bis[di(1-adamantyl)phosphino]-o-xylene | 659748-92-2

• 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: bis[di(1-adamantyl)phosphino]-o-xylene
• 英文别名: 1,2-bis(di-1-adamantylphosphinomethyl)benzene；1,2-Bis((di(adamantan-1-yl)phosphanyl)methyl)benzene；bis(1-adamantyl)-[[2-[bis(1-adamantyl)phosphanylmethyl]phenyl]methyl]phosphane
• CAS: 659748-92-2
• 化学式: C₄₈H₆₈P₂
• 分子量: 707.015
• InChiKey: MIZJPSACHCOTRL-UHFFFAOYSA-N

物化性质

• 熔点：
  229-230 °C

计算性质

• 辛醇/水分配系数(LogP)：
  11.6
• 重原子数：
  50
• 可旋转键数：
  8
• 环数：
  17.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

安全信息

• 储存条件：
  存储条件为室温、干燥环境及惰性气体中。

反应信息

• 作为反应物：
  描述：

  di(rhodium)tetracarbonyl dichloride 、 bis[di(1-adamantyl)phosphino]-o-xylene 以 二氯甲烷 为溶剂， 反应 16.0h， 以40%的产率得到[(bis[di(1-adamantyl)phosphino]-o-xylene)Rh(CO)Cl]
  参考文献：
  名称：

  Isomerizing Methoxycarbonylation of Alkenes to Esters Using a Bis(phosphorinone)xylene Palladium Catalyst

  摘要：

  The synthesis and characterization of bulky diphosphine 1,2-bis(4-phosphorinone)xylene, BPX, and its palladium complexes [(BPX)PdCl2] and [(BPX)Pd(O2CCF3)(2)] are described. BPX was evaluated as a ligand in Pd-catalyzed isomerizing methoxycarbonylation. A broad range of alkenes, including terminal, internal, branched, and functionalized alkenes, can be converted to esters with activities and selectivities matching or surpassing the performance of the state-of-the-art palladium bis(di(tert-butyl)phosphino-o-xylene (Pd-DTBPX) catalyst. A molecular structure of the precatalyst [(BPX)Pd(O2CCF3)2] was obtained showing a square planar geometry and a bite angle of 100.11(3)degrees. Rhodium carbonyl complexes [(BPX)Rh(CO)Cl] and [(DTBPX)Rh(CO)Cl] were synthesized to compare the relative electronic parameters, revealing a v(C 0) of 1956.8 and 1948.3 cm(-1), respectively, suggesting a reduced ability of BPX to donate electron density to the metal relative to DTBPX. Competitive protonation experiments between BPX and DTBPX in the presence of CH3SO3H exclusively produce [DTBPX(H)(2)](2+), providing additional evidence that BPX is a much weaker base than DTBPX. This could be due to either the effect of the electron-withdrawing ketone group in the phosphorinone ring or the compression of the C-P-C bond angle induced by the ring structure. The P-31 NMR (CDCl3) chemical shift of BPX is 5.6 ppm, upfield of DTBPX at 27.6 ppm. This anomalous result is attributed to a strong gamma substituent effect of C=0 in the BPX ligand. The improved activity of Pd-BPX, relative to Pd-DTBPX, could be attributed to a more electrophilic Pd-II center, which could accelerate the rate-determining methanolysis step.

  DOI：

  10.1021/acs.organomet.6b00813
• 作为产物：
  描述：

  金刚烷 在 光气 、 aluminum (III) chloride 、 lithium aluminium tetrahydride 、 正丁基锂 、 四甲基乙二胺 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 sodium t-butanolate 、 三氯化磷 作用下， 以 四氢呋喃 、 正己烷 、 正庚烷 、 甲苯 为溶剂， 反应 46.17h， 生成 bis[di(1-adamantyl)phosphino]-o-xylene
  参考文献：
  名称：

  Catalyst system

  摘要：

  本发明提供了一种催化剂体系，能够催化烯烃不饱和化合物的羰基化反应，该体系可通过组合以下成分获得：a) 第VIB族或第VIIIB族的金属或其化合物，b) 双齿膦、砷或锑配体，以及c) 酸。其中，与金属或金属化合物相比，配体的存在量至少是2:1的摩尔过量，而酸的存在量至少是与配体相比的2:1的摩尔过量。还提供了一种烯烃不饱和化合物羰基化的方法、反应介质以及该体系的用途。

  公开号：

  US09802185B2
• 作为试剂：
  描述：

  1-(三氟甲基磺酰基氧基)环庚烯 、 一氧化碳 在 吡啶 、 bis[di(1-adamantyl)phosphino]-o-xylene 、 氢气 、 palladium diacetate 作用下， 以 二乙二醇二甲醚 、 N,N-二甲基甲酰胺 为溶剂， 80.0 ℃ 、2.0 MPa 条件下， 反应 16.0h， 以87%的产率得到1-cycloheptene-1-carboxaldehyde
  参考文献：
  名称：

  用于乙烯基三氟甲磺酸酯甲酸酯化以形成α，β-不饱和醛的钯催化剂。

  摘要：

  DOI：

  10.1002/anie.200800994

文献信息

• [EN] PROCESS FOR THE HYDROFORMYLATION OF ETHYLENICALLY UNSATURATED COMPOUNDS<br/>[FR] PROCEDE D'HYDROFORMYLATION DE COMPOSES ETHYLENIQUEMENT INSATURES
  申请人：LUCITE INT UK LTD

  公开号：WO2005003070A1

  公开（公告）日：2005-01-13

  The present invention provides a process for the hydroformylation of ethylenically unsaturated compounds, which process comprises reacting said ethylenically unsaturated compound with carbon monoxide and hydrogen, in the presence of a catalyst system and a solvent, the catalyst system obtainable by combining: a) a metal of Group VIII or a compound thereof; and b) a bidentate phosphine, the process characterised in that a chlorine moiety is present in at least one of the said Group VIII metal compound or said solvent.

  本发明提供了一种用于乙烯不饱和化合物的氢甲酰化的方法，该方法包括在催化剂体系和溶剂的存在下，将所述乙烯不饱和化合物与一氧化碳和氢反应，所述催化剂体系可通过组合获得：a) VIII族金属或其化合物；和b)双齿膦，其特征在于至少在所述VIII族金属化合物或所述溶剂中存在氯基团。
• [EN] A CONTINUOUS PROCESS FOR THE CARBONYLATION OF ETHYLENE<br/>[FR] PROCÉDÉ CONTINU DE CARBONYLATION DE L'ÉTHYLÈNE
  申请人：LUCITE INT UK LTD

  公开号：WO2011073655A1

  公开（公告）日：2011-06-23

  A continuous process for carbonylation of ethylene in a liquid phase using carbon monoxide, a co-reactant and a suitable catalyst system is described. The process comprises the steps of: (i) forming a liquid phase comprising the co-reactant and a suitable catalyst system obtainable by combining: (a) a group VIII metal/compound; (b) a ligand of general formula (I) and c) optionally, a source of anions; wherein Q1 is optionally phosphorous; (ii) forming a gaseous phase in contact with the liquid phase by providing at least an ethylene gas input feed stream and a carbon monoxide gas input feed stream wherein the ethylene:CO molar ratio entering the liquid phase from the input feed streams is greater than 2:1; (iii) reacting ethylene with carbon monoxide in the presence of the co-reactant, and of the suitable catalyst system in the liquid phase; wherein the ethylene:CO gas molar ratio in the gaseous phase is between 20:1 and 1000:1 or wherein the molar ratio of ethylene:CO in the liquid phase is greater than 10:1.

  描述了一种在液相中使用一氧化碳、共同反应剂和适当的催化剂体系对乙烯进行羰基化的连续过程。该过程包括以下步骤：(i)形成包括共同反应剂和适当催化剂体系的液相，所述催化剂体系可通过组合获得：(a) VIII族金属/化合物；(b) 一般式(I)的配体和(c) 可选地，阴离子源；其中Q1可选为磷；(ii)通过提供至少一个乙烯气体输入流和一个一氧化碳气体输入流形成与液相接触的气相，在其中从输入流中进入液相的乙烯：CO摩尔比大于2:1；(iii)在液相中的共同反应剂和适当的催化剂体系的存在下，将乙烯与一氧化碳反应；其中气相中的乙烯：CO气体摩尔比在20:1至1000:1之间，或液相中的乙烯：CO摩尔比大于10:1。
• CONTINUOUS PROCESS FOR THE CARBONYLATION OF ETHYLENE
  申请人：Lucite International UK Limited

  公开号：US20150099896A1

  公开（公告）日：2015-04-09

  A continuous process for the production of an alkyl ester product is described. The process includes the steps of carbonylating ethylene with carbon monoxide in the presence of C1-6 alkanol co-reactant to form the alkyl ester product. The carbonylation takes place in the presence of a catalyst system that includes (a) a bidentate ligand, (b) a catalytic metal selected from a group 8, 9 or 10 metal or a compound thereof, and (c) a sulphonic acid capable of forming an acid alkyl ester with the C1-6 alkanol. The process includes the step of separating the alkyl ester product from a carbonylated crude product stream by treatment effective to vaporizing the alkyl ester product in a single stage flash distillation column and providing a purified alkyl ester product stream separated from the bidentate ligand and catalytic metal.

  描述了一种生产烷基酯产品的连续过程。该过程包括以下步骤：在C1-6烷醇共反应剂的存在下，将乙烯与一氧化碳进行羰基化反应，形成烷基酯产品。羰基化反应发生在包括（a）双齿配体、（b）选择自第8、9或10族金属或其化合物的催化金属和（c）能够与C1-6烷醇形成酸性烷基酯的磺酸的催化剂系统存在下。该过程包括将烷基酯产品从羰基化粗产品流中分离出来的步骤，通过处理有效地在单级闪蒸塔中蒸发烷基酯产品，并提供从双齿配体和催化金属分离出来的纯化的烷基酯产品流。
• PROCESS FOR THE CARBONYLATION OF AN ETHYLENICALLY UNSATURATED COMPOUND AND A CATALYST SYSTEM
  申请人：Eastham Graham Ronald

  公开号：US20100197958A1

  公开（公告）日：2010-08-05

  A process for the carbonylation of an ethylenically unsaturated compound comprising the step of reacting said compound with carbon monoxide in the presence of a co-5 reactant having a mobile hydrogen atom and a catalyst system is described. The catalyst system is obtainable by combining: (a) a metal of Group 8, 9 or 10 or a suitable compound thereof; (b) a ligand of general formula (I): and c) optionally, a source of anions. The invention is characterised in that the catalyst system includes an enhancer compound comprising an aromatic ring or ring system substituted by at least one hydroxyl group wherein the hydroxyl group pKa at 25° C. is greater than 3.0 and less than 9.1, the said enhancer compound excluding 3-quinolinol. Catalyst systems for use with the enhancer compound are described as are a method of increasing the efficacy of a catalyst system for the carbonylation of ethylenically unsaturated compounds and a method of increasing the rate of carbonylation of an ethylenically unsaturated compound comprising the step of adding such a compound to the reaction.

  本发明涉及一种用于羰基化具有乙烯基不饱和化合物的方法，包括在具有移动氢原子的共反应剂和催化剂体系存在下，将该化合物与一氧化碳反应的步骤。所述催化剂体系可通过组合以下成分获得：（a）第8、9或10族金属或其适当化合物；（b）一般式（I）的配体；以及（c）可选地，阴离子源。本发明的特点在于，催化剂体系包括增强剂化合物，该化合物包括由至少一个羟基取代的芳香环或环系，其中该羟基在25℃时的pKa大于3.0且小于9.1，所述增强剂化合物不包括3-喹啉酚。本发明还描述了用于增强剂化合物的催化剂体系，以及增加用于羰基化乙烯基不饱和化合物的催化剂体系效力和增加羰基化乙烯基不饱和化合物的反应速率的方法。
• Catalyst System
  申请人：Eastham Graham

  公开号：US20070282124A1

  公开（公告）日：2007-12-06

  The present invention provides a catalyst system capable of catalysing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof, b) a bidentate phosphine, arsine or stibine ligand, and c) an acid, wherein said ligand is present in at least a 2:1 molar excess compared to said metal or said metal in said metal compound, and that said acid is present in at least a 2:1 molar excess compared to said ligand, a process for the carbonylation of an ethylenically unsaturated compound, a reaction medium, and use of the system.

  本发明提供了一种催化剂系统，能够催化含有乙烯基不饱和化合物的羰基化反应，该系统可通过以下步骤获得：a) 一种第VIB或第VIIIB族金属或其化合物，b) 一种双齿膦、砷或锑配体，c) 一种酸。其中，所述配体的摩尔量至少比所述金属或所述金属化合物中的金属高2:1，所述酸的摩尔量至少比所述配体高2:1。本发明还提供了一种含有乙烯基不饱和化合物的羰基化反应的方法、反应介质以及该系统的使用。