4-Chloro-4,4-difluoro-3-oxo-2-(triphenyl-λ⁵-phosphanylidene)-butyric acid methyl ester | 116998-18-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-Chloro-4,4-difluoro-3-oxo-2-(triphenyl-λ⁵-phosphanylidene)-butyric acid methyl ester
• 英文别名: Methyl 4-chloro-4,4-difluoro-3-oxo-2-(triphenyl-lambda5-phosphanylidene)butanoate；methyl 4-chloro-4,4-difluoro-3-oxo-2-(triphenyl-λ5-phosphanylidene)butanoate
• CAS: 116998-18-6
• 化学式: C₂₃H₁₈ClF₂O₃P
• 分子量: 446.818
• InChiKey: SUHKPSTWYQRABM-UHFFFAOYSA-N

物化性质

• 沸点：
  510.1±60.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4-Chloro-4,4-difluoro-3-oxo-2-(triphenyl-λ⁵-phosphanylidene)-butyric acid methyl ester 150.0~220.0 ℃ 、1.33 kPa 条件下， 以66%的产率得到methyl 4,4-difluoro-4-chloro-2-butynoate
  参考文献：
  名称：

  Cyclocondensation of alkylhydrazines and .beta.-substituted acetylenic esters: synthesis of 3-hydroxypyrazoles

  摘要：

  Addition of monosubstituted alkylhydrazines to acetylenic esters with either electron-withdrawing or sterically bulky beta-substituents afforded 1-alkyl-3-hydroxy-5-substituted-pyrazoles 1 as the major regioisomeric product. By comparison, the classical cyclocondensation of alkylhydrazines with beta-keto esters gives the regioisomeric pyrazol-5-ones 2. The reaction solvent employed in these cyclocondensations can have a profound effect on regioisomeric product ratios. Addition of methylhydrazine to 5g in methylene chloride gave regiospecific formation of pyrazolinone 2o, whereas addition in water-methanol mixtures afforded hydroxypyrazole 1o as the major product. Structural assignment of regioisomers 1 and 2 are based on C-13 NMR chemical shifts, long-range heteronuclear coupling constants, and comparisons with regiochemically known hydroxypyrazoles and/or pyrazolinones. Additions of acetylene 5b to 1,1-dimethylhydrazine afforded either acyclic enehydrazone 12 or pyrazolium betaine 13 depending on the reaction conditions.

  DOI：

  10.1021/jo00047a021
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 三乙胺 作用下， 以94%的产率得到4-Chloro-4,4-difluoro-3-oxo-2-(triphenyl-λ⁵-phosphanylidene)-butyric acid methyl ester
  参考文献：
  名称：

  Cyclocondensation of alkylhydrazines and .beta.-substituted acetylenic esters: synthesis of 3-hydroxypyrazoles

  摘要：

  Addition of monosubstituted alkylhydrazines to acetylenic esters with either electron-withdrawing or sterically bulky beta-substituents afforded 1-alkyl-3-hydroxy-5-substituted-pyrazoles 1 as the major regioisomeric product. By comparison, the classical cyclocondensation of alkylhydrazines with beta-keto esters gives the regioisomeric pyrazol-5-ones 2. The reaction solvent employed in these cyclocondensations can have a profound effect on regioisomeric product ratios. Addition of methylhydrazine to 5g in methylene chloride gave regiospecific formation of pyrazolinone 2o, whereas addition in water-methanol mixtures afforded hydroxypyrazole 1o as the major product. Structural assignment of regioisomers 1 and 2 are based on C-13 NMR chemical shifts, long-range heteronuclear coupling constants, and comparisons with regiochemically known hydroxypyrazoles and/or pyrazolinones. Additions of acetylene 5b to 1,1-dimethylhydrazine afforded either acyclic enehydrazone 12 or pyrazolium betaine 13 depending on the reaction conditions.

  DOI：

  10.1021/jo00047a021

文献信息

• Stereocontrolled Synthesis of Fluorinated (E)- or (Z)-Allylic Phosphonates
  作者：Yanchang Shen、Yuming Zhang、Zenghong Zhang

  DOI：10.1055/s-2000-7596

  日期：——

  Treatment of (dicarbonylmethylene)triphenylphosphoranes 1 with [(diethoxylphosphinoyl)methyl]lithium (2a) gave 3a, followed by protonation and elimination of triphenylphosphine oxide, to afford the Z-isomer exclusively (4b, 4e, 4f, 4g); while [(dialkoxyphosphinoyl)alkyl]lithium (2b) reacted with 1 under the same conditions, to give the E-isomers exclusively (4a, 4c, 4d) or predominantly (4h, 4i, 4j). Thus this methodology provides a stereocontrolled synthesis of the title compounds.

  用[(二乙氧基膦酰基)甲基]锂(2a)处理(双羰甲基)三苯基膦1，得到3a，随后进行质子化和三苯基膦氧化物的消除，得到单一的Z型异构体(4b, 4e, 4f, 4g)；而[(二烷氧基膦酰基)烷基]锂(2b)在相同条件下与1反应，得到单一的E型异构体(4a, 4c, 4d)或主要是E型异构体(4h, 4i, 4j)。因此，这种方法提供了立体控制合成标题化合物的方法。
• Direct synthesis of .beta.-ketomethylenetriphenylphosphoranes from readily available phosphonium salts
  作者：Bruce C. Hamper

  DOI：10.1021/jo00258a035

  日期：1988.11
• HAMPER, BRUCE C., J. ORG. CHEM., 53,(1988) N 23, C. 5558-5562
  作者：HAMPER, BRUCE C.

  DOI：——

  日期：——
• Cyclocondensation of alkylhydrazines and .beta.-substituted acetylenic esters: synthesis of 3-hydroxypyrazoles
  作者：Bruce C. Hamper、Mitchell L. Kurtzweil、James P. Beck

  DOI：10.1021/jo00047a021

  日期：1992.10

  Addition of monosubstituted alkylhydrazines to acetylenic esters with either electron-withdrawing or sterically bulky beta-substituents afforded 1-alkyl-3-hydroxy-5-substituted-pyrazoles 1 as the major regioisomeric product. By comparison, the classical cyclocondensation of alkylhydrazines with beta-keto esters gives the regioisomeric pyrazol-5-ones 2. The reaction solvent employed in these cyclocondensations can have a profound effect on regioisomeric product ratios. Addition of methylhydrazine to 5g in methylene chloride gave regiospecific formation of pyrazolinone 2o, whereas addition in water-methanol mixtures afforded hydroxypyrazole 1o as the major product. Structural assignment of regioisomers 1 and 2 are based on C-13 NMR chemical shifts, long-range heteronuclear coupling constants, and comparisons with regiochemically known hydroxypyrazoles and/or pyrazolinones. Additions of acetylene 5b to 1,1-dimethylhydrazine afforded either acyclic enehydrazone 12 or pyrazolium betaine 13 depending on the reaction conditions.