1，4-二（二叔丁基膦）丁烷 | 150111-89-0

• 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 - 有机磷化合物 - 有机膦及其衍生物
• 中文名称: 1，4-二（二叔丁基膦）丁烷
• 中文别名: 1,4-双(二叔丁基膦)丁烷
• 英文名称: 1,4-bis(di-tert-butylphosphino)butane
• 英文别名: 1,4-bis-(di-t-butylphosphino)butane；dtbpb；1,2-P,P'-bis(ditertbutylphosphine)ethane；ditert-butyl(4-ditert-butylphosphanylbutyl)phosphane
• CAS: 150111-89-0
• 化学式: C₂₀H₄₄P₂
• 分子量: 346.517
• InChiKey: UIYGJYHQLCCIQS-UHFFFAOYSA-N

物化性质

• 沸点：
  394.9±25.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  22
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  dichloro( 1,5-cyclooctadiene)platinum(ll) 、 1，4-二（二叔丁基膦）丁烷 以 二氯甲烷 为溶剂， 以90%的产率得到chloroplatinum(1+);ditert-butyl-[(4Z)-cyclooct-4-en-1-yl]-(4-ditert-butylphosphanylbutyl)phosphanium;chloride
  参考文献：
  名称：

  Wurst, K.; Straehle, J., Zeitschrift fur Naturforschung, B: Chemical Sciences, 1993, vol. 48, # 4, p. 425 - 430

  摘要：

  DOI：
• 作为产物：
  描述：

  二-叔丁基膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 环己烷 为溶剂， 反应 33.0h， 生成 1，4-二（二叔丁基膦）丁烷
  参考文献：
  名称：

  Palladium Complexes with Bulky Diphosphine Ligands as Highly Selective Catalysts for the Synthesis of (Bio-) Adipic Acid from Pentenoic Acid Mixtures.

  摘要：

  A series of sterically bulky diphosphines have been prepared, including P-2 = trans-1,2-bis[(di-tert-butylphosphino)methyllcydohexane (4), (2-methylenepropane1,3-diy1)bis(di-tert-butylphosphine) (5), bis[(di-tertbutylphosphino)methyl]dimethylsilane (6), and cis- and trans11,12-bis [ (di-tert-butylphosphino)methy1]-9,10-dihydro-9,10-ethanoanthracene (10 and 11). The corresponding palladium complexes of these ligands, P2Pd(CF3CO2)(2), have been synthesized and characterized. The solid-state structures of [Pd(4)(CF3CO2)(2)], [Pd(S)(CF3CO2)(2)], [Pd(6)(CF3CO2)(2)], and [Pd(11)(CF3CO2)(2)] were obtained by single-crystal X-ray diffraction and confirm the bidentate binding mode of the ligand and a square-planar coordination geometry with a minor distortion from the ideal. The diphosphines in combination -with Pd(OAc)(2) have been applied in the hydroxycarbonylation of a mixture of pentenoic acid isomers to produce adipic acid with high selectivity (in several cases >95%). The (regio)selectivity of the hydroxycarbonylation reaction is highly dependent on the P-2 diphosphine ligand structure, particularly the steric bulk of the substituents on the diphosphine donor and the P-Pd-P bite angle in the complexes, with respectively tertiary alkyl phosphine substituents (tert-butyl, adamantyl) and a C4 backbone P-Pd-P bite angle >100 degrees being the common features of highly adipic acid selective systems. It is suggested that the regioselectivity of hydroxycarbonylation becomes largely driven by the chelation of the carboxylic acid functionality of pentenoic acid substrates, when smaller size P substituents and/or when P-2 ligands with smaller bite angles (<100 degrees) are applied.

  DOI：

  10.1021/acs.organomet.5b00517

文献信息

• A Comprehensive Mechanistic Picture of the Isomerizing Alkoxycarbonylation of Plant Oils
  作者：Philipp Roesle、Lucia Caporaso、Manuel Schnitte、Verena Goldbach、Luigi Cavallo、Stefan Mecking

  DOI：10.1021/ja508447d

  日期：2014.12.3

  olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced

  对异构化烷氧基羰基化的整个催化循环的理论研究表明，二膦配位的 Pd 中心周围的空间拥挤是选择性和生产率的决定性因素。异构化的能量分布对于可变空间体积的二膦是平坦的，但是对于空间要求高的二膦更倾向于形成直链 Pd-烷基物种。对于所有研究的 Pd-烷基物质，CO 插入是可行和可逆的，并且受二膦影响很小。与最高能量屏障相关的总体限速步骤是 Pd-酰基物质的甲醇分解。考虑到线性 Pd-酰基物质的甲醇分解，其能量势垒在所有研究的 Pd-酰基物质中最低，计算出的势垒对于更拥挤的二膦更低。计算表明，对于体积更大的二膦，线性与支化 Pd-酰基的甲醇分解能量差异更为明显，这是由于在过渡态中涉及不同数量的甲醇分子。在压力反应器条件下的实验研究表明，较短链烯烃底物的转化速度更快，但底物内的双键位置几乎没有影响。与高级烯烃相比，相同条件下的乙烯羰基化速度要快得多，这可能不仅是由于反应性线性酰基的出现，而且还因为烯
• DYE, PHOTOELECTRIC CONVERSION ELEMENT USING THE SAME, PHOTOELECTROCHEMICAL CELL, AND METHOD OF PRODUCING DYE
  申请人：Kobayashi Katsumi

  公开号：US20110213144A1

  公开（公告）日：2011-09-01

  A dye, having a structure represented by formula (1A): wherein A represents a group of atoms necessary for forming a ring together with the carbon-nitrogen bond; at least one of Y 1A and Y 2A represents an acidic group, in which when they each represent an acidic group, they may be the same as or different from each other, or when only one of them represents an acidic group, the other represents an electron-withdrawing group; D represents a group to give a dye; n represents an integer of 1 or greater; L represents a single bond or a divalent linking group; and Y 3A represents an acidic group.

  一种染料，其结构由式（1A）表示：其中A代表与碳-氮键一起形成环的原子团；Y1A和Y2A中至少一个代表酸性基团，当它们各自代表酸性基团时，它们可以相同也可以不同，或者当它们中只有一个代表酸性基团时，另一个代表电子吸引基团；D代表给染料的基团；n代表大于等于1的整数；L代表单键或二价连接基团；Y3A代表酸性基团。
• Catalyst system and method for carbonylation
  申请人：——

  公开号：US20030191339A1

  公开（公告）日：2003-10-09

  The invention relates to a catalyst system for carbonylating olefinically or acetylenically unsaturated compounds with carbon monoxide and a nucleophile compound, containing (a) palladium; (b) a phosphine and (c) a polymer containing nitrogen which is soluble in the reaction mixture, with the exception of polyvinyl polymers with aromatic radicals containing nitrogen on the polymer chain. The invention also relates to a method for carbonylation in the presence of one such catalyst system.

  这项发明涉及一种催化剂体系，用于将烯烃或乙炔不饱和化合物与一氧化碳和亲核试剂进行羰基化，包含(a) 钯；(b) 一种膦和(c) 一种含氮的聚合物，在反应混合物中可溶解，但不包括聚乙烯基链上含氮芳香基团的聚乙烯基聚合物。该发明还涉及在一种这样的催化剂体系存在下进行羰基化的方法。
• METHOD FOR PRODUCING PHENYL-SUBSTITUTED HETEROCYCLIC DERIVATIVE BY MEANS OF COUPLING METHOD USING PALLADIUM COMPOUND
  申请人：Komiyama Masato

  公开号：US20130158272A1

  公开（公告）日：2013-06-20

  The present invention provides a method for producing a xanthine oxidase inhibitor, which is a therapeutic agent for hyperuricemia, or intermediates of the same, said method being efficient and using a short process. The present invention is a novel coupling method for obtaining a compound represented by formula (3) by bringing about a coupling reaction between a compound represented by formula (1) and a compound represented by formula (2), in the presence of a palladium compound, a ligand capable of coordinating to the palladium compound, a base, a C 1 -C 40 carboxylic acid, and at least one kind of additive.

  本发明提供了一种生产黄嘌呤氧化酶抑制剂的方法，该抑制剂是治疗高尿酸血症的药物，或者其中间体，该方法高效且使用流程简短。本发明是一种新型耦合方法，通过在钯化合物、能够配位到钯化合物的配体、碱、C1-C40羧酸和至少一种添加剂的存在下，在式（1）所代表的化合物和式（2）所代表的化合物之间引发耦合反应，从而获得式（3）所代表的化合物。
• METHYL-IODIDE-FREE CARBONYLATION OF AN ALCOHOL TO ITS HOMOLOGOUS ALDEHYDE AND/OR ALCOHOL
  申请人：EASTMAN CHEMICAL COMPANY

  公开号：US20160185701A1

  公开（公告）日：2016-06-30

  Disclosed is a process for the reductive carbonylation of a low molecular weight alcohol to produce the homologous aldehyde and/or alcohol. The process includes conducting the reaction to produce the aldehyde in the presence of a catalyst complex composed of cobalt, an onium cation and iodide in a ratio of 1:2:4 with a phosphine ligand. A ruthenium co-catalyst is used in the production of the homologous alcohol. The reductive carbonylation reaction does not require an additional iodide promoter and produces a crude reductive carbonylation product substantially free of methyl iodide.

  本发明公开了一种还原羰基化低分子量醇以产生同系物醛和/或醇的过程。该过程包括在催化剂复合物的存在下进行反应，该催化剂复合物由钴、离子和碘组成，比例为1:2:4，含有膦配体，以产生醛。在同系物醇的生产中使用了钌共催化剂。还原羰基化反应不需要额外的碘促进剂，并且产生的粗还原羰基化产物基本上不含甲基碘。