trans-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: trans-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane
• 英文别名: trans-1,2-bis(di-tert-butylphosphinomethyl)cyclohexane；ditert-butyl-[[(1R,2R)-2-(ditert-butylphosphanylmethyl)cyclohexyl]methyl]phosphane
• 化学式: C₂₄H₅₀P₂
• 分子量: 400.609
• InChiKey: MTBSIBMAMUWCPA-PMACEKPBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  palladium(II) trifluoroacetate 、 trans-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane 以 二氯甲烷 为溶剂， 反应 16.0h， 以54%的产率得到
  参考文献：
  名称：

  Palladium Complexes with Bulky Diphosphine Ligands as Highly Selective Catalysts for the Synthesis of (Bio-) Adipic Acid from Pentenoic Acid Mixtures.

  摘要：

  A series of sterically bulky diphosphines have been prepared, including P-2 = trans-1,2-bis[(di-tert-butylphosphino)methyllcydohexane (4), (2-methylenepropane1,3-diy1)bis(di-tert-butylphosphine) (5), bis[(di-tertbutylphosphino)methyl]dimethylsilane (6), and cis- and trans11,12-bis [ (di-tert-butylphosphino)methy1]-9,10-dihydro-9,10-ethanoanthracene (10 and 11). The corresponding palladium complexes of these ligands, P2Pd(CF3CO2)(2), have been synthesized and characterized. The solid-state structures of [Pd(4)(CF3CO2)(2)], [Pd(S)(CF3CO2)(2)], [Pd(6)(CF3CO2)(2)], and [Pd(11)(CF3CO2)(2)] were obtained by single-crystal X-ray diffraction and confirm the bidentate binding mode of the ligand and a square-planar coordination geometry with a minor distortion from the ideal. The diphosphines in combination -with Pd(OAc)(2) have been applied in the hydroxycarbonylation of a mixture of pentenoic acid isomers to produce adipic acid with high selectivity (in several cases >95%). The (regio)selectivity of the hydroxycarbonylation reaction is highly dependent on the P-2 diphosphine ligand structure, particularly the steric bulk of the substituents on the diphosphine donor and the P-Pd-P bite angle in the complexes, with respectively tertiary alkyl phosphine substituents (tert-butyl, adamantyl) and a C4 backbone P-Pd-P bite angle >100 degrees being the common features of highly adipic acid selective systems. It is suggested that the regioselectivity of hydroxycarbonylation becomes largely driven by the chelation of the carboxylic acid functionality of pentenoic acid substrates, when smaller size P substituents and/or when P-2 ligands with smaller bite angles (<100 degrees) are applied.

  DOI：

  10.1021/acs.organomet.5b00517
• 作为产物：
  描述：

  (1S,2S)-1,2-环己烷二甲酸 在 lithium aluminium tetrahydride 、 正丁基锂 、 硫酸 、 氢溴酸 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 38.5h， 生成 trans-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane
  参考文献：
  名称：

  Carbonylation of ethylenically unsaturated compounds

  摘要：

  一种用于羰基化乙烯基不饱和化合物，包括乙烯酸酯的方法，以及用于生产3-羟基丙酸酯或酸的方法。该方法包括在羟基团源和催化剂体系的存在下，将所述化合物与一氧化碳反应。所述催化剂体系可通过组合以下物质获得：(a) 8、9或10族金属或其化合物；和(b) 一种一般式(I)的双齿配体：X1(X2)-Q2-A-R—B-Q1-X3(X4)。

  公开号：

  US09334227B2

文献信息

• エチレン性不飽和化合物のカルボニル化
  申请人：——

  公开号：JP2015110608A

  公开（公告）日：2015-06-18

  PROBLEM TO BE SOLVED: To provide a process for the carbonylation of ethylenically unsaturated compounds including vinyl esters and a process for the production of 3-hydroxypropanoate esters or 3-hydroxypropanoic acids.SOLUTION: The process comprises reacting the compound with carbon monoxide in the presence of a source of hydroxyl groups and of a catalyst system. The catalyst system is obtainable by combining: (a) a metal of Group 8, 9 or 10 or a compound thereof: and (b) a bidentate ligand of general formula (I): X(X)-Q-A-R-B-Q-X(X).

  要解决的问题是提供一种用于羰基化乙烯基不饱和化合物，包括乙烯酯的过程，以及用于生产3-羟基丙酸酯或3-羟基丙酸的过程。解决方案：该过程包括在羟基团源和催化剂体系的存在下将化合物与一氧化碳反应。该催化剂体系可通过组合以下物质获得：(a)第8、9或10族金属或其化合物；和(b)一种一般式(I)的双齿配体：X(X)-Q-A-R-B-Q-X(X)。
• CARBONYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS
  申请人：Lucite International UK Limited

  公开号：EP1957198B1

  公开（公告）日：2018-08-22
• Carbonylation of Ethylenically Unsaturated Compounds
  申请人：Eastham Graham Ronald

  公开号：US20090163724A1

  公开（公告）日：2009-06-25

  A process for the carbonylation of ethylenically unsaturated compounds including vinyl esters and a process for the production of 3-hydroxy propanoate esters or acids. The process comprises reacting said compound with carbon monoxide in the presence of a source of hydroxyl groups and of a catalyst system. The catalyst system is obtainable by combining: (a) a metal of Group 8, 9 or 10 or a compound thereof: and (b) a bidentate ligand of general formula (I): X 1 (X 2 )-Q 2 -A-R—B-Q 1 -X 3 (X 4 ).
• US9334227B2
  申请人：——

  公开号：US9334227B2

  公开（公告）日：2016-05-10