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Preparation method of isoxazoline insecticide

An isoxazoline and pesticide technology, which is applied in the chemical industry, can solve the problems of high cost of commercialized large-scale production products, long routes, long routes, etc., and achieves easy realization of reaction conditions, reduction of three waste discharges, and easy availability of raw material costs. Effect

Active Publication Date: 2021-03-09
麦蒂辛生物医药科技成都有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Chinese patent CN109879826A reports the synthesis method of isoxazoline series, the synthesis route is relatively long, and its commercialized large-scale production products are relatively expensive
[0007] Chinese patent CN111689919A and Chinese patent CN111675667A use one-pot method for synthesis, but there is not much difference between the main raw materials and patent Chinese CN109879826A, only the order of adding raw materials is changed, raw materials are still more expensive, and the route is longer, which is not suitable for large-scale industrial production. The synthetic route is as route 2 and route 3, obtains compound formula 2:
[0019] To sum up, all the above-mentioned routes are reacted through the raw material aldehyde or the derivative oxime obtained through the hydroxylamine reaction, which is expensive and difficult to obtain in the market. The price is relatively high, and the compound is unstable for a long time. Participate in the [3+2] ring formation reaction, the route is lengthy, and more hazardous waste is produced, which has many disadvantages for industrial production

Method used

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  • Preparation method of isoxazoline insecticide
  • Preparation method of isoxazoline insecticide
  • Preparation method of isoxazoline insecticide

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0051] Embodiment 1 (preparation of Freilaner 1-1)

[0052] 1.1 Coupling reaction:

[0053]

[0054] Add Cs sequentially to the 100 ml reaction vial 2 CO 3 (37.88g, 0.12mol), 3A molecular sieves (10g), Pd 2 (dba) 3 (212.0mg, 0.5%eq), Xphos (1.33g, 6%eq), nitromethane (10mL), nitrogen replacement 3 times, and then dissolve 10g of intermediate 1 (4-bromo-2-methylbenzoic acid) In 10ml of ethylene glycol dimethyl ether, the temperature was raised to 50°C, and the reaction was detected by TLC. After the reaction was complete, it was cooled to room temperature, filtered, and the filter cake was washed with dichloromethane (10mLx2), added to 20ml of ammonium chloride solution, and separated phase, the organic phase was extracted with 20ml of dichloromethane, the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was spin-dried under reduced pressure to obtain Intermediate 2 (6.36g, yield 70%).

[0055] 1.2 Ring closi...

Embodiment 2

[0065] Embodiment 2 (preparation of Afulaner 1-2)

[0066] 2.1 Coupling reaction:

[0067]

[0068] Add Cs sequentially to the 100 ml reaction vial 2 CO 3 (25.15g, 79.67mmol), 3A molecular sieves (8g), Pd 2 (dba) 3 (182.4mg, 0.5%eq), Xphos (1.14g, 6%eq), nitromethane (10mL), nitrogen replacement 3 times, and then 10g of intermediate 1 (4-bromo-1-naphthoic acid) was dissolved in 10ml In ethylene glycol dimethyl ether, the temperature was raised to 50°C, and the reaction was detected by TLC. After the reaction was complete, it was cooled to room temperature, filtered, and the filter cake was washed with dichloromethane (10mLx2), added to 20ml of ammonium chloride solution, and the phases were separated. The organic phase was extracted with 20ml of dichloromethane, the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was spin-dried under reduced pressure to obtain Intermediate 2 (5.80g, yield 63%).

[0069] 2.2...

Embodiment 3

[0078] Embodiment 3 (preparation of lotirana 1-3)

[0079] 3.1 Coupling reaction:

[0080]

[0081] Add Cs sequentially to the 100 ml reaction vial 2 CO 3 (28.55g, 90.46mmol), 3A molecular sieves (9g), Pd 2 (dba) 3 (206.0mg, 0.5%eq), Xphos (1.29g, 6%eq), nitromethane (9mL), nitrogen replacement 3 times, and then 10g of intermediate 1 (5-bromo-3-methylthiophene-2- Formic acid) was dissolved in 10ml of ethylene glycol dimethyl ether, heated to 50°C, and the reaction was detected by TLC. After sufficient reaction, cooled to room temperature, filtered, and the filter cake was washed with dichloromethane (10mLx2), and added to 20ml of ammonium chloride Solution, phase separation, the organic phase was extracted with 20ml of dichloromethane, the combined organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was spin-dried under reduced pressure to obtain intermediate 2 (6.73g, yield 74%) .

[0082] 3.2 Ring closing reaction:

...

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Abstract

The invention relates to a preparation method of an isoxazoline insecticide, which relates to the technical field of chemical industry, and comprises the following steps: 1) coupling reaction: mixingan intermediate 1 with nitromethane in a solvent, adding a palladium catalyst and a ligand to carry out catalytic coupling, reacting, and separating and purifying to obtain an intermediate 2; 2) cyclization reaction: mixing the intermediate 2 and an intermediate 3, adding the mixture into a mixed solution of a dehydrating agent and alkali, carrying out full cyclization reaction, and purifying to obtain an intermediate 4; and 3) condensation reaction: mixing the intermediate 4 and an intermediate 5, adding a condensing agent, carrying out full condensation reaction, and carrying out separationand purification to obtain an isoxazoline compound 6. The method has the advantages of short reaction route, accessible raw materials, fewer three wastes and high purity of the purified product, and is suitable for industrial production.

Description

technical field [0001] The invention relates to the technical field of chemical industry, in particular to a preparation method of an isoxazoline insecticide. Background technique [0002] Isoxazoline series insecticides are a new type of high-efficiency insecticides, which act on the GABA target of insects and cause their nervous system to overexcite and die. Compared with traditional insecticides, isoxazoline series insecticides The agent has little side effects on mammals, and besides animal parasites, it also has good insecticidal activity against most agricultural pests, and has a huge market prospect. [0003] Chinese patent CN109879826A reports the synthesis method of isoxazoline series, the synthesis route is relatively long, and its commercial mass-produced products are relatively expensive. The synthetic route is as route 1, and compound formula 1 is synthesized: [0004] Route 1: [0005] [0006] [0007] Chinese patent CN111689919A and Chinese patent CN...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D261/04C07D413/04
CPCC07D261/04C07D413/04Y02P20/55
Inventor 江新华黄凤玲刘晓丽胡龙威
Owner 麦蒂辛生物医药科技成都有限公司
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