Preparation method of luminescent compound
By using photocatalysts CdSe/CdS QDs to synthesize luminescent compounds under mild conditions, the problems of multiple metal catalysts and high-temperature reactions in existing technologies have been solved. This has enabled high-yield and environmentally friendly compound synthesis, expanding the application range and reducing costs.
Patent Information
- Application Number
- CN202511406606.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-29
- Publication Date
- 2026-01-02
AI Technical Summary
The existing methods for synthesizing (10-benzyl-9,10-dihydroacryl-9-yl)(methylthio) methylthione and its derivatives use a variety of metal catalysts and require high reaction temperatures, which does not conform to the concept of green chemistry.
Luminescent compounds were synthesized under mild conditions using photocatalysts CdSe/CdS QDs. The target product was generated through reduction with a reducing agent, reaction with benzyl bromide, and reaction with methyl dithioacetate. The reaction conditions were mild and environmentally friendly.
This technology enables the high-yield synthesis of luminescent compounds under mild reaction conditions, expanding the range of applications. Furthermore, the catalyst is reusable, reducing costs.
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Figure CN121248501A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the field of organic synthesis, in particular to a preparation method of a luminescent compound. BACKGROUND
[0002] Chemiluminescence technology is one of the core means of modern high-sensitivity detection, and its principle is to directly excite luminophore to produce photons by chemical energy without external light source. With the continuous progress of technology, acridinium ester compounds have rapidly become a new generation of chemiluminescent markers due to their high luminescent intensity and stable performance.
[0003] In the synthesis of acridinium ester compounds, (10-benzyl-9,10-dihydroacridin-9-yl)(methylthio)methanethione and its derivatives are generally used as intermediates, so (10-benzyl-9,10-dihydroacridin-9-yl)(methylthio)methanethione and its derivatives have become one of the hotspots in current synthetic chemistry.
[0004] In the prior art, the synthesis method of (10-benzyl-9,10-dihydroacridin-9-yl)(methylthio)methanethione and its derivatives is as follows:
[0005]
[0006] The metal catalyst used in the above method to obtain the target product is of many types, which does not conform to the concept of green chemistry, and the extremely low reaction temperature requires a higher reaction equipment. Therefore, it is crucial to provide a new and more green synthesis route. SUMMARY
[0007] In order to solve the technical problems existing in the prior art, the present application provides a preparation method of a luminescent compound, comprising the following steps:
[0008] Step 1: reducing the raw material a by a reducing agent to generate compound b;
[0009] Step 2: reacting compound b with benzyl bromide to generate compound c;
[0010] Step 3: reacting compound c with methyl dithioacetate under photocatalysis to generate the target product compound d; as shown below:
[0011]
[0012] Wherein, R1 and R4 are selected from one of -H, -CH3, -CH2Br; R2 and R5 are selected from one of -H, -CH3, -CH2CH3, -CH(CH3)2, -F, -Cl, -Br, -I, -CH2Br; R3 and R6 are selected from one of -H, -NH2, -Br, -CH(CH3)2.
[0013] By adopting the technical scheme, the application provides a new preparation method, the reaction condition of the method is relatively mild, and a green reaction mode such as photocatalysis is adopted, so that a good yield can be obtained under the mild reaction condition, and the method is suitable for a variety of structures of the luminescent substrate, and the application range is expanded.
[0014] Preferably, in step 1, the molar ratio of the compound a to the reducing agent is 1:(6-8); and the reducing agent is tricobalt tetraoxide.
[0015] Preferably, in step 1, the reaction temperature is 80-100℃, and the reaction time is 10-12h.
[0016] Preferably, in step 2, the molar ratio of the compound b to benzyl bromide is 1:(1.0-1.2).
[0017] Preferably, in step 2, the reaction temperature is -5-0℃, and the reaction time is 2-4h.
[0018] Preferably, in step 3, the molar ratio of the compound c to methyl dithioacetate is 1:(1.0-1.2).
[0019] Preferably, in step 3, the compound c and methyl dithioacetate are catalyzed by a photocatalyst under blue light irradiation to generate the target product compound d.
[0020] Preferably, in step 3, the photocatalyst is a semiconductor catalyst CdSe / CdS QDs.
[0021] Preferably, in step 3, the reaction temperature is 20-30℃, and the reaction time is 24-48h.
[0022] By adopting the technical scheme, the reaction condition of the preparation method is mild, and the semiconductor catalyst used can be reused, so that the cost can be reduced, and the method has great advantages compared with the prior art.
[0023] In summary, the application has the following beneficial effects:
[0024] 1. The preparation method provided by the application has relatively mild reaction conditions, and a green reaction mode such as photocatalysis is adopted, so that a good yield can be obtained under the mild reaction condition, and the method is suitable for a variety of structures of the luminescent substrate, and the application range is expanded.
[0025] 2. The preparation method provided by the application uses a semiconductor catalyst that can be reused, so that the cost can be reduced, and the method has great advantages compared with the prior art. DETAILED DESCRIPTION
[0026] Embodiment
[0027] The following embodiment is a method for preparing a luminescent compound.
[0028] The photocatalyst CdSe / CdS QDs in the following embodiment is commercially available.
[0029] Embodiment 1
[0030]
[0031] (1) 0.36 g of acridine, 3.37 g of Co3O4 and 100 mL of t-butyl alcohol were stirred and mixed, and reacted at 90°C for 11 h under H2environment. After the reaction was completed, the filtrate was filtered, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.32 g of white powder 9,10-dihydroacridine.
[0032] (2) The above 0.32 g of white powder 9,10-dihydroacridine was placed in a reaction bottle containing 48 mL of DMF, and 0.01 g of NaH was slowly added under inert gas protection at -2°C. After the addition of 0.33 g of benzyl bromide was completed, the reaction was moved to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.45 g of yellow solid 10-benzyl-9,10-dihydroacridine.
[0033] (3) The above 0.45 g of 10-benzyl-9,10-dihydroacridine, 0.19 g of methyl dithioacetate, 0.5 mg of CdSe / CdS QDs and 3 mL of acetonitrile were placed in a dry 10 mL Schlenk tube, and reacted under nitrogen protection under the irradiation of a 28°C 18W blue light LED for 35 h.
[0034] After the reaction was completed, it was naturally cooled to room temperature, and saturated NH4Cl (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 1 g of anhydrous sodium sulfate was added to the organic phase for drying, filtered, and the mother liquor was distilled under reduced pressure. The brown-yellow mixture obtained was added to 3 mL of ethanol for slurry, the mixture was filtered, and the solid was dried to obtain 0.54 g of product with a yield of 90.2%.
[0035] Embodiment 2
[0036] (1) 0.36 g acridine, 2.89 g Co3O4 and 100 mL tert-butyl alcohol were stirred and mixed, and reacted at 80°C for 12 h under H2environment. After the reaction was completed, the filtrate was filtered, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.29 g of white powder 9,10-dihydroacridine.
[0037] (2) The above 0.29 g of white powder 9,10-dihydroacridine was taken into a reaction bottle containing 48 mL of DMF, and 0.01 g of NaH was added slowly under inert gas protection at -5°C. After the addition of 0.27 g of benzyl bromide was completed, the reaction was moved to room temperature and reacted for 4 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.42 g of yellow solid 10-benzyl-9,10-dihydroacridine.
[0038] (3) The above 0.42 g of 10-benzyl-9,10-dihydroacridine, 0.16 g of methyl dithioacetate and 0.5 mg of CdSe / CdS QDs were taken into a dry 10 mL Schlenk tube, and reacted under nitrogen protection at 20°C under the irradiation of an 18 W blue light LED for 48 h.
[0039] After the reaction was completed, it was naturally cooled to room temperature, and saturated NH4Cl (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 2 g of anhydrous sodium sulfate was added to the organic phase for drying, filtered, and the mother liquor was distilled under reduced pressure. The obtained brown-yellow mixture was added to 3 mL of ethanol for slurry, the mixture was filtered, and the solid was dried to obtain 0.48 g of product with a yield of 85.1%.
[0040] Example 3
[0041] (1) 0.36 g acridine, 2.89 g Co3O4 and 100 mL tert-butyl alcohol were stirred and mixed, and reacted at 80°C for 12 h under H2environment. After the reaction was completed, the filtrate was filtered, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.29 g of white powder 9,10-dihydroacridine.
[0042] (2) Take the above 0.30 g white powder 9,10-dihydroacridine into a reaction bottle containing 48 mL of DMF, add 0.01 g of NaH under inert gas protection at 0°C, slowly add 0.34 g of benzyl bromide, after the addition is completed, move to room temperature and react for 4 h. After the reaction is completed, pour into 100 mL of ice water, stir for 10 min, then filter, wash the filter cake with pure water, and slurry with 50 mL of ethanol to obtain 0.43 g of yellow solid 10-benzyl-9,10-dihydroacridine.
[0043] (3) Put the above 0.43 g 10-benzyl-9,10-dihydroacridine, 0.20 g methyl dithioacetate, 0.05 mg CdSe / CdS QDs, and 3 mL of acetonitrile into a dry 10 mL Schlenk tube, and react under nitrogen protection under the irradiation of an 18 W blue light LED at 30°C for 24 h.
[0044] After the reaction is completed, naturally cool to room temperature, and add saturated NH4Cl (3*5 mL) aqueous solution to the reaction mixture to quench. Add 3 g of anhydrous sodium sulfate to the organic phase, dry, filter, and distill the mother liquor under reduced pressure. Add the obtained brown-yellow mixture to 3 mL of ethanol to slurry, filter the mixture, and dry the solid to obtain 0.50 g of product with a yield of 87%.
[0045] Example 4
[0046]
[0047] (1) Stir and mix 0.39 g of compound a and 3.37 g of Co3O4 in 100 mL of tert-butanol, react under H2 environment at 90°C for 11 h, filter after the reaction is completed, distill the filtrate under reduced pressure, wash the residue with water (3*30 mL), dry to obtain a red-brown powder, wash the powder with CHCl3 (3*15 mL), filter and dry to obtain 0.37 g of solid.
[0048] (2) Take the above 0.37 g solid into a reaction bottle containing 48 mL of DMF, add 0.01 g of NaH under inert gas protection at -2°C, slowly add 0.38 g of benzyl bromide, after the addition is completed, move to room temperature and react for 3 h. After the reaction is completed, pour into 100 mL of ice water, stir for 10 min, then filter, wash the filter cake with pure water, and slurry with 50 mL of ethanol to obtain 0.49 g of solid.
[0049] (3) Put the above 0.49 g solid, 0.22 g methyl dithioacetate, 0.05 mg CdSe / CdS QDs, and 3 mL of acetonitrile into a dry 10 mL Schlenk tube, and react under nitrogen protection under the irradiation of an 18 W blue light LED at 28°C for 35 h.
[0050] After the reaction is completed, the reaction mixture is cooled to room temperature naturally, saturated NH4CI (3*5 mL) aqueous solution is added to quench the reaction. 3 g of anhydrous sodium sulfate is added to the organic phase to dry, filter, and the mother liquor is distilled under reduced pressure. The brown-yellow mixture obtained is added to 3 mL of ethanol to be slurried, the mixture is filtered, and the solid is dried to obtain 0.55 g of product with a yield of 85.9%.
[0051] Example 5
[0052]
[0053] (1) 0.47 g of compound a, 3.37 g of Co3O4, and 100 mL of t-butanol are stirred and mixed, and the mixture is reacted at 90°C for 11 h under H2. After the reaction is completed, the mixture is filtered, the residue is washed with water (3*30 mL), and dried to obtain a red-brown powder. The powder is washed with CHCI3 (3*15 mL), filtered, and dried to obtain 0.38 g of solid.
[0054] (2) The above 0.38 g of solid is placed in a reaction bottle containing 48 mL of DMF, and 0.01 g of NaH is slowly added under inert gas protection at -2°C. After the addition of 0.30 g of benzyl bromide is completed, the mixture is moved to room temperature and reacted for 3 h. After the reaction is completed, the mixture is poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake is washed with pure water and slurried with 50 mL of ethanol to obtain 0.39 g of solid.
[0055] (3) The above 0.39 g of solid, 0.14 g of methyl dithioacetate, and 0.05 mg of CdSe / CdS QDs are placed in a dry 10 mL Schlenk tube, and 3 mL of acetonitrile is added. The mixture is reacted under nitrogen protection at 28°C under irradiation of an 18W blue light LED for 35 h.
[0056] After the reaction is completed, the reaction mixture is cooled to room temperature naturally, saturated NH4CI (3*5 mL) aqueous solution is added to quench the reaction. 3 g of anhydrous sodium sulfate is added to the organic phase to dry, filter, and the mother liquor is distilled under reduced pressure. The brown-yellow mixture obtained is added to 3 mL of ethanol to be slurried, the mixture is filtered, and the solid is dried to obtain 0.55 g of product with a yield of 85.9%.
[0057] Example 6
[0058]
[0059] (1) 0.41 g of compound a, 3.37 g of Co3O4 and 100 mL of tert-butyl alcohol were stirred and mixed, and then reacted at 90°C for 11 h under H2environment. After the reaction was completed, the filtrate was subjected to reduced pressure distillation, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.35 g of a solid.
[0060] (2) The above 0.35 g of solid was placed in a reaction bottle containing 48 mL of DMF, 0.01 g of NaH was added under inert gas protection at -2°C, and 0.32 g of benzyl bromide was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.41 g of a solid.
[0061] (3) The above 0.41 g of solid, 0.17 g of methyl dithioacetate and 0.05 mg of CdSe / CdS QDs were placed in a dry 10 mL Schlenk tube, and reacted under nitrogen protection under the irradiation of a 28°C 18W blue light LED for 35 h.
[0062] After the reaction was completed, it was naturally cooled to room temperature, saturated NH4Cl (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 3 g of anhydrous sodium sulfate was added to the organic phase for drying, filtered, and the mother liquor was subjected to reduced pressure distillation. The obtained brown-yellow mixture was added to 3 mL of ethanol for slurry, the mixture was filtered, and the solid was dried to obtain 0.37 g of product with a yield of 70%.
[0063] Example 7
[0064]
[0065] (1) 0.73 g of compound a, 3.37 g of Co3O4 and 100 mL of tert-butyl alcohol were stirred and mixed, and then reacted at 90°C for 11 h under H2environment. After the reaction was completed, the filtrate was subjected to reduced pressure distillation, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.67 g of a solid.
[0066] (2) The above 0.67 g of solid was placed in a reaction bottle containing 48 mL of DMF, 0.01 g of NaH was added under inert gas protection at -2°C, and 0.34 g of benzyl bromide was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.74 g of a solid.
[0067] (3) The above 0.74 g solid, 0.20 g methyl dithioacetate, 0.05 mg CdSe / CdS QDs and 3 mL acetonitrile were placed in a dry 10 mL Schlenk tube and reacted under the irradiation of 18 W blue light LED at 28°C for 35 h under the protection of nitrogen.
[0068] After the reaction was completed, the reaction mixture was naturally cooled to room temperature, saturated NH4CI (3*5 mL) aqueous solution was added to quench the reaction. 3 g of anhydrous sodium sulfate was added to the organic phase to dry it, and then filtered. The mother liquor was distilled under reduced pressure, and the brown-yellow mixture obtained was added to 3 mL of ethanol for slurry, the mixture was filtered, and the solid was dried to obtain 0.67 g of product with a yield of 76%.
[0069] Example 8
[0070]
[0071] (1) 0.67 g of compound a, 3.37 g of Co3O4 and 100 mL of t-butyl alcohol were stirred and mixed, and then reacted at 90°C for 11 h under H2. After the reaction was completed, the reaction mixture was filtered, and the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was then washed with CHCI3 (3*15 mL), filtered and dried to obtain 0.60 g of solid.
[0072] (2) The above 0.60 g solid was placed in a reaction bottle containing 48 mL of DMF, and 0.01 g of NaH was slowly added under the protection of inert gas at -2°C. After the addition of 0.33 g of benzyl bromide was completed, the reaction mixture was moved to room temperature and reacted for 3 h. After the reaction was completed, the reaction mixture was poured into 100 mL of ice water, stirred for 10 min, and then filtered. The filter cake was washed with pure water, and then slurry was obtained by adding 50 mL of ethanol to obtain 0.59 g of solid.
[0073] (3) The above 0.59 g solid, 0.18 g methyl dithioacetate, 0.05 mg CdSe / CdS QDs and 3 mL acetonitrile were placed in a dry 10 mL Schlenk tube and reacted under the irradiation of 18 W blue light LED at 28°C for 35 h under the protection of nitrogen.
[0074] After the reaction was completed, the reaction mixture was naturally cooled to room temperature, saturated NH4CI (3*5 mL) aqueous solution was added to quench the reaction. 3 g of anhydrous sodium sulfate was added to the organic phase to dry it, and then filtered. The mother liquor was distilled under reduced pressure, and the brown-yellow mixture obtained was added to 3 mL of ethanol for slurry, the mixture was filtered, and the solid was dried to obtain 0.67 g of product with a yield of 76%.
[0075] Example 9
[0076]
[0077] (1) 0.53 g of compound a, 3.37 g of Co3O4 and 100 mL of tert-butyl alcohol were stirred and mixed, and then reacted at 90°C for 11 h under H2environment. After the reaction was completed, the filtrate was subjected to reduced pressure distillation, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.44 g of a solid.
[0078] (2) The above 0.44 g of solid was placed in a reaction bottle containing 48 mL of DMF, 0.01 g of NaH was added under inert gas protection at -2°C, and 0.31 g of benzyl bromide was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.48 g of a solid.
[0079] (3) The above 0.48 g of solid, 0.17 g of methyl dithioacetate and 0.05 mg of CdSe / CdS QDs were placed in a dry 10 mL Schlenk tube, and reacted under nitrogen protection under the irradiation of a 28°C 18W blue light LED for 35 h.
[0080] After the reaction was completed, it was naturally cooled to room temperature, saturated NH4Cl (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 3 g of anhydrous sodium sulfate was added to the organic phase for drying, filtered, and the mother liquor was subjected to reduced pressure distillation. The obtained brown-yellow mixture was added to 3 mL of ethanol for slurry, the mixture was filtered, and the solid was dried to obtain 0.46 g of product with a yield of 76%.
[0081] Example 10
[0082]
[0083] (1) 0.73 g of compound a, 3.37 g of Co3O4 and 100 mL of tert-butyl alcohol were stirred and mixed, and then reacted at 90°C for 11 h under H2environment. After the reaction was completed, the filtrate was subjected to reduced pressure distillation, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.66 g of a solid.
[0084] (2) The above 0.66 g of solid was placed in a reaction bottle containing 48 mL of DMF, 0.01 g of NaH was added under inert gas protection at -2°C, and 0.34 g of benzyl bromide was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.71 g of a solid.
[0085] (3) The above 0.71 g solid, 0.2 g methyl dithioacetate, 0.05 mg CdSe / CdS QDs and 3 mL acetonitrile were placed in a dry 10 mL Schlenk tube and reacted under nitrogen protection at 28°C under 18W blue light LED irradiation for 35 h.
[0086] After the reaction was completed, it was naturally cooled to room temperature, and saturated NH4CI (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 3 g of anhydrous sodium sulfate was added to the organic phase for drying, and the mother liquor was filtered and distilled under reduced pressure. The brown-yellow mixture obtained was added to 3 mL of ethanol for slurry, and the mixture was filtered and the solid was dried to obtain 0.62 g of product with a yield of 77%.
[0087] Example 11
[0088]
[0089] (1) 0.41 g of compound a, 3.37 g of Co3O4 and 100 mL of tert-butyl alcohol were stirred and mixed, and reacted under H2environment at 90°C for 11 h. After the reaction was completed, the filtrate was filtered and distilled under reduced pressure. The residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.38 g of solid.
[0090] (2) The above 0.38 g solid was placed in a reaction bottle containing 48 mL of DMF, and 0.01 g of NaH was slowly added under inert gas protection at -2°C. After the addition of 0.34 g of benzyl bromide was completed, it was moved to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, and then filtered. The filter cake was washed with pure water, and slurry was obtained with 50 mL of ethanol to obtain 0.49 g of solid.
[0091] (3) The above 0.49 g solid, 0.21 g methyl dithioacetate, 0.05 mg CdSe / CdS QDs and 3 mL acetonitrile were placed in a dry 10 mL Schlenk tube and reacted under nitrogen protection at 28°C under 18W blue light LED irradiation for 35 h.
[0092] After the reaction was completed, it was naturally cooled to room temperature, and saturated NH4CI (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 3 g of anhydrous sodium sulfate was added to the organic phase for drying, and the mother liquor was filtered and distilled under reduced pressure. The brown-yellow mixture obtained was added to 3 mL of ethanol for slurry, and the mixture was filtered and the solid was dried to obtain 0.62 g of product with a yield of 77%.
[0093] Example 12
[0094]
[0095] (1) 0.5 g of compound a, 3.37 g of Co3O4 and 100 mL of tert-butyl alcohol were stirred and mixed, and then reacted at 90°C for 11 h under H2environment. After the reaction was completed, the filtrate was subjected to reduced pressure distillation, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.44 g of a solid.
[0096] (2) The above 0.44 g of solid was placed in a reaction bottle containing 48 mL of DMF, 0.01 g of NaH was added under inert gas protection at -2°C, and 0.33 g of benzyl bromide was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.51 g of a solid.
[0097] (3) The above 0.51 g of solid, 0.19 g of methyl dithioacetate and 0.05 mg of CdSe / CdS QDs were placed in a dry 10 mL Schlenk tube, and reacted under nitrogen protection under the irradiation of a 28°C 18W blue light LED for 35 h.
[0098] After the reaction was completed, it was naturally cooled to room temperature, saturated NH4Cl (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 3 g of anhydrous sodium sulfate was added to the organic phase for drying, filtered, and the mother liquor was subjected to reduced pressure distillation. The obtained brown-yellow mixture was added to 3 mL of ethanol for slurry, the mixture was filtered, and the solid was dried to obtain 0.47 g of product with a yield of 74%.
[0099] Example 13
[0100]
[0101] (1) 0.5 g of compound a, 3.37 g of Co3O4 and 100 mL of tert-butyl alcohol were stirred and mixed, and then reacted at 90°C for 11 h under H2environment. After the reaction was completed, the filtrate was subjected to reduced pressure distillation, the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.44 g of a solid.
[0102] (2) The above 0.44 g of solid was placed in a reaction bottle containing 48 mL of DMF, 0.01 g of NaH was added under inert gas protection at -2°C, and 0.33 g of benzyl bromide was slowly added dropwise. After the addition was completed, the temperature was raised to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.51 g of a solid.
[0103] (3) The above 0.38 g solid, 0.16 g methyl dithioacetate, 0.05 mg CdSe / CdS QDs and 3 mL acetonitrile were placed in a dry 10 mL Schlenk tube and reacted under nitrogen protection at 28°C under 18W blue light LED irradiation for 35 h.
[0104] After the reaction was completed, it was naturally cooled to room temperature, and saturated NH4CI (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 3 g of anhydrous sodium sulfate was added to the organic phase for drying, and the mother liquor was filtered and distilled under reduced pressure. The brown-yellow mixture obtained was added to 3 mL of ethanol for slurry, and the mixture was filtered and the solid was dried to obtain 0.26 g of product with a yield of 53%.
[0105] Example 14
[0106]
[0107] (1) 0.86 g of compound a, 3.37 g of Co3O4 and 100 mL of t-butyl alcohol were stirred and mixed, and reacted under H2environment at 90°C for 11 h. After the reaction was completed, the filtrate was filtered and distilled under reduced pressure. The residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCI3(3*15 mL), filtered and dried to obtain 0.70 g of solid.
[0108] (2) The above 0.70 g solid was placed in a reaction bottle containing 48 mL of DMF, and 0.01 g of NaH was slowly added under inert gas protection at -2°C. After the addition of 0.30 g of benzyl bromide was completed, it was moved to room temperature and reacted for 3 h. After the reaction was completed, it was poured into 100 mL of ice water, stirred for 10 min, and then filtered. The filter cake was washed with pure water, and slurry was obtained with 50 mL of ethanol to obtain 0.67 g of solid.
[0109] (3) The above 0.67 g solid, 0.16 g methyl dithioacetate, 0.05 mg CdSe / CdS QDs and 3 mL acetonitrile were placed in a dry 10 mL Schlenk tube and reacted under nitrogen protection at 28°C under 18W blue light LED irradiation for 35 h.
[0110] After the reaction was completed, it was naturally cooled to room temperature, and saturated NH4CI (3*5 mL) aqueous solution was added to the reaction mixture for quenching. 3 g of anhydrous sodium sulfate was added to the organic phase for drying, and the mother liquor was filtered and distilled under reduced pressure. The brown-yellow mixture obtained was added to 3 mL of ethanol for slurry, and the mixture was filtered and the solid was dried to obtain 0.26 g of product with a yield of 53%.
[0111] Example 15
[0112]
[0113] (1) 0.67 g of compound a, 3.37 g of Co3O4 and 100 mL of t-butyl alcohol were stirred and mixed, and then reacted at 90°C for 11 h under H2. After the reaction was completed, the reaction mixture was filtered, and the residue was washed with water (3*30 mL) and dried to obtain a red-brown powder. The powder was washed with CHCl3(3*15 mL), filtered and dried to obtain 0.64 g of a solid.
[0114] (2) The above 0.64 g of solid was placed in a reaction bottle containing 48 mL of DMF, and 0.01 g of NaH was added under inert gas protection at -2°C. Then, 0.35 g of benzyl bromide was slowly added dropwise. After the addition was completed, the reaction mixture was moved to room temperature and reacted for 3 h. After the reaction was completed, the reaction mixture was poured into 100 mL of ice water, stirred for 10 min, filtered, and the filter cake was washed with pure water and slurried with 50 mL of ethanol to obtain 0.69 g of a solid.
[0115] (3) The above 0.69 g of solid, 0.2 g of methyl dithioacetate and 0.05 mg of CdSe / CdS QDs were placed in a dry 10 mL Schlenk tube, and then reacted for 35 h under nitrogen protection at 28°C under irradiation of an 18W blue light LED.
[0116] After the reaction was completed, the reaction mixture was naturally cooled to room temperature, and saturated NH4Cl (3*5 mL) aqueous solution was added to quench the reaction. Then, 3 g of anhydrous sodium sulfate was added to the organic phase to dry it, and the mixture was filtered. The mother liquor was distilled under reduced pressure, and the obtained brown-yellow mixture was added to 3 mL of ethanol to perform slurry. The mixture was filtered, and the solid was dried to obtain 0.66 g of a product with a yield of 79%.
[0117] This embodiment is merely an explanation of the present application, and is not a limitation of the present application. Those skilled in the art can make modifications to this embodiment without creative contribution after reading the present specification, and the modifications are protected by the patent law as long as they are within the scope of the claims of the present application.
Claims
1. A method for preparing a luminescent compound, characterized in that, Includes the following steps: Step 1: Raw material a is reduced by a reducing agent to produce compound b; Step 2: React compound b with benzyl bromide to generate compound c; Step 3: Compound c is reacted with methyl dithioacetate under photocatalysis to generate the target product compound d; as shown below: Among them, R1 and R4 are selected from one of -H, -CH3, and -CH2Br; R2 and R5 are selected from one of -H, -CH3, -CH2CH3, -CH(CH3)2, -F, -Cl, -Br, -I, and -CH2Br; R3 and R6 are selected from one of -H, -NH2, -Br, and -CH(CH3)2.
2. The preparation method according to claim 1, characterized in that, In step 1, the molar ratio of compound a to the reducing agent is 1:(6-8); the reducing agent is cobalt tetroxide.
3. The preparation method according to claim 1 or 2, characterized in that, In step 1, the reaction temperature is 80–100°C, and the reaction time is 10–12 h.
4. The preparation method according to claim 1, characterized in that, In step 2, the molar ratio of compound b to benzyl bromide is 1:(1.0 to 1.2).
5. The preparation method according to claim 1, characterized in that, In step 2, the reaction temperature is -5 to 0°C, and the reaction time is 2 to 4 hours.
6. The preparation method according to claim 1, characterized in that, In step 3, the molar ratio of compound c to methyl dithioacetate is 1:(1.0 to 1.2).
7. The preparation method according to claim 1, characterized in that, In step 3, compound c and methyl dithioacetate are catalyzed by a photocatalyst under blue light irradiation to generate the target product compound d.
8. The preparation method according to claim 7, characterized in that, In step 3, the photocatalyst is a semiconductor catalyst CdSe / CdS QDs.
9. The preparation method according to claim 1, characterized in that, In step 3, the reaction temperature is 20–30°C, and the reaction time is 24–48 h.