tris(2-tert-butyl-4-methylphenyl)phosphite | 21177-86-6

• 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: tris(2-tert-butyl-4-methylphenyl)phosphite
• 英文别名: tri(2-tert-butyl-4-methylphenyl)phosphite；TTBMPP；tri-(2-tert-butyl-4-methylphenyl)phosphite；tris(2-t-butyl-4-methylphenyl) phosphite；tris(2-t.butyl-4-methylphenyl)phosphite；tris(2-t-butyl-4-methyl)phosphite；Phenol, 2-(1,1-dimethylethyl)-4-methyl-, phosphite (3:1)；tris(2-tert-butyl-4-methylphenyl) phosphite
• CAS: 21177-86-6
• 化学式: C₃₃H₄₅O₃P
• 分子量: 520.692
• InChiKey: HBYRZSMDBQVSHO-UHFFFAOYSA-N

物化性质

• 熔点：
  106-108 °C(Solv: ethanol (64-17-5))
• 沸点：
  542.3±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.6
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  tris(2-tert-butyl-4-methylphenyl)phosphite 在 叔丁基过氧化氢 作用下， 以 正己烷 为溶剂， 生成 Tris(2-tert-butyl-4-methylphenyl) phosphate
  参考文献：
  名称：

  phosphororganische Antioxidantien. XII. Synthesen und NMR-Spektren phosphororganischer Antioxidantien und verwandter Verbindungen

  摘要：

  The syntheses of various aliphatic, aromatic, sterically hindered, and cyclic organophosphorus compounds (phosphorous acid esters, ester chlorides and ester amides, hydrogen phosphites, phosphonates and phosphates) are reported, and general procedures for preparation are given.The compounds synthesized were investigated by means of P-31-, H-1- and C-13-n.m.r. spectroscopy, and the chemical shifts measured are listed.

  DOI：

  10.1002/prac.19923340407
• 作为产物：
  描述：

  叔-丁基对甲酚 在 tert. amine 、 三氯化磷 作用下， 反应 3.0h， 生成 tris(2-tert-butyl-4-methylphenyl)phosphite
  参考文献：
  名称：

  Koenig, T.; Habicher, W. D.; Schwetlick, K., Journal fur praktische Chemie (Leipzig 1954), 1989, vol. 331, # 6, p. 913 - 922

  摘要：

  DOI：
• 作为试剂：
  描述：

  油酸甲酯 、 一氧化碳 在 acetylacetonatodicarbonylrhodium(l) 、 tris(2-tert-butyl-4-methylphenyl)phosphite 、 氢气 作用下， 以 甲苯 为溶剂， 100.0 ℃ 、999.99 kPa 条件下， 反应 1.2h， 生成 methyl formylstearate 、 methyl 9-formyloleate 、 methyl diformylstearate
  参考文献：
  名称：

  用于不饱和脂肪酸酯加氢甲酰化的大块亚磷酸酯修饰的铑催化剂

  摘要：

  AbstractA series of hydroformylation experiments was performed with a high‐grade and a technical‐grade‐derived methyl oleate (MO) and a rhodium catalyst modified by the bulky tris(2‐tert‐butyl‐4‐methylphenyl)phosphite. In the hydroformylation of pure methyl oleate, relatively high turnover numbers were obtained (400–500 mol/mol/h) under mild conditions (molar ratio MO/Rh=910, 80–100°C and 20 bar; CO/H2=1:1, solvent toluene), leading to about 95% conversion in 3 h. Fast isomerization occurs under these conditions to produce the trans oleate. Trans oleate reacts more slowly than cis oleate. At temperatures below 50°C, isomerization does not occur. The use of technical‐grade methyl oleate, containing 14% 9,12 diene, methyl linoleate (ML), results in lower reaction rates because dienes form stable π‐allylic intermediates, which slowly undergo hydroformylation. More severe conditions were applied to obtain higher rates. The rate varied from 50 to 400 mol/mol/h, depending on conditions (molar ratio MO/Rh=910, T=50–120°C, P = 50–80 bar; CO/H2=1:1–1:6, solvent, toluene). Several isomers of ML were formed during the reaction. Subsequent hydroformylation of these isomers results in a complicated mixture of products. The product mixture consists predominantly of methyl formylstearate, methyl formyloleate, methyl diformylstearate, and some yet unidentified side products. A comparison of the classic triphenylphosphine‐modified catalyst and the bulky phosphite‐modified catalyst has shown that the latter is several times more active.

  DOI：

  10.1007/s11746-997-0127-8

文献信息

• [EN] LIQUID PHOSPHITE COMPOSITION DERIVED FROM META-CRESOLS<br/>[FR] COMPOSITION LIQUIDE DE PHOSPHITES ISSUE DE MÉTA-CRÉSOLS
  申请人：CHEMTURA CORP

  公开号：WO2011014211A1

  公开（公告）日：2011-02-03

  A composition at least two different phosphites, one of which is derived from an alkylated m-cresol, wherein the composition is a liquid at ambient conditions. The other phosphites may be derived from alkylated cresol, alkylated phenol or other alkylated hydroxyaryl compounds. The cresol may be mono-alkylated or di-alkylated with a C1-C18 alkyl group.

  一种至少含有两种不同亚磷酸盐的组成物，其中一种来自烷基化间甲酚，该组成物在常温常压下为液态。其他亚磷酸盐可以来自烷基化甲酚、烷基化酚或其他烷基化羟基芳香族化合物。甲酚可以是单烷基化或二烷基化，并具有C1-C18烷基基团。
• Novel phosphinine compounds and metal complexes thereof
  申请人：DEGUSSA AG

  公开号：US20020103375A1

  公开（公告）日：2002-08-01

  Phosphinines of formula (I) can be combined with metal salts to prepare hydroformylation catalysts. The phosphinine complexes have two phosphorus centers that may be substituted with a variety of hetero atoms or alkyl substituents to modify the ligand characteristics of the phosphinine. Phosphinine metal complexes are employed under normal hydroformylation reaction conditions. The preparatory routes to the phosphinine ligands of formula (I) allow for their convenient synthesis. 1

  式(I)的膦烯可以与金属盐结合以制备氢甲酰化催化剂。膦烯配合物具有两个磷中心，可以用各种杂原子或烷基取代物替换，以改变膦烯的配体特性。膦烯金属配合物在正常的氢甲酰化反应条件下被使用。式(I)的膦烯配体的制备途径允许进行方便的合成。
• PROCESS FOR PRODUCING POLYHYDRIC ALCOHOL
  申请人：KURARAY CO., LTD.

  公开号：US20160115108A1

  公开（公告）日：2016-04-28

  A process for producing a polyhydric alcohol includes a step (I) of hydrogenating hemiacetal having a specific structure to obtain a reaction solution (I), and a step (II) of adding water to the reaction solution (I) obtained in the step (I) and further conducting hydrogenation.

  生产多元醇的过程包括以下步骤：步骤（I）对具有特定结构的半缩醛进行加氢反应，得到反应溶液（I）；步骤（II）向步骤（I）中得到的反应溶液（I）中加入水，然后继续进行加氢反应。
• 3(4),7(8)-Bis(aminomethyl)bicyclo[4.3.0]nonane and a process for its preparation
  申请人：Springer Helmut

  公开号：US20070179319A1

  公开（公告）日：2007-08-02

  3(4),7(8)-bis(aminomethyl)bicyclo[4.3.0]nonane and a process for its preparation, wherein bicyclo[4.3.0]nona-3,7-diene is reacted with synthesis gas in a homogeneous organic phase in the presence of transition metal compounds of Group VIII of the Periodic Table containing complex-bound organophosphorus compounds, and excess organophosphorus compound, at temperatures of 70 to 160° C. and pressures of 5 to 35 MPa, and the 3(4),7(8)-bisformylbicyclo[4.3.0]nonane thus obtained is reductively aminated.

  3(4),7(8)-双(氨甲基)双环[4.3.0]壬烷及其制备方法，其中双环[4.3.0]壬烯与合成气在均相有机相中，在周期表第VIII族过渡金属化合物的存在下，含有配位有机膦化合物的配合物，和过量的有机膦化合物反应，在70到160°C的温度和5到35MPa的压力下进行反应，得到的3(4),7(8)-双甲醛基双环[4.3.0]壬烷经过还原胺化。
• Bicyclo[4.3.0]nonane-3(4),7(8)-dicarboxylic acid and a process for its preparation
  申请人：Springer Helmut

  公开号：US20070179314A1

  公开（公告）日：2007-08-02

  The compound, bicyclo[4.3.0]nonane-3(4),7(8)-dicarboxylic acid and to a process for its preparation, wherein bicyclo[4.3.0]nona-3,7-diene is reacted with synthesis gas in an homogeneous organic phase in the presence of transition metal compounds of Group VIII of the Periodic Table containing complex-bound organophosphorus compounds, and of excess organophosphorus compound, at temperatures of 70 to 160° C. and pressures of 5 to 35 MPa, and the 3(4),7(8)-bisformylbicyclo[4.3.0]nonane thus obtained is oxidized, or is first hydrogenated to 3(4),7(8)-dihydroxymethylbicyclo[4.3.0]nonane and the diol thus obtained is reacted in an alkali melt.

  该化合物为双环[4.3.0]壬烷-3(4),7(8)-二羧酸，以及其制备方法，其中双环[4.3.0]壬烯与合成气在均相有机相中，在含有周期表第VIII族过渡金属化合物的复合有机膦化合物的存在下反应，并在70至160°C的温度和5至35兆帕的压力下进行，过量的有机膦化合物，然后氧化所得的3(4),7(8)-双甲酰基双环[4.3.0]壬烷，或首先将其氢化为3(4),7(8)-二羟甲基双环[4.3.0]壬烷，然后将所得的二醇在碱熔体中反应。