A compound containing benzene cucurbitacin and its preparation method and application

Abstract

The present invention provides a benzene-cucurbit ring compound, which belongs to the technical field of macrocyclic compounds. The benzene-cucurbit ring compound is a cage-shaped compound formed by two benzene ring monomers and four glycoside urea monomers connected by 12 methylene-CH2-bridges, and the general chemical formula is C 40 H 36 N 16 O8, with a molecular weight of 868.83200, is a white solid soluble in the organic solvents formic acid, acetic acid, and trifluoroacetic acid. The product composition was accurately confirmed by mass spectrometry, nuclear magnetic resonance, and single crystal structure. The present invention also provides a preparation method and application of a benzene-containing cucurbitacin compound.

Description

Technical Field

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

[0002] Supramolecular chemistry, an emerging discipline, was first proposed by French scientist Jean-Marie Lehn. Unlike molecular chemistry, supramolecular chemistry studies the chemistry of intermolecular bonds. It encompasses the structure and function of entities formed by the union of two or more chemical species, primarily investigating interactions between non-covalent bonds. Crown ethers, cyclodextrins, calixarenes, and pillararenes are among the most studied entities in supramolecular chemistry. Following these, cucurbitacins, as macrocyclic compounds, have also been the subject of significant supramolecular research in recent years. These macrocyclic molecules are a hot topic of research at the intersection of chemistry, materials science, 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 and soluble in organic solvents such as formic acid, acetic acid and trifluoroacetic acid. It can be used to detect pyridine compounds, and the compound has adsorption properties and can be used for adsorption and impurity removal.

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

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

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

[0007]

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

[0009] The benzene-containing cucurbitacin 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 benzene-containing cucurbitacin compound, 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 carry out reflux reaction, followed by solid-liquid separation, liquid spin drying, washing and drying to obtain compound 3;

[0014] Dissolving the compound 3 in hydrochloric acid, and then adding formaldehyde solution to carry out reflux reaction to obtain a mixed solution;

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

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

[0017]

[0018] Furthermore, 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] KCNO was added to the aqueous solution of compound 1 and reacted for 72±2 h to obtain a reaction solution;

[0020] In the aqueous solution of compound 1, the concentration of 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] Furthermore, 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] Furthermore, 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:

[0025] 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;

[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 formaldehyde solution is added for reflux reaction to obtain a mixed solution, which specifically includes:

[0028] The compound 3 was dissolved in 9 mol / L hydrochloric acid, and then formaldehyde solution was added and refluxed 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] Furthermore, 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 it to obtain a mixture;

[0032] The mixture was loaded onto 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-containing cucurbitacin compound;

[0033] The crude product containing the benzene cucurbitacin compound was washed with an acetone:water solution in a volume ratio of 1:1, centrifuged, and the solid was spin-dried;

[0034] The spin-dried solid was recrystallized with 9 mol / L hydrochloric acid, filtered, washed with water and dried to obtain a benzene-containing cucurbitacin 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 a detection reagent or impurity adsorbent for or in the preparation of 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 compound, named benzene-cucurbit ring [2,4], which is a cage-shaped compound formed by two benzene ring monomers and four glycoside urea monomers connected by 12 methylene -CH2- bridges. The general chemical formula is C 40 H 36 N 16 O8, with a molecular weight of 868.83200, is a white solid that is soluble in organic solvents such as formic acid, acetic acid, and trifluoroacetic acid. The product composition has been 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 is a brief introduction to 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 paying any creative work.

[0040] Figure 1 It is a compound containing phenyl cucurbitacin [2,4] in deuterated trifluoroacetic acid. 1 H, 13 C NMR spectrum.

[0041] Figure 2 The mass spectrometry results of benzocucurbitacin [2,4] are shown.

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

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

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

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

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

[0047] Figure 8 This is a color comparison chart of benzene-containing rings [2,4] before and after iodine adsorption. DETAILED DESCRIPTION

[0048] The present invention will be described in detail below in conjunction with specific embodiments 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 embodiments and examples are for illustrating the present invention, rather than for limiting the present invention.

[0049] Throughout this specification, unless otherwise specified, the terms used herein should be understood as having the same meaning as commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event of any conflict, the present specification shall take 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 provides a method for preparing a benzene-containing cucurbitacin compound, the preparation method comprising:

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

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

[0055] S3. The compound 2 was dissolved in formic acid, and then water and glyoxal were added to reflux, followed by solid-liquid separation, the liquid was spin-dried, washed and dried to obtain compound 3;

[0056] S4. The compound 3 was dissolved in hydrochloric acid, and then a formaldehyde solution was added to reflux to obtain a mixed solution;

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

[0058] The benzene-containing cucurbitacin compound prepared by the present invention is named as benzene-containing cucurbitacin [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] KCNO was added to the aqueous solution of compound 1 and reacted for 72±2 h to obtain a reaction solution;

[0061] In the aqueous solution of compound 1, the concentration of 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 form 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 excess KCNO in the reaction.

[0067] Step S3 specifically includes:

[0068] 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;

[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 of allowing compound 2 to react completely to form compound 3.

[0071] Step S4 specifically includes:

[0072] The compound 3 was dissolved in 9 mol / L hydrochloric acid, and then formaldehyde solution was added and refluxed 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 of allowing compound 3 to react completely to form compound 4.

[0076] Step S5 specifically includes:

[0077] 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;

[0078] The mixture was loaded onto 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-containing cucurbitacin compound;

[0079] The crude product containing the benzene cucurbitacin compound was washed with an acetone:water solution in a volume ratio of 1:1, centrifuged, and the solid was spin-dried;

[0080] The spin-dried solid was recrystallized with 9 mol / L hydrochloric acid, filtered, washed with water and dried to obtain a benzene-containing cucurbitacin 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 cleanly separated on the silica gel column.

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

[0083] The following is a detailed description of a benzene-containing cucurbitacin compound, its preparation method and application in conjunction with examples and experimental data.

[0084] Example 1

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

[0086] 1. As in Formula 5 (where "rt" represents room temperature), compound 1 (6.2169 g, 12.0 mmol) was weighed into a 250 mL round-bottom flask. 120 mL of H₂O was added and stirred at room temperature until compound 1 was completely dissolved. KCNO₂ (8.5572 g, 105.5 mmol) was then added and the resulting mixture was stirred at room temperature for 72 h. The mixture was centrifuged, and the solid was washed with H₂O (3 × 40 mL) and acetone (3 × 40 mL), and dried to yield 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, compound 2 (5.3637 g, 14.6 mmol) was weighed into a 1000 mL round-bottom flask. HCOOH (250 mL) was added and stirred at 98-102°C until compound 2 was completely dissolved. H₂O (324 mL) was quickly added and the reaction mixture was refluxed with stirring until the temperature reached 98-102°C. 40 wt% aqueous glyoxal solution (3.36 mL, 29.3 mmol) was then added and refluxed for 5 h. The mixture was cooled and refrigerated overnight (to allow impurities to precipitate). The solution was centrifuged, the liquid was spin-dried, washed with H₂O (3 x 40 mL), and dried to yield 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 in Formula 7, compound 3 (3.0046 g, 7.3 mmol) was weighed into a 50 mL round-bottom flask. 9 mol / L HCl (16.254 mL) was added and stirred at 98-102°C until compound 3 was completely dissolved. 37-40% aqueous HCHO solution (960 μL) was then added and the mixture was refluxed with stirring for 7 h. After completion of the reaction, 40 mL of HCOOH was added to completely dissolve the reaction mixture. 13 g of silica gel was added and the mixture was spin-dried. The crude product was purified by column chromatography using a 1:1:HCOOH:CH3COOH ratio to obtain crude compound 4. The crude product containing phenylcucurbitacin [2,4] was washed with a 1:1 volume ratio of acetone:water. After centrifugation, the solid was spin-dried and recrystallized from 9 mol / L aqueous HCl. The solid was filtered, washed with water, and then dried to obtain compound 4 (0.7731 g, 24.35% yield). 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] Attachment 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] Attachment Figure 2 : Mass spectrometry results of phenylcucurbitacin [2,4]: HRMS Ca lcd for C 40 H 36 N 16 O8(M+H):869.2980; found:869.2985.

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

[0095] Example 2

[0096] The UV 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 mixture to dissolve it. Transfer it to a 10 mL volumetric flask and add HCOOH:H2O = 1:1 mixture to make up to volume. You can get 1×10 -3 mol / L 5,5'-dimethyl-2,2'-bipyridine stock solution; 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 conditions.

[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 mixture to dissolve it, and then 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 (5uL / time) droplet. Figure 4 It can be seen that with the addition of phenylcucurbitacin [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] Attachment Figure 4 : UV detection diagram of 5,5'-dimethyl-2,2'-bipyridine by benzyl cucurbitacin [2,4]: Among them, the UV absorption of 5,5'-dimethyl-2,2'-bipyridine is the strongest. 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 compound in this embodiment is as follows:

[0103] Weigh 0.0041 g of 5,5'-dimethyl-2,2'-bipyridine using an analytical balance and place it in a nuclear magnetic resonance tube. Use a pipette to draw 0.5 mL of HCOOH:D2O=1:1 into the nuclear magnetic resonance tube to obtain 5×10 -2 mol / L 5,5'-dimethyl-2,2'-bipyridine stock solution, and weighed 5 0.0087g of benzoguanidine [2,4] separately and placed them separately, and the 5,5'-dimethyl-2,2'-bipyridine was measured by nuclear magnetic resonance in the form of main (0.0087g / time) drops. Figure 5 It can be seen that with the addition of phenylcucurbitacin [2,4], the chemical shifts of 5,5'-dimethyl-2,2'-bipyridine and phenylcucurbitacin [2,4] changed, indicating that they underwent host-guest interaction.

[0104] Attachment Figure 5 : NMR detection diagram of 5,5'-dimethyl-2,2'-bipyridine containing phenyl cucurbitacin [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 phenyl cucurbitacin [2,4] (0.0087g / time).

[0105] Example 4

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

[0107] Weigh 20 mg of benzoguanidine [2,4] 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 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 rate 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 cucurbitacin [2,4] is:

[0109]

[0110] Where: q s is the mass of iodine captured by cucurbitacin[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 benzene-containing cucurbitacin [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] Attachment 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-containing cucurbitacin compound on iodine in an iodocyclohexane solution in this embodiment 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], benzene cucurbitacin [2,4] as adsorbent, and observe the color change trend of iodine cyclohexane solution as the adsorption time increases ( Figure 7 ).Depend on Figure 7 It can be seen that the color of the iodine cyclohexane solution is pink at first. As the adsorption time increases, the color of the solution gradually becomes lighter. When the adsorption time reaches 24 hours, the color basically disappears. This result shows that the adsorption of iodine in the cyclohexane solution by benzene-containing ring [2,4] is basically complete within 24 hours.

[0116] Attachment Figure 7 :Color change diagram of iodine adsorption in iodocyclohexane solution containing quinacrine [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 list of elements includes not only those elements, but also other elements not expressly listed, or elements 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 additional 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 may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications fall within the scope of the claims and their equivalents, the present invention is intended to include such changes and modifications.

Claims

1. A benzene-containing cucurbitacin compound, characterized in that, The structural formula of the benzene-containing cucurbitacin 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-containing cucurbitacin compound is C 40 H 36 N 16 O8, molecular weight 868.83200; The benzene-containing cucurbitacin 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 kind of preparation method containing benzene cucurbitacin compound as claimed in claim 1 or 2, is 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 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 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, 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. A method for preparing a benzene-containing cucurbitacin 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, which specifically comprises: 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, 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. A method for preparing a benzene-containing cucurbitacin 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 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, wherein 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 mixed solution, then adding silica gel and spinning it 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 1:1.8, separated and spin-dried to obtain a crude product of the benzene-containing cucurbitacin compound; The crude product containing the benzene cucurbitacin compound was washed with an acetone:water solution in a volume ratio of 1:1, centrifuged, and the solid was spin-dried; 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-containing cucurbitacin compound.

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

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

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