CN106588924A - Perfluoroalkyl-modified perylene imide and its preparation method - Google Patents

Abstract

The invention discloses a perfluoroalkyl-modified perylene imide and a preparation method thereof, the general structural formula of which is: The structural formula of R is: Among them, X represents H, F, Br, m, n are the number of alkyl C atoms and the number of perfluoroalkyl C atoms, respectively, m is 1, 2, 3, 4, 5, 6, n is 1 , 3, 5, 7; its preparation method is to take perylenetetracarboxylic anhydride and perfluoroalkylamine as raw materials, and their molar ratio is equal to 1:2～1:6, in an organic solvent, at room temperature to the reflux of the used solvent Within the temperature range, under the protection of Ar or N ₂ , stir and react for 1 to 12 hours to generate perfluoroalkyl-substituted perylene imides. The invention can significantly increase the solubility of such materials in organic solvents, and at the same time enhance their photothermal stability and device stability in field effect transistors.

Description

A perfluoroalkyl modified perylene imide and its preparation method

technical field

The invention belongs to the field of organic chemical industry and fine chemical industry, and relates to the perfluoroalkylation of organic semiconductor material peryleneimide and its halogenated derivatives, in particular to a perfluoroalkyl modified peryleneimide and its preparation method .

Background technique

Compared with the widely used inorganic semiconductor materials, organic semiconductor materials have the following advantages: they are suitable for low-cost solution processing; they can be used to prepare wearable flexible devices; they have many types and properties, which are beneficial to the design and development of new materials and devices.

Perfluoroalkyl has a rigid rod-like structure. Fluorine atoms and perfluoroalkyl compounds have extremely high stability, oxidation resistance and hydrophobicity, and fluorine atoms can also form intermolecular hydrogen bonds with adjacent hydrogen atoms to enhance the interaction between molecules (J.Am. Chem. Soc. 1969, 91, 6235-6237). Fluorine atoms or perfluoroalkyl groups have been widely used in the field of organic optoelectronics. For example, fluorine atoms are used as acceptor materials for high-efficiency bulk heterojunction cells (Progress in PolymerScience 2015,47,70-91), perfluoroalkyl groups It is used to construct air-stable field-effect transistor materials (Chem. Rev. 2011, 112, 2208-2267).

Perylene imides substituted with perfluoroalkyl groups have been proven to be excellent n-type organic semiconductors, in which perfluoroalkyl groups play a role in isolating water and oxygen and enhancing air stability (J.Am.Chem.Soc.2009, 131, 6215-6228). However, the reported perfluoroalkyl-substituted perylene imides have poor solubility and are not suitable for solution processing. Therefore, there is an urgent need to develop a new type of perfluoroalkyl-substituted perylene imide that can be solution-processed.

Contents of the invention

The purpose of the present invention is to simultaneously introduce common alkyl groups and perfluoroalkyl groups of different sizes on the N atom of perylene imide to improve the stability of perylene bis-diimide and halogenated derivatives to light, heat and oxidants properties, while significantly improving its solubility in organic solvents.

The technical scheme of the present invention is, a perfluoroalkyl modified perylene imide, starting from commercialized perylene tetracarboxylic anhydride, dibromoperylene tetracarboxylic anhydride or difluoroperylene tetracarboxylic anhydride, and perfluoroalkylamine R'NH2 is reacted in an organic solvent to generate a perfluoroalkyl-modified solution-processable peryleneimide. The general structure of the target product is:

The structural formula of R is:

Among them, X represents H, F, Br, m, n are the number of alkyl C atoms and the number of perfluoroalkyl C atoms, respectively, m is 1, 2, 3, 4, 5, 6, n is 1 , 3, 5, 7.

The specific synthesis of the raw material alkylamine R'NH2 used in the present invention refers to the literature method (Chinese J. Chem., 2004, 22, 371-376; Org. Lett. 2007, 9, 2673-2676).

The preparation method of the above-mentioned perfluoroalkyl modified perylene imide and its derivatives is characterized in that the method uses perylene tetracarboxylic anhydride and perfluoroalkylamine as raw materials, and their molar ratio is equal to 1:2～1: 6. In an organic solvent, within the range from room temperature to the reflux temperature of the solvent used, under the protection of Ar or N ₂ , stir and react for 1-12 hours to generate a perfluoroalkyl-substituted perylene imide.

Preferably, in the preparation method of perfluoroalkyl-modified perylene imides and derivatives thereof, the organic solvent is selected from quinoline, acetic acid, dimethyl sulfoxide, sulfolane, N, N'-di Methylformamide, imidazole, acetonitrile, tetrahydrofuran, N-methylpyrrolidone, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether.

The beneficial effect of the invention is that after the introduction of alkyl and perfluoroalkyl groups on the parent of peryleneimide, the solubility of this type of material in organic solvents can be significantly increased, and its photothermal stability and field effect transistor can be enhanced at the same time. Device stability in .

detailed description

A perfluoroalkyl-modified perylene imide and its preparation method according to the present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.

Example 1: Preparation of N, N'-bis(2-perfluorobutyl-1-hexylethyl)peryleneimide

Add perylenetetracarboxylic anhydride 1 (0.72mmol, 0.281g), E ₁ (2.45mmol, 0.852g), imidazole (58.76mmol, 4g) into a 25mL two-necked flask, react at 145°C for 4.5h under anaerobic conditions, and cool to 120°C ℃, add an appropriate amount of ethanol, reflux for 0.5h, add 12mol/L HCl to remove imidazole, extract with CH ₂ Cl ₂ and saturated brine, dry over anhydrous magnesium sulfate, filter with suction, rotary evaporate, and use CH ₂ Cl ₂ and petroleum ether As an eluent, silica gel was used for column separation to obtain 0.152 g of perfluoroalkyl perylene imide 2 with a yield of 20.19%. ¹ H NMR (400MHz, CDCl ₃ )δ8.74(s,2H),8.65(s,6H),5.73(s,2H),3.36(d,2H),2.55(s,2H),2.39(s, 2H),1.93(s,2H),1.24(s,8H),0.83(s,6H); HRMS(MALDI-TOF): Calcd for C ₄₈ H ₃₂ F ₂₆ N ₂ O ₄ ,1194.1950,found:1194.7520( M ^- ).

Example 2: Preparation of N, N'-bis(2-perfluorobutyl-1-hexylethyl)peryleneimide

Add perylenetetracarboxylic anhydride 1 (0.678mmol, 0.266g), E1 (1.695mmol, 0.589g), CH3COOH (10mL) to a 25mL two-necked flask, react at 115°C for 6.5h under anaerobic conditions, and extract with CH2Cl2 and saturated saline , dried over anhydrous magnesium sulfate, suction filtered, rotary evaporated, CH2Cl2 and petroleum ether were used as eluents, and silica gel was separated through a column to obtain 0.256 g of perfluoroalkyl perylene imide 2a, yield: 35.93%. 1H NMR (400MHz, CDCl3) δ8.73(d,2H),8.64(s,6H),5.72(s,2H),3.35(s,2H),2.56(s,2H),2.35(s,2H) , 1.91 (s, 2H), 1.28 (d, 16H), 0.82 (s, 6H); HRMS (MALDI-TOF): Calcd for C48H40F18N2O4, 1050.2700, found: 1050.8290 (M-).

Example 3: Preparation of N, N'-bis(2-perfluorohexyl-1-hexylethyl)peryleneimide

Add perylenetetracarboxylic anhydride 1 (0.77mmol, 0.301g), _E2 (1.49mmol, 0.67g), imidazole (73.45mmol, 5g) into a 25mL two-necked flask, react at 145°C for 6.5h under anaerobic conditions, and cool to 120°C ℃, add an appropriate amount of ethanol, reflux for 0.5h, add 12mol/L HCl to remove imidazole, extract with CH ₂ Cl ₂ and saturated brine, dry over anhydrous magnesium sulfate, filter with suction, rotary evaporate, and use CH ₂ Cl ₂ and petroleum ether As an eluent, silica gel was used for column separation to obtain 0.278 g of perfluoroalkyl perylene imide 2b with a yield of 29%. ¹ H NMR (400MHz, CDCl ₃ )δ8.73(s,2H),8.65(s,6H),5.73(s,2H),3.36(d,2H),2.55(s,2H),2.36(s, 2H),1.94(s,2H),1.24(s,16H),0.83(s,6H); HRMS(MALDI-TOF): Calcd for C ₅₂ H ₄₀ F ₂₆ N ₂ O ₄ ,1250.2570,found:1250.8600( M ^- ).

Example 4: Preparation of N, N'-bis(2-perfluorobutyl-1-butylethyl)peryleneimide

Add perylenetetracarboxylic anhydride 1 (0.39mmol, 0.281g), E ₃ (2.67mmol, 0.852g), imidazole (58.76mmol, 4g) to a 25mL two-necked flask, react at 145°C for 2.5h under anaerobic conditions, and cool to 120°C ℃, add an appropriate amount of ethanol, reflux for 0.5h, add 12mol/L HCl to remove imidazole, extract with CH ₂ Cl ₂ and saturated brine, dry over anhydrous magnesium sulfate, filter with suction, rotary evaporate, and use CH ₂ Cl ₂ and petroleum ether As an eluent, silica gel was used for column separation to obtain 0.152 g of perfluoroalkyl perylene imide 2c with a yield of 21.3%. ¹ H NMR (400MHz, CDCl ₃ )δ8.74(s,2H),8.65(s,6H),5.73(s,2H),3.36(d,2H),2.55(s,2H),2.39(s, 2H),1.93(s,2H),1.24(s,8H),0.83(s,6H); HRMS(MALDI-TOF): Calcd for C ₄₄ H ₃₂ F ₁₈ N ₂ O ₄ ,994.2070,found:994.7210( M ^- ).

Example 5: Preparation of N, N'-bis(2-perfluorohexyl-1-butylethyl)peryleneimide

Add perylenetetracarboxylic anhydride 1 (0.765mmol, 0.300g), E4 ( _1.700mmol , 0.700g), imidazole (58.76mmol, 4g) into a 25mL two-necked flask, react at 145°C for 4h under anaerobic conditions, and cool to 120°C , add an appropriate amount of ethanol, reflux for 0.5h, add 12mol/L HCl to remove imidazole, extract with CH ₂ Cl ₂ and saturated saline, dry over anhydrous magnesium sulfate, filter with suction, rotary evaporate, and make with CH ₂ Cl ₂ and petroleum ether The eluent was separated by column with silica gel to obtain 0.285 g of perfluoroalkyl perylene imide 2d, the yield: 31.19%. ¹ H NMR (400MHz, CDCl ₃ )δ8.74(s,2H),8.65(s,6H),5.73(s,2H),3.36(d,,2H),2.55(s,2H),2.39(s ,2H),1.93(s,2H),1.24(s,8H),0.83(s,6H); HRMS(MALDI-TOF): Calcd for C ₄₈ H ₃₂ F ₂₆ N ₂ O ₄ ,1194.1950,found:1194.7520 (M ^- ).

Example 6: Preparation of N, N'-bis(2-perfluorobutyl-1-hexylethyl)-1,7-dibromo-peryleneimide

Add perylene dibromotetracarboxylic anhydride dibromide 3 (0.40mmol, 0.218g), E ₁ (1.15mmol, 0.399g), imidazole (73.38mmol, 5g) into a 25mL two-necked flask, and react at 145°C for 4.5h under anaerobic conditions , cooled to 120°C, added an appropriate amount of ethanol, refluxed for 0.5h, added 12mol/L HCl to remove imidazole, extracted with CH ₂ Cl ₂ and saturated brine, dried with anhydrous magnesium sulfate, suction filtered, rotary evaporated, and distilled with CH ₂ Cl ₂ and petroleum ether as eluent, separated by silica gel column to obtain 0.314 g of perfluoroalkyl perylene imide 4a, yield: 65.6%. HRMS (MALDI-TOF): Calcd for C ₄₈ H ₃₈ Br ₂ F ₁₈ N ₂ O ₄ , 1206.0910, found: 1208.6210 (M ^- ).

Example 7: Preparation of N, N'-bis(2-perfluorobutyl-1-hexylethyl)-1,7-dibromo-peryleneimide

Add perylene dibromotetracarboxylic anhydride dibromide 3 (0.49mmol, 0.267g), E ₁ (1.32mmol, 0.459g), DMF (10mL) into a 25mL two-necked flask, react at 130°C for 3h under anaerobic conditions, cool to room temperature, Extract with CH ₂ Cl ₂ and saturated saline, dry over anhydrous magnesium sulfate, filter with suction, rotary evaporate, use CH ₂ Cl ₂ and petroleum ether as eluent, and separate through column on silica gel to obtain perfluoroalkylperyleneimide 4a 0.207g, Yield: 23%. HRMS (MALDI-TOF): Calcd for C ₄₈ H ₃₈ Br ₂ F ₁₈ N ₂ O ₄ , 1206.0910, found: 1206.6210 (M ^- ).

Example 8: Preparation of N, N'-bis(2-perfluorobutyl-1-hexylethyl)-1,7-dibromo-peryleneimide

Add perylenetetracarboxylic anhydride (0.545mmol, 0.300g), 5 (1.363mmol, 0.473g), quinoline (12mL) to a 25mL two-necked flask, react at 150°C for 4h under anaerobic conditions, cool to room temperature, and wash with CH ₂ Cl ₂ extracted with saturated brine, dried over anhydrous magnesium sulfate, suction filtered, rotary evaporated, _CH2Cl2 and petroleum ether _were used as eluents, and silica gel was separated through a column to obtain 0.245 g of pure perfluoroalkyl perylene imides. Rate: 52.35%. ¹ H NMR (400MHz, CDCl ₃ ) δ9.52(d,2H),8.97(s,1H),8.90(s,1H),8.75(d,2H),5.70(m,2H),3.45–3.24( m,2H),2.52(d,2H),2.41–2.25(m,2H),1.90(s,2H),1.43–1.15(m,16H),0.83(s,6H); HRMS(MALDI-TOF) :Calcd for C ₄₈ H ₃₈ Br ₂ F ₁₈ N ₂ O ₄ ,1206.0910,found:1208.6210(M ^- );

Example 9: Preparation of N, N'-bis(2-perfluorohexyl-1-hexylethyl)-1,7-dibromo-peryleneimide

Add perylene dibromotetracarboxylic anhydride (0.60mmol, 0.328g), _E2 (0.89mmol, 0.399g), imidazole (73.38mmol, 5g) into a 25mL two-necked flask, react at 145°C for 6h under anaerobic conditions, and cool to 120°C ℃, add an appropriate amount of ethanol, reflux for 0.5h, add 12mol/L HCl to remove imidazole, extract with CH ₂ Cl ₂ and saturated brine, dry over anhydrous magnesium sulfate, filter with suction, rotary evaporate, and use CH ₂ Cl ₂ and petroleum ether As an eluent, silica gel was used for column separation to obtain 0.714 g of perfluoroalkyl perylene imide 4b with a yield of 85%. ¹ H NMR (400MHz, CDCl ₃ ) δ9.52(d,2H),8.97(s,1H),8.90(s,1H),8.75(d,2H),5.70(m,2H),3.45–3.24( m,2H),2.52(d,2H),2.41–2.25(m,2H),1.90(s,2H),1.43–1.15(m,16H),0.83(s,6H); HRMS(MALDI-TOF) : Calcd for C ₅₂ H ₃₈ Br ₂ F ₂₆ N ₂ O ₄ , 1406.0780, found: 1408.6520 (M ^- ).

Example 10: Preparation of N, N'-bis(2-perfluorobutyl-1-butylethyl)-1,7-dibromo-peryleneimide

Add perylene dibromotetracarboxylic anhydride (0.47mmol, 0.256g), E ₃ (1.29mmol, 0.412g), imidazole (73.38mmol, 5g) into a 25mL two-necked flask, react at 145°C for 2h under anaerobic conditions, and cool to 120°C ℃, add an appropriate amount of ethanol, reflux for 0.5h, add 12mol/L HCl to remove imidazole, extract with CH ₂ Cl ₂ and saturated brine, dry over anhydrous magnesium sulfate, filter with suction, rotary evaporate, and use CH ₂ Cl ₂ and petroleum ether As an eluent, silica gel was used for column separation to obtain 0.41 g of perfluoroalkyl perylene imide 4c with a yield of 76%. ¹ H NMR (400MHz, CDCl ₃ ) δ9.51(d,2H),8.97(s,1H),8.92(s,1H),8.74(d,2H),5.72(m,2H),3.43–3.23( m,2H),2.53(d,2H),2.40–2.26(m,2H),1.92(s,2H),1.42–1.13(m,8H),0.82(s,6H); HRMS(MALDI-TOF) : Calcd for C ₄₄ H ₃₀ Br ₂ F ₁₈ N ₂ O ₄ , 1150.0280, found: 1152.5130 (M ^- ).

Example 11: Preparation of N, N'-bis(2-perfluorohexyl-1-butylethyl)-1,7-dibromo-peryleneimide

Add perylene dibromotetracarboxylic anhydride (0.59mmol, 0.322g), E4 ( _1.19mmol , 0.500g), imidazole (73.38mmol, 5g) into a 25mL two-necked flask, react at 145°C for 4h under anaerobic conditions, and cool to 120°C ℃, add an appropriate amount of ethanol, reflux for 0.5h, add 12mol/L HCl to remove imidazole, extract with CH ₂ Cl ₂ and saturated brine, dry over anhydrous magnesium sulfate, filter with suction, rotary evaporate, and use CH ₂ Cl ₂ and petroleum ether As an eluent, silica gel was used for column separation to obtain 0.633 g of perfluoroalkyl perylene imide 4d, with a yield of 80%. HRMS (MALDI-TOF): Calcd for C ₄₈ H ₃₀ Br ₂ F ₂₆ N ₂ O ₄ , 1350.0160, found: 1352.5440 (M ^- ).

Claims (3)

1. a perfluoroalkyl modified perylene imide, characterized in that its general structural formula is: The structural formula of R is: Among them, X represents H, F, Br, m, n are the number of alkyl C atoms and the number of perfluoroalkyl C atoms, respectively, m is 1, 2, 3, 4, 5, 6, n is 1 , 3, 5, 7. 2. the preparation method of the perylene imide of perfluoroalkyl modification described in claim 1 is characterized in that: the method is to be raw material with perylene tetracarboxylic anhydride and perfluoroalkyl amine, and their mol ratio equals 1: 2～1:6, in an organic solvent, within the range of room temperature to the reflux temperature of the solvent used, under the protection of Ar or _N2 , stir, react for 1～12h, and generate perfluoroalkyl-substituted peryleneimide. 3. the preparation method of the perylene imide of perfluoroalkyl modification according to claim 2 is characterized in that: described organic solvent is selected from quinoline, acetic acid, dimethyl sulfoxide, sulfolane, N, N '-Dimethylformamide, imidazole, acetonitrile, tetrahydrofuran, N-methylpyrrolidone, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether.