CN114181091A - Synthesis process of adamantane triphenylamine - Google Patents

Synthesis process of adamantane triphenylamine Download PDF

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CN114181091A
CN114181091A CN202111611923.7A CN202111611923A CN114181091A CN 114181091 A CN114181091 A CN 114181091A CN 202111611923 A CN202111611923 A CN 202111611923A CN 114181091 A CN114181091 A CN 114181091A
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adamantane
molar ratio
phenyl
chloroaniline
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CN114181091B (en
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周腾飞
凌君琦
张业欣
陈华
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Weisipu New Material Suzhou Co ltd
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Suzhou Jiuxian New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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    • C07—ORGANIC CHEMISTRY
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
    • C07C2603/74—Adamantanes

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Abstract

The invention provides a synthesis process of adamantane triphenylamine, which comprises the following steps: 1) adding adamantanol and phenol into a solvent to react to obtain adamantane phenol; 2) adding adamantane phenol, trifluoromethanesulfonic anhydride and alkali salt into a solvent for reaction to obtain adamantane phenyl trifluoromethanesulfonate; 3) adding 2-bromo-4-chloroaniline, phenylboronic acid, a catalyst and an alkali salt into a solvent for reaction to obtain 2-phenyl-4-chloroaniline; 4) adding 2-phenyl-4-chloroaniline, polyboronic acid pinacol ester, a catalyst and alkali salt into a solvent for reaction to obtain 4-amino-3-phenylboron ester; 5) adding the adamantane phenyl trifluoromethanesulfonate, 4-amino-3-phenylboronate, a catalyst and an alkali salt into a solvent to react to obtain the adamantane triphenylamine. The method has the advantages of easily obtained raw materials, simple operation, realization of hundred kilogram-level production, high purity of the obtained product and high purity of the liquid phase of more than 99.9 percent.

Description

Synthesis process of adamantane triphenylamine
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a synthesis process of adamantane triphenylamine.
Background
Electroluminescence (EL) is a physical phenomenon in which an electric field is generated by a voltage applied to two electrodes, electrons excited by the electric field collide with a luminescence center, and the electrons undergo transition, change, and recombination between energy levels to emit light. In recent years, organic electroluminescent devices (OLEDs) have been gradually introduced into the field of vision as a new generation of display technology. An OLED is an electroluminescent device formed of a multi-layered organic thin film structure in which an organic thin film is a film of an organic light emitting material formed on a substrate using an evaporation or spin coating process. Compared with the traditional display technology, the display technology has the advantages of voltage characteristic, light-emitting brightness, light-emitting efficiency, color quality, response speed, viewing angle and the like, and has low cost, thereby having wide market prospect.
Adamantane triphenylamine is an important intermediate in the field of OLEDs, a series of specific organic molecular structures such as an electron transport material, a hole blocking material and the like used by customers at home and abroad have structural parts, and particularly, in the process of seeking the localization by domestic manufacturers in recent years, more different types of materials containing the structures are urgently needed for the industrial production of the intermediate.
At present, no synthesis scheme is reported for the synthesis method of the compound, only two korean patents CN 111146349 a and CN 107148408B belong to the same korean company and report the application of the structure, and a series of photoelectric materials prepared mainly from the compound or an intermediate in the compound show excellent performance. However, the specific molecular structure of the compound has led to few studies and reports on it.
Therefore, it is necessary to design an environment-friendly synthesis process of adamantane triphenylamine, which can meet the industrial production, economic applicability and market demand.
Disclosure of Invention
The invention provides a synthesis process of adamantane triphenylamine, and aims to solve the problems that in the prior art, the synthesis process of the adamantane triphenylamine is lack, industrial production cannot be realized, and the increasing requirements of an OLED market cannot be met.
In order to achieve the above object, an embodiment of the present invention provides a synthesis process of adamantane triphenylamine, including the following steps:
1) adding adamantanol and phenol shown in the formula 1 into a dichloroethane solvent, and dropwise adding concentrated sulfuric acid to react to obtain adamantanol shown in the formula 2
Figure BDA0003435673410000021
2) Adding the adamantane phenol and triethylamine into a dichloroethane solvent for reaction, and dropwise adding trifluoromethanesulfonic anhydride after the reaction is finished to obtain adamantane phenyl trifluoromethanesulfonate shown in formula 3
Figure BDA0003435673410000022
3) Taking 2-bromo-4-chloroaniline of formula 4, phenylboronic acid and catalyst Pd (PPh)3)4Alkali salt K2CO3Adding the mixture into a toluene/ethanol solvent for reflux reaction to obtain the 2-phenyl-4-chloroaniline shown in the formula 5
Figure BDA0003435673410000023
4) Will be describedThe 2-phenyl-4-chloroaniline, the pinacol ester diboron and a catalyst Pd (dppf) Cl2Adding alkali salt KOAc into 1, 4-dioxane solvent, and refluxing to obtain 4-amino-3-phenylboron ester of formula 6
Figure BDA0003435673410000024
5) The adamantane phenyl triflate, the 4-amino-3-phenylboronate and a catalyst Pd (PPh)3)2Cl2Alkali salt K2CO3Adding into toluene solvent, and carrying out reflux reaction to obtain adamantane triphenylamine
Figure BDA0003435673410000031
Further, the reaction temperature in the step 1) is 0 ℃.
Further, the reaction temperature in the step 2) is 0 ℃.
Further, the molar ratio of the adamantanol to the phenol is 1:1-1.5, and the molar ratio of the adamantanol to the concentrated sulfuric acid is 1: 0.5-3.
Furthermore, the molar ratio of the adamantanol to the phenol is 1:1.05, and the molar ratio of the adamantanol to the concentrated sulfuric acid is 1: 2.2.
Further, the molar ratio of the adamantane phenol to the triethylamine is 1:1.1-2, and the molar ratio of the adamantane phenol to the trifluoromethanesulfonic anhydride is 1: 1.1-2.
Furthermore, the molar ratio of the adamantane phenol to the triethylamine is 1:1.3, and the molar ratio of the adamantane phenol to the trifluoromethanesulfonic anhydride is 1: 1.2.
Further, the molar ratio of the 2-bromo-4-chloroaniline to the phenylboronic acid is 1:1.1-1.5, and the 2-bromo-4-chloroaniline and a catalyst Pd (PPh)3)4The molar ratio is 1: 0.0005-0.02.
Further, the molar ratio of the 2-bromo-4-chloroaniline to the phenylboronic acid is 1:1.2, and the 2-bromo-4-chloroaniline is mixed with a catalyst Pd (PPh)3)4The molar ratio is 1: 0.002.
Further, the molar ratio of the 2-phenyl-4-chloroaniline to the pinacol diboron is 1:1.1-1.5, and the 2-phenyl-4-chloroaniline is mixed with a catalyst Pd (dppf) Cl2The molar ratio is 1: 0.0005-0.02.
Further, the molar ratio of the 2-phenyl-4-chloroaniline to the pinacol diboron is 1:1.2, and the molar ratio of the 2-phenyl-4-chloroaniline to the catalyst Pd (dppf) Cl2The molar ratio is 1: 0.002.
Further, the molar ratio of the adamantyl phenyl triflate to the 4-amino-3-phenylboronate is 1:1.1-1.5, and the adamantyl phenyl triflate is reacted with a catalyst Pd (PPh)3)2Cl2The molar ratio is 1: 0.0005-0.02.
Further, the molar ratio of the adamantyl phenyl triflate to the 4-amino-3-phenylboronate was 1:1.3, and the adamantyl phenyl triflate was reacted with a catalyst Pd (PPh)3)2Cl2The molar ratio was 1: 0.005.
Furthermore, the liquid phase purity of the adamantane triphenylamine reaches over 99.9 percent.
The scheme of the invention has the following beneficial effects:
1) the synthesis process disclosed by the scheme of the invention has economic applicability, meets the market demand, is environment-friendly and is suitable for industrial production.
2) The method has the advantages of easily obtained raw materials, simple operation and higher yield, and can realize hundred-kilogram production, and the obtained product has high purity and quality of more than 99.9 percent.
Drawings
FIG. 1 is a schematic representation of adamantanol of example 1 of the invention1H NMR；
FIG. 2 is a drawing showing the preparation of adamantane phenyl triflate of example 1 of the present invention1H NMR；
FIG. 3 is a scheme showing the preparation of 2-phenyl-4-chloroaniline of example 1 of the present invention1H NMR；
FIG. 4 is a drawing showing the preparation of 4-amino-3-phenylboron ester of example 1 of the present invention1H NMR；
FIG. 5 is a photograph of adamantane triphenylamine of example 1 of the invention1H NMR；
Fig. 6 is a liquid phase spectrum of adamantane triphenylamine of example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a synthesis process of adamantane triphenylamine aiming at the existing problems.
The synthetic route of the adamantane triphenylamine in the embodiment of the invention is as follows:
Figure BDA0003435673410000041
example 1
A synthetic method of adamantane triphenylamine comprises the following steps:
1) 150g of adamantanol and 500mL of 1, 2-dichloroethane are added into a 1L three-neck flask, stirred at room temperature, 97.83g of phenol is added, the mixture is cooled to 0 ℃ in an ice-water bath, 116mL of concentrated sulfuric acid is slowly dripped into the reaction system, the temperature of the system is maintained at about 0 ℃, after the dripping is finished, the stirring is continued for 30min at 0 ℃, the reaction temperature is raised to room temperature, and the reaction is continued for 18 h. The reaction was stopped after completion of the reaction by liquid phase monitoring. Standing for layering, removing a concentrated sulfuric acid layer, adjusting the pH value to be neutral or alkalescent with an aqueous alkali solution, standing for liquid separation, concentrating an organic layer until a large amount of solids are separated out, adding a large amount of hot water for pulping for 30min, performing heat filtration to obtain adamantane phenol, and drying to obtain 195g of white solids with the yield of 86.67%. Ms (ei): the ratio m/z 228.15 is larger than the total ratio,1h NMR as depicted in FIG. 1;
2) 195g of adamantane phenol, 500mL of 1, 2-dichloroethane and 154mL of triethylamine are added into a 1L three-neck flask, stirred and dissolved at room temperature to be in a clear and transparent state, the temperature is reduced to 0 ℃ in ice-water bath, 172mL of trifluoromethanesulfonic anhydride is slowly dripped into the reaction system, the temperature of the system is maintained to be about 0 ℃, and after the dripping is finished, the reaction system is transferred to room temperature for reaction for 30 min. Monitoring of the reaction by TLC spotting platesAfter completion of the reaction, the reaction mixture was poured into water, and the mixture was allowed to stand for liquid separation, washed with water for two liquid separations, and the organic layer was concentrated to obtain adamantyl phenyl trifluoromethanesulfonate as a colorless oily liquid in a yield of 267g (86.75%). Ms (ei): the ratio m/z 360.10 is larger than the total ratio,1h NMR as depicted in FIG. 2;
3) 300g of 2-bromo-4-chloroaniline, 1000ml of toluene, 200ml of ethanol, 600g of potassium carbonate and 200ml of water were placed in a 3L three-necked flask, and 212.6g of phenylboronic acid and Pd (PPh) were added3)43.36g, under the protection of nitrogen, and heating to 95 ℃ for reaction. After the completion of the reaction was monitored by TLC plate, the aqueous phase was first separated, washed twice with hot water, the organic phase was concentrated by liquid separation, crystallized by addition of petroleum ether, and air-dried to obtain 235g of gray crystals, yield 79.41%, ms (ei): the ratio m/z 203.01 is larger than the total ratio,1h NMR as depicted in FIG. 3;
4) in a 3L single-necked flask were placed 235g of 2-phenyl-4-chloroaniline, 351.61g of pinacol diboron ester, 339g of potassium acetate, and Pd (dppf) Cl21.68g of 1, 4-dioxane of 1.3L, and heating to 95 ℃ for reflux reaction under the protection of nitrogen. Completion of the reaction was monitored by TLC plates. Suction-filtering the reaction liquid, then spin-drying the organic phase, dissolving the organic phase with dichloroethane, then washing the organic phase twice, adding petroleum ether into the concentrated dried organic phase, pulping the organic phase until a large amount of products are separated out, and suction-filtering the organic phase to obtain 290g of gray powder solid, wherein the yield is 85.14%, and the mass fraction (MS (EI): the ratio m/z 295.17 is larger than the total ratio,1h NMR as depicted in FIG. 4;
5) 267g of adamantane phenyl triflate, 285g of 4-amino-3-phenylboronate, Pd (PPh) was added to a 3L single-neck flask3)2Cl22.6g, adding 307.7g of potassium carbonate and 300ml of water, adding 1.5L of toluene, heating to 95 ℃ for reflux reaction, monitoring the reaction completion through a TLC (thin layer chromatography) dot plate, standing to separate out a water phase, washing twice with hot water, adding activated carbon into an organic phase for decolorization, performing suction filtration to concentrate toluene, adding ethanol for crystallization, cooling to 20 ℃ and performing suction filtration to obtain a solid, repeating the toluene ethanol for crystallization for three times to obtain a white solid, drying and weighing 210g, wherein the yield is 74.68 percent, and MS (EI): the ratio m/z 379.10 is larger than the total ratio,1h NMR is shown in FIG. 5, and liquid phase spectrum is shown in FIG. 6.
Example 2
A synthetic method of adamantane triphenylamine comprises the following steps:
1) adding 500L of 1.2-dichloroethane into a 1000L reaction kettle, adding 97.83kg of melted phenol under stirring, introducing ice brine after the addition is finished, cooling to about 0 ℃, adding 150kg of solid adamantanol, cooling to zero ℃ in an ice salt bath, slowly adding 115.5L of concentrated sulfuric acid into the reaction system, and maintaining the temperature of the system at about 0 ℃. And (3) continuing introducing ice salt water after the dropwise addition is finished, keeping the temperature for 30min, introducing circulating water to recover to 25 ℃ for reaction, monitoring the reaction to be complete through a liquid phase, stopping the reaction after the reaction is complete, standing for 1h for layering, separating a concentrated sulfuric acid layer, adjusting the pH to be neutral or alkalescent by using liquid alkali, standing for liquid separation, and washing twice by using 500l of water. Evaporating the organic layer to remove 300L, precipitating a large amount of solid, adding 400L of hot water, keeping the temperature at 80 ℃ for 1h, performing hot suction filtration to obtain a yellow-white solid, drying and reducing the weight to obtain 200kg of a crude product, wherein the yield is 88.90%;
2) adding 400L of 1, 2-dichloroethane, 200kg of adamantane phenol and 150.36L of triethylamine into a 1000L reaction kettle, stirring and dissolving at room temperature to obtain a clear and transparent state, introducing ice brine, cooling to 0 ℃, slowly dropwise adding 177L of trifluoromethanesulfonic anhydride into the reaction kettle, maintaining the temperature of the system at about 0 ℃, closing the ice brine after dropwise adding is finished, and heating to room temperature for reaction for 2 hours. After the liquid phase monitoring reaction is completed, 300L of water is added into a reaction kettle to be washed for three times, an organic layer is steamed by steam and concentrated to be dry, and the adamantyl phenyl trifluoromethanesulfonate can be obtained, wherein 285kg of light red oily liquid is obtained, and the yield is 90.28%;
3) 300kg of 2-bromo-4-chloroaniline, 1000L of toluene, 200L of ethanol, 600kg of potassium carbonate and 200L of water were added into a 3000L reaction kettle, and 212.6kg of phenylboronic acid and Pd (PPh) were added3)43.36kg, nitrogen was continuously introduced, and the reaction was maintained at 95 ℃. After the liquid phase point plate monitoring reaction is completed, standing, firstly separating out a water phase, washing twice with hot water of 500L at 80 ℃, concentrating an organic phase, adding petroleum ether for crystallization, performing suction filtration and centrifugation, and performing air-blast drying to obtain 245kg of gray crystals with the yield of 82.79%;
4) adding 1000L of 1, 4-dioxane, 245kg of 2-phenyl-4-chloroaniline, 367kg of pinacol diboron and 354kg of potassium acetate into a 3000L reaction kettle, bubbling nitrogen for half an hour, and adding Pd (dppf) Cl21.76kg, heating to 95 ℃ and carrying out reflux reaction. The liquid phase monitors the reaction completion. While it is inPerforming vacuum filtration on the hot discharged material, evaporating the organic phase to dryness, dissolving the organic phase by dichloroethane, washing the organic phase twice by water, evaporating the organic phase by steam, adding petroleum ether, pulping until a large amount of products are separated out, and performing vacuum filtration to obtain 310kg of products with the yield of about 87.30%;
5) A3000L reactor was charged with 285kg of adamantylphenyl triflate, 327.88kg of potassium carbonate and 560L of water, 1000L of toluene, 304kg of boron ester and Pd (PPh)3)2Cl22.78kg, heating to 95 ℃ for reaction, keeping the reflux reaction at 95 ℃, monitoring the liquid phase for complete reaction, standing, separating out a water phase, washing twice with hot water, adding 5kg of activated carbon into an organic phase for decolorization, performing suction filtration to concentrate toluene, adding ethanol for crystallization, cooling to 20 ℃, performing suction filtration to obtain a solid, repeating the toluene and ethanol crystallization for three times to obtain a white powder solid, drying and weighing 245kg, wherein the yield is 81.6%, and the purity of the tested liquid phase is 99.95%.
Comparative example 1
The catalyst Pd (PPh) in step 5) of example 13)2Cl2Replacement by Pd (PPh)3)4The other steps are the same, and the method comprises the following specific steps:
267g of adamantane phenyl triflate, 285g of 4-amino-3-phenylboronate, Pd (PPh) was added to a 3L single-neck flask3)44.2g, adding 307.7g of potassium carbonate and 300ml of water, adding 1.5L of toluene, heating to 95 ℃ for reflux reaction, monitoring more reaction raw materials by a TLC spot plate at the same time, standing to remove a water phase, washing twice with hot water, and carrying out silica gel column chromatography separation to obtain 55g of the product with the yield of 19.56%.
Comparative example 2
The potassium phosphate was replaced by the basic potassium carbonate in step 5) of example 1, and the other steps were the same, as follows:
267g of adamantane phenyl triflate, 285g of 4-amino-3-phenylboronate, Pd (PPh) was added to a 3L single-neck flask3)2Cl22.6g, 471.2g potassium phosphate and 300ml water are added, 1.5L toluene is added, the temperature is raised to 95 ℃ for reflux reaction, the remaining amount of the reaction raw materials is monitored by TLC point plate under the same time, the water phase is separated by standing, and the mixture is washed twice by hot waterAfter this time, silica gel-loaded column chromatography gave 165g of product in 58.68% yield.
Comparative example 3
The solvent toluene in step 5) of example 1 was replaced by 1, 4-dioxane, and the other steps were the same as follows:
267g of adamantane phenyl triflate, 285g of 4-amino-3-phenylboronate, Pd (PPh) was added to a 3L single-neck flask3)2Cl22.6g, 307.7g of potassium carbonate and 300ml of water are added, 1.5L of 1, 4-dioxane is added, the temperature is increased to 95 ℃ for reflux reaction, more reaction raw materials are monitored by a TLC spot plate in the same time, the mixture is kept stand to remove a water phase, after the mixture is washed twice by hot water, silica gel loaded column chromatography is carried out for separation, the weight of the obtained product is 190g, and the yield is 67.57%.
Comparative example 4
The molar ratio of adamantane phenyl triflate to 4-amino-3-phenylboronate in step 5) of example 1 was changed from 1:1.3 to 1:1, and the other steps were the same, specifically as follows:
267g of adamantane phenyl triflate, 218.69g of 4-amino-3-phenylboronate, Pd (PPh) was added to a 3L single-neck flask3)2Cl22.6g, adding 307.7g of potassium carbonate and 300ml of water, adding 1.5L of toluene, heating to 95 ℃ for reflux reaction, monitoring more reaction raw materials by a TLC spot plate at the same time, standing to remove a water phase, washing twice with hot water, and then carrying out silica gel column chromatography separation to obtain the product weighing 150g, wherein the yield is 53.34%.
Comparative example 5
The adamantyl phenyl triflate from step 5) of example 1 was reacted with the catalyst Pd (PPh)3)2Cl2The molar ratio is changed from 1:0.005 to 1:0.0003, and other steps are the same as follows:
267g of adamantane phenyl triflate, 285g of 4-amino-3-phenylboronate, Pd (PPh) was added to a 3L single-neck flask3)2Cl20.16g, 307.7g of potassium carbonate and 300ml of water were added, 1.5L of toluene was added, the mixture was heated to 95 ℃ and refluxed, and the excess of the reaction material was monitored by TLC plate at the same timeStanding to remove the water phase, washing twice with hot water, and separating by silica gel loaded column chromatography to obtain product weighing 70g with yield of 24.89%.
Table 1 reaction conditions and yields of example 1 and comparative examples
Synthetic schemes Reaction conditions Yield%
Example 1 1.3 times of 4-amino-3-phenylboronyl ester 0.005 times of Pd (PPh)3)2Cl2Toluene Potassium carbonate 74.68
Comparative example 1 1.3 times of 4-amino-3-phenylboronyl ester 0.005 times of Pd (PPh)3)4Toluene Potassium carbonate 19.56
Comparative example 2 1.3 times of 4-amino-3-phenylboronyl ester 0.005 times of Pd (PPh)3)2Cl2Potassium toluene phosphate 58.68
Comparative example 3 1.3 times of 4-amino-3-phenylboronyl ester 0.005 times of Pd (PPh)3)2Cl2Potassium carbonate 1, 4-dioxane 67.57
Comparative example 4 1 times of 4-amino-3-phenylboronyl ester 0.005 times of Pd (PPh)3)2Cl2Toluene Potassium carbonate 53.34
Comparative example 5 1.3 times of 4-amino-3-phenylboronyl ester 0.0003 times of Pd (PPh)3)2Cl2Toluene Potassium carbonate 24.89
As can be seen from table 1, comparative example 1 compared to example 1, the catalyst was changed, and the yield was only 19.56%; comparative example 2 compared to example 1, with the base changed, the yield decreased by 16%; comparative example 3 compared to example 1, the yield was reduced by 7.11% with the solvent changed; comparative example 4 compared with example 1, the amount of 4-amino-3-phenylboron ester is reduced, and the yield is reduced by 21.34%; comparative example 5 compared with example 1, the amount of the catalyst is reduced, and the yield is only 24.89%;
in conclusion, by setting different conditions for reaction, including changing the catalyst, changing the alkali, changing the solvent and changing the proportional amount of the materials, the yield effect of the obtained intermediate product is seen, the synthesis scheme is optimal according to the optimal mode in the scheme, and meanwhile, the scheme is used for industrial production, so that higher yield is obtained, the production cost is low, the operation is simple and the quality of the obtained product is extremely high.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. The synthesis process of the adamantane triphenylamine is characterized by comprising the following steps:
1) adding adamantanol and phenol in the formula 1 into dichloroethane solvent, stirring and dissolving, and then dropwise adding concentrated sulfuric acid to react to obtain adamantanol in the formula 2
Figure FDA0003435673400000011
2) Adding the adamantane phenol and triethylamine into dichloroethane solvent, stirring and dissolving, and then dropwise adding trifluoromethanesulfonic anhydride to react to obtain adamantane phenyl trifluoromethanesulfonate shown in formula 3
Figure FDA0003435673400000012
3) Taking 2-bromo-4-chloroaniline of formula 4, phenylboronic acid and catalyst Pd (PPh)3)4Alkali salt K2CO3Adding the mixture into a toluene/ethanol solvent for reflux reaction to obtain the 2-phenyl-4-chloroaniline shown in the formula 5
Figure FDA0003435673400000013
4) The 2-phenyl-4-chloroaniline, the pinacol ester diborate and a catalyst Pd (dppf) Cl2Adding alkali salt KOAc into 1, 4-dioxane solvent, and refluxing to obtain 4-amino-3-phenylboron ester of formula 6
Figure FDA0003435673400000014
5) The adamantane phenyl triflate, the 4-amino-3-phenylboronate and a catalyst Pd (PPh)3)2Cl2Alkali salt K2CO3Adding into toluene solvent, and carrying out reflux reaction to obtain adamantane triphenylamine
Figure FDA0003435673400000021
2. The process of claim 1, wherein the reaction temperature in step 1) is 0 ℃.
3. The process of claim 1, wherein the reaction temperature in step 2) is 0 ℃.
4. The synthesis process of claim 1, wherein the molar ratio of adamantanol to phenol is 1:1-1.5, and the molar ratio of adamantanol to concentrated sulfuric acid is 1: 0.5-3.
5. The process of claim 1, wherein the molar ratio of adamantanol to triethylamine is 1:1.1-2, and the molar ratio of adamantanol to trifluoromethanesulfonic anhydride is 1: 1.1-2.
6. The synthesis process according to claim 1, wherein the molar ratio of the 2-bromo-4-chloroaniline to the phenylboronic acid is 1:1.1-1.5, and the 2-bromo-4-chloroaniline is in a mixture with a catalyst Pd (PPh)3)4The molar ratio is 1: 0.0005-0.02.
7. The process of claim 1, wherein the molar ratio of 2-phenyl-4-chloroaniline to pinacol diboron is 1:1.1-1.5, and the 2-phenyl-4-chloroaniline is in contact with a catalyst Pd (dppf) Cl2The molar ratio is 1: 0.0005-0.02.
8. The process of claim 1, wherein the molar ratio of the adamantyl phenyl triflate to 4-amino-3-phenylboronate is 1:1.1-1.5, and the adamantyl phenyl triflate is reacted with the catalyst Pd (PPh)3)2Cl2The molar ratio is 1: 0.0005-0.02.
9. The process of any one of claims 1 to 8, wherein the liquid phase purity of said adamantane triphenylamine is up to 99.9% or more.
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