[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] diphenyl phosphite | 108609-91-2

• 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: [2,4-Ditert-butyl-6-[3,5-ditert-butyl-2-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]phenyl] diphenyl phosphite
• CAS: 108609-91-2
• 化学式: C₆₈H₉₀O₆P₂
• 分子量: 1065.41
• InChiKey: SROQNNPSJJCKBY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  23.8
• 重原子数：
  76
• 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：

  acetylacetonatodicarbonylrhodium(l) 、 [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] diphenyl phosphite 以 甲苯 为溶剂， 以42%的产率得到
  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

• Solution structures of hydrido-rhodium diphosphite hydroformylation catalysts
  作者：Piet W. N. M. van Leeuwen、Godfried J. H. Buisman、Annemiek van Rooy、Paul C. J. Kamer

  DOI：10.1002/recl.19941130109

  日期：——

  The NMR spectroscopy data for five hydroformylation catalysts RhH(CO)2(P-P) (P-P = diphosphite bidentate ligand) are reported and interpreted in terms of equatorial and axial coordination of the phosphorus and carbon monoxide ligands in a trigonal bipyramidal structure.

  报道了五种加氢甲酰化催化剂RhH（CO）2（PP）（PP =二亚磷酸二齿二齿配体）的NMR光谱数据，并根据三角双锥体结构中的磷和一氧化碳配体的赤道和轴向配位进行了解释。
• 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.