Compound containing aza-spirofluorene and nitrogen six-membered heterocycle and application of compound to OLED (Organic Light Emitting Diode)

Abstract

The invention discloses a compound containing aza-spirofluorene and nitrogen six-membered heterocycle and application of the compound to an OLED (Organic Light Emitting Diode). The compound contains an aza-spirofluorene structure and an aza-six-membered heterocyclic structure; in addition, at least one N is arranged on the spirofluorene structure; and both two groups are strong electron groups, have deep HOMO energy level and high electron mobility, and are suitably used as a hole-blocking material or an electron transport material. A structure containing a hole group of the compound disclosed by the invention can balance electrons and holes of the material, so that the material can be used as a main body material of a partially-electronic luminescent layer; besides, the compound disclosed by the invention has higher group rigidity and has the characteristics of low possibilities of intermolecular crystallization and aggregation and high film-forming property; the compound serving as an organic electroluminescence functional layer material is applies to an OLED device; current efficiency, power efficiency and external quantum efficiency of the device are greatly improved; and besides, the service life of the device is obviously prolonged.

Description

technical field

[0001] The invention relates to the technical field of semiconductors, in particular to a compound containing azaspirofluorene and a nitrogen-containing six-membered heterocyclic ring, and its application in OLEDs. Background technique

[0002] Organic electroluminescent (OLED: Organic Light Emission Diodes) device technology can be used to manufacture new display products and also can be used to make new lighting products, which is expected to replace the existing liquid crystal display and fluorescent lighting, and has a wide application prospect. The OLED light-emitting device is like a sandwich structure, including electrode material film layers, and organic functional materials sandwiched between different electrode film layers. Various functional materials are superimposed on each other according to the application to form an OLED light-emitting device. As a current device, when a voltage is applied to the electrodes at both ends of the OLED light-emitt...

Examples

Embodiment 1

[0037] The synthesis of embodiment 1 intermediate A:

[0038]

[0039](1) Under a nitrogen atmosphere, weigh raw material B and dissolve it in tetrahydrofuran, then add raw material C and tetrakis(triphenylphosphine)palladium, stir the mixture, then add potassium carbonate aqueous solution, and mix the above-mentioned reactants at the reaction temperature At 70-90°C, heat to reflux for 5-20 hours. After the reaction, cooling and adding water, the mixture was extracted with dichloromethane, the extract was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure, the obtained residue was purified by silica gel column to obtain intermediate I;

[0040] The molar ratio of raw material B to raw material C is 1:1.0~1.5, the molar ratio of tetrakis(triphenylphosphine) palladium to raw material B is 0.001~0.02:1, and the molar ratio of potassium carbonate to raw material B is 1.0~2.0 :1, the ratio of THF dosage to raw material B is 1g:10~30ml.

[004...

Embodiment 2

[0063] The synthesis of embodiment 2 compound 2:

[0064]

[0065] In a 250mL three-necked flask, nitrogen was introduced, 0.01mol of raw material A1, 150ml of THF, 0.015mol of intermediate A1, 0.0001mol of tetrakis(triphenylphosphine) palladium were added, stirred, and then 0.02mol of K 2 CO 3 Aqueous solution (2M), heated to 80°C, refluxed for 15 hours, sampled and plated, the reaction was complete. Cool naturally, extract with 200ml of dichloromethane, separate layers, dry the extract with anhydrous sodium sulfate, filter, rotate the filtrate, and purify through a silica gel column to obtain the target compound with a HPLC purity of 99.1% and a yield of 77.3%. Elemental analysis structure (molecular formula C 45 h 28 N 4 ): theoretical value C, 86.51; H, 4.52; N, 8.97; test value: C, 86.49; H, 4.53; N, 8.98. ESI-MS(m / z)(M + ): The theoretical value is 624.23, and the measured value is 624.58.

Embodiment 3

[0066] The synthesis of embodiment 3 compound 4:

[0067]

[0068] In a 250mL three-necked flask, nitrogen was introduced, 0.01mol of raw material A2, 150ml of THF, 0.015mol of intermediate A2, 0.0001mol of tetrakis(triphenylphosphine) palladium were added, stirred, and then 0.02mol of K 2 CO 3 Aqueous solution (2M), heated to 80°C, refluxed for 15 hours, sampled and plated, the reaction was complete. Cool naturally, extract with 200ml of dichloromethane, separate layers, dry the extract with anhydrous sodium sulfate, filter, rotate the filtrate, and purify through a silica gel column to obtain the target compound with an HPLC purity of 99.3% and a yield of 71.9%. Element analysis structure (molecular formula C 51 h 32 N 4 ): theoretical value C, 87.40; H, 4.60; N, 7.99; test value: C, 87.42; H, 4.61; N, 7.97. ESI-MS(m / z)(M + ): The theoretical value is 700.26, and the measured value is 700.63.

technical field

[0001] The invention relates to the technical field of semiconductors, in particular to a compound containing azaspirofluorene and a nitrogen-containing six-membered heterocyclic ring, and its application in OLEDs. Background technique

[0002] Organic electroluminescent (OLED: Organic Light Emission Diodes) device technology can be used to manufacture new display products and also can be used to make new lighting products, which is expected to replace the existing liquid crystal display and fluorescent lighting, and has a wide application prospect. The OLED light-emitting device is like a sandwich structure, including electrode material film layers, and organic functional materials sandwiched between different electrode film layers. Various functional materials are superimposed on each other according to the application to form an OLED light-emitting device. As a current device, when a voltage is applied to the electrodes at both ends of the OLED light-emitt...

Examples

Embodiment 1

[0037] The synthesis of embodiment 1 intermediate A:

[0038]

[0039](1) Under a nitrogen atmosphere, weigh raw material B and dissolve it in tetrahydrofuran, then add raw material C and tetrakis(triphenylphosphine)palladium, stir the mixture, then add potassium carbonate aqueous solution, and mix the above-mentioned reactants at the reaction temperature At 70-90°C, heat to reflux for 5-20 hours. After the reaction, cooling and adding water, the mixture was extracted with dichloromethane, the extract was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure, the obtained residue was purified by silica gel column to obtain intermediate I;

[0040] The molar ratio of raw material B to raw material C is 1:1.0~1.5, the molar ratio of tetrakis(triphenylphosphine) palladium to raw material B is 0.001~0.02:1, and the molar ratio of potassium carbonate to raw material B is 1.0~2.0 :1, the ratio of THF dosage to raw material B is 1g:10~30ml.

[004...

Embodiment 2

[0063] The synthesis of embodiment 2 compound 2:

[0064]

[0065] In a 250mL three-necked flask, nitrogen was introduced, 0.01mol of raw material A1, 150ml of THF, 0.015mol of intermediate A1, 0.0001mol of tetrakis(triphenylphosphine) palladium were added, stirred, and then 0.02mol of K 2 CO 3 Aqueous solution (2M), heated to 80°C, refluxed for 15 hours, sampled and plated, the reaction was complete. Cool naturally, extract with 200ml of dichloromethane, separate layers, dry the extract with anhydrous sodium sulfate, filter, rotate the filtrate, and purify through a silica gel column to obtain the target compound with a HPLC purity of 99.1% and a yield of 77.3%. Elemental analysis structure (molecular formula C 45 h 28 N 4 ): theoretical value C, 86.51; H, 4.52; N, 8.97; test value: C, 86.49; H, 4.53; N, 8.98. ESI-MS(m / z)(M + ): The theoretical value is 624.23, and the measured value is 624.58.

Embodiment 3

[0066] The synthesis of embodiment 3 compound 4:

[0067]

[0068] In a 250mL three-necked flask, nitrogen was introduced, 0.01mol of raw material A2, 150ml of THF, 0.015mol of intermediate A2, 0.0001mol of tetrakis(triphenylphosphine) palladium were added, stirred, and then 0.02mol of K 2 CO 3 Aqueous solution (2M), heated to 80°C, refluxed for 15 hours, sampled and plated, the reaction was complete. Cool naturally, extract with 200ml of dichloromethane, separate layers, dry the extract with anhydrous sodium sulfate, filter, rotate the filtrate, and purify through a silica gel column to obtain the target compound with an HPLC purity of 99.3% and a yield of 71.9%. Element analysis structure (molecular formula C 51 h 32 N 4 ): theoretical value C, 87.40; H, 4.60; N, 7.99; test value: C, 87.42; H, 4.61; N, 7.97. ESI-MS(m / z)(M + ): The theoretical value is 700.26, and the measured value is 700.63.

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