ethyl 3-oxo-3-phenyl-2-(tosyloxy)propanoate | 81447-37-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3-oxo-3-phenyl-2-(tosyloxy)propanoate
• 英文别名: ethyl 2-(4-methylphenyl)sulfonyloxy-3-oxo-3-phenylpropanoate
• CAS: 81447-37-2
• 化学式: C₁₈H₁₈O₆S
• 分子量: 362.403
• InChiKey: LQPLLNAHEQRIBN-UHFFFAOYSA-N

物化性质

• 沸点：
  511.3±45.0 °C(Predicted)
• 密度：
  1.279±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  95.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3-oxo-3-phenyl-2-(tosyloxy)propanoate 在 水 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 2,4-二苯基-1,3-噻唑-5-羧酸
  参考文献：
  名称：

  Design, synthesis and RON receptor tyrosine kinase inhibitory activity of new head groups analogs of LCRF-0004

  摘要：

  New heteroarylcarboxamide head groups substituted with two aromatic rings analogs of thieno[3,2-b] pyridine-based kinase inhibitor LCRF-0004 were designed and synthesized. Potent inhibitors of RON tyrosine kinase with various level of selectivity for c-Met RTK were obtained. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2015.07.080
• 作为产物：
  描述：

  苯甲酰乙酸乙酯 以 二氯甲烷 为溶剂， 反应 48.0h， 生成 ethyl 3-oxo-3-phenyl-2-(tosyloxy)propanoate
  参考文献：
  名称：

  碘鎓碘化物的制备：用氟碘烷探测1,3-二羰基化合物的氟化†

  摘要：

  的碘鎓叶立德隔离8，从fluoroiodane的反应1用3-氧代-3-苯基丙5中的氟化钾的存在下，提供了强有力的证据，1,3-二羰基化合物经历与fluoroiodane加成反应1以形成可以被去质子化以生成碘鎓叶立德的碘鎓中间体。然而，在TREAT-HF的存在下，碘鎓中间体反应形成2-氟-1,3-二羰基产物，我们建议氟碘烷1通过加成/取代机理模拟亲电氟化。通过成功地使分离出的碘鎓叶立德反应获得了支持该机制的进一步证据。8用TREAT-HF，盐酸，乙酸和对甲苯磺酸分别形成2-氟-，2-氯-，2-乙酰基和2-甲苯基-1，3-酮酸酯。

  DOI：

  10.1039/c4ra15733h

文献信息

• Various α-Oxygen Functionalizations of β-Dicarbonyl Compounds Mediated by the Hypervalent Iodine(III) Reagent<i>p</i>-Iodotoluene Difluoride with Different Oxygen-Containing Nucleophiles
  作者：Jun Yu、Jun Tian、Chi Zhang

  DOI：10.1002/adsc.200900737

  日期：2010.2.15

  for the effective introduction of various oxygen-containing functionalities including tosyloxy, mesyloxy, acetoxy, phosphoryloxy, methoxy, ethoxy and isopropoxy at the α-position of β-dicarbonyl compounds. These transformations can be readily realized by the use of the combined reagent of p-iodotoluene difluoride and various oxygen-containing nucleophilic compounds such as p-toluenesulfonic acid, methanesulfonic

  p -Iodotoluene二氟乙烯（p -Tol-IF 2）已被发现是一种一般用于有效地引入各种含氧官能团包括甲苯磺酰氧基，甲磺酰氧基，乙酰氧基，磷酰甲氧基，乙氧基和异丙氧基在α位的试剂β-二羰基化合物。通过使用对-碘甲苯二氟化物和各种含氧亲核化合物如对甲苯磺酸，甲磺酸，乙酸，磷酸二苯酯，甲醇，乙醇和丙-2-醇的组合试剂，可以轻松实现这些转化。分别在温和的条件下。并且，原位生成的高价碘（III）物种通过在这种转化中，对-碘甲苯二氟化物与相应的含氧亲核试剂之间的配体交换被认为是真正的氧化剂。
• PhI- and polymer-supported PhI-catalyzed oxidative conversion of ketones and alcohols to α-tosyloxyketones with m-chloroperbenzoic acid and p-toluenesulfonic acid
  作者：Yukiharu Yamamoto、Yuhta Kawano、Patrick H. Toy、Hideo Togo

  DOI：10.1016/j.tet.2007.03.091

  日期：2007.5

  Various ketones were converted to the corresponding α-tosyloxyketones with mCPBA and p-toluenesulfonic acid in the presence of a catalytic amount of iodobenzene. Moreover, secondary alcohols were directly converted to the corresponding α-tosyloxyketones using mCPBA and catalytic amounts of iodobenzene and potassium bromide, followed by treatment with p-toluenesulfonic acid in a one-pot manner. Poly(4-iodostyrene)

  各种酮转化成相应的α-tosyloxyketones与米CPBA和p在碘苯催化量的存在对甲苯磺酸。此外，使用m CPBA和催化量的碘代苯和溴化钾将仲醇直接转化为相应的α-甲苯磺酰氧基酮，然后以对-甲苯磺酸的一锅法处理。聚（4-碘苯乙烯）也可用作与酮相同的α-甲苯磺酰化反应的可回收催化剂
• A New Application of Hypervalent Iodine (λ⁵) Reagents with Organosulfonic Acids for Direct α-Organosulfonyloxylation Carbonyl Compounds
  作者：Krishnacharya Akamanchi、Ulhas Mahajan

  DOI：10.1055/s-2008-1072508

  日期：——

  Hypervalent iodine (λ 5 ) reagents in combination with P-toluenesulfonic acid when reacted with ketones under reflux temperature in acetonitrile gave α-tosyloxy ketones in moderate to excellent yields. The reaction was developed further for both ketones and dicarbonyl compounds using Dess-Martin periodinane reagent in combination with P-toluenesulfonic acid and methanesulfonic acid, to give mono-α-tosyloxy

  当在回流温度下在乙腈中与酮反应时，高价碘 (λ 5 ) 试剂与对甲苯磺酸结合，以中等至极好的收率得到 α-甲苯磺酰氧基酮。使用 Dess-Martin 高碘烷试剂与对甲苯磺酸和甲磺酸结合，进一步开发了酮和二羰基化合物的反应，以非常高的收率得到单-α-甲苯磺酰氧基和单-α-甲磺酰氧基产物。
• Iodoarene-Mediated α-Tosyloxylation of Ketones with MCPBA and p-Toluenesulfonic Acid
  作者：Hideo Togo、Ayumi Tanaka、Katsuhiko Moriyama

  DOI：10.1055/s-0030-1260948

  日期：2011.8

  Alkyl aryl ketones and dialkyl ketones could be converted into the corresponding α-tosyloxy ketones by the reaction with MCPBA and p-toluenesulfonic acid monohydrate (PTSA˙H2O) in the presence of a catalytic amount of molecular iodine (I2) in a mixture of acetonitrile and 2,2,2-trifluoroethanol, although the yields were dependent on the ketones (method A). The same conversion of alkyl aryl ketones and dialkyl ketones into the corresponding α-­tosyloxy ketones could be smoothly carried out by the reaction with MCPBA and PTSA˙H2O in the presence of catalytic amounts of ­iodine and tert-butylbenzene in a mixture of acetonitrile and 2,2,2-trifluoroethanol (method B). In those reactions, p-iodotoluene and 4-tert-butyl-1-iodobenzene were formed at first in method A and method B, respectively, and then they were converted into p-[(hydroxy)(tosyloxy)]iodotoluene and 4-tert-butyl-1-[(hydroxy)(tosyloxy)iodo]benzene by the reaction with MCPBA and PTSA˙H2O. p-[(Hydroxy)(tosyloxy)]iodotoluene and 4-tert-butyl-1-[(hydroxy)-(tosyloxy)iodo]benzene worked as an α-tosyloxylation reagent of ketones.

  烷基芳基酮和二烷基酮可以通过与间氯过氧苯甲酸（MCPBA）和单水合对甲苯磺酸（PTSA·H2O）在催化量的碘分子（I2）存在下反应，在乙腈和2,2,2-三氟乙醇的混合物中，转化为相应的α-甲苯磺酰氧基酮，尽管产率取决于酮类（方法A）。烷基芳基酮和二烷基酮同样可以通过与MCPBA和PTSA·H2O在催化量的碘和叔丁基苯存在下反应，在乙腈和2,2,2-三氟乙醇的混合物中，顺利转化为相应的α-甲苯磺酰氧基酮（方法B）。在这些反应中，方法A和方法B分别首先形成对碘甲苯和4-叔丁基-1-碘苯，然后它们通过与MCPBA和PTSA·H2O反应转化为对[(羟基)(甲苯磺酰氧基)]碘甲苯和4-叔丁基-1-[(羟基)(甲苯磺酰氧基)碘]苯。对[(羟基)(甲苯磺酰氧基)]碘甲苯和4-叔丁基-1-[(羟基)(甲苯磺酰氧基)碘]苯作为酮的α-甲苯磺酰氧化试剂。
• 4-MeC6H4I-Mediated Efficient α-Tosyloxylation of Ketones with Oxone® and p-Toluenesulfonic Acid in Acetonitrile
  作者：Hideo Togo、Ayumi Tanaka

  DOI：10.1055/s-0029-1218370

  日期：2009.12

  Various alkyl aryl ketones, dialkyl ketones, and cycloheptanone were efficiently converted into the corresponding α-tosyl­oxy ketones in good yields by using Oxone® and p-toluenesulfonic acid monohydrate in the presence of p-iodotoluene in acetonitrile. 4-Methoxyacetophenone and 2-acetylthiophene bearing an electron-rich aromatic group could be also converted into the corresponding α-tosyloxyketones smoothly in good yields with the present method. Here, p-iodotoluene works as catalyst and p-[(hydroxy)(tosyloxy)]iodotoluene is formed in situ as a reactive species for the α-tosyloxylation of ketones. However, one equivalent of p-iodotoluene was required to obtain α-tosyloxyketones in good yields and was recovered in 80-20% yields, depending on the reaction conditions.

  通过在乙腈中使用Oxone®和p-甲苯磺酸一水合物，并在p-碘甲苯的存在下，各种烷基芳香酮、二烷基酮和环庚酮高效地转化为相应的α-甲苯磺酰氧基酮，产率良好。带有富电子芳香基团的4-甲氧基苯乙酮和2-乙酰基噻吩也可以用当前方法顺利地转化为相应的α-甲苯磺酰氧基酮，产率良好。在这里，p-碘甲苯作为催化剂，并且原位生成p-[(羟基)(甲苯磺酰氧基)]碘甲苯作为酮的α-甲苯磺酰氧化反应的活性物质。然而，为了获得良好的α-甲苯磺酰氧基酮产率，需要等量的p-碘甲苯，并且根据反应条件的不同，其回收率为80-20%。