CN111533659A - Preparation method of acetylsalicylic acid rare earth - Google Patents

Preparation method of acetylsalicylic acid rare earth Download PDF

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Publication number
CN111533659A
CN111533659A CN202010415629.8A CN202010415629A CN111533659A CN 111533659 A CN111533659 A CN 111533659A CN 202010415629 A CN202010415629 A CN 202010415629A CN 111533659 A CN111533659 A CN 111533659A
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rare earth
acetylsalicylic acid
preparing
acid rare
solvent
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CN202010415629.8A
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Inventor
陈明光
张玉玺
赵峰
曹鸿璋
于晓丽
葛瑞祥
芦婷婷
吴豪
曹露雅
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Inner Mongolia Lianfeng Rare Earth Chemical Research Institute Co ltd
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Inner Mongolia Lianfeng Rare Earth Chemical Research Institute Co ltd
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Priority to CN202010415629.8A priority Critical patent/CN111533659A/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/28Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)

Abstract

The invention relates to a preparation method of acetylsalicylic acid rare earth, which comprises the steps of dispersing acetylsalicylic acid in a solvent, dropwise adding a proper amount of alkali solution, controlling the pH value within a specific range, then adding a rare earth salt solution, reacting for a period of time at 60 ℃, generating solid precipitate, washing by distilled water, filtering, and drying at 80 ℃ to obtain a finished product. The advantages are that: the invention can be realized under normal pressure without any catalyst, and has the advantages of low preparation cost, simple and easy synthesis process, safety and reliability. In addition, the filtrate obtained after the reaction of the acetylsalicylic acid and the rare earth salt can be recycled as a solvent, so that the method is green and environment-friendly, and has no any danger or three-waste pollution. Meanwhile, the product has stable chemical property, is nontoxic and tasteless, and is easy for industrial production, storage and transportation.

Description

Preparation method of acetylsalicylic acid rare earth
The technical field is as follows:
the invention relates to a preparation method of acetylsalicylic acid rare earth, belonging to the technical field of rare earth chemical synthesis.
Background art:
acetylsalicylic acid, also known as Aspirin (ASP), is widely used clinically in the treatment of fever, headache, neuralgia, myalgia, rheumatic fever, acute rheumatic arthritis and other diseases. However, with the wide application of aspirin, its adverse reactions are also gradually increasing, mainly manifested in: nausea, vomiting, gastrointestinal discomfort, allergic reaction, liver damage and the like. Therefore, in recent years, its wide application has been greatly limited.
Rare earth is 15 lanthanide elements with atomic numbers from 57-71 in the third subgroup of the periodic table of the elements, and two elements, scandium (Sc) and yttrium (Y), closely related to the lanthanide elements. The application of rare earth in medicines is also widely researched, for example, cerium oxalate can be used for treating marine dizziness and vomiting of pregnancy, inorganic cerium salt can be used as a wound disinfectant, and besides, the rare earth also has the effects of anticoagulation, anti-inflammatory sterilization, anti-arteriosclerosis, anti-tumor and the like.
After the acetylsalicylic acid and the metal ions form a complex, the toxic and side effects of the aspirin can be obviously reduced, and the drug effect and the physiological function of the aspirin are improved. For example, after acetylsalicylic acid and zinc ions form zinc Acetylsalicylate (ASZ), the analgesic effect of the compound is obviously better than that of ASP, and copper acetylsalicylate (CuAsp) has better effects of diminishing inflammation, relieving pain, resisting rheumatism, resisting epilepsy and the like than ASP, and has the advantages of small toxic and side effects and light gastrointestinal adverse reaction. However, most of the acetylsalicylic acid complexes reported so far are concentrated on transition metal ions, and few of the acetylsalicylic acid complexes related to rare earths are reported.
The invention prepares acetylsalicylic acid rare earth with different properties by reacting rare earth ions with acetylsalicylic acid under certain conditions. Research shows that the acetylsalicylic acid rare earth has special effect in the fields of agriculture, fluorescence and the like. For example, the rare earth acetylsalicylic acid has obvious effects of disease resistance induction, early fruiting and yield increase and quality improvement on ginkgo, and a complex formed by the acetylsalicylic acid and a rare earth terbium (Tb) ion has strong green fluorescence. Besides, the rare earth ions have a plurality of 4f and 5d empty electron energy levels, and the 4f and 5d empty electron energy levels can accept lone-pair electrons of 6-12 ligands as coordination center ions. The formed acetylsalicylic acid rare earth can absorb hydrogen chloride generated by PVC decomposition, and has an important effect of slowing down the aging decomposition of PVC resin. Based on the important role of rare earth and acetylsalicylic acid in medicine, the acetylsalicylic acid rare earth also has good prospect in the field of medicine application.
The invention content is as follows:
the invention aims to provide a preparation method of acetylsalicylic acid rare earth.
The invention is implemented by the following technical scheme: a process for preparing the rare-earth acetylsalicylate includes such steps as dispersing acetylsalicylic acid in solvent, adding alkali solution to control pH value to a certain range, adding rare-earth salt solution, reacting at 60 deg.C for a certain time to generate solid deposit, washing with distilled water, filtering and drying at 80 deg.C.
Further, the solvent is one of ethanol, deionized water or acetone.
Further, the alkali is one of sodium hydroxide, potassium hydroxide, sodium bicarbonate or potassium bicarbonate.
Further, the concentration range of the alkali solution is 0.01 mol/L-0.05 mol/L.
Further, the pH value range is 7.5-9.0.
Further, the rare earth salt is nitrate or chloride of rare earth.
Further, the concentration range of the rare earth salt solution is 0.01mol/L-0.1 mol/L.
Further, the reaction time is 0.5-2 h.
The invention has the advantages that:
1. the acetylsalicylic acid rare earth prepared by the invention is reacted under normal pressure, can be realized without any catalyst, and has the advantages of low preparation cost, simple and feasible synthesis process, safety and reliability.
2. The filtrate generated by preparing the acetylsalicylic acid rare earth, namely the filtrate obtained after the reaction of the acetylsalicylic acid and the rare earth salt solution, can be used as a solvent for recycling. Therefore, the invention has no three-waste pollution, is green and environment-friendly and is easy for industrialized production.
3. The product has stable chemical property, no toxicity, no smell and easy storage and transportation. The product has good application prospect in the fields of agriculture, medicine, fluorescence, PVC heat stabilizer and the like.
The specific implementation mode is as follows:
the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1:
0.54g of acetylsalicylic acid (3mmol) is dissolved in 100ml of aqueous solution, 0.01mol/L aqueous NaOH solution is added to control the pH to 7.5, then 100ml of 0.01mol/L aqueous lanthanum nitrate solution is added, and the mixture is stirred in a beaker at the rotation speed of 200 r/min. Reacting at 60 ℃ for 0.5 hour to generate white precipitate, aging the precipitate for 1 hour, filtering, washing with distilled water for 3 times, filtering, and drying in an oven at 80 ℃ for 4 hours to obtain a white solid product with a yield of 75.4%. The filtrate from the reaction was recovered and supplemented with 15ml of water as solvent, and the reaction was repeated with the other conditions unchanged. The yield of acetylsalicylic acid rare earth is 74.6 percent.
Example 2:
0.54g of acetylsalicylic acid (3mmol) is dissolved in 100ml of ethanol solution, KOH aqueous solution with the concentration of 0.02mol/L is added to control the pH value to be 8.0, then 50ml of cerium trichloride aqueous solution with the concentration of 0.02mol/L is added, and the mixture is stirred in a beaker constantly at the rotating speed of 200 r/min. Reacting at 60 ℃ for 0.5 hour to generate white precipitate, aging the precipitate for 1 hour, filtering, washing with distilled water for 3 times, filtering, and drying in an oven at 80 ℃ for 4 hours to obtain a light yellow solid product with a yield of 78.4%. The filtrate from the reaction was recovered and supplemented with 20ml of ethanol as solvent, and the reaction was repeated with the other conditions unchanged. The yield of the acetylsalicylic acid rare earth is 77.2 percent.
Example 3:
0.54g of acetylsalicylic acid (3mmol) is dissolved in 100ml of aqueous solution, 0.02mol/L aqueous sodium bicarbonate solution is added to control the pH to 8.5, and then 50ml of 0.02mol/L aqueous europium nitrate (1mmol) solution is added, and the mixture is stirred in a beaker at the rotation speed of 200 r/min. Reacting at 60 ℃ for 1 hour to generate white precipitate, aging the precipitate for 1 hour, filtering, washing with distilled water for 3 times, filtering, and drying in an oven at 80 ℃ for 4 hours to obtain a light yellow solid product with a yield of 79.2%. The filtrate from the reaction was recovered and supplemented with 15ml of water as solvent, and the reaction was repeated with the other conditions unchanged. The yield of acetylsalicylic acid rare earth is 78.1 percent.
Example 4:
0.54g of acetylsalicylic acid (3mmol) is dissolved in 100ml of acetone solution, NaOH ethanol solution with the concentration of 0.05mol/L is added, the pH is controlled to be 8.0, then 20ml of samarium trichloride ethanol solution with the concentration of 0.05mol/L is added, and the mixture is stirred continuously in a beaker at the rotating speed of 200 r/min. Reacting at 60 ℃ for 2 hours to generate white precipitate, aging the precipitate for 1 hour, filtering, washing with distilled water for 3 times, filtering, and drying in an oven at 80 ℃ for 4 hours to obtain a light yellow solid product with the yield of 82.2%. The filtrate from the reaction was recovered and supplemented with 25ml of acetone as solvent, and the reaction was repeated with other conditions unchanged. The yield of the acetylsalicylic acid rare earth is 82.4 percent.
Example 5:
0.54g of acetylsalicylic acid (3mmol) is dissolved in 100ml of ethanol solution, potassium bicarbonate aqueous solution with the concentration of 0.05mol/L is added, the pH is controlled to be 9.0, then 20ml of ytterbium nitrate aqueous solution with the concentration of 0.05mol/L is added, and the mixture is stirred continuously in a beaker at the rotating speed of 200 r/min. Reacting at 60 ℃ for 2 hours to generate white precipitate, aging the precipitate for 1 hour, filtering, washing with distilled water for 3 times, filtering, and drying in an oven at 80 ℃ for 4 hours to obtain a white solid product with the yield of 81.6%. The filtrate from the reaction was recovered and supplemented with 20ml of acetone as solvent, and the reaction was repeated with the other conditions unchanged. The yield of the acetylsalicylic acid rare earth is 80.4 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. The preparation method of the acetylsalicylic acid rare earth is characterized by comprising the following steps: dispersing acetylsalicylic acid in a solvent, adding an alkali solution to control the pH value to be in a specific range, then adding a rare earth salt solution, reacting for a period of time at 60 ℃, generating solid precipitate, washing by distilled water, filtering, and drying at 80 ℃ to obtain a finished product.
2. The method for preparing the acetylsalicylic acid rare earth as claimed in claim 1, which is characterized in that: the solvent is one of ethanol, deionized water or acetone.
3. The method for preparing the acetylsalicylic acid rare earth as claimed in claim 1, which is characterized in that: the alkali is one of sodium hydroxide, potassium hydroxide, sodium bicarbonate or potassium bicarbonate.
4. The method for preparing the acetylsalicylic acid rare earth as claimed in claim 1, which is characterized in that: the concentration range of the alkali solution is 0.01 mol/L-0.05 mol/L.
5. The method for preparing the acetylsalicylic acid rare earth as claimed in claim 1, which is characterized in that: the pH value range is 7.5-9.0.
6. The method for preparing the acetylsalicylic acid rare earth as claimed in claim 1, which is characterized in that: the rare earth salt is nitrate or chloride of rare earth.
7. The method for preparing the acetylsalicylic acid rare earth as claimed in claim 1, which is characterized in that: the concentration range of the rare earth salt solution is 0.01mol/L-0.1 mol/L.
8. The method for preparing the acetylsalicylic acid rare earth as claimed in claim 1, which is characterized in that: the reaction time is 0.5-2 h.
CN202010415629.8A 2020-05-16 2020-05-16 Preparation method of acetylsalicylic acid rare earth Pending CN111533659A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114249651A (en) * 2021-12-21 2022-03-29 包头稀土研究院 Organic rare earth complex microsphere, preparation method thereof and application of ammonia water

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JP2009292748A (en) * 2008-06-03 2009-12-17 National Institute Of Advanced Industrial & Technology Rare earth metal complex, ink composition using the same and fluorescent labeling agent
CN103450886A (en) * 2013-08-20 2013-12-18 福建师范大学 Preparation of purple light-excited tri-stimulus composite white light complexes
CN104789213A (en) * 2015-04-21 2015-07-22 阜阳师范学院 Rare earth terbium complex and preparation method thereof
RU2643966C1 (en) * 2017-05-29 2018-02-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") Method for obtaining terbium acetylsalicylate (iii)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009292748A (en) * 2008-06-03 2009-12-17 National Institute Of Advanced Industrial & Technology Rare earth metal complex, ink composition using the same and fluorescent labeling agent
CN103450886A (en) * 2013-08-20 2013-12-18 福建师范大学 Preparation of purple light-excited tri-stimulus composite white light complexes
CN104789213A (en) * 2015-04-21 2015-07-22 阜阳师范学院 Rare earth terbium complex and preparation method thereof
RU2643966C1 (en) * 2017-05-29 2018-02-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кубанский государственный университет" (ФГБОУ ВО "КубГУ") Method for obtaining terbium acetylsalicylate (iii)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114249651A (en) * 2021-12-21 2022-03-29 包头稀土研究院 Organic rare earth complex microsphere, preparation method thereof and application of ammonia water
CN114249651B (en) * 2021-12-21 2024-04-09 包头稀土研究院 Organic rare earth complex microsphere, preparation method thereof and application of ammonia water

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