1. A compound containing a cyanoaryl group, characterized in that the structural formula is shown as the following formula (1):

wherein, X₁And X₂One of them is cyano, the other is hydrogen atom;

Ar₁and Ar₂Each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group;

l represents any one of a connecting bond, a substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group;

Ar₃represented by a cyano group or a group represented by the following formula (2);

wherein, X₃Representing an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene groupAny one of alkylene, alkyl substituted imino and aryl substituted imino;

L₁-L₄and L₁’-L₄' represents a linking site; r₁And R₂Each independently represents a bond, a hydrogen atom, or any one of the following formulae (3), (4) and (5); and R is₁And R₂One of which is necessarily or contains a bond to L, and the other of which cannot contain a bond to L;

wherein represents a fused ring connecting site, and a carbon site represented by a group represented by formula (3), formula (4) and formula (5) and L in a group represented by formula (2)₁-L₂、L₂-L₃、L₃-L₄、L’₁-L’₂、L’₂-L’₃、L’₃-L’₄Any one carbon site is subjected to ring-merging connection;

X₄-X₆each independently selected from any one of an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imino group and an aryl-substituted imino group;

R₃-R₅each independently represents any one of a single bond for linking to L, a hydrogen atom, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.

2. The compound according to claim 1, wherein the compound is any one of the compounds represented by the following formulae (6) to (11):

3. the cyanoaryl-containing compound of claim 1 or 2, wherein Ar is Ar₁And Ar₂Each independently represents a substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl;

preferably, Ar₁And Ar₂The number of heteroatoms in the heteroaryl group of (a) is at least 1;

preferably, Ar₁And Ar₂The hetero atom in the heteroaryl group of (a) is any one of N, O or S;

preferably, Ar₁And Ar₂Each independently represents any one of phenyl, biphenyl, naphthyl, anthryl, dibenzofuranyl, dibenzothienyl, azophenylcarbazolyl and fluorenyl.

4. The cyanoaryl-containing compound of claim 1 or 2, wherein L represents any one of a linking bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C5-C60 heteroarylene group;

preferably, the number of heteroatoms in the heteroaryl group of L is at least 1;

preferably, the heteroatom in the heteroaryl group of L is any one of N, O or S;

preferably, L represents a single bond and any one of the groups represented by the following formulae:

5. the cyanoaryl-containing compound of claim 1 or 2, wherein R is₃-R₅Each independently represents any one of a single bond for linking to L, a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted 5-to 30-membered heteroaryl group;

preferably, R₃-R₅The number of hetero atoms in the heteroaryl group in (a) is at least 1;

preferably, R₃-R₅The hetero atom in the heteroaryl group in (a) is any one of N, O or S;

preferably, X₃-X₆Each independently represents any one of oxygen, sulfur, C1-10 straight-chain or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl substituted imino or aryl substituted imino.

6. The cyanoaryl-containing compound of claim 1, wherein the cyanoaryl-containing compound is selected from any one of the following compounds represented by the following structural formula:

7. a method for synthesizing a cyanoaryl group-containing compound according to claim 1, which comprises selecting any one of the following synthetic routes to synthesize the cyanoaryl group-containing compound;

when L is not a connecting bond:

or

When L is a connecting bond:

preferably, the process of reactant 1 and reactant 2 comprises: mixing an alkaline substance, a catalyst, a reactant 1 and a reactant 2 to react at the temperature of 90-110 ℃;

preferably, the reaction conditions of reactant 1 and reactant 2 include: the molar ratio of the reactant 1 to the reactant 2 is 1-1.5:1, the molar ratio of the catalyst to the reactant 2 is 0.005-0.03:1, and the molar ratio of the alkaline substance to the reactant 2 is 1.5-2: 1;

preferably, the process of reactant 3 and reactant 4 comprises: mixing an alkaline substance, a catalyst, a reactant 3 and a reactant 4 to react at the temperature of 90-110 ℃;

preferably, the reaction conditions of reactant 3 and reactant 4 include: the molar ratio of the reactant 4 to the reactant 3 is 1-1.5:1, the molar ratio of the catalyst to the reactant 3 is 0.01-0.05:1, and the molar ratio of the alkaline substance to the reactant 3 is 1.5-2: 1;

preferably, the process of reactant 1 and reaction 5 comprises: mixing an alkaline substance, a catalyst, a reactant 1 and a reactant 5 to react at the temperature of 90-110 ℃;

preferably, the reaction conditions of reactant 1 and reaction 5 include: the molar ratio of the reactant 1 to the reactant 5 is 1-1.5:1, the molar ratio of the catalyst to the reactant 5 is 0.005-0.03:1, and the molar ratio of the basic substance to the reactant 5 is 1.5-2: 1.

8. An organic material comprising a cyanoaryl-containing compound according to any one of claims 1 to 6;

preferably, the organic material is a light emitting material or an electron transporting material used for preparing an organic electroluminescent device.

9. A functional layer prepared from the cyanoaryl group-containing compound according to any one of claims 1 to 6 or the organic material according to claim 8;

preferably, the functional layer comprises a light-emitting layer or an electron transport layer prepared from the organic material.

10. An organic electroluminescent device, characterized in that it comprises a functional layer according to claim 9.

Background

As a novel flat panel Display, an Organic Light Emitting Display (OLED for short) has the advantages of thinness, lightness, wide viewing angle, active Light emission, continuously adjustable Light emission color, low cost, high response speed, low energy consumption, low driving voltage, wide working temperature range, simple production process, high Light Emitting efficiency, flexible Display and the like, compared with a Liquid Crystal Display (LCD for short).

Until now, many improvements have been made for practical use of organic EL elements, and various functions have been subdivided, and an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided in this order according to the function on a substrate. In organic electroluminescent devices, high efficiency and durability have been achieved by a light emitting element of a bottom emission structure that emits light from the bottom. However, compared with the actual product application requirements, the properties of the OLED device, such as light emitting efficiency and service life, need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device, but also the continuous research and innovation of the photoelectric functional material of the OLED are needed to create the functional material of the OLED with higher performance. In order to manufacture a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric characteristics. For example, as a charge transport material, a material having a good carrier mobility, a high glass transition temperature, and the like is required, and as a host material of a light emitting layer, a material having a good polarity, a triplet level, an appropriate HOMO/LUMO level, and the like is required. At present, the development of OLED materials is far from enough and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is particularly important as a material enterprise.

In view of this, the invention is particularly proposed.

Disclosure of Invention

The invention aims to provide a compound containing a cyano aromatic group, a synthetic method thereof, an organic material, a functional layer and an organic electroluminescent device. The embodiment of the invention provides a novel compound containing a cyano-group aromatic group, which has higher glass transition temperature, higher molecular thermal stability, proper HOMO and LUMO energy levels and high electron mobility, and can effectively improve the luminous efficiency and prolong the service life of an OLED device after being applied to the manufacture of the device.

The invention is realized by the following steps:

in a first aspect, the present invention provides a compound containing a cyano aryl group, the structural formula of which is shown in the following formula (1):

wherein, X₁And X₂One of them is cyano, the other is hydrogen atom; ar (Ar)₁And Ar₂Each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; l represents any one of a connecting bond, a substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group; ar (Ar)₃Represented by a cyano group or a group represented by the following formula (2);

wherein, X₃Represents any one of an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imino group and an aryl-substituted imino group;

L₁-L₄and L₁’-L₄' represents a linking site; r₁And R₂Each independently represents a bond, a hydrogen atom, or any one of the following formulae 3, 4, and 5; and R is₁And R₂One of which is necessarily or contains a bond to L, and the other of which cannot contain a bond to L;

wherein represents a fused ring connecting site, and a carbon site represented by a group represented by formula (3), formula (4) and formula (5) and L in a group represented by formula (2)₁-L₂、L₂-L₃、L₃-L₄、L’₁-L’₂、L’₂-L’₃、L’₃-L’₄Any one carbon site is subjected to ring-merging connection; x₄-X₆Each independently selected from any one of an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imino group and an aryl-substituted imino group; r₃-R₅Each independently represents any one of a single-bonded hydrogen atom, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group bonded to L.

In a second aspect, the present invention provides a method for synthesizing a cyanoaryl group-containing compound according to the above embodiment, comprising selecting any one of the following synthetic routes to synthesize the cyanoaryl group-containing compound;

when L is not a connecting bond:

or

When L is a connecting bond:

in a third aspect, the present invention provides an organic material comprising a cyanoaryl-containing compound according to any one of the preceding embodiments;

preferably, the organic material is a light emitting material or an electron transporting material used for preparing an organic electroluminescent device.

In a fourth aspect, the present invention provides a functional layer prepared from the cyanoaryl group-containing compound of any one of the preceding embodiments or the organic material of the preceding embodiments;

preferably, the functional layer comprises a light emitting layer or an electron transport layer made of the organic material.

In a fifth aspect, the present invention provides an organic electroluminescent device comprising the functional layer according to the previous embodiments.

The invention has the following beneficial effects: the embodiment of the invention provides a novel compound containing a cyano-group aromatic group, which has higher glass transition temperature, higher molecular thermal stability, proper HOMO and LUMO energy levels and high electron mobility, and can effectively improve the luminous efficiency and prolong the service life of an OLED device after being applied to the manufacture of the device.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a HOMO distribution plot of compound 164 provided by an embodiment of the present invention;

FIG. 2 is a LUMO profile of compound 164 provided by an example of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The invention provides a compound containing a cyano-aryl, which has a structural formula shown as the following formula (1):

wherein, X₁And X₂One of them is cyano, the other is hydrogen atom; x₁And X₂One and only one is a hydrogen atom; ar (Ar)₁And Ar₂Each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; l represents any one of a connecting bond, a substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group; ar (Ar)₃Represented by a cyano group or a group represented by the following formula (2);

wherein, X₃Represents an oxygen atomAny one of a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imino group and an aryl-substituted imino group; l is₁-L₄And L₁’-L₄' represents a linking site; r₁And R₂Each independently represents a bond, a hydrogen atom, or any one of the following formulae (3), (4) and (5); and R is₁And R₂One of which is necessarily or contains a bond to L, and the other of which cannot contain a bond to L;

wherein represents a fused ring connecting site, and a carbon site represented by a group represented by formula (3), formula (4) and formula (5) and L in a group represented by formula (2)₁-L₂、L₂-L₃、L₃-L₄、L’₁-L’₂、L’₂-L’₃、L’₃-L’₄Any one carbon site is subjected to ring-merging connection; x₄And X₅Each independently selected from any one of an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imino group and an aryl-substituted imino group; r₃-R₅Each independently represents any one of a single bond for linking to L, a hydrogen atom, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.

It should be noted that: the linkage between the groups in the compound of formula (1) satisfies the rules and requirements of chemical bonding, for example, R₁And R₂One of which is necessarily or contains a bond to L, and the other of which cannot contain a bond to L; for example, Ar₃R in (1)₁And R₂Not both hydrogen or not both connecting bonds, or R₁And R₂And when the substituent is any one of the formulae 3 to 5, one R substituent is bound to be a bond and the other R substituent cannot be a bond in the corresponding formula 3 to 5, wherein R in the corresponding formula represented by the R substituent is R₃、R₄Or R₅。

Further, the compound is any one of the following compounds of formula (6) to formula (11):

the definitions of the groups of the above formulae (6) to (11) are the same as those of the group of the above formula (1), and are not described herein again.

R in the above formula (2) -formula (9)₁-R₅Indicates that the linkage or substitution may be made at any position corresponding to the benzene ring.

Further, Ar mentioned in the above formula (1), formula (6) -formula (11)₁And Ar₂And optionally substituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl; wherein Ar is₁And Ar₂The number of heteroatoms in the heteroaryl group of (a) is at least 1; ar (Ar)₁And Ar₂The hetero atom in the heteroaryl group of (a) is any one of N, O or S; for example, Ar₁And Ar₂Each independently represents any one of phenyl, biphenyl, naphthyl, anthryl, dibenzofuranyl, dibenzothienyl, azophenylcarbazolyl and fluorenyl.

Further, L mentioned in the above formula (1), formula (6) -formula (11) may also represent any one of a connecting bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C5-C60 heteroarylene group; wherein the number of heteroatoms in the heteroaryl group of L is at least 1; the hetero atom in the heteroaryl group of L is any one of N, O or S. When L is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group, L links the benzene ring and Ar₃Can be para, meta or ortho with each other, and has excellent performance when the two are para or meta with each other.

For example, L represents a single bond and any one of the groups represented by the following formulae:

in the above structural formula, -, represents a site at which the corresponding ring is bonded to the benzene ring represented by formula (1) and Ar3, and the bonding site may be any position of the corresponding ring.

Further, R mentioned in the above formula (1), formula (6) -formula (11)₃-R₅Each of which may independently represent any one of a single bond for linking to L, a hydrogen atom, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted 5-to 30-membered heteroaryl group; wherein R is₃-R₅The number of hetero atoms in the heteroaryl group in (a) is at least 1; r₃-R₅The hetero atom in the heteroaryl group in (a) is any one of N, O or S.

Further, X mentioned in the above formula (1), formula (6) -formula (11)₃-X₆Can also independently represent any one of oxygen, sulfur, C1-10 straight-chain or branched alkyl substituted alkylidene, aryl substituted alkylidene, alkyl substituted imino or aryl substituted imino

It should be noted that: the C6-C30 aryl and 5-30-membered heteroaryl mentioned in the embodiment of the invention can be a benzo heterocycle or a poly-benzo heterocycle, such as dibenzofuranyl and dibenzothienyl, or an azaphenylcarbazolyl or a fluorenyl except for an aryl group connected with a plurality of benzenes such as phenyl and biphenyl, a condensed aryl group fused with a plurality of benzene rings such as naphthyl and anthryl; the aromatic ring may be a single aromatic heterocycle having a plurality of hetero atoms such as pyridazine and piperazine, or may be another aromatic ring or heteroaromatic ring.

Meanwhile, the substituted alkyl of C1-10 straight-chain or branched alkyl substituted alkylene can be methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, the substituted aryl of aryl substituted alkylene can be phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, the substituted alkyl of alkyl substituted imino can be methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, cyclohexane, adamantane, and the substituted aryl of aryl substituted imino can be phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl.

The compound containing the cyano-aromatic group is selected from any one of the compounds shown in the following structural formulas:

the numbers of the above structural formulae correspond to the numbers of the compounds corresponding to the structural formulae below.

The cyano-benzene compound is introduced with cyano-group on the basis of disubstituted benzene ring, which ensures the rigidity and the flatness of the molecule and brings strong electron-withdrawing ability, and when the aromatic heterocycle or the cyano-group is introduced at the other side, the electron hole distribution can be adjusted. The electron-withdrawing ability of both ends is balanced, so that the electron-withdrawing material has larger electron distribution characteristics and the electron mobility is improved. The material has high electron mobility and adjustable triplet state energy level when being used as an electron transport layer, a hole blocking layer, an electron type main body and the like. The organic light emitting diode can enable electron holes to be rapidly compounded in the light emitting layer to form excitons, so that the efficiency can be greatly improved, meanwhile, the exciton combination position is arranged at the main body part, the diffusion and non-radiation loss of a large number of excitons are avoided, and the problem of the service life of an OLED device is solved. The material also has higher glass transition temperature and molecular thermal stability, and can ensure that the material is not decomposed in the evaporation process after being applied to an OLED device.

The above-described cyanoaryl-containing compounds of the embodiments of the present invention can be prepared by synthetic methods known to those skilled in the art. The synthesis can also be carried out by the preparation method provided by the embodiment of the invention, and specifically,

synthesizing a compound containing a group of formula (2): see the following synthetic route:

wherein, X₃Represents the same as described above; r₆，R₇Is OH or H; r₈，R₉，R₁₀，R₁₁Is halogen or boric acid; r₁₂is-NO₂or-OH, orY₁,Y₂Independently represents any one of a single bond, an oxygen atom, a sulfur atom, an alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted imino group and an aryl-substituted imino group; y1 and Y2 are not single bonds at the same time.

The specific operation is as follows:

(1) dissolving raw material A and raw material B in a mixed solution of toluene ethanol water, and adding Pd (PPh) in a nitrogen environment₃)₄And K₂CO₃Reacting at 90-110 deg.C for 10-24h, continuously monitoring reaction process by TLC, and waiting for raw materialAfter the reaction is completed, cooling and filtering, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain an intermediate C; the dosage of the toluene and the ethanol is 20-40mL of toluene, 10-20mL of ethanol and 10-20mL of water used per gram of the raw material A, and the molar ratio of the raw material B to the raw material A is (1-1.5): 1, Pd (PPh)₃)₄The molar ratio of the raw material A to the raw material A is (0.005-0.03): 1, K₂CO₃The mol ratio of the raw material A to the raw material A is (1.5-2): 1.

(2) dehydrocyclization was performed in different ways for different structures: weighing the intermediate C, dehydrating in a p-toluenesulfonic acid/toluene solvent reflux manner to form a furan ring structure, or dehydrating in a triphenylphosphine/o-dichlorobenzene solvent high-temperature condition to form a carbazole structure, or dehydrating in a phosphoric acid/water solution room-temperature condition to form a fluorene ring structure, and the like.

Then synthesizing the compound shown in the formula (1), wherein the synthesis method comprises the step of selecting any one of the following synthetic routes to synthesize the compound containing the cyano-aromatic group;

when L is not a connecting bond:

wherein X₁～X₂、Ar₁～Ar₃And L is as defined in the above chemical formula 1. The specific process is as follows:

dissolving reactant 1 and reactant 2 in a mixed solution of toluene ethanol and water, and adding Pd (PPh) in a nitrogen atmosphere₃)₄(catalyst) and K₂CO₃Reacting (alkaline substance) at 90-110 ℃ for 10-24h, continuously monitoring the reaction process by TLC (thin layer chromatography) in the reaction process, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a reactant 3; the dosage of the toluene and the ethanol is 20-40mL of toluene, 10-20mL of ethanol and 10-20mL of water used per gram of reactant 2, and the molar ratio of the reactant 1 to the reactant 2 is (1-1.5): 1, Pd (PPh)₃)₄And the molar ratio of the reactant 2 is (0.005-0.03): 1, K₂CO₃The molar ratio to reactant 2 is (1.5-2): 1.

will be reversedDissolving the reactant 4 and the reactant 3 in a mixed solution of toluene ethanol water, and adding Pd under the nitrogen environment₂(dpa)₃And K₂CO₃Reacting at 90-110 ℃ for 10-24h, continuously monitoring the reaction process by TLC in the reaction process, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain the final product, namely the general formula 1;

the dosage of the toluene and the ethanol is 20-40mL of toluene, 10-20mL of ethanol and 10-20mL of water used per gram of reactant 4, and the molar ratio of the reactant 4 to the reactant 3 is (1-1.5): 1, Pd₂(dpa)₃And the molar ratio of the reactant 3 is (0.01-0.05): 1, K₂CO₃The molar ratio to reactant 3 is (1.5-2): 1.

when L is a connecting bond:

wherein X₁～X₂、Ar₁～Ar₃As defined in the above chemical formula 1. The specific reaction process is as follows:

dissolving reactant 1 and reactant 5 in a mixed solution of toluene ethanol water, and adding Pd (PPh) in a nitrogen environment₃)₄(catalyst) and K₂CO₃Reacting (alkaline substance) at 90-110 ℃ for 10-24h, continuously monitoring the reaction process by TLC in the reaction process, cooling and filtering after the raw materials are completely reacted, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain the final product with the general formula 1;

the dosage of the toluene and the ethanol is 20-40mL of toluene, 10-20mL of ethanol and 10-20mL of water used per gram of reactant 1, and the molar ratio of the reactant 1 to the reactant 5 is (1-1.5): 1, Pd (PPh)₃)₄And the molar ratio of the reactant 5 is (0.005-0.03): 1, K₂CO₃The molar ratio to reactant 5 is (1.5-2): 1.

the preparation method provided by the invention is simple and feasible, and is suitable for large-scale production.

The embodiment of the invention also provides an organic material, which comprises the compound containing the cyano-aromatic group; the organic material is a luminescent material or an electron transport material for preparing an organic electroluminescent device.

The embodiment of the invention also provides a functional layer, which is prepared from the compound containing the cyano aryl group or the organic material; the organic material is used for preparing a luminescent layer or an electron transport layer.

The invention also provides an organic electroluminescent device which comprises the functional layer, wherein the organic electroluminescent device comprises a cathode, an anode and at least one functional layer arranged between the cathode and the anode, and the functional layer comprises at least one of a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

This example provides for the preparation of starting material 5, according to the following synthetic route:

(ii) a The specific process is as follows:

(1) pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), raw material H1(50mmol) and raw material J1(60mmol) are added into a reaction bottle, 600mL of mixed solution of toluene, ethanol and water (the volume ratio of the toluene, the ethanol and the water is 300: 150: 150) is added, the temperature is raised to 100 ℃ under the protection of nitrogen, and the reaction is carried out for 24 hours. After cooling, a white powder was precipitated, which was filtered off to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain intermediate S1(17.73g, yield: 93%, HPLC purity 99.2%).

(2) Adding 0.04mol of intermediate S1 and 0.048mol of p-toluenesulfonic acid into a 250ml three-necked bottle under the protection of nitrogen, dissolving with 100ml of toluene, and heating to reflux for reaction for 20 hours; TLC showed no intermediate S1 remained and the reaction was complete. Adding saturated sodium carbonate solution into the reaction system for quenching, extracting with ethyl acetate, separating liquid, and removing the solvent by rotary evaporation to obtain a product, and passing through a silica gel column to obtain an intermediate M1 with HPLC purity of 98.2% and yield of 87.4%.

The intermediate starting materials used in the examples are shown in table 1:

TABLE 1

Example 2

This example provides for the synthesis of compound 3, according to the following synthetic route:

the specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), a raw material C3(50mmol) and a raw material A3(60mmol) are added into a reaction bottle, 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of the toluene to the ethanol to the water is 300: 150: 150) is added, nitrogen is used for protection, and the temperature is raised to 100 ℃ for reaction for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 3(19.45g, yield: 92.3%, HPLC purity)>99.9％)。

Elemental analysis (C)₃₁H₁₉NO): theoretical value C, 88.34; h, 4.54; n, 3.32; and O, 3.80.

Test value C, 88.33; h, 4.52; n, 3.34; and O, 3.81.

ESI-MS (M/z) (M +): theoretical 421.50, found 421.72.

Example 3

This example provides the synthesis of compound 7, according to the following synthetic route:

the specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), starting material C7(50mmol) and starting material A7(60mmol) were addedThen 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added into the reaction bottle, and the temperature is raised to 100 ℃ for reaction for 24 hours under the protection of nitrogen. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 7(21.50g, yield: 91.2%, HPLC purity)>99.9％)。

Elemental analysis (C)₃₅H₂₁NO): theoretical value C, 89.15; h, 4.49; n, 2.97; and O, 3.39.

Test value C, 89.21; h, 4.45; n, 2.96; and O, 3.38.

ESI-MS (M/z) (M +): theoretical 471.56, found 471.88.

Example 4

This example provides for the synthesis of compound 15, according to the following synthetic route:

the specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), intermediate M2(50mmol) and raw material A15(60mmol) are added into a reaction bottle, 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, nitrogen is used for protection, and the temperature is raised to 100 ℃ for reaction for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 15(24.04g, yield: 89.5%, HPLC purity)>99.9％)。

Elemental analysis (C)₄₀H₂₇NO): theoretical value C, 89.36; h, 5.06; n, 2.61; o, 2.98.

Test value C, 89.34; h, 5.05; n, 2.63; and O, 2.99.

ESI-MS (M/z) (M +): theoretical 471.56, found 471.88.

Example 5

This example provides for the synthesis of compound 27, according to the following synthetic route:

the specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), intermediate M3(50mmol) and raw material A27(60mmol) are added into a reaction bottle, 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, nitrogen is used for protection, and the temperature is raised to 100 ℃ for reaction for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 27(25.87g, yield: 88.2%, HPLC purity)>99.9％)。

Elemental analysis (C)₄₃H₂₆N₂O): theoretical value C, 88.03; h, 4.47; n, 4.77; o, 2.73.

Test value C, 88.10; h, 4.41; n, 4.75; o, 2.71.

ESI-MS (M/z) (M +): theoretical 586.69, found 586.91.

Example 6

This example provides for the synthesis of compound 33, according to the following synthetic route:

(ii) a The specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), raw material B33(50mmol) and raw material A33(60mmol) are added into a reaction bottle, 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, nitrogen is used for protection, and the temperature is raised to 100 ℃ for reaction for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain intermediate N1(19.89g, yield: 90%, HPLC purity 96.5%).

Pd is added₂(dpa)₃(0.4mmol), potassium carbonate (80mmol), intermediate N1(40mmol) and raw material C33(50mmol) were charged into a reaction flask, and 600mL of a mixture of toluene, ethanol and water (toluene, ethanol and water) was addedThe volume ratio of water is 300: 150: 150) and raising the temperature to 100 ℃ for reaction for 24 hours under the protection of nitrogen. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 33(22.43g, yield: 93.5%, HPLC purity)>99.9％)。

Elemental analysis (C)₄₆H₃₃N): theoretical value C, 92.12; h, 5.55; and N, 2.34.

Test value C, 92.10; h, 5.57; n, 2.33.

ESI-MS (M/z) (M +): theoretical 599.78, found 599.63.

Example 7

This example provides the synthesis of compound 39, according to the following synthetic route:

the specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), intermediate M2(50mmol) and raw material A39(60mmol) are added into a reaction bottle, 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, nitrogen is used for protection, and the temperature is raised to 100 ℃ for reaction for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 39(23.55g, yield: 87.6%, HPLC purity)>99.9％)。

Elemental analysis (C)₄₀H₂₇NO): theoretical value C, 89.36; h, 5.06; n, 2.61; o, 2.98.

Test value C, 89.33; h, 5.06; n, 2.65; o, 2.97.

ESI-MS (M/z) (M +): theoretical 537.66, found 537.97.

Example 8

This example provides for the synthesis of compound 74, according to the following synthetic route:

the specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), raw material B74(50mmol) and raw material A74(60mmol) are added into a reaction bottle, 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, nitrogen is used for protection, and the temperature is raised to 100 ℃ for reaction for 24 hours. After cooling, a white powder was precipitated, which was filtered to obtain a white solid, which was dissolved in methylene chloride and passed through a silica gel funnel to obtain intermediate N2(22.9g, yield: 93.1%, HPLC purity 98.9%).

Pd is added₂(dpa)₃(0.4mmol), potassium carbonate (80mmol), intermediate N2(40mmol) and intermediate M4(50mmol) are added into a reaction bottle, 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, nitrogen is used for protection, and the temperature is raised to 100 ℃ for reaction for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 74(27.48g, yield: 84.3%, HPLC purity)>99.9％)。

Elemental analysis (C)₆₂H₄₂N₂): theoretical value C, 91.37; h, 5.19; n, 3.44.

Test value C, 91.41; h, 5.21; and N, 3.38.

ESI-MS (M/z) (M +): theoretical 815.03, found 814.73.

Example 9

This example provides for the synthesis of compound 164, according to the following synthetic route:

(ii) a The specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), raw material B164(50mmol) and raw material A164(60mmol) are added into a reaction bottle, 600mL of a mixed solution of toluene, ethanol and water (the volume ratio of the toluene, the ethanol and the water is 300: 150: 150) is added, the temperature is raised to 100 ℃ under the protection of nitrogen, and the reaction is carried out for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving in dichloromethane,intermediate N3 was obtained (22.9g, yield: 93.1%, HPLC purity 99.2%) by passing through a silica funnel.

Pd is added₂(dpa)₃(0.4mmol), potassium carbonate (80mmol), intermediate N3(40mmol) and raw material C164(50mmol) are added into a reaction bottle, 600mL of mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, the temperature is raised to 100 ℃ under the protection of nitrogen, and the reaction is carried out for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 164(23.87g, yield: 94%, HPLC purity)>99.9％)。

Elemental analysis (C)₆₂H₄₂N₂): theoretical value C, 90.82; h, 4.76; n, 4.41.

Test value C, 90.83; h, 4.78; n, 4.39.

ESI-MS (M/z) (M +): theoretical 634.78, found 634.36.

Compound 164 is analyzed and examined to obtain its HOMO profile and LUMO profile, see fig. 1 and 2, and from fig. 1 and 2, it can be seen that the LUMO orbital electrons are uniformly distributed throughout the molecular plane, and the electron mobility is very high, resulting in excellent device efficiency and lifetime.

Example 10

This example provides for the synthesis of compound 180, according to the following synthetic route:

the specific process is as follows:

pd (PPh)₃)₄(0.25mmol), potassium carbonate (100mmol), raw material B180(50mmol) and raw material A180(60mmol) are added into a reaction bottle, 600mL of mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, the temperature is raised to 100 ℃ under the protection of nitrogen, and the reaction is carried out for 24 hours. The temperature was reduced to precipitate a white powder, which was filtered to give a white solid, which was dissolved in dichloromethane and passed through a silica gel funnel to give intermediate N4(20.24g, yield: 91.6%, HPLC purity 99.1%).

Pd is added₂(dpa)₃(0.4mmol), potassium carbonate (80mmol), intermediate N4(40mmol) and raw material C180(50mmol) are added into a reaction bottle, 600mL of mixed solution of toluene, ethanol and water (the volume ratio of toluene, ethanol and water is 300: 150: 150) is added, the temperature is raised to 100 ℃ under the protection of nitrogen, and the reaction is carried out for 24 hours. Cooling, separating out white powder, vacuum filtering to obtain white solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain compound 180(20.13g, yield: 90.1%, HPLC purity)>99.9％)。

Elemental analysis (C42H26N 2): theoretical value C, 90.29; h, 4.69; and N, 5.01.

Test value C, 90.25; h, 4.66; and N, 5.09.

ESI-MS (M/z) (M +): theoretical 558.68, found 558.89.

It is to be noted that the present invention provides only examples 2 to 10, and the remaining compounds were synthesized with reference to examples 2 to 10, and the corresponding compounds were smoothly synthesized.

(1) The compound provided by the embodiment of the invention is used as a luminescent main body material of a luminescent layer:

practical application example 1

This practical application example 1 provides an organic electroluminescent device comprising a substrate, an ITO anode, a hole injection layer, a hole transport layer, a light emitting layer, a first electron transport layer, a second electron transport layer, an electron injection layer, and a cathode Al, wherein the ITO anode is 15nm thick, the hole injection layer is 5nm thick, the hole transport layer is 70nm thick, the light emitting layer is 25nm thick, the first electron transport layer is 30nm thick, the second electron transport layer is 5nm thick, the electron injection layer is 1nm thick, and the Al electrode is 14nm thick. The structural formula of the material is as follows:

preparation of organic electroluminescent device:

the glass substrate was cleaned by sonicating in isopropanol and deionized water for 30 minutes, respectively, and then exposing to ozone for about 10 minutes; mounting the resulting glass substrate with ITO anode to a vacuum sinkAssembling equipment; evaporating HAT-CN material on the ITO anode layer in a vacuum evaporation mode, wherein the thickness of the HAT-CN material is 5nm, and the HAT-CN material is used as a hole injection layer; performing vacuum evaporation on the hole injection layer to obtain a material TAPC with a thickness of 70nm as a hole transport layer; a light emitting layer was co-deposited on the hole transport layer, wherein the compound 3 prepared in example 1 was used as a host material, Ir (ppy)₃As doping material, Ir (ppy)₃The mass ratio of the compound to the compound 3 is 0.5: 9.5, and the thickness is 25 nm; vacuum evaporating a first electron transport layer on the light-emitting layer, wherein the material of the first electron transport layer is TPBI, and the thickness of the first electron transport layer is 30 nm; a second electron transport layer is vacuum-evaporated on the first electron transport layer, the material of the second electron transport layer is Alq3, and the thickness of the second electron transport layer is 5 nm; evaporating an electron injection layer LiF on the second electron transport layer in vacuum, wherein the thickness of the electron injection layer LiF is 1 nm; an Al electrode was vacuum-deposited on the electron injection layer to a thickness of 14nm to form a cathode.

Practical application examples 2 to 7

Organic light-emitting devices 2 to 7 were prepared according to the procedure of practical application example 1, except that the host compound 3 in practical application example 1 was replaced with compounds 7, 15, 27, 33, 39, and 74, respectively, and the other layers were the same.

Comparative example: a comparative organic light-emitting device was prepared according to the procedure of practical application example 1, except that the host compound 3 in practical application example 1 was replaced with CBP correspondingly, and the other layers were the same.

(2) The compound provided by the embodiment of the invention is applied as an electron transport layer:

practical application examples 8 to 9

Organic light emitting devices 2 to 7 were prepared according to the procedure of the comparative example, except that the first electron transport layer TPBi in the comparative example was replaced with compounds 164, 180, respectively, and the other layers were the same.

The organic light emitting devices prepared in the comparative example and the practical application example were tested, and the test results are shown in table 2.

TABLE 2 luminescence properties (luminance 5000 cd/m) of the devices²)

As can be seen from table 2 above, the driving voltage of the device using the cyanobenzene compound of the present invention as the light emitting host material and the electron transporting material was lower than that of the comparative device example 1. Compared with the device comparative example 1, the current efficiency and the service life of the device adopting the cyanobenzene compound as the luminescent host material and the electron transport material are both obviously improved. Therefore, the cyanobenzene compound provided by the invention can improve the luminous efficiency of a light-emitting device and prolong the service life of the device, and is an ideal luminous host material or an ideal electron transport material.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.