3,5-bis(phenylthiomethyl)aniline | 251912-40-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 3,5-bis(phenylthiomethyl)aniline
• 英文别名: 3,5-Bis(phenylsulfanylmethyl)aniline；3,5-bis(phenylsulfanylmethyl)aniline
• CAS: 251912-40-0
• 化学式: C₂₀H₁₉NS₂
• 分子量: 337.51
• InChiKey: IDSDWYRNSDWILG-UHFFFAOYSA-N

物化性质

• 沸点：
  531.9±50.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  76.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,5-bis(phenylthiomethyl)aniline 在 4-二甲氨基吡啶 、 N,N'-羰基二咪唑 、 三氟乙酸 作用下， 以 氯仿 为溶剂， 反应 50.0h， 生成 N-3,5-bis(phenylthiomethyl)phenyl-6-aminocaproamide
  参考文献：
  名称：

  Palladium-Catalyzed C−C Coupling under Thermomorphic Conditions

  摘要：

  Liquid-liquid biphasic systems that exhibit an increase in phase miscibility at elevated temperature together with soluble polymer-bound catalysts that have a strong phase preference at ambient temperature are described. In such systems, product isolation and catalyst recovery are effected by a liquid/liquid separation. This report-describes the use of such thermomorphic catalyst recovery systems for palladium-catalyzed carbon-carbon bond forming reactions. Poly(N-isopropylacrylamide) (PNIPAM)-bound phosphine ligands with a Pd(0) catalyst used previously in allylic substitution chemistry are efficient catalysts in Heck, Suzuki, and sp-sp(2) cross-coupling reactions. Air-stable tridentate SCS-Pd(II) catalysts bound to PNIPAM or poly(ethylene glycol) (PEG) are also described. A particular advantage of these SCS catalysts is that no precautions against adventitious catalyst oxidation need be taken with the polymer-bound SCS-PdCl catalysts; thus avoiding time-consuming solvent purification and degassing protocols.

  DOI：

  10.1021/ja001708g
• 作为产物：
  描述：

  5-氨基间苯二甲酸二甲酯 在 吡啶 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 氯化亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 65.0h， 生成 3,5-bis(phenylthiomethyl)aniline
  参考文献：
  名称：

  SCS夹钳Pd（II）配合物只是Heck催化的前催化剂的证据及其对催化剂回收和再利用的影响

  摘要：

  已通过酰胺或脲键将SCS-pincer Pd（II）络合物共价固定在多孔二氧化硅，交联聚合物（Merrifield树脂）和可溶性聚降冰片烯载体上，并在碘苯与丙烯酸正丁酯的Heck偶联中进行了评估。动力学实验和中毒研究表明，在所有情况下，钳子络合物仅充当预催化剂。与文献报道相反，没有证据表明在这里研究的任何条件下，完整的酰胺连接的SCS-Pd（II）配合物都可以催化。

  DOI：

  10.1002/adsc.200404264

文献信息

• Tridentate SCS Palladium(II) Complexes:  New, Highly Stable, Recyclable Catalysts for the Heck Reaction
  作者：David E. Bergbreiter、Philip L. Osburn、Yun-Shan Liu

  DOI：10.1021/ja991099g

  日期：1999.10.1

  A new pincer-type SCS ligand containing Pd(II) is a simple, robust catalyst for Heck chemistry using a variety of alkene acceptors and aryl iodides. It is less active with aryl bromides. While certain palladium(II) species insert slowly into the aryl C−H bond of an unsubstituted version of this ligand, the introduction of activating groups into the 5 position of the aromatic ring readily allows quantitative

  一种含有 Pd(II) 的新型钳式 SCS 配体是一种简单、稳健的 Heck 化学催化剂，使用各种烯烃受体和芳基碘化物。它对芳基溴的活性较低。虽然某些钯 (II) 物质缓慢插入到该配体的未取代版本的芳基 C-H 键中，但将活化基团引入芳环的 5 位很容易实现定量金属插入。这些配体是通过简单修饰廉价的起始材料合成并连接到可溶性聚合物上的。例如，5-氧基和 5-酰胺 SCS 配体分别通过醚或酰胺键成功附加到 5000 Mn 聚（乙二醇）上。在空气中的 DMF 溶液中，5-氧代和 5-酰胺配合物都具有作为 Heck 催化剂的活性。PEG 结合的 5-酰胺-SCS-Pd 复合物通过溶剂沉淀循环 3 次，没有观察到催化剂失活。虽然 5-amido-SCS-Pd 配合物非常坚固，但它们的 5-oxo 对应物在 c...
• Preparation of Tethered Palladium Catalysis Supported on Gold(111) and Its Surface Characterization by X-ray Photoelectron Spectroscopy (XPS)
  作者：Rabbani M. Gulam、Masahiro Hamada、Ikuko Takamiya、Masahiko Shimoda、Satoshi Shuto、Atsushi Nishida、Shiro Tsukamoto、Mitsuhiro Arisawa

  DOI：10.1246/bcsj.81.1012

  日期：2008.8.15

  the confinement of the ligands was confirmed by X-ray photoelectron spectroscopy (XPS). Palladium was anchored to the ligands to construct heterogeneous Pd}-L-Au(11) catalysts (L = ligand). A Pd}-Au(11) catalyst was also prepared by adsorbing the Pd complex directly on the Au(lll) substrate without a tethering ligand. Both types of catalysts were used in the Mizoroki-Heck reaction to evaluate their

  螯合的束缚配体被限制在 Au(11) 基底上，并且配体的限制由 X 射线光电子能谱 (XPS) 证实。钯被固定在配体上以构建多相 Pd}-L-Au(11) 催化剂（L = 配体）。Pd}-Au(11) 催化剂也通过将 Pd 配合物直接吸附在 Au(III) 基材上而没有束缚配体来制备。两种类型的催化剂都用于 Mizoroki-Heck 反应以评估它们的催化活性。系链连接的 Pd 催化剂 (Pd}-L-Au(111) 活性随着回收而降低，而 Pd}-Au(111) 催化剂在重复使用时非常稳定。使用 XPS 评估两种催化剂类型的表面以确定Au（111）上存在束缚配体和/或Pd。
• Palladium-Catalyzed C−C Coupling under Thermomorphic Conditions
  作者：David E. Bergbreiter、Philip L. Osburn、Allan Wilson、Erin M. Sink

  DOI：10.1021/ja001708g

  日期：2000.9.1

  Liquid-liquid biphasic systems that exhibit an increase in phase miscibility at elevated temperature together with soluble polymer-bound catalysts that have a strong phase preference at ambient temperature are described. In such systems, product isolation and catalyst recovery are effected by a liquid/liquid separation. This report-describes the use of such thermomorphic catalyst recovery systems for palladium-catalyzed carbon-carbon bond forming reactions. Poly(N-isopropylacrylamide) (PNIPAM)-bound phosphine ligands with a Pd(0) catalyst used previously in allylic substitution chemistry are efficient catalysts in Heck, Suzuki, and sp-sp(2) cross-coupling reactions. Air-stable tridentate SCS-Pd(II) catalysts bound to PNIPAM or poly(ethylene glycol) (PEG) are also described. A particular advantage of these SCS catalysts is that no precautions against adventitious catalyst oxidation need be taken with the polymer-bound SCS-PdCl catalysts; thus avoiding time-consuming solvent purification and degassing protocols.
• Evidence that SCS Pincer Pd(II) Complexes are only Precatalysts in Heck Catalysis and the Implications for Catalyst Recovery and Reuse
  作者：Kunquan Yu、William Sommer、John?M. Richardson、Marcus Weck、Christopher?W. Jones

  DOI：10.1002/adsc.200404264

  日期：2005.1

  SCS-pincer Pd(II) complexes have been covalently immobilized onto porous silica, cross-linked polymer (Merrifield resin) and soluble poly(norbornene) supports via either amide or urea linkages and evaluated in the Heck coupling of iodobenzene with n-butyl acrylate. Kinetic experiments and poisoning studies indicate that in all cases the pincer complexes merely act as precatalysts. Contrary to literature

  已通过酰胺或脲键将SCS-pincer Pd（II）络合物共价固定在多孔二氧化硅，交联聚合物（Merrifield树脂）和可溶性聚降冰片烯载体上，并在碘苯与丙烯酸正丁酯的Heck偶联中进行了评估。动力学实验和中毒研究表明，在所有情况下，钳子络合物仅充当预催化剂。与文献报道相反，没有证据表明在这里研究的任何条件下，完整的酰胺连接的SCS-Pd（II）配合物都可以催化。