阅读说明：本技术 甲基丙烯酸嘧啶氨基乙酯类化合物的合成方法 (Synthesis method of pyrimidine aminoethyl methacrylate compound ) 是由 刘鹏 田丽霞 张茜 张民 彭鹏鹏 郝俊 侯荣雪 王军 葛建民 武利斌 闫彩桥 于 2021-08-31 设计创作，主要内容包括：本发明公开了甲基丙烯酸嘧啶氨基乙酯类化合物的合成方法,涉及锂电池技术领域,所述合成方法是取氨基嘧啶类化合物与甲基丙烯酸异氰基乙酯经加成反应,即得所述甲基丙烯酸嘧啶氨基乙酯类化合物。本发明可以有效抑制加入甲基丙烯酸异氰基乙酯后发生剧烈的聚合现象产生副产物,进一步提高产品的收率；本发明的合成方法收率达到97.89％以上,纯度达99.5％以上。(The invention discloses a synthesis method of a pyrimidine amino ethyl methacrylate compound, and relates to the technical field of lithium batteries. The invention can effectively inhibit the byproduct generated by violent polymerization after adding the isocyano ethyl methacrylate, and further improve the yield of the product; the synthesis method has the advantages that the yield is more than 97.89%, and the purity is more than 99.5%.)

1. The synthesis method of the pyrimidine aminoethyl methacrylate compound is characterized by comprising the following steps: the synthesis method comprises the step of carrying out addition reaction on an aminopyrimidine compound and isocyano ethyl methacrylate to obtain the pyrimido aminoethyl methacrylate compound.

2. The method for synthesizing a pyrimidine aminoethyl methacrylate compound according to claim 1, wherein the method comprises the following steps: the pyrimidine amino ethyl methacrylate compound is 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate;

the aminopyrimidine compound is 2-amino-4-hydroxy-6-methylpyrimidine;

the synthesis method of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate comprises the steps of adding 2-amino-4-hydroxy-6-methylpyrimidine into an organic solvent for dissolving, cooling to 20-28 ℃, adding isocyanoethyl methacrylate, maintaining the temperature at 20-28 ℃ for addition reaction, filtering, washing and drying after the reaction is finished to obtain the 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate, wherein the specific chemical reaction formula is as follows:

3. the method for synthesizing a pyrimidine aminoethyl methacrylate compound according to claim 2, wherein: the molar ratio of the 2-amino-4-hydroxy-6-methylpyrimidine to the isocyanoethyl methacrylate is 1: 1.1 to 1.3.

4. A method of synthesizing a pyrimidine aminoethyl methacrylate compound as claimed in claim 2 or 3 wherein: the weight volume ratio of the 2-amino-4-hydroxy-6-methylpyrimidine to the organic solvent is 1 g: 5-8 mL.

5. A method of synthesizing a pyrimidine aminoethyl methacrylate compound as claimed in claim 2 or 3 wherein: the time of the addition reaction is 5-8 h.

6. A method of synthesizing a pyrimidine aminoethyl methacrylate compound as claimed in claim 2 or 3 wherein: the organic solvent is dimethyl sulfoxide.

7. A method of synthesizing a pyrimidine aminoethyl methacrylate compound as claimed in claim 2 or 3 wherein: the dissolving temperature is 130-140 ℃.

8. A method of synthesizing a pyrimidine aminoethyl methacrylate compound as claimed in claim 2 or 3 wherein: the washing was carried out with excess acetone.

Technical Field

The invention relates to the technical field of lithium batteries, in particular to a synthesis method of a pyrimidine amino ethyl methacrylate compound.

Background

The lithium ion battery is widely applied to the new energy automobile market at present, a plurality of problems are faced in the manufacturing process of the lithium ion battery, the core problem is the service life problem of the battery electrolyte, the lithium ion mainly depends on the movement of the lithium ion between a positive electrode and a negative electrode to work, the service life of the battery can be obviously prolonged by adding an organic electrolyte additive, and the electrolyte additive containing 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidyl) amino ] carbonyl ] amino ] ethyl methacrylate can obviously improve the stability of the battery electrolyte.

The synthesis method of the 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate on the market is complex, so that the yield and the purity of the finished product are low, and meanwhile, the environment is easily polluted by catalyzing part of synthesis methods by heavy metal, so that the synthesis method of the pyrimidine amino ethyl methacrylate compound is provided.

Disclosure of Invention

The invention aims to provide a synthesis method of a pyrimidine aminoethyl methacrylate compound, which aims to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme:

the synthesis method of the pyrimidine amino ethyl methacrylate compound comprises the step of carrying out addition reaction on the amino pyrimidine compound and isocyano ethyl methacrylate to obtain the pyrimidine amino ethyl methacrylate compound.

Further, the pyrimidineaminoethyl methacrylate compound is 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate;

the aminopyrimidine compound is 2-amino-4-hydroxy-6-methylpyrimidine;

the synthesis method of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate comprises the steps of adding 2-amino-4-hydroxy-6-methylpyrimidine into an organic solvent for dissolving, cooling to 20-28 ℃, adding isocyanoethyl methacrylate, maintaining the temperature at 20-28 ℃ for addition reaction, filtering, washing and drying after the reaction is finished to obtain the 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate, wherein the specific chemical reaction formula is as follows:

further, the molar ratio of the 2-amino-4-hydroxy-6-methylpyrimidine to the isocyanoethyl methacrylate is 1: 1.1 to 1.3.

Further, the weight volume ratio of the 2-amino-4-hydroxy-6-methylpyrimidine to the organic solvent is 1 g: 5-8 mL.

Furthermore, the time of the addition reaction is 5-8 h.

Further, the organic solvent is dimethyl sulfoxide.

Further, the dissolving temperature is 130-140 ℃.

Further, the washing is performed with an excess of acetone.

Compared with the prior art, the invention has the beneficial effects that:

quenching is carried out in a water bath environment at the temperature of 20-28 ℃, so that a byproduct generated by a severe polymerization phenomenon after adding the isocyano ethyl methacrylate can be effectively inhibited, the water bath temperature is maintained for addition reaction, the polymerization phenomenon is inhibited, the yield of a product can be further improved, the yield of a finished product is reduced due to insufficient reaction, the impurity introduced due to side reaction (polymerization reaction) caused by temperature rise is further avoided, and the purity of the product can be effectively ensured; the synthesis method has the advantages that the yield is more than 97.89%, and the purity is more than 99.5%.

Drawings

FIG. 1 is a hydrogen nuclear magnetic spectrum of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate product prepared in the first example of the present invention;

FIG. 2 is a carbon nuclear magnetic spectrum of the 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate product prepared in example one of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The first embodiment is as follows:

the synthesis method of the pyrimidine aminoethyl methacrylate compound comprises the following steps:

adding 40mL of dimethyl sulfoxide into a reaction flask, heating to 135 ℃, adding 8.0g (0.064mol) of 2-amino-4-hydroxy-6-methylpyrimidine, stirring to dissolve, moving to a water bath environment at 25 ℃ after completely dissolving, rapidly cooling to 25 ℃, rapidly adding 11.0g (0.071mol) of isocyano ethyl methacrylate, maintaining the temperature at 25 ℃ for addition reaction for 6h, and maintaining the reaction system at 25 ℃ all the time in the reaction process to inhibit violent polymerization reaction and generate byproducts. After the addition reaction, the mixture was vacuum-filtered and washed with excess acetone three times, and the resulting white solid was vacuum-dried to give 17.65g of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate in 98.39% yield and 99.5% purity, according to the following specific chemical reaction formula:

the hydrogen nuclear magnetic spectrum diagram of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate is shown in figure 1, and the carbon nuclear magnetic spectrum diagram is shown in figure 2.

Example two:

the synthesis method of the pyrimidine aminoethyl methacrylate compound comprises the following steps:

adding 64mL of dimethyl sulfoxide into a reaction flask, heating to 130 ℃, adding 8.0g (0.064mol) of 2-amino-4-hydroxy-6-methylpyrimidine, stirring to dissolve, moving to a water bath environment at 20 ℃ after completely dissolving, quickly cooling to 20 ℃, quickly adding 12.9g (0.083mol) of isocyano ethyl methacrylate, maintaining the temperature at 20 ℃ for addition reaction for 8 hours, and always maintaining the reaction system at 20 ℃ in the reaction process to inhibit violent polymerization reaction and generate byproducts. After the addition reaction was completed, vacuum filtration was performed, and then washing was performed with excess acetone three times, and the obtained white solid was vacuum-dried to obtain 17.68g of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate, in a yield of 98.56% and a purity of 99.6%.

Example three:

the synthesis method of the pyrimidine aminoethyl methacrylate compound comprises the following steps:

adding 50mL of dimethyl sulfoxide into a reaction flask, heating to 140 ℃, adding 8.0g (0.064mol) of 2-amino-4-hydroxy-6-methylpyrimidine, stirring to dissolve, moving to a water bath environment at 28 ℃ after completely dissolving, quickly cooling to 28 ℃, quickly adding 11.9g (0.077mol) of isocyano ethyl methacrylate, maintaining the temperature at 28 ℃ for addition reaction for 5 hours, and maintaining the reaction system at 28 ℃ all the time in the reaction process to inhibit violent polymerization reaction and generate byproducts. After the addition reaction was completed, vacuum filtration was performed, and then washing was performed with excess acetone three times, and the obtained white solid was vacuum-dried to obtain 17.58g of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate, in a yield of 98.00% and a purity of 99.5%.

Example four:

the synthesis method of the pyrimidine aminoethyl methacrylate compound comprises the following steps:

adding 60mL of dimethyl sulfoxide into a reaction flask, heating to 133 ℃, adding 8.0g (0.064mol) of 2-amino-4-hydroxy-6-methylpyrimidine, stirring to dissolve, moving to a water bath environment at 24 ℃ after complete dissolution, rapidly cooling to 24 ℃, rapidly adding 11.4g (0.074mol) of isocyano ethyl methacrylate, maintaining the temperature at 24 ℃ for addition reaction for 7 hours, and maintaining the reaction system at 24 ℃ all the time in the reaction process to inhibit violent polymerization reaction and generate byproducts. After the addition reaction was completed, vacuum filtration was performed, followed by washing with excess acetone three times, and the obtained white solid was vacuum-dried to obtain 17.63g of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate, in a yield of 98.28% and a purity of 99.7%.

Example five:

the synthesis method of the pyrimidine aminoethyl methacrylate compound comprises the following steps:

adding 55mL of dimethyl sulfoxide into a reaction flask, heating to 136 ℃, adding 8.0g (0.064mol) of 2-amino-4-hydroxy-6-methylpyrimidine, stirring to dissolve, moving to a water bath environment at 23 ℃ after completely dissolving, quickly cooling to 23 ℃, quickly adding 12.4g (0.080mol) of isocyano ethyl methacrylate, maintaining the temperature at 23 ℃ for addition reaction for 6h, and maintaining the reaction system at 23 ℃ all the time in the reaction process to inhibit violent polymerization reaction and generate byproducts. After the addition reaction was completed, vacuum filtration was performed, followed by washing with excess acetone three times, and the obtained white solid was vacuum-dried to obtain 17.56g of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate, in a yield of 97.89% and a purity of 99.6%.

Example six:

the synthesis method of the pyrimidine aminoethyl methacrylate compound comprises the following steps:

adding 45mL of dimethyl sulfoxide into a reaction flask, heating to 138 ℃, adding 8.0g (0.064mol) of 2-amino-4-hydroxy-6-methylpyrimidine, stirring to dissolve, moving to a water bath environment at 26 ℃ after the 2-amino-4-hydroxy-6-methylpyrimidine is completely dissolved, rapidly cooling to 26 ℃, rapidly adding 11.6g (0.075mol) of isocyano ethyl methacrylate, maintaining the temperature at 26 ℃ for addition reaction for 7 hours, and always maintaining the reaction system at 26 ℃ in the reaction process to inhibit violent polymerization reaction and generate byproducts. After the addition reaction was completed, vacuum filtration was performed, followed by washing with excess acetone three times, and the obtained white solid was vacuum-dried to obtain 17.64g of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate, in a yield of 98.34% and a purity of 99.6%.

Example seven:

the synthesis method of the pyrimidine aminoethyl methacrylate compound comprises the following steps:

adding 43mL of dimethyl sulfoxide into a reaction flask, heating to 134 ℃, adding 8.0g (0.064mol) of 2-amino-4-hydroxy-6-methylpyrimidine, stirring to dissolve, moving to a water bath environment at 27 ℃ after completely dissolving, rapidly cooling to 27 ℃, rapidly adding 11.2g (0.072mol) of isocyano ethyl methacrylate, maintaining the temperature at 27 ℃ for addition reaction for 7h, and maintaining the reaction system at 27 ℃ all the time in the reaction process to inhibit violent polymerization reaction and generate byproducts. After the addition reaction was completed, vacuum filtration was performed, followed by washing with excess acetone three times, and the obtained white solid was vacuum-dried to obtain 17.61g of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate, in a yield of 98.17% and a purity of 99.5%.

Comparative example:

the commercially available 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate was purchased as a finished product, and the product yield was found to be 75% and the purity was found to be 98.1%.

The yields and purities of the finished products of examples one to seven were compared with those of the comparative example, and the comparison results are shown in table 1:

as can be seen from Table 1, the yield and purity of 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate produced by the synthesis method of pyrimidinylaminoethyl methacrylate compounds are higher than those of commercially available products.

TABLE 1

Application test:

ternary material NCM (622) lithium is used as a positive electrode material, a negative electrode adopts mesocarbon microbeads, current collectors of the positive electrode and the negative electrode are distributed into aluminum foils and copper foils, a diaphragm adopts a ceramic diaphragm to form a soft package battery, after electrolyte is injected, the soft package battery is assembled in a glove box, and the test is carried out after the soft package battery is kept stand for 8 hours. And respectively carrying out charging and discharging at the constant temperature of 25 ℃ and at the temperature of 1/10C 3.0V to 4.2V to activate the battery, thus obtaining the battery to be tested. The electrolytes tested included base electrolyte E1 and electrolyte E2, the compositions of which are as follows:

1. basic electrolyte E1

EC：Solution-1：DEC＝3：3：4(v:v:v)，LiPF₆：1.0M，0.5％LiFSI，1％VC

2. Electrolyte E2

EC：Solution-1：DEC＝3：3：4(v:v:v)，LiPF₆：1.0M，0.5％LiFSI，1％VC，

1% 2- [ [ [ (1, 6-dihydro-4-methyl-6-oxo-2-pyrimidinyl) amino ] carbonyl ] amino ] ethyl methacrylate additive

And (3) testing results:

1. the test results after 60 ℃ cycling were as follows:

TABLE 2

2. The batteries were placed in a low temperature cabinet, the temperature was controlled at-30 ℃ or-40 ℃ respectively, the resting time was 240min, and then the capacity retention rate of the batteries was measured.

TABLE 3

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.