CN109824681A - A kind of Spirofluorene derivative species organic compound and its application on organic electroluminescence device - Google Patents

Abstract

The present invention relates to a kind of Spirofluorene derivative species organic compound and its applications on organic electroluminescence device, the structure of the compound is that spiro fluorene is connected by carbon-carbon bond with nitrogenous hexa-member heterocycle structure cyclization, the connection of carbon-carbon bond cyclization had both improved materials chemistry stability, and in turn avoid the active position of branched group exposed, and entire molecule is a biggish rigid structure, has high triplet (T1)；And steric hindrance is big, is not easy to rotate, solid space structure is more stable, therefore compound glass transition temperature with higher and molecule thermal stability；In addition, HOMO the and LUMO distributing position of the compounds of this invention is separated from each other, suitable HOMO and lumo energy are made it have；Therefore, after the compounds of this invention is applied to OLED device, the luminous efficiency and service life of device can effectively be promoted.

Description

A kind of Spirofluorene derivative species organic compound and its on organic electroluminescence device Using

Technical field

The present invention relates to technical field of semiconductors, more particularly, to a kind of Spirofluorene derivative species organic compound and its are having Application in organic electroluminescence devices.

Background technique

Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is very extensive.OLED luminescent device including electrode material film layer and is clipped in different electricity like the structure of sandwich Organic functional material between the film layer of pole, various different function materials are overlapped mutually depending on the application collectively constitutes OLED hair together Optical device.OLED luminescent device is as current device, when applying voltage to its two end electrodes, and passes through electric field action organic layer function Can positive and negative charge in film layer when, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.

Currently, OLED display technology in smart phone, applied by the fields such as tablet computer, further will also be to electricity Depending on etc. large scales application field extension, still with actual products application require compare, the luminous efficiency and use of OLED device The performances such as service life also need further to be promoted.Proposing high performance research to OLED luminescent device at present includes: to reduce the drive of device Dynamic voltage, the luminous efficiency for improving device, the service life for improving device etc..In order to realize that the continuous of performance of OLED device mentions It rises, not only needs the innovation from OLED device structure and manufacture craft, constantly study and create with greater need for oled light sulfate ferroelectric functional material Newly, the OLED functional material of higher performance is formulated out.

Oled light sulfate ferroelectric functional material applied to OLED device can be divided into two major classes from purposes, and respectively charge injects Transmission material and luminescent material.Further, it can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking Luminescent material, can also be divided into main body luminescent material and doping material by material, hole injection transmission material and hole barrier materials Material.

In order to make high performance OLED luminescent device, it is desirable that various organic functional materials have good photoelectric properties, For example, as charge transport materials, it is desirable that have good carrier mobility, high-vitrification conversion temperature etc., as luminous The material of main part of layer has good bipolarity, HOMO/LUMO energy rank appropriate etc..

The oled light sulfate ferroelectric functional material film layer for constituting OLED device includes at least two layers or more structure, applies in industry OLED device structure then includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron-transport A variety of film layers such as layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED device is injected including at least hole Material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and various The characteristics of property.In addition, used photoelectric functional material has stronger choosing for the collocation of the OLED device of different structure Selecting property, performance of the identical material in different structure device may also be completely totally different.

Therefore, for the industry application requirement of current OLED device and the different function film layer of OLED device, device Photoelectric characteristic demand, it is necessary to which selection is more suitable for, the higher OLED functional material of performance or combination of materials, is just able to achieve the height of device Efficiency, the overall characteristic of long-life and low-voltage.For current OLED shows the actual demand of 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.

Summary of the invention

In view of the above-mentioned problems existing in the prior art, the applicant provide a kind of Spirofluorene derivative species organic compound and Its application on organic electroluminescence device.The compounds of this invention contains spiro fluorene structure, glass transition temperature with higher With molecule thermal stability, suitable HOMO and lumo energy, higher Eg are optimized by device architecture, can effectively promote OLED device The photoelectric properties of part and the service life of OLED device.

Technical scheme is as follows: a kind of Spirofluorene derivative species organic compound, the structure of the organic compound As shown in general formula (1):

In general formula (1),Pass through C_L1-C_L2Key, C_L2-C_L3Key or C_L3-C_L4Key is connect with spiro fluorene；

In general formula (1), Ar is expressed as substituted or unsubstituted C_6-60Aryl replaces or not containing one or more hetero atoms One of substituted 5-60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；

In general formula (1), X is expressed as oxygen, sulphur, C_1-10The alkylene of alkylidene, aryl substitution that linear or branched alkyl group replaces One of the imido grpup that base, alkyl-substituted imido grpup or aryl replace；

In general formula (1), R is expressed as general formula (2), general formula (3), structure shown in general formula (4) or general formula (5)；

General formula (2), general formula (3), in general formula (4), X₁、X₂、X₃Independently be expressed as oxygen, sulphur, C_1-10Straight chain or C_1-10 In the imido grpup that alkylidene, alkyl-substituted imido grpup or the aryl of alkylidene, aryl substitution that branched alkyl replaces replace It is a kind of；

General formula (2), general formula (3), general formula (4) independently pass through C_L’1-C_L’2Key, C_L’2-C_L’3Key, C_L’3-C_L’4Key with General formula (1) connection；

In general formula (5), R₁、R₂Independently be expressed as substituted or unsubstituted C_6-60Aryl, containing one or more miscellaneous One of substituted or unsubstituted 5-60 unit's heteroaryl of atom；The hetero atom is nitrogen, oxygen or sulphur.

Preferably, a kind of Spirofluorene derivative species organic compound, the compound are selected from general formula (6), general formula (7), general formula (8), structure shown in general formula (9), general formula (10) or general formula (11):

Preferably, a kind of Spirofluorene derivative species organic compound, the compound are selected from general formula (12), general formula (13), lead to Structure shown in formula (14) or (15):

Preferably, a kind of Spirofluorene derivative species organic compound, the compound are selected from general formula (16), general formula (17), lead to Structure shown in formula (18) or general formula (19):

Preferably, a kind of Spirofluorene derivative species organic compound, the compound are selected from general formula (20), general formula (21), lead to Structure shown in formula (22) or general formula (23):

Preferably, a kind of Spirofluorene derivative species organic compound, the compound are selected from general formula (24), general formula (25), lead to Structure shown in formula (26) or general formula (27):

Preferably, a kind of Spirofluorene derivative species organic compound, the compound are selected from general formula (28), general formula (29), lead to Structure shown in formula (30) or general formula (31):

Preferably, a kind of Spirofluorene derivative species organic compound, the compound are selected from general formula (32), general formula (33) general formula (34) or structure shown in general formula (35):

Preferably, a kind of Spirofluorene derivative species organic compound, the Ar be expressed as phenyl, dibiphenylyl, terphenyl, Pyridyl group, pyrimidine radicals, pyridazinyl, pyrazinyl or triazine radical, dibenzofuran group, dibenzothiophene, 9,9- dimethyl fluorenyl Or one of N- phenyl carbazole base；The R₁、R₂Independently be expressed as phenyl, naphthalene, dibiphenylyl, terphenyl, naphthalene One of base, dibenzofuran group, dibenzothiophene, 9,9- dimethyl fluorenyl or N- phenyl carbazole base.

Preferably, a kind of Spirofluorene derivative species organic compound, in the general formula (1)It indicates are as follows:

In any one.

Preferably, a kind of Spirofluorene derivative species organic compound, the concrete structure formula of the compound are as follows:

In it is any one Kind.

The present invention also provides a kind of preparation method with Spirofluorene derivative species organic compound, occur in preparation process anti- Answer equation are as follows:

1) when X isAnd R is when being expressed as general formula (2), general formula (3) or general formula (4), specific reaction equation are as follows:

R3 is expressed as alkyl or C_6-60Aryl；

(1) under nitrogen protection, intermediate II, raw material I, sodium tert-butoxide, Pd are successively weighed₂(dba)₃, tri-tert-butylphosphine, It is stirred with toluene, is heated to 100~120 DEG C, back flow reaction 12~24 hours, samples contact plate, display is surplus without intermediate II It is remaining, fully reacting；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain intermediate III；

Wherein, the molar ratio of the raw material I and intermediate II is 1:1~2；The Pd₂(dba)₃With the molar ratio of raw material I For 0.006~0.02:1, the molar ratio of the tri-tert-butylphosphine and raw material I are 0.006~0.02:1；The sodium tert-butoxide and original The molar ratio for expecting I is 2.0~3.0:1；The dosage of the toluene is that 60-120ml toluene is added in 0.01mol raw material I；

(2) under nitrogen protection, intermediate III is weighed, tetrahydrofuran stirring and dissolving is added, is cooled to 0 DEG C with ice salt bath； The correspondence grignard reagent R of brand-new is slowly added dropwise into reaction system₃The tetrahydrofuran solution of-MgBr, room temperature reaction 6~12 are small When, contact plate is sampled, display is without intermediate III residue, fully reacting；Cooled to room temperature, filtering, filtrate decompression are rotated to nothing Fraction crosses neutral silica gel column, obtains intermediate compound IV, and the molar ratio of the intermediate III and grignard reagent is 1:2~4；Described four The dosage of hydrogen furans is that 20-40ml tetrahydrofuran is added in 0.01mol intermediate III；

(3) under nitrogen protection, intermediate compound IV is weighed, the H that mass fraction is 68% is added₃PO₄It is 1:3 with water volume ratio Mixed liquor, be stirred, react at room temperature 6~12 hours, sample contact plate, display without intermediate compound IV residue, fully reacting；It is added NaOH aqueous solution is neutralized to pH=7, and methylene chloride extraction is added, and layering takes organic phase to filter, and filtrate decompression, which is rotated to nothing, to be evaporated Point, neutral silica gel column is crossed, intermediate V is obtained；The dense H₃PO₄Dosage be 0.01mol intermediate compound IV be added 15-30ml it is dense H₃PO₄；

(4) under nitrogen protection, intermediate V, Ar-Br, sodium tert-butoxide, Pd are successively weighed₂(dba)₃, tri-tert-butylphosphine, use Toluene is stirred, and is heated to 100~120 DEG C, back flow reaction 12~24 hours, is sampled contact plate, and display is remaining without intermediate V, Fully reacting；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain target product； The molar ratio of the intermediate V and Ar-Br is 1:1~2；The Pd₂(dba)₃With the molar ratio of intermediate V be 0.006~ The molar ratio of 0.02:1, the tri-tert-butylphosphine and intermediate V are 0.006~0.02:1；The sodium tert-butoxide is with intermediate V's Molar ratio is 2.0~3.0:1；The dosage of the toluene is that 60-120ml toluene is added in 0.01mol intermediate V；

2) when X isAnd R is when being expressed as general formula (5), specific reaction equation are as follows:

Under nitrogen protection, intermediate VI, raw material VII, sodium tert-butoxide, Pd are successively weighed₂(dba)₃, tri-tert-butylphosphine, use Toluene is stirred, and is heated to 100~120 DEG C, back flow reaction 12~24 hours, is sampled contact plate, and display is remaining without intermediate V, Fully reacting；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain target product； The molar ratio of the intermediate VI and raw material VII is 1:1~2；The Pd₂(dba)₃With the molar ratio of intermediate VI be 0.006~ The molar ratio of 0.02:1, the tri-tert-butylphosphine and intermediate VI are 0.006~0.02:1；The sodium tert-butoxide and intermediate VI Molar ratio be 2.0~3.0:1；The dosage of the toluene is that 60-120ml toluene is added in 0.01mol raw material I.

One kind being used to prepare organic electroluminescence device with Spirofluorene derivative species organic compound by the present invention.

The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes at least one layer of function Layer contains the Spirofluorene derivative species organic compound.

Preferably, a kind of organic electroluminescence device, including electronic barrier layer, the electronic blocking layer material include described Spirofluorene derivative species organic compound.

Preferably, a kind of organic electroluminescence device, including luminescent layer, the luminescent layer include the spirofluorene derivative Class organic compound.

The present invention also provides a kind of illumination or display element, the illumination or display element include the organic electroluminescence hair Optical device.

The present invention is beneficial to be had the technical effect that

The compounds of this invention is connected using spiro fluorene as skeleton, by carbon-carbon bond with nitrogenous hexa-member heterocycle class formation cyclization, carbon The connection of carbon key cyclization had both improved stability of material, and in turn avoid the active position of branched group exposed；Such compound is in addition to spiro fluorene Outside with biggish rigidity, dimethyl acridinium class formation is also the rigid structure of one big pi bond conjugation, and steric hindrance is big, is not easy Rotation, so that the stereochemical structure of the compounds of this invention material is more stable.And the compounds of this invention triplet T1 from Density Distribution is revolved substantially on branch, and branch has high T1 energy level, therefore the compounds of this invention equally has high T1 energy level；This When electronic barrier layer materials'use of the invention compound as OLED, high T1 energy level can effectively stop energy from luminescent layer to Hole transmission layer transmitting, reduces energy loss, so that luminescent layer material of main part energy is sufficiently transmitted to dopant material, to be promoted Material is applied to the luminous efficiency after device.

The structure of organic compound of the invention balances electrons and holes more in the distribution of luminescent layer, appropriate Under HOMO energy level, hole injection and transmission performance are improved；Under suitable lumo energy, and play the work of electronic blocking With combined efficiency of the promotion exciton in luminescent layer；When light emitting functional layer materials'use as OLED luminescent device, spiro fluorene is taken Exciton utilization rate and high fluorescent radiation efficiency can be effectively improved with the branch in the scope of the invention, reduces the effect under high current density Rate is roll-offed, and is reduced device voltage, is improved current efficiency and the service life of device.Organic compound of the invention is in OLED device application When, optimized by device architecture, high membranous layer stability can be kept, can effectively promote the photoelectric properties and OLED of OLED device The service life of device.Compound of the present invention has good application effect and industrialization prospect in OLED luminescent device.

Detailed description of the invention

Fig. 1 is the structural schematic diagram that material cited by the present invention is applied to OLED device；

Wherein, 1, transparent substrate layer, 2, ito anode layer, 3, hole injection layer, 4, hole transmission layer 5, electronic barrier layer, 6, luminescent layer, 7, hole barrier/electron transfer layer, 8, electron injecting layer, 9, cathode reflection electrode layer.

Fig. 2 is the curve that current efficiency varies with temperature.

Specific embodiment

Embodiment 1: the synthesis of intermediate II and intermediate VI

A. the synthesis of intermediate II

(1) it weighs raw material A to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；It weighs bromine to be dissolved in glacial acetic acid, and delays Slowly it is added dropwise in the acetic acid solution of raw material A, 5h is stirred at room temperature, sample contact plate, display is without raw material A residue, fully reacting；Reaction knot Shu Hou is added lye into reaction solution and is neutralized to pH=7, be extracted with dichloromethane, is layered, takes organic phase to filter, filtrate decompression Revolving crosses silicagel column, obtains raw material II to no fraction；The molar ratio of the raw material A and bromine is 1:1~1.5；The acetic acid Dosage is that 20-40ml acetic acid is added in 0.01mol raw material A；

By taking the synthesis of intermediate II -1 as an example:

(1) 0.01mol raw material A -1,20ml acetic acid is added in the there-necked flask of 100mL, is cooled to 0 with ice salt bath ℃；0.8ml (0.015mol) bromine for being dissolved in 10ml glacial acetic acid is added dropwise into reaction system at 0 DEG C, is warmed to room temperature, stirs Mix 5h；Contact plate is sampled, display is remaining without raw material A -1, fully reacting；After reaction, sodium carbonate liquor is added into reaction solution Being neutralized to pH is 7, is extracted with dichloromethane, and is layered, and organic phase, dry filter are taken, and filtrate decompression is rotated to no fraction, crosses silica gel Column obtains intermediate II -1, HPLC purity 99.5%, yield 68.8%.

Elemental analysis structure (molecular formula C₁₄H₉BrO₃): theoretical value C, 55.11；H,2.97；Br,26.19；O,15.73；It surveys Examination value: C, 55.13；H,2.95；Br,26.17；O,15.75.ESI-MS(m/z)(M⁺): theoretical value 305.13, measured value are 305.47。

Intermediate II is prepared by the synthetic method of intermediate II -1, specific structure is as shown in table 1.

Table 1

B. the synthesis of intermediate VI

(1) under nitrogen protection, raw material I, 2- methyl-bromobenzoate, sodium tert-butoxide, Pd are successively weighed₂(dba)₃, three tertiary fourths Base phosphine, is stirred with toluene, is heated to 100~120 DEG C, back flow reaction 12~24 hours, is sampled contact plate, show without raw material I Residue, fully reacting；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain centre Body C；The molar ratio of the 2- methyl-bromobenzoate and raw material I are 1:1~2；The Pd₂(dba)₃With 2- methyl-bromobenzoate Molar ratio is 0.006~0.02:1, and the molar ratio of the tri-tert-butylphosphine and 2- methyl-bromobenzoate is 0.006~0.02:1； The molar ratio of the sodium tert-butoxide and 2- methyl-bromobenzoate is 2.0~3.0:1；The dosage of the toluene is 0.01mol raw material I 60-120ml toluene is added；

(2) under nitrogen protection, intermediate C is weighed, tetrahydrofuran stirring and dissolving is added, is cooled to 0 DEG C with ice salt bath；To The correspondence grignard reagent R of brand-new is slowly added dropwise in reaction system₃The tetrahydrofuran solution of-MgBr reacts at room temperature 6~12 hours, Contact plate is sampled, display is remaining without intermediate C, fully reacting；Cooled to room temperature, filtering, filtrate decompression are rotated to no fraction, Neutral silica gel column is crossed, intermediate D is obtained.The molar ratio of the intermediate C and grignard reagent is 1:2~4；The tetrahydrofuran Dosage is that 20-40ml tetrahydrofuran is added in 0.01mol intermediate C；

(3) under nitrogen protection, intermediate D is weighed, dense H is added₃PO₄The mixed liquor for being 1:3 with water volume ratio, stirring are mixed It closes, reacts at room temperature 6~12 hours, sample contact plate, display is remaining without intermediate D, fully reacting；NaOH aqueous solution is added to be neutralized to Methylene chloride extraction is added in pH=7, and layering takes organic phase to filter, and filtrate decompression is rotated to no fraction, crosses neutral silica gel column, obtains To intermediate E；The dense H₃PO₄Dosage be 0.01mol intermediate D be added the dense H of 15-30ml₃PO₄；

(4) under nitrogen protection, intermediate E, Ar-Br, sodium tert-butoxide, Pd are successively weighed₂(dba)₃, tri-tert-butylphosphine, use Toluene is stirred, and is heated to 100~120 DEG C, back flow reaction 12~24 hours, is sampled contact plate, and display is remaining without intermediate E, Fully reacting；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain intermediate F；Institute The molar ratio for stating intermediate E and Ar-Br is 1:1~2；The Pd₂(dba)₃Molar ratio with intermediate E is 0.006~0.02: 1, the molar ratio of the tri-tert-butylphosphine and intermediate E is 0.006~0.02:1；Mole of the sodium tert-butoxide and intermediate E Than for 2.0~3.0:1；The dosage of the toluene is that 60-120ml toluene is added in 0.01mol intermediate E；

(5) it weighs intermediate F to be dissolved in acetic acid, is cooled to 0 DEG C with ice salt bath；Bromine is weighed to be dissolved in glacial acetic acid, and It is slowly added dropwise into the acetic acid solution of intermediate F, 5h is stirred at room temperature, sample contact plate, display is remaining without intermediate F, fully reacting； After reaction, lye is added into reaction solution to neutralize, is extracted with dichloromethane, be layered, organic phase is taken to filter, filtrate decompression rotation It steams to no fraction, crosses silicagel column, obtain intermediate VI；The molar ratio of the intermediate F and bromine is 1:1~1.5；The acetic acid Dosage be 0.01mol intermediate F be added 20-40ml acetic acid；

By taking the synthesis of intermediate VI-1 as an example:

(1) in the there-necked flask of 500ml, lead under nitrogen protection, 0.1mol raw material I-1,0.12mol2- bromobenzoic acid is added Methyl esters, 0.3mol sodium tert-butoxide, 5 × 10^-4mol Pd₂(dba)₃, 5 × 10^-4Mol tri-tert phosphorus is dissolved with 300ml toluene, It is heated to reflux 24 hours, samples contact plate, display is remaining without raw material I-1, fully reacting；Natural cooling, filtering, filtrate revolving, mistake Silicagel column obtains intermediate C-1, HPLC purity 99.1%, yield 83.5%.Elemental analysis structure (molecular formula C₃₃H₂₃NO₂): reason By value C, 85.14；H,4.98；N,3.01；O,6.87；Test value: C, 85.15；H,4.97；N,3.03；O,6.86.ESI-MS (m/z)(M⁺): theoretical value 465.17, measured value 465.55.

(2) in the there-necked flask of 500ml, lead under nitrogen protection, 0.05mol intermediate C-1 is added, 100ml tetrahydro is added Furans stirring and dissolving is cooled to 0 DEG C with ice salt bath；The tetrahydrofuran that 63ml methyl-magnesium-bromide is slowly added dropwise into reaction system is molten Liquid (2.4mol/L) after completion of dropwise addition, 20 DEG C of temperature control, is stirred to react 12 hours, samples contact plate, and display is remaining without intermediate C-1, Fully reacting；Reaction solution is filtered, filtrate decompression is rotated to no fraction, is crossed neutral silica gel column, is obtained intermediate D-1, HPLC is pure Degree 99.3%, yield 73.2%.Elemental analysis structure (molecular formula C₃₄H₂₇NO): theoretical value C, 87.71；H,5.85；N,3.01； O,3.44；Test value: C, 87.73；H,5.83；N,3.02；O,3.42.ESI-MS(m/z)(M⁺): theoretical value 465.21, it is real Measured value is 465.53.

(3) in the there-necked flask of 500ml, lead under nitrogen protection, 0.03mol intermediate D-1,200ml mixed solvent is added (the H that mass fraction is 68%₃PO₄It is 1:3 with water volume ratio), it 20 DEG C of temperature control, reacts 6 hours, samples contact plate, show without centre Body D-1 is remaining, fully reacting；NaOH aqueous solution neutralization reaction liquid is added to pH=7, methylene chloride extraction is added, layering has taken Machine mutually filters, and filtrate decompression is rotated to no fraction, crosses neutral silica gel column, obtains intermediate E -1, HPLC purity 99.2%, yield 67.1%.Elemental analysis structure (molecular formula C₃₄H₂₅N): theoretical value C, 91.24；H,5.63；N,3.13；Test value: C, 91.22； H,5.64；N,3.14.ESI-MS(m/z)(M⁺): theoretical value 447.20, measured value 447.44.

(4) in the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate E -1,0.012mol bromobenzene be added, 0.03mol sodium tert-butoxide, 5 × 10^-5mol Pd₂(dba)₃, 5 × 10^-5Mol tri-tert phosphorus is dissolved with 100ml toluene, heating Reflux 24 hours samples contact plate, and display is remaining without intermediate E -1, fully reacting；Natural cooling, filtering, filtrate revolving cross silicon Rubber column gel column obtains intermediate F-1, HPLC purity 99.6%, yield 73.5%；Elemental analysis structure (molecular formula C₄₀H₂₉N): theoretical Value C, 91.74；H,5.58；N,2.67；Test value: C, 91.73；H,5.59；N,2.68.ESI-MS(m/z)(M⁺): theoretical value is 523.23 measured value 523.52.

(5) 0.02mol intermediate F-1,40ml acetic acid are added in the there-necked flask of 250mL, is cooled to 0 with ice salt bath ℃；1.6ml (0.03mol) bromine for being dissolved in 20ml glacial acetic acid is added dropwise into reaction system at 0 DEG C, is warmed to room temperature, stirs Mix 5h；Contact plate is sampled, display is remaining without intermediate F-1, fully reacting；After reaction, it is molten that sodium carbonate is added into reaction solution Liquid is neutralized to pH=7, is extracted with dichloromethane, layering, takes organic phase, dry filter, and filtrate decompression is rotated to no fraction, crosses silicon Rubber column gel column obtains intermediate VI-1, HPLC purity 99.5%, yield 73.4%.

Elemental analysis structure (molecular formula C₄₀H₂₈BrN): theoretical value C, 79.73；H,4.68；Br,13.26；N,2.32；It surveys Examination value: C, 79.75；H,4.66；Br,13.25；N,2.34.ESI-MS(m/z)(M⁺): theoretical value 601.14, measured value are 601.43。

Intermediate VI is prepared by the synthetic method of intermediate VI-1, specific structure is as shown in table 2.

Table 2

Embodiment 2: the synthesis of compound 1:

(1) in the there-necked flask of 500ml, lead under nitrogen protection, 0.1mol raw material I-1,0.12mol intermediate II-is added 1,0.3mol sodium tert-butoxide, 5 × 10^-4mol Pd₂(dba)₃, 5 × 10^-4Mol tri-tert phosphorus is dissolved with 300ml toluene, heating Reflux 24 hours samples contact plate, shows remaining without raw material I-1, fully reacting；Natural cooling, filtering, filtrate revolving cross silicagel column, Obtain intermediate III -1, HPLC purity 99.8%, yield 80.5%.Elemental analysis structure (molecular formula C₃₉H₂₅NO₃): theoretical value C,84.31；H,4.54；N,2.52；O,8.64；Test value: C, 84.32；H,4.52；N,2.53；O,8.63.ESI-MS(m/z) (M⁺): theoretical value 555.18, measured value 555.47.

(2) in the there-necked flask of 500ml, lead under nitrogen protection, intermediate III -1 0.05mol is added, 100ml tetra- is added Hydrogen furans stirring and dissolving is cooled to 0 DEG C with ice salt bath；The tetrahydrofuran of 63ml methyl-magnesium-bromide is slowly added dropwise into reaction system Solution (2.4mol/L) after completion of dropwise addition, 20 DEG C of temperature control, is stirred to react 12 hours, samples contact plate, is shown without intermediate III -1 Residue, fully reacting；Reaction solution is filtered, filtrate decompression is rotated to no fraction, and neutral silica gel column is crossed, intermediate compound IV -1 is obtained, HPLC purity 99.1%, yield 66.8%.Elemental analysis structure (molecular formula C₄₀H₂₉NO₂): theoretical value C, 86.46；H,5.26；N, 2.52；O,5.76；Test value: C, 86.44；H,5.25；N,2.54；O,5.77.ESI-MS(m/z)(M⁺): theoretical value is 555.22 measured value 555.39.

(3) in the there-necked flask of 500ml, lead under nitrogen protection, 0.03mol intermediate compound IV -1,200ml mixed solvent is added (the H that mass fraction is 68%₃PO₄It is 1:3 with water volume ratio), it 20 DEG C of temperature control, reacts 6 hours, samples contact plate, show without centre Body IV-1 is remaining, fully reacting；NaOH aqueous solution neutralization reaction liquid is added to pH=7, methylene chloride extraction is added, layering takes Organic phase filtering, filtrate decompression are rotated to no fraction, cross neutral silica gel column, obtain intermediate V-1, and HPLC purity 99.2% is received Rate 65.1%.Elemental analysis structure (molecular formula C₄₀H₂₇NO): theoretical value C, 89.36；H,5.06；N,2.61；O,2.98；Test Value: C, 89.34；H,5.07；N,2.64；O,2.95.ESI-MS(m/z)(M⁺): theoretical value 537.21, measured value are 537.54。

(4) in the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate V-1,0.012mol bromobenzene be added, 0.03mol sodium tert-butoxide, 5 × 10^-5mol Pd₂(dba)₃, 5 × 10^-5Mol tri-tert phosphorus is dissolved with 100ml toluene, heating Reflux 24 hours samples contact plate, and display is remaining without intermediate V-1, fully reacting；Natural cooling, filtering, filtrate revolving cross silicon Rubber column gel column obtains target product, HPLC purity 99.4%, yield 77.8%；Elemental analysis structure (molecular formula C₄₆H₃₁NO): theoretical Value C, 90.02；H,5.09；N,2.28；O,2.61；Test value: C, 90.01；H,5.07；N,2.29；O,2.63.ESI-MS(m/ z)(M⁺): theoretical value 613.24, measured value 613.51.

Embodiment 3: the synthesis of compound 12:

(1) in the there-necked flask of 500ml, lead under nitrogen protection, 0.1mol raw material I-1,0.12mol intermediate II-is added 2,0.3mol sodium tert-butoxides, 5 × 10^-4mol Pd₂(dba)₃, 5 × 10^-4Mol tri-tert phosphorus is dissolved with 300ml toluene, heating Reflux 24 hours samples contact plate, and display is remaining without raw material I-1, fully reacting；Natural cooling, filtering, filtrate revolving cross silica gel Column obtains intermediate III -2, HPLC purity 99.4%, yield 82.1%.Elemental analysis structure (molecular formula C₃₉H₂₅NO₂S): reason By value C, 81.94；H,4.41；N,2.45；O,5.60；S,5.61；Test value: C, 81.92；H,4.42；N,2.43；O,5.61； S,5.62。ESI-MS(m/z)(M⁺): theoretical value 571.16, measured value 571.48.

(2) in the there-necked flask of 500ml, lead under nitrogen protection, intermediate III -2 0.05mol are added, 100ml tetra- is added Hydrogen furans stirring and dissolving is cooled to 0 DEG C with ice salt bath；The tetrahydrofuran of 63ml methyl-magnesium-bromide is slowly added dropwise into reaction system Solution (2.4mol/L) after completion of dropwise addition, 20 DEG C of temperature control, is stirred to react 12 hours, samples contact plate, is shown without intermediate III -2 Residue, fully reacting；Reaction solution is filtered, filtrate decompression is rotated to no fraction, and neutral silica gel column is crossed, intermediate compound IV -2 is obtained, HPLC purity 99.4%, yield 68.5%.Elemental analysis structure (molecular formula C₄₀H₂₉NOS): theoretical value C, 84.03；H,5.11； N,2.45；O,2.80；S,5.61；Test value: C, 84.04；H,5.12；N,2.43；O,2.81；S,5.60.ESI-MS(m/z)(M⁺): theoretical value 571.20, measured value 571.44.

(3) in the there-necked flask of 500ml, lead under nitrogen protection, 0.03mol intermediate compound IV -2,200ml mixed solvent is added (the H that mass fraction is 68%₃PO₄It is 1:3 with water volume ratio), it 20 DEG C of temperature control, reacts 6 hours, samples contact plate, show without centre Body IV-2 is remaining, fully reacting；NaOH aqueous solution neutralization reaction liquid is added to pH=7, methylene chloride extraction is added, layering takes Organic phase filtering, filtrate decompression are rotated to no fraction, cross neutral silica gel column, obtain intermediate V-2, and HPLC purity 99.6% is received Rate 67.7%.Elemental analysis structure (molecular formula C₄₀H₂₇NS): theoretical value C, 86.77；H,4.92；N,2.53；S,5.79；Test Value: C, 86.76；H,4.93；N,2.54；S,5.77.ESI-MS(m/z)(M⁺): theoretical value 553.19, measured value are 553.47。

(4) in the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate V-2,0.012mol bromobenzene be added, 0.03mol sodium tert-butoxide, 5 × 10^-5mol Pd₂(dba)₃, 5 × 10^-5Mol tri-tert phosphorus is dissolved with 100ml toluene, heating Reflux 24 hours samples contact plate, and display is remaining without intermediate V-2, fully reacting；Natural cooling, filtering, filtrate revolving cross silicon Rubber column gel column obtains target product, HPLC purity 99.1%, yield 75.3%；Elemental analysis structure (molecular formula C₄₆H₃₁NS): theoretical Value C, 87.72；H,4.96；N,2.22；S,5.09；Test value: C, 87.73；H,4.97；N,2.23；S,5.07.ESI-MS(m/ z)(M⁺): theoretical value 629.22, measured value 629.51.

Embodiment 4: the synthesis of compound 21:

The same intermediate III -1 of the preparation method of intermediate III -3, the difference is that being replaced using intermediate II -3 intermediate Body II-1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -3, the difference is that replacing intermediate using intermediate III -3 III-1；The preparation method of intermediate V-3 is with intermediate V-1, the difference is that replacing intermediate compound IV-using intermediate compound IV -3 1；

The preparation method of compound 21 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-3.Member Element analysis structure (molecular formula C₅₂H₃₆N₂): theoretical value C, 90.67；H,5.27；N,4.07；Test value: C, 90.66；H,5.25；N, 4.09。ESI-MS(m/z)(M⁺): theoretical value 688.29, measured value 688.63.

Embodiment 5: the synthesis of compound 39:

The same intermediate III -1 of the preparation method of intermediate III -4, the difference is that replacing raw material I-1 using raw material I-2 Intermediate II -1 is replaced with intermediate II -4；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -4, the difference is that using Intermediate III -4 replaces intermediate III -1；The preparation method of intermediate V-4 is with intermediate V-1, the difference is that in Mesosome IV-4 replaces intermediate compound IV -1；

The preparation method of compound 39 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-4.Member Element analysis structure (molecular formula C₄₆H₃₁NO): theoretical value C, 90.02；H,5.09；N,2.28；O,2.61；Test value: C, 90.01； H,5.08；N,2.29；O,2.62.ESI-MS(m/z)(M⁺): theoretical value 613.24, measured value 613.45.

Embodiment 6: the synthesis of compound 51:

The same intermediate III -1 of the preparation method of intermediate III -5, the difference is that replacing raw material I-1 using raw material I-2 Intermediate II -1 is replaced with intermediate II -5；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -5, the difference is that using Intermediate III -5 replaces intermediate III -1；The preparation method of intermediate V-5 is with intermediate V-1, the difference is that in Mesosome IV-5 replaces intermediate compound IV -1；

The preparation method of compound 51 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-5.Member Element analysis structure (molecular formula C₄₉H₃₇N): theoretical value C, 91.98；H,5.83；N,2.19；Test value: C, 91.96；H,5.85；N, 2.19。ESI-MS(m/z)(M⁺): theoretical value 639.29, measured value 639.62.

Embodiment 7: the synthesis of compound 62:

The same intermediate III -1 of the preparation method of intermediate III -6, the difference is that replacing raw material I-1 using raw material I-2 Intermediate II -1 is replaced with intermediate II -6；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -6, the difference is that using Intermediate III -6 replaces intermediate III -1；The preparation method of intermediate V-6 is with intermediate V-1, the difference is that in Mesosome IV-6 replaces intermediate compound IV -1；

The preparation method of compound 62 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-6.Member Element analysis structure (molecular formula C₅₂H₃₆N₂): theoretical value C, 90.67；H,5.27；N,4.07；Test value: C, 90.65；H,5.28；N, 4.07。ESI-MS(m/z)(M⁺): theoretical value 688.29, measured value 688.64.

Embodiment 8: the synthesis of compound 68:

The same intermediate III -1 of the preparation method of intermediate III -7, the difference is that replacing raw material I-1 using raw material I-2 Intermediate II -1 is replaced with intermediate II -7；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -7, the difference is that using Intermediate III -7 replaces intermediate III -1；The preparation method of intermediate V-7 is with intermediate V-1, the difference is that in Mesosome IV-7 replaces intermediate compound IV -1；

The preparation method of compound 68 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-7.Member Element analysis structure (molecular formula C₄₆H₃₁NO): theoretical value C, 90.02；H,5.09；N,2.28；O,2.61；Test value: C, 90.04； H,5.07；N,2.27；O,2.62.ESI-MS(m/z)(M⁺): theoretical value 613.24, measured value 613.55.

Embodiment 9: the synthesis of compound 77:

The same intermediate III -1 of the preparation method of intermediate III -8, the difference is that replacing raw material I-1 using raw material I-2 Intermediate II -1 is replaced with intermediate II -8；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -8, the difference is that using Intermediate III -8 replaces intermediate III -1；The preparation method of intermediate V-8 is with intermediate V-1, the difference is that in Mesosome IV-8 replaces intermediate compound IV -1；

The preparation method of compound 77 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-8.Member Element analysis structure (molecular formula C₄₉H₃₇N): theoretical value C, 91.98；H,5.83；N,2.19；Test value: C, 91.96；H,5.86；N, 2.18。ESI-MS(m/z)(M⁺): theoretical value 639.29, measured value 639.63.

Embodiment 10: the synthesis of compound 90:

The same intermediate III -1 of the preparation method of intermediate III -9, the difference is that replacing raw material I-1 using raw material I-3 Intermediate II -1 is replaced with intermediate II -9；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -9, the difference is that using Intermediate III -9 replaces intermediate III -1；The preparation method of intermediate V-9 is with intermediate V-1, the difference is that in Mesosome IV-9 replaces intermediate compound IV -1；

The preparation method of compound 90 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-9.Member Element analysis structure (molecular formula C₄₆H₃₁NO): theoretical value C, 90.02；H,5.09；N,2.28；O,2.61；Test value: C, 90.03； H,5.08；N,2.27；O,2.62.ESI-MS(m/z)(M⁺): theoretical value 613.24, measured value 613.51.

Embodiment 11: the synthesis of compound 99:

The same intermediate III -1 of the preparation method of intermediate III -10, the difference is that replacing raw material I- using raw material I-3 1 and intermediate II -10 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -10, the difference is that adopting Intermediate III -1 is replaced with intermediate III -10；The preparation method of intermediate V-10 is with intermediate V-1, the difference is that adopting Intermediate compound IV -1 is replaced with intermediate compound IV -10；

The preparation method of compound 99 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-10. Elemental analysis structure (molecular formula C₄₉H₃₇N): theoretical value C, 91.98；H,5.83；N,2.19；Test value: C, 91.95；H,5.85； N,2.20。ESI-MS(m/z)(M⁺): theoretical value 639.29, measured value 639.65.

Embodiment 12: the synthesis of compound 109:

The same intermediate III -1 of the preparation method of intermediate III -11, the difference is that replacing raw material I- using raw material I-3 1 and intermediate II -11 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -11, the difference is that adopting Intermediate III -1 is replaced with intermediate III -11；The preparation method of intermediate V-11 is with intermediate V-1, the difference is that adopting Intermediate compound IV -1 is replaced with intermediate compound IV -11；

The preparation method of compound 109 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-11. Elemental analysis structure (molecular formula C₅₂H₃₆N₂): theoretical value C, 90.67；H,5.27；N,4.07；Test value: C, 90.65；H,5.28； N,4.07。ESI-MS(m/z)(M⁺): theoretical value 688.29, measured value 688.67.

Embodiment 13: the synthesis of compound 116:

The same intermediate III -1 of the preparation method of intermediate III -12, the difference is that replacing raw material I- using raw material I-3 1 and intermediate II -7 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -12, the difference is that adopting Intermediate III -1 is replaced with intermediate III -12；The preparation method of intermediate V-12 is with intermediate V-1, the difference is that adopting Intermediate compound IV -1 is replaced with intermediate compound IV -12；

The preparation method of compound 116 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-12. Elemental analysis structure (molecular formula C₄₆H₃₁NO): theoretical value C, 90.02；H,5.09；N,2.28；O,2.61；Test value: C, 90.05；H,5.07；N,2.26；O,2.62.ESI-MS(m/z)(M⁺): theoretical value 613.24, measured value 613.52.

Embodiment 14: the synthesis of compound 125:

The same intermediate III -1 of the preparation method of intermediate III -13, the difference is that replacing raw material I- using raw material I-3 1 and intermediate II -8 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -13, the difference is that adopting Intermediate III -1 is replaced with intermediate III -13；The preparation method of intermediate V-13 is with intermediate V-1, the difference is that adopting Intermediate III -1 is replaced with intermediate compound IV -13；

The preparation method of compound 125 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-13. Elemental analysis structure (molecular formula C₄₉H₃₇N): theoretical value C, 91.98；H,5.83；N,2.19；Test value: C, 91.97；H,5.82； N,2.21。ESI-MS(m/z)(M⁺): theoretical value 639.29, measured value 639.56.

Embodiment 15: the synthesis of compound 134:

The same intermediate III -1 of the preparation method of intermediate III -14, the difference is that replacing raw material I- using raw material I-3 1 and intermediate II -6 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -14, the difference is that adopting Intermediate III -1 is replaced with intermediate III -14；The preparation method of intermediate V-14 is with intermediate V-1, the difference is that adopting Intermediate compound IV -1 is replaced with intermediate compound IV -14；

The preparation method of compound 134 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-14. Elemental analysis structure (molecular formula C₅₂H₃₆N₂): theoretical value C, 90.67；H,5.27；N,4.07；Test value: C, 90.65；H,5.25； N,4.10。ESI-MS(m/z)(M⁺): theoretical value 688.29, measured value 688.48.

Embodiment 16: the synthesis of compound 143:

The same intermediate III -1 of the preparation method of intermediate III -15, the difference is that replacing raw material I- using raw material I-4 1 and intermediate II -8 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -15, the difference is that adopting Intermediate III -1 is replaced with intermediate III -15；The preparation method of intermediate V-15 is with intermediate V-1, the difference is that adopting Intermediate III -1 is replaced with intermediate compound IV -15；

The preparation method of compound 143 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-15. Elemental analysis structure (molecular formula C49H37N): theoretical value C, 91.98；H,5.83；N,2.19；Test value: C, 91.95；H, 5.85；N,2.20.ESI-MS(m/z)(M⁺): theoretical value 639.29, measured value 639.57.

Embodiment 17: the synthesis of compound 152:

The same intermediate III -1 of the preparation method of intermediate III -16, the difference is that intermediate II -4 replaces intermediate II-1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -16, the difference is that replacing intermediate using intermediate III -16 III-1；The preparation method of body V-16 is with intermediate V-1, the difference is that replacing intermediate compound IV -1 using intermediate compound IV -16；

The preparation method of compound 152 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-16 Bromobenzene is replaced with 3- bromo biphenyl.Elemental 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,2.02；O,2.33.ESI-MS(m/z)(M⁺): theoretical value 689.27, actual measurement Value is 689.59.

Embodiment 18: the synthesis of compound 167:

The same intermediate III -1 of the preparation method of intermediate III -17, the difference is that using in the replacement of intermediate II -12 Mesosome II-1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -17, the difference is that using in the replacement of intermediate III -17 Mesosome III-1；The preparation method of intermediate V-17 is with intermediate V-1, the difference is that being replaced using intermediate compound IV -17 intermediate Body IV-1；

The preparation method of compound 167 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-17. Elemental analysis structure (molecular formula C₄₉H₃₇NO): theoretical value C, 89.74；H,5.69；N,2.14；O,2.44；Test value: C, 89.75；H,5.68；N,2.12；O,2.45.ESI-MS(m/z)(M⁺): theoretical value 655.29, measured value 655.64.

Embodiment 19: the synthesis of compound 183:

The same intermediate III -1 of the preparation method of intermediate III -18, the difference is that replacing raw material I- using raw material I-2 1 and intermediate II -13 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -18, the difference is that adopting Intermediate III -1 is replaced with intermediate III -18；The preparation method of intermediate V-18 is with intermediate V-1, the difference is that adopting Intermediate compound IV -1 is replaced with intermediate compound IV -18；

The preparation method of compound 183 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-18. Elemental analysis structure (molecular formula C₅₅H₄₂N₂): theoretical value C, 90.38；H,5.79；N,3.83；Test value: C, 90.37；H,5.80； N,3.83。ESI-MS(m/z)(M⁺): theoretical value 730.33, measured value 730.68.

Embodiment 20: the synthesis of compound 195:

The same intermediate III -1 of the preparation method of intermediate III -19, the difference is that replacing raw material I- using raw material I-2 1 and intermediate II -14 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -19, the difference is that adopting Intermediate III -1 is replaced with intermediate III -19；The preparation method of intermediate V-19 is with intermediate V-1, the difference is that adopting Intermediate compound IV -1 is replaced with intermediate compound IV -19；

The preparation method of compound 195 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-19. Elemental analysis structure (molecular formula C₅₂H₄₃N): theoretical value C, 91.59；H,6.36；N,2.05；Test value: C, 91.58；H,6.37； N,2.05；O,2.68.ESI-MS(m/z)(M⁺): theoretical value 681.34, measured value 681.72.

Embodiment 21: the synthesis of compound 210:

The same intermediate III -1 of the preparation method of intermediate III -20, the difference is that replacing raw material I- using raw material I-3 1 and intermediate II -15 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -20, the difference is that adopting Intermediate III -1 is replaced with intermediate III -20；The preparation method of intermediate V-20 is with intermediate V-1, the difference is that adopting Intermediate compound IV -1 is replaced with intermediate compound IV -20；

The preparation method of compound 210 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-20. Elemental analysis structure (molecular formula C₄₉H₃₇NO): theoretical value C, 89.74；H,5.69；N,2.14；O,2.44；Test value: C, 89.73；H,5.68；N,2.16；O,2.43.ESI-MS (m/z) (M+): theoretical value 655.29, measured value 655.65.

Embodiment 22: the synthesis of compound 239:

The same intermediate III -1 of the preparation method of intermediate III -21, the difference is that replacing raw material I- using raw material I-3 1 and intermediate II -16 replace intermediate II -1；The same intermediate compound IV -1 of the preparation method of intermediate compound IV -21, the difference is that adopting Intermediate III -1 is replaced with intermediate III -21；The preparation method of intermediate V-21 is with intermediate V-1, the difference is that adopting Intermediate compound IV -1 is replaced with intermediate compound IV -21；

The preparation method of compound 239 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-21. Elemental analysis structure (molecular formula C₅₂H₄₃N): theoretical value C, 91.59；H,6.36；N,2.05；Test value: C, 91.57；H,6.38； N,2.05.ESI-MS (m/z) (M+): theoretical value 681.34, measured value 681.66.

Embodiment 23: the synthesis of compound 258:

The same intermediate III -1 of -22 preparation method of intermediate III, the difference is that using raw material I-4 change raw material I-1 and Intermediate II -17 changes intermediate II -1；The same intermediate compound IV -1 of -22 preparation method of intermediate compound IV, the difference is that using intermediate Body III-22 changes intermediate III -1；Intermediate V-22 preparation method is with intermediate V-1, the difference is that using intermediate compound IV- 22 change intermediate compound IV -1；

The preparation method of compound 258 is with compound 1, the difference is that replacing intermediate V-1 using intermediate V-22. Elemental analysis structure (molecular formula C₄₉H₃₇NO): theoretical value C, 89.74；H,5.69；N,2.14；O,2.44；Test value: C, 89.73；H,5.68；N,2.13；O,2.46.ESI-MS (m/z) (M+): theoretical value 655.29, measured value 655.58.

Embodiment 24: the synthesis of compound 280:

In the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol intermediate VI-1,0.012mol raw material VII- is added 1,0.03mol sodium tert-butoxide, 5 × 10^-5mol Pd₂(dba)₃, 5 × 10^-5Mol tri-tert phosphorus is dissolved with 100ml toluene, is added Heat reflux 24 hours samples contact plate, and display is remaining without intermediate VI-1, fully reacting；Natural cooling, filtering, filtrate revolving, mistake Silicagel column obtains target product, HPLC purity 99.3%, yield 81.7%.Elemental analysis structure (molecular formula C₅₂H₃₈N₂): it is theoretical Value C, 90.40；H,5.54；N,4.05；Test value: C, 90.41；H,5.55；N,4.04.ESI-MS(m/z)(M⁺): theoretical value is 690.30 measured value 690.65.

Embodiment 25: the synthesis of compound 291:

The preparation method of compound 291 is with compound 280, the difference is that replacing intermediate using intermediate VI-2 VI-1, HPLC purity 99.4%, yield 88.3%.Elemental analysis structure (molecular formula C₅₂H₃₈N₂): theoretical value C, 90.40；H, 5.54；N,4.05；O,2.17；Test value: C, 90.42；H,5.53；N,4.05.ESI-MS(m/z)(M⁺): theoretical value is 690.30 measured value 690.66.

Embodiment 26: the synthesis of compound 301:

The preparation method of compound 301 is with compound 280, the difference is that replacing raw material VII-1 using raw material VII-2 Intermediate VI-1, HPLC purity 99.6%, yield 84.2% are replaced with intermediate VI-3.Elemental analysis structure (molecular formula C₆₁H₄₆N₂): theoretical value C, 90.78；H,5.75；N,3.47；Test value: C, 90.76；H,5.76；N,3.48.ESI-MS(m/z) (M⁺): theoretical value 806.37, measured value 806.73.

Organic compound of the invention uses in luminescent device, can be used as electronic blocking layer material, can also be used as Luminescent layer material of main part uses.The test of hot property, HOMO energy level, cyclic voltammetric stability is carried out to the compounds of this invention, such as Shown in table 3.

Table 3

Note: triplet T1 is tested by the F4600 Fluorescence Spectrometer of Hitachi, and the test condition of material is 2*10^-5's Toluene solution；Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimeter) Measurement, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 1% in nitrogen atmosphere, in Japanese Shimadzu Corporation TGA-50H thermogravimetric analyzer on be measured, nitrogen flow 20mL/min；Highest occupied molecular orbital HOMO energy level be by Ionizing energy test macro (IPS3) test, is tested as atmospheric environment.Cyclic voltammetric stability is observed by cyclic voltammetry The redox characteristic of material is identified；Test condition: test sample is dissolved in the methylene chloride and acetonitrile that volume ratio is 2:1 Mixed solvent, concentration 1mg/mL, electrolyte be 0.1M tetrabutyl ammonium tetrafluoroborate or hexafluorophosphate it is organic molten Liquid.Reference electrode is Ag/Ag+ electrode, is titanium plate to electrode, and working electrode is ITO electrode, and cycle-index is 20 times, meets 0.9 ≤ Ipa/Ipc≤1.1, then cyclic voltammetric stability is excellent, is otherwise difference, and wherein Ipa is oxidation peak current, and Ipc is reduction peak electricity Stream.

When cyclic voltammetric stability refers to cyclic voltammetry, whether material oxidation reduction is reversible, and (i.e. whether receiving and losing electrons Balance)；Repeatedly whether curve deforms after circulation, if is overlapped.If testing by cyclic voltammetry, material oxidation reduction is reversible, Repeatedly test curve does not deform after circulation, and repeatability is good, and visual material has excellent chemical stability.

By upper table data it is found that organic compound of the invention has different HOMO energy levels, different function can be applied to Ergosphere, Spirofluorene derivative species organic compound triplet, higher thermal stability and chemistry with higher of the present invention are surely It is qualitative, so that the made OLED device efficiency containing organic compound of the present invention and service life get a promotion.

Below by way of device embodiments 1~25 and device comparative example 1 OLED material that the present invention will be described in detail synthesizes in device Application effect in part.Device embodiments 2~25 of the present invention, the device compared with device embodiments 1 of device comparative example 1 Manufacture craft it is identical, and use identical baseplate material and electrode material, the film thickness of electrode material is also kept Unanimously, except that device embodiments 2~14 are to use material of the present invention as electronic barrier layer application；Device is implemented The material of main part of luminescent layer in 15~25 pairs of devices of example converts.The performance test results such as table of each embodiment obtained device Shown in 4.

Device embodiments 1: as shown in Figure 1, a kind of electroluminescent device, preparation step include:

A) the ito anode layer 2 on transparent substrate layer 1 is cleaned, cleans each 15 with deionized water, acetone, EtOH Sonicate respectively Minute, then handled 2 minutes in plasma cleaner；B) on ito anode layer 2, sky is deposited by vacuum evaporation mode Layer material HAT-CN is injected in cave, and with a thickness of 10nm, this layer is as hole injection layer 3；C) on hole injection layer 3, pass through vacuum Hole mobile material NPB is deposited in vapor deposition mode, and with a thickness of 60nm, which is hole transmission layer 4；D) on hole transmission layer 4, lead to It crosses vacuum evaporation mode and electronic blocking layer material the compounds of this invention 21 is deposited, with a thickness of 20nm, which is electronic barrier layer 5； E) luminescent layer 6 is deposited on electronic barrier layer 5, uses CBP as material of main part, Ir (ppy)₃As dopant material, Ir (ppy)₃Mass ratio with CBP is 10:90, with a thickness of 30nm；F) on luminescent layer 6, electricity is deposited by vacuum evaporation mode Sub- transmission material TPBI, with a thickness of 40nm, this layer of organic material is used as hole barrier/electron transfer layer 7；G) it is hindered in hole On gear/electron transfer layer 7, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm, which is electron injecting layer 8；H) in electronics On implanted layer 8, vacuum evaporation cathode Al (100nm), the layer is cathode reflection electrode layer 9；Electroluminescent hair is made by above-mentioned steps Optical device, the current efficiency of measurement device and service life, the result is shown in shown in table 4.The molecular structural formula of associated materials is as follows:

Device embodiments 2: the present embodiment and device embodiments 1 the difference is that: the electronics of electroluminescent device hinders Barrier material is the compounds of this invention 62.Device embodiments 3: the present embodiment and device embodiments 1 the difference is that: it is electroluminescent The electronic blocking layer material of luminescent device is the compounds of this invention 68.Device embodiments 4: the present embodiment and device embodiments 1 The difference is that: the electronic blocking layer material of electroluminescent device is the compounds of this invention 77.Device embodiments 5: this implementation Example with device embodiments 1 the difference is that: the electronic blocking layer material of electroluminescent device be the compounds of this invention 90.Device Part embodiment 6: the present embodiment and device embodiments 1 the difference is that: the electronic blocking layer material of electroluminescent device is The compounds of this invention 99.Device embodiments 7: the present embodiment and device embodiments 1 the difference is that: electroluminescent device Electronic blocking layer material is the compounds of this invention 116.Device embodiments 8: the difference of the present embodiment and device embodiments 1 exists In: the electronic blocking layer material of electroluminescent device is the compounds of this invention 125.Device embodiments 9: the present embodiment and device are real Apply example 1 the difference is that: the electronic blocking layer material of electroluminescent device be the compounds of this invention 134.Device embodiments 10: the present embodiment and device embodiments 1 the difference is that: the electronic blocking layer material of electroluminescent device is the present inventionization Close object 143.Device embodiments 11: the present embodiment and device embodiments 1 the difference is that: the electronics of electroluminescent device hinders Barrier material is the compounds of this invention 210.Device embodiments 12: the present embodiment and device embodiments 1 the difference is that: electricity The electronic blocking layer material of electroluminescence device is the compounds of this invention 280.Device embodiments 13: the present embodiment and device embodiments 1 the difference is that: the electronic blocking layer material of electroluminescent device be the compounds of this invention 291.Device embodiments 14: this Embodiment and device embodiments 1 the difference is that: the electronic blocking layer material of electroluminescent device is the compounds of this invention 301.Device embodiments 15: the present embodiment and device embodiments 1 the difference is that: the electronic barrier layer of electroluminescent device Material is NPB, and the luminescent layer material of main part of electroluminescent device becomes the compounds of this invention 12, and dopant material is Ir (ppy)₃, Ir(ppy)₃Mass ratio with compound 12 is 10:90.Device embodiments 16: the present embodiment it is different from device embodiments 1 it Being in: the electronic blocking layer material of electroluminescent device is NPB, and the luminescent layer material of main part of electroluminescent device becomes this hair Bright compound 39, dopant material are Ir (ppy)₃, Ir (ppy)₃Mass ratio with compound 39 is 10:90.Device embodiments 17: The present embodiment and device embodiments 1 the difference is that: the electronic blocking layer material of electroluminescent device is NPB, electroluminescent hair The luminescent layer material of main part of optical device becomes the compounds of this invention 152, and dopant material is Ir (ppy)₃, Ir (ppy)₃And compound 152 mass ratio is 10:90.Device embodiments 18: the present embodiment and device embodiments 1 the difference is that: electroluminescent The electronic blocking layer material of device is NPB, and the luminescent layer material of main part of electroluminescent device becomes the compounds of this invention 167, mixes Miscellaneous material is Ir (ppy)₃, Ir (ppy)₃Mass ratio with compound 167 is 10:90.Device embodiments 19: the present embodiment and device Part embodiment 1 the difference is that: the electronic blocking layer material of electroluminescent device be NPB, electroluminescent device shine Layer main body material becomes the compounds of this invention 183, and dopant material is Ir (ppy)₃, Ir (ppy)₃Mass ratio with compound 183 is 10:90.Device embodiments 20: the present embodiment and device embodiments 1 the difference is that: the electronic blocking of electroluminescent device Layer material is NPB, and the luminescent layer material of main part of electroluminescent device becomes the compounds of this invention 258, dopant material Ir (ppy)₃, Ir (ppy)₃Mass ratio with compound 258 is 10:90.Device embodiments 21: the present embodiment and device embodiments 1 The difference is that: the electronic blocking layer material of electroluminescent device is NPB, and the luminescent layer material of main part of electroluminescent device becomes For the compounds of this invention 1 and compound GHN, dopant material is Ir (ppy)₃, compound 1, GHN and Ir (ppy)₃Three's mass ratio For for 60:30:10.Device embodiments 22: the present embodiment and device embodiments 1 the difference is that: electroluminescent device Electronic blocking layer material is NPB, and the luminescent layer material of main part of electroluminescent device becomes the compounds of this invention 51 and compound GHN, dopant material are Ir (ppy)₃, compound 51, GHN and Ir (ppy)₃Three's mass ratio is 60:30:10.Device

Embodiment 23: the present embodiment and device embodiments 1 the difference is that: the electronic barrier layer of electroluminescent device Material is NPB, and the luminescent layer material of main part of electroluminescent device becomes the compounds of this invention 109 and compound GHN, dopant material For Ir (ppy)₃, compound 109, GHN and Ir (ppy)₃Three's mass ratio is 60:30:10.Embodiment 24: the present embodiment and device Part embodiment 1 the difference is that: the electronic blocking layer material of electroluminescent device be NPB, electroluminescent device shine Layer main body material becomes the compounds of this invention 195 and compound GHN, and dopant material is Ir (ppy)₃, compound 195, GHN and Ir (ppy)₃Three's mass ratio is 60:30:10.Embodiment 25: the present embodiment and device embodiments 1 the difference is that: electricity The electronic blocking layer material of electroluminescence device is NPB, and the luminescent layer material of main part of electroluminescent device becomes the compounds of this invention 239 and compound GHN, dopant material are Ir (ppy)₃, compound 239, GHN and Ir (ppy)₃Three's mass ratio is 60:30: 10。

Device comparative example 1: the present embodiment and device embodiments 1 the difference is that: the electronics of electroluminescent device hinders Barrier material is NPB, and the luminescent layer material of main part of electroluminescent device is known compound CBP, and dopant material is Ir (ppy)₃, Ir(ppy)₃Mass ratio with CBP is 10:90, and the detection data of gained electroluminescent device is shown in Table 4.

Table 4

Note: life-span test system is owner of the present invention and the OLED device life test that Shanghai University is studied jointly Instrument.

It can be seen that Spirofluorene derivative species machine compound of the present invention can be applied to OLED luminescent device by the result of table 4 Production, and compared with device comparative example 1, device voltage is substantially reduced, and either efficiency or service life is than known OLED The life time decay that material obtains larger change, especially device obtains biggish promotion.

The OLED device of further material preparation of the present invention is able to maintain the long-life at high temperature, by device embodiments 1~25 and device comparative example 1 in 85 DEG C of progress high temperature driven life tests, acquired results such as table 5 shows.

Table 5

From 5 data of table it is found that the device architecture and device of the material of the present invention of device embodiments 1~25 and known materials collocation Part comparative example 1 is compared, and under high temperature, OLED device provided by the invention has the driving service life well.

In order to compare different components at higher current densities efficiency decay the case where, define efficiency attenuation coefficientCarry out table Show；

It indicates that driving current is 100mA/cm²When device maximal efficiency μ₁₀₀With the maximal efficiency μ of device_maxDifference with Maximal efficiency μ_maxBetween ratio,Value is bigger, illustrates that the efficiency roll-off of device is more serious, conversely, illustrating device in high current The problem of dropping of quickly declining under density is under control.

Organic compound of the invention uses in luminescent device, can be used as electronic blocking layer material, can also be used as Luminescent layer material of main part uses.Efficiency attenuation coefficient is carried out respectively to 1~25 device comparative example 1 of device embodimentsMeasurement, inspection Result such as table 6 is surveyed to show.

Table 6

From the data of table 6 it is found that comparing with device comparative example 1, OLED device provided by the invention is at higher current densities With more gentle efficiency roll-off trend, good prospect is provided for industrialization.

Work limitation rate is also more stable at low temperature for the OLED device of further material preparation of the present invention, by device reality It applies example 3,16,22 and device comparative example 1 and carries out efficiency test in -10~80 DEG C of sections, acquired results are as shown in Table 7 and Fig. 2.

Table 7

From the data of table 7 and Fig. 2 it is found that device embodiments 3,16,22 are material of the present invention and the device that known materials are arranged in pairs or groups Part structure is compared with device comparative example 1, and not only Efficiency at Low Temperature is high, but also in temperature elevation process, efficiency is steadily increased.

The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (17)

1. a kind of Spirofluorene derivative species organic compound, which is characterized in that the structure of the organic compound such as general formula (1) institute Show:

In general formula (1),Pass through C_L1-C_L2Key, C_L2-C_L3Key or C_L3-C_L4Key is connect with spiro fluorene；

In general formula (1), Ar is expressed as substituted or unsubstituted C_6-60It is aryl, substituted or unsubstituted containing one or more hetero atoms One of 5-60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；

In general formula (1), X is expressed as oxygen, sulphur, C_1-10Alkylidene, the alkane of alkylidene, aryl substitution that linear or branched alkyl group replaces One of the imido grpup that the imido grpup or aryl that base replaces replace；

In general formula (1), R is expressed as general formula (2), general formula (3), structure shown in general formula (4) or general formula (5)；

General formula (2), general formula (3), in general formula (4), X₁、X₂、X₃Independently be expressed as oxygen, sulphur, C_1-10Straight chain or C_1-10Branch One of the imido grpup that alkylidene, alkyl-substituted imido grpup or the aryl that alkyl-substituted alkylidene, aryl replace replace；

General formula (2), general formula (3), general formula (4) independently pass through C_L’1-C_L’2Key, C_L’2-C_L’3Key, C_L’3-C_L’4Key and general formula (1) it connects；

In general formula (5), R₁、R₂Independently be expressed as substituted or unsubstituted C_6-60Aryl contains one or more hetero atoms One of substituted or unsubstituted 5-60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur.

2. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the compound is selected from Structure shown in general formula (6), general formula (7), general formula (8), general formula (9), general formula (10) or general formula (11):

3. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the compound is selected from General formula (12), general formula (13), structure shown in general formula (14) or (15):

4. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the compound is selected from Structure shown in general formula (16), general formula (17), general formula (18) or general formula (19):

5. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the compound is selected from Structure shown in general formula (20), general formula (21), general formula (22) or general formula (23):

6. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the compound is selected from Structure shown in general formula (24), general formula (25), general formula (26) or general formula (27):

7. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the compound is selected from Structure shown in general formula (28), general formula (29), general formula (30) or general formula (31):

8. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the compound is selected from Structure shown in general formula (32), general formula (33) general formula (34) or general formula (35):

9. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the Ar is expressed as benzene Base, dibiphenylyl, terphenyl, pyridyl group, pyrimidine radicals, pyridazinyl, pyrazinyl or triazine radical, dibenzofuran group, dibenzo One of thienyl, 9,9- dimethyl fluorenyl or N- phenyl carbazole base；The R₁、R₂Independently be expressed as phenyl, naphthalene Base, dibiphenylyl, terphenyl, naphthalene, dibenzofuran group, dibenzothiophene, 9,9- dimethyl fluorenyl or N- phenyl click One of oxazolyl.

10. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that in the general formula (1)It indicates are as follows:

In any one.

11. a kind of Spirofluorene derivative species organic compound according to claim 1, which is characterized in that the compound Concrete structure formula are as follows:

In any one.

12. a kind of a kind of such as described in any item preparation methods with Spirofluorene derivative species organic compound of claim 1-11, It is characterized in that, the reaction equation occurred in preparation process are as follows:

1) when X isAnd R is when being expressed as general formula (2), general formula (3) or general formula (4), specific reaction equation are as follows:

R3 is expressed as alkyl or C_6-60Aryl；

(1) under nitrogen protection, intermediate II, raw material I, sodium tert-butoxide, Pd are successively weighed₂(dba)₃, tri-tert-butylphosphine, use first Benzene is stirred, and is heated to 100~120 DEG C, back flow reaction 12~24 hours, is sampled contact plate, display is without intermediate II residue, instead It should be complete；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain intermediate III；

Wherein, the molar ratio of the raw material I and intermediate II is 1:1~2；The Pd₂(dba)₃Molar ratio with raw material I is The molar ratio of 0.006~0.02:1, the tri-tert-butylphosphine and raw material I are 0.006~0.02:1；The sodium tert-butoxide and raw material The molar ratio of I is 2.0~3.0:1；The dosage of the toluene is that 60-120ml toluene is added in 0.01mol raw material I；

(2) under nitrogen protection, intermediate III is weighed, tetrahydrofuran stirring and dissolving is added, is cooled to 0 DEG C with ice salt bath；To anti- Answer the correspondence grignard reagent R that brand-new is slowly added dropwise in system₃The tetrahydrofuran solution of-MgBr is reacted at room temperature 6~12 hours, is taken Sampling point plate, display is without intermediate III residue, fully reacting；Cooled to room temperature, filtering, filtrate decompression are rotated to no fraction, Neutral silica gel column is crossed, obtains intermediate compound IV, the molar ratio of the intermediate III and grignard reagent is 1:2~4；The tetrahydro furan The dosage muttered is that 20-40ml tetrahydrofuran is added in 0.01mol intermediate III；

(3) under nitrogen protection, intermediate compound IV is weighed, the H that mass fraction is 68% is added₃PO₄It is the mixed of 1:3 with water volume ratio Liquid is closed, is stirred, is reacted at room temperature 6~12 hours, samples contact plate, display is without intermediate compound IV residue, fully reacting；NaOH is added Aqueous solution is neutralized to pH=7, and methylene chloride extraction is added, and layering takes organic phase to filter, filtrate decompression is rotated to no fraction, mistake Neutral silica gel column obtains intermediate V；The dense H₃PO₄Dosage be 0.01mol intermediate compound IV be added the dense H of 15-30ml₃PO₄；

(4) under nitrogen protection, intermediate V, Ar-Br, sodium tert-butoxide, Pd are successively weighed₂(dba)₃, tri-tert-butylphosphine, use toluene It is stirred, is heated to 100~120 DEG C, back flow reaction 12~24 hours, samples contact plate, display is remaining without intermediate V, reaction Completely；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain target product；It is described The molar ratio of intermediate V and Ar-Br are 1:1~2；The Pd₂(dba)₃Molar ratio with intermediate V is 0.006~0.02:1, The molar ratio of the tri-tert-butylphosphine and intermediate V are 0.006~0.02:1；The molar ratio of the sodium tert-butoxide and intermediate V For 2.0~3.0:1；The dosage of the toluene is that 60-120ml toluene is added in 0.01mol intermediate V；

2) when X isAnd R is when being expressed as general formula (5), specific reaction equation are as follows:

Under nitrogen protection, intermediate VI, raw material VII, sodium tert-butoxide, Pd are successively weighed₂(dba)₃, tri-tert-butylphosphine, use toluene It is stirred, is heated to 100~120 DEG C, back flow reaction 12~24 hours, samples contact plate, display is remaining without intermediate V, reaction Completely；Cooled to room temperature, filtering, filtrate decompression rotate to no fraction, cross neutral silica gel column, obtain target product；It is described The molar ratio of intermediate VI and raw material VII is 1:1~2；The Pd₂(dba)₃With the molar ratio of intermediate VI be 0.006~ The molar ratio of 0.02:1, the tri-tert-butylphosphine and intermediate VI are 0.006~0.02:1；The sodium tert-butoxide and intermediate VI Molar ratio be 2.0~3.0:1；The dosage of the toluene is that 60-120ml toluene is added in 0.01mol raw material I.

13. a kind of such as described in any item one kind of claim 1-11 are used to prepare organic with Spirofluorene derivative species organic compound Electroluminescent device.

14. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes at least one layer of functional layer Contain the described in any item Spirofluorene derivative species organic compounds of claim 1-11.

15. a kind of organic electroluminescence device according to claim 14, including electronic barrier layer, which is characterized in that institute Stating electronic blocking layer material includes the described in any item Spirofluorene derivative species organic compounds of claim 1-11.

16. a kind of organic electroluminescence device according to claim 14, including luminescent layer, which is characterized in that the hair Photosphere includes the described in any item Spirofluorene derivative species organic compounds of claim 1-11.

17. a kind of illumination or display element, which is characterized in that it is described illumination or display element include described in claim 14-16 Organic electroluminescence device.