CN107868049A - Organic compound and organic electroluminescence device using the fluorenes of 9,9 ' spiral shell two as core - Google Patents

Organic compound and organic electroluminescence device using the fluorenes of 9,9 ' spiral shell two as core Download PDF

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CN107868049A
CN107868049A CN201611207901.3A CN201611207901A CN107868049A CN 107868049 A CN107868049 A CN 107868049A CN 201611207901 A CN201611207901 A CN 201611207901A CN 107868049 A CN107868049 A CN 107868049A
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layer
formula
fluorenes
reaction
spiral shell
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唐丹丹
张兆超
李崇
张小庆
王立春
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Jiangsu Sunera Technology Co Ltd
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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Abstract

The present invention relates to organic compound of the one kind with the fluorenes of 9,9 ' spiral shell two for core and its application on organic electroluminescence device, the structural formula formula such as formula (1) of the organic compound are shown.Organic compound glass transition temperature provided by the invention is high, and molecule heat endurance is strong, has suitable HOMO and lumo energy and higher Eg, is optimized by device architecture, can effectively lift the photoelectric properties of OLED and the life-span of OLED.

Description

Organic compound and organic electroluminescence device using the fluorenes of 9,9 '-spiral shell two as core
Technical field
The present invention relates to organic photoelectrical material technical field, more particularly, to one kind with the fluorenes of 9,9 '-spiral shell two having for core Machine compound and its application on organic electroluminescence device.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used for make New display product is made, can be used for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is quite varied.
OLED luminescent devices just as the structure of sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it Between organic functional material, various difference in functionality materials are overlapped mutually according to purposes collectively constitutes OLED luminescent devices together. As current device, when the two end electrodes to OLED luminescent devices apply voltage, and pass through electric field action organic layer functional material Positive and negative charge in film layer, positive and negative charge is further compound in luminescent layer, that is, produces OLED electroluminescent.
Currently, OLED Display Techniques are applied in fields such as smart mobile phone, tablet personal computers, further will also be to electricity Depending on etc. large scale application field extension, still, with reality products application requirement compare, the luminous efficiency of OLED, use The performances such as life-span also need to further be lifted.
Proposing high performance research for OLED luminescent devices includes：The driving voltage of device is reduced, improves the luminous of device Efficiency, improve service life of device etc..In order to realize the continuous lifting of the performance of OLED, not only need from OLED The innovation of structure and manufacture craft, with greater need for the constantly research and innovation of oled light sulfate ferroelectric functional material, formulate out higher performance OLED Functional material.
Oled light sulfate ferroelectric functional material applied to OLED can be divided into two major classes, i.e. electric charge injection transmission from purposes Material and luminescent material, further, it can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking material Luminescent material, can also be divided into main body luminescent material and dopant material by material, hole injection transmission material and hole barrier materials.
In order to make high performance OLED luminescent devices, it is desirable to various organic functional materials possess good photoelectric characteristic, For example, as charge transport materials, it is desirable to there is good carrier mobility, high-vitrification conversion temperature etc., as luminous The material of main part of layer requires that material has good bipolarity, appropriate HOMO/LUMO energy ranks etc..
The oled light sulfate ferroelectric functional material film layer for forming OLED comprises at least more than two layers structure, is applied in industry OLED structure, then passed including hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronics A variety of film layers such as defeated layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED is noted including at least hole Enter material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and more The characteristics of sample.In addition, for the OLED collocation of different structure, used photoelectric functional material has stronger Selectivity, performance of the identical material in different structure device, it is also possible to completely totally different.
Therefore, for the difference in functionality film layer of the industry application requirement of current OLED, and OLED, device Photoelectric characteristic demand, it is necessary to which selection is more suitable for, and has high performance OLED functional materials or combination of materials, could realize device The overall characteristic of high efficiency, long-life and low-voltage.For the actual demand that current OLED shows Lighting Industry, OLED at present The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, as the organic of material enterprise development higher performance Functional material is particularly important.
The content of the invention
In view of the above-mentioned problems existing in the prior art, it is the organic of core with the fluorenes of 9,9 '-spiral shell two the invention provides one kind Compound and its applied on organic electroluminescence device.Organic compound glass transition temperature provided by the invention is high, molecule heat Stability is strong, has suitable HOMO and lumo energy and higher Eg, is optimized by device architecture, can effectively lift OLED devices The photoelectric properties of part and the life-span of OLED.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of organising using the fluorenes of 9,9 '-spiral shell two as core Compound, shown in the general structure such as formula (1) of the compound：
Wherein, m, n, o, p are equal to 0 or 1；M, it is 1 that n, o, p are at least one；
X is oxygen atom, sulphur atom, C1-10The alkylidene or C of straight chain base substitution1-10Alkylidene, the aryl of branched alkyl substitution One kind in the tertiary amine groups that substituted alkylidene, alkyl-substituted tertiary amine groups or aryl substitutes；
Ar represents phenyl, xenyl, naphthyl, anthryl, phenanthryl, pyrenyl, furyl, thienyl, pyridine radicals, pyrimidine radicals, rattled away One kind in piperazine base, pyrazinyl or triazine radical；
R1、R2Independently be expressed as hydrogen atom, formula (2), formula (3), formula (4), formula (5), formula (6), logical Structure shown in formula (7)；R1With R2It is at least one to be selected from formula (2), formula (3), formula (4), formula (5), formula (6), formula (7) structure shown in；
In formula (2), a is selected fromX1、X2、X3、X4Independently be expressed as oxygen Atom, sulphur atom, C1-10The alkylidene or C of straight chained alkyl substitution1-10Alkylidene, the alkylene of aryl substitution of branched alkyl substitution One kind in the tertiary amine groups of base, alkyl-substituted tertiary amine groups or aryl substitution；
R in formula (2), formula (3)3For hydrogen atom, halogen atom or C1-10Straight chained alkyl or C1-10Branched alkyl；
Structure shown in formula (2), formula (3) passes through in simultaneously ring and formula (1)Connection；
X in formula (5), formula (7)5For oxygen atom, sulphur atom, C1-10The alkylidene or C of straight chained alkyl substitution1-10Side chain One kind in alkyl-substituted alkylidene, the alkylidene of aryl substitution, alkyl-substituted tertiary amine groups or the tertiary amine groups of aryl substitution；
R in formula (6)4、R5Independently be expressed as phenyl, naphthyl, dibiphenylyl, terphenyl, dibenzofurans, One kind in dibenzothiophenes or 9,9- dimethyl fluorenes.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
The present invention also provides a kind of preparation method with the fluorenes of 9,9 '-spiral shell two for the organic compound of core, specific reaction side Formula is：
Specifically include following steps：
1) with the fluorenes bromo-derivative of 9,9 '-spiral shell twoAnd boronic acid compoundsIt is molten for raw material, toluene Solution, the toluene dosage are every gram 9, and the fluorenes bromo-derivative of 9 '-spiral shell two uses 30-50ml toluene, wherein, described 9, the fluorenes bromine of 9 '-spiral shell two For thingWith boronic acid compoundsMol ratio be 1:(1.2~5.0)；
2) Pd (PPh are added into above-mentioned reaction system3)4And sodium carbonate, wherein, the Pd (PPh3)4With 9,9 '-spiral shell two The mol ratio of fluorenes bromo-derivative is (0.006~0.04):1, the sodium carbonate and 9, the mol ratio of the fluorenes bromo-derivative of 9 '-spiral shell two is (2.0 ~8.0):1；
3) under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, react 10~24 hours, naturally cool to room Temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel post, obtain target product.
The present invention also provides a kind of organic electroluminescence device, further, at least one layer of functional layer contain it is above-mentioned with 9,9 '- The fluorenes of spiral shell two is the organic compound of core.
A kind of above-mentioned organic electroluminescence device of the present invention, further, including electronic barrier layer, the electronic barrier layer material Expect for the above-mentioned organic compound using the fluorenes of 9,9 '-spiral shell two as core.
A kind of above-mentioned organic electroluminescence device of the present invention, further, in addition to transparent substrate layer, ito anode layer, hole Implanted layer, hole transmission layer, luminescent layer, hole barrier/electron transfer layer, electron injecting layer and negative electrode reflection electrode layer, it is described Transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole barrier/electronics pass Defeated layer, electron injecting layer and negative electrode reflection electrode layer stack gradually arrangement from bottom to up.Specifically, the hole injection layer can be with For material HAT-CN, thickness 10nm；Or/and the hole transport/electronic blocking layer material can be above-mentioned with 9,9 '-spiral shell two Fluorenes is the organic compound of core, and its thickness is 80nm, or/and the luminescent layer is using CBP as material of main part, Ir (ppy)3Make For phosphorescence dopant material, Ir (ppy)3Mass ratio with CBP is 1：9, thickness 30nm, or/and the hole barrier/electronics pass Defeated layer, its material can be TPBI, thickness 40nm, and/or the electron injecting layer can be LiF materials, and its thickness is 1nm, and/or the negative electrode reflection electrode layer can be materials A l, and its thickness is 100nm.
The present invention also provides a kind of organic electroluminescence device, including luminescent layer, the luminescent layer include it is above-mentioned with 9,9 '- The fluorenes of spiral shell two is the organic compound of core.
A kind of organic electroluminescence device as described above of the invention, further, in addition to transparent substrate layer, ito anode layer, Hole injection layer, hole transmission layer, electronic barrier layer, hole barrier/electron transfer layer, electron injecting layer and negative electrode reflecting electrode Layer, the transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole barrier/ Electron transfer layer, electron injecting layer and negative electrode reflection electrode layer stack gradually arrangement from bottom to up.Specifically, the hole injection Layer is material HAT-CN, thickness 10nm；Or/and the hole transport/electronic blocking layer material can be NPB, thickness is 80nm, or/and the luminescent layer with it is above-mentioned with the fluorenes of 9,9 '-spiral shell two for core organic compound as material of main part, Ir (ppy)3As phosphorescence dopant material, Ir (ppy) 3 and the mass ratio with the fluorenes of 9,9 '-spiral shell two for the organic compound of core For 1：9, thickness 30nm, or/and the hole barrier/electron transfer layer, its material can be TPBI, thickness 40nm, and/ Or the electron injecting layer can be LiF materials, its thickness is 1nm, and/or the negative electrode reflection electrode layer can be material Al, its thickness are 100nm.
The beneficial effects of the invention are as follows：The compounds of this invention structure make it that electronics and hole are more flat in the distribution of luminescent layer Weighing apparatus, under appropriate HOMO energy levels, improves hole injection/transmission performance；Under suitable lumo energy, electronics is served again The effect of stop, combined efficiency of the lifting exciton in luminescent layer；Light emitting functional layer materials'use as OLED luminescent devices When, the 9 of aryl substitution, the side chain that the fluorenes of 9 '-spiral shell two is arranged in pairs or groups in the scope of the invention can effectively improve exciton utilization rate and high fluorescence spoke Efficiency is penetrated, reduces the efficiency roll-off under high current density, reduces device voltage, improves current efficiency and the life-span of device.
Compound of the present invention has good application effect in OLED luminescent devices, before having good industrialization Scape.
Brief description of the drawings
Fig. 1 is the materials application cited by the present invention in the structural representation of OLED；
Wherein, 1, transparent substrate layer, 2, ito anode layer, 3, hole injection layer, 4, hole transmission layer, 5, electronic barrier layer, 6th, luminescent layer, 7, hole barrier/electron transfer layer, 8, electron injecting layer, 9 be negative electrode reflection electrode layer.
Embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.
In formula 1, intermediateSynthesis：
If X isAtomic time：
Weigh raw material I-1 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid and slowly drip Add in raw material I-1 acetic acid solution, reaction is stirred at room temperature until reaction completely, after reaction terminates, alkali is added into reaction solution Liquid is neutralized, and is extracted with dichloromethane, is layered, takes organic phase to filter, and filtrate decompression is rotated to without cut, is crossed silicagel column, is obtained mesh Mark product Intermediate S1-1；In the reaction, the molar ratio of raw material I-1 and bromine is 1:1~3；
Under nitrogen protection, intermediate S1-1, raw material II -1, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-tert Phosphine, it is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, shows no intermediate S1-1 is remaining, and reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam extremely without cut, crosses neutral silica gel post, Obtain intermediate S2.In above-mentioned reaction, intermediate S1-1 is 1 with the mol ratio of raw material II -1：1~2；Intermediate S1-1 and potassium carbonate Mol ratio be 1:1~3；The mol ratio of intermediate S1-1 and four triphenyl phosphorus palladiums is 1:0.01~0.05；
Under nitrogen protection, intermediate S2 is weighed, tetrahydrofuran stirring and dissolving is added, is cooled to 0 DEG C with ice salt bath, slowly The tetrahydrofuran solution of the corresponding grignard reagent of brand-new is added dropwise, after being added dropwise to complete, is warmed to room temperature reaction 6~12 hours, sample point Plate, show that no intermediate S2 is remaining, reaction is complete；Naturally to place to room temperature, filtering, filtrate carries out vacuum rotary steam to without cut, Neutral silica gel post is crossed, obtains intermediate S3；In above-mentioned reaction, the mol ratio of intermediate S2 and grignard reagent is 1:2~4；
Under nitrogen protection, intermediate S3 is weighed, adds dense H3PO4It is 1 with water volume ratio:3 mixed liquor, is stirred, Incubation at room temperature reacts 6~12 hours, sample point plate, shows that no intermediate S3 is remaining, reaction is complete；The NaOH aqueous solution is added to neutralize To pH=7, dichloromethane extraction being added, layering, takes organic phase to filter, filtrate decompression is rotated to without cut, crosses neutral silica gel post, Obtain intermediate II -1；Intermediate S3 and H3PO4Mol ratio is 1:3~6；
Under nitrogen protection, intermediate II -1, raw material IV, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, It is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, shows no intermediate II -1 Residue, reaction are complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam to without cut, crosses neutral silica gel post, obtains Intermediate S4.In above-mentioned reaction, intermediate II -1 is 1 with the mol ratio of raw material IV：1~2；Intermediate II -1 is rubbed with sodium tert-butoxide You are than being 1:1~3；Intermediate II -1 and Pd2(dba)3, tri-butyl phosphine mol ratio be 1:0.01~0.05；
Under the protection of logical nitrogen, intermediate S4, connection boric acid pinacol ester, potassium acetate, Pd (dppf) Cl are weighed2, 1,4- bis- The ring of oxygen six, mix, be heated to 80~100 DEG C, react 10-24 hours, sample point plate, show that no intermediate S4 is remaining, instead Should be complete, room temperature is naturally cooled to, has solid precipitation after adding water, filters, takes filter cake to be dried with vacuum drying chamber, it is then excessively neutral Silicagel column, boric acid ester compound is obtained, dissolve boric acid ester compound with THF, add sodium metaperiodate, HCl/water solution regulation pH To 2~3, hydrolysis is stirred at room temperature 12~16 hours, sample point plate, shows that no boric acid ester compound is remaining, hydrolysis is complete, adds water dilute Reaction solution is released, is extracted with ethyl acetate, is layered, is taken organic phase to be evaporated under reduced pressure to without cut, then washed with n-hexane, in obtaining Mesosome III -1；In above-mentioned reaction, intermediate S4 is 1 with connection boric acid pinacol ester mol ratio：1~2；Intermediate S4 and potassium acetate Mol ratio is 1:1~3；Intermediate S4 and Pd (dppf) Cl2Mol ratio be 1:0.01~0.05；Intermediate S4 and sodium metaperiodate Mol ratio be 1:2~3.
If X is O atom：
Weigh raw material I -2 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Weigh bromine to be dissolved in glacial acetic acid, and slowly drip Add in the acetic acid solution containing raw material I -2, after completion of dropwise addition, be warmed to room temperature stirring reaction until reaction is complete；Reaction terminates Afterwards, alkali lye being added into reaction solution to neutralize, being extracted with dichloromethane, be layered, take organic phase to filter, filtrate decompression, which is rotated to nothing, to be evaporated Point, silicagel column is crossed, obtains intermediate S5；The raw material I -2 and the molar ratio of bromine are 1:1~2；
Under nitrogen protection, intermediate S5, Cu powder is weighed, is added in ammoniacal liquor, is stirred, is then heated to 80 DEG C, Reaction 2~6 hours, sample point plate, show that no intermediate S5 is remaining, naturally cool to room temperature, vacuum rotary steam to without cut, excessively in Property silicagel column, obtains intermediate S6.In above-mentioned reaction, intermediate S5 and Cu mol ratio are 1:0,05~0.2, ammoniacal liquor is excessive, It is used as reaction raw materials, acid binding agent and solvent simultaneously；
Under nitrogen protection, intermediate S6, raw material II -2, iodine, diethylene glycol (DEG) are sequentially added, stirring and dissolving, it is heated to 260~ 280 DEG C, react 12~24 hours, sample point plate, show that no intermediate S6 is remaining, reaction is complete；After reaction terminates, natural cooling To room temperature, there is solid precipitation, filter, filter cake is dried with vacuum drying chamber, is then crossed neutral silica gel post, is obtained intermediate S7.On State in reaction, intermediate S6 is 1 with the mol ratio of raw material II -2:The mol ratio of 1.2, intermediate S6 and iodine is 1:0.05~0.1；
Weigh intermediate S7 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, and slowly It is added dropwise in intermediate S7 acetic acid solution, reaction is stirred at room temperature until reaction is complete；After reaction terminates, added into reaction solution Alkali lye is neutralized, and is extracted with dichloromethane, is layered, takes organic phase to filter, and filtrate decompression is rotated to without cut, is crossed silicagel column, is obtained Intermediate S8；The intermediate S7 and the molar ratio of bromine are 1:1~2；
Under nitrogen protection, intermediate S8, raw material III, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, use Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, is shown that no intermediate S8 is remaining, Reaction is complete, naturally cools to room temperature, filters, and filtrate carries out vacuum rotary steam to without cut, crosses neutral silica gel post, obtains intermediate S9.In above-mentioned reaction, intermediate S8 is 1 with the mol ratio of raw material III：1~2；The mol ratio of intermediate S8 and sodium tert-butoxide is 1:1 ~3；Intermediate S8 and Pd2(dba)3, tri-butyl phosphine mol ratio be 1:0.01~0.05；
Under nitrogen protection, intermediate S9, raw material IV, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, use Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, is shown that no intermediate S9 is remaining, Reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam to without cut, crosses neutral silica gel post, obtains intermediate S10.In above-mentioned reaction, intermediate S9 is 1 with the mol ratio of raw material IV：1~2；The mol ratio of intermediate S9 and sodium tert-butoxide is 1:1 ~3；Intermediate S9 and Pd2(dba)3, tri-butyl phosphine mol ratio be 1:0.01~0.05；
Under the protection of logical nitrogen, intermediate S10, connection boric acid pinacol ester, potassium acetate, Pd (dppf) Cl are weighed2, 1,4- bis- The ring of oxygen six, mix, be heated to 80~100 DEG C, react 10~24 hours, sample point plate, show that no intermediate S10 is remaining, Reaction is complete, naturally cools to room temperature, has solid precipitation after adding water, filters, takes filter cake to be dried with vacuum drying chamber, then excessively in Property silicagel column, obtain boric acid ester compound, gained boric acid ester compound is dissolved with THF, add sodium metaperiodate, HCl/water solution adjust PH to 2~3 is saved, hydrolysis is stirred at room temperature 12~16 hours, sample point plate, shows that no boric acid ester compound is remaining, hydrolysis is complete, adds Water dilute reaction solution, is extracted with ethyl acetate, and layering, takes organic phase to be evaporated under reduced pressure to without cut, is then washed, obtained with n-hexane To intermediate III -2；In above-mentioned reaction, intermediate S10 is 1 with connection boric acid pinacol ester mol ratio：1~2；Intermediate S10 and second The mol ratio of sour potassium is 1:1~3；Intermediate S10 and Pd (dppf) Cl2Mol ratio be 1:0.01~0.05；Intermediate S10 with The mol ratio of sodium metaperiodate is 1:2~3.
If X is the N atomic time：
Under nitrogen protection, weigh raw material I -3, Potassiumiodate, iodine, acetic acid, stirring and dissolving, add the mixed of the concentrated sulfuric acid and water Liquid is closed, is heated to 40 DEG C, is reacted 2-5 hours, sample point plate, shows that no raw material I -3 is remaining, reaction is complete；Add the NaOH aqueous solution Neutralize, have solid precipitation after adding water, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain intermediate S11.In above-mentioned reaction, raw material I -3 is 1 with iodine, the mol ratio of Potassiumiodate:1~2, the mol ratio of raw material I -3 and sulfuric acid is 1: 3~6, the volume ratio of sulfuric acid and water is 1:4~6；
Under nitrogen protection, intermediate S11, SnCl are weighed2, ethanol stirring and dissolving is added, it is small to react 2-6 under counterflow condition When, sample point plate, show that no intermediate S11 is remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam To without cut, neutral silica gel post is crossed, obtains intermediate S12；Intermediate S11 and SnCl2Mol ratio is 1:2~4；
Under nitrogen protection, intermediate S12, intermediate S13, Cs are sequentially added2CO3, Cu, 18 hat 6, o-dichlorohenzene, mixing Stirring, back flow reaction 12~24 hours, sample point plate, show that no intermediate S12 is remaining, reaction is complete；Filtering, filtrate are subtracted Pressure revolving crosses neutral silica gel post, obtains intermediate S14 to without cut.In above-mentioned reaction, S13 moles of intermediate S12 and intermediate Than for 1:The mol ratio of 1~2, intermediate S12 and cesium carbonate is 1:1~3, intermediate S12 and copper, the mol ratio of 18 hats 6 are 1:0.05~0.2；
Under the protection of logical nitrogen, intermediate S14, raw material III -3, sodium tert-butoxide, Pd are weighed2(dba)3, tri-butyl phosphine, add Enter toluene to be stirred, be heated to 115 DEG C, back flow reaction 12~24 hours, sample point plate, show that no intermediate S14 is remaining, instead Should be complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam to without cut, crosses neutral silica gel post, obtains intermediate S15.In above-mentioned reaction, the molar ratio of intermediate S14 and iodo aromatic hydrocarbon is 1：1~2；Intermediate S14 and sodium tert-butoxide rub You are than being 1:1~3；Intermediate S14 and Pd2(dba)3Mol ratio with tri-butyl phosphine is 1:0.01~0.05.
Under nitrogen protection, intermediate S15, raw material IV, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, use Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, is shown that no intermediate S15 is remained Remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate S16.In above-mentioned reaction, intermediate S15 is 1 with the mol ratio of raw material IV：1~2；The mol ratio of intermediate S15 and potassium carbonate is 1:1 ~3；Intermediate S15 and Pd2(dba)3Mol ratio be 1:0.01~0.05；
Under the protection of logical nitrogen, intermediate S16, connection boric acid pinacol ester, potassium acetate, Pd (dppf) Cl are weighed2, 1,4- bis- The ring of oxygen six, mix, be heated to 80~100 DEG C, react 10~24 hours, sample point plate, show that no intermediate S16 is remaining, Reaction is complete；Naturally cool to room temperature, have solid precipitation after adding water, filter, take filter cake to be dried with vacuum drying chamber, then excessively in Property silicagel column, obtain boric acid ester compound, dissolved with THF, add sodium metaperiodate, HCl/water solution regulation pH to 2~3, room temperature stirs Mix hydrolysis 12~16 hours, sample point plate, show that no boric acid ester compound is remaining, hydrolysis is complete, is diluted with water reaction solution, uses second Acetoacetic ester extracts, and layering, takes organic phase to be evaporated under reduced pressure to without cut, is then washed with n-hexane, obtain intermediate III -3；It is above-mentioned In reaction, intermediate S16 is 1 with connection boric acid pinacol ester mol ratio：1~2；The mol ratio of intermediate S16 and potassium acetate is 1:1 ~3；Intermediate S16 and Pd (dppf) Cl2Mol ratio be 1:0.01~0.05；Intermediate S16 and sodium metaperiodate mol ratio For 1:2~3.
If X is S atom：
Weigh raw material I -4 to be dissolved in dichloromethane, 0 DEG C is cooled to ice salt bath；Chloroacetic chloride is weighed to be dissolved in dichloromethane And be slowly added dropwise into the dichloromethane solution containing raw material I -4, after completion of dropwise addition, it is warmed to room temperature, stirring reaction is until reaction Completely；After reaction terminates, it will be poured into reaction solution in separatory funnel, respectively with saturation NaHCO3The aqueous solution and saturation NaCl are water-soluble Liquid is washed, and layering, takes organic phase to filter, and filtrate decompression is rotated to without cut, is crossed silicagel column, is obtained intermediate S17；The reaction In, the molar ratio of raw material I-4 and chloroacetic chloride is 1:1~2；
Under nitrogen protection, intermediate S17, Potassiumiodate, acetic acid are weighed, at ambient temperature stirring and dissolving, adds iodine, dense The mixed solution of sulfuric acid and water, 40 DEG C are heated to, stirring reaction 2~5 hours.Sample point plate, show that no intermediate S17 is remaining, Reaction is complete；Add the NaOH aqueous solution to neutralize, there is solid precipitation, filter, filter cake is dried with vacuum drying chamber, then crosses neutral silica gel Post, obtain intermediate S18；In above-mentioned reaction, the mol ratio of intermediate S17 and iodine, Potassiumiodate is 1:1~2, intermediate S17 with The mol ratio of the concentrated sulfuric acid is 1:3~5, the volume ratio of the concentrated sulfuric acid and water is 1:3~6；
Under nitrogen protection, intermediate S18,2- bromo thiophenol, potassium carbonate, DMF are sequentially added, is stirred Dissolving, 130~150 DEG C are heated to, reacted 4~10 hours, sample point plate, show that no intermediate S18 is remaining, reaction is complete；It is cold But to room temperature, water and ethyl acetate extraction is added, layering, takes organic phase, is filtered, filtrate decompression is rotated to without cut, excessively neutral Silicagel column, obtain intermediate S19-1；In above-mentioned reaction, intermediate S18 is 1 with 2- bromo thiophenols mol ratio:1~2, intermediate S18 is 1 with potassium carbonate mol ratio：1~3.
Weigh intermediate S19-1 to be dissolved in acetic acid, 0 DEG C is cooled to ice salt bath；Weigh bromine to be dissolved in glacial acetic acid, and delay Slowly it is added dropwise in the acetic acid solution containing intermediate S19-1, after completion of dropwise addition, is warmed to room temperature, stirring reaction is until reaction is complete； After reaction terminates, alkali lye neutralization is added into reaction solution, is extracted with dichloromethane, is layered, takes organic phase to filter, filtrate decompression rotation Steam to without cut, cross silicagel column, obtain intermediate S19-2；The intermediate S19-1 and the molar ratio of bromine are 1:1~2；
Under nitrogen protection, intermediate 19-2, raw material III, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, It is stirred with toluene, is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, shows no intermediate S19-2 Residue, reaction are complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained centre Body S20.In above-mentioned reaction, intermediate S19-2 is 1 with the mol ratio of raw material III：1~2；Intermediate S19-2 and sodium tert-butoxide rub You are than being 1:1~3；Intermediate S19-2 and Pd2(dba)3, tri-butyl phosphine mol ratio be 1:0.01~0.05；
Under nitrogen protection, intermediate S20, raw material IV, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, use Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, is shown that no intermediate S20 is remained Remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate S21.In above-mentioned reaction, intermediate S20 is 1 with the mol ratio of raw material IV：1~2；The mol ratio of intermediate S20 and sodium tert-butoxide is 1:1~3；Intermediate S20 and Pd2(dba)3, tri-butyl phosphine mol ratio be 1:0.01~0.05；
Under the protection of logical nitrogen, intermediate S21, connection boric acid pinacol ester, potassium acetate, Pd (dppf) Cl are weighed2, 1,4- bis- The ring of oxygen six, mix, be heated to 80~100 DEG C, react 10~24 hours, sample point plate, show that no intermediate S21 is remaining, Reaction is complete；Naturally cool to room temperature, have solid precipitation after adding water, filter, take filter cake to be dried with vacuum drying chamber, then excessively in Property silicagel column, obtain boric acid ester compound, dissolved with THF, add sodium metaperiodate, HCl/water solution regulation pH to 2-3, room temperature stirs Mix hydrolysis 12-16 hours, sample point plate, show that no boric acid ester compound is remaining, hydrolysis is complete, is diluted with water reaction solution, uses second Acetoacetic ester extracts, and layering, takes organic phase to be evaporated under reduced pressure to without cut, is then washed with n-hexane, obtain intermediate III -4；It is above-mentioned In reaction, intermediate S21 is 1 with connection boric acid pinacol ester mol ratio：1~2；The mol ratio of intermediate S21 and potassium acetate is 1:1 ~3；Intermediate S21 and Pd (dppf) Cl2Mol ratio be 1:0.01~0.05；Intermediate S21 and sodium metaperiodate mol ratio For 1:2~3.
Under nitrogen protection, raw material I -5, raw material III -5, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, use Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, is shown that no raw material I -5 is remaining, Reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate S22. In above-mentioned reaction, raw material I -5 is 1 with the mol ratio of raw material III -5：1~2；The mol ratio of raw material I -5 and sodium tert-butoxide is 1:1~3； Raw material I -5 and Pd2(dba)3, tri-butyl phosphine mol ratio be 1:0.01~0.05；
The intermediate S22 and raw material II -5 of previous step preparation are weighed, is dissolved with toluene, under an inert atmosphere, stirring is lower to be added Enter potassium carbonate, four triphenyl phosphorus palladiums, ethanol and the aqueous solution, be warming up to 110-120 DEG C, react 10-24 hours；After reaction terminates, Room temperature is cooled to, is layered, organic phase is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate S23.It is middle in above-mentioned reaction The mol ratio of body S22 and raw material II -5 is 1：1~2；The mol ratio of intermediate S22 and potassium carbonate is 1:1~3；Intermediate S22 with The mol ratio of four triphenyl phosphorus palladiums is 1:0.01~0.05.
Under nitrogen protection, intermediate S23, raw material IV, sodium tert-butoxide, Pd are weighed successively2(dba)3, tri-butyl phosphine, use Toluene is stirred, and is heated to 110~120 DEG C, back flow reaction 12~24 hours, sample point plate, is shown that no intermediate S23 is remained Remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate S24.In above-mentioned reaction, intermediate S23 is 1 with the mol ratio of raw material IV：1~2；The mol ratio of intermediate S23 and sodium tert-butoxide is 1:1~3；Intermediate S23 and Pd2(dba)3, tri-butyl phosphine mol ratio be 1:0.01~0.05；
Under the protection of logical nitrogen, intermediate S24, connection boric acid pinacol ester, potassium acetate, Pd (dppf) Cl are weighed2, 1,4- bis- The ring of oxygen six, mix, be heated to 80~100 DEG C, react 10-24 hours, sample point plate, show that no intermediate S24 is remaining, instead Should be complete；Room temperature is naturally cooled to, has solid precipitation after adding water, filters, takes filter cake to be dried with vacuum drying chamber, it is then excessively neutral Silicagel column, boric acid ester compound is obtained, dissolved with THF, added sodium metaperiodate, HCl/water solution regulation pH to 2-3, be stirred at room temperature 12-16 hours are hydrolyzed, sample point plate, show that no boric acid ester compound is remaining, hydrolysis is complete, is diluted with water reaction solution, uses acetic acid Ethyl ester extracts, and layering, takes organic phase to be evaporated under reduced pressure to without cut, is then washed with n-hexane, obtain intermediate III -5；It is above-mentioned anti- Ying Zhong, intermediate S24 are 1 with connection boric acid pinacol ester mol ratio：1~2；The mol ratio of intermediate S24 and potassium acetate is 1:1~ 3；Intermediate S24 and Pd (dppf) Cl2Mol ratio be 1:0.01~0.05；The mol ratio of intermediate S24 and sodium metaperiodate is 1:2~3.
Respectively by taking intermediate compound I 1, intermediate N1, intermediate P1, intermediate R1 and intermediate S1A synthesis as an example：
By taking intermediate compound I 1 as an example：
1) in 250ml there-necked flask, 0.04mol dibenzo [b, d] furans -2- carboxylate methyl esters, 100ml acetic acid are added, Stirring and dissolving, then it is cooled to 0 DEG C with ice salt bath；By 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slow It is added dropwise in above-mentioned reaction system, after completion of dropwise addition, 20~25 DEG C of temperature control, stirring reaction 12 hours；Sample point plate, display is without two Benzo [b, d] furans -2- carboxylate methyl esters are remaining；After reaction terminates, the NaOH aqueous solution is added dropwise and neutralizes, add dichloromethane extraction, Layering, takes organic phase to filter, and filtrate decompression is distilled to without cut, is crossed neutral silica gel post, is obtained intermediate 1-1, HPLC purity 99.3%, yield 75.9%；
2) in 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.03mol intermediate 1-1,0.04mol hexichol And [b, d] furans -1- amine, 0.06mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, 0.0015mol tri-butyl phosphines, 150ml Toluene, mix, be heated to 115 DEG C, back flow reaction 24 hours, sample point plate, show that no intermediate 1-1 is remaining, reacted Entirely；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, crosses neutral silica gel post, it is pure to obtain intermediate 1-2, HPLC Degree 99.3%, yield 60.9%；
3) in 250ml there-necked flask, lead under nitrogen protection, add 0.04mol intermediate 1-2,100ml tetrahydrofurans and stir Dissolving is mixed, 0 DEG C is cooled to ice salt bath, the tetrahydrofuran solution (1.6M) of 63ml methyl-magnesium-bromides, completion of dropwise addition is slowly added dropwise Afterwards, 20 DEG C of temperature control, stirring reaction 12 hours, sample point plate, show that no intermediate 1-2 is remaining, reaction is complete；By reaction solution mistake Filter, filtrate carry out vacuum rotary steam to without cut, cross neutral silica gel post, obtain intermediate 1-3, HPLC purity 99.1%, yield 65.9%；
4) in 500ml there-necked flask, lead under nitrogen protection, add the dense H of 0.04mol intermediates 1-3,200ml3PO4And water Volume ratio is 1:3 mixed liquor, is stirred, 20 DEG C of temperature control, reacts 6 hours, sample point plate, shows that no intermediate 1-3 is remaining, Reaction is complete；Add NaOH aqueous solution neutralization reaction liquid to pH=7, addition dichloromethane to extract, layering, take organic phase to filter, Filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate 1-4, HPLC purity 99.2%, yield 55.1%；
5) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates 1-4,0.036mol 2,5- bis- Bromothiophene, 150ml toluene, are stirred, and add 0.09mol sodium tert-butoxides, 0.002mol Pd2(dba)3, 0.002mol tri- Tert-butyl group phosphine, 115 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no intermediate 1-4 is remaining, reaction is complete；From Room temperature so is cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate 1-5, HPLC purity 99.1%, yield 65.9%；
6) in 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.04mol intermediates 1-5,0.05mol connection boron Sour pinacol ester, 0.06mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, be stirred, add Heat is reacted 24 hours, sample point plate to 80 DEG C, shows that no intermediate 1-5 is remaining, reaction is complete；Room temperature is naturally cooled to, adds water After have solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain boric acid ester compound, use Tetrahydrofuran dissolves, and adds 0.05mol to enter sodium metaperiodate, HCl/water solution regulation pH to 2, hydrolysis 12 hours, sample point is stirred at room temperature Plate, show that no boric acid ester compound is remaining, hydrolysis is complete, is diluted with water reaction solution, is extracted with ethyl acetate, and is layered, takes organic Mutually it is evaporated under reduced pressure to without cut, is then washed with n-hexane, obtain intermediate compound I 1；HPLC purity 99.2%, yield 65.9%；
Elementary analysis structure (molecular formula C31H22BNO4S)：Theoretical value C, 72.24；H,4.30；B,2.10；N,2.72；O, 12.42；S,6.22；Test value：C,72.23；H,4.36；N,2.77.
HPLC-MS(m/z)：Theoretical value 515.14, measured value 515.16.
By taking intermediate N1 as an example：
1) in 250ml there-necked flask, 0.05mol 9,9- dimethyl -3- nitro -9H- xanthenes, 0.06mol acid iodide are added Potassium, 100ml acetic acid, stirring and dissolving, the mixing for adding 0.06mol iodine, the 2.0ml concentrated sulfuric acids and 10ml water are molten at ambient temperature Liquid, stirring are warming up to 40 DEG C, react 5 hours；Sample point plate, display is remaining without 9,9- dimethyl -3- nitro -9H- xanthenes, reaction Completely, add NaOH aqueous solution neutralization reaction liquid, there is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, it is then excessively neutral Silicagel column, obtain intermediate 2-1, HPLC purity 99.3%, yield 70.9%；
2) in 250ml there-necked flask, lead under nitrogen protection, add 0.04mol intermediates 2-1,0.08mol SnCl2、 100ml ethanol, is stirred, and is heated to flowing back, and reacts 6 hours, sample point plate, shows that no intermediate 2-1 is remaining, has reacted Entirely；Naturally place to room temperature, filtering, filtrate decompression is rotated to without cut, crosses neutral silica gel post, it is pure to obtain intermediate 2-2, HPLC Degree 99.1%, yield 80.9%；
3) in 500ml there-necked flask, lead under nitrogen protection, sequentially add 0.04mol intermediates 2-2,0.05mol 3- Iodo- 9,9- dimethyl -10- phenyl-acridan -2- amine, 0.05mol Cs2CO3, 0.004mol Cu powder, 0.004mol 18 hats 6,200ml o-dichlorohenzenes, are mixed, and are warming up to backflow, are reacted 12 hours, sample point plate, are shown that no intermediate 2-2 is remained Remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate 2-3, HPLC purity 99.2%, yield 70.5%；
4) in 250ml there-necked flask, lead under nitrogen protection, addition 0.03mol intermediate 2-3,0.032mol iodobenzene, 150ml toluene, is stirred, and adds 0.06mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, 0.0015mol tri-terts Phosphine, stirring are warming up to 115 DEG C, back flow reaction 12 hours, sample point plate, show that no intermediate 2-3 is remaining, reaction is complete；It is natural Room temperature is cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate 2-4, HPLC purity 99.3%, yield 70.9%；
5) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates 2-4,0.036mol 4,4'- Two bromo- 1,1'- biphenyl, 150ml toluene, are stirred, and add 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3、 0.0015mol tri-butyl phosphines, 115 DEG C are heated with stirring to, back flow reaction 24 hours, sample point plate, shows that no intermediate 2-4 is remained Remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate 2-5, HPLC purity 99.1%, yield 65.9%；
6) in 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.04mol intermediates 2-5,0.05mol connection boron Sour pinacol ester, 0.06mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, be stirred, add Heat is reacted 24 hours, sample point plate to 80 DEG C, shows that no intermediate 2-5 is remaining, reaction is complete；Room temperature is naturally cooled to, adds water After have solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain boric acid ester compound, use Tetrahydrofuran dissolves, and adds 0.05mol to enter sodium metaperiodate, HCl/water solution regulation pH to 2, hydrolysis 12 hours, sample point is stirred at room temperature Plate, show that no boric acid ester compound is remaining, hydrolysis is complete, is diluted with water reaction solution, is extracted with ethyl acetate, and is layered, takes organic Mutually it is evaporated under reduced pressure to without cut, is then washed with n-hexane, obtain intermediate N1；HPLC purity 99.2%, yield 65.9%；
Elementary analysis structure (molecular formula C54H44BN3O3)：Theoretical value C, 81.71；H,5.59；N,5.29；Test value：C, 81.78；H,5.51；N,5.22.
HPLC-MS(m/z)：Theoretical value 793.35, measured value 793.36.
By taking intermediate P1 as an example：
1) in 250ml there-necked flask, 0.04mol 9,9- dimethyl -9H- fluorenes -1- alcohol, 100ml acetic acid, stirring are added Dissolving, is then cooled to 0 DEG C with ice salt bath；By 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise Into above-mentioned reaction system, after completion of dropwise addition, 20~25 DEG C of temperature control stirring reaction 12 hours；Sample point plate, display is without 9,9- bis- Methyl-9 H-fluorene -1- alcohol is remaining；After reaction terminates, NaOH aqueous solution neutralization reaction liquid is added dropwise, adds dichloromethane extraction, point Layer, takes organic phase to filter, and filtrate decompression is distilled to without cut, is crossed neutral silica gel post, is obtained intermediate 3-1, HPLC purity 99.3%, yield 66.9%；
2) in 250ml there-necked flask, lead under nitrogen protection, add 0.04mol intermediates 3-1,0.004mol Cu powder, 100ml mass fractions are 30% ammoniacal liquor, are heated to 80 DEG C, insulation reaction 6 hours, sample point plate, show that no intermediate 3-1 is remained Remaining, reaction is complete；Room temperature is naturally cooled to, then vacuum rotary steam crosses neutral silica gel post, obtains intermediate 3-2 extremely without cut, HPLC purity 99.2%, yield 65.5%；
3) in 250ml there-necked flask, lead under nitrogen protection, add 0.05mol intermediates 3-2,0.06mol 2- amino Phenol, 0.005mol iodine, 80ml diethylene glycol (DEG)s, stirring and dissolving, 270 DEG C are heated to, reacted 24 hours；Sample point plate, display is without in Mesosome 3-2 is remaining, and reaction is complete；Room temperature is naturally cooled to, has solid precipitation after adding water, filters, takes filter cake vacuum drying chamber Drying, neutral silica gel post is then crossed, obtains intermediate 3-3, HPLC purity 99.1%, yield 58.5%；
4) in 250ml there-necked flask, 0.04mol intermediate 3-3,100ml acetic acid is added, stirring and dissolving, then uses ice Salt bath is cooled to 0 DEG C, by 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise to above-mentioned reactant In system, after completion of dropwise addition, 20~25 DEG C of temperature control, stirring reaction 12 hours, sample point plate, show that no intermediate 3-3 is remaining；Reaction After end, the NaOH aqueous solution is added dropwise and neutralizes, add dichloromethane extraction, layering, take organic phase to filter, filtrate decompression is distilled to nothing Cut, neutral silica gel post is crossed, obtains intermediate 3-4, HPLC purity 99.3%, yield 75.9%；
5) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates 3-4,0.032mol 9H- clicks Azoles, 150ml toluene, are stirred, and add 0.06mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, tri- tertiary fourths of 0.0015mol Base phosphine, stirring are warming up to 115 DEG C, back flow reaction 12 hours, sample point plate, show that no intermediate 3-4 is remaining, reaction is complete；From Room temperature so is cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate 3-5, HPLC purity 99.3%, yield 70.9%；
6) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediate 3-5,0.036mol Isosorbide-5-Nitrae-two Bromobenzene, 150ml toluene, are stirred, and add 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, 0.0015mol tri- Tert-butyl group phosphine, 115 DEG C are heated with stirring to, back flow reaction 24 hours, sample point plate, shows that no intermediate 3-5 is remaining, has reacted Entirely；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, crosses neutral silica gel post, it is pure to obtain intermediate 3-6, HPLC Degree 99.1%, yield 65.9%；
7) in 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.04mol intermediates 3-6,0.05mol connection boron Sour pinacol ester, 0.06mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, be stirred, add Heat is reacted 24 hours, sample point plate to 80 DEG C, shows that no intermediate 3-6 is remaining, reaction is complete；Room temperature is naturally cooled to, adds water After have solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain boric acid ester compound, use Tetrahydrofuran dissolves, and adds 0.05mol to enter sodium metaperiodate, HCl/water solution regulation pH to 2, hydrolysis 12 hours, sample point is stirred at room temperature Plate, show that no boric acid ester compound is remaining, hydrolysis is complete, is diluted with water reaction solution, is extracted with ethyl acetate, and is layered, takes organic Mutually it is evaporated under reduced pressure to without cut, is then washed with n-hexane, obtain intermediate P1；HPLC purity 99.2%, yield 65.9%；
Elementary analysis structure (molecular formula C39H29BN2O3)：Theoretical value C, 80.14；H,5.00；B,1.85；N,4.79；O, 8.21；Test value：C,80.18；H,5.06；N,4.68.
HPLC-MS(m/z)：Theoretical value 584.23, measured value 584.36.
By taking intermediate R1 as an example：
1) 0.02mol 9 is weighed, 9- dimethyl -9H- xanthene -3- amine is dissolved in 100ml dichloromethane, cooled with ice salt bath To 0 DEG C；Weigh 0.03mol chloroacetic chlorides to be dissolved in 50ml dichloromethane, and be slowly added dropwise into above-mentioned system, after completion of dropwise addition, It is warmed to room temperature, stirring reaction is until reaction is complete；After reaction terminates, it will be poured into reaction solution in separatory funnel, use saturation respectively NaHCO3The aqueous solution and the washing of the saturation NaCl aqueous solution, layering, take organic phase to filter, and filtrate decompression is rotated to without cut, excessively in Property silicagel column, obtains target product intermediate 4-1, HPLC purity 99.3%, yield 70.9%；
2) in 250ml there-necked flask, 0.05mol intermediate 4-1,0.06mol Potassiumiodate, 100ml acetic acid are sequentially added, Stirring and dissolving, 0.06mol iodine, 2.0ml sulfuric acid and 10ml water are added, be heated with stirring to 40 DEG C, reacted 5 hours；Sample point plate, Display is remaining without intermediate 4-1, and reaction is complete；NaOH aqueous solution neutralization reaction liquid is added, there is solid precipitation, filters, takes filter cake Dried with vacuum drying chamber, cross neutral silica gel post, obtain intermediate 4-2, HPLC purity 99.3%, yield 65.9%；
3) in 500ml there-necked flask, lead under nitrogen protection, add 0.04mol intermediates 4-2,0.05mol 2- bromobenzenes Thiophenol, 0.08mol potassium carbonate, 200ml DMFs, are stirred, and are heated to 135 DEG C, react 10 hours, take Sampling point plate, show that no intermediate 4-2 is remaining, reaction is complete；Room temperature is cooled to, water and ethyl acetate extraction is added, layering, has taken Machine is mutually filtered, and filtrate decompression is rotated to without cut, is then crossed neutral silica gel post, is obtained intermediate 4-3, HPLC purity 99.0%, Yield 68.5%；
4) in 250ml there-necked flask, 0.04mol intermediate 4-3,100ml acetic acid is added, stirring and dissolving, then uses ice Salt bath is cooled to 0 DEG C；By 0.05mol Br2It is dissolved in 50ml acetic acid, the acetic acid solution of bromine is slowly added dropwise to above-mentioned reactant In system, after completion of dropwise addition, 20~25 DEG C of temperature control, stirring reaction 12 hours；Sample point plate, show that no intermediate 4-3 is remaining；Reaction After end, the NaOH aqueous solution is added dropwise and neutralizes, add dichloromethane extraction, layering, take organic phase to filter, filtrate decompression is distilled to nothing Cut, neutral silica gel post is crossed, obtains intermediate 4-4, HPLC purity 99.3%, yield 75.9%；
5) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates 4-4,0.032mol 10H- fens Oxazine, 150ml toluene, are stirred, and add 0.06mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, 0.0015mol tri- Tert-butyl group phosphine, stirring are warming up to 115 DEG C, back flow reaction 12 hours, sample point plate, show that no intermediate 4-4 is remaining, reacted Entirely；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, crosses neutral silica gel post, it is pure to obtain intermediate 4-5, HPLC Degree 99.3%, yield 70.9%；
6) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediates 4-5,0.036mol 3,6- bis- Bromine pyridazine, 150ml toluene, are stirred, and add 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3、0.0015mol Tri-butyl phosphine, 115 DEG C are heated with stirring to, back flow reaction 24 hours, sample point plate, shows that no intermediate 4-5 is remaining, has reacted Entirely；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, crosses neutral silica gel post, it is pure to obtain intermediate 4-6, HPLC Degree 99.1%, yield 65.9%；
7) in 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.04mol intermediates 4-6,0.05mol connection boron Sour pinacol ester, 0.06mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane be stirred, heat To 80 DEG C, react 24 hours, sample point plate, show that no intermediate 4-6 is remaining, reaction is complete；Room temperature is naturally cooled to, after adding water There is solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, boric acid ester compound is obtained, with four Hydrogen furans dissolves, and adds 0.05mol to enter sodium metaperiodate, HCl/water solution regulation pH to 2, hydrolysis 12 hours, sample point is stirred at room temperature Plate, show that no boric acid ester compound is remaining, hydrolysis is complete, is diluted with water reaction solution, is extracted with ethyl acetate, and is layered, takes organic Mutually it is evaporated under reduced pressure to without cut, is then washed with n-hexane, obtain intermediate R1；HPLC purity 99.2%, yield 65.9%；
Elementary analysis structure (molecular formula C37H27BN4O4S)：Theoretical value C, 70.04；H,4.29；N,8.83；Test value：C, 70.09；H,4.24；N,8.85.
HPLC-MS(m/z)：Theoretical value 634.18, measured value 634.17.
By taking intermediate S1A as an example：
1) in 250ml there-necked flask, lead under nitrogen protection, addition 0.03mol 2, bromo- 5, the 10- dihydrophenazines of 8- bis-, 0.032mol iodobenzenes, 150ml toluene, are stirred, and add 0.06mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, 0.0015mol tri-butyl phosphines, stirring are warming up to 115 DEG C, back flow reaction 12 hours, sample point plate, shown without 2,8- bis- bromo- 5, 10- dihydrophenazines are remaining, and reaction is complete；Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam extremely without cut, excessively neutral Silicagel column, obtain intermediate 5-1, HPLC purity 99.3%, yield 70.9%；
2) in 250ml there-necked flask, lead under nitrogen protection, addition 0.03mol intermediate 5-1,0.032mol diphenylamines, 150ml toluene, is stirred, and adds 0.06mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, 0.0015mol tri-terts Phosphine, stirring are warming up to 115 DEG C, back flow reaction 12 hours, sample point plate, show that no intermediate 5-1 is remaining, reaction is complete；It is natural Room temperature is cooled to, is filtered, filtrate decompression is rotated to without cut, is crossed neutral silica gel post, is obtained intermediate 5-2, HPLC purity 99.3%, yield 70.9%；
3) in 250ml there-necked flask, lead under nitrogen protection, add 0.05mol intermediate 5-2,0.06mol dibenzo [b, d] furans -4- boric acid, 100ml toluene, are stirred, and add 0.0025mol Pd (PPh3)4, 0.06mol potassium carbonate, 50ml water and ethanol volume ratio are 1:1 mixed solution, stirring are warming up to 120 DEG C, back flow reaction 12 hours, sample point plate, shown Show that no intermediate 5-2 is remaining, reaction is complete；Room temperature is naturally cooled to, filters, filtrate layered, takes organic phase vacuum rotary steam to nothing Cut, neutral silica gel post is crossed, obtains intermediate 5-3, HPLC purity 99.1%, yield 55.8%；
4) in 250ml there-necked flask, lead under nitrogen protection, add 0.03mol intermediate 5-3,0.036mol Isosorbide-5-Nitrae-two Bromobenzene, 150ml toluene, are stirred, and add 0.09mol sodium tert-butoxides, 0.0015mol Pd2(dba)3, 0.0015mol tri- Tert-butyl group phosphine, 115 DEG C are heated with stirring to, back flow reaction 24 hours, sample point plate, shows that no intermediate 5-3 is remaining, has reacted Entirely；Room temperature is naturally cooled to, is filtered, filtrate decompression is rotated to without cut, crosses neutral silica gel post, it is pure to obtain intermediate 5-4, HPLC Degree 99.1%, yield 65.9%；
5) in 250ml there-necked flask, lead under nitrogen protection, sequentially add 0.04mol intermediates 5-4,0.05mol connection boron Sour pinacol ester, 0.06mol potassium acetates, 0.002mol Pd (dppf) Cl2, 100ml Isosorbide-5-Nitraes-dioxane, be stirred, add Heat is reacted 24 hours, sample point plate to 80 DEG C, shows that no intermediate 5-4 is remaining, reaction is complete；Room temperature is naturally cooled to, adds water After have solid precipitation, filter, take filter cake to be dried with vacuum drying chamber, then cross neutral silica gel post, obtain boric acid ester compound, use Tetrahydrofuran dissolves, and adds 0.05mol to enter sodium metaperiodate, HCl/water solution regulation pH to 2, hydrolysis 12 hours, sample point is stirred at room temperature Plate, show that no boric acid ester compound is remaining, hydrolysis is complete, is diluted with water reaction solution, is extracted with ethyl acetate, and is layered, takes organic Mutually it is evaporated under reduced pressure to without cut, is then washed with n-hexane, obtain intermediate S1A；HPLC purity 99.2%, yield 65.9%；
Elementary analysis structure (molecular formula C48H34BN3O3)：Theoretical value C, 81.02；H,4.82；N,5.90；Test value：C, 81.08；H,4.86；N,5.88.
HPLC-MS(m/z)：Theoretical value 711.27, measured value 711.29.
It is as shown in table 1 by raw material I, raw material II, raw material III, raw material IV, intermediate S synthetic intermediate I, concrete structure；
Table 1
Embodiment 1：The synthesis of compound 5：
Synthetic route：
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol 3- bromo- 9, the fluorenes of 9 '-spiral shell two, 0.012mol Intermediate A 1,150ml toluene are stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4mol Pd(PPh3)4, it is heated to 105 DEG C, back flow reaction 24 hours, sample point plate, show that no bromo-derivative is remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, Filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.1%, yield 72.4%；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.53；H,5.12；N,2.04；O,2.31.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.53.
Embodiment 2：The synthesis of compound 6：
Synthetic route：
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol 3- bromo- 9, the fluorenes of 9 '-spiral shell two, 0.012mol Intermediate B 1,150ml toluene are stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4mol Pd(PPh3)4, it is heated to 105 DEG C, back flow reaction 24 hours, sample point plate, show that no bromo-derivative is remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, Filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.2%, yield 71.8%；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.55；H,5.10；N,2.02；O,2.33.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.57.
Embodiment 3：The synthesis of compound 10：
Synthetic route：
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol 3- bromo- 9, the fluorenes of 9 '-spiral shell two, 0.012mol Intermediate C1,150ml toluene is stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4mol Pd(PPh3)4, it is heated to 105 DEG C, back flow reaction 24 hours, sample point plate, show that no bromo-derivative is remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, Filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.1%, yield 71.5%；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.53；H,5.13；N,2.01；O,2.33.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.55.
Embodiment 4：The synthesis of compound 13：
Synthetic route：
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol 3- bromo- 9, the fluorenes of 9 '-spiral shell two, 0.012mol Intermediate D1,150ml toluene is stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4mol Pd(PPh3)4, it is heated to 105 DEG C, back flow reaction 24 hours, sample point plate, show that no bromo-derivative is remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, Filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.3%, yield 72.1%；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.56；H,5.12；N,2.01；O,2.31.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.49.
Embodiment 5：The synthesis of compound 14：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate E 1；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.53；H,5.12；N,2.01；O,2.34.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.52.
Embodiment 6：The synthesis of compound 18：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate F1 generation；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.52；H,5.12；N,2.02；O,2.34.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.58.
Embodiment 7：The synthesis of compound 25：
Synthetic route：
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol 2- bromo- 9, the fluorenes of 9 '-spiral shell two, 0.012mol Intermediate D1,150ml toluene is stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4mol Pd(PPh3)4, it is heated to 105 DEG C, back flow reaction 24 hours, sample point plate, show that no bromo-derivative is remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, Filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 98.8%, yield 70.8%；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.55；H,5.13；N,2.01；O,2.31.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.64.
Embodiment 8：The synthesis of compound 31：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate G1；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.5；H,5.12；N,2.02；O,2.31.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.61.
Embodiment 9：The synthesis of compound 33：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate H1；
Elementary analysis structure (molecular formula C50H33N3O)：Theoretical value C, 86.81；H,4.81；N,6.07；O,2.31；Test value C,86.82；H,4.82；N,6.06；O,2.30.
HPLC-MS：Material molecule amount is 691.26, surveys molecular weight 691.48.
Embodiment 10：The synthesis of compound 44：
Synthetic route：
Prepared by the synthetic method of compound 25 in embodiment 7, difference is to replace intermediate D1 with intermediate A 1；
Elementary analysis structure (molecular formula C52H35NO)：Theoretical value C, 90.54；H,5.11；N,2.03；O,2.32；Test Value：C,90.52；H,5.11；N,2.04；O,2.33.
HPLC-MS：Material molecule amount is 689.27, surveys molecular weight 689.56.
Embodiment 11：The synthesis of compound 45：
Synthetic route：
In 250ml there-necked flask, lead to nitrogen protection under, add 0.01mol 3,6- bis- bromo- 9, the fluorenes of 9 '-spiral shell two, 0.024mol intermediates G1,150ml toluene is stirred, then addition 0.04mol sodium carbonate, and 2 × 10-4mol Pd(PPh3)4, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete；Naturally cool to room temperature, Filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel post, obtain target product, HPLC purity 98.9%, yield 68.4%；
Elementary analysis structure (molecular formula C79H54N2O2)：Theoretical value C, 89.24；H,5.12；N,2.63；O,3.01；Test Value：C,89.25；H,5.11；N,2.62；O,3.02.
HPLC-MS：Material molecule amount is 1062.42, surveys molecular weight 1062.67.
Embodiment 12：The synthesis of compound 53：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate compound I 1；
Elementary analysis structure (molecular formula C56H35NO2S)：Theoretical value C, 85.58；H,4.49；N,1.78；O,4.07；S, 4.08；Test value：C,85.59；H,4.48；N,1.76；O,4.08；S,4.09.
HPLC-MS：Material molecule amount is 785.24, surveys molecular weight 785.46.
Embodiment 13：The synthesis of compound 63：
Synthetic route：
In 250ml there-necked flask, lead under nitrogen protection, add 0.01mol 4- bromo- 9, the fluorenes of 9 '-spiral shell two, 0.012mol Intermediate J1,150ml toluene is stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4mol Pd(PPh3)4, it is heated to 105 DEG C, back flow reaction 24 hours, sample point plate, show that no bromo-derivative is remaining, reaction is complete；Room temperature is naturally cooled to, is filtered, Filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.4%, yield 71.2%；
Elementary analysis structure (molecular formula C61H43NO)：Theoretical value C, 90.90；H,5.38；N,1.74；O,1.99；Test Value：C,90.91；H,5.37；N,1.76；O,1.96.
HPLC-MS：Material molecule amount is 805.33, surveys molecular weight 805.65.
Embodiment 14：The synthesis of compound 73：
Synthetic route：
In 250ml there-necked flask, lead to nitrogen protection under, add 0.01mol 2,2 '-two bromo- 9, the fluorenes of 9 '-spiral shell two, 0.024mol intermediates K1,150ml toluene is stirred, then addition 0.04mol sodium carbonate, and 2 × 10-4mol Pd(PPh3)4, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete；Naturally cool to room temperature, Filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel post, obtain target product, HPLC purity 99.1%, yield 67.6%；
Elementary analysis structure (molecular formula C81H62N6O2)：Theoretical value C, 84.49；H,5.43；N,7.30；O,2.78；Test Value：C,84.50；H,5.42；N,7.31；O,2.77.
HPLC-MS：Material molecule amount is 1150.49, surveys molecular weight 1150.78.
Embodiment 15：The synthesis of compound 77：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate L1；
Elementary analysis structure (molecular formula C52H38N4O)：Theoretical value C, 84.99；H,5.21；N,7.62；O,2.18；Test Value：C,84.98；H,5.22；N,7.63；O,2.17.
HPLC-MS：Material molecule amount is 734.30, surveys molecular weight 734.58.
Embodiment 16：The synthesis of compound 79：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate M1；
Elementary analysis structure (molecular formula C55H41NO)：Theoretical value C, 90.25；H,5.65；N,1.91；O,2.19；Test Value：C,90.24；H,5.67；N,1.92；O,2.17.
HPLC-MS：Material molecule amount is 731.32, surveys molecular weight 731.62.
Embodiment 17：The synthesis of compound 94：
Synthetic route：
Prepared by the synthetic method of compound 63 in embodiment 13, difference is to replace intermediate J1 with intermediate N1；
Elementary analysis structure (molecular formula C79H57N3O)：Theoretical value C, 89.15；H,5.40；N,3.95；O,1.50；Test Value：C,89.14；H,5.41；N,3.93；O,1.52.
HPLC-MS：Material molecule amount is 1063.45, surveys molecular weight 1063.71.
Embodiment 18：The synthesis of compound 97：
Synthetic route：
In 250ml there-necked flask, lead to nitrogen protection under, add 0.01mol 4,4 '-two bromo- 9, the fluorenes of 9 '-spiral shell two, 0.024mol intermediates O1,150ml toluene is stirred, then addition 0.04mol sodium carbonate, and 2 × 10-4mol Pd(PPh3)4, 105 DEG C are heated to, back flow reaction 24 hours, sample point plate, shows that no bromo-derivative is remaining, reaction is complete；Naturally cool to room temperature, Filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel post, obtain target product, HPLC purity 98.7%, yield 67.6%；
Elementary analysis structure (molecular formula C79H54N2O4)：Theoretical value C, 86.63；H,4.97；N,2.56；O,5.84；Test Value：C,86.64；H,4.96；N,2.55；O,5.85.
HPLC-MS：Material molecule amount is 1094.41, surveys molecular weight 1094.66.
Embodiment 19：The synthesis of compound 113：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate P1；
Elementary analysis structure (molecular formula C64H42N2O)：Theoretical value C, 89.90；H,4.95；N,3.28；O,1.87；Test Value：C,89.92；H,4.93；N,3.26；O,1.89.
HPLC-MS：Material molecule amount is 854.33, surveys molecular weight 854.63.
Embodiment 20：The synthesis of compound 118：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate Q1；
Elementary analysis structure (molecular formula C64H42N2O)：Theoretical value C, 89.90；H,4.95；N,3.28；O,1.87；Test Value：C,89.91；H,4.96；N,3.27；O,1.86.
HPLC-MS：Material molecule amount is 854.33, surveys molecular weight 854.65.
Embodiment 21：The synthesis of compound 126：
Synthetic route：
Prepared by the synthetic method of compound 63 in embodiment 13, difference is to replace intermediate J1 with intermediate R1；
Elementary analysis structure (molecular formula C62H40N4O2S)：Theoretical value C, 82.28；H,4.45；N,6.19；O,3.54；S, 3.54；Test value：C,82.29；H,4.46；N,6.20；O,3.53；S,3.52.
HPLC-MS：Material molecule amount is 904.29, surveys molecular weight 904.55.
Embodiment 22：The synthesis of compound 137：
Synthetic route：
Prepared by the synthetic method of compound 5 in embodiment 1, difference is to replace intermediate A 1 with intermediate S1；
Elementary analysis structure (molecular formula C73H47N3O)：Theoretical value C, 89.27；H,4.82；N,4.28；O,1.63；Test Value：C,89.28；H,4.81；N,4.27；O,1.64.
HPLC-MS：Material molecule amount is 981.37, surveys molecular weight 981.63.
The compounds of this invention uses in luminescent device, can be used as electronic blocking layer material, can also be used as luminescent layer Subjective and Objective materials'use.Carry out heat respectively to the compounds of this invention 5,6,10,13,14,18,25,31,33,44,79,113,118 The test of performance, HOMO energy levels, testing result are as shown in table 2.
Table 2
Note：Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimetries Instrument) measure, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, public in Japanese Shimadzu It is measured on the TGA-50H thermogravimetric analyzers of department, nitrogen flow 20mL/min；Highest occupied molecular orbital HOMO energy levels are Tested, tested as atmospheric environment by photoelectron emissions spectrometer (AC-2 type PESA).
From upper table data, the compounds of this invention has different HOMO energy levels, can be applied to different functional layers, this Invention has higher heat endurance with the fluorenes of 9,9 '-spiral shell two for the compound of core so that made contains chemical combination of the present invention The OLED life-span upgrading of thing.
The OLED material of the invention synthesized is described in detail below by way of device embodiments 1~13 and comparative example 1 in the devices Application effect as difference in functionality layer material.Device embodiments 2~13, comparative example 1 and the phase of device embodiments 1 of the present invention Manufacture craft than the device is identical, and employed identical baseplate material and electrode material, electrode material Thickness is also consistent, except that being changed to the material of main part or electronic barrier layer of the luminescent layer in device.Each reality The performance test results for applying an obtained device are as shown in table 3.
Device embodiments 1
A kind of electroluminescent device, its preparation process include：
A) the ito anode layer 2 cleaned on transparent substrate layer 1, cleans each 15 with deionized water, acetone, EtOH Sonicate respectively Minute, then handled 2 minutes in plasma cleaner；
B) on ito anode layer 2, hole injection layer material HAT-CN, thickness 10nm are deposited by vacuum evaporation mode, This layer is as hole injection layer 3；
C) on hole injection layer 3, hole mobile material NPB, thickness 60nm, the layer are deposited by vacuum evaporation mode For hole transport 4；
D) on hole injection layer 3, hole mobile material NPB, thickness 60nm, the layer are deposited by vacuum evaporation mode For hole transport 4；
D) on hole transmission layer 4, electronic blocking layer material NPB, thickness 20nm are deposited by vacuum evaporation mode, should Layer is electronic barrier layer 5；
E) luminescent layer 6 is deposited on electronic barrier layer 5, using the compounds of this invention 5 as being used as material of main part, Ir (ppy)3As dopant material, Ir (ppy)3Mass ratio with compound 5 is 1：9, thickness 30nm；
F) on luminescent layer 6, electron transport material TPBI, thickness 40nm, this layer are deposited by vacuum evaporation mode Organic material uses as hole barrier/electron transfer layer 7；
G) on hole barrier/electron transfer layer 7, vacuum evaporation electron injecting layer LiF, thickness 1nm, the layer is electricity Sub- implanted layer 8；
H) on electron injecting layer 8, vacuum evaporation negative electrode Al (100nm), the layer is negative electrode reflection electrode layer 9；
After the making that electroluminescent device is completed according to above-mentioned steps, the current efficiency of measurement device and life-span, its result It is shown in Table 2.
The molecular machinery formula of associated materials is as follows：
Device embodiments 2
The difference of the present embodiment and device embodiments 1 is：The material of main part of the luminescent layer 6 of electroluminescent device becomes For the compounds of this invention 14, dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 14 is 1：9, the electroluminescent hair of gained The detection data of optical device are shown in Table 3.
Device embodiments 3
The difference of the present embodiment and device embodiments 1 is：The material of main part of the luminescent layer 6 of electroluminescent device becomes For the compounds of this invention 33, dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 33 is 1：9, the electroluminescent hair of gained The detection data of optical device are shown in Table 3.
Device embodiments 4
The difference of the present embodiment and device embodiments 1 is：The material of main part of the luminescent layer 6 of electroluminescent device becomes For the compounds of this invention 79, dopant material is Ir (ppy)3, Ir (ppy)3Mass ratio with compound 79 is 1：9, the electroluminescent hair of gained The detection data of optical device are shown in Table 3.
Device embodiments 5
The difference of the present embodiment and device embodiments 1 is：The material of main part of the luminescent layer 6 of electroluminescent device becomes For the compounds of this invention 6 and compound GHN, dopant material is Ir (ppy)3, compound 6, GHN and Ir (ppy)3Three's mass ratio For 60:30:10, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 6
The difference of the present embodiment and device embodiments 1 is：The material of main part of the luminescent layer 6 of electroluminescent device becomes For the compounds of this invention 10 and compound GHN, dopant material is Ir (ppy)3, compound 10, GHN and Ir (ppy)3Three's mass Than for 60:30:10, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 7
The difference of the present embodiment and device embodiments 1 is：The material of main part of the luminescent layer 6 of electroluminescent device becomes For the compounds of this invention 113 and compound GHN, dopant material is Ir (ppy)3, compound 113, GHN and Ir (ppy)3Three's matter Amount is than being 60:30:10, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 8
The difference of the present embodiment and device embodiments 1 is：The material of main part of the luminescent layer 6 of electroluminescent device becomes For the compounds of this invention 118 and compound GHN, dopant material is Ir (ppy)3, compound 118, GHN and Ir (ppy)3Three's matter Amount is than being 60:30:10, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 9
The difference of the present embodiment and device embodiments 1 is：The material of the electronic barrier layer 5 of electroluminescent device becomes For the compounds of this invention 13, the material of main part of luminescent layer 6 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3 Mass ratio with CBP is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 10
The difference of the present embodiment and device embodiments 1 is：The material of the electronic barrier layer 5 of electroluminescent device becomes For the compounds of this invention 18, the material of main part of luminescent layer 6 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3 Mass ratio with CBP is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 11
The difference of the present embodiment and device embodiments 1 is：The material of the electronic barrier layer 5 of electroluminescent device becomes For the compounds of this invention 25, the material of main part of luminescent layer 6 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3 Mass ratio with CBP is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 12
The difference of the present embodiment and device embodiments 1 is：The material of the electronic barrier layer 5 of electroluminescent device becomes For the compounds of this invention 31, the material of main part of luminescent layer 6 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3 Mass ratio with CBP is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device embodiments 13
The difference of the present embodiment and device embodiments 1 is：The material of the electronic barrier layer 5 of electroluminescent device becomes For the compounds of this invention 44, the material of main part of luminescent layer 6 is known compound CBP, and dopant material is Ir (ppy)3, Ir (ppy)3 Mass ratio with CBP is 1:9, the detection data of gained electroluminescent device are shown in Table 3.
Device comparative example 1
The difference of the present embodiment and device embodiments 1 is：The luminescent layer material of main part of electroluminescent device is changed into Known compound CBP, the detection data of gained electroluminescent device are shown in Table 3.
Table 3
Note：For device detection performance using device comparative example 1 as reference, the device property indices of comparative example 1 are set to 1.0. The current efficiency of comparative example 1 is 28cd/A (@10mA/cm2)；CIE chromaticity coordinates is (0.33,0.63)；The LT95 longevity under 5000 brightness Life decays to 2.5Hr.Life time decay test of the present invention can select model M6000OLED life-span test systems, can also adopt With M7000OLED photoelectricity and life-span integrated test system.
It can be seen that the machine compound of the present invention using the fluorenes of 9,9 '-spiral shell two as core texture can be applied by the result of table 3 Made in OLED luminescent devices, and compared with comparative example 1, either efficiency or life-span than the acquisition of known OLED material compared with Big to take on a new look, particularly the life time decay of device obtains larger lifting.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.

Claims (9)

1. a kind of organic compound with the fluorenes of 9,9 '-spiral shell two for core, it is characterised in that the general structure of the compound is as led to Shown in formula (1)：
Wherein, m, n, o, p are equal to 0 or 1；M, it is 1 that n, o, p are at least one；
X is oxygen atom, sulphur atom, C1-10The alkylidene or C of straight chain base substitution1-10The alkylidene of branched alkyl substitution, aryl substitution Alkylidene, alkyl-substituted tertiary amine groups or aryl substitution tertiary amine groups in one kind；
Ar represent phenyl, xenyl, naphthyl, anthryl, phenanthryl, pyrenyl, furyl, thienyl, pyridine radicals, pyrimidine radicals, pyridazinyl, One kind in pyrazinyl or triazine radical；
R1、R2Independently be expressed as hydrogen atom, formula (2), formula (3), formula (4), formula (5), formula (6), formula (7) structure shown in；R1With R2It is at least one to be selected from formula (2), formula (3), formula (4), formula (5), formula (6), formula (7) Shown structure；
In formula (2), a is selected fromX1、X2、X3、X4Independently be expressed as oxygen atom, Sulphur atom, C1-10The alkylidene or C of straight chained alkyl substitution1-10Alkylidene, alkylidene, the alkane of aryl substitution of branched alkyl substitution One kind in the tertiary amine groups of base substitution or the tertiary amine groups of aryl substitution；
R in formula (2), formula (3)3For hydrogen atom, halogen atom or C1-10Straight chained alkyl or C1-10Branched alkyl；
Structure shown in formula (2), formula (3) passes through in simultaneously ring and formula (1)Connection；
X in formula (5), formula (7)5For oxygen atom, sulphur atom, C1-10The alkylidene or C of straight chained alkyl substitution1-10Branched alkyl One kind in substituted alkylidene, the alkylidene of aryl substitution, alkyl-substituted tertiary amine groups or the tertiary amine groups of aryl substitution；
R in formula (6)4、R5Independently be expressed as phenyl, naphthyl, dibiphenylyl, terphenyl, dibenzofurans, hexichol One kind in bithiophene or 9,9- dimethyl fluorenes.
2. the organic compound according to claim 1 with the fluorenes of 9,9 '-spiral shell two for core, it is characterised in that describedGroup is expressed as：
In any one.
It is 3. according to claim 1 with organic compound that the fluorenes of 9,9 '-spiral shell two is core, it is characterised in that it is described with 9, The fluorenes of 9'- spiral shells two is that the concrete structure formula of the organic compound of core is：
In any one.
A kind of 4. preparation method with the fluorenes of 9,9 '-spiral shell two for the organic compound of core, it is characterised in that specific reaction equation It is：
Specifically preparation process is：
1) with the fluorenes bromo-derivative of 9,9 '-spiral shell twoAnd boronic acid compoundsFor raw material, toluene dissolving, institute Toluene dosage is stated as every gram 9, the fluorenes bromo-derivative of 9 '-spiral shell two uses 30-50ml toluene, wherein, described 9, the fluorenes bromo-derivative of 9 '-spiral shell twoWith boronic acid compoundsMol ratio be 1:(1.2~5.0)；
2) Pd (PPh are added into above-mentioned reaction system3)4And sodium carbonate, wherein, the Pd (PPh3)4With the fluorenes bromo of 9,9 '-spiral shell two The mol ratio of thing is (0.006~0.04):1, the sodium carbonate and 9, the mol ratio of the fluorenes bromo-derivative of 9 '-spiral shell two for (2.0~ 8.0):1；
3) under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, react 10~24 hours, naturally cool to room temperature, and Filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel post, obtain target product.
5. a kind of organic electroluminescence device, it is characterised in that at least one layer of functional layer contains any one of claims 1 to 3 The organic compound using the fluorenes of 9,9 '-spiral shell two as core.
6. a kind of organic electroluminescence device, including electronic barrier layer, it is characterised in that the electronic blocking layer material is right It is required that the organic compound described in 1 to 3 any one using the fluorenes of 9,9 '-spiral shell two as core.
7. a kind of organic electroluminescence device according to claim 6, it is characterised in that also including transparent substrate layer, ITO sun Pole layer, hole injection layer, hole transmission layer, luminescent layer, hole barrier/electron transfer layer, electron injecting layer and negative electrode reflection electricity Pole layer, the transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole resistance Gear/electron transfer layer, electron injecting layer and negative electrode reflection electrode layer stack gradually arrangement from bottom to up.
8. a kind of organic electroluminescence device, including luminescent layer, it is characterised in that the luminescent layer is appointed including claims 1 to 3 Organic compound described in one using the fluorenes of 9,9 '-spiral shell two as core.
9. a kind of organic electroluminescence device according to claim 8, it is characterised in that also including transparent substrate layer, ITO sun Pole layer, hole injection layer, hole transmission layer, electronic barrier layer, hole barrier/electron transfer layer, electron injecting layer and negative electrode are anti- Penetrate electrode layer, the transparent substrate layer, ito anode layer, hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, sky Cave stop/electron transfer layer, electron injecting layer and negative electrode reflection electrode layer stack gradually arrangement from bottom to up.
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CN101918511A (en) * 2007-11-23 2010-12-15 葛来西雅帝史派有限公司 Luminescent compounds and electroluminescent device using the same
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CN108659010A (en) * 2017-03-27 2018-10-16 北京绿人科技有限责任公司 A kind of organic compound and its application in organic electroluminescence device
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