2-[3-(diphenylthiophosphoryl)phenoxy]-1,3-benzothiazole | 1305316-87-3

• 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-[3-(diphenylthiophosphoryl)phenoxy]-1,3-benzothiazole
• 英文别名: 2-[3-(diphenylthiophosphoryl)phenoxy]-1,3-benzothiazol；Ph2P(S)C6H4OC7H4NS；[3-(1,3-Benzothiazol-2-yloxy)phenyl]-diphenyl-sulfanylidene-lambda5-phosphane；[3-(1,3-benzothiazol-2-yloxy)phenyl]-diphenyl-sulfanylidene-λ5-phosphane
• CAS: 1305316-87-3
• 化学式: C₂₅H₁₈NOPS₂
• 分子量: 443.53
• InChiKey: WOIABKDMNVJRCK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  82.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  二(氰基苯)二氯化钯 、 2-[3-(diphenylthiophosphoryl)phenoxy]-1,3-benzothiazole 以 neat (no solvent, solid phase) 为溶剂， 生成 (2-(1,3-benzothiazol-2-yloxy)-6-(diphenylthiophosphoryl)phenyl)palladium chloride
  参考文献：
  名称：

  The first solid phase synthesis of pincer palladium complexes

  摘要：

  二聚 μ-氯桥联和单体二齿 Pd(II) 配合物与 SCN 杂化钳型配体，带有硫代磷酰基和苯并噻唑环的亚胺部分作为配位臂，在动力学控制下与 (PhCN)2PdCl2 反应形成 (20 °C，二氯甲烷溶液）通过固相合成（纯，200 °C，15 分钟）很容易转化为相应的 SCN 钳形复合物。钳配合物的合成也可以通过加热（200℃，5分钟）初始反应物的均匀混合物来进行，即配体和（PhCN）2PdCl2，通过在研钵中手动研磨获得。固相方法的功效与恶劣条件下溶液中的类似合成相当。

  DOI：

  10.1039/c1dt10680e
• 作为产物：
  描述：

  二苯基氯化膦 在 magnesium 、 sodium hydroxide 作用下， 生成 2-[3-(diphenylthiophosphoryl)phenoxy]-1,3-benzothiazole
  参考文献：
  名称：

  Thiophosphoryl-, Thiophosphoryloxy-, and Thiophosphorylamino-Benzene Derivatives as Novel Classes of Hybrid Pincer Ligands

  摘要：

  The synthetic approaches to novel families of SCE (E = S',N,O) hybrid pincer-type ligands bearing thophosphoryl, thiophosphoryloxy, and thiophosphorylamino groups in various combinations with thiophosphoryl-, thiocarbamoyl-, and imine- (including that of benzothiazole ring) donating functions have been developed. All of the ligands readily undergo direct cyclometallation (metal = Pd(II), Pt(II)) to afford 5,5- or 5,6-membered pincer complexes. Palladium complexes displayed from high to excellent catalytic performance in the Suzuki cross-coupling reaction of aryl bromides and phenylboronic acid and the higher asymmetry for a complex served as a factor of its higher catalytic activity.

  DOI：

  10.1080/10426507.2010.507726

文献信息

• The first solid phase synthesis of pincer palladium complexes
  作者：Vladimir A. Kozlov、Diana V. Aleksanyan、Mikhail V. Korobov、Natalya V. Avramenko、Rinat R. Aysin、Olga A. Maloshitskaya、Alexander S. Korlyukov、Irina L. Odinets

  DOI：10.1039/c1dt10680e

  日期：——

  Both dimeric μ-chlorine bridged and monomeric bidentate Pd(II) complexes with SCN hybrid pincer-type ligands, bearing thiophosphoryl group and imine moiety of the benzothiazole ring as coordination arms, formed in the reaction with (PhCN)2PdCl2 under kinetic control (20 °C, dichloromethane solution) were readily converted into the corresponding SCN pincer complexes via solid phase synthesis (neat, 200 °C, 15 min). The synthesis of pincer complexes can be performed also by heating (200 °C, 5 min) of a homogeneous mixture of the initial reactants, namely, the ligand and (PhCN)2PdCl2, obtained by manual grinding in a mortar. The efficacy of solid phase approaches is comparable with the analogous synthesis in solutions under severe conditions.

  二聚 μ-氯桥联和单体二齿 Pd(II) 配合物与 SCN 杂化钳型配体，带有硫代磷酰基和苯并噻唑环的亚胺部分作为配位臂，在动力学控制下与 (PhCN)2PdCl2 反应形成 (20 °C，二氯甲烷溶液）通过固相合成（纯，200 °C，15 分钟）很容易转化为相应的 SCN 钳形复合物。钳配合物的合成也可以通过加热（200℃，5分钟）初始反应物的均匀混合物来进行，即配体和（PhCN）2PdCl2，通过在研钵中手动研磨获得。固相方法的功效与恶劣条件下溶液中的类似合成相当。
• Thiophosphoryl-, Thiophosphoryloxy-, and Thiophosphorylamino-Benzene Derivatives as Novel Classes of Hybrid Pincer Ligands
  作者：Vladimir A. Kozlov、Diana V. Aleksanyan、Andrei A. Vasil'ev、Irina L. Odinets

  DOI：10.1080/10426507.2010.507726

  日期：2011.3.31

  The synthetic approaches to novel families of SCE (E = S',N,O) hybrid pincer-type ligands bearing thophosphoryl, thiophosphoryloxy, and thiophosphorylamino groups in various combinations with thiophosphoryl-, thiocarbamoyl-, and imine- (including that of benzothiazole ring) donating functions have been developed. All of the ligands readily undergo direct cyclometallation (metal = Pd(II), Pt(II)) to afford 5,5- or 5,6-membered pincer complexes. Palladium complexes displayed from high to excellent catalytic performance in the Suzuki cross-coupling reaction of aryl bromides and phenylboronic acid and the higher asymmetry for a complex served as a factor of its higher catalytic activity.
• Hybrid Thiophosphoryl–Benzothiazole Palladium SCN-Pincer Complexes: Synthesis and Effect of Structure Modifications on Catalytic Performance in the Suzuki Cross-Coupling
  作者：Vladimir A. Kozlov、Diana V. Aleksanyan、Yulia V. Nelyubina、Konstantin A. Lyssenko、Pavel V. Petrovskii、Andrei A. Vasil’ev、Irina L. Odinets

  DOI：10.1021/om101012r

  日期：2011.6.13

  80–120 °C) to afford 5,5- and 5,6-membered κ3-SCN-palladium pincer complexes 12–15 in good to high yields. Direct cycloplatination with the related platinum precursor was successful only in the case of N-[3-(1,3-benzothiazol-2-yl)phenyl]-P,P-diphenylthiophosphinic acid amide 9. The Pd(II) complexes 12–15 were found to be highly active (pre)catalysts for the Suzuki cross-coupling of a range of electronically

  的新颖的混合钳型配体3，6，9，和11，轴承，作为供位点，硫代基和苯并噻唑环的亚胺部分结合的直接向中央苯核或通过O或附连到后者NH接头在与（PhCN）2 PdCl 2（MeCN或PhCN为溶剂，80-120°C）反应的中央苯核的C（2）位置经历直接环palpalladation，得到5,5-和5 6元κ 3 -SCN -钯配合物钳形12 - 15以良好至高产率。仅在N的情况下，用相关的铂前体直接进行环铂电镀才成功-[3-（1，3-苯并噻唑-2-基）苯基] -P，P-二苯基硫代次膦酸酰胺9。将Pd（II）配合物12 - 15被发现是用于一系列与苯基硼酸改变电子芳基溴化物的Suzuki交叉偶联高活性（前）的催化剂。活性最高的复合物14a还有效促进了氯苯乙酮的偶联，在该反应建议的最佳钳形复合物中位居前列。