CN108117567B - Tetra (4-boranophenyl) adamantane and preparation method thereof - Google Patents

Abstract

The invention provides a tetrakis(4-boronic acid phenyl) adamantane and a preparation method thereof. base) adamantane reacts with n-butyllithium first, then undergoes nucleophilic substitution reaction with boronate ester, and finally is obtained by acid hydrolysis with dilute hydrochloric acid. The product tetrakis(4-boronic acid phenyl)adamantane obtained by the invention has many accessible benzene rings, high symmetry and good rigidity, and becomes a new monomer material for synthesizing COFs with larger specific surface area.

Description

A kind of tetrakis (4-boronic acid phenyl) adamantane and preparation method thereof

technical field

The invention relates to the technical field of chemical synthesis, and relates to a tetrakis(4-boronic acid phenyl)adamantane and a preparation method thereof.

Background technique

In recent years, covalent organic frameworks (COFs) have been widely used in gas adsorption and separation, energy storage and energy storage due to their large specific surface area, uniform pores, high thermal stability and good chemical stability. It has good applications in catalysis and other aspects, so once it is discovered, it has attracted everyone's attention. The most important feature of 3D COFs is that the edges and faces of the structural units in the pores are also accessible. The larger the specific surface area, the more active sites. At present, the maximum BET specific surface area of COFs is 4210m ² /g (COF-103). Yaghi has reported that the more aromatic rings exposed in a porous material, the larger its specific surface area. However, the reported structural units for the synthesis of COFs are limited, so the primary challenge for the current synthesis of COFs with larger specific surface areas is to design novel monomer materials.

The number of intercalated layers of boric acid COFs is small, and the exposed active sites for gas adsorption and catalysis are relatively more. In addition, the adamantane compound is a highly symmetrical cage-like hydrocarbon compound with a rigid structure, and its tetrahedral structure can still be well maintained after the synthesis of COFs. Therefore, combining the advantages of boronic acid and adamantane, a new monomer, tetrakis(4-boronic acid phenyl)adamantane, is designed with more accessible benzene rings, high symmetry and good rigidity.

SUMMARY OF THE INVENTION

The primary technical problem to be solved by the present invention is to provide a new monomer tetrakis (4-boronic acid phenyl) adamantane.

The tetrakis (4-boronic acid phenyl) adamantane material of the present invention, its structural formula is as follows:

A preparation method of tetrakis (4-boronic acid phenyl) adamantane, specifically according to the following steps:

(1) Under nitrogen protection, add n-butyllithium dropwise to the tetrahydrofuran solution of tetrakis(4-X-phenyl)adamantane, control the reaction temperature to -80～0℃, stir for 0.5～3h, and then rise to -20 Stir for 30 to 120 minutes at ~25°C;

The X is Br or I;

The concentration of the tetrakis(4-X-phenyl)adamantane is: 0.0065～0.052moL/L

The molar ratio of the tetrakis(4-X-phenyl)adamantane to n-butyllithium is: 1:5～89;

(2) the reaction solution obtained in (1) is cooled to -80～0°C, and triisopropyl borate is added dropwise thereto, stirred for 30～80min, then warmed to room temperature and stirred; stirred for 10 hours. The tetrahydrofuran, The volume ratio of n-butyllithium and triisopropyl borate is 10-50:1-10:5-20.

(3) quench with dilute hydrochloric acid, adjust pH to 3～4, and stir at 0～25°C for 3～10h;

(4) remove tetrahydrofuran and unreacted triisopropyl borate in the second-step reaction solution with a rotary evaporator to obtain a solid product; dissolve the solid product with dichloromethane, then add water for extraction, collect the water phase and filter, The crude product of tetrakis(4-boronic acid phenyl) adamantane is obtained; the crude product of tetrakis(4-boronic acid phenyl) adamantane is recrystallized with one of dimethyl sulfoxide, methanol and acetone to obtain pure tetrakis (4-boronic acid phenyl)adamantane.

The concentration of tetrakis(4-X-phenyl)adamantane described in step (1) is preferably: 0.0104～0.026moL/L, and the molar ratio of tetrakis(4-X-phenyl)adamantane to n-butyllithium is preferably 1 : 17.9～59.5; control reaction temperature is preferably -78～40 ℃.

In step (2), the reaction temperature is preferably -78～40°C; the volume ratio of tetrahydrofuran, n-butyllithium and triisopropyl borate is preferably 15～40:3～8:5～20;

The pH adjustment described in step (3) is preferably 3.3-3.8; preferably, stirring is performed at 25° C. for 8-10 h. In step (3), the reagent for recrystallization of tetrakis(4-boronic acid phenyl)adamantane is preferably dimethyl sulfoxide or methanol.

An application of tetrakis (4-boronic acid phenyl) adamantane, characterized in that the tetrakis (4-boronic acid phenyl) adamantane is used for synthesizing a new monomer material of COFs with a larger specific surface area.

The reaction formula of the preparation method of the present invention is as follows:

Wherein, X is Br or I.

Compared with the prior art, the present invention has the following beneficial effects:

1. The present invention combines adamantane and boric acid for the first time. The material not only has a highly symmetrical cage-like rigid structure, but its tetrahedral structure can be well maintained after the synthesis of COFs; and the number of intercalated layers of the synthesized COFs is small, and the exposed active sites for gas adsorption and catalysis are relatively small. Therefore, this material is expected to become a new monomer material for the synthesis of COFs with larger specific surface area.

Description of drawings

Figure 1 shows the ¹ H-NMR of tetrakis(4-boronic acid phenyl)adamantane.

Figure 2 is a Fourier transform infrared spectrum.

Detailed ways

The present invention is further described and explained below in conjunction with specific embodiments, but does not limit the protection scope of the present invention.

Example 1

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, to the (31 mL) tetrahydrofuran solution of (0.4 g, 0.52 mmol) tetrakis (4-bromophenyl) adamantane whose structural formula is shown in formula (II) was added dropwise 4 mL of n-butyl Lithium, control the reaction temperature to -78°C, stir for 0.5h, then rise to 0°C and stir for 50min;

2. In the second step, the reaction solution obtained in the first step was cooled to -78 ° C, and 5 mL of triisopropyl borate was added dropwise thereto, stirred for 30 min, then warmed to room temperature and stirred overnight;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 3.5, and stirred at 0 °C for 9 h.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis(4-boronic acid phenyl)adamantane was recrystallized from methanol to obtain pure tetrakis(4-boronic acid phenyl)adamantane in 50% yield.

The obtained product was characterized by mass spectrometry and hydrogen nuclear magnetic spectrum, ¹ H-NMR is shown in FIG. 1 , and Fourier transform infrared spectrum is shown in FIG. 2 .

The structural representation data is as follows:

The ESI-MS characterization result of electrospray mass spectrometry showed that the molecular weight measured in positive mode was 616.28, which was consistent with the molecular weight of tetrakis(4-boronic acid phenyl)adamantane.

Hydrogen Spectrum ¹ H-NMR (400 MHz, DMSO, ppm): 7.96 (s, 8H, OH), 7.78 (d, 8H), 7.54 (d, 8H), 2.09 (s, 12H).

IR (KBr, v/cm ^-1 ) characterization results were 3419.2, 3083.6, 2925.4, 2898.4, 2846.9, 1611.5, 1404.7, 1342.4, 1125.0, 1016.3, 829.3, 751.7, 715.2, 653.7.

Therefore, it is proved that tetrakis (4-boronic acid phenyl) adamantane has been successfully obtained by characterization.

Example 2

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, to the (35 mL) tetrahydrofuran solution of (0.4 g, 0.42 mmol) tetrakis (4-iodophenyl) adamantane whose structural formula is shown in formula (II), 4 mL of n-butyl was added dropwise. Lithium, control the reaction temperature to -78°C, stir for 0.5h, then rise to 0°C and stir for 50min;

2. In the second step, the reaction solution obtained in the first step was cooled to -78 ° C, and 5 mL of triisopropyl borate was added dropwise thereto, stirred for 30 min, then warmed to room temperature and stirred overnight;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 3.8, and stirred at 0 °C for 9 h.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis(4-boronic acid phenyl)adamantane was recrystallized from methanol, and the product was tetrakis(4-boronic acid phenyl)adamantane by mass spectrometry, hydrogen NMR and infrared characterization, and the yield was 38%.

Example 3

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, 3 mL of n-butyl was added dropwise to the (40 mL) tetrahydrofuran solution of (0.4 g, 0.52 mmol) tetrakis(4-bromophenyl) adamantane represented by the formula (II). Lithium, control the reaction temperature to -78°C, stir for 1.5h, then rise to 0°C and stir for 30min;

2. In the second step, the reaction solution obtained in the first step was cooled to -78°C, and 2 mL of triisopropyl borate was added dropwise thereto, stirred for 40 min, and then warmed to room temperature and stirred for 10 h;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 3.3 and stirred at 25°C for 10h.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis (4-boronic acid phenyl) adamantane was recrystallized with dimethyl sulfoxide, and the product was characterized by mass spectrometry, 1H NMR and IR as tetrakis (4-boronic acid phenyl) adamantane, and the yield was 52%. .

Example 4

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, 5 mL of n-butyl group was added dropwise to the (50 mL) tetrahydrofuran solution of (0.4 g, 0.42 mmol) tetrakis(4-iodophenyl)adamantane whose structural formula is shown in formula (II). Lithium, control the reaction temperature to -78°C, stir for 1.5h, then rise to 0°C and stir for 30min;

2. In the second step, the reaction solution obtained in the first step was cooled to -78°C, and 10 mL of triisopropyl borate was added dropwise to it, stirred for 40 min, then warmed to room temperature and stirred for 10 h;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 3.0, and stirred at 25°C for 10h.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis (4-boronic acid phenyl) adamantane was recrystallized with dimethyl sulfoxide, and the product was characterized by mass spectrometry, 1H NMR and IR as tetrakis (4-boronic acid phenyl) adamantane, and the yield was 52%. .

Example 5

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, 10 mL of n-butyl was added dropwise to the (50 mL) tetrahydrofuran solution of (0.4 g, 0.52 mmol) tetrakis(4-bromophenyl) adamantane represented by the formula (II). Lithium, control the reaction temperature to -40°C, stir for 0.5h, then rise to 0°C and stir for 50min;

2. In the second step, the reaction solution obtained in the first step was cooled to -78 ° C, and 15 mL of triisopropyl borate was added dropwise thereto, stirred for 30 min, then warmed to room temperature and stirred overnight;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 3.8 and stirred at 0°C for 3 h.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis (4-boronic acid phenyl) adamantane was recrystallized from dimethyl sulfoxide, and the product was characterized by mass spectrometry, hydrogen NMR and infrared as tetrakis (4-boronic acid phenyl) adamantane, and the yield was 30%. .

Example 6

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, 12 mL of n-butyl was added dropwise to the (60 mL) tetrahydrofuran solution of (0.4 g, 0.42 mmol) tetrakis(4-iodophenyl)adamantane represented by the formula (II). Lithium, control the reaction temperature to -40°C, stir for 0.5h, then rise to 0°C and stir for 50min;

2. In the second step, the reaction solution obtained in the first step was cooled to -78 ° C, and 25 mL of triisopropyl borate was added dropwise thereto, stirred for 30 min, then warmed to room temperature and stirred overnight;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 3.3, and stirred at 0°C for 3 hours.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis (4-boronic acid phenyl) adamantane was recrystallized from dimethyl sulfoxide, and the product was characterized by mass spectrometry, 1H NMR and IR as tetrakis (4-boronic acid phenyl) adamantane, and the yield was 29%. .

Example 7

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, to the (35 mL) tetrahydrofuran solution of (0.4 g, 0.42 mmol) tetrakis (4-iodophenyl) adamantane whose structural formula is shown in formula (II), 4 mL of n-butyl was added dropwise. Lithium, control the reaction temperature to -78°C, stir for 2h, then rise to 0°C and stir for 30min;

2. In the second step, the reaction solution obtained in the first step was cooled to -78°C, and 15 mL of triisopropyl borate was added dropwise to it, stirred for 30 min, then warmed to room temperature and stirred for 10 h;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 3.3, and stirred at 0°C for 3 hours.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis (4-boronic acid phenyl) adamantane was recrystallized with dimethyl sulfoxide, and the product was characterized by mass spectrometry, H NMR and infrared to be tetrakis (4-boronic acid phenyl) adamantane, and the yield was 40%. .

Example 8

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, to the (35 mL) tetrahydrofuran solution of (0.4 g, 0.52 mmol) tetrakis (4-bromophenyl) adamantane whose structural formula is shown in formula (II) was added dropwise 4 mL of n-butyl Lithium, control the reaction temperature to -40°C, stir for 0.5h, then rise to 0°C and stir for 50min;

2. In the second step, the reaction solution obtained in the first step was cooled to -40 ° C, and 15 mL of triisopropyl borate was added dropwise thereto, stirred for 30 min, then warmed to room temperature and stirred overnight;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 4.0, and stirred at 25°C for 3h.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis (4-boronic acid phenyl) adamantane was recrystallized with acetone, and the product was tetrakis (4-boronic acid phenyl) adamantane by mass spectrometry, hydrogen NMR and infrared characterization, and the yield was 16%.

Example 9

Preparation of tetrakis(4-boronic acid phenyl)adamantane

1. Under the protection of nitrogen in the first step, to the (35 mL) tetrahydrofuran solution of (0.4 g, 0.42 mmol) tetrakis (4-iodophenyl) adamantane whose structural formula is shown in formula (II), 4 mL of n-butyl was added dropwise. Lithium, control the reaction temperature to -78°C, stir for 0.5h, then rise to 0°C and stir for 50min;

2. In the second step, the reaction solution obtained in the first step was cooled to -40 ° C, and 15 mL of triisopropyl borate was added dropwise to it, stirred for 30 min, and then warmed to room temperature and stirred for 10 h;

3. The third step was quenched with dilute hydrochloric acid, adjusted to pH 3.9, and stirred at 0°C for 3 hours.

4. In the fourth step, the tetrahydrofuran and unreacted triisopropyl borate in the reaction solution in the second step are removed with a rotary evaporator to obtain a solid product. The solid product was dissolved with dichloromethane, then extracted with water, and the aqueous phase was collected and filtered to obtain a crude product of tetrakis(4-boronic acid phenyl)adamantane. The crude product of tetrakis(4-boronic acid phenyl)adamantane was recrystallized from acetone, and the product was tetrakis(4-boronic acid phenyl)adamantane by mass spectrometry, hydrogen NMR and infrared characterization, and the yield was 15%.

Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above-mentioned specific embodiments, and those skilled in the art can make various variations or modifications within the scope of the claims, which do not affect the essential content of the present invention.

Claims (5)

1. A preparation method of tetra (4-boranophenyl) adamantane is characterized by comprising the following steps:

(1) under the protection of nitrogen, dropwise adding n-butyllithium into a tetrahydrofuran solution of tetra (4-X-phenyl) adamantane, controlling the reaction temperature to be-80-0 ℃, stirring for 0.5-3 h, then raising the temperature to-20-25 ℃, and stirring for 30-120 min;

the X is Br or I;

the concentration of the tetra (4-X-phenyl) adamantane is as follows: 0.0065-0.052 mol/L

The molar ratio of the tetra (4-X-phenyl) adamantane to the n-butyllithium is as follows: 1: 5-89;

(2) cooling the reaction liquid obtained in the step (1) to-80-0 ℃, dropwise adding triisopropyl borate into the reaction liquid, stirring for 30-80 min, and then heating to room temperature and stirring; stirring for 10 hours; the volume ratio of tetrahydrofuran to n-butyllithium to triisopropyl borate is 10-50: 1-10: 5-20;

(3) quenching with dilute hydrochloric acid, adjusting the pH to 3-4, and stirring at 0-25 ℃ for 3-10 h;

(4) removing tetrahydrofuran and unreacted triisopropyl borate in the reaction system by using a rotary evaporator to obtain a solid product; dissolving the solid product with dichloromethane, adding water for extraction, collecting water phase, and filtering to obtain crude product of tetra (4-boranophenyl) adamantane; recrystallizing the crude product of the tetra (4-boranophenyl) adamantane by using one of dimethyl sulfoxide, methanol and acetone to obtain pure tetra (4-boranophenyl) adamantane;

the structural formula of the tetra (4-boranophenyl) adamantane is as follows:

2. the process for producing tetrakis (4-boranophenyl) adamantane according to claim 1, characterized in that: the concentration of the tetra (4-X-phenyl) adamantane in the step (1) is as follows: 0.0104-0.026 mol/L, and the molar ratio of tetra (4-X-phenyl) adamantane to n-butyllithium is 1: 17.9-59.5; the volume ratio of tetrahydrofuran to n-butyllithium to triisopropyl borate is (15-40: 3-8): 5-20 ℃, and controlling the reaction temperature to be-78 to-40 ℃.

3. The process for producing tetrakis (4-boranophenyl) adamantane according to claim 1, characterized in that: in the step (2), the reaction temperature is-78 to-40 ℃.

4. The process for producing tetrakis (4-boranophenyl) adamantane according to claim 1, characterized in that: adjusting the pH value to 3.3-3.8 in the step (3); stirring for 8-10 h at 25 ℃.

5. The process for producing tetrakis (4-boranophenyl) adamantane according to claim 1, characterized in that: in the step (3), the reagent for recrystallizing the tetra (4-boranophenyl) adamantane is dimethyl sulfoxide or methanol.

Images