Benzoate compound single crystal as well as preparation method and application thereof

Abstract

The invention relates to the technical field of preparation of benzoate compound single crystals, in particular to a benzoate compound single crystal as well as a preparation method and application thereof. The preparation method comprises the following steps: S1, taking o-hydroxybenzoic acid and hexahydrofuran [3, 2-b] furan-3, 6-diol or mannitol or sorbitol as raw materials, taking ethylene glycol as a solvent, mixing, and stirring to react; and S2, after the reaction is finished, carrying out suction filtration to obtain a benzoate compound, recrystallizing and drying to obtain a benzoate compound single crystal. Experiments prove that the benzoate compound prepared by the invention can obviously promote the growth of corn roots and increase the plant biomass. The single-crystal structure has the advantages of good stability, good application effect, low experimental dosage, low toxicity, no pollution to the environment and the like, and can be widely used as a plant root-promoting stimulant.

Description

Technical Field

[0001] The present invention relates to the technical field of preparation of benzoate compound single crystals, and in particular to a benzoate compound single crystal and a preparation method and application thereof. Background Art

[0002] With the centralized management of modern agriculture, unbalanced and excessive application of fertilizers on land has seriously damaged the nutrient balance in the soil, aggravated soil acidification and compaction, severely restricted the root growth of crops, caused crops to grow slowly, and significantly reduced crop yield and quality, which is seriously affecting the development of modern agriculture.

[0003] In recent years, plant growth stimulants have received extensive attention and research, especially in promoting the growth and resistance of plant roots and stems, improving quality, increasing crop yields, and improving planting benefits. It is a technology with broad application prospects. Plant growth stimulants are a class of substances that can promote or regulate plant growth and development. They can be divided into two categories: natural and synthetic. They mainly include auxins (such as indoleacetic acid IAA), gibberellins (GA), cytokinins (such as zeatin ZEA), abscisic acid (ABA), brassinolide, seaweed extracts, rhizobia, nitrogen-fixing bacteria, beneficial fungi (such as arbuscular mycorrhizal fungi AMF), humic acid and fulvic acid, silicates and biochar, etc. They can improve soil structure, improve soil water retention and fertility, effectively regulate the production of nucleic acids, proteins and enzymes in plants during crop production, and have a growth-promoting effect at different stages of plant growth and development. They are one of the important methods to improve the resistance to stress and increase yield of modern crops.

[0004] Plant growth stimulants, especially synthetic plant growth regulators, play an important role in agriculture and horticulture, but they also have some defects and potential negative effects, such as (1) Over-reliance on plant growth regulators may lead to the degradation of the crop's own growth regulation mechanism, reducing the crop's natural adaptability and stress resistance. At the same time, excessive use may also cause plant resistance. (2) The production and use of some plant growth regulators may cause pollution, for example, by-products discharged during the synthesis process or waste packaging materials. (3) Due to the limitations of their own properties, excessive or improper use may lead to residues in plants or soil, thereby affecting food safety and soil health. (4) Long-term single use may affect soil microbial communities, change the soil ecological balance, and have adverse effects on non-target organisms.

[0005] my country is a large agricultural country that grows corn. By adding plant growth stimulants, the germination rate can be effectively increased and the root growth of crops can be promoted. Therefore, in order to better meet the needs of agricultural development, it is very necessary to develop a root promoter with significant effects, green technology and no pollution to achieve green and sustainable development of modern agriculture and ensure food safety. Summary of the invention

[0006] The first aspect of the present invention provides a single crystal of a benzoate compound having a structural formula of Formula I;

[0007]

[0008] The second aspect of the present invention provides a method for preparing a benzoate compound single crystal, comprising the following steps:

[0009] S1. using o-hydroxybenzoic acid and hexahydrofuran[3,2-b]furan-3,6-diol or mannitol or sorbitol as raw materials and ethylene glycol as solvent, mixing and stirring to react;

[0010] S2. After the reaction is completed, the benzoate compound is filtered out, and the benzoate compound single crystal is obtained by recrystallization and drying.

[0011] The reaction process of the present invention using o-hydroxybenzoic acid and hexahydrofuran [3,2-b] furan-3,6-diol is as follows:

[0012]

[0013] In some embodiments, the molar ratio of o-hydroxybenzoic acid to hexahydrofuran[3,2-b]furan-3,6-diol or mannitol or sorbitol is 1:(0.5-5).

[0014] In some embodiments, the molar ratio of o-hydroxybenzoic acid to hexahydrofuran[3,2-b]furan-3,6-diol or mannitol or sorbitol is 1:(1-2).

[0015] The CAS of the hexahydrofuran[3,2-b]furan-3,6-diol is 915288-38-9, the CAS of mannitol is 87-78-5, and the CAS of sorbitol is 51547-44-5.

[0016] In some embodiments, the reaction temperature in S1 is 105-120° C., and the reaction time is 3-5 h.

[0017] In some embodiments, the filtration time in S2 is 1.0-2.0 h.

[0018] In some embodiments, the solvent used for the recrystallization in S2 is deionized water.

[0019] The reaction principle of the present invention is a typical esterification reaction, a process in which an acid reacts with an alcohol to generate an ester and water. If the temperature is too high, the o-hydroxybenzoic acid itself will react easily, resulting in a decrease in the yield. If the temperature is too low, the esterification reaction will be incomplete and the yield will also be reduced. If the molar ratio is too high or too low, there will be excess raw materials, resulting in a decrease in the reaction yield.

[0020] The third aspect of the present invention provides the application of the above-mentioned benzoic acid ester compound single crystal, which is used as a plant root stimulant.

[0021] In some embodiments, the benzoate compound single crystal is used as a plant root stimulator for corn.

[0022] In some embodiments, the benzoate compound single crystal is used at a concentration of 10-20 ppm.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The benzoate compounds prepared by the present invention have been verified by experiments to significantly promote the growth of corn roots and increase plant biomass. The single crystal structure has the advantages of good stability, good application effect, low experimental dosage, low toxicity and no pollution to the environment, and can be widely used as a plant root stimulant.

[0025] 2. The preparation process of the present invention is green and environmentally friendly, has no by-products, and the solvent ethylene glycol can be recycled, without involving the discharge of "three wastes".

[0026] 3. Compared with the corn root promoter in the prior art, the present invention has the advantages of low dosage and lower cost than the commercially available sodium naphthoxyacetate. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is the NMR spectrum of the single crystal of the benzoate compound prepared in Example 1.

[0028] Figure 2 This is the SC-XRD structure diagram of the single crystal of benzoate compound prepared in Example 1. DETAILED DESCRIPTION

[0029] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Example 1

[0031] This embodiment provides a benzoate compound single crystal having a structural formula of Formula I;

[0032]

[0033] The method for preparing a benzoate compound single crystal comprises the following steps:

[0034] S1. Take 50 g (362 mmol) of o-hydroxybenzoic acid and 65.95 g (362 mmol) of hexahydrofuran [3,2-b] furan-3,6-diol as raw materials, use 150 mL of ethylene glycol as solvent, put in a rotor and connect a condenser, and react at 110 ° C for 4 hours;

[0035] S2. After the reaction, the benzoate compound was filtered for 1.5 hours, and then recrystallized with deionized water and dried to obtain 94.05 g of white powder benzoate compound single crystal with a yield of 99.05%.

[0036] 1 H NMR: Accurately weigh 50 mg of single crystal of benzoate compound and put it into NMR tube, add a small amount of deuterated DMSO reagent to dissolve it, and use German Bruker 500M NMR instrument for testing. 1 H NMR (500MHz, DMSO) δ10.46,7.79,7.79,7.78,7.78,7.56,7.56,7.54,7.53 ,7.00,6.99,6.98,6.97,6.95,5.37,5.36,5.35,5.34,5.20,5.19,4.85,4 .84,4.83,4.28,4.27,4.12,3.92,3.92,3.90,3.90,3.88,3.87,3.86,3.8 5,3.70,3.68,3.53,3.44,3.33,2.64,2.50,2.36,1.23,1.07,1.05,1.04. (See Figure 1 )

[0037] Mo Kα was measured on a Bruker D8-ray diffractometer using graphite monochromatization. Radiation is used as a diffraction light source to collect the diffraction intensity data of the single crystal. The (SC-XRD data of the single crystal of the benzoate compound prepared in Example 1 are obtained, and the structure is further obtained. Figure 2 ). Figure 2 The root promoter 6-hydroxyhexahydrofuran[3,2-b]-3-furanyl-2-hydroxybenzoate exhibits ester formation between o-hydroxybenzoic acid and hexahydrofuran[3,2-b]furan-3,6-diol by dehydration.

[0038] The CCDC number of this compound is 2339548 and its molecular formula is C 13 H 14 O6, molecular weight is 266.25g / mol. The single crystal structure belongs to the orthorhombic system, the space group is P212121, and the unit cell parameters are Z=4,D calc The value is 1.4378g / cm 3 , R int The value is 0.0309. The main bond lengths and angles are C8–O3–C7=114.80(13)°; C10–O4–C9=106.26(13)°; C13–O5–C11=108.56(12)°.

[0039] Example 2

[0040] The difference between this example and Example 1 is that 50 g (362 mmol) of o-hydroxybenzoic acid and 98.92 g (543 mmol) of hexahydrofuran [3,2-b] furan-3,6-diol are used as raw materials, 150 mL of ethylene glycol is used as solvent, a rotor is put into the reaction and a condenser is connected, and the reaction is carried out at 110° C. for 4 hours. 90.25 g of single crystals of benzoate compounds are obtained, with a yield of 95.05%.

[0041] Example 3

[0042] The difference between this example and Example 1 is that 50 g (362 mmol) of o-hydroxybenzoic acid and 131.89 g (724 mmol) of hexahydrofuran [3,2-b] furan-3,6-diol are used as raw materials, 150 mL of ethylene glycol is used as solvent, a rotor is put into the reaction and a condenser is connected, and the reaction is carried out at 110° C. for 4 hours. 87.55 g of single crystals of benzoate compounds are obtained, with a yield of 92.20%.

[0043] Example 4

[0044] The difference between this example and Example 1 is that 50 g (362 mmol) of o-hydroxybenzoic acid and 65.95 g (362 mmol) of hexahydrofuran [3,2-b] furan-3,6-diol are used as raw materials, 150 mL of ethylene glycol is used as solvent, a rotor is put into the reaction and a condenser is connected, and the reaction is carried out at 105° C. for 4 hours. 91.05 g of single crystals of benzoate compounds are obtained, with a yield of 95.89%.

[0045] Example 5

[0046] The difference between this example and Example 1 is that 50 g (362 mmol) of o-hydroxybenzoic acid and 65.95 g (362 mmol) of hexahydrofuran [3,2-b] furan-3,6-diol are used as raw materials, 150 mL of ethylene glycol is used as solvent, a rotor is put into the reaction and a condenser is connected, and the reaction is carried out at 120° C. for 4 hours. 92.25 g of single crystals of benzoate compounds are obtained, with a yield of 97.15%.

[0047] Performance Testing

[0048] Corn root promotion experimental method: After the corn seeds are disinfected, place them in a culture dish covered with filter paper, wet the clean sterile cotton and place it on the filter paper, add 10mL of sterile water to keep the seeds moist, and then place the culture dish in a constant temperature incubator at 28°C to ensure that the seeds can germinate normally. After the seeds germinate, select corns with the same growth potential and transplant them into the seedling tray. When the first true leaf begins to unfold, apply 10ppm, 20ppm, 50ppm, 100ppm, and 150ppm of the benzoate compound single crystal prepared in Example 1 as a plant root stimulant. After 14 days, observe the plant height, net weight and other data, as shown in Table 1. No reagents were added to the control group (Ck).

[0049] Table 1

[0050] Product test concentration 10ppm 20ppm 50ppm 100ppm 150ppm C Average plant height (cm) 48.44 45.48 43.89 39.99 37.50 42.35 Average root length (cm) 2.94 2.91 2.72 2.52 2.55 2.76 Average stem diameter (mm) 17.54 20.43 16.76 11.94 10.44 11.87 Total net weight (g) 10.49 11.05 10.60 9.22 8.19 8.31 Total root weight (g) 1.01 1.11 1.02 0.80 0.79 0.77

[0051] It can be seen from Table 1 that all five concentrations were effective. At a concentration of 10 ppm, compared with the clear water control, plant height increased by 14.38%, stem diameter increased by 6.52%, net weight increased by 29.82%, and total root net weight increased by 31.17%, indicating that single crystals of benzoic acid ester compounds can significantly improve the growth of corn roots, and the optimal usage is 10-20 ppm.

[0052] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A benzoate compound single crystal, characterized in that: Having the structural formula of Formula I; 2. A method for preparing a single crystal of a benzoate compound, characterized in that: The steps include: S1. using o-hydroxybenzoic acid and hexahydrofuran[3,2-b]furan-3,6-diol or mannitol or sorbitol as raw materials and ethylene glycol as solvent, mixing and stirring to react; S2. After the reaction is completed, the benzoate compound is filtered out, and the benzoate compound single crystal is obtained by recrystallization and drying.

3. The preparation method according to claim 2, characterized in that: The molar ratio of o-hydroxybenzoic acid to hexahydrofuran[3,2-b]furan-3,6-diol or mannitol or sorbitol is 1:(0.5-5).

4. The preparation method according to claim 3, characterized in that: The molar ratio of o-hydroxybenzoic acid to hexahydrofuran[3,2-b]furan-3,6-diol or mannitol or sorbitol is 1:(1-2).

5. The preparation method according to claim 4, characterized in that: The reaction temperature in S1 is 105-120°C, and the reaction time is 3-5h.

6. The preparation method according to claim 5, characterized in that: The filtration time in S2 is 1.0-2.0h.

7. The preparation method according to claim 6, characterized in that: The solvent used for the recrystallization in S2 is deionized water.

8. The use of the benzoate compound single crystal according to claim 1, characterized in that: The single crystals of benzoic acid ester compounds are used as plant root stimulants.

9. The use according to claim 8, characterized in that: The benzoate compound single crystal acts as a plant root growth stimulator and is used for corn.

10. The use according to claim 8, characterized in that: The use concentration of the benzoate compound single crystal is 10-20ppm.

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