diisopropyl (bromodifluoromethyl)phosphonate | 65094-24-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diisopropyl (bromodifluoromethyl)phosphonate
• 英文别名: Phosphonic acid, (bromodifluoromethyl)-, bis(1-methylethyl) ester；2-[[bromo(difluoro)methyl]-propan-2-yloxyphosphoryl]oxypropane
• CAS: 65094-24-8
• 化学式: C₇H₁₄BrF₂O₃P
• 分子量: 295.061
• InChiKey: OGCQRYPCAKIVIF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diisopropyl (bromodifluoromethyl)phosphonate 在 碘 、 镉 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 生成 diisopropyl difluoromethanephosphonate
  参考文献：
  名称：

  Synthesis of Novel Fluorinated Bisphosphonates and Bisphosphonic Acids

  摘要：

  The synthesis of novel fluorinated bisphosphonates with two, three, four, and six difluoromethylene groups (1a, 1b, 8, 12, and 15) (44-78%) by different approaches is described. The bisphosphonates were converted to the corresponding trimethylsilyl esters which on treatment with deionized water afforded the respective bisphosphonic acids (6, 10, and 14) in good yields.

  DOI：

  10.1021/jo00088a021
• 作为产物：
  描述：

  bromozinc(1+),2-[difluoromethyl(propan-2-yloxy)phosphoryl]oxypropane 在 bromination reagent 作用下， 生成 diisopropyl (bromodifluoromethyl)phosphonate
  参考文献：
  名称：

  A USEFUL ZINC REAGENT FOR THE PREPARATION OF 2-OXO-1,1-DIFLUOROALKYLPHOSPHONATES

  摘要：

  用活性锌粉在各种溶剂中处理二烷基溴二氟甲基膦酸酯，得到二烷氧基膦酰二氟甲基锌化合物2，然后与酰卤或氟化酸酐进行酰化反应，以良好产率获得了二烷基2-氧代-1,1-二氟烷基膦酸酯。

  DOI：

  10.1246/cl.1982.755

文献信息

• Synthetic and mechanistic aspects of halo-F-methylphosphonates
  作者：Richard M. Flynn、Donald J. Burton

  DOI：10.1016/j.jfluchem.2011.05.034

  日期：2011.10

  The synthesis of a variety of new halo-F-methylphosphonates has been achieved by a Michaelis–Arbuzov type reaction between a halo-F-methane and a trialkyl phosphite. This synthesis has proved to be of wide scope and utility for the high yield preparation of a number of heretofore unknown compounds. The 1H, 19F, 13C and 31P NMR spectroscopic properties are reported in detail. The mechanism for the formation

  卤代F-甲烷与亚磷酸三烷基酯之间的Michaelis-Arbuzov型反应已实现了多种新的卤代F-甲基膦酸酯的合成。已证明该合成对于高产率制备许多迄今未知的化合物具有广泛的范围和实用性。的1 H，19男，13 C和31种P NMR光谱性质报告于细节。溴二氟甲基膦酸酯的形成机理已证明是通过二氟卡宾：CF 2的中间体来进行的。已显示膦酸酯产物与多种试剂反应。氟化物和醇盐离子通过攻击在磷反应与碳-磷键的裂解和形成[：CF 2 ]从bromodifluoromethylphosphonates和CFBR 2 -从dibromofluoromethylphosphonates阴离子。碘离子和叔膦通过攻击酯碳反应生成稳定的膦酸酯盐。用50％的HCl水溶液水解膦酸酯，得到预期的膦酸。三甲基甲硅烷基溴化物侵蚀磷酰基氧，得到双（三甲基甲硅烷基）酯。
• The synthesis of novel bisphosphonates as inhibitors of phosphoglycerate kinase (3-PGK)
  作者：Neil A. Caplan、Christopher I. Pogson、David J. Hayes、G. Michael Blackburn

  DOI：10.1039/a906507e

  日期：——

  A series of conformationally-restrained analogues of 1,3-bisphospho-D-glyceric acid (1,3-BPG) 1 has been synthesised for use as inhibitors of 3-PGK (E.C. 2.7.2.3). These compounds have non-scissile phosphonate linkages and also incorporate α-halogen substituents to make them isopolar and isosteric mimics of the natural substrate. A monocyclic aryl core between the two phosphoryl centres provides both

  合成了一系列1,3-双磷酸D-甘油酸（1,3-BPG）1的构象限制类似物以用作抑制剂3-PGK（EC 2.7.2.3）。这些化合物具有非断裂性的膦酸酯键，并且还掺入了α-卤素取代基，使它们成为天然底物的等极性和等规模拟物。单环芳基两个磷酰基中心之间的核提供了连接这些部分和基因座的刚性框架，以供进一步取代。这些化合物针对人类3-PGK进行了测试，发现具有良好的竞争性抑制剂。α-氟的膦酸将对酶的亲和力提高到亚微摩尔范围。IC 50数据与p K a 3和p K a 4值的相关性表明，磷酰基的酸度对蛋白质 捆绑。
• Copper-Mediated Oxidative Cross-Coupling Reaction of Terminal Alkynes with α-Silyldifluoromethylphosphonates: An Efficient Method for α,α-Difluoropropargylphosphonates
  作者：Xueliang Jiang、Lingling Chu、Feng-Ling Qing

  DOI：10.1021/ol301113v

  日期：2012.6.1

  A copper-mediated oxidative cross-coupling reaction of terminal alkynes with readily available α-silyldifluoromethylphosphonates under mild conditions has been developed. This method allows for an efficient synthesis of a series of synthetically useful α,α-difluoropropargylphosphonates with excellent functional group compatibility.

  已经开发了在温和条件下，末端炔烃与容易获得的α-甲硅烷基二氟甲基膦酸酯的铜介导的氧化交叉偶联反应。该方法允许有效合成具有优异的官能团相容性的一系列合成上有用的α，α-二氟炔丙基膦酸酯。
• Preparation and functionalization of an alkenylcopper reagent formed by the syn addition of (dialkoxyphosphinyl)difluoromethylcopper to hexafluoro-2-butyne
  作者：Ranil D. Guneratne、Donald J. Burton

  DOI：10.1016/s0022-1139(99)00020-2

  日期：1999.8

  (Dialkoxyphosphinyl)difluoromethylcopper, readily prepared from dialkyl bromodifluoromethylphosphonate, undergoes facile, stereospecific, syn addition to hexafluoro-2-butyne, to form the cis alkenylcopper reagent in good yield. This intermediate can be functionalized with electrophiles, such as aryl, alkyl, and alkenyl halides. (C) 1999 Elsevier Science S.A. All rights reserved.

  （甲氧磷基）二溴甲基磷酰胺从二溴甲基磷酰胺中的水解反应很容易地制备。这种中间体发生了易于实现、高度选择性且顺式地加成过程，以便形成顺式交联的铜基烯。这种中间体可以被电rophiles进行功能化反应。例如，可以引入苯基、甲基和烯基卤化物等基团。（C）1999 Elsevier Science S.A. 所有权利保留。
• Facile syntheses of building blocks for the construction of phosphotyrosine mimetics
  作者：G. Stuart Cockerill、Howard J. Easterfield、Jonathan M. Percy、Stéphane Pintat

  DOI：10.1039/b004187o

  日期：——

  The copper-catalysed zinc phosphonate chemistry described by Yokomatsu and Shibuya can be used to enter the classical organometallic coupling repertoire via Stille and Suzuki–Miyaura couplings. 1,4-Diiodobenzene underwent coupling with the organozinc reagent derived from diethyl bromodifluoromethylphosphonate with copper(I) catalysis to afford diethyl (4-iodophenyl)difluoromethylphosphonate. Higher yielding couplings were run with (4-trifluoromethylsulfonyloxy)- and (4-nonafluorobutylsulfonyloxy)-iodobenzenes. The iodide and the triflate coupled under palladium-catalysed conditions with a range of stannanes and boronic acids in moderate to excellent yields. Shibuya–Yokomatsu couplings were also successful with more functionalised iodoarenes and heteroarenes presenting the important phosphate mimic on a range of scaffolds.

  横松和渋谷描述的铜催化锌膦酸酯化学可用于通过斯蒂尔（Stille）和铃木-宫浦（Suzuki-Miyaura）偶联反应进入经典的金属有机偶联反应领域。1,4-二碘苯在铜(I)催化下与由二乙基溴二氟甲基膦酸酯衍生的有机锌试剂发生偶联，生成二乙基(4-碘苯基)二氟甲基膦酸酯。与(4-三氟甲磺酰氧基)和(4-九氟丁磺酰氧基)碘苯进行的偶联反应产率更高。碘化物和三氟甲磺酸酯在钯催化条件下与一系列锡烷和硼酸发生偶联，产率从中等到优异。渋谷-横松偶联反应在具有更丰富官能团的碘芳烃和杂芳烃上也取得了成功，这些重要磷酸类似物被引入多种骨架上。