tris(2-isopropylphenyl)phosphite | 31502-35-9

• 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-isopropylphenyl)phosphite
• 英文别名: P(C6H4-2-iPr)3；tri(o-isopropylphenyl)phosphite；Tri(o-isopropylphenyl) phosphite；tris(2-propan-2-ylphenyl) phosphite
• CAS: 31502-35-9
• 化学式: C₂₇H₃₃O₃P
• 分子量: 436.531
• InChiKey: IJOFZIRWMBOMHP-UHFFFAOYSA-N

物化性质

• 沸点：
  473.4±44.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  31
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  甲醇 、 双(乙腈)氯化钯(II) 、 tris(2-isopropylphenyl)phosphite 以 二氯甲烷 为溶剂， 以63%的产率得到cis/trans-[PdCl2(P(OC6H4-2-iPr)3)2]
  参考文献：
  名称：

  The influence of steric bulk on the geometry of triarylphosphite-based palladacycles and their tricyclohexylphosphine adducts

  摘要：

  A range of complexes of the formula [PdCl2{P(OAr)(3)}(2)] have been synthesized in order to determine the effect of steric bulk on stereochemistry, one example [PdCl2{P(OC6H4-2-Bu-t)(3)}(2)] has been structurally characterized. Three palladacyclic complexes [{Pd(mu-Cl)-(kappa(2)-P, C-P(OC6H3R)(OC6H4R)(2))}(2)] have been synthesized (R = H, 2-Pr-t, 2-Bu-t) and two have been characterized by crystallography (R = H and Bu-t). The latter adopts the expected trans geometry while the former is cis. In this case, the driving force for the cis geometry seems to be intermolecular interactions in the crystal structure which are disrupted on substitution. We also report an unusual solvolysis reaction. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2005.11.014
• 作为产物：
  描述：

  异丙苯酚 在 2,3-二甲基苯胺 、 三氯化磷 作用下， 以 xylene 为溶剂， 以80%的产率得到tris(2-isopropylphenyl)phosphite
  参考文献：
  名称：

  镍催化异戊二烯区域选择性环二聚的机理

  摘要：

  对各种Ni-配体催化的异戊二烯低聚的研究表明，使用π-酸性P配体，对环二聚体的选择性达97％。引入了一种新型的配体，即。具有与-PCl 3相当的π-受体特性的亚磷酸氟烷基酯。亚磷酸三（六氟异丙基）酯的主要产物是1,4-二甲基1-4-乙烯基环己烯。给出了基于两步机制的详细说明。关于第一步，对于一系列具有相似空间特性的配体，根据Ni和烯烃之间HOMO-LUMO相互作用的逐渐变化（具有很强的π）解释了产物分布随电子配体参数变化的变化。 -酸性配体促进异戊二烯分子的头对头偶联。第二步涉及从金属中还原性消除环二聚体，显示出随着配体的π-酸度增加，对头对头和尾对尾中间体对取代的环己烯的选择性增加。

  DOI：

  10.1016/s0040-4020(01)97949-9

文献信息

• On the mechanism of the nickel-catalysed regioselective cyclodimerization of isoprene
  作者：P.W.N.M. van Leeuwen、C.F. Roobeek

  DOI：10.1016/s0040-4020(01)97949-9

  日期：——

  similar steric properties the changes in product distribution as a function of the electronic ligand parameter are explained in terms of a gradual change in HOMO-LUMO interactions between Ni and the olefins, with strong π-acidic ligands promoting the head-to-head coupling of the isoprene molecules. The second step, involving reductive elimination of a cyclodimer from the metal, shows an increasing selectivity

  对各种Ni-配体催化的异戊二烯低聚的研究表明，使用π-酸性P配体，对环二聚体的选择性达97％。引入了一种新型的配体，即。具有与-PCl 3相当的π-受体特性的亚磷酸氟烷基酯。亚磷酸三（六氟异丙基）酯的主要产物是1,4-二甲基1-4-乙烯基环己烯。给出了基于两步机制的详细说明。关于第一步，对于一系列具有相似空间特性的配体，根据Ni和烯烃之间HOMO-LUMO相互作用的逐渐变化（具有很强的π）解释了产物分布随电子配体参数变化的变化。 -酸性配体促进异戊二烯分子的头对头偶联。第二步涉及从金属中还原性消除环二聚体，显示出随着配体的π-酸度增加，对头对头和尾对尾中间体对取代的环己烯的选择性增加。
• Process for the preparation of epsilon-Caprolactam
  申请人：DSM N.V.

  公开号：EP1251122A1

  公开（公告）日：2002-10-23

  The invention relates to a process for the preparation of ε-caprolactam, wherein ε-caprolactam is prepared starting from butadiene, carbon monoxide, hydrogen and ammonia and the process comprises: 1. carbonylating butadiene in the presence of an alkanol and a catalyst comprising palladium, a multidentate phosphine ligand and an acidic co-catalyst to produce alkyl-4-, alkyl-3- and alkyl-2-pentenoate, 1'. optionally isomerising the alkyl-3- and/or alkyl-2-pentenoate into alkyl-4-pentenoate, 2. hydroformylating the alkyl-4-, alkyl-3- and alkyl-2-pentenoate in the presence of a catalyst comprising rhodium and an organic phosphorous containing ligand to produce alkyl-5-formylvalerate, 3. reductively aminating alkyl-5-formylvalerate in the presence of a hydrogenation catalyst comprising ruthenium on a carrier catalyst to produce ε-caprolactam and ε-caprolactam precursors, 4. optionally converting ε-caprolactam precursors at elevated temperature into ε-caprolactam.

  本发明涉及一种制备ε-己内酰胺的方法，其中从丁二烯、一氧化碳、氢气和氨开始制备ε-己内酰胺，该方法包括：1. 在存在烷基醇和钯、多齿膦配体和酸性协同催化剂的催化剂的存在下，将丁二烯羰基化以产生烷基-4-、烷基-3-和烷基-2-戊烯酸酯；1'。可选地，将烷基-3-和/或烷基-2-戊烯酸酯异构化为烷基-4-戊烯酸酯；2. 在存在铑和含有有机磷配体的催化剂的存在下，对烷基-4-、烷基-3-和烷基-2-戊烯酸酯进行氢羰基化，以产生烷基-5-甲酰缬氨酸；3. 在载体催化剂上存在钌的氢化催化剂的存在下，还原性地氨基化烷基-5-甲酰缬氨酸，以产生ε-己内酰胺和ε-己内酰胺前体；4. 在必要时将ε-己内酰胺前体在高温下转化为ε-己内酰胺。
• [EN] PROCESS FOR THE PREPARATION OF 3-METHYLENE-?-BUTYROLACTONE<br/>[FR] PROCÉDÉ POUR LA PRÉPARATION DE 3-MÉTHYLÈNE-G-BUTYROLACTONE
  申请人：DSM IP ASSETS BV

  公开号：WO2012116977A1

  公开（公告）日：2012-09-07

  The invention relates to a process for the preparation of 3-methylene-γ-butyrolactone (Z), the process comprising a hydroformylation step wherein 1,4-butene-diol (X) or its ester derivative cis-1,4-diacetoxy butene (Y) is subjected to H2 gas and CO gas in the presence of a hydroformylation catalyst, thereby forming an intermediate product comprising a mixture of compounds containing an aldehyde group or a hemiacetal, and an oxidation step wherein the intermediate product or hydrolyzed derivative thereof is oxidized by an oxidation agent thereby forming Z.

  本发明涉及一种制备3-亚甲基-γ-丁内酯(Z)的方法，该方法包括水合甲酰化步骤和氧化步骤。其中，在存在水合甲酰化催化剂的条件下，将1,4-丁二醇(X)或其酯衍生物顺式-1,4-二乙酰氧基丁烯(Y)与H2气体和CO气体反应，从而形成包含醛基或半缩醛的化合物混合物的中间产物；然后，在氧化剂的作用下，将中间产物或其水解衍生物氧化，从而形成Z。
• [EN] PROCESS FOR PREPARING DIARYL ALKYLPHOSPHONATES AND OLIGOMERIC/POLYMERIC DERIVATIVES THEREOF<br/>[FR] PROCEDE POUR PREPARER DES DIARYL ALKYL PHOSPHONATES, ET DES DERIVES OLIGOMERES/POLYMERES CORRESPONDANTS
  申请人：SUPRESTA LLC

  公开号：WO2006026616A1

  公开（公告）日：2006-03-09

  A process is provided for the production of diaryl alkyl phosphonate by the reaction of triaryl phosphate with dialkyl alkyl phosphonate in the presence of alkali metal iodide catalyst; and, optionally, the diaryl alkyl phosphonate is reacted in situ with aromatic diol and, optionally, with at least one branching monomer, in the absence of other or further added catalyst to provide oligomeric and/or polymeric phosphonate products.

  本发明提供了一种生产二芳基烷基膦酸酯的方法，其中三芳基磷酸酯与二烷基烷基膦酸酯在碱金属碘化物催化剂的存在下反应；并且，在无其他或进一步添加催化剂的情况下，可选地在原位与芳香族二醇反应，以及可选地与至少一种分支单体反应，以提供寡聚物和/或聚合物膦酸酯产品。
• METHOD FOR PRODUCING DIALDEHYDE
  申请人：KURARAY CO., LTD.

  公开号：US20160052852A1

  公开（公告）日：2016-02-25

  Provided is an industrially advantageous method for producing a dialdehyde having a production ratio of linear dialdehydes to branched dialdehydes of 80/20 to 90/10, with an amount of rhodium to be used that is lower than that in the related art. Specifically, provided is a method for producing a dialdehyde, including reacting a linear olefinic compound having each of an ethylenic double bond and an aldehyde group on each end of the molecule with carbon monoxide and hydrogen, in the presence of a rhodium catalyst comprised of a bisphosphite represented by General Formula (I) and a rhodium compound, in which the reaction pressure of a mixed gas formed of carbon monoxide and hydrogen is decreased as the reaction proceeds, wherein R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and W represents an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 5 to 18 carbon atoms, or an alkylene-arylene group having 7 to 11 carbon atoms, and a rhodium compound.

  本发明提供了一种工业上有利的制备双醛的方法，其线性双醛与支链双醛的生产比为80/20到90/10，所需铑的量比相关技术低。具体而言，本发明提供了一种制备双醛的方法，包括在存在由一般式（I）表示的双膦酸酯和铑化合物组成的铑催化剂的条件下，将具有分子两端乙烯双键和醛基的线性烯烃化合物与一氧化碳和氢反应，其中反应压力随着反应的进行而降低，其中R代表氢原子、具有1至4个碳原子的烷基或具有1至4个碳原子的烷氧基，W代表具有1至20个碳原子的烷基、具有5至18个碳原子的环烷基或具有7至11个碳原子的烷基-芳基基团，以及铑化合物。