CN106243086A - One class connects the preparation method and applications of the pyrimidine derivatives of four identical electron donating groups - Google Patents

One class connects the preparation method and applications of the pyrimidine derivatives of four identical electron donating groups Download PDF

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CN106243086A
CN106243086A CN201610630507.4A CN201610630507A CN106243086A CN 106243086 A CN106243086 A CN 106243086A CN 201610630507 A CN201610630507 A CN 201610630507A CN 106243086 A CN106243086 A CN 106243086A
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pyrimidine derivatives
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pyrimidine
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刘迪
张丹
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Dalian University of Technology
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    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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Abstract

One class connects the preparation method and applications of the pyrimidine derivatives of four identical electron donating groups, belongs to luminescent material and is preparing the applied technical field of organic electroluminescence device.This kind of pyrimidine derivatives utilizes the space steric effect that little group dense arrangement produces, and the conjugation between electron donor and receptor is blocked, makes HOMO realize higher degree with lumo energy and separate, and can ensure that again molecule has higher rate of irradiation constant simultaneously.These electroluminescent organic materials can utilize singlet state and triplet exciton luminous simultaneously；Additionally, these materials are all organic molecules, stable chemical nature and need not precious metal coordination, cost is relatively low, can be applied to organic electroluminescence fluorescent device as luminescent material.

Description

One class connect four identical electron donating groups pyrimidine derivatives preparation method and Application
Technical field
The present invention relates to the preparation method and applications that a class connects the pyrimidine derivatives of four identical electron donating groups, belong to The applied technical field of organic electroluminescence device is being prepared in luminescent material.
Background technology
OLED i.e. Organic Light Emitting Diode (Organic Light Emitting Diode is called for short OLED), is to utilize to have The novel light-emitting diode of machine material electroluminescent effect.Its operation principle is: produces electric field by applying voltage, is swashed by electric field The electricity percussion centre of luminescence, and cause that electronics is in transition between energy level, change, composite guide photoluminescence.Because it has making Technique is simple, draws materials extensively, structure-controllable, and ultra-thin, rollable waits various features, demonstrates pole in display and lighting field Big application prospect.Some are practical or have come out close to practical organic display device, and such as Samsung is based on actively The display screen of matrix organic electroluminescent LED large-area applications is in Galaxy series mobile phone, and its large-sized TV is also List.White organic lighting engineering is the most advanced to the target of low cost, high efficiency, long-life light source.
In electroluminescent organic material, compared with traditional fluorescent material and phosphor material, thermic delayed fluorescence material The advantage having the two concurrently, it can either make full use of singlet state and triplet exciton luminescence and make device internal quantum efficiency theoretical On reach 100%；Meanwhile, thermic delayed fluorescence material is organic molecule, stable chemical nature and need not and precious metal Coordination makes device cost be greatly reduced.Thus, study, develop novel thermic delayed fluorescence material and have highly important existing Sincere justice.
Summary of the invention
It is an object of the invention to using pyrimidine ring as electron acceptor, connect four identical donor carbazoles, the tert-butyl groups respectively Carbazole, 9-phenyl 9-hydrogen carbazole, 10-phenyl-10-hydrogen azophenlyene, 10-phenyl-10-hydrogen phenothiazine, 9,9-dimethyl-9,10- Acridan prepares novel electroluminescent organic material.
The technical solution adopted in the present invention is: a class connects the pyrimidine derivatives of four identical electron donating groups, and this is phonetic Piperidine derivatives connects four identical electron donating groups using pyrimidine as the electron acceptor of luminescent material in its periphery；Described pyrimidine The formula of derivant is
Wherein: the structure of D is
The chemical molecular structural formula of M1, M2, M3, M4, M5 and M6 is respectively as follows:
A described class pyrimidine derivatives is applied in preparing organic electroluminescence device as luminescent material.The present invention's Provide the benefit that: this kind of pyrimidine derivatives utilizes the space steric effect that little group dense arrangement produces, by electron donor be subject to Conjugation between body blocks, and makes HOMO realize higher degree with lumo energy and separates, and can ensure that again molecule has relatively simultaneously High rate of irradiation constant.Pyrimidine is as the electron acceptor of luminescent material, at its peripheral connection carbazole, tert-butyl carbazole, 9-benzene Base 9-hydrogen carbazole, 10-phenyl-10-hydrogen azophenlyene, 10-phenyl-10-hydrogen phenothiazine, 9,9-dimethyl-9,10-acridan etc. Electron donor, is prepared as electroluminescent organic material.These electroluminescent organic materials can utilize singlet state and triple simultaneously State excitonic luminescence, internal quantum efficiency can reach 100% in theory；Additionally, these materials are all organic molecules, chemical property Stablizing and need not precious metal coordination, cost is relatively low, can be applied to organic electroluminescence fluorescent device as luminescent material.
Accompanying drawing explanation
Fig. 1 is uv absorption intensity and the fluorescent emission intensity in dichloromethane and toluene of molecule M1.
Fig. 2 is uv absorption intensity and the fluorescent emission intensity in dichloromethane and toluene of molecule M2.
Fig. 3 is the highest non-occupied orbital Cloud Distribution of molecule M1.
Fig. 4 is the highest occupied molecular orbital Cloud Distribution of molecule M1.
Fig. 5 is the highest occupied molecular orbital Cloud Distribution of molecule M1.
Fig. 6 is the highest non-occupied orbital Cloud Distribution of molecule M2.
Fig. 7 is the Devices Electroluminescent spectrum of molecule M1.
Fig. 8 is the molecule M1 device external quantum efficiency variation relation figure with electric current density.
Detailed description of the invention
Below by embodiment, the invention will be further described, it is therefore intended that is best understood from present disclosure.Therefore Example is not limiting as protection scope of the present invention.
The synthesis of embodiment 1 derivant M1
1.73g (10.35mmol) carbazole is joined in the there-necked flask of 250ml, be subsequently adding 100mL N, N-dimethyl methyl Amide is as reaction dissolvent, under condition of ice bath, stirs 10min on magnetic stirring apparatus.0.22g (9.2mmol) NaH is added in batches Enter in reaction bulb, continue stirring 1h.The 2,4,5,6-tetrachloro-pyrimidine of 0.5g (2.30mmol) is dissolved in N, the N-diformazan of 20ml In base Methanamide, it is added dropwise in reaction system, after interpolation, under room temperature, reacts 24h.After reaction terminates, by reactant liquor Pour cancellation in the dilute hydrochloric acid that 150ml concentration is 10% into, after decompression sucking filtration, washing, dry, thick product petroleum ether and dichloromethane Alkane (PE:DCM=6:1) crosses post mutually for flowing, obtains white solid 1.16g, productivity 68.0%.MS(EI):m/z:740.87 ([M]+)。
The synthesis of embodiment 2 derivant M2
2.89g (10.35mmol) tert-butyl carbazole is joined in the there-necked flask of 100ml, be subsequently adding 100ml N, N-bis- Methylformamide is as reaction dissolvent, under condition of ice bath, stirs 10min on magnetic stirring apparatus.By 0.22g (9.2mmol) NaH It is dividedly in some parts in reaction bulb, continues stirring 1h.The 2,4,5,6-tetrachloro-pyrimidine of 0.5g (2.3mmol) is dissolved in the N, N-of 20ml In dimethylformamide, it is added dropwise in reaction system, after interpolation, under room temperature, reacts 24h.After reaction terminates, will be anti- Cancellation in answer liquid to pour into dilute hydrochloric acid that 100ml concentration is 10%, after decompression sucking filtration, washing, dry, thick product petroleum ether and second Acetoacetic ester (PE:DCM=6:1) crosses post, white solid 1.01g, productivity 69.3% mutually for flowing.MS(EI):m/z:1188.87 ([M]+)。
The synthesis of embodiment 3 derivant M3
Successively by 1.162g (4.408mmol) N-phenyl-3-carbazole boric acid, 200mg (0.92mmol) 2,4,5,6-tetrachloro-pyrimidine, 103mg (0.46mmol) palladium, 241mg (0.92mmol) triphenylphosphine and 1.17g (11.04mmol) Anhydrous potassium carbonate add Entering in 100ml there-necked flask, be subsequently adding 50mL glycol dimethyl ether as reaction dissolvent, reflux after removing air 24h.Instead Should reduce pressure after terminating and reaction dissolvent is distilled off, DCM was spin-dried for post after extracting three times.Obtain yellow solid 0.26g, productivity 30.6%.MS(EI):m/z:1044.39([M]+).
The synthesis of embodiment 4 derivant M4
Weighing 3.56g (21.28mmol) carbazole, 6.0g (21.28mmol) is to bromo-iodobenzene, 5.86g (42.56mmol) Carbon Dioxide Potassium, 0.76g (4.26mmol) 1,10-neighbour's phenanthrene quinoline, 0.82g (4.26mmol) Hydro-Giene (Water Science)., in 100mL there-necked flask, then adds Enter 80mL N,N-dimethylformamide as reaction dissolvent.Under nitrogen protection, reflux after removing air 24h.After reaction terminates, Reactant liquor is poured into cancellation in 240mL saturated aqueous common salt, with dichloromethane (250mL × 3) extractive reaction liquid after decompression sucking filtration, closes And extract being dried with anhydrous magnesium sulfate, screw out solvent, drying.Thick product petroleum ether and dichloromethane (PE:DCM=20: 1) carry out column chromatography purification mutually for flowing, obtain white solid 3.53g, productivity 55.2%.MS(EI):m/z:321.0166([M] +)。
Weigh 3.44g (10.72mmol) intermediate 1 in the there-necked flask that 250mL is dried, add the oxolane that 80mL is dried and make For reaction dissolvent.Under nitrogen protection, it is cooled to-78 DEG C with liquid nitrogen acetone, stirs 5min at this temperature, use syringe 10.0mL (1.6mol/L, 16.08mmol) n-BuLi it is added dropwise in reaction system.After reacting 1 hour, use syringe In reaction system drip 2.4mL (42.89mmol) methyl borate., and be allowed to nature heat up be stirred overnight.Reaction terminates Rear addition dilute hydrochloric acid solution quencher.Dichloromethane (100mL × 3) extractive reaction liquid, combining extraction liquid is used after being spin-dried for oxolane And be dried with anhydrous magnesium sulfate, screw out solvent, drying.Thick product dichloromethane and ethyl acetate are that eluent gradient carries out post Chromatographic purification, obtains White crystalline solid 2.05g, productivity 66.5%.MS(EI):m/z:287.1124([M]+).
Successively by 1.162g (4.408mmol) 4-(9H-carbazole-9-base) phenylboric acid, 200mg (0.92mmol) 2,4,5,6-tetrachloro Pyrimidine, 103mg (0.46mmol) palladium, 241mg (0.92mmol) triphenylphosphine and 1.17g (11.04mmol) anhydrous carbon Acid potassium joins in the there-necked flask of 100ml, is subsequently adding 50mL glycol dimethyl ether as reaction dissolvent, returns after removing air Stream 24h.After reaction terminates, decompression is distilled off reaction dissolvent, and DCM was spin-dried for post after extracting three times.Obtain yellow solid 0.26g, Productivity 30.6%.MS(EI):m/z:1044.39([M]+).
The synthesis of embodiment 5 derivant M5
Weighing 4.0g (21.84mmol) azophenlyene, 2.78ml (6.12g, 21.84mmol) is to bromo-iodobenzene, 14.24g (43.7mmol) Carbon Dioxide caesium, 1.64ml (0.66mmol) tri-butyl phosphine, 0.1g (0.44mmol) palladium is in 250mL tri- In mouth bottle, it is subsequently adding 100mL dry toluene as reaction dissolvent.After removing air, it is heated to 80 DEG C and reacts 20 hours.Reaction After end, decompression uses dichloromethane (100mL × 3) extractive reaction liquid after extracting solvent out, and combining extraction liquid also uses anhydrous magnesium sulfate It is dried, is spin-dried for solvent, dry.Thick product petroleum ether and dichloromethane (PE:DCM=15:1) are that eluant carries out column chromatography and carries Pure, obtain white crystalline powder 4.85g, productivity 65.8%.MS(EI):m/z:337.0125([M]+).
Weigh 4.84g intermediate 3 (14.36mmol) in the there-necked flask that 250mL is dried, add the oxolane that 80mL is dried and make For reaction dissolvent.Under nitrogen protection, it is cooled to-78 DEG C with liquid nitrogen acetone, stirs 5min at this temperature, under nitrogen protection Syringe is used to be added dropwise over the n-BuLi of 13.46mL (1.6mol/L, 21.54mmol) in reaction system.React 1 hour After, use syringe to drip the methyl borate. of 3.25ml (8.8mol/L, 28.72mmol) in reaction system, and be allowed to certainly So heat up and be stirred overnight.Reaction adds dilute hydrochloric acid solution quencher reaction after terminating.The oxolane that is spin-dried in reactant liquor and using Dichloromethane (100mL × 3) extractive reaction liquid, combining extraction liquid is also dried with anhydrous magnesium sulfate, screws out solvent, drying.Thick product Product dichloromethane and ethyl acetate are that eluent gradient carries out column chromatography purification, obtain White crystalline solid 3.02g, productivity 69%.MS(EI):m/z:303.1066([M]+).
Successively by 1.226g (4.408mmol) 4-(10H-phenoxazine-10-base) phenylboric acid, 200mg (0.92mmol) 2,4,5,6- Tetrachloro-pyrimidine, 103mg (0.46mmol) palladium, 241mg (0.92mmol) triphenylphosphine and 1.17g (11.04mmol) nothing Aqueous carbonate potassium joins in the there-necked flask of 100ml, is subsequently adding 50mL glycol dimethyl ether as reaction dissolvent, removing air Rear backflow 24h.After reaction terminates, decompression is distilled off reaction dissolvent, and DCM was spin-dried for post after extracting three times.Obtain yellow solid 0.38g, productivity 38.6%.MS(EI):m/z:1108.37([M]+).
The synthesis of embodiment 6 derivant M6
Weighing 4.0g (11.12mmol) 9,9-dimethyl-9,10-acridan, 2.44ml (5.40g, 11.12mmol) is to bromine iodine Benzene, 3.98g (38.24mmol) anhydrous tertiary butanol sodium, 1.46ml (0.58mmol) tri-butyl phosphine, 0.086g (0.38mmol) vinegar Acid palladium, in 250mL there-necked flask, is subsequently adding 100mL dry toluene as reaction dissolvent.Under nitrogen protection, it is heated to 80 DEG C instead Answer 20 hours.After reaction terminates, dichloromethane (100mL × 3) extractive reaction liquid after solvent is extracted in decompression out, and combining extraction liquid is also used Anhydrous magnesium sulfate is dried, and is spin-dried for solvent, dries.Thick product petroleum ether and dichloromethane (PE:DCM=15:1) are that eluant enters Row column chromatography purifies, and obtains white crystalline powder 4.56g, productivity 65.8%.MS(EI):m/z:363.0633([M]+)。
Weigh 3.42g intermediate 5 (9.42mmol) in the two-mouth bottle that 100mL is dried, add the oxolane that 50mL is dried and make For reaction dissolvent.Under nitrogen protection, it is cooled to-78 DEG C with liquid nitrogen acetone, stirs 5min at this temperature, under nitrogen protection Syringe is used to be added dropwise over the n-BuLi of 8.85mL (1.6mol/L, 14.13mmol) in reaction system.React 1 hour After, in reaction system, drip the methyl borate. of 2.15ml (8.8mol/L, 18.84mmol), and be allowed to nature intensification stirring Overnight.Reaction adds dilute hydrochloric acid solution quencher reaction after terminating.With dichloromethane (100mL × 3) extractive reaction liquid, merge extraction Liquid is also dried with anhydrous magnesium sulfate, screws out solvent, drying.Thick product dichloromethane and ethyl acetate are that eluent gradient is carried out Column chromatography purifies, and obtains white solid 2.18g, productivity 70.1%.MS(EI):m/z:329.1590([M]+).
Successively by 1.451g (4.408mmol) 4-(9,9-dimethyl acridinium-10-base) phenylboric acid, 200mg (0.92mmol) 2,4, 5,6-tetrachloro-pyrimidines, 103mg (0.46mmol) palladium, 241mg (0.92mmol) triphenylphosphine and 1.17g (11.04mmol), in Anhydrous potassium carbonate joins the there-necked flask of 100ml, it is subsequently adding 50mL glycol dimethyl ether as reaction Solvent, reflux after removing air 24h.After reaction terminates, decompression is distilled off reaction dissolvent, and DCM was spin-dried for post after extracting three times. Obtain yellow solid 0.26g, productivity 30.6%.MS(EI):m/z:1212.58([M]+).
Embodiment 7
Molecule M1, M2 are carried out the test of uv-vis spectra and fluorescence spectrum, M1 and M2 maximum absorption band in toluene At 443nm and 444nm, namely M1 and M2 is the most highly desirable blue-light-emitting molecule.And the emission peak in dichloromethane Along with the increase of polarity produces Red Shift Phenomena, position at 467nm and 469nm, illustrates that there is intramolecular charge transfer state sends out respectively Light.And Cloud Distribution that the calculated results of M1, M2 shows M1 and M2 is substantially consistent, minimum non-occupied orbital electronics Cloud is distributed on electronics pyrimidine ring, and highest occupied molecular orbital Cloud Distribution, on peripheral electron donor, makes minimum not occupy rail Road and highest occupied molecular orbital have less overlap, and this is the essential condition realizing thermic electroluminescent material.Meanwhile, the device of M1 Part structure is:
ITO/PEDOT/TAPC (200nm)/M1:mcp (200nm)/TmPyPB (400nm)/LiF (10nm)/Al (2000nm), ITO refers to that tin indium oxide, PEDOT refer to the polymer of EDOT (3,4-rthylene dioxythiophene monomer), and TAPC is conventional hole Transmission material, mcp is owing to its higher triplet state is as material of main part, and doping content is 7%, and TmPyPB is that conventional electronics passes Defeated material, LiF is as electron injection material, and metallic aluminium is metallic cathode.The electroluminescent position of material, 440, compensate for mesh The scarcity of front blue electroluminescent material, it will greatly improve the efficiency of electroluminescent device and accelerate electroluminescent organic material Application.

Claims (3)

1. a class connects the pyrimidine derivatives of four identical electron donating groups, it is characterised in that: this pyrimidine derivatives is made with pyrimidine Electron acceptor for luminescent material connects four identical electron donating groups in its periphery；The formula of described pyrimidine derivatives is
Wherein: the structure of D is
A class the most according to claim 1 connects the preparation method of the pyrimidine derivatives of four identical electron donating groups, its Being characterised by, this preparation method comprises the following steps:
(1) as D=D1 or D2,
D-H is joined in the there-necked flask of 250ml, be subsequently adding DMF as reaction dissolvent, ice bath bar Under part, after magnetic stirring apparatus stirs 10min, NaH is dividedly in some parts in reaction bulb, continues stirring 1h；By 2,4,5,6-tetra- Chloropyrimide is poured constant pressure funnel into and is added dropwise in there-necked flask after being dissolved in DMF, react under room temperature 24h；Described D-H:NaH:2, the mol ratio of 4,5,6-tetrachloro-pyrimidines is 4.5:4:1, after reaction terminates, pours reactant liquor into concentration Being cancellation in the dilute hydrochloric acid of 10%, reduce pressure sucking filtration, and washing is dried, and thick product petroleum ether is that post is crossed in flowing mutually with dichloromethane, Obtain target product；
(2) as D=D3, D4 or D5,
By D-B (OH)2: the mol ratio of 2,4,5,6-tetrachloro-pyrimidines is that the amount of 4.8:1 joins in flask, then by palladium: triphen Base phosphine: Anhydrous potassium carbonate joins in the there-necked flask of 100ml in molar ratio for the ratio of 1:2:24, described 2,4,5,6-tetrachloros The mol ratio of pyrimidine and palladium is 2:1, is subsequently adding glycol dimethyl ether as reaction dissolvent, and reflux after removing air 24h； After reaction terminates, decompression is distilled off reaction dissolvent, and DCM was spin-dried for post after extracting three times, obtained target product.
A class the most according to claim 1 connects the application of the pyrimidine derivatives of four identical electron donating groups, its feature It is: described pyrimidine derivatives is applied in preparing organic electroluminescence device as luminescent material.
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WO2021029463A1 (en) * 2019-08-12 2021-02-18 단국대학교 천안캠퍼스 산학협력단 Organic material and organic light emitting diode comprising same
US11440901B2 (en) 2018-09-12 2022-09-13 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
US12029116B2 (en) 2019-10-08 2024-07-02 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes

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CN109053690A (en) * 2018-08-03 2018-12-21 大连理工大学 Bipolarity electroluminescent material and its application containing carbazole group
CN109053690B (en) * 2018-08-03 2021-04-16 大连理工大学 Bipolar electroluminescent material containing carbazole group and application thereof
US11440901B2 (en) 2018-09-12 2022-09-13 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes
WO2021029463A1 (en) * 2019-08-12 2021-02-18 단국대학교 천안캠퍼스 산학협력단 Organic material and organic light emitting diode comprising same
KR20210019177A (en) * 2019-08-12 2021-02-22 단국대학교 천안캠퍼스 산학협력단 Organic materials and organic light emitting diode having the same
KR102232846B1 (en) * 2019-08-12 2021-03-26 단국대학교 천안캠퍼스 산학협력단 Organic materials and organic light emitting diode having the same
US12029116B2 (en) 2019-10-08 2024-07-02 Kyulux, Inc. Composition of matter for use in organic light-emitting diodes

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