Fused ring compound with four-nitrogen and nine-ring structure and preparation method of fused ring compound

Abstract

The invention discloses a fused ring compound with a four-nitrogen and nine-ring structure and a preparation method of the fused ring compound, namely, a benzo[4',5']isoquinoline[2',1':1,2] imidazo-[4,5-c]indol[2,3-a]carbazol-18-one derivative and a preparation method thereof. Dialkyl-indole [2,3-a] carbazole-5,6-dione and quinone derivatives and inorganic ammonium salt are added to an organic solvent, the mixture is heated in a sealed manner and subjected to a slight boiling reaction for 6-12 hours, column chromatography or recrystallization purification is performed after the mixture is cooled, and the benzo[4',5']isoquinoline[2',1':1,2] imidazo-[4,5-c]indol[2,3-a]carbazol-18-one derivative with yield of 75%-90% can be obtained. The preparation method has the advantages that the reaction step is short, operation is simple, the yield is high, the product is easy to separate and purify. The benzo[4',5']isoquinoline[2',1':1,2] imidazo-[4,5-c]indol[2,3-a]carbazol-18-one derivative is expected to be used in the field of organic optoelectronics.

Description

technical field

[0001] The present invention relates to a benzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2, 3-a] Carbazol-18-one derivatives and a preparation method thereof belong to the field of organic photoelectric materials. Background technique

[0002] Isoquinoline, imidazole, indole, and carbazole are common structural fragments in organic photoelectric materials and medical fields. Combining two or more of them through molecular design often leads to organic compounds with specific photophysical properties. Photoelectric materials, or pharmaceutical molecules with unique biological activity, such as skeleton A derivatives with imidazol[4,5-c]carbazole structure in the following formula, can be used as organic photoelectric materials (U.S. Pat. Appl., 20140374706), It can also be used as an insect repellant (IndianJ.Chem., B:1992, 31B(1), 44-49.), such as the skeleton B with indole[2,3-a]carbazole structure, which has been reported to be effective Used in ...

Examples

Embodiment 1

[0018] Example 1. 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3- a] Preparation of (3a) of carbazol-18-one

[0019]

[0020] 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3-a]carbazole -18-ketone (3a): Add 11,12-di-n-butyl-indole[2,3-a]carbazole-5,6-dione (1) (0.40g, 1mmol), acenaphthoquinone (5a) (0.18g, 1mmol), ammonium formate (0.13g, 2mmol), ammonium acetate (0.15g, 2mmol), ethanol 5mL, the condenser tube was sealed with a balloon, the reaction system was heated to a slight boil, and the reaction After 6 hours, the reaction system was cooled to room temperature, added an appropriate amount of water and stirred for 15 minutes and extracted with chloroform, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered to remove insoluble matter, and the filtrate was concentrated and purified by column chromatography (V 氯仿 :V 正己烷 =30:70), and finally obtained 0.42 g of brown-red solid with a yield of 7...

Embodiment 2

[0021] Example 2. 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3- a] Preparation of (3a) of carbazol-18-one

[0022]

[0023] 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3-a]carbazole -18-ketone (3a): Add 11,12-di-n-butyl-indole[2,3-a]carbazole-5,6-dione (1) (0.80g, 2mmol), acenaphthoquinone (5a) (0.72g, 4mmol), ammonium chloride (0.42g, 8mmol), ammonium acetate (0.62g, 8mmol), toluene 3mL, N,N-dimethylformamide 3mL, for condenser Seal the balloon, heat the reaction system to a slight boil, react for 8 hours, cool the reaction system to room temperature, add an appropriate amount of water and extract with chloroform, combine the organic phases, dry over anhydrous magnesium sulfate, remove insoluble matter by filtration, and concentrate the filtrate through the column Chromatographic purification (V 氯仿 :V 正己烷 =30:70), and finally obtained 0.89 g of brown-red solid with a yield of 80%. 1 H NMR (500MHz, CDCl 3 )δ9.00(d, J=...

Embodiment 3

[0024] Example 3. 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3- a] Preparation of (3a) of carbazol-18-one

[0025]

[0026] 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3-a]carbazole -18-ketone (3a): Add 11,12-di-n-butyl-indole[2,3-a]carbazole-5,6-dione (1) (0.80g, 2mmol), acenaphthylquinone (5a) (0.54g, 3mmol), ammonium acetate (1.82g, 20mmol), acetic acid 5mL, the condenser tube was sealed with a balloon, the reaction system was heated to a slight boil, reacted for 10 hours, and the reaction system was cooled to room temperature After adding an appropriate amount of water, extract with chloroform, the organic phases are combined, dried over anhydrous magnesium sulfate, filtered to remove insoluble matter, and the filtrate is concentrated and purified by column chromatography (V 氯仿 :V 正己烷 =30:70), 1.00 g of a brown-red solid was finally obtained, with a yield of 90%. 1 H NMR (500MHz, CDCl 3 )δ9.00(d, J=7.6Hz, 1H), 8.80–8...

technical field

[0001] The present invention relates to a benzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2, 3-a] Carbazol-18-one derivatives and a preparation method thereof belong to the field of organic photoelectric materials. Background technique

[0002] Isoquinoline, imidazole, indole, and carbazole are common structural fragments in organic photoelectric materials and medical fields. Combining two or more of them through molecular design often leads to organic compounds with specific photophysical properties. Photoelectric materials, or pharmaceutical molecules with unique biological activity, such as skeleton A derivatives with imidazol[4,5-c]carbazole structure in the following formula, can be used as organic photoelectric materials (U.S. Pat. Appl., 20140374706), It can also be used as an insect repellant (IndianJ.Chem., B:1992, 31B(1), 44-49.), such as the skeleton B with indole[2,3-a]carbazole structure, which has been reported to be effective Used in ...

Examples

Embodiment 1

[0018] Example 1. 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3- a] Preparation of (3a) of carbazol-18-one

[0019]

[0020] 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3-a]carbazole -18-ketone (3a): Add 11,12-di-n-butyl-indole[2,3-a]carbazole-5,6-dione (1) (0.40g, 1mmol), acenaphthoquinone (5a) (0.18g, 1mmol), ammonium formate (0.13g, 2mmol), ammonium acetate (0.15g, 2mmol), ethanol 5mL, the condenser tube was sealed with a balloon, the reaction system was heated to a slight boil, and the reaction After 6 hours, the reaction system was cooled to room temperature, added an appropriate amount of water and stirred for 15 minutes and extracted with chloroform, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered to remove insoluble matter, and the filtrate was concentrated and purified by column chromatography (V 氯仿 :V 正己烷 =30:70), and finally obtained 0.42 g of brown-red solid with a yield of 7...

Embodiment 2

[0021] Example 2. 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3- a] Preparation of (3a) of carbazol-18-one

[0022]

[0023] 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3-a]carbazole -18-ketone (3a): Add 11,12-di-n-butyl-indole[2,3-a]carbazole-5,6-dione (1) (0.80g, 2mmol), acenaphthoquinone (5a) (0.72g, 4mmol), ammonium chloride (0.42g, 8mmol), ammonium acetate (0.62g, 8mmol), toluene 3mL, N,N-dimethylformamide 3mL, for condenser Seal the balloon, heat the reaction system to a slight boil, react for 8 hours, cool the reaction system to room temperature, add an appropriate amount of water and extract with chloroform, combine the organic phases, dry over anhydrous magnesium sulfate, remove insoluble matter by filtration, and concentrate the filtrate through the column Chromatographic purification (V 氯仿 :V 正己烷 =30:70), and finally obtained 0.89 g of brown-red solid with a yield of 80%. 1 H NMR (500MHz, CDCl 3 )δ9.00(d, J=...

Embodiment 3

[0024] Example 3. 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3- a] Preparation of (3a) of carbazol-18-one

[0025]

[0026] 5,6-Dibutylbenzo[4',5']isoquinoline[2',1':1,2]imidazo[4,5-c]indole[2,3-a]carbazole -18-ketone (3a): Add 11,12-di-n-butyl-indole[2,3-a]carbazole-5,6-dione (1) (0.80g, 2mmol), acenaphthylquinone (5a) (0.54g, 3mmol), ammonium acetate (1.82g, 20mmol), acetic acid 5mL, the condenser tube was sealed with a balloon, the reaction system was heated to a slight boil, reacted for 10 hours, and the reaction system was cooled to room temperature After adding an appropriate amount of water, extract with chloroform, the organic phases are combined, dried over anhydrous magnesium sulfate, filtered to remove insoluble matter, and the filtrate is concentrated and purified by column chromatography (V 氯仿 :V 正己烷 =30:70), 1.00 g of a brown-red solid was finally obtained, with a yield of 90%. 1 H NMR (500MHz, CDCl 3 )δ9.00(d, J=7.6Hz, 1H), 8.80–8...

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