Dipyrrole fused perylene tetracarboxylic dianhydride as well as preparation method and application thereof

Abstract

The invention discloses dipyrrole fused perylene tetracarboxylic dianhydride as well as a preparation method and application thereof, and relates to the field of organic functional molecule synthesis. The preparation method comprises the following steps: by taking tetrachloro perylene bisimide and primary amine as raw materials, bis (tri-tert-butylphosphine) palladium (0) as a catalyst and toluene as a solvent in the presence of sodium tert-butoxide, carrying out Buchwald-Hartwisting arylation reaction to obtain PDI-2NR; the target product PDA-2NR can be obtained by acidifying PDI-2NR with acetic acid in the presence of inorganic strong alkali by taking alcohol as a solvent and extracting with an organic solvent. The synthesis process is simple and convenient, and the yield is high; pDA-2NR is easily subjected to a condensation reaction with aliphatic and aromatic primary amines, nitrogen terminal modification is realized, PDI-2NR and PDI-2NH are efficiently synthesized, and PDA-2NR and PDI-2NH can be used as organic semiconductor materials to be applied to organic electroluminescent devices, organic field effect transistors, solar cells and the like, and have good application prospects.

Description

Technical Field

[0001] The invention relates to the technical field of organic functional molecule synthesis, and in particular to a dipyrrole-fused perylene tetracarboxylic dianhydride and a preparation method and application thereof. Background Art

[0002] Perylene diimide (PDI) is widely used in the field of field effect transistors (OFETs) and organic light-emitting diodes (OLEDs) due to its excellent redox properties, environmental stability, optical and electrical properties. Organic field effect transistors have great development potential, especially in storage elements and integrated optoelectronic devices. In recent years, it has been found that the incorporation of nitrogen heterocycles at the bay position of PDI can effectively change the physicochemical properties of PDI. For example, the di-PDI molecule bay-position pyrrole ring molecule (diPDI-2N) is a PDI bowl-shaped structure with significant curvature, and the introduction of a five-membered pyrrole ring causes a significant red shift in its absorption spectrum. In addition, the use of nitrogen atoms as bridging atoms effectively regulates the molecular curvature, electronic properties and frontier orbital energy levels. In addition, similar perylene pyrrole ring derivatives also have significant characteristics such as low energy band gap, strong near-infrared absorption / emission and large two-photon absorption cross-section, and can be widely used as two-photon fluorescent labeling materials. However, there is only one report on the synthesis of PDI skeleton bay-position pyrrole molecules. The product has a single 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 function development. Summary of the invention

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

[0004] In order to achieve the above object, the present invention adopts the following technical scheme:

[0005] A dipyrrole-fused perylene tetracarboxylic dianhydride, the structural formula of which is as follows:

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

[0007] , .

[0008] The synthesis route of the dipyrrole-fused perylene tetracarboxylic dianhydride is as follows:

[0009]

[0010] Specifically, the method for preparing the dipyrrole-fused perylene tetracarboxylic dianhydride comprises the following steps:

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

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

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

[0014] In the present invention, the mass ratio of bis(tri-tert-butylphosphine)palladium(0), primary amine, tetrachloroperylene diimide, sodium tert-butoxide and toluene is 1:(1-5):(2-5):(3-5):(100-200).

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

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

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

[0018] The application of the dipyrrole-fused perylene tetracarboxylic dianhydride is used to prepare PDI-2NR molecules, and the structure of the PDI-2NR molecules is as follows:

[0019] Among them, the R1 structure is an aliphatic or aromatic group obtained by the condensation reaction of PDA-2NR with aliphatic primary amines or aromatic primary amines. It is worth noting that R1 is different from the R' at the nitrogen end of the structure of tetrachloroperylene diimide (PDI-4Cl) as a raw material. R' is derived from simple aliphatic primary amines (such as cyclohexylamine, 3-pentylamine, etc.) that are cheap and easily available, while R1 can be any aliphatic or aromatic group that meets the needs of subsequent derivatization and functionalization.

[0020] In the present invention, PDA-2NR and aliphatic primary amine or aromatic primary amine are heated to react in the presence of imidazole solvent and under the protection of argon atmosphere to obtain PDI-2NR molecules.

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

[0022] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0023] 1. In the present invention, the dipyrrole-fused perylene tetracarboxylic dianhydride molecule (PDA-2NR) can be prepared by a patterning method, and can undergo condensation reaction with a series of aliphatic and aromatic primary amines to obtain a series of PDI-2NR molecules with a yield of 50% to 90%. This method provides a new strategy for the efficient construction of nitrogen-curved surface π-molecules. At the same time, the nitrogen-terminal alkyl group (such as tert-butyl group, etc.) at the bay position can be removed by hydrolysis, which provides a prerequisite for subsequent further functional modification. The synthesis strategy of the present invention has good universality, simple separation and purification processes, and a small amount of organic solvent, so it has a high value for promotion and application.

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

[0025] 3. The introduction of the pyrrole ring in the PDI-2NR provided by the present invention makes the subsequent synthesis of PDI-2NR molecules more convenient, and the bay position is easy to be multifunctionally modified after the substituent R is removed, which is expected to give the functionalized product more specific properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Cy-PDI-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu;

[0027] Figure 2 Cy-PDI-2N t Bu's H NMR spectrum;

[0028] Figure 3 Cy-PDI-2N t Bu's NMR carbon spectrum;

[0029] Figure 4 For PDA-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu;

[0030] Figure 5 Ph-PDI-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu;

[0031] Figure 6 Ph-PDI-2N t Bu's H NMR spectrum;

[0032] Figure 7 Ph-PDI-2N t Bu's NMR carbon spectrum;

[0033] Figure 8 For Py-PDI-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu;

[0034] Fig. 9 For Py-PDI-2N t Bu's H NMR spectrum;

[0035] Fig.10 For C2-PDI-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu;

[0036] Fig.11 For C2-PDI-2N t Bu's H NMR spectrum;

[0037] Fig.12 For C2-PDI-2N t Bu's NMR carbon spectrum;

[0038] Fig.13 For C4-PDI-2N t Bu's H NMR spectrum;

[0039] Fig.14 For C4-PDI-2N t Bu's NMR carbon spectrum;

[0040] Fig.15 It is the matrix-assisted laser desorption / ionization time-of-flight mass spectrum of C4-PDI-2NH;

[0041] Fig.16 This is the H NMR spectrum of C4-PDI-2NH. DETAILED DESCRIPTION

[0042] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and more understandable, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments.

[0043] Example 1

[0044] In this embodiment, the R group is a tert-butyl dipyrrole-fused perylene tetracarboxylic dianhydride (PDA-2N t The preparation of Bu) is described as an example, and its structure is as follows:

[0045]

[0046] Step 1: Under argon protection, bis(tri-tert-butylphosphine)palladium(0), tert-butylamine, cyclohexyltetrachloroperylene diimide (Cy-PDI-4Cl), sodium tert-butoxide and toluene in a mass ratio of 1:2.56:3·82:3.76:196.1 were added to a Schlenk reaction bottle, and the mixture was stirred 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 mixture of water and dichloromethane in a volume ratio of 1:1 for extraction, repeat 3 times, and combine the organic phases;

[0048] Step 3: Dry the organic phase obtained in step 2 with anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure to recover the solvent to obtain mixture of

[0049] Step 4: Add the content obtained in step 3 A mixture of petroleum ether and dichloromethane in a volume ratio of 1: 1 was used as an eluent, and the mixture was separated by silica gel column chromatography. The product spots were collected and the solvent was recovered by distillation to obtain a yellow solid crude product with a yield of 85%;

[0050] Step 5: Recrystallize the crude product of step 4 with a mixed solvent of dichloromethane and methanol in a volume ratio of 1:10, and obtain the product by suction filtration and natural drying. ;

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

[0052] Step 7: Cool the reaction solution obtained in step 6 to room temperature, then add acetic acid to acidify, add a certain amount of a mixture of water and dichloromethane in a volume ratio of 1:1 to extract, 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 distill the filtrate under reduced pressure to recover the solvent to obtain mixture of

[0054] Step 9: Recrystallize the crude product of step 8 with a mixed solvent of dichloromethane and petroleum ether in a volume ratio of 1:10, and obtain the target product by suction filtration and natural drying. , with a yield of 72%.

[0055] Figure 1 The product is Cy-PDI-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu; Figure 2 The product is Cy-PDI-2N t Bu's H NMR spectrum: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 desorption / ionization time-of-flight mass spectrum 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 to a 15 mL storage bottle in sequence. Under argon atmosphere, the mixture was heated until the imidazole was dissolved and stirred sufficiently. After the reaction solution was cooled to room temperature, column chromatography was performed using dichloromethane as the eluent to obtain the compound , with a yield of 69%.

[0059] The reaction equation is as follows:

[0060]

[0061] Figure 5 The product is Ph-PDI-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu; Figure 6 The product is Ph-PDI-2N t Bu's H NMR spectrum: 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 4-aminopyridine and an appropriate amount of imidazole were added to a 15 mL storage bottle in sequence. Under argon atmosphere, the mixture was heated until the imidazole was dissolved and stirred thoroughly. After the reaction solution was cooled to room temperature, column chromatography was performed using dichloromethane:ethyl acetate (volume ratio, 1:1) as the eluent to obtain the compound , the yield is 60%.

[0065] The reaction equation is as follows:

[0066]

[0067] Figure 8 The product is Py-PDI-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu; Fig. 9 The product is Py-PDI-2N t Bu's H NMR spectrum: 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 3-aminopentane and an appropriate amount of imidazole were added to a 15 mL storage bottle in sequence. Under argon atmosphere, the mixture was heated until the imidazole was dissolved and stirred sufficiently. After the reaction solution was 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 is 72%.

[0071] The reaction equation is as follows:

[0072]

[0073] Fig.10 The product is C2-PDI-2N t Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of Bu; Fig.11 The product is C2-PDI-2N t Bu's H NMR spectrum: 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); Fig.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 5-aminononane and an appropriate amount of imidazole were added to a 15 mL storage bottle in sequence. Under argon atmosphere, the mixture was heated until the imidazole was dissolved and stirred thoroughly. After the reaction solution was 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] Fig.13 The product is C4-PDI-2N t Bu's H NMR spectrum: 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; Fig.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 C4-PDI-2N t Bu, 0.032 g aluminum chloride and 2 mL dichloromethane were added into a 15 mL pressure tube in sequence and stirred at room temperature until the raw materials reacted completely. 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] Fig.15Matrix-assisted laser desorption / ionization time-of-flight mass spectrum of the product C4-PDI-2NH; Fig.16 This is the hydrogen nuclear magnetic resonance 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 perylene tetracarboxylic dianhydride, characterized in that: The structural formula is as follows: ， Wherein, R is any group.

2. The method for preparing the dipyrrole-fused perylene tetracarboxylic dianhydride according to claim 1, characterized in that: The following steps are involved: 1) Using tetrachloroperylene imide and primary amine as raw materials, bis(tri-tert-butylphosphine)palladium(0) as catalyst, in the presence of sodium tert-butoxide, and toluene as solvent, PDI-2NR is obtained through Buchwald-Hartwig arylation reaction; 2) PDI-2NR is acidified with acetic acid in the presence of an inorganic strong base and alcohol as a solvent, and then extracted with an organic solvent to obtain the target product PDA-2NR.

3. The method for preparing a dipyrrole-fused perylene tetracarboxylic dianhydride according to claim 2, characterized in that: The mass ratio of bis(tri-tert-butylphosphine)palladium(0), primary amine, tetrachloroperylene diimide, sodium tert-butoxide and toluene is 1:(1~5):(2~5):(3~5):(100~200).

4. The method for preparing a dipyrrole-fused perylene tetracarboxylic dianhydride according to claim 2, characterized in that: The mass ratio of the inorganic strong base to the alcohol is (20~30):(200~300).

5. The method for preparing a dipyrrole-fused perylene tetracarboxylic dianhydride according to claim 2, characterized in that: In step 1), the reaction temperature is 100-120 °C and the reaction time is 3-48 h.

6. The method for preparing a dipyrrole-fused perylene tetracarboxylic dianhydride according to claim 2, characterized in that: In step 2), the reaction temperature is 100-120 °C and the reaction time is 3-24 h.

7. The use of a dipyrrole-fused perylene tetracarboxylic dianhydride according to claim 1, characterized in that: Used to prepare PDI-2NR molecules, the structure of the PDI-2NR molecules is as follows: ， The R1 structure is an aliphatic or aromatic group obtained by a condensation reaction between PDA-2NR and an aliphatic primary amine or an aromatic primary amine.

8. The use of a dipyrrole-fused perylene tetracarboxylic dianhydride as claimed in claim 7, characterized in that: PDA-2NR is reacted with aliphatic primary amine or aromatic primary amine in an imidazole solvent and under the protection of argon atmosphere to obtain PDI-2NR molecules.

9. The use of a dipyrrole-fused perylene tetracarboxylic dianhydride as claimed in claim 8, characterized in that: PDI-2NR molecules are hydrolyzed to obtain PDI-2NH.

Images