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Preparation method of s-isomer indoxacarb

A technology of indoxacarb and a system is applied in the field of preparation of S-indoxacarb, which can solve the problems of unrecyclable catalyst, high production cost, low catalyst efficiency, etc., and achieves benefits of industrialization, improved reaction speed, and enhanced selectivity. Effect

Active Publication Date: 2019-05-03
JINGBO AGROCHEM TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] First, cinchona base catalysts such as cinchonin are used, but the efficiency of this type of catalyst is low, and the S body content of the synthesized indoxacarb original drug is about 70%;
[0005] Second, metal complex catalysts are used. In 2007, DuPont Company of the United States reported a metal zirconium catalyst, but this type of catalyst cannot be recycled, and the production cost is relatively high, and the S body content of the obtained indoxacarb original drug is about 90%;

Method used

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  • Preparation method of s-isomer indoxacarb
  • Preparation method of s-isomer indoxacarb
  • Preparation method of s-isomer indoxacarb

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Embodiment 1 A chiral catalyst containing metal zirconium and a method for preparing S body indoxacarb using the catalyst, the preparation method is as follows:

[0038] (1) Add 22.65g (0.1mol) 3-tert-butyl-5-chloromethyl salicylaldehyde to 100mL clean anhydrous reaction flask, then add 50mL methanol, then weigh 11.4g (0.1mol) cyclohexanedi Amine, slowly added dropwise at 20-25°C.

[0039] (2) After the dropwise addition, the temperature was raised to 65-70°C for reflux reaction. After the reaction, the temperature was lowered to 10°C, and the ligand polymer was obtained by filtration, dried and weighed.

[0040] (3) 2000 mL of a clean anhydrous reaction bottle was put into the ligand polymer in step (2), then 50 mL of toluene and 3.78 g (0.1 mol) of sodium borohydride were added, and the temperature was raised to reflux for reaction.

[0041] (4) Add 24.35 g (0.05 mol) of zirconium acetylacetonate to the above reaction system, fully soak and heat up to 80° C., and kee...

Embodiment 2

[0045] Embodiment 2 A chiral catalyst containing metal zirconium and a method for preparing S body indoxacarb using the catalyst, the preparation method is as follows:

[0046] (1) Add 22.65g (0.1mol) 3-tert-butyl-5-chloromethyl salicylaldehyde to 100mL clean anhydrous reaction flask, then add 50mL methanol, then weigh 17.1g (0.15mol) cyclohexanedi Amine, slowly added dropwise at 20-25°C.

[0047] (2) After the dropwise addition, the temperature was raised to 65-70°C for reflux reaction. After the reaction, the temperature was lowered to 10°C, and the ligand polymer was obtained by filtration, dried and weighed.

[0048] (3) 2000 mL of a clean anhydrous reaction bottle was put into the ligand polymer in step (2), then 50 mL of toluene and 5.4 g (0.1 mol) of potassium borohydride were added, and the temperature was raised to reflux for reaction.

[0049] (4) Add 24.35 g (0.05 mol) zirconium acetylacetonate to the above reaction system, fully swell and heat up to 80° C., heat p...

Embodiment 3

[0053] Embodiment 3. Recycling of metal polymer catalyst

[0054] The catalyst recovered by filtration in Example 2 was added to toluene, and then 113g of tert-butyl hydroperoxide and 224g of 5-chloro-2-methoxycarbonyl-1-indanone ester and 1200mL of toluene were added to carry out the asymmetric synthesis reaction, The temperature was raised to 110° C. for reflux reaction for 4 hours. After the reaction is completed, the metal polymer catalyst is recovered by filtration, and the obtained filtrate can be distilled under reduced pressure to obtain the key intermediate 5-chloro-2-methoxycarbonyl-2-hydroxyl-1-indanone; at the same time, the recovered catalyst is put into 50mL A suspension is formed in toluene solvent to continue the asymmetric synthesis reaction; the prepared intermediate is prepared according to the conventional prior art to obtain the S body indoxacarb.

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Abstract

The invention relates to the field of chemical synthesis, and particularly discloses a brand-new catalyst and a preparation method of s-isomer indoxacarb by using the catalyst, the catalyst is prepared from 3-tert-butyl-5-chloromethyl salicylaldehyde and cyclohexanediamine as raw materials, the catalyst is used for replacing original cinchonine and other cinchona alkaloid catalysts, and is appliedto asymmetric synthesis reaction of tert-butyl hydroperoxide and 5-chloro-2-methoxycarbonyl-1-indanone ester, the selectivity of the asymmetric synthesis process is greatly improved, and the contentof the s-isomer indoxacarb is increased from 75% to more than 98%, the recycling of the high-efficiency chiral catalyst is realized, the production cost is greatly reduced, the synthesis process of the catalyst is simple, the industrialization is facilitated, and a good foundation is laid for producing high-quality indoxacarb.

Description

technical field [0001] The invention relates to the field of chemical synthesis, and specifically discloses a preparation method of S-body indoxacarb. Background technique [0002] Indoxacarb is a new type of oxadiazine insecticide with high efficiency and low toxicity developed by DuPont Company of the United States. It has dual effects of contact killing and stomach poisoning, and can effectively solve resistant pests. It has no cross-resistance with other insecticides such as pyrethroids, organophosphorus, and carbamates, and can well solve the problems of rice leaf rollers, rice stem borers and resistant diamondback moths that are difficult to control in the market. In addition, indoxacarb has a very wide insecticidal spectrum, and one drug can prevent multiple diseases. While preventing and controlling noctuid pests, it also has a good inhibitory effect on mirid bugs, so it is a very good comprehensive management tool. , can well solve the current problems of residues ...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07D273/04C07B53/00C08G12/40C08G12/06
CPCC08G12/06C07D273/04C07B53/00C07C67/31C07C2602/08B01J31/1691B01J31/2243B01J2531/0216B01J2531/48B01J2531/0252C07C69/757B01J31/2217B01J31/4015C07B2200/07
Inventor 薄蕾芳成道泉刘建成冯培良刘花敏王中洋
Owner JINGBO AGROCHEM TECH CO LTD
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