CN108178750A - A kind of preparation and its application of benzo [g] quinazoline derivative - Google Patents

A kind of preparation and its application of benzo [g] quinazoline derivative Download PDF

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CN108178750A
CN108178750A CN201711265135.0A CN201711265135A CN108178750A CN 108178750 A CN108178750 A CN 108178750A CN 201711265135 A CN201711265135 A CN 201711265135A CN 108178750 A CN108178750 A CN 108178750A
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derivative
hplc
toluene
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molecular weight
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宋思思
陈慕欣
李向阳
孔祥兴
崔丽莎
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JIUMU CHEMICAL PRODUCT CO Ltd YANTAI
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JIUMU CHEMICAL PRODUCT CO Ltd YANTAI
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Abstract

Preparation the invention discloses a kind of benzo [g] quinazoline derivant and its application on OLED luminescent devices.The present invention is to contain the derivative of benzo [g] quinazoline as luminescent layer or electron transport layer materials, the OLED device of making, the OLED luminescent devices more now applied, under the action of electric field, generated electroluminescent color can show individually particular color of light or a variety of different colors combination light such as RGB, greater advantage is respectively provided in terms of luminous efficiency and colouristic properties and service life, there is good industrialization prospect.

Description

A kind of preparation and its application of benzo [g] quinazoline derivative
Technical field
The present invention relates to organic photoelectrical material technical field, specially a kind of preparation of benzo [g] quinazoline derivative And its application.
Technical background
Organic Light Emitting Diode (Organic Light Emitting Diode) abbreviation OLED display, comparative liquid crystal are shown Show device, OLED display is with brightness height, volume is thin, response is rapid, also stablizes with low in energy consumption, performance, and contrast is high, wide The features such as visual angle, full color, wide operating temperature range, highlights very superior application prospect in display and lighting area.
OLED device uses " sandwich " structure mostly.The structure is made of the different functional layer of multiple effects, is respectively Anode layer (being usually tin indium oxide ITO), hole transmission layer (HTL), luminescent layer (EML), the electronics of transparent metal oxide pass Defeated layer (ETL) and metal cathode layer (being usually low workfunction metal Li, Ca, Al, Mg, Ag etc.) are formed.Negative and positive are pressed from both sides between the two poles of the earth Miscellaneous organic layer, radiant light are projected by the transparent conductive substrate of side.
At present, for OLED luminescent devices, mainly to the performances such as the driving voltage of device, luminous efficiency, service life into Row optimizing research.Improve the performance of OLED device, other than device architecture and manufacture craft will be innovated, OLED organic light emission materials Material will also constantly bring forth new ideas, and work out the OLED hairs of the higher performances such as luminous efficiency height, luminescent layer good film-forming property, service life length Luminescent material adapts to.OLED luminous organic materials can not meet device system in luminous efficiency, luminescent layer film forming etc. at present The requirement of quotient is made, it is particularly important to research and develop a kind of high performance OLED luminescent materials.
In view of the above-mentioned problems, applicant develops a kind of preparation of benzo [g] quinazoline derivative and its is sent out in OLED Application on optical device, the OLED device which prepares have superior photoelectric properties, and relatively aobvious extend uses the longevity Life, can be very good the requirement for meeting device manufacturer.
Technical scheme is as follows：
A kind of benzo [g] quinazoline derivant luminescent material, it is characterised in that the derivative is with benzo [g] quinazoline structure Based on, shown in the general formula such as general formula (1) of molecular structure：
In general formula (1), R1 is xenyl, terphenyl, carbazyl, naphthalene, anthryl, fluorenyl, pyrenyl, phenanthryl, benzo [g] Quinazolyl, dibenzodioxin English base, benzofuranyl, benzothienyl, benzfluorene ketone group, Fluorenone base, dibenzofurans The split of one or both of the triazine radical of base, dibenzothiophene or diaryl substitution.
The R1 is selected from：
One or both of split.
The concrete structure formula of the derivative is
The synthesis of derivative 1
The specific synthetic route of derivative 1
Under the protection of nitrogen, to the there-necked flask of 500ml, 44.6g compounds D (100mmol), 20g compounds E are added in (90mmol), 0.04g palladiums (0.2mmol), 0.04g triphenylphosphines (0.2mmol), 60g20% sodium carbonate (200mmol) Solution, 150gTHF are heated to reflux 12 hours, and TLC tracks to no compound E；Reaction is finished, and is cooled to 30 DEG C, and filtering has separated Machine phase, water phase are extracted with toluene 50ml*3, and organic phase washing 200g*3 to pH=7 merges organic phase, and dry, normal pressure crosses silica gel Column；It crosses column to finish, toluene 50ml*2 elution silicagel columns, elution is finished, and leacheate is merged decompression prolapse solvent, precipitation with crossing column liquid Agent, which is finished, adds in ethyl alcohol and toluene mixed solution recrystallization twice, and 27.07g compound F, yield are obtained after drying：72.1%, HPLC： 98.57%；
HPLC-MS：Compound F theoretical molecular weights are 304.8, and actually detected result molecular weight is 304；
Under the protection of nitrogen, to the there-necked flask of 500ml, 29.9g compounds F (98mmol), 20g compounds C are added in (89mmol), 0.2g palladiums (0.2mmol), 0.3gX-phos, 21.2g sodium carbonate (200mmol), 200g toluene heat back Stream 12 hours, TLC tracks to no compound G；Reaction is finished, and is cooled to 30 DEG C, and filtering, toluene 50ml*3 is eluted, filtrate washing 200g*3 to pH=7, after dry, normal pressure crosses silicagel column；It crosses column to finish, toluene 50ml*2 elution silicagel columns, elution is finished, will be eluted Liquid merges decompression prolapse solvent with crossing column liquid, and desolventizing, which is finished, adds in toluene and petroleum ether mixed solution recrystallization, after drying 29.6g derivatives 1, yield：74%, HPLC：99.1%；
HPLC-MS：1 theoretical molecular weight of derivative is 448, and actually detected result molecular weight is 448.5；
H- NMR:δ9.33(1H,s),8.29(2H,dd),8.16(2H,d),8.02(1H,s),7.85(2H,t),7.84 (1H,s),7.75(1H,d),7.67(2H,m),7.62(1H,d),7. 52(1H,s),7.45(2H,t),7.41(1H,t), 7.25(2H,dd),6.69(1H,s)。
The synthesis of derivative 2
The synthetic route of derivative 2
Under the protection of nitrogen, to the there-necked flask of 500ml, 10g compounds D (32mmol), 15.1g compounds C are added in The bis- Diphenyl phosphino ferrocene palladium chlorides (10mmol) of (67mmol), 0.12g, 20% wet chemicals of 66g, 70g dioxies Six rings are heated to 80 DEG C, and TLC tracks to raw material compound D, and the reaction was complete；Reaction is finished, and is cooled to 20-30 DEG C, is filtered, layering, Water phase is extracted once with dichloromethane 50g, and organic phase is washed twice with water 100g, takes off dry solvent, and grease adds in 150g dichloros Methane crosses 5% silicagel column, and with 30g eluent methylene chloride pillars, leacheate is merged decompression prolapse solvent, precipitation with crossing column liquid Agent, which is finished, adds in 100ml ethyl alcohol recrystallizations, is beaten with 50ml toluene, filtering, and filter cake is eluted with toluene.11.1g is obtained after drying to derive Object 2, yield：67.85%, HPLC：99.3%；
HPLC-MS：2 theoretical molecular weight of derivative is 510.6, and actually detected result molecular weight is 510.5；
H- NMR:δ9.31(2H,s),8.20(4H,d),8.03(2H,s),7.84(2H,s),7.70(4H,t),7.65 (1H,s),7.63(2H,s),7.52(2H,dd),7.48(2H,t),7.3 6(1H,t)。
The synthesis of derivative 3
The synthetic route of derivative 3
Under the protection of nitrogen, to the there-necked flask of 500ml, 20g compounds D (64mmol), 0.14g palladiums (640 are added in μm ol), 0.19g tri-tert-butylphosphines (960 μm of ol), 20% solution of potassium carbonate of 65g, 100g toluene is heated to 70 DEG C；Nitrogen Under gas shielded, 10.05g compounds C (45mmol) is slowly added to, TLC tracks to no compound C；Reaction is finished, and is cooled to 20-30 DEG C, filtering, toluene 50ml*3 is eluted, filtrate layered, and water layer is extracted with 50g toluene, merges organic phase, with 150g water washings, has Machine mutually crosses 5% silicagel column, and filtrate takes off dry that 0.5h is stirred at room temperature in yellow paste, the 80g mashing of addition normal heptane.Filtering, filter Cake adds in toluene and ethyl alcohol recrystallization；14.5g compound E, yield are obtained after drying：78%, HPLC：98.0%；
HPLC-MS：Compound K theoretical molecular weight is 411.3, and actually detected result molecular weight is 411.7；
Under the protection of nitrogen, to the there-necked flask of 250ml, 5.8g carbazoles (35.3mmol), 0.25g cuprous bromides are added in (1.7mmol), 22.75g cesium carbonates (70mmol), 100gDMF are heated to 50 DEG C, and the DMF solution of 14.5g compounds E is added dropwise, 110 DEG C of reactions are warming up to, TLC tracks to no compound C；Reaction is finished, and is cooled to 20~30 DEG C, filtering, filtrate takes off dry, addition Toluene 100g crosses 2.0% silicagel column, is eluted with 100g toluene, crosses column liquid and leacheate merges, dry solvent is taken off, with dimethylbenzene weight Crystallization, filtering, dries to obtain 9.98g derivatives 3；Yield：62.5%, HPLC：98.9%；
HPLC-MS：3 theoretical molecular weight of derivative is 497.6, and actually detected result molecular weight is 497.6；
H- NMR:δ9.37(1H,s),8.66(1H,d),8.23(2H,d),8.14(1H,s),8.05(1H,s),8.02 (1H,s),7.90(1H,d),7.85(1H,s),7.74(1H,s),7.71 (1H,s),7.66(2H,dd),7.61(1H,d), 7.56(1H,m),7.52(1H,d),7.50(2H,m),7.48(1H,d),7.45(1H,d),7.30(1H,t),7.29(1H,m), 7.25(1H,t)。
The synthesis of derivative 4
The synthetic route of derivative 4
Under the protection of nitrogen, to the there-necked flask of 500ml, 22.4g compounds C (100mmol), 14.1g compounds D are added in (42mmol), 0.26g palladiums (10mmol), 0.3g tri-tert-butylphosphines (15mmol), 58g30% sodium carbonate liquors (126mmol), 100gTHF are heated to reflux tracking to no compound D to TLC；Reaction is finished, and is cooled to 20~30 DEG C, is filtered, point Layer, organic phase are washed twice with 70g, are taken off dry solvent and are obtained grease, cross silica gel column purification (n-hexane：Ethyl acetate=10:1 to 2:1), column liquid is crossed to take off dry solvent and obtain 13.6g derivatives 4, yield：61%, HPLC：99.3%；
HPLC-MS：4 theoretical molecular weight of derivative is 534.6, and actually detected result molecular weight is 534.1；
H-NMR:δ9.34(2H,s),8.28(4H,d),8.05(2H,s),7.99(2H,s),7.91(4H,d),7.69 (4H,m),7.33(4H,m)。
The synthesis of derivative 5
The synthetic route of derivative 5
25.5g bromobenzenes (162mmol) tetrahydrofuran solution is configured；To the there-necked flask of 250ml, 3.96g magnesium rods (165mmol) With 20g tetrahydrofurans, the tetrahydrofuran solution of 1.4g bromobenzenes is added in into reaction solution, is warming up to 40~50 DEG C, band reaction is drawn The tetrahydrofuran solution of remaining bromobenzene is added dropwise in hair, 55~65 DEG C of temperature control, and the tetrahydrofuran that compound E is obtained after qualification to be detected is molten Liquid is treated to react in next step；
Under nitrogen protection, addition 10g Cyanuric Chlorides (54mmol), 30g tetrahydrofurans into 500ml there-necked flasks, be cooled to- 5 DEG C, the tetrahydrofuran solution of compound E is slowly added dropwise in temperature control -5~0 DEG C, finishes, and it is qualified that 0 DEG C of heat preservation to TLC detects reaction； 9g hydrochloric acid and 80g water are slowly added into reaction solution, for 10~25 DEG C of stirrings of temperature control to pH≤2, reaction solution adds in 100g toluene, Organic phase is washed, and organic phase takes off dry, obtained solid n-hexane and re-crystallizing in ethyl acetate, obtains 10.5g, yield 72.8%, HPLC:99.22%；
HPLC-MS：Compound O theoretical molecular weights are 267.7, and actually detected result molecular weight is 267.7；
Under the protection of nitrogen, to the there-necked flask of 250ml, 10.5g compounds G (39mmol), 8.9g compounds C are added in The bis- Diphenyl phosphino ferrocene palladium chlorides of (40mmol), 0.2g (300 μm of ol), 50g20% tripotassium phosphate aqueous solutions, 100g bis- Toluene is warming up to 75 DEG C, and TLC tracks to no compound G；Reaction is finished, and is cooled to 20~30 DEG C, and filtering separates organic phase, uses Twice, organic phase crosses 5% silicagel column for washing；It crosses column to finish, silicagel column is eluted with dimethylbenzene；Elution is finished, by leacheate with crossing column liquid Merge decompression prolapse solvent, desolventizing finishes addition re-crystallizing in ethyl acetate, and 11.01g derivatives 5, yield are obtained after drying： 68.7%, HPLC：99.4%；
HPLC-MS：5 theoretical molecular weight of derivative is 411.1, and actually detected result molecular weight is 411；
H-NMR:δ9.44(1H,s),8.29(4H,d),8.2(2H,d),8.05(1H,s),7.79(1H,s),7.70(2H, t),7.50(4H,m),7.39(2H,t)。
Derivative for luminescent layer or electron transfer layer as OLED luminescent devices, applied to OLED active displays or Illuminating device.
The beneficial technological invention effect of the present invention is：
1. the OLED device prepared by derivative of the present invention, under the action of electric field, generated electroluminescent color can be shown Individually particular color of light or a variety of different colors combination light such as RGB are shown；
2. the present invention can obtain luminous efficiency by using the luminous organic material of quinazoline derivative and the service life is good The product got well, the product stability in use is high, can apply practicability OLED industries, such as printer, and computer display is answered Print machine, LCD lamps etc..
Description of the drawings
Fig. 1 is OLED device structure diagram of the present invention
Wherein, 1 is transparent substrate layer, and 2 be transparent electrode layer, and 3 be hole injection layer (HIM), and 4 be hole transmission layer (HTL), 5 It is electron transfer layer (ETL) for luminescent layer (EML), 6,7 be electron injecting layer, and 8 be cathode reflection electrode layer.
Specific embodiment
With reference to diagram and embodiment, the present invention is specifically described.
There is shared 4 benzo of intermediate [g] quinazoline -4- boric acid in example, synthetic method is as follows：
40g compounds A-1 (264mmol) is added in 500ml there-necked flasks, adds in 16g formic acid, 160ml formamides are warming up to 135 DEG C of heat preservations, keep the temperature 5h, and TLC detection raw material reactions finish；Add in 200ml water, 20~30 DEG C of heat preservation 1h, filtering, filter cake use Water wash with ethyl alcohol recrystallization, obtains 36.4g compound A-2, yield 93.1%, purity 98.2%.
36.4g compounds A-2 (185mmol) is added in 500ml there-necked flasks, adds in 100ml acetonitriles, adds in 80g tribromo oxygen Phosphorus (279mmol) is warming up to 80 DEG C of reflux.TLC detection raw material reactions finish, and remove acetonitrile, add in 200g water and 60g20% Sodium carbonate liquor, 20~30 DEG C of stirring 1h, turbid solution add in 200g dichloromethane and are extracted twice, and merge organic phase, saturated common salt Water washing is primary, and organic phase takes off dry compound A, and 35.2g, yield 73%, purity 98.7% are obtained with ethyl alcohol recrystallization.
25.9g compounds A (100mmol) is added in 500ml there-necked flasks to be added in 181.3gTHF, is cooled to -78 DEG C, Butyl lithium 48mL is slowly added dropwise less than -80 DEG C for control, keeps the temperature 1h, and triisopropyl borate ester 33.8g is added dropwise less than -70 DEG C for control (180mmol), keeps the temperature 2h, and HPLC tracking reactions terminate (HPLC>90%), reaction is finished, less than 20 DEG C 20% hydrochloric acid of addition of temperature control Aqueous solution 200g, layering separate water phase, organic to be added to 80g ethyl acetate, add in 100g*3 water washing organic phase three times, nothing Water magnesium sulfate is dried, and is taken off dry solvent, is obtained white solid.Compound C18.5g is refining to obtain with doubling dose toluene, yield 82.5%, HPLC：99.56%.
HPLC-MS：Compound C theoretical molecular weights are 224, and actually detected result molecular weight is 224.1.
H-NMR:δ9.31(1H,s),8.23(1H,s),8.11(2H,d),8.01(1H,s),7.57(1H,t)7.44(1H, t), 2.67(2H,s)。
The synthesis of 1 derivative 1 of embodiment
The specific synthetic route of derivative 1
Under the protection of nitrogen, to the there-necked flask of 500ml, 44.6g compounds D (100mmol), 20g compounds E are added in (90mmol), 0.04g palladiums (0.2mmol), 0.04g triphenylphosphines (0.2mmol), 60g20% sodium carbonate (200mmol) Solution, 150gTHF are heated to reflux 12 hours, and TLC tracks to no compound E.Reaction is finished, and is cooled to 30 DEG C, and filtering has separated Machine phase, water phase are extracted with toluene 50ml*3, and organic phase washing 200g*3 to pH=7 merges organic phase, and dry, normal pressure crosses silica gel Column.It crosses column to finish, toluene 50ml*2 elution silicagel columns, elution is finished, and leacheate is merged decompression prolapse solvent, precipitation with crossing column liquid Agent, which is finished, adds in ethyl alcohol and toluene mixed solution recrystallization twice, and 27.07g compound F, yield are obtained after drying：72.1%, HPLC： 98.57%.
HPLC-MS：Compound F theoretical molecular weights are 304.8, and actually detected result molecular weight is 304.
Under the protection of nitrogen, to the there-necked flask of 500ml, 29.9g compounds F (98mmol), 20g compounds C are added in (89mmol), 0.2g palladiums (0.2mmol), 0.3gX-phos, 21.2g sodium carbonate (200mmol), 200g toluene heat back Stream 12 hours, TLC tracks to no compound G.Reaction is finished, and is cooled to 30 DEG C, and filtering, toluene 50ml*3 is eluted, filtrate washing 200g*3 to pH=7, after dry, normal pressure crosses silicagel column.It crosses column to finish, toluene 50ml*2 elution silicagel columns, elution is finished, will be eluted Liquid merges decompression prolapse solvent with crossing column liquid, and desolventizing, which is finished, adds in toluene and petroleum ether mixed solution recrystallization, after drying 29.6g derivatives 1, yield：74%, HPLC：99.1%.
HPLC-MS：1 theoretical molecular weight of derivative is 448, and actually detected result molecular weight is 448.5.
H- NMR:δ9.33(1H,s),8.29(2H,dd),8.16(2H,d),8.02(1H,s),7.85(2H,t),7.84 (1H,s),7.75(1H,d),7.67(2H,m),7.62(1H,d),7. 52(1H,s),7.45(2H,t),7.41(1H,t), 7.25(2H,dd),6.69(1H,s)。
The synthesis of 2 derivative 2 of embodiment
The synthetic route of derivative 2
Under the protection of nitrogen, to the there-necked flask of 500ml, 10g compounds D (32mmol), 15.1g compounds C are added in The bis- Diphenyl phosphino ferrocene palladium chlorides (10mmol) of (67mmol), 0.12g, 20% wet chemicals of 66g, 70g dioxies Six rings are heated to 80 DEG C, and TLC tracks to raw material compound D, and the reaction was complete.Reaction is finished, and is cooled to 20-30 DEG C, filtering.Layering, Water phase is extracted once with dichloromethane 50g, and organic phase is washed twice with water 100g, takes off dry solvent.Grease adds in 150g dichloros Methane crosses 5% silicagel column, with 30g eluent methylene chloride pillars.Leacheate is merged into decompression prolapse solvent, precipitation with crossing column liquid Agent, which is finished, adds in 100ml ethyl alcohol recrystallizations, is beaten with 50ml toluene, filtering, and filter cake is eluted with toluene.11.1g is obtained after drying to derive Object 2, yield：67.85%, HPLC：99.3%.
HPLC-MS：2 theoretical molecular weight of derivative is 510.6, and actually detected result molecular weight is 510.5.
H- NMR:δ9.31(2H,s),8.20(4H,d),8.03(2H,s),7.84(2H,s),7.70(4H,t),7.65 (1H,s),7.63(2H,s),7.52(2H,dd),7.48(2H,t),7.3 6(1H,t)。
The synthesis of 3 derivative 3 of embodiment
The synthetic route of derivative 3
Under the protection of nitrogen, to the there-necked flask of 500ml, 20g compounds D (64mmol), 0.14g palladiums (640 are added in μm ol), 0.19g tri-tert-butylphosphines (960 μm of ol), 20% solution of potassium carbonate of 65g, 100g toluene is heated to 70 DEG C；Nitrogen Under gas shielded, 10.05g compounds C (45mmol) is slowly added to, TLC tracks to no compound C.Reaction is finished, and is cooled to 20-30 DEG C, filtering, toluene 50ml*3 is eluted, filtrate layered, and water layer is extracted with 50g toluene, merges organic phase, with 150g water washings, has Machine mutually crosses 5% silicagel column, and filtrate takes off dry that 0.5h is stirred at room temperature in yellow paste, the 80g mashing of addition normal heptane.Filtering, filter Cake adds in toluene and ethyl alcohol recrystallization.14.5g compound E, yield are obtained after drying：78%, HPLC：98.0%.
HPLC-MS：Compound K theoretical molecular weight is 411.3, and actually detected result molecular weight is 411.7.
Under the protection of nitrogen, to the there-necked flask of 250ml, 5.8g carbazoles (35.3mmol), 0.25g cuprous bromides are added in (1.7mmol), 22.75g cesium carbonates (70mmol), 100gDMF are heated to 50 DEG C, and the DMF solution of 14.5g compounds E is added dropwise, 110 DEG C of reactions are warming up to, TLC tracks to no compound C.Reaction is finished, and is cooled to 20~30 DEG C, filtering, filtrate takes off dry, addition Toluene 100g crosses 2.0% silicagel column, is eluted with 100g toluene, crosses column liquid and leacheate merges, dry solvent is taken off, with dimethylbenzene weight Crystallization, filtering, dries to obtain 9.98g derivatives 3.Yield：62.5%, HPLC：98.9%.
HPLC-MS：3 theoretical molecular weight of derivative is 497.6, and actually detected result molecular weight is 497.6.
H- NMR:δ9.37(1H,s),8.66(1H,d),8.23(2H,d),8.14(1H,s),8.05(1H,s),8.02 (1H,s),7.90(1H,d),7.85(1H,s),7.74(1H,s),7.71 (1H,s),7.66(2H,dd),7.61(1H,d), 7.56(1H,m),7.52(1H,d),7.50(2H,m),7.48(1H,d),7.45(1H,d),7.30(1H,t),7.29(1H,m), 7.25(1H,t)。
The synthesis of 4 derivative 4 of embodiment
The synthetic route of derivative 4
Under the protection of nitrogen, to the there-necked flask of 500ml, 22.4g compounds C (100mmol), 14.1g compounds D are added in (42mmol), 0.26g palladiums (10mmol), 0.3g tri-tert-butylphosphines (15mmol), 58g30% sodium carbonate liquors (126mmol), 100gTHF are heated to reflux tracking to no compound D to TLC.Reaction is finished, and is cooled to 20~30 DEG C, is filtered, point Layer, organic phase are washed twice with 70g, are taken off dry solvent and are obtained grease, cross silica gel column purification (n-hexane：Ethyl acetate=10:1 to 2:1), column liquid is crossed to take off dry solvent and obtain 13.6g derivatives 4, yield：61%, HPLC：99.3%.
HPLC-MS：4 theoretical molecular weight of derivative is 534.6, and actually detected result molecular weight is 534.1.
H-NMR:δ9.34(2H,s),8.28(4H,d),8.05(2H,s),7.99(2H,s),7.91(4H,d),7.69 (4H,m),7.33(4H,m)。
The synthesis of 5 derivative 5 of embodiment
The synthetic route of derivative 5
25.5g bromobenzenes (162mmol) tetrahydrofuran solution is configured.To the there-necked flask of 250ml, 3.96g magnesium rods (165mmol) With 20g tetrahydrofurans, the tetrahydrofuran solution of 1.4g bromobenzenes is added in into reaction solution, is warming up to 40~50 DEG C, band reaction is drawn The tetrahydrofuran solution of remaining bromobenzene is added dropwise in hair, 55~65 DEG C of temperature control, and the tetrahydrofuran that compound E is obtained after qualification to be detected is molten Liquid is treated to react in next step.
Under nitrogen protection, addition 10g Cyanuric Chlorides (54mmol), 30g tetrahydrofurans into 500ml there-necked flasks, be cooled to- 5 DEG C, the tetrahydrofuran solution of compound E is slowly added dropwise in temperature control -5~0 DEG C, finishes, and it is qualified that 0 DEG C of heat preservation to TLC detects reaction. 9g hydrochloric acid and 80g water are slowly added into reaction solution, for 10~25 DEG C of stirrings of temperature control to pH≤2, reaction solution adds in 100g toluene, Organic phase is washed, and organic phase takes off dry, obtained solid n-hexane and re-crystallizing in ethyl acetate, obtains 10.5g, yield 72.8%, HPLC:99.22%
HPLC-MS：Compound O theoretical molecular weights are 267.7, and actually detected result molecular weight is 267.7.
Under the protection of nitrogen, to the there-necked flask of 250ml, 10.5g compounds G (39mmol), 8.9g compounds C are added in The bis- Diphenyl phosphino ferrocene palladium chlorides of (40mmol), 0.2g (300 μm of ol), 50g20% tripotassium phosphate aqueous solutions, 100g bis- Toluene is warming up to 75 DEG C, and TLC tracks to no compound G.Reaction is finished, and is cooled to 20~30 DEG C, and filtering separates organic phase, uses Twice, organic phase crosses 5% silicagel column for washing.It crosses column to finish, silicagel column is eluted with dimethylbenzene.Elution is finished, by leacheate with crossing column liquid Merge decompression prolapse solvent, desolventizing finishes addition re-crystallizing in ethyl acetate, and 11.01g derivatives 5, yield are obtained after drying： 68.7%, HPLC：99.4%.
HPLC-MS：5 theoretical molecular weight of derivative is 411.1, and actually detected result molecular weight is 411.
H-NMR:δ9.44(1H,s),8.29(4H,d),8.2(2H,d),8.05(1H,s),7.79(1H,s),7.70(2H, t),7.50(4H,m),7.39(2H,t)。
It is imitated below by application of the compound that the present invention will be described in detail synthesizes of Application Example 1~5 in OLED device Fruit.
The present invention can obtain luminous efficiency and service life by using the luminous organic material of benzo [g] quinazoline compound Good product, the product stability in use are high, can apply practicability OLED industries, such as printer, computer display, Duplicator, LCD lamps etc..
Comparative example 1
Comparative example 1 carries out light to the transparent electrode layer 2 (the film thickness 215nm of transparent electrode layer 2) with transparent substrate layer 1 It carves and etching, the figure of the transparent electrode layer 2 of formation rule, glass transparent substrate layer 1 carries out alkali cleaning, high-purity water washing successively, Carry out ultraviolet-ozone washing removal organic residue after drying to 2 surface of transparent electrode layer again.After washing, to transparent substrate (molybdenum crucible, evaporation rate 0.1nm/s, vacuum degree about 5.0*10 is deposited in the anode of layer 1-5Pa), following structural formula is deposited (1) organic compound shown in is 60nm as hole class material, making film thickness, and the layer is as hole injection layer 3：
On hole injection layer 3, pass through vacuum deposition apparatus (molybdenum crucible, evaporation rate 0.1nm/s, vacuum degree about 5.0* 10-5Pa), vapor deposition structural formula (2) organic compound is used as hole transmission layer 4, film thickness 10nm
The luminescent layer 5 of device is that structural formula (3) compound is vaporized on hole transmission layer 4 (molybdenum crucible, evaporation rate 0.1nm/s, vacuum degree about 5.0*10-5Pa)
Electron transfer layer 6 is on luminescent layer 5, and by evaporation coating device, (molybdenum crucible, evaporation rate 0.1nm/s, vacuum degree is about 5.0*10-5Pa), it is deposited structural formula (4) compound as electron transport material to above luminescent layer, making film thickness is The electron transfer layer of 25nm；
Electron injecting layer 7 is lithium fluoride (LiF) layer of film thickness 1nm, this layer passes through vacuum deposition apparatus (molybdenum crucible, vapor deposition Speed 0.1nm/s, vacuum degree about 5.0*10-5Pa) prepared by vapor deposition；
Reflection electrode layer 8 is aluminium (Al) layer of film thickness 140nm, this layer passes through vacuum deposition apparatus (BN crucibles, evaporation rate 0.1nm/s, vacuum degree about 5.0*10-5Pa) prepared by vapor deposition.
After the completion of element manufacturing, anode and cathode are connected with well known driving circuit, utilize briliancy analyzer (strain Formula commercial firm TOPCON systems, trade name BM7) measurement device luminous efficiency, the I-E characteristic of luminescent spectrum and device.
The manufacture craft of 1~5 device of application examples of the present invention is identical, and device uses identical substrate and electricity Pole material, while ensure that the film thickness of electrode material is identical, difference only changes luminescent layer or electron transport material into respectively Each principal structural layer compound used therefor of device such as table 1 made by material of the present invention, comparative example 1 and application examples 1~5
Table 1
Luminous organic material prepared by the present invention, using KEITHELY2400 types source measuring unit, CS-2000 spectrophotometric tests Meter detection, to evaluate luminescent device service life, luminous efficiency and color.
The results are shown in Table 2 for OLED luminescent devices made by comparative example 1 and application examples 1~5.
Table 2
Show that the luminescent device prepared using organic compound of the present invention as OLED luminescent materials is more existing by the analysis of table 2 The OLED luminescent devices of application, under the action of electric field, generated electroluminescent color can show that RGB etc. is individual Particular color of light or a variety of different colors combination light, be respectively provided in terms of luminous efficiency and colouristic properties and service life compared with Big advantage has good industrialization prospect.
From the point of view of data above application, benzo [g] quinazoline ditosylate salt organic electroluminescent compounds of the present invention are in OLED In luminescent device there is good application effect, there is good industrialization prospect.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of benzo [g] quinazoline derivant, it is characterised in that the derivative based on benzo [g] quinazoline structure, Shown in the general formula of molecular structure such as general formula (1)：
In general formula (1), R1 for xenyl, terphenyl, carbazyl, naphthalene, anthryl, fluorenyl, pyrenyl, phenanthryl, benzofuranyl, Benzothienyl, Fluorenone base, dibenzodioxin English base, benzo [g] quinazolyl, benzfluorene ketone group, dibenzofuran group, hexichol One or more of bithiophene base or the triazine radical of diaryl substitution.
2. benzo [g] quinoline azoles woods derivative according to claim 1, it is characterised in that the R1 is selected from：
One or more of combination.
3. benzo [g] quinoline azoles woods derivative according to claim 1, it is characterised in that the concrete structure formula of the derivative For
。
4. according to the preparation method and applications of benzo [g] quinoline azoles woods derivative described in claim 1, which is characterized in that Benzo [g] the quinoline azoles woods derivative follows the steps below, wherein shared intermediate C benzos [g] quinoline azoles woods -4- boron Acid, synthetic method are as follows：
40g derivatives A-1 (264mmol) is added in 500ml there-necked flasks, adds in 16g formic acid, 160ml formamides are warming up to 135 DEG C heat preservation, keep the temperature 5h, TLC detection raw material reaction finishes；200ml water is added in, 20~30 DEG C of heat preservation 1h are filtered, filter cake is drenched with water It washes, with ethyl alcohol recrystallization, obtains 36.4g derivative A-2, yield 93.1%, purity 98.2%；
36.4g derivatives A-2 (185mmol) is added in 500ml there-necked flasks, adds in 100ml acetonitriles, adds in 80g tribromo oxygen phosphorus (279mmol) is warming up to 80 DEG C of reflux；TLC detection raw material reactions finish, and remove acetonitrile, add in 200g water and 60g20% carbonic acid Sodium solution, 20~30 DEG C of stirring 1h, turbid solution add in 200g dichloromethane and are extracted twice, and merge organic phase, saturated common salt washing Wash primary, organic phase takes off dry derivative A, and 35.2g, yield 73%, purity 98.7% are obtained with ethyl alcohol recrystallization；
25.9g derivatives A (100mmol) is added in 500ml there-necked flasks to be added in 181.3gTHF, is cooled to -78 DEG C, control Butyl lithium 48mL is slowly added dropwise less than -80 DEG C, keeps the temperature 1h, triisopropyl borate ester 33.8g is added dropwise less than -70 DEG C for control (180mmol), keeps the temperature 2h, and HPLC tracking reactions terminate (HPLC>90%), reaction is finished, less than 20 DEG C 20% hydrochloric acid of addition of temperature control Aqueous solution 200g, layering separate water phase, organic to be added to 80g ethyl acetate, add in 100g*3 water washing organic phase three times, nothing Water magnesium sulfate is dried, and is taken off dry solvent, is obtained white solid.Compound C18.5g is refining to obtain with doubling dose toluene, yield 82.5%, HPLC：99.56%；
HPLC-MS：Compound C theoretical molecular weights are 224, and actually detected result molecular weight is 224.1；
H-NMR:δ9.31(1H,s),8.23(1H,s),8.11(2H,d),8.01(1H,s),7.57(1H,t)7.44(1H,t), 2.67(2H,s)。
5. according to the preparation method and applications of benzo [g] quinazoline derivant described in claim 1, which is characterized in that The synthesis of the derivative 1：
The specific synthetic route of derivative 1
Under the protection of nitrogen, to the there-necked flask of 500ml, 44.6g compounds D (100mmol), 20g compounds E are added in (90mmol), 0.04g palladiums (0.2mmol), 0.04g triphenylphosphines (0.2mmol), 60g20% sodium carbonate (200mmol) are molten Liquid, 150gTHF are heated to reflux 12 hours, and TLC tracks to no compound E；Reaction is finished, and is cooled to 30 DEG C, and filtering separates organic Phase, water phase are extracted with toluene 50ml*3, and organic phase washing 200g*3 to pH=7 merges organic phase, and dry, normal pressure crosses silicagel column； It crosses column to finish, toluene 50ml*2 elution silicagel columns, elution is finished, and leacheate is merged decompression prolapse solvent with crossing column liquid, desolventizing is finished It adds in ethyl alcohol to recrystallize twice with toluene mixed solution, 27.07g compound F, yield is obtained after drying：72.1%, HPLC： 98.57%；
HPLC-MS：Compound F theoretical molecular weights are 304.8, and actually detected result molecular weight is 304；
Under the protection of nitrogen, to the there-necked flask of 500ml, 29.9g compounds F (98mmol), 20g compounds C are added in (89mmol), 0.2g palladiums (0.2mmol), 0.3gX-phos, 21.2g sodium carbonate (200mmol), 200g toluene heat back Stream 12 hours, TLC tracks to no compound G；Reaction is finished, and is cooled to 30 DEG C, and filtering, toluene 50ml*3 is eluted, filtrate washing 200g*3 to pH=7, after dry, normal pressure crosses silicagel column；It crosses column to finish, toluene 50ml*2 elution silicagel columns, elution is finished, by leacheate Merge decompression prolapse solvent with crossing column liquid, desolventizing, which is finished, adds in toluene and petroleum ether mixed solution recrystallization, and 29.6g is obtained after drying Derivative 1, yield：74%, HPLC：99.1%；
HPLC-MS：1 theoretical molecular weight of derivative is 448, and actually detected result molecular weight is 448.5；
H-NMR:δ9.33(1H,s),8.29(2H,dd),8.16(2H,d),8.02(1H,s),7.85(2H,t),7.84(1H, s),7.75(1H,d),7.67(2H,m),7.62(1H,d),7.52(1H,s),7.45(2H,t),7.41(1H,t),7.25(2H, dd),6.69(1H,s)。
6. according to the preparation method and applications of benzo [g] quinazoline derivant described in claim 1, which is characterized in that The synthesis of the derivative 2：
The synthetic route of derivative 2
Under the protection of nitrogen, to the there-necked flask of 500ml, 10g compounds D (32mmol), 15.1g compounds C are added in The bis- Diphenyl phosphino ferrocene palladium chlorides (10mmol) of (67mmol), 0.12g, 20% wet chemicals of 66g, 70g dioxies six Ring is heated to 80 DEG C, and TLC tracks to raw material compound D, and the reaction was complete；Reaction is finished, and is cooled to 20-30 DEG C, is filtered, layering, water Mutually primary with dichloromethane 50g extractions, organic phase is washed twice with water 100g, takes off dry solvent, and grease adds in 150g dichloromethanes Alkane crosses 5% silicagel column, and with 30g eluent methylene chloride pillars, leacheate is merged decompression prolapse solvent, desolventizing with crossing column liquid Finish and add in 100ml ethyl alcohol recrystallizations, be beaten with 50ml toluene, filtering elutes filter cake with toluene.11.1g derivatives are obtained after drying 2, yield：67.85%, HPLC：99.3%；
HPLC-MS：2 theoretical molecular weight of derivative is 510.6, and actually detected result molecular weight is 510.5；
H-NMR:δ9.31(2H,s),8.20(4H,d),8.03(2H,s),7.84(2H,s),7.70(4H,t),7.65(1H,s), 7.63(2H,s),7.52(2H,dd),7.48(2H,t),7.36(1H,t)。
7. according to the preparation method and applications of benzo [g] quinazoline derivant described in claim 1, which is characterized in that The synthesis of the derivative 3:
The synthetic route of derivative 3
Under the protection of nitrogen, to the there-necked flask of 500ml, 20g compounds D (64mmol), 0.14g palladiums (640 μ are added in Mol), 0.19g tri-tert-butylphosphines (960 μm of ol), 20% solution of potassium carbonate of 65g, 100g toluene are heated to 70 DEG C；Nitrogen Under protection, 10.05g compounds C (45mmol) is slowly added to, TLC tracks to no compound C；Reaction is finished, and is cooled to 20-30 DEG C, Filtering, toluene 50ml*3 elution, filtrate layered, water layer are extracted with 50g toluene, merge organic phase, with 150g water washings, organic phase 5% silicagel column is crossed, filtrate takes off dry that 0.5h is stirred at room temperature in yellow paste, the 80g mashing of addition normal heptane.Filtering, filter cake add in Toluene and ethyl alcohol recrystallization；14.5g compound E, yield are obtained after drying：78%, HPLC：98.0%；
HPLC-MS：Compound K theoretical molecular weight is 411.3, and actually detected result molecular weight is 411.7；
Under the protection of nitrogen, to the there-necked flask of 250ml, 5.8g carbazoles (35.3mmol), 0.25g cuprous bromides are added in (1.7mmol), 22.75g cesium carbonates (70mmol), 100gDMF are heated to 50 DEG C, and the DMF solution of 14.5g compounds E is added dropwise, 110 DEG C of reactions are warming up to, TLC tracks to no compound C；Reaction is finished, and is cooled to 20~30 DEG C, filtering, filtrate takes off dry, addition first Benzene 100g crosses 2.0% silicagel column, is eluted with 100g toluene, crosses column liquid and leacheate merges, take off dry solvent, tied again with dimethylbenzene Crystalline substance, filtering, dries to obtain 9.98g derivatives 3；Yield：62.5%, HPLC：98.9%；
HPLC-MS：3 theoretical molecular weight of derivative is 497.6, and actually detected result molecular weight is 497.6；
H-NMR:δ9.37(1H,s),8.66(1H,d),8.23(2H,d),8.14(1H,s),8.05(1H,s),8.02(1H,s), 7.90(1H,d),7.85(1H,s),7.74(1H,s),7.71(1H,s),7.66(2H,dd),7.61(1H,d),7.56(1H, m),7.52(1H,d),7.50(2H,m),7.48(1H,d),7.45(1H,d),7.30(1H,t),7.29(1H,m),7.25(1H, t)。
8. according to the preparation method and applications of benzo [g] quinazoline derivant described in claim 1, which is characterized in that The synthesis of the derivative 4:
The synthetic route of derivative 4
Under the protection of nitrogen, to the there-necked flask of 500ml, 22.4g compounds C (100mmol), 14.1g compounds D are added in (42mmol), 0.26g palladiums (10mmol), 0.3g tri-tert-butylphosphines (15mmol), 58g30% sodium carbonate liquors (126mmol), 100gTHF are heated to reflux tracking to no compound D to TLC；Reaction is finished, and is cooled to 20~30 DEG C, is filtered, point Layer, organic phase are washed twice with 70g, are taken off dry solvent and are obtained grease, cross silica gel column purification (n-hexane：Ethyl acetate=10:1 to 2:1), column liquid is crossed to take off dry solvent and obtain 13.6g derivatives 4, yield：61%, HPLC：99.3%；
HPLC-MS：4 theoretical molecular weight of derivative is 534.6, and actually detected result molecular weight is 534.1；
H-NMR:δ9.34(2H,s),8.28(4H,d),8.05(2H,s),7.99(2H,s),7.91(4H,d),7.69(4H,m), 7.33(4H,m)。
9. according to the preparation method and applications of benzo [g] quinazoline derivant described in claim 1, which is characterized in that The synthesis of the derivative 5:
The synthetic route of derivative 5
25.5g bromobenzenes (162mmol) tetrahydrofuran solution is configured；To the there-necked flask of 250ml, 3.96g magnesium rods (165mmol) and 20g tetrahydrofurans add in the tetrahydrofuran solution of 1.4g bromobenzenes into reaction solution, are warming up to 40~50 DEG C, band reaction causes, control The tetrahydrofuran solution of remaining bromobenzene is added dropwise in 55~65 DEG C of temperature, and the tetrahydrofuran solution that compound E is obtained after qualification to be detected is treated down Single step reaction；
Under nitrogen protection, 10g Cyanuric Chlorides (54mmol) are added in into 500ml there-necked flasks, 30g tetrahydrofurans are cooled to -5 DEG C, The tetrahydrofuran solution of compound E is slowly added dropwise in temperature control -5~0 DEG C, finishes, and it is qualified that 0 DEG C of heat preservation to TLC detects reaction；To reaction 9g hydrochloric acid and 80g water are slowly added in liquid, for 10~25 DEG C of stirrings of temperature control to pH≤2, reaction solution adds in 100g toluene, organic phase water It washes, organic phase takes off dry, obtained solid n-hexane and re-crystallizing in ethyl acetate, obtains 10.5g, yield 72.8%, HPLC: 99.22%；
HPLC-MS：Compound O theoretical molecular weights are 267.7, and actually detected result molecular weight is 267.7；
Under the protection of nitrogen, to the there-necked flask of 250ml, 10.5g compounds G (39mmol), 8.9g compounds C are added in The bis- Diphenyl phosphino ferrocene palladium chlorides of (40mmol), 0.2g (300 μm of ol), 50g20% tripotassium phosphate aqueous solutions, 100g diformazans Benzene is warming up to 75 DEG C, and TLC tracks to no compound G；Reaction is finished, and is cooled to 20~30 DEG C, and filtering separates organic phase, is washed with water Twice, organic phase crosses 5% silicagel column；It crosses column to finish, silicagel column is eluted with dimethylbenzene；Elution is finished, and leacheate is merged with crossing column liquid Prolapse solvent is depressurized, desolventizing finishes addition re-crystallizing in ethyl acetate, and 11.01g derivatives 5, yield are obtained after drying：68.7%, HPLC：99.4%；HPLC-MS：5 theoretical molecular weight of derivative is 411.1, and actually detected result molecular weight is 411；
H-NMR:δ9.44(1H,s),8.29(4H,d),8.2(2H,d),8.05(1H,s),7.79(1H,s),7.70(2H,t), 7.50(4H,m),7.39(2H,t)。
10. according to the preparation method and applications of benzo [g] quinazoline derivant described in claim 1, which is characterized in that The derivative is for the luminescent layer or electron transfer layer as OLED luminescent devices, applied to OLED active displays or illumination Device.
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