A dipyrrole-fused perylenetetracarboxylic dianhydride, its preparation method and application

Abstract

This invention relates to a dipyrrole-fused perylenetetracarboxylic acid dianhydride, its preparation method, and its applications, relating to the field of organic functional molecule synthesis. The preparation method includes: using tetrachloroperyleneimide and a primary amine as raw materials, with bis(tri-tert-butylphosphine)palladium(O) as a catalyst, and in the presence of sodium tert-butoxide, using toluene as a solvent, a Buchwald-Hartwig arylation reaction is performed to obtain PDI-2NR; PDI-2NR is then acidified with acetic acid and extracted with an organic solvent in the presence of a strong inorganic base and an alcohol as a solvent to obtain the target product PDA-2NR. The synthesis process of this invention is simple and yields high efficiency; PDA-2NR readily undergoes condensation reactions with aliphatic and aromatic primary amines to achieve nitrogen-terminal modification, enabling the efficient synthesis of PDI-2NR and PDI-2NH. These materials can be used as organic semiconductor materials in organic electroluminescent devices, organic field-effect transistors, solar cells, etc., showing promising application prospects.

Description

Technical Field

[0001] This invention relates to the field of organic functional molecule synthesis technology, and in particular to a dipyrrole-fused perylenetetracarboxylic acid dianhydride, its preparation method, and its applications. Background Technology

[0002] Perylene diimide (PDI) is widely used in field-effect transistors (OFETs) and organic light-emitting diodes (OLEDs) due to its excellent redox properties, environmental stability, and optical and electrical properties. Organic OFETs have enormous development potential, especially in memory devices and integrated optoelectronic devices. In recent years, it has been found that incorporating nitrogen heterocycles at the bay positions of PDI can effectively alter its physicochemical properties. For example, the double PDI molecule with bay-position pyrrole rings (diPDI-2N) has a bowl-shaped structure with significant curvature; introducing a five-membered pyrrole ring causes a significant redshift in its absorption spectrum. Furthermore, using nitrogen atoms as bridging atoms effectively modulates molecular curvature, electronic properties, and frontier orbital energy levels. In addition, similar perylene-pyrrole ring derivatives also possess significant characteristics such as low band gaps, strong near-infrared absorption / emission, and large two-photon absorption cross-sections, making them widely applicable as two-photon fluorescent labeling materials. However, there is only one reported synthesis of PDI backbone bay-position pyrrole molecules to date, with a single product structure and a yield of only 12%. No product derivatization method has been developed, which is not conducive to subsequent large-scale property testing and functional development. Summary of the Invention

[0003] The purpose of this invention is to solve the above-mentioned problems in the prior art and to provide a dipyrrole-fused perylenetetracarboxylic dianhydride (PDA-2NR) and its preparation method and application. This method has the advantages of low cost, short process route and high yield.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A dipyrrole-fused perylenetetracarboxylic acid dianhydride has the following structural formula:

[0006] Where R is any group, for example R can be as follows:

[0007] , .

[0008] The synthetic route for the dipyrrole-fused perylenetetracarboxylic dianhydride is as follows:

[0009]

[0010] Specifically, the method for preparing a dipyrrole-fused perylenetetracarboxylic acid dianhydride includes the following steps:

[0011] 1) Using tetrachloroperylimide (PDI-4Cl) and primary amine as raw materials, and bis(tri-tert-butylphosphine)palladium(0) as catalyst, PDI-2NR was obtained by Buchwald-Hartwig arylation reaction in the presence of sodium tert-butoxide and in toluene as solvent.

[0012] 2) PDI-2NR is acidified with acetic acid and extracted with an organic solvent in the presence of an inorganic strong base to obtain the target product PDA-2NR.

[0013] In step 1) of this invention, the primary amine is the primary amine corresponding to the R group.

[0014] In this invention, the mass ratio of bis(tri-tert-butylphosphine)palladium(O), primary amine, tetrachloroperyleneimide, sodium tert-butoxide, and toluene is 1:(1~5):(2~5):(3~5):(100~200).

[0015] In this invention, the mass ratio of inorganic strong base to alcohol is (20~30):(200~300).

[0016] In step 1), the reaction temperature is 100~120 ℃ and the time is 3~48 h.

[0017] In step 2), the reaction temperature is 100~120 ℃ and the time is 3~24 h.

[0018] The aforementioned application of a dipyrrole-fused perylenetetracarboxylic acid dianhydride is used to prepare PDI-2NR class molecules, the structure of which is as follows:

[0019] In this structure, R1 is an aliphatic or aromatic group obtained by the condensation reaction of PDA-2NR with an aliphatic or aromatic primary amine. It is worth noting that R1 is different from the R' at the nitrogen end of the tetrachloroperyleneimide (PDI-4Cl) structure used as a raw material. R' is derived from inexpensive and readily available simple aliphatic primary amines (such as cyclohexylamine, 3-pentylamine, etc.), while R1 can be any aliphatic or aromatic group that meets the requirements of subsequent derivatization and functionalization.

[0020] In this invention, PDI-2NR is reacted with aliphatic or aromatic primary amines under the protection of imidazole solvent and argon atmosphere by heating to obtain PDI-2NR-like molecules.

[0021] In this invention, PDI-2NR molecules are hydrolyzed to obtain PDI-2NH.

[0022] Compared with the prior art, the beneficial effects achieved by the technical solution of this invention are:

[0023] 1. In this invention, dipyrrole-fused perylenetetracarboxylic acid dianhydride molecules (PDA-2NR) can be prepared by a modeling method and can undergo condensation reactions with a series of aliphatic and aromatic primary amines to obtain a series of PDI-2NR molecules in yields of 50% to 90%. This method provides a new strategy for the efficient construction of nitrogen-containing surface π-molecules. Simultaneously, the alkyl groups at the bay position (such as tert-butyl groups) can be removed by hydrolysis, providing a prerequisite for further functionalization modifications. The synthetic strategy of this invention has good universality, simple separation and purification processes, and low organic solvent consumption, thus possessing high value for widespread application.

[0024] 2. The synthesis process of PDI-2NR provided by the present invention is completed in 85% yield by Buchwald-Hartwig aromatic amination reaction. The synthesis process is simple, the reaction conditions are mild, and the cost is low.

[0025] 3. The introduction of the pyrrole ring in PDI-2NR provided by this invention makes the subsequent synthesis of PDI-2NR-like molecules more convenient, and the removal of the substituent R at the bay position makes it easy to modify for multifunctionality, which is expected to endow the functionalized products with more specific properties. Attached Figure Description

[0026] Figure 1 Cy-PDI-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu;

[0027] Figure 2 Cy-PDI-2N t The hydrogen NMR spectrum of Bu;

[0028] Figure 3 Cy-PDI-2N t The carbon NMR spectrum of Bu;

[0029] Figure 4 PDA-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu;

[0030] Figure 5 Ph-PDI-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu;

[0031] Figure 6 Ph-PDI-2N t The hydrogen NMR spectrum of Bu;

[0032] Figure 7 Ph-PDI-2N t The carbon NMR spectrum of Bu;

[0033] Figure 8 Py-PDI-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu;

[0034] Figure 9 Py-PDI-2N t The hydrogen NMR spectrum of Bu;

[0035] Figure 10 C2-PDI-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu;

[0036] Figure 11 C2-PDI-2N t The hydrogen NMR spectrum of Bu;

[0037] Figure 12 C2-PDI-2N t The carbon NMR spectrum of Bu;

[0038] Figure 13 C4-PDI-2N t The hydrogen NMR spectrum of Bu;

[0039] Figure 14 C4-PDI-2N t The carbon NMR spectrum of Bu;

[0040] Figure 15 The matrix-assisted laser desorption / ionization time-of-flight mass spectrum of C4-PDI-2NH;

[0041] Figure 16 The image shows the 1H NMR spectrum of C4-PDI-2NH. Detailed Implementation

[0042] To make the technical problems, technical solutions and beneficial effects of the present invention clearer and more understandable, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0043] Example 1

[0044] In this embodiment, a dipyrrole-fused perylenetetracarboxylic acid dianhydride (PDA-2N) with R group as tert-butyl is used. t The preparation of Bu will be illustrated using the following example, and its structure is as follows:

[0045]

[0046] Step 1: Under argon protection, add bis(tri-tert-butylphosphine)palladium(0), tert-butylamine, cyclohexyltetrachloroperyleneimide (Cy-PDI-4Cl), sodium tert-butoxide, and toluene in a mass ratio of 1:2.56:3.82:3.76:196.1 to a Schlenk reaction flask, and stir the reaction at 110 °C for 24 h.

[0047] Step 2: Cool the reaction solution obtained in Step 1 to room temperature, then add a certain amount of a 1:1 volume ratio mixture of water and dichloromethane for extraction. Repeat this process 3 times and combine the organic phases.

[0048] Step 3: Dry the organic phase obtained in Step 2 with anhydrous sodium sulfate, filter, and recover the solvent from the filtrate by vacuum distillation to obtain a solution containing... A mixture;

[0049] Step 4: Take the contents obtained in Step 3... The mixture was separated by silica gel column chromatography using a 1:1 mixture of petroleum ether and dichloromethane as eluent. The product spot was collected and the solvent was recovered by distillation, yielding a yellow solid crude product in 85% yield.

[0050] Step 5: Recrystallize the crude product from Step 4 using a mixed solvent of dichloromethane and methanol at a volume ratio of 1:10. After filtration and natural drying, obtain... ;

[0051] Step 6: Add potassium hydroxide and isopropanol in a mass ratio of 27.5:245.1 to the Schlenk reaction flask under air, and stir the reaction at 115 °C for 6 h.

[0052] Step 7: Cool the reaction solution obtained in Step 6 to room temperature, then add acetic acid for acidification, add a certain amount of water and dichloromethane mixture with a volume ratio of 1:1 for extraction, repeat 3 times, and combine the organic phases;

[0053] Step 8: Dry the organic phase obtained in Step 7 with anhydrous sodium sulfate, filter, and recover the solvent from the filtrate by vacuum distillation to obtain... A mixture;

[0054] Step 9: Recrystallize the crude product from Step 8 using a mixed solvent of dichloromethane and petroleum ether at a volume ratio of 1:10. After filtration and natural drying, the target product is obtained. The yield was 72%.

[0055] Figure 1 The product is Cy-PDI-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu; Figure 2 The product is Cy-PDI-2N t The hydrogen NMR spectrum of Bu:1 H NMR (500 MHz, CDCl3) δ 8.91 (s, 4H), 5.10 (t, J =11.9 Hz, 2H), 2.58 (d, J = 11.2 Hz, 4H), 2.20 (s, 18H), 1.85 (d, J = 11.7 Hz, 4H), 1.73 (d, J = 11.1 Hz, 4H), 1.44 (q, J = 12.0 Hz, 4H), 1.28 (dd, J =28.6, 15.7 Hz, 4H); Figure 3 The product is Cy-PDI-2N t Bu's carbon NMR spectrum: 13 C NMR (126 MHz, CDCl3) δ 165.7, 142.8, 129.5, 128.1, 123.5, 123.0, 120.0, 60.2, 54.3, 31.6, 29.2, 26.6, 25.5; Figure 4 The product is PDA-2N. t Matrix-assisted laser ablation time-of-flight mass spectra of Bu.

[0056] Example 2

[0057] compound Preparation

[0058] 0.027 g PDA-2N t Bu, 0.012 g aniline, and an appropriate amount of imidazole were added sequentially to a 15 mL storage bottle. Under an argon atmosphere, the mixture was heated until the imidazole dissolved and stirred thoroughly. After the reaction solution cooled to room temperature, column chromatography was performed using dichloromethane as the eluent to obtain the compound. The yield was 69%.

[0059] The reaction equation is as follows:

[0060]

[0061] Figure 5 The product is Ph-PDI-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu; Figure 6 The product is Ph-PDI-2N t The hydrogen NMR spectrum of Bu: 1H NMR (500 MHz, CDCl3) δ 9.05 (s, 4H), 7.59 (t, J =7.0 Hz, 4H), 7.52 (t, J = 7.5 Hz, 2H), 7.36 (s, 4H), 2.22 (s, 18H); Figure 7 The product is Ph-PDI-2N t Bu's carbon NMR spectrum: 13 C NMR (126 MHz, CDCl3) δ 165.7, 142.7, 136.6, 129.6, 129.4, 128.8, 128.6, 128.1, 123.3, 123.2, 120.5, 60.6, 31.7.

[0062] Example 3

[0063] compound Preparation

[0064] 0.027 g PDA-2N t Bu, 0.012 g of 4-aminopyridine, and an appropriate amount of imidazole were added sequentially to a 15 mL storage bottle. Under an argon atmosphere, the mixture was heated until the imidazole dissolved and stirred thoroughly. After the reaction solution cooled to room temperature, column chromatography was performed using dichloromethane:ethyl acetate (v / v, 1:1) as the eluent to obtain the compound. The yield was 60%.

[0065] The reaction equation is as follows:

[0066]

[0067] Figure 8 The product is Py-PDI-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu; Figure 9 The product is Py-PDI-2N t The hydrogen NMR spectrum of Bu: 1 H NMR (500 MHz, CDCl3) δ 9.08 (s, 4H), 8.91 (s, 4H), 7.59 (s, 4H), 2.25 (s, 18H).

[0068] Example 4

[0069] Compound C2-PDI-2N t Preparation of Bu

[0070] 0.027 g PDA-2N t Bu, 0.011 g of 3-aminopentane, and an appropriate amount of imidazole were added sequentially to a 15 mL storage bottle. Under an argon atmosphere, the mixture was heated until the imidazole dissolved and stirred thoroughly. After the reaction solution cooled to room temperature, column chromatography was performed using dichloromethane:petroleum ether (volume ratio, 2:1) as the eluent to obtain compound C2-PDI-2N. t Bu, the yield was 72%.

[0071] The reaction equation is as follows:

[0072]

[0073] Figure 10 The product is C2-PDI-2N t Matrix-assisted laser ablation time-of-flight mass spectra of Bu; Figure 11 The product is C2-PDI-2N t The hydrogen NMR spectrum of Bu: 1 H NMR (500 MHz, CDCl3) δ 8.95 (s, 4H), 5.24 – 5.12 (m, 2H), 2.30 (dd, J = 27.4, 15.5 Hz, 4H), 2.22 (s, 18H), 2.01 – 1.86 (m, 4H), 1.22 – 0.60 (m, 12H); Figure 12 The product is C2-PDI-2N t Bu's carbon NMR spectrum: 13 C NMR (126MHz, CDCl3) δ 166.0, 142.9, 129.6, 128.2, 123.3, 120.2, 60.4, 57.8, 31.7, 25.3, 11.4.

[0074] Example 5

[0075] Compound C4-PDI-2N t Preparation of Bu

[0076] 0.027 g PDA-2N t Bu, 0.018 g of 5-aminononane, and an appropriate amount of imidazole were added sequentially to a 15 mL storage bottle. Under an argon atmosphere, the mixture was heated until the imidazole dissolved and stirred thoroughly. After the reaction solution cooled to room temperature, column chromatography was performed using dichloromethane:petroleum ether (volume ratio, 2:1) as the eluent to obtain compound C4-PDI-2N. tBu, the yield is 80%.

[0077] The reaction equation is as follows:

[0078]

[0079] Figure 13 The product is C4-PDI-2N t The hydrogen NMR spectrum of Bu: 1 H NMR (500 MHz, CDCl3) δ 8.95(d, J = 20.6 Hz, 4H), 5.36 – 5.25 (m, 2H), 2.46 – 2.30 (m, 2H), 2.29 – 2.11(m, 20H), 1.97 – 1.79 (m, 4H), 1.57 – 1.33 (m, 8H), 1.32 – 1.16 (m, 6H), 1.04– 0.81 (m, 8H), 0.81 – 0.56 (m, 6H; Figure 14 The product is C4-PDI-2N t Bu's carbon NMR spectrum: 13 CNMR (126 MHz, CDCl3) δ 166.8, 165.6, 142.9, 129.6, 128.2, 123.8, 123.3, 123.0, 120.6, 119.9, 77.3, 77.0, 76.8, 60.4, 54.8, 32.5, 31.7, 29.7, 29.3, 22.7, 14.1.

[0080] Example 6

[0081] Preparation of compound C4-PDI-2NH

[0082] 0.0156 g of C4-PDI-2N t Bu, 0.032 g aluminum trichloride and 2 mL dichloromethane were added sequentially to a 15 mL pressure-resistant tube. The mixture was stirred at room temperature until the reaction was complete. The reaction solution was separated by column chromatography using dichloromethane:ethyl acetate (volume ratio, 100:1) as the eluent to obtain compound C4-PDI-2NH with a yield of 88%.

[0083] The reaction equation is as follows:

[0084]

[0085] Figure 15The matrix-assisted laser desorption / ion-time mass spectrum of the product C4-PDI-2NH; Figure 16 The proton NMR spectrum of the product C4-PDI-2NH: 1 H NMR (400 MHz, CDCl3) δ 10.40 (s, 2H), 8.69 (s, 4H),5.41 – 5.20 (m, 2H), 2.46 (s, 2H), 2.18 (s, 2H), 1.93 (s, 4H), 1.80 (s, 4H),1.46 (d, J = 32.2 Hz, 8H), 1.16 (s, 4H), 0.94 (s, 6H), 0.58 (s, 6H).

Claims

1. A dipyrrole-fused perylenetetracarboxylic acid dianhydride, characterized in that, The structure is as follows: Where R is .

2. The application of the dipyrrole-fused perylenetetracarboxylic acid dianhydride according to claim 1, characterized in that: This is used to prepare PDI-2NR class molecules, the structure of which is as follows: The R1 structure is an aliphatic or aromatic group obtained by the condensation reaction of PDA-2NR with an aliphatic primary amine or an aromatic primary amine.

3. The application of the dipyrrole-fused perylenetetracarboxylic acid dianhydride as described in claim 2, characterized in that: PDI-2NR molecules are obtained by reacting PDA-2NR with aliphatic or aromatic primary amines under an imidazole solvent and an argon atmosphere and heating.

4. The application of the dipyrrole-fused perylenetetracarboxylic acid dianhydride as described in claim 3, characterized in that: PDI-2NR molecules are hydrolyzed to obtain PDI-2NH.

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