Acylhydrazone-Mn complex as well as preparation method and application thereof

Abstract

The invention provides an acylhydrazone-Mn complex as well as a preparation method and application thereof. The structural formula of the acylhydrazone-Mn complex is shown in the specification, or in the structural formula, R is a substituent group. According to the invention, 4-diphenylaminobenzoylhydrazone reacts with MnCl2, the acylhydrazone-Mn complex is obtained by utilizing easy formation, strong coordination ability, diverse applications and biological activity of acylhydrazone compounds and utilizing N, O atoms and a plurality of metal ions to form complexes with different structures and properties, and some complexes have the characteristics of anti-tumor and antibacterial activity. A cytotoxicity test, an in-vitro proliferation inhibition activity experiment and an antibacterial experiment show that the synthesized Mn complex not only has a relatively good inhibition effect on tumor cells, but also has relatively low toxicity on normal cells; in addition, the proliferation of P.micro can be effectively inhibited.

Description

Technical Field

[0001] This invention belongs to the field of manganese complexes, specifically relating to an acylhydrazone-Mn complex, its preparation method, and its application. Background Technology

[0002] Enterosquamous squamous cell carcinoma (OSCC) is the sixth most common malignant tumor worldwide, with approximately 600,000 new cases annually, and its treatment faces significant challenges. Currently, treatment primarily relies on surgical resection combined with radiotherapy and chemotherapy, but the efficacy is limited and it often leads to functional impairment and disability. In recent years, immune checkpoint blockade therapies (such as pembrolizumab and nivolumab) have brought durable remissions to some patients, but the overall response rate is low, and the five-year survival rate remains below 20%, highlighting the urgent need to develop new treatment strategies.

[0003] In the clinical practice of OSCC, lymph node micrometastasis is one of the important risk factors affecting prognosis and a key reason for low patient survival. Studies have found that the tumor microbiota, such as *Porphyromonas gingivalis*, *Fusobacterium nucleatum*, and *Parvimonas micra* (P. micra), is closely related to tumor metastasis. *P. micra*, in particular, significantly promotes tumor metastasis by remodeling the tumor immune microenvironment, and its abundance is significantly increased in OSCC patients with lymph node metastasis. Therefore, eliminating intratumoral *P. micra* may be a new strategy to enhance the efficacy of immunotherapy and inhibit tumor metastasis. However, treatments targeting the tumor microbiota are still in their early stages, especially in the field of OSCC where effective treatments are lacking.

[0004] Currently, clearing intratumoral flora mainly relies on antibiotics, but their non-selective killing and drug resistance issues limit their clinical application. Metal ion preparations, due to their multiple biological effects and low likelihood of inducing drug resistance, have become a potential alternative strategy to antibiotics. Summary of the Invention

[0005] To address the aforementioned technical problems in the prior art, the present invention provides an acylhydrazone-Mn complex with the following structural formula:

[0006] or

[0007] Where R is a substituent.

[0008] Manganese (Mn), as one of the important trace elements in the human body, has unique advantages: It can activate the cGAS-STING pathway, enhance the innate immune response, and catalyze the response through a Fenton-like reaction. This generates cytotoxic hydroxyl radicals (·OH), inducing oxidative damage in tumor cells and bacteria. This invention utilizes the strong coordination ability and diverse biological activities of acylhydrazone ligands to generate free hydroxyl radicals (·OH), thereby inducing oxidative damage in tumor cells and bacteria. It coordinates with ligands to form complexes, improving targeting and stability.

[0009] Furthermore, R is -OH or -NH2.

[0010] This invention also provides a method for preparing acylhydrazone-Mn complexes, comprising the following steps:

[0011] Step 1) First, add 4-diphenylaminobenzaldehyde and benzoylhydrazine or their derivatives into the reaction vessel, then add ethanol to dissolve them completely, and then add concentrated sulfuric acid dropwise while shaking. Stir the reaction at a constant temperature of 60℃-70℃ for 11-12 hours.

[0012] The molar ratio of 4-diphenylaminobenzaldehyde to benzoyl hydrazine or its derivative is 1~1.6:1;

[0013] Step 2) After the reaction is complete, filter and dry to obtain a precipitate. Remove impurities from the precipitate and purify it. After drying, obtain 4-diphenylaminobenzaldehyde-benzoylhydrazone ligand L.

[0014] Step 3) Place ligand L and MnCl2 in a reaction vessel, add methanol and stir thoroughly, then seal the vessel and place it in a drying oven at 60℃-65℃ for 24h. Then raise the temperature to 80℃-85℃ and continue the reaction for 24h.

[0015] The molar ratio of ligand L to MnCl2 is 1~1.6:1;

[0016] Step 4) After the reaction is complete, cool to room temperature and filter to obtain the precipitate;

[0017] Step 5) Allow the precipitate to crystallize, and the resulting crystal is the Mn complex.

[0018] In this invention, 4-diphenylaminobenzaldehyde and hydrazide are selected for condensation reaction to obtain a ligand, which is then reacted with MnCl2 to obtain a Mn complex.

[0019] Furthermore, the derivative of the benzoyl hydrazine is 4-aminobenzoyl hydrazine or 4-hydroxybenzoyl hydrazine.

[0020] Furthermore, the method for removing impurities and purifying the precipitate in step 2) is as follows:

[0021] The precipitate was washed sequentially with saturated sodium bicarbonate and water to remove impurities; then purified by silica gel column chromatography with petroleum ether:ethyl acetate = 10:1 as the eluent.

[0022] Furthermore, step 5) involves the precipitation and crystallization process as follows:

[0023] The precipitate was placed at the bottom of a test tube with a rubber stopper. After evacuation, nitrogen gas was introduced. Dichloromethane was added with a syringe and dissolved by sonication. Then, n-hexane was slowly added along the tube wall with a syringe. After standing for 48 hours, crystals were observed at the intersection of the dichloromethane and n-hexane liquid surfaces.

[0024] The volume ratio of dichloromethane to n-hexane is 1:2.5~3.

[0025] This invention also provides the application of acylhydrazone-Mn complexes in the preparation of antibacterial drugs.

[0026] Furthermore, the bacteria targeted include Porphyromonas gingivalis, Fusobacterium nucleatum, and Micromonas.

[0027] This invention also provides the application of acylhydrazone-Mn complex in the preparation of antitumor drugs.

[0028] Furthermore, the tumors targeted include pharyngeal squamous cell carcinoma cells, human pharyngeal carcinoma pleural effusion metastatic cells, human oral squamous cell carcinoma, and mouse squamous cell carcinoma.

[0029] The beneficial effects of this invention are as follows:

[0030] This invention utilizes the reaction of 4-diphenylaminobenzoylhydrazone with MnCl2, taking advantage of the easy formation, strong coordination ability, diverse applications, and biological activity of acylhydrazones. Furthermore, it leverages the N and O atoms to form complexes with various metal ions, some of which possess inherent antitumor and antibacterial activities, to obtain acylhydrazone-Mn complexes. Cytotoxicity tests, in vitro proliferation inhibition experiments, and antibacterial experiments demonstrate that the synthesized Mn complexes not only exhibit good inhibitory effects on tumor cells and low toxicity to normal cells, but also effectively inhibit the proliferation of *P. micra*. Attached Figure Description

[0031] Figure 1 This is the mass spectrum of ligand L1 synthesized in Example 1 of the present invention;

[0032] Figure 2 This is the proton spectrum of ligand L1 synthesized in Example 1 of this invention;

[0033] Figure 3 It is the ligand L1 synthesized in Example 1 of this invention. 13 C NMR spectrum;

[0034] Figure 4 This is the mass spectrum of the acylhydrazone-Mn complex Mn1 synthesized in Example 1 of this invention;

[0035] Figure 5 This is the mass spectrum of ligand L2 synthesized in Example 2 of the present invention;

[0036] Figure 6 This is the proton spectrum of ligand L2 synthesized in Example 2 of this invention;

[0037] Figure 7 It is the ligand L2 synthesized in Example 2 of this invention. 13 C NMR spectrum;

[0038] Figure 8 This is the mass spectrum of the acylhydrazone-Mn complex Mn2 synthesized in Example 2 of this invention;

[0039] Figure 9 This is the mass spectrum of ligand L3 synthesized in Example 3 of the present invention;

[0040] Figure 10 This is the proton spectrum of ligand L3 synthesized in Example 3 of this invention;

[0041] Figure 11 It is the ligand L3 synthesized in Example 3 of this invention. 13 C NMR spectrum;

[0042] Figure 12 This is the mass spectrum of the acylhydrazone-Mn complex Mn3 synthesized in Example 3 of this invention;

[0043] Figure 13 This is the minimum inhibitory concentration of Mn1-Mn3 against P. micra in this invention. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0045] 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 pertains, and all materials publicly cited herein and cited by them are incorporated herein by reference.

[0046] Equivalent technologies of the specific embodiments described herein that are readily apparent to those skilled in the art through routine experimentation are included in this application.

[0047] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the instruments and equipment used in the following examples are all standard laboratory instruments and equipment; unless otherwise specified, the experimental materials used in the following examples were all purchased from regular biochemical reagent stores.

[0048] Example 1

[0049] This embodiment provides an acylhydrazone-Mn complex with the following structural formula:

[0050]

[0051] The specific preparation process is as follows:

[0052] Step 1) Weigh 5 mmol of 4-diphenylaminobenzaldehyde and 5 mmol of benzoylhydrazine into a flask, add 20 mL of ethanol to dissolve them completely, and then slowly add 500 μL of concentrated sulfuric acid while shaking. Stir the reaction in an oil bath at 65 °C for 12 h, filter and dry to obtain a pale yellow precipitate.

[0053] Step 2) The precipitate was washed sequentially with saturated sodium bicarbonate and water to remove impurities; then purified by silica gel column chromatography with petroleum ether:ethyl acetate = 10:1 as the eluent. After drying, ligand L1 was obtained; the yield was 78%.

[0054] Step 3) Weigh 0.05 mmol of ligand L1 and 0.05 mmol of MnCl2 into a reaction vessel, add 2 mL of methanol, stir thoroughly, seal, and place in a 60℃ drying oven for 24 h. Then, raise the temperature to 80℃ and continue the reaction for 24 h.

[0055] Step 4) After the reaction is complete, remove the sample and slowly cool it to room temperature. Filter to obtain an orange precipitate.

[0056] Step 5) Place the obtained precipitate at the bottom of a test tube with a rubber stopper, evacuate the tube, fill it with nitrogen, add 3 mL of the good solvent dichloromethane using a syringe and sonicate to dissolve it completely. Then, slowly add 9 mL of the poor solvent n-hexane along the tube wall using a syringe. After standing for 48 h, orange crystals are observed at the intersection of the liquid surfaces of the good solvent and the poor solvent, which is the target Mn complex Mn1; yield 71%.

[0057] The synthetic route for Mn1 is as follows:

[0058]

[0059] The stereostructure of the Mn1 complex is as follows:

[0060]

[0061] For ligand L1 C26 H 21 Elemental analysis of N3O yielded the following results: theoretical values: C, 79.77; H, 5.41; N, 10.73; actual values: C, 79.69; H, 5.36; N, 10.73.

[0062] Mass spectrometry, proton NMR, and nuclear magnetic resonance (NMR) were performed on ligand L1. (Mass spectrometry data is available in the original text.) Figure 1 As shown, ESI+ m / z: 390.16 [M +H];

[0063] See hydrogen spectrum Figure 2 , 1 H NMR (400 MHz, DMSO-d6) δ 11.75 (s, 1H), 8.39 (s, 1H), 7.92 (d, J = 7.2 Hz, 2H), 7.65 – 7.48 (m, 5H), 7.36 (t, J = 7.8 Hz, 4H), 7.11(dd, J = 17.2, 7.6 Hz, 6H), 6.97 (d, J = 8.6 Hz, 2H);

[0064] MRI, such as Figure 3 As shown, 13 C NMR (101 MHz, DMSO-d6) δ 163.37, 149.45, 148.02,147.02, 134.03, 132.11, 130.23, 128.92, 128.85, 128.04, 127.98, 125.46,124.49, 121.85;

[0065] As can be seen from the above, this embodiment synthesized ligand L1.

[0066] Elemental analysis of the complex Mn1:

[0067] C 52 H 42 Theoretical values ​​for Cl2MnN6O2: C, 68.73; H, 4.66; N, 9.25; Actual values: C, 68.76; H, 4.63; N, 9.23;

[0068] Mass spectrometry, such as Figure 4 As shown, the ESI+ m / z is 872.24 [M-Cl]. Therefore, this embodiment synthesizes the complex Mn1.

[0069] Example 2

[0070] This embodiment provides an acylhydrazone-Mn complex with the following structural formula:

[0071]

[0072] The synthesis of Mn complex Mn2 includes the following steps:

[0073] (1) Weigh 5 mmol of 4-diphenylaminobenzaldehyde and 5 mmol of 4-aminobenzoylhydrazine into a flask, add 20 mL of ethanol to dissolve them completely, and then slowly add 500 μL of concentrated sulfuric acid while shaking. Stir the reaction in an oil bath at 65 °C for 12 h. After filtration and drying, a pale yellow precipitate is obtained. Wash the precipitate with saturated sodium bicarbonate and water to remove impurities. Then, separate and purify it by silica gel column chromatography with petroleum ether: ethyl acetate = 10:1 as the eluent. After drying, ligand L2 is obtained with a yield of 88%.

[0074] C 26 H 22 Elemental analysis of N4O: Theoretical values: C, 76.83; H, 5.46; N, 13.784; Actual values: C, 76.79; H, 5.43; N, 13.74.

[0075] like Figure 6 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 11.34 (s, 1H), 8.32 (s, 1H), 7.66 (d, J = 7.4 Hz, 2H), 7.57 (d, J = 8.6 Hz, 2H), 7.35 (t, J = 7.6 Hz, 4H), 7.10 (dd, J = 17.0, 7.7 Hz, 6H), 6.96 (d, J = 8.6 Hz, 2H), 6.59 (d, J = 7.5Hz, 2H), 5.76 (s, 2H).

[0076] like Figure 7 As shown, 13 C NMR (101 MHz, DMSO-d6) δ 152.65, 149.05, 147.12, 130.20,129.74, 128.54, 125.29, 124.33, 122.17, 120.10;

[0077] like Figure 6 As shown, mass spectrometry, ESI+ m / z: 429.17 [M + Na].

[0078] As can be seen from the above, this embodiment synthesized ligand L2.

[0079] (2) Weigh 0.05 mmol of ligand L2 and 0.05 mmol of MnCl2 and place them in a reaction vessel. Add 2 mL of methanol and stir thoroughly. Seal the vessel and place it in a 60℃ drying oven for 24 h. Then raise the temperature to 80℃ and continue the reaction for 24 h. After the reaction is complete, remove the vessel and slowly cool it to room temperature. Filter to obtain an orange precipitate. Place the obtained precipitate at the bottom of a test tube with a rubber stopper. Vacuum the tube and fill it with nitrogen. Add 3 mL of the good solvent dichloromethane using a syringe and sonicate to dissolve it thoroughly. Then slowly add 9 mL of the poor solvent n-hexane along the tube wall using a syringe. After standing for 48 h, orange crystals are observed at the intersection of the liquid surfaces of the good solvent and the poor solvent. This is the target Mn complex Mn2. Yield: 56%.

[0080] Synthesis route:

[0081]

[0082] Elemental analysis, C 52 H 44 Theoretical values ​​for Cl2MnN8O2: C, 66.53; H, 4.72; N, 11.94. Measured values: C, 66.50; H, 4.75; N, 11.97.

[0083] Mass spectrometry, such as Figure 8 As shown, the ESI+ m / z is 902.27 [M-Cl]. This indicates that the complex Mn2 was synthesized in this embodiment. The stereostructure is as follows:

[0084]

[0085] Example 3

[0086] This embodiment provides an acylhydrazone-Mn complex with the following structural formula:

[0087]

[0088] The synthesis of Mn complex Mn3 includes the following steps:

[0089] (1) Weigh 5 mmol of 4-diphenylaminobenzaldehyde and 5 mmol of 4-hydroxybenzoylhydrazine into a flask, add 20 mL of ethanol to dissolve them completely, and then slowly add 500 μL of concentrated sulfuric acid while shaking. Stir the reaction in an oil bath at 65 °C for 12 h. After filtration and drying, a pale yellow precipitate is obtained. Wash the precipitate with saturated sodium bicarbonate and water to remove impurities. Then, separate and purify it by silica gel column chromatography with petroleum ether: ethyl acetate = 10:1 as the eluent. After drying, ligand L3 is obtained with a yield of 79%.

[0090] Elemental analysis, C 26 H 21 Theoretical N3O2 values: C, 76.64; H, 5.19; N, 10.31; Measured values: C, 76.60; H, 5.22; N, 10.33;

[0091] like Figure 10 As shown, 1 H NMR (400 MHz, DMSO-d6) δ 11.52 (s, 1H), 10.10 (s, 1H), 8.35 (s, 1H), 7.79 (d, J = 8.7 Hz, 2H), 7.58 (d, J = 8.1 Hz, 2H), 7.35 (t, J= 7.8 Hz, 4H), 7.11 (dd, J = 17.4, 7.6 Hz, 6H), 6.96 (d, J = 8.5 Hz, 2H), 6.85 (d, J = 8.6 Hz, 2H);

[0092] like Figure 11 As shown, 13 C NMR (101 MHz, DMSO-d6) δ 161.11, 149.29, 147.00, 130.17, 128.74, 128.14, 125.34, 124.41, 115.54;

[0093] like Figure 9 As shown, mass spectrometry, 408.17 [M + H];

[0094] As can be seen from the above, this embodiment synthesized ligand L3.

[0095] (2) Weigh 0.05 mmol of ligand L3 and 0.05 mmol of MnCl2 and place them in a reaction vessel. Add 2 mL of methanol, stir thoroughly, seal, and place in a 60℃ drying oven for 24 h. Then, raise the temperature to 80℃ and continue the reaction for 24 h. After the reaction is complete, remove the vessel and slowly cool it to room temperature. Filter to obtain an orange precipitate. Place the obtained precipitate at the bottom of a test tube with a rubber stopper, evacuate the tube, and fill it with nitrogen. Add 3 mL of the good solvent dichloromethane using a syringe and sonicate to dissolve it thoroughly. Then, slowly add 9 mL of the poor solvent n-hexane along the tube wall using a syringe. After standing for 48 h, orange crystals are observed at the intersection of the liquid surfaces of the good and poor solvents. This is the target Mn complex Mn3, with a yield of 62%. The synthetic route is as follows:

[0096]

[0097] C52 H 42 Elemental analysis of Cl2MnN6O4: Theoretical values: C, 66.39; H, 4.50; N, 8.93. Measured values: C, 66.42; H, 4.45; N, 8.89.

[0098] like Figure 12 As shown, mass spectrometry, ESI+ m / z: 904.24 [M-Cl].

[0099] This embodiment demonstrates the synthesis of the complex Mn3. Its stereostructure is as follows:

[0100]

[0101] To illustrate the antitumor effect of the Mn complexes of the present invention, in vitro antitumor activity experiments were conducted on the complexes Mn1-Mn3 prepared in Examples 1-3:

[0102] Proliferation inhibition activity experiments were conducted on human pharyngeal squamous cell carcinoma cells (FaDu), human pharyngeal head carcinoma pleural effusion metastatic cells (Detroit 562), human oral squamous cell carcinoma (HSC-3), mouse squamous cell carcinoma (SCC7), and human nasopharyngeal epithelial cells (NP69).

[0103] The MTT (thiazole) colorimetric assay was used to monitor cell growth and assess the inhibitory effect of the complex on cell proliferation. First, digested cells were counted and seeded into 96-well plates, with 180 μL of culture medium added to each well to dilute to a cell concentration of [missing value]. Ensure each well contains 1000-10000 cells. Then, incubate at 5% CO2 and 37°C for 24 h until a cell monolayer completely covers the bottom of the well. Next, add 20 μL of the drug to each well to achieve final concentrations of 80 μM, 40 μM, 20 μM, 10 μM, and 5 μM, with five replicates for each concentration. Continue incubation under the same conditions for 48 h, followed by microscopic observation of cell status. Add 10 μL of MTT solution (5 mg / mL PBS, i.e., 0.5% MTT) to each well and incubate for another 5 h.

[0104] After culturing, the culture medium was aspirated, and 100 μL of DMSO was added to dissolve the formazan precipitate. After shaking for 10 min, the optical density (OD) value of each well was measured using a microplate reader at a wavelength of 570 nm, with 630 nm as the reference wavelength. The number of viable cells was assessed by the measured OD value; a higher OD value indicated stronger cell viability. The IC50 of the compound was calculated using the obtained OD value using the formula: Tumor cell growth inhibition rate (%) = [(1 - average OD value of experimental group) / (average OD value of control group)] × % 50The value is the drug concentration at which a 50% inhibitory effect is achieved. The experimental results are shown in Table 1.

[0105] Table 1. IC50 of ligands and complexes for different cell lines 50 Value (μM) Agents FaDu D562 HSC-3 SCC7 NP69 L1 > 40 > 40 > 40 > 40 > 40 L2 > 40 > 40 > 40 > 40 > 40 L3 36.78 ± 2.63 > 40 32.65 ± 2.67 > 40 > 40 Mn1 12.04 ± 1.11 30.12 ± 2.58 28.85 ± 2.01 32.16 ± 2.67 27.23 ± 2.45 Mn2 10.71 ± 1.09 13.32 ± 1.45 8.22 ± 0.89 12.45 ± 1.11 33.45 ± 2.89 Mn3 6.04 ± 0.92 8.25 ± 1.33 4.94 ± 0.74 6.78 ± 1.01 27.21 ± 2.23

[0106] Experimental results show that, for cancer cells, the activity of simple 4-diphenylaminobenzaldehyde benzoylhydrazone ligands (L1, L2, L3) is not high, while that of Mn... 2+ After coordination, the activity is significantly enhanced, with Mn3 showing the best anti-tumor effect.

[0107] To demonstrate the inhibitory effect of the Mn complexes of the present invention on *P. micra*, a bacterium within human oral squamous cell carcinoma, antibacterial experiments were conducted on the complexes Mn1-Mn3 prepared in Examples 1-3 above:

[0108] The minimum inhibitory concentration (MIC) of the Mn complex against *P. micrata* was determined. The culture was first grown to the logarithmic growth phase, at which point the optical density was approximately 1.0 (OD = 1.0). To test the antibacterial activity of the Mn complex, different concentration gradients were added to each well of a 96-well plate (see [link to study]). Figure 13 (Y-axis) 100 μL of different dilutions (Mn1, Mn2, and Mn3). A group supplemented with phosphate-buffered saline (PBS) served as a control. Subsequently, 100 μL of the concentration [of PBS] was seeded into each well. The bacteria were cultured further in an incubator. The MIC was defined as the lowest concentration of antimicrobial agent that could inhibit bacterial growth after incubation at 37°C for 8 hours. This concentration was determined by measuring the optical density of bacterial growth at 600 nm, and the minimum inhibitory concentration (MIC) was derived accordingly. The experimental results are as follows: Figure 13 As shown.

[0109] Experimental results showed that the Mn complexes all had a certain inhibitory effect on P. micra. The MIC value of Mn1 against P. micra was 25 μM (parts per million), the MIC value of Mn2 was 12.5 μM, and the MIC value of Mn3 was 3.12 μM, showing the best effect. This was consistent with the order of antitumor activity, namely Mn3 > Mn2 > Mn1.

[0110] During the synthesis of ligands L1, L2, and L3, different molar ratios of 4-diphenylaminobenzaldehyde and benzoylhydrazine or their derivatives will affect the yield, but have little impact on the product. Similarly, different molar ratios of ligand and MnCl2 will result in different yields of the Mn complex, but will not affect the target product.

[0111] Therefore, the Mn complex synthesized in this invention not only has a good inhibitory effect on tumor cells and low toxicity to normal cells, but also can effectively inhibit the proliferation of P. micra.

[0112] The examples above are merely illustrative of the invention and do not constitute a limitation on the scope of protection of the invention. Any design that is the same as or similar to the invention falls within the scope of protection of the invention.

Claims

1. An acylhydrazone-Mn complex, characterized in that: The structural formula is as follows: or Wherein, R is a substituent group.

2. The acylhydrazone-Mn complex of claim 1, wherein: The R is -OH or -NH2.

3. A process for the preparation of the acylhydrazone-Mn complex as claimed in claim 1 or 2, characterized in that: The method comprises the following steps: Step 1) first, 4-diphenylmethylamino benzaldehyde and benzoyl hydrazine or its derivative are added into a reaction container, then ethanol is added to fully dissolve, concentrated sulfuric acid is added dropwise while oscillating, and the reaction is stirred at a constant temperature of 60-70 DEG C for 11-12 hours; Wherein, the molar ratio of 4-diphenylmethylamino benzaldehyde and benzoyl hydrazine or its derivative is 1-1.6:1; Step 2) after the reaction is completed, the precipitate is obtained by filtering and drying, the precipitate is purified by removing impurities, and 4-diphenylamino benzaldehyde-benzoyl hydrazone ligand L is obtained after drying; Step 3) the ligand L and MnCl2 are placed in a reaction kettle, methanol is added for fully stirring, then sealed, and then placed in a 60-65 DEG C drying box for 24 hours, and then heated to 80-85 DEG C for continuous reaction for 24 hours; Wherein, the molar ratio of the ligand L and MnCl2 is 1-1.6:1; Step 4) after the reaction is completed, the temperature is lowered to room temperature, and the precipitate is obtained by filtering; Step 5) the precipitate is crystallized, and the crystal is the Mn complex.

4. The method for preparing an acylhydrazone-Mn complex according to claim 3, characterized in that: The derivative of the benzoyl hydrazine is 4-amino benzoyl hydrazine or 4-hydroxy benzoyl hydrazine.

5. The method for preparing an acylhydrazone-Mn complex according to claim 3, characterized in that: The method for purifying the precipitate in step 2) is as follows: The precipitate is washed with saturated sodium bicarbonate and water in sequence to remove impurities, and then separated and purified by silica gel column chromatography, and the eluent is petroleum ether: ethyl acetate = 10:

1.

6. The method for preparing an acylhydrazone-Mn complex according to claim 3, characterized in that: The precipitation crystallization process is as follows: The precipitate is placed at the bottom of a test tube with a rubber stopper, vacuum is extracted, nitrogen is filled, dichloromethane is added by a syringe for fully dissolving under ultrasonic, then n-hexane is slowly added along the wall of the test tube by a syringe, the crystal is observed at the intersection of the dichloromethane and n-hexane liquid surface after standing for 48 hours; Wherein, the volume ratio of dichloromethane and n-hexane is 1:2.5-3.

7. The use of the acylhydrazone-Mn complex in the preparation of an antibacterial drug according to claim 1 or 2.

8. Use of the acylhydrazone-Mn complex according to claim 7 for the preparation of an antibacterial medicament. The antibacterial includes porphyromonas gingivalis, fusobacterium nucleatum and micromonospora.

9. The use of the acylhydrazone-Mn complex in the preparation of an antitumor drug.

10. The use of the acylhydrazone-Mn complex according to claim 7 in the preparation of an antitumor drug. The antitumor includes pharyngeal squamous cell carcinoma cells, human pharyngeal carcinoma metastatic cells, human oral squamous cell carcinoma and mouse squamous cell carcinoma.

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