CN111303157A

CN111303157A - Naphthopyrazine derivative, preparation method thereof and electronic device

Info

Publication number: CN111303157A
Application number: CN202010231029.6A
Authority: CN
Inventors: 崔林松; 朱向东; 张业欣; 陈华
Original assignee: Suzhou Jiuxian New Material Co ltd
Current assignee: Suzhou Jiuxian New Material Co ltd
Priority date: 2020-03-27
Filing date: 2020-03-27
Publication date: 2020-06-19

Abstract

The invention provides a naphthopyrazine derivative, a preparation method thereof and an electronic device, and relates to the technical field of organic photoelectric materials. The naphthopyrazine derivatives obtained by introducing the condensed ring structure of the naphthopyrazine derivatives have excellent film forming property and thermal stability and high fluorescence quantum yield, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. In addition, the naphthopyrazine derivative of the present invention can be used as a material constituting a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer, and can reduce a driving voltage, improve efficiency, luminance, and lifetime. The invention also provides a preparation method of the naphthopyrazine derivatives and an electronic device using the naphthopyrazine derivatives.

Description

Naphthopyrazine derivative, preparation method thereof and electronic device

Technical Field

The invention belongs to the technical field of organic photoelectric materials, and relates to a naphthopyrazine derivative, a preparation method thereof and an electronic device containing the naphthopyrazine derivative. More particularly, the present invention relates to naphthopyrazine derivatives suitable for electronic devices, particularly organic electroluminescent devices, organic field effect transistors, and organic solar cells, and electronic devices using the same.

Background

The organic electroluminescent device has a series of advantages of self-luminescence, low-voltage driving, full curing, wide viewing angle, simple composition and process and the like, and compared with a liquid crystal display, the organic electroluminescent device does not need a backlight source. Therefore, the organic electroluminescent device has wide application prospect.

Organic electroluminescent devices generally comprise an anode, a metal cathode and an organic layer sandwiched therebetween. The organic layer mainly comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer. In addition, a host-guest structure is often used for the light-emitting layer. That is, the light emitting material is doped in the host material at a certain concentration to avoid concentration quenching and triplet-triplet annihilation, improving the light emitting efficiency. Therefore, the host material is generally required to have a higher triplet energy level and, at the same time, a higher stability.

At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. In view of the above, the future direction of organic electroluminescent devices is to develop high efficiency, long lifetime, low cost white light devices and full color display devices, but many key issues still face for organic electroluminescent materials with deep red and near infrared colors. Therefore, designing and searching a stable and efficient compound as a novel material of an organic electroluminescent device to overcome the defects of the organic electroluminescent device in the practical application process is a key point in the research work of the organic electroluminescent device material and the future research and development trend.

Disclosure of Invention

The invention aims to provide a naphthopyrazine derivative. The naphthopyrazine derivative has the advantages of high thermal stability, good transmission performance, high fluorescence quantum yield and simple preparation method, and an organic light-emitting device prepared from the naphthopyrazine derivative has the advantages of high light-emitting efficiency, long service life, long light-emitting wavelength and low driving voltage, and is an organic electroluminescent material with excellent performance.

The adopted naphthopyrazine compounds have special condensed ring structures, and the selected and used naphthopyrazine structures have proper singlet states, triplet states, molecular orbital energy levels, strong electron withdrawing capability and excellent fluorescence quantum yield, but the research and development team finds that the independent use of the naphthopyrazine structures as parent nuclei also exposes the defect of irreconcilability, on one hand, the planar linear structures formed by the naphthopyrazine structures are easy to generate film forming aggregation or local crystallization, so that triplet state quenching is caused; on the other hand, the parapyrazine structure has high molecular polarity and intermolecular force due to the presence of the heteroatom, so that molecules are attracted and attached to each other between planes where the parapyrazine is located and are difficult to separate, the actual average molecular weight of the molecules during evaporation is larger than the molecular weight of a single molecule, and further higher preparation temperature is required during film formation by evaporation, and higher evaporation temperature has a risk of influencing the stability and the photoelectric property of the molecules. Therefore, through repeated molecular form design and experimental verification, naphthalene is connected into the pyrazine molecular structure in an asymmetric mode, an entrance is provided for separating the adsorption effect between the planes of the pyrazine structure, the polarity of molecules at one end where the naphthalene or the similar derivatives are located is small, the intermolecular attraction effect of the surface where the pyrazine is located can be uncovered through the tangential effect, the actual molecular weight during molecular evaporation is reduced, the naphthalene derivatives are further introduced, the plane form is unfolded, the film forming state of the material is well regulated through increasing the matching of branched chains, the triplet quenching effect is greatly reduced, the material has high thermal stability, chemical stability and carrier transport property, the singlet state, the triplet state, the molecular orbital energy level, the strong electron pulling capacity and the excellent fluorescence quantum yield which are suitable for the pyrazine structure are well utilized, thereby greatly improving the stability of the pyrazine structure in the vapor deposition preparation process.

Another object of the present invention is to provide an electronic device using the naphthopyrazine derivatives, which has advantages of high efficiency, high durability and long lifetime.

Namely, the present invention is as follows.

[1] A naphthopyrazine derivative is represented by the following general formula (I):

wherein,

L₁，L₂，L₃each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;

m is an integer of 0-4, p and q are integers of 0-1, and m, p and q are not 0 at the same time;

A₁-A₃each independently represents Ar₁、Ar₂、Ar₃、

Ar₁～Ar₆Each independently represents a hydrogen atom, a cyano group or optionally substituted by one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 carbon atoms;

R¹represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms;

R²represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

[2] The naphthopyrazine derivative according to [1] which is represented by the following general formula (1) or (2):

[3]according to [1]The naphthopyrazine derivatives are shown in the specification, wherein Ar is₁～Ar₆Each independently selected from a hydrogen atom, a cyano group or the following group:

wherein the dotted line represents and L₁、L₂、L₃Or a bond of an N-bond,

R¹have the meaning as defined for the general formula (I).

[4] The naphthopyrazine derivative according to any one of [1] to [3], wherein,

L₁to L₃Each independently represents a single bond, a carbonyl group, a phenyl group or a triazinyl group;

R¹and R²Each independently represents a cyano group, a phenyl group, a naphthyl group, a dimethylfluorenyl group, a dibenzothienyl group, a dibenzofuranyl group, a triazinyl group, a pyrimidinyl group, a pyridyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a pentabiphenyl group, a dianilino group, a trianilino group, a benzothienocarbazolyl group, a benzofurocarbazolyl group, a benzofluorenocarbazolyl group, a benzanthryl group, a spirobifluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, an indenocarbazolyl group, a benzimidazolyl group, a diphenyl-oxadiazolyl group, a diphenylboryl group, a triphenylphosphinoxy group, a diphenylphosphinyloxy group, a triphenylsilyl group, a tetraphenylsilyl group, an acridinyl group, a phenoxazinyl group, a.

[5] The naphthopyrazine derivative according to any one of [1] to [4], wherein the naphthopyrazine derivative represented by the general formula (I) is selected from the group consisting of:

[6] the preparation method of the naphthopyrazine derivative shown in the general formula I comprises the following steps:

[7] an electronic device comprising the naphthopyrazine derivative according to any one of [1] to [5 ].

[87] The electronic device according to [7], wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;

wherein the organic electroluminescent device comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the naphthopyrazine derivative according to any one of [1] to [5 ].

[9] The electronic device according to [8], wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.

ADVANTAGEOUS EFFECTS OF INVENTION

The naphthopyrazine derivative has good film-forming property, thermal stability and higher fluorescence quantum yield by introducing a naphthopyrazine condensed ring structure, can be used for preparing electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, particularly used as a constituent material of a hole injection layer, a hole transmission layer, a light-emitting layer, an electron blocking layer, a hole blocking layer or an electron transmission layer in the organic electroluminescent devices, can show the advantages of high luminous efficiency, long service life, long luminous wavelength and low driving voltage, and is obviously superior to the existing organic electroluminescent devices.

In addition, the preparation method of the naphthopyrazine derivative is simple, raw materials are easy to obtain, and the development requirement of industrialization can be met.

The naphthopyrazine derivative has good application effect in electronic devices such as organic electroluminescent devices, organic field effect transistors and organic solar cells, and has wide industrial prospect.

The naphthopyrazine derivatives have high electron injection and moving rates. Therefore, with the organic electroluminescent device having an electron injection layer and/or an electron transport layer prepared using the naphthopyrazine-based derivative of the present invention, the electron transport efficiency from the electron transport layer to the light emitting layer is improved, thereby improving the light emitting efficiency. And, the driving voltage is reduced, thereby enhancing durability of the resulting organic electroluminescent device.

The naphthopyrazine derivative has excellent hole blocking capacity and excellent electron transport performance, and is stable in a thin film state. Therefore, the organic electroluminescent device having a hole blocking layer prepared using the naphthopyrazine-based derivative of the present invention has high luminous efficiency, a reduced driving voltage, and improved current resistance, so that the maximum luminous brightness of the organic electroluminescent device is increased.

The naphthopyrazine derivative has excellent light-emitting characteristics, can be used as a light-emitting layer host material or doped into an organic light-emitting host material to be used as a guest light-emitting material, has a wide doping proportion range, and can reduce concentration quenching and triplet-triplet annihilation. Therefore, the organic electroluminescent device having a light emitting layer prepared using the naphthopyrazine-based derivative of the present invention has high luminous efficiency, a reduced driving voltage, and improved current resistance, so that the maximum luminous brightness of the organic electroluminescent device is increased.

The selected and used pyrazine structure has proper singlet state, triplet state, molecular orbital energy level, strong electron withdrawing capability and excellent fluorescence quantum yield, the stability and the luminous efficiency of the device are improved, the driving voltage of the device is reduced, but the defect that the independent use of the pyrazine structure as a mother nucleus is exposed and cannot be regulated is found in experiments except the idea that on one hand, film forming aggregation or local crystallization is easily generated due to the fact that the pyrazine structure forms a planar linear structure, and triplet state quenching is caused; on the other hand, the parapyrazine structure has high molecular polarity and intermolecular force due to the presence of the heteroatom, so that molecules are attracted and attached to each other between planes where the parapyrazine is located and are difficult to separate, the actual average molecular weight of the molecules during evaporation is larger than the molecular weight of a single molecule, and further higher preparation temperature is required during film formation by evaporation, and higher evaporation temperature has a risk of influencing the stability and the photoelectric property of the molecules. Therefore, through repeated molecular form design and experimental verification, naphthalene is connected into the pyrazine molecular structure in an asymmetric mode, an entrance is provided for separating the adsorption effect between the planes of the pyrazine structure, the polarity of molecules at one end where the naphthalene or the similar derivatives are located is small, the intermolecular attraction effect of the surface where the pyrazine is located can be uncovered through the tangential effect, the actual molecular weight during molecular evaporation is reduced, the naphthalene derivatives are further introduced, the plane form is unfolded, the film forming state of the material is well regulated through increasing the matching of branched chains, the triplet quenching effect is greatly reduced, the material has high thermal stability, chemical stability and carrier transport property, the singlet state, the triplet state, the molecular orbital energy level, the strong electron pulling capacity and the excellent fluorescence quantum yield which are suitable for the pyrazine structure are well utilized, thereby greatly improving the stability of the pyrazine structure in the vapor deposition preparation process.

The naphthopyrazine derivative can be used as a constituent material of a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer or an electron transport layer of an organic electroluminescent device. With the organic electroluminescent device of the present invention, excitons generated in the light emitting layer can be confined, and the possibility of recombination of holes and electrons can be further increased to obtain high luminous efficiency.

Drawings

FIG. 1 is a fluorescence spectrum (PL) of the compounds of examples 1 and 4 of the present invention (compounds 2 to 114 and 1 to 101) in a toluene solution.

FIG. 2 shows organic electroluminescence spectra of examples 7 and 10 of the present invention.

FIG. 3 is a view showing the structure of organic electroluminescent devices of examples 7 to 12.

Description of the reference numerals

1-a substrate; 2-an anode; 3-a hole injection layer; 4-a hole transport layer; 5-an electron blocking layer;

6-a light emitting layer; 7-a hole blocking layer; 8-an electron transport layer; 9-electron injection layer; 10-cathode.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The naphthopyrazine derivative of the present invention is a novel compound having a naphthopyrazine ring structure, and is represented by the following general formula (I).

Specifically, the naphthopyrazine derivatives have the following general formula (1) or (2):

in the above general formulae (I) and (1) and (2),

L₁to L₃Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms;

A₁to A₃Each independently represents Ar₁、Ar₂、Ar₃、

R¹represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)₂、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 40 carbon atoms.

<L₁To L₃>

L₁、L₂And L₃Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or an aromatic heterocyclic group having 5 to 18 carbon atoms.

In the present invention, the hetero atom in the aromatic heterocyclic group having 5 to 18 carbon atoms is preferably selected from N, O and/or S. In the present invention, the number of hetero atoms may be 1 to 5. An aromatic hydrocarbon group or aromatic heterocyclic group in the sense of the present invention means a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-hydrogen atoms), which may be, for example, carbon atoms, nitrogen atoms, oxygen atoms or carbonyl groups. For example, systems of 9, 9' -spirobifluorenes, 9, 9-diarylfluorenes, triarylamines, diaryl ethers, etc., as well as systems in which two or more aryl groups are interrupted, for example by linear or cyclic alkyl groups or by silyl groups, are also intended to be considered aromatic hydrocarbon groups in the sense of the present invention. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl or quaterphenyl, are likewise intended to be regarded as aromatic hydrocarbon groups or aromatic heterocyclic groups.

From L₁、L₂And L₃The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, hydropyranyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, perylenyl, anthryl, benzopyrenyl, terphenylenyl, terphenylindenyl, etc, Phenanthridinyl, benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthraoxazolyl, phenanthroixazolyl, isoxazolyl, 1, 2-thiazolyl, 13-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazanthryl, 2, 7-diazpyrenyl, 2, 3-diazpyrenyl, 1, 6-diazpyrenyl, 1, 8-diazpyrenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluorescentryl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, piperidyl, indolizinyl, benzothiadiazolyl, and the like.

In the present invention, preferably, L₁、L₂And L₃Each independently represents a single bond, a carbonyl group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 5 to 12 carbon atoms. More preferably, L₁、L₂And L₃Each independently represents a single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenyl group.

From L₁、L₂And L₃The aromatic hydrocarbon group having 6 to 18 carbon atoms or the aromatic heterocyclic group having 5 to 18 carbon atoms represented may be unsubstituted, but may also have a substituent. The substituents may be exemplified by the following: a deuterium atom; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, or a n-hexyl group; alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy or propoxy; alkenyl, such as vinyl or allyl; aryloxy groups such as phenoxy or tolyloxy; arylalkoxy, such as benzyloxy or phenethyloxy; aromatic hydrocarbon radicals or condensed polycyclic aromatic radicals, e.g. phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl,Indenyl, pyrenyl, perylenyl, fluoranthenyl, benzo [9,10 ]]Phenanthryl or spirobifluorenyl; an aromatic heterocyclic group such as pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuryl, dibenzothienyl, azafluorenyl, diazafluorenyl, carbolinyl, azaspirobifluorenyl or diazaspiro-bifluorenyl; arylethenyl, such as styryl or naphthylethenyl; and acyl groups such as acetyl or benzoyl and the like.

The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be linear or branched. Any of the above substituents may be further substituted with the above exemplary substituents. The above substituents may be present independently of each other, but may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom, or a sulfur atom to form a ring.

<A₁To A₃>

A₁、A₂And A₃Each independently represents Ar₁、Ar₂、Ar₃、

(Ar₁To Ar₆)

Ar₁～Ar₆Each independently represents a hydrogen atom, a cyano group or optionally substituted by one or more R¹Substituted, aromatic hydrocarbon radical having 6 to 30 carbon atoms or optionally substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From Ar₁～Ar₆The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be exemplified by: phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenylTerphenyl, fluorenyl, spirobifluorenyl, phenanthrenyl, pyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzoindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, dianilinyl, trianilino, triindenyl, isotridendenyl, spiroisotridendenyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, benzothienocarbazolyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, Phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinylimidazolyl, oxazolyl, benzoxazolyl, benzooxadiazolyl, naphthooxazolyl, anthraoxazolyl, phenanthrooxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazenanthranyl, diazpyrenyl, tetraazaperylenyl, naphthyridinyl, pyrazinyl, phenazinyl, phenoxazinyl, phenothiazinyl, fluoresceinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, Purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridodipyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenylphosphinoxy, diphenylphosphinyloxy, triphenylsilicon, tetraphenylsilyl, and the like.

In the present invention, preferably, Ar₁、Ar₂、Ar₃、Ar₄、Ar₅And Ar₆Each independently selected from a hydrogen atom, a cyano group orGroup (b):

wherein the dotted line represents and L₁、L₂And L₃Or a N-bonded bond, R¹Have the meaning as defined for the general formula (I).

From Ar₁～Ar₆The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from Ar₁～Ar₆The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by¹Substituted, aromatic hydrocarbon radicals having 5 to 30 carbon atoms or substituted by one or more R¹A substituted aromatic heterocyclic group having 5 to 30 carbon atoms.

(R¹)

R¹Represents a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, NO₂、N(R²)、OR²、SR²、C(＝O)R²、P(＝O)R²、Si(R²)₃Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 40 carbon atoms, or substituted or unsubstituted aromatic heterocyclic ring having 5 to 40 carbon atomsAnd (4) a base.

From R¹The alkyl group having 1 to 20 carbon atoms represented may be exemplified by: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, n-decyl, hexadecyl, octadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic.

From R¹The alkyl group having 1 to 20 carbon atoms represented may be unsubstituted, but may also have a substituent. Preferably, from R¹Alkyl having 1 to 20 carbon atoms represented by one or more of the following R²And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group₂The group can be represented by R²C＝CR²、C≡C、Si(R²)₃、C＝O、C＝NR²、P(＝O)R²、SO、SO₂、NR²O, S or CONR²And wherein one or more hydrogen atoms may be replaced with deuterium atom, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group.

From R¹The alkenyl group having 2 to 20 carbon atoms represented may be exemplified by: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, cyclohexenyl and the like. The alkenyl group having 2 to 20 carbon atoms may be linear, branched or cyclic.

From R¹The alkenyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents may beBy way of illustration with R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be exemplified by: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like.

From R¹The alkynyl group having 2 to 20 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by the above formula may be exemplified by the group consisting of Ar₁～Ar₆The aromatic hydrocarbon group having 6 to 30 carbon atoms or the aromatic heterocyclic group having 5 to 30 carbon atoms represented by the above formula represent the same groups.

From R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹The alkyl group having 1 to 20 carbon atoms represented by (b) may have the same substituent as that represented by the substituent(s). The substituents may take the same pattern as that of the exemplary substituents. In addition, two adjacent R¹Substituents or two adjacent R²The substituents optionally may form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system, which may be substituted by one or more R²Substitution; where two or more substituents R¹May be connected to each other and may form a ring.

Preferably represented by R¹The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms represented by (a) may be exemplified by: phenyl, biphenylTerphenyl group, quaterphenyl group, pentabiphenyl group, benzothienocarbazolyl group, benzofurocarbazolyl group, benzofluorenocarbazolyl group, benzanthracenyl group, benzophenanthryl group, fluorenyl group, spirobifluorenyl group, triazinyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, N-phenylcarbazolyl group, indenocarbazolyl group, benzimidazolyl group, diphenyl-oxadiazolyl group, diphenyl boron group, triphenylphosphoxy group, diphenylphosphinyloxy group, triphenylsilyl group, tetraphenylsilyl group and the like. The aromatic hydrocarbon group having 6 to 40 carbon atoms or the aromatic heterocyclic group having 5 to 40 carbon atoms may be substituted with one or more R²And (4) substitution.

(R²)

From R²The alkyl group having 1 to 20 carbon atoms represented by R can be enumerated by¹The alkyl groups represented by the formulae having 1 to 20 carbon atoms represent the same groups.

From R²The aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented by the formula R¹The same groups as those shown for the aromatic hydrocarbon group having 6 to 30 carbon atoms or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

From R²The alkyl group having 1 to 20 carbon atoms, the aromatic hydrocarbon group having 6 to 30 carbon atoms, or the substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms represented may be unsubstituted, or may also have a substituent. The substituents may be exemplified by: a deuterium atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; cyano, and the like.

< production method >

The naphthopyrazine derivative of the present invention can be produced, for example, by the following method:

the obtained compound can be purified by, for example, purification by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, or the like, recrystallization or crystallization using a solvent, sublimation purification, or the like. Identification of compounds can be carried out by mass spectrometry, elemental analysis.

< electronic device >

Various electronic devices containing the naphthopyrazine derivatives of the invention can be produced using the naphthopyrazine derivatives according to the invention for producing organic materials which can be configured in particular in the form of layers. In particular, the naphthopyrazine derivatives can be used for organic electroluminescent devices, organic solar cells, organic diodes, and particularly organic field effect transistors. Particularly in the case of an organic electroluminescent device or a solar cell, the assembly may have a plug structure (the device has one or more p-doped hole transport layers and/or one or more n-doped electron transport layers) or an inverted structure (from the light emitting layer, the upper electrode and the hole transport layer are located on the same side while the substrate is on the opposite side), without being limited to these structures. The injection layer, the transport layer, the light-emitting layer, the barrier layer, and the like can be fabricated, for example, by forming a layer containing or consisting of the naphthopyrazine derivative according to the present invention between electrodes. However, the use of the naphthopyrazine derivatives according to the present invention is not limited to the above exemplary embodiments.

< organic electroluminescent device >

The organic electroluminescent device of the present invention comprises: the organic light-emitting device includes a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer includes the naphthopyrazine derivative of the present invention.

Fig. 3 is a view showing the configuration of an organic electroluminescent device of the present invention. As shown in fig. 3, in the organic electroluminescent device of the present invention, for example, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 are sequentially disposed on a substrate 1.

The organic electroluminescent device of the present invention is not limited to such a structure, and for example, some organic layers may be omitted in the multi-layer structure. For example, it may be a configuration in which the hole injection layer 3 between the anode 2 and the hole transport layer 4, the hole blocking layer 7 between the light emitting layer 6 and the electron transport layer 8, and the electron injection layer 9 between the electron transport layer 8 and the cathode 10 are omitted, and the anode 2, the hole transport layer 4, the light emitting layer 6, the electron transport layer 8, and the cathode 10 are sequentially provided on the substrate 1.

The organic electroluminescent device according to the present invention may be manufactured by materials and methods well known in the art, except that the above organic layer contains the compound represented by the above general formula (I). In addition, in the case where the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

For example, the organic electroluminescent device according to the present invention may be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, the following can be made: an anode is formed by depositing metal, a metal oxide having conductivity, or an alloy thereof on a substrate by a PVD (physical vapor deposition) method such as a sputtering method or an electron beam evaporation method, an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the anode, and a substance which can be used as a cathode is deposited on the organic layer. However, the production method is not limited thereto.

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

The anode of the organic electroluminescent device of the present invention may be made of a known electrode material. For example, using electrode materials having a large work function, such as vanadium, chromium, copper, zinc,Metals such as gold or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; such as ZnO, Al or SNO₂A combination of a metal such as Sb and an oxide; poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene]And conductive polymers such as PEDOT, polypyrrole, and polyaniline. Among these, ITO is preferable.

As the hole injection layer of the organic electroluminescent device of the present invention, a known material having a hole injection property can be used. Examples thereof include: porphyrin compounds represented by copper phthalocyanine, naphthalenediamine derivatives, star-shaped triphenylamine derivatives, triphenylamine trimers such as arylamine compounds having a structure in which 3 or more triphenylamine structures are connected by a single bond or a divalent group containing no heteroatom in the molecule, tetramers, receptor-type heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the hole transport layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the naphthopyrazine derivatives of the present invention. In addition, other known materials having a hole-transporting property can be used. Examples thereof include: a compound containing a m-carbazolylphenyl group; benzidine derivatives such as N, N ' -diphenyl-N, N ' -di (m-tolyl) benzidine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -tetrakisbiphenylylbenzidine, and the like; 1, 1-bis [ (di-4-tolylamino) phenyl ] cyclohexane (TAPC); various triphenylamine trimers and tetramers; 9,9 ', 9 "-triphenyl-9H, 9' H, 9" H-3,3 ': 6', 3 "-tricarbazole (Tris-PCz), and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

In addition, in the hole injection layer or the hole transport layer, a material obtained by further P-doping tribromoaniline antimony hexachloride, an axial olefin derivative, or the like to a material generally used in the layer, a polymer compound having a structure of a benzidine derivative such as TPD in a partial structure thereof, or the like may be used.

As the electron blocking layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the naphthopyrazine derivatives of the present invention. In addition, other known compounds having an electron blocking effect may be used. For example, there may be mentioned: carbazole derivatives such as 4,4', 4 ″ -tris (N-carbazolyl) triphenylamine (TCTA), 9-bis [4- (carbazol-9-yl) phenyl ] fluorene, 1, 3-bis (carbazol-9-yl) benzene (mCP), and 2, 2-bis (4-carbazol-9-ylphenyl) adamantane (Ad-Cz); a compound having a triphenylsilyl and triarylamine structure represented by 9- [4- (carbazol-9-yl) phenyl ] -9- [4- (triphenylsilyl) phenyl ] -9H-fluorene; and compounds having an electron-blocking effect, such as monoamine compounds having a high electron-blocking property and various triphenylamine dimers. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the light-emitting layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the naphthopyrazine derivatives of the present invention. In addition to this, Alq can also be used₃Various metal complexes such as metal complexes of a first hydroxyquinoline derivative, compounds having a pyrimidine ring structure, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylene vinylene derivatives, and the like.

The light emitting layer may be composed of a host material and a dopant material.

As the host material, it is preferable to use a naphthopyrazine derivative containing the present invention. In addition to these, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylnaphthopyrazine derivatives, heterocyclic compounds having a partial structure in which an indole ring is a condensed ring, and the like can be used.

As the doping material, a material containing the naphthopyrazine derivative of the present invention is preferably used. Aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like can also be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzodipyran derivatives, rhodamine derivatives, aminostyryl derivatives, spirobifluorene derivatives, and the like. These may be used as a single layer formed by film formation alone or by mixing with other materials to form a film, or may be used as a laminated structure of layers formed by film formation alone, a laminated structure of layers formed by mixing into a film, or a laminated structure of layers formed by film formation alone and layers formed by mixing into a film. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the hole blocking layer of the organic electroluminescent device of the present invention, it is preferable to use a layer containing the naphthopyrazine derivatives of the present invention. In addition, the hole-blocking layer may be formed using another compound having a hole-blocking property. For example, a phenanthroline derivative such as 2,4, 6-tris (3-phenyl) -1,3, 5-triazine (T2T), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), Bathocuproine (BCP), a metal complex of a quinolyl derivative such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenate (BAlq), and a compound having a hole-blocking effect such as various rare earth complexes, oxazole derivatives, triazole derivatives, and triazine derivatives can be used. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

The above-described material having a hole-blocking property can also be used for formation of an electron transport layer described below. That is, by using the known material having a hole-blocking property, a layer which serves as both a hole-blocking layer and an electron-transporting layer can be formed.

As the electron transport layer of the organic electroluminescent device of the present invention, it is preferable to use a compound containing the naphthopyrazine derivatives of the present invention. In addition, the compound may be formed using other compounds having an electron-transporting property. For example, Alq can be used₃Metal complexes of quinolinol derivatives including BAlq; various metal complexes; a triazole derivative; a triazine derivative; an oxadiazole derivative; a pyridine derivative; bis (10-hydroxybenzo [ H ]]Quinoline) beryllium (Be (bq)₂) (ii) a Such as 2- [4- (9, 10-dinaphthalen-2-anthracen-2-yl) phenyl]Benzimidazole derivatives such as-1-phenyl-1H-benzimidazole (ZADN); a thiadiazole derivative; an anthracene derivative; a carbodiimide derivative; quinoxaline derivatives; pyridoindole derivatives; phenanthroline derivatives; silole derivatives and the like. These may be used as a single layer formed by separately forming a film or by mixing them with other materials to form a film, or may be used as a laminated structure of layers formed by separately forming a film, a laminated structure of layers formed by mixing films, or a laminated structure of layers formed by separately forming a film and layers formed by mixing films. These materials can be formed into a thin film by a known method such as a vapor deposition method, a spin coating method, and an ink jet method.

As the electron injection layer of the organic electroluminescent device of the present invention, a material known per se can be used. For example, alkali metal salts such as lithium fluoride and cesium fluoride; alkaline earth metal salts such as magnesium fluoride; metal complexes of quinolinol derivatives such as lithium quinolinol; and metal oxides such as alumina.

In the electron injection layer or the electron transport layer, a material obtained by further N-doping a metal such as cesium, a triarylphosphine oxide derivative, or the like can be used as a material generally used for the layer.

As the cathode of the organic electroluminescent device of the present invention, an electrode material having a low work function such as aluminum, magnesium, or an alloy having a low work function such as magnesium-silver alloy, magnesium-indium alloy, aluminum-magnesium alloy is preferably used as the electrode material.

As the substrate of the present invention, a substrate in a conventional organic light emitting device, such as glass or plastic, can be used. In the present invention, a glass substrate is selected.

Examples

The production of the compound represented by the above general formula (I) and the organic electroluminescent device comprising the same is specifically described in the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1: synthesis of Compounds 2 to 114

(Synthesis of intermediate M1)

The synthetic route for intermediate M1 is shown below:

13.8g (47.8mmol) of 4-triphenylamine borate, 8.4g (79.6mmol) of anhydrous sodium carbonate, 9.3g (39.8mmol) of 6-bromo-1, 2-naphthoquinone, 470.8mg (4.8mmol) of tetrakis (triphenylphosphine palladium), and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1(V/V)) were sequentially added to a clean 250mL three-necked flask under nitrogen. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 2: 3(V/V)) to obtain 13.5g of a reddish brown solid in 84% yield. Ms (ei): m/z: 401.53[ M ]⁺]。Anal.calcd for C₂₈H₁₉NO₂(％)：C 83.77，H 4.77；found：C83.70，H 4.74。

(Synthesis of Compounds 2 to 114)

The synthetic routes for compounds 2-114 are shown below:

in the clean stateA250 mL single-neck flask was charged with 12.0g (30mmol) of intermediate M1, 4.8g (30mmol) of 5, 6-diamino-2, 3-dicyanopyrazine and 100mL of glacial acetic acid in that order, gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 2: 3(V/V)) to obtain 12.9g of a dark green solid with a yield of 82%. Ms (ei): m/z: 525.62[ M ]⁺]。Anal.calcd for C₃₄H₁₉N₇(％)：C 77.70，H 3.64；found：C 77.60，H 3.60。

Example 2: synthesis of Compounds 1-114

(Synthesis of Compounds 1 to 114)

The synthetic routes for intermediates 1-114 are shown below:

12.0g (30mmol) of intermediate M1, 3.3g (30mmol) of 2, 3-diaminopiperazine and 100mL of glacial acetic acid were added in succession to a clean 250mL single-neck flask, gradually warmed to reflux and reacted overnight at reflux. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 2: 3(V/V)) to obtain 11.7g of a dark green solid, with a yield of 82%. Ms (ei): m/z: 475.62[ M ]⁺]。Anal.calcd for C₃₂H₂₁N₅(％)：C 80.82，H 4.45；found：C 80.60，H4.40。

Example 3: synthesis of Compounds 2-157

(Synthesis of intermediate M2)

The synthetic route for intermediate M2 is shown below:

in a clean 250mL three-neck flask under nitrogen13.8g (47.8mmol) of 4- (9H-carbazol-9-yl) phenylboronic acid, 8.4g (79.6mmol) of anhydrous sodium carbonate, 9.3g (39.8mmol) of 6-bromo-1, 2-naphthoquinone, 470.8mg (4.8mmol) of tetrakis (triphenylphosphine palladium), and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1(V/V)) were added in portions. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 2: 3(V/V)) to obtain 13.4g of a yellow solid in 84% yield. Ms (ei): m/z: 399.53[ M ]⁺]。Anal.calcd for C₂₈H₁₇NO₂(％)：C 84.19，H4.29；found：C 83.99，H 4.24。

(Synthesis of Compounds 2-157)

The synthetic route for compounds 2-157 is shown below:

12.0g (30mmol) of intermediate M2, 4.8g (30mmol) of 5, 6-diamino-2, 3-dicyanopyrazine and 100mL of glacial acetic acid were added in succession to a clean 250mL single-neck flask, gradually warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 2: 3(V/V)) to obtain 12.9g of a red solid with a yield of 82%. Ms (ei): m/z: 523.62[ M ]⁺]。Anal.calcd for C₃₄H₁₇N₇(％)：C 78.00，H 3.27；found：C77.80，H 3.21。

Example 4: synthesis of Compounds 1-101

(Synthesis of intermediate M3)

The synthetic route for intermediate M3 is shown below:

5.4g (23.0mmol) of 6-bromo-1, 2-naphthoquinone, 4.9g (29.0mmol) of diphenylamine, 3.0g (29.0mmol) of sodium tert-butoxide, 0.1g (0.3mmol) of tri-tert-butylphosphine tetrafluoroborate and 0.27g (0.3mmol) of tris (dibenzylideneacetone) dipalladium were sequentially added to a 250mL two-necked flask, and after degassing the reaction system, 150mL of toluene was added under nitrogen protection, and the mixture was stirred and heated to reflux for 12 hours. After the reaction is completed, cooling the system to room temperature, carrying out vacuum filtration, washing filter residue with a large amount of dichloromethane, concentrating the filtrate to obtain a crude product, and adding petroleum ether: dichloromethane ═ 3: 2 (volume ratio) on silica gel column to obtain 6.0g red with 92% yield. MS (EI) M/z 325.43[ M ]⁺]。Anal.calcd for C₂₂H₁₅NO₂(％)：C 81.21，H 4.65；found：C 81.01，H 4.60。

(Synthesis of Compounds 1-101)

The synthetic routes for compounds 1-101 are shown below:

9.8g (30mmol) of intermediate M3, 3.3g (30mmol) of 2, 3-diaminopiperazine and 100mL of glacial acetic acid were added in succession to a clean 250mL single-neck flask, gradually warmed to reflux and reacted overnight at reflux. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 2: 3(V/V)) to obtain 9.8g of a deep red solid in a yield of 82%. Ms (ei): m/z: 399.52[ M ]⁺]。Anal.calcd for C₂₆H₁₇N₅(％)：C 78.18，H 4.29；found：C 78.05，H3.22。

Example 5: synthesis of Compounds 2-101

(Synthesis of Compounds 2 to 101)

The synthetic route for compounds 2-101 is shown below:

9.8g (30mmol) of intermediate M3, 4.8g (30mmol) of 5, 6-diamino-2, 3-dicyanopyrazine and 100mL of glacial acetic acid were added in succession to a clean 250mL single-neck flask, gradually warmed to reflux and reacted overnight under reflux. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane 2: 3(V/V)) to obtain 11.0g of a deep red solid in a yield of 82%. Ms (ei): m/z: 449.52[ M ]⁺]。Anal.calcd for C₂₈H₁₅N₇(％)：C 74.82，H 3.36；found：C 74.75，H 3.32。

Example 6: synthesis of Compounds 2-158

(Synthesis of intermediate M4)

The synthetic route for intermediate M4 is shown below:

to a clean 250mL three-necked flask, 27.6g (95.6mmol) of triphenylamine 4-borate, 8.4g (79.6mmol) of anhydrous sodium carbonate, 7.1g (39.8mmol) of 4.5-dichloro-2.3-diaminopyrazine, 470.8mg (4.8mmol) of tetrakis (triphenylphosphine palladium), and 100mL of a mixed solvent (toluene: water: ethanol ═ 5: 1: 1(V/V)) were sequentially added under nitrogen. The system was gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the reaction system to room temperature. The reaction solution was poured into about 200mL of water and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 3: 2(V/V)) to obtain 20.0g of a reddish brown solid in 84% yield. Ms (ei): m/z: 596.49[ M ]⁺]。Anal.calcd for C₄₀H₃₂N₆(％)：C 80.51，H5.41；found：C 80.31，H 5.35。

(Synthesis of intermediate M5)

The synthetic route for intermediate M5 is shown below:

17.9g (30.0mmol) of intermediate M5, 7.1g (30.0mmol) of 6-bromo-1, 2-naphthoquinone and 100mL of glacial acetic acid were sequentially added to a clean 250mL single-neck flask, gradually warmed to reflux and reacted under reflux overnight. After the reaction is finished, stopping heating, and automatically cooling the system. The reaction solution was poured into 1L of ice water, collected by suction filtration, compressed and dried, and further purified by column chromatography (350 mesh silica gel, eluent petroleum ether: dichloromethane ═ 2: 3(V/V)) to obtain 19.6g of a deep red solid in a yield of 82%. Ms (ei): m/z: 796.62[ M ]⁺]。Anal.calcd for C₅₀H₃₃BrN₆(％)：C75.28，H 4.17；found：C75.01，H 4.13。

(Synthesis of Compounds 2-158)

The synthetic route for compounds 2-158 is shown below:

in a100 mL two-necked flask, 3.9g (4.9mmol) of M5 and 0.5g (5.1mmol) of cuprous cyanide were dissolved in 40mL of N, N-dimethylformamide under nitrogen, stirred, and heated to 150 ℃ for reaction for 24 hours. After the reaction was completed, the reaction solution was poured into 50mL of saturated sodium hydroxide solution, and filtered under suction to obtain a crude product. The crude product was dissolved in 150mL of dichloromethane and washed 3 times with 60mL of water. The organic phase is dried by anhydrous sodium sulfate and then the solvent is removed by rotary drying to obtain a crude product. The crude product was purified with dichloromethane: petroleum ether is 3: 2 (volume ratio) of eluent on silica gel column to obtain 3.2g of deep red solid with 87% of yield. MS (EI) M/z 743.36[ M ]⁺]. Calculated value of elemental analysis C₅₁H₃₈N₇(%): c82.35, H4.47; measured value: c82.11, H4.40.

Preparation of organic electroluminescent device (organic EL device)

Specifically, the ITO transparent conductive layer coated glass plate was sonicated in a commercial detergent to removeRinsing in ionized water, washing in acetone and ethanol for three times, baking in clean environment to completely remove water, washing with ultraviolet light and ozone, and bombarding the surface with low-energy cation beam. Placing ITO conductive glass into a vacuum chamber, and vacuumizing to less than 5 × 10^-4Pa. Using ITO conductive glass as an anode, and sequentially evaporating a Hole Injection Layer (HIL), a hole transport layer (HIL), an Electron Blocking Layer (EBL), an organic light emitting layer (EML), an Electron Transport Layer (ETL) and a cathode on the ITO conductive glass; wherein, the evaporation rate of the organic material is 0.2nm/s, and the evaporation rate of the metal electrode is 0.5 nm/s.

The electroluminescence spectra were collected using a photon multichannel analyzer PMA-12(Hamamatsu C10027-01), which can be detected in the spectral region of 200 and 950 nm. The external quantum efficiency of the device was obtained by measuring the forward light intensity using an integrating sphere (Hamamatsu a 10094). All measurements were performed at room temperature in an atmospheric environment.

The method for forming each structural layer in the organic electroluminescent device of the present invention is not particularly limited, and conventional vacuum evaporation methods, spin coating methods, and the like may be used.

Examples 7 to 12

The following description of OLED1-6 will be made with reference to examples 7-12, wherein OLED1-6 uses the materials shown as compounds 2-114,1-114,2-157,1-101,2-101 and 2-158 in the present invention, and the structure of each OLED device and the thickness of each layer are as follows:

OLED-l：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/10wt％2-114:TPBi(20nm)/TPBi(50nm)/Liq(2nm)/Al(100nm)

OLED-2：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/20wt％1-114:TPBi(20nm)/TPBi(50nm)/Liq(2nm)/Al(100nm)

OLED-3：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/15wt％2-157:TPBi(20nm)/TPBi(50nm)/Liq(2nm)/Al(100nm)

OLED-4：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/12wt％1-101:TPBi(20nm)/TPBi(50nm)/Liq(2nm)/Al(100nm)

OLED-5：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/15wt％2-101:TPBi(20nm)/TPBi(50nm)/Liq(2nm)/Al(100nm)

OLED-6：

ITO/HAT-CN(5nm)/NPB(60nm)/TCTA(5nm)/20wt％2-158:TPBi(20nm)/TPBi(50nm)/Liq(2nm)/Al(100nm)

the examples relate to compounds having the following structure:

TABLE 1

Device numbering	Luminescent layer	Maximum external quantum efficiency (%)	Peak electroluminescence (nm)
				OLED1	10wt％2-114:TPBi	8.05	820
OLED2	20wt％1-114:TPBi	12.75	650
				OLED3	15wt％2-157:TPBi	10.97	625
OLED4	12wt％1-101:TPBi	6.21	660
				OLED5	15wt％2-101:TPBi	3.54	825
OLED6	20wt％2-158:TPBi	8.22	800

The light emission characteristics of the organic EL devices OLEDs 1 to 6 produced in examples 1 to 6 were measured when a direct current voltage was applied in the atmosphere at normal temperature. The measurement results are shown in table 1.

As can be seen from table 1, the naphthopyrazine derivative of the present invention has excellent light emitting characteristics, a stable structure, and high color purity by modifying and introducing other different chemical groups, and simultaneously, the preparation cost thereof is low. In addition, the deep red/near infrared organic electroluminescent device prepared by the naphthopyrazine derivatives has high luminous efficiency and excellent performance.

Industrial applicability

The organic electroluminescent compounds according to the present invention have excellent luminous efficiency and excellent color purity of materials. Therefore, the compound can be used for preparing a deep red/near infrared organic electroluminescent device with excellent performance.

The above description is only an embodiment of the present application, and does not limit the scope of the present application, and all equivalent molecular structures or equivalent transformations that are made by the contents of the specification and the drawings of the present application, or that are directly or indirectly applied to other related technical fields, are included in the scope of the present application.

Claims

1. A naphthopyrazine derivative is characterized by being represented by the following general formula (I):

A₁-A₃each independently represents Ar₁、Ar₂、Ar₃、

R²represents a hydrogen atomDeuterium atom, fluorine atom, cyano group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, or substituted or unsubstituted aromatic heterocyclic group having 5 to 30 carbon atoms.

2. The naphthopyrazine derivative according to claim 1, which is represented by the following general formulae (1) to (2):

3. the naphthopyrazine derivative according to claim 1, wherein Ar₁～Ar₆Each independently selected from a hydrogen atom, a cyano group or the following group:

R¹have the meaning as defined for the general formula (I).

4. The naphthopyrazine derivative according to any one of claims 1 to 4, wherein L₁、L₂And L₃Each independently represents a single bond, a carbonyl group,Phenyl or triazinyl;

5. The naphthopyrazine derivative according to any one of claims 1 to 4, wherein the naphthopyrazine derivative represented by the general formula (I) is selected from the group consisting of:

6. a preparation method of naphthopyrazine derivatives is characterized by comprising the following steps:

7. an electronic device comprising the naphthopyrazine derivative according to any one of claims 1 to 5.

8. The electronic device according to claim 7, wherein the electronic device is an organic electroluminescent device, an organic field effect transistor, or an organic solar cell;

wherein the organic electroluminescent device comprises: a first electrode, a second electrode provided so as to face the first electrode, and at least one organic layer interposed between the first electrode and the second electrode, wherein the at least one organic layer contains the naphthopyrazine derivative according to any one of claims 1 to 5.

9. The electronic device of claim 8, wherein the at least one organic layer is a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, or an electron transport layer.