CN113603662B - Method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride - Google Patents

Abstract

The invention provides a method for preparing 4- (1-ketone-2-propargyl benzene propane) phthalic anhydride, which is prepared by adding phenylacetylene, 1,2, 4-trimellitic anhydride acyl chloride, a catalyst, an organic base and an organic solvent into the organic solvent and reacting under heating, wherein the molar ratio of the 1,2, 4-trimellitic anhydride acyl chloride, the phenylacetylene, the catalyst, the organic base and the organic solvent is 1:(1-1.1):(0.01-0.05):(1.05-1.5):(16-27). The method has the advantages of easily obtained reaction raw materials, low cost, high liquid phase purity, simple operation steps, high yield and industrial application prospect.

Description

Method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride

Technical Field

The invention relates to the technical field of polyimide dianhydride monomers, in particular to a method for preparing 4- (1-ketone-2-propargyl phenylpropane) phthalic anhydride.

Background

4- (1-ketone-2-propargyl benzene propane) phthalic anhydride is used for preparing thermosetting polyimide due to the high temperature resistance, and the heat resistance, mechanical property and tensile strength of the material can be improved. The literature reports of the preparation of 4- (1-keto-2-propargyl) phthalic anhydride are reported at present: chinese patent 201180024067.3 uses trimellitic chloride and phenylacetylene as raw materials, toluene as solvent, palladium acetate as catalyst, and triethylamine as base to react, and the yield is only 39.64%.

Disclosure of Invention

The invention aims to provide a method for preparing high-yield 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride.

Based on the problems, the technical scheme provided by the invention is that the method for preparing 4- (1-ketone-2-propargyl benzene propane) phthalic anhydride is prepared by adding phenylacetylene, 1,2, 4-trimellitic anhydride acyl chloride, a catalyst, organic base and an organic solvent into the organic solvent, and carrying out acylation reaction under the heating condition. The reaction formula is as follows:

wherein the mole ratio of the 1,2, 4-trimellitic anhydride acyl chloride, phenylacetylene, catalyst, organic base and organic solvent is 1 (1-1.1) (0.01-0.05) (1.05-1.5) (16-27). When the ratio of raw materials is low, the reaction time is prolonged, and the conversion of part of the raw materials is incomplete. Excessive proportions and excessive temperatures produce impurities and result in darkening of the product.

The organic base is one or more of triethylamine, pyridine, diethylamine, propylamine, tetramethyl diethylamine, tetramethyl guanidine or N-methylmorpholine.

The catalyst is one or two of bis (triphenylphosphine) nickel chloride, copper (triphenylphosphine) iodide, copper (triphenylphosphine) bromide, bis (triphenylphosphine) cobalt chloride and bis (triphenylphosphine) ammonium chloride.

The organic solvent is one of trimethylbenzene, methylcyclohexane, dimethylacetamide and tetrahydrofuran.

Specifically, the method comprises the following reaction steps:

1) Adding 1,2, 4-trimellitic anhydride acyl chloride, an organic solvent and organic alkali into a reaction bottle, adding a catalyst under mechanical stirring, and heating to 20-90 ℃;

2) Dissolving phenylacetylene in an organic solvent, slowly dropwise adding the phenylacetylene into the mixed solution in the step 1), and keeping the temperature for continuous reaction;

3) After the reaction of the raw material 1,2, 4-trimellitic anhydride acyl chloride is completed, cooling the reaction liquid to 10 ℃, filtering, and washing filter cakes with tetrahydrofuran and water respectively;

4) Drying in a vacuum drying oven.

Preferably, the reflux reaction temperature is 50 DEG C

Preferably, the organic solvent is tetrahydrofuran.

Preferably, the organic base is tetramethyl diethylamine.

Preferably, the catalyst is copper triphenylphosphine bromide.

Preferably, the molar ratio of 1,2, 4-trimellitic anhydride acyl chloride, phenylacetylene, copper triphenylphosphine bromide, tetramethyl diethylamine and tetrahydrofuran is 1:1.05:0.03:1.3:22.

The invention has the advantages and beneficial effects that:

the invention provides a novel method for preparing 4- (1-ketone-2-propargyl phenyl propane) phthalic anhydride, which has the advantages of easily obtained reaction raw materials, low synthesis cost, high reaction conversion rate which can reach about 90 percent, high liquid phase purity and 99.77 percent of liquid phase content; the reaction steps are simple and easy to control, and the method has industrial application prospect.

Drawings

FIG. 1 is a liquid chromatogram of a product prepared according to the present invention.

Detailed Description

The following describes the present invention in detail with reference to specific examples.

Example 1 to a reaction flask were added 10.5g of 1,2, 4-trimellitic anhydride acid chloride, 70g of tetrahydrofuran, 7.5g of tetramethyl ethylenediamine, 1.4g of triphenylphosphine copper bromide was added under mechanical stirring, the temperature was raised to 45 ℃, 5.3g of phenylacetylene in 10g of tetrahydrofuran was slowly added dropwise, the reaction was then carried out at this temperature, after the reaction of the starting material 1,2, 4-trimellitic anhydride acid chloride was completed, the reaction solution was cooled to 10 c, filtered, the filter cake was washed with tetrahydrofuran, and dried in a vacuum drying oven to obtain 4- (1-keto-2-propargyl) phthalic anhydride, 12.2g of white solid, and the yield was 88.4%.

Example 2 to a reaction flask were added 10.5g of 1,2, 4-trimellitic anhydride acid chloride, 50g of tetrahydrofuran, 7.5g of tetramethyl ethylenediamine, 0.8g of triphenylphosphine copper bromide was added under mechanical stirring, the temperature was raised to 40 ℃, 5.1g of phenylacetylene in 10g of tetrahydrofuran was slowly added dropwise, the reaction was then carried out at this temperature, after the reaction of the starting material 1,2, 4-trimellitic anhydride acid chloride was completed, the reaction solution was cooled to 10 c, filtered, the filter cake was washed with tetrahydrofuran and water, and dried in a vacuum drying oven to obtain 4- (1-keto-2-propargyl) phthalic anhydride, 8.3g of white solid, and the yield was 60.1%.

Example 3 to a reaction flask were added 10.5g of 1,2, 4-trimellitic anhydride acid chloride, 80g of tetrahydrofuran, 7.5g of tetramethyl ethylenediamine, 2.3g of triphenylphosphine copper bromide was added under mechanical stirring, the temperature was raised to 50 c, 5.6g of phenylacetylene in 20g of tetrahydrofuran was slowly added dropwise, the reaction was then carried out at this temperature, after the reaction of the starting material 1,2, 4-trimellitic anhydride acid chloride was completed, the reaction solution was cooled to 10 c, filtered, the filter cake was washed with tetrahydrofuran and water, and dried in a vacuum drying oven to obtain 4- (1-keto-2-propargyl) phthalic anhydride, 12.5g of white solid, the yield was 90.6%.

As shown in fig. 1, the liquid chromatogram of the product shows the following table 1:

TABLE 1 chromatographic peak area Condition Table

Peak number	Retention time	Area of	Height	Area percent
					1	5.273	12008	1236	0.125
2	5.571	2629	305	0.027
					3	5.788	5080	411	0.053
4	6.119	9572024	994006	99.770
					5	9.362	2339	193	0.024
Totals to		9594080	996151	100.000

The liquid phase content of the product prepared from Table 1 was 99.77%.

Example 4 to a reaction flask were added 10.5g of 1,2, 4-trimellitic anhydride acid chloride, 60g of methylcyclohexane, 7.5g of tetramethyl ethylenediamine, 1.5g of copper trisphenylphosphine bromide was further added under mechanical stirring, the temperature was raised to 40 ℃, 5.6g of phenylacetylene in 20g of methylcyclohexane was slowly added dropwise, the reaction was then carried out at this temperature, after the reaction of the starting material 1,2, 4-trimellitic anhydride acid chloride was completed, the reaction solution was cooled to 10 c, filtered, and after washing the filter cake with tetrahydrofuran and water, it was dried in a vacuum drying oven to obtain 4- (1-keto-2-propargyl) phthalic anhydride, 10.8g of a white solid, and a yield of 78.3%.

The foregoing describes several embodiments of the present invention in detail, but the description is merely a preferred embodiment of the invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.

Claims (3)

1. A method for preparing 4- (1-ketone-2-propargyl benzene propane) phthalic anhydride comprises the following raw materials of phenylacetylene, 1,2, 4-trimellitic anhydride acyl chloride, a catalyst, organic base and an organic solvent, and is characterized in that: adding phenylacetylene, 1,2, 4-trimellitic anhydride acyl chloride, a catalyst and organic base into an organic solvent, and reacting under heating;

the organic base is tetramethyl diethylamine, the catalyst is triphenyl copper phosphonium bromide, and the organic solvent is tetrahydrofuran;

the molar ratio of the 1,2, 4-trimellitic anhydride acyl chloride, phenylacetylene, copper triphenyl phosphonium bromide, tetrahydrofuran and tetrahydrofuran is 1:1.05:0.03:1.3:22.

2. The method for producing 4- (1-keto-2-propargyl) phthalic anhydride according to claim 1, wherein: the method comprises the following reaction steps:

1) Adding 1,2, 4-trimellitic anhydride acyl chloride, an organic solvent and an organic base into a reaction bottle, adding a catalyst under mechanical stirring, and heating to 20-90 ℃;

2) Dissolving phenylacetylene in an organic solvent, slowly dropwise adding the phenylacetylene into the mixed solution in the step 1), and keeping the temperature for continuous reaction;

3) After the reaction of the raw material 1,2, 4-trimellitic anhydride acyl chloride is completed, cooling the reaction liquid to 10 ℃, filtering, and washing filter cakes with tetrahydrofuran and water respectively;

4) Drying in a vacuum drying oven.

3. A process for the preparation of 4- (1-keto-2-propargyl) phthalic anhydride according to claim 2, characterised in that: the reflux reaction temperature was 50 ℃.

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