A plant growth regulator compound with good water solubility, its preparation method and application

Abstract

The present invention provides a compound shown by formula III and a preparation method thereof. The preparation process is simple, environmentally friendly, with high product purity and yield, and has obvious economic, social and environmental benefits. As a plant growth regulator, the compound shown by formula III has more than 300 times improved water solubility while maintaining good plant growth regulation performance, and has good environmental and social benefits.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and particularly relates to a plant growth regulator compound with good water solubility, a preparation method thereof, and an application thereof. Background Art

[0002] Plant growth regulators are a class of exogenous non-nutritional chemical substances. They can usually be conducted in plants to the site of action, and at a relatively low concentration, they can promote or inhibit certain steps in the plant life activity process, change the growth status of the plant, and make it grow and develop in line with human needs. Due to the special effects of plant growth regulators, the research on plant growth regulators has become one of the important fields in the development of modern agriculture. N-phenylphthalic monoamide is a plant growth regulator that has the effects of promoting the transport of nutrients to the growth points of flower buds, enhancing the vitality of plant cells, promoting the synthesis of chlorophyll, facilitating pollination and fertilization, inducing flower buds to become fruits, and preventing physiological and pre-harvest fruit drop. It has been widely used in the market. However, poor water solubility is a serious defect, which limits its wide application fields. To solve this common key technical problem, it is necessary to develop a plant growth regulator with good water solubility, overcome the defects of the existing plant growth regulators, improve its application effect and scope of use, and promote the technological upgrading and sustainable development of the plant growth regulator production enterprises. Summary of the Invention

[0003] To improve the above technical problems, the present invention provides a compound shown in Formula III:

[0004]

[0005] Wherein, each R1 is the same or different, and independently selected from H, halogen, -C 1-10 alkyl, -C 1-10 alkoxy; each R2 is the same or different, and independently selected from -SO3Na, -C 1-10 alkyl-SO3Na, -SO3K, -C 1-10 alkyl-SO3K; m is selected from 0, 1, 2, 3 or 4; n is selected from 1, 2, 3 or 4.

[0006] According to an embodiment of the present invention, R1 can be selected from H, -C 1-6 alkyl; R2 can be selected from -SO3Na, -C 1-6 alkyl-SO3Na; m can be selected from 0, 1 or 2; n can be selected from 1 or 2.

[0007] According to an embodiment of the present invention, R2 is selected from -SO3Na or -(CH2)2-SO3Na.

[0008] According to an embodiment of the present invention, the compound represented by Formula III may have the structure represented by the following formula (III-1):

[0009]

[0010] Wherein, R2 has the definition described above; preferably selected from -SO3Na or -(CH2)2-SO3Na.

[0011] According to an embodiment of the present invention, the compound of Formula III is selected from the following structures:

[0012]

[0013] The present invention also provides a method for preparing the compound represented by Formula III, comprising the following steps: reacting Compound I and Compound II to obtain the compound represented by Formula III;

[0014]

[0015] Wherein, R1, R2, m and n each independently have the definition described above;

[0016] According to an embodiment of the present invention, the molar ratio of Compound I to Compound II may be 1:(0.5 - 1.5), for example 1:(0.8 - 1.2), preferably 1:0.9, 1:1 and 0.9:1;

[0017] According to an embodiment of the present invention, the temperature of the reaction is 10 - 60 °C, for example 15 - 50 °C, and exemplarily 15 °C, 20 °C, 25 °C;

[0018] According to an embodiment of the present invention, the solvent for the reaction may be selected from at least one of N,N-dimethylformamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, 1,4-dioxane, cyclohexanone, N-methylpyrrolidone;

[0019] According to an embodiment of the present invention, the reaction further includes a post-treatment step; the post-treatment step includes: filtration, drying;

[0020] According to an embodiment of the present invention, the drying is vacuum drying, and the drying temperature is 50 - 80 °C, for example 60 °C;

[0021] According to an embodiment of the present invention, the vacuum drying time is 6 - 12 h, for example 10 h.

[0022] According to an exemplary embodiment of the present invention, the preparation method includes the following steps: In a reactor equipped with a thermometer and a stirrer, a solvent and Compound I are added. After stirring and dissolving, Compound II is added to the reaction solution in batches. After the reaction is completed at room temperature, the reactor is cooled to 5-20 °C (such as 10 °C), filtered by suction, and the filter cake is dried under vacuum to obtain the compound shown in Formula III.

[0023] The present invention also provides the use of the compound shown in Formula III as a plant growth regulator.

[0024] Beneficial effects

[0025] 1. The present invention first synthesizes the compound shown in Formula III using Compound I and Compound II, which has the advantages of simple process, environmental friendliness, high product purity, and high yield. The mother liquor in the reaction process can be recycled 5-6 times without treatment. At the same time, while further improving the product yield and saving the cost of reaction reagents, the working environment is effectively improved, and the product still maintains a high purity, ensuring the quality of the product, reducing the production cost, and having obvious economic, social, and environmental benefits.

[0026] 2. The compound III of the present invention has good water solubility and plant growth regulator performance. While maintaining good plant growth regulation performance, the water solubility is increased by more than 300 times, overcoming the technical problem of poor water solubility of the currently used N-phenylphthalic monoamide, and having good environmental and social benefits.

[0027] Term definitions and explanations

[0028] The term "C 1-10 alkyl" represents straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, and "C 1-8 alkyl" represents straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms, and "C 1-6 alkyl" represents straight-chain and branched-chain alkyl groups having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, etc., or their isomers. Specific embodiments

[0029] The technical solution of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only for illustrative explanation of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0030] Unless otherwise specified, the raw materials and reagents used in the following embodiments are all commercially available products or can be prepared by known methods.

[0031] Example 1

[0032]

[0033] Synthesis of Sodium 4-aminobenzenesulfonate

[0034] Add 50 mL of water and 8 g (0.2 mol) of sodium hydroxide to a 250 mL round-bottom flask. After stirring until completely dissolved, add 34.64 g (0.2 mol) of 4-aminobenzenesulfonic acid to the reaction solution. Stir and react for 30 min. Evaporate 40 g of water using a rotary evaporator, then place the reaction solution in an oven at 75 °C for 6 h. Take it out and let it cool naturally to room temperature, then filter by suction, wash with cold ethanol, and dry in vacuum at 60 °C for 10 h to obtain 37.58 g of white solid; Yield: 96.3%; Melting point: 288 °C; IR (KBr tablet, cm -1 ) : 3487.3, 3383.14, 3332.99, 1653, 1624.06, 1604.77, 1502.55, 1431.18, 1300.02, 1280.73, 1224.8, 1174.65, 1124.5, 1033.85, 1008.77, 835.18, 698.23, 569, 518.85, 424.34.

[0035] Synthesis of N-(Sodium sulfophenyl)phthalic monoamide

[0036] Add 14.8 g (0.1 mol) of phthalic anhydride and 100 mL of N,N-dimethylformamide to a 250 mL round-bottom flask. After stirring until the solid is completely dissolved, add 23.1 g (0.1 mol) of sodium 4-aminobenzenesulfonate to the reaction solution in batches (this reaction is an exothermic reaction, and the reaction temperature rises from 15 °C to 20 °C). Stir at room temperature for 36 h, then place the flask in a low-temperature bath and cool to 10 °C, filter by suction, and dry in vacuum at 60 °C for 10 h to obtain 33.22 g of white solid product; Yield: 96.77%; Melting point: greater than 300 °C; IR (KBr tablet, cm -1):3446.79, 3300.2, 3115.04, 3064.89, 2634.76, 2372.44, 1716.65, 1653, 1595.13, 1533.41, 1400.32, 1325.1, 1267.23, 1195.87, 1126.43, 1039.63, 1012.63, 902.69, 835.18, 792.74, 713.66, 669.3, 644.22, 605.65, 570.93; 1 1H NMR (400 MHz, CDCl3); δ (ppm): 13.05 (s, 1H), 10.39 (s, 1H), 7.86 - 7.88 (d, 1H), 7.62 - 7.66 (m, 3H), 7.54 - 7.58 (m, 4H).

[0037] Example 2

[0038]

[0039] Synthesis of sodium 3 - aminobenzenesulfonate

[0040] Add 25 mL of water and 8 g (0.2 mol) of sodium hydroxide to a 250 mL round - bottom flask. After stirring until completely dissolved, add 34.64 g (0.2 mol) of 3 - aminobenzenesulfonic acid to the reaction solution. Stir the reaction for 30 min. Evaporate 20 g of water using a rotary evaporator, then place the reaction solution in an oven at 75 °C for 6 h. Take it out and let it cool naturally to room temperature, then filter by suction, wash with cold ethanol, and dry in vacuo at 60 °C for 10 h to obtain 36.56 g of white solid; Yield: 91.1%; Melting point: 282 - 289 °C; IR (KBr pellet, cm -1 ):3431.36, 3363.86, 3342.64, 3049.46, 1624.06, 1600.92, 1483.26, 1452.4, 1313.52, 1274.95, 1207.44, 1184.29, 1128.36, 1111, 1045.42, 991.41, 894.97, 881.47, 781.17, 711.73, 690.52, 624.94, 609.51, 563.21, 526.57, 459.06, 433.98.

[0041] Synthesis of N - (m - sulfonatophenyl) phthalic monoamide

[0042] 14.8 g (0.1 mol) of phthalic anhydride and 100 mL of dimethyl sulfoxide were added to a 250 mL round-bottom flask. After stirring until the solid was completely dissolved, 23.1 g (0.1 mol) of sodium 3-aminobenzenesulfonate was added to the reaction solution in batches (this reaction is an exothermic reaction, and the reaction temperature rose from 15 °C to 20 °C). After stirring at room temperature for 36 h, the flask was placed in a low-temperature bath and cooled to 10 °C, then filtered by suction, and dried in vacuo at 60 °C for 10 h to obtain 31.56 g of a white solid product, yield: 91.93%; melting point 172 - 184 °C; IR (KBr pellet, cm -1 ): 3462.22, 3277.06, 3066.82, 2636.69, 1707, 1662.64, 1597.06, 1544.98, 1481.33, 1423.47, 1323.17, 1222.87, 1190.08, 1114.86, 1076.28, 1039.63, 995.27, 875.68, 794.67, 721.38, 688.59, 621.08, 596, 563.21, 526.57; 1 1H NMR (400 MHz, CDCl3); δ (ppm): 13.12 (s, 1H), 10.36 (s, 1H), 7.99 (s, 1H), 7.85 - 7.87 (d, 1H), 7.63 - 7.66 (m, 2H), 7.53 - 7.58 (m, 2H), 7.24 - 7.33 (m, 2H).

[0043] Example 3

[0044]

[0045] Synthesis of sodium 2-aminobenzenesulfonate

[0046] 200 mL of water and 23.8 g (0.595 mol) of sodium hydroxide were added to a 500 mL round-bottom flask. After stirring until completely dissolved, 98.81 g (0.57 mol) of 2-aminobenzenesulfonic acid was added to the reaction solution, and the mixture was stirred and reacted for 30 min. After 160 g of water was distilled off using a rotary evaporator, the reaction solution was placed in an oven at 75 °C for 6 h. After taking it out and naturally cooling to room temperature, it was filtered by suction, washed with cold ethanol, and dried in vacuo at 60 °C for 10 h to obtain 95.79 g of a white solid; yield: 86.1%; melting point > 300 °C; IR (KBr pellet, cm -1: 3415.93, 3331.07, 3068.75, 3020.53, 1627.92, 1598.99, 1577.77, 1481.33, 1454.33, 1313.52, 1255.66, 1228.66, 1186.22, 1176.58, 1143.79, 1120.64, 1064.71, 1039.63, 1024.2, 945.12, 856.39, 840.96, 744.52, 705.95, 621.08, 588.29, 576.72, 570.93, 547.78, 528.5, 486.06, 472.56。

[0047] Synthesis of N-(Sodium Sulfonate Phenyl) Phthalic Monoamide

[0048] Add 14.8 g (0.1 mol) of phthalic anhydride and 100 mL of ethylene glycol dimethyl ether into a 250 mL round-bottom flask. After stirring until the solid is completely dissolved, add 23.1 g (0.1 mol) of sodium 2-aminobenzenesulfonate to the reaction solution in batches (this reaction is an exothermic reaction, and the reaction temperature rises from 15 °C to 20 °C). Stir at room temperature for 36 h, then place the flask in a low-temperature bath and cool it to 10 °C. Filter by suction and dry in vacuum at 60 °C for 10 h to obtain 33.6 g of a white solid product; Yield: 97.87%; Melting point: greater than 300 °C.

[0049] Example 4

[0050]

[0051] Synthesis of N-(Sodium p-Sulfonate Phenyl) Phthalic Monoamide

[0052] Add 14.8 g (0.1 mol) of phthalic anhydride and 100 mL of 1,4-dioxane into a 250 mL round-bottom flask. After stirring until the solid is completely dissolved, add 23.1 g (0.1 mol) of sodium 4-aminobenzenesulfonate to the reaction solution in batches (this reaction is an exothermic reaction, and the reaction temperature rises from 15 °C to 20 °C). Stir at room temperature for 36 h, then place the flask in a low-temperature bath and cool it to 10 °C. Filter by suction and dry in vacuum at 60 °C for 10 h to obtain 32.81 g of a white solid product, Yield: 95.57%; Melting point: greater than 300 °C.

[0053] Example 5

[0054]

[0055] Synthesis of N-(Sodium m-Sulfonate Phenyl) Phthalic Monoamide

[0056] 14.8 g (0.1 mol) of phthalic anhydride and 100 mL of cyclohexanone were added to a 250 mL round-bottom flask. After stirring until the solid was completely dissolved, 23.1 g (0.1 mol) of sodium 3-aminobenzenesulfonate was added to the reaction solution in batches (this reaction is an exothermic reaction, and the reaction temperature rose from 15 °C to 20 °C). After stirring at room temperature for 36 h, the flask was placed in a low-temperature bath and cooled to 10 °C, then filtered by suction, and dried in vacuo at 60 °C for 10 h to obtain 30.28 g of a white solid product, yield: 88.2%; melting point 172 - 184 °C.

[0057] Example 6

[0058]

[0059] Synthesis of N-(sodium sulfonate phenyl) phthalic monoamide

[0060] 14.8 g (0.1 mol) of phthalic anhydride and 100 mL of N-methylpyrrolidone were added to a 250 mL round-bottom flask. After stirring until the solid was completely dissolved, 23.1 g (0.1 mol) of sodium 2-aminobenzenesulfonate was added to the reaction solution in batches (this reaction is an exothermic reaction, and the reaction temperature rose from 15 °C to 20 °C). After stirring at room temperature for 36 h, the flask was placed in a low-temperature bath and cooled to 10 °C, then filtered by suction, and dried in vacuo at 60 °C for 10 h to obtain 33.92 g of a white solid product; yield: 98.8%; melting point > 300 °C.

[0061] Example 7

[0062]

[0063] Synthesis of N-(sodium sulfonate ethyl phenyl) phthalic monoamide

[0064] 14.8 g (0.1 mol) of phthalic anhydride and 100 mL of N,N-dimethylformamide were added to a 250 mL round-bottom flask. After stirring until the solid was completely dissolved, 25.9 g (0.1 mol) of sodium 4-aminophenylethanesulfonate was added to the reaction solution in batches (this reaction is an exothermic reaction, and the reaction temperature rose from 15 °C to 20 °C). After stirring at room temperature for 36 h, the flask was placed in a low-temperature bath and cooled to 10 °C, then filtered by suction, and dried in vacuo at 60 °C for 10 h to obtain 36.65 g of a white solid product, yield: 98.7%; melting point > 300 °C; IR (KBr tablet, cm -1):3454.51, 3309.85, 3064.89, 2627.05, 2372.44, 1707, 1701.22, 1647.21, 1595.13, 1527.62, 1400.32, 1327.03, 1267.23, 1195.87, 1128.36, 1076.28, 1047.35, 1014.56, 902.69, 833.25, 715.59, 673.16, 646.15, 607.58, 570.93。

[0065] Comparative Example 1

[0066] Synthesis of N-phenylphthalic monoamide

[0067] Add 14.8 g (0.1 mol) of phthalic anhydride and 100 mL of N,N-dimethylformamide to a 250 mL round-bottom flask. After stirring until the solid is completely dissolved, add aniline 9.31 g (0.1 mol) to the reaction solution in batches (this reaction is an exothermic reaction, and the reaction temperature rises from 15 °C to 20 °C). After stirring at room temperature for 36 h, cool the flask in a low-temperature bath to 10 °C, filter by suction, and dry in vacuo at 60 °C for 10 h to obtain 23.6 g of a white solid product. Yield: 97.9%; Melting point: 170 - 172 °C; IR (KBr tablet, cm -1 ):3321.4, 3134.3, 3057.2, 2617.4, 1722.4, 1654.9, 1598.9, 1490.9, 1242.2, 692.4; 1 HNMR (400 MHz, CDCl3); δ (ppm): 13.04 (s, 1H), 10.33 (s, 1H), 7.88 (m, 1H), 7.78 (m, 3H), 7.65 (m, 2H), 7.32 (s, 2H), 7.05 (m, 1H).

[0068] Test Example 1

[0069] Solubility test method:

[0070] Measure 100 mL of water and add it to a 250 mL beaker. Heat it to 25 °C. Each time, add 0.1 g of the compound to be tested. After stirring until it is completely dissolved, continue to add 0.1 g of the compound to be tested, stir continuously, and dissolve it fully until it is just saturated. Calculate the mass of the compound added to be tested, which is the solubility of the compound.

[0071] Product solubility comparison table

[0072] Product Name Solubility (g / 100g water) Dissolution property N-sulfophenyl phthalic acid monoamide 39.5 Good N-m-sulfophenyl phthalic acid monoamide 36.7 Good N-o-sulfophenyl phthalic acid monoamide 32.9 Good N-p-ethylsulfophenyl phthalic acid monoamide 30.7 Good N-phenyl phthalic acid monoamide 0.1 Poor

[0073] Test Example 2

[0074] Test method for plant growth regulation performance at a spraying concentration of 0.35% by weight:

[0075] Prepare an aqueous solution of 0.35% by weight of the compound of the present invention and N-phenylphthalic acid monoamide respectively (if there is undissolved part of N-phenylphthalic acid monoamide, make it completely dissolved by adding an appropriate amount of sodium carbonate). Spray the aqueous solution twice during the full-bloom stage of soybeans, with an interval of 7 - 10 days, and the spraying amount each time is 25 L / mu. After the soybeans are mature, calculate the soybean yield. If the yield increases by more than 10%, it indicates that the plant growth regulation performance of the compound is good; otherwise, its plant growth regulation performance is poor.

[0076] Comparison table of yield increase effects at a spraying concentration of 0.35% by weight

[0077] Product Name Concentration (wt%) Spraying times Yield increase N-sulfophenyl phthalic acid monoamide 0.35％ 2 16.5％ N-m-sulfophenyl phthalic acid monoamide 0.35％ 2 15.2％ N-o-sulfophenyl phthalic acid monoamide 0.35％ 2 12.3％ N-p-ethylsulfophenyl phthalic acid monoamide 0.35％ 2 11.5％ N-phenyl phthalic acid monoamide 0.35％ 2 10.2％

[0078] Test method for plant growth regulation performance at a spraying concentration of 1% by weight:

[0079] Prepare an aqueous solution of 1% by weight of the exemplary compound of the present invention and N-phenylphthalic acid monoamide respectively (if there is undissolved part of N-phenylphthalic acid monoamide, make it completely dissolved by adding an appropriate amount of sodium carbonate). Spray the 1% by weight aqueous solution once during the full-bloom stage of soybeans, and the spraying amount each time is 10 L / mu. After the soybeans are mature, compare the soybean yields after spraying the test compound and N-phenylphthalic acid monoamide. If the yield increases by more than 10%, it indicates that the plant growth regulation performance of the compound is good; otherwise, its plant growth regulation performance is poor.

[0080] Comparison table of yield increase effects at a spraying concentration of 1% by weight

[0081] Product Name Concentration (wt%) Spraying times Yield increase N-sulfophenyl phthalic acid monoamide 1％ 1 22.6％ N-m-sulfophenyl phthalic acid monoamide 1％ 1 22.1％ N-o-sulfophenyl phthalic acid monoamide 1％ 1 18.7％ N-p-ethylsulfophenyl phthalic acid monoamide 1％ 1 20.5％ N-phenyl phthalic acid monoamide 1％ 1 3.6％

[0082] The above has given an exemplary description of the implementation mode of the technical solution of the present invention. It should be understood that the protection scope of the present invention is not limited to the above implementation mode. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the claims of this application.

Claims

1. A compound of formula III: Among them, R1 is selected from H, -C 1-6 alkyl; R2 is selected from -SO3Na, -C 1-6 alkyl-SO3Na; m is selected from 0, 1 or 2; n is selected from 1 or 2.

2. The compound according to claim 1, wherein, R2 is selected from -SO3Na or -(CH2)2-SO3Na.

3. The compound according to claim 1, wherein The compound of formula III has the structure shown in formula III-1: Wherein, R2 has the definition as described in claim 1.

4. The compound according to claim 1, wherein The compound of formula III is selected from the following structures:

5. A method for preparing the compound according to any one of claims 1-2, characterized in that, Comprising the following steps: reacting compound I and compound II to obtain the compound of formula III; Wherein, R1, R2, m and n each independently have the definition as described in any one of claims 1-2.

6. The preparation method according to claim 5, characterized in that, The molar ratio of compound I to compound II is 1:(0.5-1.5); And / or, the temperature of the reaction is 10-60 °C.

7. The preparation method according to claim 5, characterized in that, The molar ratio of compound I to compound II is 1:(0.8-1.2); And / or, the temperature of the reaction is 15-50 °C.

8. The preparation method according to claim 5, characterized in that, The solvent for the reaction is selected from at least one of N,N-dimethylformamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, 1,4-dioxane, cyclohexanone, N-methylpyrrolidone.

9. The preparation method according to claim 5, wherein The reaction further includes a post-treatment step; the post-treatment step includes: filtration, drying; And / or, the drying is vacuum drying, and the drying temperature is 50-80 °C; And / or, the vacuum drying time is 6-12 h.

10. The preparation method according to claim 5, characterized in that, The preparation method comprises the following steps: in a reactor equipped with a thermometer and a stirrer, add the solvent and compound I, stir to dissolve, then add compound II to the reaction solution in batches, after the reaction is completed at room temperature, cool the reaction to 5-20 °C, filter by suction, and vacuum dry the filter cake to obtain the compound of formula III.

11. Use of the compound according to any one of claims 1-4 as a plant growth regulator.

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