Furanone derivative as well as preparation method and application thereof

Abstract

The invention relates to the technical field of plant growth regulators, in particular to a furanone derivative as well as a preparation method and application thereof. The furanone derivative has a structure as shown in the following formula I or II: # imgabs0 #, R1 is selected from phenyl, substituted phenyl, thienyl and pyridyl, and X is selected from N or C; r2 and R3 are respectively and independently selected from H or methyl; and R4 is a monosubstituted or polysubstituted group on a benzene ring and is independently selected from H, halogen, C1-C3 alkyl, C1-C3 substituted alkyl, C1-C3 alkoxy and nitryl. The invention provides the furanone derivative with the effect of regulating plant growth, and the furanone derivative can be quickly and economically synthesized, so that the wide application of the furanone derivative as a green plant growth regulator is promoted.

Description

Technical Field

[0001] The present invention relates to the technical field of plant growth regulators, and particularly to a furanone derivative, a preparation method thereof, and an application thereof. Background Art

[0002] Plant growth regulators have great application potential in agriculture. They can increase crop yields and have the advantages of low dosage and obvious effects. With the in-depth study of plant hormones, in addition to the five typical plant hormones, brassinolide (BR), salicylic acid (SA), jasmonic acid (JA), and strigolactones (SLs) are also considered plant hormones. Strigolactone sesquiterpenoids include both natural strigolactones and synthetic strigolactone analogs.

[0003] The content of SLs in plants is extremely low, and it is difficult to isolate and purify them from plants. Moreover, their structures are complex, the enol ether bond between rings C and D is easily cleaved, and their stability is poor, making it impossible to achieve large-scale preparation of natural SLs, which greatly limits the application of SLs as plant growth regulators. Therefore, at present, chemical synthesis methods are mostly used to obtain SLs. Synthetic GR series strigol alcohol analogs include GR24, GR18, GR7, GR5, etc. Among them, GR24 shows good biological activity in the GR series and has thus been widely used. However, the existing synthetic routes of SLs analogs are relatively complex, which limits the large-scale production and application of synthetic SLs analogs. Therefore, for the development of agriculture, it is of great significance to develop compounds with simple structures, good stability, and good biological activity.

[0004] In view of this, the present invention is specifically proposed. Summary of the Invention

[0005] The object of the present invention is to provide a furanone derivative, a preparation method thereof, and an application thereof. The furanone derivative of the present invention has the function of regulating plant growth. At the same time, the furanone derivative of the present invention can be synthesized quickly and economically, promoting its wide application as a green plant growth regulator.

[0006] To achieve the above object of the present invention, in the first aspect of the present invention, a furanone derivative is provided, which has the structure shown in Formula I or II as follows:

[0007]

[0008] Wherein, R1 is selected from phenyl, substituted phenyl, thiophenyl, and pyridyl, and X is selected from N or C;

[0009] R2 and R3 are each independently selected from H or methyl; R4 is a mono- or poly-substituted group on the benzene ring and is independently selected from H, halogen, C1-C3 alkyl, C1-C3 substituted alkyl, C1-C3 alkoxy, and nitro.

[0010] In a specific embodiment of the present invention, in the C1-C3 substituted alkyl, the substituent is selected from halogen.

[0011] In a specific embodiment of the present invention, R2 and R3 are different.

[0012] In a specific embodiment of the present invention, the furanone derivative is any one of the following compounds:

[0013]

[0014]

[0015] The second aspect of the present invention provides a preparation method of the furanone derivative represented by formula I provided in the first aspect of the present invention, comprising the following steps:

[0016] Compound a and compound b react in a solvent under the action of a catalyst to obtain the structure shown in formula I; the structures of compound a and compound b are as follows:

[0017]

[0018] In a specific embodiment of the present invention, the solvent includes N,N-dimethylformamide.

[0019] In a specific embodiment of the present invention, the catalyst includes potassium tert-butoxide.

[0020] In a specific embodiment of the present invention, the molar ratio of compound a to compound b is 1:(1-1.5).

[0021] In a specific embodiment of the present invention, when X is N, the preparation of compound a includes: reacting a first compound with isoamyl nitrite in a solvent under the action of a first catalyst;

[0022] When X is C, the preparation of compound a includes: reacting a first compound with methyl formate in a solvent under the action of a second catalyst; the structure of the first compound is as follows:

[0023]

[0024] The third aspect of the present invention provides a preparation method of the furanone derivative represented by formula II provided in the first aspect of the present invention, comprising the following steps:

[0025] Compound e and compound f react in a solvent under the action of a catalyst to obtain the structure shown in Formula II; the structures of the compound e and the compound f are as follows respectively:

[0026]

[0027] In a specific embodiment of the present invention, the solvent includes acetonitrile.

[0028] In a specific embodiment of the present invention, the catalyst includes potassium carbonate.

[0029] In a specific embodiment of the present invention, the molar ratio of the compound e to the compound f is 1:(1.5 - 2.5).

[0030] The fourth aspect of the present invention provides the use of the furanone derivatives provided in the first aspect of the present invention in the preparation of plant growth regulators.

[0031] The fifth aspect of the present invention provides a plant growth regulator, which includes the furanone derivatives provided in the first aspect of the present invention.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] The present invention provides a furanone derivative having the function of regulating plant growth. At the same time, the furanone derivative of the present invention can be synthesized quickly and economically, promoting its wide application as a green plant growth regulator. Description of the Drawings

[0034] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0035] Figure 1 It is a comparison diagram of the effects of different compounds provided in the embodiments of the present invention on the germination of Cynomorium songaricum Rupr. seeds. Specific Embodiments

[0036] The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and specific embodiments. However, those skilled in the art will understand that the following described embodiments are some embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0037] In the first aspect of the present invention, furanone derivatives are provided, having the structures shown in the following formula I or II:

[0038]

[0039] Wherein, R1 is selected from phenyl, substituted phenyl, thienyl and pyridyl, and X is selected from N or C;

[0040] R2 and R3 are each independently selected from H or methyl; R4 is a mono-substituted or multi-substituted group on the benzene ring, and is each independently selected from H, halogen, C1-C3 alkyl, C1-C3 substituted alkyl, C1-C3 alkoxy and nitro.

[0041] Substituted phenyl means that the hydrogen on the phenyl is mono-substituted or multi-substituted by halogen, C1-C3 alkyl, C1-C3 alkoxy; further, the substituted phenyl of the present invention is selected from halogen-substituted phenyl and C1-C3 alkyl-substituted phenyl. The connection site of the thienyl or pyridyl to the structure shown in formula I can be as shown by the wavy line in the following structure:

[0042]

[0043] R4 being a mono-substituted or multi-substituted group on the benzene ring means that on the benzene ring where R4 is located, there can be one R4 substituent, or there can be two or more (such as 2, 3, 4 or 5) R4 substituents, and when there are two or more R4 substituents, the R4 substituents can be the same or different from each other.

[0044] The C1-C3 alkyl involved in the present invention refers to a straight-chain or branched-chain hydrocarbon group with 1-3 carbon atoms composed only of carbon atoms and hydrogen atoms, and may include, for example: methyl, ethyl, propyl and isopropyl; C1-C3 alkoxy may include methoxy, ethoxy, propoxy and isopropoxy; halogen includes at least one of fluorine (F), chlorine (Cl) and bromine (Br).

[0045] The C1-C3 substituted alkyl group involved in the present invention refers to a group in which at least one hydrogen atom in the C1-C3 alkyl group is substituted by a substituent such as a halogen, an amino group, a hydroxyl group, an alkoxy group, etc.

[0046] In a specific embodiment of the present invention, in the C1-C3 substituted alkyl group, the substituent is selected from halogens.

[0047] In a specific embodiment of the present invention, R2 and R3 are different. Specifically, the structure shown in Formula II of the present invention includes any one of the following structures:

[0048]

[0049] In a specific embodiment of the present invention, the furanone derivative is any one of the following compounds:

[0050]

[0051]

[0052] In a specific embodiment of the present invention, the furanone derivative is any one of the following compounds:

[0053]

[0054] The second aspect of the present invention provides a preparation method of the furanone derivative shown in Formula I provided in the first aspect of the present invention, including the following steps: Compound a and compound b react in a solvent under the action of a catalyst to obtain the structure shown in Formula I; the structures of compound a and compound b are as follows:

[0055]

[0056] Specific synthetic routes are referred to as follows:

[0057]

[0058] In a specific embodiment of the present invention, the solvent includes N,N-dimethylformamide. The amount of the solvent can be adjusted conventionally according to the reaction system to ensure the dissolution of the raw materials. For example, the ratio of N,N-dimethylformamide to compound a can be (10-30) mL:1 g, that is, compared with 1 g of compound a, the amount of N,N-dimethylformamide used can be 10-30 mL, but it is not limited thereto.

[0059] In a specific embodiment of the present invention, the catalyst includes potassium tert-butoxide. Further, the molar ratio of potassium tert-butoxide to compound b is 1:(1-1.05).

[0060] In a specific embodiment of the present invention, the molar ratio of compound a to compound b is 1:(1 to 1.5), for example, it can be 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5 or the range composed of any two of them.

[0061] In a specific embodiment of the present invention, it further includes: after the reaction is completed, ethyl acetate extraction is used, the organic phase is collected, and column chromatography purification is carried out.

[0062] The specific operation for preparing the structure shown in Formula I by reacting compound a and compound b may include: mixing compound a with a solvent, adding compound b, then adding a catalyst under ice bath conditions, maintaining the ice bath for 5 to 20 minutes until the reaction no longer releases heat, and then reacting at room temperature; monitoring the reaction progress according to TLC; after the reaction is completed, ethyl acetate extraction is used, the organic phase is collected, and after concentration, column chromatography purification is carried out. In column chromatography purification, the eluent can be petroleum ether and ethyl acetate, but is not limited thereto.

[0063] In a specific embodiment of the present invention, when X is N, the preparation of compound a includes: reacting a first compound with isoamyl nitrite in a solvent under the action of a first catalyst;

[0064] When X is C, the preparation of compound a includes: reacting a first compound with methyl formate in a solvent under the action of a second catalyst; The structure of the first compound is as follows:

[0065]

[0066] The specific synthesis route is as follows for reference:

[0067]

[0068] In a specific embodiment of the present invention, when X is N, in the preparation of compound a, the molar ratio of the first compound to isoamyl nitrite is 1:(2 to 2.5).

[0069] In a specific embodiment of the present invention, when X is N, in the preparation of compound a, the solvent includes N,N-dimethylformamide, and the amount of the solvent can be adjusted conventionally according to the reaction system to ensure that the raw materials are dissolved. For example, the ratio of N,N-dimethylformamide to the first compound can be (5 to 10) mL:1 g, that is, compared with 1 g of the first compound, the amount of N,N-dimethylformamide used can be 5 to 10 mL, but is not limited thereto.

[0070] In a specific embodiment of the present invention, when X is N, in the preparation of compound a, the first catalyst includes potassium tert-butoxide. Further, the molar ratio of potassium tert-butoxide to isoamyl nitrite is 1:(1 to 1.05).

[0071] In a specific embodiment of the present invention, when X is N, in the preparation of compound a, it further includes: after the reaction is completed, adjusting the pH of the reaction system to neutral, then extracting with ethyl acetate, collecting the organic phase, and performing column chromatography purification.

[0072] When X is N, the specific operation in the preparation of compound a may include: mixing the first compound with a solvent, slowly adding potassium tert-butoxide under ice bath conditions, then adding isoamyl nitrite, maintaining the ice bath for 5 - 20 min until the reaction no longer releases heat, and then reacting at room temperature; monitoring the reaction progress according to TLC; after the reaction is completed, adjusting the pH of the reaction system to neutral with dilute hydrochloric acid, then extracting with ethyl acetate, collecting the organic phase, concentrating, and performing column chromatography purification. In column chromatography purification, the eluent phase can be petroleum ether and ethyl acetate, but is not limited thereto.

[0073] In a specific embodiment of the present invention, when X is C, in the preparation of compound a, the molar ratio of the first compound to methyl formate is 1:(5 - 20).

[0074] In a specific embodiment of the present invention, when X is C, in the preparation of compound a, the solvent includes N,N-dimethylformamide, and the amount of the solvent can be adjusted conventionally according to the reaction system to ensure that the raw materials are dissolved. For example, the ratio of N,N-dimethylformamide to the first compound can be (1 - 3) mL:1 g, that is, compared with 1 g of the first compound, the amount of N,N-dimethylformamide used can be 1 - 3 mL, but is not limited thereto.

[0075] In a specific embodiment of the present invention, when X is C, in the preparation of compound a, the second catalyst includes sodium hydride. Further, the molar ratio of sodium hydride to the first compound is 1:(1 - 1.5).

[0076] In a specific embodiment of the present invention, when X is C, in the preparation of compound a, it further includes: after the reaction is completed, adding dilute hydrochloric acid to adjust the pH, then extracting with dichloromethane, collecting the organic phase, and performing column chromatography purification.

[0077] When X is C, the specific operation in the preparation of compound a may include: mixing the first compound with a solvent, adding methyl formate, then slowly adding sodium hydride under ice bath conditions, maintaining the ice bath for 5 - 20 min until the reaction no longer releases heat, and then reacting at room temperature; monitoring the reaction progress according to TLC; after the reaction is completed, adding dilute hydrochloric acid for neutralization, then extracting with dichloromethane, collecting the organic phase, concentrating, and performing column chromatography purification. In column chromatography purification, the eluent phase can be petroleum ether and ethyl acetate, but is not limited thereto.

[0078] In a specific embodiment of the present invention, the preparation of compound b includes: reacting 4-methyl-5-hydroxyfuran-2-one with carbon tetrabromide in a solvent under the action of a third catalyst.

[0079] The specific synthetic route is as follows:

[0080]

[0081] In a specific embodiment of the present invention, in the preparation of compound b, the solvent includes dichloromethane; the catalyst includes triphenylphosphine.

[0082] Specifically, the preparation of compound b includes: weighing 5 g (43.82 mmol) of 4-methyl-5-hydroxyfuran-2-one and adding it to a round-bottom flask. While stirring, pour 384 mL of dried dichloromethane into it. Under ice bath conditions, first slowly add 17.44 g (52.58 mmol) of carbon tetrabromide, and then add 14.94 g (56.96 mmol) of triphenylphosphine. After ice bath for 10 min, when the reaction no longer releases heat, restore to room temperature and continue the reaction. Monitor the reaction by TLC [V petroleum ether:V ethyl acetate = 2:1]. After 2.5 h, the reaction ends. Concentrate using a rotary evaporator to remove dichloromethane. Purify the concentrated reaction solution by column chromatography (the eluting phase is V 石油醚 :V 乙酸乙酯 = 3:2) to obtain compound b as a black liquid with a yield of 50.14%.

[0083] The third aspect of the present invention provides a preparation method of the furanone derivative shown in formula II provided in the first aspect of the present invention, including the following steps:

[0084] Compound e and compound f react in a solvent under the action of a catalyst to obtain the structure shown in formula II; the structures of compound e and compound f are as follows:

[0085]

[0086] In a specific embodiment of the present invention, the solvent includes acetonitrile. The dosage of the solvent can be adjusted conventionally according to the reaction system to ensure the dissolution of the raw materials. For example, the ratio of acetonitrile to compound f can be (30 - 50) mL:1 g, that is, compared with 1 g of compound f, the dosage of acetonitrile can be 30 - 50 mL, but not limited thereto.

[0087] In a specific embodiment of the present invention, the catalyst includes potassium carbonate. Further, the molar ratio of potassium carbonate to compound f is 1:(1 - 1.2).

[0088] In a specific embodiment of the present invention, the molar ratio of compound e to compound f is 1:(1.5 - 2.5).

[0089] In a specific embodiment of the present invention, in the preparation of the furanone derivatives represented by Formula II, it further includes: after the reaction is completed, extraction is carried out with ethyl acetate, the organic phase is collected, and column chromatography purification is carried out.

[0090] The specific operation for preparing the structure shown in Formula II by reacting compound e and compound f may include: mixing compound f with a solvent, adding potassium carbonate, then adding compound e, and reacting at room temperature; monitoring the reaction progress according to TLC; after the reaction is completed, extraction is carried out with ethyl acetate, the organic phase is collected, and after concentration, column chromatography purification is carried out. In column chromatography purification, the eluent can be petroleum ether and ethyl acetate, but is not limited thereto.

[0091] In a specific embodiment of the present invention, compound f includes any one of the following structures:

[0092]

[0093] Among them, compound f2 is the above-mentioned compound b, and the preparation method is the same.

[0094] The preparation method of compound f1 refers to the preparation of compound b, the only difference being that the raw material 4-methyl-5-hydroxyfuran-2-one is replaced with 5-hydroxy-3-methyl-2-(5H)-furanone in an equimolar amount, and the rest of the operations are the same; the synthetic route of compound f1 is as follows, and the yield is 56.07%:

[0095]

[0096] 5-Hydroxy-3-methyl-2-(5H)-furanone can be prepared by the method in the patent application with the publication number CN114057677A, and the yield is 51.97%.

[0097] The fourth aspect of the present invention provides the application of the furanone derivatives provided in the first aspect of the present invention in the preparation of plant growth regulators.

[0098] In a specific embodiment of the present invention, the plant growth regulator is used for at least one of promoting plant seed germination and inhibiting plant tillering.

[0099] In a specific embodiment of the present invention, the plant includes at least one of Orobanche cumana Wallr. and wheat.

[0100] Specifically, the plant growth regulator prepared from the furanone derivatives of the present invention can promote the germination of Orobanche cumana Wallr. seeds; it can inhibit wheat tillering.

[0101] For example, when the plant growth regulator prepared from the furanone derivatives of the present invention is used to promote the germination of Orobanche cumana Wallr. seeds, preferably the furanone derivatives include at least one of the following structures:

[0102]

[0103] More preferably, it includes at least one of the following structures:

[0104]

[0105] For example, when the plant growth regulator prepared from the furanone derivatives of the present invention is used to inhibit wheat tillering, it is preferred that the furanone derivatives include at least one of the following structures:

[0106]

[0107] More preferably, it includes at least one of the following structures:

[0108]

[0109] The fifth aspect of the present invention provides a plant growth regulator, which includes the furanone derivatives provided by the first aspect of the present invention.

[0110] Example 1

[0111] This example provides a preparation method of compound A1, which includes the following steps:

[0112] (1) Weigh 5 g of phenylacetonitrile (42.68 mmol) and add it to a round-bottom flask. Pressurize and pump in 35 mL of anhydrous N,N-dimethylformamide, start stirring, and slowly add 10.54 g (93.9 mmol) of potassium tert-butoxide and then 10.99 g (93.9 mmol) of isoamyl nitrite under ice bath conditions. After ice bath for 10 min, wait until the reaction no longer releases heat, and then transfer to room temperature for reaction; Monitor the reaction by TLC [V 石油醚 ﹕V 乙酸乙酯 =2﹕1]. After 4 h, the reaction ends. Under ice bath conditions, add dilute hydrochloric acid to adjust the pH to neutral, extract the reaction solution three times with ethyl acetate, combine the organic phases, add anhydrous sodium sulfate to remove water; After suction filtration, carry out vacuum concentration under a rotary evaporator, and then purify by column chromatography. The eluent is V 石油醚 ﹕V 乙酸乙酯 =4﹕1 to obtain a brown solid, and the yield of this step is 81.61%.

[0113] (2) Weigh 1 g (6.84 mmol) of the product obtained from the reaction in step (1) and add it to a round-bottom flask. Pressurize and pump in 20 mL of anhydrous N,N-dimethylformamide, start stirring, then add 1.18 g (6.67 mmol) of 5-bromo-4-methyl-2-(5H)-furanone (compound b). Finally, add 0.75 g (6.67 mmol) of potassium tert-butoxide under ice-bath conditions. After ice-bathing for 10 min until the reaction no longer releases heat, transfer it to room temperature and continue the reaction; TLC [V 石油醚 ﹕V 乙酸乙酯 =3﹕1] was used to monitor the reaction. After 10 h, the reaction ended. The reaction solution was extracted three times with ethyl acetate, the organic phases were combined, and anhydrous sodium sulfate was added to remove water; after suction filtration, it was concentrated under reduced pressure using a rotary evaporator, and then purified by column chromatography. The eluting phase was V 石油醚 ﹕V 乙酸乙酯 =6﹕1, and a light yellow solid was obtained, which was compound A1. The yield of this step was 40.49%.

[0114] Example 2

[0115] This example provides a preparation method of compound C1, which includes the following steps:

[0116] (1) Weigh 5 g (42.68 mmol) of phenylacetonitrile and add it to a round-bottom flask. Pressurize and pump in 10 mL of anhydrous N,N-dimethylformamide, start stirring, and add 30 mL of methyl formate. Under ice-bath conditions, slowly add 2.1 g (53.35 mmol) of NaH first. After ice-bathing for 10 min until the reaction no longer releases heat, transfer it to room temperature conditions for reaction; TLC [V 石油醚 ﹕V 乙酸乙酯 =4﹕1] was used to monitor the reaction. After 16 h, the reaction ended. Under ice-bath conditions, add 30 mL of 1 mol / L hydrochloric acid solution. The reaction solution was extracted three times with dichloromethane, the organic phases were combined, and anhydrous sodium sulfate was added to remove water; after suction filtration, it was concentrated under reduced pressure using a rotary evaporator, and then purified by column chromatography. The eluting phase was V 石油醚 ﹕V 乙酸乙酯 =4﹕1, and a light yellow solid was obtained. The yield of this step was 79.74%.

[0117] (2) Weigh 1 g (6.89 mmol) of the product obtained from the reaction in step (1) and add it to a round-bottom flask. Pressurize and pump in 20 mL of anhydrous N,N-dimethylformamide, start stirring, then add 1.83 g (10.33 mmol) of 5-bromo-4-methyl-2-(5H)-furanone (compound b). Under ice-bath conditions, slowly add 1.16 g (10.33 mmol) of potassium tert-butoxide. After ice-bathing for 10 min until the reaction no longer releases heat, transfer it to room temperature and continue the reaction; TLC [V 石油醚 ﹕V 乙酸乙酯Monitor the reaction at [V:V = 3:1]. After 10 h, the reaction ended. The reaction solution was extracted three times with ethyl acetate. The organic phases were combined and anhydrous sodium sulfate was added to remove water. After suction filtration, it was concentrated under reduced pressure using a rotary evaporator, and then purified by column chromatography with an eluent of V:V = 6:1 to obtain a pale yellow solid, which was compound C1. The yield of this step was 39.57%. 石油醚 : 乙酸乙酯 V = 6:1, to obtain a pale yellow solid, which was compound C1. The yield of this step was 39.57%.

[0118] Example 3

[0119] This example provides a preparation method of compound D1, which includes the following steps:

[0120] Weigh 0.8 g (4.5 mmol) of 5-bromo-3-methyl-2-(5H)-furanone (compound f1) into a round-bottom flask, add 30 mL of acetonitrile, start stirring to dissolve, add 0.68 g (4.95 mmol) of potassium carbonate, and then add 0.29 g (2.25 mmol) of p-chloroaniline. Monitor the reaction by TLC [V:V = 5:1]. After 15 h, the reaction ended. Extract three times with ethyl acetate, combine the organic phases, add anhydrous sodium sulfate to remove water, after suction filtration, concentrate under reduced pressure using a rotary evaporator, and then purify by column chromatography with an eluent of V:V = 10:1 to obtain a pale yellow solid, which was compound D1. The yield of this step was 68%. 石油醚 : 乙酸乙酯 V = 5:1]. After 15 h, the reaction ended. Extract three times with ethyl acetate, combine the organic phases, add anhydrous sodium sulfate to remove water, after suction filtration, concentrate under reduced pressure using a rotary evaporator, and then purify by column chromatography with an eluent of V:V = 10:1 to obtain a pale yellow solid, which was compound D1. The yield of this step was 68%. 石油醚 : 乙酸乙酯 V = 10:1 to obtain a pale yellow solid, which was compound D1. The yield of this step was 68%.

[0121] Example 4

[0122] This example provides a preparation method of compound H1, which includes the following steps:

[0123] Weigh 0.8 g (4.5 mmol) of 5-bromo-4-methyl-2-(5H)-furanone (compound b) into a round-bottom flask, add 30 mL of acetonitrile, start stirring to dissolve, add 0.68 g (4.95 mmol) of potassium carbonate, and then add 0.29 g (2.25 mmol) of p-chloroaniline. Monitor the reaction by TLC [V:V = 5:1]. After 15 h, the reaction ended. Extract three times with ethyl acetate, combine the organic phases, add anhydrous sodium sulfate to remove water, after suction filtration, concentrate under reduced pressure using a rotary evaporator, and then purify by column chromatography with an eluent of V:V = 10:1 to obtain a white solid, which was compound H1. The yield of this step was 72%. 石油醚 : 乙酸乙酯 V = 5:1]. After 15 h, the reaction ended. Extract three times with ethyl acetate, combine the organic phases, add anhydrous sodium sulfate to remove water, after suction filtration, concentrate under reduced pressure using a rotary evaporator, and then purify by column chromatography with an eluent of V:V = 10:1 to obtain a white solid, which was compound H1. The yield of this step was 72%. 石油醚 : 乙酸乙酯 V = 10:1 to obtain a white solid, which was compound H1. The yield of this step was 72%.

[0124] Referring to the preparation methods of Examples 1 to 4 and replacing the corresponding reaction raw materials, other corresponding compounds in Table 1 can be prepared. The corresponding structures and characterization data are shown in Table 2.

[0125] Table 1 Physical and Chemical Data of Each Compound

[0126]

[0127]

[0128]

[0129] Note: In the substitution reaction raw materials, A2 - A9 are equimolar amounts substituting the phenylacetonitrile in the preparation step of A1; C2 - C7 are equimolar amounts substituting the phenylacetonitrile in the preparation step of C1; D2 - D11 are equimolar amounts substituting the p-chloroaniline in the preparation step of D1; H2 - H11 are equimolar amounts substituting the p-chloroaniline in the preparation step of H1.

[0130] Among them, for the yields in Table 1 of compounds A1 - A9, C1 - C7, they are the total yields of the preparation of compound b, step (1) and step (2) of Example 1 or 2; for compounds D1 - D11, they are the total yields of the preparation of 5-hydroxy-3-methyl-2-(5H)-furanone, the preparation of compound f1, and the steps of Example 3; for compounds H1 - H11, they are the total yields of the preparation of compound b and the steps of Example 4.

[0131] Table 2 Chemical Structures of Each Compound and 1 H NMR, 13 C NMR and HRMS Data

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143] Experimental Example

[0144] Test materials and test agents

[0145] Seeds for activity test: Seeds of Orobanche cumana Wallr. (provided by Institute of Plant Protection, Chinese Academy of Agricultural Sciences), wheat seeds (provided by College of Plant Science and Technology, Beijing University of Agriculture), Cynomorium songaricum Rupr. seeds (provided by College of Plant Science and Technology, Beijing University of Agriculture).

[0146] Test utensils: Filter paper, glass fiber filter paper, dissection culture dish.

[0147] Test reagents: Agar, sterile water, ethanol, sodium hypochlorite.

[0148] Control agent: rac-GR24.

[0149] Test instruments

[0150] Vortex oscillator, autoclave, pipette, laminar flow hood (ZHJH-C1109C), microscope.

[0151] Cultivation treatment

[0152] 1. Determination of germination activity of Orobanche cumana Wallr. seeds

[0153] (1) Solution preparation: Dissolve each compound in ethanol to prepare a stock solution with a concentration of 10 -4 mol / L, and perform serial dilution to obtain solutions of each compound with concentrations of 10 -5 mol / L, 10 -6 mol / L, 10 -7 mol / L, 10 -8 mol / L, 10 -9 mol / L for standby. Then prepare 30 mL of 0.5% sodium hypochlorite solution and 30 mL of 70% (v / v) ethanol solution.

[0154] (2) Seed disinfection: Place the Orobanche cumana Wallr. seeds in 30 mL of 70% (v / v) ethanol, vortex for 1 min, then transfer to 30 mL of 0.5% sodium hypochlorite and vortex for 10 min. Finally, transfer to 30 mL of sterile water, vortex for 1 min, repeat three times, and transfer to the laminar flow hood for standby.

[0155] (3) Experimental treatment: Place a piece of filter paper in a petri dish (diameter d = 9 cm) and add 1 mL of sterile water to moisten it. Set six replicates for each treatment, that is, place 6 glass fiber filter papers (diameter d = 13 mm) on the filter paper, and place 30 - 60 Orobanche cumana Wallr. seeds on each glass fiber filter paper. Pipette 90 μL of the test solution and add it dropwise onto the glass fiber filter paper. Use GR24 as the positive control and sterile water as the negative control for all experiments. Finally, incubate in the dark at 25 °C.

[0156] (4) Data processing: Count the number of germinations under a microscope after 10 days. Use Sigma Plot 11.0 software to analyze the activities of GR24 and the compounds in detail, and obtain the dose - response curve and the effective concentration (EC 50 ) value. The obtained results are shown in Table 3.

[0157] 2. Determination of wheat tillering activity

[0158] (1) Seed treatment: Immerse wheat seeds in 300 mL of 10% H2O2 aqueous solution for 10 min, take them out and rinse with a large amount of sterile water to effectively remove H2O2, and finally conduct germination promotion treatment.

[0159] (2) Solution preparation: Dilute each compound with ethanol to a test solution with a concentration of 10 -6 mol / L, and add 30 μL of surfactant solution; among them, the preparation of the surfactant solution includes: weigh 0.3 g of 700# emulsifier, 0.1 g of silicone defoamer and 500 μL of absolute ethanol, add deionized water to make up to 10 g.

[0160] (3) Experimental treatment: Plant the germinated wheat seeds in pots and water regularly. When the seedlings grow to two leaves and one heart, spray 30 mL of clear water, 2 μM GR24 and the prepared test solution on the leaves respectively. Use GR24 as the positive control and sterile water as the negative control. Apply the medicine once every seven days for 3 consecutive times. Start to count the tillering rate when the wheat seedlings grow to four leaves and one heart, and count once every seven days. Repeat the experiment 3 times. The obtained results are shown in Table 4.

[0161] 3. Determination of Cynomorium songaricum Rupr. seed germination activity

[0162] (1) Solution preparation: Prepare 30 mL of 0.5% sodium hypochlorite solution and 30 mL of 70% (v / v) ethanol solution. Dissolve each compound in ethanol to prepare a stock solution of the test compound with a concentration of 10 -4 mol / L for standby.

[0163] (2) Seed disinfection: Place Cynomorium songaricum Rupr. seeds in 70% (v / v) ethanol for 1 minute, take them out and then place them in 0.5% sodium hypochlorite solution for 10 minutes, rinse several times with sterile water, and put them in a clean bench for later use.

[0164] (3) Preparation of culture medium containing compounds: Weigh 7 g of Agar, add deionized water to make up to 1000 mL. Measure 98 mL of the prepared culture solution and dispense it into conical flasks, sterilize and reserve for later use. Add 2 mL of the prepared compound stock solution to the conical flask, mix well to make a 10 -6 mol / L culture medium containing compounds in liquid form, and then pour it into petri dishes and wait for it to solidify completely.

[0165] (4) Experimental treatment: Use GR24 as the positive control and sterile water as the negative control, and set 6 replicates for each drug. Place 30 - 40 Cynomorium songaricum Rupr. seeds in each petri dish and culture them in a dark environment at 25°C.

[0166] (5) Data processing: Take them out after 15 days of culture and count the germination rate. The obtained results are shown in Figure 1 .

[0167] Table 3 Test results of the effects of different compounds on the germination activity of Orobanche cumana Wallr. seeds

[0168]

[0169]

[0170] As can be seen from the above test results, the EC 50 values of compounds A2 and A5 are 5.287e -8 mol / L and 4.923e -8 mol / L respectively, and their activities are at the same order of magnitude as the positive control GR24, with comparable activities. In particular, the EC 50 values of compounds A1 and A7 are 6.283e -9 and 1.826e -9 respectively, and their activities are one order of magnitude lower than the positive control GR24, with activities superior to the positive control GR24, showing high activities.

[0171] The EC 50 value of compound C7 is 4.873e -8 mol / L, which is at the same order of magnitude as the positive control GR24, with comparable activities, and has good activity in promoting the germination of parasitic plant seeds.

[0172] The EC 50 values of compounds D4 and D9 are 2.631e -8 mol / L and 3.905e -8mol / L, and the EC of GR24 50 values are in the same order of magnitude and the activities are comparable. The EC50 value of compound D2 is 7.910e -9 mol / L, which is one order of magnitude smaller than the EC of the positive control GR24 50 value, and its activity is better than that of GR24, showing high activity. The EC values of compounds H3 and H10 50 are 3.836e -8 mol / L and 7.396e -8 mol / L respectively, and both are in the same order of magnitude as the EC of the positive control GR24 50 value, and the activities are comparable.

[0173] Table 4 Test results of the effects of different compounds on wheat tillering

[0174]

[0175]

[0176] As can be seen from the above table, compared with the water control, the inhibitory effects of compounds A1, A7, compound C7 and GR24 on wheat tillering were not obvious at the initial stage of drug application. As wheat grew, the inhibitory activity on tillering gradually appeared. However, compound A5 showed good inhibitory tillering activity at the initial stage of drug application and had the best persistence. Among them, the tillering rate decreased by about 60% compared with the water control. Thus, it can be seen that the compounds have good activity in inhibiting wheat tillering.

[0177] The ability of compound D6 to inhibit wheat tillering is comparable to that of GR24. The abilities of compounds H5 and H6 to inhibit wheat tillering are comparable to that of GR24, and the inhibitory effects of compounds H1 and H2 are obvious, and their activities exceed that of GR24.

[0178] According to the activity results of the compounds on the germination of Orobanche cumana seeds, the compounds with better activities (A1, A2, A5, A7, C7, D2, D4, D9, H3 and H10) were selected to further determine the germination of Cynomorium songaricum seeds. From Figure 1 it can be seen that when the concentration of the compounds is 10 -6 mol / L, all compounds have a certain effect on promoting the germination of Cynomorium songaricum seeds, but their activities are slightly lower than that of the positive control GR24. Analyzing the reason, it may be that the drug effect at the concentration of 10 -6 mol / L is poor.

[0179] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A furanone derivative, characterized in that: It has the structure shown in the following formula Ⅰ or Ⅱ: wherein R1 is selected from phenyl, substituted phenyl, thienyl and pyridyl, and X is selected from N or C; R2 and R3 are each independently selected from H or methyl; R4 is a monosubstituted or polysubstituted group on the benzene ring, each independently selected from H, halogen, C1-C3 alkyl, C1-C3 substituted alkyl, C1-C3 alkoxy and nitro.

2. The furanone derivative according to claim 1, characterized in that: Having at least one of the following characteristics: (1) In the C1-C3 substituted alkyl group, the substituent is selected from halogen; (2) R2 and R3 are different.

3. The furanone derivative according to claim 1, characterized in that: The furanone derivative is any one of the following compounds:

4. The method for preparing the furanone derivatives according to any one of claims 1 to 3, characterized in that: The steps include: Compound a and compound b react in a solvent under the action of a catalyst to obtain a structure shown in Formula I; the structures of compound a and compound b are as follows:

5. The preparation method according to claim 4, characterized in that: Having at least one of the following characteristics: (1) The solvent includes N,N-dimethylformamide; (2) The catalyst comprises potassium tert-butoxide; (3) The molar ratio of the compound a to the compound b is 1:(1 to 1.5).

6. The preparation method according to claim 4, characterized in that: When X is N, the preparation of the compound a comprises: reacting a first compound with isoamyl nitrite in a solvent under the action of a first catalyst; When X is C, the preparation of the compound a comprises: reacting a first compound with methyl formate in a solvent under the action of a second catalyst; the structure of the first compound is as follows:

7. The method for preparing the furanone derivatives according to any one of claims 1 to 3, characterized in that: The steps include: Compound e and compound f react in a solvent under the action of a catalyst to obtain a structure shown in Formula II; the structures of the compound e and the compound f are as follows:

8. The preparation method according to claim 7, characterized in that: Having at least one of the following characteristics: (1) The solvent comprises acetonitrile; (2) The catalyst comprises potassium carbonate; (3) The molar ratio of the compound e to the compound f is 1:(1.5-2.5).

9. Use of the furanone derivative according to any one of claims 1 to 3 in the preparation of plant growth regulators.

10. A plant growth regulator, characterized in that The invention comprises the furanone derivatives according to any one of claims 1 to 3.

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