Preparation method of 2-(2-chloro-3-chloromethyl-4-methylsulfonyl benzoyl)-1,3-cyclohexanedione

A technology of methanesulfonylbenzoyl and methanesulfonylbenzoyl chloride is applied in the field of preparation of 2--1,3-cyclohexanedione, and can solve the problem of affecting the quality of the original drug of cyclosulfonone, without a synthesis method, and without Causes and other problems, and achieves the effect of being conducive to preparation and convenient operation, high selectivity, and guaranteed yield

Inactive Publication Date: 2019-10-22
JIANGXI TIANYU CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0009] This impurity appears as a by-product in the process of preparing the tembotrione technical drug, and it is difficult to remove due to similar properties, which seriously affects the quality of the tembotrione technical product
And at present, the research method about this impurity has not been reported yet, has not aroused the concern of relevant research, and also does not have synthetic method to synthesize this impurity, this is a restriction factor for the quality control of cycloflavone technical

Method used

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  • Preparation method of 2-(2-chloro-3-chloromethyl-4-methylsulfonyl benzoyl)-1,3-cyclohexanedione
  • Preparation method of 2-(2-chloro-3-chloromethyl-4-methylsulfonyl benzoyl)-1,3-cyclohexanedione
  • Preparation method of 2-(2-chloro-3-chloromethyl-4-methylsulfonyl benzoyl)-1,3-cyclohexanedione

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058] This example prepares 2-(2-chloro-3-chloromethyl-4-methylsulfonylbenzoyl)-1,3-cyclohexanedione through the following steps

[0059] (1) Synthesis of 2-chloro-3-chloromethyl-4-methylsulfonylbenzoic acid, the reaction formula is as follows:

[0060]

[0061] Add 2000mL 1,2-dichloroethane, 264.6g 2-chloro-3-bromomethyl-4-methylsulfonylbenzoic acid (99%, 0.8mol, prepared by referring to methods in WO2001007422 and US20040236146 ), 194.7g of concentrated hydrochloric acid (36%, 1.92mol) and 4g of sodium bromide, started stirring, and then heated up to 80°C for 10h. After the reaction was completed, 225.9 g of 2-chloro-3-chloromethyl-4-methylsulfonylbenzoic acid was obtained through layering and precipitation, with an HPLC content of 97.8% and a reaction yield of 97.6%.

[0062] LC / MS, [M+1] + (%): 283 (100).

[0063] (2) Synthesis of 2-chloro-3-chloromethyl-4-methylsulfonylbenzoyl chloride, the reaction formula is as follows:

[0064]

[0065] Add 786mL 1,2-dichlor...

Embodiment 2

[0072] This example prepares 2-(2-chloro-3-chloromethyl-4-methylsulfonylbenzoyl)-1,3-cyclohexanedione through the following steps

[0073] (1) Synthesis of 2-chloro-3-chloromethyl-4-methylsulfonylbenzoic acid, the reaction formula is as follows:

[0074]

[0075] Add 2000mL carbon tetrachloride, 264.6g 2-chloro-3-bromomethyl-4-methanesulfonylbenzoic acid (99%, 0.8mol, prepared with reference to methods in WO2001007422 and US20040236146), 162.25g Concentrated hydrochloric acid (36%, 1.6 mol) and 2.89 g of sodium bromide were started to stir, and then the temperature was raised to 90° C. for 8 h. After the reaction was completed, 223.1 g of 2-chloro-3-chloromethyl-4-methanesulfonylbenzoic acid was obtained through layering and precipitation. The HPLC content was 97.5%, and the reaction yield was 96.4%.

[0076] LC / MS, [M+1] + (%): 283 (100).

[0077] (2) Synthesis of 2-chloro-3-chloromethyl-4-methylsulfonylbenzoyl chloride, the reaction formula is as follows:

[0078] ...

Embodiment 3

[0086] This example prepares 2-(2-chloro-3-chloromethyl-4-methylsulfonylbenzoyl)-1,3-cyclohexanedione through the following steps

[0087] (1) Synthesis of 2-chloro-3-chloromethyl-4-methylsulfonylbenzoic acid, the reaction formula is as follows:

[0088]

[0089] Add 2000mL chloroform, 264.6g 2-chloro-3-bromomethyl-4-methanesulfonylbenzoic acid (99%, 0.8mol, prepare with reference to the method in WO2001007422 and US20040236146), 243.4g concentrated hydrochloric acid ( 36%, 2.4mol) and 4.11g of sodium bromide, started stirring, and then heated to 70°C for 13h. After the reaction was completed, 217.6 g of 2-chloro-3-chloromethyl-4-methanesulfonylbenzoic acid was obtained through layering and precipitation, with an HPLC content of 96.8% and a reaction yield of 94.0%.

[0090] LC / MS, [M+1] + (%): 283 (100).

[0091] (2) Synthesis of 2-chloro-3-chloromethyl-4-methylsulfonylbenzoyl chloride, the reaction formula is as follows:

[0092]

[0093] Add 786mL toluene, 217.6g 2...

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Abstract

The invention provides a preparation method of 2-(2-chloro-3-chloromethyl-4-methylsulfonyl benzoyl)-1,3-cyclohexanedione. The preparation method comprises the following steps that 2-chloro-3-bromomethyl-4-methylsulfonyl benzoic acid is taken as a raw material, through chlorination, acyl chlorination and 1,3-cyclohexanedione substitution and rearrangement reaction, and the 2-(2-chloro-3-chloromethyl-4-methylsulfonyl benzoyl)-1,3-cyclohexanedione is obtained. According to the preparation method, the new synthesis method is provided, the final yield can reach more than 90%, the HPLC detection content can reach more than 99%, purity is high, and the preparation method can be used as a reference substance, is conducive to development of the analysis method of tembotrions, more beneficial to quality control of tembotrions products, and provides a new thinking for the quality control of the products.

Description

technical field [0001] The invention belongs to the field of synthesis of pharmaceutical intermediates, and relates to a preparation method of 2-(2-chloro-3-chloromethyl-4-methylsulfonylbenzoyl)-1,3-cyclohexanedione. Background technique [0002] Tembotrione (tembotrione) is a triketone cornfield herbicide developed by Bayer in 2007. It belongs to the HPPD inhibitory herbicide. Its activity is higher than that of mesotrione and it is safe for crops. Its structural formula is as follows: [0003] [0004] Terbotrione has a strong killing effect on a variety of weeds, has no residual activity, and has strong resistance to rain erosion. It has a wide range of weeding spectrum for weeding in corn fields. It can maintain good herbicidal activity during the whole growth period of crops, and can also control broad-leaved weeds well, and will not cause harm to crops such as soybeans. It is usually used for post-emergence of corn and soybeans. Control grass weeds. [0005] The p...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C315/04C07C317/24
CPCC07C315/04C07C317/24C07C317/44
Inventor 赵东江周玲伍斌黄超群
Owner JIANGXI TIANYU CHEM CO LTD
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