CN113816910A - Green synthesis of metal-free BCN photocatalytic benzoxazole compounds - Google Patents
Green synthesis of metal-free BCN photocatalytic benzoxazole compounds Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 23
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 42
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 36
- -1 benzoxazole compound Chemical class 0.000 claims abstract description 19
- 239000001103 potassium chloride Substances 0.000 claims abstract description 18
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
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- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
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- 238000010499 C–H functionalization reaction Methods 0.000 claims abstract description 6
- 239000006227 byproduct Substances 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
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- 230000003197 catalytic effect Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
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- 239000004202 carbamide Substances 0.000 description 9
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 7
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D263/57—Aryl or substituted aryl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a green synthesis method of a metal-free BCN photocatalytic benzoxazole compound, which adopts a potassium chloride-assisted molten salt method to prepare porous boron-carbon nitride (P-BCN) with the characteristics of enhanced crystallinity and increased exposure of N-B. In the green oxidant O2And water as a byproduct under green mild conditions, and the like, firstly passes through a metal-free catalystAlcohol Oxidation/toluene SP3C-H activation, and realizes the high-efficiency heterogeneous photocatalytic tandem synthesis of the benzoxazole compounds. Various o-thio/hydroxy/amino anilines and alcohols or toluene can be converted into corresponding 2-substituted benzothiazoles, benzoxazoles and benzimidazoles, and the photocatalyst has excellent photocatalytic performance. The preparation method of the catalyst is simple and easy to operate, the reaction condition is mild, and the catalyst is easy to recycle.
Description
Technical Field
The invention relates to a green synthesis method of a metal-free BCN photocatalytic benzoxazole compound.
Background
The synthesis of heterocyclic compounds is a cornerstone of many biologically active compounds, drugs, natural products and functional materials. The development of processes for the preparation of benzothiazoles, benzoxazoles, benzimidazoles and derivatives thereof has attracted considerable attention. Conventionally, intermolecular cyclization of an o-haloaniline compound and condensation of 2-aminophenol with an aryl aldehyde have been used for preparing the above heterocyclic compounds. Intermolecular cyclization of ortho-haloaniline compounds has inherent disadvantages such as the use of reactive and toxic reagents, less common substrates, transition metal catalysts and ligands, and the formation of undesirable waste products. On the other hand, the condensation process of 2-aminophenol with aromatic aldehydes generally requires the use of toxic catalysts, high temperatures and strong dehydration reagents. Therefore, the development of new, simple and convenient synthetic methods for heterocyclic compounds is still in demand.
Boron Nitride (BN) is considered a new generation of catalytic material for selective oxidative dehydrogenation reactions. However, the large band gap and undefined reactive sites of BN limit its development. One possible approach to improving the catalytic performance of BN is to introduce carbon into BN to form BCN materials with adjustable appropriate band gap and increased charge separation/transport properties. As is well known, crystallinity generally refers to the degree of structural order in a solid catalytic material. Theoretically, a higher structural order means higher crystallinity and lower defect density. In addition, defect sites in the photocatalyst always act as photo-induced charge recombination centers, resulting in a decrease in photocatalytic performance. Therefore, increasing the crystallinity of the photocatalytic material is a promising approach to increase the photocatalytic performance.
Disclosure of Invention
According to the invention, boric acid, urea and glucose are used as raw materials, and a potassium chloride-assisted molten salt method is adopted to heat for 5 hours at 1000 ℃ in a nitrogen atmosphere, so that the porous boron-carbon nitride (P-BCN) with the characteristics of enhanced crystallinity and increased exposure of N-B is prepared. In the green oxidant O2And water as a byproduct, and the like, for the first time on a metal-free catalyst through alcohol oxidation/toluene SP3C-H activation, and realizes the high-efficiency heterogeneous photocatalytic tandem synthesis of the benzoxazole compounds. Various o-thio/hydroxy/amino anilines and alcohols or toluene can be converted into corresponding 2-substituted benzothiazoles, benzoxazoles and benzimidazoles, and the photocatalyst has excellent photocatalytic performance. The preparation method of the catalyst is simple and easy to operate, the reaction condition is mild, and the catalyst is easy to recycle.
The invention disclosesA green synthesis method of metal-free BCN photocatalytic benzoxazole compounds adopts the technical scheme that: boric acid, urea and glucose are used as raw materials, a potassium chloride-assisted molten salt method is adopted to heat for 5 hours at the temperature of 1000 ℃ in a nitrogen atmosphere, the porous boron-carbon nitride P-BCN with the characteristics of enhanced crystallinity and increased exposure of N-B is prepared, the improvement of the photocatalysis of the P-BCN is attributed to the improvement of the crystallinity and the increased exposure of the N-B promotes the generation of superoxide radical on an electron-enriched N atom, and the oxidation capacity of a valence band of a B2P track structure is improved; the green synthesis characteristic of the photocatalysis benzoxazole compound is as follows: under visible light irradiation, green oxidant O2And water as a byproduct under green mild conditions over a metal-free catalyst by alcohol oxidation/toluene SP3C-H activation realizes the high-efficiency heterogeneous photocatalytic synthesis of the benzoxazole compounds, and various o-sulfenyl/hydroxyl/amino aniline and alcohols or toluene can be converted into corresponding 2-substituted benzothiazole compounds, benzoxazole compounds and benzimidazole compounds.
The green synthesis method of the metal-free BCN photocatalytic benzoxazole compound is characterized by comprising the following steps: the potassium chloride-assisted molten salt strategy improves the exposure of N-B to obtain a novel porous boron carbonitride P-BCN photocatalytic material while realizing BCN crystallinity enhancement, and the crystallinity enhancement of P-BCN and the increase of the exposure of N-B promote the synthesis of benzoxazole compounds.
The green synthesis method of the metal-free BCN photocatalytic benzoxazole compound is characterized by comprising the following steps: the increased N-B pair exposure during BCN crystallinity enhancement promotes the formation of superoxide radicals on electron-rich N atoms and promotes increased oxidation of the valence band constituted by the B2 p orbital.
The green synthesis method of the metal-free BCN photocatalytic benzoxazole compound is characterized by comprising the following steps: by oxidation of aromatic alcohols, alkyl alcohols, toluene SP3C-H activation can realize high-efficiency heterogeneous photocatalytic multi-step synthesis of the benzoxazole compounds.
The green synthesis method of the metal-free BCN photocatalytic benzoxazole compound is characterized by comprising the following steps: the synthesis process of the metal-free multiphase BCN photocatalytic benzoxazole compound avoids the pollution of metal to products in the traditional synthesis process.
The green synthesis method of the metal-free BCN photocatalytic benzoxazole compound is characterized by comprising the following steps: the catalytic system can be irradiated by visible light, and the green oxidant O2And water is used as a byproduct, the high-temperature reaction condition is avoided in the photocatalysis process, the catalytic system has no catalytic activity in the absence of illumination, and the catalytic activity is higher under the promotion of light.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the photocatalyst comprises the following steps:
BCN: boric acid, urea and glucose are used as raw materials, and the BCN with adjustable band gap is synthesized by changing the dosage of the glucose. 10g of borate, urea and glucose in different weights (weight ratios: 4:4:2, 3:3:4 and 2:2:6) were thoroughly dissolved in 70ml of distilled water. Water was evaporated to give a white precursor. Then, the precursor was placed in a horizontal tube furnace and heated at 1000 ℃ for 5 hours under a nitrogen atmosphere at a heating rate of 5 ℃/min. Naturally cooling, grinding into powder, washing with 5% hydrochloric acid to remove excessive boric acid or boron oxide, and vacuum drying at 60 deg.C to obtain BCN. The catalyst with the weight ratio of 4:4:2 of the obtained catalyst was labeled BCN-A, the catalyst with the weight ratio of 3:3:4 was labeled BCN-B, and the catalyst with the weight ratio of 2:2:6 was labeled BCN-C.
P-BCN: and preparing the porous BCN by adopting a KCl auxiliary molten salt method. Boric acid (3 g), urea (3 g), glucose (4 g) and potassium chloride (2 g) were dissolved in distilled water (70 ml). Water was evaporated to give a white precursor. Then, the precursor was placed in a horizontal tube furnace and heated at 1000 ℃ for 5 hours under a nitrogen atmosphere at a heating rate of 5 ℃/min. Excess raw material and potassium chloride were washed off with 5% hydrochloric acid, and the resulting catalyst powder was dried under vacuum at 60 ℃.
The green synthesis method of the benzoxazole compounds catalyzed by visible light generally comprises the following steps: the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of the catalyst was weighed out and then 0.1mmol of o-aminothiophenol or o-aminophenol or o-diphenylamine, 0.3mmol of alcohol or toluene, 2ml of solvent were added to the sealed tube. After the reaction, the catalyst was recovered by centrifugation, and the resulting product was analyzed by LC and LC-MS and compared with known compounds.
Drawings
FIG. 1 shows Scanning Electron Microscope (SEM) photographs of BCN-B (a) and P-BCN (b). Transmission Electron Microscopy (TEM) image (c) of P-BCN. High resolution TEM image of P-BCN (d).
FIG. 2 is an XRD pattern (a) and FT-IR quantitative determination spectrum (B) of BCN-B and P-BCN. FT-IR quantitative measurement method: 5mg BCN-B or P-BCN was thoroughly ground with 400mg KBr and the mixture was used for FT-IR analysis.
FIG. 3 is X-ray photoelectron spectroscopy (XPS) of P-BCN. a) Full spectrum, B) B1s, C) C1 s, d) N1 s.
FIG. 4 is a transient photocurrent graph (a) of BCN-B and P-BCN. Electrochemical Impedance (EIS) spectra (B) of BCN-B and P-BCN. Photoluminescence (PL) spectra (c) of BCN-B and P-BCN at 390nm excitation. Electron Paramagnetic Resonance (EPR) spectrum (d) of P-BCN.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Example 1:
the preparation method of the photocatalyst comprises the following steps: BCN: boric acid, urea and glucose are used as raw materials, and the BCN with adjustable band gap is synthesized by changing the dosage of the glucose. 10g of borate, urea and glucose in different weights (weight ratios: 4:4:2, 3:3:4 and 2:2:6) were thoroughly dissolved in 70ml of distilled water. Water was evaporated to give a white precursor. Then, the precursor was placed in a horizontal tube furnace and heated at 1000 ℃ for 5 hours under a nitrogen atmosphere at a heating rate of 5 ℃/min. Naturally cooling, grinding into powder, washing with 5% hydrochloric acid to remove excessive boric acid or boron oxide, and vacuum drying at 60 deg.C to obtain BCN. The catalyst with the weight ratio of 4:4:2 of the obtained catalyst was labeled BCN-A, the catalyst with the weight ratio of 3:3:4 was labeled BCN-B, and the catalyst with the weight ratio of 2:2:6 was labeled BCN-C.
P-BCN: and preparing the porous BCN by adopting a KCl auxiliary molten salt method. Boric acid (3 g), urea (3 g), glucose (4 g) and potassium chloride (2 g) were dissolved in distilled water (70 ml). Water was evaporated to give a white precursor. Then, the precursor was placed in a horizontal tube furnace and heated at 1000 ℃ for 5 hours under a nitrogen atmosphere at a heating rate of 5 ℃/min. Excess raw material and potassium chloride were washed off with 5% hydrochloric acid, and the resulting catalyst powder was dried under vacuum at 60 ℃.
The green synthesis method of the benzoxazole compounds catalyzed by visible light generally comprises the following steps: the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of the catalyst was weighed out and then 0.1mmol of o-aminothiophenol or o-aminophenol or o-diphenylamine, 0.3mmol of alcohol or toluene, 2ml of solvent were added to the sealed tube. After the reaction, the catalyst was recovered by centrifugation, and the resulting product was analyzed by LC and LC-MS and compared with known compounds.
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of catalysts BCN-B (a) and P-BCN (b) prepared in example 1. Transmission Electron Microscopy (TEM) image (c) of P-BCN. High resolution TEM image of P-BCN (d). The BCN with adjustable band gap is prepared by a simple calcination method, and the P-BCN is designed and prepared by adopting a KCl auxiliary molten salt method. The morphological characteristics of BCN-B and P-BCN in FIG. 1 were studied using Scanning Electron Microscopy (SEM). BCN-B is a layered characteristic structure. P-BCN prepared by the KCl auxiliary molten salt strategy presents a porous structure. The porous structure was also detected in the TEM image (FIG. 1c), and the 0.34nm lattice fringes of the P-BCN (002) crystal plane were easily observed in the HRTEM image (FIG. 1 d). The KCl auxiliary molten salt strategy not only forms a porous structure of the P-BCN, but also improves the crystallinity of the P-BCN.
FIG. 2 is an XRD pattern (a) and FT-IR quantitative determination spectrum (B) of BCN-B and P-BCN catalysts prepared in example 1. Wherein the FT-IR quantitative determination method comprises the steps of fully grinding 5mg of BCN-B or P-BCN with 400mg of KBr, and using the mixture for FT-IR analysis. The crystal structure and surface properties of the BCN material were studied using XRD and FT-IR. In fig. 2, there are two diffraction peaks at 26 ° and 43 °, corresponding to the 002 and 100 crystal planes of BCN. Compared with XRD of BCN-B, the KCl auxiliary molten salt strategy obviously increases the peak intensity of a P-BCN (002) crystal face (figure 2a), which proves that the KCl auxiliary molten salt strategy improves the crystallinity of the P-BCN, and the high crystallinity accelerates the separation and transfer of photogenerated carriers. FIG. 1B is a quantitative FT-IR spectrum of BCN-B and P-BCN. In FT-IR, BCN-B and P-BCN at 1380cm-1And 776cm-1Two strong peaks corresponding to out-of-plane B-N bond stretching vibration and in-plane B-N-B bending vibration. Signals of C-N bond and B-N bond are 1200-1500 cm-1Are overlapped. These characteristic peaks indicate that the main backbone structure of BCN remains unchanged during the material modification process. Furthermore, the change in characteristics from BCN-B to P-BCN was investigated using quantitative FT-IR spectroscopy (FIG. 2B). The increase in peak intensity in P-BCN compared to BCN-B indicates an increase in exposure of N-B during calcination of the molten salt strategy.
FIG. 3 is X-ray photoelectron spectroscopy (XPS) of catalysts BCN-B and P-BCN prepared in example 1, and the chemical composition and coordination state of P-BCN are further analyzed by XPS in FIG. 3. P-BCN has four elements: B. c, N and O. No KCl remained in the sample. High resolution spectra of boron, carbon and nitrogen are shown in figures 3 b-d. For the B1s spectrum, there were three peaks at 191.9, 190.6 and 190.0eV, corresponding to the B-O, B-N and B-C bonds, respectively. The presence of the B-O bond is due to defect sites or surface impurities in the P-BCN. The C1 s spectrum was resolved into four peaks at 288.1,286.3,284.8 and 284.1eV, assigned to the C-O, C-N, C-C and C-B bonds, respectively. The N1 s spectrum, peaks at 398.9 and 398.1eV are assigned to N-C and N-B. The O1 s peak is mainly from unreacted B-O and surface absorbed H2And O. Similar to the FT-IR results, the increase in surface B and N element content in P-BCN compared to BCN-B resulted in exposure of the N-B pair. As the amount of B in the exposed N-B pair increases, the oxidizing power of the P-BCN valence band of the B2P orbital configuration increases accordingly. On the other hand, the electron-rich nitrogen atom in BCN will facilitate electron transfer from BCN to the adsorbed oxygen species promoting superoxide radical generation.
FIG. 4 is a transient photocurrent graph (a) of catalysts BCN-B and P-BCN prepared in example 1. Electrochemical Impedance (EIS) spectra (B) of BCN-B and P-BCN. Photoluminescence (PL) spectra (c) of BCN-B and P-BCN at 390nm excitation. Electron Paramagnetic Resonance (EPR) spectrum (d) of P-BCN. In the transient photocurrent response graph, P-BCN showed higher photocurrent response (fig. 4a), indicating that P-BCN has better photoelectron-hole separation efficiency. In addition, the EIS spectral radius of P-BCN in FIG. 4B is smaller than that of BCN-B, the smaller radius indicating a reduced photo-generated electron transfer resistance. Photoluminescence (PL) test to analyze photoexcited charge separation and transfer characteristics. The PL peak was detected at λ 570nm in fig. 4 c. It was found that as the crystallinity of BCN increases, the photogenerated electron-hole recombination is inhibited. Thus, P-BCN with increased crystallinity exhibits higher charge separation, transfer efficiency and lower charge recombination rate, which may result in better photocatalytic performance. Furthermore, Electron Paramagnetic Resonance (EPR) is used in FIG. 4d to illustrate the spatial redistribution of carriers of the prepared P-BCN. In the magnetic field 3475-3400, the Lorentzian-like magnetic lines of the catalyst indicate that unpaired electrons are generated on carbon atoms in the aromatic system. The P-BCN has a stronger EPR signal under the action of light, and the enhanced EPR signal indicates the effective generation of photoelectrons.
Example 2 (table 1, entry 3):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst BCN-A was weighed, and then 0.1mmol of o-aminothiophenol, 0.3mmol of benzyl alcohol, 2ml of DMF solvent were added to A sealed tube. After 2 hours of reaction, the 1a conversion was 36% and the 3a selectivity was 97%.
Example 3 (table 1, entry 4):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst BCN-B was weighed, and then 0.1mmol of o-aminothiophenol, 0.3mmol of benzyl alcohol, 2ml of DMF solvent were added to the sealed tube. After 2 hours of reaction, the 1a conversion was 44% and the 3a selectivity was 99%.
Example 4 (table 1, entry 5):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst BCN-C was weighed, and then 0.1mmol of o-aminothiophenol, 0.3mmol of benzyl alcohol, 2ml of DMF solvent were added to the sealed tube. After 2 hours of reaction, the 1a conversion was 35% and the 3a selectivity was 96%.
Example 5 (table 1, entry 6):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst P-BCN was weighed out and then 0.1mmol of o-aminothiophenol, 0.3mmol of benzyl alcohol, 2ml of DMF solvent were added to the sealed tube. After 2 hours of reaction, the 1a conversion was 71% and the 3a selectivity was 98%.
Example 6 (table 1, entries 7, 12):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst P-BCN was weighed out and then 0.1mmol of o-aminothiophenol, 0.3mmol of benzyl alcohol, 2ml of DMF solvent were added to the sealed tube. After 4 hours of reaction, the 1a conversion was 99% and the 3a selectivity was 98%. The conversion rate of the catalyst used for the second time after centrifugation is 97 percent, the selectivity of the catalyst used for the third time is 98 percent, the conversion rate of the catalyst used for the third time after centrifugation is 97 percent, the selectivity of the catalyst used for the third time is 98 percent, the conversion rate of the catalyst used for the fourth time after centrifugation is 89 percent, and the selectivity of the catalyst used for the third time is 98 percent.
Table 1 reaction conditions for synthesizing 2-phenylbenzothiazole from o-aminobenzenethiol and benzyl alcohol are optimized. a is
Note: a using 0.1mmol 1a, 0.3mmol 2a, 10mg catalyst, 2ml solvent at 0.75w/cm-2Blue LED (460nm) irradiation, and the reaction was carried out in a nitrogen atmosphere. DMF ═ N, N-dimethylformamide, THF ═ tetrahydrofuran. BCN-A, BCN-B and BCN-C indicate that the weight ratio of boric acid, urea and glucose is 1: 8, 2:6 and 3: 4. b, detecting the reaction conversion rate by adopting liquid chromatography. c no illumination. d no catalyst. e the fourth cycle of catalyst.
Example 7 (table 2, 3 c):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst P-BCN was weighed, and then 0.1mmol of o-aminothiophenol, 0.3mmol of P-methylbenzyl alcohol, 2ml of DMF solvent were added to a sealed tube. After 24 hours of reaction, the 1a conversion was 89% and the 3c selectivity was 99%.
TABLE 2 photocatalytic tandem synthesis of benzoxazoles with ortho-thio/hydroxy/amino anilines and alcohols. a is
Reaction conditions are as follows: a 0.1mmol of 1a, 1b or 1c, 0.3mmol of 2, 10mg of P-BCN, 2ml of DMF, N2And then irradiating the glass for 4 to 48 hours by visible light. The data in parentheses are the selectivity of the product.
Example 8 (table 2, 3 g):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst P-BCN was weighed, and then 0.1mmol of o-aminothiophenol, 0.3mmol of n-butanol, 2ml of DMF solvent were added to the sealed tube. After 24 hours of reaction, the 1a conversion was 89%, and the 3g selectivity was 99%.
Example 9 (table 2, 4 a):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst P-BCN was weighed out and then 0.1mmol of o-aminophenol, 0.3mmol of benzyl alcohol, 2ml of DMF solvent were added to the sealed tube. After 24 hours of reaction, the 1b conversion was 72% and the 4a selectivity was 98%.
Example 10 (table 2, 4 g):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst P-BCN was weighed, and then 0.1mmol of o-aminophenol, 0.3mmol of n-butanol, 2ml of DMF solvent were added to the sealed tube. After 24 hours of reaction, 1b conversion was 30% and 4g selectivity was 96%.
Example 11 (table 2, 5 a):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst P-BCN was weighed and then 0.1mmol of o-diphenylamine, 0.3mmol of benzyl alcohol, 2ml of DMF solvent were added to the sealed tube. After 24 hours of reaction, the 1c conversion was 32% and the 5a selectivity was 98%.
Example 12 (table 2, 5 e):
the reaction was carried out in a sealed reaction tube under blue light irradiation. 10mg of catalyst P-BCN is weighed, and then 0.1mmol of o-diphenylamine, 0.3mmol of P-bromobenzyl alcohol and 2ml of DMF solvent are added into a sealed tube. After 48 hours of reaction, the 1c conversion was 90% and the 5e selectivity was 98%.
Example 13 (table 3, 7 a):
reacting under the condition of filling with O2The reaction is carried out under blue light irradiation in the sealed reaction tube of (1). Weighing 10mg of catalyst P-BCN, and adding0.1mmol of o-aminothiophenol and 2ml of toluene solvent were added to the sealed tube. After 24 hours of reaction, the 1a conversion was 86% and the 7a selectivity was 98%.
Example 14 (table 3, 7 c):
reacting under the condition of filling with O2The reaction is carried out under blue light irradiation in the sealed reaction tube of (1). 20mg of catalyst P-BCN was weighed, and then 0.1mmol of o-aminobenzenethiol, 1mmol of P-methoxybenzyl alcohol and 2ml of dichloroethane solvent were added to a sealed tube. After 48 hours of reaction, 1a conversion was 47% and 7c selectivity was 95%.
Example 15 (table 3, 8 a):
reacting under the condition of filling with O2The reaction is carried out under blue light irradiation in the sealed reaction tube of (1). 10mg of catalyst P-BCN was weighed, and then 0.1mmol of o-aminophenol and 2ml of a toluene solvent were added to the sealed tube. After 24 hours of reaction, the 1b conversion was 65% and the 8a selectivity 98%.
Example 16 (table 3, 8 c):
reacting under the condition of filling with O2The reaction is carried out under blue light irradiation in the sealed reaction tube of (1). 20mg of catalyst P-BCN was weighed out and then 0.1mmol of o-aminophenol, 1mmol of P-methoxytoluene and 2ml of dichloroethane solvent were added to the sealed tube. After 48 hours of reaction, the 1b conversion was 47% and the 8c selectivity was 97%.
TABLE 3 photocatalytic tandem synthesis of benzazoles on metal-free P-BCN of ortho-thio/hydroxyaniline and toluene.
Reaction conditions are as follows: 0.1mmol of 1a or 1b, 1mmol of 6, 20mg of P-BCN, 2ml of dichloroethane solvent, 48 hours of light irradiation, 1atm of O2The data in parentheses are the product selectivities. a 10mg of P-BCN, 2ml of toluene solvent, and 24 hours of light irradiation.
Claims (6)
1. The metal-free BCN photocatalysis benzoxazole compound is synthesized in a green way, and the preparation of the catalysis material is characterized in that: the porous boron-carbon nitride P-BCN with the characteristics of enhanced crystallinity and increased exposure of N-B is prepared by adopting a potassium chloride-assisted molten salt methodThe improvement of the photocatalysis performance of the P-BCN is attributed to the improvement of the crystallinity and the increased exposure of N-B to the N atom which promotes the generation of superoxide radical on the electron enrichment, and the oxidation capability of the valence band of the B2P orbital structure is improved, and the green synthesis characteristic of the photocatalysis benzoxazole compound is as follows: under visible light irradiation, green oxidant O2And water as a byproduct under green mild conditions over a metal-free catalyst by alcohol oxidation/toluene SP3C-H activation realizes efficient heterogeneous photocatalytic tandem synthesis of the benzoxazole compounds, and various o-sulfenyl/hydroxyl/amino aniline and alcohols or toluene can be converted into corresponding 2-substituted benzothiazole compounds, benzoxazole compounds and benzimidazole compounds.
2. The metal-free BCN photocatalytic green synthesis of benzoxazole compounds according to claim 1, characterized in that: the potassium chloride-assisted molten salt strategy increases the exposure of N-B to obtain the novel porous boron carbonitride P-BCN photocatalytic material while realizing BCN crystallinity enhancement, and the improvement of the crystallinity enhancement in P-BCN and the increase of the exposure of N-B promote the synthesis of benzoxazole compounds.
3. The metal-free BCN photocatalytic green synthesis of benzoxazole compounds according to claim 1, characterized in that: the increased N-B pair exposure during BCN crystallinity enhancement promotes the formation of superoxide radicals on electron-rich N atoms and promotes increased oxidation of the valence band constituted by the B2 p orbital.
4. The metal-free BCN photocatalytic green synthesis of benzoxazole compounds according to claim 1, characterized in that: by oxidation of aromatic alcohols, alkyl alcohols, toluene SP3C-H activation can realize the high-efficiency heterogeneous photocatalytic synthesis of the benzoxazole compounds.
5. The metal-free BCN photocatalytic green synthesis of benzoxazole compounds according to claim 1, characterized in that: the synthesis process of the metal-free multiphase BCN photocatalytic benzoxazole compound avoids the pollution of metal to products in the traditional synthesis process.
6. The metal-free BCN photocatalytic green synthesis of benzoxazole compounds according to claim 1, characterized in that: the catalytic system can be irradiated by visible light, and the green oxidant O2And water is used as a byproduct, the high-temperature reaction condition is avoided in the photocatalysis process, the catalytic system has no catalytic activity in the absence of illumination, and the catalytic activity is higher under the promotion of light.
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| CN115197165B (en) * | 2022-08-25 | 2024-01-26 | 河南师范大学 | Method for preparing benzothiazole compound by reacting photocatalytic toluene compound and o-aminophenylsulfiol |
| CN116217513A (en) * | 2022-12-30 | 2023-06-06 | 重庆工商大学 | Preparation method of 2' -substituted benzothiazole |
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