Synthesis method of piperazinyl carbon trapping agent

Abstract

The invention provides a synthesis method of a piperazinyl carbon trapping agent, and relates to the technical field of organic synthesis. According to the method, alkylene oxide and N-amine alkyl piperazine with both primary amine and secondary amine are taken as raw materials, aliphatic ketone is taken as a primary amine protective agent of the N-amine alkyl piperazine, the aliphatic ketone and primary amine of the N-amine alkyl piperazine are subjected to substitution reaction to generate an N-amine alkyl piperazine intermediate, and selective protection of the primary amine is realized; carrying out nucleophilic addition reaction on the intermediate and alkylene oxide to generate a primary amino protected hydroxyalkyl piperazine intermediate; and carrying out hydrolysis reaction on water serving as a deprotection agent and the hydroxyalkyl piperazine intermediate protected by the primary amino group to generate a hydroxyalkyl amine alkyl piperazine solution. And separating, refining, homogenizing and compounding to obtain the hydroxyalkylamine alkyl piperazine carbon trapping agent. According to the method, the average yield of the target product is 85% or above, the purity is 98% or above, the reaction is controllable, and the primary amino protective agent can be recycled.

Description

technical field

[0001] The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing a piperazine-based carbon collector. Background technique

[0002] 1-Hydroxyalkyl-4-aminoalkylpiperazine as a CO2 capture agent in flue gas 2 Renewable organic amine carbon traps with excellent CO 2 Combined absorption / desorption properties. However, there are few reports on the synthetic methods of such organic amines, and the reported synthetic methods have low yield and high cost, and are not suitable for large-scale industrial production. Patent CN108947985A discloses compounds used as autophagy regulators and their preparation methods and uses, wherein 2-(2-bromoethyl) isoindoline-1,3-dione and N-hydroxyethylpiperazine are used As the raw material, the acetonitrile solution of potassium carbonate is used as the solvent to prepare 1-(2-hydroxyethyl)-4-(2-aminoethyl)piperazine after mixing reaction, filtration, concentration and column ch...

Examples

Embodiment 1

[0035] When R in compound D 1 = ethylene, R 2 = methyl (the specific compound is 1-(2-hydroxypropyl)-4-(2-aminoethyl)piperazine); R in compound B 3 = methyl, R 4 When = isobutyl (the concrete compound is methyl isobutyl ketone), its synthesis principle is:

[0036]

[0037] The specific operation steps are: add 0.1mol of N-aminoethylpiperazine and 1.5mol of methyl isobutyl ketone into a 500ml three-necked flask, control the magnetic stirring speed to be 100r / min, after the solution is mixed uniformly, add a distillation device and Heat the solution to 110°C, first collect the 87-90°C fraction until no liquid is distilled, then collect the 105-108°C fraction until no liquid is distilled, and collect the distillate in a conical flask for recycling. Add 2 mol of methanol to the remaining reaction solution, and after the solution is stirred evenly, control the temperature to 30 °C, slowly add 0.15 mol of propylene oxide dropwise to the three-necked flask with a constant pres...

Embodiment 2

[0040] When R in compound D 1 = ethylene, R 2 =H proton (the specific compound is 1-(2-hydroxyethyl)-4-(2-aminoethyl)piperazine); R in compound B 3 = methyl, R 4When = isobutyl (the concrete compound is methyl isobutyl ketone), its synthesis principle is:

[0041]

[0042] In the 500ml three-necked flask, add 0.1mol of N-aminoethylpiperazine and 150g of recovered amine-based protective agent (the mass fraction of methyl isobutyl ketone is 95.7%), control the magnetic stirring speed to be 100r / min, and wait for the solution to mix. After homogenization, add a distillation device and heat the solution to 110°C, first collect the 87-90°C fraction until no liquid is distilled, then collect the 105-108°C fraction until no liquid is distilled, and collect the distillate in a conical flask Waiting for recycling. Add 2mol methanol to the remaining reaction solution, and after the solution is stirred evenly, transfer to the autoclave, control the temperature in the kettle to be ...

Embodiment 3

[0045] When R in compound D 1 = methylene, R 2 = methyl (the specific compound is 1-(2-hydroxypropyl)-4-aminomethylpiperazine); R in compound B 3 = methyl, R 4 When = isobutyl (the specific compound is methyl isobutyl ketone), its synthesis, separation and purification steps are basically the same as in Example 1, the difference is that N-amine ethyl piperazine as raw material is replaced by N-amine Methylpiperazine. The total yield of the final product was 90% and the purity was 99.3%.

[0046] The recovery and utilization steps of the protective agent are consistent with the steps in Example 1, and the gas chromatography detection results: the mass fraction of the upper phase methyl isobutyl ketone is 98.8%, and the mass fraction of the lower phase methyl isobutyl ketone is 0.87%.

technical field

[0001] The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing a piperazine-based carbon collector. Background technique

[0002] 1-Hydroxyalkyl-4-aminoalkylpiperazine as a CO2 capture agent in flue gas 2 Renewable organic amine carbon traps with excellent CO 2 Combined absorption / desorption properties. However, there are few reports on the synthetic methods of such organic amines, and the reported synthetic methods have low yield and high cost, and are not suitable for large-scale industrial production. Patent CN108947985A discloses compounds used as autophagy regulators and their preparation methods and uses, wherein 2-(2-bromoethyl) isoindoline-1,3-dione and N-hydroxyethylpiperazine are used As the raw material, the acetonitrile solution of potassium carbonate is used as the solvent to prepare 1-(2-hydroxyethyl)-4-(2-aminoethyl)piperazine after mixing reaction, filtration, concentration and column ch...

Examples

Embodiment 1

[0035] When R in compound D 1 = ethylene, R 2 = methyl (the specific compound is 1-(2-hydroxypropyl)-4-(2-aminoethyl)piperazine); R in compound B 3 = methyl, R 4 When = isobutyl (the concrete compound is methyl isobutyl ketone), its synthesis principle is:

[0036]

[0037] The specific operation steps are: add 0.1mol of N-aminoethylpiperazine and 1.5mol of methyl isobutyl ketone into a 500ml three-necked flask, control the magnetic stirring speed to be 100r / min, after the solution is mixed uniformly, add a distillation device and Heat the solution to 110°C, first collect the 87-90°C fraction until no liquid is distilled, then collect the 105-108°C fraction until no liquid is distilled, and collect the distillate in a conical flask for recycling. Add 2 mol of methanol to the remaining reaction solution, and after the solution is stirred evenly, control the temperature to 30 °C, slowly add 0.15 mol of propylene oxide dropwise to the three-necked flask with a constant pres...

Embodiment 2

[0040] When R in compound D 1 = ethylene, R 2 =H proton (the specific compound is 1-(2-hydroxyethyl)-4-(2-aminoethyl)piperazine); R in compound B 3 = methyl, R 4When = isobutyl (the concrete compound is methyl isobutyl ketone), its synthesis principle is:

[0041]

[0042] In the 500ml three-necked flask, add 0.1mol of N-aminoethylpiperazine and 150g of recovered amine-based protective agent (the mass fraction of methyl isobutyl ketone is 95.7%), control the magnetic stirring speed to be 100r / min, and wait for the solution to mix. After homogenization, add a distillation device and heat the solution to 110°C, first collect the 87-90°C fraction until no liquid is distilled, then collect the 105-108°C fraction until no liquid is distilled, and collect the distillate in a conical flask Waiting for recycling. Add 2mol methanol to the remaining reaction solution, and after the solution is stirred evenly, transfer to the autoclave, control the temperature in the kettle to be ...

Embodiment 3

[0045] When R in compound D 1 = methylene, R 2 = methyl (the specific compound is 1-(2-hydroxypropyl)-4-aminomethylpiperazine); R in compound B 3 = methyl, R 4 When = isobutyl (the specific compound is methyl isobutyl ketone), its synthesis, separation and purification steps are basically the same as in Example 1, the difference is that N-amine ethyl piperazine as raw material is replaced by N-amine Methylpiperazine. The total yield of the final product was 90% and the purity was 99.3%.

[0046] The recovery and utilization steps of the protective agent are consistent with the steps in Example 1, and the gas chromatography detection results: the mass fraction of the upper phase methyl isobutyl ketone is 98.8%, and the mass fraction of the lower phase methyl isobutyl ketone is 0.87%.

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