ethyl dichlorophosphonoacetate | 36957-54-7

• 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: ethyl dichlorophosphonoacetate
• 英文别名: ethyl (dichlorophosphoryl)acetate；Acetic acid, (dichlorophosphinyl)-, ethyl ester；ethyl 2-dichlorophosphorylacetate
• CAS: 36957-54-7
• 化学式: C₄H₇Cl₂O₃P
• 分子量: 204.978
• InChiKey: MPBVKATWYKRMDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl dichlorophosphonoacetate 以79%的产率得到
  参考文献：
  名称：

  Stephenson G. Richard, Milne Kate, Austral. J. Chem, 47 (1994) N 8, S 1605-1612

  摘要：

  DOI：
• 作为产物：
  描述：

  phosphonoacetic acid ethyl ester 在 草酰氯 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 ethyl dichlorophosphonoacetate
  参考文献：
  名称：

  Intramolecular cyclopropanation reactions en route to novel P-heterocycles

  摘要：

  The first examples of intramolecular cyclopropanation reactions on a phosphonate template catalyzed by Rh-2(OAc)(4) are described. These reactions proceed in excellent yield and give mixtures of the P-heterocycles cis-2a-d and trans-2a-d with moderate levels of diastereoselectivity. The diastereoselectivity of this transformation is dependent upon the size of the alkyl group R contained in the alkyl alpha-diazodiallylphosphonoacetate starting materials 1a-d. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00023-4

文献信息

• A Straightforward, Purification-Free Procedure for the Synthesis of Ando and Still–Gennari Type Phosphonates
  作者：Ignacy Janicki、Piotr Kiełbasiński

  DOI：10.1055/a-1628-7586

  日期：2022.1

  Z-Selective Still–Gennari and Ando modifications of the typically E-selective Horner–Wadsworth–Emmons reaction are highly valuable synthetic tools in organic chemistry. These procedures are based on application of bis(2,2,2-trifluoroethyl) phosphonates or diaryl phosphonates, respectively, for the olefination of carbonyl groups. In our research, we present an improved, straightforward, purification-free

  典型的 E 选择性 Horner-Wadsworth-Emmons 反应的 Z-选择性 Still-Gennari 和 Ando 修饰是有机化学中非常有价值的合成工具。这些程序基于分别应用双(2,2,2-三氟乙基)膦酸酯或二芳基膦酸酯用于羰基的烯化。在我们的研究中，我们提出了一种改进的、直接的、免纯化的合成这些试剂的程序。我们程序的关键步骤是使二氯化膦与适当的醇钠反应，从而在克规模上产生 52-97% 的分离产率。整个三步过程在一锅中进行。最重要的是，经过简单萃取后，产品纯度超过95%，避免了柱层析和蒸馏。而且，
• Highly Selective Synthesis of <i>Z</i>-Unsaturated Esters by Using New Horner−Emmons Reagents, Ethyl (Diarylphosphono)acetates
  作者：Kaori Ando

  DOI：10.1021/jo970057c

  日期：1997.4.1

  New Horner-Emmons reagents, ethyl (diarylphosphono)acetates 1, were prepared from triethyl phosphonoacetate, PCl(5), and the corresponding phenols. The reaction of 1 with several kinds of aldehydes in the presence of Triton B or NaH in THF solvent revealed that these reagents are useful for the synthesis of Z-unsaturated esters. Among the reagents examined, ethyl(di-o-tolylphosphono)-, [bis(o-ethylphenyl)phosphono]-

  由膦酸三乙酯，PCl（5）和相应的酚制备新的Horner-Emmons试剂（二芳基膦酸乙酯）乙酸乙酯1。在Triton B或NaH存在下，THF中1与几种醛的反应表明，这些试剂可用于合成Z-不饱和酯。在所检查的试剂中，发现乙基（二-邻甲苯基膦酰基）-，[双（邻乙基苯基）膦基]-和[双（邻异丙基苯基）膦基]乙酸酯（1k-m）最有效，得到Z-不饱和酯，选择性为93-99％。
• New solid-supported phosphonate reagents for the synthesis of Z-α,β-unsaturated esters
  作者：Sébastien L.X. Martina、Richard J.K. Taylor

  DOI：10.1016/j.tetlet.2004.02.138

  日期：2004.4

  Novel solid-supported phosphonate reagents have been prepared and evaluated for the synthesis of α,β-unsaturated esters with a preference for the Z-alkene. The optimal reagent was a hybrid of both Still–Gennari and Ando reagents, and showed good to high yields and fair to good Z-selectivity for the conversion of both aliphatic and aromatic aldehydes.

  已经制备了新型的固体负载的膦酸酯试剂，并评价了其合成α，β-不饱和酯，优选Z-烯烃。最佳试剂是Still-Gennari试剂和Ando试剂的混合物，对于脂肪族和芳香族醛的转化，均显示出高到高收率以及Z选择性到中等到好的选择。
• Total Synthesis of the Potent Antitumor Polyketide (−)-Callystatin A
  作者：Luiz C. Dias、Paulo R. R. Meira

  DOI：10.1021/jo050352u

  日期：2005.6.1

  A highly convergent and efficient total synthesis of the potent antitumor polyketide (−)-callystatin A is described. The synthesis required 19 steps from N-propionyl oxazolidinone 23 and produced the desired product in 3.5% overall yield.

  描述了高效抗肿瘤聚酮化合物（-）-卡利他汀A的高度收敛和高效的全合成。合成需要从N-丙酰基恶唑烷酮23开始的19个步骤，并以3.5％的总产率产生所需的产物。
• New polymer-supported phosphonate reagents for the synthesis of Z-α,β-unsaturated esters
  作者：Kaori Ando、Yusaku Suzuki

  DOI：10.1016/j.tetlet.2010.02.113

  日期：2010.4

  New polymer-supported phosphonate reagents have been prepared and evaluated for the synthesis of Z-α,β-unsaturated esters. High Z-selectivity was obtained using the reagent having two o-t-BuC6H4 groups.

  已经制备了新的聚合物负载的膦酸酯试剂，并评价了其对Z -α，β-不饱和酯的合成。高ž使用具有两个试剂，得到-选择性ö -吨-BuC 6 ħ 4组的基团。