CN112552241B - Synthesis method of pyridazinone - Google Patents
Synthesis method of pyridazinone Download PDFInfo
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- CN112552241B CN112552241B CN201910852831.4A CN201910852831A CN112552241B CN 112552241 B CN112552241 B CN 112552241B CN 201910852831 A CN201910852831 A CN 201910852831A CN 112552241 B CN112552241 B CN 112552241B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three 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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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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Abstract
The invention relates to a novel process for synthesizing pyridazinone, which adopts C-TiO with a core-shell structure2The solid acid is used as a catalyst to replace the traditional glacial acetic acid, the tetramethyl ammonium bromide is used as a phase transfer catalyst, the novel process for synthesizing the pyridazinone by using the tert-butyl hydrazine and the furoic acid under a certain condition improves the reaction efficiency by adding the catalyst, saves the alkali washing and water washing procedures, and greatly reduces the generation of three wastes while improving the yield and the quality of the product.
Description
Technical Field
The invention relates to a production process of pyridazinone, belonging to the field of pesticides and fine chemical engineering.
Background
Pyridazinones are important intermediates for synthetic acaricides, insecticides NC-129, NC-194 and other pesticides, and have insecticidal properties.
The document "synthesis of pyridazinone" introduces a process of pyridazinone, which comprises: under the condition of two important intermediate raw materials of tert-butylhydrazine hydrochloride and furoic acid, tert-butylhydrazine hydrochloride and furoic acid react to generate open-chain furylhydrazone firstly, and then the open-chain furylhydrazone is reduced into ketone in the presence of organic acid, and ring synthesis of pyridazinone is initiated. On the basis of the reaction principle, the method for synthesizing pyridazinone in China at present is approximately the same, namely tert-butyl hydrazine hydrochloride is neutralized by using a dilute sodium hydroxide aqueous solution, under the freezing condition, a pure benzene solution of furfuryl chloric acid is dropwise added or pure benzene is added in advance, then under the freezing condition, furfuryl chloric acid solid is slowly added in batches, after stirring and reacting for a period of time, acetic acid is added, the temperature is increased to 35-45 ℃, heat preservation and reaction are carried out, after the reaction is finished, a water layer is removed by standing, an organic layer is washed by alkali, an organic layer is washed by water, and a solvent benzene is recovered under reduced pressure, so that pyridazinone crystals are obtained, wherein the yield (calculated by the furfuryl chloric acid) is 75-77%.
The literature of the research on synthesis of pyridaben introduces a synthesis process of pyridazinone, which comprises the following steps: adding 30% liquid caustic soda, 22.5g of water and l3.3 g of tert-butylhydrazine hydrochloride into a 100 m L four-neck flask in sequence, stirring, and transferring into a dropping funnel for dropwise addition; adding 125 m L toluene, 9g glacial acetic acid and l7.25g furoic acid into a 250 m L four-neck flask in sequence, starting a stirrer, dropwise adding a tert-butylhydrazine solution, controlling the appropriate temperature, keeping the temperature for reaction for 2 hours after the dropwise adding is finished, stopping stirring, standing for layering, dividing water, sequentially washing an oil layer with water, washing with 5% alkali, washing with water, and adjusting the ph to 7. And then performing reduced pressure distillation (the vacuum degree is 0.03-0.04M Pa, the temperature is 75-80 ℃) to obtain the pyridazinone, the melting point is 64-65 ℃ (the literature value is 65-66 ℃), the mass fraction is 90%, and the yield is more than or equal to 85%.
A paper of Lukun macro pyridazinone synthesis process of Nanjing Industrial university researches a method for synthesizing 2-tert-butyl-4, 5-dichloro-3 (2H) -pyridazinone by taking furoic acid and p-tert-butyl hydrazine hydrochloride as raw materials, and discusses the reaction mechanism. In the reaction process, a sodium hydroxide solution is dropwise added, and the 2-tert-butyl-4, 5-dichloro-3 (2H) -pyridazinone is synthesized through condensation and cyclization, wherein the yield is 76% -78%. The temperature is controlled at 40 ℃ in the heat preservation stage, acetic acid is added as a catalyst, the reaction can be promoted, the yield is improved, and the yield is about 81%. Sodium acetate is used for replacing sodium hydroxide, p-tert-butyl hydrazine hydrochloride and sodium acetate are added into an aqueous solution, perchloric acid is added in batches within 1h to generate hydrazone, a toluene solvent is added, the temperature is gradually raised to 40 ℃, and the reaction is carried out for 6 h. The method can obtain satisfactory effect without adding catalyst, the reaction is easy to control, the yield is 82% -84%, sodium acetate is used as reaction raw material in industrial production, and the sodium acetate is added according to the equimolar ratio, and the result shows that: the reaction time is shortened to about 7 hours from the original 12 hours; the purity of the product is improved from 89 percent to about 94 percent; the yield is improved by about 82 percent from the original 78 percent: meanwhile, the pollution is reduced, the sewage discharge amount is reduced by half, the requirement of environment-friendly production is met, and satisfactory economic and social benefits are brought to enterprises.
Based on the requirements of higher quality and reduction of wastewater on the pyridazinone serving as a pyridaben intermediate, the invention develops a clean production method with higher purity.
Disclosure of Invention
The purpose of the invention is as follows: the novel process of the pyridazinone is developed, the synthesis steps of the product are simplified, the product yield and the product purity are improved, alkaline washing and water washing are reduced through process optimization, the production wastewater is greatly increased, and the energy consumption is reduced.
The main technical scheme of the invention is as follows: the synthesis process of pyridazinone features that toluene as solvent and C-TiO in core-shell structure2The solid acid is used as a catalyst, the tetramethyl ammonium bromide is used as a phase transfer catalyst, and the pyridazinone is synthesized by using tert-butyl hydrazine and furfuryl chloric acid.
Generally, the method is to dropwise add tert-butylhydrazine into a toluene solution of furoic acid at the temperature of 20-40 ℃.
The molar ratio of the furoic acid to the tert-butyl hydrazine is 1: 1.05-1: 1.1.
The adding amount of the toluene is 18-20% of the weight of the furoic acid.
The addition amount of the solid acid catalyst is 6-8% of the weight of the furoic acid.
The addition amount of the phase transfer catalyst tetrabutylammonium bromide is 0.4-0.6% of the weight of the furoic acid.
And after the tert-butyl hydrazine is dripped, the heat preservation time is 2.0 h-3.0 h.
And adding the solid acid catalyst and the phase transfer catalyst into a reaction system after the temperature preservation is finished.
After the solid acid catalyst and the phase transfer catalyst are added, the reaction temperature is kept at 30-40 ℃, and the reaction lasts for 4-5 h.
After the reaction is finished, filtering is carried out, the solid acid catalyst is separated out for reuse, the filtrate is kept stand to separate an organic phase and an inorganic phase, and the organic layer is decompressed to recover the solvent toluene, so that the product pyridazinone is obtained.
The invention is C-TiO with core-shell structure2Solid acid replaces the traditional catalyst glacial acetic acid, tetrabutylammonium bromide is used as a phase transfer catalyst, tert-butylhydrazine and furfuryl chlorideA process for synthesizing pyridazinone from acid under a certain condition.
The method for synthesizing the pyridazinone has the advantages that the yield is over 88.0 percent, and the product purity is over 96.5 percent.
The invention has the advantages of
The invention omits the water washing and the alkali washing after the traditional synthesis process by changing the catalyst system, optimizes the production process and reduces the three wastes.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
Adding 50g of furfuryl chloric acid and 10g of toluene into a four-neck flask, slowly dropping 20% tert-butylhydrazine aqueous solution (wherein the concentration of tert-butylhydrazine is 24.9 g) at 40 ℃ under stirring, preserving heat for 2h after dropping, and adding 3g C-TiO2Reacting solid acid and 2g of tetrabutylammonium bromide at the reaction temperature of 20 ℃ for 4 hours, filtering out the solid acid catalyst for repeated use after the reaction is finished, standing and separating an organic phase and an inorganic phase from a filtrate, decompressing an organic layer and recovering a solvent toluene to obtain a product pyridazinone, wherein the calculated yield is 88.0%, and the analyzed product purity is 96.5%.
Example 2
Adding 50g of furfuryl chloric acid and 10g of toluene into a four-neck flask, slowly dropping 25% tert-butylhydrazine aqueous solution (wherein the tert-butylhydrazine is 26.0 g) at 35 ℃ under stirring, preserving the temperature for 3h after dropping, and adding 3.5g C-TiO2Reacting solid acid and 2.6g of tetrabutylammonium bromide at 25 ℃ for 5 hours, filtering out the solid acid catalyst for repeated use after the reaction is finished, standing and separating an organic phase and an inorganic phase from a filtrate, decompressing an organic layer and recovering a solvent toluene to obtain a product pyridazinone, wherein the calculated yield is 88.6%, and the analyzed product purity is 97.0%.
Example 3
Adding 50g of furfuryl chloric acid and 9g of toluene into a four-neck flask, slowly dropping 25% of tert-butylhydrazine aqueous solution (wherein the concentration of tert-butylhydrazine is 27.3 g) at 30 ℃ under stirring, preserving heat for 2.5h after dropping, and adding 4.0g C-TiO2Reacting the solid acid and 3.0g of tetrabutylammonium bromide for 4.5 hours at the reaction temperature of 40 ℃, and reacting the mixtureFiltering out the solid acid catalyst for reuse, standing the filtrate to separate an organic phase and an inorganic phase, decompressing and recovering the solvent toluene in the organic layer to obtain the product pyridazinone, wherein the calculated yield is 88.2 percent, and the purity of the analyzed product is 96.7 percent.
Example 4
Adding 50g of furfuryl chloric acid and 9.5g of toluene into a four-neck flask, slowly dropping 25% tert-butylhydrazine aqueous solution (28.6 g of tert-butylhydrazine) at 26 ℃ under stirring, preserving the temperature for 2.3h after dropping, and adding 4.0g C-TiO2Reacting solid acid and 3.0g of tetrabutylammonium bromide at the reaction temperature of 40 ℃ for 4.5 hours, filtering out the solid acid catalyst for repeated use after the reaction is finished, standing the filtrate to separate an organic phase and an inorganic phase, decompressing an organic layer and recovering a solvent toluene to obtain a product pyridazinone, wherein the calculated yield is 88.5%, and the purity of the analyzed product is 96.8%.
Example 5
Adding 50g of furfuryl chloric acid and 10g of toluene into a four-neck flask, slowly dropping 20% tert-butylhydrazine aqueous solution (wherein the concentration of tert-butylhydrazine is 27.8 g) at 30 ℃ under stirring, preserving heat for 2.6h after dropping, and adding 3.7g C-TiO2Reacting solid acid and 3.8g of tetrabutylammonium bromide at the reaction temperature of 40 ℃ for 4.5 hours, filtering out the solid acid catalyst for repeated use after the reaction is finished, standing the filtrate to separate an organic phase and an inorganic phase, decompressing an organic layer and recovering a solvent toluene to obtain a product pyridazinone, wherein the calculated yield is 88.3%, and the purity of the analyzed product is 96.5%. .
Example 6
Adding 50g of furfuryl chloric acid and 10g of toluene into a four-neck flask, slowly dropping 30% tert-butylhydrazine aqueous solution (wherein the concentration of tert-butylhydrazine is 27.6 g) at the temperature of below 20 ℃ under stirring, preserving heat for 2 hours after dropping, and adding 3.3g C-TiO2Reacting solid acid and 2.5g of tetrabutylammonium bromide at the reaction temperature of 20 ℃ for 4 hours, filtering out the solid acid catalyst for repeated use after the reaction is finished, standing the filtrate to separate an organic phase and an inorganic phase, decompressing an organic layer and recovering a solvent toluene to obtain a product pyridazinone, wherein the calculated yield is 88.0%, and the analyzed product purity is 96.0%.
Example 7
50g of furfuryl chloric acid and 10g of toluene were added to a four-necked flask, and stirred at 40 ℃ in a slowly dropping concentration of20% tert-butylhydrazine water solution (wherein the tert-butylhydrazine is 24.9 g), after the dropwise addition, the temperature is kept for 2h, and 3g C-TiO is added2Reacting solid acid and 2g of tetrabutylammonium bromide at the reaction temperature of 30 ℃ for 4 hours, filtering out the solid acid catalyst for repeated use after the reaction is finished, standing and separating an organic phase and an inorganic phase from a filtrate, decompressing an organic layer and recovering a solvent toluene to obtain a product pyridazinone, wherein the calculated yield is 88.0%, and the analyzed product purity is 96.5%.
Example 8
Adding 50g of furfuryl chloric acid and 9g of toluene into a four-neck flask, slowly dropping 20% tert-butylhydrazine aqueous solution (wherein the tert-butylhydrazine is 28.4 g) at 26 ℃ under stirring, preserving the temperature for 3h after dropping, and adding 3.5g C-TiO2Reacting solid acid and 2.5g of tetrabutylammonium bromide at 22 ℃ for 4.6 hours, filtering out the solid acid catalyst for repeated use after the reaction is finished, standing the filtrate to separate an organic phase and an inorganic phase, decompressing an organic layer and recovering a solvent toluene to obtain a product pyridazinone, wherein the calculated yield is 88.8%, and the purity of the analyzed product is 96.8%.
Example 9
Adding 50g of furoic acid and 9g of toluene into a four-neck flask, slowly dropping 20% tert-butylhydrazine aqueous solution (wherein the tert-butylhydrazine is 28.4 g) at 23 ℃ under stirring, keeping the temperature for 2.8h after dropping, and adding 3.5g C-TiO2Reacting solid acid and 2.5g of tetrabutylammonium bromide at the reaction temperature of 20 ℃ for 4.6h, filtering out the solid acid catalyst for reuse after the reaction is finished, standing the filtrate to separate an organic phase and an inorganic phase, decompressing an organic layer and recovering a solvent toluene to obtain a product pyridazinone, wherein the calculated yield is 88.9%, and the purity of the analyzed product is 96.8%.
Example 10
Adding 50g of furfuryl chloric acid and 9.5g of toluene into a four-neck flask, slowly dropping 30% tert-butylhydrazine aqueous solution (27.8 g of tert-butylhydrazine) at 32 ℃ under stirring, preserving the temperature for 2.3h after dropping, and adding 3.8g C-TiO2Reacting solid acid and 2.1g of tetrabutylammonium bromide at the reaction temperature of 33 ℃ for 4 hours, filtering out the solid acid catalyst for repeated use after the reaction is finished, standing the filtrate to separate an organic phase and an inorganic phase, decompressing the organic layer and recovering the solvent toluene to obtain the product pyridazinone, calculating the yield to be 88.4%, and analyzing the product purityThe degree is 96.6%.
Comparative experiment
Adding 140g of tert-butylhydrazine aqueous solution, 500 mL of toluene and 100g of furoic acid into a 1000m four-neck flask, stirring at room temperature for reaction, adding 40g of acetic acid, heating to 40-50 ℃, and continuing to stir for reaction for 4 hours. Cooling, standing and layering to separate out wastewater, washing the toluene layer with water to separate out wastewater, removing the solvent from the toluene layer under reduced pressure to obtain brownish yellow pyridazinone, recycling the removed toluene to obtain the product pyridazinone, wherein the calculated yield is 78.6%, and the analyzed product purity is 92.5%.
Claims (10)
1. A process for synthesizing pyridazinone features that toluene is used as solvent and the core-shell structure C-TiO is used2The solid acid is used as a catalyst, tetrabutylammonium bromide is used as a phase transfer catalyst, and tert-butylhydrazine and furfuryl chloric acid are used for synthesizing the pyridazinone.
2. The method of claim 1, wherein t-butylhydrazine is added dropwise to a toluene solution of furoic acid at a temperature of 20 ℃ to 40 ℃.
3. The synthesis process according to claim 1 or 2, characterized in that the molar ratio of furfuryl chloric acid to tert-butylhydrazine is 1: 1.05-1: 1.1.
4. The synthesis process according to claim 1 or 2, characterized in that toluene is added in an amount of 18% to 20% by weight of the furfuryl chloric acid.
5. The synthesis method according to claim 1, wherein the solid acid catalyst is added in an amount of 6 to 8% by weight based on the weight of the furoic acid.
6. The method according to claim 1, wherein the amount of tetrabutylammonium bromide used as a phase transfer catalyst is 0.4-0.6% by weight of the furfuryl chloric acid.
7. The synthesis method according to claim 2, wherein the incubation time is 2.0-3.0 h after the dropwise addition of the tert-butylhydrazine.
8. The synthesis method according to claim 7, wherein the solid acid catalyst and the phase transfer catalyst are added to the reaction system after the completion of the temperature maintenance.
9. The synthesis method according to claim 8, wherein the reaction temperature is kept at 30-40 ℃ after the solid acid catalyst and the phase transfer catalyst are added, and the reaction is carried out for 4-5 hours.
10. The synthesis process as claimed in claim 1, wherein the reaction is completed, the solid acid catalyst is separated by filtration and reused, the filtrate is left to stand to separate organic phase and inorganic phase, and the organic layer is decompressed to recover the solvent toluene, thus obtaining the product pyridazinone.
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| CN101747322A (en) * | 2010-01-20 | 2010-06-23 | 贵州大学 | Pyridazinone derivatives with 1,2,4-triazole schiff base, preparation method and application thereof |
| CN104383942A (en) * | 2014-11-13 | 2015-03-04 | 三明学院 | C@TiO2 solid acid catalyst in core-shell structure and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6110560A (en) * | 1984-06-23 | 1986-01-18 | Nissan Chem Ind Ltd | Preparation of 2-tertiary-butyl-4,5-dichloro-3(2h)-pyridazinone |
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| CN1108242A (en) * | 1993-11-11 | 1995-09-13 | 壳牌国际研究有限公司 | Preparation of pivaloyl hydrazide |
| CN101747322A (en) * | 2010-01-20 | 2010-06-23 | 贵州大学 | Pyridazinone derivatives with 1,2,4-triazole schiff base, preparation method and application thereof |
| CN104383942A (en) * | 2014-11-13 | 2015-03-04 | 三明学院 | C@TiO2 solid acid catalyst in core-shell structure and preparation method thereof |
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| 一步合成核壳结构C-TiO2复合材料及UV-Vis光催化降解染料;刘维刚等;《黑龙江大学工程学报》;20160930;第7卷(第3期);第32-40+46页 * |
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Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee before: CHINA PETROLEUM & CHEMICAL Corp. |