Method for preparing 2-[1H-pyrazole-5-radical]-4H-3, 1-benzoxazine-4-ketone compound

A technology of -4H-3 and ketone compounds, applied in the direction of organic chemistry, can solve the problems of dangerous oxidation operation, long steps, large amount of waste water, etc.

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A technology of -4H-3 and ketone compounds, applied in the direction of organic chemistry, can solve the problems of dangerous oxidation operation, long steps, large amount of waste water, etc.

CN101550134BInactive Publication Date: 2011-04-27中国中化股份有限公司 +1

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Embodiment 1

[0046] Example 1: Synthesis of 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid

[0047]

[0048] Add 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid ethyl ester (15.90 g, 50.00 mmol ), THF (100 milliliters), water (100 milliliters), sodium hydroxide (3.03 grams, 75.00 millimoles), react at room temperature for 6 hours, remove THF under reduced pressure, add water (50 milliliters) and ethyl acetate (20 milliliters) Extraction, the inorganic phase was acidified to pH = 2 with hydrochloric acid, and then extracted with dichloromethane (75 ml × 3 times), the organic phase was washed with anhydrous MgSO 4 Drying, desolvation under reduced pressure gave 12.68 grams of white crystalline powder, HPLC normalized content was 98% (analysis conditions: chromatographic column is ZORBAX Eclipse XDB-C8 4.6 * 150mm 5 μm, mobile phase is acetonitrile: water=70: 30), m.p. 57-59°C, yield 95%.

[0049] 1 H NMR (300MHz, CDCl 3 ( dd, 1H). ...

Embodiment 2

[0050] Example 2: Synthesis of 3-bromo-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid

[0051]

[0052] Add 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid ethyl ester (18.50 g, 50.78 mmol ), THF (100 milliliters), water (100 milliliters), sodium hydroxide (3.06 grams, 76.17 millimoles), react at room temperature for 6 hours, remove THF under reduced pressure, add water (50 milliliters) and ethyl acetate (20 milliliters) Extraction, the inorganic phase was acidified to pH = 2 with hydrochloric acid, and then extracted with dichloromethane (75 ml × 3 times), the organic phase was washed with anhydrous MgSO 4 Drying, desolvation under reduced pressure gave 15.25 grams of white crystalline powder, HPLC normalized content was 98% (analysis conditions: chromatographic column is ZORBAX Eclipse XDB-C8 4.6 * 150mm 5 μm, mobile phase is acetonitrile: water=70: 30), m.p.66-68°C, yield 96%.

[0053] 1 H NMR (300MHz, CDCl 3 ( dd, 1H).

...

Embodiment 3

[0055] Example 3: 6-chloro-2-[3-chloro-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzene Synthesis of oxazin-4-one

[0056]

[0057] Methanesulfonyl chloride (6.02 g, 52.57 mmol) was added to a 250 ml reaction flask, and 3-chloro-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole was added dropwise -A solution of 5-formic acid (12.68 g, 47.77 mmol), acetonitrile (50 ml) and triethylamine (5.31 g, 52.57 mmol) was reacted at room temperature for 1 hour, and 2-amino-5-chloro-3- Toluic acid (8.87 g, 47.77 mmol), reacted for 30 minutes, added dropwise triethylamine (10.62 g, 105.14 mmol), reacted for 1 hour, added dropwise methanesulfonyl chloride (6.02 g, 52.57 mmol), reacted 6 hours. Stand still, filter, the filter cake is a yellow solid, wash the filter cake with THF (20 ml × 2 times), the filtrate is precipitated under reduced pressure, and column chromatography (ethyl acetate / petroleum ether=1 / 5) gives 7.38 g of a yellow solid , the HPLC normalized content was ...

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Abstract

The invention provides a method for preparing a 2-[1H- pyrazole-5-base]-4H-3, 1-benzoxazine-4-ketone compound (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, coupling and simultaneously carrying out an oxidation reaction. A reaction formula is shown as follows, and radicals in the formula are presented in the specification. The invention also provides a compound of a general formula (II) and a preparation method thereof.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for preparing 2-[1H-pyrazol-5-yl]-4H-3,1-benzoxazin-4-one compounds. Background technique [0002] 2-[1H-pyrazol-5-yl]-4H-3,1-benzoxazin-4-one compound 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. WO 2004 / 011447 A2, WO 03 / 015519 A1 and WO 2006 / 023783 Al disclose the preparation of 2-[1H-pyrazol-5-yl]-4H-3,1-benzoxazin-4-one compounds method. According to the prior art, 2-[1H-pyrazol-5-yl]-4H-3,1-benzoxazin-4-one compounds need to be prepared through three steps of oxidation, hydrolysis and coupling, the reaction formula as follows: [0003] [0004] In the formula: [0005] X is selected from Cl or Br; [0006] R 1 from C 1 -C 4 alkyl; [0007...

Claims

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Application Information

Patent Timeline

27 Apr 2011

Publication

CN101550134B

IPC: C07D413/14

Inventors: 吴鸿飞; 李斌