Oxime-triazole compound, and preparation method therefor and use thereof

Abstract

The present invention belongs to the technical field of plant growth regulators, and relates to an oxime-triazole compound, and a preparation method therefor and the use thereof. The oxime-triazole compound of the present invention has the effect of controlling excessive vegetative growth, and can effectively control the excessive vegetative growth of crops such as peanuts, rice and soybeans, thereby improving the yield and quality of crops. The oxime-triazole compound has the characteristics of strong excessive vegetative growth controlling effect, low application amount, high crop safety, etc. The experiment results show that the oxime-triazole compound of the present invention has the effects of inhibiting the plant height of rice and promoting the root growth of rice, the effect of inhibiting the hypocotyl elongation of cucumber and tomato seedlings, and the effects of inhibiting the excessive vegetative growth of peanut plants and increasing the chlorophyll content, fresh fruit weight and fruit number of peanuts.

Description

Oxime-based triazole compound and preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to an oxime-based triazole compound and a preparation method and application thereof, and belongs to the technical field of plant growth regulators. BACKGROUND

[0002] In modern agricultural production, plant growth regulators are increasingly widely used. Among them, plant growth retardants represented by paclobutrazol, uniconazole, calcium chlormequat, mepiquat, and chlorocholine are effective in controlling the growth and development of crops and improving the yield and quality of crops. However, these traditional plant growth retardants have certain limitations in practical application. For example, paclobutrazol has a large application amount and is easily retained in the soil, which adversely affects subsequent crop rotation. Calcium chlormequat has a short period of efficacy and needs to be applied in large amounts multiple times, which is costly. Therefore, it is necessary to develop a plant growth retardant that has good growth control effect and less soil residue. SUMMARY

[0003] The present application aims to provide an oxime-based triazole compound that can solve the problem of poor growth control effect of current plant growth retardants.

[0004] The second object of the present application is to provide a preparation method of an oxime-based triazole compound that can solve the problem of poor growth control effect of current plant growth retardants.

[0005] The third object of the present application is to provide an application of an oxime-based triazole compound that can solve the problem of poor growth control effect of current plant growth retardants.

[0006] To achieve the above objects, the technical solution adopted by the oxime-based triazole compound of the present application is as follows:

[0007] An oxime-based triazole compound has the structure shown in formula I:

[0008] In formula I, R is a phenyl group or a substituted phenyl group. When the substituted phenyl group is a monosubstituted phenyl group, the substituent is -F, -Cl, -Br, -I, a nitro group, C1-C3 alkoxy, trifluoromethyl, or C1-C5 alkyl. When the substituted phenyl group is a disubstituted phenyl group, each substituent is independently selected from -F, -Cl, -Br, -I, a nitro group, C1-C3 alkoxy, trifluoromethyl, or C1-C5 alkyl.

[0009] The oxime triazole compound has a growth control effect, can effectively control the vigorous growth of crops such as peanuts, rice and soybeans, improve the yield and quality of crops, has the characteristics of strong growth control effect, small application amount, safety to crops and the like. Experimental results show that the oxime triazole compound has the effects of inhibiting the plant height of rice, promoting the root growth of rice, inhibiting the hypocotyl length of cucumber and tomato seedlings, inhibiting the vigorous growth of peanut plants, improving the chlorophyll content of peanut leaves, fresh fruit weight and fruit number.

[0010] Preferably, the substituted phenyl is phenyl substituted with one substituent, and the substituent is located at the para position of the phenyl.

[0011] Preferably, the substituted phenyl is phenyl substituted with two substituents, and the substituents are located at the ortho and para positions of the phenyl.

[0012] Preferably, the substituted phenyl is phenyl substituted with two substituents, and the substituents are -F and -Cl. That is, both substituents can be F, or both can be Cl, or one can be F and the other can be Cl.

[0013] The technical scheme adopted by the preparation method of the oxime triazole compound of the present application is as follows:

[0014] A preparation method of the oxime triazole compound as described above, comprising the following steps: oximation reaction of a compound shown in formula II and hydroxylamine hydrochloride to obtain an oxime triazole compound;

[0015] In formula II, R is phenyl or substituted phenyl, the substituted phenyl is phenyl substituted with one or two substituents, when the substituted phenyl is phenyl substituted with one substituent, the substituent is -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl or C1-C5 alkyl, and when the substituted phenyl is phenyl substituted with two substituents, each substituent is independently selected from -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl or C1-C5 alkyl.

[0016] The preparation method of the oxime triazole compound of the present application has simple process, low operation cost, high product yield and can be produced on a large scale.

[0017] Preferably, R in formula II is phenyl substituted with one substituent, and the substituent is located at the para position of the phenyl.

[0018] Preferably, R in formula II is phenyl substituted with two substituents, and the substituents are located at the ortho and para positions of the phenyl, and the substituents are -F and -Cl.

[0019] The technical scheme adopted by the application of the oxime triazole compound of the present application as a plant growth regulator is as follows:

[0020] Use of an oxime triazole compound as described above as a plant growth regulator.

[0021] The oxime triazole compound of the present application has a growth control effect, can effectively control the vigorous growth of crops such as peanuts, rice, soybeans and the like, and improve the yield and quality of crops, and has the characteristics of strong growth control effect, small application amount, safety to crops and the like. Experimental results show that the oxime triazole compound of the present application has the effects of inhibiting the plant height of rice, promoting the root growth of rice, inhibiting the hypocotyl length of cucumber and tomato seedlings, and inhibiting the vigorous growth of peanut plants, improving the chlorophyll content, fresh fruit weight and fruit number of peanuts.

[0022] Preferably, the plant growth regulator is a plant growth retardant.

[0023] Preferably, the plant growth regulator is a plant growth regulator for inhibiting the plant height of rice, promoting the root growth of rice, a plant growth regulator for inhibiting the hypocotyl length of cucumber and tomato seedlings, and a plant growth regulator for inhibiting the vigorous growth of peanut plants, improving the chlorophyll content, fresh fruit weight and fruit number of peanuts. BRIEF DESCRIPTION OF DRAWINGS

[0024] Fig. 1 is a nuclear magnetic spectrum of the oxime triazole compound prepared in Experimental Example 1 of the present application;

[0025] Fig. 2 is a nuclear magnetic spectrum of the oxime triazole compound prepared in Experimental Example 2 of the present application;

[0026] Fig. 3 is a nuclear magnetic spectrum of the oxime triazole compound prepared in Experimental Example 3 of the present application;

[0027] Fig. 4 is a nuclear magnetic spectrum of the oxime triazole compound prepared in Experimental Example 4 of the present application;

[0028] Fig. 5 is a nuclear magnetic spectrum of the oxime triazole compound prepared in Experimental Example 5 of the present application;

[0029] Fig. 6 is a nuclear magnetic spectrum of the oxime triazole compound prepared in Experimental Example 6 of the present application;

[0030] Fig. 7 is a nuclear magnetic spectrum of the oxime triazole compound prepared in Experimental Example 7 of the present application. DETAILED DESCRIPTION

[0031] The oxime triazole compound of the present application is an original invention. The oxime triazole compound of the present application has the structure shown in Formula I:

[0032] In formula I, R is phenyl or substituted phenyl, the substituted phenyl is phenyl substituted by one or two substituents, when the substituted phenyl is phenyl substituted by one substituent, the substituent is -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl, and when the substituted phenyl is phenyl substituted by two substituents, the two substituents are independently selected from -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl.

[0033] The oxime triazole compound has a growth control effect, can effectively control the vigorous growth of crops such as peanuts, rice and soybeans, improve the yield and quality of crops, has the characteristics of strong growth control effect, small application amount, safety to crops and the like. Experimental results show that the oxime triazole compound has the effects of inhibiting the plant height of rice, promoting the root growth of rice, inhibiting the hypocotyl length of cucumber and tomato seedlings, inhibiting the vigorous growth of peanut plants, improving the chlorophyll content of peanut leaves, fresh fruit weight and fruit number.

[0034] The preparation method of the oxime triazole compound is as follows: oximation reaction is carried out on the compound shown in formula II and hydroxylamine hydrochloride to obtain the oxime triazole compound. The reaction equation is as follows:

[0035] In formula II, R is phenyl or substituted phenyl, the substituted phenyl is phenyl substituted by one or two substituents, when the substituted phenyl is phenyl substituted by one substituent, the substituent is -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl, and when the substituted phenyl is phenyl substituted by two substituents, the two substituents are independently selected from -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl.

[0036] The preparation method of the oxime triazole compound is simple in process, low in operation cost, high in product yield, and can be produced on a large scale.

[0037] In some preferred embodiments, the oximation reaction is a mixing reaction of the compound shown in formula II, hydroxylamine hydrochloride, an alkaline compound and a solvent.

[0038] In some preferred embodiments, the molar ratio of the compound shown in formula II to hydroxylamine hydrochloride is 1:(1-3).

[0039] In some preferred embodiments, the temperature of the oximation reaction is -10℃ to the boiling point of the solvent used in the oximation reaction. For example, it can be 70-75℃.

[0040] In some preferred embodiments, the time of the oximation reaction is 0.5-36h. For example, it can be 12-36h.

[0041] In some preferred embodiments, the solvent is ethyl acetate, acetonitrile, methanol, ethanol, acetone, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, n-butanol, tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone, sulfolane, petroleum ether, toluene, xylene.

[0042] In some preferred embodiments, the basic compound is triethylamine, N,N-dimethylaniline, sodium ethoxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, cesium carbonate, sodium hydride.

[0043] In some preferred embodiments, the molar ratio of the compound of formula II to the basic compound is 1:(1-10).

[0044] In some preferred embodiments, the compound of formula II is prepared by substitution reaction of a compound of formula III and a compound of formula IV; the reaction equation is as follows:

[0045] In formula III, X is -Cl, -Br; R is phenyl or substituted phenyl, the substituted phenyl is one or two substituents substituted phenyl, when the substituted phenyl is one substituent substituted phenyl, the substituent is -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl, when the substituted phenyl is two substituents substituted phenyl, each substituent is independently selected from -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl; R2 is tert-butyl.

[0046] In some preferred embodiments, the substitution reaction of the compound of formula III and the compound of formula IV is mixing reaction of the compound of formula III, the compound of formula IV, the basic compound and the solvent. A catalyst can be further added to promote the reaction. The catalyst can be selected from benzyltriethylammonium chloride, and the mass of the catalyst can be controlled to be 5-10% of the mass of the compound of formula III, for example, 6-7%.

[0047] In some preferred embodiments, the molar ratio of the compound of formula III to the compound of formula IV is 1:(0.5-2).

[0048] In some preferred embodiments, the solvent used in the reaction of the compound of formula III and the compound of formula IV is acetonitrile, tetrahydrofuran, toluene, xylene, methanol, ethanol, water, and the basic compound used is triethylamine, N,N-dimethylaniline, sodium ethoxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, cesium carbonate, sodium hydride.

[0049] In some preferred embodiments, the reaction of the compound of formula III and the compound of formula IV is carried out at a temperature of -10℃ to the boiling point of the solvent used, for a time period of 0.5-36h. For example, the reaction can be carried out at a temperature of 60-70℃ for a time period of 5-36h.

[0050] In some preferred embodiments, the compound of formula IV is prepared by reacting a compound of formula V with 1H-1,2,4-triazole; the reaction is shown in the following equation:

[0051] In formula V, X is -Cl or -Br; R2 is tert-butyl.

[0052] In some preferred embodiments, the reaction of the compound of formula V and 1H-1,2,4-triazole is carried out by mixing the compound of formula V, 1H-1,2,4-triazole, a basic compound and a solvent.

[0053] In some preferred embodiments, the molar ratio of the compound of formula V and 1H-1,2,4-triazole is 1:(0.5-2).

[0054] In some preferred embodiments, the reaction of the compound of formula V and 1H-1,2,4-triazole is carried out at a temperature of -10℃ to the boiling point of the solvent used, for a time period of 0.5-36h. For example, the reaction can be carried out at a temperature of 75-80℃ for a time period of 8-36h.

[0055] In some preferred embodiments, the solvent used in the reaction of the compound of formula V and 1H-1,2,4-triazole is ethyl acetate, acetonitrile, tetrahydrofuran, toluene, xylene, methanol or ethanol; the basic compound used is triethylamine, N,N-dimethylaniline, sodium ethoxide, sodium methoxide, sodium tert-butoxide, potassium tert-butoxide, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium carbonate, cesium carbonate or sodium hydride.

[0056] The preparation process of the oxime triazole compound of the present application is as follows:

[0057] The oxime triazole compound of the present application has the activity of controlling the vigorous growth of plants, and can be used for peanut, corn, soybean, rice, wheat and other field crops, apple, pear, peach, cherry, citrus and other fruit trees, spinach, lettuce, cabbage, tomato and other vegetables, tobacco, nuts, sugarcane, tea, pepper and ornamental plants.

[0058] The oxime triazole compound of the present application can effectively control the vigorous growth of crops such as peanut, rice and soybean, improve the yield and quality of crops, and has the characteristics of strong control of vigorous growth, small amount of application, safety to crops, etc.

[0059] The oxime triazole compound of the present application can be used in a growth control composition, and the oxime triazole compound is contained in the growth control composition in an amount of 1 to 99% by weight. The growth control composition can be applied in the form of a formulation, and the oxime triazole compound of the present application is dissolved or dispersed in a carrier or formulated into a formulation (wettable powder, water dispersible granule, suspension concentrate or emulsifiable concentrate) to be used as a growth control agent, and a liquid or solid carrier and a suitable surfactant can be added as needed.

[0060] The oxime triazole compound of the present application can control the growth of plants, and when used, a growth control composition containing the oxime triazole compound is applied to plants, and the suitable effective amount is 5 to 300 g per hectare, and the preferred effective amount is 10 to 150 g per hectare.

[0061] The oxime triazole compound of the present application can also be mixed with other plant protection carriers or diluents to be formulated into various formulations such as a mixture, a granule, an emulsion, etc., and can also be mixed with other pesticides such as a fungicide, an insecticide, a herbicide, a plant growth regulator, etc. and used simultaneously, thereby producing additional advantages and effects.

[0062] The experimental results show that the oxime triazole compound of the present application has the effects of inhibiting the growth of rice plants, promoting the growth of rice roots, inhibiting the growth of cucumber and tomato seedling hypocotyls, inhibiting the growth of peanut plants, increasing the chlorophyll content, fresh fruit weight and fruit number of peanuts.

[0063] The technical solutions of the present application will be further described below in combination with specific examples. The raw materials involved in the following examples are all commercially available conventional goods.

[0064] First, the oxime triazole compound of the present application and the preparation method thereof are as follows:

[0065] Example 1

[0066] The oxime triazole compound of the present application is as shown in the following formula:

[0067] The preparation method of the oxime triazole compound of the present application is as follows:

[0068] (1) The starting material (i.e., 1H-1,2,4-triazole) 70 g, ethyl acetate 350 g, and anhydrous potassium carbonate 155 g were sequentially added into a reaction bottle, and chloroacetone 150 g was added dropwise into the reaction bottle at 20 °C under stirring. After the dropwise addition was completed, the material in the reaction bottle was warmed to 75-80 °C, and was kept under stirring for 8 h. Then, the reaction system was cooled to room temperature, and was filtered to remove the solid potassium carbonate in the system. The liquid obtained by the filtration was heated and evaporated until the volume of the remaining liquid was 1 / 4 of the volume of the liquid before evaporation. White crystals were precipitated in the liquid after evaporation, which were filtered and dried to obtain a triazolone 152.5 g, with a yield of 90 %;

[0069] (2) The triazolone 152.5 g obtained in step (1), toluene 1000 g, p-chlorobenzyl chloride 160 g, and a catalyst benzyltriethylammonium chloride 10.4 g were sequentially added into a reaction bottle. The material in the reaction bottle was warmed to 60 °C, and then 100 g of a 40 % sodium hydroxide aqueous solution was slowly added dropwise into the reaction bottle. After the dropwise addition was completed, the material in the reaction bottle was kept under stirring at 70 °C for 5 h. After the reaction was completed, 40 g of water was added into the reaction bottle, and then the system was left to stand and separate into layers. The water layer was washed with 100 mL of toluene twice, and then the organic phases were combined. The organic phase was heated and evaporated until the volume of the remaining liquid was 400 mL. Then, the liquid was filtered, and the solid obtained by the filtration was dried to obtain an intermediate chlorotriazolone 234.2 g, with a yield of 88 %.

[0070] (3) The chlorotriazolone 234.2 g obtained in step (2), ethyl acetate 1000 g, triethylamine 122 g, and hydroxylamine hydrochloride 111.5 g were sequentially added into a reaction bottle. The material in the reaction bottle was refluxed at 75 °C for 12 h. After the reaction was completed, the solvent in the reaction system was evaporated to obtain a residue. The residue was recrystallized using 1000 mL of ethanol and water in a volume ratio of 1:1. White crystals were precipitated after cooling, which were filtered and dried to obtain an oxime-based triazolone compound (named as S1) 209.3 g, with a yield of 85 % and a purity of 95 %. The oxime-based triazolone compound prepared in the example was subjected to nuclear magnetic characterization, and the results are shown in FIG. 1. The nuclear magnetic hydrogen spectrum data of the oxime-based triazolone compound prepared in the example are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.59 (s, 1H), 8.62 (s, 1H), 7.93 (s, 1H), 7.26 (d, J = 8.5 Hz, 2H), 7.17 (d, J = 8.4 Hz, 2H), 3.83 (dd, J = 13.7, 8.2 Hz, 1H), 3.68 (dd, J = 13.7, 7.7 Hz, 1H), 0.96 (s, 9H). The mass spectrum test data of the oxime-based triazolone compound prepared in the example are MS [M+H] + : 306.

[0071] Example 2

[0072] The oxime triazole compound of this example is shown in the following formula:

[0073] The preparation method of the oxime triazole compound of this example is as follows:

[0074] (1) This step is the same as step (1) of the preparation method of the oxime triazole compound of Example 1;

[0075] (2) The oxazolone 152.5 g prepared in step (1), toluene 1200 g, p-bromochlorobenzyl 206 g, and catalyst benzyl triethyl ammonium chloride 10.4 g were sequentially added to a reaction bottle, and then the materials in the reaction bottle were heated to 60°C. Then 100 g of 40% mass fraction sodium hydroxide aqueous solution was slowly added dropwise into the reaction bottle. After the dropwise addition was completed, the materials in the reaction bottle were kept at 70°C and stirred for 5 h. After the reaction was completed, 40 g of water was added to the reaction bottle, and then it was left to separate into layers. The water layer was washed with 100 mL of toluene twice, and then the organic phases were combined. Then the organic phase was heated and evaporated until the volume of the remaining liquid was 350 mL. The temperature was lowered to 20-30°C, and then it was filtered, and the solid was dried to obtain 276 g of intermediate bromo-oxazolone, with a yield of 90%;

[0076] (3) The bromo-oxazolone 276 g prepared in step (2), ethyl acetate 1000 g, triethylamine 125 g, and hydroxylamine hydrochloride 114 g were sequentially added to a reaction bottle. Then the materials in the reaction bottle were refluxed at 75°C for 12 h. After the reaction was completed, the solvent in the reaction system was evaporated to obtain a residue. Then the residue was recrystallized using 1000 mL of ethanol and water in a volume ratio of 1:1. White crystals were precipitated after cooling, and then they were filtered and dried to obtain 231 g of the oxime triazole compound (named S2), with a yield of 80% and a purity of 94%. The oxime triazole compound prepared in this example was subjected to nuclear magnetic resonance characterization, and the results are shown in FIG. 2. The nuclear magnetic resonance hydrogen spectrum data of the oxime triazole compound prepared in this example are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.20 (s, 1H), 8.60 (s, 1H), 7.92 (s, 1H), 7.41 (d, J = 8.3 Hz, 2H), 7.11 (d, J = 8.3 Hz, 2H), 5.29 (t, J = 7.9 Hz, 1H), 3.80 (dd, J = 13.7, 8.2 Hz, 1H), 3.66 (dd, J = 13.7, 7.7 Hz, 1H), 0.96 (s, 9H). The mass spectrometry test data of the oxime triazole compound prepared in this example are MS [M+H] + : 350.

[0077] Example 3

[0078] The oxime triazole compound of this example is shown in the following formula:

[0079] The preparation method of the oxime triazole compound of this example is as follows:

[0080] (1) The step is the same as step (1) of the preparation method of the oxime triazole compound of Example 1;

[0081] (2) The oxazolone 152.5 g, toluene 1500 g, chlorobenzyl trifluoromethyl 195 g, and catalyst benzyl triethyl ammonium chloride 10.4 g prepared in step (1) were sequentially added into a reaction bottle, and then the materials in the reaction bottle were heated to 60°C. Then 100 g of 40% sodium hydroxide aqueous solution was slowly added dropwise into the reaction bottle. After the dropwise addition was completed, the materials in the reaction bottle were kept at 70°C and stirred for 5 h. After the reaction was completed, 40 g of water was added into the reaction bottle, and then the reaction bottle was allowed to stand and separate into layers. The water layer was washed with 100 mL of toluene twice, and then the organic phases were combined. Then the organic phase was heated and evaporated until the volume of the remaining liquid was 400 mL. The temperature was lowered to 20-30°C, and then the mixture was filtered and the solid was dried to obtain 252 g of intermediate fluoro-oxazolone, with a yield of 85%;

[0082] (3) The fluoro-oxazolone (oxazolone containing trifluoromethyl) 252 g, ethyl acetate 1500 g, triethylamine 118 g, and hydroxylamine hydrochloride 108 g prepared in step (2) were sequentially added into a reaction bottle, and then the materials in the reaction bottle were refluxed at 75°C for 12 h. After the reaction was completed, the solvent in the reaction system was evaporated to obtain a residue. The residue was recrystallized using 800 mL of ethanol and water in a volume ratio of 1:1. White crystals were precipitated after cooling, and then the crystals were filtered and dried to obtain 197 g of the oxime triazole compound (named as S3), with a yield of 77% and a purity of 96%. The oxime triazole compound prepared in this example was subjected to nuclear magnetic resonance characterization, and the results are shown in FIG. 3. The nuclear magnetic resonance hydrogen spectrum data of the oxime triazole compound prepared in this example are as follows: 1H NMR (400 MHz, CDCl3) δ 10.15 (s, 1H), 8.61 (s, 1H), 7.93 (s, 1H), 7.55 (d, J = 8.1 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 5.34 (t, J = 7.9 Hz, 1H), 3.90 (dd, J = 13.7, 8.0 Hz, 1H), 3.79 (dd, J = 13.7, 7.7 Hz, 1H), 0.96 (s, 9H). The mass spectrometry test data of the oxime triazole compound prepared in this example are as follows: MS [M+H] + : 340.

[0083] Example 4

[0084] The oxime triazole compound of the present embodiment is shown in the following formula:

[0085] The preparation method of the oxime triazole compound of the present embodiment is as follows:

[0086] (1) The step is the same as step (1) of the preparation method of the oxime triazole compound of Example 1;

[0087] (2) The azolone 152.5 g prepared in step (1), toluene 1500 g, p-nitrochlorobenzene 172 g, and catalyst benzyltriethylammonium chloride 10.4 g were sequentially added to a reaction bottle, and then the materials in the reaction bottle were heated to 60°C. Then, 100 g of 40% sodium hydroxide aqueous solution was slowly added dropwise into the reaction bottle. After the dropwise addition was completed, the materials in the reaction bottle were kept at 70°C and stirred for 5 h. After the reaction was completed, 40 g of water was added to the reaction bottle, and then the reaction bottle was allowed to stand and separate into layers. The water layer was washed with 100 mL of toluene twice, and then the organic phases were combined. Then, the organic phase was heated and evaporated until the volume of the remaining liquid was 400 mL. The temperature was lowered to 20-30°C, and then the mixture was filtered. The solid was dried to obtain 223 g of the intermediate nitro-containing azolone, with a yield of 81%;

[0088] (3) The nitro-containing azolone 223 g prepared in step (2), ethyl acetate 1500 g, triethylamine 112 g, and hydroxylamine hydrochloride 103 g were sequentially added to a reaction bottle. Then, the materials in the reaction bottle were refluxed at 75°C for 12 h. After the reaction was completed, the solvent in the reaction system was evaporated to obtain a residue. Then, the residue was recrystallized using 800 mL of ethanol and water in a volume ratio of 1:1. White crystals were precipitated after cooling, and then the crystals were filtered and dried to obtain 182 g of the oxime triazole compound (named S4), with a yield of 75% and a purity of 96%. The oxime triazole compound prepared in the present embodiment was subjected to nuclear magnetic resonance characterization, and the results are shown in FIG. 4. The nuclear magnetic resonance hydrogen spectrum data of the oxime triazole compound prepared in the present embodiment are as follows: 1 H NMR (500 MHz, CDCl3) δ 11.00 (s, 1H), 8.66 (s, 1H), 8.22-8.09 (m, 2H), 7.96 (s, 1H), 7.45 (d, J = 8.3 Hz, 2H), 5.37 (s, 1H), 4.10-3.74 (m, 2H), 0.96 (s, 9H). The mass spectrometry test data of the oxime triazole compound prepared in the present embodiment are MS [M+H] + : 318.

[0089] Example 5

[0090] The oxime triazole compound of the present embodiment is shown in the following formula:

[0091] The preparation method of the oxime triazole compound of the present embodiment is as follows:

[0092] (1) The step is the same as step (1) of the preparation method of the oxime triazole compound of Example 1;

[0093] (2) The oxazolone 152.5 g prepared in step (1), toluene 1500 g, p-methoxy chlorobenzyl 195 g, and catalyst benzyl triethyl ammonium chloride 10.4 g were sequentially added into a reaction bottle, and then the materials in the reaction bottle were heated to 60°C. Then, 100 g of 40% sodium hydroxide aqueous solution was slowly added dropwise into the reaction bottle. After the dropwise addition was completed, the materials in the reaction bottle were kept at 70°C and reacted for 5 h under stirring. After the reaction was completed, 40 g of water was added into the reaction bottle, and then the reaction bottle was allowed to stand and separate into layers. The water layer was washed with 100 mL of toluene twice, and then the organic phases were combined. Then, the organic phase was heated and evaporated until the volume of the remaining liquid was 400 mL. The temperature was lowered to 20-30°C, and then the mixture was filtered. The solid was dried to obtain 236 g of the intermediate oxazolone containing methoxy group, with a yield of 90%.

[0094] (3) The oxazolone containing methoxy group 236 g prepared in step (2), ethyl acetate 1500 g, triethylamine 124 g, and hydroxylamine hydrochloride 114 g were sequentially added into a reaction bottle. Then, the materials in the reaction bottle were refluxed at 75°C for 12 h. After the reaction was completed, the solvent in the reaction system was evaporated to obtain a residue. Then, the residue was recrystallized using 800 mL of ethanol and water in a volume ratio of 1:1. White crystals were precipitated after cooling, and then the crystals were filtered and dried to obtain 206 g of the oxime triazole compound (named as S5), with a yield of 80% and a purity of 97%. The oxime triazole compound prepared in the present embodiment was subjected to nuclear magnetic resonance characterization, and the results are shown in FIG. 5. The nuclear magnetic resonance hydrogen spectrum data of the oxime triazole compound prepared in the present embodiment are as follows: 1 HNMR (500 MHz, CDCl3) δ 10.83 (s, 1H), 8.67 (s, 1H), 7.93 (s, 1H), 7.16 (d, J = 8.3 Hz, 2H), 6.82 (d, J = 8.3 Hz, 2H), 5.30 (t, J = 8.0 Hz, 1H), 3.91-3.82 (m, 1H), 3.77 (d, J = 7.5 Hz, 3H), 3.65 (dd, J = 13.8, 7.6 Hz, 1H), 0.98 (s, 9H). The mass spectrum test data of the oxime triazole compound prepared in the present embodiment are MS [M+H] + : 303.

[0095] Example 6

[0096] The oxime triazole compound of the present embodiment is as shown in the following formula:

[0097] The preparation method of the oxime triazole compound of the present embodiment is as follows:

[0098] (1) The step is the same as step (1) of the preparation method of the oxime triazole compound of Example 1;

[0099] (2) The oxazolone 152.5 g prepared in step (1), toluene 1500 g, 2,4-dichloro-chlorobenzene 195 g, and catalyst benzyl triethyl ammonium chloride 10.4 g were sequentially added into a reaction bottle, and then the materials in the reaction bottle were heated to 60°C. Then, 100 g of 40% sodium hydroxide aqueous solution was slowly added dropwise into the reaction bottle. After the dropwise addition was completed, the materials in the reaction bottle were kept at 70°C and stirred for 5 h. After the reaction was completed, 40 g of water was added into the reaction bottle, and then the reaction bottle was left to stand and separate into layers. The water layer was washed with 100 mL of toluene twice, and then the organic phases were combined. Then, the organic phase was heated and evaporated until the volume of the remaining liquid was 400 mL. The temperature was lowered to 20-30°C, and then the mixture was filtered. The solid was dried to obtain 256 g of the intermediate containing 2,4-dichloro oxazolone, with a yield of 86%;

[0100] (3) The intermediate containing 2,4-dichloro oxazolone 256 g prepared in step (2), ethyl acetate 1500 g, triethylamine 118 g, and hydroxylamine hydrochloride 108 g were sequentially added into a reaction bottle. Then, the materials in the reaction bottle were refluxed at 75°C for 12 h. After the reaction was completed, the solvent in the reaction system was evaporated to obtain a residue. Then, the residue was recrystallized using 800 mL of ethanol and water in a volume ratio of 1:1. White crystals were precipitated after cooling, and then the crystals were filtered and dried to obtain 223 g of the oxime triazole compound (named as S6), with a yield of 79% and a purity of 95%. The oxime triazole compound prepared in the present embodiment was subjected to nuclear magnetic resonance characterization, and the results are shown in FIG. 6. The nuclear magnetic resonance hydrogen spectrum data of the oxime triazole compound prepared in the present embodiment are as follows: 1 H NMR (500 MHz, CDCl3) δ 10.68 (s, 1H), 8.69 (s, 1H), 7.94 (d, J = 2.6 Hz, 1H), 7.41 (t, J = 2.4 Hz, 1H), 7.11-6.79 (m, 1H), 5.45 (t, J = 8.1 Hz, 1H), 4.09-3.76 (m, 2H), 0.97 (s, 9H). The mass spectrometry test data of the oxime triazole compound prepared in the present embodiment are MS [M+H] + : 341.

[0101] Example 7

[0102] The oxime triazole compound of the present embodiment is as shown in the following formula:

[0103] The preparation method of the oxime-based triazole compound of the present embodiment is as follows:

[0104] (1) The step is the same as step (1) of the preparation method of the oxime-based triazole compound of Example 1;

[0105] (2) The oxazolone 152.5 g, toluene 1500 g, 2,4-difluoro-chlorobenzyl 163 g, and catalyst benzyl triethyl ammonium chloride 10.4 g prepared in step (1) were sequentially added into a reaction bottle, and then the materials in the reaction bottle were heated to 60°C. Then, 100 g of 40% sodium hydroxide aqueous solution was slowly added dropwise into the reaction bottle. After the dropwise addition was completed, the materials in the reaction bottle were kept at 70°C and reacted for 5 h under stirring. After the reaction was completed, 40 g of water was added into the reaction bottle, and then the reaction bottle was left to stand and separate into layers. The water layer was washed with 100 mL of toluene twice, and then the organic phases were combined. Then, the organic phase was heated and evaporated until the volume of the remaining liquid was 400 mL. The temperature was lowered to 20-30°C, and then the filtrate was filtered and dried to obtain 222 g of intermediate difluoro-oxazolone, with a yield of 83%;

[0106] (3) The difluoro-oxazolone 222 g, ethyl acetate 1500 g, triethylamine 115 g, and hydroxylamine hydrochloride 105 g prepared in step (2) were sequentially added into a reaction bottle. Then, the materials in the reaction bottle were refluxed at 75°C for 12 h. After the reaction was completed, the solvent in the reaction system was evaporated to obtain a residue. Then, the residue was recrystallized using 800 mL of ethanol and water in a volume ratio of 1:1. White crystals were precipitated after cooling, and then the crystals were filtered and dried to obtain 180 g of the oxime-based triazole compound (named as S7), with a yield of 73% and a purity of 96%. The oxime-based triazole compound prepared in the present embodiment was subjected to nuclear magnetic characterization, and the results are shown in FIG. 7. The nuclear magnetic hydrogen spectrum data of the oxime-based triazole compound prepared in the present embodiment are as follows: 1 H NMR (500 MHz, CDCl3) δ 10.45 (s, 1H), 8.70 (s, 1H), 7.90 (s, 1H), 7.14 (td, J = 8.4, 6.3 Hz, 1H), 6.80 (ddd, J = 8.6, 6.1, 2.2 Hz, 2H), 5.37 (t, J = 8.0 Hz, 1H), 4.05-3.84 (m, 1H), 3.80-3.25 (m, 1H), 1.04 (s, 9H). The mass spectrum test data of the oxime-based triazole compound prepared in the present embodiment are MS [M+H] + : 309.

[0107] Secondly, specific embodiments of the application of the oxime-based triazole compound of the present embodiment are as follows:

[0108] Example 8

[0109] The oxime triazole compounds S1, S2, S3, S4, S5, S6 and S7 prepared in Examples 1-7 are mixed with dispersants, wetting agents and carriers to prepare wettable powders. The wettable powders of the oxime triazole compounds S1, S2, S3, S4, S5, S6 and S7 are named P1, P2, P3, P4, P5, P6 and P7, respectively. The compositions of the wettable powders P1, P2, P3, P4, P5, P6 and P7 are shown in Table 1. The wettable powders are prepared according to the conventional wettable powder processing technology. The suspensibility, pH value, wetting time and fineness of the wettable powders P1, P2, P3, P4, P5, P6 and P7 meet the standard requirements. The test methods and evaluation standards of the indicators are as follows: the suspensibility is determined and evaluated according to the standard GB / T 14825, the pH value is determined and evaluated according to the standard GB / T 1601, the wetting time is determined and evaluated according to the standard GB / T 5451, and the fineness is determined and evaluated according to the standard GB / T 16150.

[0110] Table 1 Compositions of wettable powders P1, P2, P3, P4, P5, P6 and P7

[0111] Example 9

[0112] The oxime triazole compounds S1, S2, S3, S4, S5, S6 and S7 prepared in Examples 1-7 are mixed with dispersants, wetting agents, thickeners, antifreezing agents, preservatives, antifoaming agents and water to prepare suspensions. The suspensions of the oxime triazole compounds S1, S2, S3, S4, S5, S6 and S7 are named P8, P9, P10, P11, P12, P13 and P14, respectively. The compositions of the suspensions P8, P9, P10, P11, P12, P13 and P14 are shown in Table 2. The suspensions are prepared according to the conventional suspension processing technology. The suspensibility, pH value, pouring property, persistent foaming property and wet sieve test of the suspensions P8, P9, P10, P11, P12, P13 and P14 meet the standard requirements. The test methods and evaluation standards of the indicators are as follows: the suspensibility is determined and evaluated according to the standard GB / T 14825, the pH value is determined and evaluated according to the standard GB / T 1601, the pouring property is determined and evaluated according to the standard GB / T 31737, the persistent foaming property is determined and evaluated according to the standard GB / T 28137, and the wet sieve test is performed and evaluated according to the standard GB / T 16150.

[0113] Table 2 Compositions of suspensions P8, P9, P10, P11, P12, P13 and P14

[0114] Experimental Example 1

[0115] The seed was treated by soaking method to evaluate the effects of wettable powder P1, P2, P3, P4, P5, P6 and P7 on the seedling height and root length of rice. The specific experimental method is as follows:

[0116] Test crop: rice (three varieties: Yliang 2098, Longjiang 3013, Zhongfu 9).

[0117] Application method: seed soaking treatment.

[0118] Test treatment: wettable powder P1, P2, P3, P4, P5, P6 and P7, and the control agent is 5% uniconazole WP (produced by Jiangsu Jianpai Agricultural Chemicals), and a water control (CK) is set.

[0119] Test method: The wettable powder P1, P2, P3, P4, P5, P6 and P7 were diluted 2000 times, 1000 times and 500 times, and the control agent was diluted 333 times, and then the seeds of different varieties of rice were treated by seed soaking, and then washed with clean water after 48 hours, and then sowed after soaking in clean water. The seedling height and root length were investigated 30 days after treatment. The names, dilution multiples and active ingredient concentrations of the dilutions obtained after dilution of the wettable powder P1, P2, P3, P4, P5, P6 and P7 and the dilutions obtained after dilution of the control agent are shown in Table 3, and the seedling height and root length of the rice seeds treated with different dilutions after sowing are shown in Table 4.

[0120] Table 3 Names, dilution multiples and active ingredient concentrations of the dilutions obtained after dilution of the wettable powder P1, P2, P3, P4, P5, P6 and P7 and the dilutions obtained after dilution of the control agent

[0121] Table 4 Seedling height and root length of rice seeds treated with different dilutions after sowing

[0122] As shown in Table 4, after the rice Yliang 2098, Longjiang 3013 and Zhongfu 9 were treated with P1, P2, P3, P4, P5, P6 and P7 and the control agent by seed soaking, the plant height of the rice was inhibited, and the root growth was promoted. Compared with the blank treatment experiment CK, after treated with P1, P2, P3, P4, P5, P6 and P7, the plant height inhibition rate of Yliang 2098 was 22-67%, and the root length promotion rate was up to 41%; the plant height inhibition rate of Longjiang 3013 was 32-63%, and the root length promotion rate was up to 32%; the plant height inhibition rate of Zhongfu 9 was 18-78%, and the root length promotion rate was up to 33%. Combined with the phenotype data of the control agent, the best use dose of oxime-based triazole compounds S1, S2, S3, S4, S5, S6 and S7 on rice is 250 mg / L.

[0123] Experimental Example 2

[0124] In this experimental example, the hole disc irrigation treatment method was used to treat tomato and cucumber to evaluate the effects of suspending agents P8, P9, P10, P11, P12, P13 and P14 on the hypocotyl length of tomato and cucumber. The specific experimental method is as follows:

[0125] Test crops: tomato, cucumber.

[0126] Application method: hole disc irrigation treatment.

[0127] Test treatment: suspending agents P8, P9, P10, P11, P12, P13 and P14, control agent 15% calcium prohexadione WDG (produced by Zhengzhou Zhengshi Chemical Co., Ltd.), and water control (CK) were set up.

[0128] Test method: suspending agents P8, P9, P10, P11, P12, P13 and P14 were diluted 5000 times, 2500 times and 1250 times, and the control agent was diluted 1000 times, and then the potted tomato seedlings and cucumber seedlings were treated by root irrigation, the amount of liquid medicine was 25 mL / plant, 10 days after treatment, the hypocotyl length (the length from the substrate surface to the cotyledon node) was investigated, the inhibition rate was calculated, the calculation method of inhibition rate was: (average hypocotyl length of each treatment - average hypocotyl length of control) / average hypocotyl length of control x 100%. The names, dilution multiples and active ingredient concentrations of the dilutions obtained after dilution of suspending agents P8, P9, P10, P11, P12, P13 and P14 and the dilutions obtained after dilution of the control agent are shown in Table 5, the hypocotyl lengths and inhibition rates of tomato and cucumber seedlings treated with different dilutions are shown in Table 6.

[0129] Table 5 Names, dilution multiples and active ingredient concentrations of the dilutions obtained after dilution of suspending agents P8, P9, P10, P11, P12, P13 and P14 and the dilutions obtained after dilution of the control agent

[0130] Table 6 Hypocotyl lengths and inhibition rates of tomato and cucumber seedlings treated with different dilutions

[0131] From Table 6, it can be seen that the suspending agents P8, P9, P10, P11, P12, P13, and P14 have inhibitory effects on the hypocotyl growth of cucumber and tomato seedlings. The greater the treatment concentration, the more obvious the inhibitory effect on the hypocotyl length of cucumber and tomato seedlings. Compared with the control agent, the oxime-based triazole compounds S1, S2, S3, S4, S5, S6, and S7 can achieve similar or even more significant inhibitory effects on hypocotyl elongation at a low dose (50 mg / L), thus having higher biological activity and being beneficial to the cultivation of strong seedlings and the increase of seedling resistance.

[0132] Experimental Example 3

[0133] In this experimental example, peanuts were treated by spraying to evaluate the effects of the suspending agents P8, P9, P10, P11, P12, P13, and P14 on the plant height, chlorophyll content, fresh fruit weight, and fruit number of peanuts. The specific experimental method is as follows:

[0134] Test crop: peanuts (field).

[0135] Application method: spraying treatment.

[0136] Test treatment: suspending agents P8, P9, P10, P11, P12, P13, and P14, control agent 15% paclobutrazol SC (produced by Quanfeng Biology), and water control (CK).

[0137] Test method: After the suspending agents P8, P9, P10, P11, P12, P13, and P14 were diluted 1000 times, 500 times, and 250 times, and the control agent was diluted 300 times, the peanut plants were sprayed at the flowering stage, with a liquid volume of 30 L / acre. The blank treatment was sprayed with an equal amount of water. The plant height was measured at 7 days and 14 days after treatment, and the chlorophyll content (SPAD value), fresh fruit weight, and fruit number (only double fruit and single fruit were counted) were measured before harvest. The names, dilution ratios, and active ingredient concentrations of the diluted suspending agents P8, P9, P10, P11, P12, P13, and P14 and the diluted control agent are shown in Table 7. The plant height, chlorophyll content, fresh fruit weight, and fruit number of peanuts treated with different dilutions are shown in Table 8.

[0138] Table 7 Names, dilution ratios, and active ingredient concentrations of the diluted suspending agents P8, P9, P10, P11, P12, P13, and P14 and the diluted control agent

[0139] Table 8 Plant height, chlorophyll content, fresh fruit weight, and fruit number of peanuts treated with different dilutions

[0140] From table 8, after the peanut is treated by spraying the suspending agent P8, P9, P10, P11, P12, P13, P14, the plant height of the peanut at 7d, 14d after the treatment is lower than that of the peanut in the clear water control group, the plant height of the peanut treated by spraying the suspending agent P8, P9, P10, P11, P12, P13, P14 is respectively reduced by 4.3-10.8cm, 6.5-14.5cm at 7d, 14d after the treatment, the plant height of the peanut treated by spraying the control agent is respectively reduced by 8.5cm, 11.3cm at 7d, 14d after the treatment, under the same concentration treatment, compared with the control agent, the suspending agent P8, P9, P10, P11, P12, P13, P14 has similar or even more obvious control effect on the plant growth; before the harvest, the chlorophyll content of the peanut treated by spraying the suspending agent P8, P9, P10, P11, P12, P13, P14 and the peanut treated by spraying the control agent is higher than that of the peanut in the blank group, which indicates that the suspending agent P8, P9, P10, P11, P12, P13, P14 and the control agent have the early senescence prevention effect, which is beneficial to the continuous accumulation of photosynthetic products and the increase of yield; the fresh fruit weight and fruit number data show that the suspending agent P8, P9, P10, P11, P12, P13, P14 and the control agent increase the yield of the peanut by increasing the fruit number (the sum of double fruit number and single fruit number).

[0141] Finally, the preparation method of the oxime triazole compound in Example 1 is repeated, and the difference is that the p-chlorobenzyl is replaced by chlorobenzyl, p-ethoxychlorobenzyl, p-propoxychlorobenzyl, o-nitrochlorobenzyl, m-nitrochlorobenzyl, p-fluorochlorobenzyl, p-methylchlorobenzyl, p-pentylchlorobenzyl, p-iodochlorobenzyl, and then the prepared oxime triazole compound is tested according to the method of the experimental example. The experimental results show that the corresponding prepared oxime triazole compound has similar plant growth regulating activity to the oxime triazole compound prepared in Example 1.

[0142] From the experimental results, it can be seen that for the oxime triazole compound of the present application, when it has the structure shown in formula I, and R in formula I is phenyl or substituted phenyl (the substituted phenyl is one or two substituents substituted phenyl, when the substituted phenyl is one substituent substituted phenyl, the substituent is -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl, and when the substituted phenyl is two substituents substituted phenyl, each substituent is independently selected from -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl), the oxime triazole compound has plant growth control effect and can be used as a plant growth retardant.

Claims

1. An oxymethyltriazole compound, characterized by, having the structure of Formula I: In formula I, R is phenyl or substituted phenyl, the substituted phenyl is phenyl substituted with one or two substituents, when the substituted phenyl is phenyl substituted with one substituent, the substituent is -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl, and when the substituted phenyl is phenyl substituted with two substituents, each substituent is independently selected from -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl.

2. The oxymethyltriazole compound according to claim 1, wherein The substituted phenyl is phenyl substituted with one substituent, and the substituent is located at the para position of the phenyl.

3. The oxymethyltriazole compound according to claim 1, wherein The substituted phenyl is phenyl substituted with two substituents, and the substituents are located at the ortho and para positions of the phenyl.

4. The oxymethyltriazole compound according to claim 1 or 3, wherein The substituted phenyl is phenyl substituted with two substituents, and the substituents are -F and -Cl.

5. A process for the preparation of an oxime triazole compound according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: oximation of a compound shown in formula II with hydroxylamine hydrochloride to obtain an oxime triazole compound; In formula II, R is phenyl or substituted phenyl, the substituted phenyl is phenyl substituted with one or two substituents, when the substituted phenyl is phenyl substituted with one substituent, the substituent is -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl, and when the substituted phenyl is phenyl substituted with two substituents, each substituent is independently selected from -F, -Cl, -Br, -I, nitro, C1-C3 alkoxy, trifluoromethyl, C1-C5 alkyl.

6. The method of claim 5, wherein the oxime triazole compound is prepared by the reaction of the compound of formula (2) with the compound of formula (3) in the presence of a base. In formula II, R is phenyl substituted with one substituent, and the substituent is located at the para position of the phenyl.

7. The method for preparing the oxime-triazole compound as described in claim 5, characterized in that, In formula II, R is phenyl substituted with two substituents, and the substituents are located at the ortho and para positions of the phenyl, and the substituents are -F and -Cl.

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

9. Use according to claim 8, wherein the compound is ###0002### The plant growth regulator is a plant growth retardant.

10. Use according to claim 8 or 9, characterized in that, The plant growth regulator is a plant growth regulator for inhibiting the height of rice plants, promoting the growth of rice root systems, a plant growth regulator for inhibiting the hypocotyl length of cucumber and tomato seedlings, and a plant growth regulator for inhibiting the vigorous growth of peanut plants, increasing the chlorophyll content of peanut leaves, fresh fruit weight, and fruit number. The plant growth regulator is a plant growth retardant.

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