzenesulfonic acid
• CAS: 1380204-84-1
• 化学式: C₁₄H₂₃O₃PS
• 分子量: 302.375
• InChiKey: ALKUSUYLGAHFJP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  62.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(di-tert-butylphosphonium)benzenesulfonate 在 四氟硼酸-二乙醚络合物 作用下， 以 四氢呋喃 、 氘代四氢呋喃 为溶剂， 反应 24.34h， 生成
  参考文献：
  名称：

  由乙烯和苯铂（II）配合物形成的苯乙烯容易形成，可观察到氢化铂（II）

  摘要：

  A new 2-(di-tert-butylphosphanyl)benzenesulfonate-supported phenylplatinum(II) complex instantaneously but reversibly binds ethylene at room temperature. Direct and rapid styrene formation at room temperature via insertion of the Pt-II-bound ethylene into the Pt-II-Ph fragment followed by beta-hydride elimination results in the formation of a solution-stable Pt-II-H complex. The Pt-II-H fragment is resistant toward protonolysis by acetic acid. Oxidation of the Pt-II-H fragment by excess Cu-II(OTf)(2) leads to an inorganic Pt-II complex incapable of C-H activation.

  DOI：

  10.1021/acs.organomet.6b00892
• 作为产物：
  描述：

  在 copper(I) bromide dimethylsulfide complex 作用下， 以 四氢呋喃 为溶剂， 反应 2.25h， 以73%的产率得到2-(di-tert-butylphosphonium)benzenesulfonate
  参考文献：
  名称：

  由乙烯和苯铂（II）配合物形成的苯乙烯容易形成，可观察到氢化铂（II）

  摘要：

  A new 2-(di-tert-butylphosphanyl)benzenesulfonate-supported phenylplatinum(II) complex instantaneously but reversibly binds ethylene at room temperature. Direct and rapid styrene formation at room temperature via insertion of the Pt-II-bound ethylene into the Pt-II-Ph fragment followed by beta-hydride elimination results in the formation of a solution-stable Pt-II-H complex. The Pt-II-H fragment is resistant toward protonolysis by acetic acid. Oxidation of the Pt-II-H fragment by excess Cu-II(OTf)(2) leads to an inorganic Pt-II complex incapable of C-H activation.

  DOI：

  10.1021/acs.organomet.6b00892

文献信息

• <i>P</i>-Chiral Phosphine–Sulfonate/Palladium-Catalyzed Asymmetric Copolymerization of Vinyl Acetate with Carbon Monoxide
  作者：Akifumi Nakamura、Takeharu Kageyama、Hiroki Goto、Brad P. Carrow、Shingo Ito、Kyoko Nozaki

  DOI：10.1021/ja3044344

  日期：2012.8.1

  phosphine-sulfonate ligand enabled asymmetric copolymerization of vinyl acetate with carbon monoxide. The obtained γ-polyketones have head-to-tail and isotactic polymer structures. The origin of the regio- and stereoregularities was elucidated by stoichiometric reactions of acylpalladium complexes with vinyl acetate. The present report for the first time demonstrates successful asymmetric coordination-insertion

  使用带有 P-手性膦磺酸盐配体的钯催化剂可以实现乙酸乙烯酯与一氧化碳的不对称共聚。得到的γ-聚酮具有头对尾和全同立构的聚合物结构。通过酰基钯配合物与乙酸乙烯酯的化学计量反应阐明了区域和立体规则性的起源。本报告首次证明了醋酸乙烯酯的成功不对称配位插入（共）聚合。
• Incorporation of Vinyl Chloride in Insertion Polymerization
  作者：Hannes Leicht、Inigo Göttker-Schnetmann、Stefan Mecking

  DOI：10.1002/anie.201209724

  日期：2013.4.2

  palladium‐catalyzed insertion copolymerization of vinyl chloride (VC) and ethylene gave chlorinated polyethylene with CH3CHCl(CH2)n units (see scheme; C blue, O red, Pd orange, S yellow). The CH3CHCl end groups form by 2,1‐insertion of VC into palladium hydride complexes, as revealed by detailed labeling studies. This first example of VC incorporation (up to 0.4 mol %) clearly shows that insertion (co)polymerization

  钯催化的氯乙烯（VC）和乙烯的插入共聚反应生成了n单元为CH 3 CHCl（CH 2）的氯化聚乙烯（参见方案； C蓝色，O红色，Pd橙色，S黄色）。详细的标记研究表明，CH 3 CHCl端基是通过将VC以2,1插入氢化钯络合物中而形成的。VC掺入的第一个实例（至多0.4mol％）清楚地表明，VC的插入（共）聚合在原则上是可行的。
• Structure-Activity Relationship of Palladium Phosphanesulfonates: Toward Highly Active Palladium-Based Polymerization Catalysts
  作者：Laurence Piche、Jean-Christophe Daigle、Gregor Rehse、Jerome P. Claverie

  DOI：10.1002/chem.201103694

  日期：2012.3.12

  lead to the most active catalysts. Thus, the catalyst based on phosphane bis‐tert‐butyl‐phosphanyl‐benzenesulfonic acid (R=tBu) exhibits unprecedented high activity, rapidly polymerizing ethylene at room temperature to yield a linear polymer of high molecular weight (Mw=116 000 g mol−1). The influence of the R group on the catalyst ability to incorporate methyl acrylate is also investigated.

  钯phosphanesulfonate [R 2 P（C 6 H ^ 4 - ö -SO 3）PdMeL]催化剂允许一个特殊的大量官能烯烃与乙烯的共聚。然而，这些催化剂通常具有降低的活性。我们在这里对膦取代基R对活性和分子量的影响进行了系统的研究。具有强σ-给体特性的磷光体被证明是活性最高的催化剂。因此，基于膦基双叔丁基-膦酰基-苯磺酸（R = t Bu）的催化剂表现出空前的高活性，可在室温下迅速聚合乙烯以生成高分子量的线性聚合物（M w = 116 000 g mol -1）。还研究了R基团对催化剂引入丙烯酸甲酯能力的影响。
• Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes
  作者：Zi-Heng Zhang、Li-Jun Han、Shuang-Shuang Ma、Yi-Ran Du、Zheng-Kun Yu、Jin-Qing Lin、Bao-Hua Xu

  DOI：10.1021/acs.joc.2c02245

  日期：2023.1.20

  The Pd(cod)Cl2-catalyzed alkoxycarbonylation of conjugated dienes to β,γ-unsaturated esters was approached by both intramolecular phosphinesulfonate L1 and intermolecular PPh3/PTSA in this study. However, the poor solubility of the Pd/L1 complex and the labile monodentate Pd/PPh3 structure restricts the system efficiency, especially for the scale-up application. By contrast, the stable and well-soluble

  本研究采用分子内膦磺酸盐 L 1和分子间 PPh 3 /PTSA 来研究Pd(cod)Cl 2催化的共轭二烯烷氧基羰基化生成 β,γ-不饱和酯。然而，Pd/L 1配合物的溶解度差和不稳定的单齿Pd/PPh 3结构限制了系统效率，特别是对于放大应用。相比之下，稳定且易溶的双齿 Xantphos 系统允许在弱碱性N2中在 6 小时内以克为单位定量形成 3-戊烯酸酯 (96%)- 甲基吡咯烷酮 (NMP)，它还充当促进限速醇解步骤的碱性位点，同时将配体的用量降低至理论值。
• Quantification of the Steric Influence of Alkylphosphine–Sulfonate Ligands on Polymerization, Leading to High-Molecular-Weight Copolymers of Ethylene and Polar Monomers
  作者：Yusuke Ota、Shingo Ito、Jun-ichi Kuroda、Yoshikuni Okumura、Kyoko Nozaki

  DOI：10.1021/ja505558e

  日期：2014.8.27

  A series of palladium/alkylphosphine-sulfonate catalysts were synthesized and examined in the homopolymerization of ethylene and the copolymerization of ethylene and polar monomers. Catalysts with alkylphosphine-sulfonate ligands containing sterically demanding alkyl substituents afforded (co)polymers whose molecular weight was increased by up to 2 orders of magnitude relative to polymers obtained from previously reported catalyst systems. The polymer molecular weight was found to be closely correlated to the Sterimol B5 parameter of the alkyl substituents in the alkylphosphine-sulfonate ligands. Thus, the use of bulky alkylphosphine-sulfonate ligands represents an effective and versatile method to prepare high-molecular-weight copolymers of ethylene and various polar monomers, which are difficult to obtain by previously reported methods.