CN112707897A - Thiophene allyl ethylene dicyan structure compound and preparation method thereof - Google Patents
Thiophene allyl ethylene dicyan structure compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thiophene allyl chloride dicyan structure compound and a preparation method thereof, wherein the structural formula is as follows:
the thiophene allyl ethyl dicyan structure compound is obtained through multi-step Suzuki coupling and condensation reaction, and has larger ultraviolet-visible absorption wavelength due to a larger conjugated system. The malononitrile unit in the compound is easy to combine with an adjacent electron donor to form a weak intermolecular hydrogen bond, which is beneficial to stabilizing the excited state energy of molecules, so that the malononitrile unit has stronger aggregation state fluorescence. Different electronic structure units are introduced into modifiable structural sites in the molecular mother-son carbazole structure, so that the electronic structure of the compound is adjusted, and molecules with yellow to red fluorescence are obtained. Preparation method of thiophene allyl ethyl dicyan structure compound with long-wavelength aggregation-induced emission effectSimple and can realize the adjustment of different wavelengths. Has application prospect in the aspects of explosive identification, biomolecule imaging, photodynamic cancer treatment and organic electronic luminescent materials.
Description
Technical Field
The invention relates to the technical field of fluorescent molecular material preparation, in particular to a thiophene allyl ethyl dicyan structure compound and a preparation method thereof.
Background art:
at present, the mechanism of aggregation-induced emission (AIE) is gradually recognized, and a variety of molecules with AIE properties are designed and synthesized, and many molecules are used in the application field. Compared with the traditional fluorescent molecules, the compound with AIE activity usually has stronger fluorescence in a solid state and an aggregation state, which is also the main reason that AIE has practical application value. The AIE molecules studied and most used in the market are also mainly tetraphenylethylene and related derivatives. The tetraphenylethylene molecule is mainly composed of carbon and hydrogen-containing atoms, and its bulk fluorescence is blue. To obtain AIE molecules with longer wavelengths such as yellow, orange and red fluorescence, the molecules must be designed by continually extending the conjugated system of the molecule. However, derivatization of tetraphenylethylene is often challenging, and the obtainment of tetraphenylethylene-related halides is often achieved by severe reaction conditions, such as the use of n-butyllithium. The use of fluorescent molecules in the traditional sense to construct molecules with AIE activity is often challenging because the extension of the conjugated system of molecules often leads to packing structures between molecules that tend to be close packed and the fluorescence of the molecules will be quenched.
Disclosure of Invention
The invention aims to provide a thiophene allyl ethyl dicyan structure compound and a preparation method thereof, and aims to overcome the defect that fluorescence quenching is easily caused by prolonging of a molecular conjugated system of AIE activity in the prior art.
The technical solution of the present invention will now be described in detail according to the following aspects:
in a first aspect, a thiophene allyl chloride structural compound is provided, which has the following structure:
wherein, the intermediate R1And R2Including one or more of the following structures:
in a second aspect, a method for preparing a thiophene allyl ethyl dicyan structure compound is provided, which comprises the following steps:
3-bromine-carbazole and halogenated aromatic ring or halogenated aromatic heterocyclic compound are subjected to carbon-nitrogen coupling reaction under the action of cuprous iodide to obtain a 3-bromine-nitrogen-aromatic ring or aromatic heterocyclic carbazole compound;
coupling reaction of the obtained 3-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole and bis-pinacol borate with potassium acetate and 1,4 dioxane under the action of a palladium catalyst to obtain a 3-pinacol borate-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
obtaining a synthetic compound of 3-thiophenecarboxaldehyde-nitrogen aromatic ring or aromatic heterocyclic carbazole by reacting the obtained 3-pinacol borate-nitrogen aromatic ring or aromatic heterocyclic carbazole with 5-bromothiophene-2-formaldehyde under the action of palladium catalysis;
carrying out bromination reaction on the obtained 3-thiophenecarboxaldehyde-nitrogen aromatic ring or aromatic heterocyclic carbazole and bromosuccinimide (NBS) to obtain a 3-thiophenecarboxaldehyde-6-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
obtaining the 3-thiophenecarboxaldehyde-6-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole and 2-thiopheneboronic acid under the action of palladium catalysis to obtain a 3-thiophenecarboxaldehyde-6-thiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
carrying out bromination reaction on the obtained 3-thiophenecarboxaldehyde-6-thiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole and bromosuccinimide (NBS) to obtain a 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
the obtained 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole and corresponding thiopheneboronic acid are subjected to palladium catalysis to obtain a 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
reacting the obtained 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole with dicyano in an organic solution, and then cooling, crystallizing, washing and drying to obtain the thiophene allyl cyanide structure compound.
In combination with the second aspect, the palladium-catalyzed reaction is:
reacting in an organic solvent under the action of potassium carbonate and a palladium catalyst;
wherein the palladium catalyst comprises any one of tetrakis (triphenylphosphine) palladium and ferrocene palladium dichloride.
In combination with the second aspect, the organic solvent comprises a combination of one or more of tetrahydrofuran, toluene, DMF, water, or 1, 4-dioxane.
In combination with the second aspect, the bromination reaction includes any one of a thiophene group reaction and a carbazole group reaction.
With reference to the second aspect, the method for reacting the obtained 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or heteroaromatic carbazole with dicyano in an organic solution comprises:
reacting the obtained 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole with dicyan under the action of piperidine in acetonitrile, chloroform or a mixture of the acetonitrile and the chloroform.
In combination with the second aspect, the halogen in the halogenated aromatic ring or halogenated aromatic heterocyclic compound is one or more of fluorine, chlorine, bromine, and iodine.
The invention has the advantages that: the thiophene allyl ethylene dicyan structure compound and the preparation method thereof have the advantages of simple synthesis method, mild reaction conditions and no need of using a violent synthesis method to realize synthesis; the synthesized thiophene ethylene propylene dicyan structure compound has strong long-wavelength solid fluorescence.
Drawings
FIG. 1 is a schematic diagram of a preparation process of 3-thiophenecarbonitrile-6-bithiophene-azaarylphenylcarbazole in the present invention.
FIG. 2 is a schematic diagram of nuclear magnetic resonance hydrogen spectra of an intermediate 3-thiophenecarboxaldehyde-6-bromothiophene-azaarylcarbazole prepared in example 1 of the present invention.
FIG. 3 is a schematic diagram of nuclear magnetic resonance carbon spectrum of the intermediate 3-thiophenecarboxaldehyde-6-bromothiophene-azaarylcarbazole prepared in example 1 of the present invention.
FIG. 4 is a schematic diagram of nuclear magnetic resonance hydrogen spectra of an intermediate 3-thiophenecarboxaldehyde-6-bithiophene-azaarylphenylcarbazole prepared in example 2 of the present invention.
FIG. 5 is a schematic diagram of nuclear magnetic resonance carbon spectrum of the intermediate 3-thiophenecarboxaldehyde-6-bithiophene-azaarylphenylcarbazole prepared in example 2 of the present invention.
FIG. 6 is a schematic diagram of a hydrogen nuclear magnetic resonance spectrum of 3-thiophenecarbonitrile-6-bithiophene-azaarylcarbazole prepared in example 3 of the present invention.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
A thiophene ethylene propylene dicyan structure compound is characterized in that the compound has the following structure:
wherein, the intermediate R1And R2Including one or more of the following structures:
a preparation method of a thiophene ethylene propylene dicyan structure compound comprises the following steps:
the method comprises the following steps: 3-bromine-carbazole and halogenated aromatic ring or halogenated aromatic heterocyclic compound are subjected to carbon-nitrogen coupling reaction under the action of cuprous iodide to obtain a 3-bromine-nitrogen-aromatic ring or aromatic heterocyclic carbazole compound;
wherein, the halogen in the halogenated aromatic ring or the halogenated aromatic heterocyclic compound is one or more of fluorine, chlorine, bromine and iodine;
the specific implementation steps are as follows:
weighing 3-bromo-carbazole and a corresponding halogenated aromatic ring or halogenated aromatic heterocyclic compound, adding cuprous iodide and DMF (dimethyl formamide), performing nitrogen protection, heating for 12-24 hours, cooling, adding a large amount of water, extracting with dichloromethane, and passing through a column with petroleum ether/dichloromethane to obtain a corresponding 3-bromo-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
step two: coupling reaction of the obtained 3-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole and bis-pinacol borate with potassium acetate and 1,4 dioxane under the action of a palladium catalyst to obtain a 3-pinacol borate-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
the specific implementation steps are as follows:
weighing 3-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole, bippinacol boric acid ester and potassium acetate, putting into a single-mouth bottle, adding 1,4 dioxane, adding a ferrocene palladium dichloride catalyst through nitrogen for 10 minutes, continuously introducing nitrogen, heating to 100 ℃, and reacting for 12 hours. Cooling, adding water, extracting with dichloromethane, and passing through a column to obtain a 3-pinacol borate-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
step three: obtaining a synthetic compound of 3-thiophenecarboxaldehyde-nitrogen aromatic ring or aromatic heterocyclic carbazole by reacting the obtained 3-pinacol borate-nitrogen aromatic ring or aromatic heterocyclic carbazole with 5-bromothiophene-2-formaldehyde under the action of palladium catalysis;
the specific implementation steps are as follows:
weighing 3-pinacol borate-nitrogen aromatic ring or aromatic heterocyclic carbazole, 5-bromothiophene-2-formaldehyde and potassium carbonate, introducing nitrogen for 10 minutes, adding a mixed solvent of 1, 4-dioxane and water in a volume ratio of 10:1, continuously introducing nitrogen for 10 minutes, heating to 95 ℃, and reacting for 8 hours. After cooling, adding water, extracting with dichloromethane, and obtaining the 3-thiophenecarboxaldehyde-nitrogen aromatic ring or aromatic heterocyclic carbazole compound through chromatographic column or pulping (dichloromethane and petroleum ether);
step four: carrying out bromination reaction on the obtained 3-thiophenecarboxaldehyde-nitrogen aromatic ring or aromatic heterocyclic carbazole and bromosuccinimide (NBS) to obtain a 3-thiophenecarboxaldehyde-6-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
the specific implementation steps are as follows:
weighing a mixture with a molar ratio of 1: 1, adding a proper amount of dichloromethane solvent into 3-thiophenecarboxaldehyde-nitrogen aromatic ring or aromatic heterocyclic carbazole and bromosuccinimide (NBS). Heating to reflux, reacting for 21 hours, cooling, adding a large amount of dichloromethane and water, extracting, and passing through a column or pulping to obtain a 3-thiophenecarboxaldehyde-6-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
step five: obtaining the 3-thiophenecarboxaldehyde-6-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole and 2-thiopheneboronic acid under the action of palladium catalysis to obtain a 3-thiophenecarboxaldehyde-6-thiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
the specific implementation steps are as follows:
weighing 3-thiophenecarboxaldehyde-6-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole, 2-thiopheneboronic acid and potassium carbonate, adding a mixed solvent of 1, 4-dioxane and water with a volume ratio of 10:1, introducing nitrogen for 10 minutes, adding palladium tetratriphenylphosphine, continuing introducing nitrogen for 10 minutes, heating to 95 ℃, and reacting for 12 hours. After cooling, obtaining the 3-thiophenecarboxaldehyde-6-thiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound by a chromatographic column or a pulping method (dichloromethane and petroleum ether);
step six: carrying out bromination reaction on the obtained 3-thiophenecarboxaldehyde-6-thiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole and bromosuccinimide (NBS) to obtain a 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
the specific implementation steps are as follows:
weighing 3-thiophenecarboxaldehyde-6-thiophen-nitrogen aromatic ring or aromatic heterocyclic carbazole and bromosuccinimide (NBS) in equal molar ratio, adding a dichloromethane solvent, heating to reflux, reacting for 24 hours, cooling, adding a large amount of water and dichloromethane, extracting, and obtaining a corresponding 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound through a chromatographic column or pulping;
step seven: the obtained 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole and corresponding thiopheneboronic acid are subjected to palladium catalysis to obtain a 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
the specific implementation steps are as follows:
the obtained 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole and corresponding thiopheneboronic acid are subjected to chromatographic column or pulping (dichloromethane and petroleum ether) in a mixed solvent with the volume ratio of 1, 4-dioxane to water being 10:1 under the catalysis of potassium carbonate and palladium tetratriphenylphosphine to obtain a 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
step eight: reacting the obtained 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole with dicyan in acetonitrile, chloroform or a mixture of the acetonitrile and the chloroform under the action of piperidine, and then cooling, crystallizing, washing and drying to obtain a thiophene allyl ethylene dicyan structure compound;
the specific implementation steps are as follows:
reacting the obtained 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole with dicyandiamide in acetonitrile or acetonitrile/chloroform under the action of catalytic amount of piperidine, cooling, crystallizing, washing with water, and drying to obtain corresponding thiophene allyl ethyl dicyandiamide structure compound with aggregation-induced emission effect
The steps are as follows: the reaction of palladium catalysis is that potassium carbonate reacts with palladium catalyst in organic solvent;
the palladium catalyst comprises any one of tetrakis (triphenylphosphine) palladium and ferrocene palladium dichloride;
the organic solvent comprises one or more of tetrahydrofuran, toluene, DMF, water or 1, 4-dioxane;
the bromination reaction includes any one of thiophene group reaction and carbazole group reaction.
The following protocol is further illustrated by the examples:
example 1:
preparation of intermediate 3-bromo-carbazole-aminophenylcarbazole 1, as shown in FIG. 1
3-bromocarbazole (0.1mmol) and iodobenzene (0.15mmol) were added together to a 30mL portion of DMF solvent, and the mixture was stirred at room temperature for 0.5 hour, and a catalytic amount of CuI (0.005mmol) was added. The reaction was also heated to 100 ℃ and reacted overnight. When the reaction was also cooled to room temperature, a large amount of water was added, extraction was performed with ethyl acetate, and the organic phase was collected and purified by a chromatography column to obtain a white solid with a yield of 93%.
Example 2:
preparation of intermediate 3-pinacol borate-aminophenylcarbazole 2, as shown in figure 1
The obtained 3-bromo-carbazole-azaphenylcarbazole (0.1mmol) and the bipyridyl borate (0.2mmol) were put into a 1, 4-dioxane solvent containing 30mL, nitrogen was introduced thereinto for ten minutes, and potassium acetate (0.3mmol) and Pd (dppf) were added2Cl2(0.001mmol), and nitrogen was continued for ten minutes. The reaction was also heated to reflux for 12 hours, after the reaction was cooled, a large amount of water was heated, extracted with dichloromethane, the organic phase was collected and passed through a chromatographic column to give a white solid with a yield of 95%.
Example 3:
preparation of intermediate 3-thiophenecarboxaldehyde-N-arylphenylcarbazole 3, as shown in figure 1
The obtained 3-pinacol borate-aminophenylcarbazole (0.1mmol) and 5-bromothiophene-2-carbaldehyde (0.1mmol) are put into a container with a volume ratio of 10:1, 4-dioxane and water (30mL) were stirred for 0.5 h, potassium carbonate (0.3mmol) was added, nitrogen was passed through for ten minutes, palladium tetratriphenylphosphine (0.001mmol) was further added, and nitrogen was passed through for ten minutes. Heated to 95 ℃ and reacted for 12 hours. After the reaction was cooled, a large amount of water was added, extracted with dichloromethane, and the organic phase was collected and passed through a chromatographic column to give a yellow solid with a yield of 90%.
Example 4:
preparation of intermediate 3-thiophenecarboxaldehyde-6-bromo-azaphenylcarbazole 4 as shown in figure 1
The obtained 3-thiophenecarboxaldehyde-N-arylphenylcarbazole (0.1mmol) and NBS (0.1mmol) were put into a dichloromethane solvent containing 30mL, heated and refluxed for 12 hours, and then the reaction system was cooled. The reaction solution was poured into a beaker containing 100mL of water, 300mL of a dichloromethane solution was added, extraction was performed, and the organic phase was collected. Drying the organic phase, mixing with silica gel, loading the sample by a dry method, and purifying by passing through a column by using petroleum ether as a developing agent to obtain an intermediate 3-thiophenecarboxaldehyde-6-bromothiophene-N-arylphenylcarbazole with the yield of 85%.
Example 5:
preparation of intermediate 3-thiophenecarboxaldehyde-6-bromo-azaphenylcarbazole 5, as shown in FIG. 1
The obtained intermediate 3-thiophenecarboxaldehyde-6-bromo-azaphenylpolycarbazole (0.1mmol) and thiopheneboronic acid (0.15mmol) are added into a reactor containing a mixture of thiophene and boric acid in a volume ratio of 10:1, 4-dioxane and water (30mL) were stirred for 0.5 h, potassium carbonate (0.3mmol) was added, nitrogen was passed through for ten minutes, palladium tetratriphenylphosphine (0.001mmol) was further added, and nitrogen was passed through for ten minutes. Heated to 95 ℃ and reacted for 12 hours. After the reaction was cooled, a large amount of water was added to precipitate a solid, which was filtered and dried to give a yellow solid with a yield of 80%.
Example 6:
preparation of intermediate 3-thiophenecarboxaldehyde-6-bromothiophene-azaphenylpolycarbazole 6 as shown in figure 1
3-thiophenecarboxaldehyde-6-thiophene-N-arylphenylcarbazole (0.1mmol) and NBS (0.1mmol) are put into a dichloromethane solvent containing 30mL for heating reflux, and after 12 hours, the reaction system is cooled. The reaction solution was poured into a beaker containing 500mL of water, 300mL of a dichloromethane solution was added, extraction was performed, and the organic phase was collected. Drying the organic phase, mixing with silica gel, loading the sample by a dry method, and purifying by a column using petroleum ether as a developing agent to obtain an intermediate 3-thiophenecarboxaldehyde-6-bromothiophene-N-arylphenylcarbazole with a yield of 90%. The hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance of the 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen arylphenylcarbazole are shown in figures 1 and 2. 1H NMR (500MHz, CDCl3) δ:9.93(s,1H),8.50(s,1H),8.42(s,1H),7.81(d,2H, J ═ 3.8Hz),7.77-7.73(m,2H),7.69-7.66(m,2H),7.60(d,2H, J ═ 7.7Hz),7.56(m,1H),7.52(d,1H, J ═ 3.8Hz),7.46-7.41(m,3H),7.33(d,1H, J ═ 5.0Hz),7.17-7.15(m,1H), 13C NMR (125MHz, CDCl3) δ:182.5,155.7,145.1,141.8,141.5,141.0,137.7,137.0,130.0,128.1,128.0,127.5,126.9,125.4,125.3,125.0,124.1,123.9,123.5,123.2,122.5,118.6,117.9,110.6,110.5;
example 7:
preparation of intermediate 3-thiophenecarboxaldehyde-6-bithiophene-azaphenylpolycarbazole 7 as shown in figure 1
Putting the intermediate 3-thiophenecarboxaldehyde-6-bromothiophene-azaarylphenylcarbazole 6(0.1mmol), thiopheneboronic acid (0.1mmol) and potassium carbonate (0.1mmol) into a mixed solvent containing 50mL of 1, 4-dioxane and water (the volume ratio is 10:1), and introducing nitrogen for 10 minutes. Tetratriphenylphosphine palladium was weighed and put into the above one-neck flask. The reaction was cooled overnight under continued reflux under nitrogen, and the reaction solution was poured into a beaker containing 500mL of water, whereupon a large amount of solid precipitated, and stirring was continued for 0.5 hour. The solid was filtered by suction filtration through a buchner funnel and a solid sample was collected and dried. Dissolving a solid sample in a dichloromethane solvent, stirring silica gel, loading the sample by a dry method, and purifying by using dichloromethane as a developing agent through a column to obtain an intermediate 3-thiophenecarboxaldehyde-6-bithiophene-N-arylphenylcarbazole 7 with the yield of 85%. The hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance of the 3-thiophenecarboxaldehyde-6-bithiophene-N-arylphenylcarbazole are shown in figures 3 and 4.1H NMR(500MHz,CDCl3)δ:9.95(s,2H),8.85(s,2H),8.01(d,2H,J＝3.9Hz),7.92(dd,2H,J＝8.6,1.6Hz),7.78-7.73(m,4H),7.70(d,2H,J＝7.5Hz),7.64-7.61(m,1H),7.49(d,2H,J＝8.6Hz).13C NMR(125MHz,CDCl3)δ:128.5,155.2,141.8,141.6,137.7,136.5,130.1,128.2,126.8,125.2,123.2,118.5,110.7；
Example 8:
preparation of 3-thiophenecarbonitrile-6-bithiophene-azaarylphenylcarbazole 8 with AIE effect, as shown in FIG. 1
The intermediate 3-thiophenecarboxaldehyde-6-bithiophene-azaphenylparbazole 7(0.1mmol), propylene dicyan (0.5mmol) and piperidine (0.01mmol) were dissolved in 10mL acetonitrile solution. Heated to 50 ℃ and held for 24 hours. After the reaction is finished, cooling to room temperature, cooling the reaction suspension to 0 ℃, filtering the reaction suspension by suction when no solid is precipitated in the bottle, and collecting the solid. The obtained solid is dissolved in dichloromethane, and then petroleum ether with the same volume is added, stirred overnight, filtered and dried to obtain 3-thiophenepropanedicyano-6-bithiophene-N-arylphenylcarbazole 8 with the yield of 91%. 3-ThiophenepropanylThe hydrogen nuclear magnetic resonance spectrum of dicyan-6-bithiophene-azaphenylphenylcarbazole 8 is shown in fig. 5.1H NMR(500MHz,CDCl3)δ:8.48(s,1H),8.40(s,1H),7.79(s,1H),7.76-7.74(m,5H),7.57-7.51(m,4H),7.42-7.38(m,2H),7.33(d,1H,J＝3.8Hz),7.25-7.23(m,2H),7.21(d,1H,J＝3.8Hz),7.07-7.04(m,1H)。
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.
Claims (7)
1. A thiophene ethylene propylene dicyan structure compound is characterized by having the following structure:
wherein, the intermediate R1And R2Including one or more of the following structures:
-H
2. the method for preparing a thiophene ethylene propylene dicyan structural compound according to claim 1, characterized in that: the method comprises the following steps:
3-bromine-carbazole and halogenated aromatic ring or halogenated aromatic heterocyclic compound are subjected to carbon-nitrogen coupling reaction under the action of cuprous iodide to obtain a 3-bromine-nitrogen-aromatic ring or aromatic heterocyclic carbazole compound;
coupling reaction of the obtained 3-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole and bis-pinacol borate with potassium acetate and 1,4 dioxane under the action of a palladium catalyst to obtain a 3-pinacol borate-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
obtaining a synthetic compound of 3-thiophenecarboxaldehyde-nitrogen aromatic ring or aromatic heterocyclic carbazole by reacting the obtained 3-pinacol borate-nitrogen aromatic ring or aromatic heterocyclic carbazole with 5-bromothiophene-2-formaldehyde under the action of palladium catalysis;
carrying out bromination reaction on the obtained 3-thiophenecarboxaldehyde-nitrogen aromatic ring or aromatic heterocyclic carbazole and bromosuccinimide (NBS) to obtain a 3-thiophenecarboxaldehyde-6-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
obtaining the 3-thiophenecarboxaldehyde-6-bromine-nitrogen aromatic ring or aromatic heterocyclic carbazole and 2-thiopheneboronic acid under the action of palladium catalysis to obtain a 3-thiophenecarboxaldehyde-6-thiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
carrying out bromination reaction on the obtained 3-thiophenecarboxaldehyde-6-thiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole and bromosuccinimide (NBS) to obtain a 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
the obtained 3-thiophenecarboxaldehyde-6-bromothiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole and corresponding thiopheneboronic acid are subjected to palladium catalysis to obtain a 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole compound;
reacting the obtained 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole with dicyano in an organic solution, and then cooling, crystallizing, washing and drying to obtain the thiophene allyl cyanide structure compound.
3. The method for preparing a thiophene ethylene propylene dicyan structural compound according to claim 2, characterized in that: the palladium-catalyzed reaction is:
reacting in an organic solvent under the action of potassium carbonate and a palladium catalyst;
wherein the palladium catalyst comprises any one of tetrakis (triphenylphosphine) palladium and ferrocene palladium dichloride.
4. The method for preparing a thiophene ethylene propylene dicyan structural compound according to claim 3, characterized in that: the organic solvent comprises one or more of tetrahydrofuran, toluene, DMF, water or 1, 4-dioxane in combination.
5. The method for preparing a thiophene ethylene propylene dicyan structural compound according to claim 4, wherein: the bromination reaction includes any one of thiophene group reaction and carbazole group reaction.
6. The method for preparing a thiophene ethylene propylene dicyan structural compound according to claim 5, wherein: the method for reacting the obtained 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole with dicyanobenzene in an organic solution comprises the following steps:
reacting the obtained 3-thiophenecarboxaldehyde-6-bithiophene-nitrogen aromatic ring or aromatic heterocyclic carbazole with dicyan under the action of piperidine in acetonitrile, chloroform or a mixture of the acetonitrile and the chloroform.
7. The method for preparing a thiophene ethylene propylene dicyan structural compound according to any one of claims 2 to 6, characterized in that: the halogen in the halogenated aromatic ring or the halogenated aromatic heterocyclic compound is one or more of fluorine, chlorine, bromine and iodine.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150004099A (en) * | 2013-07-02 | 2015-01-12 | 덕산하이메탈(주) | An organic electronic element comprising a layer for improving light efficiency, and an electronic device comprising the same |
| CN109569026A (en) * | 2018-01-11 | 2019-04-05 | 南开大学 | It prepares the chromatographic stationary phases that porous framework material is matrix and is used for chiral separation |
| CN111620859A (en) * | 2020-06-08 | 2020-09-04 | 南昌航空大学 | Novel material with AIE activity |
-
2020
- 2020-12-28 CN CN202011580491.3A patent/CN112707897A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150004099A (en) * | 2013-07-02 | 2015-01-12 | 덕산하이메탈(주) | An organic electronic element comprising a layer for improving light efficiency, and an electronic device comprising the same |
| CN109569026A (en) * | 2018-01-11 | 2019-04-05 | 南开大学 | It prepares the chromatographic stationary phases that porous framework material is matrix and is used for chiral separation |
| CN111620859A (en) * | 2020-06-08 | 2020-09-04 | 南昌航空大学 | Novel material with AIE activity |
Non-Patent Citations (4)
| Title |
|---|
| TAINAN DUAN 等: "New organic dyes containingtert -Butyl-capped N-Arylcarbazole moiety for Dye-sensitized solar cells", 《RSC ADVANCES》 * |
| XIANGQIAN LI 等: "Carbazole based new organic dye recognizes hydrazine and hydrogen sulfide via signal difference protocols", 《DYES AND PIGMENTS》 * |
| YU-XIN PENG 等: "Construction of a Layered Hydrogen-Bonded Organic Framework Showing High-Contrast Mechanoresponsive Luminescence Turn-On", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
| 张正垠 等: "具有D-π-A结构的咔唑衍生物的制备及其性能", 《化学世界》 * |
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