ethyl 3-trifluoromethyl-3-oxo-propionate | 106260-08-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 3-trifluoromethyl-3-oxo-propionate
• 英文别名: Ethyl trifluoroacetoacetate；3-Hydroxy-4,4,4-trifluoro-2-butenoic acid ethyl ester；ethyl (Z)-4,4,4-trifluoro-3-hydroxybut-2-enoate
• CAS: 106260-08-6
• 化学式: C₆H₇F₃O₃
• 分子量: 184.115
• InChiKey: SJNDOEWQCSKXBD-ARJAWSKDSA-N

物化性质

• 沸点：
  206.1±40.0 °C(Predicted)
• 密度：
  1.330±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3-trifluoromethyl-3-oxo-propionate 在 sodium nitrite 作用下， 以 溶剂黄146 为溶剂， 反应 1.0h， 以82%的产率得到4,4,4-Trifluoro-2-(hydroxyimino)-3-oxobutanoic acid, ethyl ester
  参考文献：
  名称：

  含氟代烷基的2-氧亚氨基-1,3-二羰基化合物的合成及其与水合肼的反应

  摘要：

  含氟代烷基的1，3-酮酸酯和1，3-二酮与它们的铜螯合物与亚硝酸钠反应，得到相应的2-羟基亚氨基取代的配体和螯合物。1,1,1-三氟-3-羟基亚氨基-4-苯基1-2,4-丁二酮与水合肼反应生成4-羟基亚氨基吡唑。具有九氟丁基取代基的1，3-酮酯可得到稳定的3-九氟丁基-3-二羟基-4-羟基亚氨基吡唑烷酮-5。三氟乙酰乙酸乙酯肟的类似反应生成吡唑烷酮-5（可脱水成4-氧亚氨基吡唑啉酮-5）和4,4,4-三氟-2-羟基亚氨基-3-二羟基丁酸酯的酰肼。

  DOI：

  10.1016/s0022-1139(97)00054-7
• 作为产物：
  描述：

  ethyl (Z)-4,4,4-trifluoro-3-(2,2,2-trifluoroacetyl)oxybut-2-enoate 、 水 生成 ethyl 3-trifluoromethyl-3-oxo-propionate
  参考文献：
  名称：

  SAVOSTYANOVA, I. A.;OLENEVA, G. I.;SHIPOV, A. G.;BAUKOV, YU. I., FOSFORORGAN. I KREMNIJORGAN. SOEDIN., LENINGRAD, 1985, 90-101

  摘要：

  DOI：

文献信息

• A PROCESS FOR THE PREPARATION OF ALKYL 3-DIFLUOROMETHYL-1-METHYL-1H-PYRAZOLE-4-CARBOXYLATE AND ITS ANALOGS
  申请人：KingChem LLC.

  公开号：US20150158808A1

  公开（公告）日：2015-06-11

  The disclosure provides a process for the preparation of alkyl 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylate and its analogs. The process includes a reaction workup method for Claisen condensation, wherein the enolate salt is acidified after removing remaining starting material and byproducts such as, ethanol and excessive ethyl acetate. The process also includes a method for completely drying alkyl difluoroacetoacetate and its analogs before use in the next step by reacting trialkyl orthoformate with the residual water. The process includes using Na 2 CO 3 and/or K 2 CO 3 to promote the ring-closure reaction to produce the alkyl 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylate. The process also includes effectively removing the regioisomer, alkyl 3-difluoromethyl-2-methyl-1H-pyrazole-4-carboxylate formed as a byproduct of the ring closure by a precipitation in a mixed solvent system and thereby eliminating the need for recrystallization of the final product.

  该披露提供了一种制备烷基3-二氟甲基-1-甲基-1H-吡唑-4-羧酸酯及其类似物的过程。该过程包括一种用于Claisen缩合的反应工作方法，其中在去除剩余的起始物质和副产物（如乙醇和过量的乙酸乙酯）后，使烯醇盐酸化。该过程还包括一种在下一步使用烷基二氟乙酰乙酸酯及其类似物之前完全干燥的方法，即通过将三烷基正甲酸酯与残留水反应。该过程包括使用Na2CO3和/或K2CO3促进环闭合反应，以产生烷基3-二氟甲基-1-甲基-1H-吡唑-4-羧酸酯。该过程还包括通过在混合溶剂体系中沉淀的方式有效去除环闭合的副产物烷基3-二氟甲基-2-甲基-1H-吡唑-4-羧酸酯，从而消除了对最终产品的再结晶的需要。
• [EN] PROCESS FOR PREPARING ALKYL 3-DIFLUOROMETHYL-1-METHYL-1H-PYRAZOLE-4-CARBOXYLATE AND ITS ANALOGS<br/>[FR] PROCÉDÉ DE PRÉPARATION DE 3-DIFLUOROMÉTHYL-1-MÉTHYL-1H-PYRAZOLE-4-CARBOXYLATE D'ALKYLE ET DE SES ANALOGUES
  申请人：KING CHEM LLC

  公开号：WO2015085464A1

  公开（公告）日：2015-06-18

  The disclosure provides a process for the preparation of alkyl 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylate and its analogs. The process includes a reaction workup method for Claisen condensation, wherein the enolate salt is acidified after removing remaining starting material and byproducts such as, ethanol and excessive ethyl acetate. The process also includes a method for completely drying alkyl difluoroacetoacetate and its analogs before use in the next step by reacting trialkyl orthoformate with the residual water. The process includes using Na2CO3 and /or K2CO3 to promote the ring-closure reaction to produce the alkyl 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylate. The process also includes effectively removing the regioisomer, alkyl 3-difluoromethyl-2-methyl-1H-pyrazole-4-caboxylate formed as a byproduct of the ring closure by a precipitation in a mixed solvent system and thereby eliminating the need for recrystallization of the final product.

  该披露提供了一种制备烷基3-二氟甲基-1-甲基-1H-吡唑-4-羧酸酯及其类似物的过程。该过程包括一种用于Claisen缩合的反应工作方法，其中在去除剩余的起始物质和副产物（如乙醇和过量的乙酸乙酯）后，使烯醇盐酸化。该过程还包括一种在下一步使用烷基二氟乙酮酸酯及其类似物之前完全干燥的方法，即通过将三烷基正甲酸酯与残留水反应。该过程包括使用Na2CO3和/或K2CO3促进环闭合反应，以产生烷基3-二氟甲基-1-甲基-1H-吡唑-4-羧酸酯。该过程还包括通过在混合溶剂系统中沉淀的方式有效地去除环闭合的副产物烷基3-二氟甲基-2-甲基-1H-吡唑-4-羧酸酯，从而消除了对最终产品的再结晶的需求。
• Synthesis of 2-arylhydrazones of aliphatic fluorine-containing 1,2,3-tricarbonyl compounds and their reactions with dinucleophiles
  作者：O. G. Kuzueva、Ya. V. Burgart、V. I. Saloutin

  DOI：10.1007/bf02495977

  日期：1998.4

  New fluorinated 2-arylhydrazones of 1,2,3-tricarbonyl compounds were obtained by coupling fluorine-containing 3-oxo esters, 1,3-diketones, and their copper chelates with aryldiazonium chlorides. Reactions of these arylhydrazones with hydrazine hydrate, phenylhydrazine, thiosemicarbazide, and hydroxylamine gave the corresponding pyrazole and isoxazole derivatives.

  通过将含氟 3-氧代酯、1,3-二酮及其铜螯合物与芳基重氮氯化物偶联，获得了 1,2,3-三羰基化合物的新型氟化 2-芳基腙。这些芳基腙与水合肼、苯肼、氨基硫脲和羟胺反应得到相应的吡唑和异恶唑衍生物。
• Inversion of Enantioselectivity during the Platinum-Catalyzed Hydrogenation of an Activated Ketone
  作者：Matthias von Arx、Tamas Mallat、Alfons Baiker

  DOI：10.1002/1521-3773(20010618)40:12<2302::aid-anie2302>3.0.co;2-p

  日期：2001.6.18

  Two competing reaction pathways, which lead to opposite enantiomers, occur in the hydrogenation of 1 over chirally modified platinum, as revealed by catalytic and NMR spectroscopic experiments: the fast reduction of the ketoform 1 a (minor species) and the slow hydrogenolysis of the hydrate 3 (major species).

  催化和NMR光谱实验表明，在手性修饰的铂上进行1的氢化时，会发生两种竞争的反应途径，从而导致相反的对映异构体：酮型1a（次要物种）的快速还原和水合物的缓慢氢解3（主要物种）。
• Reaction of fluoroalkyl-containing 1,3-dicarbonyl compounds with benzylideneacetone
  作者：Ya. V. Burgart、A. S. Fokin、I. T. Bazyl'、V. I. Saloutin

  DOI：10.1007/bf02496126

  日期：1997.5

  The reaction of fluoroalkyl-containing 1,3-dicarbonyl compounds with benzylideneacetone with the use of pyridine or triethylamine as a catalyst gave new 3-fluoroalkyl-4-ethoxycarbonyl(acyl)-5-phenylcyclohexan-3-ol-I-ones in yields of 16–33%.

  含氟烷基的 1,3-二羰基化合物与亚苄基丙酮在吡啶或三乙胺作为催化剂的反应得到新的 3-氟烷基-4-乙氧基羰基（酰基）-5-苯基环己-3-醇-I-酮的产率16–33%。

表征谱图