CN113149912A

CN113149912A - Cycloalkanepyrimidine derivative and preparation method and application thereof

Info

Publication number: CN113149912A
Application number: CN202110357850.7A
Authority: CN
Inventors: 朱向东; 刘向阳; 崔林松; 张业欣; 陈华
Original assignee: Suzhou Jiuxian New Material Co ltd
Current assignee: Suzhou Jiuxian New Material Co ltd
Priority date: 2021-04-01
Filing date: 2021-04-01
Publication date: 2021-07-23

Abstract

The invention discloses a cycloparaffin and pyrimidine derivative and a preparation method and application thereof, belongs to the technical field of organic photoelectric materials, and particularly relates to a cycloparaffin and pyrimidine derivative and a preparation method and application thereof. The cycloparaffin and pyrimidine derivative has excellent film forming property and thermal stability by introducing a cycloparaffin and pyrimidine rigid structure, and can be used for preparing organic electroluminescent devices, organic field effect transistors and organic solar cells. In addition, the cycloparaffin pyrimidine 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, and can reduce driving voltage, improve efficiency, brightness, life and the like. In addition, the preparation method of the cycloparaffin pyrimidine derivative is simple, raw materials are easy to obtain, and the industrial development requirement can be met.

Description

Cycloalkanepyrimidine derivative and preparation method and application thereof

Technical Field

The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a cycloparaffin pyrimidine derivative and a preparation method and application thereof.

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 successively. 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 the industrialization of the technology still faces many key problems. 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 first object of the present invention is to provide a cycloparaffin pyrimidine derivative which has high thermal stability and good transport performance and is an organic electroluminescent material with excellent performance.

The cycloparaffin pyrimidine derivative has a special biphenyl structure, has high thermal stability, chemical stability and carrier transport property, and more importantly has proper singlet state, triplet state and molecular orbital energy level. Therefore, the organic electroluminescent material is introduced into molecules with electroluminescent characteristics, so that the stability and the luminous efficiency of a device are improved, and the driving voltage of the device is reduced.

The invention is as follows:

a cycloparaffinopyrimidine derivative represented by the following general formula (1):

wherein L is₁And L₂Each independently selected from the group consisting of a single bond, carbonyl, C₆-C₁₈Of an aromatic hydrocarbon group or C₅-C₁₈One or more of the aromatic heterocyclic groups of (a);

A₁and A₂Each independently selected from Ar₁、Ar₂、

One or more of;

wherein Ar is₁-Ar₄Each independently selected from the group consisting of¹Substituted, C₆-C₃₀Or with one or more R¹Substituted, C₅-C₃₀The aromatic heterocyclic group of (1);

x represents C₁-C₇Alkyl or a single bond of (a);

m and n are independently selected from integers of 0-5, and m and n are not 0 at the same time;

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)₃Substituted or unsubstituted C₁-C₂₀Alkyl, substituted or unsubstituted C₂-C₂₀Alkenyl of (a), substituted or unsubstituted C₂-C₂₀Alkynyl, substituted or unsubstituted C₆-C₄₀Or substituted or unsubstituted C₅-C₄₀The aromatic heterocyclic group of (1);

R²represents a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a substituted or unsubstituted C₁-C₂₀Alkyl, substituted or unsubstituted C₆-C₃₀Or substituted or unsubstituted C₅-C₃₀The aromatic heterocyclic group of (1).

Further, the above-mentioned cycloalkane-pyrimidine derivative is represented by the following general formula (I) and/or (II):

L₁、L₂and Ar₁-Ar₄Has the meaning as defined for the general formula (1).

Further, the above-mentioned cycloalkane-pyrimidine derivative, wherein Ar is₁、Ar₂、Ar₃And Ar₄Each independently selected from the following groups:

wherein the dotted line represents and L₁、L₂Or a N-bonded bond, R¹Has the meaning as defined for the general formula (1).

Further, the above-mentioned cycloalkane-pyrimidine derivative, R¹And R²Each independently selected from one or more of phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boronyl, triphenyl phosphoroxy, diphenyl phosphoroxy, triphenyl silyl, or tetraphenyl silyl.

Further, the above-mentioned cycloparaffin pyrimidine derivative, wherein the cycloparaffin pyrimidine derivative represented by the general formula (1) is selected from one or more of the following compounds:

the second object of the present invention is to provide a process for producing the above-mentioned cycloalkane-pyrimidine derivative, which is simple and has good stability.

A preparation method of the cycloparaffin pyrimidine derivative comprises the following chemical reaction equations:

further, in the preparation method of the cycloparaffin pyrimidine derivative, the prepared product needs to be purified, and the purification treatment comprises one or more of column chromatography, adsorption purification, crystallization, recrystallization and sublimation purification; wherein the column chromatography is column chromatography for purification, and the adsorption purification is adsorption purification by one or more of silica gel, active carbon or active clay, and crystallization or recrystallization in solvent; identification of the resulting products of preparation includes mass spectrometry and/or elemental analysis.

The third purpose of the invention is to provide an electronic device prepared by adopting the cycloparaffin pyrimidine derivative obtained by the preparation method, 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: the organic electroluminescence 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 contains a cycloalkane-pyrimidine derivative. The organic electroluminescent device has the advantages of high luminous efficiency, high durability, long service life, low driving voltage and the like.

Further, 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.

The cycloparaffin and pyrimidine derivative has good film forming property and thermal stability by introducing a cycloparaffin and pyrimidine rigid 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 and low driving voltage, and is obviously superior to the existing organic electroluminescent devices.

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

The cycloparaffin pyrimidine derivative has good application effect in electronic devices such as organic electroluminescent devices, organic field effect transistors, organic solar cells and the like, and has wide industrialization prospect.

The cycloparaffin pyrimidine derivative has high electron injection and moving speed. Therefore, with the organic electroluminescent device having an electron injection layer and/or an electron transport layer prepared using the cycloparaffin pyrimidine-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 cycloparaffin pyrimidine derivative has excellent hole blocking capacity and excellent electron transporting performance, and is stable in a thin film state. Therefore, the organic electroluminescent device having a hole-blocking layer prepared using the cycloparaffin pyrimidine-based derivative of the present invention has high luminous efficiency, a reduced driving voltage, and improved current resistance, resulting in an increase in the maximum luminous brightness of the organic electroluminescent device.

The cycloparaffin pyrimidine 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. In addition, the driving voltage is so low that high durability can be achieved.

Drawings

FIG. 1: fluorescence spectrum (PL) of compound 58 prepared in example 2 in dichloromethane solution.

FIG. 2: the electroluminescence spectra of the

organic EL devices

5,6, 17, and 18.

FIG. 3: the organic electroluminescent devices of examples 8 to 23 and the organic electroluminescent devices of comparative examples 1 and 2 are schematically illustrated in their structural configurations.

Description of 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

The technical solution of the present invention will be described in detail by the following specific examples.

The cycloalkane pyrimidine derivative of the present invention is a novel compound having a pyrimidine structure, and is represented by the following general formula (1).

Specifically, the cycloparaffin pyrimidine derivative has the following general formula (I) and/or (II):

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

L₁and L₂Each independently selected from the group consisting of a single bond, carbonyl, C₆-C₁₈Of an aromatic hydrocarbon group or C₅-C₁₈The aromatic heterocyclic group of (1);

A₁and A₂Each independently selected from Ar₁、A₂、

Ar₁-Ar₄Each independently selected from the group consisting of¹Substituted, C₆-C₃₀Or with one or more R¹Substituted, C₅-C₃₀The aromatic heterocyclic group of (1);

x represents C₁-C₇Alkyl or a single bond of (a);

First, L₁And L₂：

L₁And L₂Each independently selected from the group consisting of a single bond, carbonyl, C₆-C₁₈Of an aromatic hydrocarbon group or C₅-C₁₈The aromatic heterocyclic group of (1).

In the present invention, C₅-C₁₈The hetero atom in the aromatic heterocyclic group of (a) is preferably N, O and/or S. In the present invention, the number of hetero atoms may be 1 to 5. Aromatic hydrocarbon or aromatic heterocyclic groups in the sense of the present invention mean systems which do 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, and two or more aryl groups, e.g. substituted by straight chainsOr cyclic alkyl groups or systems interrupted by silyl groups, systems of 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc. 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 L₁And L₂Is represented by C₆-C₁₈Of an aromatic hydrocarbon group or C₅-C₁₈The aromatic heterocyclic group of (b) may be exemplified by: phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, anthryl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, quinolyl, etc, Isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, phenothiazinyl, phenoxazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoxazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxaloimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroixazolyl, isoxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazahthranyl, 2, 7-diazapyranyl, 2, 3-diazapyryl, 1, 6-diazapyryl, 1, 8-diazepenyl, 4,5,9, 10-tetraazaperylenyl, pyrazinyl, and pyrazinyl,Phenazinyl, phenoxazinyl, phenothiazinyl, fluorerynyl, 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, pteridinyl, indolizinyl, benzothiadiazolyl, and the like.

In the present invention, preferably, L₁And L₂Each independently represents a single bond, carbonyl group, C₆-C₁₂Of an aromatic hydrocarbon group or C₅-C₁₂The aromatic heterocyclic group of (1). More preferably, L₁And L₂Each independently represents a C-C single bond, a carbonyl group, a phenyl group, a triazinyl group or a biphenylyl group.

From L₁And L₂Is represented by C₆-C₁₈Of an aromatic hydrocarbon group or C₅-C₁₈The aromatic heterocyclic group of (b) may be unsubstituted, but may 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; c₁-C₆Alkyl of (a), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl or n-hexyl; c₁-C₆Alkoxy groups 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, fluoranthryl, benzo [9,10 ] benzo]Phenanthryl or spirobifluorenyl; aromatic heterocyclic groups, e.g. pyridyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuryl, benzothienyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, quinoxalinyl, and pharmaceutically acceptable salts thereof,A benzimidazole group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, an azafluorenyl group, a diazafluorenyl group, a carbolinyl group, an azaspirobifluorenyl group, or a diazafluorosbifluorenyl group; arylethenyl, such as styryl or naphthylethenyl; and acyl groups such as acetyl or benzoyl and the like.

Having a structure of C₁-C₆Alkyl and C₁-C₆The alkoxy group of (a) 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 C-C single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.

Second, A₁And A₂：

A₁And A₂Each independently selected from Ar₁、Ar₂、

Third, Ar₁To Ar₄：

Ar₁-Ar₄Each independently selected from the group consisting of¹Substituted, C₆-C₃₀Or with one or more R¹Substituted, C₅-C₃₀The aromatic heterocyclic group of (1).

From Ar₁-Ar₄Is represented by C₆-C₃₀Of an aromatic hydrocarbon group or C₅-C₃₀The aromatic heterocyclic group of (b) may be exemplified by: phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, benzofluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, pentabiphenyl, terphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, cis-or trans-monobenzindenofluorenyl, cis-or trans-dibenzoindenofluorenyl, trimeric indenyl, isotridecylindenyl, spirotrimeric indenyl, spiroisotridecylindenyl, furanyl, benzofuranA group selected from the group consisting of a phenyl group, an isobenzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, an isobenzothienyl group, a dibenzothienyl group, a benzothienocarbazolyl group, a pyrrolyl group, an indolyl group, an isoindolyl group, a carbazolyl group, an indolocarbazolyl group, an indenocarbazolyl group, a pyridyl group, a bipyridyl group, a terpyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a benzo-5, 6-quinolyl group, a benzo-6, 7-quinolyl group, a benzo-7, 8-quinolyl group, a phenothiazinyl group, a phenoxazinyl group, a pyrazolyl group, an indazolyl group, an imidazolyl group, a benzimidazolyl group, a naphthoimidazolyl group, a pyridoimidazolyl group, a pyrazinyl group, a quinoxalinyl group, an oxazolyl group, a benzoxazolyl group, a benzooxadiazolyl group, a naphthooxazolyl group, an anthraoxazolyl group, a phenanthrooxazolyl group, Isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiadiazolyl, pyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, quinazolinyl, azafluorenyl, diazenanthranyl, diazepine, tetraazaperylenyl, naphthyridinyl, pyrazinyl, phenazinyl, phenothiazinyl, fluoresceinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, triazolyl, benzotriazolyl, oxadiazolyl, thiadiazolyl, triazinyl, tetrazolyl, tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenocarbazolyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenylboranyl, phenanthrolinyl, pyridopyrrolyl, pyridotriazolyl, xanthenyl, benzofurocarbazolyl, benzofluorenecarbazyl, N-phenylcarbazolyl, diphenyl-benzimidazolyl, diphenyl-oxadiazolyl, diphenyl-boronyl, diphenyl-yl, and the like, Triphenylphosphoxy, diphenylphosphinyloxy, triphenylsilyl, tetraphenylsilyl, and the like.

In the present invention, preferably, Ar₁、Ar₂、Ar₃And Ar₄Each independently selected from one or more of the following groups:

wherein the dotted line represents and L₁、L₂Or an N-bonded bond;

R¹has the meaning as defined for the general formula (1).

From Ar₁-Ar₄Is represented by C₆-C₃₀Of an aromatic hydrocarbon group or C₅-C₃₀The aromatic heterocyclic group of (a) may be unsubstituted, but may have a substituent. Preferably, from Ar₁-Ar₄Is represented by C₆-C₃₀Of an aromatic hydrocarbon group or C₅-C₃₀Is substituted by one or more R¹Substituted, C₆-C₃₀Or by one or more R¹Substituted, C₅-C₃₀The aromatic heterocyclic group of (1).

Fourth, 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 C₁-C₂₀Alkyl, substituted or unsubstituted C₂-C₂₀Alkenyl of (a), substituted or unsubstituted C₂-C₂₀Alkynyl, substituted or unsubstituted C₆-C₄₀Or substituted or unsubstituted C₅-C₄₀The aromatic heterocyclic group of (1).

From R¹Is represented by C₁-C₂₀Alkyl groups of (a) 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. C₂-C₂₀The alkyl group of (a) may be linear, branched or cyclic.

From R¹Is represented by C₁-C₂₀The alkyl group of (a) may be unsubstituted, but may have a substituent. Preferably, from R¹Is represented by C₁-C₂₀By one or more of the following R²And (4) substitution. In addition, one or more non-adjacent CH in the alkyl group₂The radicals may be substituted 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 by a hydrogen atom having deuterium, fluorine, chlorine, bromine, iodine, cyano, nitro.

From R¹Is represented by C₂-C₂₀The alkenyl group of (a) may exemplify: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, 2-ethylhexenyl, allyl, or cyclohexenyl, and the like. C₂-C₂₀The alkenyl group of (a) may be linear, branched or cyclic.

From R¹Is represented by C₂-C₂₀The alkenyl group of (a) may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹Is represented by C₁-C₂₀The alkyl group of (1) may have the same substituent as shown in the substituent. The substituents may take the same pattern as that of the exemplary substituents.

From R¹Is represented by having C₂-C₂₀The alkynyl group of (a) may illustrate: ethynyl, isopropynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl and the like.

From R¹Is represented by C₂-C₂₀The alkynyl group of (a) may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹Is represented by C₁-C₂₀The alkyl group of (1) optionally having a substituentThe same substituents are shown. The substituents may take the same pattern as that of the exemplary substituents.

From R¹Is represented by C₆-C₄₀Of an aromatic hydrocarbon group or C₅-C₄₀The aromatic heterocyclic group of (A) may be exemplified by the aforementioned aromatic heterocyclic group represented by Ar₁-Ar₄Is represented by C₆-C₃₀Of an aromatic hydrocarbon group or C₅-C₃₀The aromatic heterocyclic group of (2) represents the same group.

From R¹Is represented by C₆-C₄₀Of an aromatic hydrocarbon group or C₅-C₄₀The aromatic heterocyclic group of (b) may be unsubstituted or may have a substituent. The substituents can be exemplified by the group consisting of R¹Is represented by C₁-C₂₀The alkyl group of (1) may have the same substituent as shown in the substituent. 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 R¹Is represented by C₆-C₄₀Of an aromatic hydrocarbon group or C₅-C₄₀The aromatic heterocyclic group of (b) may include: phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazolyl, benzofurocarbazolyl, benzofluorenocarbazolyl, benzanthracenyl, benzophenanthryl, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boron, triphenyl phosphonium, diphenyl phosphonium, triphenyl silicon, tetraphenyl silicon, and the like. Said C is₆-C₄₀Of an aromatic hydrocarbon group or C₅-C₄₀The aromatic heterocyclic group of (a) may be substituted by one or more R²And (4) substitution.

Fifth, R²：

From R²Is represented by C₁-C₂₀The alkyl groups of (A) can be exemplified by the aforementioned groups represented by R¹Is represented by C₁-C₂₀The alkyl groups of (a) represent the same groups.

From R²Is represented by C₆-C₃₀Or substituted or unsubstituted C₅-C₃₀The aromatic heterocyclic group of (A) may be mentioned as the above-mentioned group represented by R¹Is represented by C₆-C₃₀Or substituted or unsubstituted C₅-C₃₀The aromatic heterocyclic group of (2) represents the same group.

From R²Is represented by C₁-C₂₀Alkyl of (C)₆-C₃₀Or substituted or unsubstituted C₅-C₃₀The aromatic heterocyclic group of (a) may be unsubstituted or may 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.

Sixth, X:

x represents C₁-C₇Alkyl or a single bond.

Seventh, m and n:

m and n are each independently an integer of 0 to 5, and m and n are not both 0.

The preparation method comprises the following steps:

the cycloalkane-pyrimidine derivative of the present invention can be produced by the following method:

the obtained compound can be purified by purification using 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.

Specific examples of preferred compounds among the cycloalkane-pyrimidine derivatives of the present invention are shown below, but the present invention is by no means limited to these compounds:

an electronic device:

various electronic devices containing the cycloparaffinpyrimidine derivatives of the invention can be produced using the cycloparaffinpyrimidine derivatives according to the invention for producing organic materials which can be configured in particular in the form of layers. In particular, the cycloparaffin pyrimidine derivative can be used for organic electroluminescent devices, organic solar cells, organic diodes, 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 made, for example, by forming a layer containing or consisting of the naphthyropyrimidine derivative according to the present invention between electrodes. However, the use of the cycloalkane-pyrimidine type derivative according to the invention is not limited to the above-described exemplary embodiment.

Organic electroluminescent device:

the organic electroluminescent device of the present invention comprises: the organic electroluminescence 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 cycloalkane-pyrimidine derivative of the present invention.

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 (1). 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, an electrode material having a large work function, such as a metal of vanadium, chromium, copper, zinc, gold, or an alloy 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 hetero atom 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, a compound containing the cycloalkane-pyrimidine derivative of the present invention is preferably used. 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 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, a compound containing the cycloalkane-pyrimidine derivative of the present invention is preferably used. 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, or may be formed 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 cycloalkane pyrimidine derivative 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, a compound containing the cycloalkane-pyrimidine derivative of the present invention is preferably used. In addition to these, mCBP, mCP, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene 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, an aromatic amine derivative, a styryl amine compound, a boron complex, a fluoranthene compound, a metal complex, or the like can be used. Examples thereof include pyrene derivatives, anthracene derivatives, quinacridones, coumarins, rubrenes, perylenes and their derivatives, benzopyran 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, an ink jet method, or the like.

As the hole blocking layer of the organic electroluminescent device of the present invention, a compound containing the cycloalkane-pyrimidine derivative of the present invention is preferably used. 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 quinolol derivative such as aluminum (III) bis (2-methyl-8-hydroxyquinoline) -4-phenylphenate (BAlq), 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, an ink jet method, or the like.

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, a compound containing the cycloalkane-pyrimidine derivative of the present invention is preferably used. 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)An agent; 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.

The production of the compound represented by the above general formula (1) 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 compound 57:

(1) synthesis of intermediate 1-1:

the synthetic route of intermediate 1-1 is shown below:

in a 250mL single-neck flask were added trifluoromethanesulfonic anhydride (6.4g, 22.8mmol), 4-bromobenzonitrile (7.6 g, 42mmol) and 120mL of anhydrous dichloromethane in that order, and the mixture was stirred at room temperature for 30 min. A solution of 20mL cyclopentanone (1.7g, 20mmol) in dichloromethane was slowly added dropwise. After the dropwise addition, the reaction was continued at room temperature with stirring for 24 hours. After the reaction was completed, 50mL of a saturated sodium bicarbonate solution was carefully added to the system. The organic phase was separated and washed with brine. The organic phase is dried and concentrated to give a crude solid which is further purified by column chromatography (petroleum ether: dichloromethane ═ 1: 2 (V/V)). The solvent was evaporated and dried to give 6.2g of a white solid in 72% yield. Ms (ei): m/z: 430.02[ M ]⁺]。Anal.calcd for C₁₉H₁₄Br₂N₂(％)：C 53.05，H 3.28，N 6.51；found：C 53.02，H 3.30，N 6.48。

(2) Synthesis of compound 57:

the synthetic route for compound 57 is shown below:

under nitrogen protection, intermediate 1-1(2.1g, 5mmol), carbazole (1.8g, 11mmol), palladium acetate (22.4mg, 0.1mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25 mmol), sodium tert-butoxide (1.9g, 20mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). After evaporation of the solvent and drying, 2.3g of a white solid was obtained in 76% yield. Ms (ei): m/z: 602.38[ M ]⁺]。Anal.calcd for C₄₃H₃₀N₄(％)：C85.69，H 5.02，N 9.30；found：C 85.68，H 5.05， N 9.28。

Example 2: synthesis of compound 58:

the synthetic route for compound 58 is shown below:

under the protection of nitrogen, adding the intermediate 1-1(2.1g, 5mmol) and 7, 7-dimethyl-5, 7-dihydroindeno [2,1-b ] into a 250mL Schlenk bottle in sequence]Carbazole (3.0g, 10.4mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were reacted under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 3.0g of a white solid was obtained in a yield of 72%. Ms (ei): m/z: 834.76[ M ]⁺]。Anal.calcd for C₆₁H₄₆N₄(％)：C87.74， H 5.55，N 6.71；found：C 87.72，H 5.58，N 6.68。

The fluorescence spectrum of compound 58 in dichloromethane is shown in FIG. 1.

Example 3: synthesis of Compound 59

(1) Synthesis of intermediates 1-2:

the synthetic route of intermediate 1-2 is shown below:

in a 250mL single-neck flask were added trifluoromethanesulfonic anhydride (6.4g, 22.8mmol), 4-bromobenzonitrile (7.6 g, 42mmol) and 120mL of anhydrous dichloromethane in that order, and the mixture was stirred at room temperature for 30 min. A solution of 20mL cyclohexanone (2.0 g, 20mmol) in methylene chloride was slowly added dropwise. After the dropwise addition, the reaction was continued at room temperature with stirring for 24 hours. After the reaction was completed, 50mL of a saturated sodium bicarbonate solution was carefully added to the system. Is divided outThe organic phase was washed with brine. The organic phase is dried and concentrated to give a crude solid which is further purified by column chromatography (petroleum ether: dichloromethane ═ 1: 2 (V/V)). The solvent was evaporated and dried to give 6.2g of a white solid with a yield of 70%. Ms (ei): m/z: 444.05[ M ]⁺]。Anal.calcd for C₂₀H₁₆Br₂N₂(％)：C 54.08，H 4.63，N 6.31；found：C 54.06，H 4.66，N 6.28。

(2) Synthesis of compound 59:

the synthetic route for compound 59 is shown below:

under the protection of nitrogen, the intermediates 1-2(2.2g, 5mmol) and 5-phenyl-5, 7-dihydroindeno [2,3-b ] are added in sequence into a 250mL Schlenk bottle]Carbazole (3.4g, 10.4mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were reacted under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 3.3g of a white solid was obtained in a yield of 69%. Ms (ei): m/z: 947.06[ M ]⁺]。Anal.calcd for C₆₈H₄₆N₆(％)：C 86.23， H 4.90，N 8.87；found：C 86.20，H 4.92，N 8.84。

Example 4: synthesis of Compound 1

(1) Synthesis of intermediates 1 to 3:

the synthetic route of intermediates 1-3 is shown below:

to a 250mL single neck flask was added sequentially trifluoromethanesulfonic anhydride (6.4g,22.8mmol), 4-bromobenzonitrile (7.6 g, 42mmol) and 120mL of anhydrous dichloromethane were stirred at room temperature for 30 min. A solution of 20mL cyclobutanone (1.4 g, 20mmol) in methylene chloride was slowly added dropwise. After the dropwise addition, the reaction was continued at room temperature with stirring for 24 hours. After the reaction was completed, 50mL of a saturated sodium bicarbonate solution was carefully added to the system. The organic phase was separated and washed with brine. The organic phase is dried and concentrated to give a crude solid which is further purified by column chromatography (petroleum ether: dichloromethane ═ 1: 2 (V/V)). The solvent was evaporated and dried to give 6.0g of a white solid in 72% yield. Ms (ei): m/z: 416.05[ M ]⁺]。Anal.calcd for C₁₈H₁₂Br₂N₂(％)：C 51.96，H 2.91，N 6.73；found：C 51.90，H 2.88，N 6.70。

(2) Synthesis of Compound 1:

the synthetic route for compound 1 is shown below:

under nitrogen protection, intermediate 1-2(2.1g, 5mmol), diphenylamine (1.7g, 10.4mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). After evaporation of the solvent and drying, 2.5g of a white solid was obtained in 85% yield. Ms (ei): m/z: 592.06[ M ]⁺]。Anal.calcd for C₄₂H₃₂N₄(％)：C 85.11，H 5.44，N 9.45；found：C 85.10， H 5.43，N 9.42。

Example 5: synthesis of Compound 60

(1) Synthesis of intermediates 1 to 4:

the synthetic routes for intermediates 1-4 are shown below:

in a 250mL single-neck flask were added trifluoromethanesulfonic anhydride (6.4g, 22.8mmol), 4-bromobenzonitrile (7.6 g, 42mmol) and 120mL of anhydrous dichloromethane in that order, and the mixture was stirred at room temperature for 30 min. A solution of 20mL cycloheptanone (2.2g, 20mmol) in methylene chloride was slowly added dropwise. After the dropwise addition, the reaction was continued at room temperature with stirring for 24 hours. After the reaction was completed, 50mL of a saturated sodium bicarbonate solution was carefully added to the system. The organic phase was separated and washed with brine. The organic phase is dried and concentrated to give a crude solid which is further purified by column chromatography (petroleum ether: dichloromethane ═ 1: 2 (V/V)). The solvent was evaporated and dried to give 6.0g of a white solid in 65% yield. Ms (ei): m/z: 458.02[ M ]⁺]。Anal.calcd for C₂₁H₁₈Br₂N₂(％)：C 55.05，H 3.96，N 6.11；found：C 55.02，H 3.95，N 6.06。

The synthetic route for compound 60 is shown below:

under the protection of nitrogen, adding the intermediate 1-1(2.3g, 5mmol) and 7, 7-dimethyl-5, 7-dihydroindeno [2,1-b ] into a 250mL Schlenk bottle in sequence]Carbazole (3.0g, 10.4mmol), palladium acetate (11mg, 0.05mmol), tri-tert-butylphosphine tetrafluoroborate (29mg, 0.1mmol), sodium tert-butoxide (960mg, 10mmol) and 120mL of toluene were reacted under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 3.5g of a white solid was obtained in a yield of 73%. Ms (ei): m/z: 960.38[ M ]⁺]。Anal.calcd for C₆₉H₄₉N₆(％)：C 86.22，H 5.03， N 8.74；found：C 86.11，H 5.00，N 8.72。

Example 6

Synthesis of compound 62:

(1) synthesis of intermediates 1 to 5:

the synthetic routes for intermediates 1-5 are shown below:

in a 250mL single-neck flask were added trifluoromethanesulfonic anhydride (6.4g, 22.8mmol), m-bromobenzonitrile (7.6 g, 42mmol) and 120mL of anhydrous dichloromethane in that order, and the mixture was stirred at room temperature for 30 min. A solution of 20mL cyclopentanone (1.7g, 20mmol) in dichloromethane was slowly added dropwise. After the dropwise addition, the reaction was continued at room temperature with stirring for 24 hours. After the reaction was completed, 50mL of a saturated sodium bicarbonate solution was carefully added to the system. The organic phase was separated and washed with brine. The organic phase is dried and concentrated to give a crude solid which is further purified by column chromatography (petroleum ether: dichloromethane ═ 1: 2 (V/V)). The solvent was evaporated and dried to give 6.2g of a white solid in 72% yield. Ms (ei): m/z: 430.05[ M ]⁺]。Anal.calcd for C₁₉H₁₄Br₂N₂(％)：C 53.05，H 3.28，N 6.51；found：C 52.98，H 3.26，N 6.47。

(2) Synthesis of compound 62:

the synthetic route for compound 62 is shown below:

under nitrogen protection, intermediates 1 to 5(2.1g, 5mmol), carbazole (1.8g, 11mmol), palladium acetate (22.4mg, 0.1mmol), tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25 mmol), sodium tert-butoxide (1.9g, 20mmol) and 120mL of toluene were added in this order to a 250mL Schlenk flask, and the reaction was stirred under reflux for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. Evaporating off the solventAfter that, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). After evaporation of the solvent and drying, 2.3g of a white solid was obtained in 76% yield. Ms (ei): m/z: 602.26[ M ]⁺]。Anal.calcd for C₄₃H₃₀N₄(％)：C 85.69，H 5.02，N 9.30；found：C 85.56，H 5.00， N 9.25。

Example 7

Synthesis of compound 66:

(1) synthesis of intermediates 1 to 6:

the synthetic routes for intermediates 1-6 are shown below:

in a 250mL single-neck flask were added trifluoromethanesulfonic anhydride (6.4g, 22.8mmol), 2-bromobenzonitrile (7.6 g, 42mmol) and 120mL of anhydrous dichloromethane in that order, and the mixture was stirred at room temperature for 30 min. A solution of 20mL cyclopentanone (1.7g, 20mmol) in dichloromethane was slowly added dropwise. After the dropwise addition, the reaction was continued at room temperature with stirring for 24 hours. After the reaction was completed, 50mL of a saturated sodium bicarbonate solution was carefully added to the system. The organic phase was separated and washed with brine. The organic phase is dried and concentrated to give a crude solid which is further purified by column chromatography (petroleum ether: dichloromethane ═ 1: 2 (V/V)). The solvent was evaporated and dried to give 6.0g of a white solid with a yield of 70%. Ms (ei): m/z: 430.14[ M ]⁺]。Anal.calcd for C₁₉H₁₄Br₂N₂(％)：C 53.05，H 3.28，N 6.51；found：C 53.03，H 3.28，N 6.50。

(2) Synthesis of compound 66:

the synthetic route for compound 66 is shown below:

under the protection of nitrogen, 1-6(2.1g, 5mmol) of intermediate, 1.8g, 11mmol of carbazole, 22.4mg, 0.1mmol of palladium acetate and the like are sequentially added into a 250mL Schlenk bottle,Tri-tert-butylphosphine tetrafluoroborate (73mg, 0.25 mmol), sodium tert-butoxide (1.9g, 20mmol) and 120mL of toluene were reacted under reflux with stirring for 12 hours. After the reaction was completed, the solvent was distilled off, the residue was dissolved in 200mL of methylene chloride and 50mL of water, washed with water, the organic layer was separated, the aqueous layer was extracted twice with 15mL of methylene chloride, and the organic layers were combined. After the solvent was distilled off, the residue was separated by column chromatography (petroleum ether: dichloromethane ═ 2: 1 (V/V)). The solvent was distilled off, and after drying, 2.2g of a white solid was obtained in a yield of 73%. Ms (ei): m/z: 602.44[ M ]⁺]。Anal.calcd for C₄₃H₃₀N₄(％)：C 85.69，H 5.02，N 9.30；found：C 85.59，H 5.02， N 9.28。

Example 8: preparation of organic electroluminescent device 1 (organic EL device 1):

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 were sequentially formed on a transparent anode 2 previously formed on a glass substrate 1 to prepare an organic electroluminescent device as shown in fig. 3.

Specifically, a glass substrate on which an ITO film having a film thickness of 100nm was formed was subjected to ultrasonic treatment in a Decon90 alkaline cleaning solution, rinsed in deionized water, washed three times in acetone and ethanol, baked in a clean environment to completely remove moisture, cleaned with ultraviolet light and ozone, and bombarded on the surface with a low-energy cation beam. Placing the glass substrate with ITO electrode into a vacuum chamber, and vacuumizing to 4 × 10^-4-2×10^-5Pa. Then, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN) was deposited on the ITO electrode-equipped glass substrate at a deposition rate of 0.2 nm/sec to form a layer having a film thickness of 10nm as a hole injection layer. N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was vapor-deposited over the hole injection layer at a vapor deposition rate of 0.2nm/s to form a layer having a film thickness of 40nm as a hole transport layer. 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl (mCBP) was deposited on the hole transport layer at a deposition rate of 0.2nm/s to form a layer having a thickness of 10nm as an Electron Blocking Layer (EBL). Over the electron blocking layer, with the compound of example 1 (compound) as the host materialSubstance 57) was subjected to double-source co-evaporation at a deposition rate of 0.2nm/s and a deposition rate of 0.16nm/s for GD1 as a dopant material to form a layer having a thickness of 20nm as a light-emitting layer, and the proportion by weight of the dopant in GD1 was 8 wt%. Above the light-emitting layer, aluminum (III) bis (2-methyl-8-quinolinolato) -4-phenylphenolate (BALq) was evaporated at an evaporation rate of 0.2nm/s to form a layer having a film thickness of 10nm as a hole-blocking layer (HBL). Above the hole-blocking layer, BALq was evaporated at an evaporation rate of 0.2nm/s to form a layer having a film thickness of 40nm as an electron-transporting layer (ETL). 8-hydroxyquinoline-lithium (Liq) was vapor-deposited over the electron transport layer at a vapor deposition rate of 0.1nm/s to form a layer having a film thickness of 2nm as an electron injection layer. Finally, aluminum is deposited at a deposition rate of 0.5nm/s or more to form a cathode having a film thickness of 100 nm.

Examples 9 to 23: preparation of organic EL devices 2-16

Organic EL devices, denoted as organic EL devices 2 to 16, were fabricated under the same conditions as organic EL device 1, except that the compounds in table 1 below were used instead of the compounds in each layer of example 8, respectively.

Comparative examples 1 to 2: preparation of organic EL devices 17-18

An organic EL device 17 and an organic EL device 18 were each produced under the same conditions as the organic EL device 1 except that the compounds in table 1 below were used instead of the compounds in each layer of example 6.

The examples and comparative examples relate to the following structures of compounds:

TABLE 1 selection of materials for respective layers in organic EL devices prepared in examples 8 to 23 and comparative examples 1 to 2

The light emission characteristics of the organic EL devices 1 to 10 produced in examples 6 to 15 and the organic EL devices 11 to 12 produced in comparative examples 1 to 2 were measured at normal temperature in the atmosphere when a direct-current voltage was applied. The measurement results are shown in table 2.

The current-luminance-voltage characteristics of the device were obtained from a Keithley source measuring system (Keithley 2400 Sourcemeter, Keithley 2000 Currentmeter) with calibrated silicon photodiodes, the electroluminescence spectra were measured by a Photo research PR655 spectrometer, and the external quantum efficiencies of the devices were calculated by the method of the documents adv.mater, 2003,15, 1043-.

The lifetime of the device was measured as: the emission luminance (initial luminance) at the start of light emission was set to 10000cd/m²Constant current driving is performed until the light emission luminance decays to 9500cd/m²(corresponding to 95%, where the initial brightness is taken as 100%: 95% decay). Device lifetime with GD1 as dopant is in the order of 10000cd/m²For initial luminance, attenuation to 9500cd/m²(corresponding to 95%, where the initial brightness is taken as 100%: 95% decay). The lifetime of the device with 4CzIPN as dopant is 10000cd/m²For initial luminance, attenuation to 9500cd/m²(corresponding to 95% where the initial brightness is taken as 100%: 95% decay). All devices were encapsulated in a nitrogen atmosphere.

TABLE 2 test results of light emitting characteristics of the organic EL devices prepared in examples 8 to 23 and comparative examples 1 to 2

As can be seen from Table 2, the cycloparaffin pyrimidine derivatives of the present invention gave excellent performance data.

The organic EL devices 18 and 6 used GD1 as a dopant, and the host material constituting the organic EL device 6 was the compound 59 of the present invention. As can be seen from the comparison of the device performance data, the organic EL device 6 has a lower operating voltage, the external quantum efficiency is relatively improved by about 17%, and the device life (95%) is also significantly longer.

In addition, both the organic EL device 17 and the organic EL device 5 adopt 4CzIPN as a dopant, the host material of the organic EL device 5 is the compound 59 of the present invention, and the organic EL device 5 has a longer device life as can be seen from a comparison of device performance data.

Compared with the common materials in the prior art, the cycloparaffin pyrimidine derivative can effectively reduce the working voltage, improve the external quantum efficiency and prolong the service life of devices.

The electroluminescence spectra of the

organic EL devices

5,6, 17, and 18 are shown in fig. 2.

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.

Industrial applicability:

the cycloparaffin pyrimidine derivative has excellent luminous efficiency, long service life and low driving voltage. Therefore, an organic electroluminescent device having an excellent lifetime can be prepared from the compound.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit of the present invention are included in the scope of the present invention.

Claims

1. A cycloparaffinopyrimidine derivative characterized in that: which is represented by the following general formula (1):

A₁and A₂Each independently selected from Ar₁、Ar₂、

One or more of;

x represents C₁-C₇Alkyl or a single bond of (a);

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)₃Substituted or unsubstituted C₁-C₂₀Alkyl, substituted or unsubstituted C₂-C₂₀Alkenyl of (a), substituted or unsubstituted C₂-C₂₀Alkynyl, substituted or unsubstituted C₆-C₄₀Or substituted or unsubstituted C₅-C₄₀The aromatic heterocyclic group of (1);

2. The cycloalkane-pyrimidine derivative according to claim 1, wherein: the cycloparaffin pyrimidine derivative is represented by the following general formula (I) and/or (II):

3. the cycloalkane-pyrimidine derivative according to claim 1, wherein: ar (Ar)₁、Ar₂、Ar₃And Ar₄Each independently selected from one or more of the following groups:

wherein the dotted line represents and L₁、L₂Or an N-bonded bond.

4. As claimed in claim 1The cycloparaffin pyrimidine derivative is characterized in that: r¹And R²Each independently selected from one or more of phenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, benzothienocarbazole, benzofurocarbazole, benzofluorenocarbazole, benzanthracene, triphenylene, fluorenyl, spirobifluorenyl, triazinyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, indenocarbazolyl, benzimidazolyl, diphenyl-oxadiazolyl, diphenyl boronyl, triphenyl phosphoroxy, diphenyl phosphoroxy, triphenyl silyl, or tetraphenyl silyl.

5. The cycloalkane-pyrimidine derivative according to claim 1, wherein: the cycloalkane pyrimidine derivative represented by the general formula (1) is selected from one or more of the following compounds:

6. a process for producing the cycloalkane-pyrimidine derivative according to any one of claims 1 to 5, wherein: the chemical reaction equation in the preparation method is as follows:

7. the process for producing a cycloalkane-pyrimidine derivative according to claim 6, wherein: and after the chemical reaction is finished, purifying the reaction product, wherein the purification treatment comprises one or more of column chromatography, adsorption purification, crystallization, recrystallization and sublimation purification.

8. An electronic device produced by using the cycloalkane-pyrimidine derivative produced by the production process according to claim 7.

9. The electronic device of claim 8, 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: the organic electroluminescence 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 contains a cycloalkane-pyrimidine derivative.

10. The electronic device of claim 9, 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.