4-chloro-2-[1-ethoxy-meth-(E)-ylidene]-4,4-difluoro-3-oxo-butyric acid ethyl ester | 1462461-45-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 4-chloro-2-[1-ethoxy-meth-(E)-ylidene]-4,4-difluoro-3-oxo-butyric acid ethyl ester
• 英文别名: 4-chloro-2-[1-ethoxymeth-(E)-ylidene]-4,4-difiuoro-3-oxobutyric acid ethyl ester；ethyl (E)-4-chloro-2-(ethoxymethylene)-4,4-difluoro-3-oxobutanoate；Ethyl 2-ethoxymethylene-4,4-difluoro-4-chloroacetoacetate；ethyl (2E)-4-chloro-2-(ethoxymethylidene)-4,4-difluoro-3-oxobutanoate
• CAS: 1462461-45-5
• 化学式: C₉H₁₁ClF₂O₄
• 分子量: 256.634
• InChiKey: GUYVVVAWKNQEAD-AATRIKPKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  4-氯-4,4-二氟乙酰乙酸乙酯 、 原甲酸三乙酯 在 三乙胺 作用下， 110.0 ℃ 、30.0 kPa 条件下， 以33.333%的产率得到
  参考文献：
  名称：

  [EN] MANUFACTURE OF 1-SUBSTITUTED METHYLIDENE COMPOUNDS
  [FR] FABRICATION DE COMPOSÉS DE MÉTHYLIDÈNE 1-SUBSTITUÉS

  摘要：

  式(I)的化合物，其中R2，A是某些取代基，Y是酯基，腈基或酰胺基，Z是O，S或N + R2，例如，作为吡唑类杀菌剂的中间体有用，可以通过化合物R2-C（O）-CH2Y与正甲酸酯HC-（OR3）3在碱存在下反应制备，特别是在胺存在下，例如三乙胺。

  公开号：

  WO2013171102A1

文献信息

• Method for the manufacture of heterocycles
  申请人：SOLVAY SA

  公开号：EP2644598A1

  公开（公告）日：2013-10-02

  Heterocyclic compounds, e.g. alkyl 1-alkyl-3-halomethyl-pyrazole-4-carboxylates, can be manufactured using a hydrazinium-CO2 compound, monosubstituted by an R1 group, to introduce a =N-N(alkyl) group into the heterocycle. R1 is an organic substituent selected from the group consisting of C1 to C12 alkyl ; C3 to C8 cycloalkyl ; C2 to C12 alkenyl ; C2 to C12 alkynyl ; C6 to C8 aryl ; C7 to C19 arylalkyl ; and C7 to C19 alkylaryl ; each of which may be substituted by one or more groups selected from the group consisting of R', X, OR', SR', NR'2, SiR'3, COOR', C(O)R', CN and CONR'2 wherein R' is H or a C1 to C12 group.

  杂环化合物，例如烷基1-烷基-3-卤甲基吡唑-4-羧酸酯，可以使用一种被R1基团单取代的联氮-CO2化合物进行制备，将=N-N(烷基)基团引入杂环化合物中。其中，R1是从以下基团中选择的有机取代基：C1至C12烷基；C3至C8环烷基；C2至C12烯基；C2至C12炔基；C6至C8芳基；C7至C19芳基烷基；和C7至C19烷基芳基；每个基团可能被一个或多个来自以下基团的取代基所取代：R'、X、OR'、SR'、NR'2、SiR'3、COOR'、C(O)R'、CN和CONR'2，其中R'是氢或C1至C12基团。
• [EN] IMPROVED PROCESS FOR THE PREPARATION OF ESTERS OF 1-H-PYRAZOLE-4-CARBOXYLIC ACIDS<br/>[FR] PROCÉDÉ PERFECTIONNÉ POUR LA PRÉPARATION D'ESTERS D'ACIDES 1H-PYRAZOLE-4-CARBOXYLIQUES
  申请人：SOLVAY

  公开号：WO2012025469A1

  公开（公告）日：2012-03-01

  Process for the manufacture of an ester of a 1-H-pyrazole-4-carboxylic acid of formula (I) wherein - R1 is H or an organic residue - R2 is H or an organic residue - R3 is H, an alkyl group having from 1 to 12 carbon atoms, an halogenated alkyl group having from 1 to 12 carbon atoms, an aralkyl group, an aryl group, a halogen. which comprises reacting a compound of formula (II): wherein R4 is C1-C8-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, benzyl or phenyl,R1 and R3, are as defined above with a hydrazine of formula (III): R2NHNH2 (III) wherein R2 is as defined above, in the presence of an organic solvent comprising at least one halogen.

  制备1-H-吡唑-4-羧酸酯（化学式（I））的方法如下：其中- R1为H或有机残基，- R2为H或有机残基，- R3为H、含有1至12个碳原子的烷基、含有1至12个碳原子的卤代烷基、芳基烷基、芳基、卤素。该方法包括将化合物（II）与化学式（III）的肼在至少含有一种卤素的有机溶剂中反应。其中化合物（II）的化学式为：其中R4为C1-C8-烷基、C3-C8-环烷基、C2-C8-烯基、苄基或苯基，R1和R3如上定义，R2如上定义。
• [EN] PROCESS FOR THE PREPARATION OF ESTERS OF 1-SUBSTITUTED-3-FLUOROALKYL-PYRAZOLE-4-CARBOXYLIC ACIDS<br/>[FR] PROCÉDÉ DE PRÉPARATION D'ESTERS D'ACIDES 3-FLUOROALKYL-PYRAZOLE-4-CARBOXYLIQUES SUBSTITUÉS EN POSITION 1
  申请人：SOLVAY

  公开号：WO2012010692A1

  公开（公告）日：2012-01-26

  Process for the manufacture of an ester or the respective free acid of a 1-substituted-3-fluoroalkyl-pyrazole-4-carboxylic acid of formula (I) wherein - Y is H, F or an alkyl group having from 1 to 12 carbon atoms which is optionally substituted by at least one halogen atom, an aralkyl group or an aryl group, - R1 is H or an organic residue, - R2 is H or an organic residue, which comprises submitting a compound of formula (II) wherein Y is as defined above - X is CI, Br or I, - R1 is H or an organic residue, - R2 is H or an organic residue, to a reduction reaction.

  制备1-取代-3-氟烷基吡唑-4-羧酸酯或相应的1-取代-3-氟烷基吡唑-4-羧酸的过程，其化学式为(I)，其中- Y为H，F或含有1至12个碳原子的烷基基团，该基团可选择地被至少一个卤素原子取代，也可以是芳基烷基基团或芳基基团，- R1为H或有机残基，- R2为H或有机残基，包括将化学式(II)的化合物进行还原反应，其中Y如上定义，- X为Cl，Br或I，- R1为H或有机残基，- R2为H或有机残基。
• METHOD FOR PREPARING HALOGENATED 3-OXOCARBOXYLATES CARRYING A 2-ALKOXYMETHYLIDENE OR A 2-DIALKYLAMINOMETHYLIDENE GROUP
  申请人：BASF SE

  公开号：EP3178813A1

  公开（公告）日：2017-06-14

  The present invention relates to a process for preparing compounds of the formula I, wherein R1 and R2 are each independently from one another selected from hydrogen, fluorine, bromine, chlorine and trifluoromethyl, R3 is selected from fluorine chlorine and trifluoromethyl, R4 is selected from C1-C4-alkyl, and X is either -OR5 or -NR6R7, wherein R5 is selected from C1-C4-alkyl, and R6 and R7 are each independently from one another selected from C1-C4-alkyl, which comprises the reaction of a compound of the formula II with a reagent of the formula III, wherein the variables R1, R2, R3, R4, R5 and X given in formulae II and III have the above defined meanings, in the presence of a catalyst selected from Brønsted acids, ammonium salts of Brønsted acids and Lewis acids; wherein the reaction is performed essentially in the absence of a carboxylic acid anhydride.

  本发明涉及一种制备式 I 化合物的工艺、 其中 R1 和 R2 各自独立地选自氢、氟、溴、氯和三氟甲基、 R3 选自氟、氯和三氟甲基、 R4 选自 C1-C4- 烷基，以及 X 是-OR5 或-NR6R7，其中 R5 选自 C1-C4-烷基，R6 和 R7 各自独立地选自 C1-C4-烷基、 其中 R5 选自 C1-C4-烷基，R6 和 R7 各自独立地选自 C1-C4-烷基。 与式 III 的试剂反应、 式 II 和式 III 中的变量 R1、R2、R3、R4、R5 和 X 具有上述定义的含义、 在选自布伦斯特酸、布伦斯特酸的铵盐和路易斯酸的催化剂存在下； 其中，反应基本上在没有羧酸酐的情况下进行。
• CONTINUOUS FLOW SYNTHESIS OF FLUORINATED OR NON-FLUORINATED PYRAZOLES
  申请人：Fujian Yongjing Technology Co., Ltd.

  公开号：EP3650443A1

  公开（公告）日：2020-05-13

  In one aspect the invention relates to the use of an amine compound in a process for the manufacture of a fluorinated or non-fluorinated 5- or 6-membered heterocyclic compound containing two nitrogen atoms in the ring system of the said compound, preferably of pyrazoles or pyrimidones. The invention also relates to a process for the manufacture of pyrazoles or pyrimidones, which may be fluorinated or may not be fluorinated (non-flourinated). Especially, the invention relates to process for the manufacture of fluorinatedpyrazoles or pyrimidones, and in particular the invention relates to process for the manufacture of such fluorinatedpyrazolesor pyrimidones, which each are very important building blocks for pharmaceutical and agro-applications. For example, the fungicides are Bixafen, Fluxapyroxad, Fluindapyr, Sedaxane, Isopyrazam and Benzovindifupyr strongly depend on such fluorinatedpyrazoles as key building blocks, or for Florasulam and Clorasulam-methyl (Diclosulam), respectively.

  在一个方面，本发明涉及胺化合物在制造氟化或非氟化 5 元或 6 元杂环化合物（在所述化合物的环系中含有两个氮原子，最好是吡唑或嘧啶酮）过程中的用途。本发明还涉及吡唑或嘧啶酮的生产工艺，它们可以是氟化的，也可以不是氟化的（非氟化的）。特别是，本发明涉及制造氟化吡唑或嘧啶酮的工艺，尤其是本发明涉及制造这种氟化吡唑或嘧啶酮的工艺，它们都是医药和农业应用中非常重要的构件。例如，杀菌剂 Bixafen、Fluxapyroxad、Fluindapyr、Sedaxane、Isopyrazam 和 Benzovindifupyr 都非常依赖于此类含氟吡唑作为关键构件，或者分别依赖于 Florasulam 和 Clorasulam-methyl (Diclosulam)。