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Synthesis method of polysubstituted allyl carboxylic acid compounds

A technology of allyl carboxylic acid and synthesis method, which is applied in the direction of electrolysis process, electrolysis components, electrolysis organic production, etc., can solve the problems of large amount of diethylzinc reagent usage, demand, and limited application of synthesis methods, etc., and achieve good reference Significance, environmental friendliness, good practical value effect

Inactive Publication Date: 2018-09-21
WUYI UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In recent years, researchers have developed several synthetic methods based on transition metal-catalyzed synthesis strategies guided by the concept of sustainable development, such as the hydrocarboxylation reaction of styrene compounds in the presence of diethylzinc and carbon dioxide ( J.Am.Chem.Soc.2008,130,14936.), this method has the shortcoming that diethyl zinc reagent usage amount is big; The asymmetric cyclization carboxylation reaction of 1,5-double conjugated dienes (J. Am.Chem.Soc.2004,126,5956), this method has the shortcoming that needs special substrate, and these have all limited the application of synthetic method

Method used

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  • Synthesis method of polysubstituted allyl carboxylic acid compounds
  • Synthesis method of polysubstituted allyl carboxylic acid compounds
  • Synthesis method of polysubstituted allyl carboxylic acid compounds

Examples

Experimental program
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Embodiment 1

[0023]

[0024] In a 10mL hydrogenation tube electrolyzer, load positive (Mg) / negative (Pt) (1.0x 1.0cm 2 ) electrode, add an ultra-dry DMF solution (0.15g / 6.0mL) of tetraethylammonium p-toluenesulfonate (0.15g / 6.0mL) after exhausting the air through carbon dioxide, pass through the carbon dioxide after drying the concentrated sulfuric acid solution for 30 minutes, and then add palladium acetate (0.015mmol, 3.4mg, 5mol%), ligand 1,2-bisdiphenylphosphinebenzene (0.016mmol, 7.2mg, 5.3mol%), substrate 1a (0.3mmol, 76.5mg, 1.0equiv), and ethanol (0.3mmol , 17.5uL, 1.0equiv), connect the electrode, set the current to 8mA, turn on the power, electrolyze under the carbon dioxide gas flow for 3h, then turn off the power. 1M dilute hydrochloric acid was acidified, an equal volume of ethyl acetate was extracted 3 times, the organic phase was washed 4 times with saturated ammonium chloride, dried over anhydrous sodium sulfate, concentrated, and purified by flash column chromatography ...

Embodiment 2

[0027]

[0028] In a 10mL hydrogenation tube electrolyzer, load positive (Mg) / negative (Pt) (1.0x 1.0cm 2 ) electrode, add an ultra-dry DMF solution (0.15g / 6.0mL) of tetraethylammonium p-toluenesulfonate (0.15g / 6.0mL) after exhausting the air through carbon dioxide, pass through the carbon dioxide after drying the concentrated sulfuric acid solution for 30 minutes, and then add palladium acetate (0.015mmol, 3.4mg, 5mol%), ligand 1,2-bisdiphenylphosphinebenzene (0.016mmol, 7.2mg, 5.3mol%), substrate 1b (0.3mmol, 52.8mg, 1.0equiv), and ethanol (0.3mmol , 17.5uL, 1.0equiv), connect the electrode, set the current to 8mA, turn on the power, electrolyze under the carbon dioxide gas flow for 3h, then turn off the power. Acidify with 1M dilute hydrochloric acid, extract 3 times with equal volume of ethyl acetate, wash the organic phase 4 times with saturated ammonium chloride, dry over anhydrous sodium sulfate, concentrate, and purify by flash column chromatography to obtain the ta...

Embodiment 3

[0031]

[0032] In a 10mL hydrogenation tube electrolyzer, install a positive (Mg) / negative (Pt) (1.0x 1.0cm2) electrode, and add an ultra-dry DMF solution of tetraethyl ammonium p-toluenesulfonate (0.15g / 6.0 mL), passed through the carbon dioxide after drying concentrated sulfuric acid solution for 30 minutes, then added palladium acetate (0.015mmol, 3.4mg, 5mol%), ligand 1,2-bisdiphenylphosphinebenzene (0.016mmol, 7.2mg, 5.3 mol%), substrate 1c (0.3mmol, 57.1mg, 1.0equiv), and ethanol (0.3mmol, 17.5uL, 1.0equiv), connect the electrode, set the current to 8mA, power on, electrolyze for 3h under the flow of carbon dioxide, then turn off power supply. Acidify with 1M dilute hydrochloric acid, extract with equal volume of ethyl acetate 3 times, wash the organic phase 4 times with saturated ammonium chloride, dry over anhydrous sodium sulfate, concentrate, and purify by flash column chromatography to obtain the target product 2c (white solid, 35.0 mg, Yield 65%).

[0033] Pr...

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Abstract

The invention discloses a synthesis method of polysubstituted allyl carboxylic acid compounds. The reaction general formula is described in the description. The synthesis method is characterized in that polysubstituted allylic acetate compounds and carbon dioxide are adopted, and highly selective carboxylation of the polysubstituted allylic acetate compounds is realized in presence of a catalyst under the condition of electrocathode reduction; furthermore, the reaction is compatible with various halogen atom substitutions on the aromatic ring. The synthesis method also has the characteristicsof being mild in reaction conditions, environmentally-friendly, high in yield and good in purity, and is suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a synthetic method of multi-substituted allyl carboxylic acid compounds. technical background [0002] Multi-substituted allyl carboxylic acids are an important class of organic molecules, which have a wide range of applications in chemical raw materials and pharmaceuticals. Therefore, the synthesis method of multi-substituted allyl carboxylic acid has become the focus of people. In recent years, researchers have developed several synthetic methods based on transition metal-catalyzed synthesis strategies guided by the concept of sustainable development, such as the hydrocarboxylation reaction of styrene compounds in the presence of diethylzinc and carbon dioxide ( J.Am.Chem.Soc.2008,130,14936.), this method has the shortcoming that diethyl zinc reagent usage amount is big; The asymmetric cyclization carboxylation reaction of 1,5-double conjugated dienes (J. Am.Chem.So...

Claims

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Application Information

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IPC IPC(8): C25B3/00
CPCC25B3/00
Inventor 梅天胜李伊倩张历朴焦科进徐学涛张焜李冬利
Owner WUYI UNIV