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

Abstract

The invention discloses a synthesis method of N-(2-oxopropyl)-bis (3-pyridine methylene) carbonyl dihydrazone, and relates to the field of chemical engineering. 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 present invention relates to the field of chemical engineering, and particularly relates to a method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide. Background Art

[0002] N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide, abbreviated as nicotinaldehyde hydrazone, English name: N-(2-oxopropyl)-N'-(pyridin-3-ylmethylene)-2-(pyridin-3-ylmethylene)hydrazine-1-carbohydrazide, relative molecular weight 308.24, and the structural formula is as follows:

[0003]

[0004] Nicotinaldehyde hydrazone is an important novel compound with stable properties, a relatively high melting point (245 - 246 °C), 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-grade cosmetics. Developing its industrial production method is of great significance. Currently, the research on the synthesis method of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide at home and abroad is limited.

[0005] The purpose of the present invention is to provide a method for synthesizing the compound N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide, so as to provide new ideas for the industrial production of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide. Summary of the Invention

[0006] In order to solve the above technical problems, the present invention provides a method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide. This method synthesizes N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide through the reaction of carbohydrazide, pyridine-3-carboxaldehyde, and 1-chloroacetone, and is suitable for industrial production.

[0007] The purpose of the present invention can be achieved through the following technical solutions:

[0008] A method for preparing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide includes the following steps:

[0009] Step S1: Add carbohydrazide to an aqueous solution of pyridine-3-carboxaldehyde, stir and react at 30 - 40 °C until a large amount of white solid precipitates, then stir and react at 30 - 50 °C for 2 - 4 h, filter by suction, wash with water, and dry to obtain carbohydrazone;

[0010] Further, the mass ratio of carbohydrazide to 3-pyridinecarboxaldehyde aqueous solution is (50 - 55):(630 - 635).

[0011] Further, the mass fraction of 3-pyridinecarboxaldehyde aqueous solution is 18%.

[0012] Step S2: Under stirring, add carbohydrazone and a catalyst into a solvent, heat up to 35 - 45 °C, dropwise add 1-chloroacetone and finish the dropping within 1 - 2 h, then add a dechlorinating agent, stir and react for 2 - 2.5 h, carry out suction filtration, washing with water, pressure filtration and drying to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide.

[0013] Further, the dosage ratio of carbohydrazone, catalyst, solvent, 1-chloroacetone, and dechlorinating agent is (135 - 145) g:(1 - 1.2) g:(500 - 550) mL:(55 - 60) g:(50 - 52) g.

[0014] Further, the catalyst is selected from one of tetrabutylammonium bromide, benzyltriethylammonium chloride, polyethylene glycol, and cyclic crown ethers.

[0015] Further, the solvent is selected from one of toluene, acetonitrile, and DMF.

[0016] Further, the dechlorinating agent is selected from one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate.

[0017] Further, the synthetic route of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide is as follows:

[0018]

[0019] Beneficial effects of the present invention: The present invention discloses a method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide. N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide is a completely new compound not reported globally. The pure product is a white powdery solid, with a melting point of 245 - 246 °C, slightly soluble in organic solvents such as water, ethanol, and dichloromethane, and easily soluble in DMF and dimethyl sulfoxide. This 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-grade cosmetics, having important industrial production value. The N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide provided by the present invention is prepared from easily available raw materials such as carbohydrazide, 3-pyridinecarboxaldehyde, and 1-chloroacetone through two simple reactions. This synthetic method has the advantages of high yield, simple process route, low cost, good product quality, and easy large-scale production, and is worthy of popularization and use. Description of the Drawings

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0021] Figure 1 1H NMR spectrum of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide prepared in Example 4. Detailed implementation manners

[0022] The following will clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0023] Example 1

[0024] Step S1: Add 630 g of an aqueous solution of pyridine-3-carboxaldehyde with a mass fraction of 18% to a 1000 mL reaction flask, start stirring, add 50 g of carbohydrazide, control the temperature at 35°C. As the reaction proceeds, a large amount of white solid precipitates. Stir the reaction at 40°C for 2 h, filter by suction, wash with water, and dry to obtain carbohydrazone with a content of 99% and a yield of 90%;

[0025] Step S2: Add 500 mL of acetonitrile to a 1000 mL reaction flask. Under stirring, add 135 g of the carbohydrazone and 1 g of tetrabutylammonium bromide, heat up to 45°C, dropwise add 55 g of 1-chloroacetone within 1 h, then add 50 g of sodium hydroxide, stir the reaction for 2 h, filter by suction, wash with water, filter under pressure, and dry to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide with a content of 99% and a yield of 95%.

[0026] Example 2

[0027] Step S1: Add 630 g of an aqueous solution of pyridine-3-carboxaldehyde with a mass fraction of 18% to a 1000 mL reaction flask, start stirring, add 50 g of carbohydrazide, control the temperature at 30°C. As the reaction proceeds, a large amount of white solid precipitates. Stir the reaction at 35°C for 2.5 h, filter by suction, wash with water, and dry to obtain carbohydrazone with a content of 99% and a yield of 96%;

[0028] Step S2: Add 500 mL of DMF into a 1000 mL reaction flask. While stirring, add 135 g of carbohydrazone and 1 g of polyethylene glycol. Heat up to 40 °C, dropwise add 60 g of 1-chloroacetone within 1.5 h, then add 50 g of sodium hydroxide, stir and react for 2.2 h, filter by suction, wash with water, filter under pressure and dry to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide, with a content of 98% and a yield of 92%.

[0029] Example 3

[0030] Step S1: Add 630 g of an aqueous solution of pyridine-3-carbaldehyde with a mass fraction of 18% into a 1000 mL reaction flask. Start stirring, add 50 g of carbohydrazide, control the temperature at 30 °C. As the reaction proceeds, a large amount of white solid precipitates. Stir and react at 40 °C for 2.6 h, filter by suction, wash with water, and dry to obtain carbohydrazone, with a content of 99% and a yield of 92.5%.

[0031] Step S2: Add 500 mL of DMF into a 1000 mL reaction flask. While stirring, add 135 g of carbohydrazone and 1 g of 18-crown-6. Heat up to 45 °C, dropwise add 60 g of 1-chloroacetone within 1.6 h, then add 50 g of sodium bicarbonate, stir and react for 2.3 h, filter by suction, wash with water, filter under pressure and dry to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide, with a content of 98% and a yield of 93%.

[0032] Example 4

[0033] Step S1: Add 630 g of an aqueous solution of pyridine-3-carbaldehyde with a mass fraction of 18% into a 1000 mL reaction flask. Start stirring, add 55 g of carbohydrazide, control the temperature at 35 °C. As the reaction proceeds, a large amount of white solid precipitates. Stir and react at 40 °C for 2.6 h, filter by suction, wash with water, and dry to obtain carbohydrazone, with a content of 99% and a yield of 97%.

[0034] Step S2: Add 500 mL of acetonitrile into a 1000 mL reaction flask. While stirring, add 135 g of carbohydrazone and 1 g of tetrabutylammonium bromide. Heat up to 40 °C, dropwise add 55 g of 1-chloroacetone within 1.5 h, then add 50 g of potassium bicarbonate, stir and react for 2.7 h, filter by suction, wash with water, filter under pressure and dry to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide, with a content of 99% and a yield of 96%.

[0035] The applicant declares that the present invention illustrates a kind of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide of the present invention through the above embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must rely on the above detailed methods to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide, characterized in that: It includes the following steps: Step S1: Add carbohydrazide into the pyridine-3-carboxaldehyde solution, and at the same time control the temperature condition to react to obtain carbohydrazone; Step S2: Add carbohydrazone, catalyst, and dechlorinating agent into the solvent, and dropwise add 1-chloroacetone to react at a certain reaction temperature to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide.

2. The synthesis method of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide according to claim 1, characterized in that: The synthetic route of the said N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide is as follows: 。 3. The synthesis method of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide according to claim 1, characterized in that: In the said step S1, the mass ratio of carbohydrazide to the aqueous solution of pyridine-3-carboxaldehyde is (50 - 55):(630 - 635).

4. The synthesis method of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide according to claim 1, characterized in that: In the said step S1, the mass fraction of the aqueous solution of pyridine-3-carboxaldehyde is 18%.

5. A method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide according to claim 4, characterized in that: In the said step S1, control the temperature condition: Stir and react at 30 - 40 °C until a large amount of white solid precipitates, and then stir and react at 30 - 50 °C for 2 - 4 h.

6. The synthesis method of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide according to claim 1, characterized in that: In the said step S2, the dosage ratio of carbohydrazone, 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. A method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbohydrazide according to claim 1, characterized in that: In the said step S2, the catalyst is selected from one of tetrabutylammonium bromide, benzyltriethylammonium chloride, polyglycol, cyclic crown ethers, etc.

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

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

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

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