A method for photocatalytic reaction of arylacetic acid and aryl halides using boron, carbon, nitrogen, and nickel.

Abstract

This invention proposes a method for photocatalyzing aryl acetic acid and aryl halides using a boron-carbon-nitrogen (h-BCN) system. The method comprises: using aromatic acetic acid compounds and aryl halides as raw materials, employing h-BCN as a non-metallic photocatalyst and NiCl2 as a co-catalyst, the two synergistically catalyze the reaction of aryl acetic acid and aryl halides at room temperature under inert gas protection and visible light irradiation, to efficiently synthesize C(sp2)-C(sp3) cross-coupled products. This invention replaces expensive, toxic, and scarce iridium-based photocatalysts with a h-BCN catalytic system. The h-BCN photocatalyst can be easily prepared by high-temperature calcination of boric acid, urea, and glucose precursors. The operation is simple, the conditions are mild, it completely avoids precious metals, and it combines selectivity and high efficiency, meeting practical production needs and possessing significant application potential.

Description

Technical Field

[0001] This invention relates to the field of photocatalytic organic synthesis technology, and in particular to a method for photocatalyzing arylacetic acid and aryl halides using boron, carbon, nitrogen, and nickel. Background Technology

[0002] C(sp2)-C(sp3) structural units are of particular importance in drug development. They can impart three-dimensional spatial complexity through C(sp3)-rich molecular skeletons, thus playing a crucial role in drug design and discovery. Furthermore, such skeletons can significantly improve the solubility, bioavailability, and pharmacokinetic properties of compounds, making them highly sought after in drug molecule development.

[0003] The decarboxylation cross-coupling of carboxylic acids and aryl halides has become a key transformation in organic synthesis for the formation of C(sp2)-C(sp3) bonds. While significant progress has been made in achieving this using metal photoredox chemistry, the use of noble metal photocatalysts (Ir) is required to achieve efficient redox processes and tunable properties (Science 2014, 345, 437-440). However, Ir suffers from drawbacks such as high cost, scarcity, and toxicity, making the search for suitable noble metal photocatalyst alternatives crucial. Therefore, the development of simple, efficient, and green catalytic strategies for the decarboxylation cross-coupling of carboxylic acids and aryl halides remains a research hotspot in this field. However, examples of using metal-free and recyclable boron, carbon, nitrogen, and NiCl2 as co-catalysts to synergistically catalyze the construction of C(sp2)-C(sp3) bonds between aryl acetic acid and aryl halides via visible light catalysis have not yet been reported. Summary of the Invention

[0004] In view of the above, the main objective of this invention is to provide a method for photocatalyzing arylacetic acid and aryl halides using boron, carbon, nitrogen, and nickel to solve the aforementioned technical problems.

[0005] This invention proposes a method for photocatalytic reaction of arylacetic acid and aryl halides using boron, carbon, nitrogen, and nickel, the method comprising the following steps:

[0006] Step 1: Aromatic acetic acid compounds, aryl halides, boron carbon nitrogen photocatalysts, nickel catalysts, ligands, and bases are sequentially added to an organic solvent to form a reaction mixture;

[0007] Step 2: Irradiate the reaction mixture with visible light under an inert gas atmosphere and carry out the reaction at room temperature to obtain the reaction solution;

[0008] Step 3: Filter the solution after the reaction to separate and recover the boron, carbon and nitrogen photocatalyst to obtain filtrate;

[0009] Step 4: Extract and concentrate the filtrate sequentially to obtain the crude product; purify the crude product by column chromatography to obtain the cross-coupled product.

[0010] The preparation of the boron-carbon-nitrogen photocatalyst includes the following steps:

[0011] Boric acid, urea and glucose are mixed evenly in a certain proportion and then ground into powder to obtain a precursor mixture.

[0012] The precursor mixture was calcined in an argon atmosphere to obtain a calcined mixture.

[0013] The calcined mixture was naturally cooled to room temperature, washed with distilled water and hydrochloric acid, and then vacuum dried to obtain the boron-carbon-nitrogen photocatalyst.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0015] 1. The synthesis method of the present invention avoids the use of precious metals, reduces reaction costs, and reduces byproducts generated during the catalytic process;

[0016] 2. The synthesis method of the present invention is simple and easy to implement, with mild conditions and safe operation. It can achieve a high yield under visible light at room temperature, and is energy-saving and environmentally friendly.

[0017] 3. The synthesis method of this invention is a heterogeneous reaction, the catalyst is easy to separate and can be recycled and reused;

[0018] 4. The synthesis method of the present invention has good adaptability to functional groups, broad substrate adaptability, and is environmentally friendly, and has good prospects for industrial application.

[0019] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by means of embodiments of the invention. Attached Figure Description

[0020] Figure 1 This is the proton spectrum of the product obtained in Example 1 of the present invention;

[0021] Figure 2 This is the carbon spectrum of the product obtained in Example 1 of the present invention;

[0022] Figure 3 This is the proton spectrum of the product obtained in Example 2 of the present invention;

[0023] Figure 4 This is the carbon spectrum of the product obtained in Example 2 of the present invention;

[0024] Figure 5 This is the proton spectrum of the product obtained in Example 3 of the present invention;

[0025] Figure 6 This is the carbon spectrum of the product obtained in Example 3 of the present invention;

[0026] Figure 7 This is the proton NMR spectrum of the product obtained in Example 4 of this invention;

[0027] Figure 8 This is the carbon spectrum of the product obtained in Example 4 of the present invention;

[0028] Figure 9 This is a graph showing the cycle stability test of boron, carbon, and nitrogen photocatalysts;

[0029] Figure 10 These are X-ray diffraction patterns of the boron, carbon, and nitrogen photocatalyst before and after cycling. Detailed Implementation

[0030] Embodiments of the present invention are described in detail below. Examples of these embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0031] These and other aspects of the embodiments of the present invention will become clear from the following description and accompanying drawings. In these descriptions and drawings, some specific embodiments of the present invention are specifically disclosed to illustrate some ways of implementing the principles of the embodiments of the present invention; however, it should be understood that the scope of the embodiments of the present invention is not limited thereto.

[0032] Example 1

[0033] Please see Figure 1 and Figure 2 This embodiment provides a method for photocatalyzing arylacetic acid and aryl halides using boron, carbon, nitrogen, and nickel, the method comprising the following steps:

[0034] Step 1: Add 0.6 mmol of p-methoxyphenylacetic acid, 0.2 mmol of p-bromobenzaldehyde, 10 mg of boron carbon nitrogen photocatalyst (h-BCN), 0.02 mmol of nickel catalyst (NiCl2), 0.03 mmol of 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy), and 0.6 mmol of potassium carbonate sequentially to 6 mL of acetonitrile to form a reaction mixture;

[0035] Step 2: Under an argon atmosphere, irradiate the reaction mixture with visible light at a wavelength of 420 nm and react at room temperature for 20 h to obtain the reaction solution;

[0036] Step 3: Filter the solution after the reaction to separate and recover the boron, carbon and nitrogen photocatalyst to obtain filtrate;

[0037] Step 4: Extract and concentrate the filtrate sequentially to obtain the crude product; purify the crude product by column chromatography to obtain the cross-coupled product, denoted as A1, with a yield of 77%.

[0038] The preparation of boron-carbon-nitrogen photocatalysts includes the following steps:

[0039] Boric acid (boron source), urea (nitrogen source), and glucose (carbon source) were mixed in a ratio of 1:1:100 and then ground into powder to obtain a precursor mixture.

[0040] The precursor mixture was calcined at 1000°C for 4 hours under an argon atmosphere to obtain a calcined mixture;

[0041] The calcined mixture was naturally cooled to room temperature, washed three times with distilled water and hydrochloric acid, and then vacuum dried to obtain the boron-carbon-nitrogen photocatalyst.

[0042] The proton and carbon spectra of the cross-coupling product A1 obtained in this example are shown below. Figure 1 and Figure 2 As shown, its structural characterization data are as follows:

[0043] 1 H NMR (400MHz, CDCl3) δ=10.00(s,1H),7.83(d,J=7.8,2H),7.37(d,J=7.8,2H),7.13(d,J=8.2,2H),6.88(d,J=8.3,2H),4.03(s,2H),3.82(s,3H).

[0044] 13 C NMR (101MHz, CDCl3) δ=191.99,158.26,148.96,134.61,131.84,130.04,129.95,129.44,114.10,55.27,41.22.

[0045] The structure of the cross-coupled product inferred from the above data is shown below:

[0046] ;

[0047] 4-(4-methoxybenzyl)benzaldehyde.

[0048] It should be noted that, in Figure 1 In this context, f1 represents the frequency dimension, and ppm represents parts per million.

[0049] Example 2

[0050] Please see Figure 3and Figure 4 This embodiment provides a method for photocatalyzing arylacetic acid and aryl halides using boron, carbon, nitrogen, and nickel, the method comprising the following steps:

[0051] Step 1: Add 0.6 mmol of p-methoxyphenylacetic acid, 0.2 mmol of methyl p-bromobenzoate, 10 mg of boron carbon nitrogen photocatalyst (h-BCN), 0.02 mmol of nickel catalyst (NiCl2), 0.03 mmol of 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy), and 0.6 mmol of potassium carbonate sequentially to 6 mL of acetonitrile to form a reaction mixture;

[0052] Step 2: Under an argon atmosphere, irradiate the reaction mixture with visible light at a wavelength of 420 nm and react at room temperature for 20 h to obtain the reaction solution;

[0053] Step 3: Filter the solution after the reaction to separate and recover the boron, carbon and nitrogen photocatalyst to obtain filtrate;

[0054] Step 4: Extract and concentrate the filtrate sequentially to obtain the crude product; purify the crude product by column chromatography to obtain the cross-coupled product, denoted as A2, with a yield of 80%.

[0055] The preparation of boron-carbon-nitrogen photocatalysts includes the following steps:

[0056] Boric acid (boron source), urea (nitrogen source), and glucose (carbon source) were mixed in a ratio of 1:1:100 and then ground into powder to obtain a precursor mixture.

[0057] The precursor mixture was calcined at 1000°C for 4 hours under an argon atmosphere to obtain a calcined mixture;

[0058] The calcined mixture was naturally cooled to room temperature, washed three times with distilled water and hydrochloric acid, and then vacuum dried to obtain the boron-carbon-nitrogen photocatalyst.

[0059] The proton and carbon spectra of the cross-coupling product A2 obtained in this example are shown below. Figure 3 and Figure 4 As shown, its structural characterization data are as follows:

[0060] 1 H NMR (400MHz, CDCl3) δ=7.98(d,J=7.1,2H),7.27(d,J=8.3,2H),7.12(d,J=7.3,2H),6.87(d,J=7.1,2H),4.00(s,2H),3.93(s,3H),3.82(s,3H).

[0061] 13 C NMR (101MHz, CDCl3) δ=167.12,158.17,147.04,132.23,129.94,129.81,128.83,128.00,114.02,55.26,52.02,41.04.

[0062] Based on the above data, the structure of the product is inferred as follows:

[0063] ;

[0064] methyl 4-(4-methoxybenzyl)benzoate.

[0065] Example 3

[0066] Please see Figure 5 and Figure 6 This embodiment provides a method for photocatalyzing arylacetic acid and aryl halides using boron, carbon, nitrogen, and nickel, the method comprising the following steps:

[0067] Step 1: Add 0.6 mmol of p-methoxyphenylacetic acid, 0.2 mmol of p-bromobenzonitrile, 10 mg of boron carbon nitrogen photocatalyst (h-BCN), 0.02 mmol of nickel catalyst (NiCl2), 0.03 mmol of 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy), and 0.6 mmol of potassium carbonate sequentially to 6 mL of acetonitrile to form a reaction mixture;

[0068] Step 2: Under an argon atmosphere, irradiate the reaction mixture with visible light at a wavelength of 420 nm and react at room temperature for 20 h to obtain the reaction solution;

[0069] Step 3: Filter the solution after the reaction to separate and recover the boron, carbon and nitrogen photocatalyst to obtain filtrate;

[0070] Step 4: Extract and concentrate the filtrate sequentially to obtain the crude product; purify the crude product by column chromatography to obtain the cross-coupled product, denoted as A3, with a yield of 70%.

[0071] The preparation of boron-carbon-nitrogen photocatalysts includes the following steps:

[0072] Boric acid (boron source), urea (nitrogen source), and glucose (carbon source) were mixed in a ratio of 1:1:100 and then ground into powder to obtain a precursor mixture.

[0073] The precursor mixture was calcined at 1000°C for 4 hours under an argon atmosphere to obtain a calcined mixture;

[0074] The calcined mixture was naturally cooled to room temperature, washed three times with distilled water and hydrochloric acid, and then vacuum dried to obtain the boron-carbon-nitrogen photocatalyst.

[0075] The proton and carbon spectra of the cross-coupling product A3 obtained in this example are shown below. Figure 5 and Figure 6 As shown, its structural characterization data are as follows:

[0076] 1 H NMR (400MHz, CDCl3) δ=7.59(d,J=7.7,2H),7.29(d,J=7.1,2H),7.10(d,J=8.1,2H),6.88(d,J=8.1,2H),4.00(s,2H),3.82(s,3H).

[0077] 13 C NMR (101MHz, CDCl3) δ=158.36,147.24,132.28,131.39,129.95,129.51,119.04,114.15,109.93,55.28,41.10.

[0078] Based on the above data, the structure of the product is inferred as follows:

[0079] ;

[0080] 4-(4-methoxybenzyl)benzonitrile.

[0081] Example 4

[0082] Please see Figure 7 and Figure 8 This embodiment provides a method for photocatalyzing arylacetic acid and aryl halides using boron, carbon, nitrogen, and nickel, the method comprising the following steps:

[0083] Step 1: Add 0.6 mmol of p-methoxyphenylacetic acid, 0.2 mmol of 6-bromoquinoline, 10 mg of boron carbon nitrogen photocatalyst (h-BCN), 0.02 mmol of nickel catalyst (NiCl2), 0.03 mmol of 4,4'-di-tert-butyl-2,2'-bipyridine (dtbbpy), and 0.6 mmol of potassium carbonate sequentially to 6 mL of acetonitrile to form a reaction mixture;

[0084] Step 2: Under an argon atmosphere, irradiate the reaction mixture with visible light at a wavelength of 420 nm and react at room temperature for 20 h to obtain the reaction solution;

[0085] Step 3: Filter the solution after the reaction to separate and recover the boron, carbon and nitrogen photocatalyst to obtain filtrate;

[0086] Step 4: Extract and concentrate the filtrate sequentially to obtain the crude product; purify the crude product by column chromatography to obtain the cross-coupled product, denoted as A4, with a yield of 65%.

[0087] The preparation of boron-carbon-nitrogen photocatalysts includes the following steps:

[0088] Boric acid (boron source), urea (nitrogen source), and glucose (carbon source) were mixed in a ratio of 1:1:100 and then ground into powder to obtain a precursor mixture.

[0089] The precursor mixture was calcined at 1000°C for 4 hours under an argon atmosphere to obtain a calcined mixture;

[0090] The calcined mixture was naturally cooled to room temperature, washed three times with distilled water and hydrochloric acid, and then vacuum dried to obtain the boron-carbon-nitrogen photocatalyst.

[0091] The proton and carbon spectra of the cross-coupling product A4 obtained in this embodiment are shown below. Figure 7 and Figure 8 As shown, its structural characterization data are as follows:

[0092] 1 H NMR (400MHz, CDCl3) δ=8.93-8.84(m,1H),8.11(d,1H),8.06(d,1H),7.59(d,2H),7.39(dd,1H),7.17(d,2H),6.88(d,2H),4.14(s,2H),3.81(s,3H).

[0093] 13 C NMR(101MHz, CDCl3)δ=158.18,149.65,146.97,140.17,135.91,132.47,131.34,130.01,129.31,128.36,126.60,121.15,114.04,55.28,40.99.

[0094] Based on the above data, the structure of the product is inferred as follows:

[0095] ;

[0096] 6-(4-methoxybenzyl)quinoline.

[0097] To verify the effectiveness of this invention, the recycled boron, carbon, and nitrogen photocatalyst was subjected to cycle stability testing:

[0098] After the reaction in Example 1 was completed, the boron carbon nitrogen photocatalyst (h-BCN) was separated from the reaction solution and recovered by simple filtration. It was then thoroughly washed with ethanol and vacuum dried at room temperature. It could be used directly in the next round of reaction without additional activation. The recovered boron carbon nitrogen photocatalyst was cycled 5 times under the conditions of Example 3 to systematically evaluate the cycle stability of the boron carbon nitrogen photocatalyst.

[0099] Experimental results show that after five cycles of experimentation, the yield of the cross-coupling product of the boron-carbon-nitrogen photocatalyst can be maintained above 75% (e.g., Figure 9 As shown in the figure, this indicates that the recycled boron-carbon-nitrogen photocatalyst still maintains high photocatalytic activity for the reaction in Example 3 above; at the same time, the X-ray diffraction of the boron-carbon-nitrogen photocatalyst remains basically unchanged after 5 cycles of recycling (as shown in the figure). Figure 10 As shown, the positions and relative intensities of the main diffraction peaks before and after the reaction are basically the same, with no new impurity peaks or disappearance of existing peaks, which fully demonstrates that the boron-carbon-nitrogen photocatalyst has good stability.

[0100] It should be understood that although the steps in the flowcharts of the various embodiments of the present invention are shown sequentially according to the arrows, these steps are not necessarily executed in the order indicated by the arrows. Unless explicitly stated herein, there is no strict order restriction on the execution of these steps, and they can be executed in other orders. Moreover, at least some steps in the various embodiments may include multiple sub-steps or multiple stages. These sub-steps or stages are not necessarily completed at the same time, but can be executed at different times. The execution order of these sub-steps or stages is not necessarily sequential, but can be performed alternately or in turn with other steps or at least a portion of the sub-steps or stages of other steps.

[0101] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0102] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of this patent should be determined by the appended claims.

Claims

1. A process for photocatalytic ary l acetic acid and ary l halide by boron carbon nitride-nickel characterized by, The method comprises the following steps: Step 1, sequentially adding an aromatic acetic compound, an aryl halide, a boron-carbon-nitrogen photocatalyst, a nickel catalyst, a ligand and a base into an organic solvent to form a reaction mixture; The ligand is 4,4'-di-tert-butyl-2,2'-bipyridine, the base is potassium carbonate, and the organic solvent is acetonitrile; Step 2, irradiating the reaction mixture with visible light under an inert gas atmosphere, and performing a reaction at room temperature to obtain a reacted solution; Step 3, filtering and separating the reacted solution, and recovering the boron-carbon-nitrogen photocatalyst after separation to obtain a filtrate; Step 4, sequentially extracting and concentrating the filtrate to obtain a crude product, and purifying the crude product by column chromatography to obtain a cross-coupling product; The preparation of the boron-carbon-nitrogen photocatalyst comprises the following steps: Mixing boronic acid, urea and glucose in a certain proportion, grinding into powder to obtain a precursor mixture; Performing calcination on the precursor mixture under an argon atmosphere to obtain a calcined mixture; Cooling the calcined mixture to room temperature naturally, washing with distilled water and hydrochloric acid, and vacuum drying to obtain the boron-carbon-nitrogen photocatalyst; The proportion of the boronic acid, urea and glucose is 1:1:100, the calcination temperature is 1000℃, the calcination time is 4h, and the washing frequency is 3 times.

2. The process for photocatalytic ary l acetic acid and ary l halide by boron carbon nitride-nickel according to claim 1, characterized by, In the process of obtaining the reaction mixture in step 1, the aromatic acetic compound is p-methoxyphenylacetic acid, and the aryl halide is one of p-bromobenzaldehyde, methyl p-bromobenzoate, p-bromobenzonitrile and 6-bromoquinoline.

3. The method of photocatalytic ary l acetic acid and ary l halide by boron carbon nitride-nickel according to claim 2, characterized in that, The amount of the aromatic acetic compound is 0.6mmol, and the amount of the aryl halide is 0.2mmol.

4. The process for photocatalytic ary l acetic acid and ary l halide by boron carbon nitride-nickel as claimed in claim 1, wherein, The amount of the boron carbonitride photocatalyst is 10 mg, the specific surface area of the boron carbonitride photocatalyst is 500-1500 m 2 / g, the absorption band edge of the boron carbonitride photocatalyst is 400-600 nm, and the amount of the nickel catalyst is 0.02 mmol.

5. The method of photocatalytic ary l acetic acid and ary l halide by boron carbon nitride-nickel according to claim 1, characterized in that, The amount of the ligand is 0.03mmol, the amount of the base is 0.6mmol, and the volume of the organic solvent is 6mL.

6. The method of photocatalytic ary l acetic acid and ary l halide by boron carbon nitride-nickel according to claim 1, characterized in that, The inert gas is argon, the visible light is provided by a light-emitting diode, the wavelength of the visible light is 420nm, and the reaction time is 20h.

Images