Diphenylphosphinsaeure-tert.-butylester | 1706-92-9

• 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: Diphenylphosphinsaeure-tert.-butylester
• 英文别名: tert-Butyl diphenylphosphinate；[(2-methylpropan-2-yl)oxy-phenylphosphoryl]benzene
• CAS: 1706-92-9
• 化学式: C₁₆H₁₉O₂P
• 分子量: 274.299
• InChiKey: WUHWGOPWFWLXMK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine(2-))BBr 、 Diphenylphosphinsaeure-tert.-butylester 以 甲苯 为溶剂， 以68%的产率得到(S)-2,4-di-tert-butyl-6-((diphenylphosphoryl)oxy)-6H-6l4-benzo[e]benzo[4,5][1,3,2]oxazaborolo[2,3-b][1,3,2]oxazaborinin-12-ium
  参考文献：
  名称：

  Mononuclear Schiff Base Boron Halides:  Synthesis, Characterization, and Dealkylation of Trimethyl Phosphate

  摘要：

  A series of mononuclear boron halides of the type LBX2 [LH = N-phenyl-3,5-di-tert-butylsalicylaldimine, X = Cl (2), Br (3)] and LBX [LH2 = N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (7), Br (8); LH2 = N-(2-hydroxyethyl)- 3,5-di-tert-butylsalicylaldimine, X = Cl (9), Br (10); and LH2 = N-(3-hydroxypropyl)-3,5-di-tert-butylsalicylaldimine, X = Cl (11), Br (12)] were synthesized from their borate precursors LB(OMe)(2) (1) (LH = N-phenyl-3,5-di-tert-butylsalicylaldimine) and LB(OMe) [LH2 = N-(2-hydroxyphenyl)-3,5-di-tert-butylsalicylaldimine (4), N-(2-hydroxyethyl)-3,5-di-tert-butylsalicylaldimine (5), N-(3-hydroxypropyl)-3,5-di-tert-butylsalicylaldimine (6)]. The boron halide compounds were air and moisture sensitive, and upon hydrolysis, compound 7 resulted in the oxo-bridged compound 13 that contained two seven-membered boron heterocycles. The boron halide compounds dealkylated trimethyl phosphate in stoichiometric reactions to produce methyl halide and unidentified phosphate materials. Compounds 8 and 12 were found to be the most effective dealkylating agents. On reaction with tertbutyl diphenyl phosphinate, compound 8 produced a unique boron phosphinate compound LB(O)OPPh2 (14) containing a terminal phosphinate group. Compounds 1-14 were characterized by H-1, C-13, B-11, P-31 NMR, IR, MS, EA, and MP. Compounds 5, 6, and 11-14 also were characterized by single-crystal X-ray diffraction.

  DOI：

  10.1021/ic0607890
• 作为产物：
  描述：

  tert-butyl diphenylphosphinite 在 双氧水 作用下， 以 水 、 苯 为溶剂， 反应 1.0h， 以80%的产率得到Diphenylphosphinsaeure-tert.-butylester
  参考文献：
  名称：

  Synthesis and characterisation of severely hindered P-OR compounds

  摘要：

  P-Cl substrates were converted into their P-OR analogues from hindered alcohols using an amine base. Where the system was severely hindered, more forcing conditions were required that necessitated the presence of a metal alkoxide nucleophile before successful reactions were observed. In some instances, the products were thermally unstable and reverted to alkenes by elimination reactions, while others were sensitive to moisture. Here, hydrolysis products prevailed if moisture was not rigorously excluded. Details are presented to obtain the P(III) and P(V) esters, diesters and half esters. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2009.10.008

文献信息

• 一种以含P(O)-OH类化合物与醇高效酯化制 备有机膦酸酯类化合物的方法
  申请人：湖南理工学院

  公开号：CN106749396B

  公开（公告）日：2020-12-15

  本发明提供了一种高效、高选择性合成含不同取代官能团的有机膦酸酯类衍生物的方法，其采用多肽催化剂作为缩合试剂，以含P(O)‑OH类化合物与醇作为反应底物，反应体系加入了有机溶剂。该方法的优点：催化剂廉价易得；底物适用性高；反应条件温和，安全可靠；所得目标产物的选择性接近100%，产率高达90%以上。该方法解决了传统合成有机膦酸酯类化合物的反应选择性差、反应步骤繁琐、产率低以及需要用到对环境有害试剂等不足，具有良好的工业应用前景。本发明同时还提供了对应的含不同取代官能团的有机膦酸酯类衍生物。
• Nickel-catalyzed C–P cross-coupling reactions of aryl iodides with H-phosphinates
  作者：Atsushi Kinbara、Momoko Ito、Tohru Abe、Takehiro Yamagishi

  DOI：10.1016/j.tet.2015.07.073

  日期：2015.10

  Synthesis of aryl phosphinates was achieved through cross-coupling reactions of aryl iodides with H-phosphinates catalyzed by nickel under mild conditions. The method was applicable to various aryl iodides and H-phosphinates having defined stereochemistry at the phosphorus atom.

  芳基次膦酸酯的合成是通过芳基碘化物与镍催化的H-次膦酸酯在温和条件下的交叉偶联反应而实现的。该方法适用于在磷原子上具有确定的立体化学的各种芳基碘化物和H-次膦酸酯。
• Aminophosphine oxides in a pyridine series. Studies on the cleavage of pyridine-2- and pyridine-4-yl-(N-benzylamino)-methyldiphenylphosphine oxides in acidic solutions
  作者：Waldemar Goldeman、Tomasz K. Olszewski、Bogdan Boduszek、Wanda Sawka-Dobrowolska

  DOI：10.1016/j.tet.2006.02.048

  日期：2006.5

  synthesis and reactions of 1-(N-benzylamino)-1-(2-pyridyl)- and 1-(N-benzylamino)-1-(4-pyridyl)-methyldiphenylphosphine oxides are described. It was found that these compounds were exceptionally easy to cleave in aqueous sulfuric acid solutions to form diphenylphosphinic acid and the corresponding N-(pyridylmethyl)-benzylamines. The structure of a single diastereoisomer, that is, the (R)-(+)-1-[N-(α-met

  摘要 描述了1-(N-苄基氨基)-1-(2-吡啶基)-和1-(N-苄基氨基)-1-(4-吡啶基)-甲基二苯基氧化膦的合成和反应。发现这些化合物在硫酸水溶液中非常容易裂解形成二苯基次膦酸和相应的 N-(吡啶基甲基)-苄胺。单个非对映异构体的结构，即 (R)-(+)-1-[N-​​(α-甲基苄基氨基)]-1-(4-吡啶基)-(S)-甲基二苯基氧化膦的结构由 X-射线晶体学。通过 31P NMR 光谱研究了所选模型手性吡啶氨基膦氧化物的酸性醇解作用。还研究了裂解动力学。在获得的结果的基础上，制定了裂解机制。
• Synthesis of new thiazole-2, -4, and -5-yl-(amino)methylphosphonates and phosphinates: unprecedented cleavage of thiazole-2 derivatives under acidic conditions
  作者：Tomasz Krzysztof Olszewski、Bogdan Boduszek

  DOI：10.1016/j.tet.2010.09.026

  日期：2010.11

  An efficient and reliable synthesis of new thiazole-(amino)methylphosphonic, phosphinic acids, and phosphine oxides is reported. The synthetic protocol is based on nucleophilic addition of phosphorous species to thiazole derived imines. Unexpectedly, it was discovered that heating of thiazole-2-yl-(amino)methylphosphonates and phosphinates with aqueous HCl leads to their decomposition resulting in

  报道了新的噻唑-（氨基）甲基膦酸，次膦酸和氧化膦的高效可靠合成。合成规程基于将磷物质亲核加成到噻唑衍生的亚胺中。出乎意料的是，发现噻唑-2-基-（氨基）甲基膦酸酯和次膦酸酯与HCl水溶液一起加热会导致它们分解，导致C-P键断裂，排斥含磷片段并形成相应的仲N-（噻唑-2-基-甲基）-烷基胺。提出了用于这种切割的两种替代机制。
• Ni-catalyzed C–F activation to construct C–P bond with P–P(O) and P(O)OR mediation
  作者：Jia Yang、Lei Fan、Chen Chen、Mingyue Wang、Bingqian Sun、Shuai Wang、Hong Zhong、Yongbo Zhou

  DOI：10.1039/d2ob02047e

  日期：——

  Here we developed an efficient Ni-catalyzed C–F bond phosphorylation of aryl fluorides via the crucial intermediates of P–P(O) and P(O)OR. P–P(O) mediated organophosphorus generation is observed for active aryl fluorides, whereas inactive aryl fluorides can also be activated and phosphorylated via a P(O)OR-mediated pathway, which is barely reported yet. Facile scale-up to the gram level and the upgrading

  在这里，我们通过 P−P(O) 和 P(O)OR 的关键中间体开发了一种高效的 Ni 催化的芳基氟化物 C−F 键磷酸化。对于活性芳基氟化物观察到 P−P(O) 介导的有机磷生成，而非活性芳基氟化物也可以通过 P(O)OR 介导的途径被激活和磷酸化，这几乎没有报道过。易于放大到克级和生物活性分子的升级使该协议在合成化学中有前景的应用。