CN114057711A - Anthracene ketone spiro derivative and preparation method and application thereof - Google Patents

Anthracene ketone spiro derivative and preparation method and application thereof Download PDF

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CN114057711A
CN114057711A CN202010749708.2A CN202010749708A CN114057711A CN 114057711 A CN114057711 A CN 114057711A CN 202010749708 A CN202010749708 A CN 202010749708A CN 114057711 A CN114057711 A CN 114057711A
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phenanthroline
group
anthrone
spirocyclic
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王鹰
王瑞芳
胡晓晓
高洪磊
高腾
董相宇
汪鹏飞
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention discloses a spiro derivative of anthrone and a preparation method and application thereof. The structure of the spirocyclic derivative of the anthroneThe general formula is:
Figure DDA0002609607910000011
wherein X is a carbon atom, a carbonyl group, a sulfur atom or a sulfonyl group; r1、R2、R3And R4Independently selected from at least one of hydrogen atom, aryl group with 6 to 30 carbon atoms, substituted aryl group with 6 to 30 carbon atoms and heterocyclic aryl group with 5 to 50 carbon atoms, which are same or different and have electron donating capability, when X is sulfur atom or sulfonyl group, R is3、R4Not a hydrogen atom. The spirocyclic derivative of the anthrone has excellent fluorescence property, and can obviously improve the efficiency of the device when being used as a luminescent layer of an organic electroluminescent diode.

Description

Anthracene ketone spiro derivative and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent display. More particularly, relates to a spirocyclic derivative of anthrone and a preparation method and application thereof.
Background
An organic light-emitting diode (OLED) is a display device which utilizes the recombination of electrons and holes in an organic film to emit light. Currently, research on OLEDs is receiving attention both in the academic world and in the industrial field.
In the structure of an OLED, the light emitting layer material, as one of the important components in an OLED device, can directly affect the performance of the device. OLED emissive materials have undergone a progression from fluorescent to phosphorescent materials, and have achieved high exciton utilization and device efficiencies in excess of 20%. However, the phosphorescent material introduces a transition metal element, so that the device cost is increased, and the phosphorescent OLED device has the problems of obvious efficiency roll-off, lack of a blue phosphorescent material and the like. In 2012, the Adachi project group used pure organic small molecules with Thermally Activated Delayed Fluorescence (TADF) properties for the preparation of high efficiency OLED devices. Since then, it has become a hot research topic in recent years that OLED devices based on D-a type TADF materials for intramolecular charge transfer can achieve both low cost and high efficiency. With the continuous development of TADF material diversification and device structure simplification, stability becomes a major problem facing such devices. Among them, the stability of the luminescent material and the long lifetime of the delayed fluorescence become two problems that need to be solved in this type of device.
The spiro aromatic compound has a larger conjugated system and a special spiro conjugated effect, and the special structural characteristic not only endows the material with good thermal stability, but also avoids the crystallization of molecules in the film forming process, improves the morphological stability of the material, and can effectively improve the stability of an OLED device. In addition, the sp which breaks the conjugation in the spiro structure3The existence of carbon atoms and a rigid structure formed by two mutually vertical groups can effectively inhibit the interaction of pi electrons in two systems, so that the material has good solubility. Based on these unique advantages, materials of spiro systems have been widely used in the fields of various photoelectric devices such as OLEDs, OPVs (organic photovoltaic solar cells), and the like.
Disclosure of Invention
The invention aims to provide the spirocyclic derivative of the anthrone, which realizes luminescent materials with different colors and different performances by selecting donor groups with different electron donating capabilities.
The second object of the present invention is to provide a process for producing the above spirocyclic derivative of an anthrone.
The third purpose of the invention is to provide an application of the spirocyclic derivative of the anthrone.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a spirocyclic derivative of an anthrone, wherein the structural general formula of the spirocyclic derivative of an anthrone is as follows:
Figure BDA0002609607900000021
wherein X is a carbon atom, a carbonyl group, a sulfur atom or a sulfonyl group; that is, the above formula may be the following structural formulas:
Figure BDA0002609607900000022
R1、R2、R3and R4Independently selected from at least one of a hydrogen atom, an aryl group of 6 to 30 carbon atoms having an electron donating ability, a substituted aryl group of 6 to 30 carbon atoms, a heterocyclic aryl group of 5 to 50 carbon atoms, which may be the same or different; when X is a sulfur atom or a sulfonyl group, R3、R4Not a hydrogen atom.
The spirocyclic derivative of the anthrone has excellent fluorescence property, and can obviously improve the efficiency of the device when used as a luminescent layer of an organic electroluminescent diode.
Based on the spirocyclic derivative of anthrone, preferably, the aryl group with 6 to 30 carbon atoms is selected from at least one of perylene group, pyrenyl group, fluorenyl group and spirobifluorenyl group;
the substituted aryl group with 6 to 30 carbon atoms is selected from at least one of o-tolyl, m-tolyl, p-tolyl, xylyl, o-cumyl, m-cumyl, p-cumyl, trimethylphenyl and 9, 9' -dimethylfluorenyl;
the heterocyclic aryl group of 5 to 50 carbon atoms is selected from the group consisting of 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl, Dibenzofuran-2-yl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 3-carbazolyl, 9-carbazolyl, N-phenylcarbazolyl, 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-dimethyl-9, 10-dihydroacridinyl, 1, 7-phenanthrolin-2-yl, 1, 7-phenanthrolin-3-yl, 1, 7-phenanthrolin-4-yl, 1, 7-phenanthrolin-5-yl, 1, 7-phenanthrolin-6-yl, 1, 7-phenanthrolin-8-yl, 1-phenanthrolin-6-yl, 1, 7-phenanthroline-9-yl group, 1, 7-phenanthroline-10-yl group, 1, 8-phenanthroline-2-yl group, 1, 8-phenanthroline-3-yl group, 1, 8-phenanthroline-4-yl group, 1, 8-phenanthroline-5-yl group, 1, 8-phenanthroline-6-yl group, 1, 8-phenanthroline-7-yl group, 1, 8-phenanthroline-9-yl group, 1, 8-phenanthroline-10-yl group, 1, 9-phenanthroline-2-yl group, 1, 9-phenanthroline-3-yl group, 1, 9-phenanthroline-4-yl group, 1, 9-phenanthroline-5-yl group, 1, 9-phenanthroline-6-yl group, 1, 9-phenanthroline-7-yl group, 1, 9-phenanthroline-8-yl group, 1, 9-phenanthroline-10-yl group, 1, 10-phenanthroline-2-yl group, 1, 10-phenanthroline-3-yl group, 1, 10-phenanthroline-4-yl group, 1, 10-phenanthroline-5-yl group, 2, 9-phenanthroline-1-yl group, 2, 9-phenanthroline-3-yl group, 2, 9-phenanthroline-4-yl group, 2, 9-phenanthroline-5-yl group, 2, 9-phenanthroline-6-yl group, 2, 9-phenanthroline-7-yl group, 2, 9-phenanthroline-8-yl group, 2, 9-phenanthroline-10-yl group, 2, 2, 8-phenanthroline-1-yl, 2, 8-phenanthroline-3-yl, 2, 8-phenanthroline-4-yl, 2, 8-phenanthroline-5-yl, 2, 8-phenanthroline-6-yl, 2, 8-phenanthroline-7-yl, 2, 8-phenanthroline-9-yl, 2, 8-phenanthroline-10-yl, 2, 7-phenanthroline-1-yl, 2, 7-phenanthroline-3-yl, 2, 7-phenanthroline-4-yl, 2, 7-phenanthroline-5-yl, 2, 7-phenanthroline-6-yl, 2, 7-phenanthroline-8-yl, 2, 7-phenanthroline-9-yl, 2, 7-phenanthroline-10-yl, 1-phenothiazinyl, 2-phenazinyl, phenothiazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, 10-phenothiazinyl, phenoxazinyl, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazanyl, 2-thienyl, 3-thienyl, dibenzothiophen-2-yl.
In a preferred embodiment of the present invention, R1、R2、R3And R4And is selected from aryl of 6 to 30 carbon atoms, substituted aryl of 6 to 30 carbon atoms or heterocyclic aryl of 5 to 50 carbon atoms having electron donating ability.
In this preferred embodiment, the structural formula of the spirocyclic derivative of an anthrone is shown as follows:
Figure BDA0002609607900000031
in this preferred embodiment, preferably, R1、R2、R3And R4And (b) are selected from carbazole, perylenyl, pyrenyl, fluorenyl, spirobifluorenyl, phenothiazinyl and N-phenylcarbazolyl.
In a preferred embodiment of the present invention, the structural formula of the spirocyclic derivative of an anthrone is as follows:
Figure BDA0002609607900000041
Figure BDA0002609607900000051
Figure BDA0002609607900000061
Figure BDA0002609607900000071
Figure BDA0002609607900000081
in a second aspect, the present invention provides a method for preparing one or more spirocyclic derivatives of anthrones, comprising the steps of:
(1) the intermediate for synthesizing the spirocyclic derivatives of the anthrones has any one of the following structural formulas of 1-6 and 9-16:
Figure BDA0002609607900000082
(2) the above intermediates and the compounds having R1Or R2Suzuki reaction of substituted pinacol borate or reaction with R-bearing boronic acid pinacol ester1Or R2And (3) carrying out Ullmann reaction on the nitrogen-containing heterocyclic compound of the substituent group to obtain the spirocyclic derivatives of the anthrone.
In a third aspect, the invention provides an application of the spirocyclic derivative of more than one anthrone in an organic electroluminescent device.
Based on the application of the present invention, preferably, the organic electroluminescent device is an organic electroluminescent device based on thermally activated delayed fluorescence.
Based on the application of the present invention, preferably, the organic light emitting layer of the organic electroluminescent device is a spiro derivative of the above anthrones or a mixture thereof with 1, 3-dicarbazolylbenzene (MCP).
In a specific embodiment of the present invention, the organic electroluminescent device has a structure that: substrate-anode-hole transport layer-organic light emitting layer-electron transport layer-cathode;
wherein the organic light-emitting layer is a mixture of a spiro derivative of the above anthrones and MCP; the substrate is one of glass, polyester and polyimide compounds; the anode is one of indium tin oxide, zinc oxide, tin zinc oxide, gold, silver, copper, polythiophene/sodium polyvinyl benzene sulfonate and polyaniline; the hole transport layer is made of triarylamine materials; the electron transport layer is a nitrogen heterocyclic material; the cathode is an electrode layer formed by lithium, magnesium, calcium, strontium, aluminum or indium, or an alloy of one of the above and copper, gold or silver, or the above metal or alloy and metal fluoride alternately.
The invention has the following beneficial effects:
1. the spirocyclic derivative of the anthrone of the invention is prepared by introducing different electron donating groups R1-R4Can improve the carrier transmission characteristics of the material, and can effectively separate the highest occupied orbit of the spirocyclic derivative of the anthrone through group modification with different electron donating abilitiesThe (HOMO) level and the lowest unoccupied orbital (LUMO) level not only reduce the energy level difference between the singlet state and the triplet state, but also can realize light emission with different efficiencies, thereby preparing a high-efficiency organic electroluminescent device.
2. Due to the unique spiro structure of the spirocyclic derivative of the anthrone, the chemical stability and the morphological stability of the material are improved, so that the prepared organic electroluminescent device has higher stability; in addition, the material is endowed with better solubility due to a more symmetrical molecular configuration.
3. The synthetic method adopted by the spirocyclic derivatives of anthrones is simple and convenient, is easy to operate, and is convenient for researching the structure-performance relationship.
4. The thermally activated delayed fluorescence organic electroluminescent device prepared by using the spirocyclic derivative of anthrone as the guest luminescent material has the excellent performances of high efficiency and low efficiency roll-off.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, the following detailed description of the embodiments of the present invention is provided.
It is noted that all numerical designations of the invention (e.g., temperature, time, concentration, weight, and the like, including ranges for each) may generally be approximations that vary (+) or (-) by increments of 0.1 or 1.0, as appropriate. All numerical designations should be understood as preceded by the term "about".
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
This example synthesizes intermediates 1 and 3
Preparation of intermediate M3:
the reaction equation is as follows:
Figure BDA0002609607900000091
1, 4-dibromo-2-nitrobenzene (14.0g,50mmol), p-bromothiophenol (8.46g,45mmol) and potassium carbonate (6.8g) were dissolved in 10mL of DMF, heated to 120 ℃ and refluxed for 10min, cooled to room temperature, distilled water was added to precipitate, the precipitate was obtained by suction filtration, dried in a vacuum oven overnight, and column chromatography was carried out to obtain 18.5g of a yellow solid M1.
Intermediate M1(18.5g,47.5mmol) and zinc dust (9.26g,0.14mol) were added to 60mL of methanol, heated to 65 ℃ and stirred under reflux for 3h, cooled to room temperature, methanol was added, the filtrate was suction filtered over celite to give 15.4g of M2 as a white solid which was spin-dried.
M2(8.9g,24.8mmol) was dissolved in acetonitrile (240mL) under ice bath conditions, hydrochloric acid (10mL) was added dropwise with stirring, and then a mixed aqueous solution of sodium nitrite (3.43g,49.7mmol) and potassium iodide (10.3g,62.1mmol) was added dropwise to the above solution. After the completion of the dropwise addition, the reaction was carried out at room temperature for 2 hours. After completion of the reaction, the reaction was quenched with saturated sodium thiosulfate (20mL), and extracted three times with dichloromethane. The organic phases were combined and washed three times with deionized water and dried over anhydrous sodium sulfate. After removal of the organic solvent by rotary evaporation, the crude product was purified by column chromatography (n-hexane) to give the white crystalline product M3.
Preparation of intermediate M6:
the reaction equation is as follows:
Figure BDA0002609607900000101
anthrone (21.25g,0.11mol) was gradually added to 142mL of fuming nitric acid coolant (5 ℃ C.) with constant stirring, the addition was completed after about 1.5h, the reaction was added to 430mL of glacial acetic acid as the reaction was gradually raised to room temperature, and the reaction was allowed to stand for one week in a steady state after the stopper was closed. After the reaction, the precipitate was collected by filtration, washed three times with glacial acetic acid and n-hexane, respectively, and then dried. The crude product was dispersed in 4L of glacial acetic acid, heated under reflux for about 2h to remove nitrous acid, the mixture was cooled to room temperature and left to stand for 48h, the final precipitate was collected by filtration and washed three times with glacial acetic acid and n-hexane, respectively, to give M4(10.34g) as a pale yellow solid.
While stirring, Na was added dropwise to an aqueous solution of M4(9.4g,31.5mmol) in NaOH (13.5g,0.5M)2S·9H2O (31.4g,142mmol) in ethanol (340mL) was then heated at reflux for 6 h. After the reaction was completed, the reaction mixture was cooled to room temperature, allowed to stand overnight, spin-dried with ethanol and then suction-filtered, and the precipitate was collected, washed with distilled water several times, dried and recrystallized with ethanol/water to give M5(10.34g) as an orange solid.
Respectively adding anhydrous copper bromide (I) (6.8g,30.5mmol), tert-butyl nitrite (4.3mL,36mmol) and 150mL of anhydrous acetonitrile into a round-bottom three-necked bottle, heating the mixture to 65 ℃, slowly adding M5(2.9g, 12mmol) into the mixed solution within 5min, after the reaction is finished, cooling the reactant to room temperature, pouring the cooled reactant into a hydrochloric acid solution (100mL, 20% w/v), filtering, collecting a solid product, washing the solid product with diethyl ether for multiple times, and purifying the crude product by column chromatography (normal hexane/dichloromethane) to obtain a pale yellow solid M6(2.6 g).
Preparation of intermediate 1:
the reaction equation is as follows:
Figure BDA0002609607900000111
m3(1.41g,3mmol) was placed in a two-necked flask, and after evacuation by nitrogen, it was dissolved in 20mL of anhydrous THF, cooled to-78 deg.C, n-BuLi (1.25mL,2.4M) was added dropwise with stirring, after reacting at low temperature for 1h, a solution of M6(1mg,2.7mmol) in THF was added dropwise, and after completion of the addition, the reaction was gradually returned to room temperature overnight. After the reaction is finished, NH is used4The reaction was quenched with saturated aqueous Cl and extracted three times with dichloromethane. The organic phases were combined and washed three times with deionized water and dried over anhydrous sodium sulfate. After removing the organic solvent by rotary evaporation, directly adding 10mL of acetic acid and 2mL of methanesulfonic acid without further purification to obtain a crude product, heating and refluxing for 2h, cooling after the reaction is finished, adding water to precipitate, and purifying the crude product obtained by suction filtration by column chromatography (normal hexane/dichloromethane) to obtain an intermediate 1(0.83 g).
Preparation of intermediate 3:
Figure BDA0002609607900000112
the obtained intermediate 1(1.38g,2mmol) was dissolved in dichloromethane (30mL), a dichloromethane solution (10mL) of m-chloroperoxybenzoic acid (413mg,2.4mmol) was added dropwise under ice bath conditions, the reaction was moved to room temperature after completion of the dropwise addition and stirred overnight, the reaction was terminated, the solvent was spin-dried under reduced pressure, and column chromatography was performed to obtain intermediate 3(1.20 g).
Example 2
This example is the preparation of spiro derivatives of anthrones of the formulae Comp-1 and Comp-2:
Figure BDA0002609607900000121
adding the intermediate 1(1.38g and 2mmol) or the intermediate 3(1.45mg and 2mmol) obtained in example 1, N-phenylcarbazole pinacol borate (2.5g and 8.8mmol) into a 100mL double-neck bottle, adding a catalyst of 50mg of palladium tetratriphenylphosphine and potassium carbonate aqueous solution (20mL and 2M) and a toluene solvent 50mL, refluxing for 10h under the protection of nitrogen, removing the solvent under reduced pressure, extracting with dichloromethane and water, combining organic phases, evaporating the solvent under reduced pressure, and carrying out column chromatography to obtain the spirocyclic derivatives Comp-1 and Comp-2 of the anthrone.
Example 3
This example preparation of spirocyclic derivatives of anthrones of the formulae Comp-3 and Comp-4:
Figure BDA0002609607900000122
the spirobifluorene-3-boronic acid pinacol ester was used in place of the N-phenylcarbazole pinacol ester boronic acid pinacol ester in the same manner as in example 2 to obtain the spirocyclic derivatives Comp-3 and Comp-4 of anthrone.
Example 4
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-5 and Comp-6:
Figure BDA0002609607900000123
the same procedure as in example 2 was repeated except that the 1-pyrenyl pinacol borate was used in place of the N-phenylcarbazole pinacol borate to obtain the spirocyclic derivatives Comp-5 and Comp-6 of the anthrone type.
Example 5
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-7 and Comp-8:
Figure BDA0002609607900000131
in the same manner as in example 2, the pinacol ester of N-phenylcarbazole borate was replaced by the pinacol ester of 3-peryleneboronic acid to obtain the spirocyclic derivatives Comp-7 and Comp-8 of anthrone.
Example 6
This example is the preparation of spiro derivatives of anthrones of the formulae Comp-9 and Comp-10:
Figure BDA0002609607900000132
in the same manner as in example 2, triphenylamine pinacol borate was used in place of N-phenylcarbazole pinacol borate to obtain spirocyclic derivatives of anthrone, Comp-9 and Comp-10.
Example 7
This example, the preparation of spiro derivatives of anthrones of the structural formulae Comp-11 and Comp-12, includes:
preparation of intermediates 2 and 4:
Figure BDA0002609607900000133
synthesis of intermediate 2 similar to that of intermediate 1 of example 1, intermediate M6 was replaced with M7 to afford intermediate 2.
Synthesis of intermediate 4 the same as for intermediate 3 of example 1 was used to replace intermediate 1 with intermediate 2 to give intermediate 4.
This example is the preparation of spirocyclic derivatives based on anthrones of the formulae Comp-11 and Comp-12:
Figure BDA0002609607900000141
intermediate 2 or intermediate 4 was used in place of intermediate 1 or intermediate 3 in the same manner as in example 2 to give anthracenone spiro derivatives Comp-11 and Comp-12.
Example 8
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-13 and Comp-14:
Figure BDA0002609607900000142
in the same manner as in example 2, intermediate 2 or intermediate 4 was used instead of intermediate 1 or intermediate 3, and triphenylamine pinacol borate was used instead of N-phenylcarbazole pinacol borate to obtain spirocyclic derivatives of anthrone, Comp-13 and Comp-14.
Example 9
This example, the preparation of spiro derivatives of anthrones of the structural formulae Comp-15 and Comp-16, involves the following procedure:
preparation of intermediates 5 and 6:
Figure BDA0002609607900000143
synthesis of intermediate 5, same as that of intermediate 1 in example 1, intermediate M3 was replaced with 2-iodophenylphenylsulfane to afford intermediate 5.
Synthesis of intermediate 6 the same procedure as for the synthesis of intermediate 3 of example 1 was followed, substituting intermediate 5 for intermediate 1, to give intermediate 6.
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-15 and Comp-16:
Figure BDA0002609607900000151
in the same manner as in example 2, intermediate 5 or intermediate 6 was used instead of intermediate 1 or intermediate 3 to give the spirocyclic derivatives of the anthracenone group, Comp-15 and Comp-16.
Example 10
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-17 and Comp-18:
Figure BDA0002609607900000152
after reacting intermediate 1(1.38g,2mmol) obtained in example 1, or intermediate 3(1.45mg,2mmol), carbazole (1.47g, 8.8mmol), sodium tert-butoxide (768mg,8mmol), palladium acetate (45mg), and 0.5mL of tri-tert-butylphosphine in 50mL of anhydrous toluene solvent under nitrogen protection under reflux for 15h, the solvent was removed under reduced pressure, extracted with dichloromethane and water, the organic phases were combined, the solvent was evaporated under reduced pressure, and column chromatography gave maleimide derivatives Comp-17 and Comp-18.
Example 11
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-19 and Comp-20:
Figure BDA0002609607900000153
in the same manner as in example 10, phenothiazine was used in place of carbazole to obtain spirocyclic derivatives Comp-19 and Comp-20 of anthrone.
Example 12
This example is the preparation of spiro derivatives of anthrones of the formulae Comp-21 and Comp-22:
Figure BDA0002609607900000161
in the same manner as in example 10, 9-dimethyl-9, 10-dihydroacridine was used in place of carbazole to give the spirocyclic derivatives Comp-21 and Comp-22 of anthrone.
Example 13
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-23 and Comp-24:
Figure BDA0002609607900000162
in the same manner as in example 10, intermediate 5 or intermediate 6 was used in place of intermediate 1 or intermediate 3, and 9, 9-dimethyl-9, 10-dihydroacridine was used in place of carbazole, to give spirocyclic derivatives Comp-23 and Comp-24 of anthrone.
Example 14
This example, the preparation of spirocyclic derivatives based on anthrones of the formulae Comp-25 and Comp-26, comprises the following steps:
synthesis of intermediate M8:
Figure BDA0002609607900000163
2-benzyl aniline is used for replacing M2, the mixture is dissolved in acetonitrile, hydrochloric acid is added dropwise in ice bath for acidification, then mixed aqueous solution of sodium nitrite and potassium iodide is added dropwise into the solution, and reaction is carried out for 2 hours at room temperature after dropwise addition. After completion of the reaction, the reaction was quenched with saturated sodium thiosulfate (20mL), and extracted three times with dichloromethane. The organic phases were combined and washed three times with deionized water and dried over anhydrous sodium sulfate. After removal of the organic solvent by rotary evaporation, the crude product was purified by column chromatography (n-hexane) to give the white crystalline product M7. Post bromination affords M8.
Synthesis of intermediate 9: synthesis of intermediate 1 using M8 instead of M3 gave intermediate 9.
Preparation of intermediate 11:
Figure BDA0002609607900000171
intermediate 9(1.35g, 2mmol) dissolved in o-xylene (10mL) was addedMnO2Catalyst (17.4mg,0.2mmol), reaction heated under reflux for 9h, reaction completed, solvent dried under reduced pressure, column chromatography afforded intermediate 11(1.13 g).
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-25 and Comp-26:
Figure BDA0002609607900000172
intermediate 9 or intermediate 11 was used in place of intermediate 1 or intermediate 3 in the same manner as in example 2 to give the spirocyclic derivatives of the anthracenone group, Comp-25 and Comp-26.
Example 15
This example is the preparation of spirocyclic derivatives based on anthrones of the formulae Comp-27 and Comp-28:
Figure BDA0002609607900000173
in the same manner as in example 2, intermediate 9 or intermediate 11 was used in place of intermediate 1 or intermediate 3, and triphenylamine pinacol borate was used in place of N-phenylcarbazole pinacol borate to obtain spirocyclic derivatives of anthrone, Comp-27 and Comp-28.
Example 16
This example, the preparation of spirocyclic derivatives based on anthrones of the formulae Comp-29 and Comp-30, comprises the following steps:
synthesis of intermediates 10 and 12 analogous intermediates 9 and 11
This example is the preparation of spirocyclic derivatives based on anthrones of the structural formulae Comp-29 and Comp-30:
Figure BDA0002609607900000181
the same as in example 2, intermediate 10 or intermediate 12 was used instead of intermediate 1 or intermediate 3 to give spirocyclic derivatives of anthracenone, Comp-29 and Comp-30.
Example 17
This example, the preparation of spiro derivatives of anthrones of the structural formulae Comp-31 and Comp-32, involves the following procedure:
synthesis of intermediate 13, the same as in example 1, intermediate M3 was replaced with 1-phenyl-2-iodobenzene to afford intermediate 13.
Synthesis of intermediate 14 was the same as that of intermediate 11 in example 14.
Figure BDA0002609607900000182
This example is the preparation of spirocyclic derivatives based on anthrones of the formulae Comp-31 and Comp-32:
Figure BDA0002609607900000183
in the same manner as in example 2, intermediate 13 or intermediate 14 was used instead of intermediate 1 or intermediate 3 to obtain spirocyclic derivatives of anthrones, Comp-31 and Comp-32.
Example 18
This example, the preparation of spirocyclic derivatives of anthrones of the structural formulae Comp-33 and Comp-34, involves the following procedure:
synthesis of intermediate 15 similar to that of intermediate 1 in example 1, intermediate 15 was obtained by substituting 1-phenyl-2-iodobenzene for intermediate M3 and 2, 6-dibromoanthraquinone for M6.
Synthesis of intermediate 16 was the same as that of intermediate 11 in example 14.
Figure BDA0002609607900000191
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-33 and Comp-34:
Figure BDA0002609607900000192
in the same manner as in example 2, intermediate 15 or intermediate 16 was used instead of intermediate 1 or intermediate 3 to obtain spirocyclic derivatives of anthracenone, Comp-33 and Comp-34.
Example 19
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-35 and Comp-36:
Figure BDA0002609607900000193
in the same manner as in example 10, intermediate 9 or intermediate 11 was used in place of intermediate 1 or intermediate 3, and 9, 9-dimethyl-9, 10-dihydroacridine was used in place of carbazole, whereby anthrone derivatives Comp-35 and Comp-36 were obtained.
Example 20
This example is the preparation of spiro derivatives of anthrones of the structural formulae Comp-37 and Comp-38:
Figure BDA0002609607900000201
in the same manner as in example 10, intermediate 10 or intermediate 12 was used in place of intermediate 1 or intermediate 3, and 9, 9-dimethyl-9, 10-dihydroacridine was used in place of carbazole, whereby anthrone derivatives Comp-37 and Comp-38 were obtained.
Example 21
This example is the preparation of spiro derivatives of anthrones of the formulae Comp-39 and Comp-40:
Figure BDA0002609607900000202
in the same manner as in example 10, intermediate 13 or intermediate 14 was used in place of intermediate 1 or intermediate 3, and 9, 9-dimethyl-9, 10-dihydroacridine was used in place of carbazole, to give anthrone derivatives Comp-39 and Comp-40.
Example 22
This example is the preparation of spiro derivatives of anthrones of the formulae Comp-41 and Comp-42:
Figure BDA0002609607900000203
in the same manner as in example 10, intermediate 15 or intermediate 16 was used in place of intermediate 1 or intermediate 3, and 9, 9-dimethyl-9, 10-dihydroacridine was used in place of carbazole, whereby anthrone derivatives Comp-41 and Comp-42 were obtained.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. The spirocyclic derivative of anthrone is characterized in that the structural general formula of the spirocyclic derivative of anthrone is as follows:
Figure FDA0002609607890000011
wherein X is a carbon atom, a carbonyl group, a sulfur atom or a sulfonyl group;
R1、R2、R3and R4Independently selected from at least one of a hydrogen atom, an aryl group of 6 to 30 carbon atoms having an electron donating ability, a substituted aryl group of 6 to 30 carbon atoms, a heterocyclic aryl group of 5 to 50 carbon atoms, which may be the same or different; when X is a sulfur atom or a sulfonyl group, R3、R4Not a hydrogen atom.
2. The spirocyclic derivative of an anthrone according to claim 1, wherein said aryl group of 6 to 30 carbon atoms is selected from at least one of perylenyl, pyrenyl, fluorenyl, spirobifluorenyl;
the substituted aryl group with 6 to 30 carbon atoms is selected from at least one of o-tolyl, m-tolyl, p-tolyl, xylyl, o-cumyl, m-cumyl, p-cumyl, trimethylphenyl and 9, 9' -dimethylfluorenyl;
the heterocyclic aryl group of 5 to 50 carbon atoms is selected from the group consisting of 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyridyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl, 7-benzofuryl, Dibenzofuran-2-yl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalyl, 5-quinoxalyl, 6-quinoxalyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 3-carbazolyl, 9-carbazolyl, N-phenylcarbazolyl, 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-dimethyl-9, 10-dihydroacridinyl, 1, 7-phenanthrolin-2-yl, 1, 7-phenanthrolin-3-yl, 1, 7-phenanthrolin-4-yl, 1, 7-phenanthrolin-5-yl, 1, 7-phenanthrolin-6-yl, 1, 7-phenanthrolin-8-yl, 1-phenanthrolin-6-yl, 1, 7-phenanthroline-9-yl group, 1, 7-phenanthroline-10-yl group, 1, 8-phenanthroline-2-yl group, 1, 8-phenanthroline-3-yl group, 1, 8-phenanthroline-4-yl group, 1, 8-phenanthroline-5-yl group, 1, 8-phenanthroline-6-yl group, 1, 8-phenanthroline-7-yl group, 1, 8-phenanthroline-9-yl group, 1, 8-phenanthroline-10-yl group, 1, 9-phenanthroline-2-yl group, 1, 9-phenanthroline-3-yl group, 1, 9-phenanthroline-4-yl group, 1, 9-phenanthroline-5-yl group, 1, 9-phenanthroline-6-yl group, 1, 9-phenanthroline-7-yl group, 1, 9-phenanthroline-8-yl group, 1, 9-phenanthroline-10-yl group, 1, 10-phenanthroline-2-yl group, 1, 10-phenanthroline-3-yl group, 1, 10-phenanthroline-4-yl group, 1, 10-phenanthroline-5-yl group, 2, 9-phenanthroline-1-yl group, 2, 9-phenanthroline-3-yl group, 2, 9-phenanthroline-4-yl group, 2, 9-phenanthroline-5-yl group, 2, 9-phenanthroline-6-yl group, 2, 9-phenanthroline-7-yl group, 2, 9-phenanthroline-8-yl group, 2, 9-phenanthroline-10-yl group, 2, 2, 8-phenanthroline-1-yl, 2, 8-phenanthroline-3-yl, 2, 8-phenanthroline-4-yl, 2, 8-phenanthroline-5-yl, 2, 8-phenanthroline-6-yl, 2, 8-phenanthroline-7-yl, 2, 8-phenanthroline-9-yl, 2, 8-phenanthroline-10-yl, 2, 7-phenanthroline-1-yl, 2, 7-phenanthroline-3-yl, 2, 7-phenanthroline-4-yl, 2, 7-phenanthroline-5-yl, 2, 7-phenanthroline-6-yl, 2, 7-phenanthroline-8-yl, 2, 7-phenanthroline-9-yl, 2, 7-phenanthroline-10-yl, 1-phenothiazinyl, 2-phenazinyl, phenothiazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, 10-phenothiazinyl, phenoxazinyl, 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 3-furazanyl, 2-thienyl, 3-thienyl, dibenzothiophen-2-yl.
3. Spirocyclic derivative of anthrone according to claim 1, wherein R is1、R2、R3And R4And is selected from aryl of 6 to 30 carbon atoms, substituted aryl of 6 to 30 carbon atoms or heterocyclic aryl of 5 to 50 carbon atoms having electron donating ability.
4. The spirocyclic derivative of an anthrone according to claim 3, wherein said spirocyclic derivative of an anthrone has the following general structural formula:
Figure FDA0002609607890000021
5. the spirocyclic derivative of an anthrone according to claim 4, wherein R is1、R2、R3And R4Same, selected from carbazole, perylenel, pyrenyl, fluorenyl, spirobifluorenyl, phenothiazineA group, an N-phenylcarbazolyl group.
6. The spirocyclic derivative of an anthrone according to claim 1, wherein said spirocyclic derivative of an anthrone has the following structural formula:
Figure FDA0002609607890000031
Figure FDA0002609607890000041
Figure FDA0002609607890000051
Figure FDA0002609607890000061
Figure FDA0002609607890000071
7. a process for preparing a spiro derivative of an anthrone according to any one of claims 1 to 6, which comprises the steps of:
(1) the intermediate for synthesizing the spirocyclic derivatives of the anthrones has any one of the following structural formulas of 1-6 and 9-16:
Figure FDA0002609607890000072
(2) the above intermediates and the compounds having R1Or R2Suzuki reaction of substituted pinacol borate or reaction with R-bearing boronic acid pinacol ester1Or R2The substituent nitrogen heterocyclic compound is subjected to Ullmann reaction to obtain anthraceneA ketone spiro derivative.
8. Use of spirocyclic derivatives of anthrones according to any one of claims 1 to 6 in organic electroluminescent devices.
9. Use according to claim 8, wherein the organic electroluminescent device is an organic electroluminescent device based on thermally activated delayed fluorescence.
10. Use according to claim 8, wherein the organic light-emitting layer of the organic electroluminescent device is a spirocyclic derivative of an anthrone according to any one of claims 1 to 6 or a mixture thereof with 1, 3-dicarbazolylbenzene.
CN202010749708.2A 2020-07-30 2020-07-30 Anthracene ketone spiro derivative and preparation method and application thereof Pending CN114057711A (en)

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Application publication date: 20220218