WO2020259078A1 - Method for preparing adamantyl-containing triphenylamine derivative - Google Patents

Abstract

Provided is a method for preparing an adamantyl-containing triphenylamine derivative, the method comprising first reacting an aryl halogenated adamantane or an aryl adamantane ester with a primary aromatic amine without separation or purification after a reaction, and directly adding a halogenated aromatic hydrocarbon for reaction. The method not only has fewer reaction steps and can ensure one final separation and purification, but can also reduce the content of impurities, further increases the yield of the product, and prepares the target product in a higher yield. In addition, the steps of the present invention are simple, the raw materials used are basic chemical raw materials, the yield is high, and the finally prepared product has a high purity. The method is superior to the prior art in terms of the cost of raw materials, the actual operability and the working hours required for operation, and is very suitable for industrial production.

Description

Method for preparing adamantyl-containing triphenylamine derivatives Technical field

The invention belongs to the field of electroluminescence, and relates to a preparation method of organic electroluminescence compounds. More specifically, the invention relates to a preparation method of adamantyl-containing triphenylamine derivatives.

Background technique

Electroluminescence (Electroluminescence), also known as electroluminescence, or EL for short, is an electric field generated by the voltage applied to the two electrodes. The electrons excited by the electric field hit the luminous center, which causes the electrons to transition, change, and recombine between energy levels. A physical phenomenon that causes luminescence. In recent years, organic electroluminescent devices (OLED, Organic electroluminescent devices) have gradually entered people's field of vision as a new generation of display technology. OLED is an electroluminescent device formed by a multi-layer organic thin film structure. The organic thin film is a film of organic light-emitting material formed on a substrate by evaporation or spin coating. Compared with traditional display technology, it has great advantages in terms of voltage characteristics, luminous brightness, luminous efficiency, color quality, response speed and viewing angle, and low cost, so it has a broad market prospect.

Commonly used electroluminescent materials are adamantane derivatives, such as triphenylamine derivatives containing adamantyl groups. When the adamantyl-containing triphenylamine derivatives are prepared in a one-pot reaction, the yield of the target product is very low due to too many impurities. For this reason, researchers have studied a stepwise reaction method. At present, the conventional preparation method of triphenylamine derivatives containing adamantyl group is to use aryl halide adamantane or aryl menthol esters to react with a first-grade aromatic amine, and then through post-treatment, separation, and purification to obtain higher purity The intermediate (secondary aromatic amine compound) is then used to react with another halogenated aromatic hydrocarbon to produce the target product (tertiary aromatic amine compound). For example, in the patent document CN201680003736.1 (hereinafter referred to as the comparative document), it adopts N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluorene-2- Amine prepares triphenylamine derivatives containing adamantyl, but N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine is actually required It is prepared by the reaction of 2-amino-9,9-dimethylfluorene and 4-bromobiphenyl or 2-bromo-9,9-dimethylfluorene and 4-aminobiphenyl, so in fact, compared with the literature used It is the above method to synthesize the target product. However, this step-by-step reaction method has many reaction steps, and each step is separated and purified separately, resulting in a low total yield.

Summary of the invention

Aiming at the problems in the prior art, the present invention provides a method for preparing adamantyl-containing triphenylamine derivatives, which improves the yield.

The present invention is realized through the following technical solutions:

A preparation method of adamantyl-containing triphenylamine derivatives specifically includes the following steps:

Step 1. Add the compound of Chemical Formula 2, the compound of Chemical Formula 3, the base, the ligand, and the catalyst to the solvent to carry out the reaction;

Step 2: Put the compound represented by Chemical Formula 4 directly into the reaction solution obtained by the reaction in Step 1, and then continue the reaction to obtain the adamantyl-containing triphenylamine derivative represented by Chemical Formula 1;

Ar ₁ —NH ₂ chemical formula 3;

Ar ₂ —Y chemical formula 4;

X is selected from Cl, Br, I and CF ₃ SO ₃ ;

Y is selected from Cl, Br and I;

L is selected from substituted or unsubstituted arylene groups with 6-30 carbon atoms, substituted or unsubstituted heteroarylene groups with 6-30 carbon atoms;

Ar ₁ and Ar _{2 are the} same or different, and are independently selected from substituted or unsubstituted alkyl groups having 1 to 35 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 35 carbon atoms, substituted or unsubstituted The alkynyl groups with 2-35 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3-35 carbon atoms, substituted or unsubstituted heterocycloalkyl groups with 2-35 carbon atoms, substituted or unsubstituted Substituted aralkyl groups with 7-40 carbon atoms, substituted or unsubstituted heteroaralkyl groups with 2-40 carbon atoms, substituted or unsubstituted aryl groups with 6-40 carbon atoms, substituted or Unsubstituted heteroaryl groups with 1-40 carbon atoms;

The substituents of Ar ₁ and Ar ₂ are the same or different, and are independently selected from hydrogen, deuterium, halogen, cyano, nitro, alkyl with 1-40 carbon atoms, alkenyl with 2-40 carbon atoms, Alkynyl groups with 2-40 carbon atoms, aryl groups with 6-60 carbon atoms, heteroaryl groups with 5-60 carbon atoms, aryloxy groups with 6-60 carbon atoms, and carbon atoms 1-40 alkoxy, 6-60 arylamino, 3-40 cycloalkyl, 3-40 heterocycloalkyl, carbon 1 -40 alkylsilyl group, alkylboron group with 1-40 carbon atoms, arylboron group with 6-60 carbon atoms, arylphosphino group with 6-60 carbon atoms and the number of carbon atoms Substitution with 6-60 arylsilyl groups;

The substituent of L is selected from hydrogen, deuterium, halogen, cyano, nitro, alkyl with 1-40 carbon atoms, alkenyl with 2-40 carbon atoms, alkynyl with 2-40 carbon atoms, carbon Aryl groups with 6 to 60 atoms, heteroaryl groups with 5 to 60 carbon atoms, aryloxy groups with 6 to 60 carbon atoms, alkoxy groups with 1 to 40 carbon atoms, carbon atoms It is an arylamino group with 6-60 carbon atoms, a cycloalkyl group with 3-40 carbon atoms, a heterocycloalkyl group with 3-40 carbon atoms, an alkylsilyl group with 1-40 carbon atoms, and a carbon atom Alkyl boron group with 1-40, aryl boron with 6-60 carbon atoms, arylphosphino with 6-60 carbon atoms, and arylsilyl group with 6-60 carbon atoms .

Preferably, in step 1, the reaction temperature is 100-105°C, and the reaction time is 2-24h; in step 2, the reaction temperature is 100-105°C, and the reaction time is 2-48h.

Preferably, when X is Cl, Br or I, chemical formula 2 is obtained by reacting 1-adamantanol with the compound shown in chemical formula 5 for 2-3h, and the reaction formula is as follows:

Preferably, when X is CF ₃ SO ₃ , chemical formula 2 is synthesized by using the compound shown in chemical formula 6 and trifluoromethanesulfonic anhydride, the reaction formula is as follows:

Preferably, the solvent is selected from toluene and xylene, and the base is selected from potassium phosphate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, cesium carbonate, sodium tert-butoxide and potassium tert-butoxide.

Preferably, the catalyst is selected from Pd ₂ dba ₃ , Pd(OAc) ₂ and Pd(dppf)Cl ₂ .

Preferably, the ligand is selected from (t-Bu) ₃ P, x-PHOS and s-PHOS.

Preferably, the molar ratio of the compounds represented by Chemical Formula 2, Chemical Formula 3 and Chemical Formula 4 is 1:1:0.98.

Preferably, L is selected from 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, dibenzofuran and diphenyl And thiophene.

Optionally, L is selected from 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, dibenzofuranyl, Dibenzothienyl, N-phenylcarbazolyl, or a group formed by connecting any two or three of the above groups through a single bond.

Optionally, Ar ₁ and Ar ₂ are each independently selected from 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl , Dibenzofuranyl, dibenzothienyl, N-phenylcarbazolyl, or a group formed by connecting two or three of the above groups through a single bond.

Optionally, in the method for preparing adamantyl-containing triphenylamine derivatives of the present application, the compound represented by Chemical Formula 1 is selected from the compounds represented by the following structures:

In this application, aryl refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aryl group can be a monocyclic aryl group or a polycyclic aryl group. In other words, the aryl group can be a monocyclic aryl group, a condensed ring aryl group, two or more monocyclic aryl groups conjugated by carbon-carbon bonds, A monocyclic aryl group and a fused ring aryl group conjugated by carbon-carbon bonds, and two or more fused ring aryl groups conjugated by a carbon-carbon bond. That is, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as aryl groups in the present application. Among them, the aryl group does not contain heteroatoms such as B, N, O, S, P, and Si. For example, in this application, biphenyl, terphenyl, etc. are aryl groups. Examples of aryl groups may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, benzo[9,10] Phenanthryl, pyrenyl, benzofluoranthene,

Base etc.

In this application, the substituted aryl group may be one or more hydrogen atoms in the aryl group, such as deuterium atom, halogen group, -CN, aryl, heteroaryl, trialkylsilyl, alkyl, Cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, arylamino, heterocyclic and other groups are substituted. Specific examples of heteroaryl-substituted aryl groups include, but are not limited to, dibenzofuranyl-substituted phenyl groups, dibenzothiophene-substituted phenyl groups, pyridine-substituted phenyl groups, and the like. It should be understood that the number of carbon atoms of a substituted aryl group refers to the total number of carbon atoms of the aryl group and the substituents on the aryl group. For example, a substituted aryl group with 18 carbon atoms refers to an aryl group and its The total number of carbon atoms of the substituent is 18.

In this application, a heteroaryl group refers to a monovalent aromatic ring containing at least one heteroatom in the ring or a derivative thereof. The heteroatom may be at least one of B, O, N, P, Si, and S. The heteroaryl group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. In other words, the heteroaryl group can be a single aromatic ring system or multiple aromatic ring systems conjugated by carbon-carbon bonds, and any aromatic The ring system is an aromatic monocyclic ring or an aromatic fused ring. The "heteroaryl group" in this application may include 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 heteroatoms selected from B, O, N, P, Si, Se and S The number of carbon atoms can be 3-40. In some embodiments, the number of carbon atoms of the heteroaryl group can be 3-30. In other embodiments, the number of carbon atoms of the heteroaryl group can be 3-20. , Or 3-18, or 3-12, or 12-18. For example, the number of carbon atoms of the heteroaryl group can also be 5, 8, 9, 12, 18, 20 or 40. Of course, the number of carbon atoms can also be other numbers, which will not be repeated here. List one by one. In this application, the explanation of aryl can be applied to arylene, the explanation of heteroaryl can be applied to heteroarylene, the explanation of alkyl can be applied to alkylene, and the explanation of cycloalkyl can be Applied to cycloalkylene.

Exemplarily, heteroaryl groups may include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, Acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazine Azinyl, isoquinolinyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, thiophene Thienyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, silylfluorenyl, dibenzofuranyl and N-arylcarbazole Group (such as N-phenylcarbazolyl), N-heteroarylcarbazolyl (such as N-pyridylcarbazolyl), N-alkylcarbazolyl (such as N-methylcarbazolyl), etc., Not limited to this. Among them, thienyl, furanyl, phenanthrolinyl, etc. are heteroaryl groups of a single aromatic ring system type, and N-arylcarbazolyl and N-heteroarylcarbazolyl are multiple groups conjugated through carbon-carbon bonds. Ring system type heteroaryl.

Substitution of trialkylsilyl, alkyl, cycloalkyl, alkoxy, alkylthio, haloalkyl, aryloxy, arylthio, silyl, alkylamino, arylamino, heterocyclic and other groups . Specific examples of aryl-substituted heteroaryl groups include, but are not limited to, phenyl-substituted dibenzofuranyl, phenyl-substituted dibenzothienyl, phenyl-substituted pyridyl, and the like. It should be understood that the number of carbon atoms of the substituted heteroaryl group refers to the total number of carbon atoms of the heteroaryl group and the substituent on the heteroaryl group. Compared with the prior art, the present invention has the following beneficial technical effects:

The present invention first adopts the reaction of aryl halide adamantane or aryl masticate and the first-grade aromatic amine, without separating and purifying after the reaction, directly throwing in halogenated aromatic hydrocarbon for reaction. In this way, not only the reaction steps are few, the final separation and purification can be ensured, but also the content of impurities can be reduced, and the product yield can be further improved, and the target product (tertiary aromatic amine compound) can be prepared with a higher yield. At the same time, the steps of the present invention are simple, the raw materials used are basic chemical raw materials, and the yield is high. The final product has high purity. It is much better than the prior art in terms of raw material cost, actual operability and man-hours required for operation, and is very applicable For industrial production.

Furthermore, at present, the preparation method of adamantane derivatives needs to be synthesized through multiple steps, and the Suzuki coupling reaction is often used in the synthesis of the target product. In the choice of reactants, the Suzuki reaction rate of most chlorinated compounds is very slow, the yield is very low, and each step needs to be separated and purified, the catalyst utilization rate is low, resulting in increased costs. For example, in CN201680003736.1, 4-(adamantan-1-yl)benzene trifluoromethanesulfonate is used to react with 4'-chloro-4-ylbiphenylboronic acid to obtain aryl halide adamantane. This method has a slow reaction rate, a longer reaction time, and a larger amount of catalyst, leading to higher costs. However, in the present invention, 1-adamantanol and chemical formula 5 are used to prepare aryl halide adamantane, the reaction time is short, no expensive catalyst is needed, and the cost is low.

Detailed ways

The present invention will be further described in detail below in conjunction with specific embodiments, which are to explain rather than limit the present invention.

The present invention aims to provide a method for preparing triphenylamine derivatives containing adamantyl groups. Under the condition that the pH is greater than or equal to 10, using aryl halide adamantane or aryl mantane ester, first-class aromatic amine as raw materials, using alkali, catalyst, ligand, toluene or xylene as solvent, reflux reaction 2-24 Hours; cooling down, adding water, extracting with organic solvent, washing with water, drying, and removing the solvent to obtain the crude product, which is then purified by column or recrystallization.

An organic electroluminescent device includes an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer includes at least one layer, and at least one of the above-mentioned organic layers includes the preparation method of the present invention. compound of. The organic layer containing the above compound is selected from a hole injection layer, a hole transport layer, a red light enhancement layer, an electron blocking layer, an electron transport layer, an electron injection layer, a lifetime improvement layer, a light-emitting layer, and a light-emitting auxiliary layer.

In this application, MC refers to CH ₂ Cl ₂ , dichloromethane.

Example 1 Preparation of Compound 1

Under the protection of nitrogen, add 133.75mmol of 1-adamantanol, 127.38mmol of 4-chloro-p-terphenyl, and 337mL of dichloromethane to the reaction flask. After adding, stir to dissolve at room temperature, then cool to 5°C, add concentrated sulfuric acid dropwise while keeping warm. 318.45 mmol. After the dripping is completed, the reaction is kept for 3 hours and quenched by adding water. Liquid separation, extraction, washing with water, drying, filtering, and concentration. Pass the column with a mixed solvent of dichloromethane and n-heptane and recrystallize to LC>95%. Dry to obtain a white solid (1S, 3S)-1-(4"-chloro-[1,1':4',1"-terphenyl]-4-yl)adamantane. Yield: 68%.

Under the protection of nitrogen, add (1S,3S)-1-(4″-chloro-[1,1':4',1″-terphenyl]-4-yl)adamantane 86.618mmol, 2 -Aminobiphenyl 86.618mmol, toluene 691mL, sodium tert-butoxide 259.854mmol, stirring, heating to 70℃, slowly add Pd ₂ dba ₃ 0.86618mmol, s-PHOS 1.7324mmol, after the addition, continue to heat up to 105℃ The reaction was refluxed for 12 hours, then the temperature was lowered to 70°C, 84.886mmol of 4-bromobiphenyl was added, and the temperature was increased to 105°C for reflux reaction for 10 hours. After the reaction was completed, the temperature was lowered, extracted with dichloromethane, the organic phase was washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 1. Yield: 60%.

Example 2 Preparation of Compound 2

Under the protection of nitrogen, add 133.75mmol of 1-adamantanol, 127.38mmol of 2-bromophenol, and 220mL of dichloromethane to the reaction flask. After adding, stir to dissolve at room temperature, then cool to 15°C, and add concentrated sulfuric acid dropwise while keeping warm. After the dripping is completed, the reaction is kept for 2h, and then quenched by adding water. Liquid separation, extraction, washing with water, drying, filtering, and concentration. Pass the column with a mixed solvent of dichloromethane and n-heptane and recrystallize to LC>95%. Dry 4-((3R, 5R, 7R)-adamantan-1-yl)-2-bromophenol as a white solid. Yield: 80%.

Under nitrogen protection, add 4-((3R,5R,7R)-adamantan-1-yl)-2-bromophenol 101.90mmol, phenylboronic acid 101.90mmol, toluene 186mL, ethanol 62mL, water 62mL, Potassium carbonate 203.81mmol, add, stir, heat to 50℃, quickly add 0.5095mmol of tetratriphenylphosphine palladium, after addition, continue to heat up to 70℃ and reflux for 3h. After the reaction is complete, cool down and extract with dichloromethane , The organic phase is washed with water, dried, filtered and concentrated. Recrystallize with dichloromethane and n-heptane mixed solvent to LC>98%. Dry white 5-((3R,5R,7R)-adamantan-1-yll)-[1,1'-biphenyl]-2-ol. Yield: 85%.

Under the protection of nitrogen, add 5-((3R,5R,7R)-adamantan-1-yl)-[1,1'-biphenyl]-2-ol 86.618mmol, dichloromethane 266mL, 259.85mmol of pyridine, stirred until the dissolution is clear, then cooled to -5°C, 129.93mmol of trifluoromethanesulfonic anhydride was added dropwise while keeping, the addition was completed, the reaction was kept for 2h, and the reaction was stopped. Quench with water, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. Recrystallize with dichloromethane and n-heptane mixed solvent to LC>98%. Dry white 5-((3R,5R,7R)-adamantan-1-yl)-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate. Yield: 95%.

Under the protection of nitrogen, add 5-((3R,5R,7R)-adamantan-1-yl)-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate 82.287mmol to the reaction flask , 2-amino-9,9-dimethylfluorene 82.287mmol, toluene 720mL, sodium tert-butoxide 246.86mmol, stirring, heating to 70℃, slowly add Pd2dba3 0.82287mmol, s-PHOS 1.6457mmol, after adding , Continue to heat up to 100°C for reflux reaction for 6h, then lower the temperature to 70°C, add 80.641mmol of 2-bromo-9,9-dimethylfluorene, continue to heat up to 100°C for reflux reaction for 8h, after the reaction is complete, cool down with dichloromethane Extract, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 2. Yield: 63%.

Example 3 Preparation of Compound 3

Under the protection of nitrogen, add 133.75mmol of 1-adamantanol, 127.38mmol of 4-bromobiphenyl, and 297mL of dichloromethane to the reaction flask. After the addition, stir to dissolve at room temperature, then cool to 15°C, and add concentrated sulfuric acid dropwise while maintaining. After the dripping is completed, the reaction is kept for 2h, and then quenched by adding water. Liquid separation, extraction, washing with water, drying, filtering, and concentration. Pass the column with a mixed solvent of dichloromethane and n-heptane and recrystallize to LC>95%. Dry 4-bromo-4'-adamantyl biphenyl as a white solid. Yield: 75%.

Under the protection of nitrogen, add 4-bromo-4'-adamantyl biphenyl 95.535mmol, 2-amino-9,9-dimethylfluorene 95.535mmol, toluene 702mL, and sodium tert-butoxide 286.605mmol into the reaction flask. Stir, heat to 70°C, slowly add Pd ₂ dba ₃ 0.95535mmol, s-PHOS 1.9107mmol, after the addition, continue to heat up to 102°C and reflux for 2h, then cool to 70°C, add 4-bromobiphenyl 93.624 mmol, continue to heat up to 102°C and reflux for 8 hours. After the reaction is completed, the temperature is lowered, and the mixture is extracted with dichloromethane, the organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 3. Yield: 65%.

Example 4 Preparation of Compound 4

Under the protection of nitrogen, add 133.75mmol of 1-adamantanol, 127.38mmol of 2-bromo-9,9-dimethylfluorene, and 348mL of dichloromethane into the reaction flask. After adding, stir to dissolve at room temperature, and then lower the temperature to 15℃. , Add concentrated sulfuric acid dropwise to keep warm After the dripping is completed, the reaction is kept for 2h, and then quenched by adding water. Liquid separation, extraction, washing with water, drying, filtering, and concentration. Pass the column with a mixed solvent of dichloromethane and n-heptane and recrystallize to LC>95%. Drying to obtain white solid 2-bromo-7-adamantyl-9,9-dimethylfluorene. Yield: 65%.

Under nitrogen protection, add 2-bromo-7-adamantyl-9,9-dimethylfluorene 82.797mmol, 2-amino-9,9-dimethylfluorene 82.797mmol, toluene 675mL, tertiary Sodium butoxide 248.391mmol, stir, heat to 70-80°C, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up at 105°C and reflux for 4h, then cool to 70°C, Add 81.141mmol of 4-bromobiphenyl, continue to heat up to 105°C and reflux for 6h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 4. Yield: 58%.

Example 5 Preparation of Compound 5

Under the protection of nitrogen, add 133.75mmol of 1-adamantanol, 127.38mmol of 1-bromonaphthalene, and 264mL of dichloromethane into the reaction flask. After the addition, stir to dissolve at room temperature, then lower the temperature to 15°C, and add concentrated sulfuric acid dropwise while maintaining. After the dripping is completed, the reaction is kept for 2h, and then quenched by adding water. Liquid separation, extraction, washing with water, drying, filtering, and concentration. Pass the column with a mixed solvent of dichloromethane and n-heptane and recrystallize to LC>95%. Dry 4-bromo-1-adamantyl naphthalene as a white solid. Yield: 70%.

Under the protection of nitrogen, add 4-bromo-1-adamantylnaphthalene 89.166mmol, 2-amino-9,9-dimethylfluorene 89.166mmol, toluene 609mL, and sodium tert-butoxide 267.498mmol into the reaction flask and stir, Heat to 70°C, slowly add Pd ₂ dba ₃ 0.89166mmol, s-PHOS 1.7833mmol, after the addition, continue to heat up to 105°C and reflux for 3h, then cool to 70°C, add 87.383mmol of 4-bromobiphenyl, Continue to heat up to 105°C and reflux for 10 hours. After the reaction is completed, the temperature is lowered, and the mixture is extracted with dichloromethane, the organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dried to obtain compound 5. Yield: 55%.

Example 6 Preparation of Compound 6

According to the method of Example 3, 4-bromo-4'-adamantyl biphenyl was synthesized.

Under the protection of nitrogen, add 82.797mmol of 4-bromo-4'-adamantylbiphenyl, [1,1':3',1″-terphenyl]-4'-amine 82.797mmol, toluene into the reaction flask 608mL, sodium tert-butoxide 248.391mmol, stir, heat to 70℃, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105℃, reflux for 6h, then cool to 70 ℃, add 81.141mmol of 2-bromo-9,9-dimethylfluorene, continue to heat up to 105℃ and reflux for 12h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. Use two The mixed solvent of methyl chloride and n-heptane was passed through the column and recrystallized to LC>99.95%. Drying to obtain compound 6. Yield: 65%.

Example 7 Preparation of Compound 7

According to the method of Example 3, 4-bromo-4'-adamantyl biphenyl was synthesized.

Under the protection of nitrogen, add 82.797mmol of 4-bromo-4'-adamantyl biphenyl, 82.797mmol of 2-aminobiphenyl, 608mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat to 70℃. , Slowly add Pd2dba3 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 2h, then lower the temperature to 70°C, add 81.141mmol of 3-bromo-9-phenylcarbazole, and continue to heat to The reaction was refluxed at 105°C for 4 hours. After the reaction was completed, the temperature was lowered, extracted with dichloromethane, the organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 7. Yield: 70%.

Example 8 Preparation of Compound 8

According to the method of Example 3, 4-bromo-4'-adamantyl biphenyl was synthesized.

Under the protection of nitrogen, add 82.797mmol of 4-bromo-4'-adamantyl biphenyl, 82.797mmol of 2-aminobiphenyl, 608mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat to 70℃. , Slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 2h, then lower the temperature to 70°C, add 3-(4-bromophenyl)-9-benzene 81.141mmol of methyl-9H-carbazole, continue to heat up to 105°C and reflux for 5h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 8. Yield: 72%.

Example 9 Preparation of Compound 9

According to the method of Example 4, 2-bromo-7-adamantyl-9,9-dimethylfluorene was synthesized.

Under nitrogen protection, add 2-bromo-7-adamantyl-9,9-dimethylfluorene 82.797mmol, 2-amino-9,9-dimethylfluorene 82.797mmol, toluene 675mL, tertiary Sodium butoxide 248.391mmol, stir, heat to 70°C, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 4h, then cool to 70°C, add 4-bromobiphenyl 81.141mmol, continue to heat up to 105°C and reflux for 6h. After the reaction is completed, the temperature is lowered, extracted with dichloromethane, the organic phase is washed with water, dried, filtered and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 9. Yield: 53%.

Example 10 Preparation of Compound 10

According to Example 2, 5-((3R,5R,7R)-adamantan-1-yl)-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate was synthesized.

Under the protection of nitrogen, add 5-((3R,5R,7R)-adamantan-1-yl)-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate 82.287mmol to the reaction flask , 2-amino-9,9-dimethylfluorene 82.287mmol, toluene 720mL, sodium tert-butoxide 246.86mmol, stirring, heating to 70℃, slowly adding Pd ₂ dba ₃ 0.82287mmol, s-PHOS 1.6457mmol, After the addition, continue to heat up to 105°C for reflux reaction for 6h, then lower the temperature to 70°C, add 80.641mmol of 2-bromo-9-phenylcarbazole, continue to heat up to 105°C for reflux reaction for 4h, after the reaction is complete, cool down, use dichloro Methane extraction, organic phase washing, drying, filtering, and concentration. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Oven to obtain compound 10. Yield: 60%.

Example 11 Preparation of Compound 11

Under the protection of nitrogen, add 82.797mmol of 4-adamantyl bromobenzene, 82.797mmol of 2-amino-9,9-dimethylfluorene, 482mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat up to 70℃, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105℃ and reflux for 2h, then reduce the temperature to 70℃, add 2-bromo-9,9-dimethyl Fluorene 81.141mmol, continue to heat up to 105°C and reflux for 6h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 11. Yield: 65%.

Example 12 Preparation of Compound 12

Under the protection of nitrogen, add 82.797mmol of 4-adamantyl bromobenzene, 82.797mmol of 2-amino-9,9-dimethylfluorene, 482mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat up to 70°C, slowly add Pd2dba3 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 2h, then lower the temperature to 70°C, add 81.141mmol of 4-bromobiphenyl, continue heating to 105°C and reflux After reacting for 3 hours, after the reaction is complete, the temperature is lowered, the mixture is extracted with dichloromethane, the organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Oven to obtain compound 12. Yield: 63%.

Example 13 Preparation of Compound 13

Under the protection of nitrogen, add 82.797mmol of 4-adamantyl bromobenzene, 82.797mmol of 2-amino-9,9-dimethylfluorene, 482mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat up to 70℃, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105℃ and reflux for 2h, then cool to 70℃, add 1-bromo-4-phenylnaphthalene 81.141mmol , Continue to heat up to 105°C and reflux for 8h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Oven to obtain compound 13. Yield: 81%.

Example 14 Preparation of Compound 14

Under the protection of nitrogen, add 82.797mmol of 4-adamantyl bromobenzene, 82.797mmol of 2-amino-9,9-dimethylfluorene, 482mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat up to 70℃, slowly add Pd2dba3 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105℃ and reflux for 2h, then reduce the temperature to 70℃, add 81.141mmol of 2-bromobiphenyl, continue heating to 105℃ for reflux After reacting for 12 hours, after the reaction is complete, the temperature is lowered, the mixture is extracted with dichloromethane, the organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, recrystallized to LC>99.95%. Dry to obtain compound 14. Yield: 60%.

Example 15 Preparation of Compound 15

According to Example 2, 5-((3R,5R,7R)-adamantan-1-yl)-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate was synthesized.

Under nitrogen protection, add 2-bromo-7-adamantyl-9,9-dimethylfluorene 82.797mmol, 2-amino-9,9-dimethylfluorene 82.797mmol, toluene 675mL, tertiary Sodium butoxide 248.391mmol, stir, heat to 70°C, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 4h, then cool to 70°C, add 81.141mmol of 2-bromobiphenyl, continue to heat up to 105°C and reflux for 12h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 15. Yield: 50%.

Example 16 Preparation of Compound 16

According to the method of Example 3, 4-bromo-4'-adamantyl biphenyl was synthesized.

Under the protection of nitrogen, add 82.797mmol of 4-bromo-4'-adamantyl biphenyl, 82.797mmol of 2-aminobiphenyl, 608mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat to 70℃. , Slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 2h, then lower the temperature to 70°C, add 81.141mmol of 3-bromodibenzofuran, and continue to heat to The reaction was refluxed at 105°C for 5 hours. After the reaction was completed, the temperature was lowered, extracted with dichloromethane, the organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Oven to obtain compound 16. Yield: 63%.

Example 17 Preparation of Compound 17

According to the method of Example 3, 4-bromo-4'-adamantyl biphenyl was synthesized.

Under the protection of nitrogen, add 82.797mmol of 4-bromo-4'-adamantyl biphenyl, 82.797mmol of 3-aminobiphenyl, 608mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stirring, and heating to 70℃ , Slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 2h, then lower the temperature to 70°C, add 81.141mmol of 3-bromodibenzofuran, and continue to heat to The reaction was refluxed at 105°C for 8 hours. After the reaction was completed, the temperature was lowered, extracted with dichloromethane, the organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 17. Yield: 65%.

Example 18 Preparation of Compound 18

According to Example 2, 5-((3r,5r,7r)-adamantan-1-yl)-[1,1'-biphenyl]-2-yltrifluoromethanesulfonate was synthesized.

Under the protection of nitrogen, add 5-((3R,5R,7R)-adamantan-1-yl)-[1,1'-biphenyl]-2-yl trifluoromethanesulfonate 82.287mmol to the reaction flask , 3-aminobiphenyl 82.287mmol, toluene 720mL, sodium tert-butoxide 246.86mmol, stirring, heating to 70℃, slowly add Pd2dba3 0.82287mmol, s-PHOS 1.6457mmol, after the addition, continue to heat up to 105℃ reflux After reacting for 6 hours, the temperature was lowered to 70°C, 80.641 mmol of 3-bromodibenzofuran was added, and the temperature was continued to be heated to 105°C and refluxed for 4 hours. After the reaction was completed, the temperature was lowered, the organic phase was extracted with dichloromethane, washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 18. Yield: 53%.

Example 19 Preparation of Compound 19

Under the protection of nitrogen, add 82.797 mmol of 4-bromo-4'-adamantyl biphenyl, 82.797 mmol of 2-amino-9,9-dimethylfluorene, 608 mL of toluene, and 248.391 mmol of sodium tert-butoxide into the reaction flask. Stir, heat to 70℃, slowly add Pd2dba3 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat to 105℃, reflux for 2h, then cool to 70℃, add 2-bromo-9,9-bis 81.141mmol of methylfluorene, continue to heat up to 105°C and reflux for 3h. After the reaction is completed, the temperature is lowered, extracted with dichloromethane, the organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of toluene and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 19. Yield: 78%.

Example 20 Preparation of Compound 20

Under the protection of nitrogen, add 82.797mmol of 4-bromo-4'-adamantyl biphenyl, 82.797mmol of 4-aminobiphenyl, 608mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask. Stir and heat to 70℃. , Slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 2h, then lower the temperature to 70°C, add 81.141mmol of 3-bromodibenzothiophene, and continue heating to The reaction was refluxed at 105°C for 5 hours. After the reaction was completed, the temperature was lowered, extracted with dichloromethane, the organic phase was washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Oven to obtain compound 20. Yield: 68%.

Example 21 Preparation of Compound 21

Using the same method for preparing 4-bromo-4'-adamantyl biphenyl in Example 3, 4-adamantyl bromobenzene was prepared with a yield of 80%.

Under the protection of nitrogen, add 82.797mmol of 4-adamantyl bromobenzene, 82.797mmol of 2-amino-9,9-dimethylfluorene, 482mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat up to 70℃, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105℃ and reflux for 2h, then reduce the temperature to 70℃, add 2-(4-bromophenyl)naphthalene 81.141 mmol, continue to heat up to 105°C and reflux for 12h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 21. Yield: 80%.

Example 22 Preparation of Compound 22

Using the same method for preparing 4-bromo-4'-adamantyl biphenyl in Example 3, 4-adamantyl bromobenzene was prepared with a yield of 80%.

Under the protection of nitrogen, add 82.797mmol of 4-adamantyl bromobenzene, 82.797mmol of 2-amino-9,9-dimethylfluorene, 482mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask, stir, and heat up to 70℃, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105℃ and reflux for 2h, then reduce the temperature to 70℃, add 4'-bromo-1,1':3 ',1″-terphenyl 81.141mmol, continue to heat up to 105°C and reflux for 24h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. Recrystallize after passing through the column with dichloroethane To LC>99.95%. Drying to obtain compound 22. Yield: 62%.

Example 23 Preparation of Compound 23

The method of Example 4 was used to synthesize 2-bromo-7-adamantyl-9,9-dimethylfluorene.

Under the protection of nitrogen, add 82.797 mmol of 2-bromo-7-adamantyl-9,9-dimethylfluorene, 82.797 mmol of 4-aminobiphenyl, 675 mL of toluene, and 248.391 mmol of sodium tert-butoxide into the reaction flask, and stir. , Heating to 70°C, slowly adding Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 24h, then lower the temperature to 70°C, add 1-bromonaphthalene 81.141mmol, Continue to heat up to 105°C for reflux reaction for 48 hours. After the reaction is completed, the temperature is lowered, the mixture is extracted with dichloromethane, the organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 23. Yield: 63%.

Example 24 Preparation of Compound 24

The method of Example 4 was used to synthesize 2-bromo-7-adamantyl-9,9-dimethylfluorene.

Under the protection of nitrogen, add 82.797 mmol of 2-bromo-7-adamantyl-9,9-dimethylfluorene, 82.797 mmol of 4-aminobiphenyl, 675 mL of toluene, and 248.391 mmol of sodium tert-butoxide into the reaction flask, and stir. , Heating to 70°C, slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat to 105°C and reflux for 4h, then lower the temperature to 70°C, add 81.141mmol of 2-bromobiphenyl , Continue to heat up to 105°C and reflux for 10 hours. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Dry to obtain compound 24. Yield: 58%.

Example 25 Preparation of Compound 25

The method of Example 3 was used to synthesize 4-bromo-4'-adamantyl biphenyl.

Under the protection of nitrogen, add 82.797mmol of 4-bromo-4'-adamantyl biphenyl, 82.797mmol of 4-aminobiphenyl, 608mL of toluene, and 248.391mmol of sodium tert-butoxide into the reaction flask. Stir and heat to 70℃. , Slowly add Pd ₂ dba ₃ 0.82797mmol, s-PHOS 1.6560mmol, after the addition, continue to heat up to 105°C and reflux for 2h, then lower the temperature to 70°C, add 2-bromo-9,9-diphenylfluorene 81.141 mmol, continue to heat up to 105°C and reflux for 6h. After the reaction is complete, cool down, extract with dichloromethane, wash the organic phase with water, dry, filter, and concentrate. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99.95%. Oven to obtain compound 25. Yield: 87%.

Comparative example 1

Use one-pot method to prepare compound 1

Under the protection of nitrogen, add 133.75mmol of 1-adamantanol, 127.38mmol of 4-chloro-p-terphenyl, and 337mL of dichloromethane to the reaction flask. After adding, stir to dissolve at room temperature, then cool to 5°C, add concentrated sulfuric acid dropwise while keeping warm 318.45 mmol. After the dripping is completed, the reaction is kept for 3 hours and quenched by adding water. Liquid separation, extraction, washing with water, drying, filtering, and concentration. Pass the column with a mixed solvent of dichloromethane and n-heptane and recrystallize to LC>95%. Dry to obtain a white solid (1S, 3S)-1-(4"-chloro-[1,1':4',1"-terphenyl]-4-yl)adamantane. Yield: 68%.

Under the protection of nitrogen, add (1S,3S)-1-(4″-chloro-[1,1':4',1″-terphenyl]-4-yl)adamantane 86.618mmol, 2 -Aminobiphenyl 86.618mmol, 4-bromobiphenyl 84.886mmol, toluene 691mL, sodium tert-butoxide 259.854mmol, stirring, heating to 70℃, slowly adding Pd ₂ dba ₃ 0.86618mmol, s-PHOS 1.7324mmol, add After completion, continue to heat up to 105°C and reflux for 10 hours. After the reaction is completed, the temperature is lowered, and the mixture is extracted with dichloromethane. The organic phase is washed with water, dried, filtered, and concentrated. After passing through the column with a mixed solvent of dichloromethane and n-heptane, it is recrystallized to LC>99%. Dry to obtain compound 1. Yield: 10%.

It can be seen from Comparative Example 1 that the method of generating the target product (tertiary aromatic amine compound) through a one-pot reaction of aryl haloadamantane, primary aromatic amine and halogenated aromatic hydrocarbon, the yield of the target product is very low, only 10 %, and in Example 1 of the present invention, this step is adjusted to react the aryl halide adamantane with the first-grade aromatic amine, and then add the halogenated aromatic hydrocarbon for the reaction, so that the yield of the target product reaches 60%, which is a very obvious improvement.

Comparative example 2

Comparative literature uses four-step reaction to synthesize compound 110 (compound 1 of the present invention), and the specific process is as follows:

After 108 g (0.50 mol) of 1-bromoadamantane was added to 188 g (2.0 mol) of benzene, it was heated at 120°C for 12 hours. After the reaction is over, after it is placed at room temperature, it is added to a 2L beaker for precipitation while stirring. After filtration, the precipitate was washed 3 times with hot water, and after fully vacuum drying, 91.3 g of 4-(adamantan-1-yl)benzene was obtained, and the yield was 80%.

After dissolving 91g (0.40mol) 4-(adamantan-1-yl)benzene and 63g (0.80mol) pyridine in 500ml dichloromethane, lower the temperature to 0℃, and slowly add 135g (0.48mol) trifluoromethanesulfonate Acid anhydride. After stirring for 3 hours, 1N hydrochloric acid was added after the reaction, and then 300ml of water was added for extraction. The organic layer was dried with MgSO4, the filtrate was distilled, and n-hexanoic acid/dichloromethane was subjected to column chromatography to obtain 122 g of 4-(adamantan-1-yl)benzene trifluoromethanesulfonate. The yield was Is 85%.

Combine 54.1g (0.15mol) 4-(adamantan-1-yl)benzene trifluoromethanesulfonate and 41.8g (0.18mol) (4'-chloro-[1,1'-biphenyl]-4- After the boronic acid was dissolved in 800 ml of toluene, 200 ml of ethanol, 200 ml of water, 62.2 g (0.45 mol) of potassium carbonate, and 5.2 g (4.5 mmol) of tetrakistriphenylphosphine palladium were added, followed by reflux for 12 hours. After the reaction is completed, it is placed at room temperature, and the organic layer is extracted with 500 ml of dichloromethane and 300 ml of H ₂ O. The organic layer was dried with MgSO ₄ , the filtrate was distilled, column chromatography was performed with dichloromethane, and recrystallized with n-hexanoic acid/dichloromethane to obtain 53.5 g of 1-(4"-chloro-[1, 1':4',1"-terphenyl]-4-yl)adamantane, the yield was 90%.

Combine 5.42g (15.0mmol) N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine and 6.58g (16.5mmol) 1-( 4”-chloro-[1,1':4',1”-terphenyl]-4-yl)adamantane was dissolved in 100ml of toluene, and 4.32g (45.0mmol) sodium tert-butoxide, 246mg (0.60mmol) were added After 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 275 mg (0.30 mmol) of tris(dibenzylideneacetone)palladium(0), it was refluxed for 12 hours. After the reaction is completed, it is placed at room temperature, and the organic layer is extracted with 100 ml of dichloromethane and 50 ml of H ₂ O. The organic layer was dried with MgSO ₄ , and the filtrate was distilled, and column chromatography was performed with n-hexanoic acid/dichloromethane to obtain 1.7 g of compound 110 with a yield of 16%.

Comparative literature uses a four-step reaction to synthesize compound 110 (that is, compound 1 synthesized in Example 1 of the present invention), the number of steps is longer, and the overall synthesis process takes longer.

In contrast, the compound 1 synthesis method provided by the method of the present invention is a two-step synthesis, which greatly simplifies the route, improves the total yield, reduces the preparation time, and is very suitable for industrial production.

The main differences are:

The raw material N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine in the last step of the comparison literature is used directly, but those skilled in the art know N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine itself requires the use of 2-amino-9,9-dimethylfluorene and 4-bromobiphenyl or 2-bromo-9,9-dimethylfluorene and 4-aminobiphenyl are reacted to prepare. Therefore, in general, the prior art requires two steps to prepare tertiary amine compounds from primary amine compounds. To complete, first prepare a secondary amine compound from the primary amine compound, and then prepare a tertiary amine compound from the secondary amine compound. Compared with the literature, the yield of this step is 16%, which is a relatively low level. The invention uses cheap and easily available raw materials to synthesize the product in one step with a yield of 60%. Obviously better than the comparative literature.

For applicants of the comparative literature, they directly purchased the raw material N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine, although this raw material It is easy to buy in the market, but the quality is different and the cost is relatively high. The overall cost will be at a higher level. In addition, the comparative literature uses a three-step reaction to synthesize intermediate 1-(4"-chloro-[1,1':4',1"-terphenyl]-4-yl)adamantane, with a total yield of 61.2% in the three steps. The method of the present invention is synthesized in one step with a yield of 68%. Obviously better than the comparative literature.

Comparative example 3

Comparative Literature Synthesis Example 17: Preparation of Compound 40 (ie Compound 13 synthesized in Example 13 of the present invention):

Using 6.17g (15.0mmol) 9,9-dimethyl-N-(4-phenylnaphthalene-1-yl)-9H-fluoren-2-amine and 5.95g, (16.5mmol) 4-(adamantane- After 1-yl)phenyl trifluoromethanesulfonate, compound 40 was produced using the same method as conventional synthesis. Yield: 77%.

Although the comparative literature adopts a one-step reaction to synthesize compound 40 (that is, compound 13 synthesized in Example 13 of the present invention), it actually requires two-step synthesis because 9,9-dimethyl-N-(4-phenylnaphthalene-1-yl) )-9H-fluoren-2-amine needs to be synthesized by a primary amine compound. Although the single-step yield is as high as 77%, the overall yield of the total synthesis process is low (estimated to be about 60%), which indirectly causes high costs and is not conducive to mass production.

In contrast, the synthesis method of compound 13 (ie compound 40 provided in the reference document) in the present invention is a one-step synthesis. From the perspective of the total synthesis process, the number of steps is reduced by one step, the total yield is higher, and the preparation time is reduced, which is very suitable For industrial production.

Table 1 shows the comparison of the final target product yields of the same compounds in the examples of the present invention and the comparative documents.

Table 1

Compound	Example yield%	Comparative literature yield%
1	60	16
2	63	-
3	65	20
4	58	-
5	70	-
6	65	-
7	70	-
8	72	-
9	53	-
10	60	-
11	65	-
12	63	-
13	81	77
14	60	-
15	50	-
16	63	-
17	65	-
18	53	-

19	78	36
20	68	-
twenty one	80	-
twenty two	62	twenty three
twenty three	63	-
twenty four	58	-
25	87	-

It can be seen from Table 1 that the yield of the target product prepared by the method of the present invention is significantly improved compared with the comparative literature.

It can be seen that due to the complex reaction process and the production of many impurities, the yield of the one-pot reaction is very low; while the complete sub-step reaction has reduced impurities, but due to the separation and purification operation of the intermediate process, some products are lost, resulting in the final product The yield is not high. The method of the invention can not only avoid the problem of a large amount of impurities caused by a one-pot reaction, but also avoid the loss of the intermediate process, so that the yield of the final product is obviously improved.

Claims (11)

1. A method for preparing adamantyl-containing triphenylamine derivatives is characterized in that it specifically includes the following steps:

   Step 1. Add the compound of Chemical Formula 2, the compound of Chemical Formula 3, the base, the ligand, and the catalyst to the solvent to carry out the reaction;

   Step 2: Put the compound represented by Chemical Formula 4 directly into the reaction solution obtained by the reaction in Step 1, and then continue the reaction to obtain the adamantyl-containing triphenylamine derivative represented by Chemical Formula 1;

   

   Ar ₁ —NH ₂ chemical formula 3;

   Ar ₂ —Y chemical formula 4;

   X is selected from Cl, Br, I and CF ₃ SO ₃ ;

   Y is selected from Cl, Br and I;

   L is selected from substituted or unsubstituted arylene groups with 6-30 carbon atoms, substituted or unsubstituted heteroarylene groups with 6-30 carbon atoms;

   Ar ₁ and Ar _{2 are the} same or different, and are independently selected from substituted or unsubstituted alkyl groups having 1 to 35 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 35 carbon atoms, substituted or unsubstituted The alkynyl groups with 2-35 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3-35 carbon atoms, substituted or unsubstituted heterocycloalkyl groups with 2-35 carbon atoms, substituted or unsubstituted Substituted aralkyl groups with 7-40 carbon atoms, substituted or unsubstituted heteroaralkyl groups with 2-40 carbon atoms, substituted or unsubstituted aryl groups with 6-40 carbon atoms, substituted or Unsubstituted heteroaryl groups with 1-40 carbon atoms;

   The substituents of Ar ₁ and Ar ₂ are the same or different, and are independently selected from hydrogen, deuterium, halogen, cyano, nitro, alkyl with 1-40 carbon atoms, alkenyl with 2-40 carbon atoms, Alkynyl groups with 2-40 carbon atoms, aryl groups with 6-60 carbon atoms, heteroaryl groups with 5-60 carbon atoms, aryloxy groups with 6-60 carbon atoms, and carbon atoms 1-40 alkoxy, 6-60 arylamino, 3-40 cycloalkyl, 3-40 heterocycloalkyl, carbon 1 -40 alkylsilyl group, alkylboron group with 1-40 carbon atoms, arylboron group with 6-60 carbon atoms, arylphosphino group with 6-60 carbon atoms and the number of carbon atoms Substitution with 6-60 arylsilyl groups;

   The substituent of L is selected from hydrogen, deuterium, halogen, cyano, nitro, alkyl with 1-40 carbon atoms, alkenyl with 2-40 carbon atoms, alkynyl with 2-40 carbon atoms, Aryl groups with 6-60 carbon atoms, heteroaryl groups with 5--60 carbon atoms, aryloxy groups with 6-60 carbon atoms, alkoxy groups with 1-40 carbon atoms, carbon atoms The number is 6-60 arylamino group, carbon number 3-40 cycloalkyl group, carbon number 3-40 heterocycloalkyl group, carbon number 1-40 alkylsilyl group, carbon Alkyl boron group with 1-40 atoms, aryl boron group with 6-60 carbon atoms, arylphosphino group with 6-60 carbon atoms, and arylsilyl group with 6-60 carbon atoms replace.
2. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein in step 1, the reaction temperature is 100-105°C, and the reaction time is 2-24 h; in step 2, the reaction temperature is It is 100-105°C, and the reaction time is 2-48h.
3. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein when X is Cl, Br or I, chemical formula 2 uses 1-adamantanol to react with the compound shown in chemical formula 5. Obtained in 2-3h, the reaction formula is as follows:

   
4. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein when X is CF ₃ SO ₃ , chemical formula 2 is synthesized by using the compound represented by chemical formula 6 and trifluoromethanesulfonic anhydride , The reaction formula is as follows:

   
5. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein the solvent is selected from toluene and xylene, and the base is selected from potassium phosphate, sodium carbonate, potassium carbonate, sodium hydroxide, hydrogen Potassium oxide, cesium carbonate, sodium tert-butoxide and potassium tert-butoxide.
6. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein the catalyst is selected from Pd ₂ dba ₃ , Pd(OAc) ₂ and Pd(dppf)Cl ₂ .
7. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein the ligand is selected from (t-Bu) ₃ P, x-PHOS and s-PHOS.
8. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein the molar ratio of the compounds represented by Chemical Formula 2, Chemical Formula 3 and Chemical Formula 4 is 1:1:0.98.
9. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein L is selected from 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, phenyl , Biphenyl, terphenyl, naphthyl, anthracenyl, dibenzofuran and dibenzothiophene.
10. The method for preparing adamantyl-containing triphenylamine derivatives according to claim 1, wherein said L, Ar ₁ and Ar ₂ are each independently selected from 9,9-dimethylfluorenyl, 9 , 9-Diphenylfluorenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, dibenzofuranyl, dibenzothienyl, N-phenylcarbazolyl, or each of the above groups In the group, two or three of them may be connected via a single bond.
11. The method for preparing adamantyl-containing triphenylamine derivatives according to any one of claims 1-10, wherein the compound of Chemical Formula 1 is selected from the group of compounds represented by the following structures: