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Method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine

An unsaturated and alkyne technology, applied in chemical instruments and methods, preparation of organic compounds, carboxylate preparation, etc., to achieve high efficiency, good industrial application prospects, and mild reaction conditions

Active Publication Date: 2016-06-22
NANKAI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The present invention can overcome the disadvantages of the existing alkyne hydrocarboxylation without using toxic carbon monoxide gas, the catalyst consumption is small, the reaction conditions are mild, and it has good industrial application prospects

Method used

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  • Method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine
  • Method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine
  • Method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine

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Experimental program
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Effect test

Embodiment 1

[0031] Preparation of Ligand 1

[0032]1,2-bis(dicyclohexyl)phosphinobenzene (1): Weigh 5 (280mg, 1mmol) in a dry and clean 50mL Schlenk bottle in the glove box. After taking it out, 10 mL of anhydrous THF was added, and the temperature was lowered to -78°C under the protection of nitrogen. Subsequently, cyclohexylmagnesium bromide (1MinTHF, 6mL) was added dropwise using a syringe. After the dropwise addition, the temperature was naturally raised to room temperature, and stirring was continued for 12 h. h 1 After the complete reaction was monitored by NMR, the workup was started. First drain the THF solution, then add n-hexane to dissolve it, and then add saturated ammonium chloride to quench the reaction. The organic phase was extracted with n-hexane. The organic phase was dried using anhydrous sodium sulfate. After removing the desiccant by suction filtration, the system was desolvated with a rotary evaporator to remove the oily liquid. Using petroleum ether and eth...

Embodiment 2

[0035] Preparation of Ligand 2 1,2-Di(tert-butylmethyl)phosphinobenzene (2): Weigh 5 (560mg, 2mmol) in a dry and clean 50mL Schlenk bottle in the glove box. After taking it out, 10 mL of anhydrous THF was added, and the temperature was lowered to -78°C under the protection of nitrogen. Subsequently, tert-butylmagnesium chloride (1.7MinEt 2 O, 2.4mL). After the dropwise addition, the temperature was naturally raised to room temperature, and stirring was continued for 5 h. h 1 After the complete reaction was monitored by NMR, methylmagnesium chloride (3MinTHF, 2.0mL) was added dropwise using a syringe, stirring was continued for 2h and post-treatment began. First drain the THF solution, then add n-hexane to dissolve it, and then add saturated ammonium chloride to quench the reaction. The organic phase was extracted with n-hexane. The organic phase was dried using anhydrous sodium sulfate. After removing the desiccant by suction filtration, the system was desolvated with ...

Embodiment 3

[0038] Preparation of Ligand 3 1,2-Di(tert-butylethyl)phosphinobenzene (3): Weigh 5 (560mg, 2mmol) in a dry and clean 50mL Schlenk bottle in the glove box. After taking it out, 10 mL of anhydrous THF was added, and the temperature was lowered to -78°C under the protection of nitrogen. Subsequently, tert-butylmagnesium chloride (1.7MinEt 2 O, 2.4mL). After the dropwise addition, the temperature was naturally raised to room temperature, and stirring was continued for 5 h. h 1 After the complete reaction was monitored by NMR, ethylmagnesium chloride (3MinTHF, 2.0mL) was added dropwise using a syringe. After the dropwise addition, the temperature was raised to reflux, and after stirring for 2h, post-treatment began. First drain the THF solution, then add n-hexane to dissolve it, and then add saturated ammonium chloride to quench the reaction. The organic phase was extracted with n-hexane. The organic phase was dried using anhydrous sodium sulfate. After removing the desicc...

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Abstract

The invention relates to a method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine, in particular to a method for synthesizing alpha, beta-unsaturated acid by using formic acid and alkine under the effect of a nickel catalyst. The consumption of the catalyst is 0.01 to 2 mol percent of the quantity of a substrate substance; the consumption of estolide is 3 to 30 mol percent of the quantity of the substrate substance; the pressure of acetylene gas is 1 to 10 MPa; the reaction temperature is 25 to 100 DEG C; the reaction time is 5 to 12 hours. The method has the advantages that the existing alkine hydrocarboxylation defects are overcome; the use of toxic carbon monoxide gas does not needed; the reaction conditions of the whole process are mild; the efficiency is high; the selectivity is good; the method belongs to a method for preparing the alpha, beta-unsaturated acid with the advantages that the method conforms to green chemistry and has good application aspects; good industrial application prospects are realized.

Description

technical field [0001] The invention relates to a method for synthesizing α, β-unsaturated acids by using formic acid and alkynes, specifically a method for synthesizing α, β-unsaturated acids by using formic acid and alkynes under the action of a nickel catalyst. Background technique [0002] a,b—Unsaturated acids, especially acrylic acid, are very important chemical raw materials, which can form a variety of polymer materials with different properties and uses through self-polymerization or multi-polymerization with other unsaturated hydrocarbons. These materials are widely used in fields such as construction, papermaking, leather, textiles, coatings, plastic processing, packaging materials, daily chemicals and water treatment. At present, acrylic acid is mainly synthesized in industry by using propylene produced in petroleum refining through a two-stage oxidation method. However, with the depletion of petroleum resources, the method of synthesizing acrylic acid from acet...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C51/353C07C57/42C07C57/03C07C57/60B01J31/24
CPCB01J31/24B01J2231/321B01J2531/004B01J2531/847C07C51/353C07C57/03C07C57/42C07C57/60
Inventor 周其林侯静谢建华
Owner NANKAI UNIV
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