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Synthesis method of 7-mercaptoisobenzofuran-1(3H)-one compound

A ketone compound and synthesis method technology, applied in the field of pesticide synthesis, can solve the problems of high cost, potential safety hazards, low purity of the target product, etc., reduce production operations and energy consumption, reduce the generation of three wastes, and be suitable for industrial production. Effect

Active Publication Date: 2020-12-29
烟台药物研究所
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There are following problems in this route: (1) two-step reaction obtains Ia, and the step is longer; (2) the catalytic hydrogenation step needs to react with hydrogen in an autoclave, and there are potential safety hazards in production; (3) diazotization and mercaptolation steps The composition of the product is complex, and the purity of the target product Ia is low
There are following problems in this route: (1) two-step reaction obtains Ia, and step is longer; (2) preparation compound IV yield is low, only 75%; (3) the price of reducing agent sodium borohydride is higher
[0009] In summary, the preparation of compound Ia from compound IIa in the prior art route is a two-step reaction, and has the disadvantages of low yield and high cost

Method used

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  • Synthesis method of 7-mercaptoisobenzofuran-1(3H)-one compound
  • Synthesis method of 7-mercaptoisobenzofuran-1(3H)-one compound
  • Synthesis method of 7-mercaptoisobenzofuran-1(3H)-one compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] The synthetic method of 7-mercapto-3-methylisobenzofuran-1 (3H)-ketone, the steps are as follows:

[0032] (1) Add compound II and sodium sulfide to DMF, react at 15°C for 5 hours, filter, and evaporate the filtrate to remove the solvent under reduced pressure to obtain a brown solid-liquid mixture;

[0033] Among them, compound II is

[0034] The molar ratio of the compound II and sodium sulfide is 1:1.1;

[0035] (2) Add 30mL water, 30mL methylene chloride and 80wt% acetic acid to the brown solid-liquid mixture gained in step (1), adjust the pH to 5-6, filter, separate liquids, and evaporate the organic solvent under reduced pressure in the organic phase to obtain light Yellow oil, namely 7-mercapto-3-methylisobenzofuran-1(3H)-one; the HPLC area-normalized purity of the product in the reaction solution was 80.71%, and the yield was 82%.

[0036] Analyze the resulting product, 1 H NMR (400MHz, CDCl 3 )δ7.46(t, J=7.7Hz, 1H), 7.28(d, J=7.8Hz, 1H), 7.10(d, J=7.5Hz, ...

Embodiment 2

[0038] The synthetic method of 7-mercapto-3-methylisobenzofuran-1 (3H)-ketone, the steps are as follows:

[0039] (1) Add compound II, sodium sulfide and elemental sulfur to DMF, react at 25°C for 2 hours, filter, and distill the filtrate to remove the solvent under reduced pressure to obtain a brown solid-liquid mixture;

[0040] Among them, compound II is

[0041] The molar ratio of compound II, sodium sulfide and elemental sulfur is 1:1.5:1.65;

[0042] (2) Add 30mL water, 30mL methylene chloride and 80wt% acetic acid to the brown solid-liquid mixture gained in step (1), adjust the pH to be 5-6, filter, separate liquids, and evaporate the organic solvent under reduced pressure in the organic phase to obtain light Yellow oil, namely 7-mercapto-3-methylisobenzofuran-1(3H)-one; the HPLC area-normalized purity of the product in the reaction solution was 88.29%, and the yield was 90%.

Embodiment 3

[0044] The synthetic method of 7-mercapto-3-methylisobenzofuran-1 (3H)-ketone, the steps are as follows:

[0045] (1) Add compound II, sodium sulfide and elemental sulfur to DMF, react at 0°C for 5 hours, filter, and evaporate the filtrate to remove the solvent under reduced pressure to obtain a brown solid-liquid mixture;

[0046] Among them, compound II is

[0047] The molar ratio of compound II, sodium sulfide and elemental sulfur is 1:1.5:1.65;

[0048] (2) Add 30mL water, 30mL methylene chloride and 80wt% acetic acid to the brown solid-liquid mixture gained in step (1), adjust the pH to be 5-6, filter, separate liquids, and evaporate the organic solvent under reduced pressure in the organic phase to obtain light Yellow oil, namely 7-mercapto-3-methylisobenzofuran-1(3H)-one; the HPLC area-normalized purity of the product in the reaction solution was 80.99%, and the yield was 85%.

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Abstract

The invention relates to a preparation method of a pyrimidinylthiobenzoic acid herbicide intermediate, in particular to a synthesis method of a 7-mercaptoisobenzofuran-1(3H)-one compound, and belongsto the technical field of pesticide synthesis. According to the method, the reaction steps are shortened, two-step reaction is changed into one-step reaction, and production operation and energy consumption are reduced. In the production process, the step of catalytic hydrogenation is omitted, and potential safety hazards existing in production are avoided; diazotization and sulfhydrylation stepsare omitted, so that the output of three wastes is reduced; cheap and easily available alkali metal sulfide or alkali metal hydrosulfide and elemental sulfur are used, so that the process route cost is lower, and the method is more suitable for industrial production; under the condition that elemental sulfur is not used, the yield of a target product can reach 80% or above; and under the conditionthat elemental sulfur is used, the yield of a target object can reach 85% or above and even reach 99% and is higher than that of an existing route, the purity is high, and the production cost is further reduced.

Description

technical field [0001] The invention relates to a method for preparing a pyrimidinethiosalicylic acid herbicide intermediate, in particular to a method for synthesizing 7-mercapto-isobenzofuran-1(3H)-one compounds, and belongs to the technical field of pesticide synthesis. Background technique [0002] Pyrimidinethiosalicylic acid herbicides are a new class of acetolactate synthase (ALS) inhibitors developed in recent years, and the listed varieties include clofenclofen, sulfoxyfen and so on. This type of herbicide has the advantages of broad spectrum, low toxicity, short half-life, and less phytotoxicity to subsequent crops. [0003] 7-Mercapto-isobenzofuran-1(3H)-ones are intermediates of pyrimidinethiosalicylic acid herbicides. Take 7-mercapto-3-methylisobenzofuran-1(3H)-one (Ia) as an example, which is an intermediate of the rice herbicide fenpyrafen. [0004] In the existing literature, Pest Manag. Sci., 2001, 57:205-224. reported the synthesis method of Ia for the fi...

Claims

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Application Information

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IPC IPC(8): C07D307/88
CPCC07D307/88
Inventor 李忠李亚平王琛迟永建李为
Owner 烟台药物研究所