Biphenyl vinyl diketopyrrolopyrrole compound and preparation method thereof

Abstract

The invention relates to a biphenyl vinyl diketopyrrolopyrrole compound and a preparation method of the biphenyl vinyl diketopyrrolopyrrole compound. The biphenyl vinyl diketopyrrolopyrrole compound has a structure as shown in a general formula (I), wherein R represents C1-C12 alkyl or C1-C6 alkoxy, C6-C12 aryl and C1-C6 alkyl which are optionally substituted by halogen; and Ar represents a biphenyl group. In addition, the preparation method provided by the invention has relatively high yield and mild conditions. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a diphenyl vinyl pyrrolopyrrole diketo compound and a preparation method thereof. Background Art

[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 processing, and good compatibility with plastic substrates, their research and development is of great strategic significance for promoting the development of information, energy, medical care, national defense and other fields.

[0003] Materials such as diketopyrrolopyrrole (DPP) are a type of organic semiconductor material that is currently widely used. These compounds have the characteristics of good photothermal stability, low band gap, wide absorption spectrum range 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. However, the synthesis method of materials and the development of new materials still face some problems and challenges.

[0004] To this end, people have been trying to synthesize DPP compounds with different structures and properties and improve their synthesis methods through various means 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 diphenyl vinyl pyrrolopyrrole diketo compound having a structure of general formula (I):

[0006]

[0007] wherein R represents optionally substituted alkyl, cycloalkyl, cycloalkylalkyl, aryl or alkoxyarylalkyl;

[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 group consisting of cyano, halogen, hydroxy, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio and C6-C 12 Aryl;

[0009] Further preferably, R represents a C1-C 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 a biphenyl group, such as 2-biphenyl, 3-biphenyl or 4-biphenyl.

[0012] In a second aspect, 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 as defined above,

[0015] The biphenyl carboxaldehyde is 2-biphenyl carboxaldehyde, 3-biphenyl carboxaldehyde or 4-biphenyl carboxaldehyde.

[0016] In a third aspect, the compound of the general formula (I) of the present invention is used as a semiconductor material.

[0017] The beneficial effects of the present invention are that the compound of the general formula (I) of the present invention has application prospects in the field of organic semiconductors and the preparation method thereof has a high yield (more than 80%) and mild conditions. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

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

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

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

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

[0025] Figure 8This is the mass spectrum of the compound C26-2DP-DPP of the present invention prepared in Example 4. DETAILED DESCRIPTION

[0026] In the present invention, unless otherwise stated, all operations are carried out at room temperature (25° C.) and normal pressure (101 KPa).

[0027] The inventors have found in their research that by selecting a specific reaction substrate, the compound of the general formula (I) of the present invention can be obtained in a relatively high yield. The prepared compound of the general formula (I) of the present invention has good photoelectric properties and is suitable for use in organic photoelectric fields such as organic field effect transistors and solar cells.

[0028] Therefore, in a first aspect, the present invention provides a diphenyl vinyl pyrrolopyrrole diketo compound having a structure of general formula (I):

[0029]

[0030] wherein R represents optionally substituted alkyl, cycloalkyl, cycloalkylalkyl, aryl or alkoxyarylalkyl;

[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 group consisting of cyano, halogen, hydroxy, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio and C6-C 12 Aryl;

[0032] Further preferably, R represents a C1-C 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 a biphenyl group, such as 2-biphenyl, 3-biphenyl or 4-biphenyl.

[0035] In a second aspect, 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 as defined above,

[0038] The biphenyl carboxaldehyde is selected from 2-biphenyl carboxaldehyde, 3-biphenyl carboxaldehyde and 4-biphenyl carboxaldehyde.

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

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

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

[0043] Preferably, the reaction temperature may be 35-80°C, preferably 40-65°C, more preferably 45-60°C.

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

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

[0046] 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, and preferably n-hexane, dichloromethane, ethyl acetate or a mixture thereof is used for gradient elution.

[0047] In the present invention, the compound of formula (a) is a diketopyrrolopyrrole compound, and its preparation method is known. For example, it can be synthesized by referring to the method described in Chem. Mater. 2024, 36, 4215-4225, or it can be directly purchased.

[0048] By using the process of the present invention, the biphenyl vinyl pyrrolopyrrole diketo compounds of the present invention can be formed with unexpectedly high yields.

[0049] In a third aspect, the present invention relates to the use of the compound of general formula (I) as an organic semiconductor material.

[0050] In the present invention, the term "organic semiconductor material" refers to an organic material having 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 described in detail herein.

[0051] The various embodiments described herein can be combined with each other. Combinations that violate the laws of nature and combinations that are excluded by a person skilled in the art based on his / her expertise are not included.

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

[0053] 1. Preparation Example

[0054] Example 1

[0055] Under nitrogen atmosphere, a mixture of compound C4-DPP (138.2 mg, 0.5 mmol), 4-biphenylcarboxaldehyde (1.1 mmol) and piperidine (1 mmol) was dissolved in 4 mL of acetonitrile and stirred at 55 ° C for 13 hours. The progress of the reaction 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 with 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 obtain C4-4DP-DPP with a yield of 84%.

[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 nitrogen atmosphere, a mixture of compound C26-DPP (194.3 mg, 0.5 mmol), 4-biphenylcarboxaldehyde (1.1 mmol) and piperidine (1 mmol) was dissolved in 4 mL of acetonitrile and stirred at 55 ° C for 13 hours. The progress of the reaction 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 obtain C26-4DP-DPP with a yield of 87%.

[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 nitrogen atmosphere, a mixture of compound C4-DPP (138.2 mg, 0.5 mmol), 2-biphenylcarboxaldehyde (1.1 mmol) and piperidine (1 mmol) was dissolved in 4 mL of acetonitrile and stirred at 55 ° C for 13 hours. The progress of the reaction 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 with 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 obtain C4-2DP-DPP with a yield of 82%.

[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 nitrogen atmosphere, a mixture of compound C26-DPP (194.3 mg, 0.5 mmol), 2-biphenylcarboxaldehyde (1.1 mmol) and piperidine (1 mmol) was dissolved in 4 mL of acetonitrile and stirred at 55 ° C for 13 hours. The progress of the reaction 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 with 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 obtain C26-2DP-DPP with a yield of 86%.

[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 biphenyl vinyl pyrrolopyrrole diketo compound, characterized in that: It has the structure of general formula (I): in R represents a C1-C 12 Alkyl or C1-C6 alkoxy C6-C 12 Aryl C1-C6 alkyl; Ar represents a biphenyl group.

2. The compound according to claim 1, characterized in that R represents n-butyl or 2-ethylhexyl.

3. A method for preparing a compound of general formula (I), comprising the steps of: reacting a compound of formula (a) with biphenylaldehyde in a solvent at a temperature of 30-80°C and in the presence of piperidine; wherein R is as defined in claim 1 or 2, The biphenyl carboxaldehyde is selected from 2-biphenyl carboxaldehyde, 3-biphenyl carboxaldehyde and 4-biphenyl carboxaldehyde.

4. The method according to claim 3, characterized in that The amount of biphenyl carboxaldehyde used is 2-3 equivalents, preferably 2-2.5 equivalents, and most preferably 2.2-2.5 equivalents, based on the amount of the compound of formula (a).

5. The method according to claim 3 or 4, characterized in that: The amount of piperidine used is 2-3 equivalents, preferably 2-2.5 equivalents, most preferably 2.2-2.5 equivalents, based on the amount of the compound of formula (a).

6. The method according to claim 3 or 4, characterized in that: The solvent is acetonitrile.

7. The method according to claim 3 or 4, characterized in that: The reaction temperature is 40-65°C, more preferably 45-60°C.

8. The method according to claim 3 or 4, characterized in that: The reaction time is 6-24 hours, preferably 8-18 hours, more preferably 10-15 hours.

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