Preparation method and application of benzothienobenzothiophene (BTBT) and benzoselenophenobenzoselenophenes (BSBS) micromolecular materials

Abstract

The invention belongs to the technical field of molecular synthesis and materials, and discloses a preparation method and application of [1] benzothiophene [3, 2-b] [1] benzothiophene (BTBT) and [1] benzoselenophenol [3, 2-b] [1] benzoselenophenol (BSBS) micromolecular materials. According to the method, sodium hydrosulfide hydrate or sodium hydrogen selenide is added into a mixed solvent of N, N-dimethylacetamide and dimethyl sulfoxide to serve as a sulfur source or a selenium source, dipotassium phosphate serves as alkali, and a series of condensed ring thiophene / selenophen small molecular materials are synthesized through simple and efficient series cyclization reaction. The raw materials are cheap and easily available; no metal participates; the operation is simple in an air atmosphere; the reaction efficiency is high, and two thiophene rings or selenophenol rings can be simultaneously constructed through one-step reaction; the yield is high, and the reaction yield of an amplification amount (10 mmol) still can reach 55%. Therefore, the method is suitable for industrial production.

Description

Technical Field

[0001] The present invention belongs to the field of molecular synthesis and material technology, and in particular relates to a preparation method and application of [1]benzothiophene [3,2-b][1]benzothiophene (BTBT) and [1]benzoselenophene [3,2-b][1]benzoselenol (BSBS) small molecule materials. Background Art

[0002] Since the invention of the first polythiophene field-effect transistor in 1986, people have devoted great enthusiasm to the research of organic semiconductor materials, such as organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic cells (OPVs), which have been widely studied and applied. Organic semiconductor materials are a type of organic optoelectronic materials that contain π-electron structures and have optical, electrical and magnetic properties. Compared with traditional inorganic semiconductor materials, they have the advantages of easy molecular structure control, simple preparation process, low manufacturing cost, good flexibility and ductility, and easy large-scale preparation. In recent decades, with the continuous improvement of the performance of organic semiconductor devices, compared with polycyclic aromatic hydrocarbon materials represented by pentacene, heterocyclic aromatic hydrocarbon materials represented by BTBT and its derivatives have become a hot spot in the research of organic semiconductor devices due to their high mobility and good air stability. For example, 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) blended with polystyrene as the semiconductor layer of field-effect transistors has a maximum mobility of 43 cm 2 V -1 s -1 ; [See Y. Yuan, G. Giri, A. L. Ayzner, A. P. Zoombelt, S. C. B. Mannsfeld, J. Chen, D. Nordlund, M. F. Toney, J. Huang, Z. Bao, Nature Communications 2014, 5, 3005.] 2-Tridecyl[1]benzothieno[3,2-b]benzothiophene (C 13 -BTBT) can achieve a hole mobility of 17.2 cm in a low-voltage operating device 2 V -1 s -1 [See AYAmin, A. Khassanov, K. Reuter, TM Friedrichsen, M. Halik, Journal of the American Chemical Society 2012, 134, 16548-16550.] Several common methods for synthesizing [1]benzothiophene [3,2-b] [1]benzothiophene (BTBT) are summarized as follows:

[0003] (1) Method 1: Intramolecular CS coupling cyclization reaction

[0004]

[0005] This method requires step-by-step synthesis and harsh reaction conditions. The overall yield is low and the raw materials are not easily available, so the practical value is low. [See M. Saito, T. Yamamoto, I. Osaka, E. Miyazaki, K. Takimiya, H. Kuwabara, M. Ikeda, Tetrahedron Letters 2010, 51, 5277-5280.]

[0006] (2) Method 2: Intermolecular CS coupling cyclization reaction

[0007]

[0008] This method requires a temperature as high as 180°C and has a low yield, so it has low practical value. [See M. Saito, I. Osaka, E. Miyazaki, K. Takimiya, H. Kuwabara, M. Ikeda, Tetrahedron Letters 2011, 52, 285-288.]

[0009] (3) Method 3: Copper-catalyzed intramolecular CS coupling cyclization reaction

[0010]

[0011] This method has low practical value because it is difficult to obtain the substrate, uses expensive cuprous iodide catalyst, and has complicated post-processing. [See Y. Li, C. Nie, H. Wang, X. Li, F. Verpoort, C. Duan, European Journal Of Organic Chemistry 2011, 7331-7338.]

[0012] (4) Method 4: Intermolecular CS coupling cyclization reaction

[0013]

[0014] This method requires a reaction temperature of up to about 270°C, has complex post-processing, and has a low yield, so its practical value is low. [See B. V. J.SVOBODA,Collection of CzechoslovakChemical Communications 2002,67,645-664.]

[0015] (5) Method 5: Palladium-catalyzed intermolecular CS coupling cyclization reaction

[0016]

[0017] This method requires the use of expensive palladium catalysts and the substrate is difficult to obtain, so it has low practical value. [See S.V.Cespedes, A.Ferry, L.Candish, F.Glorius, Angewandte Chemie International Edition 2015, 54, 5772-5776.]

[0018] (6) Method 6: SI exchange reaction

[0019]

[0020] This method is difficult to obtain the substrate, is sensitive to air, has complex post-processing, and has a low yield, so it has low practical value. [See M. Wang, Q. Fan, X. Jiang, Organic Letters 2016, 18, 5756-5759.]

[0021] In summary, the existing technologies for synthesizing [1]benzothiophene [3,2-b][1]benzothiophene (BTBT) mostly have the following problems: 1) multi-step synthesis, difficult to obtain substrates, and expensive; 2) expensive palladium catalysts are required, which is costly; 3) harsh reaction conditions and too high reaction temperatures; 4) complex post-treatment and low product purity; 5) low yield. The above problems restrict the industrial production and broader application of BTBT and BSBS small molecule materials. Therefore, we developed a simple and efficient method for synthesizing [1]benzothiophene [3,2-b][1]benzothiophene (BTBT) and [1]benzoselenophene [3,2-b][1]benzoselenol (BSBS) small molecule materials. Summary of the invention

[0022] In view of the problems existing in the prior art, the present invention provides a method for preparing BTBT and BSBS small molecule materials.

[0023] The present invention is achieved in that the preparation method thereof comprises the following steps:

[0024] Using o-fluorobenzaldehyde, o-chlorobenzaldehyde, o-bromobenzaldehyde, o-iodobenzaldehyde or other o-halogenated aryl benzaldehyde as raw materials1, sodium hydrosulfide hydrate or sodium selenide as sulfur source or selenium source, a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide as solvent, dipotassium hydrogen phosphate, potassium bicarbonate, potassium phosphate, potassium acetate, potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, N,N-diisopropylethylamine, N-methylpiperidine, 4-dimethylaminopyridine or 2,6-lutidine as base, a series of BTBT and BSBS small molecule materials2 were synthesized through tandem cyclization reactions.

[0025] The synthetic route is as follows:

[0026]

[0027] Compared with other synthetic routes, the reaction conditions are relatively mild and the yield is higher; compared with the route of Kazuo Takimiya's group, the addition of base and the replacement of solvent greatly improve the reaction yield. [See M. Saito, I. Osaka, E. Miyazaki, K. Takimiya, H. Kuwabara, M. Ikeda, Tetrahedron Letters 2011, 52, 285-288.]

[0028] The Ar is selected from any one of an aryl group, a heteroaryl group, and an aryl group containing a substituent; the aryl group is any one of a phenyl group, a naphthyl group, and an anthracene group; the heteroaryl group is any one of a furan group, a thiophene group, a pyridine group, and a pyrrole group; the substituent R is one or more of hydrogen, a halogen group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a trifluoromethyl group, a trifluoromethoxy group, a hydroxyl group, an aryl group, an acyl group, an ester group, a nitro group, an amino group, a cyano group, and a (C1-C30 alkyl)amine group, and the position of the substituent is any position on the Ar ring; the base is any one of dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium bicarbonate, potassium phosphate, potassium dihydrogen phosphate, potassium acetate, potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, N-methylmorpholine, N,N-diisopropylethylamine, N-methylpiperidine, 4-dimethylaminopyridine, or 2,6-lutidine; and the solvent is a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide.

[0029] Typical conditions for the metal-free tandem cyclization reaction are as follows: 1 equivalent of compound 1, 1 equivalent of dipotassium hydrogen phosphate and 3 equivalents of sodium hydrosulfide hydrate or sodium selenide are added to a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide, and reacted at 145° C. for 24 hours.

[0030] Another object of the present invention is to provide a method for preparing the BTBT and BSBS small molecule materials, whose molecular structures are as follows:

[0031]

[0032] Another object of the present invention is to provide an organic semiconductor device manufactured from the BTBT and BSBS small molecule materials.

[0033] Another object of the present invention is to provide a digital camera manufactured using the organic semiconductor device.

[0034] Another object of the present invention is to provide a mobile phone manufactured using the organic semiconductor device.

[0035] Another object of the present invention is to provide a handheld computer manufactured using the organic semiconductor device.

[0036] The advantages and positive effects of the present invention are: the raw materials of the present invention are cheap and easy to obtain; no metal is involved; the operation is simple in air atmosphere; the reaction efficiency is high, and two thiophene rings or selenophene rings can be constructed simultaneously in one step; the addition of base and the replacement of solvent greatly improve the reaction yield, and the reaction yield of a large amount (10 mmol) can still reach 55%. Therefore, the method is suitable for industrial production.

[0037] Figure 1 It is a flow chart of the preparation method of BTBT and BSBS small molecule materials provided in an embodiment of the present invention.

[0038] Figure 2 It is a schematic diagram of the cyclic voltammetry curve of 3-C8-BTBT provided in an embodiment of the present invention (solvent dichloromethane, highest occupied orbital energy level: -5.54 eV).

[0039] Figure 3 It is a schematic diagram of the cyclic voltammetry curve of 3-tBu-BTBT provided in an embodiment of the present invention (solvent dichloromethane, highest occupied orbital energy level: -5.55 eV).

[0040] Figure 4 It is a schematic diagram of the cyclic voltammetry curve of 3-C8Ph-BTBT provided in an embodiment of the present invention (solvent dichloromethane, highest occupied orbital energy level: -5.59 eV).

[0041] Figure 5 3- is provided in the embodiment of the present invention t Schematic diagram of the cyclic voltammetry curve of BuPh-BTBT (solvent dichloromethane, highest occupied orbital energy level: -5.58 eV). DETAILED DESCRIPTION

[0042] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0043] The present invention is described in detail below in conjunction with the accompanying drawings.

[0044] The molecular structures of the BTBT and BSBS small molecule materials provided in the embodiments of the present invention are as follows:

[0045]

[0046] like Figure 1 As shown, the preparation method of BTBT and BSBS small molecule materials provided in the embodiment of the present invention comprises the following steps:

[0047] Using o-fluorobenzaldehyde, o-chlorobenzaldehyde, o-bromobenzaldehyde and o-iodobenzaldehyde or other o-halogenated aromatic benzaldehyde as raw materials1, sodium hydrosulfide hydrate or sodium selenide as sulfur source or selenium source, a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide as solvent, dipotassium hydrogen phosphate, potassium bicarbonate, potassium phosphate, potassium acetate, potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, N,N-diisopropylethylamine, N-methylpiperidine, 4-dimethylaminopyridine or 2,6-lutidine as base, a series of BTBT and BSBS small molecule materials2 were synthesized through tandem cyclization reaction.

[0048] The synthetic route of the preparation method of the BTBT and BSBS small molecule materials provided in the embodiment of the present invention is as follows:

[0049] Ar is selected from any one of an aryl group, a heteroaryl group, and an aryl group containing a substituent; the aryl group is a phenyl group,

[0050]

[0051] The invention relates to any one of naphthyl and anthracenyl; the heteroaryl is any one of furan, thiophene, pyridine and pyrrole; the substituent R is one or more of hydrogen, halogen, C1-C30 alkyl, C1-C30 alkoxy, trifluoromethyl, trifluoromethoxy, hydroxyl, aryl, acyl, ester, nitro, amino, cyano, (C1-C30 alkyl) amine, and the position of the substituent is any position on the Ar ring; the base is any one of dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium bicarbonate, potassium phosphate, potassium dihydrogen phosphate, potassium acetate, potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, N-methylmorpholine, N,N-diisopropylethylamine, N-methylpiperidine, 4-dimethylaminopyridine or 2,6-lutidine; the solvent is a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide.

[0052] Typical conditions for the metal-free tandem cyclization reaction are as follows: 1 equivalent of compound 1, 1 equivalent of dipotassium hydrogen phosphate and 3 equivalents of sodium hydrosulfide hydrate or sodium selenide are added to a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide, and reacted at 145° C. for 24 hours.

[0053] Synthesis of thiophene compounds by metal-free tandem cyclization reactions, including fused ring thienothiophene, fused ring selenophene and selenophene, fused ring thienothiophene, fused ring pyridothiophene, fused ring pyridoselenophene, fused ring pyrrolothiophene, fused ring pyrroloselenophene and their derivatives (alkyl chain substitution, aromatic compound substitution, halogen substitution, and trifluoromethyl, trifluoromethoxy and other substitution groups);

[0054] The sulfur source is sodium sulfide nonahydrate, sodium hydrosulfide hydrate, potassium sulfide, elemental sulfur, etc., and sodium hydrosulfide hydrate is preferred;

[0055] The selenium source is sodium selenohydride;

[0056] The base is dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium bicarbonate, potassium phosphate, potassium dihydrogen phosphate, potassium acetate, potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, N-methylmorpholine, N,N-diisopropylethylamine, N-methylpiperidine, 4-dimethylaminopyridine, 2,6-lutidine, etc., preferably dipotassium hydrogen phosphate;

[0057] The solvent is a mixture of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, preferably a mixture of N,N-dimethylacetamide and dimethyl sulfoxide;

[0058] The temperature of the metal-free tandem cyclization reaction is generally 145°C;

[0059] The reaction time of metal-free tandem cyclization is generally 24 h;

[0060] Preparation and application of organic field effect transistors based on the BTBT and BSBS small molecule materials in this patent.

[0061] The application principle of the present invention is further described below in conjunction with specific embodiments.

[0062] Example 1 [1] Synthesis of benzothiophene [3,2-b] [1] benzothiophene

[0063]

[0064] 1) Accurately weigh o-fluorobenzaldehyde (125 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2a with a yield of 44% (52.1 mg, 0.22 mmol). 1H NMR (600MHz, deuterated chloroform): δ7.93 (d, J = 8.0 Hz, 1H), 7.89 (d, J = 7.3 Hz, 1H), 7.47 (t, J = 7.5 Hz, 1H), 7.44-7.38 (m, 1H). 13C NMR (151MHz, deuterated chloroform): δ142.34, 133.52, 133.19, 125.10, 124.98, 124.14, 121.70. High resolution mass spectrometry (ESI): m / z for C 14 H8S2[M] + Calculated value: 240.0062, measured value: 240.0055.

[0065] 2) Accurately weigh o-chlorobenzaldehyde (141 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2a with a yield of 57% (66.8 mg, 0.285 mmol).

[0066] 3) Accurately weigh o-bromobenzaldehyde (185 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2a with a yield of 77% (92.0 mg, 0.385 mmol).

[0067] 4) Accurately weigh o-iodobenzaldehyde (232 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2a with a yield of 52% (62.1 mg, 0.26 mmol).

[0068] Example 2 Synthesis of 3,8-dimethylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0069]

[0070] 1) Accurately weigh 2-bromo-5-methylbenzaldehyde (199 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2b with a yield of 60% (80.3 mg, 0.30 mmol). 1H NMR (400 MHz, deuterated chloroform): δ7.79 (d, J = 8.2 Hz, 1H), 7.68 (s, 1H), 7.22 (d, J = 8.5 Hz, 1H), 2.52 (s, 3H). 13C NMR (101 MHz, deuterated chloroform): δ139.33, 134.87, 133.46, 133.39, 126.66, 123.72, 121.75, 21.55. High resolution mass spectrometry (ESI): m / z for C 16 H 12 S2[M] + Calculated value: 268.0375, measured value: 268.0369.

[0071] Example 3 Synthesis of 2,7-dimethylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0072]

[0073] 1) Accurately weigh 2-bromo-4-methylbenzaldehyde (199 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2c with a yield of 14% (18.1 mg, 0.07 mmol). 1H NMR (400 MHz, deuterated chloroform): δ7.73 (d, J = 8.0 Hz, 1H), 7.69 (d, J = 0.8 Hz, 1H), 7.25 (d, J = 7.6 Hz, 1H). 13C NMR (101 MHz, deuterated chloroform): δ142.50, 134.97, 132.54, 131.06, 126.50, 124.00, 121.11, 21.75. High resolution mass spectrometry (ESI): m / z for C 16 H 12 S2[M] + Calculated value: 268.0375, measured value: 268.0356.

[0074] Example 4 Synthesis of 3,8-dioctylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0075]

[0076] 1) Accurately weigh 2-chloro-5-bromobenzaldehyde (1316 mg, 6 mmol), ethylene glycol (1 mL, 18 mmol), p-toluenesulfonic acid (115 mg, 0.6 mmol), and add them to a 100 mL Schlenk bottle in sequence, evacuate and replace with nitrogen three times, add toluene under nitrogen protection, deoxygenate with nitrogen bubbling for 15 minutes, add a water separator under nitrogen protection and place in a 150 ° C heating module to react for 10 hours. After the reaction is completed, use sodium bicarbonate to neutralize the acid, extract with dichloromethane, separate the water layer, dry with anhydrous magnesium sulfate, remove the solvent under reduced pressure, separate with a silica gel column, and use petroleum ether as an eluent to obtain 2-(3-bromo-6-chlorophenyl)-1,3-dioxolane with a yield of 99% (1572.4 mg, 5.96 mmol). 1H NMR (400MHz, deuterated chloroform): δ7.73 (d, J = 2.4 Hz, 1H), 7.40 (dd, J = 8.5, 2.5 Hz, 1H), 7.23 (d, J = 8.5 Hz, 1H), 6.08 (s, 1H), 4.18-4.10 (m, 2H), 4.10-4.02 (m, 2H). 13C NMR (101MHz, deuterated chloroform): δ137.22, 133.33, 132.56, 131.28, 130.75, 120.73, 100.18, 65.65.

[0077] 2) Accurately weigh the product obtained in step 1) (1318 mg, 5 mmol), add it to a 100 mL Schlenk bottle, evacuate and replace it with nitrogen three times, add anhydrous tetrahydrofuran under nitrogen protection, place it in a 0°C low-temperature condensation device, deoxygenate it with nitrogen bubbling for 15 minutes, add 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride (II) dichloromethane complex under nitrogen protection, add n-octylmagnesium bromide (3 mL, 6 mmol) dropwise, place it in a 66°C heating module to react for 18 hours. After the reaction is completed, add hydrochloric acid and stir at room temperature for 15 minutes, extract it with dichloromethane, separate the water layer, dry it with anhydrous magnesium sulfate, remove the solvent under reduced pressure, separate it with a silica gel column, and use petroleum ether and dichloromethane as eluents to obtain 5-(n-octyl)-2-chlorobenzaldehyde with a yield of 95% (1178.4 mg, 4.68 mmol). 1H NMR (400MHz, deuterated chloroform): δ10.45 (s, 1H), 7.72 (t, J = 1.3 Hz, 1H), 7.33 (d, J = 1.8 Hz, 2H), 2.64-2.57 (m, 2H), 1.58 (dd, J = 13.5, 5.9 Hz, 2H), 1.32-1.20 (m, 10H), 0.86 (t, J = 6.8 Hz, 3H).13C NMR (101 MHz, deuterated chloroform): δ 190.31, 142.57, 135.54, 135.32, 132.15, 130.45, 129.05, 35.21, 31.93, 31.21, 29.47, 29.30, 29.22, 22.76, 14.22.

[0078] 3) Accurately weigh the product obtained in step 2) (430 mg, 1.7 mmol), sodium hydrosulfide hydrate (408 mg, 5.1 mmol), and potassium dihydrogen phosphate (296 mg, 1.7 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (3 mL) and dimethyl sulfoxide (1.5 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2d with a yield of 62% (243.2 mg, 0.52 mmol). 1H NMR (400MHz, deuterated chloroform): δ7.80 (d, J = 8.3 Hz, 1H), 7.65 (d, J = 1.6 Hz, 1H), 7.22 (dd, J = 8.3, 1.7 Hz, 1H), 2.80-2.71 (m, 2H), 1.69 (p, J = 7.6 Hz, 2H), 1.41-1.22 (m, 10H), 0.91-0.84 (m, 3H).13C NMR (101 MHz, deuterated chloroform): δ 140.10, 139.52, 133.46, 126.07, 123.75, 121.11, 36.07, 31.99, 29.61, 29.48, 29.38, 22.77, 14.22. High resolution mass spectrometry (ESI): m / z for C 30 H 40 S2[M+H] + Calculated value 465.2644, measured value 465.2641.

[0079] Example 5 Synthesis of 3,8-di-tert-butylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0080]

[0081] 1) Accurately weigh 5-(tert-butyl)-2-chlorobenzaldehyde (984 mg, 5 mmol), sodium hydrosulfide hydrate (1200 mg, 15 mmol), and potassium dihydrogen phosphate (870 mg, 5 mmol), and add them to a 100 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (10 mL) and dimethyl sulfoxide (5 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2e with a yield of 52% (456.3 mg, 1.3 mmol). 1H NMR (400MHz, deuterated chloroform): δ7.87-7.82 (m, 2H), 7.47 (dd, J=8.5, 2.0Hz, 1H), 1.43 (s, 9H). 13C NMR (101MHz, deuterated chloroform): δ148.43, 139.27, 133.79, 133.29, 123.62, 123.33, 117.91, 34.99, 31.71. High resolution mass spectrometry (ESI): m / z for C 22 H 24 S2[M]+ calculated value 352.1314, measured value 352.1300.

[0082] Example 6 Synthesis of 2,7-bis(trifluoromethyl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0083]

[0084] 1) Accurately weigh 2-bromo-4-(trifluoromethyl)benzaldehyde (253 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2f with a yield of 46% (80.0 mg, 0.23 mmol). 1H NMR (600MHz, deuterated tetrachloroethane): δ8.24 (s, 1H), 8.03 (d, J = 8.3Hz, 1H), 7.73 (d, J = 8.4Hz, 1H). 13C NMR (151MHz, deuterated tetrachloroethane): δ142.76, 135.58, 135.20, 128.05 (q, J = 31.7Hz), 124.33 (q, J = 271.8Hz), 122.44, 122.22 (q, J = 3.0Hz), 121.71 (q, J = 4.5Hz, 1H). High resolution mass spectrometry (ESI): m / z for C16 H6F6S2[M] + Calculated value: 375.9810, measured value: 375.9819.

[0085] Example 7 Synthesis of 3,8-bis(trifluoromethyl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0086]

[0087] 1) Accurately weigh 2-bromo-5-(trifluoromethyl)benzaldehyde (253 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain 2 g of the target product with a yield of 30% (55.8 mg, 0.15 mmol). 1H NMR (400MHz, deuterated chloroform): δ8.15 (dd, J=1.8, 0.9Hz, 1H), 8.03 (d, J=8.5Hz, 1H), 7.66 (dd, J=8.5, 1.7Hz, 1H). 13C NMR (101MHz, deuterated chloroform): δ145.59, 134.81, 132.45, 127.89 (q, J=33.3Hz), 124.74, 124.35 (q, J=273.7Hz), 121.96 (q, J=4.0Hz), 118.94 (q, J=4.0Hz). High resolution mass spectrometry (ESI): m / z for C 16 H6F6S2[M] + Calculated value: 375.9810, measured value: 375.9827.

[0088] Example 8 Synthesis of 3,8-bis(trifluoromethoxy)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0089]

[0090] 1) Accurately weigh 2-bromo-5-(trifluoromethoxy)benzaldehyde (269 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2h with a yield of 33% (65.9 mg, 0.165 mmol). 1H NMR (400MHz, deuterated chloroform): δ7.92 (d, J=8.8Hz, 1H), 7.72 (d, J=1.1Hz, 1H), 7.33-7.29 (m, 1H). 13C NMR (101MHz, deuterated chloroform): δ147.13, 140.54, 135.00, 133.62, 125.31, 119.19, 114.26. High resolution mass spectrometry (ESI): m / z for C 16 H6O2S2F6[M] + Calculated value 407.9708, measured value 407.9699.

[0091] Example 9 Synthesis of 2,7-bis(trifluoromethoxy)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0092]

[0093] 1) Accurately weigh 2-bromo-4-(trifluoromethoxy)benzaldehyde (269 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N,N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and the target product 2i is obtained by separation using a silica gel column and petroleum ether as an eluent. The yield is 2% (3.8 mg, 0.01 mmol). 1H NMR (400 MHz, deuterated chloroform): δ7.88 (d, J = 8.8 Hz, 1H), 7.79 (s, 1H), 7.35 (d, J = 8.8 Hz, 1H). High resolution mass spectrometry (ESI): m / z for C 16 H6O2S2F6[M] + Calculated value 407.9708, measured value 407.9701.

[0094] Example 10 Synthesis of 3,8-difluorobenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0095]

[0096] 1) Accurately weigh 2-bromo-5-fluorobenzaldehyde (203 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2j with a yield of 30% (41.2 mg, 0.15 mmol). 1H NMR (400MHz, deuterated chloroform): δ7.85 (dd, J=8.8, 4.7Hz, 1H), 7.56 (dd, J=8.9, 2.5Hz, 1H), 7.19 (td, J=8.8, 2.5Hz, 1H). 13C NMR (101MHz, deuterated chloroform): δ162.36, 159.93, 136.28 (d, J=263.6Hz), 133.96 (d, J=10.1Hz), 125.33 (d, J=9.1Hz), 114.11 (d, J=25.3Hz), 107.9 (d, J=24.2Hz). High resolution mass spectrometry (ESI): m / z for C 14 H6F2S2[M] + Calculated value: 275.9873, measured value: 275.9866.

[0097] Example 11 Synthesis of 1,6-difluorobenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0098]

[0099] 1) Accurately weigh 2-bromo-3-fluorobenzaldehyde (203 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2k with a yield of 7% (9.8 mg, 0.036 mmol). 1H NMR (600MHz, deuterated tetrachloroethane): δ7.71 (d, J = 7.9 Hz, 1H), 7.47 (td, J = 7.9, 5.0 Hz, 1H), 7.23-7.13 (m, 1H). 13C NMR (151MHz, deuterated tetrachloroethane): δ158.22 (d, J = 247.6 Hz), 135.77 (d, J = 4.5 Hz), 134.57 (d, J = 3.0 Hz), 129.21 (d, J = 18.1 Hz), 126.94 (d, J = 7.6 Hz), 117.71 (d, J = 3.0 Hz), 111.01 (d, J = 19.6 Hz). High resolution mass spectrometry (ESI): m / z for C 14 H6F2S2[M] + Calculated value: 275.9879, measured value: 275.9878.

[0100] Example 12 Synthesis of 3,8-dibromobenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0101]

[0102] 1) Accurately weigh 5-bromo-2-iodobenzaldehyde (311 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N,N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, methanol is added, and the target compound is precipitated. It is washed with methanol and water and vacuum dried to obtain the target product 21 with a yield of 27% (52.7 mg, 0.135 mmol). 1H NMR (400 MHz, deuterated chloroform): δ8.02 (s, 1H), 7.77 (d, J = 8.7 Hz, 1H), 7.52 (d, J = 7.9 Hz, 1H). High resolution mass spectrometry (ESI): m / z for C 14 H6Br2S2[M] + Calculated value 397.8257, measured value 397.8248.

[0103] Example 13 Synthesis of 3,8-dichlorobenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0104]

[0105] 1) Accurately weigh 2-bromo-5-chlorobenzaldehyde (219 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, methanol is added, and the target compound is precipitated, washed with methanol and water, and vacuum dried to obtain the target product 2m with a yield of 45% (68.9 mg, 0.225 mmol). 1 H NMR (400 MHz, deuterated tetrachloroethane): δ7.89-7.84 (m, 2H), 7.41 (dd, J=8.6, 2.0 Hz, 1H). High resolution mass spectrometry (ESI): m / z for C 14 H6Cl2S2[M] + Calculated value 307.9288, measured value 307.9280.

[0106] Example 14 Synthesis of 3,8-dinitrobenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0107]

[0108] 1) Accurately weigh 2-bromo-5-nitrobenzaldehyde (230 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2n with a yield of 10% (17.2 mg, 0.05 mmol). 1 HNMR (400 MHz, deuterated chloroform): δ7.51 (d, J = 8.1 Hz, 1H), 7.45 (d, J = 2.5 Hz, 1H), 7.10 (dd, J = 8.7, 2.5 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): δ 215.51, 144.59, 142.44, 142.31, 124.28, 122.62, 111.55.

[0109] Example 15 Synthesis of 1,6-pyridyl[b]pyridyl[4,5]thieno[2,3-d]thiophene

[0110]

[0111] 1) Accurately weigh 2-bromo-3-pyridinecarboxaldehyde (186 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and the silica gel column treated with triethylamine is used for separation, and petroleum ether is used as the eluent to obtain the target product 2o with a yield of 46% (55.4 mg, 0.23 mmol). 1 H NMR (600 MHz, deuterated chloroform): δ 8.63 (dd, J = 4.7, 1.6 Hz, 1H), 8.20 (dd, J = 8.0, 1.6 Hz, 1H), 7.43 (dd, J = 8.0, 4.7 Hz, 1H). 13 C NMR (151 MHz, deuterated chloroform): δ 163.41, 147.29, 129.69, 129.43, 127.81, 120.16. High resolution mass spectrometry (ESI): m / z for C 12 H6N2S2[M+H] + Calculated value 243.0045, measured value 243.0038.

[0112] Example 16 Synthesis of 2,7-pyridinyl[b]pyridinyl[4,5]thieno[2,3-d]thiophene

[0113]

[0114] 1) Accurately weigh 3-bromo-4-pyridinecarboxaldehyde (186 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and the silica gel column treated with triethylamine is used for separation, and petroleum ether is used as the eluent to obtain the target product 2p with a yield of 45% (54.5 mg, 0.225 mmol). 1H NMR (400 MHz, deuterated chloroform): δ 9.26 (s, 1H), 8.68 (d, J = 5.4 Hz, 1H), 7.86 (dd, J = 5.4, 1.1 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): δ146.21, 144.44, 139.44, 137.83, 136.41, 116.30. High resolution mass spectrometry (ESI): m / z for C 12 H6N2S2[M+H] + Calculated value: 243.0045, measured value: 243.0045.

[0115] Example 17 Synthesis of 4,9-pyridinyl[b]pyridinyl[4,5]thieno[2,3-d]thiophene

[0116]

[0117] 1) Accurately weigh 3-bromo-2-pyridinecarboxaldehyde (186 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and the product is separated using a silica gel column treated with triethylamine and petroleum ether as an eluent to obtain the target product 2q with a yield of 18% (21.5 mg, 0.09 mmol). 1H NMR (400 MHz, deuterated chloroform): δ8.77 (dd, J = 4.6, 1.4 Hz, 1H), 8.30 (dd, J = 8.2, 1.4 Hz, 1H), 7.38 (dd, J = 8.2, 4.6 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): δ149.42, 147.55, 137.13, 136.40, 132.34, 120.07. High resolution mass spectrometry (ESI): m / z for C 12 H6N2S2[M] + Calculated value 243.0045, measured value 243.0042.

[0118] Example 18 Synthesis of naphtho[1,2-b]naphtho[2',1':4,5]thieno[2,3-d]thiophene

[0119]

[0120] 1) Accurately weigh 1-bromo-2-naphthaldehyde (235 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, methanol is added, and the target compound is precipitated, washed with methanol and water, and vacuum dried to obtain the target product 2r with a yield of 21% (35.5 mg, 0.105 mmol). 1 HNMR (400MHz, deuterated chloroform): δ7.96 (s, 1H), 7.62 (d, J = 7.7 Hz, 1H), 7.56 (d, J = 7.7 Hz, 1H), 8.17 (d, J = 8.2 Hz, 1H), 7.99 (s, 1H), 7.87 (d, J = 8.7 Hz, 1H). High resolution mass spectrometry (ESI): m / z for C 22 H 12 S2[M+H] + Calculated value 341.0453, measured value 341.0048.

[0121] Example 19 Synthesis of 3,8-diphenylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0122]

[0123] 1) Accurately weigh 2-chloro-5-bromobenzaldehyde (219 mg, 1 mmol), phenylboric acid (147 mg, 1.2 mmol), potassium carbonate (276 mg, 2 mmol), potassium fluoride (58 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, evacuate and replace with nitrogen three times, add ethylene glycol dimethyl ether and deionized water (volume ratio 4:1) under nitrogen protection, deoxygenate with nitrogen bubbling for 15 minutes, add tetrakis(triphenylphosphine)palladium (116 mg, 0.1 mmol) under nitrogen protection, and place in a 75°C heating module for reaction for 10 hours. After the reaction is completed, extract with dichloromethane, separate the water layer, dry with anhydrous magnesium sulfate, remove the solvent under reduced pressure, and use dichloromethane and petroleum ether for chromatography to obtain 2-chloro-5-phenylbenzaldehyde with a yield of 69% (148.9 mg, 0.69 mmol). 1H NMR (400 MHz, deuterated chloroform): δ 10.40 (s, 1H), 8.13 (d, J = 2.3 Hz, 1H), 7.70 (d, J = 8.3 Hz, 1H), 7.66 (dd, J = 8.3, 2.3 Hz, 1H), 7.60-7.56 (m, 2H), 7.45 (t, J = 7.4 Hz, 2H), 7.40 (d, J = 7.2 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): δ 191.94, 141.23, 138.71, 134.38, 133.82, 133.70, 129.19, 128.41, 128.23, 127.03, 126.04. High resolution mass spectrometry (ESI mode): m / z for C 13 H9ClO[M] + Calculated value: 216.0336, measured value: 216.0329.

[0124] 2) Accurately weigh the product obtained in step 1) (130 mg, 0.5 mmol), sodium hydrosulfide hydrate (120 mg, 1.5 mmol), and potassium dihydrogen phosphate (87 mg, 0.5 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and chromatographic separation is performed using dichloromethane and petroleum ether to obtain the target product 2s with a yield of 34% (33 mg, 0.085 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ 8.08 (d, J = 1.8 Hz, 1H), 7.99 (d, J = 8.4 Hz, 1H), 7.71 (d, J = 7.0 Hz, 2H), 7.66 (dd, J = 8.4, 1.8 Hz, 1H), 7.50 (t, J = 7.6 Hz, 2H), 7.39 (t, J = 7.4 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): δ 141.33, 140.96, 138.68, 134.21, 133.73, 129.02, 127.56, 124.75, 124.40, 120.12. High resolution mass spectrometry (ESI): m / z for C 26 H 16 S2[M+H] + Calculated value: 393.0766, measured value: 393.0751.

[0125] Example 20 Synthesis of 3,8-bis(4-propylphenyl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0126]

[0127] 1) Accurately weigh 2-bromo-5-iodobenzaldehyde (311 mg, 1 mmol), p-propylphenylboric acid (181 mg, 1.1 mmol), potassium carbonate (276 mg, 2 mmol), potassium fluoride (58 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, evacuate and replace with nitrogen three times, add ethylene glycol dimethyl ether and deionized water (volume ratio 4:1) under nitrogen protection, deoxygenate with nitrogen bubbling for 15 minutes, add tetrakis(triphenylphosphine)palladium (92 mg, 0.08 mmol) under nitrogen protection, and place in a 75°C heating module for reaction for 10 hours. After the reaction is completed, extract with dichloromethane, separate the water layer, dry with anhydrous magnesium sulfate, remove the solvent under reduced pressure, and use dichloromethane and petroleum ether for chromatography to obtain 2-bromo-5-(4-propylphenyl)benzaldehyde with a yield of 72% (217.5 mg, 0.72 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ 10.40 (d, J = 0.7 Hz, 1H), 8.12 (d, J = 2.2 Hz, 1H), 7.73-7.64 (m, 2H), 7.51 (d, J = 8.1 Hz, 2H), 7.26 (d, J = 8.0 Hz, 2H), 2.66-2.60 (m, 2H), 1.67 (dt, J = 15.0, 7.4 Hz, 2H), 0.99-0.93 (m, 3H). 13 C NMR (101 MHz, deuterated chloroform): δ 192.06, 143.20, 141.20, 136.03, 134.31, 133.67, 133.64, 129.31, 128.03, 126.85, 125.67, 37.77, 24.61, 13.95. High resolution mass spectrometry (ESI mode): m / z for C 16 H15BrO[M+H] + Calculated value 303.0379, measured value 303.0371.

[0128] 2) Accurately weigh the product obtained in step 1) (236 mg, 0.78 mmol), sodium hydrosulfide hydrate (188 mg, 2.34 mmol), and potassium dihydrogen phosphate (136 mg, 0.78 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and chromatographic separation is performed using dichloromethane and petroleum ether to obtain the target product 2t with a yield of 39% (71.8 mg, 0.151 mmol). 1H NMR (400 MHz, deuterated chloroform): δ8.06 (d, J=1.7 Hz, 1H), 7.96 (d, J=8.5 Hz, 1H), 7.67-7.60 (m, 3H), 7.30 (d, J=8.2 Hz, 2H), 2.71-2.61 (m, 2H), 1.77-1.65 (m, 2H), 0.99 (t, J=7.4 Hz, 3H). 13 C NMR (101 MHz, deuterated chloroform): δ 142.21, 141.01, 138.60, 138.31, 134.14, 133.73, 129.16, 127.35, 124.62, 124.32, 119.89, 37.82, 24.73, 14.01. High resolution mass spectrometry (ESI): m / z for C 32 H 28 S2[M+H] + Calculated value 477.1705, measured value 477.1701.

[0129] Example 21 Synthesis of 3,8-bis(4-octylphenyl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0130]

[0131] 1) Accurately weigh 2-chloro-5-bromobenzaldehyde (833 mg, 3.8 mmol), 4-octylphenylboronic acid (984 mg, 4.2 mmol), potassium carbonate (1050 mg, 7.6 mmol), potassium fluoride (221 mg, 3.8 mmol), and add them to a 100 mL Schlenk bottle in sequence, evacuate and replace with nitrogen three times, add ethylene glycol dimethyl ether and deionized water (volume ratio 4:1) under nitrogen protection, nitrogen bubbling deoxygenation for 15 minutes, add tetrakis (triphenylphosphine) palladium (351 mg, 0.3 mmol) under nitrogen protection, place in a 75 ° C heating module for 10 hours. After the reaction is completed, extract with dichloromethane, separate the water layer, dry with anhydrous magnesium sulfate, remove the solvent under reduced pressure, and use dichloromethane and petroleum ether for chromatography to obtain 2-chloro-5-(4-octylphenyl)benzaldehyde with a yield of 78% (972.2 mg, 3.07 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ 10.52 (s, 1H), 8.13 (d, J = 2.4 Hz, 1H), 7.74 (dd, J = 8.3, 2.4 Hz, 1H), 7.54-7.46 (m, 3H), 7.29-7.25 (m, 2H), 2.68-2.59 (m, 2H), 1.63 (p, J = 7.5 Hz, 2H), 1.38-1.23 (m, 10H), 0.91-0.83 (m, 3H).13 C NMR (101 MHz, deuterated chloroform): δ 190.01, 143.42, 140.60, 136.59, 136.00, 133.42, 132.59, 131.03, 129.23, 127.51, 126.88, 35.70, 31.97, 31.54, 29.56, 29.42, 29.35, 22.76, 14.20. High resolution mass spectrometry (ESI mode): m / z for C 21 H 25 ClO[M+H] + Calculated value 328.1588, measured value 328.1574.

[0132] 2) Accurately weigh the product obtained in step 1) (984 mg, 3 mmol), sodium hydrosulfide hydrate (720 mg, 9 mmol), and potassium dihydrogen phosphate (522 mg, 3 mmol), and add them to a 100 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (6 mL) and dimethyl sulfoxide (3 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and chromatographic separation is performed using dichloromethane and petroleum ether to obtain the target product 2u with a yield of 50% (460.3 mg, 0.75 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ 8.06 (d, J = 1.8 Hz, 1H), 7.96 (dd, J = 8.4, 1.4 Hz, 1H), 7.67-7.59 (m, 3H), 7.33-7.27 (m, 2H), 2.67 (t, J = 7.7 Hz, 2H), 1.66 (p, J = 7.2 Hz, 2H), 1.41-1.21 (m, 10H), 0.88 (td, J = 6.9, 1.6 Hz, 3H). 13 C NMR (101 MHz, deuterated chloroform): δ 142.48, 141.00, 138.62, 138.26, 134.13, 133.74, 129.09, 127.36, 124.61, 124.30, 119.88, 35.74, 32.01, 31.65, 29.61, 29.48, 29.39, 22.78, 14.22. High resolution mass spectrometry (ESI): m / z for C 42 H 48 S2[M+H] + Calculated value: 617.3270, measured value: 617.3266.

[0133] Example 22 Synthesis of 3,8-bis(4-(tert-butyl)phenyl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0134]

[0135] 1) Accurately weigh 2-chloro-5-bromobenzaldehyde (1810 mg, 8.25 mmol), 4-tert-butylphenylboric acid (1100 mg, 9.1 mmol), potassium carbonate (2277 mg, 16.5 mmol), potassium fluoride (479 mg, 8.25 mmol), and add them to a 100 mL Schlenk bottle in sequence. Vacuum and replace with nitrogen three times. Add ethylene glycol dimethyl ether and deionized water (volume ratio 4:1) under nitrogen protection, deoxygenate with nitrogen bubbling for 15 min, add tetrakis(triphenylphosphine)palladium (762 mg, 0.66 mmol) under nitrogen protection, and place in a 75°C heating module for reaction for 10 hours. After the reaction, dichloromethane was used for extraction, the water layer was separated, and the mixture was dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and dichloromethane and petroleum ether were used for chromatography to obtain 2-chloro-5-(4-tert-butylphenyl)benzaldehyde with a yield of 77% (1729.8 mg, 6.36 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ 10.52 (d, J = 0.9 Hz, 1H), 8.14 (dd, J = 2.4, 0.8 Hz, 1H), 7.74 (ddd, J = 8.4, 2.4, 0.9 Hz, 1H), 7.56-7.46 (m, 5H), 1.36 (d, J = 1.0 Hz, 9H). 13 C NMR (101 MHz, deuterated chloroform): δ 190.01, 151.56, 140.45, 136.64, 135.78, 133.44, 132.60, 131.05, 127.52, 126.71, 126.14, 34.73, 31.39. High resolution mass spectrometry (ESI mode): m / z for C 17 H 17 ClO[M] + Calculated value: 272.0962, measured value: 272.0952.

[0136] 2) Accurately weigh the product obtained in step 1) (1707 mg, 5.4 mmol), sodium hydrosulfide hydrate (1296 mg, 16.2 mmol), and potassium dihydrogen phosphate (940 mg, 5.4 mmol), and add them to a 100 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (12 mL) and dimethyl sulfoxide (6 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and chromatographic separation is performed using dichloromethane and petroleum ether to obtain the target product 2v with a yield of 31% (407.3 mg, 0.832 mmol). 1H NMR (600 MHz, deuterated chloroform): δ8.06 (dd, J=1.8, 0.6 Hz, 1H), 7.96 (dd, J=8.4, 0.6 Hz, 1H), 7.65 (dd, J=8.4, 2.0 Hz, 3H), 7.54-7.50 (m, 2H), 1.39 (s, 9H). 13 C NMR (101 MHz, deuterated chloroform): δ 150.62, 141.04, 138.57, 138.06, 134.14, 133.71, 127.17, 125.97, 124.62, 124.31, 119.94, 34.68, 31.48. High resolution mass spectrometry (ESI): m / z for C 34 H 32 S2[M+H] + Calculated value: 505.2018, measured value: 505.2011.

[0137] Example 23 Synthesis of 2,7-bis(4-octylphenyl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0138]

[0139] 1) Accurately weigh 2-chloro-4-bromobenzaldehyde (833 mg, 3.8 mmol), 4-octylphenylboric acid (984 mg, 4.2 mmol), potassium carbonate (1050 mg, 7.6 mmol), potassium fluoride (221 mg, 3.8 mmol), and add them to a 100 mL Schlenk bottle in sequence. Vacuum and replace with nitrogen three times. Add ethylene glycol dimethyl ether and deionized water (volume ratio 4:1) under nitrogen protection, deoxygenate with nitrogen bubbling for 15 min, add tetrakis(triphenylphosphine)palladium (351 mg, 0.3 mmol) under nitrogen protection, and place in a 75°C heating module for reaction for 10 hours. After the reaction, dichloromethane was used for extraction, the water layer was separated, and the mixture was dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and dichloromethane and petroleum ether were used for chromatography separation to obtain 2-chloro-4-(4-octylphenyl)benzaldehyde with a yield of 87% (1078.9 mg, 3.29 mmol). 1 H NMR (600 MHz, deuterated chloroform): δ 10.48 (s, 1H), 7.96 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 1.7 Hz, 1H), 7.58 (dd, J = 9.0, 0.9 Hz, 1H), 7.52 (d, J = 8.2 Hz, 2H), 7.28 (d, J = 8.2 Hz, 2H), 2.71-2.60 (m, 2H), 1.69-1.59 (m, 2H), 1.38-1.21 (m, 10H), 0.87 (t, J = 7.0 Hz, 3H). 13C NMR (151 MHz, deuterated chloroform): δ 189.59, 148.29, 144.39, 138.46, 135.71, 130.85, 129.85, 129.32, 128.73, 127.21, 125.77, 35.76, 31.97, 31.48, 29.56, 29.41, 29.35, 22.76, 14.20. High resolution mass spectrometry (ESI mode): m / z for C 21 H 25 ClO[M+H] + Calculated value 329.1667, measured value 329.1661.

[0140] 2) Accurately weigh the product obtained in step 1) (984 mg, 3 mmol), sodium hydrosulfide hydrate (720 mg, 9 mmol), and potassium dihydrogen phosphate (522 mg, 3 mmol), and add them to a 100 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (6 mL) and dimethyl sulfoxide (3 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and chromatographic separation is performed using dichloromethane and petroleum ether to obtain the target product 2w, with a yield of 6% (69.3 mg, 0.113 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ8.11 (d, J=1.5 Hz, 1H), 7.92 (d, J=8.2 Hz, 1H), 7.69 (d, J=8.6 Hz, 1H), 7.60 (d, J=7.9 Hz, 2H), 7.29 (d, J=7.8 Hz, 2H), 2.66 (t, J=7.8 Hz, 2H), 1.65 (q, J=7.5 Hz, 2H), 1.31 (d, J=25.5 Hz, 10H), 0.91-0.84 (m, 3H). 13 C NMR (101 MHz, deuterated chloroform): δ 176.21, 166.98, 155.82, 141.31, 135.12, 129.06, 127.96, 127.13, 124.58, 122.19, 121.79, 35.70, 31.99, 31.60, 29.58, 29.46, 29.36, 22.76, 14.20. High resolution mass spectrometry (ESI): m / z for C 42 H 48 S2[M+H] + Calculated value: 617.3270, measured value: 617.3262.

[0141] Example 24 Synthesis of 2,7-bis(4-(tert-butyl)phenyl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0142]

[0143] 1) Accurately weigh 2-chloro-4-bromobenzaldehyde (2190 mg, 10 mmol), 4-tert-butylphenylboric acid (1958 mg, 11 mmol), potassium carbonate (2760 mg, 20 mmol), potassium fluoride (580 mg, 10 mmol), and add them to a 100 mL Schlenk bottle in sequence, evacuate and replace with nitrogen three times, add ethylene glycol dimethyl ether and deionized water (volume ratio 4:1) under nitrogen protection, deoxygenate with nitrogen bubbling for 15 min, add tetrakis(triphenylphosphine)palladium (925 mg, 0.8 mmol) under nitrogen protection, and place in a 75°C heating module for reaction for 10 hours. After the reaction, dichloromethane was used for extraction, the water layer was separated, and the mixture was dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure, and dichloromethane and petroleum ether were used for chromatography separation to obtain 2-chloro-4-(4-tert-butylphenyl)benzaldehyde with a yield of 86% (2316.7 mg, 8.52 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ10.48 (s, 1H), 7.97 (d, J = 8.1 Hz, 1H), 7.66 (s, 1H), 7.59 (d, J = 9.1 Hz, 1H), 7.55 (d, J = 7.5 Hz, 2H), 7.50 (d, J = 8.3 Hz, 2H), 1.36 (s, 9H). 13 C NMR (101 MHz, deuterated chloroform): δ 189.57, 152.52, 148.15, 138.45, 135.50, 130.90, 129.86, 128.76, 127.04, 126.23, 125.80, 34.82, 31.35. High resolution mass spectrometry (ESI mode): m / z for C 17 H 17 ClO[M+H] + Calculated value 273.1041, measured value 273.1033.

[0144] 2) Accurately weigh the product obtained in step 1) (1360 mg, 5 mmol), sodium hydrosulfide hydrate (1200 mg, 15 mmol), and potassium dihydrogen phosphate (870 mg, 5 mmol), and add them to a 100 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (10 mL) and dimethyl sulfoxide (5 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and chromatographic separation is performed using dichloromethane and petroleum ether to obtain the target product 2x with a yield of 8% (95.6 mg, 0.19 mmol). 1HNMR (400MHz, deuterated chloroform): δ8.04 (s, 1H), 7.92 (d, J = 8.4 Hz, 1H), 7.61 (d, J = 8.2 Hz, 3H), 7.49 (d, J = 8.0 Hz, 2H), 1.37 (s, 9H). High resolution mass spectrometry (ESI): m / z for C 34 H 32 S2[M+H] + Calculated value: 505.2018, measured value: 505.2011.

[0145] Example 25 Synthesis of benzo[b]benzo[4,5]selenopheno[2,3-d]selenopheno

[0146]

[0147] 1) Sodium borohydride (133 mg, 3.5 mmol) and elemental selenium (276 mg, 3.5 mmol) were accurately weighed and added to a 25 mL Schlenk bottle in sequence, and ethanol (616 μL) was added to react at room temperature for 4 hours. After the reaction was completed, the solvent was removed under reduced pressure, and o-bromobenzaldehyde (185 mg, 1 mmol), dipotassium hydrogen phosphate (174 mg, 1 mmol), N,N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL) were added, and the mixture was placed in a 145 ° C heating module for 24 hours. After the reaction was completed, the solvent was removed under reduced pressure, and a silica gel column was used for separation, and petroleum ether was used as the eluent to obtain the target product 2y with a yield of 12% (19.8 mg, 0.06 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ 7.95 (d, J = 8.0 Hz, 1H), 7.79 (d, J = 7.9 Hz, 1H), 7.44 (t, J = 7.5 Hz, 1H), 7.32 (t, J = 7.6 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): δ 141.37, 137.92, 134.39, 126.92, 125.50, 125.25, 123.96. High resolution mass spectrometry (ESI): m / z for C 14 H8Se2[M+H] + Calculated value: 336.9029, measured value: 336.9015.

[0148] Example 26 Synthesis of benzo[b]benzo[4,5]selenobenzo[2,3-d]thiophene

[0149]

[0150] 1) Sodium borohydride (133 mg, 3.5 mmol) and elemental selenium (276 mg, 3.5 mmol) were accurately weighed and added to a 25 mL Schlenk bottle in sequence, and ethanol (616 μL) was added to react at room temperature for 4 hours. After the reaction was completed, the solvent was removed under reduced pressure, and o-bromobenzaldehyde (185 mg, 1 mmol), dipotassium hydrogen phosphate (174 mg, 1 mmol), N,N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL) were added, and the mixture was placed in a 145 ° C heating module for 24 hours. After the reaction was completed, the solvent was removed under reduced pressure, and a silica gel column was used for separation, and petroleum ether was used as the eluent to obtain the target product 2z with a yield of 14% (19.9 mg, 0.07 mmol). 1 H NMR (400 MHz, deuterated chloroform): δ 7.95 (dt, J = 8.1, 0.9 Hz, 1H), 7.92 (dt, J = 7.8, 0.9 Hz, 1H), 7.87 (ddd, J = 7.9, 1.3, 0.6 Hz, 1H), 7.83-7.79 (m, 1H), 7.45 (dddd, J = 7.8, 6.3, 5.2, 1.2 Hz, 2H), 7.42-7.37 (m, 1H), 7.33 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H). 13 C NMR (101 MHz, deuterated chloroform): δ 142.26, 141.36, 135.81, 135.78, 135.37, 131.85, 127.13, 125.45, 125.33, 125.06, 125.04, 123.94, 123.22, 122.37. High resolution mass spectrometry (ESI): m / z for C 14 H8SeS[M+H] + Calculated value: 288.9585, measured value: 288.9576.

[0151] Example 27 Synthesis of 8-methyl-2-(trifluoromethyl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene

[0152]

[0153] 1) Accurately weigh 2-bromo-5-methylbenzaldehyde (100 mg, 0.5 mmol), 2-bromo-4-(trifluoromethyl)benzaldehyde (127 mg, 0.5 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and dipotassium hydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain the target product 2aa with a yield of 19% (29.8 mg, 0.095 mmol). 1 H NMR (600 MHz, deuterated chloroform): δ8.19 (s, 1H), 7.94 (dd, J = 9.1, 0.8 Hz, 1H), 7.81 (d, J = 8.3 Hz, 1H), 7.73 (s, 1H), 7.67 (d, J = 8.4 Hz, 1H), 7.28 (d, J = 6.5 Hz, 1H), 2.53 (s, 3H). 13 C NMR (101 MHz, deuterated chloroform): δ 142.03, 139.85, 137.97, 135.64, 135.28, 132.95, 127.61, 125.93, 123.86, 122.36, 122.16, 121.80, 121.73, 121.62, 121.45, 29.80 High resolution mass spectrometry (ESI): m / z for C 16 H9F3S2[M] + Calculated value 322.0098, measured value 322.0096.

[0154] Example 28 Synthesis of Thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thiophene

[0155]

[0156] 1) Accurately weigh 3-bromothiophene-2-carboxaldehyde (191 mg, 1 mmol), sodium hydrosulfide hydrate (240 mg, 3 mmol), and potassium dihydrogen phosphate (174 mg, 1 mmol), and add them to a 25 mL Schlenk bottle in sequence, add N, N-dimethylacetamide (2 mL) and dimethyl sulfoxide (1 mL), and place in a 145 ° C heating module to react for 24 hours. After the reaction is completed, the solvent is removed under reduced pressure, and a silica gel column is used for separation, and petroleum ether is used as an eluent to obtain a trace amount of the target product 2ab. High-resolution mass spectrometry (ESI): m / z for C 16 H9F3S2[M] + Calculated value 322.0098, measured value 322.0096.

[0157] Example 29 Measurement of the highest occupied molecular orbital of 3-C8-BTBT using electrochemical cyclic voltammetry

[0158] The electrochemical properties of the product 3-C8-BTBT obtained in Example 4 were tested using an electrochemical workstation, with ferrocene as the internal standard and a dichloromethane solution of tetrabutylammonium hexafluorophosphate (concentration of 0.001 M) as the electrolyte. A standard three-electrode system was used for testing, with a platinum wire as the counter electrode and a silver chloride electrode as the reference electrode. The cyclic voltammetry curve was measured as follows: Figure 2 As shown, the highest occupied molecular orbital energy level of 3-C8-BTBT can be calculated to be -5.54 eV.

[0159] Example 30 Using electrochemical cyclic voltammetry to measure 3- t Bu-BTBT highest occupied molecular orbital

[0160] The product 3- obtained in Example 5 was subjected to electrochemical workstation t The electrochemical properties of Bu-BTBT were tested, with ferrocene as the internal standard and tetrabutylammonium hexafluorophosphate in dichloromethane (0.001 M concentration) as the electrolyte. The standard three-electrode system was used for testing, with platinum wire as the counter electrode and silver chloride electrode as the reference electrode. The cyclic voltammetry curve was measured as follows: Figure 3 As shown, we can calculate 3- t The highest occupied molecular orbital energy level of Bu-BTBT is -5.55 eV.

[0161] Example 31 Measurement of the highest occupied molecular orbital of 3-C8Ph-BTBT by electrochemical cyclic voltammetry

[0162] The electrochemical properties of the product 3-C8Ph-BTBT obtained in Example 21 were tested using an electrochemical workstation, with ferrocene as the internal standard and a dichloromethane solution of tetrabutylammonium hexafluorophosphate (concentration of 0.001 M) as the electrolyte. The test was performed using a standard three-electrode system, with a platinum wire as the counter electrode and a silver chloride electrode as the reference electrode. The cyclic voltammetry curve was measured as follows: Figure 4 As shown, the highest occupied molecular orbital energy level of 3-C8Ph-BTBT can be calculated to be -5.59 eV.

[0163] Example 32 Electrochemical Cyclic Voltammetry Measurement of 3- t BuPh-BTBT highest occupied molecular orbital

[0164] The product 3- obtained in Example 22 was subjected to electrochemical workstation tThe electrochemical properties of BuPh-BTBT were tested, with ferrocene as the internal standard and tetrabutylammonium hexafluorophosphate in dichloromethane (0.001 M concentration) as the electrolyte. The standard three-electrode system was used for testing, with platinum wire as the counter electrode and silver chloride electrode as the reference electrode. The cyclic voltammetry curve was measured as follows: Figure 5 As shown, we can calculate 3- t The highest occupied molecular orbital energy level of BuPh-BTBT is -5.58 eV.

[0165] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a [1]benzothiophene [3,2-b] [1]benzothiophene (BTBT) and [1]benzoselenophene [3,2-b] [1]benzoselenophene (BSBS) small molecule material, characterized in that The following steps are involved: Using o-fluorobenzaldehyde, o-chlorobenzaldehyde, o-bromobenzaldehyde and o-iodobenzaldehyde or other o-halogenated aromatic benzaldehyde as raw materials1, sodium hydrosulfide hydrate or sodium selenide as sulfur source or selenium source, a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide as solvent, dipotassium hydrogen phosphate, potassium bicarbonate, potassium phosphate, potassium acetate, potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, N,N-diisopropylethylamine, N-methylpiperidine, 4-dimethylaminopyridine or 2,6-lutidine as base, a series of BTBT and BSBS small molecule materials2 were synthesized through tandem cyclization reaction.

2. The method for preparing BTBT and BSBS small molecule materials according to claim 1, characterized in that The synthetic route is as follows: Compared with other synthetic routes, the reaction conditions are relatively mild and the yield is higher; compared with the route of Kazuo Takimiya's group, the addition of base and the replacement of solvent greatly improve the reaction yield. [See M. Saito, Itaru Osaka, E. Miyazaki, K. Takimiya, H. Kuwabara, M. Ikeda, Tetrahedron Letters 2011, 52, 285-288.].

3. The method for preparing BTBT and BSBS small molecule materials according to claim 2, characterized in that: The Ar is selected from any one of an aryl group, a heteroaryl group, and an aryl group containing a substituent; the aryl group is any one of a phenyl group, a naphthyl group, and an anthracene group; the heteroaryl group is any one of a furan group, a thiophene group, a pyridine group, and a pyrrole group; the substituent R is one or more of hydrogen, a halogen group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a trifluoromethyl group, a trifluoromethoxy group, a hydroxyl group, an aryl group, an acyl group, an ester group, a nitro group, an amino group, a cyano group, and a (C1-C30 alkyl)amine group, and the position of the substituent is any position on the Ar ring; the base is any one of dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium bicarbonate, potassium phosphate, potassium dihydrogen phosphate, potassium acetate, potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, N-methylmorpholine, N,N-diisopropylethylamine, N-methylpiperidine, 4-dimethylaminopyridine, or 2,6-lutidine; and the solvent is a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide.

4. The method for preparing BTBT and BSBS small molecule materials according to claim 2, characterized in that: Typical conditions for the metal-free tandem cyclization reaction are as follows: 1 equivalent of compound 1, 1 equivalent of dipotassium hydrogen phosphate and 3 equivalents of sodium hydrosulfide hydrate or sodium selenide are added to a mixed solvent of N,N-dimethylacetamide and dimethyl sulfoxide, and reacted at 145° C. for 24 hours.

5. A BTBT and BSBS small molecule material prepared by the preparation method according to claim 1, characterized in that: Its molecular structure is as follows:

6. An organic semiconductor device made from the BTBT and BSBS small molecule materials according to claim 5.

7. A digital camera manufactured using the organic semiconductor device according to claim 6.

8. A mobile phone manufactured using the organic semiconductor device according to claim 6.

9. A handheld computer manufactured using the organic semiconductor device according to claim 6.

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