(2,2-dimethylpropane-1,3-diyl)bis(diphenylphosphane) | 80326-98-3

• 物质功能分类: 有机原料 - 有机膦化合物
• 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: (2,2-dimethylpropane-1,3-diyl)bis(diphenylphosphane)
• 英文别名: 2,2-dimethyl 1,3-bis(diphenylphosphanyl)propane；1,3-bis(diphenylphosphino)-2,2-dimethylpropane；dppdmp；2,2-dimethyl-1,3-bis(diphenylphosphino) propane；2,2-Dimethyl-1,3-bis(diphenylphosphino)propane；(3-diphenylphosphanyl-2,2-dimethylpropyl)-diphenylphosphane
• CAS: 80326-98-3
• 化学式: C₂₉H₃₀P₂
• 分子量: 440.505
• InChiKey: JHPBVORIWHFCDS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  31
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.17
• 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：

  (2,2-dimethylpropane-1,3-diyl)bis(diphenylphosphane) 在 KF 、 18-crown-6 作用下， 以 四氢呋喃 、 吡啶 、 苯 为溶剂， 生成 bis(1,3-bis(diphenylphosphino)-2,2-dimethylpropane)palladium
  参考文献：
  名称：

  氟化物诱导的钯（II）和铂（II）膦配合物的还原

  摘要：

  A novel redox reaction involving fluoride and phosphine complexes of palladium(II) is reported. The scope of this reaction has been investigated using the ligands PPh3, Ph2P(CH2)nPPh2 (n = 1-4), Ph2PCH2C(CH3)2CH2PPh2, Ph2PCH3, and P(CH2CH2CN)3; several solvents including DMSO, pyridine, acetonitrile, and THF; and either n-Bu4NF.3H2O or KF/18-crown-6 as the fluoride source. The reduction products are palladium(0) phosphine complexes for which this reaction offers a convenient synthetic route. P-31 and F-19 NMR spectra permitted identification of the initial oxidation products as difluorophosphoranes (R3PF2), which subsequently hydrolyzed, forming phosphine oxides if a hydrated fluoride source is used. Results implicating a fluoride-induced redox reaction in the thermal decomposition of [(Ph3P)3PdCl]BF4 to yield [Pd3Cl(PPh2)2(PPh3)3] BF4 are also presented. Preliminary results indicate that platinum complexes also undergo this reaction, but nickel complexes yield NiF2. The X-ray parameters for Pd(dppp)2 (dppp = 1,3-bis(diphenyphosphino)propane) are: monoclinic, space group C2/c (No. 15), a = 18.396 (2) angstrom, b = 13.290 (1) angstrom, c = 20.186 (2) angstrom, beta = 109.383 (5)-degrees, and Z = 4.

  DOI：

  10.1021/om00042a040
• 作为产物：
  描述：

  2,2-二甲基-1,3-二氯丙烷 在 sodium 作用下， 以 二丁醚 为溶剂， 以85%的产率得到(2,2-dimethylpropane-1,3-diyl)bis(diphenylphosphane)
  参考文献：
  名称：

  WO2006/84878

  摘要：

  公开号：
• 作为试剂：
  描述：

  苯乙酮 在 (2,2-dimethylpropane-1,3-diyl)bis(diphenylphosphane) 、 二苯基(硅烷-d2) 、 二苯基硅烷 、 copper(l) chloride 、 sodium t-butanolate 、 甲醇 、 sodium hydroxide 作用下， 以 甲苯 为溶剂， 反应 2.0h， 生成 甲基苯甲醇-D1 、 苏合香醇
  参考文献：
  名称：

  铜催化酮氢化硅烷化的机理研究

  摘要：

  铜催化的酮不对称氢化硅烷化是合成手性对映纯仲醇的有效方法。在此，我们提出了铜（I）催化反应的详细计算研究（DFT/B3LYP）。特别是，已经确定了催化循环中涉及的两个过渡态。发现酮插入 Cu-H 键具有比烷氧基铜中间体与硅烷的反应更低的活化势垒，硅烷与甲硅烷基醚产物一起再生 Cu-H。我们的研究结果还揭示了氢化铜二聚体在控制对酮的反应性方面的重要性。这些结论得到了实验机制研究的支持，包括动力学研究、动力学同位素效应和同位素标记测量。

  DOI：

  10.1002/ejic.200900961

文献信息

• Method for the Production of N-Substituted (3-Dihalomethyl-1-Methyl-Pyrazole-4-yl) Carboxamides
  申请人：Zierke Thomas

  公开号：US20100174094A1

  公开（公告）日：2010-07-08

  The present invention relates to a process for preparing N-substituted (3-dihalomethylpyrazol-4-yl)carboxamides of the formula (I) in which R 1 is optionally substituted phenyl or C 3 -C 7 -cycloalkyl, R 1a is hydrogen or fluorine, or R 1a together with R 1 is optionally substituted C 3 -C 5 -alkanediyl or C 5 -C 7 -cycloalkanediyl, R 2 is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl or C 1 -C 4 -alkoxy-C 1 -C 2 -alkyl, X is F or Cl and n is 0, 1, 2 or 3; which comprises A) providing a compound of the formula (II) in which X is F or Cl, Y is Cl or Br and R 2 has one of the meanings given above and B) reacting a compound of the formula (II) with carbon monoxide and a compound of the formula (III) in which R 1 , R 1a and n have one of the meanings given above; in the presence of a palladium catalyst; to intermediates used for the preparation according to the process according to the invention, and also to processes for their preparation.

  本发明涉及一种制备式(I)的N-取代(3-二卤甲基吡唑-4-基)羧酰胺的方法 其中R1是可选的取代苯基或C3-C7环烷基，R1a是氢或氟，或者R1a与R1一起是可选的取代C3-C5-烷二基或C5-C7-环烷二基，R2是C1-C6-烷基，C2-C6-烯基，C2-C6-炔基或C1-C4-烷氧基-C1-C2-烷基，X是F或Cl，n为0、1、2或3；包括 A)提供式(II)的化合物 其中X是F或Cl，Y是Cl或Br，R2具有上述给定的含义之一 B)将式(II)的化合物与一氧化碳和式(III)的化合物反应 其中R1、R1a和n具有上述给定的含义之一；在钯催化剂的存在下； 用于根据本发明的方法制备的中间体，以及用于它们的制备的方法。
• [EN] PROCESS FOR PREPARING SUBSTITUTED ISOXAZOLINE COMPOUNDS AND THEIR PRECURSORS<br/>[FR] PROCÉDÉ DE PRÉPARATION DE COMPOSÉS ISOXAZOLINE SUBSTITUÉS ET DE LEURS PRÉCURSEURS
  申请人：BASF SE

  公开号：WO2010125130A1

  公开（公告）日：2010-11-04

  Process for preparing substituted isoxazoline compounds and their precursors The present invention relates to a new method of preparing halogenated styrene compounds of Formula (VIII), which are precursors in the process of synthesis of substituted isoxazoline compounds of Formula (I), wherein R1 to R5, R8 and R9 are described as in the description. The present invention relates further to the synthesis of compounds of formula (I) starting from acetophenones. The desired styrenes of formula are prepared from the appropriate substituted acetophenone. Asides bromo anilines react with formoxime. Obtained oximes undergo a cycloaddition with the styrenes and give isoxazolines. Compounds of formula (I) can then be prepared in a palladium catalyzed carbonylative ami- nation reaction of the isoxazolines.

  制备取代异恶唑啉化合物及其前体的工艺 本发明涉及一种制备公式(VIII)中卤代苯乙烯化合物的新方法，该卤代苯乙烯化合物是合成公式(I)中取代异恶唑啉化合物的前体，其中R1至R5、R8和R9如说明中所述。本发明进一步涉及从 acetophenones 开始合成公式(I)化合物的过程。所需的公式苯乙烯由相应的取代 acetophenone 制备。除此之外，溴苯胺与甲氧基胺反应。获得的肟与苯乙烯进行环加成并给出异恶唑啉。然后，可以在钯催化的羰基化胺化反应中制备公式(I)的化合物。
• [EN] PROCESS FOR PREPARING AMINALE AND THEIR USE FOR PREPARING 1,3-DISUBSTITUTED PYRAZOLE COMPOUNDS<br/>[FR] PROCÉDÉ DE PRÉPARATION D'AMINAL ET UTILISATION AFFÉRENTE POUR LA PRÉPARATION DE COMPOSÉS 1,3-PYRAZOLE DISUBSTITUÉS
  申请人：BASF SE

  公开号：WO2011054733A1

  公开（公告）日：2011-05-12

  Process for preparing aminale and their use for preparing 1,3-disubstituted pyrazole compounds.

  制备氨基和它们用于制备1,3-二取代吡唑化合物的过程。
• Process for preparing arylamines
  申请人：JUNG Joerg

  公开号：US20080039633A1

  公开（公告）日：2008-02-14

  The invention relates to a process for preparing arylamines or heteroarylamines or arylamides or heteroarylamides by cross-coupling of primary or secondary amines or amides with substituted aryl or heteroaryl compounds in the presence of a Brønsted base and a catalyst or precatalyst, wherein the catalyst comprises a) a transition metal, a complex, a salt or a compound of this transition metal selected from the group consisting of Ni, Pd and b) at least one ligand selected from the group consisting of bidentate bis(phosphino)alkanediyls having the following formula in a solvent or solvent mixture, where the radicals Ar 1-4 are each, independently of one another, an aryl or heteroaryl substituent selected from the group consisting of phenyl, naphthyl, pyridyl and biphenyl or Ar 1-4 is hydrogen, C 1 -, C 2 -alkyl, straight-chain, branched or cyclic C 3 -C 8 -alkyl, and L is an alkanediyl bridge which has from 1 to 20 carbon atoms.

  该发明涉及一种在Brønsted碱和催化剂或前催化剂存在下，通过一次或二次胺或酰胺与取代芳基或杂芳基化合物的交叉偶联制备芳基胺或杂芳基胺或芳酰胺或杂芳酰胺的方法，其中催化剂包括 a) 过渡金属，该过渡金属的配合物、盐或化合物，所述过渡金属选自Ni、Pd组成的群体，以及 b) 至少一种来自双齿膦烷二基的配体，其具有以下公式，在溶剂或溶剂混合物中， 其中基团Ar 1-4 分别独立地选自苯基、萘基、吡啶基和联苯基等芳基或杂芳基取代基，或Ar 1-4 为氢、C 1 -、C 2 -烷基、直链、支链或环状C 3 -C 8 -烷基，以及 L是具有1至20个碳原子的烷二基桥。
• Thorpe-Ingold Effect in Branch-Selective Alkylation of Unactivated Aryl Fluorides
  作者：Matthew J. O'Neill、Tim Riesebeck、Josep Cornella

  DOI：10.1002/anie.201804479

  日期：2018.7.16

  Presented herein is a general protocol for the alkylation of simple aryl fluorides with unbiased secondary Grignard reagents by means of nickel catalysis. This study revealed a general Thorpe–Ingold effect in the ligand backbone which confers a high degree of selectivity for the secondary carbon center in the C−C coupling event. This protocol is characterized by mild reaction conditions, robustness

  本文提出了通过镍催化用无偏的二次格氏试剂将简单的芳基氟化物烷基化的一般方案。这项研究揭示了配体主链上普遍的索普-英戈尔德效应，在CC偶合事件中赋予了次级碳中心高度的选择性。该协议的特点是反应条件温和，稳健且简单。富电子和缺电子的芳基氟化物都是该转化的合适候选物。同样适合的是各种杂环，允许偶联而在亲电子位点没有过度烷基化。