2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(10-phenoxaphosphino)xanthene | 221463-01-0

• 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: 2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(10-phenoxaphosphino)xanthene
• 英文别名: 10-(2,7-Ditert-butyl-9,9-dimethyl-5-phenoxaphosphinin-10-ylxanthen-4-yl)phenoxaphosphinine
• CAS: 221463-01-0
• 化学式: C₄₇H₄₄O₃P₂
• 分子量: 718.812
• InChiKey: AGNHAZVHSZAGDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.3
• 重原子数：
  52
• 可旋转键数：
  4
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.23
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  acetylacetonatodicarbonylrhodium(l) 、 2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(10-phenoxaphosphino)xanthene 以 氘代苯 为溶剂， 生成 (2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(10-phenoxaphosphino)xanthene)Rh(CO)2H 、 氢气
  参考文献：
  名称：

  New Phosphacyclic Diphosphines for Rhodium-Catalyzed Hydroformylation

  摘要：

  The use of phosphacyclic diphosphines based on the xanthene backbone as ligands in rhodium-catalyzed hydroformylation was studied. New phosphacyclic xantphos ligands with wide natural bite angles were synthesized, and a short, efficient route toward the synthesis of 10-chlorophenoxaphosphine and 10-chlorophenothiaphosphine was developed. The effect of the phosphacyclic moieties on the coordination chemistry in the (diphosphine)Rh(CO)(2)H complexes was investigated using NMR and IR spectroscopy. Both NMR and IR spectroscopy showed that the phosphacyclic xantphos ligands exhibit an enhanced preference for diequatorial(ee) chelation compared to the diphenylphosphino-substituted parent compound. In the hydroformylation of 1-octene the introduction of the phosphacyclic moieties leads to higher reaction rates. More importantly, the dibenzophospholyl- and phenoxaphosphino-substituted xantphos ligands exhibit an unprecedented high activity and selectivity in the hydroformylation of trans 2- and 4-octene to linear nonanal. The high activities of the phosphacyclic xantphos ligands are explained by the lower phosphine basicity and the wider natural bite angles of the phosphacyclic ligands. The extraordinary high activity of the phenoxaphosphino - substituted xantphos ligand can be attributed to the 4- to 6 -fold higher rate of CO dissociation compared to the other xantphos ligands. CO dissociation rates from the (diphosphine)Rh(Co)(2)H complexes were determined using (CO)-C-13 labeling in rapid-scan IR experiments.

  DOI：

  10.1021/om990523j
• 作为产物：
  描述：

  二苯醚 在 正丁基锂 、 四甲基乙二胺 、 三氯化磷 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 68.0h， 生成 2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(10-phenoxaphosphino)xanthene
  参考文献：
  名称：

  用新型铑催化剂将内部烯烃加氢甲酰化为线性醛。

  摘要：

  使用具有刚性二膦配体的铑催化剂，在内部辛烯加氢甲酰化为线性产物中观察到前所未有的高活性和选择性。分别具有120和119°咬合角的二苯并磷腈1和苯氧磷烷类似物适用于此。

  DOI：

  10.1002/(sici)1521-3773(19990201)38:3<336::aid-anie336>3.0.co;2-p
• 作为试剂：
  描述：

  一氧化碳 、 4-乙烯基-1-环己烯 在 1,3-bis(2,4,6-trimethylphenyl)imidazolinium-2-carboxylate 、 acetylacetonatodicarbonylrhodium(l) 、 2,7-di-tert-butyl-9,9-dimethyl-4,5-bis(10-phenoxaphosphino)xanthene 作用下， 以 正庚烷 为溶剂， 80.0 ℃ 、4.0 MPa 条件下， 反应 20.0h， 以94%的产率得到1,6-di(cyclohex-3-en-1-yl)-4-hydroxyhexan-3-one
  参考文献：
  名称：

  高效的多米诺加氢甲酰化/联苯甲醛缩合：α-羟基酮的高度选择性合成

  摘要：

  已开发出一种改进的多米诺加氢甲酰化/安息香缩合生成α-羟基酮的方法。容易获得的烯烃可以以高收率平稳地转化为相应的α-羟基酮，并具有出色的区域选择性。成功的关键是使用由铑/膦配合物和N杂环卡宾的CO 2加合物组成的特定催化体系。

  DOI：

  10.1002/chem.201502982

文献信息

• Method for the production of 1,7-octadiene and use thereof
  申请人：Bohm Volker

  公开号：US20070083066A1

  公开（公告）日：2007-04-12

  The invention relates to a method for the production of 1,7 octadiene by reacting metathesis of cyclohexene with ethylene. The invention also relates to the production of 1,10-decandiol by hydroformulating 1,7 octadiene produced according to said method. The invention further relates to a method for the production of muscone or olefinically unsaturated analogs thereof using 1,10 decandiol which is obtainable in said manner.

  该发明涉及一种通过环己烯与乙烯进行交换反应生产1,7-辛二烯的方法。该发明还涉及通过对按照该方法生产的1,7-辛二烯进行氢甲酰化制备1,10-癸二醇的方法。该发明还涉及一种利用以该方式获得的1,10-癸二醇生产麝香酮或其烯烃不饱和类似物的方法。
• Valeraldehyde and process for its preparation
  申请人：Celanese GmbH

  公开号：US06342605B1

  公开（公告）日：2002-01-29

  Bidentate phosphine ligands of the formula wherein the substituents are as defined in the specification and a process for preparing linear aldehydes by hydroformylating internal olefins using such phosphine ligands.

  本发明涉及一种双膦配体，其化学式为所述规范中定义的取代基，并且涉及一种使用这种膦配体通过氢甲酰化内部烯烃制备线性醛的方法。
• VERFAHREN ZUR KONTINUIERLICHEN HERSTELLUNG VON ALDEHYDEN
  申请人：BASF SE

  公开号：EP1678113B1

  公开（公告）日：2008-07-16
• Method for the continuous production of aldehydes
  申请人：Volland Martin

  公开号：US20070004939A1

  公开（公告）日：2007-01-04

  The invention relates to a method for the continuous production of aldehydes comprising between 5 and 21 carbon atoms, by the isomerising hydroformylation in a homogenous phase of olefin compositions comprising between 4 and 20 carbon atoms and containing α-olefins and olefins with internal double bonds, by means of a synthesis gas, in the presence of a homogeneous rhodium catalyst that is complexed with an organophosphorus ligand containing oxygen atoms and/or nitrogen atoms and a free ligand. Said production is carried out at high temperature and high pressure in a multi-stage reaction system consisting of at least two reaction zones. According to said method, the olefin composition is first reacted in a first reaction zone or a group of several first reaction zones at a total pressure of between 10 and 40 bar, using a synthesis gas with a CO/H 2 molar ratio of between 4:1 and 1:2 until a 40 to 95% conversion of the α-olefins is obtained. The hydroformylation product from the first reaction zone or group of several first reaction zones is then reacted in a subsequent reaction zone or group of several reaction zones at a total pressure of between 5 and 30 bar, using a synthesis gas with a CO/H 2 molar ratio of between 1:4 and 1:1000. The total pressure in the subsequent reaction zone or zones is respectively 1 to (G1−Gf) bar lower than that of the preceding reaction zone, whereby G1 represents the total pressure in the respective preceding reaction zone and Gf represents the total pressure in the respective reaction zone that succeeds said first reaction zone or zones, with the proviso that the difference between G1 and Gf is greater than 1 bar and the partial CO pressure in the subsequent reaction zone or zones is respectively lower than that of the preceding reaction zone.
• Method for Hydroformylating Olefins in the Presence of Organophosphoric Compounds
  申请人：Borgmann Cornelia

  公开号：US20070282130A1

  公开（公告）日：2007-12-06

  (EN) The invention relates to the use of novel organophosphoric compounds and metal complexes thereof in catalytic reactions, and to the hydroformylation of olefins in the presence of these compounds.