阅读说明：本技术 基于氯喹那多废渣制备8-羟基-2-甲基喹啉的方法 (Method for preparing 8-hydroxy-2-methylquinoline based on chloroquinate waste residue ) 是由 王琨 孙滨 张宾 张治中 张彤 李建功 魏越 于 2020-12-28 设计创作，主要内容包括：本发明涉及有机废渣回收技术领域,具体涉及一种基于氯喹那多废渣制备8-羟基-2-甲基喹啉的方法。将氯喹那多废渣溶于溶剂中,在还原剂与催化剂作用下发生反应,反应后加水淬灭,调节pH值,再萃取、浓缩,制得8-羟基-2-甲基喹啉。本发明本发明利用高活性新型还原剂2-氢双(二甲氧乙氧基)铝酸钠和催化剂氯化铵,避免了钯碳、雷尼镍、铂碳等重金属催化剂对于芳香环上氯代物反应活性的不足以及对环境的污染,同时避免了高温与高压等苛刻的反应条件以及氢气的使用,提高了8-羟基-2-甲基喹啉的收率,使反应更易于控制,更加安全,生产周期短,易于工业化。(The invention relates to the technical field of organic waste residue recovery, and particularly relates to a method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldine waste residue. Dissolving the waste residue of the chloroquinalder in a solvent, reacting under the action of a reducing agent and a catalyst, adding water for quenching after the reaction, adjusting the pH value, extracting and concentrating to prepare the 8-hydroxy-2-methylquinoline. The invention utilizes the high-activity novel reducing agent 2-hydrogen bis (dimethoxyethoxy) sodium aluminate and the catalyst ammonium chloride, avoids the defects of the reaction activity of heavy metal catalysts such as palladium carbon, Raney nickel, platinum carbon and the like on the aromatic ring chloride and the pollution to the environment, simultaneously avoids the harsh reaction conditions such as high temperature, high pressure and the like and the use of hydrogen, improves the yield of 8-hydroxy-2-methylquinoline, and ensures that the reaction is easier to control, safer, short in production period and easy to industrialize.)

1. A method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue is characterized in that: dissolving the waste residue of the chloroquinalder in a solvent, reacting under the action of a reducing agent and a catalyst, adding water for quenching after the reaction, adjusting the pH value, extracting and concentrating to prepare the 8-hydroxy-2-methylquinoline.

2. The method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue according to claim 1, wherein: the reducing agent is 70 wt.% toluene solution of sodium 2-hydro-bis (dimethoxyethoxy) aluminate.

3. The method for preparing 8-hydroxy-2-methylquinoline based on a waste residue of chloroquinaldo as claimed in claim 2, wherein: the mass ratio of the chloroquinalder waste residue to the reducing agent is 1: 0.5-8.

4. The method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue according to claim 1, wherein: the catalyst is ammonium chloride.

5. The method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue according to claim 4, wherein: the mass ratio of the chloroquinalder waste residue to the catalyst is 1: 0.01-0.05.

6. The method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue according to claim 1, wherein: the solvent is toluene or tetrahydrofuran, and the mass ratio of the chloroquinader waste residue to the solvent is 1: 2-10.

7. The method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue according to claim 1, wherein: the reaction temperature is 0-100 ℃.

8. The method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue according to claim 1, wherein: and (3) adjusting the pH value to 1-3 by using dilute hydrochloric acid.

9. The method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue according to claim 8, wherein: the concentration of the dilute hydrochloric acid is 1-1.5 mol/L.

10. The method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residue according to claim 1, wherein: the solvent adopted in the extraction is toluene, ethyl acetate or dichloromethane.

Technical Field

The invention relates to the technical field of organic waste residue recovery, and particularly relates to a method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldine waste residue.

Background

The chloroquinadol is a yellow needle crystal with slight pungent smell. Has antimicrobial activity against fungi, trichomonad, bacteria (G + and G-), chlamydia and mycoplasma, and is a broad-spectrum bacteriostatic agent. Because the medicine is slightly soluble in water, pathogenic microorganisms generally enter pathogen cells through endocytosis, the pH value of the pathogen cells is changed, the pathogen metabolism is inhibited, and the like, the pathogen is finally killed, and human epithelial cells have no phagocytic function on the chloroquinalder, so that the medicine has little adverse reaction on a human body when being externally used.

The chloroquinate is synthesized by taking 8-hydroxy-2-methylquinoline as a raw material through one-step chlorination reaction, but a large amount of polychlorinated products are generated in the chlorination reaction process, and a small amount of chloroquinate products are remained in waste residues in the chloroquinate refining process. If the waste residues are not treated, not only is the production cost greatly wasted, but also great pressure is caused on environmental protection treatment, and the economic competitiveness of the product is reduced.

Chinese patent CN108409651A discloses a method for preparing 8-hydroxy-2-methylquinoline by using waste residue of chloroquinate, which comprises the steps of catalyzing and hydrogenating the waste residue of chloroquinate by using a hydrogenation catalyst in the presence of an acid binding agent, filtering, retaining a solid, dissolving an acid solution, adjusting the pH value of the solution, extracting, retaining an organic phase, drying and distilling to obtain the 8-hydroxy-2-methylquinoline. The patent uses hazardous gas hydrogen, is easy to cause explosion, uses heavy metal palladium carbon, pollutes the environment, has high three-waste treatment cost, and is not beneficial to industrial production.

Disclosure of Invention

The invention aims to provide a method for preparing 8-hydroxy-2-methylquinoline based on chloroquinaldo waste residues, which avoids the use of heavy metals such as palladium carbon and the like and the pollution to the environment, avoids harsh reaction conditions such as high temperature, high pressure and the like and the use of hydrogen, and is easy for industrial production.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the method for preparing 8-hydroxy-2-methylquinoline based on the waste residue of the chloroquinaldine comprises the following steps: dissolving the waste residue of the chloroquinalder in a solvent, reacting under the action of a reducing agent and a catalyst, adding water for quenching after the reaction, adjusting the pH value, extracting and concentrating to prepare the 8-hydroxy-2-methylquinoline.

Wherein:

the reducing agent is 70 wt.% toluene solution of sodium 2-hydro-bis (dimethoxyethoxy) aluminate.

The mass ratio of the chloroquinalder waste residue to the reducing agent is 1: 0.5-8.

The catalyst is ammonium chloride.

The mass ratio of the chloroquinalder waste residue to the catalyst is 1: 0.01-0.05.

The solvent is toluene or tetrahydrofuran, and the mass ratio of the chloroquinader waste residue to the solvent is 1: 2-10.

The reaction temperature is 0-100 ℃.

And (3) adjusting the pH value to 1-3 by using dilute hydrochloric acid. The concentration of the dilute hydrochloric acid is 1-1.5mol/L, and 1mol/L is preferred.

The solvent adopted in the extraction is toluene, ethyl acetate or dichloromethane.

The main components of the waste residue of the chloroquinate are polychlorinated substitutes (I, II, III and IV), a small amount of chloroquinate (V) and a small amount of 8-hydroxy-2-methylquinoline (VI).

The process for reducing the chloroquinate waste residue by the 2-hydro-bis (dimethoxyethoxy) sodium aluminate comprises the following steps:

the invention has the following beneficial effects:

(1) sodium 2-hydrobis (dimethoxyethoxy) aluminate is a reducing agent with unique activity and can reduce aliphatic and aromatic chlorides, bromides and iodides, but in the reaction of the invention, sodium 2-hydrobis (dimethoxyethoxy) aluminate can only reduce aromatic ring chlorine and has no reduction on methyl chlorine, so that ammonium chloride is added into the reaction system as a catalyst to effectively reduce methyl chlorine. Under the combined action of 2-hydro-bis (dimethoxyethoxy) sodium aluminate and ammonium chloride, the invention utilizes the chloroquinalder waste residue to prepare 8-hydroxy-2-methylquinoline, and improves the yield of 8-hydroxy-2-methylquinoline.

(2) The invention utilizes the high-activity novel reducing agent sodium 2-hydrobis (dimethoxyethoxy) aluminate to avoid the defects of the reaction activity of heavy metal catalysts such as palladium carbon, Raney nickel, platinum carbon and the like on aromatic ring chlorinated substances and the pollution to the environment, and simultaneously avoids the harsh reaction conditions such as high temperature, high pressure and the like and the use of hydrogen, so that the reaction is easier to control, safer, short in production period and easy to industrialize.

(3) According to the invention, the yield of 8-hydroxy-2-methylquinoline is more than or equal to 65 percent and the purity is more than or equal to 99.0 percent based on the total mass of the chloroquinalder waste residue. The invention recycles the waste residue of the chloroquinalder, changes waste into valuable, saves resources, reduces environmental pollution, reduces production cost, improves product competitiveness and has good economic benefit.

Detailed Description

The present invention is further described below with reference to examples.

Example 1

Under the protection of nitrogen, 10g of chloroquinader waste residue and 50ml of toluene are added into a 500ml four-mouth bottle, the temperature is reduced to 0 ℃, 5g of 70 wt.% toluene solution of sodium 2-hydro-bis (dimethoxyethoxy) aluminate is added dropwise, 0.1g of ammonium chloride is added for reaction, water is added for quenching after the reaction is finished, 1mol/L of dilute hydrochloric acid is used for adjusting the pH value to be 1, ethyl acetate is used for extraction, and the solvent is concentrated to prepare 6.8g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 68 percent, and the purity is 99.3 percent.

Example 2

Under the protection of nitrogen, 50g of chloroquinader waste residue and 500ml of tetrahydrofuran are added into a 1000ml four-mouth bottle, 400g of 70 wt.% toluene solution of 2-hydro-bis (dimethoxyethoxy) sodium aluminate is dropwise added at room temperature, 2.5g of ammonium chloride is added for reaction, water is added for quenching after the reaction is finished, 1mol/L of dilute hydrochloric acid is adopted to adjust the pH value to be 3, ethyl acetate is used for extraction, and the solvent is concentrated to prepare 35g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 70 percent, and the purity is 99.2 percent.

Example 3

Under the protection of nitrogen, 50g of chloroquinader waste residue and 150ml of toluene are added into a 1000ml four-mouth bottle, the bottle is heated to 100 ℃, 250g of 70 wt.% toluene solution of sodium 2-hydro-bis (dimethoxyethoxy) aluminate is added dropwise, 1g of ammonium chloride is added for reaction, water is added for quenching after the reaction is finished, 1mol/L of dilute hydrochloric acid is adopted to adjust the pH value to be 1, the toluene is used for extraction, and the solvent is concentrated to prepare 32.5g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 65 percent, and the purity is 99.3 percent.

Example 4

Under the protection of nitrogen, 10g of chloroquinader waste residue and 20ml of tetrahydrofuran are added into a 500ml four-mouth bottle, the temperature is reduced to 10 ℃, 20g of 70 wt.% toluene solution of 2-hydro-bis (dimethoxyethoxy) sodium aluminate is added dropwise, 0.3g of ammonium chloride is added for reaction, water is added for quenching after the reaction is finished, 1mol/L of dilute hydrochloric acid is used for adjusting the pH value to be 2, dichloromethane is used for extraction, and the solvent is concentrated to prepare 6.6g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 66 percent, and the purity is 99.1 percent.

Example 5

Under the protection of nitrogen, 20g of chloroquinader waste residue and 160ml of toluene are added into a 500ml four-mouth bottle, the mixture is heated to 60 ℃, 20g of 70 wt.% toluene solution of sodium 2-hydro-bis (dimethoxyethoxy) aluminate is added dropwise, 0.8g of ammonium chloride is added for reaction, water is added for quenching after the reaction is finished, 1mol/L of dilute hydrochloric acid is used for adjusting the pH value to be 2, the toluene is used for extraction, and the solvent is concentrated to prepare 14g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 70 percent, and the purity is 99.2 percent.

Comparative example 1

The method for treating the chloroquinader waste residue by using palladium hydroxide carbon comprises the following specific steps:

under the protection of nitrogen, 10g of chloroquinader waste residue and 50ml of toluene are added into a 500ml four-mouth bottle, 5g of palladium-carbon hydroxide is added, heating reflux is carried out, after the reaction is finished, water is added for quenching, the pH value is adjusted to 1 by adopting 1mol/L diluted hydrochloric acid, ethyl acetate is used for extraction, and the solvent is concentrated, thus obtaining 5.2g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 52 percent, and the purity is 96.6 percent.

Comparative example 2

The method for treating the chloroquinader waste residue by using palladium carbon comprises the following specific steps:

under the protection of nitrogen, 10g of chloroquinader waste residue and 50ml of toluene are added into a 500ml four-mouth bottle, 5g of palladium carbon is added, heating reflux is carried out, after the reaction is finished, thermal filtration is carried out, water is added for quenching, the pH value is adjusted to 1 by adopting 1mol/L diluted hydrochloric acid, ethyl acetate is used for extraction, and the solvent is concentrated to prepare 3.7g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 37 percent, and the purity is 85.9 percent.

Comparative example 3

The method for treating the waste residue of the chloroquinate by using the Raney nickel comprises the following specific steps:

under the protection of nitrogen, 10g of chloroquinader waste residue and 50ml of toluene are added into a 500ml four-mouth bottle, 5g of raney nickel is added, heating reflux is carried out, after the reaction is finished, heat filtration is carried out, water is added for quenching, the pH value is adjusted to 1 by 1mol/L of dilute hydrochloric acid, ethyl acetate is used for extraction, and the solvent is concentrated to prepare 2.3g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 23 percent, and the purity is 86.3 percent.

Comparative example 4

The reaction was carried out as in example 1 without adding 70 wt.% toluene solution of sodium 2-hydrobis (dimethoxyethoxy) aluminate.

Comparative example 5

The method comprises the following specific steps of without adding ammonium chloride:

under the protection of nitrogen, 10g of chloroquinader waste residue and 50ml of toluene are added into a 500ml four-mouth bottle, the temperature is reduced to 0 ℃, 5g of sodium 2-hydro-bis (dimethoxyethoxy) aluminate 70 wt.% toluene solution is added dropwise for reaction, water is added for quenching after the reaction is finished, 1mol/L diluted hydrochloric acid is adopted for adjusting the pH value to 1, ethyl acetate is used for extraction, and the solvent is concentrated to prepare 4.7g of 8-hydroxy-2-methylquinoline. Based on the total mass of the chloroquinalder waste residue, the yield of the 8-hydroxy-2-methylquinoline is 47 percent, and the purity is 88.1 percent.

Comparative example 6

The reaction was carried out in the same manner as in example 1 except that 70 wt.% toluene solution of sodium 2-hydrobis (dimethoxyethoxy) aluminate and ammonium chloride were not added.