1,1,1-tris(di(4-methylphenyl)phosphinomethyl)ethane | 22031-15-8

• 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: 1,1,1-tris(di(4-methylphenyl)phosphinomethyl)ethane
• 英文别名: H₃CC[CH₂P(p-tol)₂]₃；1,1,1-tris{bis(4-methylphenyl)phosphinomethyl}ethane；[3-Bis(4-methylphenyl)phosphanyl-2-[bis(4-methylphenyl)phosphanylmethyl]-2-methylpropyl]-bis(4-methylphenyl)phosphane
• CAS: 22031-15-8
• 化学式: C₄₇H₅₁P₃
• 分子量: 708.843
• InChiKey: KRNHOTYJRGAQEC-UHFFFAOYSA-N

物化性质

• 沸点：
  758.1±60.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  11.5
• 重原子数：
  50
• 可旋转键数：
  12
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.23
• 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：

  1,1,1-tris(di(4-methylphenyl)phosphinomethyl)ethane 在 水 、 lithium 作用下， 生成 [2-methyl-3-(4-methylphenyl)phosphanyl-2-[(4-methylphenyl)phosphanylmethyl]propyl]-(4-methylphenyl)phosphane
  参考文献：
  名称：

  Diastereoselectivity in the Reaction of RCH ₂ C[CH ₂ P (Ar)(Lr)] ₃ with Electrophiles: Enhancement of Diastereoselective Control by η ³ ‐Coordination in {RCH ₂ C[CH ₂ P(Ar)(Li) ₃ }Mo(Co) ₃

  摘要：

  AbstractFollowing a procedure developed for H3CC[CH2P(Ph)2]3 (1a) as the starting compound, various tripod ligands RCH2C[CH2P(Ar)2]3 (1) have been transformed into the trilithiotriphosphides RCH2C[CH2P(Ar)(Li)]3 with various electrophiles R′ — Hal leads to the two diastereomers of RCH2C[CH2P‐(Ar)(R)]3 (6) with an (RRR/SSS : RRS/SSR) ratio close to the statistical value of 1:3, except when ArPh and R′Bzl, where the RRS/SSR diastereomer is obtained almost exclusively. In contrast, the reaction of [RCH2C[CH2P(Ar)(Li)[3]‐Mo(CO)3 (4) with electrophiles R′ — Hal tends to favour the formation of the homochiral RRR/SSS diastereomers. The triphosphide coordination compounds 4 are available by two different routes: either the complexes (RCH2C[CH2P‐(Ar)(H)]3Mo(CO)3, obtained from 2 and (CH3CN)3Mo(CO)3, are deprotonated by MeLi, or the trilithiotriphosphides RCH2C[CH2P(Ar)(Li)]3 are reacted with (CH3CN)3Mo(CO)3 to produce 4 in high yields. The ration in which the two diastereomeric forms of 5 are obtained depends on the nature of the electrophile: the greatest diastereomeric discrimination is obtained for ArPh, RPh, R′Bzl, where the homochiral relative to the RRS/SSR pair. Two‐dimensional NMR spectra and simulations of one‐dimensional spectra are used to ascertain the diastereomeric excess in each case. X‐ray analyses of three compounds of type 5 (5d, ArPh, RH, R′Ph, R′Bzl) indicate the remarkable conformational stability of the tripod metal scaffolding, with the conformations observed for these three compounds in three different solid‐state environments being closely similar, even with respect to the torsional arrangement of the phosphorus‐bound benzyl groups.

  DOI：

  10.1002/cber.19971301006
• 作为产物：
  描述：

  在 三乙烯二胺 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以72%的产率得到1,1,1-tris(di(4-methylphenyl)phosphinomethyl)ethane
  参考文献：
  名称：

  三磷酸衍生物和二膦如钌催化的胺化醇用NH配体3 †

  摘要：

  据报道，钌-三磷和二膦催化氨醇化。合成了各种类型的具有给电子官能团的三醇衍生物，并将其用作Ru催化的NH 3醇胺化反应的配体。三光衍生物对于伯胺的形成是有效的。另一方面，如果使用半不稳定的二膦作为三齿配体，则可获得仲胺与伯胺的混合物。发现甚至简单的二膦也可以用作选择性形成仲胺的配体。二膦系统允许Ru催化形成仲胺的新途径。

  DOI：

  10.1039/c5dt04870b
• 作为试剂：
  描述：

  二氧化碳 在 氢气 、 双三氟甲烷磺酰亚胺 、 1,1,1-tris(di(4-methylphenyl)phosphinomethyl)ethane 、 cobalt acetylacetonate 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 24.0h， 生成 甲醇
  参考文献：
  名称：

  CO2的均相催化加氢制为甲醇–定制配体的改进

  摘要：

  已经开发出了用于将二氧化碳加氢成甲醇的改进的分子限定的钴催化剂。生产率提高的关键因素（是三聚体配体上取代基的特殊性质）（是以前最先进的系统的两倍）。另外，已经研究了金属前体的作用以及添加剂的变化。

  DOI：

  10.1002/adsc.201801314

文献信息

• Eine einfache synthese von tripod-liganden H3CC(CH2PAr2)3: Anwendungsbreite und komplexchemie
  作者：A. Muth、O. Walter、G. Huttner、A. Asam、L. Zsolnai、Ch. Emmerich

  DOI：10.1016/0022-328x(94)80044-8

  日期：1994.4

  The reaction of 1,1,1-tris(chlormethyl)ethane H3CC(CH2Cl)3 with Ar2PH in DMSO as the solvent using KOH/H2O as the base gives good yields of tripod ligands H3CC(CH2PAr2)3, 2. Using Ph2PH as the phosphine component, it is shown that the chloride substituents of H3CC(CH2Cl)3 are exchanged in sequence by the formation of H3CC(CH2Cl)2(CH2PPh2), 1a, and H3CC(CH2Cl)(CH2PPh2)2, 1b, respectively. The product

  1,1,1-三（氯甲基）乙烷H 3 CC（CH 2 Cl）3与Ar 2 PH在DMSO中的溶剂以KOH / H 2 O为碱的反应产生了良好的三脚架配体H 3 CC收率（CH 2 PAR 2）3，2。使用Ph 2 PH作为膦组分，表明H 3 CC（CH 2 Cl）3的氯取代基通过形成H 3 CC（CH 2 Cl）2（CH 2 PPh 2）依次交换，图1A和H 3 CC（CH 2 Cl）的（CH 2 PPH 2）2，1B，分别。产品组成几乎完全由所应用的化学计量确定。获得三脚架配体2，其中Ar =苯基，2a，3-甲苯基，2b，4-甲苯基，2c，4-叔丁基苯基，2d，1-萘基，2f和Ar 2 P二苯并磷酰基，2e作为Ar 2个P组。它们在钼和铁的配合物的面部的协调能力是通过所述类型的化合物的表征证实三球的Mo（CO）3，3，和[三脚架-铁（NCCH 3）3 ]（BF 4）2，4。化合物1-4的
• Tailor-Made Ruthenium-Triphos Catalysts for the Selective Homogeneous Hydrogenation of Lactams
  作者：Markus Meuresch、Stefan Westhues、Walter Leitner、Jürgen Klankermayer

  DOI：10.1002/anie.201509650

  日期：2016.1.22

  tailored tridentate ligand enabled the synthesis of a molecular ruthenium‐triphos catalyst, eliminating dimerization as the major deactivation pathway. The novel catalyst design showed strongly increased performance and facilitated the hydrogenation of highly challenging lactam substrates with unprecedented activity and selectivity.

  定制的三齿配体的开发实现了分子钌-三磷催化剂的合成，消除了二聚化作为主要的失活途径。新颖的催化剂设计显示出强劲的性能提升，并促进了具有挑战性的内酰胺底物的氢化，具有前所未有的活性和选择性。
• METHOD FOR PRODUCING ALCOHOL BY HYDROGENATING LACTONE AND CARBOXYLIC ACID ESTER IN LIQUID PHASE
  申请人：Maeda Hirofumi

  公开号：US20100113842A1

  公开（公告）日：2010-05-06

  Disclosed is a method for producing an alcohol from a lactone or a carboxylic acid ester, which enables to produce an alcohol from a lactone or a carboxylic acid ester under relatively mild conditions with high yield and high catalytic efficiency. This method also enables to produce an optically active alcohol from an optically active lactone or an optically active carboxylic acid ester. Specifically disclosed is a method for producing an alcohol by hydrogen reducing a lactone or a carboxylic acid ester in the presence of a catalyst containing ruthenium and a phosphine compound represented by the following general formula (1): wherein R 1 represents a spacer; R 2 , R 3 , R 4 , R 5 , R 6 and R 7 independently represent a hydrogen atom, an alkyl group having 1-12 carbon atoms, an aryl group or a heterocyclic group; and R 8 , R 9 , R 10 , R 11 , R 12 and R 13 independently represent an alkyl group having 1-12 carbon atoms, an aryl group or a heterocyclic group.

  本发明公开了一种从内酯或羧酸酯中制备醇的方法，该方法可以在相对温和的条件下高收率、高催化效率地从内酯或羧酸酯中制备醇。该方法还可以从手性内酯或手性羧酸酯中制备手性醇。具体公开了一种通过在催化剂中加入钌和以下通式（1）所代表的膦化合物的存在下，氢化还原内酯或羧酸酯制备醇的方法：其中R1代表间隔物，R2、R3、R4、R5、R6和R7分别独立地代表氢原子、具有1-12个碳原子的烷基、芳基或杂环基，R8、R9、R10、R11、R12和R13分别独立地代表具有1-12个碳原子的烷基、芳基或杂环基。
• METHOD FOR PRODUCING ALCOHOL BY HYDROGENATING LACTONE OR CARBOXYLIC ACID ESTER IN LIQUID PHASE
  申请人：Takasago International Corporation

  公开号：EP2141142B1

  公开（公告）日：2015-03-04
• US8013193B2
  申请人：——

  公开号：US8013193B2

  公开（公告）日：2011-09-06