CN102603618A - Biphenyl compound, synthetic method and application thereof - Google Patents

Abstract

The invention discloses a biphenyl compound and its synthesis method and application. The specific synthesis route of the compound (its structural formula is as follows) starts from the raw material 2,2'-biphenyl diphenol, and undergoes bromination, etherification, column layer The intermediate B was obtained by analysis, and then the catalyst was obtained by suzuki coupling reaction and column chromatography. The catalyst can catalyze and oxidize water to produce hydrogen peroxide under hydrothermal condition with metal copper salt. The invention adopts a hydrothermal cleaning production process, only pure water is used as a solvent, no organic solvent is added, no toxic waste gas is produced, no intermediate product needs to be separated, and the process flow is shortened.

Description

A kind of biphenyl compound and its synthesis method and application

technical field

The invention relates to a biphenyl compound and its synthesis method and application.

Background technique

Hydrogen peroxide is widely used in medicine, military industry and industry, and with the continuous expansion of urbanization scale, pollution sources containing high-concentration organic wastewater are increasing, and the degradation technology of organic pollutants has become the first choice to effectively solve the problem of sewage treatment At present, the treatment of organic pollutants with hydrogen peroxide has become an effective means of wastewater treatment. The reason is that the hydroxyl radical (OH) obtained by the decomposition of hydrogen peroxide has a very high oxidation potential (2.8V), and its oxidation ability is extremely strong. Some organic pollutants can undergo a rapid chain reaction to oxidize harmful substances into CO ₂ , H ₂ O or mineral salts without secondary pollution. At present, the technologies for producing hydrogen peroxide in various countries are basically prepared by the anthraquinone method of DuPont Company in 1958. This method uses alkyl anthraquinone as a medium to produce hydrogen peroxide through cyclic oxidation and reduction, but the cost of this technology is relatively high. During the hydrogen peroxide process, waste gas containing a large amount of trimethylbenzene and xylene and waste water containing a large amount of organic pollutants are discharged.

Contents of the invention

The purpose of the present invention is to overcome above-mentioned deficiencies in the prior art, and a kind of biphenyl compound is provided, and it can co-catalyze oxidation with copper salt (copper nitrate, copper perchlorate, copper trifluorosulfonate) under hydrothermal condition A new type of catalyst for producing hydrogen peroxide from water. This invention is expected to have wide application prospects in the clean production of hydrogen peroxide and realize the green production of hydrogen peroxide.

The invention also provides a synthesis method of the biphenyl compound.

The invention also provides a method for producing hydrogen peroxide by using biphenyl compounds to catalyze and oxidize water.

To achieve the above object, the present invention adopts the following technical solutions:

A kind of biphenyl compound, its chemical designation is 5,5'-bis(4-pyridyl)-2,2'-biphenyldiol bis-3-pyridine methyl ether, and its structural formula is as follows:

The synthetic method of above-mentioned biphenyl compound, comprises the following steps:

(1) Use 5,5'-dibromo-2,2'-biphenyldiol as raw material, and react with 3-chloromethylpyridine hydrochloride to produce intermediate B. The structure of intermediate B is as follows:

(2) Suzuki coupling reaction between intermediate B and pyridine-4-boronic acid to prepare the target compound.

Step (1) is specifically: using 5,5'-dibromo-2,2'-diphenol as raw material, and 3-chloromethylpyridine hydrochloride, acid-binding agent K ₂ CO ₃ , and catalyst KI in the Stir in DMF at room temperature for 24-36 hours, pour the reactant into water, filter with suction, and perform silica gel column chromatography on the filter cake, the eluent is CH ₂ Cl ₂ : _{CH 3} OH=25:1 v/v to obtain intermediate B; The molar ratio of 5,5'-dibromo-2,2'-biphenyldiol to 3-chloromethylpyridine hydrochloride is 1:(2-2.5).

In step (1), the molar ratio of acid-binding agent K ₂ CO ₃ , catalyst KI and 5,5'-dibromo-2,2'-biphenyldiol (15-20):(0.3-0.5):1 .

In the step (1), the molar ratio of DMF to 5,5'-dibromo-2,2'-diphenol is 1:30-34.

Step (2) is specifically: under the protection of N ₂ , intermediate B, pyridine-4-boronic acid, and acid-binding agent K ₂ CO ₃ are placed in a reaction vessel, and the volume ratio of toluene, ethanol and water is 1:1: 1 Prepare the mixed solution as a solvent, add catalyst Pd(PPh ₃ ) ₄ , heat to reflux, control the temperature at 90°C-110°C, control the reflux time at 24-36h, TLC tracking, let stand after the reaction, cool, and separate the liquid , the organic phase was spin-dried, silica gel column chromatography, the eluent was CH ₂ Cl ₂ :CH ₃ OH=20:1v/v, and the catalyst was obtained; wherein the molar ratio of intermediate B to pyridine-4-boronic acid was 1:( 2-2.5).

Step (2) The molar ratio of acid-binding agent K ₂ CO ₃ , catalyst Pd(PPh ₃ ) ₄ and intermediate B is (12-15):0.1:1.

The molar ratio of the mixed solution prepared with toluene, ethanol and water to the intermediate B in step (2) is 450-500:1.

The application of the above-mentioned compound in the reaction of catalyzing the oxidation of water.

The specific method of application is: the molar ratio of catalyst, copper salt and water is 1: (4-6): (100-120) sealed in a glass tube, at 145-150 ° C, constant temperature 3800-4320min, and then through 2800 -3000min to 25-30°C to obtain a solution containing hydrogen peroxide.

Put the catalyst, copper salt and water in a glass tube at a constant temperature of 150°C for 4320min, and then drop it to 30°C after 3000min to obtain a solution containing hydrogen peroxide.

The copper salt is Cu(NO ₃ ) ₂ ·6H ₂ O, Cu(ClO ₄ ) ₂ ·6H ₂ O or Cu(SO ₃ CF ₃ ) ₂ .

The synthesis route of the catalyst synthesized by the present invention is as follows:

a: Synthesis of intermediate B using 2,2'-Biphenol as raw material

b: Catalyst L synthesized by Suzuki reaction

Compared with the classic method of obtaining hydrogen peroxide in the past, the present invention has the following beneficial effects:

1. The hydrothermal cleaning production process is adopted. The solvent only uses pure water, no organic solvent is added, no toxic waste gas is produced, no intermediate products need to be separated, and the process flow is shortened.

2. The yellow monovalent copper salt polymer as a by-product can be directly precipitated from the solution, so that the hydrogen peroxide solution and the by-product can be separated by simple filtration, and no organic waste that pollutes the environment will be produced. Compared with Classical method, the production process of the present invention is more green and clean.

3. The pH value of the aqueous solution in the present invention decreases after the reaction, and can be directly used as an acid stabilizer for hydrogen peroxide without additional addition, which saves costs.

4. Since monovalent copper ions are easily oxidized by oxygen in the air, the by-products can be applied again after being oxidized.

Description of drawings

Figure 1 is a single crystal structure diagram of the catalyst of the present invention.

Fig. 2 is the EPR signal measured by adding the hydroxyl radical scavenger DMPO to the solution obtained by catalytic oxidation of water with the catalyst of Example 3 of the present invention and Cu(NO ₃ ) ₂ , indicating that hydroxyl radicals are generated in the hydrogen peroxide part of the obtained solution.

Fig. 3 is the EPR signal measured by adding the hydroxyl radical scavenger DMPO to the solution obtained by catalytic oxidation of water with the catalyst of Example 4 of the present invention and Cu(ClO ₄ ) ₂ , indicating that the hydrogen peroxide in the obtained solution partially generates free hydroxyl groups.

Fig. 4 is the EPR signal measured by adding the hydroxyl radical scavenger DMPO to the solution obtained by catalytic oxidation of water with the catalyst of Example 5 of the present invention and Cu(SO ₃ CF ₃ ) ₂ , indicating that the hydrogen peroxide in the obtained solution partially generates free hydroxyl groups.

Figure 5 is a photograph of the color change measured with a colorimetric tube for oxidizing water to produce hydrogen peroxide, indicating that the resulting solution contains hydrogen peroxide.

Detailed ways

The present invention is specifically described below through the examples, and it is necessary to point out that: the present examples are only used to further illustrate the present invention, but do not limit its scope. Various improvements made by those skilled in the art without departing from the essence of the present invention after reading the present invention are all obvious, and all belong to the protection scope of the present invention.

Embodiment 1: the preparation of catalyst

1.5,5'-dibromo-2,2'-diphenol (3.44g, 10mmol), 3-chloromethylpyridine hydrochloride (3.80g, 25mmol), K ₂ CO ₃ (27.6g, 200mmol) , KI (0.60g, 3.6mmol), DMF 25mL, stirred at room temperature for 36h, poured the reactant into water, filtered with suction, and filtered the cake through silica gel column chromatography (CH ₂ Cl ₂ :CH ₃ OH=25:1) to obtain a white Solid intermediate B 4.27g, yield 812%.

2. Under N ₂ protection, intermediate B (5.26g, 10mmol), pyridine-4-boronic acid (3.08g, 25mmol), K ₂ CO ₃ (17.25g, 125mmol), placed in a 250mL three-necked flask, toluene, ethanol Use water as a solvent, add catalyst Pd(PPh ₃ ) ₄ (1.2g, 1mmol), heat to reflux, control the temperature at 90°C-110°C, and control the reflux time at 24h. TLC tracking, after the reaction was completed, let stand, cooled, separated, the organic phase was spin-dried, and silica gel column chromatography (CH ₂ Cl ₂ : _{CH 3} OH=20:1) gave 4.16 g of a light yellow solid, with a yield of 79.6%. The product obtained in embodiment 1 is obtained the colorless flaky crystal of compound in the mixed solution of ethanol and water, determines the structure of compound (as shown in Figure 1) through x-ray single crystal diffraction, as can be seen from the figure, the The obtained compound is the target compound.

Embodiment 2: the preparation of catalyst

1.5,5'-dibromo-2,2'-diphenol (3.44g, 10mmol), 3-chloromethylpyridine hydrochloride (3.04g, 20mmol), K ₂ CO ₃ (20.7g, 150mmol) , KI (0.80g, 4.8mmol), DMF 25mL, stirred at room temperature for 24h, poured the reactant into water, filtered with suction, and filtered the cake through silica gel column chromatography (CH ₂ Cl ₂ :CH ₃ OH=25:1) to obtain a white Solid intermediate B4.12g, yield 78.3%.

2. Under N ₂ protection, intermediate B (5.26g, 10mmol), pyridine-4-boronic acid (2.46g, 20mmol), K ₂ CO ₃ (20.7g, 150mmol), placed in a 250mL three-necked flask, toluene, ethanol Use water as a solvent, add catalyst Pd(PPh ₃ ) ₄ (1.2g, 1mmol), heat to reflux, control the temperature at 90°C-110°C, and control the reflux time at 36h. TLC tracking, standing still after the reaction, cooling, liquid separation, spin-dried organic phase, silica gel column chromatography (CH ₂ Cl ₂ : _{CH 3} OH=20:1), yielded 4.02 g of light yellow solid with a yield of 76.9%.

Embodiment 3: Cu(NO ₃ ) _Hydrogen peroxide is produced by oxidizing water under hydrothermal conditions

5.22 mg (0.01 mmol) of the catalyst ligand L prepared in Example 1, 12.0 mg (0.04 mmol) of Cu(NO ₃ ) ₂ 6H ₂ O, and 2 mL of water were sealed in a 10 cm glass tube, and the program was set through The temperature was raised to 150°C in 300 minutes, kept at a constant temperature for 4320 minutes, and then lowered to 30°C after 3000 minutes to obtain a yellow monovalent copper salt polymer and a solution containing hydrogen peroxide.

Figure 3 shows the EPR signal measured by adding the hydroxyl radical scavenger DMPO to the solution obtained by catalyst and Cu(NO ₃ ) ₂ catalyzed oxidation of water, from which it can be concluded that the water is oxidized to hydrogen peroxide and partially generates hydroxyl radicals.

Embodiment 4: Cu(Cl0 ₄ ) _Hydrogen peroxide is produced by oxidizing water under hydrothermal conditions

5.22 mg (0.01 mmol) of catalyst ligand L prepared in Example 1, 12.4 mg (0.03 mmol) of Cu(ClO ₄ ) ₂ 6H ₂ O, and 2 mL of water were sealed in a 10 cm glass tube, and the program was set through The temperature was raised to 150°C in 300 minutes, kept at a constant temperature for 4320 minutes, and then lowered to 30°C after 3000 minutes to obtain a yellow monovalent copper salt polymer and a solution containing hydrogen peroxide.

Figure 4 shows the EPR signal measured by adding the hydroxyl radical scavenger DMPO to the solution obtained by catalyst and Cu(NO ₃ ) ₂ catalyzed oxidation of water, from which it can be concluded that the water is oxidized to hydrogen peroxide and partially generates hydroxyl radicals.

Example 5: Cu(SO ₃ CF ₃ ) ₂ hydrothermally oxidizes water to produce hydrogen peroxide

Put 5.22mg (0.01mmol) of the catalyst ligand L prepared in Example 2, 15.1mg (0.04mmol) of Cu(SO ₃ CF ₃ ) ₂ , and 2mL of water into a 10cm glass tube, and set the temperature to rise after 300min To 150°C, keep the temperature constant for 4320min, then drop to 30°C after 3000min, to obtain a yellow monovalent copper salt polymer and a solution containing hydrogen peroxide.

Figure 5 shows the EPR signal measured by adding the hydroxyl radical scavenger DMPO to the solution obtained by catalyst and Cu(NO ₃ ) ₂ to catalyze the oxidation of water, so it can be concluded that the water is oxidized to hydrogen peroxide and partially generates hydroxyl radicals.

Embodiment 6: oxidized water produces the color change that hydrogen peroxide measures with colorimetric tube

The white reagent in the hydrogen peroxide colorimetric tube is quickly added to the colorless solution obtained by catalyst (prepared by Example 3) and copper salt catalyzed oxidation water, as shown in Figure 5, the left vial is obtained by the oxidation water of the present invention The color change of the solution after adding the H ₂ O ₂ colorimetric tube reagent, the vial on the right is the color change after adding 30% H ₂ O ₂ to the H ₂ O ₂ colorimetric tube reagent. After 30 seconds, it can be compared with the hydrogen peroxide concentration color chart, and the obtained hydrogen peroxide concentration is about 1mg/L. Under the reaction conditions of 150°C, a considerable part of the hydrogen peroxide produces oxygen.

Claims (10)

1. a biphenyl compound is characterized in that, its chemical name is 5,5 '-two (4-pyridyl)-2,2 '-'-biphenyl diphenol, two-3-pyridine methyl ether, and its structural formula is following:

2. the compound method of the described biphenyl compound of claim 1 is characterized in that, may further comprise the steps:

(1) with 5,5 '-two bromo-2,2 '-'-biphenyl diphenol are raw material, make intermediate B with 3-chloromethyl pyridine hydrochloride generation etherification reaction, and the intermediate B structure is following:

(2) intermediate B and pyridine-4-boric acid generation suzuki linked reaction are processed target compound.

3. compound method as claimed in claim 2 is characterized in that, step (1) is specially: with 5,5 '-two bromo-2,2 '-'-biphenyl diphenol are raw material, with 3-chloromethyl pyridine hydrochloride, acid binding agent K ₂CO ₃, catalyzer KI stirring at normal temperature 24-36h in DMF, reactant is poured in the water, suction filtration, filter cake silica gel column chromatography, eluent are CH ₂Cl ₂: CH ₃OH=25: 1v/v makes intermediate B; 5,5 '-two bromo-2 wherein, 2 '-'-biphenyl diphenol and 3-chloromethyl pyridine hydrochloride molar ratio are 1: (2-2.5).

4. compound method as claimed in claim 3 is characterized in that, acid binding agent K in the step (1) ₂CO ₃, catalyzer KI and 5,5 '-two bromo-2, the molar ratio of 2 '-'-biphenyl diphenol (15-20): (0.3-0.5): 1.

5. compound method as claimed in claim 2 is characterized in that, step (2) is specially: N ₂Under the protection, with intermediate B, pyridine-4-boric acid, acid binding agent K ₂CO ₃Place reaction vessel, make solvent, add catalyst P d (PPh with the mixing solutions of toluene, the preparation in 1: 1: 1 by volume of second alcohol and water ₃) ₄, reflux, controlled temperature is at 90 ℃-110 ℃, and the control return time is at 24-36h, and TLC follows the tracks of, and reaction is left standstill after finishing, cooling, separatory, organic phase is revolved dried, and silica gel column chromatography, eluent are CH ₂Cl ₂: CH ₃OH=20: 1v/v gets catalyzer; Wherein the mol ratio of intermediate B and pyridine-4-boric acid is 1: (2-2.5).

6. compound method as claimed in claim 5 is characterized in that, step (2) acid binding agent K ₂CO ₃, catalyst P d (PPh ₃) ₄With the molar ratio of intermediate B be (12-15): 0.1: 1.

7. application rights requires the application of 1 described compound in catalyzed oxidation water generates ydrogen peroxide 50.

8. application as claimed in claim 7; It is characterized in that; Concrete grammar is: with catalyzer, mantoquita and hydromassage you than being 1: (4-6): (100-120) be sealed in the Glass tubing; At 145-150 ℃ of constant temperature 3800-4320min, reduce to 25-30 ℃ through 2800-3000min then, obtain containing the solution of ydrogen peroxide 50.

9. application as claimed in claim 8 is characterized in that concrete grammar is: catalyzer, mantoquita and water in Glass tubing, at 150 ℃ of constant temperature 4320min, are reduced to 30 ℃ through 3000min then, obtain containing the solution of ydrogen peroxide 50.

10. like claim 8 or 9 described application, it is characterized in that said mantoquita is Cu (NO ₃) ₂6H ₂O, Cu (ClO ₄) ₂6H ₂O or Cu (SO ₃CF ₃) ₂

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