(4-溴苯甲酰基)膦酸二甲酯 | 33493-31-1

• 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: (4-溴苯甲酰基)膦酸二甲酯
• 英文名称: p-Brombenzoyl-dimethyl-phosphonat
• 英文别名: Dimethyl(4-bromophenyloxomethyl)phosphonate；(4-bromophenyl)-dimethoxyphosphorylmethanone
• CAS: 33493-31-1
• 化学式: C₉H₁₀BrO₄P
• 分子量: 293.054
• InChiKey: QSFIDWDIXNEVSR-UHFFFAOYSA-N

物化性质

• 沸点：
  341.5±44.0 °C(Predicted)
• 密度：
  1.538±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2931900090

反应信息

• 作为反应物：
  描述：

  (4-溴苯甲酰基)膦酸二甲酯 在 盐酸 、 sodium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 36.0h， 生成 dimethyl ((4-bromophenyl)(diazo)methyl)phosphonate
  参考文献：
  名称：

  α-重氮芳基甲基膦酸酯的双功能双官能化：氟化膦酸酯的合成†

  摘要：

  描述了通过α-重氮芳基甲基膦酸酯的双双官能化反应制备各种氟化膦酸酯的一般方法。重氮官能度（RR'C Ñ 2）被成功地转换为RR'CF 2，RR'CHF，RR'CFBr或RR'CFNR'' 2组分别采用不同的氟化试剂的基团。从普通类型的前体中可以很容易地获得各种氟化有机磷化合物，收率很高。

  DOI：

  10.1039/c6ob01858k
• 作为产物：
  描述：

  dimethyl (hydroxy(4-bromophenyl)methyl)phosphonate 在 chromium (VI) oxide 作用下， 以 乙腈 为溶剂， 反应 20.0h， 生成 (4-溴苯甲酰基)膦酸二甲酯
  参考文献：
  名称：

  1-羟基膦酸酯的异质氧化制备酰基膦酸酯

  摘要：

  研究了使用三种异质体系MnO 2，KMnO 4和CrO 2将羟基膦酸酯氧化为酰基膦酸酯。用CrO 2在回流的乙腈中可获得最佳结果。

  DOI：

  10.1016/s0040-4039(98)01933-9

文献信息

• New Efficient Synthesis of 1-Hydroxymethylene-1,1-Bisphosphonate Monomethyl Esters
  作者：Marc Lecouvey、Evelyne Migianu、Erwann Guénin

  DOI：10.1055/s-2004-837226

  日期：——

  A new efficient procedure for the synthesis of 1-hydroxymethylene-1,1-bisphosphonate monomethyl esters in three steps from acid chlorides is reported here.

  本文报道了一种从酰氯分三步合成 1-羟基亚甲基-1,1-二膦酸单甲酯的新有效方法。
• Enantio- and Diastereoselective Vinylogous Mukaiyama Aldol Reactions of α-Keto Phosphonates with 2-(Trimethylsilyloxy)- furan Catalyzed by Bis(oxazoline)-Copper Complexes
  作者：Gang Hou、Jipan Yu、Chengbin Yu、Guiping Wu、Zhiwei Miao

  DOI：10.1002/adsc.201200810

  日期：2013.1.9

  The asymmetric vinylogous Mukaiyama aldol reaction between α-keto phosphonate and 2-(trimethylsilyloxy)furan was performed by using bis(oxazoline)-copper complexes as the catalyst and 2,2,2-trifluoroethanol as additive in dichloromethane. The present method is highly tolerable for functionalized α-keto phosphonates and enabled us to obtain the corresponding 3- and 4-substituted benzyl-functionalized

  以双（恶唑啉）-铜络合物为催化剂，以2,2,2-三氟乙醇为添加剂，在二氯甲烷中进行α-酮膦酸酯与2-（三甲基甲硅烷氧基）呋喃的不对称乙烯基Mukaiyama aldol反应。本方法对官能化的α-酮膦酸酯具有很高的耐受性，使我们能够以高收率（高达86％）和高对映体选择性（高达90％）获得相应的3-和4-取代的苄基官能化的叔α-羟基膦酸酯。 98％ee）和非对映选择性（最高达99：1，抗选择性）。
• A new and direct approach to functionalized biaryl α-ketophosphonic acids via aqueous Suzuki coupling on solid support
  作者：Xianfeng Li、Anna Katrin Szardenings、Christopher P. Holmes、Liang Wang、Ashok Bhandari、Lihong Shi、Marc Navre、Larry Jang、J. Russell Grove

  DOI：10.1016/j.tetlet.2005.10.122

  日期：2006.1

  A new method for the synthesis of functionalized biaryl α-ketophosphonic acids has been developed. The key step involves the use of sodium bromobenzoyl phosphonates to react with polymer-bound boronic acids via microwave-assisted aqueous Suzuki coupling. This approach provides rapid access to a wide range of diverse biaryl analogues containing an α-ketophosphonic acid moiety.

  已经开发了一种合成官能化的联芳基α-酮膦酸的新方法。关键步骤涉及使用溴苯甲酰基膦酸钠通过微波辅助的Suzuki水性偶联与聚合物结合的硼酸反应。该方法提供了对包含α-酮膦酸部分的多种多样的联芳基类似物的快速访问。
• Enantioselective Synthesis of Tertiary α-Hydroxy Phosphonates Catalyzed by Carbohydrate/Cinchona Alkaloid Thiourea Organocatalysts
  作者：Shasha Kong、Weidong Fan、Guiping Wu、Zhiwei Miao

  DOI：10.1002/anie.201204287

  日期：2012.8.27

  A pinch of sugar: The new bifunctional carbohydrate/cinchonine‐based thiourea 1 has been designed for the asymmetric addition reaction of α‐ketophosphonates and trimethylsilyl cyanide, the product of which can be hydrolyzed to afford tertiary α‐hydroxy phosphonates with excellent enantioselectivities.

  一小撮糖：基于双功能碳水化合物/金鸡宁的新型硫脲1是专为α-酮膦酸酯和三甲基甲硅烷基氰化物的不对称加成反应而设计的，它们的产物可以水解得到具有优异对映选择性的叔α-羟基膦酸酯。
• Bisphosphonate prodrugs: Synthesis and biological evaluation in HuH7 hepatocarcinoma cells
  作者：Maelle Monteil、Evelyne Migianu-Griffoni、Odile Sainte-Catherine、Mélanie Di Benedetto、Marc Lecouvey

  DOI：10.1016/j.ejmech.2014.02.054

  日期：2014.4

  We investigated the biological effects of new synthesized bisphosphonates (BPs) on HuH7 hepatocarcinoma cells. BPs containing p-bromophenyl (R-1 = p-Br, Ph, 2) in their side chain were the more potent to inhibit HuH7 cell viability. In addition, phenyl diesterified analogues (R-2 = R-3 = Ph, 2a) were more potent than methyl (R-2 = R-3 = Me, 2b) or non-esterified BPs (2) inducing more necrosis suggesting that they better entered into cells. Phosphodiesterase inhibitor (IBMX) reversed the effect of the esterified BPs and not that of non-esterified ones suggesting role of cell phosphodiesterases to release active BPs. BP analogues inhibited HuH7 cell migration but esterified ones had no effect on invasion due to the hiding of phosphonic groups. All together, these results indicated the therapeutic interest of these new BP prodrugs. (c) 2014 Elsevier Masson SAS. All rights reserved.