A fluorenevinylpyrrolopyrrole dione compound and its preparation method

Abstract

This invention relates to a fluorenevinylpyrrolopyrrole dione compound having the structure of general formula (I), wherein R represents a C1-C optionally substituted with a halogen. 12 Alkyl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl. This invention also relates to a method for preparing compounds of general formula (I). The preparation method of this invention is simple, efficient, and under mild conditions, and the fluorenevinylpyrrolopyrrole dione compounds of general formula (I) of this invention have great application prospects in the field of organic semiconductors.

Description

Technical Field

[0001] This invention belongs to the field of organic chemical synthesis technology, specifically relating to a fluorenevinylpyrrolopyrroledione 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 dione (DPP) materials are a widely used class of organic semiconductor materials. These materials have the characteristics of good photothermal stability, low band gap, wide absorption spectrum, and high fluorescence quantum yield, and can be widely used in organic field-effect transistors, organic solar cells, organic light-emitting diodes, and biological fluorescent probes.

[0004] Therefore, people have long hoped to obtain novel pyrrolopyrrole dione compounds through simple and efficient synthetic methods. Summary of the Invention

[0005] In view of this, in a first aspect, the present invention provides a fluorenevinylpyrrolopyrrole 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 C1-C 12 Alkyl or C1-C6 alkoxy C6-C 12Aryl C1-C6 alkyl, such as C1-C6 alkyl (e.g., n-butyl or 2-ethylhexyl), octyl or methoxyphenylmethyl.

[0011] In a second aspect, the present invention also provides a method for preparing fluorenevinylpyrrolopyrrole dione compounds of general formula (I), comprising the following steps:

[0012] (1) The compound of formula (a) is subjected to a temperature of 30-80°C and in the presence of piperidine.

[0013]

[0014] Where R is defined above,

[0015] The compound is reacted with 2-biphenylaldehyde in the first solvent to give the compound of formula (b);

[0016]

[0017] The first solvent is acetonitrile;

[0018] Where Ar represents 2-biphenyl;

[0019] (2) At a temperature of 5-80℃, the compound of formula (b) is reacted with an oxidizing agent in a second solvent to obtain the compound of general formula (I).

[0020] The oxidizing agent is selected from at least one of ferric chloride, [bis(trifluoroacetoxy)iodo]benzene (PIFA), and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ);

[0021] The second solvent is selected from dichloromethane, trichloromethane, carbon tetrachloride, tetrachloroethane, nitromethane, chlorobenzene, tetrahydrofuran, dioxane, and mixtures thereof, preferably dichloromethane, nitromethane, or mixtures thereof.

[0022] Thirdly, the present invention relates to the application of compounds of general formula (I) as organic semiconductor materials.

[0023] The beneficial effect of the present invention is that the fluorenevinylpyrrolopyrrole dione compound of general formula (I) of the present invention can be used as an organic semiconductor material and can be synthesized in a simple, efficient and mild manner. Attached Figure Description

[0024] Figure 1 The proton NMR spectrum of the DPP compound C4-Flu prepared in Example 1 of the present invention;

[0025] Figure 2 The proton NMR spectrum of the DPP compound C26-Flu prepared in Example 2 of the present invention;

[0026] Figure 3 Mass spectra of the DPP compound C4-Flu prepared in Example 1 of the present invention;

[0027] Figure 4 The mass spectra of the DPP compound C26-Flu prepared in Example 2 of the present invention. Detailed Implementation

[0028] In this invention, unless otherwise stated, all operations are performed at room temperature (25°C) and atmospheric pressure (101 kPa).

[0029] The inventors discovered during their research that, by using specific oxidizing agents, the fluorenevinylpyrrolopyrrole dione compound of general formula (I) of this invention can be obtained in relatively high yield. The prepared fluorenevinylpyrrolopyrrole dione compound of general formula (I) can be used as an organic semiconductor material.

[0030] Therefore, in a first aspect, the present invention provides a fluorenevinylpyrrolopyrroledione compound having the structure of general formula (I):

[0031]

[0032] Where R represents an alkyl, cycloalkyl, cycloalkylalkyl, aryl, or alkoxyarylalkyl group that is optionally substituted;

[0033] 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;

[0034] More preferably, R represents C1-C optionally substituted with halogen. 12 Alkyl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl;

[0035] More preferably, R represents C1-C 12 Alkyl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl, such as C1-C6 alkyl (e.g., n-butyl or 2-ethylhexyl), octyl or methoxyphenylmethyl.

[0036] 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.

[0037] In a second aspect, the present invention also provides a method for preparing fluorenevinylpyrrolopyrrole dione compounds of general formula (I), comprising the following steps:

[0038] (1) The compound of formula (a) is subjected to a temperature of 30-80°C and in the presence of piperidine.

[0039]

[0040] Where R is defined above,

[0041] The compound is reacted with 2-biphenylaldehyde in the first solvent to give the compound of formula (b);

[0042]

[0043] The first solvent is acetonitrile;

[0044] Where Ar represents 2-biphenyl;

[0045] (2) At a temperature of 5-80℃, the compound of formula (b) is reacted with an oxidizing agent in a second solvent to obtain the compound of general formula (I).

[0046] The oxidizing agent is selected from at least one of ferric chloride, [bis(trifluoroacetoxy)iodo]benzene (PIFA), and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ);

[0047] The second solvent is selected from dichloromethane, trichloromethane, carbon tetrachloride, tetrachloroethane, nitromethane, chlorobenzene, tetrahydrofuran, dioxane, and mixtures thereof, preferably dichloromethane, nitromethane, or mixtures thereof.

[0048] Preferably, in step (1), the amount of 2-biphenylaldehyde of the present 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).

[0049] Preferably, in step (1), 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).

[0050] Preferably, in steps (1) and (2), the reaction is carried out under an inert atmosphere, and the inert gas used may be nitrogen, argon, helium, or a mixture thereof.

[0051] Preferably, in step (2), the amount of the oxidizing agent of the present invention is 1-10 equivalents, more preferably 2-8 equivalents, most preferably 2.5-6 equivalents, and even more preferably 3-5 equivalents, based on the amount of the compound of formula (b).

[0052] Preferably, the oxidizing agent is selected from at least one of ferric chloride, [bis(trifluoroacetoxy)iodo]benzene (PIFA), and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ), with ferric chloride being preferred; optionally, the oxidizing agent is used in solution form. The inventors unexpectedly discovered that compounds of general formula (I) can be well prepared and obtained using the type of oxidizing agent defined in this invention, while compounds of general formula (I) are difficult to obtain or obtain in high yields using other oxidizing agents, including inorganic oxidizing agents such as potassium permanganate, hydrogen peroxide, and chromium trioxide, and organic oxidizing agents such as trifluoroacetic acid, azobisisobutyronitrile, and benzoyl peroxide. Therefore, for the technical solution of this invention, the oxidizing agent used in this invention is a specific oxidizing agent.

[0053] In a preferred embodiment of the invention, the oxidizing agent is added dropwise to a solution of the compound of formula (b) in the form of a solution. The content of the oxidizing agent in the oxidizing agent solution is (0.1-1.0 mmol) / mL solvent, preferably (0.15-0.8 mmol) / mL solvent, more preferably (0.2-0.5 mmol) / mL solvent. The solvent used here is the second solvent mentioned above, preferably nitromethane. The content of the compound of formula (b) in the solution of the compound of formula (b) is (0.001-0.5 mmol) / mL solvent, preferably (0.01-0.2 mmol) / mL solvent, more preferably (0.015-0.1 mmol) / mL solvent. The solvent used here is the second solvent mentioned above, preferably dichloromethane. It should be understood that the above contents refer to the contents before the two reactants are mixed. The oxidizing agent solution and the solution of the compound of formula (b) can use the same or different solvents.

[0054] Preferably, in the method of the present invention, in step (1), the reaction temperature can be 35-80°C, more preferably 40-65°C, and even more preferably 45-60°C; in step (2), the reaction temperature can be 8-60°C, more preferably 10-50°C, and even more preferably 12-45°C. It should be understood here that when the boiling point of the solvent used at room temperature and pressure is lower than the maximum value of the above-mentioned reaction temperature range, the upper limit of the reaction temperature is the boiling point temperature of the solvent used, which is well known to those skilled in the art.

[0055] Preferably, in the method of the present invention, in step (1), the reaction time can be 6-24 hours, preferably 8-18 hours, more preferably 10-15 hours; in step (2), the reaction time can be 4-24 hours, preferably 5-18 hours, more preferably 8-15 hours, and the reaction process of the present invention can be monitored by thin-layer chromatography.

[0056] After the reaction of the present invention is completed, separation can be carried out by conventional separation methods, such as column chromatography. The appropriate eluent can be determined by experiment. Preferably, gradient elution is carried out in step (1) using n-hexane and dichloromethane, and gradient elution is carried out in step (2) using n-hexane, dichloromethane and ethyl acetate.

[0057] 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.

[0058] By using the method of the present invention, the fluorenevinylpyrrolopyrrole dione compound of general formula (I) of the present invention can be obtained in a simple, efficient and mild manner.

[0059] Thirdly, the present invention also relates to the use of fluorenevinylpyrrolopyrrole dione compounds of general formula (I) as organic semiconductor materials.

[0060] In this invention, the term "organic semiconductor material" refers to organic materials that possess semiconductor properties. The application of pyrrolopyrrole dione compounds in the field of organic semiconductors is well known to those skilled in the art and will not be elaborated upon herein.

[0061] 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.

[0062] 1. Preparation Examples

[0063] Example 1

[0064] Step (1)

[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] Step (2)

[0070] C4-2DP-DPP (604.3 mg, 1 mmol) and dichloromethane (50 mL) were added to a 100 mL round-bottom flask, followed by the dropwise addition of 4 eq FeCl3 (dissolved in 20 mL nitromethane). The reaction mixture was stirred at room temperature for 12 hours. The reaction progress was monitored by thin-layer chromatography (TLC). The reactants were washed with 200 mL of water. The organic phase was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure. After cooling to room temperature, the product was washed with water, dried, and concentrated. The crude product was purified by column chromatography on silica gel (gradient elution: from n-hexane, dichloromethane to ethyl acetate) to give C4-Flu (53% yield).

[0071]

[0072] 1H NMR (400MHz, CDCl3, 298K): δ = 7.78 -7.61(m,8H),7.40(tt,J=7.4,1.3Hz,4H),7.30(td,J=7.5,1.1Hz,2H),7.25-7.19(m,2H),7.14 (s,2H),3.73(t,J=7.2Hz,4H),1.62(p,J=7.3Hz,4H),1.38-1.27(m,4H),0.87(t,J=7.3Hz,6H);

[0073] MS(MALDI-TOF)m / z calcd(%)for C 42 H 36 N2O2:600.180,found[M+H]+:601.214,[M+Na] + :623.197.

[0074] Example 2

[0075] Step (1)

[0076] 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.

[0077]

[0078] 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=15.9Hz,2H),3.47-3.33(m,4H),1.50(s,2H),1.24(q,J=10.8,7.0Hz,16H),0.88(dt,J=

[0079] 15.0, 7.1 Hz, 12 Hz);

[0080] MS(MALDI-TOF)m / z calcd(%)for C 50 H 56N2O2: 716.326, found [M+H] + :717.325.

[0081] Step (2)

[0082] In a 100 mL round-bottom flask, C26-2DP-DPP (716.3 mg, 1 mmol) and dichloromethane (50 mL) were added, followed by the dropwise addition of 4 eq FeCl3 (dissolved in 20 mL nitromethane). The reaction mixture was stirred at room temperature for 12 hours. The reaction progress was monitored by thin-layer chromatography (TLC). The reactants were washed with 200 mL of water. The organic phase was separated, dried over Na2SO4, filtered, and concentrated under reduced pressure. After cooling to room temperature, the product was washed with water, dried, and concentrated. The crude product was purified by column chromatography on silica gel (gradient elution: from n-hexane, dichloromethane to ethyl acetate) to give C26-Flu (55% yield).

[0083]

[0084] 1 H NMR (400MHz, CDCl3, 298K): δ=7.78-7.61(m,8H),7.40(tt,J=7.4,1.3Hz,4H),7.30(td,J=7.5,1.1Hz,2H),7.25– 7.19(m,2H),7.14(s,2H),3.73(t,J=7.2Hz,4H),1.62(p,J=7.3Hz,4H),1.38–1.27(m,4H),0.87(t,J=7.3Hz,6H);

[0085] MS(MALDI-TOF)m / z calcd(%)for C 50 H 54 N2O2:712.281,found[M+H]+:713.296,[M+Na] + :735.283.

[0086] Comparative Example 1

[0087] The steps of Example 1 were repeated, except that the oxidizing agent was trifluoroacetic acid, and the yield was less than 5%.

[0088] Comparative Example 2

[0089] The steps of Example 1 were repeated, except that the oxidizing agent was potassium permanganate, and no reaction products were detected after the reaction.

Claims

1. A method for preparing compounds of general formula (I), Where R represents C1-C 12 alkyl, The method includes the following steps: (1) The compound of formula (a) is subjected to a temperature of 30-80°C and in the presence of piperidine. The compound is reacted with 2-biphenylaldehyde in the first solvent to give the compound of formula (b); The first solvent is acetonitrile; Where Ar represents 2-biphenyl; (2) At a temperature of 5-80℃, the compound of formula (b) is reacted with an oxidizing agent in a second solvent to obtain the compound of general formula (I). The oxidizing agent is selected from ferric chloride. The second solvent is selected from dichloromethane, trichloromethane, carbon tetrachloride, tetrachloroethane, nitromethane, chlorobenzene, tetrahydrofuran, dioxane, and mixtures thereof.

2. The method according to claim 1, wherein R represents n-butyl or 2-ethylhexyl.

3. The method according to claim 1, wherein the second solvent is selected from dichloromethane, nitromethane, or mixtures thereof.

4. The method according to claim 1, wherein in step (2), the amount of the oxidizing agent is 1-10 equivalents, based on the amount of the compound of formula (b).

5. The method according to claim 4, wherein in step (2), the amount of the oxidizing agent is 2-8 equivalents, based on the amount of the compound of formula (b).

6. The method according to claim 5, wherein in step (2), the amount of the oxidizing agent is 4-6 equivalents, based on the amount of the compound of formula (b).

7. The method according to claim 1 or 2, wherein in step (2), the reaction temperature is 10-50°C.

8. The method according to claim 7, wherein in step (2), the reaction temperature is 12-45°C.

9. The method according to claim 1 or 2, wherein in step (2), the reaction time is 6-24 hours.

10. The method according to claim 9, wherein in step (2), the reaction time is 8-18 hours.

11. The method according to claim 10, wherein in step (2), the reaction time is 10-15 hours.

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