Adamantyl aniline derivative and preparation method thereof

Abstract

The invention relates to the technical field of organic synthesis, and discloses an adamantyl aniline derivative and a preparation method thereof.The preparation method comprises the steps that 1-(4-bromophenyl) adamantane and acetamide serve as raw materials and are subjected to high-temperature acylation and then react with NBS to obtain bromo-adamantyl acetanilide, then the bromo-adamantyl acetanilide reacts with strong base to obtain bromo-adamantyl acetanilide; according to the present invention, the raw materials are easily available, the operation is simple, the yield is high, and the purity of the obtained product is high, such that the method has characteristics of easily available raw materials, easily available raw materials, easily available raw materials, easily available raw materials, easily available raw materials, easily available raw materials, easily available raw materials, easily available raw materials, easily available raw materials and easily available raw materials.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to an adamantylaniline derivative and a preparation method thereof. Background Art

[0002] Triarylamine organic compounds have developed rapidly as organic electroluminescent materials in recent years. With the continuous development and research and development of organic electroluminescent materials, adamantyl aromatic hydrocarbons are increasingly used in OLED organic light-emitting materials. The market has a wider demand for aromatic amine organic intermediates containing adamantyl groups. Therefore, continuous research and development and innovation are needed to provide the market with more readily available materials.

[0003] Existing methods for preparing triarylamine organic compounds primarily involve nitration of adamantylbenzene in concentrated sulfuric acid and nitric acid followed by reduction. This method, however, requires a highly hazardous process, generates a large amount of waste acid, and is environmentally unfriendly. Alternatively, the method involves reacting excess benzamide with 1-adamantanol in concentrated sulfuric acid or trifluoroacetic acid at high temperatures. This method also suffers from poor selectivity, the requirement for a large excess of benzamide, poor atom economy, poor selectivity, numerous isomers, and difficulty in purification.

[0004] Based on this, the present invention provides a method for preparing adamantylaniline derivatives, which can solve the problems existing in the prior art. Summary of the Invention

[0005] (1) Technical problems solved

[0006] In view of the deficiencies in the prior art, the present invention provides an adamantylaniline derivative and a preparation method thereof.

[0007] (2) Technical solution

[0008] A method for preparing an adamantylaniline derivative comprises the following steps:

[0009] Step 1: 1-(4-bromophenyl)adamantane and acetamide are added to an organic solvent, and an acylation reaction is carried out in the presence of a catalyst and a co-catalyst to obtain intermediate I;

[0010] Step 2: using N-bromosuccinimide to react with intermediate I to obtain intermediate II;

[0011] Step 3: adding intermediate II and a strong base to a mixed solution of ethanol and deionized water to react to obtain intermediate III;

[0012] Step 4: Add intermediate III, arylboronic acid, palladium catalyst, alkali salt and tetrabutylammonium bromide to a mixed solution of toluene and deionized water for reaction to obtain an adamantylaniline derivative.

[0013] As a further embodiment of the present invention, in step 1, the organic solvent is N,N-dimethylformamide or N,N-dimethylacetamide.

[0014] As a further embodiment of the present invention, in step 1, the catalyst is cuprous halide; and the co-catalyst is N,N'-dimethylethylenediamine.

[0015] As a further embodiment of the present invention, in step three, the strong base is potassium hydroxide.

[0016] As a further embodiment of the present invention, in step three, the volume ratio of ethanol to deionized water is 2:1.

[0017] As a further embodiment of the present invention, in step 4, the aryl boronic acid is any one of phenylboronic acid, 1-naphthaleneboronic acid, 2-naphthaleneboronic acid, 4-biphenylboronic acid, 3-biphenylboronic acid, 2-biphenylboronic acid, 3,5-diphenylphenylboronic acid, dibenzofuran-4-boric acid, dibenzofuran-3-boric acid, dibenzofuran-2-boric acid, dibenzofuran-1-boric acid, dibenzothiophene-4-boric acid, dibenzothiophene-3-boric acid, dibenzothiophene-2-boric acid or dibenzothiophene-1-boric acid.

[0018] As a further embodiment of the present invention, in step 4, the palladium catalyst is tetrakistriphenylphosphine palladium.

[0019] As a further embodiment of the present invention, in step 4, the alkali salt is potassium carbonate or sodium carbonate.

[0020] As a further embodiment of the present invention, in step 4, the volume ratio of toluene to deionized water is 3:1.

[0021] An adamantylaniline derivative is prepared by the above preparation method.

[0022] (3) Beneficial technical effects

[0023] 1) The present invention uses cuprous halide as a catalyst, ethylenediamine as a co-catalyst, and xylene as a solvent, which can provide a suitable reaction temperature for the reaction and can obtain the product in high yield.

[0024] 2) Adamantyl acetamide can be directly brominated with NBS without deacetylation, which can give the brominated product with high conversion rate and high yield.

[0025] 3) After the bromination is completed, the acetyl group is removed and then reacted with an arylboronic acid or boric ester, which has a higher overall yield and lower cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0027] Figure 1 is the H NMR spectrum of 4-(1-adamantyl)-2-phenylaniline;

[0028] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of 4-(1-adamantyl)-2-(naphthalene-2-yl)aniline;

[0029] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of 4-(1-adamantyl)-2-(dibenzofuran-4-yl)aniline. DETAILED DESCRIPTION

[0030] To facilitate understanding of the present invention, the present invention will be described in more detail below. Preferred embodiments of the present invention are provided below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0031] Example 1

[0032] Preparation of 4-(1-adamantyl)-2-phenylaniline:

[0033] Step 1: Add 100g (343.37mmol) of 1-(4-bromophenyl)adamantane) into a three-necked flask, 30.42g (515.05mmol) of acetamide, 13.07g (68.67mmol) of cuprous iodide, 6.05g (68.67mmol) of N,N'-dimethylethylenediamine, 95g (686.74mmol) of potassium carbonate, and 600ml of xylene. The mixture was heated to 128°C and reacted for 16h. After the reaction was complete by liquid phase monitoring, the reaction was stopped and the reaction temperature was lowered to room temperature. 600ml of pure water was added and the mixture was directly filtered. The solid was washed with 600ml of water again and drained. After pulping with 300ml of ethanol, the mixture was drained and dried to give 72g of the product, which was a white solid powder of adamantane acetanilide (intermediate I). HPLC=99.14%, the yield was 90%.

[0034] Step 2: Add 72g (267.27mmol) of adamantane acetanilide and 500ml of dichloromethane to a three-necked flask, stir and dissolve at room temperature to a clear and transparent state, and cool to 0°C in an ice-water bath. Then, add 52g of N-bromosuccinimide (293.99mmol) to the reaction system in ten portions, maintain the system temperature at about 0°C, move to room temperature after addition, and react for 30min. After the reaction is complete by liquid phase monitoring, the reaction solution is washed with water, concentrated and dried, and dispersed with petroleum ether to obtain 86.6g of 2-bromoadamantane acetanilide, a white powder solid 2-bromoadamantane acetanilide (intermediate II), HPLC=99.45%, and a yield of 93%.

[0035] Step 3: Add 86.6 g (248.65 mmol) of 2-bromoadamantanacetanilide, 83.7 g (1.49 mol) of potassium hydroxide, 420 ml of ethanol, and 210 ml of water to a three-necked flask, replace the atmosphere with nitrogen three times, stir, turn on the heat, and raise the temperature to 65°C under nitrogen protection for reaction. After the reaction is complete by liquid phase monitoring, extract with dichloromethane, wash with water, separate the aqueous phase, wash with water twice, separate and concentrate the organic phase, and disperse the solid with petroleum ether after drying to obtain 59.4 g of white powder solid, 2-bromoadamantananiline (Intermediate III), HPLC = 99.68%, yield 78%;

[0036] Step 4: Add 59.4 g (193.96 mmol) of 2-bromoadamantananiline, 24.83 g (203.66 mmol) of phenylboric acid, 66.92 g (484.9 mmol) of potassium carbonate, 6.25 g (19.4 mmol) of tetrabutylammonium bromide, 240 ml of toluene, and 80 ml of deionized water to a three-necked flask. The temperature was raised to 48 ° C., 0.67 g (0.58 mmol) of tetrakistriphenylphosphine palladium catalyst was added, and the temperature was continued to rise to 75 ° C. After the reaction for 9 hours, the liquid phase detection reaction was completed, and the post-treatment was washed with water. The aqueous phase was extracted with toluene, and the organic phase was dried over anhydrous sodium sulfate and then passed through a silica gel column. After concentration, it was recrystallized from toluene and dried to obtain the product 4-(1-adamantyl)-2-phenylaniline as a white solid 51.29 g with a yield of 87.14%.

[0037] The preparation route of the 4-(1-adamantyl)-2-phenylaniline is as follows:

[0038]

[0039] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of 4-(1-adamantyl)-2-phenylaniline.

[0040] Example 2

[0041] Preparation of 4-(1-adamantyl)-2-(naphthalene-2-yl)aniline:

[0042] Steps 1 to 3 are the same as in Example 1;

[0043] Step 4: In a 1-liter three-necked flask, 59.4g (193.96mmol) of 2-bromoadamantananiline, 35.03g (203.66mmol) of 2-naphthaleneboric acid, 66.92g (484.9mmol) of potassium carbonate, 6.25g (19.4mmol) of tetrabutylammonium bromide, 240ml of toluene, and 80ml of deionized water were added. 0.67g (0.58mmol) of tetrakistriphenylphosphine palladium catalyst was added, and the mixture was warmed to 75°C. After the reaction for 6h, the reaction was terminated by liquid phase detection. After post-treatment, water was added to wash the liquid separatory. The organic phase was dried over anhydrous sodium sulfate and passed through a silica gel column. After concentration, the product 4-(1-adamantyl)-2-(naphthalene-2-yl)aniline was recrystallized from toluene and dried to obtain 60.48g of a white solid in an 88% yield.

[0044] The preparation route of the 4-(1-adamantyl)-2-(naphthalene-2-yl)aniline is as follows:

[0045]

[0046] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of 4-(1-adamantyl)-2-(naphthalen-2-yl)aniline.

[0047] Example 3

[0048] Preparation of 4-(1-adamantyl)-2-(dibenzofuran-4-yl)aniline:

[0049] Steps 1 to 3 are the same as in Example 1;

[0050] Step 4: In a 1-liter three-necked flask, 50 g (163.27 mmol) of 2-bromoadamantananiline, 50 g (36.35 mmol) of dibenzofuran-4-boric acid, 45.06 g (362.54 mmol) of potassium carbonate, 5.24 g (16.3 mmol) of tetrabutylammonium bromide, 200 ml of toluene, and 60 ml of deionized water were added. 0.94 g (0.81 mmol) of tetrakistriphenylphosphine palladium catalyst was added, and the temperature was raised to 75 ° C. After the reaction for 4 hours, the liquid phase was detected to be complete. After post-treatment, water was added to wash the separated liquid. The organic phase was dried over anhydrous sodium sulfate and then passed through a silica gel column. After concentration, it was recrystallized from toluene and dried to obtain 58.47 g of the product 4-(1-adamantyl)-2-(dibenzofuran-4-yl)aniline as a white solid with a yield of 91%.

[0051] The preparation route of the 4-(1-adamantyl)-2-(dibenzofuran-4-yl)aniline is as follows:

[0052]

[0053] Figure 3 The hydrogen nuclear magnetic resonance spectrum of 4-(1-adamantyl)-2-(dibenzofuran-4-yl)aniline is shown in FIG.

[0054] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal description of the claims, or if they include equivalent structural elements that are not substantially different from the literal description of the claims, then these other embodiments should also be included in the scope of the claims.

[0055] Based on the ideal embodiments of the present invention, and with reference to the above description, relevant personnel can make various changes and modifications without departing from the technical scope of the present invention. The technical scope of the present invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. A method for preparing an adamantylaniline derivative, characterized in that: The following steps are involved: Step 1: 1-(4-bromophenyl)adamantane and acetamide are added to an organic solvent, and an acylation reaction is carried out in the presence of a catalyst and a co-catalyst to obtain intermediate I; Step 2: using N-bromosuccinimide to react with intermediate I to obtain intermediate II; Step 3: adding intermediate II and a strong base to a mixed solution of ethanol and deionized water to react to obtain intermediate III; Step 4: Add intermediate III, arylboronic acid, palladium catalyst, alkali salt and tetrabutylammonium bromide to a mixed solution of toluene and deionized water for reaction to obtain an adamantylaniline derivative.

2. The method for preparing an adamantylaniline derivative according to claim 1, wherein: In step 1, the organic solvent is xylene.

3. The method for preparing an adamantylaniline derivative according to claim 1, wherein: In step 1, the catalyst is cuprous halide; and the co-catalyst is N,N'-dimethylethylenediamine.

4. The method for preparing an adamantylaniline derivative according to claim 1, wherein: In step 3, the strong base is potassium hydroxide.

5. The method for preparing an adamantylaniline derivative according to claim 1, wherein: In step 3, the volume ratio of the ethanol to deionized water is 2:

1.

6. The method for preparing an adamantylaniline derivative according to claim 1, wherein: In step 4, the aryl boronic acid is any one of phenylboronic acid, 1-naphthaleneboronic acid, 2-naphthaleneboronic acid, 4-biphenylboronic acid, 3-biphenylboronic acid, 2-biphenylboronic acid, 3,5-diphenylphenylboronic acid, dibenzofuran-4-boric acid, dibenzofuran-3-boric acid, dibenzofuran-2-boric acid, dibenzofuran-1-boric acid, dibenzothiophene-4-boric acid, dibenzothiophene-3-boric acid, dibenzothiophene-2-boric acid or dibenzothiophene-1-boric acid.

7. The method for preparing an adamantylaniline derivative according to claim 1, wherein: In step 4, the palladium catalyst is tetrakistriphenylphosphine palladium.

8. The method for preparing an adamantylaniline derivative according to claim 1, wherein: In step 4, the alkali salt is potassium carbonate or sodium carbonate.

9. The method for preparing an adamantylaniline derivative according to claim 1, wherein: In step 4, the volume ratio of toluene and deionized water is 3:

1.

10. An adamantylaniline derivative, characterized in that The method is as described in any one of claims 1 to 9.

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