Antimony-sulfur compound as well as preparation method and application thereof

Abstract

The invention discloses an antimony-sulfur compound as well as a preparation method and application thereof. Sulfohydrazide is used as a sulfur source of metal antimony sulfide, NHC-BH3 is used as an accelerant, and all the used raw materials have no stink. The method has the advantages of low cost, higher yield, simplicity and convenience in operation, one-step reaction, no need of pre-synthesis of active intermediate products, no metal catalysis, no stink, few additives, easiness in separation and the like, and has potential industrial application prospects as a water-resistant and antioxidant stable metal vulcanization reagent. And the obtained antimony-sulfur compound has different degrees of inhibition effects on different cancer cells, and is a potential anti-cancer drug.

Description

[Technical field]

[0001] The invention belongs to the field of metal sulfiding reagent synthesis, and in particular relates to an antimony sulfide compound and a preparation method and application thereof. [Background technology]

[0002] N-heterocyclic carbene borane (NHC-BH3) is a stable compound that is easy to prepare and handle and is widely used in synthetic chemistry. 36 Currently, it is used to form CB (Org. Lett. 2022, 24, 2232-2237) and SB (J. Am. Chem. Soc. 2013, 135, 10484-10491) bonds. In addition, NHC-BH3 has been used for reduction reactions, including the reduction of ketones to alcohols (Org. Lett. 2012, 14, 4540-4543), the elimination of cyano groups (Angew. Chem., Int. Ed. 2024, 63, e202405779), and the reduction of thioethers to thiols (Org. Lett. 2022, 24, 8559-8563). In addition, this reagent can be used to activate CX (X = F, Cl, I) to form CH (Organic Letters 2024, 26, 928-932.) or C (sp 3 )-C(sp 3 )(J.Am.Chem.Soc.2023,145,991-999) bond. Nevertheless, there are no reports on its application in the construction of metal sulfides, especially metal antimony sulfides.

[0003] Thiols have always been the most reliable source for sulfurization reactions in industry (Org. Lett. 2018, 20, 2848-2852), but their stench and toxicity hinder their further application. Disulfides are also common substrates for transition metal-catalyzed CS bond formation (J. Org. Chem. 2019, 84, 13073-13091.). In some of these reactions, the existing metal sulfur intermediates are very active and usually produce relative sulfidation targets through autoreduction elimination (Org. Lett. 2022, 24, 6159-6164). Due to their high reactivity, these organometallic sulfides are difficult to separate, especially under humid conditions. It will be crucial to develop an air-stable and active metal sulfur complex as a sulfurization reagent. There is currently a method for preparing antimony sulfide compounds (Org. Lett. 2022, 24, 6159-6164), and the obtained antimony sulfide compounds are stable in air and can be used as sulfiding agents for alkyne substrates to obtain sulfided (Z)-olefins. The obtained antimony sulfide reagent can also be cross-coupled with halogenated alkanes or halogenated aromatics to obtain corresponding sulfide compounds. However, when synthesizing antimony sulfide compounds, the process undergoes a two-step reaction, and the starting substrate is a disulfide, which has a bad smell, and the reaction intermediates are highly active and unstable. [Summary of the invention]

[0004] The present invention patent reports a method for preparing antimony sulfide compounds. The process starts from odorless sulfonyl hydrazide and synthesizes the target compound in one step, and involves few additives. The present invention solves the problems that cannot be solved in some literature reports, such as o- / m-methyl antimony sulfide, iso-triphenyl antimony sulfide, trifluoromethylphenyl antimony sulfide, p-tert-butylphenyl antimony sulfide and p-trifluoromethoxyphenyl antimony sulfide. At present, NHC-BH 3 The antimony sulfide compounds obtained by the present invention are used as promoters to synthesize metal antimony sulfide compounds. The antimony sulfide compounds obtained by the present invention are applied to the inhibition detection of cancer cells, and it is found that some products have moderate anticancer effects.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] An antimony sulfide compound, wherein the antimony sulfide compound has the chemical formula of antimony sulfide compound I or antimony sulfide compound II:

[0007]

[0008] Wherein, Ar is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-m-trimethylphenyl, 4-p-tert-butylphenyl, 4-p-methoxyphenyl, 4-p-trifluoromethoxyphenyl, 2-naphthyl, N,N-dimethylnaphthyl-1-amine, biphenyl, 2,3-dihydrobenzofuranyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 4-iodophenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-methylformylphenyl, 4-trifluoromethylphenyl, 4-cyanophenyl, 2-thienyl, 1-methyl-1H-pyrazol-4-yl and 3-pyridyl; Alkyl is selected from methyl, propyl, dodecyl, cyclohexyl and benzyl.

[0009] A method for preparing an antimony sulfide compound comprises the following steps: using a sulfonyl hydrazide compound III or a sulfonyl hydrazide compound IV as a raw material, NHC-BH 3 As a catalyst, the reaction is carried out at 120-150°C for 12 hours in a nitrogen environment to obtain antimony sulfide compound I or antimony sulfide compound II; the chemical formula of sulfonyl hydrazide compound III is:

[0010] Alkyl-SO 2 NHNH 2

[0011] III

[0012] The chemical formula of sulfonylhydrazide compound IV is:

[0013] Ar-SO 2 NHNH 2

[0014] IV.

[0016] In a further improvement, the organic solvent is m-xylene.

[0017] Further improvement, based on raw materials, NHC-BH 3 The amount added was 2 equivalents.

[0018] Further improvement, in the chemical formula, Ar is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 3-methylphenyl, m-trimethylphenyl, 4-p-tert-butylphenyl, 4-p-methoxyphenyl, 4-p-trifluoromethoxyphenyl, 2-naphthyl, N,N-dimethylnaphthyl-1-amine, biphenyl, 2,3-dihydrobenzofuranyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 4-iodophenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-methylformylphenyl, 4-trifluoromethylphenyl, 4-cyanophenyl, 2-thienyl, 1-methyl-1H-pyrazol-4-yl and 3-pyridyl; Alkyl is selected from methyl, propyl, dodecyl, cyclohexyl and benzyl.

[0019] A use of the antimony sulfide compound as described above, wherein the antimony sulfide compound is used as a drug for treating or preventing cancer.

[0020] In a further improvement, the cancer includes but is not limited to human breast cancer.

Brief Description of the Drawings

[0021] Figure 1 This invention provides a NHC-BH 3 A roadmap for the preparation of antimony sulfide compounds based on sulfonylhydrazide-facilitated synthesis.

[0022] Figure 2 This is a graph showing the inhibitory activity of different antimony sulfide compounds on different cancer cells. [Specific implementation method]

[0023] Sulfonylhydrazide compounds III and IV were used as raw materials, m-xylene was used as solvent (1 mL), 2 equivalents of NHC-BH3 (V), 0.1 mmol of antimony chloride compound (VI), reaction conditions were 140 ° C, reaction was carried out under nitrogen environment for 12 hours, and after the reaction was completed, column chromatography was used to separate the target product.

[0024] The present invention will be further described below in conjunction with specific preparation examples:

[0025] Preparation Example 1

[0026] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140℃, reaction under nitrogen environment for 12h. After the reaction, 6-Phenyl-12-(phenylthio)-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=phenyl) was obtained by column chromatography as a white solid with a yield of 70%. Mp:188–189℃, 1H NMR(400MHz,Chloroform-d)δ8.29(dd,J=7.4,1.4Hz,2H),7.46–7.41(m,2H),7.2 9(td,J=7.4,1.4Hz,2H),7.23(td,J=7.4,1.5Hz,2H),7.15(d,J=1.9Hz,1H),7.14– 7.11(m,2H),7.11–7.08(m,1H),7.06(dd,J=5.5,2.2Hz,3H),7.04(s,1H),7.03–6 .98(m,1H),6.94(t,J=7.3Hz,1H),4.57(d,J=15.0Hz,2H),4.32(d,J=15.0Hz,2H). 13 C{ 1 H}NMR(101MHz,Chloroform-d)δ148.3,143.5,137.5,136.0,134.3,129.3,128 .9,128.9,128.6,126.1,125.4,123.6,118.7,59.2.HRMS(ESI-TOF)m / z:[M+H] + calcd.for C 26 H 23 Nb + 502.0584; found 502.0580.

[0027] Preparation Example 2

[0028] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 6-Phenyl-12-(p-tolylthio)-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-methylphenyl) is obtained by column chromatography to obtain a white solid with a yield of 92%.

[0029] Preparation Example 3

[0030] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3(V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 6-Phenyl-12-(o-tolylthio)-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=2-methylphenyl) is obtained by column chromatography to obtain a yellow oil with a yield of 79%.

[0031] Preparation Example 4

[0032] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 6-Phenyl-12-(m-tolylthio)-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=3-methylphenyl) is obtained by column chromatography as a white solid with a yield of 68%.

[0033] Preparation Example 5

[0034] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140℃, reaction for 12h under nitrogen environment. After the reaction, 12-((2,4,6-trimethylphenyl)thio)-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=m-trimethylphenyl) was obtained by column chromatography as a green solid with a yield of 36%. Mp:150-151℃. 1 H NMR(400MHz,Chloroform-d)δ8.63(d,J=7.4Hz,2H),7.42(t,J=7.4Hz,2H),7.32(t,J=7.4Hz,2H),7.20(q,J=7.4,6.9Hz,4H),7.0 7(d,J=8.1Hz,2H),7.00(t,J=7.3Hz,1H),6.87(s,2H),4.63(d,J=14.9Hz,2H),4.36(d,J=15.0Hz,2H),2.49(s,6H),2.21(s,3H).13 C{ 1 H}NMR(101MHz,Chloroform-d)δ148.8,143.5,142.9,138.1,136.3,135.7,132.5,129.3 ,128.9,128.9,128.8,126.1,123.4,118.5,59.1,24.5,21.0.HRMS(ESI-TOF)m / z:[M+H] + calcd.for C 29 H 29 Nb + 544.1053; found 544.1050.

[0035] Preparation Example 6

[0036] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((4-tertbutylphenyl)thio)-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-tert-butylphenyl) is separated by column chromatography to obtain a yellow solid with a yield of 63%.

[0037] Preparation Example 7

[0038] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((4-Methoxyphenyl)thio)-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-p-methoxyphenyl) is separated by column chromatography to obtain a white solid with a yield of 96%.

[0039] Preparation Example 8

[0040] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((4-trifluoromethoxyphenyl)thio)-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-trifluoromethoxyphenyl) is separated by column chromatography to obtain a white solid with a yield of 89%.

[0041] Preparation Example 9

[0042] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((2-naphthyl)thio)-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=2-naphthyl) is separated by column chromatography to obtain a yellow solid with a yield of 96%.

[0043] Preparation Example 10

[0044] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((5-(dimethylamino)-1-naphthyl)thio)-6-phenyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=N,N-dimethylnaphthyl-1-amine) is obtained by column chromatography to obtain a brown solid with a yield of 22%.

[0045] Preparation Example 11

[0046] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3(V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen for 12h. After the reaction is completed, 11-phenyl-5-[(4-phenylphenyl)sulfanyl]-10,12-dihydro-5H-5λ8,11λ4-benzo[3,4][1,2]azastibolo[1,2-a]benzo[c][1,2]azastibole (Ar=biphenyl) is separated by column chromatography to obtain a white solid with a yield of 87%.

[0047] Preparation Example 12

[0048] Sulfonamide compound IV (0.1 mmol) was added to a 10 mL reaction tube, m-xylene was used as solvent (1 mL), 2 equivalents of NHC-BH3 (V), 0.1 mmol of antimony chloride compound (VI), and the reaction conditions were 140°C and 12 hours under nitrogen. After the reaction, 5-(2,3-dihydro-1-benzofuran-5-ylsulfanyl)-11-phenyl-10,12-dihydro-5H-5λ8,11λ4-benzo[3,4][1,2]azastibolo[1,2-a]benzo[2,1-c][1,2]azastibole (Ar=2,3-dihydrobenzofuranyl) was obtained by column chromatography to obtain a white solid with a yield of 71%.

[0049] Preparation Example 13

[0050] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((4-Fluorophenyl)thio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-fluorophenyl) is separated by column chromatography to obtain a white solid with a yield of 87%.

[0051] Preparation Example 14

[0052] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3(V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-(4-Chlorophenyl)thio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-chlorophenyl) is separated by column chromatography to obtain a white solid with a yield of 90%.

[0053] Preparation Example 15

[0054] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((4-Bromophenyl)thio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-bromophenyl) is separated by column chromatography to obtain a white solid with a yield of 93%.

[0055] Preparation Example 16

[0056] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((3-Bromophenyl)thio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=3-bromophenyl) is separated by column chromatography to obtain a white solid with a yield of 66%.

[0057] Preparation Example 17

[0058] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3(V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen for 12h. After the reaction is completed, 12-((4-iodophenyl)thio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-iodophenyl) is separated by column chromatography to obtain a white solid with a yield of 44%.

[0059] Preparation Example 18

[0060] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 12-((4-Nitrophenyl)thio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-nitrophenyl) is separated by column chromatography to obtain a green solid with a yield of 34%.

[0061] Preparation Example 19

[0062] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140℃, reaction for 12h under nitrogen environment. After the reaction, methyl 4-[(11-phenyl-10,12-dihydro-5H-5λ8,11λ4-benzo[3,4][1,2]azastibolo[1,2-a]benzo[c][1,2]azastibol-5-yl)sulfanyl]benzoate (Ar=4-methylformylphenyl) was obtained by column chromatography as a white solid with a yield of 32%.

[0063] Preparation Example 20

[0064] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3(V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen for 12h. After the reaction is completed, 12-((trifluoromethyl)thio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-trifluoromethylphenyl) is separated by column chromatography to obtain a green solid with a yield of 92%.

[0065] Preparation Example 21

[0066] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 4-((6-Phenyl-6,7-dihydrodibenzo[c,f][1,5]azastibocin-12(5H)-yl)thio)benzonitrile (Ary=4-cyanophenyl) is obtained as a white solid by column chromatography separation, and the yield is 81%.

[0067] Preparation Example 22

[0068] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 6-Phenyl-12-(thiophen-2-ylthio)-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Ary=2-thienyl) is obtained by column chromatography as a white solid with a yield of 44%.

[0069] Preparation Example 23

[0070] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3(V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, reaction for 12h under nitrogen environment. After the reaction, 5-[(1-methylpyrazol-4-yl)sulfanyl]-11-phenyl-10,12-dihydro-5H-5λ8,11λ4-benzo[3,4][1,2]azastibolo[1,2-a]benzo[2,1-c][1,2]azastibole (Ary=1-methyl-1H-pyrazol-4-yl) was separated by column chromatography to obtain a pink solid with a yield of 6%.

[0071] Preparation Example 24

[0072] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, and the reaction is carried out under nitrogen for 12h. After the reaction is completed, 11-phenyl-5-(pyridin-3-ylsulfanyl)-10,12-dihydro-5H-5λ8,11λ4-benzo[3,4][1,2]azastibolo[1,2-a]benzo[2,1-c][1,2]azastibole (Ary=3-pyridyl) is obtained by column chromatography as a white solid with a yield of 77%.

[0073] Preparation Example 25

[0074] In a 10 mL reaction tube, sulfonamide compound III (0.1 mmol) was added, m-xylene was used as solvent (1 mL), and 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, reaction for 12h under nitrogen environment. After the reaction, 12-(Methylthio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Alkyl=methyl) was obtained by column chromatography as a colorless solid with a yield of 52%.

[0075] Preparation Example 26

[0076] In a 10 mL reaction tube, sulfonamide compound III (0.1 mmol) was added, m-xylene was used as solvent (1 mL), and 2 equivalents of NHC-BH 3(V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, reaction for 12h under nitrogen environment. After the reaction, 6-Phenyl-12-(propylthio)-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Alkyl=propyl) was obtained by column chromatography as a yellow solid with a yield of 43%.

[0077] Preparation Example 27

[0078] Sulfonamide compound IV (0.1 mmol) was added to a 10 mL reaction tube, m-xylene was used as solvent (1 mL), and 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, reaction for 12h under nitrogen environment. After the reaction, 12-(dodecylthio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Alkyl=dodecyl) was obtained by column chromatography as a colorless oil with a yield of 56%.

[0079] Preparation Example 28

[0080] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, reaction for 12h under nitrogen environment. After the reaction, 12-(Cyclohexylthio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Alkyl=cyclohexyl) was obtained by column chromatography as a colorless oil with a yield of 42%.

[0081] Preparation Example 29

[0082] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3(V), 0.1mmol of antimony chloride (VI), reaction conditions are 140°C, reaction for 12h under nitrogen environment. After the reaction, 12-(Benzylthio)-6-phenyl-5,6,7,12tetrahydrodibenzo[c,f][1,5]azastibocine (Alkyl=benzyl) was obtained by column chromatography as a yellow solid with a yield of 22%.

[0083] Preparation Example 30

[0084] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 120°C, and reaction is carried out under nitrogen environment for 12h. After the reaction is completed, 6-Phenyl-12-(p-tolylthio)-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-methyl) is obtained by column chromatography to obtain a white solid with a yield of 70%.

[0085] Preparation Example 31

[0086] In a 10 mL reaction tube, sulfonamide compound IV (0.1 mmol) and m-xylene (1 mL) were added. 2 equivalents of NHC-BH 3 (V), 0.1mmol of antimony chloride (VI), reaction conditions are 150°C, and reaction is carried out under nitrogen atmosphere for 12h. After the reaction is completed, 6-Phenyl-12-(p-tolylthio)-5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine (Ar=4-methyl) is obtained by column chromatography as a white solid with a yield of 88%.

[0087] The following is a further description of the present invention in combination with the test of antimony sulfide compounds on different cancer cells:

[0088] Experimental steps: The biological activity of the organometallic complex was determined by the CCK-8 method. DMSO was added to each organometallic complex to be tested to dissolve the concentration of the organometallic complex to 10 mM. Subsequently, 10×103 cells were inoculated in each well of a 96-well plate with complete culture medium containing 10% fetal bovine serum. After they adhered to the wall, a 20uM concentration of the complex to be tested was added and cultured for 24 hours. A 10% CCK-8 solution was added and incubated at 37°C for 1 hour. Subsequently, a microplate absorbance meter was used to measure the absorbance of formazan formed in the cells at 450nm. The survival rates of different cells were obtained as shown in the following figure. Figure 2 shown.

[0089] Through experiments, it was found that all the compounds in the cases had different degrees of influence on different cancer cells. Among them, the antimony sulfur compounds described in Examples 12, 25 and 26 had obvious inhibitory effects on MDA-MB-231 (human breast cancer cells). Examples 18, 23 and 24 had obvious inhibitory effects on 4T1 (mouse breast cancer cell line). This shows that antimony sulfur compounds have anticancer activity and are potential anticancer agents.

Claims

1. An antimony sulfide compound, characterized in that The antimony sulfide compound has the chemical formula of antimony sulfide compound I or antimony sulfide compound II: Wherein, Ar is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-m-trimethylphenyl, 4-p-tert-butylphenyl, 4-p-methoxyphenyl, 4-p-trifluoromethoxyphenyl, 2-naphthyl, N,N---methylnaphthyl-1-amine, biphenyl, 2,3-dihydrobenzofuranyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 4-iodophenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-methylformylphenyl, 4-trifluoromethylphenyl, 4-cyanophenyl, 2-thienyl, 1-methyl-1H-pyrazol-4-yl and 3-pyridyl; Alkyl is selected from methyl, propyl, dodecyl, cyclohexyl and benzyl.

2. A method for preparing an antimony sulfide compound, characterized in that: The method comprises the following steps: in an organic solvent, using a sulfonylhydrazide compound III or a sulfonylhydrazide compound IV as a raw material, NHC-BH3 as a catalyst, reacting at 120-150° C. for 12 hours under a nitrogen environment to obtain an antimony sulfide compound I or an antimony sulfide compound II; The chemical formula of sulfonylhydrazide compound III is: Alkyl-SO2NHNH2 III The chemical formula of sulfonylhydrazide compound IV is: Ar-SO2NHNH2 IV 3. The method for preparing an antimony sulfide compound according to claim 1, characterized in that: The organic solvent is m-xylene.

4. The method for preparing an antimony sulfide compound according to claim 1, characterized in that: Based on the raw material, the amount of NHC-BH3 added was 2 equivalents.

5. The method for preparing an antimony sulfide compound according to claim 1, characterized in that: In the chemical formula, Ar is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 3-methylphenyl, m-trimethylphenyl, 4-p-tert-butylphenyl, 4-p-methoxyphenyl, 4-p-trifluoromethoxyphenyl, 2-naphthyl, N,N-dimethylnaphthyl-1-amine, biphenyl, 2,3-dihydrobenzofuranyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 3-bromophenyl, 4-iodophenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-methylformylphenyl, 4-trifluoromethylphenyl, 4-cyanophenyl, 2-thienyl, 1-methyl-1H-pyrazol-4-yl and 3-pyridyl; Alkyl is selected from methyl, propyl, dodecyl, cyclohexyl and benzyl.

6. Use of the antimony sulfide compound according to claim 1, characterized in that: The antimony sulfide compound is useful as a drug for treating or preventing cancer.

7. The use of the antimony sulfide compound according to claim 6, characterized in that: Such cancers include but are not limited to human breast cancer.

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