Glycidin-based ester compound as well as preparation and application thereof

Abstract

The invention discloses a daidzein ester compound as well as preparation and application thereof. The chemical structural formula of the daidzein ester compound is shown as a formula (I), a formula (II) or a formula (III). The prepared daidzein ester compound is adjustable in polarity, contains ester bonds, hydroxyl and the like, and is easy to process; the daidzein-based precursor and the carboxylic acid compound used for the esterification reaction are both biomass raw materials and are green and environment-friendly, the conversion rate of the esterification reaction is extremely high, and a final product can directly separate out crystals and is relatively high in purity; in the esterification reaction process, the aromatic acetic anhydride food additive with high added value can be generated at the same time, and the final product daidzein ester compound can be applied to synthesis of intermediates, food additives, medical care intermediates and the like. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of organic complexes, and in particular relates to a soy ester compound and a preparation and application thereof. Background Art

[0002] Soybean is one of the isoflavones naturally present in plants such as soybeans, kudzu root, alfalfa, and four-leaf clover. Soybean has been shown to be used as a variety of bioactive agents, including antioxidants, hormone balancers, etc., and can be used to prevent osteoporosis and cancer. On the other hand, since the framework structure of soybean contains carbonyl and carbon-carbon double bonds, ester molecules containing different polar structures can be prepared by reduction reaction. Unfortunately, although soybean has a broad prospect for use in the field of medical care, its bisphenol hydroxyl structure causes it to be absorbed by the human body and has a low absorption rate through the epidermis. Therefore, the relevant modification research of soybean has always been a hot spot in the field of bio-based small molecule synthesis, including preparing it into a water-soluble soybean base complex (CN103961716A, a method for producing water-soluble soy isoflavones), or preparing it into an ester complex (J.Phys.Chem.B 2010,114,43,13904-13910.Retinylisoflavonoid as a NovelMembrane Antioxidant.).

[0003] The preparation of early soybean isoflavones as the central fragment, by adding polar aprotic solvents, tetrahydrofuran, triethylamine, etc. and acetic anhydride, soybean isoflavone acetate is generated (J.Phys.Chem.B 2010,114,43,13904-13910.Retinylisoflavonoid as a Novel Membrane Antioxidant.). However, the above-mentioned preparation route is complicated, and the solvent in the esterification process is poisonous. During subsequent treatment, residual solvents can limit the further application of the product. Secondly, using the product prepared by the method, the polarity of the central fragment of the product is difficult to further adjust, which is unfavorable for its further processing when used as food health care and pharmaceutical intermediates. And by other composite methods, such as the soybean isoflavones (CN118355997A, a preparation method of a protein-based gel system of efficient loaded soybean isoflavones) established by means such as dispersion and coating. Its essence is still soy isoflavones. The change of physical processing method has not improved its chemical properties. When applied, especially when absorbed across the cell membrane, its conversion rate is much lower than that of ester complexes. Moreover, the above-mentioned methods for improving soy isoflavones cannot utilize all the products in the esterification process, and its atomic yield does not meet the standards of green chemistry. Summary of the invention

[0004] In view of the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a soy ester compound to overcome the problems of low yield, complex preparation route, and unadjustable product polarity of soy ester compounds in the prior art.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned soy bean ester compounds. The present invention uses soy bean extractable from plants as a raw material, selects other biomass acids, and prepares a high-yield soy bean ester complex by one-step esterification under acidic conditions, wherein the polarity of the product can be selectively reduced to change the soy bean to be directional-adjusted to prepare soy bean precursors with different polarities, and the product has a large chemical modification space and strong reprocessability; and the ethyl propionic anhydride generated by the solvent reaction during the esterification process can be used in food processing and other fields, and the product atomic conversion rate and designability are far better than previous routes.

[0006] Another object of the present invention is to provide applications of the above-mentioned soy ester compounds.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] A soy bean ester compound having a structure represented by the following formula (I), (II) or (III):

[0009]

[0010] Wherein R is one of 1 to 10,

[0011]

[0012] The above-mentioned method for preparing a soy ester compound comprises the following steps:

[0013] A soy bean precursor and a bio-based acid containing a carboxylic acid structure are added to glacial acetic acid and heated to dissolve to obtain a mixed solution; a mixed solvent of acetic anhydride and propionic anhydride is added to the obtained mixed solution to continue the esterification reaction; after the reaction is completed, the mixed solution is directly cooled to obtain white crystals; the esterification reaction is carried out under the protection of nitrogen or an inert gas.

[0014] Preferably, the structural formula of the soy bean precursor is one of 11 to 13:

[0015]

[0016] Preferably, the structural formula of the bio-based acid is one of 14 to 23:

[0017]

[0018] Preferably, the molar ratio of the soy bean precursor to the bio-based acid is 1:(0.5-2), more preferably 1:(0.5-1.5).

[0019] Preferably, the soy bean precursor is mixed with the bio-based acid and glacial acetic acid in a molar ratio of 1:(0.5-1.5):(1-100), and the temperature for heating and dissolving is 40-150°C.

[0020] Preferably, the molar ratio of the added amount of acetic anhydride and propionic anhydride to the soy bean-based precursor is (0.01-100):(0.01-100):1.

[0021] Preferably, the reaction temperature is 40 to 150° C., and the reaction time is 1 to 24 hours.

[0022] More preferably, the reaction time is 6 to 12 hours.

[0023] Preferably, the preparation of the soy bean precursor 12 comprises the following steps:

[0024] Lithium tri-tert-butoxyaluminum hydride, copper bromide and tetrahydrofuran are mixed, stirred in an ice-salt bath under N2 protection, and then ethanol is added, followed by the soymilk-based precursor 11 and continued stirring for 0.5 to 4 hours. After obtaining a mixed solution, it is poured into dilute hydrochloric acid to precipitate and filtered again. Finally, the obtained solid is dried to obtain the soymilk-based precursor 12;

[0025] The added amounts are calculated by molar ratio, soy bean precursor 11: lithium tri-tert-butoxyaluminum hydride: copper bromide: tetrahydrofuran: ethanol = 1: (0.5-2): (0.1-50): (0.001-50): (0.01-50);

[0026] The preparation of the soy bean precursor 13 comprises the following steps:

[0027] Ce trichloride heptahydrate, sodium borohydride and methanol are stirred in an ice-salt bath under N2 protection, and then ethanol and soymilk-based precursor 11 are added, and stirring is continued for 0.1 to 2 hours to obtain a mixed solution, which is then poured into dilute hydrochloric acid to precipitate and filtered again. Finally, the obtained solid is dried to obtain soymilk-based precursor 13;

[0028] The added amounts are calculated in molar ratios as follows: soy bean-based precursor 11: cerium trichloride heptahydrate: sodium borohydride: methanol: ethanol = 1: (0.5-10): (0.5-10): (0.01-50): (0.01-50).

[0029] Preferably, the pH value of the dilute hydrochloric acid is 2 to 3, and its usage is 10 to 50 times the mass of the total reaction system; the ice-salt bath is a mixture of sodium chloride and ice.

[0030] Preferably, the drying is carried out in a vacuum drying oven at 80° C. for 12 h.

[0031] The above-mentioned soy bean ester compounds are used in chemical synthesis intermediates, food additives and medical care intermediates.

[0032] Compared with the prior art, the present invention has the following advantages:

[0033] (1) The carboxylic acids used in the present invention are all prepared from renewable biomass raw materials, which have sufficient raw material sources, low prices, stable processes, and high environmental, economic and social values.

[0034] (2) The polarity of the soy bean ester compounds of the present invention can be adjusted according to the application, the product conversion rate and purity are high, and the by-products also have high added application value and can be applied to multiple scenarios including fine chemical intermediates, food processing, medical care, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The synthetic route of the soybean base precursor 12 of the present invention and 1 H-NMR spectrum.

[0036] Figure 2 The synthetic route of the soy bean precursor 13 of the present invention and 1 H-NMR spectrum.

[0037] Figure 3 The structure of the soy ester compound of Example 1 of the present invention is 1 H-NMR spectrum.

[0038] Figure 4 The structure of the soy ester compound of Example 2 of the present invention is 1 H-NMR spectrum.

[0039] Figure 5 The structure of the soy ester compound of Example 3 of the present invention is 1 H-NMR spectrum.

[0040] Figure 6 The structure of the soy ester compound of Example 4 of the present invention is 1 H-NMR spectrum.

[0041] Figure 7 The structure of the soybean ester compound of Example 5 of the present invention is 1 H-NMR spectrum.

[0042] Figure 8 The structure of the soy ester compound of Example 6 of the present invention is 1 H-NMR spectrum.

[0043] Fig. 9 The structure of the soy ester compound of Example 7 of the present invention is 1 H-NMR spectrum.

[0044] Fig.10 The structure of the soy ester compound of Example 8 of the present invention is 1 H-NMR spectrum.

[0045] Fig.11 The structure of the soy ester compound of Example 9 of the present invention is 1 H-NMR spectrum.

[0046] Fig.12 The structure of the soybean ester compound of Example 10 of the present invention is 1 H-NMR spectrum. DETAILED DESCRIPTION

[0047] The present invention is further described in detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto. The raw materials involved in the present invention can be directly purchased from the market, and the process parameters not specifically noted can be carried out with reference to conventional techniques.

[0048] The structural analysis of the soy ester compounds in the examples was conducted using a Bruker AVANCE III HD 500. The water contact angle test was conducted using a dataphysics OCA50.

[0049] Example 1

[0050] (1) Synthesis of soy bean-based precursor 12

[0051] Lithium tri-tert-butoxyaluminum hydride (2.0342 g, 8 mmol), copper bromide (0.5738 g, 4 mmol) and tetrahydrofuran (20 mL) were mixed in a flask, stirred in an ice-salt bath under N2 protection, and then ethanol (25 mL) was added. Then, soymilk-based precursor 11 (3.4916 g, 8 mmol) was added and stirred for 2 h. After obtaining a mixed solution, it was poured into dilute hydrochloric acid (pH = 3, 100 mL) to precipitate and filter again. Finally, the obtained solid was dried in a vacuum drying oven at 80 ° C for 12 h to obtain soymilk-based precursor 12 with a yield of 85%. Its structure is shown below:

[0052]

[0053] (2) Synthesis of soy ester compounds

[0054] Soybean-based precursor 12 (3.5076 g, 8 mmol) and bio-based acid 14 containing a carboxylic acid structure (1.5370 g, 8 mmol) were added to glacial acetic acid (15 mL) and heated at 120°C for 6 h to obtain a mixed solution; a mixed solvent of acetic anhydride (15 mL) and propionic anhydride (10 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 40°C, and the reaction time was 10 h. The structure of the product soybean-based ester compound is shown below.

[0055]

[0056] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Figure 3 shown.

[0057] The yield of the soybean ester compound prepared in this embodiment is 80%. After being pressed into a thin sheet, the water contact angle is tested to be 40°. Placing it in a polyimide precursor can quickly improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 10 minutes, it quickly penetrates the skin and is absorbed, confirming its strong transmembrane absorption capacity.

[0058] Example 2

[0059] (1) Synthesis of soy bean-based precursor 13

[0060] The preparation step of the soy bean precursor 13 is to stir cerium trichloride heptahydrate (2.9807g, 8mmol), sodium borohydride (0.3024g, 8mmol) and methanol (15mL) in an ice-salt bath under N2 protection, then add ethanol (20mL) and soy bean precursor 11 (3.5000g, 8mmol), continue stirring for 1h, and after obtaining a mixed solution, pour it into dilute hydrochloric acid (pH=2, 80mL) to precipitate and filter again. Finally, the obtained solid was dried in a vacuum drying oven at 80°C for 10h to obtain precursor 13 with a yield of 90%. Its structure is shown below:

[0061]

[0062] (2) Synthesis of soy ester compounds

[0063] Soybean-based precursor 13 (3.5000 g, 8 mmol) and bio-based acid 15 (1.5370 g, 8 mmol) containing a carboxylic acid structure were added to glacial acetic acid (15 mL) and heated at 120°C for 4 h to obtain a mixed solution; a mixed solvent of acetic anhydride (15 mL) and propionic anhydride (10 mL) was added to the mixed solution to continue the esterification reaction for 1 h; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 80°C, and the reaction time was 12 h. The structure of the product soybean-based ester compound is shown below.

[0064]

[0065] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Figure 4 shown.

[0066] The yield of the soybean ester compound prepared in this embodiment is 98%. After being pressed into a thin sheet, the water contact angle is tested to be 55°. Placing it in a polyimide precursor can improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 15 minutes, it quickly penetrates the skin and is absorbed, confirming its strong transmembrane absorption capacity.

[0067] Example 3

[0068] (1) Synthesis of soy bean-based precursor 12

[0069] Lithium tri-tert-butoxyaluminum hydride (2.0342 g, 8 mmol), copper bromide (0.5738 g, 4 mmol) and tetrahydrofuran (20 mL) were mixed in a flask, stirred in an ice-salt bath under N2 protection, and then ethanol (25 mL) was added. Then, soymilk-based precursor 11 (1.7458 g, 4 mmol) was added and stirred for 2 h. After obtaining a mixed solution, it was poured into dilute hydrochloric acid (pH = 3, 100 mL) to precipitate and filter again. Finally, the obtained solid was dried in a vacuum drying oven at 80 ° C for 24 h to obtain soymilk-based precursor 12 with a yield of 75%. Its structure is shown below:

[0070]

[0071] (2) Synthesis of soy ester compounds

[0072] The soy bean precursor 12 (3.5076 g, 8 mmol) and the bio-based acid 16 (0.7206 g, 8 mmol) containing a carboxylic acid structure were added to glacial acetic acid (20 mL) and heated at 150 ° C for 10 h to obtain a mixed solution; a mixed solvent of acetic anhydride (15 mL) and propionic anhydride (5 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection. The heating temperature was 150 ° C. The reaction time was 10 h. The structure of the product soy bean ester compound is shown below.

[0073]

[0074] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Figure 5 shown.

[0075] The yield of the soybean ester compound prepared in this embodiment is 78%. After being pressed into a thin sheet, the water contact angle is tested to be 53°. Placing it in a polyimide precursor can improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 12 minutes, it quickly penetrates the skin and is absorbed, confirming its strong transmembrane absorption capacity.

[0076] Example 4

[0077] (1) Synthesis of soy ester compounds

[0078] Soybean-based precursor 11 (3.4916 g, 8 mmol) and bio-based acid 17 (1.2007 g, 8 mmol) containing a carboxylic acid structure were added to glacial acetic acid (15 mL) and heated at 100 ° C for 8 h to obtain a mixed solution; a mixed solvent of acetic anhydride (15 mL) and propionic anhydride (15 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 70 ° C, and the reaction time was 10 h. The structure of the product soybean-based ester compound is shown below.

[0079]

[0080] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Figure 6 shown.

[0081] The yield of the soybean ester compound prepared in this embodiment is 88%. After being pressed into a thin sheet, the water contact angle is tested to be 28°. Placing it in a polyimide precursor can improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 5 minutes, it quickly penetrates the skin and is absorbed, confirming its strong transmembrane absorption capacity.

[0082] Example 5

[0083] (1) Synthesis of soy ester compounds

[0084] The soy bean precursor 11 (3.4916 g, 8 mmol) and the bio-based acid 18 (0.5364 g, 4 mmol) containing a carboxylic acid structure were added to glacial acetic acid (10 mL) and heated at 40 ° C for 12 h to obtain a mixed solution; a mixed solvent of acetic anhydride (5 mL) and propionic anhydride (15 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 100 ° C, and the reaction time was 8 h. The structure of the product soy bean ester compound is shown below.

[0085]

[0086] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Figure 7 shown.

[0087] The yield of the soybean ester compound prepared in this embodiment is 75%. After being pressed into a thin sheet, the water contact angle is tested to be 35°. Placing it in a polyimide precursor can improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 7 minutes, it quickly penetrates the skin and is absorbed, confirming its strong transmembrane absorption capacity.

[0088] Example 6

[0089] (1) Synthesis of soy ester compounds

[0090] Soybean-based precursor 11 (3.4916 g, 8 mmol) and bio-based acid 19 (0.9286 g, 8 mmol) containing a carboxylic acid structure were added to glacial acetic acid (15 mL) and heated to 60°C for 12 h to obtain a mixed solution; a mixed solvent of acetic anhydride (10 mL) and propionic anhydride (10 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 80°C, and the reaction time was 10 h. The structure of the product soybean-based ester compound is shown below.

[0091]

[0092] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Figure 8 shown.

[0093] The yield of the soybean ester compound prepared in this embodiment is 85%. After being pressed into a thin sheet, the water contact angle is tested to be 40°. Placing it in a polyimide precursor can improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 9 minutes, it quickly penetrates the skin and is absorbed, confirming its strong transmembrane absorption capacity.

[0094] Example 7

[0095] (1) Synthesis of soy ester compounds

[0096] The soy bean precursor 11 (3.4916 g, 8 mmol) and the bio-based acid 20 (0.8970 g, 8 mmol) containing a carboxylic acid structure were added to glacial acetic acid (15 mL) and heated at 130 ° C for 14 h to obtain a mixed solution; a mixed solvent of acetic anhydride (15 mL) and propionic anhydride (20 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 80 ° C, and the reaction time was 6 h. The structure of the product soy bean ester compound is shown below.

[0097]

[0098] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Figure 8 shown.

[0099] The yield of the soybean ester compound prepared in this embodiment is 88%. After being pressed into a thin sheet, the water contact angle is tested to be 103°. Placing it in a polyimide precursor can slightly improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 30 minutes, it penetrates the skin and is absorbed, and most of it remains on the surface.

[0100] Example 8

[0101] (1) Synthesis of soy bean-based precursor 13

[0102] The preparation step of the soy bean precursor 13 is to stir cerium trichloride heptahydrate (5.9614 g, 16 mmol), sodium borohydride (0.3024 g, 8 mmol) and methanol (30 mL) in an ice-salt bath under N2 protection, then add ethanol (30 mL) and soy bean precursor 11 (3.5000 g, 8 mmol), continue stirring for 1 h, and after obtaining a mixed solution, pour it into dilute hydrochloric acid (pH = 2, 150 mL) to precipitate and filter again. Finally, the obtained solid was dried in a vacuum drying oven at 80 ° C for 10 h to obtain precursor 13 with a yield of 83%. Its structure is shown below:

[0103]

[0104] (2) Synthesis of soy ester compounds

[0105] Soybean-based precursor 13 (3.5000 g, 8 mmol) and bio-based acid 21 (1.2487 g, 8 mmol) containing a carboxylic acid structure were added to glacial acetic acid (30 mL) and heated at 120°C for 6 h to obtain a mixed solution; a mixed solvent of acetic anhydride (20 mL) and propionic anhydride (20 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 80°C, and the reaction time was 12 h. The structure of the product soybean-based ester compound is shown below.

[0106]

[0107] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Fig.10 shown.

[0108] The yield of the soybean ester compound prepared in this embodiment is 88%. After being pressed into a thin sheet, the water contact angle is tested to be 83°. Placing it in a polyimide precursor can slightly improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 16 minutes, it penetrates the skin and is absorbed, and some residues remain.

[0109] Example 9

[0110] (1) Synthesis of soy bean-based precursor 13

[0111] The preparation step of the soy bean precursor 13 is to stir cerium trichloride heptahydrate (1.4904g, 4mmol), sodium borohydride (0.3024g, 8mmol) and methanol (20mL) in an ice-salt bath under N2 protection, then add ethanol (10mL) and soy bean precursor 11 (3.5000g, 8mmol), continue stirring for 4h, and after obtaining a mixed solution, pour it into dilute hydrochloric acid (pH=2, 50mL) to precipitate and filter again. Finally, the obtained solid was dried in a vacuum drying oven at 80°C for 8h to obtain precursor 13 with a yield of 80%. Its structure is shown below:

[0112]

[0113] (2) Synthesis of soy ester compounds

[0114] Soybean-based precursor 13 (3.5000 g, 8 mmol) and bio-based acid 22 (1.2487 g, 8 mmol) containing a carboxylic acid structure were added to glacial acetic acid (30 mL) and heated at 140 ° C for 10 h to obtain a mixed solution; a mixed solvent of acetic anhydride (20 mL) and propionic anhydride (20 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 80 ° C, and the reaction time was 12 h. The structure of the product soybean-based ester compound is shown below.

[0115]

[0116] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Fig.11 shown.

[0117] The yield of the soybean ester compound prepared in this embodiment is 88%. After being pressed into a thin sheet, the water contact angle is tested to be 83°. Placing it in a polyimide precursor can slightly improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 16 minutes, it penetrates the skin and is absorbed, with some residues.

[0118] Example 10

[0119] (1) Synthesis of soy bean-based precursor 12

[0120] Lithium tri-tert-butoxyaluminum hydride (2.0342 g, 8 mmol), copper bromide (0.2869 g, 2 mmol) and tetrahydrofuran (10 mL) were mixed in a flask, stirred in an ice-salt bath under N2 protection, and then ethanol (20 mL) was added. Then, the soy bean-based precursor 11 (3.4916 g, 8 mmol) was added and stirred for 2 h. After obtaining a mixed solution, it was poured into dilute hydrochloric acid (pH = 3, 80 mL) to precipitate and filtered again. Finally, the obtained solid was dried in a vacuum drying oven at 80 ° C for 12 h to obtain precursor 12 with a yield of 90%. Its structure is shown below:

[0121]

[0122] (2) Synthesis of soy ester compounds

[0123] The soy bean precursor 12 (1.7538 g, 4 mmol) and the bio-based acid 23 (1.5370 g, 8 mmol) containing a carboxylic acid structure were added to glacial acetic acid (15 mL) and heated at 150 ° C for 6 h to obtain a mixed solution; a mixed solvent of acetic anhydride (15 mL) and propionic anhydride (15 mL) was added to the mixed solution to continue the esterification reaction; after the reaction, the mixed solution was directly cooled to obtain white crystals; the reaction was always carried out under nitrogen protection, the heating temperature was 80 ° C, and the reaction time was 6 h. The structure of the product soy bean ester compound is shown below.

[0124]

[0125] The NMR hydrogen spectrum of the soybean ester compound prepared in this example is as follows Fig.12 shown.

[0126] The yield of the soybean ester compound prepared in this embodiment is 98%. After being pressed into a thin sheet, the water contact angle is tested to be 43°. Placing it in a polyimide precursor can improve the surface polarity of the material, making the material more hydrophilic, and can be used in hydrophilic filtration, hydrophilic sensing, and medical materials that contact the human body in vitro. Secondly, it is dissolved in a highly hydrophilic ethanol solution and sprayed on the surface of the hairless mouse skin. After 8 minutes, it quickly penetrates the skin and is absorbed, confirming its strong transmembrane absorption capacity.

[0127] Comparative Example 1

[0128] According to the method reported in the literature J.Phys.Chem.B 2010,114,43,13904-13910.Retinylisoflavonoid as a Novel Membrane Antioxidant, the esterification step used to prepare soy ester compounds usually involves polar aprotic solvents (DMSO) and organic solvents (THF), catalysts (triethylamine), etc. The route is relatively complicated and requires multiple washing and filtering. In addition, the product structure is single, its polarity cannot be designed and adjusted, and the by-products cannot be used in the next step. The structure of the soy ester prepared by the soy ester is as follows:

[0129]

[0130] Compared with the product structure in the above invention, the main chain of the product of the present invention contains more hydroxyl groups and benzene rings, and its main chain rigidity and polarity can be adjusted synchronously, which has a better prospect of molecular design flexibility in the processing of fine chemical intermediates. In addition, the model of the prepared ester complex is adjusted in one step in the present invention. By introducing biomass acid, hydrophobic esters can be chemically modified into hydrophilic complexes, which will greatly improve the absorption conversion rate when used as medical and health products. More importantly, the route designed by the present invention can simultaneously generate high value-added products such as ethyl propionic anhydride for food processing.

[0131] In summary, a comprehensive analysis of the examples of the present invention and the results of the comparative examples shows that the preparation method of the present invention can be used to obtain soybean ester compounds with relatively excellent comprehensive performance in a more economical, environmentally friendly and efficient manner.

[0132] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A soy ester compound, characterized in that It has the structure shown in the following formula (I), (II) or (III): Wherein R is one of 1 to 10, 2. The method for preparing a soy ester compound according to claim 1, characterized in that: The following steps are involved: A soy bean precursor and a bio-based acid containing a carboxylic acid structure are added to glacial acetic acid and heated to dissolve to obtain a mixed solution; a mixed solvent of acetic anhydride and propionic anhydride is added to the obtained mixed solution to continue the esterification reaction; after the reaction is completed, the mixed solution is directly cooled to obtain white crystals; the esterification reaction is carried out under the protection of nitrogen or an inert gas.

3. The method for preparing a soy ester compound according to claim 2, characterized in that: The structural formula of the soy bean precursor is one of 11 to 13:

4. The method for preparing a soy ester compound according to claim 2, characterized in that: The structural formula of the bio-based acid is one of 14 to 23:

5. The method for preparing a soy ester compound according to claim 2, characterized in that: The molar ratio of the soy bean precursor to the bio-based acid is 1:(0.5-2), and the temperature for heating and dissolving is 40-150°C.

6. The method for preparing a soy ester compound according to claim 2, characterized in that: The molar ratio of the added amount of acetic anhydride and propionic anhydride to the soy bean-based precursor is (0.01-100):(0.01-100):

1.

7. The method for preparing a soy ester compound according to claim 2, characterized in that: The reaction temperature is 40-150° C., and the reaction time is 1-24 hours.

8. The method for preparing a soy ester compound according to claim 3, characterized in that: The preparation of the soy bean-based precursor 12 comprises the following steps: Lithium tri-tert-butoxyaluminum hydride, copper bromide and tetrahydrofuran are mixed, stirred in an ice-salt bath under N2 protection, and then ethanol is added, followed by the addition of soymilk-based precursor 11 and continued stirring for 0.5 to 4 hours. After obtaining a mixed solution, it is poured into dilute hydrochloric acid to precipitate and filtered again. Finally, the obtained solid is dried to obtain soymilk-based precursor 12; The added amounts are calculated by molar ratio, soy bean precursor 11: lithium tri-tert-butoxyaluminum hydride: copper bromide: tetrahydrofuran: ethanol = 1: (0.5-2): (0.1-50): (0.001-50): (0.01-50); The preparation of the soy bean precursor 13 comprises the following steps: Ce trichloride heptahydrate, sodium borohydride and methanol are stirred in an ice-salt bath under N2 protection, and then ethanol and soymilk-based precursor 11 are added, and stirring is continued for 0.1 to 2 hours to obtain a mixed solution, which is then poured into dilute hydrochloric acid to precipitate and filtered again. Finally, the obtained solid is dried to obtain soymilk-based precursor 13; The added amounts are calculated in molar ratios as follows: soy bean-based precursor 11: cerium trichloride heptahydrate: sodium borohydride: methanol: ethanol = 1: (0.5-10): (0.5-10): (0.01-50): (0.01-50).

9. The method for preparing a soy ester compound according to claim 8, characterized in that: The pH value of the dilute hydrochloric acid is 2-3, and its usage is 10-50 times the mass of the total reaction system; the ice-salt bath is a mixture of sodium chloride and ice.

10. Use of the soy bean ester compound according to claim 1 in chemical synthesis intermediates, food additives and medical care intermediates.

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