A sulfonamide compound, a preparation method and application thereof, a pesticide preparation, a pharmaceutical

Abstract

The present invention relates to the field of pesticides and discloses a sulfonamide compound, its preparation method and application, a pesticide formulation, and a medicament. The compound has a structure represented by formula (I). The sulfonamide compound represented by formula (I) provided by the present invention can significantly enhance the ability of plant seedlings to emerge from the soil and delay the flowering period of plants, thus having high application value. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the field of pesticides, and in particular to a sulfonamide compound, a preparation method and application thereof, a pesticide preparation containing the sulfonamide compound, and an agent for enhancing the emergence ability of plant seedlings and / or delaying the flowering period of plants. Background Art

[0002] The timing of seed emergence affects the emergence rate and uniformity of the seedlings. Especially under conditions of soil compaction or adverse stress, early seed emergence allows for earlier photosynthesis, thereby improving adaptability to the environment. Seed emergence primarily depends on hypocotyl / coleoptile elongation, which is primarily related to the plant's sensitivity to light quality. Photomorphogenesis is a key mechanism by which plants rely on light to control their growth and development. Plants sense changes in the external photoperiod through various photoreceptor proteins; the plant photoreceptor protein family primarily includes phytochromes, cryptochromes, phototropism 1, and UVR8 proteins. Cryptochrome (CRY), a key member of the plant photoreceptor protein family, is a highly conserved blue light receptor that senses external blue light signals and regulates processes such as photomorphogenesis, photoperiodic flowering, circadian rhythms, and stomatal opening. Modulating CRY protein activity can effectively regulate plant photomorphogenesis, photoperiodic flowering, vegetative and reproductive growth, and plays a crucial role in regulating crop growth, development, and quality. Inhibiting the activity of CRY can relieve the inhibition of CRY on the elongation of hypocotyl / coleoptile under blue light and promote the emergence of seedlings; it can inhibit stomatal guard cells, promote stomatal closure, and inhibit transpiration; it can also inhibit the photoperiod flowering process, delay the flowering process, and regulate the flowering period.

[0003] Cryptochromes have a wide range of biological activities, and plant growth regulators targeting cryptochromes have important potential applications. In recent years, a research team has obtained the cryptochrome inhibitor 3-bromo-7-nitroindazole (3B7N) through high-throughput screening technology, which can relieve the inhibition of blue light on hypocotyl elongation (see WO2018074554A1 for details). However, the activity of this compound is still unsatisfactory and its stability is poor, which limits its application in agriculture.

[0004] Therefore, the design and synthesis of compounds that modulate cryptochrome activity, and thereby regulate plant photomorphogenesis and growth, is a hot area of chemical research. Research and development of compounds that regulate photomorphogenesis could improve the uniformity of seedlings and enhance their adaptability to the external environment by promoting earlier emergence. Research and development of compounds that modulate cryptochrome activity could also regulate the flowering period of plants. Summary of the Invention

[0005] The present invention aims to provide a sulfonamide compound, so as to enhance the emergence ability of plant seedlings and delay the flowering period of plants.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides a sulfonamide compound or its stereoisomers, geometric isomers, tautomers, or agrochemically acceptable salts, prodrugs, hydrates, solvates, and metabolites, wherein the compound has a structure represented by formula (I):

[0007]

[0008] Wherein, in formula (I),

[0009] R1 is selected from -CH2R5, -CHR6R7, -C(R8)3, hydroxy substituted C 3-8 Cycloalkyl;

[0010] R5 is C 2-4 Ester group or -L1-R a ;

[0011] L1 is C 1-6 Alkylene, R a Selected from -CH(OH)CH2OH, halogen, amino, C 2-4 ester group, carboxyl group; or L1 is phenylene, R a is selected from carboxyl, hydroxyl, hydroxymethyl; or L1 is -CH(OH)-, R a Selected from hydroxymethyl, -CH(OH)CH2OH;

[0012] R6 and R7 are each independently selected from substituted or unsubstituted C 1-6 Alkyl, carboxyl, C 2-4 Ester group, -CONH2;

[0013] The substituents optionally contained in R6 and R7 are selected from hydroxyl, imidazole, amino, C 2-4 Ester group, thiol group, phenyl group, hydroxyphenyl group, indolyl group, -NHC(NH)NH2, -CONH2, -SC 1-3 At least one of the alkyl groups of

[0014] R8 is selected from hydroxy substituted C 1-6 Alkyl;

[0015] R2 is selected from H, hydroxy, amino, halogen;

[0016] R3 and R4 are each independently selected from any one of H, amino, halogen, hydroxyl, and -SO2NHR1.

[0017] A second aspect of the present invention provides a method for preparing a sulfonamide compound having a structure represented by formula (I) or its stereoisomers, geometric isomers, tautomers, or agrochemically acceptable salts, prodrugs, hydrates, solvates, or metabolites, the method comprising: contacting a compound represented by formula (A) with a compound represented by formula (B) in the presence of a solvent;

[0018] H2N-R1 formula (B),

[0019] Among them, in formula (A), R 3 、R 4 Each independently selected from H, amino, halogen, hydroxyl,

[0020] In formula (A) and formula (B), the definitions of R1 and R2 are the same as those described in the first aspect.

[0021] The third aspect of the present invention provides a pesticide formulation comprising the sulfonamide compound described in the first aspect or at least one of its stereoisomers, geometric isomers, tautomers, or agrochemically acceptable salts, prodrugs, hydrates, solvates, metabolites, and agriculturally acceptable carriers.

[0022] The fourth aspect of the present invention provides the use of the sulfonamide compound or its stereoisomers, geometric isomers, tautomers, or agrochemically acceptable salts, prodrugs, hydrates, solvates, and metabolites according to the first aspect in enhancing the ability of plant seedlings to emerge from the soil and / or delaying the flowering period of plants.

[0023] The fifth aspect of the present invention provides an agent for enhancing the ability of plant seedlings to emerge from the soil and / or delaying the flowering period of plants, characterized in that the active ingredient of the agent is the sulfonamide compound described in the first aspect or at least one of its stereoisomers, geometric isomers, tautomers, or agrochemically acceptable salts, prodrugs, hydrates, solvates, and metabolites, and the content of the active ingredient is 0.1-100 weight % based on the total weight of the agent.

[0024] The sulfonamide compound represented by formula (I) provided by the present invention can significantly enhance the ability of plant seedlings to emerge from the soil, delay the flowering period of plants, and has high application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a length phenotype of the hypocotyl of Arabidopsis thaliana treated with Compound 10 (at a concentration of 5 μM) and the control group (DMSO) in Test Example 1 after being cultured at room temperature for 5 days under continuous irradiation with a blue light intensity of 1300 lux.

[0026] Figure 2 This is a statistical graph of the hypocotyl lengths of Arabidopsis thaliana treated with Compound 10 (at a concentration of 5 μM) and a control group (DMSO) in Test Example 1 after being cultured at room temperature for 5 days under continuous irradiation with a blue light intensity of 1300 lux.

[0027] Figure 3 This is a length phenotype of the hypocotyl of Arabidopsis thaliana treated with compounds 21, 22, 30, and 32 (at a concentration of 5 μM) in Test Example 1 and a control group (DMSO) after being cultured at room temperature for 5 days under continuous irradiation with a blue light intensity of 400 lux.

[0028] Figure 4 This is a statistical graph of the hypocotyl lengths of Arabidopsis thaliana treated with compounds 21, 22, 30, and 32 (at a concentration of 5 μM) and a control group (DMSO) in Test Example 1 after being cultured at room temperature for 5 days under continuous irradiation with a blue light intensity of 400 lux.

[0029] Figure 5 This is a phenotypic diagram of the hypocotyl length of Arabidopsis thaliana treated with different concentrations of Compound 10 in Test Example 2 under continuous irradiation with a blue light intensity of 1300 lux.

[0030] Figure 6 This is a statistical graph of the hypocotyl length of Arabidopsis thaliana treated with different concentrations of Compound 10 in Test Example 2 under continuous irradiation with a blue light intensity of 1300 lux.

[0031] Figure 7 This is a phenotypic graph of the hypocotyl length of wild-type Arabidopsis thaliana (Col-0), cry1 mutant (cry1), cry2 mutant (cry2), cry1-cry2 double mutant (cry1cry2), CRY1-overexpressing Arabidopsis thaliana (CRY1-OX), and CRY2-overexpressing Arabidopsis thaliana (CRY2-OX) treated with 5 μM concentration of Compound 10 in Test Example 3 after being cultured at room temperature for 5 days under continuous irradiation with a blue light intensity of 1300 lux.

[0032] Figure 8 This is a statistical graph of the hypocotyl length of wild-type Arabidopsis thaliana (Col-0), cry1 mutant (cry1), cry2 mutant (cry2), cry1-cry2 double mutant (cry1cry2), CRY1-overexpressing Arabidopsis thaliana (CRY1-OX), and CRY2-overexpressing Arabidopsis thaliana (CRY2-OX) treated with 5 μM concentration of Compound 10 in Test Example 3 after being cultured at room temperature for 5 days under continuous irradiation with a blue light intensity of 1300 lux.

[0033] Figure 9a 、 Figure 9bThe specific binding ability of compounds 10 and 21 to the receptor protein Arabidopsis cryptochrome AtCRY2 was determined by microthermophoresis (MST) in Test Example 4; wherein,

[0034] Figure 9a This is a schematic diagram of the MST test results of compound 10 and receptor protein AtCRY2;

[0035] Figure 9b This is a schematic diagram of the MST test results of compound 21 and receptor protein AtCRY2.

[0036] Figure 10 This is a comparison chart of the results of compound 10 in test example 5 promoting the elongation of the hypocotyl of mung bean in 4 cm deep nutrient soil; Figure 10 The middle (left) is a picture of mung bean seedlings growing in the soil. Figure 10 The middle one is a picture of the length of the hypocotyl of mung bean seedlings. Figure 10 The middle (right) is a statistical chart of the hypocotyl length of mung bean seedlings.

[0037] Figure 11 This is a comparison chart of the results of compound 10 in test example 5 promoting the elongation of the hypocotyl of mung bean in 6 cm deep nutrient soil; wherein, Figure 11 The middle (left) is a picture of mung bean seedlings growing in the soil. Figure 11 The middle one is a picture of the length of the hypocotyl of mung bean seedlings. Figure 11 The middle (right) is a statistical chart of the hypocotyl length of mung bean seedlings.

[0038] Figure 12 This is a comparison chart of the results of compound 10 in test example 5 promoting the elongation of the hypocotyl of mung bean in 8 cm deep nutrient soil; wherein, Figure 12 The middle (left) is a picture of mung bean seedlings growing in the soil. Figure 12 The middle one is a picture of the length of the hypocotyl of mung bean seedlings. Figure 12 The middle (right) is a statistical chart of the hypocotyl length of mung bean seedlings.

[0039] Figure 13a This is a comparison chart of the results of compounds 17, 21, and 22 in Test Example 6 promoting wheat seedling emergence.

[0040] Figure 13b This is a statistical chart showing the results of compounds 17, 21, and 22 in Test Example 6 promoting wheat seedling emergence.

[0041] Figure 14a This is a comparison chart of the results of Compounds 17, 21, and 22 in Test Example 7 in delaying the flowering period of Arabidopsis thaliana.

[0042] Figure 14b This is a statistical graph of the number of rosette leaves of Arabidopsis thaliana treated with compounds 17, 21, and 22 in Test Example 7.

[0043] Figure 14c This is a statistical graph showing the results of compounds 17, 21, and 22 in Test Example 7 delaying the flowering period of Arabidopsis thaliana. DETAILED DESCRIPTION

[0044] The endpoints of the ranges and any values disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0045] The following terms are explained for the present invention:

[0046] In this article, the wavy lines in the groups Indicates the bonding position.

[0047] "Halogen" includes fluorine, chlorine, bromine and iodine.

[0048] “C 2-4 "ester group" means an ester group having a total carbon number of 2 to 4, for example, the group can be wait.

[0049] “C 1-6 "Alkylene" means an alkylene group having 1 to 6 carbon atoms, which can be 1, 2, 3, 4, 5 or 6. For example, C 1-6 The alkylene group may be methylene, ethylene, n-propylene, isopropylene, butylene, pentylene, n-hexylene, etc. 1-4 The "alkylene" has a similar explanation, except that the number of carbon atoms is different.

[0050] In the present invention, the alkylene group refers to the residue after an alkane loses two hydrogen atoms. The two hydrogen atoms can be two hydrogen atoms on the same carbon atom or two hydrogen atoms on different carbon atoms. The group can be linear or branched. For example, the ethylene group can be -CH2CH2- or -CH(CH3)-.

[0051] In the present invention, "phenylene" can be wait.

[0052] "Substituted or unsubstituted C 1-6 "alkyl" means an alkyl group having 1 to 6 carbon atoms, including C 1-6 Straight chain alkyl, C 1-6 The number of carbon atoms may be 1, 2, 3, 4, 5 or 6, and optionally C1-6 At least one H in the alkyl group is substituted by a corresponding group as defined herein. 1-4 The "alkyl group" has a similar explanation, except that the number of carbon atoms is different.

[0053] "Hydroxy-substituted C 3-8 "Cycloalkyl" means that at least one H in a cycloalkyl group having 3, 4, 5, 6, 7 or 8 carbon atoms is replaced by a hydroxyl group. For example, the group can be etc. For “Hydroxy-substituted C 3-6 The "cycloalkyl" has a similar interpretation, except that the number of carbon atoms is different.

[0054] "Hydroxy-substituted C 1-6 "Hydroxy-substituted alkyl" means that at least one H in a straight or branched alkyl group with a total carbon number of 1 to 6 is replaced by a hydroxyl group. For example, the group can be -CH2OH, -CH2CH2OH, -CH(CH3)OH, -CH2CH2CH2OH, etc. 1-4 The "alkyl group" has a similar explanation, except that the number of carbon atoms is different.

[0055] In the present invention, "-SC 1-3 The "alkyl" can be -SCH2CH2CH3, -SCH2CH3, -SCH3, -SCH(CH3)2, etc.

[0056] In the present invention, in "-SO2NHR1", R1 is the same as R1 in formula (I), selected from -CH2R5, -CHR6R7, -C(R8)3, hydroxy-substituted C 3-8 Any one of the cycloalkyl groups.

[0057] "Hydrate" refers to the compound of formula (I) provided herein, which forms a solid or liquid molecular compound by hydration with water. It can also be said to be an association compound formed when the solvent molecule is water. Solid hydrates contain water in a stoichiometric ratio as so-called water of crystallization, wherein the water molecules are not necessarily equivalent to their bound state. For example, the hydrate may be a monohydrate, a dihydrate, etc.

[0058] "Solvate" refers to an association formed between one or more solvent molecules and the compound of the present invention. Solvents that form solvates include but are not limited to water, isopropanol, ethanol, methanol, dimethyl sulfoxide, ethyl acetate, and the like.

[0059] "Prodrug" refers to the compound of the above general formula (I) provided by the present invention, which itself may be biologically active or inactive, but can be converted into a corresponding biologically active form (eg, by metabolism, solvent or other means).

[0060] "Metabolites" refer to products produced by the metabolism of a specific compound or its salt in a plant. Metabolites of a compound can be identified using techniques known in the art, and their activity can be characterized using assays such as those described herein. Such products can be obtained by oxidation, reduction, hydrolysis, amidation, deamidation, esterification, defatting, enzymatic cleavage, or the like of the administered compound.

[0061] As mentioned above, the first aspect of the present invention provides a sulfonamide compound or its stereoisomers, geometric isomers, tautomers, or agrochemically acceptable salts, prodrugs, hydrates, solvates, or metabolites, wherein the compound has a structure shown in formula (I):

[0062]

[0063] Wherein, in formula (I),

[0064] R1 is selected from -CH2R5, -CHR6R7, -C(R8)3, hydroxy substituted C 3-8 Cycloalkyl;

[0065] R5 is C 2-4 Ester group or -L1-R a ;

[0066] L1 is C 1-6 Alkylene, R a Selected from -CH(OH)CH2OH, halogen, amino, C 2-4 ester group, carboxyl group; or L1 is phenylene, R a is selected from carboxyl, hydroxyl, hydroxymethyl; or L1 is -CH(OH)-, R a It is hydroxymethyl, -CH(OH)CH2OH;

[0067] R6 and R7 are each independently selected from substituted or unsubstituted C 1-6 Alkyl, carboxyl, C 2-4 Ester group, -CONH2;

[0068] The substituents optionally contained in R6 and R7 are selected from hydroxyl, imidazole, amino, C 2-4 Ester group, thiol group, phenyl group, hydroxyphenyl group, indolyl group, -NHC(NH)NH2, -CONH2, -SC 1-3 At least one of the alkyl groups;

[0069] R8 is selected from hydroxy substituted C 1-6 Alkyl;

[0070] R2 is selected from H, hydroxy, amino, halogen;

[0071] R3 and R4 are each independently selected from any one of H, amino, halogen, hydroxyl, and -SO2NHR1.

[0072] Preferably, R1 is selected from -CH2R5, -CHR6R7, -C(R8)3, hydroxy-substituted C 3-6 more preferably, R1 is selected from -CH2R5, -CHR6R7, -C(R8)3, hydroxy-substituted cyclohexyl, hydroxy-substituted cyclopentyl.

[0073] Preferably, L1 is C 1-4 Alkylene, R a Selected from bromine, amino, C 2-4 ester group, carboxyl group, -CH(OH)CH2OH; or L1 is phenylene, R a is selected from carboxyl, hydroxyl, hydroxymethyl; or L1 is -CH(OH)-, R a Selected from hydroxymethyl, -CH(OH)CH2OH.

[0074] Preferably, R6 and R7 are each independently selected from substituted or unsubstituted C 1-4 Alkyl, carboxyl, C 2-4 Ester group, -CONH2.

[0075] Preferably, the substituents optionally contained in R6 and R7 are selected from hydroxyl, amino, C 2-4 Ester, thiol, phenyl, -NHC(NH)NH2, -CONH2, -SC 1-3 At least one of the alkyl groups.

[0076] Preferably, R8 is selected from hydroxy substituted C 1-4 More preferably -CH2OH or -CH2CH2OH.

[0077] Preferably, R2 is selected from H, hydroxy, amino, and bromine.

[0078] Preferably, R3 and R4 are independently selected from any one of H, amino, bromine, hydroxyl, and -SO2NHR1.

[0079] The present invention provides several preferred embodiments below to illustrate the preferred aspects of the compound represented by formula (I) of the present invention.

[0080] Preferred embodiment 1:

[0081] In formula (I),

[0082] R1 is selected from -CH2R5, -CHR6R7, -C(R8)3, hydroxy substituted C 3-6 Cycloalkyl;

[0083] R5 is C 2-4 Ester group or -L1-R a ;

[0084] L1 is C 1-4 Alkylene, R a Selected from -CH(OH)CH2OH, bromine, amino, C 2-4 ester group, carboxyl group; or L1 is phenylene, R a is selected from carboxyl, hydroxyl, hydroxymethyl; or L1 is -CH(OH)-, R a Selected from hydroxymethyl, -CH(OH)CH2OH;

[0085] R6 and R7 are each independently selected from substituted or unsubstituted C 1-4 Alkyl, carboxyl, C 2-4 Ester group, -CONH2;

[0086] The substituents optionally contained in R6 and R7 are selected from hydroxyl, amino, C 2-4 Ester, thiol, phenyl, -NHC(NH)NH2, -CONH2, -SC 1-3 At least one of the alkyl groups of

[0087] R8 is selected from hydroxy substituted C 1-4 Alkyl;

[0088] R2 is selected from H, hydroxy, amino, fluorine, chlorine, bromine;

[0089] R3 and R4 are each independently selected from any one of H, amino, fluorine, chlorine, bromine, hydroxyl, and -SO2NHR1.

[0090] Preferred embodiment 2:

[0091] In formula (I),

[0092] R1 is selected from -CH2R5, -CHR6R7, -C(R8)3, hydroxy-substituted cyclohexyl, hydroxy-substituted cyclopentyl;

[0093] R5 is selected from -COOCH3, -CH2NH2, -CH2CH2NH2, -CH2Br, -CH2CH2Br, -CH2(CH2)2Br, -CH2COOCH3, -CH(OH)CH(OH)CH2OH, -CH2CH(OH)CH2OH, -CH(OH)CH2OH;

[0094] R6 and R7 are each independently selected from -CH3, -CH(CH3)CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -COOH, -CONH2, -CH2SH, -CH2CH2SCH3, -CH2OH, -CH(OH)CH3, -CH2(CH2)3NH2, -COOCH3, -COOCH2CH3, -CH2COOCH3, -CH2CH2COOCH3, -CH2COOCH2CH3, -CH2CH2CONH2, -CH2CONH2,

[0095] R8 is selected from -CH2OH, -CH2CH2OH;

[0096] R2 is selected from H, hydroxy, amino, bromine;

[0097] R3 and R4 are each independently selected from any one of H, amino, bromine, hydroxyl, and -SO2NHR1.

[0098] Preferred embodiment 3:

[0099] The sulfonamide compound of the present invention is selected from any one of the following compounds:

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106] As mentioned above, the second aspect of the present invention provides a method for preparing a sulfonamide compound of the structure represented by formula (I) or its stereoisomers, geometric isomers, tautomers, or agrochemically acceptable salts, prodrugs, hydrates, solvates, and metabolites, the method comprising: contacting a compound represented by formula (A) with a compound represented by formula (B) in the presence of a solvent;

[0107] H2N-R1 formula (B),

[0108] Among them, in formula (A), R 3 、R 4 Each independently selected from H, amino, halogen, hydroxyl,

[0109] In formula (A) and formula (B), the definitions of R1 and R2 are the same as those described in the first aspect. The present invention will not be described in detail here, and those skilled in the art should not be construed as limiting the present invention.

[0110] Preferably, the contacting conditions include: a reaction temperature of 0-200°C and a reaction time of 0.5-24 hours. The contacting in the present invention is preferably carried out under stirring conditions. The present invention does not particularly limit the stirring speed, and those skilled in the art can use known technical means to carry out the contacting.

[0111] Preferably, the solvent is selected from at least one of tetrahydrofuran, 1,4-dioxane, N,N-dimethylformamide, dimethyl sulfoxide, ethyl acetate, acetone, ethanol, water, dichloromethane, chloroform, and acetonitrile.

[0112] Preferably, the amount of the solvent used is 1-100 mL relative to 1 mmol of the compound represented by formula (A).

[0113] Preferably, the molar ratio of the compound represented by formula (A) to the compound represented by formula (B) is 1:0.8-2.4.

[0114] The aforementioned preparation method of the present invention may also involve various post-processing operations known in the art, such as extraction, washing, filtration, column chromatography, recrystallization, etc. The present invention has no particular limitation thereto, and those skilled in the art should not interpret this as a limitation of the present invention.

[0115] The raw materials involved in the preparation method of the present invention can be synthesized according to the raw material structural formula in combination with organic synthesis methods in the art, or can be obtained commercially. The preparation methods of a few raw materials are exemplified below, and those skilled in the art should not be construed as limiting the present invention.

[0116] As mentioned above, the third aspect of the present invention provides a pesticide formulation, which includes the sulfonamide compound described in the first aspect or its stereoisomers, geometric isomers, tautomers, or its agrochemically acceptable salts, prodrugs, hydrates, solvates, metabolites, and at least one of an agriculturally acceptable carrier.

[0117] As mentioned above, the fourth aspect of the present invention provides the use of the sulfonamide compound described in the first aspect or its stereoisomers, geometric isomers, tautomers, or its agrochemically acceptable salts, prodrugs, hydrates, solvates, metabolites in enhancing the ability of plant seedlings to emerge from the soil and / or delaying the flowering period of plants.

[0118] Preferably, the plant is selected from at least one of wheat, peanut, corn, cotton, mung bean, rice, soybean, Arabidopsis, sorghum and rapeseed.

[0119] As described above, the fifth aspect of the present invention provides an agent for enhancing the ability of plant seedlings to emerge from the soil and / or delaying the flowering period of plants, wherein the active ingredient of the agent is the sulfonamide compound described in the first aspect or at least one of its stereoisomers, geometric isomers, tautomers, or agrochemically acceptable salts, prodrugs, hydrates, solvates, and metabolites, and the content of the active ingredient is 0.1-100 weight % based on the total weight of the agent.

[0120] Preferably, the content of the active ingredient is 5-90% by weight. Exemplarily, the content of the active ingredient is 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, etc.

[0121] The agent for enhancing the emergence ability of plant seedlings and / or delaying the flowering period of plants of the present invention may further contain various additives, auxiliary materials, solvents, etc. commonly used in the art, and the present invention has no particular limitation thereto.

[0122] Preferably, the dosage form of the medicament is at least one selected from hydrate, powder, granule, suspension and emulsion.

[0123] The sulfonamide compounds represented by the aforementioned formula (I) of the present invention are prepared according to the aforementioned preparation method provided by the present invention. To avoid repetition, the examples of the present invention only list the preparation methods of some specific compounds. Those skilled in the art can obtain compounds 1 to 53 of the present invention by replacing the raw materials according to the synthesis methods of the listed compounds, and those skilled in the art should not interpret this as a limitation of the present invention.

[0124] The present invention will be described in detail below through preparation examples and test examples. In the following preparation examples and test examples, unless otherwise specified, the raw materials used are all commercially available products.

[0125] Unless otherwise specified, room temperature below refers to 25±3°C.

[0126] Preparation Example 1: Preparation of Compound 9

[0127]

[0128] Step 1: In a 100-mL single-necked round-bottom flask at room temperature, add 40 mL of thionyl chloride, 0.2 mL of N,N-dimethylformamide, and 4.96 g of sodium anthraquinone-1-sulfonate. The reaction system is then heated to 80°C and refluxed for 5 hours. After completion of the reaction, the remaining thionyl chloride is removed using a rotary evaporator, and the remaining mixture is slowly added to ice water. A large amount of solid material precipitates, which is then filtered under reduced pressure and dried to yield 9,10-anthracenedione-1-sulfonyl chloride as a yellow solid in a 90% yield.

[0129] Step 2: To a 100 mL single-necked round-bottom flask, add 20 mL of distilled water, 9,10-anthracenedione-1-sulfonyl chloride (2.0 mmol), L-serine (2.0 mmol), and Cs2CO3 (2.5 mmol) in that order. Stir and react at room temperature for 12 hours. After the reaction, adjust the pH to 3 with 1.0 mol / L hydrochloric acid. Extract the desired product with ethyl acetate (3 times, 20 mL), dry over anhydrous sodium sulfate, and purify by column chromatography to obtain a light yellow solid in a 70% yield.

[0130] 1 H NMR(400MHz,DMSO-d6)δ12.86(s,1H),8.53(dd,1H),8.46(dd,1H),8.33–8.15(m,2H) ,8.09(t,1H),7.99(ddd,2H),5.22(s,1H),4.02(dt,1H),3.69(ddd,2H),3.35(s,1H). 13 C NMR(101MHz,DMSO-d6)δ183.14,182.07,171.56,141.21,135.82,135.56,135.36 ,135.33,134.89,134.13,132.28,131.67,131.62,127.83,127.02,62.92,59.05.

[0131] Preparation Example 2: Preparation of Compound 10

[0132]

[0133] To a 100 mL single-necked round-bottom flask, 20 mL of 1,4-dioxane, 9,10-anthracenedione-1-sulfonyl chloride (2.0 mmol), L-serine methyl ester hydrochloride (2.0 mmol), and triethylamine (1.0 mL) were added sequentially and stirred at room temperature for 6 hours. After the reaction, all solvents were removed using a rotary evaporator. 20 mL of saturated brine was added to the mixture, and the desired product was extracted with ethyl acetate (20 mL x 3). The organic layer was collected, dried over anhydrous sodium sulfate, and purified by column chromatography to obtain a light yellow solid in a 75% yield.

[0134] 1 H NMR(400MHz, CDCl3)δ8.64(dd,1H),8.53(dd,1H),8.35(s,1H),8.32–8.26(m, 1H),7.99–7.82(m,4H),4.32(dd,1H),4.05(d,2H),3.53(s,3H),2.29(s,1H). 13 C NMR (101MHz, CDCl3) δ181.84,170.10,140.68,135.85,135.26,134.89,134 .73,134.12,133.75,132.10,131.98,128.25,127.06,64.05,58.59,52.75.

[0135] Preparation Example 3: Preparation of Compound 47

[0136]

[0137] Step 1: In a 100-mL single-necked round-bottom flask at room temperature, add 40 mL of thionyl chloride, 0.2 mL of N,N-dimethylformamide, and 3.55 g of dipotassium anthraquinone-1,8-disulfonate. The mixture was then heated to 80°C and refluxed for 5 hours. After the reaction was complete, the remaining thionyl chloride was removed using a rotary evaporator, and the remaining mixture was slowly added to ice water. A large amount of solid material precipitated, which was filtered under reduced pressure and dried to obtain a yellow solid compound, anthraquinone-1,8-disulfonyl chloride, in an 85% yield.

[0138] Step 2: In a 100 mL single-necked round-bottom flask, add 20 mL of 1,4-dioxane, anthraquinone-1,8-disulfonyl chloride (2.0 mmol), L-serine methyl ester hydrochloride (4.4 mmol), and triethylamine (2 mL) in sequence. Stir and react at room temperature for 6 hours. After the reaction, remove all solvents using a rotary evaporator. Add 20 mL of saturated brine to the mixture, and extract the desired product with ethyl acetate (20 mL x 3). Collect the organic layer and dry it over anhydrous sodium sulfate. The filtrate is then drained under reduced pressure and purified by column chromatography to obtain a reddish-brown solid.

[0139] 1 H NMR (400MHz, DMSO-d6) δ8.46(ddd,4H),8.08(t,2H),7.24(t,2H),4.32(m,2H),4.05(m,4H),3.53(s,6H). 13 C NMR (101MHz, DMSO-d6) δ184.55,181.20,140.90,136.09,135.07,134.58,133.24,131.07,64.08,58.62,52.78.

[0140] Other compounds of the present invention can be prepared by similar methods to the above preparation examples by adjusting the raw materials and process conditions according to the characteristics of the structural formula. The NMR data are:

[0141] Compound 1:

[0142] 1 H NMR (400MHz, DMSO-d6) δ8.54-8.52(dd,1H),8.50-8.47(dd,1H),8.20-8.17(m,2H),8.14-8.10(t,1H),7.99-7.95(m,2H),3.19(t,2H),2.92(t,2H). 13 C NMR(101MHz,DMSO-d6)δ182.23,181.59,139.92,135.79,135.36,134.98,134 .71,134.29,133.87,131.95,131.66,131.30,127.01,126.56,40.60,38.93.

[0143] Compound 2:

[0144] 1H NMR(400MHz,DMSO-d6)δ8.50-8.47(ddd,2H),8.16(td,2H),8.10(t,1H),7.94(m,2H),7. 20(q,1H),4.92(d,1H),4.62(t,1H),3.46(m,1H),3.27(m,1H),3.19(m,2H),2.83(m,1H). 13 C NMR(101MHz,DMSO-d6)δ182.88,181.61,140.19,135.76,135.48,134.96,134.75 ,134.33,133.87,131.91,131.48,131.22,127.21,126.50,69.60,63.54,46.66.

[0145] Compound 3:

[0146] 1 H NMR(400MHz,DMSO-d6)δ8.50-8.47(ddd,2H),8.16(td,2H),8.10(t,1H),7.94(m,2H),7. 20(q,1H),4.92(d,1H),4.62(t,1H),3.46(m,1H),3.27(m,1H),3.19(m,2H),2.83(m,1H). 13 C NMR(101MHz,DMSO-d6)δ182.88,181.61,140.19,135.76,135.48,134.96,134.75 ,134.33,133.87,131.91,131.48,131.22,127.21,126.50,69.60,63.54,46.66.

[0147] Compound 4:

[0148] 1 H NMR (400MHz, CDCl3) δ9.88(s,1H),8.27–8.16(m,2H),7.72(m,2H),7.62(dd,1H),7.58–7.52(m,1H),7.02(d,1H),4.37(q,2H),3.88(t,2H). 13 C NMR (101MHz, CDCl3) δ185.37,183.43,150.36,135.64,134.05,133.29,126.83,126.76,116.86,116.56,66.61,37.37.

[0149] Compound 5:

[0150] 1 H NMR(600MHz,DMSO-d6)δ8.55–8.50(m,2H),8.21(ddd,2H),8.10(t,1H),8. 01–7.95(m,2H),7.15(d,1H),4.66(s,2H),3.40(m,3H),3.32–3.28(m,2H). 13 C NMR (151MHz, DMSO-d6) δ183.21,182.24,141.98,136.10,135.46,135.39,135.25,134.82,134.38,132.40,131.53,127.76,126.96,60.66,57.89.

[0151] Compound 6:

[0152] 1 H NMR (400MHz, DMSO-d6) δ8.68–8.56(m,2H),8.29(s,2H),8.18(s,1H),8.07(s,2H),4.70(s,3H),3.59(d,6H). 13 C NMR(101MHz,DMSO-d6)δ183.33,182.24,144.40,135.69,135.43,135.21,134 .81,134.75,134.42,132.39,131.21,131.14,127.75,126.93,65.16,61.63.

[0153] Compound 7:

[0154] 1 H NMR(400MHz, CDCl3)δ8.58(dd,1H),8.49(dd,1H),8.35–8.24(m,1H),8.24–8.16(m,1H),7.90 (t,1H),7.86–7.74(m,3H),4.27(dd,1H),4.00(q,2H),3.93(m,2H),2.66(s,1H),1.01(t,3H). 13CNMR(101MHz,CDCl3)δ183.36,181.87,169.67,140.72,135.78,135.30,134.90,134.70 ,134.07,133.80,132.02,131.94,131.82,128.18,127.01,64.05,62.01,58.73,13.90.

[0155] Compound 8:

[0156] 1 H NMR(400MHz, CDCl3)δ8.64(dd,1H),8.53(dd,1H),8.35(s,1H),8.32–8.26(m, 1H),7.99–7.82(m,4H),4.32(dd,1H),4.05(d,2H),3.53(s,3H),2.29(s,1H). 13 C NMR (101MHz, CDCl3) δ181.84,170.10,140.68,135.85,135.26,134.89,134.73 ,134.12,133.75,132.10,131.98,128.25,127.06,77.04,64.05,58.59,52.75.

[0157] Compound 11:

[0158] 1 H NMR(600MHz,DMSO-d6)δ8.51(t,2H),8.23–8.16(m,2H),8.10(t,1H),7.97(dt,2H),7.13(d,1H),4. 53–4.31(m,1H),3.59–3.51(m,1H),3.25(m,1H),1.67(m,2H),1.35–1.26(m,1H),1.12–1.03(m,1H). 13 C NMR (101MHz, DMSO) δ183.71,183.33,182.05,142.16,136.38,135.55,135.37,135.22,134.85,13 4.48,132.53,131.79,131.54,127.60,126.96,67.95,64.58,52.95,51.96,34.07,31.31,28.31.

[0159] Compound 12:

[0160] 1H NMR(400MHz,DMSO-d6)δ8.41(d,1H),8.35(d,1H),8.17(t,2H),8.05–7.87(m,3H),7 .78(t,1H),7.04(d,2H),6.91(d,2H),5.31–4.75(m,1H),4.26(s,2H),4.17(d,2H). 13 CNMR(101MHz,DMSO-d6)δ182.76,182.02,141.76,136.00,135.72,135.39,135.09,13 4.52,134.33,132.25,131.51,131.15,128.03,127.55,126.89,126.53,62.89,47.07.

[0161] Compound 13:

[0162] 1 H NMR(400MHz,DMSO-d6)δ8.53(dd,1H),8.46(dd,1H),8.30–8.23(m,1H),8.21(dd,1H),8.10(t,1H),7.99(d dd,2H),7.52(d,1H),7.36(s,1H),7.06(s,1H),5.03(t,1H),3.95–3.81(m,1H),3.61(m,1H),3.51(m,1H). 13 C NMR(101MHz,DMSO-d6)δ182.89,182.11,170.88,141.01,135.83,135.54,135.47 ,135.29,134.78,134.20,132.26,131.71,131.64,127.85,126.99,63.25,59.24.

[0163] Compound 14:

[0164] 1 H NMR(400MHz, CDCl3)δ8.60(d,1H),8.51(d,1H),8.38–8.28(m,1H),8.28–8.13( m,1H),7.92(s,1H),7.88–7.75(m,2H),7.48(t,1H),4.06(s,2H),3.52(s,3H). 13C NMR (101MHz, CDCl3) δ183.62,181.85,169.62,140.83,135.77,135.30,134.85, 134.85,134.70,134.12,133.76,132.10,131.85,128.10,127.04,52.38,44.96.

[0165] Compound 15:

[0166] 1 H NMR(400MHz, CDCl3)δ8.59(dd,1H),8.50(dd,1H),8.36–8.28(m,1H),8.28–8.22(m,1H ),7.91(t,1H),7.87–7.79(m,2H),7.50(s,1H),4.29(q,1H),3.41(s,3H),1.50(d,3H). 13 C NMR (101MHz, CDCl3) δ183.46,181.84,172.43,141.04,135.75,135.26,134.86, 134.69,134.15,133.71,132.09,131.78,128.14,127.03,52.47,52.33,19.79.

[0167] Compound 16:

[0168] 1 H NMR (400MHz, CDCl3) δ8.61(ddd,2H),8.36–8.23(m,2H),7.96(t,1H),7.90–7.78(m,2H),3.62(s,3H),3.39(q,2H),2.62(t,2H). 13 C NMR (101MHz, CDCl3) δ183.91,181.89,172.04,140.95,136.05,135.98,134.95, 134.78,134.30,133.96,132.12,131.99,128.18,127.12,52.02,39.32,34.41.

[0169] Compound 17:

[0170] 1H NMR (400MHz, CDCl3) δ8.70–8.55(m,1H),8.55–8.41(m,1H),8.38–8.31(m,1H),8.31–8.24(m,1H),7.91(t,1 H),7.88–7.80(m,2H),7.73(d,1H),4.40–4.25(m,1H),4.15(dd,1H),3.42(s,3H),2.07(s,1H),1.41(d,3H). 13 C NMR (101MHz, CDCl3) δ183.38,181.90,170.61,140.94,135.74,135.05,134.88,134.69 ,134.16,133.69,132.11,131.83,131.80,128.24,127.04,68.50,62.02,52.47,20.08.

[0171] Compound 18:

[0172] 1 H NMR (400MHz, DMSO-d6) δ8.48(dd,1H),8.26(dd,1H),8.13(m,2H),8.00–7.79(m,3H),3.66(s,3H),3.09(m,3H),1.19(m,,4H). 13 C NMR(101MHz,DMSO-d6)δ182.67,182.04,172.99,171.64,141.08,135.82,135.60,135.56,135.3 1,134.81,134.17,132.35,131.72,131.65,127.65,127.07,55.85,52.46,51.84,29.69,27.26.

[0173] Compound 19:

[0174] 1 H NMR(600MHz,DMSO-d6)8.49(t,2H),8.38(d,1H),8.27(s,1H),8.15(m,2H),8.07 (t,1H),7.90-7.98(m,4H),7.43(t,1H),4.48(dd,1H),3.36(s,3H),3.04(m,2H). 13C NMR(101MHz,DMSO-d6)δ182.26,181.39,170.87,138.84,138.32,134.95,134.77,134.31 ,133.57,132.73,131.92,131.16,127.14,126.96,126.61,117.04,55.90,52.07,30.27.

[0175] Compound 20:

[0176] 1 H NMR(400MHz, CDCl3)δ8.61(ddd,3H),8.42(dd,1H),8.34–8.28(m,2H),7.95(t,1H),7.88(t,1H),4.11(m, 5.0Hz,1H),3.33(s,3H),3.11(d,2H),1.87–1.75(m,1H),1.75–1.65(m,1H),1.59(dt,4H),1.51(dd,2H). 13 C NMR (101MHz, CDCl3) δ184.29,183.43,181.80,171.72,140.88,140.73,136.12,135.17,134.86,1 34.80,134.31,133.90,133.67,128.14,127.02,77.06,56.39,52.25,43.40,32.78,29.21,22.30.

[0177] Compound 21:

[0178] 1 H NMR(400MHz,DMSO-d6)δ8.55(dd,1H),8.47(dd,1H),8.27–8.20(m,2H),8.11( t,1H),8.06–7.94(m,3H),4.49(d,1H),3.53(s,3H),3.33(s,2H),2.90(d,2H). 13 C NMR(101MHz,DMSO-d6)δ182.92,182.01,171.01,170.84,141.32,135.87,135.53,135.45,13 5.36,134.88,134.15,132.41,131.69,131.52,127.68,127.07,53.29,52.76,52.19,37.34.

[0179] Compound 22:

[0180] 1 H NMR(400MHz,DMSO-d6)δ8.54(d,1H),8.43(d,1H),8.23(ddd,2H),8.10(t,1H),8.00(td, 2H),7.89(d,1H),4.12(m,1H),3.55(s,3H),3.30(s,3H),2.42(t,2H),2.13–1.86(m,2H). 13 C NMR(101MHz,DMSO-d6)δ182.67,182.04,172.99,171.64,141.08,135.82,135.60,135.56,135.3 1,134.81,134.17,132.35,131.72,131.65,127.65,127.07,55.85,52.46,51.84,29.69,27.26.

[0181] Compound 23:

[0182] 1 H NMR (400MHz, DMSO-d6) δ8.55(dd,1H),8.47(dd,1H),8.24(m,2H),8.11(t,1H),8.03(m,3H),4.45(d,1H),3.53(s,3H),3.13(m,2H),2.67(d,2H). 13 C NMR(101MHz,DMSO-d6)δ182.82,182.05,171.11,169.84,141.22,135.86,135.52,135.44 ,135.39,134.88,134.15,132.41,131.59,131.42,127.61,127.02,53.29,52.09,37.24.

[0183] Compound 24:

[0184] 1 H NMR(400MHz,DMSO-d6)δ8.54(d,1H),8.45(d,1H),8.23(m,2H),8.08(t,1H),7 .98(m,2H),7.89(d,1H),4.15(m,1H),3.45(s,3H),2.18(t,2H),2.05(m,2H). 13C NMR(101MHz,DMSO-d6)δ182.66,182.08,173.84,171.54,141.02,135.80,135.61,135.53,13 5.31,134.79,134.27,132.31,131.62,131.65,127.65,127.07,55.85,51.89,33.12,26.26.

[0185] Compound 25:

[0186] 1 H NMR (400MHz, DMSO-d6) δ8.54(m,1H),8.40(m,1H),8.24(m,2H),8.10(t,1H),8.01(m,2H),7.62(d,1H),4.28(m,1H),3.62(s,3H),3.29(m,2H). 13 C NMR(101MHz,DMSO-d6)δ183.25,181.81,171.42,140.65,135.91,135.67,135.49,13 5.44,134.95,134.15,132.37,131.89,131.70,127.75,127.09,64.12,58.62,25.86.

[0187] Compound 26:

[0188] 1 H NMR(400MHz,DMSO-d6)δ8.54(dd,1H),8.45(dd,1H),8.23(ddd,2H),8.10(t,1H),8.05–7.94 (m,2H),7.91(d,1H),4.22(m,1H),3.32(s,3H),2.54(d,1H),2.49–2.39(m,1H),1.98(m,5H). 13 CNMR(101MHz,DMSO-d6)δ182.68,182.03,171.83,141.18,135.85,135.63,135.53,135. 29,134.79,134.20,132.39,131.70,127.63,127.07,55.54,52.47,31.57,29.78,14.88.

[0189] Compound 27:

[0190] 1H NMR(400MHz,DMSO-d6)δ8.55(dd,1H),8.44(dd,1H),8.27–8.20(m,2H),8.11(t,1H),8.04– 7.96(m,2H),7.62(d,1H),3.66–3.55(m,1H),3.26(s,3H),2.15–2.02(m,1H),0.90(dd,6H). 13 C NMR(101MHz,DMSO-d6)δ183.30,181.88,171.46,140.61,135.93,135.57,135.49,135.44,1 34.95,134.15,132.37,131.89,131.70,127.75,127.09,62.29,52.28,31.11,19.19,18.36.

[0191] Compound 28:

[0192] 1 H NMR(400MHz,DMSO-d6)δ8.55(dd,1H),8.43(dd,1H),8.27–8.20(m,2H),8.10(t,1H),8.04–7.96(m ,2H),7.62(d,1H),3.62(m,1H),3.25(s,3H),2.14(m,1H),1.55(m,2H),1.11(d,3H),0.99(t,3H). 13 C NMR (101MHz, DMSO-d6) δ183.30,181.88,171.46,140.61,135.93,135.57,135.49,135.44,134. 95,134.15,132.37,131.89,131.70,127.75,127.09,62.28,52.20,35.40,25.12,15.14,11.34.

[0193] Compound 29:

[0194] 1 H NMR(400MHz,DMSO-d6)δ8.54(dd,1H),8.45(dd,1H),8.28–8.17(m,2H),8.10(t,1H),8.05–7 .95(m,2H),7.77(d,1H),4.06(d,1H),3.24(s,3H),1.71(s,2H),1.46(s,1H),0.85(dd,6H). 13C NMR(101MHz,DMSO-d6)δ182.76,181.98,172.34,141.09,135.80,135.54,135.31,1 34.81,134.17,132.34,131.72,127.66,127.06,55.29,52.28,24.39,23.03,21.42.

[0195] Compound 30:

[0196] 1 H NMR(400MHz,DMSO-d6)δ8.46(dd,1H),8.27(dd,1H),8.23–8.16(m,2H),8.02–7.97(m,3H), 7.77(d,1H),7.05(dd,2H),6.97–6.87(m,3H),4.27(m,1H),3.46(s,3H),3.08–2.92(m,2H). 13 CNMR(101MHz,DMSO-d6)δ182.22,181.99,171.69,140.74,136.64,135.82,135.52,135.30,135.26,13 4.71,134.07,132.21,131.48,130.96,129.57,128.39,127.65,126.98,126.90,58.27,52.52,37.60.

[0197] Compound 31:

[0198] 1 H NMR(400MHz,DMSO-d6)δ8.44(dd,1H),8.22(dd,1H),8.21(m,2H),8.01(m,3H),7.7 7(d,1H),7.05(dd,2H),6.97–6.87(m,3H),4.23(t,1H),3.66(s,3H),3.18(m,2H). 13 CNMR(101MHz,DMSO-d6)δ182.32,181.84,171.59,155.72,140.64,136.64,135.71,135.52,135.3 0,135.26,134.71,134.07,132.21,131.48,130.26,128.39,127.65,126.80,58.27,52.52,37.60.

[0199] Compound 32:

[0200] 1 H NMR(400MHz,DMSO-d6)δ10.57(d,1H),8.30(dd,1H),8.16(ddd,2H),8.09–8.05(m,1H),8.00–7.93(m,2H),7.83(t,1H) ,7.38(d,1H),7.12–7.02(m,2H),6.79–6.69(m,2H),6.58(ddd,1H),4.39–4.13(m,1H),3.60(s,3H),3.21–3.01(m,2H). 13 C NMR(101MHz,DMSO-d6)δ181.73,181.52,172.15,139.35,136.18,135.34,135.12,134.94,134.20,133.73,132.13 ,131.49,130.30,127.56,126.84,126.75,125.50,121.37,118.90,117.97,111.69,108.10,57.18,52.63,28.14.

[0201] Compound 33:

[0202] 1 H NMR(400MHz,DMSO-d6)δ8.50-8.45(m,2H),8.14(m,2H),8.10(t,1H),7.94(m,2H),7 .20(q,1H),4.92(d,1H),4.62(t,1H),3.62-3.45(m,6H),3.40(m,1H),3.27(m,1H). 13 CNMR(101MHz,DMSO-d6)δ182.82,181.51,140.18,135.72,135.41,134.92,134.78,1 34.31,133.77,131.99,131.58,131.21,127.21,126.50,75.61,73.32,63.81,42.15.

[0203] Compound 34:

[0204] 1 H NMR(400MHz,DMSO-d6)δ8.50-8.42(m,2H),8.13(m,2H),8.08(t,1H),7.95 (m,2H),7.16(q,1H),3.60(m,2H),3.55(m,1H),3.16(t,2H),1,68(m,2H). 13C NMR(101MHz,DMSO-d6)δ182.81,181.55,140.12,135.75,135.47,134.92,134.78,13 4.31,133.87,131.90,131.51,131.26,127.21,126.54,71.21,66.25,36.64,31.54.

[0205] Compound 35:

[0206] 1 H NMR (400MHz, DMSO-d6) δ8.51(dd,1H),8.46(dd,1H),8.20(m,2H),8.14(d,2H),8.09(t,1H),6.95(d,2H),6.71(d,2H),3.96(s,2H). 13 C NMR(101MHz,DMSO-d6)δ182.28,182.15,156.55,141.08,136.25,135.68,135.57, 135.23,134.74,134.42,131.05,130.57,130.04,128.12,127.09,115.81,46.13.

[0207] Compound 36:

[0208] 1 H NMR(400MHz,DMSO-d6)δ8.52(dd,1H),8.47(dd,1H),8.23–8.16(m,2H),8.1 5(d,2H),8.10(t,1H),7.97(m,2H),7.50(t,1H),7.37(d,2H),4.02(s,2H). 13 C NMR(101MHz,DMSO-d6)δ182.28,182.05,168.28,146.82,141.08,136.25,135.68,135.47, 135.13,134.74,132.42,132.05,131.57,130.14,128.22,127.49,126.94,126.81,46.22.

[0209] Compound 37:

[0210] 11H NMR (400 MHz, DMSO-d6) δ 8.52 (dd, 1H), 8.47 (dd, 1H), 8.23–8.16 (m, 2H), 8.10 (t, 1H), 7.97 (m, 2H), 7.50 (t, 1H), 3.48 (t, 2H), 3.07 (q, 2H), 1.96 (m, 2H). 13 13C NMR (101 MHz, DMSO-d6) δ 182.25, 182.11, 141.06, 136.21, 135.78, 135.42, 135.13, 134.74, 132.42, 132.05, 131.57, 127.49, 126.99, 42.05, 39.94, 32.93, 32.32.

[0211] Compound 38:

[0212] 1 1H NMR (400 MHz, CDCl3) δ 8.66–8.56 (m, 2H), 8.32–8.24 (m, 2H), 7.95 (t, 1H), 7.90–7.81 (m, 2H), 6.78 (t, 1H), 3.39 (t, 2H), 3.15 (q, 2H), 1.92 (m, 2H), 1.70 (m, 2H). 13 13C NMR (101 MHz, CDCl3) δ 184.26, 181.72, 140.86, 136.11, 135.90, 134.88, 134.77, 134.20, 133.95, 132.05, 132.01, 131.86, 127.96, 127.07, 77.10, 42.77, 33.00, 29.53, 28.39.

[0213] Compound 39:

[0214] 1 1H NMR (400 MHz, CDCl3) δ 8.29 (dd, 2H), 7.94 (d, 1H), 7.85 -7.78 (m, 2H), 7.34 (d, 1H), 6.27 (br, 2H), 4.34 (dd, 1H), 4.08 (d, 2H), 3.54 (s, 3H), 2.32 (s, 1H). 13 13C NMR (101 MHz, CDCl3) δ 185.7, 182.1, 171.2, 154.1, 137.6, 137.2, 133.6, 133.4, 132.1, 132.4, 131.5, 126.8, 126.5, 120.1, 112.9, 64.1, 58.5, 52.6.

[0215] Compound 40:

[0216] 1 H NMR (400MHz, CDCl3) δ8.12-8.20(m,2H),7.89(d,1H),7.31-7.40(m,2H),6.84(d,1H),4.36(dd,1H),4.10(d,2H),3.50(s,3H),2.30(s,1H). 13 C NMR (101MHz, CDCl3) δ182.1,182.0,171.5,150.9,136.4,134.2,134.4,133.9,132.4,130.0,127.0,123.4,112.6,116.8,64.1,58.5,52.7.

[0217] Compound 41:

[0218] 1 H NMR (400MHz, CDCl3) δ8.29-8.25(m,2H),8.08(d,1H),7.98(d,1H),7.85 -7.78(m,2H),4.34(dd,1H),4.08(d,2H),3.54(s,3H),2.32(s,1H). 13 C NMR (101MHz, CDCl3) δ182.4,182.1,171.5,139.8,138.6,135.3,133.6,133.4,132.8,132.1,126.8,126.7,125.6,64.1,58.5,52.6.

[0219] Compound 42:

[0220] 1 H NMR (400MHz, CDCl3) δ8.20(d,2H),8.08(d,1H),7.89(d,1H),7.83(m,1H),7.61(dd,1H),4.34(dd,1H),4.08(d,2H),3.54(s,3H). 13 C NMR (101MHz, CDCl3) δ182.4,182.1,171.4,141.2,136.4,134.4,133.9,133.1,132.8,132.4,127.0,125.8,122.4,64.2,58.5,52.6.

[0221] Compound 43:

[0222] 1H NMR (400MHz, CDCl3) δ8.29-8.26(m,2H),7.92(d,1H),7.85 -7.78(m,2H),7.35(d,1H)4.35(dd,1H),4.05(d,2H),3.51(s,3H),2.30(s,1H). 13 C NMR (101MHz, CDCl3) δ182.3,182.1,171.5,165.1,137.8,133.6,133.4,132.1,131.8,131.6,126.8,126.3,122.3,119.6,64.1,58.5,52.6.

[0223] Compound 44:

[0224] 1 H NMR(400MHz, CDCl3)δ8.20(d,1H),8.09(d,1H),8 7.85 -7.74(m,2H),7.65(dd,1H),7.06(d,1H),4.38(dd,1H),4.10(d,2H),3.52(s,3H),2.35(s,1H). 13 C NMR (101MHz, CDCl3) δ182.4,182.1,161.9,140.8,136.4,136.2,133.9,133.1,132.4,130.0,127.0,124.1,116.3,64.2,58.4,52.6.

[0225] Compound 45:

[0226] 1 H NMR (400MHz, DMSO-d6) δ8.50(d,2H),8.44(d,2H),8.06(t,2H),6.84(s,2H),4.70(s,4H),3.38(d,8H),3.25(m,2H). 13 C NMR (101MHz, DMSO-d6) δ184.79,181.75,141.88,135.56,134.39,134.32,133.21,130.83,60.79,58.47.

[0227] Compound 46:

[0228] 1H NMR (400MHz, DMSO-d6) δ8.50(d,2H),8.44(d,2H),8.06(t,2H),6.84(s,2H),4.61(s,6H),3.52(s,12H). 13 C NMR (101MHz, DMSO-d6) δ184.79,181.75,141.88,135.56,134.39,134.32,133.21,130.83,61.62,58.40.

[0229] Compound 48:

[0230] 1 H NMR (400MHz, DMSO-d6) δ8.52(d,2H),8.47(d,2H),8.02(t,2H),6.85(s,2H),4.35(m,2H),4.15(m,2H),3.64(s,6H),1.16(d,6H). 13 C NMR (101MHz, DMSO-d6) δ184.55,181.20,140.90,136.09,135.07,134.58,133.24,131.07,63.82,58.62,52.72,19.41.

[0231] Compound 49:

[0232] 1 H NMR (400MHz, DMSO-d6) δ8.46(m,4H),8.09(t,2H),7.25(t,2H),4.28(m,2H),3.62(s,6H),3.29(m,4H). 13 C NMR (101MHz, DMSO-d6) δ184.55,181.20,140.90,136.09,135.07,134.58,133.24,131.07,64.12,58.62,25.86.

[0233] Compound 50:

[0234] 1 H NMR (400MHz, DMSO-d6) δ8.46(m,4H),8.19(t,2H),7.28(t,2H),4.12(m,2H),3.69(s,6H),2.65(t,4H),2.17(m,4H). 13C NMR (101MHz, DMSO-d6) δ184.55,181.20,140.90,136.09,135.07,134.58,133.24,131.07,55.21,51.92,30.15,29.72,15.44.

[0235] Compound 51:

[0236] 1 H NMR (400MHz, DMSO-d6) δ8.46(m,4H),8.09(t,2H),7.25(t,2H),4.70(s,4H),3.38(d,8H),3.25(m,2H). 13 C NMR (101MHz, DMSO-d6) δ182.55,141.45,136.92,135.28,135.13,131.76,130.31,60.88,58.51.

[0237] Compound 52:

[0238] 1 H NMR (400MHz, DMSO-d6) δ8.46(m,4H),8.09(t,2H),7.25(t,2H),4.28(m,2H),3.62(s,6H),3.29(m,4H). 13 C NMR (101MHz, DMSO-d6) δ182.55,140.90,136.09,135.07,134.58,133.24,131.07,64.12,58.62,25.86.

[0239] Compound 53:

[0240] 1 H NMR (400MHz, DMSO-d6) δ8.46(m,4H),8.08(t,2H),7.24(t,2H),4.35(m,2H),4.15(m,2H),3.64(s,6H),1.16(d,6H). 13 C NMR (101MHz, DMSO-d6) δ182.58,140.95,136.19,135.20,134.68,133.34,131.17,63.82,58.62,52.72,19.41.

[0241] Test Example 1

[0242] This test example is used to illustrate the activity of the sulfonamide compound represented by the structure of formula (I) in relieving the inhibition of hypocotyl elongation by blue light.

[0243] Initial screening test (MS culture medium method):

[0244] The plant under investigation was wild-type (Columbia type, Col-0) Arabidopsis thaliana.

[0245] The sterilized and vernalized Arabidopsis seeds were cultured in a light incubator at 23°C, 16 hours of light, and 8 hours of darkness. When the Arabidopsis seeds germinated and turned white, they could be transplanted for use.

[0246] Compounds 1 to 53 were added to MS medium at a final concentration of 5 μM. All compounds were dissolved in DMSO and tested in a 0.5% (volume fraction) DMSO-containing medium. A blank control was used in MS medium containing 0.5% (volume fraction) DMSO. Arabidopsis seedlings of uniform growth were selected for grafting. After grafting, the seedlings were placed vertically in an incubator at 23°C and under continuous blue light of 1300 lux or 400 lux. Images were taken after 5 days of growth.

[0247] For example, in Figure 1 The hypocotyl length phenotype of Arabidopsis thaliana seedlings treated with compound 10 and blank control under blue light (1300 lux) is shown in FIG; Figure 2 The statistical graph of hypocotyl length of Arabidopsis thaliana seedlings treated with compound 10 and blank control under blue light irradiation is given in FIG. Figure 3 The hypocotyl length images of Arabidopsis thaliana seedlings treated with compound 21, compound 22, compound 30, and compound 32 and the blank control under blue light (400 lux) are given in the figure; Figure 4 The hypocotyl length statistics of Arabidopsis thaliana seedlings treated with Compound 21, Compound 22, Compound 30, and Compound 32 and the blank control under blue light irradiation are given in FIG. Figures 1 to 4 It can be seen that compared with the control group, compound 10, compound 21, compound 22, compound 30, and compound 32 can promote hypocotyl elongation and enhance the ability of plant seedlings to emerge from the soil.

[0248] The hypocotyl length of each Arabidopsis seedling was measured using ImageJ-2x software, the average hypocotyl length of the total number of seeds on the culture dish was calculated, and the ratio of the hypocotyl length of the experimental group (treated with the compound represented by formula (I)) to the control group was calculated. The results are shown in Table 1.

[0249] Calculation method of hypocotyl length ratio:

[0250]

[0251] Table 1. Experimental results of Compounds 1 to 53 relieving the inhibition of hypocotyl elongation induced by blue light (400 lux) (Arabidopsis hypocotyl length ratio).

[0252]

[0253]

[0254] From the results in Table 1, it can be seen that the sulfonamide compound of the structure represented by formula (I) provided by the present invention can effectively relieve the inhibitory activity of cryptochrome on hypocotyl elongation under blue light.

[0255] Test Example 2:

[0256] Experimental method for treating Arabidopsis thaliana with different concentrations of compound 10:

[0257] The plants under investigation were wild-type (Columbia type, Col-0) Arabidopsis thaliana;

[0258] The sterilized and vernalized Arabidopsis seeds were cultured in a light incubator at 23°C, 16 hours of light, and 8 hours of darkness. When the Arabidopsis seeds germinated and turned white, they could be transplanted for use.

[0259] Compound 10 was added to MS culture medium at final concentrations of 5 μM, 2.5 μM, 1 μM, and 0.1 μM, respectively. A 0 μM control group (0.5% DMSO aqueous solution) was used. After transplanting, the seedlings were sealed and placed vertically in an incubator under continuous blue light (1300 lux) at 23°C. After 5 days of growth, the seedlings were photographed.

[0260] Figure 5 The figure shows the length of the hypocotyl of Arabidopsis thaliana treated with the control group (DMSO) and different concentrations of compound 10 under continuous irradiation with a blue light intensity of 1300 lux. Figure 6 The length statistics of the hypocotyls of Arabidopsis thaliana treated with compound 10 are given in FIG. Figure 5 、 Figure 6 It can be seen that the ability of compound 10 to relieve the inhibition of hypocotyl elongation by cryptochrome is concentration-dependent.

[0261] Test Example 3

[0262] Experimental methods for treating wild-type Arabidopsis thaliana, cry1 mutant, cry2 mutant, cry1-cry2 double mutant, CRY1-overexpressing Arabidopsis thaliana, and CRY2-overexpressing Arabidopsis thaliana with compound 10:

[0263] The plants studied were wild type (Columbia type, Col-0), mutants (cry1 mutant, cry2 mutant, cry1-cry2 double mutant), CRY1 overexpression (CRY1-OX), and CRY2 overexpression (CRY2-OX) Arabidopsis thaliana;

[0264] The sterilized and vernalized Arabidopsis seeds were cultured in a light incubator at 23°C, 16 hours of light, and 8 hours of darkness. When the Arabidopsis seeds germinated and turned white, they could be transplanted for use.

[0265] Compound 10 was added to MS culture medium at a final concentration of 5 μM for testing, and a blank control was a 0.5% DMSO aqueous solution. After transplanting, the seedlings were sealed and placed vertically in a 23°C incubator under continuous blue light (blue light intensity of 1300 lux) and were photographed after 5 days of growth.

[0266] exist Figure 7 、 Figure 8 The length of the hypocotyl of wild-type Arabidopsis and cryptochrome mutant plants treated with compound 10 under continuous irradiation with a blue light intensity of 1300 lux is shown in the figure ( Figure 7 ) and length statistics chart ( Figure 8 ),from Figure 7 、 Figure 8 It can be seen that compound 10 targets plant cryptochrome protein, thereby regulating the elongation of the hypocotyl.

[0267] Test Example 4

[0268] Microthermophoresis (MST): In a microthermophoresis experiment, the Arabidopsis cryptochrome AtCRY2 protein was labeled with the Kit RED fluorescent probe; Compounds 10 and 21 were dissolved in a 5% DMSO buffer solution (20 mM HEPES, 100 mM NaCl), diluted in equal proportions, mixed with a 10 μM AtCRY2 protein solution, and transferred to a capillary tube. The thermophoresis of the interaction between the AtCRY2 protein and different concentrations of inhibitors was measured on the MST instrument to obtain the dissociation constant K. d The results are as follows Figure 9a 、 Figure 9b The test results show that the K d The values were 4.18 μM ( Figure 9a ) and 1.02 μM ( Figure 9b ), proving that compounds 10 and 21 have strong binding ability with AtCRY2 protein.

[0269] Test Example 5

[0270] Mung bean seedling emergence experiment: In the same culture pot, add the same mass of nutrient soil, transplant 12 mung bean seeds respectively, and then cover the seeds with 4cm, 6cm and 8cm of nutrient soil respectively. Add 100mL of a 10μM solution of compound 10 (a 0.4% DMSO aqueous solution) to the culture pot; add 100mL of a 10μM solution of compound 3-bromo-7-nitroindazole (3B7N) to the positive control group (a 0.4% DMSO aqueous solution); add 100mL of a 0.4% DMSO aqueous solution to the blank control group, and culture all culture pots in the dark at 23°C. When the mung bean seedlings emerge, take the seedlings out of the soil, take pictures and count the length of the hypocotyl of the mung bean seedlings. The results are as follows. Figures 10 to 12 shown. Specifically,

[0271] Figure 10 The results show the effects of compound 10, positive control (3B7N) and blank control (DMSO) on the hypocotyl elongation of mung bean seedlings in 4 cm deep nutrient soil. Figure 10 The middle (left) is a picture of mung bean seedlings growing in the soil. Figure 10 The middle one is a picture of the length of the hypocotyl of mung bean seedlings. Figure 10 The middle (right) is a statistical chart of the hypocotyl length of mung bean seedlings.

[0272] Figure 11 The results show the effects of compound 10, positive control (3B7N) and blank control (DMSO) on the hypocotyl elongation of mung bean seedlings in 6 cm deep nutrient soil. Figure 11 The middle (left) is a picture of mung bean seedlings growing in the soil. Figure 11 The middle one is a picture of the length of the hypocotyl of mung bean seedlings. Figure 11 The middle (right) is a statistical chart of the hypocotyl length of mung bean seedlings.

[0273] Figure 12 The results show the effects of compound 10, positive control (3B7N) and blank control (DMSO) on the hypocotyl elongation of mung bean seedlings in 8 cm deep nutrient soil. Figure 12 The middle (left) is a picture of mung bean seedlings growing in the soil. Figure 12 The middle one is a picture of the length of the hypocotyl of mung bean seedlings. Figure 11 The middle (right) is a statistical chart of the hypocotyl length of mung bean seedlings.

[0274] Depend on Figures 10 to 12 The results showed that after treatment with compound 10, the length of the hypocotyl of mung bean seedlings in the experimental group was greater than that in the blank control group (DMSO) and the positive control group (3B7N).

[0275] Test Example 6

[0276] Wheat seedling emergence experiment: Take the same culture pots (large pot + small pot), fill the small pot with the same mass of nutrient soil, move in the same number (150) of wheat seeds (variety: Shannong No. 46), and cover with the same thickness (5cm) of 20-mesh river sand. Add 2L of 10μM compounds 17, 21, 22 (DMSO aqueous solution with a volume fraction of 0.4% by volume) to the large pot; add 2L of DMSO aqueous solution with a volume fraction of 0.4% by volume to the blank control group. Then put the small pot into the large pot, and after the aqueous solution in the large pot is saturated with the sand in the small pot, place all the culture pots at 23°C for culture, and take pictures every day to record the number of wheat seedlings. The results are as follows. Figure 13a 、 13b As shown, in Figure 13a Compared with the control group (CK), compound 17, compound 21 and compound 22 accelerated the emergence rate of wheat seedlings. Figure 13b It can be seen that after treatment with Compound 17, Compound 21, and Compound 22 provided by the present invention, the emergence time of wheat seedlings was significantly advanced and the emergence rate was significantly improved. Among them, after treatment with Compound 17, Compound 21, and Compound 22, the emergence rate of wheat seedlings was 1.88 times, 1.59 times, and 1.47 times that of the control group (CK), respectively. (Wheat seedling emergence rate = number of seedlings emerging / total number of seeds)

[0277] Test Example 7

[0278] Arabidopsis delayed flowering experiment: wild-type Arabidopsis seedlings with the same growth (cultivated for 20 days, the seedlings are strong and the flower buds have differentiated) were taken and treated with 5 μM concentration of compound 17, compound 21, compound 22 (V DMSO :V 水 =1:10000) soaked in soil and planted, watered once every 20 days, 500 mL each time; the blank control group was added with an equal amount of DMSO aqueous solution (V DMSO :V 水 =1:10000). The flowering period was from seed germination to the appearance of the first flower of the Arabidopsis plant; the flowering period and number of rosette leaves of each Arabidopsis plant were recorded. Figure 14a 、 14b , 14c, by Figure 14a It can be seen that after applying compound 17, compound 21, and compound 22, the flowering period of Arabidopsis thaliana was significantly later than that of the control group; Figure 14b It can be seen that the number of rosette leaves of Arabidopsis thaliana treated with compound 17, compound 21, and compound 22 was significantly higher than that of the control group; Figure 14cIt can be seen that the flowering period of Arabidopsis thaliana treated with compound 17, compound 21 and compound 22 (30.8 days, 30.7 days and 28.3 days, respectively) was delayed by 6.1 days, 6 days and 3.6 days respectively compared with the control group (24.7 days).

[0279] In summary, the sulfonamide compounds provided by the present invention can effectively eliminate the inhibitory activity of cryptochrome on hypocotyl elongation under blue light, and significantly enhance the ability of plant seedlings to emerge from the soil; at the same time, the compounds provided by the present invention can delay the flowering period of plants.

[0280] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A sulfonamide compound or its stereoisomers, tautomers, or agrochemically acceptable salts thereof, characterized in that: The compound has the structure shown in formula (I): Formula (I), Wherein, in formula (I), R1 is selected from -CH2R5, -CHR6R7, -C(R8)3, hydroxy-substituted cyclohexyl, hydroxy-substituted cyclopentyl; R5 is selected from -COOCH3, -CH2NH2, -CH2CH2NH2, -CH2Br, -CH2CH2Br, -CH2(CH2)2Br, -CH2COOCH3, , , , -CH(OH)CH(OH)CH2OH, -CH2CH(OH)CH2OH, -CH(OH)CH2OH; R6 and R7 are each independently selected from -CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)CH3, -COOH, -CONH2, -CH2SH, -CH2CH2SCH3, -CH2OH, -CH(OH)CH3, -CH2(CH2)3NH2, -COOCH3, -COOCH2CH3, -CH2COOCH3, -CH2CH2COOCH3, -CH2COOCH2CH3, -CH2CH2CONH2, -CH2CONH2, 、 、 、 、 ; R8 is selected from -CH2OH, -CH2CH2OH; R2 is selected from H, hydroxy, amino, bromine; R3 and R4 are each independently selected from any one of H, amino, bromine, hydroxyl, and -SO2NHR1.

2. The sulfonamide compound according to claim 1, or its stereoisomer, tautomer, or agrochemically acceptable salt thereof, wherein: The compound is selected from any one of the following compounds: Compound 1: Compound 2: Compound 3: Compound 4: Compound 5: Compound 6: Compound 7: Compound 8: Compound 9: Compound 10: Compound 11: Compound 12: Compound 13: Compound 14: Compound 15: Compound 16: Compound 17: Compound 18: Compound 19: Compound 20: Compound 21: Compound 22: Compound 23: Compound 24: Compound 25: Compound 26: Compound 28: Compound 29: Compound 30: Compound 31: Compound 32: Compound 33: Compound 34: Compound 35: Compound 36: Compound 37: Compound 38: Compound 39: Compound 40: Compound 41: Compound 42: Compound 43: Compound 44: Compound 45: Compound 46: Compound 47: Compound 48: Compound 49: Compound 50: Compound 51: Compound 52: Compound 53: .

3. A method for preparing a sulfonamide compound of formula (I) according to claim 1 or 2, or a stereoisomer, a tautomer, or an agrochemically acceptable salt thereof, characterized in that: The method comprises: contacting a compound represented by formula (A) with a compound represented by formula (B) in the presence of a solvent; Formula (A), H2N-R1 Formula (B), Among them, in formula (A), R 3 、R 4 Each independently selected from H, amino, halogen, hydroxyl, ; In formula (A) and formula (B), the definitions of R1 and R2 are the same as those in claim 1 or 2.

4. The method according to claim 3, wherein: The contact conditions include: reaction temperature of 0-200° C., and reaction time of 0.5-24 h.

5. The method according to claim 3 or 4, wherein: The solvent is selected from tetrahydrofuran, 1,4-dioxane, N , N - At least one of dimethylformamide, dimethyl sulfoxide, ethyl acetate, acetone, ethanol, water, dichloromethane, chloroform, and acetonitrile.

6. A pesticide formulation, characterized in that The pesticide preparation comprises at least one of the sulfonamide compound according to claim 1 or 2 or its stereoisomers, tautomers, or agrochemically acceptable salts.

7. Use of the sulfonamide compound according to claim 1 or 2, or its stereoisomers, tautomers, or agrochemically acceptable salts thereof, for enhancing the emergence ability of plant seedlings and / or delaying the flowering period of plants.

8. A pharmaceutical agent for enhancing the emergence ability of plant seedlings and / or delaying the flowering period of plants, characterized in that: The active ingredient of the agent is at least one of the sulfonamide compound or its stereoisomers, tautomers, or agrochemically acceptable salts according to claim 1 or 2, and the content of the active ingredient is 0.1-100% by weight based on the total weight of the agent.

9. The pharmaceutical preparation according to claim 8, wherein The content of the active ingredient is 5-90% by weight.

10. The pharmaceutical agent according to claim 8 or 9, wherein The dosage form of the medicament is selected from at least one of hydrate, powder, granule, suspension and emulsion.

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