A nine-membered macrocyclic compound, and a preparation method and application thereof

Abstract

The application provides a nine-membered macrocyclic compound, belongs to the technical field of macrocyclic compounds, and is named as a cucurbit[3,6] containing benzene, which is a gourd-shaped compound formed by connecting 3 benzene monomers and 6 urea monomers through 18 methylene-CH2-bridges. 60 H 54 N 24 O 12 The chemical composition general formula of the cucurbit[3,6] containing benzene is C 60 H 54 N 24 O 12 1303.24800, the cucurbit[3,6] containing benzene is white solid, and is dissolved in at least one of organic solvents dimethyl sulfoxide, formic acid, acetic acid and trifluoroacetic acid. The application further provides a preparation method and application of the nine-membered macrocyclic compound.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of macrocyclic compounds, and particularly relates to a nine-membered macrocyclic compound and a preparation method and application thereof. BACKGROUND

[0002] Supramolecular chemistry is a newly emerging discipline, which is first proposed by a French scientist Jean-Marie Lehn. Unlike molecular chemistry, supramolecular chemistry studies the chemistry of intermolecular bonds, and covers the structure and function of entities formed by the combination of two or more chemical substances, and mainly studies the interaction between non-covalent bonds. Crown ether, cyclodextrin, calixarene and pillararene are main bodies in supramolecular chemistry, and cucurbituril is a macrocyclic compound studied after them, and is also a main body in supramolecular chemistry studied in recent years. Supramolecular chemistry studies the science of intermolecular non-covalent bond interaction, and mainly studies molecular recognition, molecular self-assembly, supramolecular reaction and catalysis, molecular transport, carrier design and supramolecular devices, and these macrocyclic molecules are hotspots in the cross-research of chemistry, materials, biology and physics. SUMMARY

[0003] In order to obtain a novel macrocyclic compound, the application provides a nine-membered macrocyclic compound, which is a white solid, is soluble in organic solvents dimethyl sulfoxide, formic acid, acetic acid and trifluoroacetic acid, can be used for detecting pyridine compounds, and has adsorption performance and can be used for adsorbing impurities.

[0004] The application further provides a preparation method and application of the nine-membered macrocyclic compound.

[0005] The application is achieved by the following technical scheme:

[0006] The application provides a nine-membered macrocyclic compound, which is named as benzene-containing cucurbit[3,6], and a structural formula of the benzene-containing cucurbit[3,6] is shown as formula 4.

[0007]

[0008] Further, a chemical composition general formula of the benzene-containing cucurbit[3,6] is C 60 H 54 N 24 O 12 , and a molecular weight is 1303.24800.

[0009] The benzene-containing cucurbit[3,6] is a white solid, and is soluble in at least one of organic solvents dimethyl sulfoxide, formic acid, acetic acid and trifluoroacetic acid.

[0010] Based on the same inventive concept, the present application provides a preparation method of a nine-membered macrocyclic compound, which comprises:

[0011] KCNO is added to an aqueous solution of compound 1, and the reaction is carried out 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] Compound 2 is dissolved in formic acid, and then water and glyoxal are added to carry out a reflux reaction, followed by solid-liquid separation, liquid spin-drying, washing and drying to obtain compound 3;

[0014] Compound 3 is dissolved in hydrochloric acid, and then a formaldehyde solution is added to carry out a reflux reaction to obtain a mixed solution;

[0015] A benzoguacol[3,6] containing compound is separated from the mixed solution;

[0016] The structural formulae of compound 1, compound 2 and compound 3 are shown in formulae 1-3, respectively:

[0017]

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

[0019] KCNO is added to the aqueous solution of compound 1, and the reaction is carried out for 72±2h to obtain a reaction solution;

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

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

[0022] Further, the step of subjecting the reaction solution to solid-liquid separation, washing and drying the obtained solid to obtain compound 2 specifically comprises:

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

[0024] Further, the step of dissolving compound 2 in formic acid, then adding water and glyoxal to carry out a reflux reaction, and then subjecting to solid-liquid separation, liquid spin-drying, washing and drying to obtain compound 3 specifically comprises:

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

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

[0027] Further, the compound 3 is dissolved in hydrochloric acid, and then a formaldehyde solution is added to carry out a reflux reaction to obtain a mixed solution, and the specific steps include:

[0028] The compound 3 is dissolved in 9 mol / L hydrochloric acid, and then a formaldehyde solution is added to carry out a reflux reaction at 98-102 DEG C for 9-10 h to obtain a mixed solution.

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

[0030] Further, the benzocyclophane [3,6] is separated from the mixed solution, and the specific steps include:

[0031] Formic acid is added to the mixed solution to dissolve solid substances, and then silica gel is spin-dried to obtain a mixture.

[0032] The mixture is loaded on a silica gel column, and then a formic acid:acetic acid solution with a volume ratio of 1:1.5 is used for elution, and the benzocyclophane [3,6] crude product is separated and spin-dried.

[0033] The benzocyclophane [3,6] crude product is washed with an acetone:water solution with a volume ratio of 1:1, and then centrifuged, and the solid is spin-dried.

[0034] Trifluoroacetic acid is added to the spin-dried solid, and then centrifuged, and the supernatant is spin-dried, and then washed with 1 mol / L NaOH aqueous solution, and stirred for 4-5 h; and then centrifuged, washed and dried to obtain the benzocyclophane [3,6].

[0035] Preferably, the added amount of the silica gel is 4-5 times of the total mass of the mixed solution after removing the solvent.

[0036] Further, the mass ratio of the silica gel to the compound 3 is 7:1.5008.

[0037] Based on the same inventive concept, the application further provides an application of the nine-membered macrocyclic compound in a detection reagent or an impurity adsorbent for pyridine compounds or preparation of the pyridine compounds.

[0038] The one or more technical solutions in the embodiments of the application have at least the following technical effects or advantages:

[0039] The present application is a nine-membered macrocyclic compound, named as containing cucurbit[3,6], which is a gourd-shaped compound formed by 3 benzene ring monomers and 6 urea monomers through 18 methylene-CH2-bridges, and the chemical composition general formula is C 60 H 54 N 24 O 12 , and the molecular weight is 1303.24800; the containing cucurbit[3,6] is white solid, soluble in organic solvents dimethyl sulfoxide, formic acid, acetic acid and trifluoroacetic acid, and the product composition is accurately confirmed by mass spectrometry, nuclear magnetic resonance and single crystal structure, the containing cucurbit[3,6] can be used for detecting pyridine compounds, and the compound has adsorption performance and can be used for adsorbing impurities. BRIEF DESCRIPTION OF DRAWINGS

[0040] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0041] Figure 1 The mass spectrum of the containing cucurbit[3,6] in deuterated trifluoroacetic acid. 1 H, 13 C nuclear magnetic resonance spectrum.

[0042] Figure 2 The mass spectrum of the containing cucurbit[3,6].

[0043] Figure 3 The single crystal structure diagram of the containing cucurbit[3,6].

[0044] Figure 4 The ultraviolet detection diagram of the containing cucurbit[3,6] on 5,5'-dimethyl-2,2'-dipyridine.

[0045] Figure 5 The adsorption performance diagram of the containing cucurbit[3,6] on solid iodine vapor.

[0046] Figure 6 The adsorption color change diagram of the containing cucurbit[3,6] on iodine in iodine cyclohexane solution.

[0047] Figure 7 The color comparison diagram of the containing cucurbit[3,6] before and after iodine adsorption. DETAILED DESCRIPTION

[0048] The advantages and various effects of the present application will be more clearly presented hereinafter in conjunction with specific embodiments and examples. Those skilled in the art should understand that these embodiments and examples are used to illustrate the present application, rather than limit the present application.

[0049] Throughout the specification, unless otherwise specifically indicated, the terms used herein are to be understood in the manner as commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as generally understood by those skilled in the art to which the present application pertains. If there is a conflict, the present specification takes precedence.

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

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

[0052] The present application is a preparation method of a benzocyclophane compound, and the preparation method comprises:

[0053] S1. KCNO is added to an aqueous solution of compound 1, and the reaction is carried out for a period of time to obtain a reaction liquid;

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

[0055] S3. Compound 2 is dissolved in formic acid, and then water and glyoxal are added to carry out a reflux reaction, and then subjected to solid-liquid separation, liquid spin-drying, washing and drying to obtain compound 3;

[0056] S4. Compound 3 is dissolved in hydrochloric acid, and then a formaldehyde solution is added to carry out a reflux reaction to obtain a mixed solution;

[0057] S5. A benzocyclophane [3,6] is separated from the mixed solution.

[0058] In the benzocyclophane [3,6] of the present application, the first number in the square brackets represents the number of benzene in the macrocycle, and the second number represents the number of glycoluril in the macrocycle.

[0059] Step S1 specifically comprises:

[0060] KCNO is added to an aqueous solution of compound 1, and the reaction is carried out for 72±2h to obtain a reaction liquid;

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

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

[0063] In the present application, the purpose of adding KCNO to the aqueous solution of compound 1 for reaction is to make compound 1 react to generate compound 2, and the molar ratio of compound 1 to KCNO is 12:105.5, which has the advantage of ensuring that compound 1 is as completely reacted as possible.

[0064] Step S2 specifically includes:

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

[0066] In the present application, 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] After compound 2 is dissolved in formic acid, water is added for reflux reaction at 98-102℃, then glyoxal is added for reflux reaction for 5±0.5h, and after cooling, solid-liquid separation is performed, the liquid is spin-dried, then washed with water, and dried to obtain compound 3;

[0069] The molar ratio of compound 2 to glyoxal is 14.6:29.3.

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

[0071] Step S4 specifically includes:

[0072] Compound 3 is dissolved in 9mol / L hydrochloric acid, then a formaldehyde solution is added for reflux reaction at 98-102℃ for 9-10h to obtain a mixed solution;

[0073] The molar ratio of compound 3 to formaldehyde is 1:2.

[0074] In the present application, the molar ratio of compound 3 to formaldehyde is 1:2, which has the advantage of making compound 3 completely react to generate compound 4.

[0075] Step S5 specifically includes:

[0076] Formic acid is added to the mixed solution to dissolve solid substances, then silica gel is added and spin-dried to obtain a mixture;

[0077] The mixture is packed into a silica gel column, eluted with a formic acid:acetic acid solution in a volume ratio of 1:1.5, and separated and spin-dried to obtain a benzocyclophospha[3,6] crude product;

[0078] The benzocyclophospha[3,6] crude product is washed with an acetone:water solution in a volume ratio of 1:1, and after centrifugation, the solid is spin-dried;

[0079] To the solid after rotary evaporation, trifluoroacetic acid was added, and then centrifuged, and the liquid was rotary evaporated and washed with 1 mol / L NaOH aqueous solution, stirred for 4-5 h; and then centrifuged, washed and dried to obtain a benzocyclophane [3, 6].

[0080] In the present application, the advantages of using a volume ratio of 1:1.5 formic acid: acetic acid solution for elution are that the benzocyclophane [3, 6] is fully dissolved and separated cleanly on the silica gel column.

[0081] In the present application, the benzocyclophane [3, 6] is separated from other points far away from the column, and the column chromatography stationary phase is silica gel.

[0082] The nine-membered macrocyclic compound, the preparation method and application thereof will be described in detail below with reference to examples and experimental data.

[0083] Example 1

[0084] The preparation method of the nine-membered macrocyclic compound in this example comprises the following steps:

[0085] 1. As shown in formula 5, compound 1 (6.2169 g, 12.0 mmol) was weighed into a 250 mL round-bottom flask, 120 mL H2O was added, and the compound 1 was stirred at room temperature until it was completely dissolved. Then KCNO (8.5572 g, 105.5 mmol) was added, and the resulting mixture was stirred at room temperature for 72 h. Centrifugation, the solid was washed with H2O (3 x 40 mL) and acetone (3 x 40 mL), and dried to obtain compound 2: 4.1844 g, yield 95.15%. mp. 341-342℃ (dec); 1 H NMR (400 MHz, CF3CO2D) δ 7.41 (s, 2H), 4.59 (s, 8H); 13 C NMR (100 MHz, CF3CO2D) δ 163.25, 137.01, 132.58, 43.95; HRMS Ca lcdfor C 14 H 22 N8O4 (M+Na): 389.1662; found: 389.1668.

[0086]

[0087] 2. As in Formula 6, weigh compound 2 (5.3637 g, 14.6 mmol) into a 1000 mL round bottom flask, add HCOOH (250 mL), stir at 98-102 °C until compound 2 is completely dissolved, quickly add H2O (324 mL), stir at reflux until the temperature of the reaction system rises to 98-102 °C, then add 40 wt% aqueous glyoxal solution (3.36 mL, 29.3 mmol), reflux for 5 h. Cool, put in the refrigerator overnight, centrifuge, wash the liquid with H2O (3 x 40 mL) after drying, and dry to obtain compound 3: 2.0342 g, yield 33.86%. mp. 353-354 °C (dec); 1 H NMR (400 MHz, CF3CO2D) δ 7.35 (s, 2H), 5.78 (d, J = 8.0 Hz, 2H), 5.66 (d, J = 8.0 Hz, 2H), 4.83 (d, J = 16.0 Hz, 4H), 4.52 (d, J = 16.0 Hz, 4H); 13 C NMR (100 MHz, CF3CO2D) δ 163.68, 138.59, 133.16, 77.26, 64.73, 47.29; HRMS CaIc for C 18 H 18 N8O4 (M+H): 411.1529; found: 411.1526.

[0088]

[0089] 3. As in Formula 7, weigh compound 3 (1.5008 g, 3.65 mmol) into a 50 mL round bottom flask, add 9 mol / L HC1 (8.130 mL), stir at 98-102 °C until compound 3 is completely dissolved, then add 37-40% aqueous HCHO solution (480 uL), stir at reflux for 10 h. After the reaction is completed, add 20 mL HCOOH to the reaction solution to completely dissolve the reaction mixture, add 7 g of silica gel and spin dry, elute with a volume ratio of 1:1.5 formic acid: acetic acid solution, separate and spin dry to obtain a crude product containing benzocyclophane [3,6]. Wash the crude product containing benzocyclophane [3,6] with a volume ratio of 1:1 acetone: water solution (3 x 40 mL), spin dry the solid after centrifugation. Add trifluoroacetic acid (4 mL) to the solid, centrifuge, spin dry the liquid after washing with 1 mol / L aqueous NaOH solution (30 mL), stir for 5 h. Centrifuge, wash the solid with CH3OH (3 x 10 mL), centrifuge, and dry the solid to obtain product 4: 0.0682 g, yield 4.30%. mp. 341-342 °C (dec); 1H NMR (400 MHz, CF3CO2D) δ 7.32 (s, 6H), 6.07 (d, J = 16.0 Hz, 6H), 5.63 (s, 12H), 4.77 (d, J = 16.0 Hz, 12H), 4.56 (d, J = 16.0 Hz, 12H), 4.46 (d, J = 16.0 Hz, 6H); 13 CNMR (100 MHz, CF3CO2D) δ 159.91, 137.63, 133.40, 72.87, 72.09, 53.89, 47.80; HRMS Ca lcd for C 60 H 54 N 24 O 12 (M+Na): 1325.4251; found: 1325.4242.

[0090]

[0091] Figure 1 : Mass spectrum results for cucurbit[3,6]arene-containing: HRMS Ca lcd for C 1 H, 13 C nuclear magnetic resonance spectrum: 1 H NMR (400 MHz, CF3CO2D) δ 7.32 (s, 6H), 6.07 (d, J = 16.0 Hz, 6H), 5.63 (s, 12H), 4.77 (d, J = 16.0 Hz, 12H), 4.56 (d, J = 16.0 Hz, 12H), 4.46 (d, J = 16.0 Hz, 6H); 13 C NMR (100 MHz, CF3CO2D) δ 159.91, 137.63, 133.40, 72.87, 72.09, 53.89, 47.80.

[0092] Figure 2 : Mass spectrum results for cucurbit[3,6]arene-containing: HRMS Ca lcd for C 60 H 54 N 24 O 12 (M+Na): 1325.4251; found: 1325.4242.

[0093] Figure 3 : Single crystal structure of cucurbit[3,6]arene-containing: CCDC 2380524, color: C, gray; H, green; N, blue; O, red.

[0094] Example 2

[0095] The embodiment is a kind of nine-membered macrocyclic compound for the ultraviolet detection of 5,5'-dimethyl-2,2'-dipyridine, as follows:

[0096] 1. 0.0018 g of 5,5'-dimethyl-2,2'-dipyridine was weighed with an analytical balance and placed in a 5 mL centrifuge tube. After dissolving with 1 mL of HCOOH:H2O = 1:1 mixture, it was transferred to a 10 mL volumetric flask and diluted with HCOOH:H2O = 1:1 mixture to obtain a 1 × 10 -3 mol / L 5,5'-dimethyl-2,2'-dipyridine stock solution; 0.5 mL (1 × 10 -3 mol / L) of 5,5'-dimethyl-2,2'-dipyridine stock solution was accurately measured with a pipette and transferred to a 5 mL volumetric flask and diluted with HCOOH:H2O = 1:1 mixture to obtain a 1 × 10 -4 mol / L 5,5'-dimethyl-2,2'-dipyridine stock solution; 2.5 mL (1 × 10 -4 mol / L) of 5,5'-dimethyl-2,2'-dipyridine stock solution was accurately measured with a pipette and transferred to a 5 mL volumetric flask and diluted with HCOOH:H2O = 1:1 mixture to obtain a 5 × 10 -5 mol / L 5,5'-dimethyl-2,2'-dipyridine stock solution; 2.5 mL (1 × 10

[0097] 2. 0.0013 g of benzoguarel [3,6] was weighed with an analytical balance and placed in a 1.5 mL centrifuge tube. 0.10 mL of HCOOH:H2O = 1:1 mixture was accurately measured with a pipette to dissolve, which obtained a 1 × 10 -2 mol / L benzoguarel [3,6] host solution.

[0098] 3. 3.0 mL of 5 × 10 -5 mol / L 5,5'-dimethyl-2,2'-dipyridine stock solution was accurately measured with a pipette and placed in a cuvette for ultraviolet determination in the form of host (6 uL / each) drop guest. From Figure 4 It can be seen that with the addition of benzoguarel [3,6], the ultraviolet absorption of 5,5'-dimethyl-2,2'-dipyridine is enhanced, indicating that they have host-guest interaction.

[0099] Appendix Figure 4 : Ultraviolet detection diagram of benzoguarel [3,6] for 5,5'-dimethyl-2,2'-dipyridine: the ultraviolet absorption of 5,5'-dimethyl-2,2'-dipyridine is the weakest, and the absorption is enhanced after the addition of benzoguarel [3,6].

[0100] Example 3

[0101] The adsorption performance of a nine-membered macrocyclic compound of this embodiment on solid iodine vapor is as follows:

[0102] Weigh 20 mg of benzoguanidine [3,6] with an analytical balance and place it in an open glass bottle. Weigh and record the weight. Place it and 100 mg of solid iodine in a glass bottle with a cap. After tightening the cap, place the glass bottle in a 70°C oven for adsorption. Take out the glass bottle at regular intervals and let it cool to room temperature. Then 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 5 ,Depend on Figure 5 It can be seen that in the first 10.0h of adsorption, the adsorption rate of iodine vapor by benzyl cucurbitacin [3,6] increased rapidly; the adsorption rate increased slowly from 10.0h to 20.0h; after 20.0h, the adsorption rate of iodine vapor by benzyl cucurbitacin [3,6] did not change significantly, indicating that the adsorption of iodine vapor by the adsorbent benzyl cucurbitacin [3,6] reached equilibrium at around 20.0h and could maintain relative adsorption stability for 40h.

[0103] The adsorption capacity of solid iodine vapor by benzene-containing cucurbitacin [3,6] is as follows:

[0104]

[0105] Where: q s is the mass of iodine captured by cucurbitacin[3,6] (g·g -1 ); m0 is the mass of the benzene-containing ring [3,6] at the initial moment (g); m n is the mass (g) of the benzene-containing cucurbitacin [3,6] at a certain moment.

[0106] Color comparison of benzene ring [3,6] before and after adsorption Figure 7 As shown (the left picture is before adsorption, and the right picture is after adsorption).

[0107] Attachment Figure 5 :The adsorption performance diagram of solid iodine vapor containing benzene cucurbitacin [3,6] 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 [3,6].

[0108] Example 4

[0109] The adsorption performance of a nine-membered macrocyclic compound of this embodiment on iodine in iodocyclohexane solution is as follows:

[0110] At a mass concentration of 30 mg·L -1 In the iodine cyclohexane solution (where the elemental iodine impurity concentration is 25-35 mg·L -1), 4 mg of cucurbit[3,6]uril was added as adsorbent, and the color change trend of the iodine cyclohexane solution was observed (see Fig. 4) as the adsorption time increased. Figure 6 As can be seen from Fig. 4, the color of the iodine cyclohexane solution was pink at the beginning, and the color of the solution gradually became lighter as the adsorption time increased. When the adsorption time reached 4.0 h, the color basically disappeared, which indicated that the cucurbit[3,6]uril was basically completely adsorbed to the iodine in the cyclohexane solution at 4 h. Figure 6

[0111] The color change of the iodine cyclohexane solution caused by the adsorption of cucurbit[3,6]uril to iodine is shown in Fig. 4. From left to right, the color gradually became lighter. Figure 6

[0112] Finally, it is also necessary to note that the terms "comprising", "containing", or any other similar term are intended to encompass non-exclusive inclusions, such that a process, method, article, or apparatus that comprises a list of elements does not necessarily include only those elements, but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0113] Although preferred embodiments of the present application have been described, those skilled in the art will be able to make additional changes and modifications to these embodiments once they have the benefit of the present disclosure. Therefore, the appended claims are intended to cover all such changes and modifications that fall within the scope of the present application.

[0114] Obviously, those skilled in the art can make various modifications and variations to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is also intended to include these modifications and variations.​​

Claims

1. A nine-membered macrocyclic compound, characterized in that The nine-membered macrocyclic compound is named as benzene-containing cucurbitacin [3,6], and the structural formula of the benzene-containing cucurbitacin [3,6] is shown in Formula 4: The chemical composition formula of the benzene-containing cucurbitacin [3,6] is C 60 H 54 N 24 O 12 , molecular weight is 1303.24800.

2. A nine-membered macrocyclic compound according to claim 1, characterized in that The benzene-containing cucurbitacin [3,6] is in the form of a white solid and is soluble in at least one of the organic solvents dimethyl sulfoxide, formic acid, acetic acid and trifluoroacetic acid.

3. The method for preparing a nine-membered macrocyclic compound according to claim 1 or 2, wherein: 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 carry out reflux reaction, followed by solid-liquid separation, liquid spin drying, washing and drying to obtain compound 3; Dissolving the compound 3 in hydrochloric acid, and then adding formaldehyde solution to carry out reflux reaction to obtain a mixed solution; Separating the benzene-containing cucurbitacin [3,6] 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. The method for preparing a nine-membered macrocyclic compound according to claim 3, wherein 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: KCNO was added to the aqueous solution of compound 1 and reacted for 72±2 h to obtain a reaction solution; In the aqueous solution of compound 1, the concentration of compound 1 is 0.1±0.01 mol / L; The molar ratio of the compound 1 to the KCNO is 12:105.

5.

5. The method for preparing a nine-membered macrocyclic compound according to claim 3, wherein: The reaction solution is subjected to solid-liquid separation, and the obtained solid is washed and dried to obtain compound 2. The specific steps include: 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. The method for preparing a nine-membered macrocyclic compound according to claim 3, wherein: The compound 2 is dissolved in formic acid, and then water and glyoxal are added to carry out reflux reaction, and then solid-liquid separation, liquid spin drying, washing and drying are carried out to obtain compound 3, which specifically includes: Compound 2 was dissolved in formic acid and then refluxed with water at 98-102° C., followed by glyoxal addition and reflux reaction for 5±0.5 h. After cooling, solid-liquid separation was performed, the liquid was spin-dried, 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. The method for preparing a nine-membered macrocyclic compound according to claim 3, wherein: The compound 3 is dissolved in hydrochloric acid, and then formaldehyde solution is added for reflux reaction to obtain a mixed solution, which specifically includes: The compound 3 was dissolved in 9 mol / L hydrochloric acid, and then a formaldehyde solution was added and refluxed at 98-102° C. for 9-10 hours to obtain a mixed solution; Wherein, the molar ratio of the compound 3 to formaldehyde is 1:

2.

8. The method for preparing a nine-membered macrocyclic compound according to claim 3, wherein: The method of separating the benzene-containing cucurbitacin [3,6] from the mixed solution specifically comprises: Formic acid was added to the mixed solution to dissolve the solid matter, and then silica gel was added and spin-dried to obtain a mixture; The mixture was loaded onto a silica gel column, eluted with a formic acid:acetic acid solution with a volume ratio of 1:1.5, separated and spin-dried to obtain a crude product containing phenylcucurbitacin [3,6]; The crude product containing phenylcucurbitacin [3,6] was washed with acetone:water in a volume ratio of 1:1, centrifuged and the solid was dried by spin drying; Trifluoroacetic acid was added to the spin-dried solid, followed by centrifugation. The supernatant was then spin-dried and washed with a 1 mol / L NaOH aqueous solution and stirred for 4-5 hours. After centrifugation, washing, and drying, the benzene-containing cucurbitacin was obtained [3,6].

9. The method for preparing a nine-membered macrocyclic compound according to claim 8, wherein: The mass ratio of the silica gel to the compound 3 is 7:1.5008.

10. Use of the nine-membered macrocyclic compound according to claim 1 or 2 as a detection reagent for pyridine compounds or an impurity adsorbent or iodine adsorbent for pyridine compounds or in the preparation of such a reagent.

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