CN113754582A - Preparation method of amorphous diacetyl mono (2-pyridine) hydrazone - Google Patents
Preparation method of amorphous diacetyl mono (2-pyridine) hydrazone Download PDFInfo
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- CN113754582A CN113754582A CN202111216123.5A CN202111216123A CN113754582A CN 113754582 A CN113754582 A CN 113754582A CN 202111216123 A CN202111216123 A CN 202111216123A CN 113754582 A CN113754582 A CN 113754582A
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- aqueous solution
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
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Abstract
The invention belongs to the technical field of chemical reagent preparation, and particularly relates to a preparation method of amorphous diacetyl mono (2-pyridine) hydrazone. The method comprises the following steps: (1) dissolving 2-hydrazinopyridine hydrochloride in water to obtain a 2-hydrazinopyridine hydrochloride aqueous solution; (2) dissolving butanedione in water to obtain butanedione aqueous solution; (3) pumping the 2-hydrazinopyridine hydrochloride aqueous solution obtained in the step (1) and the butanedione aqueous solution obtained in the step (2) into a microchannel reactor for reaction, collecting a reaction solution containing yellow precipitates, cooling to 10 ℃, and then aging, filtering and drying to obtain the amorphous diacetyl mono (2-pyridine) hydrazone. The invention adopts the 2-hydrazinopyridine hydrochloride which has easily obtained raw materials and low price, is easy to dissolve in water, takes the water as a reaction system, has mild reaction conditions, improves the reaction selectivity, reduces the dosage of the 2-hydrazinopyridine hydrochloride, avoids impurities generated by side reactions, and improves the yield and the purity of the product.
Description
Technical Field
The invention belongs to the technical field of chemical reagent preparation, and particularly relates to a preparation method of amorphous diacetyl mono (2-pyridine) hydrazone.
Background
Diacetyl mono (2-pyridine) hydrazone) with CAS number 74158-10-4 can be used as inorganic ion color developer. However, in the prior art, few research reports on the preparation of diacetyl mono (2-pyridine) hydrazone are reported, 2-hydrazinopyridine and diacetyl are adopted to react in a traditional solvent-water system, a buffer solution is required to be added to control the pH condition, the reaction condition is difficult to control, and the production yield is low due to the generation of a large amount of diacetyl bis (2-pyridine) hydrazone byproducts, which is always an urgent problem to be solved in the field of preparation of diacetyl mono (2-pyridine) hydrazone.
In view of the above, the invention provides a preparation method of amorphous diacetyl mono (2-pyridine) hydrazone, which has the advantages of mild reaction conditions, high reaction selectivity, high yield and high product purity.
Disclosure of Invention
In order to solve the problems of low reaction yield, more reaction side reactions and easy pollution in the preparation process of diacetyl mono (2-pyridine) hydrazone in the prior art, the invention provides the preparation method of the diacetyl mono (2-pyridine) hydrazone with mild reaction conditions, high reaction selectivity, high yield and high product purity, a microchannel reactor is adopted, water is taken as a reaction system, and the high-purity diacetyl mono (2-pyridine) hydrazone product can be generated at low temperature, so that the preparation method is green and efficient.
The invention aims to provide a preparation method of amorphous diacetyl mono (2-pyridine) hydrazone, which comprises the following steps:
(1) dissolving 2-hydrazinopyridine hydrochloride in water to obtain a 2-hydrazinopyridine hydrochloride aqueous solution; 2-hydrazinopyridine hydrochloride which is stable and low in price is adopted to replace 2-hydrazinopyridine, the 2-hydrazinopyridine hydrochloride is easy to dissolve in water, water is adopted as a reaction system, toxic and harmful wastes generated by an organic solvent are avoided, and the method is green and pollution-free;
(2) dissolving butanedione in water to obtain butanedione aqueous solution;
(3) pumping the 2-hydrazinopyridine hydrochloride aqueous solution obtained in the step (1) and the butanedione aqueous solution obtained in the step (2) into a microchannel reactor for reaction, collecting a reaction solution containing yellow precipitates, cooling to 10 ℃, and then aging, filtering and drying to obtain the amorphous diacetyl mono (2-pyridine) hydrazone.
Further, the molar concentration of the 2-hydrazinopyridine hydrochloride aqueous solution in the step (1) is 2.5-3.5 mol/L.
Further, the molar concentration of the butanedione aqueous solution in the step (2) is 3.5-5.5 mol/L.
Preferably, the 2-hydrazinopyridine hydrochloride aqueous solution and the butanedione aqueous solution in the step (3) are used in a molar ratio of the 2-hydrazinopyridine hydrochloride to the butanedione of 1 (1.05-1.15). Compared with the prior art, the method reduces the using amount of the 2-hydrazinopyridine hydrochloride, avoids the phenomenon that the rapidly generated product diacetyl mono (2-pyridine) hydrazone (which has high generation rate and poor solubility) can sandwich the raw material 2-hydrazinopyridine hydrochloride, further avoids the generation of impurity diacetyl bis (2-pyridine) hydrazone by the further reaction of the diacetyl mono (2-pyridine) hydrazone and improves the yield and the purity of the product.
Preferably, the temperature of the reaction in step (3) is 35-40 ℃ and the reaction time is 15 seconds. The method has low reaction temperature, avoids generating byproducts, and is also favorable for improving the yield and the purity of the product.
Preferably, the aging time in step (3) is 15-20 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts the 2-hydrazinopyridine hydrochloride which has easily obtained and low price as raw material and is easy to dissolve in water to react with the butanedione aqueous solution in a water reaction system, replaces the traditional solvent-water system, avoids using buffer solution, has low reaction temperature, avoids generating byproducts easily at high temperature, improves reaction selectivity and saves energy.
(2) Compared with the prior art, the method reduces the using amount of the 2-hydrazinopyridine hydrochloride, avoids the phenomenon that the rapidly generated product diacetyl mono (2-pyridine) hydrazone (which has high generation rate and poor solubility) can sandwich the raw material 2-hydrazinopyridine hydrochloride, further avoids the reaction of the diacetyl di (2-pyridine) hydrazone and improves the yield (more than 90%) and the purity (more than 97%) of the product.
Detailed Description
The technical solutions in the embodiments of the present invention are 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. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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
A method for preparing amorphous diacetyl mono (2-pyridine) hydrazone comprises the following steps:
(1) dissolving 36.5g (0.2mol) of 2-hydrazinopyridine hydrochloride in 60mL of pure water at room temperature to obtain an aqueous solution of 2-hydrazinopyridine hydrochloride;
(2) dissolving 19.0g (0.22mol) of butanedione in 60mL of pure water at room temperature to obtain a butanedione aqueous solution;
(3) and (2) adjusting the temperature of the microchannel reactor to 35 ℃, pumping 60mL of the 2-hydrazinopyridine hydrochloride aqueous solution obtained in the step (1) and 60mL of the butanedione aqueous solution obtained in the step (2) into the microchannel reactor for reacting for 15 seconds, collecting a reaction solution containing yellow precipitates after the reaction is finished, cooling to 10 ℃, then aging for 15-20min, filtering, and drying to obtain 32.8g of a product.
By HPLC analysis, the content of amorphous diacetyl mono (2-pyridine) hydrazone in the product is 97.5%, the yield is 90.2%, and the content of diacetyl bis (2-pyridine) hydrazone is less than 0.2%.
Example 2
A method for preparing amorphous diacetyl mono (2-pyridine) hydrazone comprises the following steps:
(1) dissolving 36.5g (0.2mol) of 2-hydrazinopyridine hydrochloride in 70mL of pure water at room temperature to obtain an aqueous solution of 2-hydrazinopyridine hydrochloride;
(2) dissolving 19.85g (0.23mol) of butanedione in 50mL of pure water at room temperature to obtain a butanedione aqueous solution;
(3) and (2) adjusting the temperature of the microchannel reactor to 35 ℃, pumping 70mL of the 2-hydrazinopyridine hydrochloride aqueous solution obtained in the step (1) and 50mL of the butanedione aqueous solution obtained in the step (2) into the microchannel reactor for reacting for 15 seconds, collecting a reaction solution containing yellow precipitates after the reaction is finished, cooling to 10 ℃, then aging for 15-20min, filtering, and drying to obtain 33.2g of a product.
By HPLC analysis, the content of amorphous diacetyl mono (2-pyridine) hydrazone in the product is 97.3%, the yield is 91.1%, and the content of diacetyl bis (2-pyridine) hydrazone is less than 0.2%.
Example 3
A method for preparing amorphous diacetyl mono (2-pyridine) hydrazone comprises the following steps:
(1) dissolving 36.5g (0.2mol) of 2-hydrazinopyridine hydrochloride in 75mL of pure water at room temperature to obtain an aqueous solution of 2-hydrazinopyridine hydrochloride;
(2) dissolving 18.1g (0.21mol) of butanedione in 40mL of pure water at room temperature to obtain a butanedione aqueous solution;
(3) and (2) adjusting the temperature of the microchannel reactor to 40 ℃, pumping 75mL of the 2-hydrazinopyridine hydrochloride aqueous solution obtained in the step (1) and 40mL of the butanedione aqueous solution obtained in the step (2) into the microchannel reactor for reacting for 15 seconds, collecting a reaction solution containing yellow precipitates after the reaction is finished, cooling to 10 ℃, then aging for 15-20min, filtering, and drying to obtain 32.4g of a product.
By HPLC analysis, the content of amorphous diacetyl mono (2-pyridine) hydrazone in the product is 98.5%, the yield is 90.0%, and the content of diacetyl bis (2-pyridine) hydrazone is less than 0.2%.
Example 4
A method for preparing amorphous diacetyl mono (2-pyridine) hydrazone comprises the following steps:
(1) dissolving 36.5g (0.2mol) of 2-hydrazinopyridine hydrochloride in 80mL of pure water at room temperature to obtain an aqueous solution of 2-hydrazinopyridine hydrochloride;
(2) dissolving 18.5g (0.215mol) of butanedione in 40mL of pure water at room temperature to obtain a butanedione aqueous solution;
(3) and (2) adjusting the temperature of the microchannel reactor to 37 ℃, pumping 80mL of the 2-hydrazinopyridine hydrochloride aqueous solution obtained in the step (1) and 40mL of the butanedione aqueous solution obtained in the step (2) into the microchannel reactor for reacting for 15 seconds, collecting a reaction solution containing yellow precipitates after the reaction is finished, cooling to 10 ℃, then aging for 15-20min, filtering, and drying to obtain 32.6g of a product.
By HPLC analysis, the content of amorphous diacetyl mono (2-pyridine) hydrazone in the product is 98.2%, the yield is 90.3%, and the content of diacetyl bis (2-pyridine) hydrazone is less than 0.2%.
Example 5
A method for preparing amorphous diacetyl mono (2-pyridine) hydrazone comprises the following steps:
(1) dissolving 36.5g (0.2mol) of 2-hydrazinopyridine hydrochloride in 60mL of pure water at room temperature to obtain an aqueous solution of 2-hydrazinopyridine hydrochloride;
(2) dissolving 18.9g (0.22mol) of butanedione in 60mL of pure water at room temperature to obtain a butanedione aqueous solution;
(3) and (2) adjusting the temperature of the microchannel reactor to 40 ℃, pumping 60mL of the 2-hydrazinopyridine hydrochloride aqueous solution obtained in the step (1) and 60mL of the butanedione aqueous solution obtained in the step (2) into the microchannel reactor for reacting for 15 seconds, collecting a reaction solution containing yellow precipitates after the reaction is finished, cooling to 10 ℃, then aging for 15-20min, filtering, and drying to obtain 33.0g of a product.
By HPLC analysis, the content of amorphous diacetyl mono (2-pyridine) hydrazone in the product is 97.8%, the yield is 91.1%, and the content of diacetyl bis (2-pyridine) hydrazone is less than 0.2%.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of amorphous diacetyl mono (2-pyridine) hydrazone is characterized by comprising the following steps:
(1) dissolving 2-hydrazinopyridine hydrochloride in water to obtain a 2-hydrazinopyridine hydrochloride aqueous solution;
(2) dissolving butanedione in water to obtain butanedione aqueous solution;
(3) pumping the 2-hydrazinopyridine hydrochloride aqueous solution obtained in the step (1) and the butanedione aqueous solution obtained in the step (2) into a microchannel reactor for reaction, collecting a reaction solution containing yellow precipitates, cooling to 10 ℃, and then aging, filtering and drying to obtain the amorphous diacetyl mono (2-pyridine) hydrazone.
2. The method for preparing amorphous diacetyl mono (2-pyridine) hydrazone according to claim 1, wherein the molar concentration of the 2-hydrazinopyridine hydrochloride in the aqueous solution in the step (1) is 2.5 to 3.5 mol/L.
3. The method of claim 1, wherein the molar concentration of the aqueous solution of butanedione in step (2) is 3.5-5.5 mol/L.
4. The method for preparing amorphous diacetyl mono (2-pyridine) hydrazone according to claim 1, wherein the 2-hydrazinopyridine hydrochloride aqueous solution and the butanedione aqueous solution are used in step (3) in a molar ratio of 2-hydrazinopyridine hydrochloride to butanedione of 1 (1.05-1.15).
5. The method for preparing amorphous diacetyl mono (2-pyridine) hydrazone according to claim 1, wherein the temperature of the reaction in step (3) is 35-40 ℃ and the reaction time is 15 seconds.
6. The method for preparing an amorphous diacetyl mono (2-pyridine) hydrazone according to claim 1, wherein the aging time in step (3) is 15-20 min.
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| US20190292371A1 (en) * | 2018-03-21 | 2019-09-26 | Ecole Polytechnique Federale De Lausanne (Epfl) | Azacyanine dyes and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20190292371A1 (en) * | 2018-03-21 | 2019-09-26 | Ecole Polytechnique Federale De Lausanne (Epfl) | Azacyanine dyes and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| M. M. RODRIGUEZ ET AL.: "Studies on Pyridylhydrazones Derived from Biacetyl as Analytical Reagents", 《MICROCHEMICAL JOURNAL》, vol. 25, pages 309 - 322 * |
| SUDATH HAPUARACHCHIGE ET AL.: "Design and Synthesis of a New Class of Membrane-Permeable Triazaborolopyridinium Fluorescent Probes", 《J. AM. CHEM. SOC.》, vol. 2019, pages 6780 - 6790 * |
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