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Method for preparing 3-halo-1-(3-chloro -2-pyridyl)-1H-pyrazole-5-formyl halide

A pyridyl, formyl halide technology, applied in the field of preparing 3-halogenated-1--1H-pyrazole-5-formyl halide, can solve the problems of dangerous oxidation operation, long steps, large amount of waste water and the like

Active Publication Date: 2009-10-07
SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The reaction has disadvantages such as dangerous oxidation operation, long steps, and large amount of waste water.

Method used

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  • Method for preparing 3-halo-1-(3-chloro -2-pyridyl)-1H-pyrazole-5-formyl halide

Examples

Experimental program
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Effect test

Embodiment 1

[0036] Example 1: Synthesis of 3-chloro-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-formyl chloride

[0037] Step 1: Synthesis of 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid

[0038]

[0039] Add 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid ethyl ester (70.0 g, 210.4 mmol ), THF (250 milliliters), water (250 milliliters), sodium hydroxide (12.6 grams, 315.0 millimoles), react at room temperature for 6 hours, remove THF under reduced pressure, add water (250 milliliters) and ethyl acetate (80 milliliters) Extraction, the inorganic phase was acidified with hydrochloric acid to pH = 2, and then extracted with dichloromethane (200 ml × 3 times), the organic phase was extracted with anhydrous MgSO 4 Drying, desolvation under reduced pressure gave 44.1 grams of white crystalline powder, HPLC normalized content of 98% (analysis conditions: chromatographic column is ZORBAX Eclipse XDB-C8 4.6 * 150mm 5 μm, mobile phase is acetonit...

Embodiment 2

[0045] Example 2: Synthesis of 3-chloro-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-formyl chloride

[0046]

[0047] Add 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid (the product of step 1 of Example 1, 26.6 g, 100.0 mmol), n-hexane (500 ml), phosphorus pentachloride (210.0 g, 1000.0 mmol), reflux reaction for 8 hours, cooled to room temperature, filtered, and the filtrate was precipitated under reduced pressure to obtain 25.0 g of brown oil , the HPLC normalized content was 95%, and the yield was 85%.

[0048] 1 H NMR (300MHz, CDCl 3 ) δ (ppm) 8.510 (dd, 1H), 7.945 (dd, 1H), 7.488 (dd, 1H), 7.213 (s, 1H).

Embodiment 3

[0049] Example 3: Synthesis of 3-chloro-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-formyl chloride

[0050]

[0051] Add 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid (the product of step 1 of Example 1, 6.2 grams, 23.4 millimoles), thionyl chloride (40.0 grams, 332.8 millimoles), reflux reaction for 6 hours, precipitation under reduced pressure, obtained 5.7 grams of brown oil, HPLC normalized content was 98%, yield was 86% .

[0052] 1 H NMR (300MHz, CDCl 3 ) δ (ppm) 8.510 (dd, 1H), 7.947 (d, 1H), 7.490 (dd, 1H), 7.211 (s, 1H).

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Abstract

The invention provides a method for preparing 3-halo-1-(3-chlorine-2-pyridyl)-1H-pyrazole-5-formyl halide (I). 3-halo-1-(3-chlorine-2-pyridyl)-4 and 5-dihydro-1H-pyrazole-5-formic ether (III) are used as raw materials, and a target product is prepared by hydrolyzing, acyl halogenation and simultaneously carrying out an oxidation reaction. A reaction formula is shown as the right formula, and in the formula, R is selected from C1-C4 alkyl; X is selected from Cl or Br; and Y is selected from halogens. The invention also provides a composition of a general formula (II) and a preparation method thereof.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a method for preparing 3-halo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carbonyl halide. Background technique [0002] 3-Halo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carbonyl halide is the preparation of insecticide 3-bromo-N-[4-chloro-2-methyl-6 -[(methylamino)formyl]phenyl]-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (Chlorantraniliprole, chlorantraniliprole) and other anthranilamides important intermediates of compounds. Methods for the preparation of 3-halo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carbonyl chloride are disclosed in WO 03 / 016283A1, WO 03 / 015519A1 and WO 2006 / 102025A1. According to the prior art, 3-halo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-formyl chloride needs to be prepared through three steps of oxidation, hydrolysis and acid chloride, and the reaction formula is as follows: [0003] [0004] Where: R 1 from C 1 -C 4 Alkyl, X is selected from Cl or Br. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D401/04
CPCC07D401/04
Inventor 吴鸿飞李斌杨辉斌程岩相东
Owner SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD