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Preparation method of prothioconazole

A technology of prothioconazole and sodium bisulfate, applied in the direction of organic chemistry, can solve the problems of instability of hydrazine intermediate compounds, increase of solid waste in reaction routes, and low synthesis yield, so as to reduce the use of reagents, The effect of less pollution of three wastes and simple steps

Active Publication Date: 2017-07-28
JIANGSU SEVENCONTINENT GREEN CHEM CO LTD
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Problems solved by technology

[0004] In the synthetic route of US6201128, when compound IV is prepared, a large excess of hydrazine hydrate is used as a reaction reagent, so that the waste liquid increases, and the hydrazine intermediate compound in the free state is relatively unstable, and side reactions are prone to occur, resulting in a high yield Reduce; when preparing prothioconazole by compound IV, need to use the sulfur powder of air / catalytic amount or excessive sulfur powder as reaction reagent, carry out at higher temperature, generate the by-product that has peculiar smell, and synthetic yield not tall
[0005] In the synthesis route of US6559317, a large excess of hydrazine hydrate was also used as a reaction reagent in the preparation of compound IV. After the reaction, hydrogen chloride was introduced to stabilize the hydrazine intermediate compound in the form of a salt, and alkali was added in the subsequent reaction. Carrying out dissociation not only increases the operation steps, but also increases the generation of solid waste in the reaction route; when preparing prothioconazole by compound IV, an excessive amount of ferric chloride is used as a reaction reagent, resulting in a large amount of solid waste generated by the reaction

Method used

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Examples

Experimental program
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Embodiment 1

[0042] 2-(1-Chloro-cycloprop-1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thione of this example) The preparation method of -1-yl)-propane has the following steps:

[0043] Step (1), dissolve 2-(1-chlorocyclopropyl)-3-chloro-1-(2-chlorophenyl)-2-propanol I (28.0g, 0.10mol) in acetonitrile (50mL) , Then potassium carbonate (13.8g, 0.10mol) and ethyl carbazate II (11.5g, 0.11mol) were added. The reaction solution was stirred at 80°C for 4 hours. After the reaction, water (50 mL) was added to the reaction solution, followed by extraction with ethyl acetate (extraction three times, 50 mL each time), the organic phases were combined, dried over sodium sulfate and concentrated. 36.8 g of crude product was obtained, with a content of 83.4%. The obtained crude product was recrystallized with ethanol to obtain compound III (30.7 g), a pale yellow solid, with a content of 95% and a yield of 84%. The NMR data of compound III are as follows:

[0044] 1 H NMR(400MHz, CDCl 3 )...

Embodiment 2

[0048] 2-(1-Chloro-cycloprop-1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thione of this embodiment) The preparation method of -1-yl)-propane has the following steps:

[0049] Step (1), dissolve 2-(1-chlorocyclopropyl)-3-chloro-1-(2-chlorophenyl)-2-propanol I (28.0g, 0.10mol) in acetonitrile (50mL) , Then add triethylamine (10.1g, 0.10mol) and ethyl carbazate II (11.5g, 0.11mol). The reaction solution was stirred at 80°C for 3 hours. After the reaction, water (50 mL) was added to the reaction solution, followed by extraction with ethyl acetate (extraction three times, 50 mL each time), the organic phases were combined, dried over sodium sulfate and concentrated. 37.5 g of crude product was obtained, with a content of 86%. The obtained crude product was recrystallized with ethanol to obtain compound III (33.1 g), a pale yellow solid, with a content of 95% and a yield of 91%.

[0050] Step (2): Add sodium hydroxide (3.60 g, 0.09 mol) to a toluene (60 mL) and water (...

Embodiment 3

[0052] 2-(1-Chloro-cycloprop-1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thione of this embodiment) The preparation method of -1-yl)-propane has the following steps:

[0053] Step (1), dissolve 2-(1-chlorocyclopropyl)-3-chloro-1-(2-chlorophenyl)-2-propanol I (28.0g, 0.10mol) in acetonitrile (50mL) , Then add triethylamine (10.1g, 0.10mol) and acetylhydrazine II (8.15g, 0.11mol). The reaction solution was stirred at 80°C for 3 hours. After the reaction, water (50 mL) was added to the reaction solution, followed by extraction with ethyl acetate (extraction three times, 50 mL each time), the organic phases were combined, dried over sodium sulfate and concentrated. 36.3 g of crude product was obtained, with a content of 81%. The obtained crude product was recrystallized with ethanol to obtain compound III (30.0 g), a pale yellow solid, with a content of 95% and a yield of 90%.

[0054] Step (2): Add potassium hydroxide (5.05 g, 0.09 mol) to a toluene (60 mL) and wate...

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Abstract

The invention relates to a preparation method of prothioconazole. The preparation method comprises that a compound IV undergoes a reaction at 20 to 120 DEG C in the presence of an oxidizing agent and a solvent, and after the reaction, the product is treated to form prothioconazole. The preparation method has mild reaction conditions, utilizes cheap and easily available raw materials, has simple processes, is environmentally friendly and clean in regents and reaction processes, greatly reduces three wastes, is suitable for industrial production, and realizes a high yield of a final product and high content.

Description

Technical field [0001] The invention relates to a preparation method of the fungicide prothioconazole. Background technique [0002] ProthIVoconazole is a low-toxicity, high-efficiency, and broad-spectrum triazole thione fungicide developed by Bayer. It is mainly used to prevent and control many diseases such as cereals, wheat and legumes. By 2-(1-chloro-cycloprop-1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thione-1- Propane (compound IV) to synthesize prothioconazole can not only avoid the generation of heterogeneous solid waste from the source, but also avoid the use of hazardous chemicals, high temperature and a series of reaction conditions that are not suitable for industrial production. Currently, through oxidation of 2-(1-chloro-cycloprop-1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thione -1-yl)-propane has been reported to prepare prothioconazole, for example: US6201128, US6559317 and PCT IVnt.Appl.2001046158 and so on. However, the existi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D249/12
CPCC07D249/12
Inventor 安静刘玉超吴天宇孟楠宋春翠
Owner JIANGSU SEVENCONTINENT GREEN CHEM CO LTD
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