A biphenyl ethenyl pyrrolopyrylium compound and a method for preparing the same

Abstract

The present application relates to a kind of biphenyl ethenyl pyrrolopyrrole diketone compounds and preparation method thereof.The biphenyl ethenyl pyrrolopyrrole diketone compound has the structure of general formula (I), wherein R represents C1-C 12 Alkyl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl;Ar represents biphenyl.In addition, the preparation method of the present application has high yield and mild conditions.

Description

Technical Field

[0001] This invention belongs to the field of organic chemical synthesis technology, specifically relating to a biphenylvinylpyrrolopyrrole dione compound and its preparation method. Background Technology

[0002] Due to the low cost, light weight, and easily tunable optoelectronic properties of organic semiconductor materials, as well as their abundant material sources, solution-processable nature, and good compatibility with plastic substrates, their research and development is of great strategic significance for promoting the development of fields such as information, energy, medicine, and defense.

[0003] Pyrrolopyrrole diones (DPPs) and similar materials are currently a widely used class of organic semiconductor materials. These compounds possess excellent photothermal stability, low band gaps, broad absorption spectral ranges, and high fluorescence quantum yields, making them suitable for applications in organic field-effect transistors, organic solar cells, organic light-emitting diodes, and bioluminescent probes. However, the synthesis methods and the development of new materials still face some challenges and problems.

[0004] Therefore, people have been trying to synthesize DPP-type compounds with different structures and properties and improve their synthesis methods through various means in order to solve the above-mentioned technical problems and broaden their applications. Summary of the Invention

[0005] In view of this, in a first aspect, the present invention provides a biphenylvinylpyrrolopyrrole dione compound having the structure of general formula (I):

[0006]

[0007] Where R represents an alkyl, cycloalkyl, cycloalkylalkyl, aryl, or alkoxyarylalkyl group that is optionally substituted;

[0008] Preferably, R represents C1-C 12 Alkyl, C3-C 12 cycloalkyl, C6-C 12 Aryl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl; optionally, the above substituents may be further substituted by substituents selected from the following: cyano, halogen, hydroxy, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, and C6-C6 alkyl. 12 Aryl;

[0009] More preferably, R represents C1-C optionally substituted with halogen. 12 Alkyl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl;

[0010] More preferably, R represents butyl or 2-ethylhexyl;

[0011] Ar represents biphenyl, such as 2-biphenyl, 3-biphenyl, or 4-biphenyl.

[0012] Secondly, the present invention also provides a method for preparing a compound of general formula (I), comprising the following steps: reacting a compound of formula (a) with biphenylaldehyde in a solvent at a temperature of 30-80°C and in the presence of piperidine.

[0013]

[0014] Where R is defined above,

[0015] The biphenyl formaldehyde mentioned therein is 2-biphenyl formaldehyde, 3-biphenyl formaldehyde, or 4-biphenyl formaldehyde.

[0016] Thirdly, the application of the compound of general formula (I) of the present invention as a semiconductor material.

[0017] The beneficial effects of the present invention are that the compounds of general formula (I) of the present invention have application prospects in the field of organic semiconductors and their preparation method has a high yield (more than 80%) and mild conditions. Attached Figure Description

[0018] Figure 1 The proton NMR spectrum of the compound C4-4DP-DPP of the present invention prepared in Example 1;

[0019] Figure 2 The proton NMR spectrum of compound C26-4DP-DPP of the present invention prepared in Example 2;

[0020] Figure 3 The proton NMR spectrum of the compound C4-2DP-DPP of the present invention prepared in Example 3;

[0021] Figure 4 The proton NMR spectrum of compound C26-2DP-DPP of the present invention prepared in Example 4;

[0022] Figure 5 Mass spectra of the compound C4-4DP-DPP of the present invention prepared in Example 1;

[0023] Figure 6 Mass spectra of the compound C26-4DP-DPP of the present invention prepared in Example 2;

[0024] Figure 7 Mass spectra of the compound C4-2DP-DPP of the present invention prepared in Example 3;

[0025] Figure 8The mass spectra of the compound C26-2DP-DPP of the present invention prepared in Example 4. Detailed Implementation

[0026] In this invention, unless otherwise stated, all operations are performed at room temperature (25°C) and atmospheric pressure (101 kPa).

[0027] The inventors discovered in their research that by selecting specific reaction substrates, compounds of general formula (I) of this invention can be obtained in high yields. The prepared compounds of general formula (I) of this invention exhibit excellent photoelectric properties and are suitable for application in organic optoelectronic fields such as organic field-effect transistors and solar cells.

[0028] Therefore, in a first aspect, the present invention provides a biphenylvinylpyrrolopyrrole dione compound having the structure of general formula (I):

[0029]

[0030] Where R represents an alkyl, cycloalkyl, cycloalkylalkyl, aryl, or alkoxyarylalkyl group that is optionally substituted;

[0031] Preferably, R represents C1-C 12 Alkyl, C3-C 12 cycloalkyl, C6-C 12 Aryl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl; optionally, the above substituents may be further substituted by substituents selected from the following: cyano, halogen, hydroxy, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, and C6-C6 alkyl. 12 Aryl;

[0032] More preferably, R represents C1-C optionally substituted with halogen. 12 Alkyl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl;

[0033] More preferably, R represents n-butyl or 2-ethylhexyl;

[0034] Ar represents biphenyl, such as 2-biphenyl, 3-biphenyl, or 4-biphenyl.

[0035] Secondly, the present invention also provides a method for preparing a compound of general formula (I), comprising the following steps: reacting a compound of formula (a) with biphenylaldehyde in a solvent at a temperature of 30-80°C and in the presence of piperidine.

[0036]

[0037] Where R is defined above,

[0038] The biphenylaldehyde mentioned therein is selected from 2-biphenylaldehyde, 3-biphenylaldehyde and 4-biphenylaldehyde.

[0039] Preferably, the amount of biphenyl formaldehyde used in this invention is 2-3 equivalents, more preferably 2-2.5 equivalents, and most preferably 2.2-2.5 equivalents, based on the amount of the compound of formula (a).

[0040] Preferably, the amount of piperidine used is 2-3 equivalents, more preferably 2-2.5 equivalents, and most preferably 2.2-2.5 equivalents, based on the amount of the compound of formula (a).

[0041] Preferably, the biphenylaldehyde is selected from 2-biphenylaldehyde and 4-biphenylaldehyde.

[0042] In this invention, the solvent may be an organic solvent that is inert to the reaction of this invention, preferably acetonitrile.

[0043] Preferably, the reaction temperature is 35-80℃, more preferably 40-65℃, and even more preferably 45-60℃.

[0044] Preferably, the reaction of the present invention is carried out under an inert atmosphere, and the inert gas used may be nitrogen, argon, helium, or a mixture thereof.

[0045] Preferably, the reaction time of the present invention can be 6-24 hours, more preferably 8-18 hours, and even more preferably 10-15 hours. The reaction process of the present invention can be monitored by thin-layer chromatography.

[0046] After the reaction of the present invention is completed, separation can be performed by conventional separation methods, such as column chromatography. The appropriate eluent can be determined by experiment, and gradient elution is preferably performed using n-hexane, dichloromethane, ethyl acetate or a mixture thereof.

[0047] In this invention, the compound of formula (a) is a pyrrolopyrrole dione compound, the preparation method of which is known, for example, it can be synthesized with reference to the method described in Chem. Mater. 2024, 36, 4215-4225, or it can be purchased directly.

[0048] By using the method of the present invention, the biphenylvinylpyrrolopyrrole dione compounds of the present invention can be formed with unexpectedly high yields.

[0049] Thirdly, the present invention relates to the application of compounds of general formula (I) as organic semiconductor materials.

[0050] In this invention, the term "organic semiconductor material" refers to organic materials that possess semiconductor properties. The application of DPP compounds in the field of organic semiconductors is well-known to those skilled in the art and will not be elaborated upon herein.

[0051] The various implementation schemes described herein can be combined with each other. This excludes combinations that violate the laws of nature and combinations that are excluded by a person skilled in the art based on his / her professional knowledge.

[0052] The present invention will be described in more detail below with reference to the following embodiments. These embodiments disclosed below are for illustrative purposes only and are not intended to limit the invention. Those skilled in the art can make various modifications, additions, and substitutions to the embodiments of the invention without departing from the scope and spirit of the invention.

[0053] I. Preparation Examples

[0054] Example 1

[0055] Under a nitrogen atmosphere, a mixture of compound C4-DPP (138.2 mg, 0.5 mmol), 4-biphenylcarbaldehyde (1.1 mmol), and piperidine (1 mmol) was dissolved in 4 mL of acetonitrile and stirred at 55 °C for 13 h. The reaction progress was monitored by thin-layer chromatography (TLC). After completion, the reaction mixture was diluted with 15 mL of dichloromethane and washed with 15 mL of water. The organic phase was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (gradient elution: from n-hexane to dichloromethane) to give C4-4DP-DPP in 84% yield.

[0056]

[0057] 1 H NMR (400MHz, CDCl3, 298K) δ = 8.95 (d, J = 15.8Hz, 2H), 7.75 (d, J = 8.4Hz, 4H), 7.71-7.60 (m, 8H), 7.47 (t, J = 7.7Hz, 4H), 7.38 (t, J = 7. 2Hz,2H),6.92(d,J=15.9Hz,2H),3.87(t,J=7.4Hz,4H),1.72(p,J=7.5Hz4H),1.47(dt,J=14.7,7.4Hz,4H),1.01(t,J=7.3Hz,6H);

[0058] MS(MALDI-TOF)m / z calcd(%)for C 42 H 40N2O2: 604.252, found [M+H] + :605.255.

[0059] Example 2

[0060] Under a nitrogen atmosphere, a mixture of compound C26-DPP (194.3 mg, 0.5 mmol), 4-biphenylcarbaldehyde (1.1 mmol), and piperidine (1 mmol) was dissolved in 4 mL of acetonitrile and stirred at 55 °C for 13 h. The reaction progress was monitored by thin-layer chromatography (TLC). After completion, the reaction mixture was diluted with 15 mL of dichloromethane and washed with 15 mL of water. The organic phase was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (gradient elution: from n-hexane to dichloromethane) to give C26-4DP-DPP in 87% yield.

[0061]

[0062] 1 H NMR (400MHz, CDCl3, 298K) δ = 8.93 (d, J = 15.8Hz, 2H), 7.73 (d, J = 8.2Hz, 4H), 7.69-7.61 (m, 8H), 7.47 (t, J = 7.6Hz, 4H), 7.38 ( t,J=7.3Hz,2H),6.94(d,J=15.8Hz,2H),3.83-3.69(m,4H),1.78(s,2H),1.52-1.25(m,16H),0.95(dt,J=22.6,7.2Hz,12H);

[0063] MS(MALDI-TOF)m / z calcd(%)for C 50 H 56 N₂O₂: 716.335, found [M+H] + :717.343.

[0064] Example 3

[0065] Under a nitrogen atmosphere, a mixture of compound C4-DPP (138.2 mg, 0.5 mmol), 2-biphenylcarbaldehyde (1.1 mmol), and piperidine (1 mmol) was dissolved in 4 mL of acetonitrile and stirred at 55 °C for 13 h. The reaction progress was monitored by thin-layer chromatography (TLC). After completion, the reaction mixture was diluted with 15 mL of dichloromethane and washed with 15 mL of water. The organic phase was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (gradient elution: from n-hexane to dichloromethane) to give C4-2DP-DPP in 82% yield.

[0066]

[0067] 1 H NMR (400MHz, CDCl3, 298K) δ = 8.68 (d, J = 16.0Hz, 2H), 7.68 (dd, J = 5.5, 3.7Hz, 2H), 7.50 -7.29(m,16H),6.42(d,J=16.0Hz,2H),3.45(t,J=7.3Hz,4H),1.37(dt,J=14.5,7.2Hz,4H),1.24(dq,J=14.4,7.2Hz,4H),0.90(t,J=7.2Hz,6H);

[0068] MS(MALDI-TOF)m / z calcd(%)for C 42 H 40 N2O2: 604.192, found [M+H] + :605.255.

[0069] Example 4

[0070] Under a nitrogen atmosphere, a mixture of compound C26-DPP (194.3 mg, 0.5 mmol), 2-biphenylcarbaldehyde (1.1 mmol), and piperidine (1 mmol) was dissolved in 4 mL of acetonitrile and stirred at 55 °C for 13 h. The reaction progress was monitored by thin-layer chromatography (TLC). After completion, the reaction mixture was diluted with 15 mL of dichloromethane and washed with 15 mL of water. The organic phase was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (gradient elution: from n-hexane to dichloromethane) to give C26-2DP-DPP in 86% yield.

[0071]

[0072] 1 H NMR (400MHz, CDCl3, 298K) δ = 8.72 (d, J = 15.9Hz, 2H), 7.71-7.64 (m, 2H), 7.51-7.27 (m, 16H), 6.53 (d, J = 15.9 Hz,2H),3.47-3.33(m,4H),1.50(s,2H),1.24(q,J=10.8,7.0 Hz,16H),0.88(dt,J=15.0,7.1 Hz,12H);

[0073] MS(MALDI-TOF)m / z calcd(%)for C 50 H56 N2O2:716.326,found[M+H] + :717.325。

Claims

1. A method for preparing compounds of general formula (I), Equation (I) in, R represents n-butyl or 2-ethylhexyl; Ar represents 2-biphenyl, 3-biphenyl, or 4-biphenyl; the method includes the step of reacting a compound of formula (a) with biphenylformaldehyde in acetonitrile at a temperature of 30-80°C and in the presence of piperidine. Equation (a), The biphenylaldehyde mentioned therein is selected from 2-biphenylaldehyde, 3-biphenylaldehyde and 4-biphenylaldehyde.

2. The method according to claim 1, characterized in that, The amount of biphenyl formaldehyde used is 2-3 equivalents, based on the amount of the compound of formula (a).

3. The method according to claim 2, characterized in that, The amount of biphenyl formaldehyde used is 2-2.5 equivalents, based on the amount of the compound of formula (a).

4. The method according to claim 3, characterized in that, The amount of biphenylaldehyde used is 2.2-2.5 equivalents, based on the amount of the compound of formula (a).

5. The method according to claim 1, characterized in that, The amount of piperidine used is 2-3 equivalents, based on the amount of the compound of formula (a).

6. The method according to claim 5, characterized in that, The amount of piperidine used is 2-2.5 equivalents, based on the amount of the compound of formula (a).

7. The method according to claim 6, characterized in that, The amount of piperidine used is 2.2-2.5 equivalents, based on the amount of the compound of formula (a).

8. The method according to claim 1, characterized in that, The reaction temperature is 40-65℃.

9. The method according to claim 8, characterized in that, The reaction temperature is 45-60℃.

10. The method according to claim 1, characterized in that, The reaction time is 6-24 hours.

11. The method according to claim 10, characterized in that, The reaction time is 8-18 hours.

12. The method according to claim 11, characterized in that, The reaction time is 10-15 hours.

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