Synthetic methods for polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives

Abstract

This invention relates to a method for synthesizing polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives. This invention is the first to employ a technical solution that uses an organic base to activate elemental sulfur under the catalysis of an iodine compound, with a sulfoxide compound acting as a co-oxidant, to convert indole compounds and elemental sulfur into polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives in an air atmosphere. The technical solution has the following advantages: (1) The required reagents are stable, require no pretreatment, and are inexpensive and readily available; (2) The one-pot synthesis method has obvious advantages in terms of step economy, saving time and effort; (3) No transition metal catalysis is required, thus eliminating the problem of metal residue from the source; (4) Inexpensive iodine compounds are used for catalysis, reducing environmental pollution and saving reaction costs; (5) The entire reaction system is simple, has excellent selectivity, requires few reaction devices, and is easy to operate; (6) It is particularly suitable for preparing functional materials, bioactive molecules, and drug molecules.

Description

Technical Field

[0001] This invention relates to a method for synthesizing polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives, belonging to the field of organic compound synthesis technology. Background Technology

[0002] Polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives constitute an important subclass of indole compounds, and many bioactive molecules contain this type of polysulfide indole structure. These molecules contain a "-S4-" bond, and their eight-membered ring structure is composed of "S4C4". This unique non-planar tetrasulfide eight-membered ring structure gives [1,2,3,4]tetrathio[5,6-b:7,8-b']diindole compounds unique properties and demonstrates potential applications in the pharmaceutical field. (After Montanari L, Pavanetto F, Mazza M.Il Farmaco; edizione scientifica, 1984, 36(10):856-861. and Gordon W Rewcastle, Tomasz Janosik, Jan Bergman. Tetrahedron 2001,57(33):7185-7189.DOI:10.1016 / S0040-4020(01)00660-3)

[0003] To date, the synthetic methods for polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole have the following drawbacks: (1) the use of stoichiometric lithium metal reagents to promote sulfidation, involving multiple steps; (2) regioselectivity is difficult to control; (3) the use of highly toxic and malodorous sulfur chloride or phosphorus pentasulfide as the sulfur source; and (4) the preparation under high-temperature conditions in reflux with DMF (N,N-dimethylformamide), resulting in low yields when the indole nitrogen position is substituted. (Based on Tomasz Janosik, Jan Bergman, Birgitta Stensland, Claes) J.Chem.Soc.,Perkin Trans.1,2002,(3):330-334.DOI:10.1039 / B109840C and Wayne Carpenter,MS Grant,HR Snyder,J.Am.Chem.Soc.1960,82(11):2739-2742.DOI:10.1021 / ja01496a022.) Therefore, it is essential to develop a one-pot regioselective synthesis method for polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole compounds using simple and inexpensive starting materials under transition metal-free conditions. Summary of the Invention

[0004] This invention provides a method for synthesizing polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives.

[0005] The technical solution adopted by this invention to solve its technical problem is: the polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives, the general formula of which is Formula I:

[0006]

[0007] in

[0008] R 1 Selected from:

[0009] Hydrogen atom; C1-C10 straight-chain alkyl, branched alkyl, cyclic alkyl; substituted or unsubstituted C6-C20 aryl groups; substituted or unsubstituted heterocyclic groups containing nitrogen, oxygen, and sulfur atoms; halogens, methoxy groups, benzyloxy groups;

[0010] R 2 Selected from:

[0011] Hydrogen atom; C1-C10 straight-chain alkyl, oxygen-containing alkyl, branched alkyl, cyclic alkyl; substituted or unsubstituted C6-C20 aryl;

[0012] The synthesis method is as follows: using an iodine-containing compound as a catalyst, an organic base as an elemental sulfur activator, and a sulfoxide compound as a pro-oxidant, it includes the following synthetic steps:

[0013] S1: Add indole compounds, elemental sulfur, catalyst, organic base, sulfoxide compound and organic solvent;

[0014] S2: Mix the reactants thoroughly and heat them in air.

[0015] S3: Purification to obtain polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives.

[0016] Preferably, in the synthesis method of the present invention, the indole compound is selected from C7-C30 aromatic indoles, and its general formula is Formula II:

[0017]

[0018] Preferably, in the synthesis method of the present invention, the indole compound is selected from: 1-methylindole, 1,4-dimethylindole, 1-methyl-4-fluoroindole, 1,5-dimethylindole, 1-methyl-5-methoxyindole, 1-methyl-5-benzyloxyindole, 1-methyl-5-fluoroindole, 1-methyl-5-chloroindole, 1-methyl-5-bromoindole, 1,6-dimethylindole, 1-methyl-6-methoxyindole, 1-methyl 1-Methyl-6-chloroindole, 1,7-dimethylindole, 1-methyl-7-methoxyindole, 1-methyl-7-fluoroindole, NH-indole, 1-ethylindole, 1-isopropylindole, 1-propylindole, 1-(2-methoxyethyl)indole, 1-benzylindole, 1-n-octyl-5-bromoindole, 1-phenylindole, 1-methyl-5,6-dichloroindole, 1-methyl-7-azaindole.

[0019] Preferably, in the synthesis method of the present invention, the organic base compound has the general formula III:

[0020]

[0021] in

[0022] R 3 Selected from: hydrogen atoms; C1-C10 straight-chain alkyl, branched alkyl, cyclic alkyl; substituted or unsubstituted C6-C20 aryl groups; substituted or unsubstituted heterocyclic groups containing nitrogen, oxygen, and sulfur atoms;

[0023] R 4 Selected from: hydrogen atoms; C1-C10 straight-chain alkyl, branched alkyl, cyclic alkyl; substituted or unsubstituted C6-C20 aryl groups; substituted or unsubstituted heterocyclic groups containing nitrogen, oxygen, and sulfur atoms;

[0024] R 5 Selected from: hydrogen atoms; C1-C10 straight-chain alkyl, branched alkyl, cyclic alkyl; substituted or unsubstituted C6-C20 aryl groups; substituted or unsubstituted heterocyclic groups containing nitrogen, oxygen, and sulfur atoms;

[0025] Ar is selected from: aromatic five-membered ring, aromatic six-membered ring, aromatic benzo[a] fused ring;

[0026] Preferably, in the synthesis method of the present invention, the organic base compound is selected from one or more of the following: diethylamine, triethylamine, triethylenetetramine, 1,8-diazabicycloundec-7-ene, triethylenediamine, tetrahydropyrrole, piperidine, morpholine, pyrrole, 1-methylpyrrole, 2-methylpyrrole, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, quinoline, and isoquinoline.

[0027] Preferably, in the synthesis method of the present invention, the iodine-containing compound is selected from one or more of the following: elemental iodine, hydroiodic acid, potassium iodide, sodium iodide, ammonium iodide, iodine chloride, iodine bromide, iodine trichloride, N-iodosuccinimide, tetramethylamine iodide, tetrabutylammonium iodide, [bis(trifluoroacetoxy)iodo]benzene, iodophenyldiacetic acid, and trimethyl sulfoxide.

[0028] Preferably, in the synthesis method of the present invention, the sulfoxide compound is selected from one or more of dimethyl sulfoxide, dibutyl sulfoxide, methyl phenyl sulfoxide, dibenzyl sulfoxide, diphenyl sulfoxide, and tetramethylene sulfoxide.

[0029] Preferably, in the synthesis method of the present invention, the reaction atmosphere is: air atmosphere; the molar ratio of indole compound, organic base compound, sulfoxide compound, elemental sulfur and iodine-containing compound is 2.0-10:5.0-25:4.0-25:10-50:0.2-5.0; simultaneously, the reaction temperature is 140℃-160℃; the reaction time is 2h-24h; and the organic solvent is one or more of mesitylene, chlorobenzene, o-dichlorobenzene, 1,4-dioxane, and ethylbenzene.

[0030] The beneficial effects of this invention compared to the prior art are as follows:

[0031] (I) This invention is the first to adopt a technical solution in which an organic base activates elemental sulfur under the catalysis of an iodine-containing compound, and a sulfoxide compound is used as a co-oxidant to convert indole compounds and elemental sulfur into a novel polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole in an air atmosphere, thereby obtaining a polysulfide indole product with stable structure and excellent chemical properties and its by-products.

[0032] (II) Under the catalysis of iodine-containing compounds, organic bases activate elemental sulfur, sulfoxides act as pro-oxidants, and in air atmosphere, indole compounds and elemental sulfur are converted into a polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole. The reaction raw materials are inexpensive and readily available, and no pretreatment is required. The reaction has high atom economy.

[0033] (III) Under the catalysis of iodine-containing compounds, organic bases activate elemental sulfur, and sulfoxide compounds act as pro-oxidants. In an air atmosphere, indole compounds and elemental sulfur are converted into a polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole. The reaction does not require the use of metal catalysts or equivalent metal oxidants. It only requires the use of inexpensive iodine-containing compounds and sulfoxide compounds, which reduces environmental pollution, saves raw materials, and lowers reaction costs.

[0034] (IV) Under the catalysis of iodine-containing compounds, organic bases activate elemental sulfur, sulfoxides act as pro-oxidants, and in air atmosphere, indole compounds and elemental sulfur are converted into a polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole. This technical solution adopts a "one-pot" direct selective synthesis of the target product, which overcomes the huge waste of human, financial and material resources caused by existing multi-step synthesis methods, and saves a lot of research and development time and production cycle.

[0035] (V) Under the catalysis of iodine-containing compounds, organic bases activate elemental sulfur, and sulfoxide compounds act as pro-oxidants. In an air atmosphere, indole compounds and elemental sulfur are converted into a polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole. This technical solution overcomes the difficulties of providing sulfur source with elemental sulfur, low sulfur atom introduction rate, and difficulty in controlling the number of introduced atoms. This allows the actual application of the product to be brought forward significantly, creating the basic conditions for early industrial production.

[0036] (VI) Under the catalysis of iodine-containing compounds, organic bases activate elemental sulfur, and sulfoxides act as pro-oxidants. In an air atmosphere, indole compounds and elemental sulfur are converted into a polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole. This scheme is scientific, reasonable, easy to operate, has few reaction steps, and requires little equipment.

[0037] (VII) Under the catalysis of iodine-containing compounds, organic bases activate elemental sulfur, and sulfoxides act as pro-oxidants. In an air atmosphere, indole compounds and elemental sulfur are converted into a polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole. This technical solution has the advantages of wide availability of raw materials, low input, high output, and easy to further mass-produce and promote.

[0038] (VIII) Under the catalysis of iodine-containing compounds, organic bases activate elemental sulfur, and sulfoxide compounds act as pro-oxidants. In an air atmosphere, indole compounds and elemental sulfur are converted into a polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole. This technical solution has the characteristics of simple reaction system, mild reaction conditions, selective provision of S4 source by elemental sulfur to generate double CS bonds, simple and safe experimental operation, wide availability of raw materials, easy expansion of users and applications, high product utilization value, and promising market commercialization prospects.

[0039] This invention relates to polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives, as well as their synthetic methods. These methods can be widely applied in optoelectronics, printing and dyeing, pharmaceuticals, and other fields. They are particularly suitable for the research and development of highly efficient and selective synthesis of polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole compounds using a metal-free, multi-component, one-pot method. Attached Figure Description

[0040] To demonstrate the product of this invention, the present invention provides NMR hydrogen and NMR carbon spectra of some embodiments. a is the hydrogen spectrum, and b is the carbon spectrum.

[0041] Figure 1a and 1b The NMR spectrum of the product of Example 1; Figure 2a and 2b The NMR spectrum of the product of Example 2;

[0042] Figure 3a and 3b The NMR spectrum of the product of Example 3; Figure 4a and 4b The NMR spectrum of the product of Example 4;

[0043] Figure 5a and 5b The NMR spectrum of the product of Example 5; Figure 6a and 6b The NMR spectrum of the product of Example 6;

[0044] Figure 7a and 7b The NMR spectrum of the product of Example 7; Figure 8a and 8b The NMR spectrum of the product of Example 8;

[0045] Figure 9a and 9b The NMR spectrum of the product of Example 9; Figure 10a and 10b The NMR spectrum of the product of Example 10;

[0046] Figure 11a and 11b The NMR spectrum of the product of Example 11; Figure 12a and 12b The NMR spectrum of the product of Example 12;

[0047] Figure 13a and 13b The NMR spectrum of the product of Example 13; Figure 14a and 14b The NMR spectrum of the product of Example 14;

[0048] Figure 15a and 15b The NMR spectrum of the product of Example 17; Figure 16a and 16b The NMR spectrum of the product of Example 18;

[0049] Figure 17a and 17b The NMR spectrum of the product of Example 19; Figure 18a and 18b The NMR spectrum of the product of Example 20;

[0050] Figure 19a and 19b The NMR spectrum of the product of Example 21; Figure 20a and 20b The NMR spectrum of the product of Example 22;

[0051] Figure 21a and 21b The NMR spectrum of the product of Example 23; Figure 22a and 22b The NMR spectrum of the product of Example 24;

[0052] Figure 23a and 23b The NMR spectrum of the product of Example 25; Figure 24a and 24b The NMR spectrum of the product of Example 26; Detailed Implementation

[0053] The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic diagrams, illustrating only the basic structure of the invention, and therefore only show the components relevant to the invention.

[0054] The reaction equation is:

[0055] Where air is air (but there is no need to limit the gas atmosphere; nitrogen or argon environments are also acceptable).

[0056]

[0057] Examples 1-26

[0058] Examples 1-26 are methods for synthesizing polysubstituted-5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives.

[0059] Includes the following steps:

[0060] Step 1: Add indole compounds (specific substances are shown in Table 1), organic bases (specific substances are shown in Table 1), sulfoxide compounds (specific substances are shown in Table 1), and elemental sulfur to the reaction vessel. Add iodine-containing compounds (specific substances are shown in Table 1) and organic solvents (specific substances are shown in Table 1) to the reaction vessel separately. Alternatively, a mixture of iodine-containing compounds (specific substances are shown in Table 1) and organic solvents (specific substances are shown in Table 1) can be added to the vessel separately.

[0061] Step 2: Heat and stir the reaction vessel uniformly (e.g., in an oil bath) to the temperature described in Table 1. The indole compounds and elemental sulfur react in the solvent for the time described in Table 1.

[0062] Step 3: Purify to obtain polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives.

[0063] Table 1: Molar ratios, reaction temperatures, and reaction times of indole compounds, organic base compounds, iodine-containing compounds, sulfoxide compounds, organic solvents, (indole compounds, organic base compounds, sulfoxide compounds, elemental sulfur, and iodine-containing compounds) in Examples 1-26.

[0064]

[0065]

[0066]

[0067] * indicates the molar ratio of indole compounds, organic base compounds, sulfoxide compounds, elemental sulfur, and iodine-containing compounds.

[0068] In the reactions described above, two molecules of indole compounds undergo C3-position self-coupling under the action of an iodine-containing compound to generate a 3,3'-binindole intermediate. Elemental sulfur, activated by an organic base, provides the "S4" building block through ring-opening and bond breaking, and then undergoes a [4+4] cyclization reaction with the 3,3'-binindole intermediate under the action of iodides and sulfoxides to construct a [1,2,3,4]tetrathio[5,6-b:7,8-b']diindole skeleton, generating the target compound.

[0069] The conversion rate of the substances in the reaction vessel after step 3 was detected and nuclear magnetic resonance was performed. The results of some embodiments are as follows:

[0070] The NMR data of the product from Example 1 are as follows:

[0071] 1 H NMR (400MHz, CDCl3, ppm) δ7.48–7.41(m,4H),7.40–7.34(m,2H),7.13–7.06(m,2H),4.00(s,6H); 13 C NMR (100MHz, CDCl3, ppm) δ137.4,128.0,126.7,124.8,121.238,120.9,120.34,110.3,30.7.

[0072] The NMR data of the product from Example 2 are as follows:

[0073] 1 H NMR (400MHz, CDCl3, ppm) δ7.28–7.21(m,4H),6.90–6.82(m,2H),3.99(s,6H),1.96(s,6H); 13 CNMR (100MHz, CDCl3, ppm) δ137.4,132.9,130.1,127.2,124.6,121.8,121.7,108.0,30.8,19.2.

[0074] The NMR data of the product in Example 3 are as follows:

[0075] 1 H NMR (400MHz, CDCl3, ppm) δ7.28–7.20 (m, 2H), 7.05 (d, J = 8.4Hz, 2H), 6.91–6.80 (m, 2H), 3.88 (s, 6H); 13 C NMR (100MHz, CDCl3, ppm) δ156.1 (d, J = 252.6Hz), 142.4, 138.9 (d, J = 9.0Hz), 125.5 (d, J = 7.8H z), 117.6 (d, J = 17.7Hz), 116.8 (d, J = 3.9Hz), 107.4 (d, J = 18.8Hz), 106.8 (d, J = 4.4Hz), 32.1.

[0076] The NMR data of the product in Example 4 are as follows:

[0077] 1H NMR (400MHz, CDCl3, ppm) δ7.31 (d, J=8.5Hz, 2H), 7.26–7.24 (m, 2H), 7.20 (dd, J=8.4, 1.7Hz, 2H), 3.96 (s, 6H), 2.37 (s, 6H); 13 C NMR (100MHz, CDCl3, ppm) δ135.9,129.8,128.1,126.9,126.6,120.5,120.4,110.0,30.7,21.4.

[0078] The NMR data of the product in Example 5 are as follows:

[0079] 1 H NMR (500MHz, Chloroform-d) δ7.33 (d, J = 8.9 Hz, 2H), 7.05 (dd, J = 9.0, 2.1 Hz, 2H), 6.85 (s, 1H), 3.99 (s, 3H), 3.68 (s, 3H); 13 C NMR (126MHz, CDCl3) δ154.7,132.9,128.2,126.8,120.5,116.2,111.3,101.5,55.8,30.9.

[0080] The NMR data of the product in Example 6 are as follows:

[0081] 1 H NMR (400MHz, CDCl3, ppm) δ7.38–7.34(m,6H),7.33–7.28(m,4H),7.28–7.23(m,2 H),7.14(dd,J=9.0,2.4Hz,2H),6.93(d,J=2.4Hz,2H),4.87(s,4H),4.00(s,6H); 13 C NMR (100MHz, CDCl3, ppm) δ153.8,137.1,133.0,128.4,127.8,127.6,126.8,120.3,116.7,111.6,102.9,70.6,30.9.

[0082] The NMR data of the product in Example 7 are as follows:

[0083] 1 H NMR (400MHz, CDCl3, ppm) δ7.35 (dd, J=9.0, 4.2Hz, 2H), 7.13 (td, J=9.1, 2.5Hz, 2H), 7.06 (dd, J=9.0, 2.5Hz, 2H), 3.98 (s, 6H); 13C NMR (100MHz, CDCl3, ppm) δ158.0 (d, J = 237.6Hz), 134.1, 129.7, 126.6 (d, J = 9.8Hz), 12 0.0(d,J=5.1Hz), 113.8(d,J=26.8Hz), 111.4(d,J=9.3Hz), 105.4(d,J=23.6Hz), 31.0.

[0084] The NMR data of the product in Example 8 are as follows:

[0085] 1 H NMR (400MHz, CDCl3, ppm) δ7.66 (d, J = 1.9Hz, 2H), 7.28 (dd, J = 8.8, 2.0Hz, 2H), 7.21 (d, J = 8.8Hz, 2H), 3.90 (s, 6H); 13 C NMR (100MHz, CDCl3, ppm) δ142.7,135.0,129.8,128.1,125.2,120.0,118.5,111.8,31.8.

[0086] The NMR data of the product from Example 9 are as follows:

[0087] 1 H NMR (400MHz, CDCl3, ppm) δ7.35 (dd, J=9.0, 4.2Hz, 2H), 7.13 (td, J=9.1, 2.5Hz, 2H), 7.06 (dd, J=9.0, 2.5Hz, 2H), 3.98 (s, 6H); 13 C NMR (100MHz, CDCl3, ppm) δ142.5,135.2,130.3,127.7,123.1,118.4,115.6,112.1,31.8.

[0088] The NMR data of the product of Example 10 are as follows:

[0089] 1 H NMR (400MHz, CDCl3, ppm) δ7.35(d,J=8.2Hz,2H),7.20(s,2H),6.93(d,J=8.2Hz,2H),3.94(s,6H),2.51(s,6H); 13 C NMR (100MHz, CDCl3, ppm) δ137.8,134.9,127.1,124.7,122.3,121.1,120.9,110.0,30.6,22.1.

[0090] The NMR data of the product of Example 11 are as follows:

[0091] 1 H NMR (500MHz, Chloroform-d) δ7.34(d,J=8.7Hz,2H),6.81(s,2H),6.76(dd,J=8.7,2.4Hz,2H),3.95(s,3H),3.91(s,3H); 13 C NMR (126MHz, CDCl3) δ158.7,138.4,126.3,122.1,121.5,121.2,111.2,92.8,55.7,30.7.

[0092] The NMR data of the product of Example 12 are as follows:

[0093] 1 H NMR (400MHz, CDCl3, ppm) δ7.39–7.32(m,2H),7.09(dd,J=9.6,2.2Hz,2H),6.87(td,J=9.1,2.2Hz,2H),3.95(s,6H); 13 C NMR (100MHz, CDCl3, ppm) δ161.6 (d, J = 242.5Hz), 137.6 (d, J = 12.2Hz), 128.4 (d, J = 3.5H z), 123.1, 122.3 (d, J = 10.4Hz), 120.8, 109.8 (d, J = 25.1Hz), 96.5 (d, J = 26.4Hz), 30.9.

[0094] The NMR data of the product in Example 13 are as follows:

[0095] 1 H NMR (400MHz, CDCl3, ppm) δ7.42(d,J=1.8Hz,2H),7.31(d,J=8.5Hz,2H),7.06(dd,J=8.6,1.8Hz,2H),3.95(s,3H); 13 C NMR (100MHz, CDCl3, ppm) δ137.7,131.0,129.0,125.0,121.9,121.4,120.4,110.3,30.9.

[0096] The NMR data of the product in Example 14 are as follows:

[0097] 1H NMR (400MHz, CDCl3, ppm) δ7.28–7.20 (m, 2H), 7.06 (d, J = 7.1Hz, 2H), 6.98–6.88 (m, 2H), 4.30 (s, 6H), 2.86 (s, 6H); 13 C NMR (101MHz, CDCl3) δ136.6,128.9,127.5,122.1,121.8,121.6,120.4,119.5,33.8,20.5.

[0098] The NMR data of the product in Example 17 are as follows:

[0099] 1 H NMR (400MHz, DMSO-d6, ppm) δ12.16 (s, 2H), 7.49 (d, J = 8.2Hz, 2H), 7.35–7.31 (m, 2H), 7.30–7.25 (m, 2H), 7.07 (t, J = 7.5Hz, 2H); 13 C NMR (100MHz, DMSO-d6), ppm) δ136.2,126.9,124.8,124.5,120.2,120.1,119.2,112.1.

[0100] The NMR data of the product of Example 18 are as follows:

[0101] 1 H NMR (400MHz, CDCl3, ppm) δ7.55–7.42(m,4H),7.39–7.33(m,2H),7.14–7.05(m,2H),4.69–4.55(m,2H),4.54–4.43(m,2H),1.49(t,J=7.2Hz,6H); 13 C NMR (100MHz, ppm) δ136.4,127.2,126.9,124.6,121.5,121.0,120.2,110.2,39.0,15.7.

[0102] The NMR data of the product of Example 19 are as follows:

[0103] 1 H NMR (400MHz, CDCl3, ppm) δ7.67 (d, J = 8.5Hz, 2H), 7.49–7.47 (m, 2H), 7.39–7.29 (m, 2H) ),7.13–7.04(m,2H),5.56–5.43(m,2H),1.80(d,J=7.0Hz,6H),1.73(d,J=7.1Hz,6H); 13C NMR (100MHz, ppm) δ135.4,127.9,127.7,124.0,121.8,121.3,119.8,112.2,48.3,21.6.

[0104] The NMR data of the product from Example 20 are as follows:

[0105] 1 H NMR (500MHz, Chloroform-d) δ7.50–7.41(m,4H),7.39–7.31(m,2H),7.08(t,J=7.5Hz,2H),4.64–4.24(m,4H),2.08–1.83(m,4H),1.03(t,J=7.4Hz,6H); 13 C NMR (126MHz, ppm) δ136.9,127.8,126.8,124.6,121.4,120.9,120.2,110.5,45.8,23.9,11.6.

[0106] The NMR data of the product of Example 21 are as follows:

[0107] 1 H NMR(500MHz,Chloroform-d)δ7.51(d,J=8.4Hz,2H),7.48–7.42(m,2H),7.39–7.32 (m,2H),7.13–7.05(m,2H),4.75–4.56(m,4H),3.80(t,J=6.3Hz,4H),3.36(s,6H); 13 CNMR (126MHz, CDCl3) δ137.4,127.8 126.8,124.8,121.3,121.3,120.5,110.7,71.6,59.2,43.9.

[0108] The NMR data of the product of Example 22 are as follows:

[0109] 1 H NMR (400MHz, CDCl3, ppm) δ7.54 (d, J = 8.1Hz, 2H), 7.41–7.19 (m, 10H), 7.20–7.00 (m, 6H), 5.87–5.57 (m, 4H); 13 C NMR (100MHz, ppm) δ137.5,137.2,128.7,128.4,127.4,127.0,126.6,125.0,121.4,121.2,120.6,110.9,47.6.

[0110] The NMR data of the product of Example 23 are as follows:

[0111] 1 H NMR (400MHz, CDCl3, ppm) δ7.82 (d, J=1.9Hz, 2H), 7.38 (dd, J=8.8, 1.9Hz, 2H), 7.16 (d, J= 8.8Hz,2H),4.44–4.08(m,4H),1.81–1.64(m,4H),1.40–1.17(m,24H),0.98–0.69(m,6H); 13 C NMR (100MHz, ppm) δ142.3,134.5,130.5,127.5,123.2,118.1,115.4,112.2,45.5,31.7,30.8,29.1,29.1,26.8,22.6,14.1.

[0112] The NMR data of the product of Example 24 are as follows:

[0113] 1 H NMR (400MHz, CDCl3, ppm) δ7.97–7.89(m,2H),7.5 1-7.41(m,10H),7.35–7.29(m,2H),7.23–7.18(m,4H); 13 C NMR (100MHz, CDCl3, ppm) δ139.1,136.3,131.4,129.9,129.6,126.7,124.3,122.9,120.9,119.8,110.7,108.4.

[0114] The NMR data of the product from Example 25 are as follows:

[0115] 1 H NMR (500MHz, CDCl3, ppm) δ7.74(s,2H),7.40(s,2H),3.86(s,6H); 13 C NMR (125MHz, CDCl3, ppm) δ143.4,135.2,129.1,128.3,126.7,121.6,118.6,112.2,31.9.

[0116] The NMR data of the product of Example 26 are as follows:

[0117] 1 H NMR (400MHz, CDCl3, ppm) δ8.56–8.48 (m, 2H), 7.73 (dd, J = 7.9, 1.6Hz, 2H), 7.15–7.00 (m, 2H), 4.11 (s, 6H);13 C NMR (100MHz, CDCl3, ppm) δ147.7,146.5,128.9,128.8,119.5,118.2,116.8,29.5.

[0118] Table 2: Conversion rates and product diagrams of reactions in Examples 1-26

[0119]

[0120]

[0121] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A method for synthesizing polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives. The structural formulas of the polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives are as follows: The method includes the following steps: Step 1: Add indole compounds, organic bases, sulfoxide compounds and elemental sulfur to the reaction vessel. Add iodine-containing compounds and organic solvents to the reaction vessel separately, or add a mixture of iodine-containing compounds and organic solvents to the vessel. Step 2: The reaction vessel is heated and stirred uniformly to 160°C, and the indole compounds and elemental sulfur react in the solvent for 2 hours. Step 3: Purify to obtain polysubstituted-5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives; The indole compound is 1,5-dimethylindole; the iodine-containing compound is N-iodosuccinimide: hydroiodic acid in a ratio of 1:2; the organic base is 4-methylpyridine; the sulfoxide compound is methylphenyl sulfoxide; The molar ratio of indole compounds, organic bases, sulfoxide compounds, elemental sulfur, and iodine-containing compounds is 2:5:5:10:0.4; the organic solvent is 1,4-dioxane.

2. A method for synthesizing polysubstituted-5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives, wherein the structural formula of the polysubstituted-5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives is as follows: The method includes the following steps: Step 1: Add indole compounds, organic bases, sulfoxide compounds, and elemental sulfur to the reaction vessel. Add iodine-containing compounds and organic solvents to the reaction vessel separately, or add a mixture of iodine-containing compounds and organic solvents to the vessel. Step 2: The reaction vessel is heated and stirred uniformly to 160°C, and the indole compounds and elemental sulfur react in the solvent for 4 hours. Step 3: Purify to obtain polysubstituted-5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives; The indole compound is 1-methyl-6-fluoroindole; the iodine-containing compound is tetramethylamine iodide: hydroiodic acid = 1:1; the organic base is 3-methylpyridine: piperidine = 3:1; the sulfoxide compound is dimethyl sulfoxide: tetramethylene sulfoxide = 2:1; The molar ratio of indole compounds, organic bases, sulfoxide compounds, elemental sulfur, and iodine-containing compounds is 4:10:10:20:1; the organic solvent is ethylbenzene:chlorobenzene = 1:

3.

3. A method for synthesizing polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives. The structural formulas of the polysubstituted -5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives are as follows: The method includes the following steps: Step 1: Add indole compounds, organic bases, sulfoxide compounds, and elemental sulfur to the reaction vessel. Add iodine-containing compounds and organic solvents to the reaction vessel separately, or add a mixture of iodine-containing compounds and organic solvents to the vessel. Step 2: The reaction vessel is uniformly heated and stirred to 145°C, and the indole compounds and elemental sulfur react in the solvent for 20 hours. Step 3: Purify to obtain polysubstituted-5,10-dihydro[1,2,3,4]tetrathio[5,6-b:7,8-b']diindole and its derivatives; The indole compound is 1,7-dimethylindole; the iodine-containing compound is iodine trichloride: hydroiodic acid = 1:2; the organic base is isoquinoline: pyrrole = 2:1; the sulfoxide compound is dibenzyl sulfoxide; The molar ratio of indole compounds, organic base compounds, sulfoxide compounds, elemental sulfur, and iodine-containing compounds is 2:5:4:10:0.4; the organic solvent is o-dichlorobenzene.

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