Preparation method of thiosemicarbazone binuclear gallium coordination compound
The thiourea product is generated through the condensation reaction and reacted with gallium nitrate to prepare the thiourea binuclear gallium coordination compound, which solves the problems of fewer synthesis methods and mild reaction conditions in the prior art, and realizes synthesis under moderate conditions suitable for large-scale production, and is determined to be a metal organic MOFs material through scientific testing.
Patent Information
- Application Number
- CN202411840082.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-13
- Publication Date
- 2025-04-08
AI Technical Summary
In the prior art, there are fewer methods for synthesis of thiourea-gallium coordination compounds, and the reaction conditions are usually not mild, making it difficult to apply to large-scale production.
Thiourea compounds are condensed with 2-methyl-1,3-cyclohexanedione to form thiourea products, and react oxidative active hydrogen and gallium nitrate solution to form thiourea binuclear gallium coordination compound. It is determined that it is a metal organic MOFs material by X-ray single crystal diffraction and powder X-ray diffraction test.
The synthesis of thiourea binuclear gallium coordination compound has been achieved under mild conditions, suitable for large-scale production, and it has been determined by scientific testing that it is a metal-organic MOFs material, with good medicinal potential.
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Figure CN119775182A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of inorganic coordination chemistry, and in particular relates to a method for preparing a thiosemicarbazone binuclear gallium coordination compound. Background Art
[0002] Gallium is located in the fourth period, group IIIA of the periodic table. It is the first metal element predicted by theory and later discovered by experiment. In the field of life medicine, gallium is the second most important metal after platinum. It has a long history of research. Its compounds are widely used in the treatment of antibacterial, anti-inflammatory, anti-tumor and bone metabolic diseases. Gallium nitrate is used in the treatment of hypercalcemia caused by clinical tumors.
[0003] Thiosemicarbazone compounds are a class of compounds formed by the condensation of thiosemicarbazone and compounds containing aldehyde or ketone carbonyl groups, and are a special type of Schiff base. Thiosemicarbazone (TSC) is an important class of ligands that provide N and S, and has a wide range of biological activities, including anti-tumor, antibacterial, antiviral and antifungal activities, and can be used to treat a variety of diseases.
[0004] Therefore, the compound of thiosemicarbazone compound coordinated with gallium metal has great medicinal potential. At present, there are few reports on the synthesis method of thiosemicarbazone gallium coordination compound. Therefore, how to obtain a thiosemicarbazone gallium coordination compound with mild reaction conditions and suitable for production and a synthesis method is of great significance. Summary of the invention
[0005] The purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a thiosemicarbazone binuclear gallium coordination compound. The conditions are mild and the operation is easy. First, a thiosemicarbazone compound is subjected to a condensation reaction with 2-methyl-1,3-cyclohexanedione to generate a thiosemicarbazone product; then, active hydrogen is oxidized and a gallium nitrate solution is added to generate a thiosemicarbazone binuclear gallium coordination compound, which is determined to be a metal organic MOFs material by an X-ray single crystal diffraction method and a powder X-ray diffraction (PXRD) test.
[0006] The technical solution to achieve the above object is: a method for preparing a thiosemicarbazone binuclear gallium coordination compound, the synthesis route of the thiosemicarbazone binuclear gallium coordination compound is as follows:
[0007]
[0008] Wherein, R is selected from H, Me or Ph.
[0009] The method for preparing the above-mentioned thiosemicarbazone binuclear gallium coordination compound comprises the following steps:
[0010] S1, placing 2-methyl-1,3-cyclohexanedione and a semicarbazide compound in a molar ratio of 1:2 in a reaction vessel, adding methanol, and then adding an acid as a catalyst, reflux at 60° C. for 6 to 10 hours, washing the filtered solid with methanol several times, and then drying it in an oven at 60° C. to obtain a semicarbazide compound;
[0011] S2, dissolving the thiosemicarbazone compound obtained in step S1 in N,N'-dimethylformamide or methanol to prepare a solution, and stirring at room temperature overnight. When the solution is completely dissolved, the active hydrogen of the carbon atom No. 2 in the six-membered ring of the thiosemicarbazone compound is unstable and thus oxidized to a hydroxyl group;
[0012] S3, adding 1 mol / L gallium nitrate methanol solution to the solution of step S2 with stirring, and continuing stirring until fine crystals or powder are precipitated. After the precipitation is complete, filtering and rinsing the precipitate, and drying the precipitate in an oven at 60° C. to obtain the final product, a semicarbazide binuclear gallium coordination compound.
[0013] In the above-mentioned method for preparing a semicarbazide binuclear gallium coordination compound, in step S1, the amount of 2-methyl-1,3-cyclohexanedione is 5 mmol; the amount of the semicarbazide compound is 10 mmol; the amount of methanol is 30 mL to 50 mL; and the catalyst is glacial acetic acid or hydrochloric acid.
[0014] In the above-mentioned method for preparing a thiosemicarbazone binuclear gallium coordination compound, the amount of methanol used is 50 mL.
[0015] In the above-mentioned method for preparing a thiosemicarbazone binuclear gallium coordination compound, the catalyst is 0.2-1 mL of glacial acetic acid or 0.1 mL of hydrochloric acid.
[0016] In the above-mentioned method for preparing a thiosemicarbazone binuclear gallium coordination compound, in step S2, the thiosemicarbazone compound is dissolved in N,N'-dimethylformamide to prepare a 0.05-0.2 mol / L solution.
[0017] In the above method for preparing a thiosemicarbazone binuclear gallium coordination compound, in step S2, the thiosemicarbazone compound is dissolved in N,N'-dimethylformamide to prepare a 0.1 mol / L solution.
[0018] In the above-mentioned method for preparing a thiosemicarbazone binuclear gallium coordination compound, in step S2, the thiosemicarbazone compound is dissolved in methanol to prepare a 0.1 mol / L solution, and a saturated NaOH methanol solution is added to assist dissolution, and the pH value is adjusted to 8.
[0019] The above-mentioned method for preparing a semicarbazide binuclear gallium coordination compound, wherein step S3 is replaced by the following process: in the solution of step S2, 1 mol / L gallium nitrate methanol solution is added with stirring, and stirring is continued until the mixture is evenly mixed to obtain a clear solution, and then the solution is sealed with a sealing film, and small air-permeable holes are opened on the sealing film, and then the solution is allowed to stand until crystals are precipitated. After the precipitation is complete, the precipitate is filtered and rinsed, and the precipitate is placed in an oven at 60°C to dry the precipitate to obtain the final product, the semicarbazide binuclear gallium coordination compound.
[0020] In the above-mentioned method for preparing a thiosemicarbazone binuclear gallium coordination compound, the amount of 1 mol / L gallium nitrate methanol solution used is 1.5 times the mass of the thiosemicarbazone compound.
[0021] The preparation method of the semicarbazide binuclear gallium coordination compound of the present invention has mild reaction conditions and is suitable for production. The compound is determined to be a metal organic MOFs material through an X-ray single crystal diffraction method and a powder X-ray diffraction (PXRD) test. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 is the H NMR spectrum of compound 1;
[0023] Figure 2 is the coordination environment diagram of the coordination compound G1 (symmetry code Ⅰ in the figure represents: -x+4 / 3, -y+5 / 3, -z+2 / 3);
[0024] Figure 3 is the powder X-ray diffraction pattern of coordination compound G1;
[0025] Figure 4 is the H NMR spectrum of compound 2;
[0026] Figure 5 is the coordination environment diagram of the coordination compound G2 (the symmetry code Ⅰ in the figure represents: -x+2, -y+1, -z+1);
[0027] Figure 6 is the powder X-ray diffraction pattern of coordination compound G2;
[0028] Figure 7 is the H NMR spectrum of compound 3;
[0029] Figure 8 is the coordination environment diagram of the coordination compound G3 (the symmetry code Ⅰ in the figure represents: -x+2, -y, -z+1);
[0030] Fig. 9 This is the powder X-ray diffraction pattern of the coordination compound G3. DETAILED DESCRIPTION
[0031] In order to enable those skilled in the art to better understand the technical solution of the present invention, the specific implementation methods thereof are described in detail below in conjunction with the accompanying drawings:
[0032] Embodiment 1:
[0033] See also Figure 1 , Figure 2 and Figure 3 The synthetic route of the thiosemicarbazone binuclear gallium coordination compound G1 (referred to as coordination compound G1) is as follows:
[0034]
[0035] Wherein, R is H.
[0036] The thiosemicarbazone binuclear gallium coordination compound G1 (referred to as coordination compound G1) is prepared by the following preparation method:
[0037] S1, 5 mmol of 2-methyl-1,3-cyclohexanedione and 10 mmol of thiosemicarbazide compound were placed in a 100 mL round-bottom flask, 50 mL of methanol and 1 mL of glacial acetic acid were added as a catalyst, and the mixture was refluxed at 60° C. for 6 hours, a light yellow solid was filtered out, and the solid was washed with methanol three times, and dried in an oven at 60° C. to obtain thiosemicarbazide compound 1 (referred to as compound 1);
[0038] S2, compound 1 is dissolved in N,N'-dimethylformamide to prepare a 0.1 mol / L solution, and stirred at room temperature overnight, and the solution slowly changes from a yellow clear solution to a dark red clear solution; when completely dissolved, the active hydrogen of the carbon atom No. 2 in the six-membered ring of the thiosemicarbazone compound is unstable and thus oxidized to a hydroxyl group;
[0039] S3. While continuing to stir, add 1.5 times the amount of 1 mol / L gallium nitrate methanol solution (calculated according to the amount of thiosemicarbazone compound 1 added) to the solution in step S2, and continue stirring for 1 hour. The solution changes from dark red to orange, and light yellow crystals precipitate. The solution is filtered, rinsed three times with N,N'-dimethylformamide, and then rinsed once with methanol, and dried in an oven at 60°C to obtain coordination compound G1.
[0040] The obtained coordination compound G1 crystal was subjected to X-ray single crystal diffraction test, and refined by Olex2 software to draw the molecular structure of the complex; the single crystal powder X-ray diffraction pattern was further simulated using the X-ray single crystal diffraction test data, and compared with the actual measured powder X-ray diffraction pattern, the peak position was consistent. Thus, it was determined that the coordinated thiosemicarbazone binuclear gallium compound G1 was a metal organic MOFs material.
[0041] Embodiment 2:
[0042] See also Figure 4 , Figure 5 and Figure 6 The synthetic route of the thiosemicarbazone binuclear gallium coordination compound G2 (referred to as coordination compound G2) is as follows:
[0043]
[0044] Wherein, R is Me.
[0045] The thiosemicarbazone binuclear gallium coordination compound G2 (referred to as coordination compound G2) is prepared by the following preparation method:
[0046] S1. Place 5 mmol of 2-methyl-1,3-cyclohexanedione and 10 mmol of 4-methylthiosemicarbazide in a 100 mL round-bottom flask, add 50 mL of methanol, add 1 mL of glacial acetic acid as a catalyst, reflux at 60° C. for 6 hours, filter out the light yellow solid, rinse with methanol three times, and dry in an oven at 60° C. to obtain thiosemicarbazide compound 2 (referred to as compound 2).
[0047] S2, compound 2 is dissolved in methanol to prepare a solution with a concentration of 0.01 mol / L, 1 mol / L NaOH methanol solution is added, the pH value is adjusted to about 8, and stirred at room temperature overnight for 1 hour. The solution slowly changes from green to dark red. When it is completely dissolved, the active hydrogen of carbon atom No. 2 in the six-membered ring of the thiosemicarbazone compound is unstable and thus oxidized to a hydroxyl group; then 1 mol / L HNO3 aqueous solution is added to adjust the pH to 7, methanol is removed by rotary evaporation, and after washing three times with purified water, methanol is added to dissolve to prepare a solution with a concentration of 0.1 mol / L (calculated based on the amount of thiosemicarbazone compound 2 added).
[0048] S3. While continuing to stir the solution in step S2, add 1.5 times the amount of 1 mol / L gallium nitrate methanol solution (calculated according to the amount of thiosemicarbazone compound 2 added). After stirring evenly, the solution changes from red to orange. After standing, yellow crystals slowly precipitate. The crystals are filtered, rinsed three times with methanol, and dried in an oven at 60°C to obtain coordination compound G2.
[0049] The obtained coordination compound G2 crystal was subjected to X-ray single crystal diffraction test, and refined by Olex2 software to draw the molecular structure of the complex; the single crystal powder X-ray diffraction pattern was simulated by Mercury software, and compared with the actual measured powder X-ray diffraction pattern, the peak position was consistent. Thus, it was determined that the coordinated thiosemicarbazone binuclear gallium compound G2 was a metal organic MOFs material.
[0050] Embodiment 3:
[0051] See also Figure 7 , Figure 8 and Fig. 9 The synthetic route of the thiosemicarbazone binuclear gallium coordination compound G3 (referred to as coordination compound G3) is as follows:
[0052]
[0053] Wherein, R is Ph.
[0054] The thiosemicarbazone binuclear gallium coordination compound G3 (referred to as coordination compound G3) is prepared by the following preparation method:
[0055] S1, 5 mmol of 2-methyl-1,3-cyclohexanedione and 10 mmol of 4-phenylthiosemicarbazide compound were placed in a 100 mL round-bottom flask, 50 mL of methanol and 1 mL of glacial acetic acid were added as a catalyst, refluxed at 60° C. for 6 hours, a yellow solid was filtered out, washed with methanol three times, and dried in an oven at 60° C. to obtain thiosemicarbazide compound 3 (referred to as compound 3);
[0056] S2, dissolving compound G3 in N,N'-dimethylformamide to prepare a 0.1 mol / L solution, and stirring at room temperature overnight. When the solution is completely dissolved, the active hydrogen of carbon atom No. 2 in the six-membered ring of the thiosemicarbazone compound is unstable and thus oxidized to a hydroxyl group;
[0057] S3. Add 1.5 times the amount of 1 mol / L gallium nitrate methanol solution (calculated according to the amount of thiosemicarbazone compound 3 added) to the solution in step S2 while continuing to stir. Stir for 1 hour until the color of the solution becomes lighter and yellow crystals precipitate. Filter and rinse with N,N'-dimethylformamide three times and then with methanol once. Dry in an oven at 60°C to obtain coordination compound G3.
[0058] The obtained coordination compound G3 crystal was subjected to X-ray single crystal diffraction test, and refined by Olex2 software to draw the molecular structure diagram of the complex; the single crystal powder X-ray diffraction pattern was simulated by Mercury software, and compared with the actual measured powder X-ray diffraction pattern, the peak position was consistent. Therefore, it was determined that the coordinated thiosemicarbazone binuclear gallium compound G3 was a metal organic MOFs material.
[0059] In summary, the preparation method of the semicarbazide binuclear gallium coordination compound of the present invention has mild conditions and is easy to operate. It is determined to be a metal organic MOFs material through X-ray single crystal diffraction method and powder X-ray diffraction (PXRD) test.
[0060] Those skilled in the art should recognize that the above embodiments are only used to illustrate the present invention, and are not intended to limit the present invention. As long as they are within the spirit of the present invention, any changes or modifications to the above embodiments will fall within the scope of the claims of the present invention.
Claims
1. A method for preparing a thiosemicarbazone binuclear gallium coordination compound, characterized in that: The synthetic route of the thiosemicarbazone binuclear gallium coordination compound is as follows: Wherein, R is selected from H, Me or Ph.
2. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 1, characterized in that: The following steps are involved: S1, placing 2-methyl-1,3-cyclohexanedione and a semicarbazide compound in a molar ratio of 1:2 in a reaction vessel, adding methanol, and then adding an acid as a catalyst, reflux at 60° C. for 6 to 10 hours, washing the filtered solid with methanol several times, and then drying it in an oven at 60° C. to obtain a semicarbazide compound; S2, dissolving the thiosemicarbazone compound obtained in step S1 in N,N'-dimethylformamide or methanol to prepare a solution, and stirring at room temperature overnight. When the solution is completely dissolved, the active hydrogen of the carbon atom No. 2 in the six-membered ring of the thiosemicarbazone compound is unstable and thus oxidized to a hydroxyl group; S3, adding 1 mol / L gallium nitrate methanol solution to the solution of step S2 with stirring, and continuing stirring until fine crystals or powder are precipitated. After the precipitation is complete, filtering and rinsing the precipitate, and drying the precipitate in an oven at 60° C. to obtain the final product, a semicarbazide binuclear gallium coordination compound.
3. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 2, characterized in that: In step S1, the amount of 2-methyl-1,3-cyclohexanedione is 5 mmol; the amount of the semicarbazide compound is 10 mmol; the amount of methanol is 30 mL to 50 mL; and the catalyst is glacial acetic acid or hydrochloric acid.
4. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 3, characterized in that: The amount of methanol used is 50 mL.
5. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 3, characterized in that: The catalyst is 0.2-1 mL of glacial acetic acid or 0.1 mL of hydrochloric acid.
6. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 2, characterized in that: In step S2, the thiosemicarbazide compound is dissolved in N,N'-dimethylformamide to prepare a 0.05-0.2 mol / L solution.
7. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 6, characterized in that: In step S2, the thiosemicarbazide compound is dissolved in N,N'-dimethylformamide to prepare a 0.1 mol / L solution.
8. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 2, characterized in that: In step S2, the thiosemicarbazide compound is dissolved in methanol to prepare a 0.1 mol / L solution, and a saturated NaOH methanol solution is added to assist dissolution, and the pH value is adjusted to 8.
9. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 2, characterized in that: Step S3 is replaced by the following process: add 1 mol / L gallium nitrate methanol solution to the solution of step S2 with stirring, continue stirring until the mixture is evenly mixed to obtain a clear solution, then seal it with a sealing film, open small air-permeable holes on the sealing film, and then let it stand until crystals precipitate. After the precipitation is complete, filter and rinse the precipitate, and place it in an oven at 60° C. to dry the precipitate to obtain the final product, a semicarbazide binuclear gallium coordination compound.
10. The method for preparing a thiosemicarbazone binuclear gallium coordination compound according to claim 2 or 9, characterized in that: The amount of 1 mol / L gallium nitrate methanol solution used is 1.5 times the mass of the thiosemicarbazone compound.