Preparation method of prothioconazole intermediate

A technology for prothioconazole and intermediates, which is applied in the field of preparation of prothioconazole intermediates, can solve the problems of decreased product yield and purity, cumbersome post-processing, large waste liquid and solid waste, and the like, and achieves shortened reaction time, The post-processing method is simple and the effect of less three wastes

Active Publication Date: 2017-12-08
JIANGSU SEVENCONTINENT GREEN CHEM CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Compared with Example 5, this example has a change in the feeding order, resulting in a significant decline in the yield and purity of the product. It can be seen that for this type of reaction, the feeding order has a great influence on the product yield and purity
[0010] In addition, the various examples of CN1137103C show that after the reaction is completed, it needs to be diluted with 100ml of dichloromethane, the solid is filtered out, and the organic liquid phase is concentrated under reduced pressure to obtain the product.

Method used

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  • Preparation method of prothioconazole intermediate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Dissolve 44 grams of [1-(2-chlorophenyl)-2-(1-chlorocyclopropyl)-2-hydroxyl]-propylhydrazine in 80mL of toluene, keep it warm at 30°C, and slowly add it dropwise with a mass concentration of 37 % formaldehyde aqueous solution 15 grams, drop completely in about 30 minutes, then add 12.2 grams of ammonium thiocyanate, slowly add dropwise the hydrochloric acid (35 grams) that mass concentration is 30%, drop completely in about 30 minutes, keep warm for one hour, GC It was detected that the reaction was complete, the system was lowered to 20°C for recrystallization, and the product 2-(1-chloro-cyclopropan-1-yl)-1-(2-chlorophenyl)-2-hydroxyl-3-(1, About 50 g of 2,4-triazolidine-5-thione-1-yl)-propane (purity>95%), yield 90%.

[0034] Product m.p:152-154℃. 1 H NMR (400MHz, CDCl 3)δ7.65-7.47(m,1H),7.43-7.31(m,1H),7.26-7.09(m,2H),6.11(s,1H),5.11(t,J=11.2Hz,1H),4.58 (d, J=12.3Hz, 2H), 4.48(dd, J=12.8, 6.7Hz, 1H), 4.17(s, 2H), 3.63(d, J=14.0Hz, 1H), 3.08(d, J= 14.0Hz,1H),1.32...

Embodiment 2

[0036] Dissolve 44 grams of [1-(2-chlorophenyl)-2-(1-chlorocyclopropyl)-2-hydroxyl]-propylhydrazine in 80mL of toluene, keep it warm at 33°C, and slowly add it dropwise with a mass concentration of 37 % formaldehyde aqueous solution 15 grams, drop completely in about 30 minutes, then add 13 grams of sodium thiocyanate, slowly add hydrochloric acid (35 grams) with a mass concentration of 30%, drop completely in about 30 minutes, keep warm for one hour, GC It was detected that the reaction was complete, the system was lowered to 20°C for recrystallization, and the product 2-(1-chloro-cyclopropan-1-yl)-1-(2-chlorophenyl)-2-hydroxyl-3-(1, About 51 g of 2,4-triazolidine-5-thione-1-yl)-propane (purity>95%), yield 92%.

Embodiment 3

[0038] Dissolve 44 grams of [1-(2-chlorophenyl)-2-(1-chlorocyclopropyl)-2-hydroxyl]-propylhydrazine in 80mL of toluene, keep it warm at 35°C, and slowly add it dropwise with a mass concentration of 37 % paraformaldehyde aqueous solution 13 grams (4.81 grams of paraformaldehyde solids are dissolved in 8.19 grams of water), drop completely in about 30 minutes, then add potassium thiocyanate 15.6 grams, slowly add mass concentration and be 30% hydrochloric acid (35 gram), about 30 minutes to drop completely, keep warm for one hour, GC detects that the reaction is complete, the system is reduced to 20 ° C for recrystallization, and the product 2-(1-chloro-cyclopropan-1-yl)-1-(2 About 51 g of -chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiol-1-yl)-propane (purity>95%), yield 92%.

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Abstract

The invention relates to a preparation method of a prothioconazole intermediate. The preparation method comprises the following steps: dissolving [1-(2-chlorophenyl)-2-(1-chlorocyclopropyl)-2-hydroxy]-propyl hydrazine into methyl benzene; dropwise adding a formaldehyde aqueous solution or a polyformaldehyde aqueous solution under 30 to 35 DEG C; then adding in thiocyanate after completion of dropwise adding; then dropwise adding hydrochloric acid or sulfuric acid aqueous solution; keeping warm and reacting for 50 to 70 minutes after completion of dropwise adding; directly using a reaction solution for follow-up reaction or filtering the reaction solution after cooling; thus obtaining the prothioconazole intermediate 2-(1-chloro-cyclopropyl-1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thioketone-1-yl)-propane. Through optimization on a whole route, for example, reaction temperature, reagents, a feeding procedure and the like, of the preparation method, an after-treatment method is simple, three wastes such as waste gas, waste water and waste residues are few, the reaction time is shortened, the purity and the yield of a product are higher, and the preparation method is suitable for industrial production.

Description

technical field [0001] The present invention relates to a preparation method of prothioconazole intermediate, in particular to a 2-(1-chloro-cyclopropan-1-yl)-1-(2-chlorophenyl)-2-hydroxyl-3- Process for the preparation of (1,2,4-triazolidine-5-thione-1-yl)-propane. Background technique [0002] Prothioconazole (Prothioconazole) is a broad-spectrum, high-efficiency triazolethione fungicide developed by Bayer Corporation of Germany. The English common name: Prothioconazole, the English trade name: Proline, and the original drug is a light brown needle Crystal, CA No. 178928-70-6, chemical name (RS)-2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2 ,4-Dihydro-1,2,4-triazole-3-thione is mainly used to control many diseases of cereals, wheat and beans. [0003] Prothioconazole is a racemate, which not only exhibits good systemic activity, excellent protective, therapeutic and eradicating activities for crops, but also has a long duration of action. Through a la...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D249/12
CPCC07D249/12
Inventor 安静周炜吴天宇周莹周志豪
Owner JIANGSU SEVENCONTINENT GREEN CHEM CO LTD
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