Kilogram-level preparation method of organic photoelectric conjugated tin reagent

Abstract

The invention provides a kilogram-level preparation method of an organic photoelectric conjugated tin reagent, and belongs to the field of organic synthesis and organic photoelectric materials. The method comprises the following steps: in a dry 20L reaction device, dissolving a conjugated thiophene compound in tetrahydrofuran, keeping nitrogen positive pressure protection, dropwise adding a tetrahydrofuran solution of n-butyllithium and a tetrahydrofuran solution of trimethyltin chloride in a low-temperature reaction system, stirring for reaction, after the reaction is completed, standing for phase splitting, collecting an organic phase, drying, and concentrating filtrate to obtain the conjugated thiophene compound. And recrystallizing to obtain the organic photoelectric conjugated tin reagent. According to the method, efficient macro preparation of various conjugated tin reagents can be achieved, 1-1.2 kg of target products can be prepared through single-batch reaction, and the method has the advantages of being high in yield, easy and convenient to operate, low in cost, good in environmental friendliness and the like.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis and organic optoelectronic materials, and particularly relates to a method for preparing organic optoelectronic conjugated tin reagents at the kilogram level. Background Technology

[0002] Conjugated polymers, with their tunable band gap, flexibility, and solution processability, show significant promise for applications in organic optoelectronic fields such as organic solar cells, organic field-effect transistors, and organic light-emitting diodes. The precise synthesis of these materials, particularly the construction of alternating copolymers, relies primarily on cross-coupling reactions catalyzed by transition metals such as Stille and Suzuki. Among these, the Stille coupling reaction, due to its excellent substrate compatibility, high stability of tin reagents in air, and superior reaction selectivity, has become a key method for the synthesis of aromatic heterocyclic functional polymers. As the core raw material for this reaction, the conjugated tin reagent, through cross-coupling with halides under palladium catalysis, directly determines the structural integrity and photoelectric properties of the conjugated polymer, serving as a crucial intermediate connecting basic organic synthesis with the industrialization of polymer materials.

[0003] However, existing conjugated tin reagent preparation techniques have significant bottlenecks, severely limiting the large-scale application of conjugated polymer materials.

[0004] First, traditional synthesis methods generally face challenges related to toxicity and safety. Organotin reagents are highly toxic, posing not only a risk of permanent harm to operators but also acting as charge trapping sites, quenching electron transport in devices and significantly reducing the efficiency and lifespan of organic electronic devices. Furthermore, existing preparation processes often rely on sensitive reagents such as organolithium compounds and Grignard reagents, requiring strict anhydrous and oxygen-free conditions. This not only makes the process complex but also poses potential safety hazards, making it difficult to meet safety standards for industrial production.

[0005] Secondly, existing technologies have fundamental limitations in terms of scale-up production capacity. Most reported methods for preparing conjugated tin reagents remain at the millimolecular scale in the laboratory. For example, the typical reaction scale for alkenyltin reagents prepared by catalytic lithiation and transmetalation of polycyclic aromatic hydrocarbons is only 0.25 mmol, and it requires fine purification steps such as column chromatography, with yields fluctuating between 58% and 85%. This small-scale synthesis not only fails to meet the raw material requirements for kilogram-scale production of conjugated polymers but also faces problems of decreased yield and poor uniformity due to scale-up effects. As the reaction scale increases, uneven heat and mass transfer exacerbates side reactions, and traditional purification methods are extremely inefficient in large-scale production, further leading to insufficient product purity. This directly triggers homopolymer structural defects and metal residues in the synthesis of conjugated polymers, causing a series of chain reactions such as increased defect state density and decreased charge mobility in the material film.

[0006] Furthermore, existing processes suffer from significant shortcomings in terms of both economy and environmental friendliness. Traditional methods not only consume large amounts of tin raw materials and have low conversion rates, but also often use toxic organic solvents, generating hazardous waste that is difficult to manage, which contradicts the trend of green chemistry. Although Stille coupling is indispensable in precise synthesis, the inherent defects of tin reagents have led to their gradual replacement by the Suzuki reaction, which is more environmentally friendly and safer due to the use of organoboronic acid derivatives. Against this backdrop, developing a process for preparing conjugated tin reagents that can overcome toxicity limitations, achieve stable kilogram-level production, and combine high purity with low cost has become an urgent need to promote the industrialization of conjugated polymer materials from the laboratory.

[0007] With the rapid expansion of the flexible electronics market, such as smart wearable devices, the demand for high-performance conjugated polymer materials is growing exponentially, exacerbating the already acute contradiction between existing reagent supply capacity and industry demand. There is an urgent need to address the safety, economic, and quality control challenges in the large-scale preparation of conjugated tin reagents through process innovation, laying a crucial raw material foundation for the industrial production of organic optoelectronic materials. Summary of the Invention

[0008] To address the aforementioned technical problems, this invention proposes a kilogram-scale preparation method for organic photoelectric conjugated tin reagents. This method enables the efficient and large-scale preparation of various conjugated tin reagents and has advantages such as high yield, simple operation, low cost, and good environmental friendliness.

[0009] To achieve the above objectives, the present invention provides the following technical solution:

[0010] This invention proposes a kilogram-scale preparation method for organic photoelectric conjugated tin reagents, comprising the following steps:

[0011] (1) In a dry 20L reaction apparatus, the conjugated thiophene compound was dissolved in tetrahydrofuran, the reaction apparatus was purged with nitrogen to maintain positive pressure protection, and the temperature was lowered by a liquid nitrogen-ethanol cold bath system.

[0012] (2) In the low-temperature reaction system of step (1), add tetrahydrofuran solution of n-butyllithium and tetrahydrofuran solution of trimethyltin chloride, and stir the reaction.

[0013] (3) After the reaction is complete, the reaction system is brought to room temperature and stirred overnight. Water is added to terminate the reaction. After standing and separating the phases, the organic phase is collected. The aqueous phase is extracted with dichloromethane and the organic phases are combined. Anhydrous magnesium sulfate is added to the combined organic phase for drying. The desiccant is removed by filtration and the filtrate is concentrated to obtain the crude product. The crude product is recrystallized with acetone to obtain the organic photoelectric conjugated tin reagent.

[0014] Further, in step (1), the conjugated thiophene compound is selected from 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene, 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene, 4,8-bis[4-fluoro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene, thiophene, 2,2'-diphenyltri ... Thiophene, thiophene[3,2-b]thiophene, 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bidithiophene, 4,4,9,9-tetrahexyl-4,9-dihydro-s-indargen[1,2-b:5,6-b']dithiophene, 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bidithiophene, 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indargen[1,2-b:5,6-b']dithiophene.

[0015] Further, in step (1), the amount of tetrahydrofuran used is 4-6 L per mole of conjugated thiophene compound.

[0016] Furthermore, in step (1), the temperature is lowered to below -78°C using a liquid nitrogen-ethanol cold bath system.

[0017] Further, in step (2), the molar ratio of n-butyllithium to conjugated thiophene compound is (2.0-2.5):1, and the addition time of the tetrahydrofuran solution of n-butyllithium is 3-5 hours.

[0018] Further, in step (2), the molar ratio of trimethyltin chloride to the conjugated thiophene compound is (2.0-2.2):1; the concentration of trimethyltin chloride in the tetrahydrofuran solution of trimethyltin chloride is 2-3 mol / L.

[0019] Furthermore, in step (2), the stirring time after adding the tetrahydrofuran solution of n-butyllithium is 2-3 hours; after adding the tetrahydrofuran solution of trimethyltin chloride, the system is kept warm for 2 hours at a temperature not higher than -40℃.

[0020] In further step (2), during the addition of tetrahydrofuran solution of n-butyllithium, the reaction temperature is controlled to not exceed -78℃; during the addition of tetrahydrofuran solution of trimethyltin chloride, the system temperature is controlled to not exceed -40℃.

[0021] Further, the organic photoelectric conjugated tin reagent includes 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophen-2,6-bis(trimethyltin), 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophen-2,6-bis(trimethyltin), (4,8-bis(4-fluoro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2,6-diyl)bistrimethyltin, 2,5-bis(trimethyltinyl)thiophene, and 5,5'-bis(trimethyltinyl)-2,2' -Bis(dithiophene), 2,5-bis(trimethyltin)thiophene[3,2-b]-dithiophene, 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bis(dithiophene-5,5'-bis(trimethyltin), 4,4,9,9-tetrahexyl-4,9-dihydro-s-indargen[1,2-b:5,6-b']dithiophene-2,7-bis(trimethyltin), 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bis(dithiophene-5,5'-bis(trimethyltin) and 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indargen[1,2-b:5,6-b']dithiophene-2,7-bis(trimethyltin).

[0022] Technical principle of the invention:

[0023] In the preparation process of this invention, the organolithium reagent (n-butyllithium) and organotin intermediate (trimethyltin chloride) are prone to coupling side reactions at high temperatures (such as self-coupling of butyllithium and detinning of tin intermediates). Therefore, controlling the low-temperature environment can significantly reduce the activation energy of side reactions and reduce ineffective consumption. At the same time, the low temperature below -78℃ can precisely control the lithiation sites of conjugated thiophene compounds, avoiding structural impurities caused by multi-site lithiation and ensuring the formation efficiency of the target intermediate. Conjugated thiophene compounds need to generate the target product through a double lithiation and double tinning process. A slight excess of n-butyllithium (2.0-2.5 times) can ensure complete lithiation of the raw materials (avoiding unlithiated raw material residue), while the precise ratio of trimethyltin chloride (2.0-2.2 times) can avoid impurities caused by excess tin reagent. The holding and stirring time provides sufficient time for the "lithiation-tinning" reaction to ensure that the reaction reaches equilibrium and reduces unreacted intermediates.

[0024] Compared with the prior art, the present invention has the following advantages and technical effects:

[0025] (1) By precisely controlling the thermodynamic and kinetic conditions of the reaction, the present invention suppresses side reactions and ensures full conversion of raw materials, fundamentally solving the problem of yield decline from laboratory pilot to industrial scale-up, significantly improving the reaction yield, with a crude yield of 75%-88%, and solving the problem of yield decline during scale-up;

[0026] (2) This invention transforms the complex organotin synthesis into a repeatable industrial process by standardizing operation steps, quantifying parameters, and fixing equipment. It refines the operation process, reduces experimental difficulty, and improves production efficiency. A single batch of reaction can prepare 1-1.2 kg of target product.

[0027] (3) This invention reduces costs through three pathways: raw material optimization, solvent recycling, and efficiency improvement, and develops a new synthesis process with lower cost and higher efficiency, which significantly reduces production costs;

[0028] (4) This invention effectively controls the source of raw materials, reduces dependence on foreign markets, and improves the stability of the supply chain;

[0029] (5) Traditional processes often use toxic solvents (such as chlorobenzene and carbon tetrachloride) or produce metal complex waste (such as palladium catalyst residue), which makes environmental treatment difficult. The waste of the present invention is "easy to treat" and has no high-risk pollutants, thus reducing environmental pressure. Attached Figure Description

[0030] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0031] Figure 1 The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectrum of 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) prepared in Example 1 are shown in the following figures (from top to bottom).

[0032] Figure 2 The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectra of 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) prepared in Example 2 are shown in the following figures (from top to bottom).

[0033] Figure 3 The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectra of (4,8-bis(4-fluoro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2,6-diyl)bistrimethyltin prepared in Example 3 are shown in the following figures (from top to bottom).

[0034] Figure 4The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectrum of 2,5-bis(trimethyltinyl)thiophene prepared in Example 4 are shown (from top to bottom).

[0035] Figure 5 The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectrum of 5,5'-bis(trimethyltinyl)-2,2'-bidithiophene prepared in Example 5 are shown in the following figures (from top to bottom).

[0036] Figure 6 The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectrum of 2,5-bistrimethyltinthiophene[3,2-b]thiophene prepared in Example 6 are shown in the following figures (from top to bottom).

[0037] Figure 7 The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectrum (from top to bottom) of 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltinyl) prepared in Example 7 are shown.

[0038] Figure 8 The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectra of 4,4,9,9-tetrahexyl-4,9-dihydro-s-indazanop[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin prepared in Example 8 are shown in the following figures (from top to bottom).

[0039] Figure 9 The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectra of 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltinyl) prepared in Example 9 are shown in the following figures (from top to bottom).

[0040] Figure 10 The 1H NMR, 1C NMR, and MALDI-TOF-MS spectra of 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indargen[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin prepared in Example 10 are shown in the image (from top to bottom). Detailed Implementation

[0041] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0042] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0043] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0044] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0045] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0046] This invention provides a kilogram-scale preparation method for organic photoelectric conjugated tin reagents, specifically including the following steps:

[0047] (1) Fluorination step: In a dry 20L reaction apparatus (20L straight four-necked reaction flask or 20L double-layered glass reaction vessel, wherein the 20L straight four-necked reaction flask is equipped with a T-type stirring paddle, the upper opening of the double-layered glass reaction vessel is connected to a condenser, the reaction apparatus is also equipped with a mechanical stirring device (stirring speed of 260 rpm) and a thermometer with a measurement range of -100℃ to 100℃, and the cold bath system uses ethanol as the medium), the conjugated thiophene compound is dissolved in tetrahydrofuran, the amount of tetrahydrofuran is 4-6L per mole of conjugated thiophene compound, and the mixture is stirred until the raw material is completely dissolved; the reaction apparatus is purged with high-purity nitrogen for more than 10 minutes and a balloon is connected to maintain positive nitrogen pressure protection; the reaction temperature is controlled below -78℃ through the liquid nitrogen-ethanol cold bath system, and the temperature is monitored at all times to ensure that it does not exceed -78℃;

[0048] (2) Preparation steps of metallic tin reagent: In the low-temperature reaction system of step (1), a 2.5M n-butyllithium tetrahydrofuran solution is slowly added dropwise through a constant-pressure dropping funnel. During the dropwise addition, the reaction temperature is controlled not to exceed -78℃ (if the conjugated thiophene compound is thiophene, the temperature is controlled not to exceed 30℃), and the dropwise addition time is 3-5 hours. After the dropwise addition is completed, the feeding device is cleaned with 200-500mL of tetrahydrofuran, and the mixture is kept at -40℃ to -78℃ and stirred for 2-3 hours (if the conjugated thiophene compound is thiophene). When the compound is 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bidithiophene or 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bidithiophene, the holding temperature is -30℃ to 0℃, after which it is allowed to naturally return to room temperature and the reaction continues for 3 hours; then the reaction temperature is lowered to below -78℃ using a liquid nitrogen-ethanol cold bath system, and then a tetrahydrofuran solution of trimethyltin chloride is slowly added dropwise through a constant pressure dropping funnel, while controlling the system temperature not to exceed -40℃ during the addition process;

[0049] (3) Post-processing steps: After the reaction is completed, the reaction system is slowly warmed to room temperature in a cold bath and stirred overnight (stirring time is 10-12 hours); 5L of water is slowly added and stirred for 30 minutes to terminate the reaction. After standing and phase separation, the upper organic phase is collected; the aqueous phase is extracted once with 3L of dichloromethane and the organic phases are combined; 600g of anhydrous magnesium sulfate is added to the combined organic phase and stirred for half an hour to dry; the desiccant is removed by vacuum filtration using a 15cm diameter ceramic Buchner funnel and a 10L vacuum flask, and the filter cake is washed with dichloromethane; the filtrate is collected and concentrated under reduced pressure using a rotary evaporator to obtain the crude product; the crude product is recrystallized with acetone to obtain the target conjugated tin reagent.

[0050] In step (1) of the preferred embodiment of the present invention, the conjugated thiophene compound is selected from 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene, 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene, 4,8-bis[4-fluoro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene, thiophene, 2,2'-bidithiophene, thiophene[3,2-b] thiophene, 3,3'-bis(2,4-dithiophene). The organic photoelectric conjugated tin reagents prepared from any one of the following—(6-triisopropylphenyl)-2,2'-bidithiophene, 4,4,9,9-tetrahexyl-4,9-dihydro-s-indarsen[1,2-b:5,6-b']dithiophene, 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bidithiophene, and 4,4,9,9-tetrahexyl(4-hexylphenyl)-4,9-dihydro-s-indarsen[1,2-b:5,6-b']dithiophene—are 4,8-bis[5-(2-ethylhexyl)thiophene-2-yl]-benzo[1,2-b:4] (4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin), (4,8-bis(4-fluoro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bistrimethyltin, 2,5-bis(trimethyltinyl)thiophene, 5,5'-bis(trimethyltinyl)-2,2'-bidithiophene, 2,5-bistrimethyltinthiophene[3,2-b] ... Phenophenanthrene, 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltin), 4,4,9,9-tetrahexyl-4,9-dihydro-s-indargen[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin, 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltin) and 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indargen[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin.

[0051] All raw materials in the embodiments of this invention were purchased commercially.

[0052] In the embodiments of this invention, "room temperature / normal temperature" both refer to "25±2℃".

[0053] The technical solution of the present invention will be further illustrated by the following embodiments.

[0054] Example 1

[0055] The kilogram-scale preparation of 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) reagent was carried out via the following reaction route:

[0056]

[0057] The specific preparation method is as follows:

[0058] In a 20L straight four-necked reaction flask, place the flask in a cold bath device (at room temperature) using ethanol as the medium, and install a mechanical stirrer using a T-type impeller. Insert a thermometer measuring -100℃ to 100℃ into the side opening of the four-necked flask to ensure a dry environment inside the reaction flask. Pour in 6L of tetrahydrofuran, start stirring at 260 rpm, and add 849.8g (1.4mol) of 4,8-bis[5-(2-ethylhexyl)thiophene-2-yl]benzo[1,2-b:4,5-b']dithiophene at room temperature, stirring until the raw materials are completely dissolved. Use a high-purity nitrogen cylinder to purge the reaction flask with nitrogen for ten minutes as a protective condition, and connect a balloon to ensure a positive pressure nitrogen atmosphere within the system. Slowly add liquid nitrogen in batches to the cold bath device, using the liquid nitrogen-ethanol cold bath system to cool the reaction flask system to below -78℃. Continuously monitor the temperature change of the reaction vessel system to ensure that the temperature reaches -80℃. Slowly add 1.24 L (3.1 mol) of a 2.5 M n-butyllithium tetrahydrofuran solution, controlling the dropping rate and constantly monitoring the temperature to ensure it remains at -80 °C. The addition of the n-butyllithium solution takes 4 hours. After the addition is complete, rinse the feeding device with 200 mL of tetrahydrofuran to remove any remaining butyllithium. Maintain the reaction system temperature at -40 °C to -78 °C and stir continuously for 3 hours. Add liquid nitrogen to the cold bath to bring the reaction flask system temperature to -80 °C. Then, slowly add 636.8 g of a trimethyltin chloride tetrahydrofuran solution (3.2 mol / 9.6 L concentration of trimethyltin chloride) through a constant pressure dropping funnel, controlling the dropping rate and monitoring the temperature to ensure the system temperature remains at -42 °C. After adding trimethyltin chloride, the system was kept at -42°C for 2 hours, then slowly brought to room temperature in a cold bath and stirred overnight (stirring continued for 10 hours). 5L of water was slowly added and stirred for 30 minutes. The system was allowed to stand and separate phases. The upper organic phase was collected, and the aqueous phase was extracted once with 3L of dichloromethane. The organic phases were combined, and 600g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15cm diameter ceramic Buchner funnel and a 10L vacuum flask. The filtrate was collected and concentrated under reduced pressure using a rotary evaporator to obtain a crude yellow solid. Preliminary purification was achieved by recrystallization with 3L of acetone, yielding 1085.8g of the target product, 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin), in a crude yield of 85%. It was a light yellow solid with a purity of 99%.

[0059] The 1H NMR, 1C NMR, and MALDI-TOF-MS spectra of 4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) prepared in Example 1 are shown below (from top to bottom). Figure 1 .

[0060] Example 2

[0061] The kilogram-scale preparation of 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) reagent is described by the following reaction equation:

[0062]

[0063] The specific preparation method is as follows:

[0064] In a 20L straight four-necked reaction flask, place the flask in a cold bath device (at room temperature) using ethanol as the medium, and install a mechanical stirrer using a T-type impeller. Insert a thermometer measuring -100℃ to -100℃ into the side opening of the four-necked flask, ensuring a dry environment inside the reaction flask. Pour in 6L of tetrahydrofuran, start stirring at 260 rpm, and add 852.2g (1.3mol) of 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophene-2-yl]benzo[1,2-b:4,5-b']dithiophene at room temperature. Stir until the raw materials are completely dissolved. Use a high-purity nitrogen cylinder to purge the reaction flask with nitrogen for ten minutes as a protective condition, and connect a balloon to ensure a positive pressure nitrogen atmosphere within the system. Add liquid nitrogen to the cold bath device in batches, and use the liquid nitrogen-ethanol cold bath system to cool the reaction flask system to below -78℃. Observe the temperature change of the reaction vessel system constantly, ensuring that the temperature of the reaction vessel system reaches -80℃. Slowly add 1.16 L (2.9 mol) of a 2.5 M n-butyllithium tetrahydrofuran solution, controlling the dropping rate and constantly monitoring the temperature to ensure it remains at -80 °C. The addition of the n-butyllithium tetrahydrofuran solution takes 4 hours. After the addition is complete, rinse the feeding device with 200 mL of tetrahydrofuran and maintain the reaction system temperature at -40 °C to -78 °C, stirring continuously for 3 hours. Add liquid nitrogen to the cold bath to bring the reaction flask system temperature to -80 °C. Then, slowly add 597 g of a trimethyltin chloride tetrahydrofuran solution (trimethyltin chloride concentration of 3.0 mol / 9 L), controlling the dropping rate and monitoring the temperature. Maintain the system temperature at -42 °C during the addition. After the trimethyltin chloride is complete, maintain the temperature at -42 °C for 2 hours, then slowly return to room temperature in the cold bath and stir overnight (stirring for another 10 hours). 5L of water was slowly added and stirred for 30 minutes. The mixture was allowed to stand and separate into two phases. The upper organic phase was collected, and the aqueous phase was extracted once with 3L of dichloromethane. The organic phases were combined, and 600g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15cm diameter ceramic Buchner funnel and a 10L vacuum filtration flask. The filtrate was collected and concentrated under reduced pressure using a rotary evaporator to obtain a crude product solid powder. The product was preliminarily purified by recrystallization with 3L of acetone, yielding 1101.3g of the target product 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) in a crude yield of 88%. The product was a light yellow solid with a purity of 99%.

[0065] The 1H NMR, 1C NMR, and MALDI-TOF-MS spectra of 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) prepared in Example 2 are shown below (from top to bottom). Figure 2 .

[0066] Example 3

[0067] The kilogram-scale preparation of 4,8-bis[4-fluoro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bis(trimethyltin) reagent is described by the following reaction equation:

[0068]

[0069] The specific preparation method is as follows:

[0070] In a 20L straight four-necked reaction flask, place the flask in a room-temperature cold bath device with ethanol as the medium, and install a mechanical stirrer using a T-type impeller. Insert a thermometer with a temperature of -100℃ to 100℃ into the side opening of the four-necked flask, ensuring a dry environment inside the reaction flask. Pour in 6L of tetrahydrofuran, start stirring at 260 rpm, and add 900.1g (1.4mol) of 4,8-bis[4-fluoro-5-(2-ethylhexyl)thiophene-2-yl]benzo[1,2-b:4,5-b']dithiophene at room temperature. Stir until the raw materials are completely dissolved. Use a high-purity nitrogen cylinder to purge nitrogen into the reaction flask for ten minutes as a protective condition, and connect a balloon to ensure a positive pressure nitrogen atmosphere within the system. Add liquid nitrogen in batches to the cold bath device, and use the liquid nitrogen-ethanol cold bath system to cool the reaction flask system to below -78℃. Observe the temperature change of the reaction vessel system at all times, ensuring that the temperature of the reaction vessel system reaches -80℃. Slowly add 1.16 L (2.9 mol) of a 2.5 M n-butyllithium tetrahydrofuran solution, controlling the dropping rate and constantly monitoring the temperature to ensure it remains at a constant temperature. The addition of the n-butyllithium tetrahydrofuran solution takes 4 hours. After the addition is complete, rinse the feeding device with 500 mL of tetrahydrofuran solution and maintain the reaction system temperature at -40°C to -78°C, stirring continuously for 3 hours. Add liquid nitrogen to the cold bath to maintain the reaction flask system temperature at -80°C. Then, slowly add 636.8 g of a trimethyltin chloride tetrahydrofuran solution (trimethyltin chloride concentration of 3.2 mol / 230 mL), controlling the dropping rate and monitoring the temperature. Maintain the system temperature at -42°C during the addition. After the trimethyltin chloride is complete, maintain the temperature at -42°C for 2 hours, then slowly return to room temperature in the cold bath and stir overnight (stirring for another 10 hours). 5L of water was slowly added and stirred for 30 minutes. The mixture was allowed to stand and separate into two phases. The upper organic phase was collected, and the aqueous phase was extracted once with 3L of dichloromethane. The organic phases were combined, and 600g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15cm diameter ceramic Buchner funnel and a 10L vacuum flask. The filtrate was collected and concentrated under reduced pressure using a rotary evaporator to obtain a crude product solid powder. The product was preliminarily purified by recrystallization with 3L of acetone, yielding 1131.1g of the target product (4,8-bis(4-fluoro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2,6-diyl)bistrimethyltin in a crude yield of 85%. The product was a light yellow solid with a purity of 98%.

[0071] The 1H NMR, 1C NMR, and MALDI-TOF-MS spectra of (4,8-bis(4-fluoro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2,6-diyl)bistrimethyltin prepared in Example 3 are shown below (from top to bottom). Figure 3 .

[0072] Example 4

[0073] The kilogram-scale preparation of 2,5-bis(trimethyltinyl)thiophene reagent is carried out by the following reaction equation:

[0074]

[0075] The specific preparation method is as follows:

[0076] A 20L double-walled glass reactor was selected, with a condenser connected to the top. A thermometer measuring -50℃ to 100℃ was inserted, ensuring a dry environment inside the reactor. 3L of tetrahydrofuran was added, and stirring was started at 260 rpm. At room temperature, 312.2g (3.7mol) of thiophene was added, and stirring was resumed. A high-purity nitrogen cylinder was used to purge the reactor with nitrogen for ten minutes as a protective measure, and a balloon was connected to ensure a positive nitrogen atmosphere within the system. The circulating thermostat in the reactor jacket was opened, and the temperature was set to -30℃. Feeding began after the system temperature in the reactor cooled to below 5℃. 3.26 L (8.16 mol) of 2.5 M n-butyllithium tetrahydrofuran solution was slowly added dropwise to the reaction vessel using a constant-pressure dropping funnel. The reaction was exothermic during the addition process, so the dropping rate should be controlled and the temperature constantly monitored to ensure it remained at 30 °C. The entire process of adding the n-butyllithium tetrahydrofuran solution took 3.5 hours. After the addition was complete, the feeding device was rinsed with 200 mL of tetrahydrofuran. The constant-temperature bath was set at 30 °C, and the reaction system was kept at 10 °C-30 °C for one hour. Afterward, the temperature of the constant-temperature bath was increased to 70 °C, and the system was refluxed. Stir continuously for three hours. At this point, the reaction system is a suspension of a large amount of white solids. Switch the constant temperature bath to the chiller and set it to -30°C. When the temperature of the reaction system reaches -12°C, slowly add a tetrahydrofuran solution containing 1413g of trimethyltin chloride (the concentration of trimethyltin chloride in the solution is 7.1mol / 500mL). Control the dropping rate and pay attention to temperature changes. During the dropping process, keep the system temperature at -2°C. After the trimethyltin chloride is added, keep it at -12°C for 2 hours. Then, slowly return it to room temperature in the cold bath and stir overnight (continue stirring for 10 hours). 5 L of water was slowly added and stirred for 30 minutes. The mixture was allowed to stand and separate into two phases. The upper organic phase was collected, and the aqueous phase was extracted once with 3 L of dichloromethane. The organic phases were combined, and 600 g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15 cm diameter ceramic Buchner funnel and a 10 L suction flask. The filter cake was washed with dichloromethane, and the filtrate was collected and concentrated under reduced pressure using a rotary evaporator to obtain 1550 g of crude gray solid. The product was initially purified by recrystallization with 1.8 L of acetone, yielding 1154.1 g of crude 2,5-bis(trimethyltinyl)thiophene in a crude yield of 75%. The crude product was a light gray crystal with a purity of 99%.

[0077] The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectra of 2,5-bis(trimethyltinyl)thiophene prepared in Example 4 are shown below (from top to bottom). Figure 4 .

[0078] Example 5

[0079] The kilogram-scale preparation of 5,5'-bis(trimethylstanyl)-2,2'-bidithiophene reagent is carried out by the following reaction equation:

[0080]

[0081] The specific preparation method is as follows:

[0082] A 20L double-walled glass reactor was selected, with a condenser connected to the top and a thermometer for -50 to 100℃ inserted. The reactor was kept in a dry environment. 3L of tetrahydrofuran was added, and stirring was started at 260 rpm. At room temperature, 432.4g (2.6mol) of 2,2'-dithiophene was added and stirred until the raw materials were fully dissolved. A high-purity nitrogen cylinder was used to purge the reactor with nitrogen for ten minutes as a protective measure, and a balloon was connected to ensure a positive nitrogen atmosphere within the system. The circulating thermostat in the reactor jacket was opened and the temperature was set to -30℃. After the system temperature in the reactor cooled to -12℃, further addition of materials began. 2.3 L (5.7 mol) of 2.5 M n-butyllithium tetrahydrofuran solution was slowly added dropwise to the reaction vessel using a constant-pressure dropping funnel. The dropping rate was controlled during the process, and the temperature was constantly monitored to ensure it remained at 18 °C. The entire process of adding the n-butyllithium tetrahydrofuran solution took 4 hours. After the addition was complete, the feeding device was rinsed with 200 mL of tetrahydrofuran. The constant-temperature bath was set at 30 °C, and the reaction system was kept at 10 °C-30 °C for two hours. At this point, the reaction system contained a large amount of white... For the suspension of the colored solid, the constant temperature bath was switched to chiller mode and set to -30℃. Once the reaction system temperature reached -12℃, a tetrahydrofuran solution containing 1194g of trimethyltin chloride (6.0mol / 430mL concentration of trimethyltin chloride) was slowly added dropwise. The dropping rate was controlled, and temperature changes were monitored. During the addition, the system temperature was maintained at -2℃. After the addition of trimethyltin chloride, the system was kept at 8℃ for 2 hours, then slowly cooled to room temperature in a cold bath and stirred overnight (stirring continued for 10 hours). 5L of water was slowly added and stirred for 30 minutes. The mixture was allowed to stand and separate phases. The organic phase was collected, and the aqueous phase was extracted once with 3L of dichloromethane. The organic phases were combined, and 600g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15cm diameter ceramic Buchner funnel and a 10L suction flask. The filter cake was washed with dichloromethane, and the filtrate was collected. The filtrate was then concentrated under reduced pressure using a rotary evaporator to obtain 1480g of crude gray solid. Preliminary purification was achieved by recrystallization with 2L of acetone, yielding 1143g of crude product 5,5'-bis(trimethyltinyl)-2,2'-bidithiophene in a crude yield of 80%. The product was a light green solid with a purity of 99%.

[0083] The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectra of 5,5'-bis(trimethylstanyl)-2,2'-dithiophene prepared in Example 5 are shown below (from top to bottom). Figure 5 .

[0084] Example 6

[0085] The kilogram-scale preparation of 2,5-bis(trimethyltin)thiophene[3,2-b]thiophene reagent is carried out using the following reaction equation:

[0086]

[0087] The specific preparation method is as follows:

[0088] A 20L double-walled glass reactor was selected, and a thermometer measuring -50 to 100℃ was inserted. The reactor was kept in a dry environment. 3L of tetrahydrofuran was added, and stirring was started at 260 rpm. At room temperature, 392g (2.8mol) of thiophene was added, and stirring continued until the raw materials were fully dissolved. A high-purity nitrogen cylinder was used to purge the reactor with nitrogen for ten minutes as a protective measure, and a balloon was connected to ensure a positive nitrogen atmosphere within the system. The circulating thermostat in the reactor jacket was opened, and the temperature was set to -30℃. Once the system temperature in the reactor cooled to 3℃, the raw materials were added. 2.5 L (6.2 mol) of 2.5 M n-butyllithium tetrahydrofuran solution was slowly added dropwise to the reaction vessel using a constant-pressure dropping funnel. The dropping rate was controlled during the process, and the temperature was constantly monitored to ensure it remained at 30 °C. The entire process of adding the n-butyllithium tetrahydrofuran solution took 3.5 hours. After the addition was complete, the feeding device was rinsed with 500 mL of tetrahydrofuran. The constant-temperature bath was then set at 30 °C, and the reaction system was kept at 10 °C-30 °C for two hours. At this point, the reaction system contained a large amount of... For the white solid suspension, the constant temperature bath was switched to chiller mode and set to -30℃. Once the reaction system temperature reached -12℃, a tetrahydrofuran solution containing 1273.6g of trimethyltin chloride (6.4mol / 430mL) was slowly added dropwise, controlling the dropping rate and monitoring temperature changes. During the addition, the system temperature was maintained at -2℃. After the addition of trimethyltin chloride, the solution was kept at 8℃ for 2 hours, then slowly cooled to room temperature in a cold bath and stirred overnight (stirring continued for 10 hours). 5L of water was slowly added and stirred for 30 minutes. The mixture was allowed to stand and separate phases. The organic phase was collected, and the aqueous phase was extracted once with 3L of dichloromethane. The organic phases were combined, and 600g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15cm diameter ceramic Buchner funnel and a 10L suction flask. The filter cake was washed with dichloromethane, and the filtrate was collected and concentrated under reduced pressure using a rotary evaporator to obtain 1300g of the crude product, a grayish-green solid. Preliminary purification was achieved by recrystallization with 2.3 L of acetone, yielding 1024.8 g of the target product, 2,5-bis(trimethyltin)thiophene[3,2-b]thiophene, in a crude yield of approximately 81%. The product was a grayish-green crystal with a purity of 99%.

[0089] The 1H NMR spectrum, 1C NMR spectrum, and MALDI-TOF-MS spectra of 2,5-bis(trimethyltin)thiophene[3,2-b]thiophene prepared in Example 6 are shown below (from top to bottom). Figure 6 .

[0090] Example 7

[0091] The kilogram-scale preparation of the 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltinyl) reagent is described by the following reaction equation:

[0092]

[0093] The specific preparation method is as follows:

[0094] In a 20L straight four-necked reaction flask, place the flask in a cold bath (at room temperature) with ethanol as the medium, and install a mechanical stirrer using a T-type impeller. Insert a thermometer measuring -100℃ to -100℃ into the side opening of the four-necked flask, ensuring a dry environment inside the reaction flask. Pour in 6L of tetrahydrofuran, start stirring at 260 rpm, and add 817.4g (1.5mol) of 3,3'-bis(2,4,6-triisopropylbenzene)-2,2'-dithiophene at room temperature. Heat to 50℃ and stir until the raw materials are fully dissolved. Cool to room temperature, and purge the reaction flask with nitrogen gas for ten minutes using a high-purity nitrogen cylinder as a protective condition. Connect a balloon to ensure a positive pressure nitrogen atmosphere within the system. Add liquid nitrogen in batches to the cold bath, using a liquid nitrogen-ethanol cold bath system to cool the reaction flask system to -80℃. Observe the temperature change of the reaction flask system constantly to ensure that the temperature of the reaction flask system is maintained at -80℃. Slowly add 1.32 L (3.3 mol) of 2.5 M n-butyllithium tetrahydrofuran solution, controlling the dropping rate and constantly observing the temperature change to ensure the temperature is maintained at -42 °C. The process of adding the n-butyllithium tetrahydrofuran solution takes 3 hours. After the n-butyllithium tetrahydrofuran solution is completely added, keep the reaction system temperature at -30 °C to 0 °C and stir continuously for 3 hours. Then allow it to return to room temperature naturally and react at room temperature for 3 hours. The feeding apparatus was cleaned with 500 mL of tetrahydrofuran. Liquid nitrogen was added to the cold bath to maintain the temperature of the reaction flask system at -80℃. 696.5 g of a tetrahydrofuran solution of trimethyltin chloride (3.5 mol / 250 mL) was slowly added dropwise, controlling the dropping rate and monitoring temperature changes. The system temperature was maintained at -42℃ during the dropping process. After the addition of trimethyltin chloride was completed, the system was kept at -42℃ for 2 hours, then slowly brought to room temperature in the cold bath and stirred overnight (stirring continued for 12 hours). 5 L of water was slowly added and stirred for 30 minutes. The system was allowed to stand and separate phases. The upper organic phase was collected, and the aqueous phase was extracted once with 3 L of dichloromethane. The organic phases were combined, and 600 g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15 cm diameter ceramic Buchner funnel and a 10 L vacuum flask. The filtrate was collected and concentrated under reduced pressure using a rotary evaporator to obtain a crude product solid powder. The product 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltinyl) was obtained in crude yield of 85% with a crude yield of 1108.6g. The product was a gray-green solid with a purity of 99%.

[0095] The 1H NMR, 1C NMR, and MALDI-TOF-MS spectra of 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltinyl) prepared in Example 7 are shown below (from top to bottom). Figure 7 .

[0096] Example 8

[0097] The kilogram-scale preparation of 4,4,9,9-tetrahexyl-4,9-dihydro-s-indarene[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin reagent was carried out using the following reaction equation:

[0098]

[0099] The specific preparation method is as follows:

[0100] In a 20L straight four-necked reaction flask, place the flask in a cold bath (at room temperature) with ethanol as the medium, and install a mechanical stirrer using a T-type impeller. Insert a thermometer measuring -100℃ to -100℃ into the side opening of the four-necked flask, ensuring a dry environment inside the reaction flask. Pour in 4L of tetrahydrofuran, start stirring at 260 rpm, and add 844.2g (1.4mol) of 4,4,9,9-tetrahexyl-4,9-dihydro-S-indarsen[1,2-b:5,6-b']dithiophene at room temperature. Stir until the raw materials are fully dissolved. Use a high-purity nitrogen cylinder to purge the reaction flask with nitrogen for ten minutes as a protective condition, and connect a balloon to ensure a positive pressure nitrogen atmosphere within the system. Add liquid nitrogen in batches to the cold bath device, using a liquid nitrogen-ethanol cold bath system to cool the reaction flask system to below -78℃. Observe the temperature change of the reaction vessel system constantly, ensuring that the temperature of the reaction vessel system is maintained at -80℃. Slowly add 1.24 L (3.1 mol) of a 2.5 M n-butyllithium tetrahydrofuran solution, controlling the dropping rate and constantly monitoring the temperature to ensure it does not reach -62 °C. The addition of the n-butyllithium tetrahydrofuran solution takes 5 hours. After the addition is complete, maintain the reaction system temperature at -40 °C to -78 °C and stir continuously for 3 hours. Clean the feeding device with 200 mL of tetrahydrofuran and add liquid nitrogen to the cold bath to bring the reaction flask system temperature to -80 °C. Then, slowly add 636.8 g of a trimethyltin chloride tetrahydrofuran solution (trimethyltin chloride concentration of 3.2 mol / 220 mL), controlling the dropping rate and monitoring the temperature. Maintain the system temperature at -42 °C during the addition. After the trimethyltin chloride is complete, maintain the temperature at -42 °C for 2 hours, then slowly return to room temperature in the cold bath and stir overnight (continue stirring for 10 hours). 5L of water was slowly added and stirred for 30 minutes. The mixture was allowed to stand and separate into two phases. The upper organic phase was collected, and the aqueous phase was extracted once with 3L of dichloromethane. The organic phases were combined, and 600g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15cm diameter ceramic Buchner funnel and a 10L vacuum flask. The filtrate was collected and concentrated under reduced pressure using a rotary evaporator to obtain a crude product solid powder. The powder was heated and stirred with 3L of acetone, then frozen and filtered. After preliminary purification, 1040.5g of the target product 4,4,9,9-tetrahexyl-4,9-dihydro-s-indarene[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin was obtained in crude yield of 81%. The product was a deep yellow solid with a purity of 99%.

[0101] The 1H NMR, 1C NMR, and MALDI-TOF-MS spectra (from top to bottom) of 4,4,9,9-tetrahexyl-4,9-dihydro-s-indargeno[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin prepared in Example 8 are shown below. Figure 8 .

[0102] Example 9

[0103] The kilogram-scale preparation of the 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltinyl) reagent is described by the following reaction equation:

[0104]

[0105] The specific preparation method is as follows:

[0106] In a 20L straight four-necked reaction flask, place the flask in a cold bath (at room temperature) with ethanol as the medium, and install a mechanical stirrer using a T-type impeller. Insert a thermometer measuring -100℃ to -100℃ into the side opening of the four-necked flask, ensuring a dry environment inside the reaction flask. Pour in 6L of tetrahydrofuran, start stirring at 260 rpm, and add 714.4g (1.9mol) of 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-dithiophene at room temperature. Using a high-purity nitrogen cylinder, purge the reaction flask with nitrogen for ten minutes as a protective condition, and connect a balloon to ensure a positive pressure nitrogen atmosphere within the system. Add liquid nitrogen in batches to the cold bath, using a liquid nitrogen-ethanol cold bath system to cool the reaction flask system to below -78℃, constantly monitoring the temperature change to ensure the system temperature reaches -80℃. Slowly add 1.7 L of a 2.5 M tetrahydrofuran solution of n-butyllithium, controlling the dropping rate and constantly monitoring the temperature to ensure it remains at -42 °C. The addition of the tetrahydrofuran solution of n-butyllithium takes 3 hours. After the addition is complete, maintain the reaction system temperature at -30 °C to 0 °C. After 3 hours, allow the system to return to room temperature naturally and stir continuously at room temperature for 3 hours. Clean the feeding device with 500 mL of tetrahydrofuran and add liquid nitrogen to the cold bath to maintain the reaction flask temperature at -80 °C. Slowly add 875.6 g (4.4 mol) of a tetrahydrofuran solution of trimethyltin chloride (totaling 310 mL of tetrahydrofuran), controlling the dropping rate and monitoring the temperature. Maintain the system temperature at -42 °C during the addition. After the addition of trimethyltin chloride, maintain the system temperature at -42 °C for 2 hours, then slowly return it to room temperature in the cold bath and stir overnight (continue stirring for 12 hours). Slowly add 5L of water and stir for 30 minutes. Allow to stand and separate the phases. Collect the upper organic phase. Extract the aqueous phase once with 3L of dichloromethane. Combine the organic phases and add 600g of anhydrous magnesium sulfate. Stir for half an hour. Use a 15cm diameter ceramic Buchner funnel and a 10L vacuum filtration flask to remove magnesium sulfate solid. Collect the filtrate and concentrate it under reduced pressure using a rotary evaporator to obtain a crude product solid powder. Heat to reflux with 2L of acetone, cool, and freeze-filter for preliminary purification. Obtain 1106.3g of the target product in crude yield of 84% as a yellow solid with a purity of 99%.

[0107] The 1H NMR, 1C NMR, and MALDI-TOF-MS spectra of 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bidithiophene-5,5'-bis(trimethyltinyl) prepared in Example 9 are shown below (from top to bottom). Figure 9 .

[0108] Example 10

[0109] The kilogram-scale preparation of 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indarseno[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin reagent was carried out using the following reaction equation:

[0110]

[0111] The specific preparation method is as follows:

[0112] In a 20L straight four-necked reaction flask, place the flask in a cold bath (at room temperature) with ethanol as the medium, and install a mechanical stirrer using a T-type impeller. Insert a thermometer measuring -100℃ to -100℃ into the side opening of the four-necked flask, ensuring a dry environment inside the reaction flask. Pour in 6L of tetrahydrofuran, start stirring at 260 rpm, and add 1179.6g (1.3mol) of 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-S-indarsen[1,2-b:5,6-b']dithiophene at room temperature. Stir until the raw materials are fully dissolved. Use a high-purity nitrogen cylinder to purge the reaction flask with nitrogen for ten minutes as a protective condition, and connect a balloon to ensure a positive pressure nitrogen atmosphere within the system. Add liquid nitrogen to the cold bath in batches, using a liquid nitrogen-ethanol cold bath system to cool the reaction flask system to below -78℃, constantly observing the temperature change of the reaction vessel system, ensuring that the temperature of the reaction vessel system reaches -80℃. Slowly add 1.24 L of a 2.5 M tetrahydrofuran solution of n-butyllithium, controlling the dropping rate and constantly monitoring the temperature to ensure it remains at -80 °C. The addition of the tetrahydrofuran solution of n-butyllithium takes 4 hours. After the addition is complete, rinse the feeding device with 200 mL of tetrahydrofuran and maintain the reaction system temperature at -40 °C to -78 °C, stirring continuously for 3 hours. Add liquid nitrogen to the cold bath to maintain the reaction flask temperature at -80 °C. Then, slowly add 835.8 g (3.0 mol) of a tetrahydrofuran solution of trimethyltin chloride (containing a total of 300 mL of tetrahydrofuran), controlling the dropping rate and monitoring the temperature. Maintain the system temperature at -42 °C during the addition. After the addition of trimethyltin chloride, maintain the temperature at -42 °C for 2 hours, then slowly return to room temperature in the cold bath and stir overnight (stirring for another 10 hours). 5L of water was slowly added and stirred for 30 minutes. The mixture was allowed to stand and separate into two phases. The upper organic phase was collected, and the aqueous phase was extracted once with 3L of dichloromethane. The organic phases were combined, and 600g of anhydrous magnesium sulfate was added and stirred for half an hour. The magnesium sulfate solid was removed by vacuum filtration using a 15cm diameter ceramic Buchner funnel and a 10L vacuum flask. The filtrate was collected and concentrated under reduced pressure using a rotary evaporator to obtain a crude product solid powder. The product was initially purified by recrystallization with 3L of acetone, yielding 1233.0g of the target product 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indarsen[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin in a crude yield of 80%. The product was an orange-yellow solid with a purity of 99%.

[0113] The 1H NMR, 1C NMR, and MALDI-TOF-MS spectra (from top to bottom) of 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indarseno[1,2-b:5,6-b']dithiophene-2,7-bistrimethyltin prepared in Example 10 are shown below. Figure 10 .

[0114] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for the preparation of kilograms of organo-photocorronated tin reagents, characterized in that, The method comprises the following steps: (1) in a dry 20L reaction device, the conjugated thiophene compound is dissolved in tetrahydrofuran, the reaction device is purged with nitrogen, the nitrogen overpressure protection is maintained, and the cooling is performed through a liquid nitrogen-ethanol cooling bath system; (2) in the low-temperature reaction system of step (1), the tetrahydrofuran solution of n-butyllithium and the tetrahydrofuran solution of trimethyltin chloride are added dropwise, and the stirring reaction is performed; (3) after the reaction is completed, the reaction system is raised to room temperature and stirred overnight, water is added to terminate the reaction, the organic phase is collected after phase separation, the water phase is extracted with dichloromethane, the organic phases are combined, anhydrous magnesium sulfate is added to the combined organic phase for drying, the drying agent is removed by filtration, and the crude product is obtained by concentrating the filtrate; the crude product is recrystallized with acetone to obtain the organic photoelectric conjugated tin reagent.

2. The process according to claim 1 for the preparation of the organic photoconductive tin reagent on a kilogram scale, characterized in that, In step (1), the conjugated thiophene compound is selected from any one of 4,8-bis[5-(2-ethylhexyl)thiophene-2-yl]-benzo[1,2-b:4,5-b']dithiophene, 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophene-2-yl]-benzo[1,2-b:4,5-b']dithiophene, 4,8-bis[4-fluoro-5-(2-ethylhexyl)thiophene-2-yl]-benzo[1,2-b:4,5-b']dithiophene, thiophene, 2,2'-bithiophene, thieno[3,2-b]thiophene, 3,3'-bis(2,4,6-triisopropylphenyl)-2,2'-bithiophene, 4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene, 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bithiophene, and 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene.

3. The process according to claim 1 for the preparation of the organic photoconductive tin reagent on a kilogram scale, characterized in that, In step (1), the amount of tetrahydrofuran used per mole of conjugated thiophene compound is 4-6L.

4. The process according to claim 1 for the preparation of the organic photoconductive tin reagent on a kilogram scale, characterized in that, In step (1), the cooling is performed to below-78°C through a liquid nitrogen-ethanol cooling bath system.

5. The process according to claim 1, wherein the process is a process for the preparation of the organic photoconductive tin agent on a kilogram scale, characterized in that, In step (2), the molar ratio of n-butyllithium to conjugated thiophene compound is (2.0-2.5):1, and the dropwise addition time of the tetrahydrofuran solution of n-butyllithium is 3-5 hours.

6. The process according to claim 1, wherein the process is a process for the preparation of the organic photoconductive tin agent on a kilogram scale, characterized in that, In step (2), the molar ratio of trimethyltin chloride to conjugated thiophene compound is (2.0-2.2):

1.

7. The process according to claim 6, wherein the process is carried out on a kilogram scale. In the tetrahydrofuran solution of trimethyltin chloride, the concentration of trimethyltin chloride is 2-3mol / L.

8. The process according to claim 1, wherein the process is a process for the preparation of the organic photoelectric conjugated tin reagent on a kilogram scale, characterized in that, In step (2), the heat preservation and stirring time after the completion of the dropwise addition of the tetrahydrofuran solution of n-butyllithium is 2-3 hours; after the completion of the dropwise addition of the tetrahydrofuran solution of trimethyltin chloride, the heat preservation is performed for 2 hours under the condition that the system temperature is not higher than-40°C.

9. The process according to claim 1, wherein the process is a process for the preparation of the organic photoelectric conjugated tin reagent on a kilogram scale, characterized in that, In step (2), the reaction temperature is controlled to be not higher than-78°C during the dropwise addition of the tetrahydrofuran solution of n-butyllithium; and the system temperature is controlled to be not higher than-40°C during the dropwise addition of the tetrahydrofuran solution of trimethyltin chloride.

10. The process according to claim 1, wherein the process is a process for the preparation of the organic photoconductive tin agent on a kilogram scale, characterized in that, The organic photoelectric conjugated tin reagents include 4,8-bis[5-(2- ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6-bistrimethyltin, 4,8-bis[4-chloro-5-(2-ethylhexyl)thiophen-2-yl]-benzo[1,2-b:4,5-b']dithiophene-2,6- bistrimethyltin, (4,8-di(4-fluoro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene- 2,6-diyl)bis(trimethyltin), 2,5-bis(trimethylstannyl)thiophene, 5,5'-bis(trimethylstannyl)-2,2'- bithiophene, 2,5-bistrimethyltin thiopheno[3,2-b]thiophene, 3,3'-bis(2,4,6-triisopropylphenyl)- 2,2'-bithiophene-5,5'-bis(trimethylstannyl), 4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6- b']dithiophene-2,7-bistrimethyltin, 3,3'-bis(2,4,6-trimethylphenyl)-2,2'-bithiophene-5,5'- bis(trimethylstannyl), and 4,4,9,9-tetra(4-hexylphenyl)-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene- 2,7-bistrimethyltin.

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