A method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone

Abstract

This invention discloses a method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone. This method synthesizes N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone by reacting carbohydrazide, pyridine-3-carboxaldehyde, and 1-chloroacetone. This method has the advantages of high yield, simple process, low cost, good product quality, and ease of large-scale production, making it worthy of widespread use.

Description

Technical Field

[0001] The present 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 nicotinaldehyde hydrazone, has an English name: N-(2-oxopropyl)-N'-(pyridin-3-ylmethylene)-2-(pyridin-3-ylmethylene)hydrazine-1-carbohydrazide, a relative molecular weight of 308.24, and a structural formula as follows:

[0003]

[0004] Nicotinaldehyde hydrazone is an important new compound with stable properties, a high melting point (245-246°C), low volatility, and activity against pathogenic fungi. It is widely used in pharmaceuticals and pesticides and is also a key intermediate in high-end cosmetics. The development of industrial production methods is of great significance. Currently, research on the synthesis of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone is limited both domestically and internationally.

[0005] The purpose of the present invention is to provide a method for synthesizing the 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

[0006] 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 carbonyldihydrazide, pyridine-3-carboxaldehyde, and 1-chloroacetone. The method is suitable for industrial production.

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

[0008] An N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone, the preparation of which comprises the following steps:

[0009] 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;

[0010] Furthermore, 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%;

[0011] Step S2: adding carbonylhydrazone and a catalyst to a solvent under stirring, raising the temperature to 35-45° C., adding 1-chloroacetone dropwise over 1-2 hours, then adding a dechlorinating agent, stirring and reacting for 2-2.5 hours, filtering, washing with water, filter pressing, and drying to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone;

[0012] Furthermore, the amount 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; 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; and the dechlorinating agent is selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate.

[0013] The synthetic route of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone is as follows:

[0014]

[0015] Beneficial Effects of the Invention: Disclosed is a method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone. This novel compound, previously unreported, 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 readily soluble in DMF and dimethyl sulfoxide. This compound is an important new material with extensive applications in pharmaceuticals and pesticides. It is also a key intermediate for high-end cosmetics and possesses significant industrial production value. The N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone is prepared from readily available raw materials such as carbohydrazide, pyridine-3-carboxaldehyde, and 1-chloroacetone via a simple two-step reaction. This synthesis method offers the advantages of high yield, a simple process, low cost, high product quality, and ease of large-scale production, making it worthy of widespread application. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. 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 any creative work.

[0017] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone prepared in Example 4. DETAILED DESCRIPTION

[0018] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0019] Example 1

[0020] Step S1, add 630g of 18% mass fraction of pyridine-3-carboxaldehyde aqueous solution to a 1000mL reaction bottle, start stirring, add 50g of carbohydrazide, control the temperature to 35°C, and as the reaction proceeds, a large amount of white solid precipitates. 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%;

[0021] Step S2, 500 mL of acetonitrile was added to a 1000 mL reaction bottle, 135 g of the carbonylhydrazone and 1 g of tetrabutylammonium bromide were added under stirring, the temperature was raised to 45 ° C, 55 g of 1-chloroacetone was added dropwise and the addition was completed within 1 hour, and then 50 g of sodium hydroxide was added, stirred for 2 hours, filtered, washed with water, filter pressed and dried to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone, with a content of 99% and a yield of 95%.

[0022] Example 2

[0023] Step S1, add 630g of 18% mass fraction of pyridine-3-carboxaldehyde aqueous solution to a 1000mL reaction bottle, start stirring, add 50g of carbohydrazide, control the temperature to 30°C, and as the reaction proceeds, a large amount of white solid precipitates. 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%;

[0024] Step S2: 500 mL of DMF was added to a 1000 mL reaction bottle, 135 g of the carbonylhydrazone and 1 g of polyethylene glycol were added under stirring, the temperature was raised to 40° C., 60 g of 1-chloroacetone was added dropwise within 1.5 h, and then 50 g of sodium hydroxide was added. The mixture was stirred for 2.2 h, filtered, washed with water, filter-pressed, and dried to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone with a content of 98% and a yield of 92%.

[0025] Example 3

[0026] Step S1, add 630g of 18% mass fraction of pyridine-3-carboxaldehyde aqueous solution to a 1000mL reaction bottle, start stirring, add 50g of carbohydrazide, control the temperature to 30°C, and as the reaction proceeds, a large amount of white solid precipitates. 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%;

[0027] Step S2: 500 mL of DMF was added to a 1000 mL reaction bottle, 135 g of the carbonylhydrazone and 1 g of 18-crown ether-6 were added under stirring, the temperature was raised to 45 ° C, 60 g of 1-chloroacetone was added dropwise within 1.6 h, and then 50 g of sodium bicarbonate was added. The mixture was stirred for 2.3 h, filtered, washed with water, filter-pressed and dried to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone with a content of 98% and a yield of 93%.

[0028] Example 4

[0029] Step S1, add 630g of 18% mass fraction of pyridine-3-carboxaldehyde aqueous solution to a 1000mL reaction bottle, start stirring, add 55g of carbohydrazide, control the temperature to 35°C, and as the reaction proceeds, a large amount of white solid precipitates. 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%;

[0030] Step S2, 500 mL of acetonitrile was added to a 1000 mL reaction bottle, and 135 g of the carbonylhydrazone and 1 g of tetrabutylammonium bromide were added under stirring. The temperature was raised to 40 ° C. 55 g of 1-chloroacetone was added dropwise within 1.5 hours, and then 50 g of potassium bicarbonate was added. The mixture was stirred for 2.7 hours, filtered, washed with water, filter-pressed and dried to obtain N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone with a content of 99% and a yield of 96%.

[0031] The applicant states that while the above examples illustrate the N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone of the present invention, the present invention is not limited to the above detailed methods. This does not necessarily mean that the present invention must rely on these detailed methods for implementation. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for raw materials in the products of the present invention, addition of auxiliary ingredients, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for synthesizing N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone, characterized by: The steps include: Step S1, adding carbohydrazide to a pyridine-3-carboxaldehyde aqueous solution while controlling the temperature to react to obtain carbohydrazone; Step S2, adding carbonylhydrazone, a catalyst, and a dechlorinating agent into a solvent, and dropwise adding 1-chloroacetone to react at a certain reaction temperature to obtain nicotinaldehydehydrazone; The structure of the N-(2-oxopropyl)-bis(3-pyridylmethylene)carbonyldihydrazone is as follows: The structure of the carbonylhydrazone is as follows: The catalyst is selected from one of tetrabutylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium chloride, polyethylene glycol, and cyclic crown ethers; and the dechlorination agent is selected from one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate.

2. 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%.

3. 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 at 30-40°C before a large amount of white solid is precipitated.

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 30-50°C after 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 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.

6. 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.

7. 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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