Tree-like molecule supramolecular gelator and application thereof

Abstract

The application relates to the field of supramolecular chemistry and discloses a dendrimer supramolecular gel factor and application thereof. The molecular structure of the gel factor is a polybenzyl ether dendrimer modified by peripheral halogen atoms (chlorine, bromine or iodine). The gelation performance of the gel factor can be precisely controlled by changing the type, substitution number and position of the peripheral halogen, and the type and generation of the dendrimer. The dendrimer gel factor provided by the application has very excellent gelation performance. The dendrimer gel factor can effectively gelate in dozens of solvents such as polar solvents, non-polar solvents and mixed solvents containing water, and the minimum gelation concentration CGC is 1.5 mg / mL, belonging to a super gel factor. In addition, the gel factor has a simple preparation method and high yield, and is very suitable for being developed into a general and commercial supramolecular gel factor and applied to the preparation of various soft material functional materials.

Description

Technical Field

[0001] The invention relates to the technical field of blank production, in particular to a type of dendrimer supramolecular gel factor and application thereof. Background Art

[0002] Supramolecular gels are important soft materials formed by the self-assembly of low-molecular-weight gelling agents in organic solvents or water through reversible non-covalent interactions. They possess unique advantages in constructing functional soft materials such as multi-stimulus responsiveness, optoelectronic functional materials, nanomaterials, controlled drug release, wastewater treatment, electronic devices, and biocompatibility, attracting extensive and in-depth research by numerous researchers. Unlike traditional polymer gels, which are primarily based on covalently cross-linked networks, the networks in supramolecular gels are formed through non-covalent interactions between gelling agents, including π-π interactions, electrostatic interactions, hydrogen bonds, hydrophobic interactions, and van der Waals forces. Currently, developing supramolecular gelling agents based on novel non-covalent forces, expanding the application areas of supramolecular gels, and elucidating their gelation mechanisms remain both challenging and cutting-edge research areas in this field.

[0003] Dendrimers are a novel class of three-dimensional, highly ordered polymers whose size, shape, structure, and functional groups can be controlled at the molecular level. Their highly branched structure and unique monodispersity endow these compounds with unique properties and functions. Dendrimer gelators combine the advantages of both organic small molecule gelators and polymer gelators, offering the following unique advantages: 1) The multiple non-covalent interactions provided by the numerous branching units of the dendrimer facilitate the formation of stable, high-mechanical-strength gel systems; 2) The macromolecular structure of the dendrimer effectively minimizes the impact of the introduction of functional groups on the final gelation properties; and 3) Assembly properties can be precisely and intelligently tuned by precisely designing the outer and inner layers of the dendrimer, as well as controlling the type and generation of the dendrimer. Therefore, dendrimers are an ideal structure for constructing supramolecular gels. Previous studies have shown that the type, number, and location of the functional groups modified on the dendrimer's periphery, as well as the type and generation of the dendrimer, significantly influence the gelation properties of supramolecular gels. Chinese patent CN118894783A discloses a type of AB3-type polybenzyl ether dendrimer gel factor with peripheral halogen functionalization. The dendrimer gel factor is obtained by modifying the 3,5-positions of the polybenzyl ether dendrimer with different halogen atoms (F, Cl, Br). The minimum gelation concentration CGC is 2.6 mg / mL. However, the gelation performance of the obtained dendrimer gel factor is not ideal, the variety of gelation solvents is limited, the application is limited, and the commercialization cost is high. Summary of the Invention

[0004] To address the above-mentioned technical issues, and to further improve the gelling properties of dendrimer supramolecular gelators (low gelling concentration and wide range of gelling solvents), a low-cost, commercially viable supramolecular gelator has been developed. Using polybenzyl ether dendrimers as a backbone, the present invention modifies the types of peripheral halogens (Cl, Br, I), the number and position of substitutions, and the type and generation size of the dendrimers to develop a library of dendrimer gelators with excellent gelling properties, diverse and stable structures, simple and efficient synthesis, and easy post-functionalization. The provided dendrimer gelators can form stable supramolecular organogels in dozens of organic solvents or mixed solvents, representing a class of super gelators.

[0005] In order to achieve the above technical objectives, the dendrimer supramolecular gelator provided by the present invention has the following structure:

[0006]

[0007] in,

[0008] In formulas (I) and (II), R 1 、R 2 、R 3 、R 4 and R 5 are each independently selected from hydrogen, chlorine, bromine or iodine atoms, and R 1 、R 2 、R 3 、R 4 and R 5 There is at least one chlorine, bromine or iodine atom optionally present; n = 0, 1;

[0009] R 6 Each independently selected from COOC m H 2m+1 , COOH, CONHNH2, CONHCH2CH2Br, CH2OH, CHO, CH2Br or CH2CN.

[0010] Preferably, R 6 Each independently selected from COOCH3, COOH, CONHNH2, CH2OH, CHO, CH2Br or CH2CN;

[0011] Furthermore, the R 1 is selected from one of chlorine, bromine or iodine atoms, R 2 、R 3 、R 4 and R 5 selected from hydrogen;

[0012] Or, the R 2 is selected from one of chlorine, bromine or iodine atoms, R1 、R 3 、R 4 and R 5 selected from hydrogen;

[0013] Or, the R 3 is selected from one of chlorine, bromine or iodine atoms, R 1 、R 2 、R 4 and R 5 selected from hydrogen;

[0014] Or, the R 1 、R 2 is selected from one of chlorine, bromine or iodine atoms, R 3 、R 4 and R 5 selected from hydrogen;

[0015] Or, the R 1 、R 3 is selected from one of chlorine, bromine or iodine atoms, R 2 、R 4 and R 5 selected from hydrogen;

[0016] Or, the R 1 、R 4 is selected from one of chlorine, bromine or iodine atoms, R 2 、R 3 and R 5 selected from hydrogen;

[0017] Or, the R 1 、R 5 is selected from one of chlorine, bromine or iodine atoms, R 2 、R 3 and R 4 selected from hydrogen;

[0018] Or, the R 3 、R 4 is selected from one of chlorine, bromine or iodine atoms, R 1 、R 2 and R 5 selected from hydrogen;

[0019] Or, the R 1 、R 2 、R 4 is selected from one of chlorine, bromine or iodine atoms, R 3 and R 5 selected from hydrogen;

[0020] Or, the R 1 、R 2 、R 3 、R4 is selected from one of chlorine, bromine or iodine atoms, R 5 Selected from hydrogen.

[0021] Another object of the present invention is to provide an organogel material comprising a dendrimer supramolecular gelator having structures represented by formulas (I)-(II), wherein the single organic gelling solvent is any one of toluene, acetonitrile, ethyl acetate, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, benzyl alcohol, n-butanol, n-pentanol, n-hexanol, n-octanol, 1-decyl alcohol, nitromethane, and acetone; and the mixed solvent is any one of a mixed solution of tetrahydrofuran and methanol, a mixed solution of anisole and n-hexane, or a mixed solution of pyridine and water. The minimum gelling concentration of the supramolecular gelator is 1.5 mg / mL.

[0022] The dendrimer supramolecular gelator provided by the present invention is a type of gelator or assembly unit with excellent gelation (assembly) performance and can be widely used in preparing various functional supramolecular gels or supramolecular self-assembly systems.

[0023] The beneficial effects and advantages of the present invention are as follows:

[0024] (1) The dendrimer supramolecular gelator provided by the present invention can form stable supramolecular gels in dozens of organic solvents or aqueous mixtures. Not only is the gelling solvent broad, including polar solvents, non-polar solvents, and aqueous mixed solvents, but the gelling concentration is also low, with the lowest gelling concentration reaching 1.5 mg / mL. This type of dendrimer gelator can be called a "universal and super gelator."

[0025] (2) The gelling properties of the dendrimer supramolecular gelator provided by the present invention can be effectively regulated by the type, number, and substitution position of the peripheral halogen groups. Furthermore, the type and generation size of the dendrimer can also be regulated;

[0026] (3) The driving force for gelation of the dendrimer supramolecular gelator provided by the present invention is mainly multiple halogen bond interactions (including X…X and X-π interactions, etc.), π-π interactions and weak hydrogen bond interactions;

[0027] (4) The core functional groups of the dendrimer supramolecular gel factor provided by the present invention are easily convertible, which provides convenience for introducing functional groups to prepare various functional gel systems. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are merely for explaining the present invention and are not intended to limit the present invention. In order to better illustrate the present invention, further examples are given below.

[0029] Example 1:

[0030] Take the preparation of target molecule G-1a as an example:

[0031]

[0032] To a 250 mL two-necked flask equipped with a magnetic stirrer, methyl 3,5-dihydroxybenzoate (1.68 g, 10 mmol), 2-chlorobenzyl bromide (6.37 g, 31 mmol), K2CO3 (6.21 g, 45 mmol), and ultra-dry DMF (50 mL) were added sequentially. The reaction system was allowed to react in a metal bath at 80°C under nitrogen for 12 h, with TLC monitoring the reaction progress. After completion of the reaction, 200 mL of water was added to the reaction system to precipitate the product, which was then filtered and washed with copious amounts of water. The crude solid was dissolved in 30 mL of THF and then added dropwise to 200 mL of rapidly stirred methanol. A large amount of solid precipitate formed, which was filtered, washed several times with methanol, and dried under vacuum to obtain G-1a, a white solid in 93% yield. 1 HNMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.18 (s, ArCH2O, 4H), 6.83 (t, J = 2.4Hz, ArH, 1H), 7 .25-7.32(m,ArH,4H),7.33(d,J=2.4Hz,ArH,2H),7.38-7.42(m,ArH,2H),7.54-7.56(m,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.7, 159.6, 134.2, 132.8, 132.3, 129.5, 129.2, 128.9, 127.0, 108.6, 107.1, 67.5, 52.3.

[0033] Example 2-19

[0034] The corresponding compounds can be obtained by similar methods, and their specific characteristics are as follows:

[0035] Example 2

[0036]

[0037] White solid, yield 95%. 1H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.15 (s, ArCH2O, 4H), 6.83 (t, J = 2.2Hz, ArH, 1H), 7.20 ( t,J=7.3Hz,ArH,2H),7.33-7.36(m,ArH,4H),7.54(d,J=7.4Hz,ArH,2H),7.59(d,J=7.9Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.7, 159.5, 135.8, 132.7, 132.3, 129.5, 129.1, 127.6, 122.6, 108.7, 107.1, 69.7, 52.4.

[0038] Example 3

[0039]

[0040] White solid, yield 94%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.05 (s, ArCH2O, 4H), 6.82 (t, J = 2.3Hz, ArH, 1H), 7.01-7.05 (m, ArH, 2H),7.33(d,J=2.3Hz,ArH,2H),7.37(t,J=7.5Hz,ArH,2H),7.50(d,J=7.4Hz,ArH,2H),7.86(d,J=7.4Hz,ArH,2H). 13 CNMR (100MHz, CDCl3, δ): 166.7, 159.5, 139.4, 138.6, 132.3, 129.7, 128.9, 128.5, 108.8, 107.2, 97.6, 74.2, 52.4.

[0041] Example 4

[0042]

[0043] White solid, yield 95%. 1 H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 5.05 (s, ArCH2O, 4H), 6.77 (t, J = 2.3Hz, ArH, 1H), 7.28-7.32 (m, ArH, 8H), 7.43 (s, ArH, 2H). 13C NMR (100MHz, CDCl3, δ): 166.6, 159.5, 138.5, 134.6, 132.2, 129.9, 128.3, 127.5, 125.4, 108.5, 107.2, 69.4, 52.4.

[0044] Example 5

[0045]

[0046] White solid G-1a, yield 96%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.05 (s, ArCH2O, 4H), 6.77 (t, J = 2.3Hz, ArH, 1H), 7 .24-7.29(m,ArH,4H),7.35(d,J=7.6Hz,ArH,2H),7.47(d,J=7.8Hz,ArH,2H),7.60(s,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.6, 159.5, 138.7, 132.2, 131.2, 130.4, 130.2, 125.9, 122.8, 108.5, 107.2, 69.4, 52.4.

[0047] Example 6

[0048]

[0049] White solid G-1a, yield 95%. 1 H NMR (400MHz, CDCl3, δ): 3.89 (s, COOCH3, 3H), 4.99 (s, ArCH2O, 4H), 6.75 (t, J = 2.2Hz, ArH, 1H), 7.11 (t, J = 7.8Hz ,ArH,2H),7.27(d,J=2.2Hz,ArH,2H),7.36(d,J=7.6Hz,ArH,2H),7.65(d,J=7.9Hz,ArH,2H),7.78(s,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.6, 159.5, 138.7, 137.2, 136.3, 132.2, 130.4, 126.6, 108.5, 107.2, 94.6, 69.2, 52.4.

[0050] Example 7

[0051]

[0052] White solid G-1a, yield 97%. 1 HNMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 5.04 (s, ArCH2O, 4H), 6.75 (t, J = 2.4Hz, ArH, 1H), 7.27 (d, J = 2.4Hz, ArH, 2H), 7.36 (s, ArH, 8H). 13 CNMR (100MHz, CDCl3, δ): 166.6, 159.5, 134.9, 134.0, 132.2, 128.8, 108.4, 107.3, 69.5, 52.4.

[0053] Example 8

[0054]

[0055] White solid G-1a, yield 96%. 1 HNMR (400MHz, CDCl3, δ): 3.89 (s, COOCH3, 3H), 5.00 (s, ArCH2O, 4H), 6.73 (t, J = 2.3Hz, Ar H,1H),7.26(d,J=2.4Hz,ArH,2H),7.28(d,J=8.2Hz,ArH,4H),7.50(d,J=8.0Hz,ArH,4H). 13 C NMR (100MHz, CDCl3, δ): 166.6, 159.5, 135.5, 132.2, 131.8, 129.1, 122.1, 108.5, 107.3, 69.5, 52.4.

[0056] Example 9

[0057]

[0058] White solid G-1a, yield 93%. 1 HNMR (400MHz, CDCl3, δ): 3.89 (s, COOCH3, 3H), 4.99 (s, ArCH2O, 4H), 6.73 (t, J = 2.3Hz, Ar H,1H),7.15(d,J=8.2Hz,ArH,4H),7.25(d,J=2.3Hz,ArH,2H),7.70(d,J=8.2Hz,ArH,4H). 13 C NMR (100MHz, CDCl3, δ): 166.6, 159.5, 137.8, 136.1, 132.2, 129.3, 108.5, 107.3, 93.8, 69.6, 52.4.

[0059] Example 10

[0060]

[0061] White solid, yield 96%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.13 (s, ArCH2O, 4H), 6.78 (t, J = 2.4Hz, ArH, 1H), 7.26 (d, J = 2.2Hz, ArH, 1H ),7.27(d,J=2.1Hz,ArH,1H),7.31(d,J=2.1Hz,ArH,2H),7.42(d,J=2.4Hz,ArH,2H),7.47(s,ArH,1H),7.49(s,ArH,1H). 13 C NMR (100MHz, CDCl3, δ): 166.5, 159.3, 134.4, 133.4, 132.8, 132.4, 129.7, 129.3, 127.4, 108.7, 107.0, 66.9, 52.4.

[0062] Example 11

[0063]

[0064] White solid, yield 95%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.08 (s, ArCH2O, 4H), 6.77 (t, J = 2.3Hz, ArH, 1H), 7.3 1(d,J=2.3Hz,ArH,2H),7.40-7.42(m,ArH,2H),7.46-7.49(m,ArH,2H),7.76(d,J=1.9Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.5, 159.3, 135.1, 134.9, 132.4, 130.8, 130.1, 122.9, 122.3, 108.8, 107.0, 69.2, 52.4.

[0065] Example 12

[0066]

[0067] White solid, yield 96%. 1H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.30 (s, ArCH2O, 4H), 6.87 (s, ArH, 1H), 7.23-7.27 (m, ArH, 2H), 7.36 (s, ArH, 2H), 7.38-7.39 (m, ArH, 4H). 13 C NMR (100MHz, CDCl3, δ): 166.5, 159.3, 136.0, 133.1, 132.5, 130.6, 130.5, 129.1, 128.6, 108.8, 107.0, 66.8, 52.4.

[0068] Example 13

[0069]

[0070] White solid, yield 97%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.06 (s, ArCH2O, 4H), 6.81 (t, J = 2.3Hz, ArH, 1H), 7.2 9(d,J=2.4Hz,ArH,1H),7.31-7.32(m,ArH,3H),7.41-7.43(m,ArH,2H),7.70(d,J=2.3Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.5, 159.2, 137.8, 134.0, 132.4, 132.4, 131.6, 121.7, 120.7, 108.8, 107.0, 69.0, 52.4.

[0071] Example 14

[0072]

[0073] White solid, yield 95%. 1 H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 5.02 (s, ArCH2O, 4H), 6.74 (t, J = 2.3Hz, ArH, 1H), 7.23 (d, J = 2.0Hz, ArH, 1H ),7.25(d,J=2.4Hz,ArH,1H),7.27(d,J=2.4Hz,ArH,2H),7.44(s,ArH,1H),7.46(s,ArH,1H),7.53(d,J=2.0Hz,ArH,2H). 13C NMR (100MHz, CDCl3, δ): 166.5, 159.3, 136.6, 132.8, 132.3, 132.2, 130.6, 129.3, 126.5, 108.5, 107.2, 68.8, 52.4.

[0074] Example 15

[0075]

[0076] White solid, yield 96%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.01 (s, ArCH2O, 4H), 6.74 (t, J = 2.3Hz, ArH, 1H), 7.22 (d, J1 = 2 .3Hz,J2=8.2Hz,ArH,2H),7.27(d,J=2.4Hz,ArH,2H),7.63(d,J=8.2Hz,ArH,2H),7.71(d,J=1.8Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.5, 159.3, 137.4, 133.8, 132.4, 132.3, 127.4, 125.1, 124.4, 108.5, 107.2, 68.7, 52.4.

[0077] Example 16

[0078]

[0079] White solid, yield 96%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.03 (s, ArCH2O, 4H), 6.76 (t, J = 2.4Hz, ArH, 1H), 7.28 (d, J = 2.4Hz, ArH, 2H), 7.32-7.34 (m, ArH, 6H). 13 C NMR (100MHz, CDCl3, δ): 166.4, 159.3, 139.8, 135.3, 132.4, 128.3, 125.6, 108.6, 107.2, 68.7, 52.4.

[0080] Example 17

[0081]

[0082] White solid, yield 97%. 1H NMR (400MHz, CDCl3, δ): 3.94 (s, COOCH3, 3H), 5.15 (s, ArCH2O, 4H), 6.82 (t, J = 2.4Hz, ArH ,1H),7.33(d,J=2.4Hz,ArH,2H),7.46(d,J=2.4Hz,ArH,2H),7.51(d,J=2.4Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.4, 159.1, 137.7, 133.9, 133.2, 132.6, 129.4, 128.9, 126.6, 108.8, 107.0, 67.2, 52.5.

[0083] Example 18

[0084]

[0085] White solid, yield 97%. 1 H NMR (400MHz, CDCl3, δ): 3.94 (s, COOCH3, 3H), 5.14 (s, ArCH2O, 4H), 6.82 (t, J = 2.3Hz, ArH, 1H), 7.34 (d, J = 2.4Hz, ArH, 2H), 7.66 (s, ArH, 2H). 13 CNMR (100MHz, CDCl3, δ): 166.3, 159.0, 135.1, 133.5, 132.7, 132.7, 132.3, 130.3, 127.1, 108.9, 107.1, 67.0, 52.5.

[0086] Example 19

[0087]

[0088] To a 250 mL two-necked flask equipped with a magnetic stirrer, methyl 3,4,5-trihydroxybenzoate (1.84 g, 10 mmol), 2-bromobenzyl bromide (7.75 g, 31 mmol), K2CO3 (6.21 g, 45 mmol), and ultra-dry DMF (100 mL) were added sequentially. The reaction system was allowed to react in a metal bath at 80°C under nitrogen for 12 h, with TLC monitoring the reaction progress. After completion of the reaction, 200 mL of water was added to the reaction system to precipitate the product, which was then filtered and washed with copious amounts of water. The crude solid was dissolved in THF (30 mL) and then added dropwise to 200 mL of rapidly stirred methanol. A large amount of solid precipitate formed, which was filtered, washed several times with methanol, and dried under vacuum to afford G-2a as a white solid in 96% yield. 1H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.19 (s, ArCH2O, 4H), 5.26 (s, ArCH2O, 2H), 7.11 (t, J = 7.8Hz, ArH, 1H), 7.17-7.21 (m, ArH, 3H) ,7.28(t,J=7.3Hz,ArH,2H),7.48(d,J=7.9Hz,ArH,1H),7.54(d,J=7.7Hz,ArH,2H),7.58(d,J=7.9Hz,ArH,2H),7.67(d,J=7.8Hz,ArH,1H). 13 CNMR (100MHz, CDCl3, δ):166.6,152.2,142.1,137.2,135.8,132.6,132.3,129 .8,129.4,129.3,129.1,127.6,127.2,125.6,122.5,108.9,74.5,70.5,52.4.

[0089] The corresponding compounds of Examples 20-35 can be obtained by similar methods, and their specific characteristics are as follows:

[0090] Example 20

[0091]

[0092] White solid G-2b, yield 94%. 1 H NMR(400MHz,CDCl3,δ):3.92(s,COOCH3,3H),5.11(s,ArCH2O,4H),5.19(s,ArCH2O,2H),6.93( td,J1=1.4Hz,J2=7.7Hz,ArH,1H),7.02(td,J1=1.4Hz,J2=7.8Hz,ArH,2H),7.18(t,J=7.5Hz,A rH,1H),7.32(t,J=7.5Hz,ArH,2H),7.44(s,ArH,2H),7.50(dd,J1=1.0Hz,J1=7.7Hz,ArH,2H), 7.63 (dd, J1=1.0Hz, J1=7.7Hz, ArH, 1H), 7.74 (d, J=7.8Hz, ArH, 1H), 7.85 (d, J=7.8Hz, ArH, 2H). 13C NMR (100MHz, CDCl3, δ):166.6,152.2,142.1,140.2,139.3,138.9,138.7,129.7 ,129.4,129.3,129.2,128.4,128.1,125.6,108.9,97.6,97.4,79.1,75.0,52.4.

[0093] Example 21

[0094]

[0095] White solid, yield 93%. 1 H NMR(400MHz,CDCl3,δ):3.91(s,COOCH3,3H),5.07(s,ArCH2O,2H),5.11(s,ArCH2O,4H),7.19–7.29 (m,ArH,3H),7.32-7.34(m,ArH,6H),7.38(s,ArH,2H),7.41(t,J=1.6Hz,ArH,1H),7.45(s,ArH,2H). 13 C NMR (100MHz, CDCl3, δ):166.4,152.2,141.9,139.2,138.5,134.6,134.2,130 .0,129.6,128.3,128.2,127.5,126.3,125.6,125.4,109.0,74.3,70.4,52.4.

[0096] Example 22

[0097]

[0098] White solid, yield 94%. 1 H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 5.06 (s, ArCH2O, 2H), 5.10 (s, ArCH2O, 4H), 7.16 (t, J = 7.8Hz, ArH, 1H), 7.25–7.29 (m, ArH, 3H),7.32-7.37(m,ArH,3H),7.38(s,ArH,2H),7.41(d,J=7.8Hz,ArH,1H),7.48(d,J=7.8Hz,ArH,2H),757(s,ArH,1H),7.61(s,ArH,2H). 13C NMR (100MHz, CDCl3, δ):166.4,152.2,141.9,139.5,138.7,131.2,131.2,131.1, 130.4,130.3,130.0,126.8,125.9,125.6,122.7,122.4,109.1,74.3,70.3,52.4.

[0099] Example 23

[0100]

[0101] White solid, yield 96%. 1 H NMR (400MHz, CDCl3, δ): 3.90 (s, COOCH3, 3H), 5.02 (s, ArCH2O, 2H), 5.06 (s, ArCH2O, 4H), 7.03 (t, J = 7.8Hz, ArH, 1H), 7.13 (t, J = 7. 8Hz,ArH,2H),7.36–7.40(m,ArH,5H),7.61(d,J=7.9Hz,ArH,1H),7.67(d,J=7.9Hz,ArH,2H),7.76(s,ArH,1H),7.81(s,ArH,2H). 13 C NMR (100MHz, CDCl3, δ):166.4,152.3,141.9,139.6,138.8,137.2,137.1,137.1 ,136.3,130.4,130.2,127.5,126.6,125.6,109.1,94.5,94.3,74.2,70.2,52.4.

[0102] Example 24

[0103]

[0104] White solid, yield 94%. 1 H NMR(400MHz,CDCl3,δ):3.89(s,COOCH3,3H),5.04(s,ArCH2O,2H),5.08(s,ArCH 2O,4H),7.19-7.23(m,ArH,2H),7.26-7.29(m,ArH,2H),7.32-7.37(m,ArH,10H). 13C NMR (100MHz, CDCl3, δ): 166.4, 152.3, 141.9, 135.8, 134.9, 134.0, 133.9, 129.8, 128.9, 128.8, 128.4, 125.5, 109.0, 74.3, 70.4, 52.4.

[0105] Example 25

[0106]

[0107] White solid, yield 97%. 1 H NMR (400MHz, CDCl3, δ): 3.89 (s, COOCH3, 3H), 5.02 (s, ArCH2O, 2H), 5.06 (s, ArCH2O, 4H), 7.20 (d, J=8.2Hz, Ar H,2H),7.27(d,J=8.2Hz,ArH,4H),7.34(s,ArH,2H),7.37(d,J=8.3Hz,ArH,2H),7.51(d,J=8.3Hz,ArH,4H),. 13 C NMR (100MHz, CDCl3, δ): 166.4, 152.4, 141.9, 136.3, 135.4, 131.8, 131.4, 130.1, 129.1, 125.5, 122.1, 122.1, 109.0, 74.4, 70.4, 52.4.

[0108] Example 26

[0109]

[0110] White solid, yield 98%. 1 H NMR (400MHz, CDCl3, δ): 3.89 (s, COOCH3, 3H), 5.00 (s, ArCH2O, 2H), 5.04 (s, ArCH2O, 4H), 7.06 (d, J=8.3H z,ArH,2H),7.13(d,J=8.3Hz,ArH,4H),7.33(s,ArH,2H),7.55-7.57(m,ArH,2H),7.69-7.72(m,ArH,4H). 13 C NMR (100MHz, CDCl3, δ): 166.4, 152.2, 141.9, 137.7, 137.3, 136.9, 136.1, 130.2, 129.3, 125.5, 108.9, 93.8, 93.8, 74.5, 70.5, 52.4.

[0111] Example 27

[0112]

[0113] White solid, yield 96%. 1 H NMR (400MHz, CDCl3, δ): 3.93 (s, COOCH3, 3H), 5.21 (s, ArCH2O, 4H), 5.25 (s, ArCH2O, 2H), 7.08 (t, J=7.9Hz, ArH, 1H), 7.19(t,J=7.9Hz,ArH,2H),7.35(dd,J1=1.5Hz,J2=8.0Hz,ArH,1H),7.42–7.45(m,ArH,6H),7.54-7.56(m,ArH,1H). 13 CNMR (100MHz, CDCl3, δ):166.4,152.0,142.0,137.8,136.4,133.2,132.7,130.9, 130.6,129.9,129.5,127.5,127.3,127.0,127.0,125.9,108.9,72.7,68.7,52.4.

[0114] Example 28

[0115]

[0116] White solid, yield 95%. 1 H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 5.00 (s, ArCH2O, 2H), 5.05 (s, ArCH2O, 4H), 7.15 (dd, J1 = 1.9Hz, J2 = 8.2Hz, ArH, 1H), 7.20 (dd, J1 =1.9Hz, J2=8.2Hz, ArH,2H), 7.52(d,J=8.1Hz, ArH,1H), 7.64(t,J=8.2Hz, ArH,2H), 7.65(d,J1=1.8Hz, ArH,1H), 7.71(d,J1=1.8Hz, ArH,2H). 13 C NMR (100MHz, CDCl3, δ):166.4,151.9,142.0,140.0,138.5,133.2,132.7,128.5, 128.1,127.7,127.6,125.9,125.9,125.4,124.6,124.0,109.0,75.6,71.6,52.5.

[0117] Example 29

[0118]

[0119] White solid, yield 94%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.16 (s, ArCH2O, 4H), 5.17 (s, ArCH2O, 2H), 7.11 (dd, J1 = 2.1Hz, J2 = 8.3Hz, ArH, 1H), 7. 23(d,J=2.1Hz,ArH,1H),7.25(d,J=2.1Hz,ArH,1H),7.29(d,J=2.1Hz,ArH,1H),7.41–7.43(m,ArH,6H),7.51(d,J=8.3Hz,ArH,1H). 13 C NMR (100MHz, CDCl3, δ):166.3,152.0,141.9,134.5,134.1,134.0,133.5,133.3, 132.7,130.4,130.0,129.3,128.9,127.3,126.9,125.9,108.9,71.8,67.8,52.4.

[0120] Example 30

[0121]

[0122] White solid, yield 97%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 5.11 (s, ArCH2O, 4H), 5.13 (s, ArCH2O, 2H), 7.30 (dd, J1 = 1.9Hz, J2 = 8.2Hz, ArH, 1H) ,7.33-7.35(m,ArH,2H),7.41-7.42(m,ArH,3H),7.43-7.47(m,ArH,2H),7.62(d,J=1.9Hz,ArH,1H),7.74(d,J=1.9Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ):166.3,151.9,141.9,136.2,135.1,134.8,134.6,130 .8,130.6,130.4,125.9,123.2,122.8,122.4,121.9,109.0,74.1,70.1,52.4.

[0123] Example 31

[0124]

[0125] White solid, yield 96%. 1 H NMR(400MHz,CDCl3,δ):3.93(s,COOCH3,3H),5.18(s,ArCH2O,2H),5.21(s,ArCH2O,4H),7.14–7.17(m,ArH,1H),7.2 1-7.25(m,ArH,3H),7.31-7.33(m,ArH,2H),7.45(s,ArH,2H),7.54(d,J=2.2Hz,ArH,2H),7.66(d,J=2.2Hz,ArH,1H). 13 CNMR (100MHz, CDCl3, δ):166.3,152.0,142.0,137.0,135.8,133.1,132.9,130 .8,130.5,130.5,130.1,129.3,129.2,128.9,126.0,109.2,71.8,68.0,52.4.

[0126] Example 32

[0127]

[0128] White solid, yield 95%. 1 H NMR (400MHz, CDCl3, δ): 3.94 (s, COOCH3, 3H), 5.29 (s, ArCH2O, 2H), 5.32 (s, ArCH2O, 4H), 7.00–7.07(m,ArH,3H),7.23-7.27(m,ArH,2H),7.34-7.36(m,ArH,4H),7.50(s,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.8, 153.1, 141.8, 137.5, 137.2, 132.8, 132.0, 130.4, 129.9, 128.4, 127.9, 125.6, 108.8, 68.8, 66.1, 52.3.

[0129] Example 33

[0130]

[0131] White solid, yield 94%. 1H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 5.02 (s, ArCH2O, 2H), 5.07 (s, ArCH2O, 4H), 7.18 (dd, J1 = 1.9Hz, J2 = 8.2Hz, ArH, 1H), 7.24 (dd, J1 = 1.8Hz ,J1=8.2Hz,ArH,2H),7.34(d,J=4.2Hz,ArH,1H),7.36(s,ArH,2H),7.46(d,J=8.2Hz,ArH,2H),7.48(d,J=1.8Hz,ArH,1H),7.53(d,J=1.8Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ):166.2,152.0,141.7,137.4,136.5,132.9,132.5,132.3, 132.1,130.7,130.3,130.0,129.3,127.3,126.6,125.8,109.0,73.8,69.8,52.5.

[0132] Example 34

[0133]

[0134] White solid, yield 95%. 1 H NMR(400MHz,CDCl3,δ):3.92(s,COOCH3,3H),5.03(s,ArCH2O,2H),5.08(s,ArCH2O,4H),7.26–7.27( m,ArH,1H),7.28-7.29(m,ArH,2H),7.31-7.31(m,ArH,4H),7.34-7.34(m,ArH,2H),7.37(s,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 166.1, 152.0, 141.7, 140.4, 139.6, 135.4, 135.0, 128.4, 128.2, 126.2, 126.0, 125.6, 109.2, 73.7, 69.9, 52.5.

[0135] Example 35

[0136]

[0137] White solid, yield 96%. 1H NMR(400MHz,CDCl3,δ):3.94(s,COOCH3,3H),5.18(s,ArCH2O,4H),5.19(s,ArCH 2O,2H),7.36(d,J=2.4Hz,ArH,1H),7.45(s,ArH,6H),7.62(d,J=2.3Hz,ArH,1H). 13 C NMR (100MHz, CDCl3, δ):166.1,151.7,141.8,138.9,137.3,134.0,133.4,133.2, 133.0,129.7,129.3,129.0,128.4,127.0,126.8,126.2,109.3,72.2,68.4,52.5.

[0138] Example 36

[0139] Take the preparation of target molecule G-3d as an example:

[0140]

[0141] To a 250 mL single-necked flask equipped with a magnetic stirrer, G-1d (1.73 g, 2.0 mmol) and 100 mL of ultra-dry tetrahydrofuran (THF) were added sequentially. LiAlH₄ (0.09 g, 2.4 mmol) was slowly added in an ice bath. After the addition, the ice bath was removed, a reflux condenser was installed, and the mixture was heated to reflux in a 100°C metal bath for 1 h. The reaction was monitored by TLC. After the reaction was complete, approximately 0.1 mL of H₂O, 0.2 mL of 15% NaOH solution, and 0.3 mL of H₂O were added sequentially in an ice bath. A white solid appeared, which was filtered and washed three times with THF (3 x 50 mL). The filtrate was then dried over anhydrous sodium sulfate for 1 h. After filtration, the organic solvent was removed under reduced pressure to afford G-3d as a white solid in a 95% yield. 1 H NMR (400MHz, CDCl3, δ): 4.45 (d, J=5.8Hz, ArCH2OH, 2H), 5.09 (s, ArCH2O, 4H), 5.24 (t, J=5.8Hz, ArCH2O H,1H),6.55(t,J=2.2Hz,ArH,1H),6.61(d,J=2.2Hz,ArH,2H),7.36-7.43(m,ArH,6H),7.50(s,ArH,2H). 13 CNMR (100MHz, CDCl3, δ): 159.6, 145.8, 140.2, 133.6, 130.8, 128.2, 127.7, 126.5, 105.7, 100.7, 68.7, 63.2.

[0142] The corresponding compounds of Examples 37-41 can be obtained by similar methods, and their specific characteristics are as follows:

[0143] Example 37

[0144]

[0145] White solid, yield 96%. 1 H NMR (400MHz, CDCl3, δ): 4.64 (s, ArCH2OH, 2H), 4.99 (s, ArCH2O, 4H), 6.47 (t, J = 2.3Hz, ArH, 1H), 6.60 (d, J = 2.3Hz, Ar H,2H),7.22(d,J=2.0Hz,ArH,1H),7.24(d,J=2.0Hz,ArH,1H),7.44(d,J=8.2Hz,ArH,2H),7.52(d,J=2.0Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 159.7, 143.8, 137.1, 132.8, 132.0, 130.6, 129.2, 126.5, 105.9, 101.3, 68.6, 65.0.

[0146] Example 38

[0147]

[0148] White solid, yield 95%. 1 H NMR (400 MHz, d 6 -acetone,δ):4.25(t,J=1.8Hz,ArCH2OH,1H),4.60(d,J=1.7Hz,ArCH2OH,2H),5.17(s,ArCH2O,4H),6.60 (t,J=2.3Hz,ArH,1H),6.71(d,J=2.3Hz,ArH,2H),7.45(t,J=2.0Hz,ArH,2H),7.50(d,J=2.0Hz,ArH,4H). 13 C NMR (100 MHz, d 6 -acetone, δ):159.5,145.6,141.9,134.7,127.4,125.7,105.5,100.4,67.9,63.6.

[0149] Example 39

[0150]

[0151] White solid, yield 95%. 1 H NMR (400MHz, CDCl3, δ): 4.59 (s, ArCH2OH, 2H), 4.99 (s, ArCH2O, 2H), 5.06 (s, ArCH2O, 4H), 6.66 (s, ArH, 2H), 7.19-7.31 (m, ArH, 9H), 7.43 (d, J = 1.6Hz, ArH, 3H). 13 C NMR (100MHz, CDCl3, δ):152.7,139.6,138.9,137.3,137.1,134.5,134.1,129 .9,129.6,128.4,128.1,128.1,127.3,126.4,125.3,106.3,74.4,70.4,65.2.

[0152] Example 40

[0153]

[0154] White solid, yield 97%. 1 H NMR (400MHz, CDCl3, δ): 4.43 (d, J = 5.6Hz, ArCH2OH, 2H), 4.93 (s, ArCH2O, 2H), 5.10 (s ,ArCH2O,4H),5.25(t,J=5.7Hz,ArCH2OH,1H),6.77(s,ArH,2H),7.33(dd,J1=1.6Hz, J2=8.2Hz,ArH,1H),7.41(dd,J1=1.5Hz,J2=8.3Hz,ArH,2H),7.51(d,J=8.2Hz,ArH,1 H),7.57(d,J=1.5Hz,ArH,1H),7.64(d,J=8.2Hz,ArH,1H),7.68(d,J=1.4Hz,ArH,2H). 13 C NMR (100MHz, CDCl3, δ):156.8,144.2,144.1,143.5,140.6,136.3,136.1,135 .8,135.6,135.4,134.8,134.6,133.6,133.0,132.9,110.4,78.1,73.8,68.0.

[0155] Example 41

[0156]

[0157] White solid, yield 98%. 1H NMR (400MHz, CDCl3, δ): 4.62 (s, ArCH2OH, 2H), 4.96 (s, ArCH2O, 2H), 5.04 (s, ArCH2O, 4H), 6.66(s,ArH,2H),7.26–7.27(m,ArH,2H),7.29-7.31(m,ArH,5H),7.32-7.33(m,ArH,2H). 13 C NMR (100MHz, CDCl3, δ): 152.4, 140.8, 140.1, 137.5, 137.1, 135.3, 134.9, 128.2, 128.1, 126.3, 125.5, 106.5, 73.8, 69.8, 65.0.

[0158] Example 42

[0159]

[0160] To a 250 mL single-necked flask equipped with a magnetic stirrer, G-1e (2.81 g, 5.0 mmol), 10 M KOH aq. (25.0 mmol), and THF-MeOH (3:1, v / v, 100 mL) were added sequentially. The reaction system was heated under reflux overnight under nitrogen, with TLC monitoring of the reaction progress. After the reaction, 2 M hydrochloric acid solution was added three times to acidify the solution (to a pH of approximately 1-2). Precipitation occurred. Most of the tetrahydrofuran was removed in vacuo, and the solution was filtered. The solid was washed three times with distilled water and dried in vacuo to obtain G-5e as a white powder in 97% yield. 1 H NMR (400 MHz, d 6 -DMSO,δ):5.17(s,ArCH2O,4H),6.96(t,J=2.3Hz,ArH,1H),7.18(d,J=2.4Hz,ArH,2H),7.37(t,J=7.8Hz,ArH ,2H),7.47(d,J=7.6Hz,ArH,2H),7.53-7.55(m,ArH,2H),7.67(t,J=1.5Hz,ArH,2H),13.11(bs,ArCOOH,1H). 13 C NMR (100 MHz, d 6 -DMSO, δ):167.3,159.7,140.0,133.4,131.2,131.1,130.7,127.0,122.2,108.6,107.1,69.0.

[0161] Example 43

[0162]

[0163] White solid, yield 98%. 1 H NMR (400 MHz, d 6 -DMSO,δ):5.05(s,ArCH2OH,2H),5.21(s,ArCH2O,4H),7.27(t,J=7.8Hz,ArH,1H),7.35–7.40(m,ArH,5H),7. 46-7.51(m,ArH,3H),7.55(d,J=7.8Hz,ArH,2H),7.59(s,ArH,1H),7.70(s,ArH,2H),13.04(bs,ArCOOH,1H). 13 CNMR(100MHz,d 6 -DMSO,δ):167.2,152.2,141.1,140.5,140.0,132.3,131.2,131.1,131 .1,130.8,130.6,127.4,126.9,126.8,122.2,122.0,108.8,73.8,69.7.

[0164] Example 44

[0165]

[0166] To a 500 mL single-necked flask equipped with a magnetic stirrer, G-5e (5.63 g, 10.0 mmol) and 200 mL of ultra-dry tetrahydrofuran (THF) were added sequentially. Borane tetrahydrofuran complex (2.0 M in THF, 6 mL, 12.0 mmol) was slowly added in an ice bath. The ice bath was removed and the mixture was stirred overnight at room temperature, monitored by TLC. After completion of the reaction, methanol was slowly added in an ice bath to quench the reaction. Then, 300 mL of ethyl acetate was added to the mixture, followed by washing with dilute hydrochloric acid (0.5 M, 50 mL), dilute sodium hydroxide (0.5 M, 50 mL), and saturated brine (50 mL). The organic phase was dried over anhydrous sodium sulfate for 2 h, filtered, and the solvent removed under reduced pressure to afford G-3e as a white solid in 98% yield. 1 H NMR (400 MHz, d 6-DMSO,δ):4.63(s,ArCH2OH,2H),5.00(s,ArCH2O,4H),5.21(s,ArCH2O,4H),6.50(t,J=2.2Hz,ArH,1H),6.61(d,J=2 .2Hz,ArH,2H),7.24(t,J=7.8Hz,ArH,2H),7.33(d,J=7.7Hz,ArH,2H),7.45(d,J=7.9Hz,ArH,2H),7.58(s,ArH,2H). 13 C NMR (100 MHz, d 6 -DMSO, δ):159.8,143.6,139.1,131.1,130.3,130.2,125.9,122.7,105.8,101.2,69.1,65.2.

[0167] Example 45

[0168]

[0169] White solid, yield 97%. 1 H NMR (400 MHz, d 6 -DMSO,δ):4.44(s,ArCH2OH,2H),4.94(s,ArCH2O,2H),5.13(s,ArCH2O,4H),6.79(s,ArH,2H),7.27(t,J=7.8Hz,ArH,1H),7.36(t,J =7.8Hz,ArH,2H),7.40(d,J=7.9Hz,ArH,1H),7.45-7.50(m,ArH,3H),7.54(d,J=7.9Hz,ArH,2H),7.59(s,ArH,1H),7.69(s,ArH,2H). 13 C NMR (100 MHz, d 6 -DMSO, δ):152.3,140.9,140.4,139.3,135.9,131.1,130.8,130.5,128.9,127.3,126.8,122.2,122.0,105.7,73.8,69.6,63.3.

[0170] Example 46

[0171]

[0172] To a 500 mL two-necked flask equipped with a magnetic stirrer, methyl 3,5-dihydroxybenzoate (5.52 g, 30 mmol), G-3d (96 mmol), PPh3 (135 mmol), ultra-dry tetrahydrofuran (THF, 50 mL), and a magnetic stirrer were added sequentially. DIAD (135 mmol) was then slowly added dropwise to the reaction system under an ice bath. After 10 minutes of addition, the ice bath was removed and the reaction was carried out in a metal bath at 50°C under nitrogen for 24 hours. TLC was used to monitor the reaction progress. After the reaction, while maintaining the temperature, 250 mL of methanol was added to the reaction system to precipitate the product. The product was filtered and washed with methanol until the color of the solid faded from red to white. The initial product was dissolved in 30 mL of THF and then added dropwise to 200 mL of rapidly stirred methanol. A large amount of solid precipitate formed during this time. The solid precipitate was filtered and washed three times with methanol. The crude product was purified by silica gel column chromatography to obtain G-7a as a white solid in 89% yield. 1 H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 5.01 (s, ArCH2O, 12H), 6.53 (t, J = 2.2Hz, ArH, 2H), 6 .66(d,J=2.2Hz,ArH,4H),6.76(t,J=2.3Hz,ArH,1H),7.25-7.32(m,ArH,10H),7.42(s,ArH,4H). 13 CNMR (100MHz, CDCl3, δ):159.9,159.6,139.1,138.8,134.5,132.1,132.1, 129.9,128.2,127.5,125.4,108.4,107.1,106.5,107.7,70.0,69.3,52.3.

[0173] The corresponding compounds of Examples 47-49 can be obtained by similar methods, and their specific characteristics are as follows:

[0174] Example 47

[0175]

[0176] White solid, yield 91%. 1H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 5.00 (s, ArCH2O, 8H), 5.01 (s, ArCH2O, 4H), 6.53 (t, J = 2.2Hz, ArH, 2H), 6.67 (d, J = 2.2Hz, ArH, 4H), 6.76 ( t,J=2.3Hz,ArH,1H),7.24(t,J=7.8Hz,ArH,4H),7.28(d,J=2.3Hz,ArH,2H),7.33(d,J=7.7Hz,ArH,4H),7.45(d,J=7.9Hz,ArH,4H),7.58(s,ArH,4H). 13 C NMR (100MHz, CDCl3, δ):166.7,159.9,159.6,139.1,139.0,132.1,131.1, 130.4,130.2,125.9,122.7,108.4,107.1,106.5,101.6,70.0,69.2,52.4.

[0177] Example 48

[0178]

[0179] White solid, yield 92%. 1 H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 4.98 (s, ArCH2O, 8H), 5.01 (s, ArCH2O, 4H), 6.50 (t, J=2.3Hz, ArH, 2H), 6.64 (d, J=2.4Hz, ArH, 4H), 6.74 (t, J= 2.3Hz,ArH,1H),7.21(d,J=2.0Hz,ArH,2H),7.23(d,J=2.0Hz,ArH,2H),7.27 (d,J=2.3Hz,ArH,2H),7.43(d,J=8.2Hz,ArH,4H),7.51(d,J=2.0Hz,ArH,4H). 13 C NMR (100MHz, CDCl3, δ):166.7,159.7,159.6,139.2,136.9,132.8,132.2, 132.1,130.6,129.2,126.5,108.4,107.1,106.5,101.7,69.9,68.7,52.4.

[0180] Example 49

[0181]

[0182] White solid, yield 92%. 1 H NMR (400MHz, CDCl3, δ): 3.91 (s, COOCH3, 3H), 4.99 (s, ArCH2O, 8H), 5.02 (s, ArCH2O, 4H), 6.51 (t, J=2.3Hz, Ar H,2H),6.66(d,J=2.2Hz,ArH,4H),6.76(t,J=2.4Hz,ArH,1H),7.28(d,J=2.4Hz,ArH,2H),7.30(s,ArH,12H). 13 C NMR (100MHz, CDCl3, δ): 166.6, 159.6, 159.6, 140.1, 139.3, 135.3, 132.2, 128.2, 125.5, 108.5, 107.1, 106.6, 101.7, 69.9, 68.6, 52.4.

[0183] Example 50

[0184]

[0185] To a 500 mL two-necked flask equipped with a magnetic stirrer, methyl 3,5-dihydroxybenzoate (5.52 g, 30 mmol), G-4c (96 mmol), PPh3 (135 mmol), ultra-dry tetrahydrofuran (THF, 50 mL), and a magnetic stirrer were added sequentially. DIAD (135 mmol) was then slowly added dropwise to the reaction system under an ice bath. After 10 minutes of addition, the ice bath was removed and the reaction was carried out in a metal bath at 50°C under nitrogen for 36 hours. TLC was used to monitor the reaction progress. After the reaction, while maintaining the temperature, 250 mL of methanol was added to the reaction system to precipitate the product. The product was filtered and washed with methanol until the color of the solid faded from red to white. The initial product was dissolved in 30 mL of THF and then added dropwise to 200 mL of rapidly stirred methanol. A large amount of solid precipitate formed during this time. The solid precipitate was filtered and washed three times with methanol. The crude product was purified by silica gel column chromatography to obtain G-7e as a white solid in a 91% yield. 1 H NMR(400MHz,CDCl3,δ):3.92(s,COOCH3,3H),4.97(s,ArCH2O,4H),5.01(s,ArCH2O,4H),5.08(s,ArCH2O,8H ),6.72(s,ArH,4H),6.74(t,J=2.3Hz,ArH,1H),7.20-7.33(m,ArH,20H),7.43(s,ArH,4H),7.44(s,ArH,2H). 13C NMR (100MHz, CDCl3, δ):166.7,159.5,152.7,139.5,138.8,137.7,134.5,134.1,132.4,132.1, 129.9,129.6,128.4,128.2,128.1,127.3,126.4,125.3,108.4,107.1,74.4,70.4,70.2,52.4.

[0186] The corresponding compounds of Examples 51-53 can be obtained by similar methods, and their specific characteristics are as follows:

[0187] Example 51

[0188]

[0189] White solid, yield 92%. 1 H NMR(400MHz,CDCl3,δ):3.92(s,COOCH3,3H),4.97(s,ArCH2O,4H),5.00(s,ArCH2O,4H),5.07(s,A rCHO2O,8H),6.72(s,ArH,4H),6.74(t,J=2.3Hz,ArH,1H),7.16(t,J=7.8Hz,ArH,2H),7.22(d,J=7. 8Hz,ArH,2H),7.25(d,J=2.6Hz,ArH,2H),7.28(t,J=2.3Hz,ArH,2H),7.32(d,J=8.3Hz,ArH,4H),7 .35(d,J=8.2Hz,ArH,2H),7.40(d,J=7.9Hz,ArH,2H),7.44(d,J=8.0Hz,ArH,4H),7.58(s,ArH,6H). 13 C NMR (100MHz, CDCl3, δ):166.7,159.6,152.8,139.8,139.1,137.8,132.5,132.2,131.3,131.1,131 .0,130.3,130.2,129.9,126.9,125.8,122.7,122.4,108.5,107.2,107.2,74.4,70.4,70.2,52.4.

[0190] Example 52

[0191]

[0192] White solid, yield 93%. 1H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 4.96 (s, ArCH2O, 4H), 4.97 (s, ArCH2O, 4H), 5.04 (s, ArCH2O, 8H), 6.69 (s, ArH, 4H), 6.70 (t, J=2.4Hz, ArH,1H),7.19(s,ArH,2H),7.21(s,ArH,4H),7.27(d,J=2.2Hz,ArH,2H),7.35(d,J=8.1Hz,ArH,2H),7.45(d,J=8.0Hz,ArH,4H),7.30(s,ArH,6H). 13 C NMR (100MHz, CDCl3, δ):166.6,159.5,152.5,137.7,137.6,136.8,132.8,132.7,132.4,132.2,130 .7,130.6,130.3,130.1,129.2,129.2,127.4,127.3,126.5,108.4,107.1,73.8,69.9,69.8,52.5.

[0193] Example 53

[0194]

[0195] White solid, yield 91%. 1 H NMR (400MHz, CDCl3, δ): 3.92 (s, COOCH3, 3H), 4.98 (s, ArCH2O, 8H), 5.05 (s, ArCH2O, 8H), 6.70(s,ArH,4H),6.73(t,J=2.3Hz,ArH,1H),7.27-7.29(m,ArH,12H),7.31(s,ArH,8H). 13 C NMR (100 MHz, CDCl3-d 4 -C2D2Cl4,δ):166.6,159.5,152.3,149.8,141.2,140.4,137.0,135.1,134.7,1 33.2,128.1,127.9,126.4,125.6,118.5,108.5,106.9,73.7,69.6,69.0,52.6.

[0196] Effect example:

[0197] In a 1 cm diameter, 5 mL sample vial, 12 mg of supramolecule was weighed, 0.2 mL of solvent was added, and the solution was heated in a 100°C water bath until the supramolecule completely dissolved. The hot solution was then allowed to slowly cool to room temperature and allowed to stand for 1 hour before being observed: 1) Invert the sample vial. If the system does not flow, a stable gel has formed, indicated by "G"; 2) If only a partial gel has formed, indicated by "PG"; 3) If a precipitate has formed, indicated by "P"; 4) If the system remains a clear solution (>60 mg / mL), indicated by "S". If the supramolecule is insoluble in the solvent at the time of initial heating, indicated by "I". The minimum gel concentration is the minimum mass of supramolecule required to form a stable gel at 25°C. The results are shown in Tables 1-3.

[0198] Table 1 Gelation properties of gel factors

[0199]

[0200]

[0201] Table 2 Gelation properties of supramolecular gel factors

[0202]

[0203]

[0204] Table 3 Gelation properties of supramolecular gel factors

[0205]

[0206] The above gelation performance tests demonstrate that the dendrimer supramolecular gelators provided by the present invention can vary the type of peripheral halogens (Cl, Br, I), the number and position of substitutions, as well as the type and generation size of the dendrimer. This has led to the development of a library of dendrimer gelators with excellent gelation performance, diverse and stable structures, simple and efficient synthesis, and easy post-functionalization. The provided dendrimer gelators can form stable supramolecular organogels in dozens of organic solvents or mixed solvents, representing a class of super gelators. Furthermore, this class of dendrimer gelators offers the following advantages:

[0207] 1) By changing the type, modification position and number of peripheral halogen atoms, as well as the type and generation of the dendrimer, the polarity and dipole moment of the entire dendrimer can be easily controlled, thereby adjusting its gelling concentration and the type of gelling solvent;

[0208] 2) Dendrimers belong to a class of macromolecular compounds. Modification of functional groups will not significantly affect their gel-forming properties. They are a very ideal type of gel factor that can be commercially used.

[0209] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A type of dendrimer supramolecular gel factor, characterized in that: The dendrimer supramolecular gel factor has a structure shown in Formula I or Formula II: ， Among them, R 1 、R 2 、R 3 、R 4 and R 5 are each independently selected from hydrogen, chlorine, bromine or iodine atoms, and R 1 、R 2 、R 3 、R 4 and R 5 There is at least one chlorine, bromine or iodine atom on the R 6 Each independently selected from COOC m H 2m+1 , COOH, CONHNH2, CONHCH2CH2Br, CH2OH, CHO, CH2Br or CH2CN.

2. The dendrimer supramolecular gelator according to claim 1, characterized in that The R 1 is selected from one of chlorine, bromine or iodine atoms, R 2 、R 3 、R 4 and R 5 selected from hydrogen; Or, the R 2 is selected from one of chlorine, bromine or iodine atoms, R 1 、R 3 、R 4 and R 5 selected from hydrogen; Or, the R 3 is selected from one of chlorine, bromine or iodine atoms, R 1 、R 2 、R 4 and R 5 selected from hydrogen; Or, the R 1 、R 2 is selected from one of chlorine, bromine or iodine atoms, R 3 、R 4 and R 5 selected from hydrogen; Or, the R 1 、R 3 is selected from one of chlorine, bromine or iodine atoms, R 2 、R 4 and R 5 selected from hydrogen; Or, the R 1 、R 4 is selected from one of chlorine, bromine or iodine atoms, R 2 、R 3 and R 5 selected from hydrogen; Or, the R 1 、R 5 is selected from one of chlorine, bromine or iodine atoms, R 2 、R 3 and R 4 selected from hydrogen; Or, the R 3 、R 4 is selected from one of chlorine, bromine or iodine atoms, R 1 、R 2 and R 5 selected from hydrogen; Or, the R 1 、R 2 、R 4 is selected from one of chlorine, bromine or iodine atoms, R 3 and R 5 selected from hydrogen; Or, the R 1 、R 2 、R 3 、R 4 is selected from one of chlorine, bromine or iodine atoms, R 5 Selected from hydrogen.

3. The dendrimer supramolecular gelator according to claim 1, characterized in that The R 6 independently selected from COOCH3, COOH, CONHNH2, CH2OH, CHO, CH2Br or CH2CN.

4. The use of the dendrimer supramolecular gelator according to any one of claims 1 to 3, characterized in that: The dendrimer supramolecular gel factor is used to prepare functional supramolecular gel or supramolecular self-assembly system.

5. The use according to claim 4, characterized in that The dendrimer supramolecular gel factor is heated and dissolved in a solvent, and then cooled and allowed to stand to obtain a functional supramolecular gel or a supramolecular self-assembly system.

6. The use according to claim 5, characterized in that The solvent is selected from any one of toluene, acetonitrile, ethyl acetate, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, benzyl alcohol, n-butanol, n-pentanol, n-hexanol, n-octanol, 1-decyl alcohol, nitromethane, acetone, or a mixed solution of tetrahydrofuran and methanol, or a mixed solution of anisole and n-hexane, or a mixed solution of pyridine and water.

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