CN110437112B - Preparation method of formamidosulfuron or derivative intermediate thereof - Google Patents
Preparation method of formamidosulfuron or derivative intermediate thereof Download PDFInfo
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Abstract
The invention provides a preparation method of formamidosulfuron or a derivative intermediate thereof. The preparation method comprises the following steps: saccharin is taken as a raw material, and after ammoniation and nitration, 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide, namely the formamidosulfuron intermediate, is obtained. The preparation method of the formamidosulfuron intermediate compound by using saccharin as a raw material has the advantages of less pollution, low cost, fewer preparation reaction steps, mild reaction conditions, safety, easiness in operation, more environment-friendly production and suitability for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a preparation method of formamidosulfuron or a derivative intermediate thereof.
Background
Formamidosulfuron (test code: AEF 130360, common name: foramsulfuron, trade name: Cornstar, Conyza, other name: foramsulfuron) is a novel sulfonylurea herbicide developed by the company Anonta. The chemical name is 1- (4, 6-dimethoxypyrimidin-2-yl) -3- (2-dimethylaminocarbonyl-5-carboxamidophenylsulfonyl) urea, and the English chemical name is 1- (4, 6-dimethoxyhydrazinidin-2-y 1) -3- (2-dimethoxycarbaryl-5-formamidophenyl y ls fonyl) urea.
The formamidosulfuron is an ALS (acetolactate synthase) inhibitor which is a key enzyme for biosynthesis of branched chain amino acid, can be absorbed by the roots and leaves of weeds, can be rapidly conducted in plants, can block the synthesis of valine, isoleucine and leucine, and can inhibit cell division and growth. After the sensitive weed roots and leaves absorb the medicament, the sprouts and roots stop growing rapidly, and tender tissues turn yellow and die later.
The existing preparation method of 2-dimethylamino-5-nitrobenzenesulfonamide mainly comprises the following steps: the method comprises the steps of using p-nitrotoluene-o-sulfonic acid as an initial raw material, oxidizing the p-nitrotoluene-o-sulfonic acid with nitric acid at high temperature to prepare 2-carboxylic acid-5-nitrobenzene sulfonic acid, using thionyl chloride and dimethylamine hydrochloride as raw materials to obtain 2-dimethylamino-5-nitrobenzene sulfonic acid, using triphosgene as a halogenating reagent to prepare 2-dimethylamino-5-nitrobenzene sulfonyl chloride, and ammoniating the 2-dimethylamino-5-nitrobenzene sulfonamide with ammonia water.
In the preparation method, glacial acetic acid is used as a solvent, a nitric acid high-temperature oxidation method is needed, the danger is high, and triphosgene is used as a halogenating reagent, so that the industrial production potential safety hazard is high.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a formamidosulfuron intermediate, which has the advantages of few reaction steps, safe and simple process, capability of reducing the discharge of three wastes and environmental friendliness.
The second purpose of the invention is to provide a preparation method of formamidosulfuron.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of a formamidosulfuron or a derivative intermediate thereof comprises the following steps: saccharin is taken as a raw material, and after ammoniation and nitration, 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide, namely the formamidosulfuron intermediate, is obtained.
Meanwhile, the invention also provides a preparation method of the formamidosulfuron, which comprises the following steps: firstly, preparing 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide according to the method; then, the prepared 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide is used as a raw material to prepare the formamidosulfuron or the derivative thereof.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, the saccharin is used as a raw material to prepare the formamidosulfuron intermediate compound, so that the pollution is less, the cost is low, the preparation reaction steps are less, the reaction condition is mild, the operation is safe and easy, the production is more environment-friendly, and the method is suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a nuclear magnetic spectrum of 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide, a product of example 1;
FIG. 2 is a NMR spectrum of the product of step (a) of example 2, Compound IV.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The preparation method provided by the invention is a method for preparing a formamidosulfuron intermediate compound, and more specifically is a method for preparing 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide.
Different from the traditional preparation method taking the p-nitrotoluene compound as the starting material, the saccharin is creatively taken as the starting material and the target compound is obtained through two-step reaction, so that the reaction process is simplified, the reaction condition is milder, and the pollution is less.
The preparation method of the formamidosulfuron or the derivative intermediate thereof provided by the invention can refer to the following steps: saccharin is taken as a raw material, and after ammoniation and nitration, 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide, namely the formamidosulfuron intermediate, is obtained.
In some embodiments of the invention, the amidosulfuron intermediate described above may be obtained from reaction scheme (I) as shown below:
the specific reaction steps comprise:
(a) adding a catalyst and an ammoniation reagent into a solution in which a compound I is dissolved, and reacting to obtain a compound II;
(b) and adding a catalyst and a nitrating reagent into the solution in which the compound II is dissolved, and reacting to obtain a compound III.
In some preferred embodiments of the present invention, as in step (a) of scheme (I) above, the solvent used to dissolve compound I comprises one or more of methanol, acetonitrile, 1, 4-dioxane, N, N-dimethylformamide, benzene, toluene, or xylene;
preferably, the molar amount of the solvent is 5 to 90 times of that of the raw material compound I.
In some preferred embodiments of the present invention, as in scheme (I) step (a) above, the catalyst comprises: at least one of sulfuric acid, hydrochloric acid, acetic acid and p-toluenesulfonic acid;
preferably, the molar ratio of catalyst to compound I is (0.01-4): 1, the molar ratio of the two can be, but is not limited to, 0.05:1, 0.1:1, 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1, etc.
In some preferred embodiments of the present invention, as in scheme (I) step (a) above, the ammoniating reagent comprises: at least one of dimethylamine and dimethylamine hydrochloride;
preferably, dimethylamine hydrochloride can be added as a solid;
preferably, dimethylamine can be added as a solid or as a solution of dimethylamine, for example, dimethylamine methanol solution, dimethylamine ethanol solution, dimethylamine tetrahydrofuran solution, and the like.
Preferably, the molar ratio of ammoniating agent to compound I is (1-20): 1, but not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 7:1, 10:1, 12:1, 15:1, 17:1, 20:1, etc.
In some preferred embodiments of the present invention, as in step (a) of scheme (I) above, the reaction temperature is from-10 ℃ to 150 ℃ (e.g., can be, but is not limited to, 0 ℃, 10 ℃, 20 ℃, 50 ℃, 70 ℃, 90 ℃, 100 ℃, 120 ℃, 150 ℃, etc.), the reaction time is from 0.5 to 24h (e.g., can be, but is not limited to, 1h, 3h, 5h, 7h, 10h, 12h, 15h, 18h, 24h, etc.);
preferably, the step (a) further comprises, after the reaction, distilling the reaction solution under reduced pressure and recrystallizing the reaction solution to obtain the compound II.
In some preferred embodiments of the present invention, as in scheme (I) step (b) above, the solvent used to dissolve compound II comprises: one or more of sulfuric acid, acetic anhydride, dichloromethane, 1, 2-dichloroethane and acetone;
preferably, the molar amount of the solvent is 2-95 times of that of the raw material II.
In some preferred embodiments of the present invention, as in scheme (I) step (b) above, the catalyst comprises: acetic anhydride, KNO3，NaNO3，AgNO3，Ca(NO3)2，Ni(NO3)2One or more of;
preferably, the molar ratio of catalyst to compound II is (0.01-4): 1, the molar ratio of the two can be, but is not limited to, 0.05:1, 0.1:1, 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1, etc.
In some preferred embodiments of the present invention, as in scheme (I) step (b) above, the nitrating agent comprises: nitric acid (concentrated, preferably fuming nitric acid), KNO3，NaNO3，AgNO3，Ca(NO3)2And Ni (NO)3)2One or more of;
preferably, the molar ratio of the nitrating agent to the compound II is (1-20): 1, but not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 7:1, 10:1, 12:1, 15:1, 17:1, 20:1, etc.
In some preferred embodiments of the present invention, step (b), as in scheme (I) above, comprises: controlling the temperature at-10 ℃ to 10 ℃ (for example, but not limited to-5 ℃, 0 ℃, 5 ℃, etc.), adding the nitrating agent into a solvent (the solvent used comprises one or more of sulfuric acid, acetic anhydride, dichloromethane, 1, 2-dichloroethane, acetone), and mixing (for example, stirring, etc.) to obtain a mixed solution;
adding a catalyst into a solution dissolved with a compound II, adding a mixed solution containing a nitrating reagent, reacting for 0.5h-24h (for example, but not limited to 1h, 2h, 4h, 6h, 12h, 18h, 24h and the like) at the temperature of-20 ℃ -80 ℃ (for example, but not limited to-10 ℃, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and the like), pouring a reaction solution into an ice water mixture after the reaction is finished, separating (for example, filtering and separating) the obtained precipitate, drying, and recrystallizing to obtain a compound III (2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide), namely the formamidosulfuron intermediate.
In some embodiments of the invention, the amidosulfuron intermediate described above may be obtained from reaction scheme (II) as shown below:
the method comprises the following specific steps:
(a) adding a catalyst into the solution in which the compound I is dissolved, and reacting to obtain a compound IV;
(b) adding an ammoniation reagent into the solution in which the compound IV is dissolved, and reacting to obtain a compound II;
(c) and adding a catalyst and a nitrating reagent into the solution dissolved with the compound II to obtain a compound III.
In some preferred embodiments of the present invention, as in scheme (II) step (a) above, the solvent used to dissolve compound I comprises: methanol and optionally other solvents;
wherein the other solvents include: one or more of acetonitrile, 1, 4-dioxane, N, N-dimethylformamide, benzene, toluene or xylene;
preferably, the molar amount of the solvent is 5 times or more the molar amount of the raw material compound I.
In some preferred embodiments of the present invention, as in scheme (II) step (a) above, the catalyst comprises one or both of sulfuric acid or hydrochloric acid;
preferably, the molar ratio of catalyst to compound I is (0.01-4): 1, the molar ratio of the two can be, but is not limited to, 0.05:1, 0.1:1, 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1, etc.
In some preferred embodiments of the present invention, step (a), as in scheme (II) above, comprises: controlling the temperature to be 0-25 ℃ (for example, but not limited to 5 ℃, 10 ℃, 15 ℃, 20 ℃ and the like), adding a catalyst into the solution dissolved with the compound I, reacting for 0.5-24h (for example, but not limited to 1h, 2h, 4h, 6h, 12h, 18h, 24h and the like) under the condition of 0-80 ℃ (for example, but not limited to 5 ℃, 10 ℃, 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and the like) after the addition is finished, cooling to room temperature after the reaction is finished, and recrystallizing to obtain the compound IV.
In some preferred embodiments of the present invention, as in scheme (II) step (b) above, the solvent used to dissolve compound IV comprises: one or more of methanol, ethanol, dichloromethane, 1, 2-dichloroethane, tetrahydrofuran and acetonitrile;
preferably, the molar amount of the solvent is more than 2 times of the molar amount of the raw material IV.
In some preferred embodiments of the present invention, as in scheme (II) step (b) above, the ammoniating reagent comprises: at least one of dimethylamine and dimethylamine hydrochloride;
preferably, dimethylamine hydrochloride can be added as a solid;
preferably, dimethylamine can be added as a solid or as a solution of dimethylamine, for example, dimethylamine methanol solution, dimethylamine ethanol solution, dimethylamine tetrahydrofuran solution, and the like.
Preferably, the molar ratio of ammoniating agent to compound IV is (1-20): 1, but not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 7:1, 10:1, 12:1, 15:1, 17:1, 20:1, etc.
In some preferred embodiments of the present invention, step (b) of scheme (II) above comprises: adding an ammoniating reagent into a solution in which the compound IV is dissolved, reacting for 0.5-48h (for example, but not limited to, 1h, 2h, 4h, 6h, 12h, 18h, 24h, 30h, 36h and the like) under the condition of 0-80 ℃ (for example, but not limited to, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and the like), and after the reaction is finished, distilling the reaction solution under reduced pressure to obtain the compound II.
In some preferred embodiments of the present invention, as in scheme (II) above, step (c) may be carried out with reference to the operation of step (b) in scheme (I).
In some preferred embodiments of the present invention, as in scheme (II) step (c) above, the solvent used to dissolve compound II comprises: one or more of sulfuric acid, acetic anhydride, dichloromethane, 1, 2-dichloroethane and acetone;
preferably, the molar amount of the solvent is 2-95 times of that of the raw material II.
In some preferred embodiments of the present invention, as in scheme (II) step (c) above, the catalyst comprises: acetic anhydride, KNO3，NaNO3，AgNO3，Ca(NO3)2，Ni(NO3)2One or more of;
preferably, the molar ratio of catalyst to compound II is (0.01-4): 1, the molar ratio of the two can be, but is not limited to, 0.05:1, 0.1:1, 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1, etc.
In the present inventionIn certain preferred embodiments, as in scheme (II) step (c) above, the nitrating agent comprises: nitric acid (concentrated, preferably fuming nitric acid), KNO3，NaNO3，AgNO3，Ca(NO3)2And Ni (NO)3)2One or more of;
preferably, the molar ratio of the nitrating agent to the compound II is (1-20): 1, but not limited to, 1:1, 2:1, 3:1, 4:1, 5:1, 7:1, 10:1, 12:1, 15:1, 17:1, 20:1, etc.
In some preferred embodiments of the present invention, step (c), as in scheme (II) above, comprises: controlling the temperature at-10 ℃ to 10 ℃ (for example, but not limited to-5 ℃, 0 ℃, 5 ℃, etc.), adding the nitrating agent into a solvent (the solvent used comprises one or more of sulfuric acid, acetic anhydride, dichloromethane, 1, 2-dichloroethane, acetone), and mixing (for example, stirring, etc.) to obtain a mixed solution;
adding a catalyst into a solution dissolved with a compound II, adding a mixed solution containing a nitrating reagent, reacting for 0.5h-24h (for example, but not limited to 1h, 2h, 4h, 6h, 12h, 18h, 24h and the like) at the temperature of-20 ℃ -80 ℃ (for example, but not limited to-10 ℃, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and the like), pouring a reaction solution into an ice water mixture after the reaction is finished, separating (for example, filtering and separating) the obtained precipitate, drying, and recrystallizing to obtain a compound III (2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide), namely the formamidosulfuron intermediate.
Further, based on the preparation method, the invention can also provide a preparation method of formamidosulfuron, in the preparation method, firstly, 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide is obtained according to the method, and then, the 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide is used as a raw material to obtain a final product formamidosulfuron (for example, refer to the prior art, such as the method disclosed in CN1414955A and the like).
Taking the method disclosed in CN1414955A as an example, and 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide as a raw material, the reaction equation for preparing formamidosulfuron can be referred to as follows:
example 1 preparation of a formamidosulfuron intermediate:
(a) adding 25g of saccharin (compound I) and 250mL of acetonitrile into a 500mL three-neck bottle at room temperature, starting stirring, slowly dropwise adding 2.68g of concentrated sulfuric acid, then adding 55.75g of dimethylamine hydrochloride, starting heating to 70 ℃ after the addition is finished, and reacting for 8 hours; after the reaction was completed, distillation under reduced pressure was started, and the residue was purified by silica gel column chromatography to obtain 26.5g of a white solid (compound II) with a yield of 85%.
The nuclear magnetic resonance hydrogen spectrum analysis of the product is as follows:
1H NMR(400MHz,CDCl3)：δ9.39(s,2H),7.87–7.75(m,2H),7.71–7.60(m,2H),2.81(s,6H)。
the reaction equation is as follows:
(b) 30mL of glacial acetic acid is added into a 150mL three-neck bottle, the temperature is reduced to 0 ℃, and 30mL of concentrated nitric acid is added dropwise to prepare mixed acid.
Adding 24g of the compound II into a 100mL three-necked bottle, adding 48mL of glacial acetic acid, stirring at a constant speed, cooling to 0 ℃, starting to dropwise add mixed acid, controlling the reaction temperature between 0 ℃ and 15 ℃, and reacting for 4 hours. The reaction solution was poured onto crushed ice, and the precipitate was filtered, vacuum dried, and purified by silica gel column chromatography to give 24.5g of a gray solid (compound III, 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide), with a yield of 85%, and the nuclear magnetism of the product as shown in fig. 1.
The reaction equation is as follows:
example 2
(a) Adding 25g of I and 100mL of methanol into a 250mL three-neck flask at room temperature, starting stirring, controlling the temperature to be between 10 and 25 ℃, slowly dropwise adding 8.03g of concentrated sulfuric acid, after the addition is finished, heating a reaction system to 70 ℃, and reacting for 12 hours; after the reaction, the temperature is reduced to room temperature, white solid IV 26.14g is obtained by recrystallization, the yield is 89%, and the nuclear magnetism of the product is shown in figure 2.
The reaction equation is as follows:
hydrogen nuclear magnetic resonance spectroscopy was as follows:
1H NMR(400MHz,CDCl3)δ8.16(d,J＝7.2Hz,1H),7.87(d,J＝7.2Hz,1H),7.71–7.59(m,2H),5.72(s,2H),4.00(s,3H)。
(b) adding 25g of IV and 100mL of tetrahydrofuran into a 500mL three-necked bottle, starting stirring, controlling the temperature to be between 10 and 25 ℃, slowly dropwise adding 290mL of 2M dimethylamine tetrahydrofuran solution, and reacting for 20 hours after the addition is finished; after the reaction, distillation under reduced pressure was started, and recrystallization gave 23.86g of a white solid II in a yield of 90%.
The reaction equation is as follows:
(c) 30mL of glacial acetic acid is added into a 150mL three-neck bottle, the temperature is reduced to 0 ℃, and 30mL of concentrated nitric acid is added dropwise to prepare mixed acid.
Adding 24g of the compound II into a 100mL three-necked bottle, adding 20mL of glacial acetic acid, stirring at a constant speed, cooling to 0 ℃, starting to dropwise add mixed acid, controlling the reaction temperature between 0 ℃ and 15 ℃, and reacting for 4 hours. The reaction solution was poured onto crushed ice, and the precipitate was filtered, vacuum dried, and purified by silica gel column chromatography to give 24.5g of a gray solid (compound III, 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide), with a yield of 85%, and the nuclear magnetism of the product as shown in fig. 1.
The reaction equation is as follows:
example 3
(a) Adding 25g of saccharin (compound I) and 150mL of N, N-dimethylformamide into a 500mL three-necked bottle at room temperature, starting stirring, slowly dropwise adding 11.06g of concentrated hydrochloric acid, then adding 55.75g of dimethylamine hydrochloride, starting heating to 100 ℃ after the addition is finished, and reacting for 6 hours; after completion of the reaction, distillation under reduced pressure was started, and the residue was purified by silica gel column chromatography to obtain 21.81g of a white solid (compound II) in a yield of 70%.
The reaction equation is as follows:
(b) adding 20g of compound II into a 250mL three-neck flask, adding 120mL of concentrated sulfuric acid, stirring at a constant speed, cooling to 0 ℃, and adding 11.18g of NaNO3The reaction temperature is controlled between 0 ℃ and 15 ℃ and the reaction is carried out for 6 hours. The reaction solution was poured onto crushed ice, and the precipitate was filtered, vacuum-dried, and purified by silica gel column chromatography to obtain 17.96g of a gray solid (compound III, 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide) in a yield of 75%.
The reaction equation is as follows:
example 4
(a) Adding 25g of I and 100mL of methanol into a 250mL three-neck flask at room temperature, starting stirring, controlling the temperature to be between 10 and 25 ℃, slowly dropwise adding 13.39g of concentrated sulfuric acid, after the addition is finished, heating a reaction system to 70 ℃, and reacting for 10 hours; after the reaction is finished, cooling to room temperature, and recrystallizing to obtain 23.5g of white solid IV with the yield of 80%;
the reaction equation is as follows:
(b) adding 20g of IV and 120mL of tetrahydrofuran into a 250mL three-necked bottle, starting stirring, controlling the temperature to be between 10 and 25 ℃, adding 22.74g of dimethylamine hydrochloride, heating a reaction system to 70 ℃ after the addition is finished, and reacting for 12 hours; after the reaction was completed, distillation under reduced pressure was started, and recrystallization gave 11.67g of a white solid II in 55% yield.
The reaction equation is as follows:
(c) adding 20g of compound II into a 250mL three-neck flask, adding 120mL of concentrated sulfuric acid, stirring at a constant speed, cooling to 0 ℃, and adding 11.18g of NaNO3The reaction temperature is controlled between 0 ℃ and 15 ℃ and the reaction is carried out for 6 hours. The reaction solution was poured onto crushed ice, and the precipitate was filtered, vacuum-dried, and purified by silica gel column chromatography to obtain 17.96g of a gray solid (compound III, 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide) in a yield of 75%.
The reaction equation is as follows:
while particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to include in the appended embodiments all such changes and modifications that are within the scope of this invention.
Claims (10)
1. The preparation method of the formamidosulfuron intermediate is characterized by comprising the following steps:
(1a) adding a catalyst and an ammoniation reagent into a solution in which a compound I is dissolved, and reacting to obtain a compound II;
(1b) adding a catalyst and a nitrating reagent into the solution in which the compound II is dissolved, and reacting to obtain a compound III, namely a formamidosulfuron intermediate;
the reaction formula is as follows:
wherein, in the step (1a), the catalyst is at least one selected from sulfuric acid, hydrochloric acid, acetic acid and p-toluenesulfonic acid; the ammoniation reagent is selected from at least one of dimethylamine and dimethylamine hydrochloride;
in the step (1b), the catalyst is selected from glacial acetic acid, and the nitrating reagent is selected from mixed acid of concentrated nitric acid and glacial acetic acid;
or, in the step (1b), the catalyst is selected from concentrated sulfuric acid, and the nitrating reagent is selected from NaNO3；
Or, the preparation method of the formamidosulfuron intermediate comprises the following steps:
(2a) adding a catalyst into the solution in which the compound I is dissolved, and reacting to obtain a compound IV;
(2b) adding an ammoniation reagent into the solution in which the compound IV is dissolved, and reacting to obtain a compound II;
(2c) adding a catalyst and a nitrating reagent into the solution in which the compound II is dissolved to obtain a compound III;
the reaction formula is as follows:
wherein, in the step (2a), the catalyst is selected from one or two of sulfuric acid or hydrochloric acid;
in the step (2b), the ammoniation reagent is at least one selected from dimethylamine and dimethylamine hydrochloride;
in the step (2c), the catalyst is selected from glacial acetic acid, and the nitrating reagent is selected from mixed acid of concentrated nitric acid and glacial acetic acid;
or, in the step (2c), the catalyst is selected from concentrated sulfuric acid, and the nitrating reagent is selected from NaNO3。
2. The preparation method of the formamidosulfuron intermediate as claimed in claim 1, wherein the molar ratio of the catalyst to the compound I in the step (1a) is (0.01-4): 1.
3. the preparation method of the formamidosulfuron intermediate as claimed in claim 1, wherein the molar ratio of the amination reagent to the compound I in step (1a) is (1-20): 1.
4. the preparation method of the formamidosulfuron intermediate as claimed in claim 1, wherein the molar ratio of the catalyst to the compound II in the step (1b) is (0.01-4): 1.
5. the preparation method of the formamidosulfuron intermediate as claimed in claim 1, wherein the molar ratio of the nitrating agent to the compound II in the step (1b) is (1-20): 1.
6. the preparation method of the formamidosulfuron intermediate as claimed in claim 1, wherein the molar ratio of the catalyst to the compound I in the step (2a) is (0.01-4): 1.
7. the preparation method of the formamidosulfuron intermediate as claimed in claim 1, wherein the molar ratio of the amination reagent to the compound IV in the step (2b) is (1-20): 1.
8. the preparation method of the formamidosulfuron intermediate as claimed in claim 1, wherein the molar ratio of the catalyst to the compound II in the step (2c) is (0.01-4): 1.
9. the preparation method of the formamidosulfuron intermediate as claimed in claim 1, wherein the molar ratio of the nitrating agent to the compound II in the step (2c) is (1-20): 1.
10. a preparation method of formamidosulfuron is characterized by comprising the following steps:
preparing 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide according to the process of any one of claims 1 to 9;
then, the prepared 2-dimethylaminocarbonyl-5-nitrobenzenesulfonamide is used as a raw material to prepare the formamidosulfuron.
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