2-Butenoic acid lactone thioacetate compounds and preparation method and application thereof

Abstract

The present invention relates to the technical field of plant growth regulators, and in particular to a 2-butenoic acid lactone thioacetate compound, its preparation method, and its application. The 2-butenoic acid lactone thioacetate compound has a structure as shown in Formula I below: The present invention provides a 2-butenoic acid lactone thioacetate compound that effectively promotes the germination of root-parasitic seeds, has a simple structure, good stability, and a simple synthetic route. This compound is of great significance to the development of the field of plant growth regulators.

Description

Technical Field

[0001] The present invention relates to the technical field of plant growth regulators, in particular to a 2-butenoic acid lactone thioacetate compound and a preparation method and application thereof. Background Art

[0002] In many countries, crops such as corn and sorghum are often harmed by parasitic plants like Striga and Orobancha, resulting in significant yield losses. Strigolactones (SLs) are a new class of plant hormones. Their ability to promote seed germination and regulate plant branching has broad implications for the development of new herbicides and plant-type regulators. Currently, natural SLs are present in very low concentrations in plants, have complex structures, and are easily hydrolyzed, making them difficult to obtain through separation and extraction methods. GR24, considered the most effective and widely used SL analogue, is artificially synthesized. However, due to its complex synthesis steps and low yield, its production costs are high, limiting its large-scale promotion and application in agricultural production.

[0003] Therefore, the development of new compounds that can promote the germination of root parasitic seeds and have simple structures and good stability is of great significance to the development of the field of plant growth regulators. Summary of the Invention

[0004] One object of the present invention is to provide 2-butenoic acid lactone thioacetate compounds, which can effectively promote the germination of root parasitic seeds, have a simple structure, good stability, and a simple synthesis route.

[0005] Another object of the present invention is to provide a method for preparing 2-butene hydroxy acid lactone thioacetate compounds.

[0006] Another object of the present invention is to provide an application of 2-butenoic acid lactone thioacetate compounds in regulating plant growth activity.

[0007] In order to achieve the above-mentioned object of the present invention, the present invention provides a 2-butene hydroxy acid lactone thioacetate compound having the structure shown in the following formula I:

[0008]

[0009] Wherein, R1 and R2 are each independently selected from any one of H, an alkyl group with 1 to 4 carbon atoms and a benzene ring; R3 is monosubstituted or polysubstituted, and the substituents are each independently selected from any one of halogen, an alkyl group with 1 to 6 carbon atoms and an alkoxy group with 1 to 6 carbon atoms.

[0010] In a specific embodiment of the present invention, the R3 is monosubstituted, and the substituent is at least one of methyl, Br and Cl; the R2 is at least one of H, methyl and benzene ring; and the R1 is at least one of H and methyl.

[0011] In a specific embodiment of the present invention, the 2-butene hydroxy acid lactone thioacetate compound is any one of the following compounds:

[0012]

[0013]

[0014] Another aspect of the present invention provides a method for preparing any one of the above-mentioned 2-butene hydroxy acid lactone thioacetate compounds, comprising the following steps:

[0015] (a) Compound A reacts with chloroacetyl chloride in a solvent under the action of a first catalyst and an acid binding agent to obtain an intermediate B;

[0016] (b) reacting the intermediate B with the compound D in a solvent under the action of a second catalyst and a base to obtain a product;

[0017] The structures of the compound A, the intermediate B and the compound D are as follows:

[0018]

[0019] In a specific embodiment of the present invention, in step (a), the molar ratio of the compound A to the chloroacetyl chloride is 1: (1 to 1.5).

[0020] In a specific embodiment of the present invention, in step (a), the first catalyst comprises DMAP. Further, the amount of the first catalyst used is 8 mol.% to 12 mol.% of the compound A.

[0021] In a specific embodiment of the present invention, in step (a), the acid binding agent comprises pyridine. Furthermore, the molar ratio of the acid binding agent to the compound A is 1:(1-1.2).

[0022] In a specific embodiment of the present invention, in step (a), the reaction temperature is 0 to 30° C., and the reaction time is 1 to 5 hours.

[0023] In a specific embodiment of the present invention, step (a) further comprises: adjusting the pH of the reacted material to neutral, then extracting with ethyl acetate, collecting the organic phase, and purifying it by column chromatography.

[0024] In a specific embodiment of the present invention, in step (b), the molar ratio of the intermediate B to the compound D is 1:(1-1.5).

[0025] In a specific embodiment of the present invention, in step (b), the second catalyst comprises DMAP. Further, the amount of the second catalyst used is 8 mol.% to 12 mol.% of the intermediate B.

[0026] In a specific embodiment of the present invention, in step (b), the base comprises potassium carbonate. Furthermore, the molar ratio of the base to the intermediate B is 1: (1 to 1.2).

[0027] In a specific embodiment of the present invention, in step (b), the reaction temperature is 0 to 30° C., and the reaction time is 1 to 5 hours.

[0028] In a specific embodiment of the present invention, step (b) further comprises: extracting the reacted material with ethyl acetate, collecting the organic phase, and performing column chromatography purification.

[0029] Another aspect of the present invention provides the use of 2-butenoic acid lactone thioacetate compounds in regulating plant growth activity.

[0030] In a specific embodiment of the present invention, the plant growth regulating activity includes at least one of inducing seed germination of parasitic plants, inhibiting plant tillering, inhibiting plant hypocotyl elongation, promoting plant maturation and regulating fruit sweetness.

[0031] In a specific embodiment of the present invention, the plant includes at least one of sunflower broomrape, wheat, Arabidopsis thaliana and strawberry.

[0032] Another aspect of the present invention provides a plant growth regulator comprising any one of the above-mentioned 2-butene hydroxylactone thioacetate compounds.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] The present invention provides a 2-butene hydroxylactone thioacetate compound that can effectively promote the germination of root parasitic seeds, has a simple structure, good stability, and a simple synthesis route, and is of great significance to the development of the field of plant growth regulators. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0036] Figure 1 This is a comparative diagram of the inhibitory effects of different compounds provided by the present invention on the hypocotyl length of Col-type Arabidopsis;

[0037] Figure 2 This is a comparison chart showing the promoting effects of different compounds provided by the present invention on strawberry ripening. DETAILED DESCRIPTION

[0038] The technical scheme of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. Those who do not specify specific conditions in the embodiments are carried out according to normal conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified by the manufacturer are conventional products that can be purchased commercially.

[0039] Orobancha is a parasitic weed found primarily in northern temperate zones. It lacks photosynthetic leaves and chloroplasts, and lacks roots capable of absorbing nutrients and water from the soil. It primarily parasitizes the roots of crops, absorbing water and nutrients from the host to sustain its own growth, causing severe yield reductions. Strigolactones and their derivatives are a class of terpene lactones produced in plant roots. They consist of an ABC tricyclic ring system and a butenolide D ring connected by an enol ether bridge. They are a novel plant hormone that regulates the overall structural morphology of plants, inhibiting plant branching, stimulating seed germination of parasitic weeds, and promoting branching of arbuscular fungal hyphae. Orobancha is almost exclusively dependent on its host for survival; without a host nutrient source, it will die within a week after germination. Strigolactone is the main substance that induces the germination of Broomrape seeds. Broomrape seeds will commit suicide germination under the induction of strigolactone. Applying strigolactone or its analogues directly to the soil of crops harmed by Broomrape is the most ideal measure to prevent and control Broomrape weeds.

[0040] Research has found that the enol ether bond in substances that promote root parasitic seed germination plays a key role in maintaining the compound's germination-stimulating activity. Based on this, the structural designs of a large number of reported novel root parasitic seed germination-stimulating substances have retained an enol ether-substituted butene hydroxylactone ring structure. However, the high production costs of existing compounds have limited their large-scale application.

[0041] Based on this, the present invention establishes a simple and efficient route to synthesize a novel structure from inexpensive and readily available raw materials. This not only ensures efficacy, but also provides a short, low-cost, environmentally friendly synthetic route and facilitates structural modification and regulation. The development of the present structure and route can, to a certain extent, provide sufficient compound support for long-term research in agronomy and biology, and also promote its application as an environmentally friendly herbicide and plant architecture regulator.

[0042] In one aspect, the present invention provides a 2-butene hydroxylactone thioacetate compound having the structure shown in Formula I below:

[0043]

[0044] Wherein, R1 and R2 are each independently selected from any one of H, an alkyl group with 1 to 4 carbon atoms and a benzene ring; R3 is monosubstituted or polysubstituted, and the substituents are each independently selected from any one of halogen, an alkyl group with 1 to 6 carbon atoms and an alkoxy group with 1 to 6 carbon atoms.

[0045] An alkyl group with 1 to 4 carbon atoms refers to a straight or branched hydrocarbon group consisting solely of carbon and hydrogen atoms, having 1 to 4 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, etc. Correspondingly, an alkyl group with 1 to 6 carbon atoms refers to a hydrocarbon group having 1 to 6 carbon atoms, such as 1, 2, 3, 4, 5, or 6 carbon atoms, and may be straight or branched.

[0046] R3 being monosubstituted or polysubstituted means that there may be one R3 substituent or two or more R3 substituents on the benzene ring where R3 is located. Halogen includes at least one of fluorine (F), chlorine (Cl) and bromine (Br).

[0047] In a specific embodiment of the present invention, R3 is monosubstituted, and the substituent is at least one of methyl, Br and Cl; R2 is at least one of H, methyl and benzene ring; R1 is at least one of H and methyl.

[0048] For example, when 2-butenoic acid lactone thioacetate compounds are used to induce seed germination of parasitic plants (such as Orobancha), in the corresponding 2-butenoic acid lactone thioacetate compounds, R3 is monosubstituted, and the substituent is at least one of methyl, Br and Cl; R2 is at least one of H, methyl and benzene ring; R1 is at least one of H and methyl.

[0049] For example, when 2-butenoic acid lactone thioacetate compounds are used to inhibit plant tillering (such as wheat), in the corresponding 2-butenoic acid lactone thioacetate compounds, R3 is monosubstituted, and the substituent is at least one of Br and Cl; R2 is at least one of H and a benzene ring; and R1 is a methyl group.

[0050] For example, when 2-butenoic acid lactone thioacetate compounds are used to inhibit plant hypocotyl elongation (such as Col wild-type Arabidopsis thaliana), in the corresponding 2-butenoic acid lactone thioacetate compounds, R3 is monosubstituted, and the substituent is at least one of methyl, Br and Cl; R2 is at least one of H, methyl and benzene ring; R1 is at least one of H and methyl.

[0051] For example, when 2-butenoic acid lactone thioacetate compounds are used to promote plant ripening (such as Suizhu strawberry), in the corresponding 2-butenoic acid lactone thioacetate compounds, R3 is monosubstituted, and the substituent is at least one of methyl and Cl; R2 is at least one of H and methyl; R1 is at least one of H and methyl.

[0052] For example, when 2-butenoic acid lactone thioacetate compounds are used to adjust the sweetness of fruits (such as Suizhu strawberries), in the corresponding 2-butenoic acid lactone thioacetate compounds, R3 is monosubstituted, and the substituent is methyl; R2 is at least one of H, methyl and benzene ring; R1 is at least one of H and methyl.

[0053] In a specific embodiment of the present invention, the 2-butene hydroxy acid lactone thioacetate compound is any one of the following compounds:

[0054]

[0055] Another aspect of the present invention provides a method for preparing any one of the above-mentioned 2-butene hydroxy acid lactone thioacetate compounds, comprising the following steps:

[0056] (a) Compound A reacts with chloroacetyl chloride in a solvent under the action of a first catalyst and an acid binding agent to obtain an intermediate B;

[0057] (b) intermediate B reacts with compound D in a solvent under the action of a second catalyst and a base to obtain a product;

[0058] The structures of compound A, intermediate B and compound D are as follows:

[0059]

[0060] Compound D can be obtained by purchasing or making it yourself. If it is made by yourself, you can refer to the following route for preparation:

[0061] When R2 is H, it can be prepared according to the following route:

[0062]

[0063] When R2 is a benzene ring, it can be prepared according to the following route:

[0064]

[0065] Specifically, some of the compounds D involved in the subsequent examples can be prepared according to the following method, but are not limited thereto. They are only listed here for illustration. The compounds D with other structures can be prepared according to conventional methods with reference to the above route.

[0066] Weigh 10 g (84.68 mmol) of methylmalonic acid and 17.82 g (40% aqueous solution, 123 mmol) of glyoxal into a 250 mL round-bottom flask, add 100 mL of water, stir magnetically to dissolve, slowly add 1.12 mL (1.43 mmol) of concentrated H2SO4 while stirring, and heat under reflux to react. TLC [V 石油醚 ﹕V 乙酸乙酯 =3:2] to monitor the reaction. After 20 h, the reaction was completed and extracted with 30 mL of ethyl acetate × 3 times. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated under reduced pressure, and purified by column chromatography. 石油醚 ﹕V 乙酸乙酯 =2:1, to obtain 5-hydroxy-3-methyl-2-(5H)-furanone as a yellow solid, yield: 50.56%.

[0067] Weigh 6.6 g (40 mmol) of phenylalanine and 35.2 g (0.4 mol) of pyruvic acid, add them into a 250 mL round-bottom flask, add 10 mL of water, stir magnetically to dissolve and fully contact, and heat under reflux at 80°C to react. TLC[V 石油醚 ﹕V 乙酸乙酯 =3:1] to monitor the reaction. After 24 h, the reaction was completed and extracted with ethyl acetate (3×30 mL). The organic phases were combined and dried over anhydrous sodium sulfate. The organic phases were filtered, concentrated under reduced pressure, and purified by column chromatography. 石油醚 ﹕V 乙酸乙酯 =4:1, to obtain 5-hydroxy-3-methyl-4-phenyl-2(5)-furanone as a white solid, yield: 48.7%.

[0068] In a specific embodiment of the present invention, in step (a), the molar ratio of compound A to chloroacetyl chloride is 1:(1-1.5). For example, in different embodiments, in step (a), the molar ratio of compound A to chloroacetyl chloride can be 1:1, 1:1.2, 1:1.4, 1:1.5, or a range consisting of any two thereof.

[0069] In a specific embodiment of the present invention, in step (a), the first catalyst comprises DMAP. Further, the amount of the first catalyst used is 8 mol.% to 12 mol.% of compound A.

[0070] In a specific embodiment of the present invention, in step (a), the acid-binding agent comprises pyridine. Furthermore, the molar ratio of the acid-binding agent to compound A is 1:(1-1.2).

[0071] In a specific embodiment of the present invention, in step (a), the solvent comprises dichloromethane. Further, in step (a), the reaction temperature is 0 to 30° C., and the reaction time is 1 to 5 hours.

[0072] In actual operation, compound A was mixed with the solvent first, and then chloroacetyl chloride and DMAP were added, pyridine was slowly added at 0°C, stirred for 10 to 20 minutes, and reacted at room temperature. The results were analyzed by TLC [V 石油醚 ﹕V 乙酸乙酯 =40:1] to monitor the progress of the reaction.

[0073] In a specific embodiment of the present invention, step (a) further comprises: adjusting the pH of the reacted material to neutral, then extracting with ethyl acetate, collecting the organic phase, and purifying it by column chromatography.

[0074] In actual operation, after the reaction is completed, the pH is adjusted to neutral by adding dilute hydrochloric acid, and then extracted with ethyl acetate three times, the organic phases are combined, and dried over anhydrous sodium sulfate; filtered, concentrated under reduced pressure, and purified by column chromatography (petroleum ether and ethyl acetate can be used as the elution phase).

[0075] In a specific embodiment of the present invention, in step (b), the molar ratio of intermediate B to compound D is 1:(1-1.5). For example, in different embodiments, in step (b), the molar ratio of intermediate B to compound D can be 1:1, 1:1.2, 1:1.4, 1:1.5, or a range consisting of any two thereof.

[0076] In a specific embodiment of the present invention, in step (b), the second catalyst comprises DMAP. Further, the amount of the second catalyst used is 8 mol.% to 12 mol.% of the intermediate B.

[0077] In a specific embodiment of the present invention, in step (b), the base comprises potassium carbonate. Furthermore, the molar ratio of the base to the intermediate B is 1: (1 to 1.2).

[0078] In a specific embodiment of the present invention, in step (b), the solvent comprises tetrahydrofuran. Further, in step (b), the reaction temperature is 0 to 30° C., and the reaction time is 1 to 5 hours.

[0079] In actual operation, compound D, potassium carbonate and DMAP were first mixed, and a solvent was added to dissolve the mixture under nitrogen protection, and then intermediate B was added and stirred at room temperature for reaction. The results were analyzed by TLC [V 石油醚 ﹕V 乙酸乙酯 =5:1] to monitor the reaction progress.

[0080] In a specific embodiment of the present invention, step (b) further comprises: extracting the reacted material with ethyl acetate, collecting the organic phase, and performing column chromatography purification.

[0081] In actual operation, after the reaction is completed, ethyl acetate is used for extraction three times, the organic phases are combined, and dried over anhydrous sodium sulfate; filtered, concentrated under reduced pressure, and purified by column chromatography (the elution phase can be petroleum ether and ethyl acetate).

[0082] Another aspect of the present invention provides the use of 2-butenoic acid lactone thioacetate compounds in regulating plant growth activity.

[0083] In a specific embodiment of the present invention, regulating plant growth activity includes at least one of inducing seed germination of parasitic plants, inhibiting plant tillering, inhibiting plant hypocotyl elongation, promoting plant ripening, and regulating fruit sweetness.

[0084] In a specific embodiment of the present invention, the plant includes at least one of sunflower broomrape, wheat, Arabidopsis thaliana, and strawberry.

[0085] For example, the 2-butene hydroxylactone thioacetate compounds of the present invention can induce seed germination of the parasitic plant sunflower broomrape; inhibit wheat tillering; inhibit Col wild-type Arabidopsis hypocotyl elongation; promote the ripening of Suizhu strawberry; and regulate the sweetness of Suizhu strawberry.

[0086] Another aspect of the present invention provides a plant growth regulator comprising any one of the above-mentioned 2-butene hydroxylactone thioacetate compounds.

[0087] Example 1

[0088] This example provides a method for preparing compound W1, comprising the following steps:

[0089] (1) Weigh 3.73 g (30 mmol) of p-methylthiophenol into a 250 mL round-bottom flask, add 30 mL of dichloromethane and stir magnetically to dissolve it, then add 4.08 g (36 mmol) of chloroacetyl chloride and 0.36 g (3 mmol) of DMAP, slowly add 2.61 g (33 mmol) of pyridine at 0°C, stir for 15 min, then return the reaction system to room temperature and react for 2.5 h; TLC [V 石油醚 ﹕V乙酸乙酯 =40:1] After the reaction was completed, dilute hydrochloric acid was added at 0°C to adjust the pH to neutral, and 3×30 mL of ethyl acetate was extracted. The organic phases were combined and dried over anhydrous sodium sulfate; filtered, concentrated under reduced pressure, and purified by column chromatography. 石油醚 ﹕V 乙酸乙酯 =80:1, a yellow solid was obtained with a yield of 87%.

[0090] (2) 0.69 g (6 mmol) of 5-hydroxy-3-methyl-2-(5H)-furanone, 0.83 g (6 mmol) of anhydrous potassium carbonate, and 0.06 g (0.5 mmol) of DMAP were weighed and placed in a 250 mL round-bottom flask. Anhydrous tetrahydrofuran was added to dissolve the mixture under nitrogen protection. After stirring for 15 min, 1.01 g (5 mmol) of the reaction product from step (1) was added and stirred at room temperature for 3 h. TLC [V 石油醚 ﹕V 乙酸乙酯 =5:1] After the reaction was completed, 3×20 mL of ethyl acetate was extracted, and the organic phases were combined and dried over anhydrous sodium sulfate; filtered, concentrated under reduced pressure, and purified by column chromatography. 石油醚 ﹕V 乙酸乙酯 =15:1, a yellow oily compound W1 was obtained with a yield of 20.7%.

[0091] Example 2

[0092] This example provides a method for preparing compound Y3, comprising the following steps:

[0093] (1) 3.78 g (20 mmol) of p-bromothiophenol was weighed and added to a 250 mL round-bottom flask. 30 mL of dichloromethane was added and magnetic stirring was performed to dissolve the mixture. 2.72 g (24 mmol) of chloroacetyl chloride and 0.24 g (2 mmol) of DMAP were then added. 1.74 g (22 mmol) of pyridine was slowly added at 0°C and stirred for 15 min. The reaction system was then returned to room temperature and reacted for 2.5 h. TLC [V 石油醚 ﹕V 乙酸乙酯 =40:1] After the reaction was completed, dilute hydrochloric acid was added at 0°C to adjust the pH to neutral, and 3×30 mL of ethyl acetate was extracted. The organic phases were combined and dried over anhydrous sodium sulfate; filtered, concentrated under reduced pressure, and purified by column chromatography. 石油醚 ﹕V 乙酸乙酯 =80:1, a yellow solid was obtained, yield: 92.45%.

[0094] (2) 0.69 g (6 mmol) of 5-hydroxy-4-methyl-2-(5H)-furanone, 0.83 g (6 mmol) of anhydrous potassium carbonate, and 0.06 g (0.5 mmol) of DMAP were weighed and placed in a 250 mL round-bottom flask. Anhydrous tetrahydrofuran was added to dissolve the mixture under nitrogen protection. After stirring for 15 min, 1.33 g (5 mmol) of the reaction product of step (1) was added and stirred at room temperature for 3 h. TLC [V 石油醚 ﹕V 乙酸乙酯 =3:1] After the reaction was completed, 3×20 mL of ethyl acetate was extracted, and the organic phases were combined and dried over anhydrous sodium sulfate; filtered, concentrated under reduced pressure, and purified by column chromatography. 石油醚 ﹕V 乙酸乙酯 =10:1, to obtain yellow solid compound Y3 with a yield of 41.8%.

[0095] By referring to the preparation methods of Example 1 and Example 2 and replacing the corresponding substituents, other corresponding compounds in Table 1 can be prepared. The corresponding structures and characterization data are shown in Table 2.

[0096] Table 1 Physicochemical data of each compound

[0097]

[0098]

[0099] Note: Among the replacement reaction raw materials, W2 to W10 replace the p-methylthiophenol in the preparation step (1) of W1; Y1 to Y10 (except Y3) replace the p-bromothiophenol in the preparation step (1) of Y3; C1 to C10 replace the 5-hydroxy-3-methyl-2-(5H)-furanone in the preparation step (1) compared with W1 to W10, respectively.

[0100] Table 2 Chemical structures of the compounds 1 HNMR, 13 C-NMR and HRMS data

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] Experimental Example 1

[0111] Determination of the bioactivity of compounds in promoting seed germination of sunflower Orobancha

[0112] The sunflower broomrape seeds were sterilized with 70% (v / v) ethanol and 0.5% sodium hypochlorite for 1 min and 15 min respectively. Then rinse with sterile water several times and dry naturally in a clean bench. Place the filter paper in a culture dish (diameter d = 9 cm) and add 1 mL of sterile water. Six glass fiber filter papers with a diameter of d = 13 mm were placed on the filter paper, and the test solution was dripped on the glass fiber filter paper. All experiments used GR24 as the positive control and clean water as the negative control, and 6 replicates were set for each treatment. 30 to 80 sunflower broomrape seeds were placed on each glass fiber filter paper and then cultured in the dark at 23 to 25°C. The number of radicle buds was counted at 10 days. The effective concentration (EC 50 The test was repeated 3 times, and the results are shown in Table 3.

[0113] Table 3 Effective concentrations of each compound in promoting germination of sunflower seeds

[0114]

[0115]

[0116] As shown in Table 3, compounds W1, Y1, Y3, Y4, C3, and C8 have good activity in promoting the germination of sunflower seeds, and the EC 50 The values ​​were compared with the positive control GR24 (EC 50 The value is 1.04881E -7 mol / L) was comparable (p<0.01), or even slightly superior, indicating that the compounds of the present invention have good activity in promoting the germination of sunflower Orobancha seeds.

[0117] Experimental Example 2

[0118] Effects of compounds on wheat tillering

[0119] 400 wheat seeds of uniform size and full size were selected and soaked in 300 mL of a 10% H₂O₂ aqueous solution for 15 minutes. After disinfection, the seeds were rinsed with copious amounts of sterile water to remove residual H₂O₂. The seeds were then soaked in 300 mL of sterile water for 24 hours to accelerate germination. The germinated wheat seeds were then sown. When the seedlings had two leaves and one stalk, the leaves were sprayed with water, 2 μM GR24, and the compound provided by the present invention, respectively. Applications were repeated every seven days for three consecutive times. The number of wheat tillers was counted after three weeks. The experiment was repeated three times. The results are shown in Table 4.

[0120] Table 4 Effects of various compounds on wheat tillering

[0121]

[0122]

[0123] As shown in Table 4, compared with the water control, GR24 and this series of compounds have a good inhibitory effect on wheat tillering. Among them, compounds W3, W5, W8, C5, and C8 have a very good inhibitory effect and are better than GR24.

[0124] Experimental Example 3

[0125] Effects of compounds on Arabidopsis

[0126] Col wild-type and Max-deficient Arabidopsis seeds were placed in two microcentrifuge tubes, sterilized with ethanol and sodium hypochlorite solution, then rinsed with sterile water and transferred to a clean bench. Half-strength Murashige-Skoog medium (MS) was prepared with 0.8% agar, 1% sucrose, and 0.5 g / L MES, adjusted to pH 5.7, and sterilized in an autoclave. Culture media containing rac-GR24 and the target compound at concentrations of 2, 10, and 20 μmol / L were then prepared. Sterilized Arabidopsis seeds were sown on the sterilized medium supplemented with the test compound. Each culture medium was incubated at 0°C in the dark for 3 days and then placed vertically in a light box at 24°C and 60% relative humidity. All plants were maintained under 16 h light / 8 h dark conditions for 7 days. Subsequently, the Arabidopsis seedlings were scanned, and hypocotyl length was measured using publicly available ImageJ software.

[0127] To rapidly screen and evaluate plant hormone properties, the inhibitory potency of all target compounds was evaluated using an Arabidopsis hypocotyl elongation assay. The inhibitory efficacy of GR24 and target compounds W1, Y1, and C1 in half-strength MS medium at concentrations of 2, 10, and 20 μM was first investigated in Col-type Arabidopsis seedlings. As shown in Table 5, the hypocotyl length of the blank control (CK) was 1.47 ± 0.03 cm, while that of GR24 at a concentration of 2 μM was 0.80 ± 0.03 cm. The target compounds W1, Y1, and C1 exhibited an inhibitory effect, with hypocotyl lengths around 1 cm. As the compound concentration increased, the inhibitory effect on hypocotyl elongation in Col-At seedlings became more pronounced.

[0128] Table 5 Inhibitory data of GR24, W1, Y1, and C1 on Col-type Arabidopsis hypocotyls at concentrations of 2, 10, and 20 μM

[0129]

[0130] All target compounds were prepared into 2 μM half-strength MS medium to study the hypocotyl elongation inhibition of Col and Max Arabidopsis seedlings. The results of the inhibition of hypocotyl length of Col Arabidopsis are shown in Figure 2. Figure 1 As shown, all target compounds inhibited hypocotyl elongation in Col-type Arabidopsis, indicating that the newly synthesized compounds play an active role in the retention of the D-loop. Compounds W1, Y1, Y2, Y3, and C1 showed the strongest inhibitory effects. Table 6 shows the results of inhibition of hypocotyl length in Max-type Arabidopsis. Max-type Arabidopsis mutants have base changes in the Max protein, resulting in a unique structural alteration and the loss of their original functional gene fragment. Therefore, the data show that the target compounds and GR24 had little inhibitory effect on hypocotyl elongation.

[0131] Table 6 Inhibition data of different compounds on the hypocotyls of Max-type Arabidopsis at a concentration of 2 μM

[0132]

[0133]

[0134] Note: In Table 6, except for those marked as 20 μm, which correspond to half-strength MS culture medium prepared at 20 μM, the others are prepared at half-strength MS culture medium prepared at 2 μM.

[0135] Experimental Example 4

[0136] Effects of Compounds on Strawberry

[0137] First, the nutrient pots where Suizhu strawberries were planted were disinfected. Strawberry seedlings with similar growth, but not yet bearing fruit but about to bloom, were selected and transplanted into the nutrient pots. A 2μM solution of the target compound (in ethanol) was sprayed on the surface of the strawberry leaves. Water and a 2μM GR24 solution were used as controls, respectively. The spraying was repeated every seven days. Water was applied once every morning, and photos were taken and recorded between 3 and 4 p.m., with watering at 7 p.m. The first day was when the fruit, which had grown uniformly and fully formed, was green, and the second day was when the fruit began to turn red. The time interval until the fruit completely turned red was recorded. The sugar content of the fruit was measured on the second day after the fruit matured.

[0138] The results are as follows Figure 2 As shown, the strawberry fruits of compounds GR24, W1, and Y2 matured in 6 days, while the strawberry fruits of compound C1 and the blank group matured in 7 days. It was preliminarily determined that compounds GR24, W1, and Y2 had a promoting effect on the ripening of Suizhu strawberries.

[0139] As shown in Table 7, the strawberry fruit sweetness of the blank control group was 4.77±0.38%, that of GR24 was 6.13±0.45%, and that of the target compounds W1, Y1, and C1 was 5.53±0.31%, 5.87±0.70%, and 4.93±0.25%, respectively. All target compounds exhibited higher sweetness than the control group. Preliminary results indicate that the newly synthesized compounds can enhance the sweetness of strawberry fruit, and that the D-ring compound with a methyl group at the 4th position exhibits greater activity than the D-ring compounds with a methyl group at the 3rd position and a phenyl group at the 4th position.

[0140] Table 7 Effects of compounds on the sweetness of strawberry fruit

[0141]

[0142] According to the above experimental results, the compound of the present invention has the ability to promote the growth rate of Suizhu strawberry and regulate the sweetness of the fruit.

[0143] 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 it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, 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 embodiments of the present invention.

Claims

1. 2-Butene hydroxy acid lactone thioacetate compound, characterized in that, It has the structure shown in the following formula I: Wherein, R1 and R2 are each independently selected from any one of H, an alkyl group with 1 to 4 carbon atoms and a benzene ring; R3 is monosubstituted or polysubstituted, and the substituents are each independently selected from any one of halogen, an alkyl group with 1 to 6 carbon atoms and an alkoxy group with 1 to 6 carbon atoms.

2. The 2-butene hydroxylactone thioacetate compound according to claim 1, characterized in that: The R3 is monosubstituted, and the substituent is at least one of methyl, Br and Cl; The R2 is at least one of H, methyl and benzene ring; the R1 is at least one of H and methyl.

3. The 2-butene hydroxylactone thioacetate compound according to claim 1, characterized in that: Any one of the following compounds:

4. The method for preparing 2-butene hydroxylactone thioacetate compounds according to any one of claims 1 to 3, characterized in that: The steps include: (a) Compound A reacts with chloroacetyl chloride in a solvent under the action of a first catalyst and an acid binding agent to obtain an intermediate B; (b) reacting the intermediate B with the compound D in a solvent under the action of a second catalyst and a base to obtain a product; The structures of the compound A, the intermediate B and the compound D are as follows:

5. The preparation method according to claim 4, characterized in that In step (a), at least one of the following characteristics is present: (1) The molar ratio of the compound A to the chloroacetyl chloride is 1:(1-1.5); (2) the first catalyst comprises DMAP; (3) The amount of the first catalyst is 8 mol% to 12 mol% of the compound A; (4) The acid binding agent includes pyridine; (5) The molar ratio of the acid binding agent to the compound A is 1:(1-1.2); (6) In step (a), the reaction temperature is 0 to 30° C., and the reaction time is 1 to 5 hours; (7) Step (a) further comprises: adjusting the pH of the reacted material to neutral, then extracting with ethyl acetate, collecting the organic phase, and purifying it by column chromatography.

6. The preparation method according to claim 4, characterized in that In step (b), at least one of the following characteristics is present: (1) The molar ratio of the intermediate B to the compound D is 1:(1-1.5); (2) the second catalyst comprises DMAP; (3) The amount of the second catalyst is 8 mol% to 12 mol% of the intermediate B; (4) The base comprises potassium carbonate; (5) The molar ratio of the base to the intermediate B is 1:(1-1.2); (6) In step (b), the reaction temperature is 0 to 30° C., and the reaction time is 1 to 5 hours; (7) Step (b) further comprises: extracting the reacted material with ethyl acetate, collecting the organic phase, and performing column chromatography purification.

7. Use of the 2-butenoic acid lactone thioacetate compound according to any one of claims 1 to 3 in regulating plant growth activity.

8. The use according to claim 7, characterized in that The plant growth regulating activity includes at least one of inducing seed germination of parasitic plants, inhibiting plant tillering, inhibiting plant hypocotyl elongation, promoting plant maturation and regulating fruit sweetness.

9. The use according to claim 7, characterized in that The plant comprises at least one of sunflower broomrape, wheat, Arabidopsis thaliana and strawberry.

10. A plant growth regulator, characterized in that The invention comprises the 2-butene hydroxy acid lactone thioacetate compound according to any one of claims 1 to 3.

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