di(1-adamantyl)-tert-butylphosphine | 321921-71-5

• 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
• 英文名称: di(1-adamantyl)-tert-butylphosphine
• 英文别名: tert-butyl-di-1-adamantylphosphine；Di(adamantan-1-yl)(tert-butyl)phosphine；bis(1-adamantyl)-tert-butylphosphane
• CAS: 321921-71-5
• 化学式: C₂₄H₃₉P
• 分子量: 358.547
• InChiKey: XJIXVSYABXKOAQ-UHFFFAOYSA-N

物化性质

• 熔点：
  100°C
• 沸点：
  449.6±12.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  8.0
• 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

安全信息

• 安全说明：
  S24/25
• WGK Germany：
  3
• 海关编码：
  2902199090
• 危险品运输编号：
  NONH for all modes of transport
• 包装等级：
  III
• 危险类别：
  6.1
• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P310+P330,P302+P352+P312,P304+P340+P311,P305+P351+P338,P332+P313,P337+P313,P403+P233,P405,P501
• 危险性描述：
  H301+H311+H331,H315,H319,H335

制备方法与用途

用途

正丁基二(1-金刚烷基)膦是一种催化剂，主要用于钯催化的交叉偶联反应，如Heck和Suzuki偶联反应。作为一种富含电子的膦配体，它在这些反应中表现出优异的效果。

应用

正丁基二(1-金刚烷基)膦是一种新颖且高效的膦配体，可通过一步反应由二(1-金刚烷基)膦与二正丁醚制备得到。尽管目前广泛使用的催化剂为钯(0)/镍(0)化合物，但用于活化和精制卤代芳香化合物的钯和镍催化剂同样重要，包括钯(II)和/或镍(II)，以及钯(0)和/或镍(0)络合物。

制备

正丁基二(1-金刚烷基)膦的制备过程如下：首先将4.6克（15毫摩尔）二(1-金刚烷基)膦溶解在50毫升二正丁醚中，然后加入20毫升2.5M n-BuLi甲苯溶液（50毫摩尔）。反应混合物回流1小时后冷却，并逐滴加入2.8克（30毫摩尔）的1-丁基氯。随后将该混合物继续回流30分钟，然后冷却并用饱和氯化铵溶液洗涤三次（每次3毫升）。分离有机相并在硫酸钠上干燥，最后在减压下蒸馏掉溶剂。通过高真空下的球管蒸馏进一步纯化产物。最终产量为4.6克（13毫摩尔，85%）正丁基二(1-金刚烷基)膦。

反应信息

• 作为产物：
  描述：

  (1-金刚烷基)氯化镁 在 1-Adamantyllithium 作用下， 以 乙醚 、 正庚烷 为溶剂， 反应 1.5h， 生成 di(1-adamantyl)-tert-butylphosphine
  参考文献：
  名称：

  Lavrova, E. A.; Koidan, G. N.; Marchenko, A. P., Russian Journal of General Chemistry, 1994, vol. 64, # 9.2, p. 1393 - 1394

  摘要：

  DOI：
• 作为试剂：
  描述：

  2-氨基-4-溴苯甲酰胺 在 palladium diacetate 、 di(1-adamantyl)-tert-butylphosphine sodium acetate 、 三乙胺 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 水 、 二甲基亚砜 、 甲苯 为溶剂， 反应 2.17h， 生成 (S)-N-((1-(2-(tert-butyl)-4-hydroxyquinazolin-7-yl)pyrrolidin-3-yl)methyl)methanesulfonamide
  参考文献：
  名称：

  HETEROCYCLIC ANTIVIRAL COMPOUNDS

  摘要：

  具有公式I的化合物，其中R1、R2、R3和X的定义如本文所述，是丙型肝炎病毒NS5b聚合酶抑制剂。还公开了用于治疗HCV感染和抑制HCV复制的组合物和方法。

  公开号：

  US20120009144A1

文献信息

• Production of novel phosphane ligands and use in catalytical reactions
  申请人：——

  公开号：US20040068131A1

  公开（公告）日：2004-04-08

  The invention relates to novel phosphane ligands of formula (Ia) and (Ib): (adamantyl)nP(alkyl)m(1a); (adamantyl)o(Alkyl)qP (alkylen′)P(adamantyl)r(alkyl)s (1b), wherein adamantyl represents an adamantyl radical (IIa, IIb) bonded to the phosphorous atom in position 1 or 2. The invention also relates to the production and use of the above-mentioned ligands in the presence of transitional metal compounds of the 8th. Subgroup of PSE for catalytic reactions, particularly for the refining of halogen aromatics for producing aryl olefins, dienes, diarylene, benzoic acid and acrylic acid derivatives, aryl alkanes and also amines.

  该发明涉及公式(Ia)和(Ib)的新型膦配体：(脱氢胆固醇)nP(烷基)m(1a)；(脱氢胆固醇)o(烷基)qP(烷基)P(脱氢胆固醇)r(烷基)s(1b)，其中脱氢胆固醇代表与磷原子在1或2位置结合的脱氢胆固醇基团(IIa, IIb)。该发明还涉及在第8周期元素周期表的过渡金属化合物存在下制备和使用上述配体，特别用于催化反应，尤其用于精炼卤代芳烃以生产芳基烯烃、二烯烃、二芳基烯、苯甲酸和丙烯酸衍生物、芳基烷烃以及胺类。
• METHOD FOR PRODUCING FLUOROVINYL ETHER COMPOUND
  申请人：DAIKIN INDUSTRIES, LTD.

  公开号：US20210284593A1

  公开（公告）日：2021-09-16

  An object of the present invention is to provide, for example, a novel method for synthesizing a fluorovinyl ether compound from a fluorine-containing vinyl compound. This problem is solved by a method for producing a compound represented by formula (1): wherein R a1 is a hydrogen atom, a halogeno group, an alkyl group, a fluoroalkyl group, or an aromatic group optionally having one or more substituents, Rf is a fluoro group or a perfluoroalkyl group, R a2 is a hydrogen atom, a halogeno group, an alkyl group, a fluoroalkyl group, or an aromatic group optionally having one or more substituents, or (i) R a1 and R a2 , (ii) R a1 and Rf, or (iii) Rf and R a2 may be linked to each other, R b1 is R S , R b2 is a hydrogen atom or R S , R b3 is a hydrogen atom or R S , or two or three of R b1 , R b2 , and R b3 , taken together with the adjacent carbon atom, may form a ring optionally having one or more substituents, and R S , in each occurrence, is the same or different and represents a hydrocarbon group optionally having one or more substituents, the method comprising step A of reacting a compound represented by formula (2): wherein R x is a leaving group, and other symbols are as defined above, with a compound represented by formula ( 3 ): wherein the symbols in the formula are as defined above, in the presence of a transition metal catalyst.

  本发明的一个目标是提供一种从含氟乙烯化合物合成氟乙烯醚化合物的新方法。这个问题通过以下方法解决：生产一个由以下式表示的化合物的方法(1)：其中Ra1是氢原子、卤素基团、烷基基团、氟烷基基团或可能具有一个或多个取代基的芳香基团，Rf是氟基团或全氟烷基基团，Ra2是氢原子、卤素基团、烷基基团、氟烷基基团或可能具有一个或多个取代基的芳香基团，或(i) Ra1和Ra2、(ii) Ra1和Rf或(iii) Rf和Ra2可能连接在一起，Rb1是RS，Rb2是氢原子或RS，Rb3是氢原子或RS，或者Rb1、Rb2和Rb3中的两个或三个，与相邻的碳原子一起，可以形成一个可能具有一个或多个取代基的环，RS在每次出现时相同或不同，表示一个可能具有一个或多个取代基的碳氢基团，该方法包括以下步骤：步骤A，将由以下式表示的化合物(2)：其中Rxis是一个离去基团，和上述其他符号的定义相同，与由以下式表示的化合物(3)：其中式中的符号与上述定义相同，在过渡金属催化剂存在下反应。
• Process for Production of 2-(Substituted Phenyl)-3,3,3-Trifluoropropene Compound
  申请人：Matoba Kazutaka

  公开号：US20100160683A1

  公开（公告）日：2010-06-24

  There is provided a novel process for production of a 2-(substituted phenyl)-3,3,3-trifluoropropene. Disclosed is a process for production of a 2-(substituted phenyl)-3,3,3-trifluoropropene compound represented by the formula (7) or a salt thereof The process comprises reacting a compound represented by the formula (1) (X is an alkyl group, etc.) with a compound represented by the formula (2) (Y is a halogen atom, etc.) in the presence of a catalyst represented by the formula (3) (M is an ion of a metal belonging to Group 10 on the elementary periodic table which has an oxidation state number of 1 to 8; G is a unidentate or multidentate ligand; L is a phosphine compound represented by the formula (4) which is bound to the center metal M or is a carbene selected from those represented by the formulae (5) and (6), provided that L's may be same as or different from one another when a is 2 to 5; A represents a univalently or multivalently charged anion; b represents an integer of 1 to 3; a represents an integer of 1 to 5·b; c represents 0 or an integer of 1 to 4·b; and n represents an integer of 1 to 6).

  提供了一种生产2-(取代苯基)-3,3,3-三氟丙烯的新型工艺。公开了一种生产由式(7)表示的2-(取代苯基)-3,3,3-三氟丙烯化合物或其盐的工艺。该工艺包括在催化剂的存在下，将由式(1)表示的化合物（其中X为烷基等）与由式(2)表示的化合物（其中Y为卤素原子等）反应。催化剂由式(3)表示（其中M是元素周期表上属于第10族金属的离子，其氧化态数为1至8；G是单齿或多齿配体；L是与中心金属M结合的磷化合物，由式(4)表示，或者是从由式(5)和(6)表示的卡宾中选择的卡宾，但当a为2至5时，L可能相同也可能不同；A表示单价或多价带电阴离子；b表示1至3的整数；a表示1至5·b的整数；c表示0或1至4·b的整数；n表示1至6的整数）。
• PROCESS FOR THE PRODUCTION OF ANILINES
  申请人：Walter Harald

  公开号：US20090221855A1

  公开（公告）日：2009-09-03

  The present invention relates to a process for the preparation of compounds of formula wherein R 1 , R 2 and R 3 are each independently of the others hydrogen or C 1 -C 4 alkyl, by a) reacting compounds of formula (II) wherein R 1 , R 2 and R 3 are as defined for formula (I) and X is bromine or chlorine, with a compound of formula (III) wherein R 4 is hydrogen or C 1 -C 4 alkyl, in the presence of a base and catalytic amounts of at least one palladium complex compound, to form compounds of formula (IV) wherein R 1 , R 2 , R 3 and R 4 are as defined for formula (I), and b) converting those compounds, using a reducing agent, into compounds of formula (I).

  本发明涉及一种制备式化合物的方法，其中R1、R2和R3各自独立地为氢或C1-C4烷基，通过a)在碱和至少一种钯配合物催化剂存在下，将式（II）化合物与式（III）化合物反应，其中R1、R2和R3如式（I）所定义，X为溴或氯，形成式（IV）化合物，其中R1、R2、R3和R4如式（I）所定义；b)使用还原剂将这些化合物转化为式（I）化合物。
• PROCESS FOR THE PREPARATION OF AMINES
  申请人：Tobler Hans

  公开号：US20090221856A1

  公开（公告）日：2009-09-03

  The present invention relates to a novel a process for the preparation of the compound of the general formula (I), wherein R 1 and R 2 are independently H or C 1-6 alkyl, which comprises treating with a reducing agent either a compound of the general formula (II), wherein R 1 and R 2 have the meanings given for the compound of the formula (I), R 3 is H or C 1-4 alkyl and Ph is phenyl, or a compound of the general formula (III), wherein R 1 , R 2 , R 3 and Ph have the meanings given for the compound of the formula (II), the reducing agent being effective to cleave the benzyl moiety Ph-CH(R 3 )— from the benzylamino moiety PhCH(R 3 )NH— in the compound of the formula (II) or in the compound of the formula (III) to leave an amino group and, in addition, in the case of the compound of the formula (III), to reduce both the 2,3-double bond and the double bond joining the R 1 R 2 C— moiety to the 9-position of the benzonorbornene ring to single bonds. It also relates to processes for the preparation of the compounds (II) and (III) and their precursors and to the compounds (II) and (III) themselves and certain of their precursors, which are novel compounds. The compounds (I) are useful for the preparation of various fungicidal heterocyclyl-carboxylic acid benzonorbornen-5-yl-amides.

  本发明涉及一种制备通式（I）化合物的新型方法，其中R1和R2独立地表示H或C1-6烷基，包括以下步骤：使用还原剂处理通式（II）化合物或通式（III）化合物，其中R1和R2具有通式（I）化合物中所给定的含义，R3为H或C1-4烷基，Ph为苯基，所述还原剂能够从通式（II）化合物或通式（III）化合物的苄基Ph-CH（R3）中切除苄基PhCH（R3）NH-，以留下氨基，并且在通式（III）化合物的情况下，还能够将2,3-双键和连接R1R2C-基团到苯并[2.2.1]环庚烯环的9位的双键还原为单键。本发明还涉及制备化合物（II）和（III）及其前体的方法，以及化合物（II）和（III）本身及其某些前体，这些是新型化合物。通式（I）化合物可用于制备各种杀真菌的杂环羧酸苯并[2.2.1]环庚烯-5-基酰胺。