(2(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diylphosphite),2'(bis(4-Cl-phenyl)phosphite)-3,3,5',5'-tetra-tert-butyl-1,1'-biphenyl) | 166603-67-4

• 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(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diylphosphite),2'(bis(4-Cl-phenyl)phosphite)-3,3,5',5'-tetra-tert-butyl-1,1'-biphenyl)
• 英文别名: Bis(4-chlorophenyl) [2,4-ditert-butyl-6-[3,5-ditert-butyl-2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]phenyl] phosphite
• CAS: 166603-67-4
• 化学式: C₆₈H₈₈Cl₂O₆P₂
• 分子量: 1134.3
• InChiKey: OHKOMURVTNADCL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  25.1
• 重原子数：
  78
• 可旋转键数：
  17
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  三(三苯基膦)羰基氢化铑 、 (2(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diylphosphite),2'(bis(4-Cl-phenyl)phosphite)-3,3,5',5'-tetra-tert-butyl-1,1'-biphenyl) 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  Bulky Diphosphite-Modified Rhodium Catalysts:  Hydroformylation and Characterization

  摘要：

  The rhodium-catalyzed hydroformylation with the diphosphites P[O(2,2'-(4-X-6-Y-C6H2)(2)O][O(2,2'-(4-X-6-Y-C6H6)(2))OP][O(4-Z-C6H4](2) (X = Y = tert-butyl, Z = H (1), Z = OMe (2), Z = C6H5 (3), Z = Cl (4); X = OMe, Y = tert-butyl, Z = H (5)), [PO(2,2'-(4,6-(tert-C4H9)(2)C6H2)(2))O](2)R [R = O(CH2)(2)O (6), R = O(CH2)(3)O (7)], [PO(2,2'-(C6H4)(2))O](2)R, R = O(2,2'-(4-MeO-6-tert-C4H9C6H2)(2)O (8), R = O(2,2'-(4,6-tert-C4H9)(2)C6H2)(2)O (9)], and [PO(2,2'-(4,6-(tert-C4H9)(2)C6H2)(2))O](2)[O(2,2'-(C6H4)(2))O] (10) as ligands is studied with oct-1-ene and styrene as substrates. For oct-1-ene the highest normal to branched ratio obtained is 48 (5). For styrene the product selectivity depends strongly on the reaction temperature; a branched to normal ratio of 19 is found for 7 when T = 40 degrees C vs a branched to normal ratio of 0.19 for 1 when T = 120 degrees C. A bulky and bisequatorially (ee) coordinating diphosphite is required to obtain a high regioselectivity for linear aldehydes, while flexible diphosphites or equatorially-axially tea) coordinating diphosphites lead to an enhancement of the formation of branched aldehydes. The hydroformylation of oct-l-ene has a first-order dependency in the oct-1-ene concentration, the order in CO is approximately -0.65, and the order in Hz is approximately 0.2. This is consistent with a kinetic scheme in which alkene addition is the rate-determining step. The crystal structures of RhAcac(4) and RhH(CO)(2)(4) (11), are presented. The hydride ligand in 11 could not be located. The structure reveals a distorted TBP with 4 ee coordinated, the P(1)-Rh-P(2) angle being 115.95(9)degrees. The distortion is indicative of a crowded rhodium center which explains the obtained high linearity of the hydroformylation products.

  DOI：

  10.1021/om950549k

文献信息

• NMR spectra and crystal structure of a regioselective hydroformylation catalyst complex RhH(diphosphite)(CO)2
  作者：Annemiek van Rooy、Paul C.J. Kamer、Piet W.N.M. van Leeuwen、Nora Veldman、Anthony L. Spek

  DOI：10.1016/0022-328x(95)05465-2

  日期：1995.5

  The crystal structure and characterization in solution are described for a very regioselective hydroformylation catalyst, RhH(CO)2(diphosphite) with as the diphosphite. The complex is formed under COH2 pressure from Rh(CO)2 Acac and has a distorted TBP geometry with both phosphorus atoms in equatorial positions.

  描述了具有非常区域选择性的加氢甲酰化催化剂RhH（CO）2（二亚磷酸酯）和二亚磷酸酯作为溶液的晶体结构和表征。复杂的是下COH形成2选自Rh（CO）压力2 ACAC并且具有在赤道位置既磷原子一个扭曲的TBP几何形状。
• HYDROFORMYLATION PROCESS USING A SYMMETRIC BISPHOSPHITE LIGAND FOR IMPROVED CONTROL OVER PRODUCT ISOMERS
  申请人：Brammer Michael A.

  公开号：US20110144392A1

  公开（公告）日：2011-06-16

  A process for hydroformylating an α-olefin to produce two or more aldehydes comprising a normal aldehyde and one or more iso-aldehydes with a target molar ratio of the normal aldehyde to one or more iso-aldehydes in a selectable range from 3/1 to 60/1. The process uses a transition metal-ligand complex catalyst comprising a symmetric calixarene bisphosphite ligand. The target N/I ratio is selected by controlling carbon monoxide partial pressure.
• US8507731B2
  申请人：——

  公开号：US8507731B2

  公开（公告）日：2013-08-13
• Bulky Diphosphite-Modified Rhodium Catalysts:  Hydroformylation and Characterization
  作者：Annemiek van Rooy、Paul C. J. Kamer、Piet W. N. M. van Leeuwen、Kees Goubitz、Jan Fraanje、Nora Veldman、Anthony L. Spek

  DOI：10.1021/om950549k

  日期：1996.1.23

  The rhodium-catalyzed hydroformylation with the diphosphites P[O(2,2'-(4-X-6-Y-C6H2)(2)O][O(2,2'-(4-X-6-Y-C6H6)(2))OP][O(4-Z-C6H4](2) (X = Y = tert-butyl, Z = H (1), Z = OMe (2), Z = C6H5 (3), Z = Cl (4); X = OMe, Y = tert-butyl, Z = H (5)), [PO(2,2'-(4,6-(tert-C4H9)(2)C6H2)(2))O](2)R [R = O(CH2)(2)O (6), R = O(CH2)(3)O (7)], [PO(2,2'-(C6H4)(2))O](2)R, R = O(2,2'-(4-MeO-6-tert-C4H9C6H2)(2)O (8), R = O(2,2'-(4,6-tert-C4H9)(2)C6H2)(2)O (9)], and [PO(2,2'-(4,6-(tert-C4H9)(2)C6H2)(2))O](2)[O(2,2'-(C6H4)(2))O] (10) as ligands is studied with oct-1-ene and styrene as substrates. For oct-1-ene the highest normal to branched ratio obtained is 48 (5). For styrene the product selectivity depends strongly on the reaction temperature; a branched to normal ratio of 19 is found for 7 when T = 40 degrees C vs a branched to normal ratio of 0.19 for 1 when T = 120 degrees C. A bulky and bisequatorially (ee) coordinating diphosphite is required to obtain a high regioselectivity for linear aldehydes, while flexible diphosphites or equatorially-axially tea) coordinating diphosphites lead to an enhancement of the formation of branched aldehydes. The hydroformylation of oct-l-ene has a first-order dependency in the oct-1-ene concentration, the order in CO is approximately -0.65, and the order in Hz is approximately 0.2. This is consistent with a kinetic scheme in which alkene addition is the rate-determining step. The crystal structures of RhAcac(4) and RhH(CO)(2)(4) (11), are presented. The hydride ligand in 11 could not be located. The structure reveals a distorted TBP with 4 ee coordinated, the P(1)-Rh-P(2) angle being 115.95(9)degrees. The distortion is indicative of a crowded rhodium center which explains the obtained high linearity of the hydroformylation products.