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Preparation method of (+)methyl 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate

A technology of methyl carboxylate and dimethyl carbonate, which is applied in the preparation of carboxylate, the preparation of organic compounds, chemical instruments and methods, etc., can solve the problems of low optical purity of products, prolonged period, incomplete reaction, etc. The effect of reducing cost, increasing content and increasing yield

Inactive Publication Date: 2016-04-06
JINGBO AGROCHEM TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the existing production process, the salt-forming reaction solvent is DMF, DMC, etc., the reaction temperature is lower than 90°C, and the reaction time is short, the reaction is incomplete, the yield is low, and the cost is high; the product is taken out after acidification, and the process is complicated and The cycle is extended; the oxidation reaction generally uses tert-butyl hydroperoxide, and it is added in a single drop, resulting in low catalytic efficiency of Sinclair and lower optical purity of the final product; short oxidation reaction time, low oxidation efficiency of Sinclair, and salt formation , acidification and oxidation total yield is lower

Method used

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  • Preparation method of (+)methyl 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] A preparation method of (+)-5-chloro-2,3-dihydro-2-hydroxyl-1-oxo-1H-indene-2-carboxylic acid methyl ester, the specific steps are:

[0019] (1) Add 0.75mol sodium hydride, 1.68mol dimethyl carbonate, 400g toluene to a 1000ml dry flask, heat up to reflux, start to drop 0.375mol 5-chloro-1-indanone, and the dropping time is 1.5h;

[0020] (2) Continue the reflux reaction for 3.5 hours after the dropwise addition is completed. After the reaction is completed, lower the temperature to 25° C., add 36.5 g of concentrated hydrochloric acid and 365 g of ice to the reaction system, stir for 30 min, let stand for liquid separation, and extract the aqueous phase with 200 g of toluene. Washing with water three times, each time with 200ml of water, the washing temperature is 35°C, and then concentrating to remove 50-70% of the mass of toluene to obtain the toluene solution of intermediate I;

[0021] (3) Dissolve 0.03 mol of Sinconin in 48.6 g of toluene, raise the temperature to 4...

Embodiment 2

[0023] (1) Add 0.83mol sodium hydride, 1.32mol dimethyl carbonate, and 313g toluene to a 1000ml dry flask, heat up to reflux, start to drop 0.375mol 5-chloro-1-indanone, and the dropping time is 2.1h;

[0024] (2) Continue reflux reaction for 4 hours after the dropwise addition is completed. After the reaction is completed, lower the temperature to 25°C, add 73g of concentrated hydrochloric acid and 730g of ice to the reaction system, stir for 30min, let stand to separate the liquid, extract the water phase with 200g of toluene, and then wash with water Three times, each time using 200ml of water, washing with water at a temperature of 35°C, and then concentrating to remove 50-70% of the mass of toluene to obtain the toluene solution of intermediate I;

[0025] (3) Dissolve 0.035 mol of Sinkenin in 56.6 g of toluene, raise the temperature to 44°C, add 0.86 mol of cumene hydroperoxide and the toluene solution of intermediate I dropwise to it at the same time, and keep the temper...

Embodiment 3

[0027] A preparation method of (+)-5-chloro-2,3-dihydro-2-hydroxyl-1-oxo-1H-indene-2-carboxylic acid methyl ester, the specific steps are:

[0028] (1) Add 1.0mol sodium hydride, 1.5mol dimethyl carbonate, 386g toluene to a 1000ml dry flask, heat up to reflux, start to drop 0.375mol 5-chloro-1-indanone, and the dropping time is 2h;

[0029] (2) After the dropwise addition, continue to reflux for 3.7 hours. After the reaction is completed, lower the temperature to 25°C, add 54g of concentrated hydrochloric acid and 540g of ice to the reaction system, stir for 30min, let stand for liquid separation, extract the water phase with 200g of toluene, and combine The two toluene phases were then washed three times with 200 ml of water each time at a temperature of 35° C., and then concentrated to remove 50-70% by mass of toluene to obtain a toluene solution of intermediate I;

[0030] (3) Dissolve 0.037 mol of Sinconin in 59.8 g of toluene, raise the temperature to 42°C, add 0.75 mol o...

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Abstract

The invention relates to the field of pesticide synthesis, and in particular provides a preparation method of an intermediate of indoxacarb, namely (+)methyl 5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylate, and 5-chloro-1-indanone, dimethyl carbonate, sodium hydride, cumene hydroperoxide and cinchonine are mainly adopted as reactants, and a double dropping way of the cumene hydroperoxide and 5-chloro-2-methoxycarbonyl group-1-indanone is adopted, the disadvantages in the prior art of low yield and low content of S-isomer are changed, the yield is improved, the cost is reduced, and the content of an effective body is improved.

Description

technical field [0001] The invention relates to the field of pesticide synthesis, and specifically provides an indoxacarb intermediate (+)-5-chloro-2,3-dihydro-2-hydroxyl-1-oxo-1H-indene-2-carboxylic acid Method for the preparation of methyl esters. Background technique [0002] Indoxacarb, test code: DPX-KN128, DPX-KN127, DPX-MP062, DPX-JW062, was developed by DuPont Company of the United States in 1992 and registered in 2001 as a chiral-enriched insecticide containing oxadiazine , its chemical name is: 4(aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-(trifluoromethoxy)-phenyl]amino]carbonyl]indene And[1,2-e][1,3,4]oxadiazine-4a(3H)-methyl carboxylate, the common name is indoxacarb, and the trade names are ammate (home run 30% water dispersant), vatar (hitting 15% suspending agent) and so on. Indoxacarb can effectively control almost all Lepidoptera pests such as cotton bollworm, noctuid moth and diamondback moth, etc. It is safe for humans, the environment and non-tar...

Claims

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Application Information

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IPC IPC(8): C07C67/00C07C67/31C07C69/757
CPCC07C67/00C07C67/31
Inventor 王平韦能春戴荣华王宗王建刚李洪侠
Owner JINGBO AGROCHEM TECH CO LTD
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