2,4,8,10-Tetramethyl-6-[[13-(2,4,8,10-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxy-3-tetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9(14),10,12-hexaenyl]oxy]benzo[d][1,3,2]benzodioxaphosphepine | 1312012-19-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: 2,4,8,10-Tetramethyl-6-[[13-(2,4,8,10-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxy-3-tetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9(14),10,12-hexaenyl]oxy]benzo[d][1,3,2]benzodioxaphosphepine
• CAS: 1312012-19-3
• 化学式: C₄₈H₄₄O₆P₂
• 分子量: 778.821
• InChiKey: SBXVWQGFHKZRPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.8
• 重原子数：
  56
• 可旋转键数：
  4
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  71
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  acetylacetonatodicarbonylrhodium(l) 、 2,4,8,10-Tetramethyl-6-[[13-(2,4,8,10-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxy-3-tetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9(14),10,12-hexaenyl]oxy]benzo[d][1,3,2]benzodioxaphosphepine 、 氢气 在 一氧化碳 作用下， 以 氘代甲苯 为溶剂， 90.0 ℃ 、1.2 MPa 条件下， 反应 2.0h， 生成 [(tMe-Rucaphosphite)Rh(H)(CO)₂] 、 [(tMe-Rucaphosphite)Rh(H)(CO)₂]
  参考文献：
  名称：

  Inter- and Intramolecular Interactions in Triptycene-Derived Bisphosphite Hydroformylation Catalysts: Structures, Energies, and Caveats for DFT-Assisted Ligand Design

  摘要：

  The hydroformylation catalyst (L)RhH(CO)(2), with a triptycene-derived bisphosphite ligand, and its iridium analogue were studied in solution, in the solid state, and computationally (DFT) in order to determine their molecular structures and to understand the equilibria between isomers. The predicted intramolecular distance of the two biphenyl side groups of these ligands strongly depends upon the treatment of inter- and intramolecular noncovalent interactions. A balanced treatment of these "weak" interactions is a prerequisite for obtaining reasonable structures and consequently also for determining relative energies of the different P-coordination modes. Low-temperature NMR studies confirm the equilibrium between axial-equatorial and equatorial-equatorial isomers in solution and have been used to estimate their relative stability in the equilibrium.

  DOI：

  10.1021/om301027x
• 作为试剂：
  描述：

  乙二醇 、 1,3-丁二烯 在 [Rh(acac)(CO)2] 、 癸烷 、 一氧化碳 、 2,4,8,10-Tetramethyl-6-[[13-(2,4,8,10-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxy-3-tetracyclo[6.6.2.02,7.09,14]hexadeca-2(7),3,5,9(14),10,12-hexaenyl]oxy]benzo[d][1,3,2]benzodioxaphosphepine 、 氢气 、 三氟乙酸 作用下， 以 甲苯 、 苯 为溶剂， 80.0 ℃ 、3.0 MPa 条件下， 反应 2.0h， 以70%的产率得到己二酸
  参考文献：
  名称：

  用于生产1,6-二取代己烷衍生物的氢甲酰化方法

  摘要：

  本发明涉及由1,3‑二不饱和烃(优选丁二烯)生产1,6‑二官能化己烷衍生物的方法，其中与一氧化碳和氢气的氢甲酰化是在至少二元链烷醇存在下进行的，且氢甲酰化期间温度升高。该反应产生1,6‑己二醛衍生物的缩醛，将其分离并进一步反应以获得所需的1,6‑二官能化己烷衍生物，特别是1,6‑己二胺、1,6‑己二醇和己二酸。

  公开号：

  CN108137451A

文献信息

• Iridium Models of Rhodium Intermediates in Hydroformylation Catalysis: Isolation and Molecular Structures of Fluxional ae and ee Isomers
  作者：Golnar Abkai、Sebastian Schmidt、Tobias Rosendahl、Frank Rominger、Peter Hofmann

  DOI：10.1021/om401139u

  日期：2014.6.23

  (equatorial–equatorial) ligand P coordination and fluxional behavior in solution. L2 is a new chelating bisphosphite with unprecedented high selectivity in Rh-catalyzed bis-hydroformylation of butadiene to adipic aldehyde. These Ir analogues are ideal stabilized structural models for nonseparable ae and ee Rh-hydroformylation resting state isomers [(L2)Rh(H)(CO)2]. With Ir, both stereoisomers with

  我们报道了具有ae（轴向-赤道）和ee（赤道-赤道）配体的三角-双锥体氢化二羰基二羰Ir配合物[（L 2）Ir（H）（CO）2 ]的两种立体异构体的合成和单晶分子结构溶液中的P配位和通量行为。L 2是一种新型的螯合双亚磷酸酯，在Rh催化的丁二烯双加氢甲酰化为己二醛中具有空前的高选择性。这些Ir类似物是不可分离的ae和ee Rh加氢甲酰基化静止状态异构体[（L 2）Rh（H）（CO）2 ]的理想稳定结构模型。使用Ir可以首次对具有相同配体的两种立体异构体进行独立表征。
• Method for the hydroformylation of 2-substituted butadienes and the production of secondary products thereof, especially ambrox
  申请人：BASF SE

  公开号：US10315975B2

  公开（公告）日：2019-06-11

  The present invention relates to a method for the regioselective hydroformylation of polyunsaturated acyclic hydrocarbons, which are 1, 3 butadienes, which, in the 2 position, bear a saturated or monounsaturated or polyunsaturated acyclic hydrocarbon radical. The present invention also relates to the production of secondary products of these hydroformylation products, especially of ambrox.

  本发明涉及一种对多不饱和无环烃进行区域选择性加氢甲酰化的方法，这些多不饱和无环烃是 1, 3 丁二烯，在 2 位上带有饱和或单不饱和或多不饱和无环烃基。本发明还涉及这些加氢甲酰化产物，特别是氨溴索的次级产品的生产。
• Hydroformylation process for producing 1,6-disubstituted hexane derivatives
  申请人：BASF SE

  公开号：US10647651B2

  公开（公告）日：2020-05-12

  The invention relates to a process for the production of 1,6-difunctionalized hexane derivatives from 1,3-diunsaturated hydrocarbons, preferably butadiene, wherein a hydroformylation with carbon monoxide and hydrogen is performed in the presence of an at least dihydric alkanol and during the hydroformylation the temperature is increased. The reaction yields the acetals of the 1,6-hexanedial derivatives which are isolated and further reacted to obtain the desired 1,6-difunctionalized hexane derivatives, in particular 1,6-hexanediamine, 1,6-hexanediol and adipic acid.

  本发明涉及一种从 1,3-二不饱和碳氢化合物（最好是丁二烯）生产 1,6-二官能化己烷衍生物的工艺，其中在至少有二元烷醇存在的情况下，用一氧化碳和氢进行加氢甲酰化，在加氢甲酰化过程中温度升高。反应生成 1,6-己二醛衍生物的乙缩醛，将其分离出来并进一步反应，可得到所需的 1,6-二官能化己烷衍生物，特别是 1,6-己二胺、1,6-己二醇和己二酸。
• Hydroformylation process for producing 1,6-hexanediol derivatives
  申请人：BASF SE

  公开号：US10941092B2

  公开（公告）日：2021-03-09

  The present invention relates to a two-stage hydroformylation process for producing pound of the formula (I) and to a process for producing a compound of the formula (V) comprising the two-stage hydroformylation process for producing a compound of the formula (I) followed by hydrogenation of the compound of the formula (I).

  本发明涉及一种生产式(I)化合物的两阶段加氢甲酰化工艺，以及一种生产式(V)化合物的工艺，该工艺包括生产式(I)化合物的两阶段加氢甲酰化工艺，然后对式(I)化合物进行氢化。
• Rhodium-Catalyzed Hydroformylation of 1,3-Butadiene to Adipic Aldehyde: Revealing Selectivity and Rate-Determining Steps
  作者：Sebastian Schmidt、Eszter Baráth、Christoph Larcher、Tobias Rosendahl、Peter Hofmann

  DOI：10.1021/om501015z

  日期：2015.3.9