ethyl 2-fluoro-2-nitroacetate | 3620-16-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 2-fluoro-2-nitroacetate
• 英文别名: ethyl fluoronitroacetate；ethyl α-fluoro-α-nitroacetate；ethyl nitrofluoroacetate；Fluor-nitro-essigsaeure-ethylester；Fluornitroessigsaeure-aethylester；Fluornitroessigsaeure-ethylester；Ethyl fluoro(nitro)acetate
• CAS: 3620-16-4
• 化学式: C₄H₆FNO₄
• 分子量: 151.094
• InChiKey: SLKHGQVZEQYSTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 2-fluoro-2-nitroacetate 在 溴 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以27%的产率得到乙酸,溴氟硝基-,乙基酯
  参考文献：
  名称：

  Transformation of fluoronitroacetate esters

  摘要：

  DOI：

  10.1007/bf00956686
• 作为产物：
  描述：

  硝基乙酸乙酯 以52%的产率得到ethyl 2-fluoro-2-nitroacetate
  参考文献：
  名称：

  Catalyzed fluorination of carbonyl compounds

  摘要：

  本发明提供了一种在α位上用氟替代羰基化合物的方法，包括将含有金属催化剂的氟化试剂与羰基化合物接触。反应导致氢原子被氟取代。所使用的催化剂以催化有效量使用，最好是过渡金属。在一类方法中，催化剂是过渡金属化合物。在另一类方法中，催化剂是元素金属，此时羰基化合物的碳原子上连接有活化基团。

  公开号：

  US06300511B1

文献信息

• Elemental fluorine. Part 9
  作者：Richard D. Chambers、John Hutchinson

  DOI：10.1016/s0022-1139(98)00254-1

  日期：1998.10

  Catalysis of the reaction between fluorine and a range of 2-substituted carbonyl compounds has been investigated. Most notably, the preparation of diethyl-2-fluoromalonate has been achieved in high yield by fluorination of diethylmalonate in the presence of hydrated copper nitrate. Reactions between fluorine and carbanions derived from 2-substituted carbonyl compounds, including phosphonates, sulphones

  已经研究了氟与一定范围的2-取代的羰基化合物之间反应的催化作用。最值得注意的是，通过在水合硝酸铜存在下氟化二乙基丙二酸二乙酯，可以高产率地制备2-氟丙二酸二乙酯。还讨论了氟与衍生自2-取代羰基化合物（包括膦酸酯，砜和腈）的碳负离子之间的反应。
• Highly enantioselective synthesis of α-fluoro-α-nitro esters via organocatalyzed asymmetric Michael addition
  作者：Hai-Feng Cui、Peng Li、Xiao-Wei Wang、Zhuo Chai、Ying-Quan Yang、Yue-Peng Cai、Shi-Zheng Zhu、Gang Zhao

  DOI：10.1016/j.tet.2010.11.041

  日期：2011.1

  amines catalyzed the asymmetric Michael addition of ethyl 2-fluoro-2-nitroacetate to enones to provide chiral α-fluoro-α-nitro ester ketones with two contiguous stereogenic centers, one of which is a fluorinated quaternary chiral center, with excellent enantioselectivities and in moderate to good yields.

  伯胺催化2-氟-2-硝基乙酸乙酯向烯酮的不对称迈克尔加成，从而提供具有两个连续的立体中心的手性α-氟-α-硝基酯酮，其中一个是氟化的季手性中心，具有出色的对映选择性和中等至良好的产量。
• Asymmetric Michael addition of α-fluoro-α-nitro esters to nitroolefins: towards synthesis of α-fluoro-α-substituted amino acids
  作者：Jacek Kwiatkowski、Yixin Lu

  DOI：10.1039/c4ob02486a

  日期：——

  α-Fluoro-α-nitro esters were used as reaction partners in Michael addition to nitroalkenes, and the products were obtained in excellent chemical yields and with high enantioselectivities. Moreover, α-fluoro-α-amino ester with a quaternary α-carbon was prepared for the first time.

  α-氟-α-硝基酯被用作迈克尔与硝基烯烃的加成反应伙伴，并且以优异的化学收率和高对映选择性获得了产物。此外，首次制备了具有季α-碳的α-氟-α-氨基酯。
• Synthetic Studies for Novel Structure of .ALPHA.-Nitrogenously Functionalized .ALPHA.-Fluorocarboxylic Acids II. Synthesis and Some Reactions of .ALPHA.-Fluoro-.ALPHA.-nitrocarboxylic Ester and Carboxamide Derivatives.
  作者：Yoshio TAKEUCHI、Kumiko TAKAGI、Kazuhiro NAGATA、Toru Koizumi

  DOI：10.1248/cpb.39.3120

  日期：——

  The first synthesis of α-fluoro-α-nitrocarboxamides 11b, c has been achieved by ammonolysis of the corresponding ethyl esters 6b, c. However, α-fluoro-α-nitrocarboxylic acids 8a-c derived from the corresponding esters 6a-c were found to decarboxylate readily to form 1-fluoro-1-nitroalkanes 9a-c. Reduction of the α-fluoro-α-nitrocarboxamide derivatives 11b, c produced the defluorination products 12b, c instead of the desired novel α-fluoro-α-aminocarboxamide 2.

  通过氨解相应的乙酯 6b、c，首次合成了 α-氟-α-硝基甲酰胺 11b、c。然而，从相应的酯 6a-c 生成的 α-氟-α-硝基羧酸 8a-c 很容易脱羧生成 1-氟-1-硝基烷烃 9a-c。α-氟-α-硝基甲酰胺衍生物 11b、c 的还原反应生成了脱氟产物 12b、c，而不是所需的新型α-氟-α-氨基甲酰胺 2。
• Fluorination and chlorination of nitroalkyl groups
  作者：Philip Butler、Bernard T. Golding、Gilles Laval、Hossein Loghmani-Khouzani、Reza Ranjbar-Karimi、Majid M. Sadeghi

  DOI：10.1016/j.tet.2007.08.020

  日期：2007.11

  Heterocycles substituted with a nitromethyl (CH2NO2) or phenyl-nitromethyl (CHPhNO2) group were prepared by reaction of a methyl- or phenylmethyl-substituted heterocycle, respectively, with lithium di-isopropylamide followed by quenching the intermediate carbanion with methyl nitrate. Conversion of CH2NO2 attached to an alkyl or aryl moiety into a dichloronitromethyl (CCl2NO2) group was achieved using N-chlorosuccinimide and 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) in dichloromethane. Similarly, CH2NO2 attached to an alkyl or aryl group was converted into difluoronitromethyl (CF2NO2) using either 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis( tetrafluoroborate) (Selectfluor (TM)) or N-fluorobenzenesulfonimide with DBU as base and dichloromethane as solvent. Reaction of omega-nitroacetophenone with Selectfluor/DBU in dimethylformamide followed by acidification and distillation gave the parent difluoronitromethane in a useful 'one-pot' procedure. (c) 2007 Elsevier Ltd. All rights reserved.