P,P-二(3,5-二甲基苯基)-N,N-二乙基亚膦酰胺 | 1636-15-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: P,P-二(3,5-二甲基苯基)-N,N-二乙基亚膦酰胺
• 英文名称: (diethylamino)diphenylphosphine
• 英文别名: N,n-diethylaminodiphenylphosphine；N-ethyl-N-(diphenylphosphino)ethanamine；N,N-diethyl-1,1-diphenylphosphinamine；Ph2PNEt2；N-diphenylphosphanyl-N-ethylethanamine
• CAS: 1636-15-3
• 化学式: C₁₆H₂₀NP
• 分子量: 257.315
• InChiKey: AEOFYYUGLYQJHY-UHFFFAOYSA-N

物化性质

• 沸点：
  140-142 °C(Press: 0.7 Torr)
• 密度：
  1.043 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

安全信息

• 海关编码：
  2929909090

反应信息

• 作为反应物：
  描述：

  P,P-二(3,5-二甲基苯基)-N,N-二乙基亚膦酰胺 在 盐酸 作用下， 反应 0.75h， 生成 二苯基氯化膦
  参考文献：
  名称：

  Carbohydrate Phosphinites as Practical Ligands in Asymmetric Catalysis:  Electronic Effects and Dependence of Backbone Chirality in Rh-Catalyzed Asymmetric Hydrogenations. Synthesis of R- or S-Amino Acids Using Natural Sugars as Ligand Precursors

  摘要：

  Vicinal diarylphosphinites derived from carbohydrates are excellent ligands for the Rh(I)-catalyzed enantioselective asymmetric hydrogenation of dehydroamino acid derivatives, producing the highest enantioselectivity of any ligands directly prepared from natural products. The enantioselectivity can be enhanced by the appropriate choice of substituents on the aromatic rings of the phosphinites. For example, the use of phosphinites with electron-donating bis(3,5-dimethylphenyl) groups on phosphorus provides ee's up to 99% for a wide range of amino acids including some with easily removable N-protecting groups. Electron-withdrawing aryl substituents, on the other hand, decrease the enantioselectivity. Sense of chiral induction in the amino acid product depends on the relative juxtaposition of the vicinal diphosphinites on a given sugar backbone. When readily available D-glucopyranosides are used as the starting sugars, 2,3-phosphinites give the S-amino acids and 3,4-phosphinites give the R-amino acids. In the case of aromatic and heteroaromatic amino acids, enantioselectivities > 95% are consistently obtained. Practical considerations such as the ease of ligand synthesis, rates of reactions, catalyst turnover, and scope and limitations in terms of substrates are discussed. A possible explanation for the enhancement of enantioselectivity by electron-rich phosphinites is offered.

  DOI：

  10.1021/jo970884d
• 作为产物：
  描述：

  Allyl-diphenyl-diethylamido-phosphonium bromid 在 氰化四丁基铵 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 P,P-二(3,5-二甲基苯基)-N,N-二乙基亚膦酰胺
  参考文献：
  名称：

  Horner, Leopold; Jordan, Manfred, Phosphorus and Sulfur and the Related Elements, 1980, vol. 8, p. 215 - 220

  摘要：

  DOI：
• 作为试剂：
  描述：

  麻黄碱 在 六氟磷酸钾 、 P,P-二(3,5-二甲基苯基)-N,N-二乙基亚膦酰胺 作用下， 反应 15.0h， 生成 N,N-(1,5-pentylene)diphenylephosium hexafluorophosphate
  参考文献：
  名称：

  New chiral zwitterionic iron hydride complexes with ‘ephosium’ and ‘valphosium’ ligands

  摘要：

  New chiral cationic phosphinite ligands based on ephedrine or valinol skeletons, and corresponding zwitterionic hydridotricarbonylfenate complexes are described. IR data indicate an unusual cis-H-Fe-P arrangement in these complexes, and NMR studies show an unusual variation of (2)J(PH) with temperature and solvent. The possibility that both these rare features are dictated by a stabilizing back folding of the [NMeR2](+) terminus onto the [FeH](-) center is discussed. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00686-x

文献信息

• Method for catalytic preparation of hydromorphone and hydrocodone
  申请人：Cody Laboratories Inc.

  公开号：US07399859B1

  公开（公告）日：2008-07-15

  The present invention generally relates to catalysts of formula (III) [M(P(Ra)(Rb)N(Rc)(Rd))2Xn]mYp that selectively convert morphine/codeine to hydromorphone/hydrocodone, and methods of use thereof.

  本发明通常涉及公式（III）的催化剂 [M(P(Ra)(Rb)N(Rc)(Rd))2Xn]mYp 该催化剂选择性地将吗啡/可待因转化为羟吗啡/羟考酮，并使用方法。
• Phosphino-amine (PN) Ligands for Rapid Catalyst Discovery in Ruthenium-Catalyzed Hydrogen-Borrowing Alkylation of Anilines: A Proof of Principle
  作者：Lewis Marc Broomfield、Yichen Wu、Eddy Martin、Alexandr Shafir

  DOI：10.1002/adsc.201500562

  日期：2015.11.16

  A general synthetic protocol for the synthesis of simple phosphino-amine (PN) ligands is described with 19 ligands being isolated in good yields. High-throughput ligand screening uncovered the success of two of these ligands for aromatic amine alkylations via ruthenium-catalyzed hydrogen borrowing reactions. The combination of N,N′-bis(diphenylphosphino)-N,N′-dimethylpropylenediamine with a ruthenium(II)

  描述了用于合成简单膦胺（PN）配体的一般合成方案，其中以高收率分离出19个配体。高通量配体筛选揭示了其中两个配体通过钌催化的氢借位反应成功用于芳族胺烷基化的过程。的组合Ñ，N' -双（二苯基膦基） - ñ，N'具有钌（II）源和氢氧化钾（15摩尔％）的-二甲基丙二胺是芳香胺选择性单苄基化的最佳体系（方法A）。在温和的反应条件下（120°C和1.05当量的苄醇）形成14种仲芳族胺，已获得超过70％的分离产率。另一方面，N，N-双（二苯基膦基）-异丙胺是用于芳香胺的选择性单甲基化和单乙基化反应的配体（方法B）。在此，将醇作为反应介质和底物加入，并且公开了9个实施例，所有分离的产率均超过70％。这些方法已应用于基于氨基二茂铁的重要合成构件的合成。
• Efficient Method for the Preparation of Carboxylic Acid Alkyl Esters or Alkyl Phenyl Ethers by a New-Type of Oxidation–Reduction Condensation Using 2,6-Dimethyl-1,4-benzoquinone and Alkoxydiphenylphosphines
  作者：Taichi Shintou、Wataru Kikuchi、Teruaki Mukaiyama

  DOI：10.1246/bcsj.76.1645

  日期：2003.8

  A new-type of oxidation–reduction condensation proceeded smoothly to afford carboxylic acid alkyl esters or alkyl phenyl ethers in good to high yields by combined use of alkoxydiphenylphosphines (1...

  一种新型氧化还原缩合反应顺利进行，通过结合使用烷氧基二苯基膦（1...
• Synthesis of Some New Phosphino Acetylenes
  作者：A. J. Carty、N. K. Hota、T. W. Ng、H. A. Patel、T. J. O'Connor

  DOI：10.1139/v71-449

  日期：1971.8.15

  The synthesis and characterization of the new phosphino acetylenes (C6H5)2PC≡CCF3, (C6H5)2PC≡CC(CH3)3, (C6H5)2PC≡CP(C6F5)2, (C6F5)2PC≡CCH3, (C6F5)2PC≡CC6H5, (C6H5)2PC≡CP[N-(C2H5)2]2, the mixed arsine–phosphine (C6H5)2PC≡CAs(C6H5)2 and the arsino acetylene (C6H5)2AsC≡CCF3, are reported.

  新型膦基乙炔(C6H5)2PC≡CCF3、(C6H5)2PC≡CC(CH3)3、(C6H5)2PC≡CP(C6F5)2、(C6F5)2PC≡CCH3、(C6F5)2PC≡的合成与表征报道了 CC6H5、(C6H5)2PC≡CP[N-(C2H5)2]2、混合胂-膦 (C6H5)2PC≡CAs(C6H5)2 和胂乙炔 (C6H5)2AsC≡CCF3。
• Mitsunobu Reaction Using Basic Amines as Pronucleophiles
  作者：Hai Huang、Jun Yong Kang

  DOI：10.1021/acs.joc.7b00622

  日期：2017.7.7

  reaction to include amine nucleophiles to form C–N bonds through the utilization of N-heterocyclic phosphine-butane (NHP-butane) has been developed. Both aliphatic alcohols and benzyl alcohols are suitable substrates for C–N bond construction. Various acidic nucleophiles such as benzoic acids, phenols, thiophenol, and secondary sulfonamide also provide the desired products of esters, ethers, thioether

  已经开发出一种新的方案，该方案通过利用N-杂环膦-丁烷（NHP-丁烷）扩展了Mitsunobu反应的范围，使其包括胺亲核试剂以形成C–N键。脂族醇和苄醇都是适合于C–N键结构的底物。各种酸性亲核试剂（例如苯甲酸，苯酚，苯硫酚和仲磺酰胺）也可提供所需的酯，醚，硫醚和叔磺酰胺产物，产率为43-93％。重要的是，在这种Mitsunobu反应体系下，由市售胺一步合成了含C–N键的药物Piribedil和Cinnarizine。