A kind of 3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile derivative, its preparation and application
A technology of dioxo rings and derivatives, which is applied in the preparation and application of organic photoelectric materials, can solve the problems of poor film formation and poor stability, achieve easy operation, improve external quantum efficiency and luminous brightness, and solve the problem of organic film Effect of Layer Pollution
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[0040] The present invention also provides a preparation method of 3,6-dioxocyclohexa-1,4-diene-1,2-dinitrile derivatives, comprising the following steps:
[0041] (1) RCOOH reacts with potassium tert-butoxide to obtain RCOOK;
[0042] (2) RCOOK and 2,3-dichloro-5,6-dicyano-p-benzoquinone undergo a palladium-catalyzed decarboxylation cross-coupling reaction to obtain the 3,6-dioxocyclohexa-1,4-diene- 1,2-Dinitrile derivatives.
[0043] The 3,6-dioxocyclohexa-1,4-diene-1,2-dicarbonitrile derivatives in the present invention, through the 3,6-dioxocyclohexa-1,4-diene-1 , 2-dinitrile is obtained by inserting an electron-withdrawing group R, which is used as a P-type dopant in the hole injection layer of OLED.
[0044] The invention also provides the application of the 3,6-dioxocyclohexa-1,4-diene-1,2-dinitrile derivative in organic electroluminescent devices.
[0045] In some embodiments, the 3,6-dioxocyclohexa-1,4-diene-1,2-dinitrile derivative is used as a P-type dopant for a...
Embodiment 1
[0051] Taking the 3,6-dioxocyclohexa-1,4-diene-1,2-dinitrile derivative as shown in compound 1 as an example, the following synthetic route is adopted:
[0052]
[0053] Potassium 4-cyanobenzoate synthesis:
[0054] Add 4-cyanobenzoic acid (5g), potassium tert-butoxide (3.9g), and ethanol (40ml) into a 250ml beaker, stir at room temperature for 40min, filter with suction to get the upper layer solid, dry at 45°C for 2h to get 8.5 g (93%).
[0055] Synthesis of compound 1:
[0056] Potassium 4-cyanobenzoate (2.5g), 2,3-dichloro-5,6-dicyano-p-benzoquinone (1g), Pd(OAC) 2 (0.04g), three (o-methylphenyl) phosphorus (0.1g) join in the flask of 50ml, replace N 2 Three times, inject 20ml of diethylene glycol dimethyl ether into it, stir at room temperature for 10min, raise the temperature to 140°C for 24h, distill off diethylene glycol dimethyl ether under reduced pressure, and pass through the column to obtain 0.08g (3.7%) of solid .
[0057] MS(APCI)(m / z):[M+H + ] calcd, 3...
Embodiment 2
[0059] Taking the 3,6-dioxocyclohexa-1,4-diene-1,2-dinitrile derivative as shown in compound 4 as an example, the following synthetic route is adopted:
[0060]
[0061] Potassium 4-cyano-3,5-difluorobenzoate Preparation:
[0062] Add 4-cyano-3,5-difluorobenzoic acid (3.2g), potassium tert-butoxide (1.96g), and ethanol (30ml) into a 250ml beaker, stir at room temperature for 40min, and filter with suction to obtain the upper layer solid , dried at 45° C. for 2 h to yield 3.7 g (95.8%).
[0063] Synthesis of compound 4:
[0064] Potassium 4-cyano-3,5-difluorobenzoate (3.7g), 2,3-dichloro-5,6-dicyano-p-benzoquinone (1.3g), Pd(OAC) 2 (0.04g), three (o-methylphenyl) phosphorus (0.2g) join in the flask of 50ml, replace N 2 Three times, inject 20ml of diethylene glycol dimethyl ether into it, stir at room temperature for 10min, raise the temperature to 140°C for 24h, distill off diethylene glycol dimethyl ether under reduced pressure, pass through the column to obtain 0.13g (5...
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