benzoyl dimethyl phosphate | 91489-49-5

• 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: benzoyl dimethyl phosphate
• 英文别名: BzOP(O)(OMe)2；benzoyl-phosphoric acid dimethyl ester；Benzoyl-phosphorsaeure-dimethylester；Dimethoxyphosphoryl benzoate；dimethoxyphosphoryl benzoate
• CAS: 91489-49-5
• 化学式: C₉H₁₁O₅P
• 分子量: 230.157
• InChiKey: AGISSQVSNOUSJZ-UHFFFAOYSA-N

物化性质

• 沸点：
  284.8±23.0 °C(Predicted)
• 密度：
  1.273±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  benzoyl dimethyl phosphate 在 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 72.0h， 以93%的产率得到benzoyl methyl phosphate sodium salt
  参考文献：
  名称：

  Benzoyl methyl phosphates as efficient reagents in the one-pot tandem approach for the synthesis of 2-phenylbenzimidazoles in water

  摘要：

  本研究开发了一种在水中合成 2-苯基苯并咪唑的无害环境、无催化剂和无助剂的新型高效方法。苯甲酰基甲基磷酸酯作为生物仿生酰化剂在无需额外催化剂的一锅串联法中发挥了重要作用。

  DOI：

  10.1039/c3ra46749j
• 作为产物：
  描述：

  dimethyl α-diazobenzylphosphonate 在 氧气 作用下， 以 solid matrix 为溶剂， 生成 (苯基氧代甲基)膦酸二甲酯 、 benzoyl dimethyl phosphate
  参考文献：
  名称：

  Photochemistry of matrix-isolated (.alpha.-diazobenzyl)phosphonate. Observation and reactions of phosphonylphenylcarbene, phosphonyl phenyl ketone oxide, and phenylphosphonyldioxirane

  摘要：

  Photolysis of dimethyl alpha-diazobenzylphosphonate (1) in an Ar matrix at 10 K resulted in the appearance of new absorption bands at 1268, 788, and 536 cm-1, attributable to the carbene 2. The assignment was based on the observation that the new absorptions disappeared upon thawing of the CO-containing matrix to produce the ketene 3, which can be generated by photolysis of (alpha-diazophenacyl)phosphonate 4. Photolysis of 1 in an Ar matrix doped with 20% O2 at 10 K produced benzoylphosphonate 5 along with benzoyl phosphate 8. Generation of 2 in a 0.3% O2-containing matrix, followed by warming of the matrix to 35 K in the dark, resulted in the total disappearance of the band arising from 2 and the concurrent appearance of a new intermediate, identified as the carbonyl oxide 6. Photolysis of 6 with visible light (lambda > 480 nm) gave the corresponding dioxirane 7, which was converted to the ester 8 by further irradiation (lambda > 350 nm); none of the phosphate 9, expected to arise via phenyl migration in the photoisomerization of 7, was detected.

  DOI：

  10.1021/jo00049a032

文献信息

• An Efficient Protocol for the Amidation of Carboxylic Acids Promoted by Trimethyl Phosphite and Iodine
  作者：Qun-Li Luo、Lina Lv、Yu Li、Jian-Ping Tan、Wenhui Nan、Qun Hui

  DOI：10.1002/ejoc.201101030

  日期：2011.12

  A practical, one-pot protocol is described for the conversion of carboxylic acids into amides through carboxyl activation by the reagent combination of trimethyl phosphite and iodine. This method integrates several advantages: (1) it allows amines to be chemoselectively acylated with excellent results in the presence of sulfur and oxygen nucleophiles; (2) the method shows wide generality in respect

  描述了一种实用的一锅法，用于通过亚磷酸三甲酯和碘的试剂组合通过羧基活化将羧酸转化为酰胺。这种方法综合了几个优点：（1）它允许胺在硫和氧亲核试剂的存在下被化学选择性地酰化，并获得优异的结果；(2)该方法在溶剂、碱和底物方面具有广泛的通用性；(3) 使用的试剂广泛可用且比普通偶联试剂便宜得多，并且 (4) 该过程非常方便，允许提取、重结晶和柱色谱作为可选的后处理程序。该方法的化学选择性和通用性、成本低、试剂的广泛可用性以及易用性使其成为一个非常有利的过程。
• Preparation of Esters and Amides from Carboxylic Acids by Activation with Dialkyl Phosphite-Carbon Tetrachloride Mixture
  作者：Zsuzsa M. Jászay、Imre Petneházy、László Tőoke

  DOI：10.1080/00397919808004849

  日期：1998.8

  Abstract A simple one pot phase transfer catalytic method is described for the synthesis of carboxylic amides and esters from carboxylic acids and amines or alcohols, respectively. For the activation of the carboxylic acids “in situ” generated phosphoric acid diester chlorides were applied.

  摘要 描述了一种简单的一锅相转移催化方法，用于分别由羧酸和胺或醇合成羧酸酰胺和酯。为了活化羧酸“原位”生成的磷酸二酯氯化物被应用。
• Benzoyl methyl phosphate as an efficient reagent for the selective monobenzoylation of N-Bz-FTY720
  作者：Hidemasa Hikawa、Maiko Hamada、Yuusaku Yokoyama、Isao Azumaya

  DOI：10.1039/c4ra02401j

  日期：——

  A novel and efficient method for the selective monobenzoylation of N-Bz-FTY720 with benzoyl methyl phosphate (BMP) promoted by Zn(OAc)₂ and Cs₂CO₃ was developed. Benzoyl methyl phosphate plays an important role as a biomimetic acylating agent for the monobenzoylation of 1,3-diols.

  开发了一种新颖高效的方法，利用Zn(OAc)₂和Cs₂CO₃促进的苯甲酰甲基磷酸酯（BMP）对N-Bz-FTY720进行选择性单苯甲酰化。苯甲酰甲基磷酸酯在1,3-二醇的单苯甲酰化中发挥着重要作用，作为一种生物模拟酰化试剂。
• Activation of Acyl Phosphate Monoesters by Lanthanide Ions:  Enhanced Reactivity of Benzoyl Methyl Phosphate
  作者：Ronald Kluger、Lisa L. Cameron

  DOI：10.1021/ja016600v

  日期：2002.4.1

  accelerating reactions much more than comparable levels of magnesium ion. Detailed kinetic analysis of the hydrolysis reactions reveals formation of a 1:1 complex, followed by rapid reaction with a nucleophile. The hydroxide-dependent hydrolysis rate in the europium complex is about 10(5) times that of free substrate with hydroxide. A mechanism that accounts for the data and observed behavior involves bidentate

  酰基磷酸单酯是许多生化酰化反应的中间体，例如涉及氨酰腺苷酸的反应。磷酸苯甲酰甲酯是一种典型的酰基磷酸单酯，在中性溶液中缓慢水解，但与胺反应迅速。由于酰基磷酸单酯的生化过程涉及与以氧为中心的亲核试剂的加速反应，我们寻找用于苯甲酰甲基磷酸酯水解和甲醇分解的催化剂来模拟生化结果。镧系元素离子是特别有效的催化剂，比同等水平的镁离子更能加速反应。水解反应的详细动力学分析揭示了 1:1 复合物的形成，然后与亲核试剂快速反应。铕络合物中依赖于氢氧化物的水解速率约为具有氢氧化物的游离底物的 10(5) 倍。解释数据和观察到的行为的机制涉及酰基磷酸盐通过磷酸盐和羰基氧对金属离子的双齿配位，降低四面体加成中间体和相关过渡态的能量。金属离子催化过程对氢氧根离子浓度的依赖性与作为亲核试剂的配位氢氧化物一致。在 0.0001 M 三氟甲磺酸镧存在下，苯甲酰甲基磷酸酯与甲醇形成苯甲酸甲酯和磷酸甲酯的反应速度快 30 000
• Symes, Jill; Modro, Tomasz A., Canadian Journal of Chemistry, 1986, vol. 64, p. 1702 - 1708
  作者：Symes, Jill、Modro, Tomasz A.

  DOI：——

  日期：——