Benzene-containing cucurbituril compound as well as preparation method and application thereof

Abstract

The invention provides a benzene-containing cucurbituril compound, and belongs to the technical field of macrocyclic compounds, the benzene-containing cucurbituril compound is a cage compound formed by bridging two benzene ring monomers and four glycoluril monomers through 12 methylene-CH2-, the chemical composition general formula is C40H36N16O8, the molecular weight is 868.83200, the compound is a white solid, the compound is dissolved in an organic solvent formic acid, and the molecular weight of the compound is 868.83200. The composition of the product is accurately confirmed through mass spectrum, nuclear magnetism and single crystal structure. The invention also provides a preparation method and application of the benzene-containing cucurbituril compound.

Description

Technical Field

[0001] The invention belongs to the technical field of macrocyclic compounds, and particularly relates to a benzene-cucurbitacin-containing compound and a preparation method and application thereof. Background Art

[0002] Supramolecular chemistry is an emerging discipline first proposed by French scientist Jean-Marie Lehn. Unlike molecular chemistry, supramolecular chemistry studies the chemistry of intermolecular bonds. It covers the structure and function of entities formed by the combination of two or more chemical substances, and mainly studies the interactions between non-covalent bonds. Crown ethers, cyclodextrins, calixarene and pillararene are the subjects that are studied more in supramolecular chemistry. Cucurbitacin, as a macrocyclic compound studied after them, is also the subject that has been studied more in supramolecular chemistry in recent years. These macrocyclic molecules are the hot spots of cross-disciplinary research in chemistry, materials, biology and physics. Summary of the invention

[0003] In order to obtain a new macrocyclic compound, the present invention provides a benzene-cucurbitacin-containing compound, which is a white solid, soluble in organic solvents such as formic acid, acetic acid and trifluoroacetic acid, can be used to detect pyridine compounds, and has adsorption properties and can be used for adsorption and impurity removal.

[0004] The invention also provides a preparation method and application of the benzene cucurbitacin-containing compound.

[0005] The present invention is achieved through the following technical solutions:

[0006] The present invention provides a benzene cucurbitacin-containing compound, the structural formula of the benzene cucurbitacin-containing compound is shown in Formula 4:

[0007]

[0008] Furthermore, the chemical composition formula of the benzene cucurbitacin compound is C 40 H 36 N 16 O8, molecular weight 868.83200;

[0009] The benzene cucurbitacin-containing compound is in the form of a white solid and is soluble in at least one of the organic solvents formic acid, acetic acid and trifluoroacetic acid.

[0010] Based on the same inventive concept, the present invention provides a method for preparing a compound containing a benzene cucurbitacin ring, the preparation method comprising:

[0011] Add KCNO to the aqueous solution of compound 1 and react for a period of time to obtain a reaction solution;

[0012] The reaction solution is subjected to solid-liquid separation, and the obtained solid is washed and dried to obtain compound 2;

[0013] The compound 2 is dissolved in formic acid, and then water and glyoxal are added to perform a reflux reaction, followed by solid-liquid separation, liquid spin drying, washing and drying to obtain a compound 3;

[0014] The compound 3 is dissolved in hydrochloric acid, and then a formaldehyde solution is added for reflux reaction to obtain a mixed solution;

[0015] separating the benzene-containing cucurbitacin compound from the mixed solution;

[0016] The structural formulas of the compound 1, the compound 2 and the compound 3 are shown in Formulas 1 to 3 respectively:

[0017]

[0018] Further, the step of adding KCNO to the aqueous solution of compound 1 and reacting for a period of time to obtain a reaction solution specifically comprises:

[0019] Add KCNO to the aqueous solution of compound 1 and react for 72±2h to obtain a reaction solution;

[0020] In the aqueous solution of the compound 1, the concentration of the compound 1 is 0.1±0.01 mol / L;

[0021] The molar ratio of the compound 1 to the KCNO is 12:105.5.

[0022] Further, the reaction solution is subjected to solid-liquid separation, and the obtained solid is washed and dried to obtain compound 2, which specifically includes:

[0023] The reaction solution was subjected to solid-liquid separation, and the obtained solid was washed with water and acetone in sequence, and dried to obtain compound 2.

[0024] Further, the compound 2 is dissolved in formic acid, and then water and glyoxal are added for reflux reaction, and then solid-liquid separation, liquid spin drying, washing and drying are performed to obtain compound 3, which specifically includes:

[0025] The compound 2 is dissolved in formic acid and then water is added at 98-102° C. for reflux reaction, and then glyoxal is added for reflux reaction for 5±0.5h, and then solid-liquid separation is performed after cooling, and the liquid is spin-dried and washed with water, and dried to obtain compound 3;

[0026] Wherein, the molar ratio of the compound 2 to the glyoxal is 14.6:29.3.

[0027] Furthermore, the compound 3 is dissolved in hydrochloric acid, and then a formaldehyde solution is added for reflux reaction to obtain a mixed solution, which specifically includes:

[0028] The compound 3 is dissolved in 9 mol / L hydrochloric acid, and then a formaldehyde solution is added to react under reflux at 98-102° C. for 5-7 hours to obtain a mixed solution;

[0029] Wherein, the molar ratio of the compound 3 to formaldehyde is 1:2.

[0030] Further, the separation of the benzene-containing cucurbitacin compound from the mixed solution specifically includes:

[0031] Adding formic acid to the mixed solution to dissolve the solid precipitated in the reaction mixed solution, and then adding silica gel and spinning to obtain a mixture;

[0032] The mixture is loaded into a silica gel column, eluted with a formic acid:acetic acid solution with a volume ratio of 1:1.8, separated and spin-dried to obtain a crude product of the benzene cucurbitacin-containing compound;

[0033] Wash the crude product of the benzene cucurbitacin compound with an acetone:water solution in a volume ratio of 1:1, centrifuge and spin-dry the solid;

[0034] The spin-dried solid was recrystallized with 9 mol / L hydrochloric acid and then filtered. The solid was washed with water and then dried to obtain a benzene cucurbitacin-containing compound.

[0035] Furthermore, the mass ratio of the silica gel to the compound 3 is 13:3.0046.

[0036] Based on the same inventive concept, the present invention provides an application of a benzene cucurbitacin-containing compound as or in the preparation of a detection reagent or impurity adsorbent for pyridine compounds.

[0037] One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:

[0038] The present invention discloses a benzene-cucurbit ring-containing compound, named benzene-cucurbit ring-containing [2,4], which is a cage-shaped compound formed by 2 benzene ring monomers and 4 glycoside urea monomers connected by 12 methylene -CH2- bridges, and has a general chemical composition formula of C 40 H 36 N 16 O8, molecular weight is 868.83200, the compound is a white solid, soluble in organic solvents such as formic acid, acetic acid and trifluoroacetic acid. The product composition is accurately confirmed by mass spectrometry, nuclear magnetic resonance and single crystal structure. The benzene ring [2,4] can be used to detect pyridine compounds, and the compound has adsorption properties and can be used for adsorption and impurity removal. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0040] Figure 1 For the benzoic acid ring [2,4] in deuterated trifluoroacetic acid 1 H, 13 C NMR spectrum.

[0041] Figure 2 These are the mass spectrometry results for compounds containing benzocuculline [2,4].

[0042] Figure 3 This is a single crystal structure diagram of a benzoic acid ring [2,4].

[0043] Figure 4 This is the UV detection diagram of 5,5'-dimethyl-2,2'-bipyridine containing benzoic acid [2,4].

[0044] Figure 5 This is the NMR detection image of 5,5'-dimethyl-2,2'-bipyridine containing benzoic acid [2,4].

[0045] Figure 6 This is a graph showing the adsorption performance of solid iodine vapor containing benzene cucurbitacin [2,4].

[0046] Figure 7 This is the color change diagram of iodine adsorption in iodocyclohexane solution containing phenylcucurbitacin [2,4].

[0047] Figure 8 This is a color comparison chart of the benzyl alcohol ring [2,4] before and after iodine adsorption. DETAILED DESCRIPTION

[0048] The present invention will be described in detail below in conjunction with specific implementations and examples, and the advantages and various effects of the present invention will be more clearly presented. It should be understood by those skilled in the art that these specific implementations and examples are used to illustrate the present invention, rather than to limit the present invention.

[0049] Throughout the specification, unless otherwise specifically stated, the terms used herein should be understood as meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art to which the present invention belongs. In the event of a conflict, the present specification takes precedence.

[0050] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0051] The overall idea of ​​the present invention is as follows:

[0052] The present invention discloses a method for preparing a compound containing benzene cucurbitacin rings, the method comprising:

[0053] S1. adding KCNO to an aqueous solution of compound 1 and reacting for a period of time to obtain a reaction solution;

[0054] S2. The reaction solution is subjected to solid-liquid separation, and the obtained solid is washed and dried to obtain compound 2;

[0055] S3. The compound 2 is dissolved in formic acid, and then water and glyoxal are added to reflux the reaction, followed by solid-liquid separation, liquid spin drying, washing and drying to obtain compound 3;

[0056] S4. dissolving the compound 3 in hydrochloric acid, and then adding formaldehyde solution to reflux reaction to obtain a mixed solution;

[0057] S5. Separating the benzene-containing cucurbitacin compound from the mixed solution.

[0058] The benzene-cucurbitacin-containing compound prepared by the present invention is named as benzene-cucurbitacin-containing compound [2,4], wherein the first number in the square brackets represents the number of benzenes in the macrocycle, and the second number represents the number of glycoside urea in the macrocycle.

[0059] Step S1 specifically includes:

[0060] Add KCNO to the aqueous solution of compound 1 and react for 72±2h to obtain a reaction solution;

[0061] In the aqueous solution of the compound 1, the concentration of the compound 1 is 0.1±0.01 mol / L;

[0062] The molar ratio of the compound 1 to the KCNO is 12:105.5.

[0063] In the present invention, the purpose of adding KCNO to the aqueous solution of compound 1 for reaction is to react compound 1 to generate compound 2. The advantage of the molar ratio of compound 1 to KCNO being 12:105.5 is to ensure that compound 1 reacts as completely as possible.

[0064] Step S2 specifically includes:

[0065] The reaction solution was subjected to solid-liquid separation, and the obtained solid was washed with water and acetone in sequence, and dried to obtain compound 2.

[0066] In the present invention, the purpose of washing the obtained solid with water and acetone in sequence is to wash away the excess KCNO in the reaction.

[0067] Step S3 specifically includes:

[0068] The compound 2 is dissolved in formic acid and then water is added at 98-102° C. for reflux reaction, and then glyoxal is added for reflux reaction for 5±0.5h, and then solid-liquid separation is performed after cooling, and the liquid is spin-dried and washed with water, and dried to obtain compound 3;

[0069] Wherein, the molar ratio of the compound 2 to the glyoxal is 14.6:29.3.

[0070] In the present invention, the molar ratio of compound 2 to glyoxal is 14.6:29.3, which has the advantage that compound 2 can react completely to generate compound 3.

[0071] Step S4 specifically includes:

[0072] The compound 3 is dissolved in 9 mol / L hydrochloric acid, and then a formaldehyde solution is added to react under reflux at 98-102° C. for 5-7 hours to obtain a mixed solution;

[0073] Wherein, the molar ratio of the compound 3 to formaldehyde is 1:2.

[0074] In the present invention, the concentration of hydrochloric acid is 9 mol / L, because the benzyl cucurbitacin [2,4] is easily precipitated in a 9 mol / L HCl aqueous solution, which is beneficial to the recrystallization and purification of the benzyl cucurbitacin [2,4].

[0075] In the present invention, the molar ratio of compound 3 to formaldehyde is 1:2, which has the advantage that compound 3 can react completely to generate compound 4.

[0076] Step S5 specifically includes:

[0077] Add formic acid to the mixed solution to dissolve the solid matter, then add silica gel and spin-dry to obtain a mixture;

[0078] The mixture is loaded into a silica gel column, eluted with a formic acid:acetic acid solution with a volume ratio of 1:1.8, separated and spin-dried to obtain a crude product of the benzene cucurbitacin-containing compound;

[0079] Wash the crude product of the benzene cucurbitacin compound with an acetone:water solution in a volume ratio of 1:1, centrifuge and spin-dry the solid;

[0080] The spin-dried solid was recrystallized with 9 mol / L hydrochloric acid and then filtered. The solid was washed with water and then dried to obtain a benzene cucurbitacin-containing compound.

[0081] In the present invention, the advantage of using a formic acid:acetic acid solution with a volume ratio of 1:1.8 for elution is that the phenyl cucurbitacin [2,4] is fully dissolved and separated cleanly on the silica gel column.

[0082] In the present invention, the benzene-containing ring [2,4] is far away from other points and is easy to be separated by column, and the column chromatography stationary phase is silica gel.

[0083] The following is a detailed description of a benzene cucurbitacin-containing compound, a preparation method and an application of the present invention in combination with examples and experimental data.

[0084] Example 1

[0085] The present embodiment provides a method for preparing a compound containing benzene cucurbitacin, which is specifically as follows:

[0086] 1. As in Formula 5 (where "rt" stands for room temperature), weigh compound 1 (6.2169 g, 12.0 mmol) in a 250 mL round-bottom flask, add 120 mL H2O, stir at room temperature to dissolve compound 1 completely, then add KCNO (8.5572 g, 105.5 mmol), and stir the resulting mixture at room temperature for 72 h. Centrifuge, wash the solid with H2O (3×40 mL) and acetone (3×40 mL), and dry to obtain compound 2: 4.1844 g, with a yield of 95.15%. mp.341-342°C (dec); 1 H NMR (400MHz, CF3CO2D) δ7.41 (s, 2H), 4.59 (s, 8H); 13 C NMR (100MHz, CF3CO2D) δ163.3,137.0,132.6,44.0; HRMS Ca lcd for C 14 H 22 N8O4(M+Na):389.1662; found:389.1668.

[0087]

[0088] 2. As in Formula 6, weigh compound 2 (5.3637 g, 14.6 mmol) in a 1000 mL round-bottom flask, add HCOOH (250 mL), stir at 98-102°C to completely dissolve compound 2, quickly add H2O (324 mL), reflux and stir until the temperature of the reaction system rises to 98-102°C, then add 40 wt% glyoxal aqueous solution (3.36 mL, 29.3 mmol), reflux for 5 h. Cool, put in the refrigerator overnight (to cool and precipitate impurities), centrifuge, spin dry the liquid, wash with H2O (3×40 mL), and dry to obtain compound 3: 2.0342 g, with a yield of 33.86%. mp.353-354°C (dec);1 H NMR (400MHz, CF3CO2D) δ7.35 (s, 2H), 5.78 (d, J = 8.0Hz, 2H), 5.66 (d, J = 8.0Hz, 2H), 4.83 (d, J = 16.0Hz, 4H), 4.52 (d, J = 16.0Hz, 4H); 13 C NMR (100MHz, CF3CO2D) δ163.7,138.6,133.2,77.3,64.7,47.3; HRMS Calcd for C 18 H 18 N8O4(M+H):411.1529; found:411.1526.

[0089]

[0090] 3. As shown in formula 7, weigh compound 3 (3.0046 g, 7.3 mmol) in a 50 mL round-bottom flask, add 9 mol / L HCl (16.254 mL), stir at 98-102 ° C to completely dissolve compound 3, then add 37-40% HCHO aqueous solution (960 uL), reflux and stir for 7 hours. After the reaction is completed, add 40 mL HCOOH to the reaction solution to completely dissolve the reaction mixture, add 13 g silica gel and spin dry, pass through a column with HCOOH: CH3COOH = 1: 1.8 to obtain a crude compound 4, wash the crude product containing phenyl cucurbitacin [2,4] with acetone: aqueous solution with a volume ratio of 1: 1, spin dry the solid after centrifugation, recrystallize the solid with 9 mol / L HCl aqueous solution, filter, wash the solid with water and dry it, and obtain compound 4: 0.7731 g, with a yield of 24.35%. mp.389-390 ° C (dec); 1 H NMR (400MHz, CF3CO2D) δ7.25 (s, 4H), 6.02 (d, J = 16.0Hz, 4H), 5.80 (d, J = 8.0Hz ,4H),5.68(d,J=12.0Hz,4H),4.90(d,J=16.0Hz,8H),4.48(d,J=16.0Hz,12H); 13 C NMR (100MHz, CF3CO2D) δ159.9,138.5,132.7,73.8,72.7,53.9,47.7; HRMS Ca lcd for C 40 H 36 N 16 O8(M+H):869.2980; found:869.2985.

[0091]

[0092] Attached Figure 1 : containing phenyl cucurbitacin [2,4] in deuterated trifluoroacetic acid 1 H, 13 C NMR spectrum: 1 H NMR (400MHz, CF3CO2D) δ7.25 (s, 4H), 6.02 (d, J = 16.0Hz, 4H), 5.80 (d, J = 8.0Hz ,4H),5.68(d,J=12.0Hz,4H),4.90(d,J=16.0Hz,8H),4.48(d,J=16.0Hz,12H); 13 CNMR(100MHz,CF3CO2D)δ159.9,138.5,132.7,73.8,72.7,53.9,47.7.

[0093] Attached Figure 2 : Mass spectrometry results of benzocucurbitacin [2,4]: HRMS Ca lcd for C 40 H 36 N 16 O8(M+H):869.2980; found:869.2985.

[0094] Attached Figure 3 : Single crystal structure diagram of benzocuculline [2,4]: CCDC: 2380509, color: C, gray; H, green; N, blue; O, red.

[0095] Example 2

[0096] The ultraviolet detection of 5,5'-dimethyl-2,2'-bipyridine by a benzene-cucurbit ring compound in this embodiment is as follows:

[0097] 1. Use an analytical balance to weigh 0.0018 g of 5,5'-dimethyl-2,2'-bipyridine and place it in a 5 mL centrifuge tube. Add 1 mL of HCOOH:H2O=1:1 mixed solution to dissolve it. Transfer it to a 10 mL volumetric flask and add HCOOH:H2O=1:1 mixed solution to make up the volume. You can get 1×10 -3 mol / L 5,5'-dimethyl-2,2'-bipyridine stock solution; use a pipette to accurately measure 0.5 mL (1×10 -3 mol / L) of 5,5'-dimethyl-2,2'-bipyridine stock solution was transferred to a 5 mL volumetric flask and fixed to volume with HCOOH:H2O=1:1 mixture to obtain 1×10 -4 mol / L 5,5'-dimethyl-2,2'-bipyridine stock solution; then use a pipette to accurately measure 2.5 mL (1×10 -4mol / L) of 5,5'-dimethyl-2,2'-bipyridine stock solution was transferred to a 5 mL volumetric flask and fixed to volume with HCOOH:H2O=1:1 mixture to obtain 5×10 -5 mol / L stock solution of 5,5'-dimethyl-2,2'-bipyridine to be tested under UV.

[0098] 2. Use an analytical balance to weigh 0.0013 g of benzoic acid [2,4] and place it in a 1.5 mL centrifuge tube. Use a pipette to accurately measure 0.15 mL of HCOOH:H2O = 1:1 mixed solution to dissolve it, and obtain 1×10 -2 mol / L containing benzyl cucurbitacin [2,4] main solution.

[0099] 3. Use a pipette to accurately measure 3.0 mL of 5×10 -5 mol / L 5,5'-dimethyl-2,2'-bipyridine stock solution was placed in a cuvette and UV measurement was performed in the form of a main drop (5uL / time). Figure 4 It can be seen that with the addition of the phenyl cucurbit ring [2,4], the ultraviolet absorption of 5,5'-dimethyl-2,2'-bipyridine weakened and its absorption wavelength red-shifted, indicating that they underwent host-guest interaction.

[0100] Attached Figure 4 : UV detection diagram of 5,5'-dimethyl-2,2'-bipyridine by benzyl cucurbitacin [2,4]: Among them, 5,5'-dimethyl-2,2'-bipyridine has the strongest UV absorption. After adding benzyl cucurbitacin [2,4], the absorption weakens and its absorption wavelength red-shifts.

[0101] Example 3

[0102] The nuclear magnetic resonance detection of 5,5'-dimethyl-2,2'-bipyridine by a benzene-cucurbit ring-containing compound in this embodiment is as follows:

[0103] Weigh 0.0041 g of 5,5'-dimethyl-2,2'-bipyridine with an analytical balance and place it in a NMR tube. Use a pipette to draw 0.5 mL of HCOOH:D2O=1:1 into the NMR tube to obtain 5×10 -2 mol / L 5,5'-dimethyl-2,2'-bipyridine stock solution, and weigh out 5 0.0087g of benzoic acid [2,4] separately, and perform NMR determination of 5,5'-dimethyl-2,2'-bipyridine in the form of main (0.0087g / time) drops. Figure 5 It can be seen that with the addition of the benzocucurbitacin [2,4]-containing ring, the chemical shifts of 5,5'-dimethyl-2,2'-bipyridine and the benzocucurbitacin [2,4]-containing ring changed, indicating that they underwent host-guest interaction.

[0104] Attached Figure 5 : NMR detection image of 5,5'-dimethyl-2,2'-bipyridine containing benzocucurbitacin [2,4]: The bottom is the NMR hydrogen spectrum of 5,5'-dimethyl-2,2'-bipyridine, and 5,5'-dimethyl-2,2'-bipyridine was measured from bottom to top with benzocucurbitacin [2,4] (0.0087g / time).

[0105] Example 4

[0106] The adsorption performance of a benzene cucurbitacin-containing compound of this embodiment on solid iodine vapor is as follows:

[0107] Weigh 20 mg of benzocaproic acid [2,4] with an analytical balance and place it in an open glass bottle, then weigh and record the weight. Place it and 100 mg of solid iodine in a glass bottle with a cap, tighten the cap, and place the glass bottle in a 70°C oven for adsorption. Take out the glass bottle at regular intervals, let it cool to room temperature, take out the open glass bottle, weigh and record the weight until the mass no longer changes. Plot the graph with time as the horizontal axis and adsorption capacity as the vertical axis. Figure 6 ,Depend on Figure 6 It can be seen that in the first 2.5 hours of adsorption, the adsorption rate of iodine vapor by benzyl cucurbitacin [2,4] increased rapidly; the adsorption rate increased slowly from 2.5 to 5.0 hours; after 5.0 hours, the adsorption of iodine vapor by benzyl cucurbitacin [2,4] did not change significantly, indicating that the adsorption of iodine vapor by the adsorbent benzyl cucurbitacin [2,4] reached equilibrium in about 5.0 hours and could maintain relative adsorption stability for 20 hours.

[0108] The adsorption formula of solid iodine vapor by benzene-containing rings [2,4] is:

[0109]

[0110] Where: q s is the mass of iodine captured by benzocuculline [2,4] (g·g -1 ); m0 is the mass of the benzene ring [2,4] at the initial moment (g); m n is the mass (g) of the benzoic acid ring [2,4] at a certain moment.

[0111] Color comparison of benzene ring [2,4] before and after adsorption Figure 8 As shown (the left picture is before adsorption, and the right picture is after adsorption).

[0112] Attached Figure 6 : The adsorption performance diagram of solid iodine vapor containing benzene cucurbitacin [2,4] is plotted with time as the horizontal axis and adsorption capacity as the vertical axis to obtain the adsorption performance diagram of solid iodine vapor containing benzene cucurbitacin [2,4].

[0113] Example 5

[0114] The adsorption performance of a benzene cucurbitacin-containing compound of this embodiment on iodine in an iodocyclohexane solution is as follows:

[0115] At a mass concentration of 100 mg·L -1 In the iodine cyclohexane solution (where the elemental iodine impurity concentration is 90-110 mg·L -1 ), add 20 mg of benzene cucurbitacin [2,4] as adsorbent, and observe the color change trend of iodocyclohexane solution as the adsorption time increases ( Figure 7 ).Depend on Figure 7 It can be seen that the color of the iodocyclohexane solution was pink at first. As the adsorption time increased, the color of the solution gradually became lighter. When the adsorption time reached 24 hours, the color basically disappeared. This result shows that the iodine adsorption of the cyclohexane solution containing benzene ring [2,4] was basically complete at 24 hours.

[0116] Attached Figure 7 : Color change diagram of iodine adsorption in iodocyclohexane solution containing benzoic acid [2,4]: the color gradually becomes lighter from left to right.

[0117] Finally, it should be noted that the terms "comprises," "includes," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements that are inherent to such process, method, article, or apparatus.

[0118] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0119] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A benzene-containing cucurbitacin compound, characterized in that: The structural formula of the benzene cucurbitacin-containing compound is shown in Formula 4:

2. A benzene-containing cucurbitacin compound according to claim 1, characterized in that, The chemical composition formula of the benzene cucurbitacin compound is C 40 H 36 N 16 O8, molecular weight 868.83200; The benzene cucurbitacin-containing compound is in the form of a white solid and is soluble in at least one of the organic solvents formic acid, acetic acid and trifluoroacetic acid.

3. A method for preparing a benzene-containing cucurbitacin compound as claimed in claim 1 or 2, characterized in that, The preparation method comprises: Add KCNO to the aqueous solution of compound 1 and react for a period of time to obtain a reaction solution; The reaction solution is subjected to solid-liquid separation, and the obtained solid is washed and dried to obtain compound 2; The compound 2 is dissolved in formic acid, and then water and glyoxal are added to perform a reflux reaction, followed by solid-liquid separation, liquid spin drying, washing and drying to obtain a compound 3; The compound 3 is dissolved in hydrochloric acid, and then a formaldehyde solution is added for reflux reaction to obtain a mixed solution; separating the benzene-containing cucurbitacin compound from the mixed solution; Wherein, the structural formulas of the compound 1, the compound 2 and the compound 3 are shown in Formulas 1 to 3 respectively:

4. A method for preparing a benzene-containing cucurbitacin compound according to claim 3, characterized in that, The step of adding KCNO to the aqueous solution of compound 1 and reacting for a period of time to obtain a reaction solution specifically comprises: Add KCNO to the aqueous solution of compound 1 and react for 72±2h to obtain a reaction solution; In the aqueous solution of the compound 1, the concentration of the compound 1 is 0.1±0.01 mol / L; The molar ratio of the compound 1 to the KCNO is 12:105.

5.

5. A method for preparing a benzene-containing cucurbitacin compound according to claim 3, characterized in that, The reaction solution is subjected to solid-liquid separation, and the obtained solid is washed and dried to obtain compound 2, which specifically includes: The reaction solution was subjected to solid-liquid separation, and the obtained solid was washed with water and acetone in sequence, and dried to obtain compound 2.

6. A method for preparing a benzene-containing cucurbitacin compound according to claim 3, characterized in that: The compound 2 is dissolved in formic acid, and then water and glyoxal are added for reflux reaction, followed by solid-liquid separation, liquid spin drying, washing and drying to obtain compound 3, which specifically includes: The compound 2 is dissolved in formic acid and then water is added at 98-102° C. for reflux reaction, and then glyoxal is added for reflux reaction for 5±0.5h, and then solid-liquid separation is performed after cooling, and the liquid is spin-dried and washed with water, and dried to obtain compound 3; Wherein, the molar ratio of the compound 2 to the glyoxal is 14.6:29.

3.

7. A method for preparing a benzene-containing cucurbitacin compound according to claim 3, characterized in that: The compound 3 is dissolved in hydrochloric acid, and then a formaldehyde solution is added for reflux reaction to obtain a mixed solution, which specifically includes: The compound 3 is dissolved in 9 mol / L hydrochloric acid, and then a formaldehyde solution is added to react under reflux at 98-102° C. for 5-7 hours to obtain a mixed solution; Wherein, the molar ratio of the compound 3 to formaldehyde is 1:

2.

8. A method for preparing a benzene-containing cucurbitacin compound according to claim 3, characterized in that: The method of separating the benzene-containing cucurbitacin compound from the mixed solution specifically comprises: Adding formic acid to the mixed solution to dissolve the solid precipitated in the reaction mixed solution, and then adding silica gel and spinning to obtain a mixture; The mixture is loaded into a silica gel column, eluted with a formic acid:acetic acid solution with a volume ratio of 1:1.8, separated and spin-dried to obtain a crude product of the benzene cucurbitacin-containing compound; Wash the crude product of the benzene cucurbitacin compound with an acetone:water solution in a volume ratio of 1:1, centrifuge and spin-dry the solid; The spin-dried solid was recrystallized with 9 mol / L hydrochloric acid and then filtered. The solid was washed with water and then dried to obtain a benzene cucurbitacin-containing compound.

9. A method for preparing a benzene-containing cucurbitacin compound according to claim 8, characterized in that, The mass ratio of the silica gel to the compound 3 is 13:3.0046.

10. Use of a benzene cucurbit ring-containing compound as claimed in claim 1 or 2 as a detection reagent or impurity adsorbent for or in the preparation of pyridine compounds.

Images