Synthesis method of a dithiazolylimide monomer and its derivatives

Abstract

The present invention provides a method for synthesizing a dithiazolylimide monomer and its derivatives. The structural formula of the compound is where R1 is an alkyl group with 1 to 18 carbon atoms; R2 is a halogen atom, an alkenyl group, or an aryl group. The present invention uses thiourea and dibromobutanedione as raw materials to synthesize a dibromodithiazolylimide monomer through six steps, and then obtains a series of small molecule luminescent materials by coupling unsaturated hydrocarbons such as alkenyl groups, aryl groups, or heteroaryl groups through Suzuki or Stille reactions.

Description

Technical Field

[0001] The present invention belongs to the field of organic semiconductor materials, and specifically relates to the synthesis of a dithiazolyl imide monomer, as well as a synthesis method and properties of a series of functionalized dithiazolyl imide compounds. Background Art

[0002] In recent years, with the in-depth study of organic optoelectronic materials, a large number of novel conjugated electron acceptor molecules have been developed. Aromatic imides are one of the most important electron acceptors. Due to their strong electron-withdrawing ability, the ability of N substituents to enhance solubility and influence molecular aggregation behavior, and the ease of functionalization through derivatization of the aromatic core, they have found widespread application in flexible optoelectronic devices, chemical sensors, and supramolecular assemblies.

[0003] The properties of aromatic imides depend largely on their π-conjugated cores. By introducing different groups, the lowest unoccupied molecular orbital (LUMO) of aromatic imides can be adjusted to give them different electrical properties. Since seven-membered ring aromatic imides have good flexibility and can be fused with different aromatic rings, thereby regulating intramolecular interactions and frontier orbital energy levels, they have gradually attracted people's attention. In 2008, the Marks group designed and synthesized dithiophene imide (BTI). Compared with six-membered ring imide building blocks such as naphthalene diimide (NDI) and perylene diimide (PDI), the BTI receptor building block not only effectively reduces steric hindrance, has good planarity and close molecular spacing, but also has strong electron-withdrawing ability. Therefore, the design and synthesis of new BTI-based polymers provides an excellent opportunity for the development of high-performance n-type semiconductors and has opened up a design boom for seven-membered ring aromatic imides. Among them, dithiazolyl imide (BTzI) has received widespread attention since it was first synthesized in 2018, and has been used in various organic optoelectronic devices. Its structure is

[0004] At present, the application of BTzI derivatives is mainly focused on the research of BTzI-based polymers in organic field effect transistors (OFETs) and organic solar cells (OSCs), while the application of BTzI-based small molecules as luminescent materials has been rarely reported. By isomerizing the nitrogen and sulfur elements in the BTzI structural unit to form a monomer dithiazolyl imide (iBTzI), the nitrogen atom is smaller than the sulfur atom, which is conducive to a more planar aromatic imide, and is conducive to intermolecular stacking and charge transfer, which is expected to fill the gap in its application in the field of luminescent materials. The structure of iBTzI is wherein R1 is an alkyl group having 1 to 18 carbon atoms.

[0005] The present invention realizes the synthesis of iBzTI structural units and develops a series of functionalized iBTzI compounds, which are expected to become a class of potential luminescent functional materials. Summary of the Invention

[0006] The object of the present invention is to provide a method for synthesizing iBTzI monomers and their derivatives.

[0007] To achieve the above-mentioned invention object, the present invention provides the following technical solutions:

[0008] The present invention synthesizes dibromodithiazolimide monomers through six steps, and then uses the dithiazolimide monomers as the main body for structural modification. By introducing flexible alkyl chains, its solubility is improved; by introducing auxochromic groups or chromogenic groups such as aromatic rings, the conjugation length is increased to enhance the delocalization ability of the electron cloud of its π system, thereby improving the electron transport ability and fluorescence quantum efficiency, changing its chemical properties, solubility, luminescence performance and electronic properties, improving its application performance, and designing and synthesizing a series of iBTzI derivatives. The reaction general formula is as follows:

[0009]

[0010] Wherein R1 is an alkyl group with 1 to 18 carbon atoms; X of the iBTzI monomer is a halogen atom, preferably bromine; R2 of the iBTzI derivative is a halogen atom, an alkenyl group, group, and the preferred structure is as follows:

[0011]

[0012] The specific steps of the method for synthesizing iBTzI monomers and their derivatives of the present invention are: using thiourea and dibromobutanedione as raw materials, synthesizing the thiazole ring by 1) the Hantzsch thiazole synthesis method, 2) replacing the amino group with bromine by the Sandmeyer reaction, 3) introducing an ester group by using Knochel-Hauser base, 4) hydrolyzing the ester group, 5) dehydrating and condensing dicarboxylic acid, and 6) imidization reaction to synthesize dibromodithiazolimide monomers, and then obtaining a series of iBTzI derivatives by coupling unsaturated hydrocarbons such as alkenyl groups, aryl groups or heteroaryl groups through Suzuki or Stille reactions.

[0013] Beneficial effects: The synthesis method of the present invention has the advantages of easily available raw materials, low cost, high yield, and can be prepared in grams in large quantities. Description of the Drawings

[0014] The present invention will be further described in detail below with reference to the drawings and specific embodiments.

[0015] Figure 1.7c - 7h UV - Vis absorption spectra in toluene solution (c = 1.0×10 -5 mol L -1 )

[0016] Figure 2 .7c - 7h Fluorescence emission spectra in toluene solution (c = 1.0×10 -5 mol L -1 ) Detailed implementation manners

[0017] Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by those skilled in the art related to this subject matter.

[0018] The present invention will be further described below in conjunction with embodiments, but the present invention is not limited to these examples.

[0019] Example 1:

[0020] Taking the synthesis of N - isopentyl - dibromodithiazolimide as an example, its structure is as follows:

[0021]

[0022] Step 1: Synthesis of 2,2’ - diamino - 4,4’ - bisthiazole (1)

[0023] The reaction formula is shown in the following figure:

[0024]

[0025] Dissolve thiourea (6.384 g, 84 mmol) and dibromobutanedione (9.760 g, 40 mmol) in chromatographic grade methanol (80 mL), and react overnight at 50 °C. After the reaction, spin out the methanol, add saturated sodium carbonate solution, stir and filter, and vacuum dry to obtain 7.795 g of 2,2’ - diamino - 4,4’ - bisthiazole, with a yield of 98%.

[0026] The spectral data of the obtained product are as follows:

[0027] 1 H NMR (400 MHz, DMSO - d6) δ6.12 (s, 4H), 5.71 (s, 2H). 13 C NMR (101 MHz, DMSO - d6) δ168.61, 146.76, 102.83.

[0028] Step 2: Synthesis of 2,2’ - dibromo - 4,4’ - bisthiazole (2)

[0029] The reaction formula is shown in the following figure:

[0030] 1) H2SO4, H3PO4, HBF4

[0031]

[0032] Dissolve 2,2'-diamino-4,4'-bisthiazole (3.960 g, 20 mmol) in a mixed solution of 20 mL:20 mL:20 mL of concentrated sulfuric acid, concentrated phosphoric acid and 40% fluoboric acid at 0 °C, and slowly drip into an aqueous solution (8 mL) of sodium nitrite (3580 g, 52 mmol) at 0 °C. After reacting for 2 hours, transfer the reaction solution to an aqueous solution (80 mL) containing sodium bromide (10.7 g, 104 mmol) and copper sulfate (8.320 g, 52 mmol) at 0 °C, and stir for 3 hours. After the reaction is completed, filter, and mix the obtained filter cake with magnesium sulfate and dichloromethane, and perform ultrasonic treatment and water washing. The obtained crude product is separated by column chromatography to obtain 3.501 g of 2,2'-dibromo-4,4'-bisthiazole, with a yield of 54%.

[0033] The spectral data of the obtained product are as follows:

[0034] 1 H NMR (400 MHz, CHCl3-d) δ 7.75 (s, 2H). 13 C NMR (101 MHz, CHCl3-d) δ 149.63, 136.85, 119.47.

[0035] Step 3: Synthesis of diethyl 2,2'-dibromo-[4,4'-bisthiazole]-5,5'-dicarboxylate (3)

[0036]

[0037] Under anhydrous and anaerobic conditions, dissolve 2,2'-dibromo-4,4'-bisthiazole (978 mg, 3 mmol) in freshly distilled tetrahydrofuran (30 mL), and slowly drip a solution of TMPMgCl·LiCl (18 mmol) in tetrahydrofuran (18 mL) at -40 °C. After reacting for 4.5 hours, add ethyl cyanoformate (18 mmol), and raise the temperature to room temperature and react for 22 hours. After the reaction is completed, add dichloromethane and water for extraction, evaporate the organic phase to dryness, and perform column chromatography separation to obtain 1.040 g of diethyl 2,2'-dibromo-[4,4'-bisthiazole]-5,5'-dicarboxylate, with a yield of 74%.

[0038] The spectral data of the obtained product are as follows:

[0039] 1 H NMR (400 MHz, CHCl3-d) δ 4.21 (q, J = 7.1 Hz, 4H), 1.22 (t, J = 7.1 Hz, 6H).13 13C NMR (101 MHz, CDCl3) δ 159.42, 150.16, 140.47, 131.73, 62.21, 14.05.

[0040] Step 4: Synthesis of 2,2'-Dibromo-[4,4'-bithiazole]-5,5'-dicarboxylic acid (4)

[0041]

[0042] To a reaction flask containing diethyl 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylate (1.004 g, 2.1 mmol) was added tetrahydrofuran (6.4 mL) and water (6.4 mL), and then lithium hydroxide (153 mg, 6.4 mmol) was added. The mixture was stirred at 50 °C overnight. After the reaction was completed, the tetrahydrofuran was evaporated, concentrated hydrochloric acid was added, and the mixture was filtered. The filter cake was dried under vacuum to obtain 884 mg of 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylic acid, with a yield of 88%.

[0043] The spectral data of the obtained product are as follows:

[0044] 1 1H NMR (400 MHz, DMSO-d6) δ 13.98. 13 13C NMR (101 MHz, DMSO-d6) δ 160.88, 149.58, 140.08, 133.50.

[0045] Step 5: Synthesis of Dibromodithiazole anhydride (5)

[0046]

[0047] To a reaction flask containing 2,2'-dibromo-[4,4'-bithiazole]-5,5'-dicarboxylic acid (828 mg, 2 mmol) was added acetic anhydride (6 mL). The mixture was stirred and refluxed at 120 °C overnight. After the reaction was completed, the mixture was filtered and dried under vacuum to obtain 626 mg of dibromodithiazole anhydride, with a yield of 78%.

[0048] The spectral data of the obtained product are as follows:

[0049] 13 13C NMR (101 MHz, CDCl3) δ 151.36, 147.71, 147.20, 131.76.

[0050] Step 6: Synthesis of N-Isopentyl-Dibromodithiazolimide (6)

[0051]

[0052] Chloroform (20 mL) was added to a reaction flask containing dibromodithiazole anhydride (788 mg, 2 mmol), and then a chloroform solution (10 mL) of isopentylamine (191 mg, 2.2 mmol) was added to the reaction flask. The mixture was refluxed at 60 °C for 2 hours. After the reaction was completed, the chloroform was evaporated to dryness, and thionyl dibromide (6 mL) was added. The mixture was stirred and refluxed at 130 °C for 3 hours. After the reaction was completed, dichloromethane and water were added for extraction. The organic phase was evaporated to dryness, and column chromatography was carried out to obtain 511 mg of N-isopentyl-dibromodithiazolimide with a yield of 55%.

[0053] The spectral data of the obtained product are as follows:

[0054] 1 H NMR (400 MHz, CHCl3-d) δ 4.17 - 4.08 (m, 2H), 1.70 - 1.60 (m, J = 13.2, 6.5 Hz, 1H), 1.56 - 1.45 (m, 2H), 0.94 (d, J = 6.5 Hz, 6H). 13 C NMR (101 MHz, CHCl3-d) δ 158.09, 146.13, 145.18, 138.66, 44.70, 35.89, 26.64, 22.50.

[0055] Example 2:

[0056] Taking the synthesis of N-isopentyl-monobromo-monovinyldithiazolimide (7a) as an example, its structure is as follows:

[0057]

[0058] The raw materials used and their synthesis methods are as follows:

[0059]

[0060] Under anaerobic conditions, N-isobutyl-dibromodithiazolimide (45.1 mg, 0.1 mmol), vinylboronic acid pinacol ester (15.4 mg, 0.1 mmol), [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) (6.5 mg, 0.08 mmol) and cesium carbonate (65.2 mg, 0.2 mmol) were dissolved in a mixed solution of toluene (2.7 mL) and water (0.3 mL). The mixture was heated and refluxed at 100 °C for 6 hours. After the reaction was completed, dichloromethane and water were added for extraction. The organic phase was evaporated to dryness, and column chromatography was carried out to obtain forty-two mg of the product with a yield of 34%.

[0061] The spectral data of the obtained product are as follows:

[0062] 1 H NMR (400 MHz, CHCl3-d) δ 7.06 (m, J = 17.6, 10.9 Hz, 1H), 6.30 (d, J = 17.6 Hz, 1H), 5.86 (d, J = 10.9 Hz, 1H), 4.12 (d, J = 7.4 Hz, 2H), 2.17 (m, J = 13.8, 7.0 Hz, 1H), 0.95 (d, J = 6.7 Hz, 6H).

[0063] Example 3:

[0064] Taking the synthesis of N-isopentyl-dithienodithiazolylimide (7b) as an example, its structure is as follows:

[0065]

[0066] The raw materials used and their synthesis methods are as follows:

[0067] 1) The raw materials used in the Suzuki coupling reaction and their synthesis methods are as follows:

[0068]

[0069] Under anaerobic conditions, N-isopentyl-dibromodithiazolylimide (186 mg, 0.4 mmol), 2-thiopheneboronic acid (154 mg, 1.2 mmol), potassium phosphate (339 mg, 1.6 mmol) and chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos Pd G2) (38 mg, 0.0048 mmol) were dissolved in a mixed solution of tetrahydrofuran (8 mL) and water (4 mL), and heated to reflux at 50 °C for 3 hours. After the reaction, dichloromethane and water were added for extraction, and the organic phase was dried by rotary evaporation and separated by column chromatography to obtain 151 mg of N-isopentyl-dithienodithiazolylimide with a yield of 80%.

[0070] The spectral data of the obtained product are as follows:

[0071] 1 H NMR (400 MHz, CHCl3-d) δ 7.78 (d, J = 3.7 Hz, 2H), 7.59 (d, J = 5.1 Hz, 2H), 7.17 (dd, J = 5.0, 3.8 Hz, 2H), 4.35 - 4.19 (m, 2H), 1.79 - 1.67 (m, 1H), 1.65 - 1.58 (m, 2H), 1.01 (d, J = 6.5 Hz, 6H). 1313C NMR (101 MHz, CHCl3-d) δ 168.15, 159.20, 146.75, 135.92, 134.41, 131.14, 130.03, 128.51, 44.69, 36.14, 26.74, 22.55.

[0072] 2) The raw materials used in the Stille coupling reaction and their synthesis methods are as follows:

[0073]

[0074] Under anhydrous and anaerobic conditions, N-isopentyl-dibromodithiazolimide (6) (46.5 mg, 0.1 mmol), 2-tributylstannylthiophene (328 mg, 0.22 mmol), potassium phosphate, and [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) (9 mg, 0.012 mmol) were dissolved in toluene (5 mL) solution and heated under reflux at 110 °C for 6 hours. After the reaction was completed, potassium fluoride solution was added and stirred for 3 hours, then dichloromethane was added for extraction. The organic phase was evaporated to dryness and separated by column chromatography to obtain 40 mg of N-isopentyl-dithienodithiazolimide (7b) with a yield of 85%.

[0075] The spectral data of the obtained product are as follows:

[0076] 1 1H NMR (400 MHz, CHCl3-d) δ 7.78 (d, J = 3.7 Hz, 2H), 7.59 (d, J = 5.1 Hz, 2H), 7.17 (dd, J = 5.0, 3.8 Hz, 2H), 4.35 - 4.19 (m, 2H), 1.79 - 1.67 (m, 1H), 1.65 - 1.58 (m, 2H), 1.01 (d, J = 6.5 Hz, 6H). 13 13C NMR (101 MHz, CHCl3-d) δ 168.15, 159.20, 146.75, 135.92, 134.41, 131.14, 130.03, 128.51, 44.69, 36.14, 26.74, 22.55.

[0077] Example 4:

[0078] Taking the synthesis of N-isobutyl-bis(4-(9-carbazolyl)phenyl)dithiazolimide (7c) as an example, its structure is as follows:

[0079]

[0080] The raw materials used and their synthesis methods are as follows:

[0081]

[0082] Under anaerobic conditions, N-isobutyl-dibromodithiazolylimide (22.5 mg, 0.05 mmol), bis(4-(9-carbazolyl)phenyl)boronic acid (NBAPC) (36 mg, 0.125 mmol), [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) (6 mg, 0.0075 mmol) and potassium phosphate (42 mg, 0.2 mmol) were dissolved in a mixed solution of toluene (2.7 mL) and water (0.3 mL), and heated under reflux at 100 °C for 6 hours. After the reaction, dichloromethane and water were added for extraction, the organic phase was dried by rotary evaporation, and column chromatography separation was carried out to obtain 34 mg of the product with a yield of 88%. The maximum ultraviolet absorption wavelength (λ abs max ) was 340, 359 nm (Note: All were measured in toluene solution), the maximum fluorescence emission wavelength (λ em max ) was 458 nm (Note: All were measured in toluene solution), the fluorescence quantum yield (Φ FL ) was 28.1% (Note: Φ FL was the absolute fluorescence quantum yield of a 0.1 wt% doped thin film in PMMA), and the thermal decomposition temperature (T d ) was 470 °C (Note: T d was the temperature of 5% thermal weight loss). The ultraviolet absorption spectrum is shown in Appendix Figure 1 , and the fluorescence emission spectrum is shown in Appendix Figure 2 .

[0083] The spectral data of the obtained product are as follows:

[0084] 1 H NMR (400 MHz, CHCl3-d) δ 8.44 (d, J = 8.5 Hz, 4H), 8.16 (d, J = 7.7 Hz, 4H), 7.80 (d, J = 8.4 Hz, 4H), 7.52 (d, J = 8.2 Hz, 4H), 7.48 - 7.40 (m, 4H), 7.33 (t, J = 7.4 Hz, 4H), 4.24 (d, J = 7.3 Hz, 2H), 2.28 (m, J = 13.3, 7.0 Hz, 1H), 1.04 (d, J = 6.7 Hz, 6H). 13 C NMR (101 MHz, CHCl3-d) δ 173.43, 159.81, 147.28, 141.35, 140.37, 135.52, 130.91, 129.22, 127.30, 126.30, 123.94, 120.69, 120.56, 109.83, 52.10, 27.38, 20.45.

[0085] Example 5:

[0086] Taking the synthesis of N-isobutyl-bis(4-(diphenylamino)phenyl)dithiazolimide (7d) as an example, its structure is as follows:

[0087]

[0088] The raw materials used and their synthesis methods are as follows:

[0089] Its synthesis method refers to Example 4. The boric acid reagent used is 4-(diphenylamino)phenylboronic acid, and the yield is 80%. λ em max is 496 nm, Φ FL is 44.3%, T d is 419 °C. The ultraviolet absorption spectrum is shown in Appendix Figure 1 , and the fluorescence emission spectrum is shown in Appendix Figure 2 .

[0090] The spectral data of the obtained product are as follows:

[0091] 1 H NMR (400 MHz, CHCl3-d) δ 7.97 (d, J = 8.8 Hz, 4H), 7.37 - 7.28 (m, 8H), 7.15 (m, J = 18.0, 7.4 Hz, 12H), 7.06 (d, J = 8.8 Hz, 4H), 4.17 (d, J = 7.3 Hz, 2H), 2.23 (m, J = 13.7, 6.8 Hz, 1H), 0.98 (d, J = 6.8 Hz, 6H). 13 C NMR (101 MHz, CHCl3-d) δ 174.38, 159.91, 151.39, 147.44, 146.62, 133.78, 129.71, 128.82, 125.88, 124.95, 124.61, 120.84, 51.88, 27.33, 20.47.

[0092] Example 6:

[0093] Taking the synthesis of N-isobutyl-bis(4-(1,2,2-triphenylethenyl)phenyl)dithiazolimide (7e) as an example, its structure is as follows:

[0094]

[0095] The raw materials used and their synthesis methods are as follows:

[0096] Its synthesis method refers to Example 4. The boric acid reagent used is (4-(1,2,2-triphenylethenyl)phenyl)boronic acid, and the yield is 89%. λem max is 505 nm, Φ FL is 50.1%, T d is 431 °C. The ultraviolet absorption spectrum is shown in Appendix Figure 1 , and the fluorescence emission spectrum is shown in Appendix Figure 2 .

[0097] The spectral data of the obtained product are as follows:

[0098] 1 H NMR (400 MHz, CHCl3-d) δ 7.88 (d, J = 8.1 Hz, 4H), 7.16 - 7.04 (m, 34H), 4.17 (d, J = 7.3 Hz, 2H), 2.22 (m, J = 13.7, 6.9 Hz, 1H), 0.98 (d, J = 6.7 Hz, 6H). 13 C NMR (101 MHz, CHCl3-d) δ 174.52, 159.84, 148.19, 147.23, 143.34, 143.26, 143.10, 142.70, 139.91, 134.68, 132.15, 131.47, 131.42, 131.39, 130.15, 128.06, 127.99, 127.82, 127.08, 126.90, 51.95, 27.31, 20.44.

[0099] Example 7:

[0100] Taking the synthesis of N-isobutyl-bis(4-(10H-phenoxazin-10-yl)phenyl)dithiazolyl imide (7f) as an example, its structure is as follows:

[0101]

[0102] The raw materials used and their synthesis methods are as follows:

[0103] Its synthesis method refers to Example 4. The boric acid reagent used is 10-(4-boronic acid pinacol ester phenyl)phenoxazine, and the yield is 84%, λ em max is 628 nm, Φ FL is 44.2%, T d is 426 °C. The ultraviolet absorption spectrum is shown in Appendix Figure 1 , and the fluorescence emission spectrum is shown in Appendix Figure 2 .

[0104] The spectral data of the obtained product are as follows:

[0105] 11H NMR (400 MHz, CDCl3) δ 8.43 - 8.33 (m, 4H), 7.56 (d, J = 8.3 Hz, 4H), 6.76 - 6.54 (m, 12H), 5.95 (d, J = 7.9 Hz, 4H), 4.21 (d, J = 7.3 Hz, 2H), 2.33 - 2.21 (m, 1H), 1.03 (d, J = 6.6 Hz, 6H). 13 13C NMR (101 MHz, CDCl3) δ 173.25, 159.80, 147.19, 144.01, 142.57, 135.75, 133.72, 132.17, 131.84, 130.30, 123.36, 121.89, 115.80, 113.29, 52.15, 27.40, 20.53.

[0106] Example 8:

[0107] Taking the synthesis of N-isobutyl-bis((9,9-dimethyl-9,10-dihydroacridin-10-yl)phenyl)dithiazolyl imide (7 g) as an example, its structure is as follows:

[0108]

[0109] The raw materials used and their synthesis methods are as follows:

[0110] Its synthesis method refers to Example 4. The boric acid reagent used is 10-(4-boronic acid pinacol ester phenyl)-9,9-dimethyl-9,10-dihydroacridine, and the yield is 73%. λ em max is 557 nm, Φ FL is 40.0%, T d is 395 °C. The ultraviolet absorption spectrum is shown in Appendix Figure 1 , and the fluorescence emission spectrum is shown in Appendix Figure 2 .

[0111] The spectral data of the obtained product are as follows:

[0112] 1 1H NMR (400 MHz, CDCl3) δ 8.43 (d, J = 8.5 Hz, 4H), 7.53 (d, J = 8.5 Hz, 4H), 7.48 (m, J = 7.4, 1.9 Hz, 4H), 7.05 - 6.92 (m, 8H), 6.34 (m, J = 7.8, 1.7 Hz, 4H), 4.23 (d, 2H), 2.35 - 2.23 (m, 1H), 1.70 (s, 12H), 1.04 (d, J = 6.7 Hz, 6H). 1313C NMR (101 MHz, CHCl3-d) δ 172.68, 158.84, 146.30, 144.07, 139.50, 134.63, 131.05, 130.93, 129.57, 129.25, 125.54, 124.49, 120.17, 113.28, 51.11, 35.13, 30.26, 26.35, 19.48.

[0113] Example 9:

[0114] Taking the synthesis of N-isobutyl-bis((9,9-diphenyl-9,10-dihydroacridin-10-yl)phenyl)dithiazolyl imide (7h) as an example, its structure is as follows:

[0115]

[0116] The raw materials used and their synthesis methods are as follows:

[0117] Its synthesis method refers to Example 4. The boric acid reagent used is 10-(4-boronic acid pinacol ester phenyl)-9,9-diphenyl-9,10-dihydroacridine, and the yield is 68%. λ em max is 528 nm, Φ FL is 40.1%, T d is 454 °C. The ultraviolet absorption spectrum is shown in Appendix Figure 1 and the fluorescence emission spectrum is shown in Appendix Figure 2 .

[0118] The spectral data of the obtained product are as follows:

[0119] 1 1H NMR (400 MHz, Methylene Chloride-d2) δ 8.32 (d, J = 8.4 Hz, 4H), 7.28 (m, J = 6.3, 4.3, 2.3 Hz, 16H), 7.09 (m, J = 8.5, 5.4, 3.4 Hz, 4H), 7.04 - 6.97 (m, 8H), 6.96 - 6.88 (m, 8H), 6.52 (d, J = 8.2 Hz, 4H), 4.19 (d, J = 7.3 Hz, 2H), 2.23 (m, J = 13.3, 6.6 Hz, 1H), 1.00 (d, J = 6.7 Hz, 6H).

[0120] Table 1. List of spectral properties of 7c - 7h

[0121]

Claims

1. A method for preparing dithiazolyl imide, characterized in that, The general structural formula of the dithiazolyl imide is as follows: wherein R1 is an alkyl group with 1 to 18 carbon atoms; R2 is a bromine atom, The method specifically includes the following steps: a. Dissolve thiourea and dibromobutanedione in chromatographic grade methanol, react overnight at 50 °C. After the reaction is completed, spin out the methanol, add saturated sodium carbonate solution, stir and filter, and vacuum dry to obtain 2,2'-diamino-4,4'-bisthiazole, and its structural formula is: b. Dissolve the 2,2'-diamino-4,4'-bisthiazole obtained in step a in a mixed solution of concentrated sulfuric acid, concentrated phosphoric acid and 40% fluoboric acid at 0 °C in a volume ratio of 1mL:1mL:1mL, slowly dropwise add an aqueous solution of sodium nitrite at 0 °C, after reacting for 2 hours, transfer the reaction solution to an aqueous solution containing sodium bromide and copper sulfate at 0 °C, stir for 3 hours, after the reaction is completed, filter, mix the obtained filter cake with magnesium sulfate and dichloromethane, ultrasonicate and wash with water, and perform column chromatography separation on the obtained crude product to obtain 2,2'-dibromo-4,4'-bisthiazole, and its structural formula is: c. Under anhydrous and anaerobic conditions, dissolve the 2,2'-dibromo-4,4'-bisthiazole obtained in step b in redistilled tetrahydrofuran, slowly dropwise add a tetrahydrofuran solution of TMPMgCl·LiCl at -40 °C, after reacting for 4.5 h, add ethyl cyanoformate, raise the temperature to room temperature and react for 22 hours. After the reaction is completed, add dichloromethane and water for extraction, spin dry the organic phase, and perform column chromatography separation to obtain diethyl 2,2'-dibromo-[4,4'-bisthiazole]-5,5'-dicarboxylate, and its structural formula is: d. Add tetrahydrofuran and water to the reaction flask containing diethyl 2,2'-dibromo-[4,4'-bisthiazole]-5,5'-dicarboxylate obtained in step c, then add lithium hydroxide, stir overnight at 50 °C. After the reaction is completed, spin out the tetrahydrofuran and then add concentrated hydrochloric acid, filter, and vacuum dry the filter cake to obtain the product 2,2'-dibromo-[4,4'-bisthiazole]-5,5'-dicarboxylic acid, and its structural formula is: e. Add acetic anhydride to the reaction flask containing 2,2'-dibromo-[4,4'-bisthiazole]-5,5'-dicarboxylic acid obtained in step d, stir and reflux overnight at 120 °C. After the reaction is completed, filter, and vacuum dry to obtain the target product dibromodithiazole anhydride, and its structural formula is: f. Add chloroform to the reaction flask containing dibromodithiazole anhydride obtained in step e, then add a chloroform solution of the amine to the reaction flask, reflux and react at 60 °C for 2 hours. After the reaction is completed, spin dry the chloroform, add thionyl dibromide, stir and reflux at 130 °C for 3 hours. After the reaction is completed, add dichloromethane and water for extraction, spin dry the organic phase, and perform column chromatography separation to obtain N-alkyl-dibromodithiazolyl imide, R2 is bromine, and its structural formula is: The structure of the amine described is R1-NH2.

2. A method for preparing a dithiazolylimide derivative, characterized in that, The general structural formula of the dithiazolyl imide derivative is as follows: wherein R1 is an alkyl group having 1 to 18 carbon atoms; R2 is an alkenyl group, The specific steps of the method can be carried out according to the following two synthetic methods: Method 1 is the Suzuki coupling reaction method: Under anaerobic conditions, dissolve the dibromodithiazolimide obtained in Claim 1, a boric acid compound, a catalyst {[1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos Pd G2)} and potassium phosphate in a mixed solution of toluene / water or tetrahydrofuran / water, heat under reflux at 100 °C or 50 °C for 3 to 6 hours. After the reaction is completed, add dichloromethane and water for extraction, dry the organic phase by evaporation, and perform column chromatography separation to obtain the functionalized dithiazolimide compound, and its structural formula is: Method 2 is the Stille coupling reaction method: Under anhydrous and anaerobic conditions, dissolve the dibromodithiazolimide obtained in Claim 1, an organotin compound and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium dichloromethane complex (Pd(dppf)Cl2·CH2Cl2) in a toluene solution, heat under reflux at 110 °C for 6 hours. After the reaction is completed, add a potassium fluoride solution and stir for 3 hours, then add dichloromethane for extraction, dry the organic phase by evaporation, and perform column chromatography separation to obtain the functionalized dithiazolimide compound, and its structural formula is:

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