Synthesis method of N-(2-oxopropyl)-bis (3-pyridine methylene) carbonyl dihydrazone

Abstract

The invention discloses a synthetic method of N-(2-oxopropyl)-bis (3-pyridine methylene) carbonyl dihydrazone. The structural formula of the N-(2-oxopropyl)-bis (3-pyridine methylene) carbonyl dihydrazone is shown in the According to the invention, N-(2-oxopropyl)-bis (3-pyridylmethylene) carbonyl dihydrazone is synthesized through a reaction of carbonyl dihydrazone, pyridine-3-formaldehyde and 1-chloroacetone, and then N-(2-oxopropyl)-bis (3-pyridylmethylene) carbonyl dihydrazone is synthesized. The synthesis method disclosed by the invention has the advantages of high yield, simple process route, low cost, good product quality, easiness in large-scale production and the like, and is worthy of popularization and application.

Description

Technical Field

[0001] The invention relates to the field of chemical engineering, and in particular to a method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone. Background Art

[0002] N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone, also known as nicotinaldehydehydrazone, has the following structure: N-(2-oxopropyl)-N'-(pyridin-3-ylmethylene)-2-(pyridin-3-ylmethylene)hydrazine-1-carbohydrazide, with a relative molecular weight of 308.24:

[0003] Nicotinaldehyde hydrazone is an important new compound with stable properties, high melting point (245-246℃), low volatility, and activity against pathogenic fungi. It is widely used in the fields of medicine and pesticides. At the same time, it is also a key intermediate for high-end cosmetics. The development of its industrial production method is of great significance. At present, there is limited research on the synthesis method of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone at home and abroad.

[0004] The purpose of the present invention is to provide a method for synthesizing a compound N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone, so as to provide a new idea for the industrial production of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone. The method synthesizes N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone by reacting carbonyldihydrazine, pyridine-3-carboxaldehyde and 1-chloroacetone, and the method is suitable for industrial production.

[0006] The purpose of the present invention can be achieved through the following technical solutions: A N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone, the preparation of which comprises the following steps: Step S1, adding carbohydrazide to a pyridine-3-carboxaldehyde aqueous solution, stirring and reacting at 30-40° C. until a large amount of white solid precipitates, stirring and reacting at 30-50° C. for 2-4 hours, filtering, washing with water, and drying to obtain carbohydrazone; Further, the dosage ratio of carbohydrazide and pyridine-3-carboxaldehyde aqueous solution is 50-55 g: 630-635 g, and the mass fraction of pyridine-3-carboxaldehyde aqueous solution is 18%; Step S2, adding carbonylhydrazone and a catalyst to a solvent under stirring, heating to 35-45° C., adding 1-chloroacetone dropwise within 1-2 hours, then adding a dechlorinating agent, stirring for 2-2.5 hours, filtering, washing with water, filter pressing and drying to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone; Furthermore, the dosage ratio of carbonylhydrazone, catalyst, solvent, 1-chloroacetone and dechlorinating agent is 135-145g: 1-1.2g: 500-550mL: 55-60g: 50-52g; the catalyst is selected from tetrabutylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium chloride, polyethylene glycol and cyclic crown ethers; the solvent is selected from toluene, acetonitrile and DMF; the dechlorinating agent is selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate and potassium bicarbonate; The synthetic route of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone is as follows:

[0007] Beneficial effects of the invention: The invention discloses a method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone. N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone is a brand-new compound that has not been reported in the world. The pure product is a white powdery solid with a melting point of 245-246°C. It is slightly soluble in organic solvents such as water, ethanol, and dichloromethane, and is easily soluble in DMF and dimethyl sulfoxide. The compound is an important new material and is widely used in the fields of medicine and pesticides. At the same time, it is also a key intermediate for high-end cosmetics and has important industrial production value. The N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone is prepared from readily available raw materials such as carbonyldihydrazine, pyridine-3-carboxaldehyde, and 1-chloroacetone through two simple reactions. The synthesis method has the advantages of high yield, simple process route, low cost, good product quality, and easy large-scale production, and is worthy of promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0009] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone prepared in Example 4. DETAILED DESCRIPTION

[0010] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0011] Example 1 Step S1, add 630g of 18% pyridine-3-carboxaldehyde aqueous solution into a 1000mL reaction bottle, start stirring, add 50g of carbohydrazide, control the temperature to 35°C, and precipitate a large amount of white solid as the reaction proceeds. Stir the reaction at 40°C for 2h, filter, wash with water, and dry to obtain carbohydrazone with a content of 99% and a yield of 90%; Step S2, add 500 mL of acetonitrile to a 1000 mL reaction bottle, add 135 g of the carbonyl hydrazone and 1 g of tetrabutylammonium bromide under stirring, heat to 45 ° C, add 55 g of 1-chloroacetone dropwise and complete the addition within 1 hour, then add 50 g of sodium hydroxide, stir and react for 2 hours, filter, wash with water, filter press and dry to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyl dihydrazone, with a content of 99% and a yield of 95%.

[0012] Example 2 Step S1, add 630g of 18% mass fraction pyridine-3-carboxaldehyde aqueous solution into a 1000mL reaction bottle, start stirring, add 50g of carbohydrazide, control the temperature to 30°C, and precipitate a large amount of white solid as the reaction proceeds. Stir the reaction at 35°C for 2.5h, filter, wash with water, and dry to obtain carbohydrazone with a content of 99% and a yield of 96%; Step S2, add 500 mL of DMF to a 1000 mL reaction bottle, add 135 g of the carbonyl hydrazone and 1 g of polyethylene glycol under stirring, heat to 40° C., add 60 g of 1-chloroacetone dropwise within 1.5 h, then add 50 g of sodium hydroxide, stir and react for 2.2 h, filter, wash with water, filter press and dry to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone, with a content of 98% and a yield of 92%.

[0013] Example 3 Step S1, add 630g of 18% pyridine-3-carboxaldehyde aqueous solution into a 1000mL reaction bottle, start stirring, add 50g of carbohydrazide, control the temperature to 30°C, and precipitate a large amount of white solid as the reaction proceeds. Stir the reaction at 40°C for 2.6h, filter, wash with water, and dry to obtain carbohydrazone with a content of 99% and a yield of 92.5%; Step S2, add 500 mL of DMF to a 1000 mL reaction bottle, add 135 g of the carbonyl hydrazone and 1 g of 18-crown ether-6 under stirring, heat to 45 ° C, add 60 g of 1-chloroacetone dropwise and complete the addition within 1.6 hours, then add 50 g of sodium bicarbonate, stir and react for 2.3 hours, filter, wash with water, filter press and dry to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyl dihydrazone, with a content of 98% and a yield of 93%.

[0014] Example 4 Step S1, add 630g of 18% mass fraction pyridine-3-carboxaldehyde aqueous solution into a 1000mL reaction bottle, start stirring, add 55g of carbohydrazide, control the temperature to 35°C, and precipitate a large amount of white solid as the reaction proceeds. Stir the reaction at 40°C for 2.6h, filter, wash with water, and dry to obtain carbohydrazone with a content of 99% and a yield of 97%; Step S2, add 500 mL of acetonitrile to a 1000 mL reaction bottle, add 135 g of the carbonyl hydrazone and 1 g of tetrabutylammonium bromide under stirring, heat to 40 ° C, add 55 g of 1-chloroacetone dropwise and complete the addition within 1.5 hours, then add 50 g of potassium bicarbonate, stir and react for 2.7 hours, filter, wash with water, filter press and dry to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyl dihydrazone, with a content of 99% and a yield of 96%.

[0015] The applicant declares that the present invention uses the above-mentioned embodiment to illustrate a N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone of the present invention, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone, characterized in that: The steps include: Step S1, adding carbohydrazide to a pyridine-3-carboxaldehyde solution, while controlling the temperature and other conditions, to react to obtain carbohydrazone; Step S2, adding carbonyl hydrazone, a catalyst, and a dechlorinating agent into a solvent, and adding 1-chloroacetone dropwise to react at a certain reaction temperature to obtain nicotinaldehyde hydrazone.

2. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: The synthesis route of the N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone is as follows: 。 3. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: In step S1, the usage ratio of carbohydrazide and pyridine-3-carboxaldehyde aqueous solution is 50-55 g:630-635 g, and the mass fraction of pyridine-3-carboxaldehyde aqueous solution is 18%.

4. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: In step S1, the reaction temperature is controlled to be 30-40°C before a large amount of white solid is precipitated.

5. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: In step S1, the reaction temperature is controlled to be 30-50°C after a large amount of white solid is precipitated.

6. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: In step S2, the usage ratio of carbonylhydrazone, catalyst, solvent, 1-chloroacetone and dechlorinating agent is 135-145 g: 1-1.2 g: 500-550 mL: 55-60 g: 50-52 g.

7. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: In step S2, the catalyst is selected from one of tetrabutylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium chloride, polyethylene glycol, and cyclic crown ethers.

8. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: In step S2, the solvent is selected from one of toluene, acetonitrile and DMF.

9. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: In step S2, the dechlorinating agent is selected from one of sodium hydroxide, potassium hydroxide, sodium bicarbonate and potassium bicarbonate.

10. The method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone according to claim 1, characterized in that: In step S2, the reaction temperature is controlled at 35-45°C.

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