Preparation method of iodine atom-substituted bis-fluorophenyl heterocyclic conjugated monomer

Abstract

The invention relates to a preparation method of an iodine atom-substituted bis-fluorophenyl heterocyclic conjugated monomer. The preparation method comprises the following steps: firstly enabling a chemical compound with a bis-fluorophenyl heterocyclic conjugated structure to be reacted with lithium diisopropylamide, then adding an iodine elementary substance into a reaction system and finally introducing iodine atoms onto a benzene ring of the bis-fluorophenyl heterocyclic conjugated monomer. According to the method, the use of fuming sulfuric acid and other hazardous reagents is avoided, the synthetic efficiency and the experimental operation safety are improved, the yield is much higher than that obtained by a traditional iodization method, and the scale preparation and production are facilitated.

Description

technical field

[0001] The invention belongs to the technical field of fine organic chemistry, and specifically relates to a preparation method of a difluorobenzoheterocyclic conjugated monomer substituted with an iodine atom. Background technique

[0002] With the development of the times, human beings' demand for energy is increasing, but traditional resources such as oil and coal will eventually be exhausted, which makes people feel more and more urgent about the development and utilization of new energy. Solar energy has always been the object of research and utilization by many scientists due to its universal, harmless, and long-lasting advantages. Among them, solar cells that utilize solar energy by photoelectric conversion have become one of the research focuses. Silicon-based solar cells are the longest-developing and most mature technology, and have been commercialized at present, and the laboratory efficiency of monocrystalline silicon cells has reached 25.0%. How...

Examples

preparation example Construction

[0023] (1) Preparation of Lithium Diisopropylamide (LDA): Under a nitrogen atmosphere, a solution of 0.1 g / mL diisopropylamine (1.1 equivalents) in tetrahydrofuran was cooled to -78°C, and 1 equivalent of n-butyl was slowly added dropwise to the solution. Lithium (2.5mol / L n-hexane solution), kept at -78°C for 1 hour after the dropwise addition.

[0024] (2) Iodination reaction: 1.0 equivalent of the substrate (difluorobenzoheterocyclic conjugated compound) was prepared into a 0.1g / L solution with anhydrous organic solvent, and then gradually added dropwise to LDA, at -78°C Under reaction 1 hour; The iodine simple substance of 2.3 equivalents (preparation of diiodine substitution monomer 2) or 1.15 equivalents (preparation of single iodine substitution monomer 3) and anhydrous organic solvent are made into the solution of 0.06g / L, and it is directly Added dropwise to the reaction system, the system naturally rose to room temperature, and stirred overnight.

[0025] (3) Post-p...

Embodiment 1

[0028] Preparation of 4,7-diiodo-2-dodecyl-5,6-difluoro-2H-benzo[d][1,2,3]triazole

[0029] The synthetic route is as follows:

[0030]

[0031] In a 250mL long-necked three-neck flask, under an argon atmosphere, add diisopropylamine (1.73g, 17.03mmol, 2.2eq) and 30mL of tetrahydrofuran, cool down to -78°C, add dropwise n-butyllithium (15.48mmol, 6.2mL, 2.5 mol / L, equivalent), completed, reacted for 1 hour, then 2-dodecyl-5,6 difluoro-2H-benzo[d][1,2,3]triazole (2.5g, 7.74mmol , 1 equivalent) and 25mL of tetrahydrofuran were made into a solution, and gradually added dropwise to the reaction solution. After completion of the reaction for 40 minutes, a tetrahydrofuran solution of iodine (4.52g, 17.8mmol, 2.3 equivalents, 75mL of tetrahydrofuran) was added dropwise thereto, and the reaction was completed. , stirred for 15 minutes, placed at room temperature, stirred overnight. Post-processing: add sodium sulfite and stir to remove iodine, then pour into water, extract with d...

Embodiment 2

[0033] Preparation of 4,7-diiodo-5,6-difluorobenzo[d][1,2,5]thiadiazole

[0034]

[0035]In a 250mL long-necked three-neck flask, under an argon atmosphere, add diisopropylamine (3.9g, 15.3mmol, 2.2eq) and 30mL of tetrahydrofuran, cool down to -78°C, add dropwise n-butyllithium (34.8mmol, 14.0mL, 2.5 mol / L, 2 equivalents), completed, reacted for 1 hour, and then 5,6 difluorobenzo[d][1,2,5]thiadiazole (3g, 17.4mmol, 1 equivalent) was compounded with 30mL of tetrahydrofuran Form a solution, gradually add dropwise to the reaction solution, complete, react for 40 minutes, then add iodine tetrahydrofuran solution (10.16g, 40.02mmol, 2.3 equivalents, 170mL tetrahydrofuran) dropwise therein, complete, after stirring for 15 minutes, place at room temperature , stirred overnight. Post-processing: add sodium sulfite and stir to remove iodine, then pour into water, extract with dichloromethane, wash with saturated aqueous sodium chloride, and dry over anhydrous magnesium sulfate. Th...

technical field

[0001] The invention belongs to the technical field of fine organic chemistry, and specifically relates to a preparation method of a difluorobenzoheterocyclic conjugated monomer substituted with an iodine atom. Background technique

[0002] With the development of the times, human beings' demand for energy is increasing, but traditional resources such as oil and coal will eventually be exhausted, which makes people feel more and more urgent about the development and utilization of new energy. Solar energy has always been the object of research and utilization by many scientists due to its universal, harmless, and long-lasting advantages. Among them, solar cells that utilize solar energy by photoelectric conversion have become one of the research focuses. Silicon-based solar cells are the longest-developing and most mature technology, and have been commercialized at present, and the laboratory efficiency of monocrystalline silicon cells has reached 25.0%. How...

Examples

preparation example Construction

[0023] (1) Preparation of Lithium Diisopropylamide (LDA): Under a nitrogen atmosphere, a solution of 0.1 g / mL diisopropylamine (1.1 equivalents) in tetrahydrofuran was cooled to -78°C, and 1 equivalent of n-butyl was slowly added dropwise to the solution. Lithium (2.5mol / L n-hexane solution), kept at -78°C for 1 hour after the dropwise addition.

[0024] (2) Iodination reaction: 1.0 equivalent of the substrate (difluorobenzoheterocyclic conjugated compound) was prepared into a 0.1g / L solution with anhydrous organic solvent, and then gradually added dropwise to LDA, at -78°C Under reaction 1 hour; The iodine simple substance of 2.3 equivalents (preparation of diiodine substitution monomer 2) or 1.15 equivalents (preparation of single iodine substitution monomer 3) and anhydrous organic solvent are made into the solution of 0.06g / L, and it is directly Added dropwise to the reaction system, the system naturally rose to room temperature, and stirred overnight.

[0025] (3) Post-p...

Embodiment 1

[0028] Preparation of 4,7-diiodo-2-dodecyl-5,6-difluoro-2H-benzo[d][1,2,3]triazole

[0029] The synthetic route is as follows:

[0030]

[0031] In a 250mL long-necked three-neck flask, under an argon atmosphere, add diisopropylamine (1.73g, 17.03mmol, 2.2eq) and 30mL of tetrahydrofuran, cool down to -78°C, add dropwise n-butyllithium (15.48mmol, 6.2mL, 2.5 mol / L, equivalent), completed, reacted for 1 hour, then 2-dodecyl-5,6 difluoro-2H-benzo[d][1,2,3]triazole (2.5g, 7.74mmol , 1 equivalent) and 25mL of tetrahydrofuran were made into a solution, and gradually added dropwise to the reaction solution. After completion of the reaction for 40 minutes, a tetrahydrofuran solution of iodine (4.52g, 17.8mmol, 2.3 equivalents, 75mL of tetrahydrofuran) was added dropwise thereto, and the reaction was completed. , stirred for 15 minutes, placed at room temperature, stirred overnight. Post-processing: add sodium sulfite and stir to remove iodine, then pour into water, extract with d...

Embodiment 2

[0033] Preparation of 4,7-diiodo-5,6-difluorobenzo[d][1,2,5]thiadiazole

[0034]

[0035]In a 250mL long-necked three-neck flask, under an argon atmosphere, add diisopropylamine (3.9g, 15.3mmol, 2.2eq) and 30mL of tetrahydrofuran, cool down to -78°C, add dropwise n-butyllithium (34.8mmol, 14.0mL, 2.5 mol / L, 2 equivalents), completed, reacted for 1 hour, and then 5,6 difluorobenzo[d][1,2,5]thiadiazole (3g, 17.4mmol, 1 equivalent) was compounded with 30mL of tetrahydrofuran Form a solution, gradually add dropwise to the reaction solution, complete, react for 40 minutes, then add iodine tetrahydrofuran solution (10.16g, 40.02mmol, 2.3 equivalents, 170mL tetrahydrofuran) dropwise therein, complete, after stirring for 15 minutes, place at room temperature , stirred overnight. Post-processing: add sodium sulfite and stir to remove iodine, then pour into water, extract with dichloromethane, wash with saturated aqueous sodium chloride, and dry over anhydrous magnesium sulfate. Th...

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