Method for synthesizing piperazine and derivatives thereof by gas-solid phase catalysis of monoethanolamine

A technology of monoethanolamine and gas-solid phase, applied in the direction of organic chemistry, can solve the problems of reducing the strength and quantity of surface acid centers, poisoning or reducing, and harsh reaction conditions, etc., to achieve cheap and easy-to-obtain catalysts, improve selectivity, and catalytic activity high effect

Active Publication Date: 2017-09-29
XIAN MODERN CHEM RES INST +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] CN1182744A, CN14179423A and CN1234401A have introduced the method for preparing triethylenediamine with monoethanolamine, ethyleneamine, piperazine or morpholine as raw material under high temperature, and the zeolite catalyst used is to use caustic alkali aqueous solution, oxalic acid aqueous solution or silicon-containing compound respectively After treatment, ZSM-5 zeolite in the form of hydrogen or ammonium, the above three modification methods can poison or reduce a part of the acid centers on the surface of the catalyst, reduce the strength and quantity of surface acid centers, and improve the selectivity of triethylenediamine. But the conversion of monoethanolamine and piperazine in this process is lower than 72%, and the selectivity of triethylenediamine is still lower than 30%.
[0010] In summary: At present, the raw materials for the synthesis of piperazine and triethylenediamine need to be mixed with a large amount of diluent, resulting in a waste of raw materials, and some processes require high temperature and high pressure conditions, and the reaction conditions are harsh

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Disperse 16.33g of sodium-based montmorillonite in 800g of 20% nitric acid aqueous solution by mass fraction to prepare a 2% montmorillonite suspension, stir, activate at 104°C for 4 hours, and use a centrifuge at 8000 rpm Centrifuge for 6 minutes, wash the precipitate with distilled water until neutral, place it in an oven to dry at 80°C for 12 hours, place it in a muffle furnace to raise the temperature to 550°C at a rate of 2.0°C / min, roast at a constant temperature for 4 hours, and naturally cool to room temperature , taken out, pressed into tablets, granulated, passed through a 40-60 mesh sieve, and prepared into acid-activated montmorillonite with a specific surface area of ​​220.25m 2 / g, the pore volume is 0.61cm 3 / g, the average pore diameter is 11.15nm, and the silicon-aluminum ratio is 32:1 (molar ratio).

[0024] Fill the prepared acid-activated montmorillonite into a fixed-bed tubular reactor with an inner diameter of 12mm and a tube length of 250mm, with...

Embodiment 2

[0026] Dispersing 16.33g of sodium-based montmorillonite in 800g of 20% nitric acid aqueous solution by mass fraction was prepared into a 2% montmorillonite suspension, stirred, activated at 104°C for 24 hours, and other steps were the same as in Example 1 , prepared into acid-activated montmorillonite with a specific surface area of ​​191.69m 2 / g, the pore volume is 0.96cm 3 / g, the average pore diameter is 20.02nm, and the silicon-aluminum ratio is 46:1 (molar ratio).

[0027] The prepared acid-activated montmorillonite was catalyzed to react monoethanolamine for 10 hours according to the method of implementation 1. According to gas chromatography analysis, the conversion rate of monoethanolamine was 100%, the selectivity of piperazine was 9.2%, and the selectivity of triethylenediamine was 13.7%. , N-ethylpiperazine selectivity was 8.76%, 2-ethylpyrazine selectivity was 34.2%.

Embodiment 3

[0029] In Example 2, the sodium-based montmorillonite was replaced with an equal mass of calcium-based montmorillonite, and the other steps were the same as in Example 2 to prepare an acid-activated montmorillonite with a specific surface area of ​​213.9m 2 / g, the pore volume is 0.89cm 3 / g, the average pore diameter is 16.6nm, and the silicon-aluminum ratio is 42:1 (molar ratio).

[0030] The prepared acid-activated montmorillonite was catalyzed to react monoethanolamine for 10 hours according to the method of implementation 1. According to gas chromatography analysis, the conversion rate of monoethanolamine was 99.3%, the selectivity of piperazine was 30.6%, and the selectivity of triethylenediamine was 3.2%. , The selectivity to N-ethylpiperazine was 5.0%, and the selectivity to 2-ethylpyrazine was 32.4%.

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Abstract

The invention discloses a method for synthesizing piperazine and derivatives of the piperazine through monoethanolamine gas-solid phase catalysis. According to the method, monoethanolamine is used as raw materials; acid activated montmorillonite or acid activated imvite loaded with phosphate is used as a catalyst; piperazine, triethylene diamine, N-ethylpiperazine and 2-ethylpiperazine are synthesized at ordinary pressure at 250 to 350 DEG C. The method is simple; the conditions are controllable; the used catalyst is low in cost and can be easily obtained; the catalytic activity is high; the stability is good; the conversion rate of monoethanolamine can reach higher than 99 percent; in addition, the piperazine, the triethylene diamine, the N-ethylpiperazine and the 2-ethylpiperazine with higher yield and high value can be obtained.

Description

technical field [0001] The invention belongs to the technical field of synthesis of pharmaceutical intermediate piperazine and derivatives thereof, and specifically relates to a method for synthesizing piperazine, triethylenediamine, N-ethylpiperazine and 2-ethylpyrazine with monoethanolamine. Background technique [0002] Piperazine and its derivatives are an important class of organic chemical intermediates, widely used in pharmaceuticals, pesticides, surfactants and dyes and other industries. For example: piperazine can be used to synthesize piperazine phosphate, piperazine citrate, and fluphenazine, laxidine, rifampin and other drugs for the synthesis of anthelmintic drugs; triethylenediamine is the initiator of pesticide production and is the Hardener, and also a catalyst for epoxy resin curing, ethylene and epoxide polymerization; N-ethylpiperazine is an important intermediate for the synthesis of veterinary drug ethyl ciprofloxacin (anthrafloxacin), and it is also a d...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D295/023C07D295/027C07D295/03C07D241/12C07D487/08
CPCC07D241/12C07D295/023C07D295/027C07D295/03C07D487/08
Inventor 刘忠文侯艳霞吕剑黄贵秋杨建明刘昭铁
Owner XIAN MODERN CHEM RES INST
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