CN111995559A - Hexacarboxy chelating agent and preparation method thereof - Google Patents
Hexacarboxy chelating agent and preparation method thereof Download PDFInfo
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- CN111995559A CN111995559A CN202011003300.7A CN202011003300A CN111995559A CN 111995559 A CN111995559 A CN 111995559A CN 202011003300 A CN202011003300 A CN 202011003300A CN 111995559 A CN111995559 A CN 111995559A
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- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a hexacarboxyl chelating agent and a preparation method thereof, wherein the preparation method comprises the following steps: 1) adding 1, 3-diaminopropane and cyclobut-3-ene diformic anhydride into a three-neck flask, introducing nitrogen, and performing nucleophilic addition-elimination reaction to generate imide; followed by LiAlH4Reducing a carbonyl group for a reducing agent; adding sodium chloroacetate for quaternization. 2) Diluting the product, adding potassium permanganate, heating to perform oxidation reaction to generate carboxyl; and after the reaction is finished, adding sodium sulfite to remove excessive potassium permanganate, filtering by adopting diatomite and extracting impurities by adopting ethyl acetate, collecting a water phase, adjusting the pH value to be 2-4 to separate out a product, and filtering and drying to constant weight to obtain a final product. The hexacarboxyl chelating agent can be used as a carboxylic acid type chelating agent for reducing and controlling the concentration of metal ions, and can be used in the fields of daily chemical industry, textile industry and the like.
Description
Technical Field
The invention belongs to the field of chelating agents, and particularly relates to a hexacarboxyl chelating agent and a preparation method thereof.
Background
Chelating agents, also known as complexing agents, are organic or inorganic compounds capable of chelating metal ions to form stable water-soluble cyclic complexes, thereby inactivating the metal ions. The compound at least contains a pair of lone electron pairs, and can coordinate with the empty electron orbit of the metal ions to form a coordination bond, so that a flocculation complex with a ring structure is formed, and the aim of removing the heavy metal ions is fulfilled. Therefore, chelating agents are widely used for softening, rust prevention, washing, and the like. The carboxylic acid type chelating agent is widely used, and can be used for the aspects of soil heavy metal pollution remediation, sewage treatment, domestic washing, printing and dyeing and the like. However, the existing carboxylic acid type chelating agent has the defects of weak dispersing ability, difficult biodegradation, weak complexing ability, small application range and the like.
Disclosure of Invention
In order to enrich the types of carboxylic acid chelating agents, the invention designs and prepares a hexacarboxyl chelating agent and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hexacarboxy chelating agent of the formula:
a preparation method of a hexacarboxyl chelating agent comprises the following steps:
mixing 1, 3-diaminopropane and cyclobut-3-ene diformic anhydride, introducing nitrogen, and performing nucleophilic addition-elimination reaction at 150-200 ℃ to generate imide; with LiAlH4Reducing carbonyl by a reducing agent at 0-35 ℃; adding sodium chloroacetate to perform quaternization reaction at 80-90 ℃;
adding an oxidant potassium permanganate into the quaternization reaction product, heating to 90-100 ℃ for oxidation reaction to generate carboxyl, and carrying out post-treatment to obtain a final product.
As a further improvement of the present invention, the molar ratio of 1, 3-diaminopropane to cyclobut-3-enedicarboxylic anhydride in the nucleophilic addition-elimination reaction is 1: 4.
As a further improvement of the invention, in the reduction reaction, LiAlH4The molar ratio of the 1, 3-diaminopropane to the water is 2-2.4: 1.
As a further improvement of the method, the molar ratio of the sodium chloroacetate to the 1, 3-diaminopropane in the quaternization reaction is 2-2.5: 1.
As a further improvement of the invention, in the oxidation reaction, the amount of the potassium permanganate substance is 2-4 times of the amount of the 1, 3-diaminopropane substance.
As a further improvement of the invention, in the oxidation reaction, after the quaternization reaction product is diluted, potassium permanganate is slowly added at 0 ℃, and then the temperature is raised for reaction.
As a further development of the invention, the post-treatment comprises:
and after the reaction is finished, adding sodium sulfite to remove excessive potassium permanganate, filtering by adopting diatomite and extracting impurities by adopting ethyl acetate, collecting a water phase, adjusting the pH value to be 2-4 to separate out a product, and filtering and drying to constant weight to obtain a final product.
Compared with the prior art, the invention has the following advantages:
the invention adopts 1, 3-diaminopropane and cyclobut-3-ene diformic anhydride to carry out a first nucleophilic addition-elimination reaction to generate imide, and then LiAlH is used4Reducing imide by a reducing agent, carrying out quaternization reaction by adopting sodium chloroacetate, adding potassium permanganate, and carrying out oxidation reaction to obtain a final product. The whole process is continuous, the steps are simple, and the cost is low.
The prepared hexacarboxyl chelating agent can be used as a carboxylic acid type chelating agent to be used in the fields of reducing and controlling the concentration of metal ions, daily chemical industry, textile and the like.
Drawings
FIG. 1 is a scheme showing the synthesis of the hexacarboxy chelating agent obtained in example 4.
Detailed Description
The invention relates to a hexacarboxyl chelating agent, the reaction equation of the preparation process is as follows:
according to the reaction mechanism, the invention adopts the following technical scheme:
a hexacarboxyl chelate having the structural formula:
as shown in fig. 1, the method for preparing the hexacarboxyl chelating agent comprises the following steps:
1) dropwise adding 1, 3-diaminopropane and cyclobut-3-ene dicarboxylic anhydride in sequence into a three-neck flask provided with a reflux condenser pipe, introducing nitrogen, reacting for 2-5 h at 150-200 ℃, and performing a first-step nucleophilic addition-elimination reaction to generate imide, wherein the molar ratio of the 1, 3-diaminopropane to the cyclobut-3-ene dicarboxylic anhydride is 1: 4; followed by LiAlH4Reduction of imide for reducing agent, in which LiAlH4The molar ratio of the 1, 3-diaminopropane to the 1, 3-diaminopropane is 2-2.4: 1, the reduction temperature is 0-35 ℃, and the reduction time is 4-6 hours; carrying out quaternization reaction on sodium chloroacetate, wherein the molar ratio of the sodium chloroacetate to the 1, 3-diaminopropane is 2-2.5: 1, the reaction temperature is 80-90 ℃, and the reaction time is 2-4 h.
2) Diluting the product, slowly adding potassium permanganate at 0 ℃, and heating to react for 10-12 h, wherein the amount of potassium permanganate is 2-4 times that of 1, 3-diaminopropane; and reducing excessive potassium permanganate by using sodium sulfite, dropwise adding dilute hydrochloric acid until the pH of the reaction solution is 2-4, separating out the product, and filtering and drying to constant weight to obtain the final product.
The technical solution in the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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
(1) 1, 3-diaminopropane (7.4g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (49.6g, 0.4mol) were added dropwise in this order to a 250mL three-necked flask equipped with a reflux condenser, nitrogen was introduced 3 times, and then the mixture was heated to 180 ℃ for reaction for 3 hours, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 120mL of tetrahydrofuran dried with sodium metal was charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 7.6g of LiAlH was slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 25 ℃ after the addition is finished to react for 4 h. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 7.6mLH under ice salt bath2O, 7.6mL 15% aqueous NaOH and 22.8mLH2O quenching excess LiAlH4. Filtration was carried out, and the filtrate and 23.3g of sodium chloroacetate were charged into a three-necked flask and reacted at 80 ℃ for 2 hours. The reaction solution is decompressed and concentrated, and an intermediate is obtained through column separation.
(3) Adding the product and 80mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(40g, the adding time is 40min), after all the components are added, slowly raising the temperature to 90 ℃ for reaction for 12 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 2 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure final product.
The product obtained in example 1 was obtained in 54% yield.
Example 2
(1) In a 250mL three-necked flask equipped with a reflux condenser, 7.4g, 0.1mol of 1, 3-diaminopropane and 49.6g, 0.4mol of cyclobutane-3-enedicarboxylic anhydride were sequentially dropped, and after 3 times of nitrogen introduction, the mixture was heated to 150 ℃ for 2 hours, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 135mL of tetrahydrofuran dried with sodium metal were charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 8.36g of LiAlH were slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 30 ℃ after the addition for reaction for 5 h. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 8.4mLH into the mixture under ice salt bath2O, 8.4mL 15% aqueous NaOH and 25.2mLH2O quenching excess LiAlH4After filtration, the filtrate and 25.63g of sodium chloroacetate were charged into a three-necked flask and reacted at 85 ℃ for 2.5 hours. The reaction solution is decompressed and concentrated, and an intermediate is obtained through column separation.
(3) Adding the product and 80mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(31.6g, the addition time is 40min), and after the addition is finished, the temperature is slowly raised to 100 ℃ for reaction for 10 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 3 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure final product.
The product obtained in example 2 is obtained in 59% yield.
Example 3
(1) 1, 3-diaminopropane (7.4g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (49.6g, 0.4mol) were added dropwise in this order to a 250mL three-necked flask equipped with a reflux condenser, nitrogen was introduced 3 times, and then the mixture was heated to 200 ℃ for 5 hours, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 150mL of tetrahydrofuran dried with sodium metal was charged into a 250mL three-necked flask, cooled to 0 ℃ using a cold salt bath, and 9.12g of LiAlH was slowly added in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 35 ℃ after the addition for reacting for 6 h. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 9.2mLH under ice salt bath2O, 9.2mL 15% aqueous NaOH and 27.6mLH2O quenching excess LiAlH4After filtration, the filtrate and 27.96g of sodium chloroacetate were charged in a three-necked flask and reacted at 90 ℃ for 3 hours. The reaction solution is decompressed and concentrated, and an intermediate is obtained through column separation.
(3) Adding the product and 80mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(50g, the adding time is 40min), and after the adding is finished, slowly raising the temperature to 90 ℃ for reaction for 12 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 4 by using dilute hydrochloric acid to precipitate solids, and filtering and drying to obtain a pure final product.
The product obtained in example 3 was obtained in 68% yield.
Example 4
(1) 1, 3-diaminopropane (7.4g, 0.1mol) and cyclobutane-3-enedicarboxylic anhydride (49.6g, 0.4mol) were added dropwise in this order to a 250mL three-necked flask equipped with a reflux condenser, nitrogen was introduced 3 times, and then the mixture was heated to 190 ℃ for 5 hours, and the completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to room temperature, adding 50mL of distilled water, extracting for 3 times by adopting 80mL of ethyl acetate, drying by anhydrous magnesium sulfate, filtering, concentrating under reduced pressure to obtain a crude product, and finally separating by a column to obtain colorless oily imide.
(2) 120mL of tetrahydrofuran dried with sodium metal was charged into a 250mL three-necked flask and cooled with an ice-salt bathTo 0 ℃ 9.5g of LiAlH are added slowly in portions4After stirring for 3min, slowly dropwise adding the imide dissolved in tetrahydrofuran into a three-neck flask, and raising the temperature to 25 ℃ after the addition is finished to react for 6 h. The completion of the reaction was monitored by TLC (Thin Layer Chromatography). After the reaction is finished, cooling to 0 ℃, and sequentially adding 9.5mLH into the mixture under ice salt bath2O, 9.5mL 15% aqueous NaOH and 28.5mLH2O quenching excess LiAlH4After filtration, the filtrate and 29.13g of sodium chloroacetate were charged into a three-necked flask and reacted at 85 ℃ for 3 hours. The reaction solution is decompressed and concentrated, and an intermediate is obtained through column separation.
(3) Adding the product and 80mL of distilled water into a 250mL three-neck flask, placing the three-neck flask in an ice salt bath, cooling to 0 ℃, and slowly adding potassium permanganate KMnO4(63.2g, the addition time is 40min), after the addition is finished, the temperature is slowly raised to 100 ℃ for reaction for 10 h. Excess KMnO was quenched by adding 80mL of saturated aqueous sodium sulfite solution to a three-necked flask4(ii) a After the purple color is faded, slowly cooling and filtering MnO generated in the reaction by diatomite while the MnO is hot2Obtaining clear filtrate; then extracting the filtrate for 3 times by using ethyl acetate to remove impurities, collecting a water phase, adjusting the pH value of the water phase to 2 by using dilute hydrochloric acid to precipitate a solid, and filtering and drying to obtain a pure final product.
The yield of the product obtained in example 4 was 65%.
In order to characterize the structural characteristics of a hexacarboxy chelating agent, nuclear magnetic hydrogen spectroscopy was performed on the hexacarboxy chelating agent synthesized in example 4, with the following results:
1H NMR(300MHz,DMSO):13.03-12.13(m,6H),3.30(s,4H),2.78(t,J=7.2Hz,4H),2.34-2.06(m,12H),1.56(m,2H)ppm。
the foregoing is a more detailed description of the invention and it is not intended that the invention be limited to the specific embodiments described herein, but that various modifications, alterations, and substitutions may be made by those skilled in the art without departing from the spirit of the invention, which should be construed to fall within the scope of the invention as defined by the appended claims.
Claims (8)
2. the preparation method of the hexacarboxyl chelating agent is characterized by comprising the following steps:
mixing 1, 3-diaminopropane and cyclobut-3-ene diformic anhydride, introducing nitrogen, and performing nucleophilic addition-elimination reaction at 150-200 ℃ to generate imide; with LiAlH4Reducing carbonyl by a reducing agent at 0-35 ℃; adding sodium chloroacetate to perform quaternization reaction at 80-90 ℃;
adding an oxidant potassium permanganate into the quaternization reaction product, heating to 90-100 ℃ for oxidation reaction to generate carboxyl, and carrying out post-treatment to obtain a final product.
3. The production method according to claim 2, wherein the molar ratio of 1, 3-diaminopropane to cyclobut-3-enedicarboxylic anhydride in the nucleophilic addition-elimination reaction is 1: 4.
4. The method according to claim 2, wherein LiAlH is added to the reaction mixture in the reduction reaction4The molar ratio of the 1, 3-diaminopropane to the water is 2-2.4: 1.
5. The method according to claim 2, wherein the molar ratio of sodium chloroacetate to 1, 3-diaminopropane in the quaternization reaction is 2 to 2.5: 1.
6. The method according to claim 2, wherein the amount of potassium permanganate is 2 to 4 times the amount of 1, 3-diaminopropane in the oxidation reaction.
7. The preparation method according to claim 2, wherein in the oxidation reaction, after the quaternization reaction product is diluted, potassium permanganate is slowly added at 0 ℃, and then the temperature is raised for reaction.
8. The method of manufacturing according to claim 2, wherein the post-treatment comprises:
and after the reaction is finished, adding sodium sulfite to remove excessive potassium permanganate, filtering by adopting diatomite and extracting impurities by adopting ethyl acetate, collecting a water phase, adjusting the pH value to be 2-4 to separate out a product, and filtering and drying to constant weight to obtain a final product.
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101070024A (en) * | 2006-05-08 | 2007-11-14 | 株式会社理光 | Reversible thermosensitive coloring material and reversible thermosensitive recording material using the reversible thermosensitive coloring material |
CN103242216A (en) * | 2013-05-07 | 2013-08-14 | 兰州梦唐精细化工有限公司 | Synthesis method of N-Boc-hexahydro-5-oxo-cyclopenta (C) pyrrole |
-
2020
- 2020-09-22 CN CN202011003300.7A patent/CN111995559A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101070024A (en) * | 2006-05-08 | 2007-11-14 | 株式会社理光 | Reversible thermosensitive coloring material and reversible thermosensitive recording material using the reversible thermosensitive coloring material |
CN103242216A (en) * | 2013-05-07 | 2013-08-14 | 兰州梦唐精细化工有限公司 | Synthesis method of N-Boc-hexahydro-5-oxo-cyclopenta (C) pyrrole |
Non-Patent Citations (4)
Title |
---|
M. S. RAASCH ET AL.: "2,2-DIFLUOROSUCCINIC ACID", 《ORGANIC SYNTHESES》 * |
TAKU KITANOSONO ET AL.: "Toward Chemistry-Based Design of the Simplest Metalloenzyme-Like Catalyst That Works Efficiently in Water", 《CHEM. ASIAN J.》 * |
YUBIN ZHAO ET AL.: "Study on tunable crosslinking anion exchange membranes fabrication and degradation mechanism", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
岳红等: "《高等有机化学》", 31 October 2002, 机械工业出版社 * |
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