Heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives, their preparation methods and applications

Abstract

This invention relates to a class of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives, their preparation methods, and applications, with the chemical formula: (n-Bu4N)3[Mo6O 18 [=N=NCO-HC]; where HC represents pyridinyl, thiophene, furanyl, or pyrazinyl, and n-Bu represents n-butyl; the preparation method includes the following steps: refluxing an organic ligand, a dehydrating agent, and tetrabutylammonium octamolybdate in an organic solvent, wherein the organic ligand is a heterocyclic hydrazide; after reflux, a heterocyclic ethylenediazene hexamolybdate tetrabutylammonium derivative is obtained by separation. This invention utilizes a heterocyclic hydrazide to covalently modify a hexamolybdate cluster, and the resulting heterocyclic ethylenediazene hexamolybdate tetrabutylammonium derivative exhibits certain inhibitory activity against Mycobacterium tuberculosis.

Description

Technical Field

[0001] This invention belongs to the field of anti-tuberculosis drug technology, specifically relating to a class of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives, their preparation methods, and applications. Background Technology

[0002] Tuberculosis (TB) is a chronic infectious disease caused by Mycobacterium tuberculosis. The World Health Organization (WHO) estimates that 7.5 million new TB cases were diagnosed globally in 2022, and approximately 1.3 million people die from the disease each year. Isoniazid (INH), also known as isoniazid, is a heterocyclic hydrazide compound with extremely strong inhibitory activity against Mycobacterium tuberculosis. Since its introduction for TB treatment in the 1950s, isoniazid remains a first-line drug (Lancet 2019, 393, (10181), 1642-1656). Given the increasing resistance of Mycobacterium tuberculosis to currently used anti-TB drugs and the growing number of TB cases globally, there is an urgent need to develop novel anti-TB drugs. A common strategy for developing new drugs is to modify the structure of existing drugs to regulate their performance.

[0003] Polyoxometalates (POMs) are a class of isolated polymetallic anionic oxygen clusters formed by former transition metals and oxygen ligands. These polyoxometalates not only possess diverse structures and rich compositions, but also exhibit biological activities such as antitumor, antibacterial, and antiviral activity, in addition to acidity, redox activity, magnetic properties, and photoelectric properties. Yamase et al. discovered that (NH3Pr...) i )6[Mo7O 26 (Mo7) exhibits excellent antitumor activity against xenografts of CO4-positive human colon cancer and OAT-positive human lung cancer. Larnicol and Bussereau et al. found that at cell-safe doses, (NH4) 17 Na[NaSb9W 21 O 86 HPA-23 (HPA-23) exhibits good antiviral activity against myeloma virus (MLSV), rotavirus (RV), rhabdomyovirus, and herpesvirus (EBV), and is a potential inorganic non-nucleoside analogue (Chem. Rev., 98 (1998) 327-357). However, polysaccharides, due to their large molecular weight, require large dosages and have high tissue toxicity, which are major obstacles to their clinical application. Improving the bioactivity and reducing the tissue toxicity of polysaccharide drugs is a trend in their development. Currently, there are no reports of polysaccharides as inhibitors of Mycobacterium tuberculosis. Summary of the Invention

[0004] The purpose of this invention is to overcome the above-mentioned technical deficiencies and provide a class of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives, their preparation methods, and applications, thereby solving the technical problem of the need to develop new drugs due to the increased drug resistance of anti-tuberculosis drugs in the prior art.

[0005] To achieve the above-mentioned technical objectives, the technical solution provided by this invention is as follows:

[0006] In a first aspect, the present invention provides a class of heterocyclic ethylenediazene hexamolybdate tetrabutylammonium derivatives, the structural formula of which is shown in Formula I below:

[0007]

[0008] HC includes pyridyl, thiophenyl, furanyl or pyrazinyl, and n-Bu represents n-butyl.

[0009] In a second aspect, the present invention provides a method for preparing a heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative, comprising the following steps: refluxing an organic ligand, a dehydrating agent and tetrabutylammonium octamolybdate in an organic solvent, wherein the organic ligand is a heterocyclic hydrazide; after refluxing, the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative is obtained by separation.

[0010] Thirdly, the present invention provides a pharmaceutical composition comprising the above-mentioned heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative.

[0011] Fourthly, the present invention provides the use of a heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative or pharmaceutical composition in the preparation of a medicament for the prevention and / or treatment of tuberculosis.

[0012] Fifthly, the present invention provides the use of a heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative or pharmaceutical composition in the preparation of a Mycobacterium tuberculosis proliferation inhibitor.

[0013] Compared with the prior art, the beneficial effects of the present invention include:

[0014] (1) The heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative of the present invention is an organic derivative obtained by covalently modifying hexamolybdate clusters with heterocyclic acyl hydrazides. Polyacids are non-nucleoside compounds and are not prone to drug resistance; while after heterocyclic acyl hydrazides are used as organic ligands to covalently modify polyacids, the resulting heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative has a certain inhibitory activity against Mycobacterium tuberculosis; and the inhibitory activity of the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative of the present invention against Mycobacterium tuberculosis has not been reported in the literature, which has a certain guiding role in the development of novel anti-H37Rv drugs;

[0015] (2) The synthesis process of the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative of the present invention is simple, easy to purify and separate, and convenient for large-scale production. Attached Figure Description

[0016] Figure 1 This is a crystal structure diagram of the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives POM-1 and POM-3 prepared in Example 1 of the present invention. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0018] In view of the fact that Mycobacterium tuberculosis has developed resistance to current anti-tuberculosis drugs, there is an urgent need to develop a new generation of anti-tuberculosis drugs. This invention provides a class of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives, their preparation methods and applications. Heterocyclic acyl hydrazides and other organic ligands are used to covalently modify hexamolybdate clusters to develop a new generation of heterocyclic acyl hydrazide-modified polyacid organic derivatives with inhibitory activity against Mycobacterium tuberculosis.

[0019] The organic modification of polyacid clusters in this invention, namely, the substitution of terminal oxygen and / or bridging oxygen by organic ligands, not only regulates the structure of polyacid clusters but also their properties. The covalent bond between the organic ligand and the polyacid cluster not only exhibits the "additive bonding" between the organic ligand and the polyacid cluster, but also, due to the synergistic effect between the polyacid and the organic ligand, produces new properties, giving the resulting heterocyclic ethylenediazine hexamolybdic acid derivative a certain inhibitory activity against Mycobacterium tuberculosis.

[0020] In a first aspect, the present invention provides a class of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives, the chemical formula of which is: (n-Bu4N)3[Mo6O 18 (=N=NCO-HC]; its structural formula is shown in Equation I below:

[0021]

[0022] HC includes heterocycles such as pyridyl, thiophenyl, furanyl, and pyrazinyl, and n-Bu represents n-butyl.

[0023] Preferably, the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives include:

[0024] (TBA)3[Mo6O 18 (=N=NCO-4-Pyridyl](POM-1);

[0025] (TBA)3[Mo6O 18 (=N=NCO-3-Pyridyl](POM-2);

[0026] (TBA)3[Mo6O18 (=N=NCO-2-Thienyl)](POM-3);

[0027] (TBA)3[Mo6O 18 (=N=NCO-3-Thienyl)](POM-4);

[0028] (TBA)3[Mo6O 18 (=N=NCO-2-Furyl)](POM-5);

[0029] (TBA)3[Mo6O 18 (=N=NCO-3-Furyl)](POM-6);

[0030] (TBA)3[Mo6O 18 (=N=NCO-2-Pyrazinyl)](POM-7).

[0031] Wherein, TBA = [N(C4H9)4]; Pyridyl-pyridyl, Thienyl-thienyl, Furyl-furanyl, Pyrazinyl-pyrazinyl.

[0032] The heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives POM-1 to POM-7 of the present invention have been verified to exhibit certain inhibitory activity against Mycobacterium tuberculosis (H37Rv) through anti-tuberculosis inhibitory activity evaluation.

[0033] Secondly, the present invention provides a method for preparing a class of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives, comprising the following steps:

[0034] The organic ligand, dehydrating agent, and tetrabutylammonium octamolate were refluxed in an organic solvent, the organic ligand being a heterocyclic hydrazide;

[0035] After reflux, a heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative was obtained.

[0036] Preferably, the dehydrating agent includes dicyclohexyldiimide (DCC); heterocyclic hydrazides include isoniazid (L1), nicotinic hydrazide (L2), 2-thiophenecarboxylhydrazide (L3), 3-thiophenecarboxylhydrazide (L4), 2-furanocarboxylhydrazide (L5), 3-furanocarboxylhydrazide (L6), and 2-pyrazinocarboxylhydrazide (L7).

[0037] Preferably, the organic ligand, the dehydrating agent, and tetrabutylammonium octamolate ((Bu4N)4[Mo8O) are present. 26 The molar ratio of ]) is (1.1~1.6):(2.0~2.5):1.

[0038] Preferably, the organic solvent includes anhydrous acetonitrile.

[0039] Preferably, reflux is performed by heating under stirring for 5–10 hours. It is understood that the heating temperature of the reflux reaction should be controlled near the boiling point of the organic solvent to maintain the reaction system in a boiling state.

[0040] Preferably, the steps for separating and obtaining the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative specifically include: cooling the reflux reaction system to room temperature, filtering to remove impurities, diffusing the obtained filtrate with diethyl ether or methyl tert-butyl ether, and collecting the obtained black or brownish-red crystals to obtain the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative.

[0041] This invention utilizes heterocyclic hydrazides as organic ligands, along with a dehydrating agent and tetrabutylammonium octamolate ((Bu4N)4[Mo8O) 26 The dicyclohexylurea generated is removed by reflux in a dry anhydrous organic solvent at a certain molar ratio. The resulting blackish-red filtrate is diffused through diethyl ether or methyl tert-butyl ether in the gas phase to obtain brownish-red or blackish-red crystals, which are the target products. The process is simple and easy to scale up.

[0042] Thirdly, the present invention provides a pharmaceutical composition comprising the above-mentioned heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative.

[0043] Preferably, it also includes pharmaceutically acceptable carriers or excipients.

[0044] Preferably, the dosage form of the pharmaceutical composition includes any one of granules, tablets, pills, capsules, injections, and dispersants; the dispersant includes suspensions or emulsions.

[0045] Fourthly, the present invention provides the use of a heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative or pharmaceutical composition in the preparation of a medicament for the prevention and / or treatment of tuberculosis.

[0046] Fifthly, the present invention provides the use of a heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative or pharmaceutical composition in the preparation of a Mycobacterium tuberculosis proliferation inhibitor.

[0047] In this invention, the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative achieves its anti-tuberculosis effect by inhibiting the proliferation of Mycobacterium tuberculosis.

[0048] Preferably, the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative has a minimum inhibitory concentration of 1.14–4.55 ug / mL against Mycobacterium tuberculosis in vitro.

[0049] Biological experiments have revealed that the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative of this invention possesses certain inhibitory activity against Mycobacterium tuberculosis and has the potential to become a drug for treating Mycobacterium tuberculosis infection. For example, the MIC of POM-1 against H37Rv is 1.14 ug / mL; the MIC of POM-3 against H37Rv is 4.55 ug / mL; and the MIC of POM-7 against H37Rv is 2.27 ug / mL.

[0050] The present invention will be further described in detail below through specific embodiments; unless otherwise specified, the materials and operating methods used in the following embodiments are known in the art.

[0051] Examples 1-7

[0052] A method for preparing a heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative includes the following steps:

[0053] Weigh 2.16 g of (Bu4N)4[Mo8O into a dry round-bottom flask. 26 1.00 mmol of acetonitrile, 0.43 g of DCC (2.10 mmol), and the corresponding organic ligand (1.33 mmol) were added to 10 mL of anhydrous acetonitrile, stirred and refluxed for 6 h, and then cooled to room temperature. The white precipitate was removed by filtration, and the resulting black filtrate was diffused with methyl tert-butyl ether. After two weeks, a large amount of black or brownish-red blocky crystals were obtained, which were the target products POM-1 to POM-7.

[0054] Table 1 Actual dosage of organic ligands in Examples 1-7

[0055]

[0056] Performance testing

[0057] (1) The structures of the target products POM-1, POM-3 and POM-7 were characterized, and the results are as follows:

[0058] POM-1 (Bu4N)3[Mo6O 18 Yield: 0.17g (10%). (=N=NCOC5H4N) 1 H NMR (300MHz, DMSO-d6, 300K): δ = 0.94 (t, 36H, CH3-, [Bu4N] + ), 1.33 (m, 24H, -CH2-), 1.58(m, 24H, -CH2-, [Bu4N] + ), 3.17 (t, 24H, NCH2-, [Bu4N] +), 7.63 (d, 2H, ArH), 8.54 (d, 2H, ArH). IR (KBr pellet, cm -1 ): 2961 (s), 2874(s), 1592(m), 1538(m), 1483(s), 1382(m), 1343(m), 1314(m), 1275(s), 1205(w), 1153(w), 1108(w), 1060(w), 1028(w), 967(s, shoulder), 946(vs), 883(w), 793(vs), 769(s, shoulder), 695(w), 577(w). UV / Vis (MeCN): λ max = 386 nm.

[0059] POM - 3 (Bu4N)3[Mo6O 18 (=N=NCOC4H3S)] Yield 0.44 g (25%). 1 1H NMR (300 MHz, DMSO - d6, 300 K): δ = 0.88 (t, 36H, CH3-, [Bu4N] + ), 1.28 (m, 24H, -CH2-, [Bu4N] + ), 1.52 (m, 24H, -CH2-, [Bu4N] + ), 3.15 (t, 24H, NCH2-, [Bu4N] + ), 6.99 (s, 1H, ArH), 7.37 (s, 1H, ArH) 7.41 (d, 1H, ArH). IR (KBr, cm -1 ): 2961 (s), 2874(s), 1583(s), 1483(s), 1367(w), 1344(m), 1254(s), 1214(m), 1152(w), 1088(w), 1068(w), 1025(w), 964(s, shoulder), 939(vs), 884(w), 791(vs), 767(s, shoulder), 603(w). UV / Vis (MeCN): λ max = 385 nm.

[0060] POM - 7 (Bu4N)3[Mo6O 18Yield: 0.17g (10%). (=N=NCOC4H3N2) 1 H NMR (300MHz, DMSO-d6, 300K): δ = 0.93 (t, 36H, CH3-, [Bu4N] + ), 1.31 (m, 24H, -CH2-), 1.57(m, 24H, -CH2-, [Bu4N] + ), 3.17 (t, 24H, NCH2-, [Bu4N] + ), 8.58(d, 2H, ArH), 8.92(d, 2H, ArH). IR (KBr pellet, cm -1 ): 2961 (s), 2874(s), 1592(m), 1538(m), 1483(s), 1382(m), 1343(m), 1314(m), 1275(s), 1205(w), 1153(w), 1108(w), 1060(w),1028(w), 967(s, shoulder), 946(vs), 883(w), 793(vs), 769(s, shoulder), 695(w), 577(w). UV / Vis (MeCN): λ max = 386nm.

[0061] (2) Among them, the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative (Bu4N)3[Mo6O 18 (=N=NCOC5H4N)](POM-1), (Bu4N)3[Mo6O 18 The crystal structure of (POM-3) is suitable for single-crystal structure analysis, and its unit cell parameters are as follows:

[0062] POM-1: Monoclinic system, space group P2(1), a = 17.713(4) Å, b = 24.676(5) Å, c = 27315(6) Å, β = 108.30(3)°, V = 11336(4) Å 3 ;

[0063] POM-3: Monoclinic system, space group P2(1) / n, a = 16.301(3) Å, b = 24.041(5) Å, c = 18.920(4) Å, β = 90.97(3)°, V = 7414(3) Å 3 .

[0064] Crystal structure analysis shows that the molecular formulas of POM-1 and POM-3 are C1, C2, C3, C4, C5, C6, C7, C8, C9 ... 54 H 112 Mo6N6O 19 and C 53 H 111 Mo6N5O 19 S, its anion structure ORTEP diagram is shown below Figure 1 As shown in the figure; combined with the above infrared spectrum, ultraviolet-visible spectrum and nuclear magnetic resonance hydrogen spectrum data, it is fully demonstrated that the synthesized compound is the target product.

[0065] (3) Detection of the inhibitory activity of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivative on Mycobacterium tuberculosis H37Rv:

[0066] Take 10 mg of each drug sample and dissolve it in 100 mL of deionized water to prepare an aqueous solution. Then autoclave to obtain the drug solution. Add 0.5 mL of the drug solution to 5.0 mL of 7H10 culture medium. Then dilute the drug solution to the eighth tube using the two-fold dilution method. The ninth tube contains only culture medium (without drug solution) as a control. The tenth tube contains no sample and is an empty tube.

[0067] Using sterile physiological saline containing 0.5% Tween-80, add H37Rv colonies and sterile PBS buffer until the turbidity matches that of a standard McFarland turbidity tube, thus preparing a 1 mg / ml bacterial suspension. Using a heat-sterilized 22 SWG standard inoculation loop, take two loops of the bacterial suspension and add them to a culture tube containing 2 ml of sterile physiological saline to dilute the above bacterial suspension to a final concentration of 10. -3 mg / ml. Using a 22 SWG standard inoculation loop, take one loopful (0.01 ml) of H37Rv bacterial suspension from each of the drug-containing and control culture tubes and streak it evenly onto the surface of the control and drug-containing culture media. Place the inoculated media on a culture rack and incubate at 37°C. Observe the culture progress on days 3 and 7 post-inoculation, and then weekly until the end of the fourth week. After each culture medium check, record the colony growth as required in Table 2.

[0068] Table 2 Colony growth and reporting methods

[0069]

[0070] Visual inspection: Typical colony morphology of Mycobacterium tuberculosis is: opaque pale yellow, rough, dry, raised above the culture medium, sometimes resembling cauliflower. If liquefaction or mold growth is observed in the culture medium, contamination should be reported. Colonies below 4+ have an inhibitory effect on Mycobacterium tuberculosis; the minimum concentration at which this effect is observed is the minimum inhibitory concentration (MIC).

[0071] The inhibitory activity of tetrabutylammonium hexamolybdate (POM-0), heterocyclic ethylenediazine tetrabutylammonium hexamolybdate derivatives POM-1, POM-3, and POM-7 on H37Rv was detected using these drug samples. The results are shown in Table 3.

[0072] Table 3 shows the inhibitory activity of each compound against H37Rv.

[0073]

[0074] The # symbol indicates that the data is from J. Med. Chem. 2004, 47, 3755-3764.

[0075] The anion suppression concentration is the mass concentration of the remaining anion after removing the tetrabutylammonium cation.

[0076] Experimental results showed that POM-1, POM-3, and POM-7 all exhibited varying degrees of inhibitory activity against Mycobacterium tuberculosis H37Rv, with POM-1 showing the best inhibitory effect. The minimum inhibitory concentrations (MICs) of POM-1, POM-3, and POM-7 against Mycobacterium tuberculosis were 1.14 ug / mL, 4.55 ug / mL, and 2.27 ug / mL, respectively. Therefore, the heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives prepared in this invention all showed varying degrees of inhibitory activity against Mycobacterium tuberculosis H37Rv.

[0077] This invention provides a class of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives with inhibitory activity against Mycobacterium tuberculosis (H37Rv). These derivatives have the potential to be prepared into anti-H37Rv drugs and have certain clinical application prospects.

[0078] The specific embodiments of the present invention described above do not constitute a limitation on the scope of protection of the present invention. Any other corresponding changes and modifications made in accordance with the technical concept of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A class of heterocyclic ethylenediazine hexamolybdate tetrabutylammonium derivatives, characterized in that, The structural formula is shown as formula I: HC represents pyridyl, thienyl, furanyl or pyrazyl, and n-Bu represents n-butyl.

2. The heterocyclic azomethine hexamolybdate tetrabutylammonium derivative according to claim 1, characterized by The heterocyclic hydrazoethylenediazene hexamolybdate tetrabutylammonium derivative is: (TBA)3[Mo6O 18 (=N=NCO-4-pyridine] (TBA)3[Mo6O 18 (=N=NCO-3-pyridine]; (TBA)3[Mo6O 18 (=N=NCO-2- thiophene); (TBA)3[Mo6O 18 (=N=NCO-3- thiophene); (TBA)3[Mo6O 18 (=N=NCO-2- furan); (TBA)3[Mo6O 18 (=N=NCO-3- furan); (TBA)3[Mo6O 18 (=N=NCO-2-pyrazine); TBA=N(C4H9)4.

3. Process for the preparation of heterocyclic azomethine hexamolybdate tetrabutylammonium derivatives according to any one of claims 1-2, characterized in that, The method comprises the following steps: The organic ligand is a heterocyclic hydrazide; The heterocyclic hydrazoethylenediazene hexamolybdate tetrabutylammonium derivative is obtained after the refluxing; The dehydrating agent is dicyclohexyl diimide; The heterocyclic hydrazide is isoniazid, nicotinoyl hydrazide, 2-thiophenecarboxylic hydrazide, 3-thiophenecarboxylic hydrazide, 2-furancarboxylic hydrazide, 3-furancarboxylic hydrazide, 2-pyrazinecarboxylic hydrazide.

4. The process for the preparation of the tetraalkylammonium hexamolybdate derivatives of heterocyclic ethylene diazenes according to claim 3, characterized in that, The molar ratio of the organic ligand, the dehydrating agent and the tetrabutylammonium octamolybdate is (1.1-1.6):(2.0-2.5):

1.

5. The process for the preparation of tetraalkylammonium hexamolybdate derivatives of heterocyclic ethylene diazenes according to claim 3, characterized in that, The organic solvent comprises anhydrous acetonitrile; The refluxing is heated under stirring for 5-10 hours; The step of obtaining the heterocyclic hydrazoethylenediazene hexamolybdate tetrabutylammonium derivative comprises cooling the refluxing reaction system to room temperature, filtering out impurities, diffusing the obtained filtrate with diethyl ether or methyl tert-butyl ether, and collecting the crystals to obtain the heterocyclic hydrazoethylenediazene hexamolybdate tetrabutylammonium derivative.

6. A pharmaceutical composition, characterized by, The pharmaceutical composition comprises the heterocyclic hydrazoethylenediazene hexamolybdate tetrabutylammonium derivative according to any one of claims 1-2.

7. The pharmaceutical composition of claim 6, wherein, The pharmaceutical composition further comprises pharmaceutically acceptable adjuvants; The dosage form of the pharmaceutical composition is granules, tablets, pills, capsules, injections or dispersants.

8. Use of the heterocyclic hydrazoethylenediazene hexamolybdate tetrabutylammonium derivative according to any one of claims 1-2 or the pharmaceutical composition according to claim 6 in the preparation of a drug for preventing and / or treating tuberculosis caused by Mycobacterium tuberculosis H37Rv infection.

9. Use of the heterocyclic hydrazoethylenediazene hexamolybdate tetrabutylammonium derivative according to any one of claims 1-2 or the pharmaceutical composition according to claim 6 in the preparation of a Mycobacterium tuberculosis H37Rv proliferation inhibitor.

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