Application of Ru-Pt alloy catalysts in the synthesis of quinazolinones by catalytic acceptor-free dehydrogenation of alcohols

Abstract

The present invention relates to an application of a Ru-Pt alloy catalyst in catalyzing the acceptor-free dehydrogenation of alcohols to synthesize quinazolinone compounds. The Ru-Pt alloy catalyst includes a carbon black support and active components ruthenium and platinum supported on the carbon black support. In the method for synthesizing quinazolinone compounds by acceptor-free dehydrogenation of alcohols, the present invention adopts the Ru-Pt alloy catalyst. The Ru-Pt alloy catalyst can efficiently catalyze the reaction of aminobenzamide compounds with relatively low-equivalent alcohols without adding additives such as acid-base additives, oxidants, or hydrogen acceptors, thereby achieving a high yield of quinazolinone compounds. Furthermore, the Ru-Pt alloy catalyst can achieve good cycle performance by only undergoing a simple washing and drying process without requiring activation treatments such as oxidation or reduction.

Description

Technical Field

[0001] The present invention relates to the technical field of organic catalysis, and in particular to application of a Ru-Pt alloy catalyst in catalyzing the receptor-free dehydrogenation of alcohols to synthesize quinazolinone compounds. Background Art

[0002] Quinazolinones are important organic heterocyclic scaffolds found in a wide range of bioactive natural products, specific therapeutic drugs, pesticides, and functional materials. They possess anti-allergic, anti-cancer, anti-tumor, anti-inflammatory, and anti-hypertensive properties. Quinazolinone derivatives also exhibit cytotoxic, cardiovascular, and diuretic activities, such as the sedative-hypnotic drug methaqualone and the anticonvulsant and anticonvulsant drug benzylquinol. In the pesticide field, they primarily demonstrate effective bactericidal, insecticidal, and antiviral effects. The commercially effective fungicide fluquinazole and the acaricide quinazaquin were both developed from quinazolinone compounds. Due to their broad application prospects in medicine, industrial production, and pesticides, the synthesis of quinazolinone compounds has garnered increasing attention.

[0003] Currently, the existing synthesis methods are relatively complex. For example, CN112645887A discloses a method for preparing a quinazolinone derivative, which involves dissolving the raw materials in a solvent and heating the reaction under the combined action of a CuCl2 catalyst, a ligand, and a base to produce a product. CN113045503A discloses a method for preparing a 2-trifluoromethyl-substituted quinazolinone compound, which involves adding a palladium catalyst, a ligand, a carbon monoxide substitute, an additive, trifluoroethylimidoyl chloride, and an amine to an organic solvent to react and obtain the corresponding product. In other words, most current synthesis methods require the addition of additives such as acids and bases to assist in catalysis, resulting in a complex reaction system.

[0004] In addition, the catalysts used in existing synthesis methods are sensitive to air and require oxidation or reduction to achieve catalyst recycling, resulting in a decrease in catalytic efficiency.

[0005] Therefore, how to improve the process of catalytic alcohol acceptor-free dehydrogenation to synthesize quinazolinone compounds and provide a catalyst that omits acid and base additives and ensures good catalyst cycle performance has become an urgent problem to be solved. Summary of the Invention

[0006] In response to the shortcomings of the prior art, the present invention provides a Ru-Pt alloy catalyst for use in the catalytic acceptor-free dehydrogenation of alcohols to synthesize quinazolinone compounds. In the present invention's method for synthesizing quinazolinone compounds by acceptor-free dehydrogenation of alcohols, the Ru-Pt alloy catalyst is employed. The catalyst can efficiently catalyze the reaction of aminobenzamide compounds with relatively low-equivalent alcohols without the addition of additives such as acidic or alkaline additives, oxidants, or hydrogen acceptors, thereby achieving a high yield of quinazolinone compounds. Furthermore, the Ru-Pt alloy catalyst achieves excellent cycling performance through simple washing and drying, without requiring activation treatments such as oxidation or reduction.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] The present invention provides an application of a Ru-Pt alloy catalyst in catalyzing the acceptor-free dehydrogenation of alcohols to synthesize quinazolinone compounds. The Ru-Pt alloy catalyst comprises a carbon black carrier and active components supported on the carbon black carrier, wherein the active components are metallic ruthenium and platinum.

[0009] The catalyst provided by the present invention is specifically for the catalytic reaction of synthesizing quinazolinone compounds by the receptor-free dehydrogenation of alcohols. The catalyst uses carbon black as a carrier and the active components are a combination of metal ruthenium and platinum. It can effectively catalyze the receptor-free dehydrogenation of alcohols to synthesize quinazolinone compounds without adding additives such as acid-base additives, oxidants, and hydrogen acceptors, and the product yield is high, even reaching more than 85%.

[0010] In addition, the catalyst provided in the present invention can be recycled after a simple washing and drying process, and can be recycled more than 5 times while still maintaining an excellent catalytic effect.

[0011] The catalyst of the present invention specifically uses carbon black (CB) as a carrier, more specifically, uses conductive carbon black as a carrier, such as Ketjen black, Cabot black, acetylene black, Orion carbon black, etc. Specific product brands include:

[0012] AKZO Ketjenblack EC-600JD, EC-300J; Lion Ketjenblack ECP600JD, CARBON ECP600JD; Cabot BP2000, Vulcan XC-72; Orion FW200, Printex XE2B.

[0013] The catalyst of the present invention uses carbon black as a carrier, which can better achieve the loading of the active components ruthenium and platinum. The three can achieve synergistic cooperation and jointly exert a better catalytic effect.

[0014] In the present invention, once the carrier of the catalyst is replaced by other carbon carriers such as activated carbon, carbon nanotubes, graphene oxide, carbon nanofibers and nanodiamonds, the catalytic effect of the catalyst will be greatly reduced, and the yield of quinazolinone compounds will be reduced to below 60%.

[0015] In the present invention, when the carbon black carrier of the catalyst is replaced with other common carriers, such as aluminum oxide, zirconium oxide, titanium dioxide, etc., the catalytic effect will decrease further, and the yield of quinazolinone compounds can only reach about 20%, which is too low.

[0016] The active components of the catalyst of the present invention adopt a specific combination of ruthenium and platinum, and the two are combined to form an alloy structure, which is loaded on a carbon black carrier, can better achieve catalysis and a higher product yield.

[0017] When only one of ruthenium or platinum is used as the active component of the catalyst, even if a carbon black carrier is used, the yield of quinazolinone compounds after catalysis is at most about 50%, and the catalytic effect is significantly inferior to the Ru-Pt alloy catalyst of the present invention; when a catalyst composed of ruthenium and platinum and carbon black is used and the two are physically mixed, although the yield of quinazolinone compounds is improved, it is at most about 60%, and the catalytic effect is still not high.

[0018] The catalyst active components ruthenium and platinum in the present invention have a synergistic relationship. When ruthenium is replaced by other elements, such as nickel, copper, etc., or platinum is replaced by other elements, such as copper, nickel, cobalt, etc., the yield of quinazolinone compounds will be greatly reduced, reaching only about 30% or even lower, and the catalytic efficiency will deteriorate.

[0019] The active components in the present invention are composed only of ruthenium and platinum. When a third active component, such as nickel, copper or other elements, is added, the yield of quinazolinone compounds is greatly reduced and the catalytic effect is poor.

[0020] Preferably, the molar ratio of the active components ruthenium and platinum in the present invention is 1:0.5 to 1:0.8, for example, 1:0.5, 1:0.6, 1:0.7 or 1:0.8.

[0021] When the present invention catalyzes the acceptor-free dehydrogenation of alcohols to synthesize quinazolinone compounds, when the molar ratio of the active components ruthenium and platinum in the catalyst is 1:0.5 to 1:0.8, a high yield of quinazolinone compounds of more than 88% can be achieved. On this basis, regardless of whether the content of ruthenium is increased or decreased, or whether the content of platinum is decreased or increased, when the molar ratio of the two is not within the above range, it will lead to a significant decrease in the yield of quinazolinone compounds and a significant deterioration in catalytic efficiency.

[0022] Preferably, when the carbon black carrier in the present invention is Ketjen black and / or Cabot black, compared with other carbon black carriers, such as acetylene black, Orion carbon black, etc., it can better play the role of carrier, better cooperate with the active components ruthenium and platinum, and have a better catalytic effect.

[0023] Preferably, the Ru-Pt alloy catalyst is prepared by a solvothermal method, which specifically comprises the following steps:

[0024] (1) Dissolve the ruthenium source and platinum source precursors in a solvent and ultrasonically stir them, and then ultrasonically disperse the carbon black in the solvent;

[0025] (2) The solution containing the ruthenium source and platinum source precursors obtained in step (1) is mixed with the carbon black dispersion, ultrasonically stirred, treated at 200-250° C., centrifugally washed and dried, and the obtained powder is calcined to obtain the Ru-Pt alloy catalyst.

[0026] The catalyst of the present invention is preferably prepared by a solvothermal method. Compared with other preparation methods, such as the reduction method, the solvothermal method can load more active components of ruthenium and platinum in the form of alloys on the carbon black carrier, with a particle size of about 2 nm and a uniform distribution, more active sites, and a better catalytic effect.

[0027] Preferably, the ruthenium source in step (1) is any one of ruthenium chloride, ruthenium acetylacetonate, ruthenium acetate or ruthenium trichloride hexaamine, or a combination of at least two of them.

[0028] Preferably, the platinum source is any one of chloroplatinic acid, platinum dinitrate, tetraammineplatinum acetate, platinum tetrachloride or platinum acetylacetonate, or a combination of at least two thereof.

[0029] As a further preferred technical solution, in step (1) of the present invention, the ruthenium source is ruthenium chloride, and the platinum source is platinum acetylacetonate.

[0030] In the present invention, when preparing the catalyst, the selection of ruthenium source and platinum source precursors will affect the catalytic performance of the final catalyst. When a specific combination of ruthenium chloride as the ruthenium source and platinum acetylacetonate as the platinum source is used, the catalyst prepared will have a higher yield of quinazolinone compounds catalyzed by it.

[0031] In step (1) of the present invention, the solvent used to dissolve the ruthenium source and platinum source precursors can be selected from any one of ethanol, acetone, ethylene glycol, isopropanol or methanol, preferably ethanol or acetone.

[0032] In step (1) of the present invention, the solvent used to dissolve the carbon black carrier can be selected from any one of ethanol, ethylene glycol, isopropanol or methanol. Preferably, ethanol (anhydrous ethanol) is used to disperse the carbon black carrier, which can make the carbon black more fully dispersed and the catalytic effect of the prepared catalyst more excellent.

[0033] Preferably, the temperature of the calcination treatment in step (2) is 100-300°C, such as 100°C, 120°C, 150°C, 200°C, 220°C, 250°C or 300°C, and preferably 150-250°C.

[0034] In the Ru-Pt alloy catalyst of the present invention, the content of the active component ruthenium is 3-7% of the total mass of the catalyst, for example, 3%, 4%, 5%, 6% or 7%.

[0035] Preferably, in the present invention, the method for synthesizing quinazolinone compounds by catalytic alcohol acceptor-free dehydrogenation comprises:

[0036] In the style Japanese style The compound shown is a reaction raw material, and the Ru-Pt alloy catalyst and solvent are added to react to obtain the quinazolinone compound;

[0037] Mode 、 Mode ;

[0038] Wherein, R1 is any one of hydrogen, halogen, alkyl, cycloalkyl, aryl or heteroaryl; R2 and R3 are each independently any one of hydrogen, alkyl, cycloalkyl, aryl or heteroaryl.

[0039] The halogen may be, for example, F, Cl, Br or I; the alkyl may be, for example, methyl, ethyl, isopropyl, etc.; the cycloalkyl may be, for example, cyclopentyl, cyclohexyl, etc.; the aryl may be, for example, phenyl, naphthyl, etc.; the heteroaryl may be, for example, furan, pyrrole, thiophene, pyridine, etc.

[0040] Preferably, the formula Japanese style The molar ratio of the compounds is 1:1.5 to 1:2, such as 1:1.5, 1:1.6, 1:1.8 or 1:2, etc.

[0041] In the present invention, by using the catalyst, the formula The molar amount of the alcohol compound shown in the synthesis reaction is reduced, and the yield of the quinazolinone compound is still high at a relatively low alcohol equivalent.

[0042] Preferably, the reaction system does not require the addition of acidic or alkaline additives, nor does it require the addition of oxidants, hydrogen acceptors, etc. In a system without corresponding additives, sufficient catalysis can still be achieved and quinazolinone compounds can be obtained in a high yield.

[0043] The Ru-Pt alloy catalyst of the present invention is not likely to lose its activity when stored in air, and can be used without any treatment (reduction or oxidation) before repeated use, and has stable performance.

[0044] For example, in the reaction system, the active component ruthenium in the catalyst is The molar ratio of the compounds shown is 3%, which is not particularly limited in the present invention.

[0045] Compared with the prior art, the present invention has at least the following beneficial effects:

[0046] (1) In the method for synthesizing quinazolinone compounds by acceptor-free dehydrogenation of alcohols of the present invention, the Ru-Pt alloy catalyst is used, which can efficiently catalyze the reaction of aminobenzamide compounds with alcohols of lower equivalents without adding additives such as acid-base additives, oxidants or hydrogen acceptors, so that the yield of quinazolinone compounds reaches a high level.

[0047] (2) The Ru-Pt alloy catalyst of the present invention can achieve good cycle performance by only a simple washing and drying process without the need for activation treatment such as oxidation or reduction. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 This is the TEM characterization image of the Ru-Pt alloy catalyst prepared in Preparation Example 1.

[0049] Figure 2 This is the HAADF-STEM characterization image of the Ru-Pt alloy catalyst prepared in Preparation Example 1.

[0050] Figure 3-A and Figure 3-B This is the XPS characterization diagram of the Ru-Pt alloy catalyst prepared in Preparation Example 4.

[0051] Figure 4-A and Figure 4-B This is the XPS characterization diagram of the Ru-Pt alloy catalyst prepared in Preparation Example 6.

[0052] Figure 5 These are XRD characterization diagrams of the Ru-Pt alloy catalyst prepared in Preparation Example 1 and the single metal Ru and Pt catalysts prepared in Comparative Preparation Examples 1 and 2.

[0053] Figure 6XPS characterization diagrams of the Ru-Pt alloy catalyst prepared in Preparation Example 1 and the single metal Ru catalyst prepared in Comparative Preparation Example 1.

[0054] Figure 7 These are XPS characterization images of the Ru-Pt alloy catalyst prepared in Preparation Example 1 and the single metal Pt catalyst prepared in Comparative Preparation Example 2.

[0055] Figure 8 This is the hydrogen spectrum of the quinazolinone compound synthesized in Example 1.

[0056] Figure 9 This is the carbon spectrum of the quinazolinone compound synthesized in Example 1.

[0057] Figure 10 This is a graph showing the yield of quinazolinone compounds obtained by repeating the catalysis of the catalyst used in Example 1 five times. DETAILED DESCRIPTION

[0058] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific embodiments. It should be understood by those skilled in the art that the specific embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0059] In each preparation example and comparative preparation example, the carbon black carrier is uniformly referred to as "CB".

[0060] Preparation Example 1

[0061] This preparation example provides a Ru-Pt alloy catalyst, which is composed of a Ketjen black carrier (Lion ECP600JD from Japan) and active components ruthenium and platinum supported on the Ketjen black carrier. The molar ratio of the active components ruthenium to platinum is 1:0.5, and the active component ruthenium accounts for 5% of the catalyst mass.

[0062] The Ru-Pt alloy catalyst is prepared by the following method, comprising:

[0063] 11.4 mg of ruthenium chloride (RuCl3) and 10.8 mg of platinum acetylacetonate (Pt(acac)2) were dissolved in anhydrous ethanol and ultrasonically stirred. At the same time, 100 mg of Ketjen black was ultrasonically dispersed in anhydrous ethanol. The two were then mixed and ultrasonically stirred. The mixture was then placed in a high-pressure reactor and treated at 220°C for 4 hours. The mixture was centrifuged and washed, and vacuum-dried at 60°C. The resulting powder was calcined in a muffle furnace at 200°C for 3 hours to obtain a catalyst labeled Ru-0.5Pt / CB.

[0064] The prepared Ru-Pt alloy catalyst is characterized as follows Figure 1 and Figure 2It can be seen that the particle size of the catalyst is about 2 nm, the carrier is in an amorphous state, the active components are well dispersed, and the ruthenium and platinum in the catalyst form an alloy structure.

[0065] Preparation Example 2

[0066] This preparation example provides a Ru-Pt alloy catalyst, which is composed of a Cabot black carrier (Vulcan XC-72) and active components ruthenium and platinum supported on the Cabot black carrier. The molar ratio of the active components ruthenium to platinum is 1:0.7, and the content of the active component ruthenium is 5% of the catalyst mass.

[0067] The Ru-Pt alloy catalyst is prepared by the following method, comprising:

[0068] 11.6 mg of ruthenium chloride (RuCl3) and 15.3 mg of platinum acetylacetonate (Pt(acac)2) were dissolved in acetone and ultrasonically stirred. At the same time, 100 mg of Cabot Black was ultrasonically dispersed in anhydrous ethanol. The two were then mixed and ultrasonically stirred. The mixture was then placed in a high-pressure reactor and treated at 200°C for 6 hours. The mixture was centrifuged and washed, and vacuum-dried at 70°C. The resulting powder was calcined in a muffle furnace at 250°C for 3 hours to obtain a catalyst labeled Ru-0.7Pt / CB.

[0069] Preparation Example 3

[0070] This preparation example provides a Ru-Pt alloy catalyst, which is composed of a Ketjenblack carrier (AKZO Ketjenblack EC-600JD) and active components ruthenium and platinum supported on the Ketjenblack carrier. The molar ratio of the active components ruthenium to platinum is 1:0.8, and the content of the active component ruthenium is 5% of the mass of the catalyst.

[0071] The Ru-Pt alloy catalyst is prepared by the following method, comprising:

[0072] 11.9 mg of ruthenium chloride (RuCl3) and 18.0 mg of platinum acetylacetonate (Pt(acac)2) were dissolved in anhydrous ethanol and ultrasonically stirred. At the same time, 100 mg of Ketjen black was ultrasonically dispersed in anhydrous ethanol. The two were then mixed and ultrasonically stirred. The mixture was then placed in a high-pressure reactor and treated at 250°C for 4 hours. The mixture was centrifuged and washed, and vacuum-dried at 65°C. The resulting powder was placed in a muffle furnace and calcined at 150°C for 3 hours to obtain a catalyst labeled Ru-0.8Pt / CB.

[0073] Preparation Example 4 to Preparation Example 8

[0074] Compared with Preparation Example 1, the molar ratio of the active components ruthenium and platinum was adjusted from 1:0.5 to 1:0.3 (Preparation Example 4), 1:0.4 (Preparation Example 5), 1:1 (Preparation Example 6), 1:2 (Preparation Example 7), and 1:3 (Preparation Example 8), respectively. The rest was the same as Preparation Example 1.

[0075] Preparation Examples 4 to 8 are marked as: Ru-0.3Pt / CB, Ru-0.4Pt / CB, Ru-Pt / CB, Ru-2Pt / CB, Ru-3Pt / CB, respectively.

[0076] Figure 3-A and Figure 3-B as well as Figure 4-A and Figure 4-B The XPS characterization diagrams of the Ru-Pt alloy catalysts prepared in Preparation Example 4 and Preparation Example 6 respectively show that when the molar ratio of ruthenium and platinum is changed to 1:0.3 (Preparation Example 4) and 1:1 (Preparation Example 6), the binding energy of the spectrum peak will change, that is, the interaction between ruthenium and platinum will change, which is not conducive to the catalytic alcohol acceptor-free dehydrogenation reaction.

[0077] Preparation Example 9 to Preparation Example 11

[0078] Compared with Preparation Example 1, the Ketjen black carrier was replaced with Cabot black BP2000 (Preparation Example 9), acetylene black (Preparation Example 10), and Orion FW200 (Preparation Example 11). Other conditions were the same as in Preparation Example 1.

[0079] The catalysts prepared in Preparation Examples 9 to 11 were marked as Ru-0.5Pt / CB9, Ru-0.5Pt / CB10, and Ru-0.5Pt / CB11, respectively.

[0080] Preparation Example 12

[0081] Compared with Preparation Example 1, the preparation method was adjusted to a sodium borohydride reduction method, comprising the following steps:

[0082] 11.4 mg of ruthenium chloride (RuCl3) and 10.8 mg of acetylacetonate platinum (Pt(acac)2) were dissolved in anhydrous ethanol and ultrasonically stirred. At the same time, 100 mg of Ketjen black was ultrasonically dispersed in anhydrous ethanol. The two were then mixed and ultrasonically stirred. After the end, freshly prepared NaBH4 was added to the mixture for reduction. After the reduction process, the mixture was centrifuged and washed, and vacuum dried at 60°C. The resulting powder was placed in a muffle furnace and calcined at 200°C for 3 hours to obtain a catalyst labeled Ru-0.5Pt / CB12.

[0083] Preparation Example 13

[0084] Compared with Preparation Example 1, the preparation method was adjusted to a hydrogen reduction method, comprising the following steps:

[0085] 11.4 mg of ruthenium chloride (RuCl3) and 10.8 mg of platinum acetylacetonate (Pt(acac)2) were dissolved in anhydrous ethanol and ultrasonically stirred. At the same time, 100 mg of Ketjen black was ultrasonically dispersed in anhydrous ethanol. The two were then mixed, ultrasonically stirred, centrifuged and washed, and vacuum dried at 60°C. The resulting powder was placed in a tube furnace for hydrogen reduction at 300°C for 2h. After cooling under argon, the resulting powder was placed in a muffle furnace for calcination at 200°C for 3h and labeled as Ru-0.5Pt / CB13.

[0086] Preparation Example 14 to Preparation Example 16

[0087] Compared with Preparation Example 1, the types of ruthenium source and platinum source precursors in step (1) of the preparation method were adjusted from ruthenium chloride and platinum acetylacetonate to: a combination of ruthenium chloride and chloroplatinic acid (Preparation Example 14), a combination of ruthenium acetylacetonate and platinum acetylacetonate (Preparation Example 15), and a combination of ruthenium acetylacetonate and chloroplatinic acid (Preparation Example 16), and the rest were the same as in Preparation Example 1.

[0088] The catalysts prepared in Preparation Examples 14 to 16 were marked as Ru-0.5Pt / CB14, Ru-0.5Pt / CB15 and Ru-0.5Pt / CB16, respectively.

[0089] Preparation Example 17 to Preparation Example 18

[0090] Compared with Preparation Example 1, the solvent for dispersing Ketjen Black in step (1) of the preparation method was adjusted from anhydrous ethanol to ethylene glycol (Preparation Example 17) and isopropyl alcohol (Preparation Example 18), respectively. Other conditions were the same as those in Preparation Example 1.

[0091] The catalysts prepared in Preparation Examples 17 and 18 were marked as Ru-0.5Pt / CB17 and Ru-0.5Pt / CB18, respectively.

[0092] Preparation Example 19 to Preparation Example 20

[0093] Compared with Preparation Example 1, the calcination temperature in step (2) of the preparation method was adjusted from 200°C to 100°C (Preparation Example 19) and 300°C (Preparation Example 20), respectively. The rest was the same as Preparation Example 1.

[0094] The catalysts prepared in Preparation Examples 19 and 20 were marked as Ru-0.5Pt / CB19 and Ru-0.5Pt / CB20, respectively.

[0095] Comparative Preparation Example 1

[0096] Compared with Preparation Example 1, the active component in this comparative preparation example is only ruthenium, and the ruthenium content is 5% of the catalyst mass. In the preparation method of the catalyst, the precursor is only ruthenium chloride, and the rest is the same as Preparation Example 1.

[0097] Comparative Preparation Example 2

[0098] Compared with Preparation Example 1, the active component in this comparative preparation example is only platinum, and the platinum content is 5% of the catalyst mass. In the preparation method of the catalyst, the precursor is only platinum acetylacetonate, and the rest is the same as Preparation Example 1.

[0099] Figure 5 The XRD patterns of the Ru-Pt alloy catalyst prepared in Preparation Example 1 and the single metal Ru and Pt catalysts prepared in Comparative Preparation Example 1 and Comparative Preparation Example 2 are shown. Figure 6 and Figure 7 The XPS characterization diagrams are respectively of the Ru-Pt alloy catalyst prepared in Preparation Example 1 and the single metal Ru and Pt catalysts prepared in Comparative Preparation Example 1 and Comparative Preparation Example 2. Figures 5 to 7 It can be seen that compared with single metal, the peak positions of each metal in the Ru-Pt alloy catalyst are shifted, indicating that there is a strong interaction between ruthenium and platinum, that is, an alloy is formed.

[0100] Comparative Preparation Example 3

[0101] Compared with Preparation Example 1, the catalyst provided in this Comparative Preparation Example is obtained by physically mixing the catalysts of Comparative Preparation Example 1 and Comparative Preparation Example 2 according to a molar ratio of ruthenium to platinum of 1:0.5.

[0102] Comparative Preparation Examples 4 to 8

[0103] Compared with Preparation Example 1, the carbon black carrier of the catalyst is adjusted to: activated carbon (Comparative Preparation Example 4), carbon nanotubes (Comparative Preparation Example 5), graphene oxide (Comparative Preparation Example 6), carbon nanofibers (Comparative Preparation Example 7), and nanodiamonds (Comparative Preparation Example 8), and the rest are the same as Preparation Example 1.

[0104] Comparative Preparation Example 9 to Comparative Preparation Example 11

[0105] Compared with Preparation Example 1, the carbon black carrier of the catalyst was adjusted to: aluminum oxide (Comparative Preparation Example 9), zirconium oxide (Comparative Preparation Example 10), and titanium dioxide (Comparative Preparation Example 11), and the rest was the same as Preparation Example 1.

[0106] Comparative Preparation Examples 12 to 17

[0107] Compared with Preparation Example 1, the active components in the catalyst are adjusted as follows: ruthenium and copper are combined in a molar ratio of 1:0.5 (Comparative Preparation Example 12); ruthenium and nickel are combined in a molar ratio of 1:0.5 (Comparative Preparation Example 13); ruthenium and cobalt are combined in a molar ratio of 1:0.5 (Comparative Preparation Example 14); platinum and nickel are combined in a molar ratio of 1:0.5 (Comparative Preparation Example 15); nickel and platinum are combined in a molar ratio of 1:0.5 (Comparative Preparation Example 16); ruthenium, platinum and nickel are combined in a molar ratio of 1:0.5:0.2 (Comparative Preparation Example 17), and the rest are the same as Preparation Example 1.

[0108] Example 1

[0109] A method for synthesizing a quinazolinone compound comprises:

[0110] Mix according to the molar ratio of 1:1.5 as follows Japanese style The compound shown in the preparation example 1 is added with the Ru-Pt alloy catalyst and mesitylene, so that the Ru in the metal active component of the Ru-Pt alloy catalyst is reacted with the compound of formula The molar ratio of 3% was 3%, and the reaction was carried out at 170° C. for 24 h under an argon atmosphere to obtain the quinazolinone compound. The reaction process is as follows:

[0111] .

[0112] The characterization of the quinazolinone compound is as follows:

[0113] 1 H NMR (500 MHz, DMSO-d6): δ 8.14 (dd, J = 8.0, 1.6 Hz, 1H), 8.09 (d, J= 8.2 Hz, 2H), 7.82 (ddd, J = 8.5, 7.1, 1.6 Hz, 1H), 7.74 – 7.70 (m, 1H),7.53 – 7.47 (m, 1H), 7.34 (d, J = 8.0 Hz, 2H), 2.38 (s, 3H); 13 C NMR (126 MHz, DMSO-d6) δ 162.74, 152.70, 149.29, 141.93, 135.03, 130.36, 129.66, 128.15,127.88, 126.86, 126.31, 121.35, 21.45.

[0114] Figure 8 and Figure 9 The hydrogen spectrum and carbon spectrum of the quinazolinone compound synthesized in Example 1 are respectively shown.

[0115] Example 2

[0116] A method for synthesizing a quinazolinone compound comprises:

[0117] Mix according to the molar ratio of 1:2 as follows Japanese style The compound shown in the preparation example 2 is added with the Ru-Pt alloy catalyst and mesitylene, so that the Ru in the metal active component of the Ru-Pt alloy catalyst is reacted with the compound of formula The molar ratio of 3% was 3%, and the reaction was carried out at 170° C. for 24 h under an argon atmosphere to obtain the quinazolinone compound. The reaction process is as follows:

[0118] .

[0119] The characterization of the quinazolinone compound is as follows:

[0120] 1 H NMR (500 MHz, CDCl3): δ 8.34 (d, J = 7.9 Hz, 1H), 8.08 (s, 1H), 7.95 (t, J = 9.1 Hz, 1H), 7.89 (d, J = 6.9 Hz, 2H), 7.76 (s, 2H), 7.63–7.47(m, 4H), 3.52(s, 3H). 13 C NMR (126 MHz, CDCl3): δ 162.7, 156.3, 147.2, 134.4,133.7, 132.9, 132.4, 128.8, 128.7, 128.3, 127.9, 127.6, 127.4, 127.14, 127.08, 126.8, 124.8, 120.6, 34.6 ppm.

[0121] Example 3

[0122] A method for synthesizing a quinazolinone compound comprises:

[0123] Mix according to the molar ratio of 1:1.8 as follows Japanese style The compound shown in the preparation example 3 is added with the Ru-Pt alloy catalyst and mesitylene, so that the Ru in the metal active component of the Ru-Pt alloy catalyst is reacted with the compound of formula The molar ratio of 3% was 3%, and the reaction was carried out at 170° C. for 24 h under an argon atmosphere to obtain the quinazolinone compound. The reaction process is as follows:

[0124] .

[0125] The characterization of the quinazolinone compound is as follows:

[0126] 1 H NMR (500 MHz, DMSO-d6): δ=12.06 (br s, 1 H), 8.07 (d, J=7.8 Hz, 1 H), 7.75 (t, J=7.6 Hz, 1 H), 7.58 (d, J=8.2 Hz, 1 H), 7.43 (t, J=7.5 Hz, 1 H), 2.57 (tt, J=11.8 Hz and J=3.2 Hz, 1 H, CH), 1.89 (d, J=12.4 Hz, 2 H), 1.78(d, J=12.8 Hz, 1 H), 1.67(d, J=11.9 Hz, 1 H), 1.54–1.61 (m, 2 H), 1.20–1.33 ppm (m, 3 H); 13 C NMR (126 MHz, DMSO-d6): δ=161.9, 160.7, 148.9, 134.1,126.9, 125.8, 125.6, 120.9, 42.8, 30.2, 25.5, 25.3 ppm.

[0127] Example 4 to Example 8

[0128] Compared with Example 1, the catalyst was replaced with the catalyst of Preparation Examples 4 to 8, and the rest was the same as Example 1. The yields of the quinazolinone compounds prepared are shown in Table 1.

[0129]

[0130] It can be seen from Examples 1 to 3 that when the molar ratio of the active components ruthenium and platinum in the catalyst of the present invention is 1:0.5 to 1:0.8, the yield of quinazolinone compounds can reach more than 88%; by comparing Example 1 with Examples 4 to 8, it can be seen that when the molar ratio of the active components ruthenium and platinum is adjusted from 1:0.5 to 1:0.3 or 1:0.4, that is, when the platinum content is reduced, the yield of quinazolinone compounds will drop to about 50%. When the platinum content is increased to a molar ratio of the active components ruthenium and platinum of 1:1 or 1:2, although the yield of the product is increased compared to the molar ratio of 1:0.3 or 1:0.4, it is still lower than the yield at a molar ratio of 1:0.5. When the platinum content is further increased to a molar ratio of ruthenium and platinum of 1:3, the yield continues to show a downward trend and can only reach about 60%.

[0131] The above data fully demonstrate that for the molar ratio of the active components ruthenium and platinum in the catalyst, when the molar ratio is 1:0.5 to 1:0.8, a high yield of quinazolinone compounds can be achieved, reaching more than 88%. On this basis, regardless of increasing or decreasing the ruthenium content, or decreasing or increasing the platinum content, when the molar ratio of the two is not within the above range, it will lead to a significant decrease in the yield of quinazolinone compounds and a significant deterioration in the catalytic efficiency.

[0132] Example 9 to Example 11

[0133] Compared with Example 1, the catalyst was replaced with the catalyst of Preparation Examples 9 to 11, and the other steps were the same as in Example 1. The yields of the quinazolinone compounds prepared are shown in Table 2.

[0134]

[0135] By comparing Example 1 with Examples 9 to 11, it can be seen that when Ketjen black or Cabot black is used as the carrier of the catalyst, a better catalytic effect can be achieved compared to using acetylene black or Orion carbon black.

[0136] Example 12 to Example 20

[0137] Compared with Example 1, the catalyst was replaced with the catalyst of Preparation Examples 12 to 20, and the other steps were the same as in Example 1. The yields of the quinazolinone compounds prepared are shown in Table 3.

[0138]

[0139] By comparing Example 1 with Examples 12 to 13, it can be seen that the catalyst prepared by the solvothermal method in Example 1 can better catalyze the receptor-free dehydrogenation of alcohols to synthesize quinazolinone compounds than the sodium borohydride or hydrogen reduction method, thereby increasing the product yield to more than 93%.

[0140] By comparing Example 1 with Examples 14 to 16, it can be seen that when using the specific combination of ruthenium chloride and platinum acetylacetonate, compared with the use of combinations of ruthenium chloride and chloroplatinic acid, or ruthenium acetylacetonate and platinum acetylacetonate, or ruthenium acetylacetonate and chloroplatinic acid, which are all chlorides, as a precursor, it can increase the active sites of the catalyst and enhance the synergistic effect with the carbon black carrier, thereby increasing the product yield from less than 70% to more than 93%, achieving a more excellent catalytic effect.

[0141] By comparing Example 1 with Examples 17 to 18, it can be seen that for the solvent for dispersing carbon black in the catalyst preparation method, using anhydrous ethanol as a solvent compared with ethylene glycol and isopropanol can better achieve the dispersion of the carbon black carrier, the active components are better loaded on the carrier, and the synergistic effect between the carrier and the active components is fully exerted, and the catalytic effect is more obvious.

[0142] Comparison of Example 1 with Examples 19 to 20 shows that the calcination temperature during catalyst preparation has an impact on the catalytic effect. When the calcination temperature is as low as 100°C, the active sites of the catalyst are insufficient, resulting in a poor catalytic effect. When the calcination temperature is as high as 300°C, the active sites of the catalyst are damaged, and the catalytic effect is also poor. When the calcination temperature is between 150-250°C, the catalytic activity of the catalyst is increased, thereby improving the yield of the catalytic product.

[0143] Example 21

[0144] Compared with Example 1, the solvent mesitylene in the synthesis method was replaced by anisole, and the other procedures were the same as in Example 1. The yield of the synthesized quinazolinone compound was 68%.

[0145] Example 22

[0146] Compared with Example 1, the solvent mesitylene in the synthesis method was replaced by n-decane, and the other procedures were the same as in Example 1. The yield of the synthesized quinazolinone compound was 70%.

[0147] By comparing Example 1 with Examples 21 to 22, it can be seen that in the synthesis method, the reaction solvent affects the product yield. When mesitylene is used, it can make the product yield higher than other solvents, such as anisole and n-decane.

[0148] Example 23

[0149] Compared with Example 1, Japanese style The molar ratio of the compounds was adjusted to 1:2.5, and the other steps were the same as in Example 1. The yield of the synthesized quinazolinone compound was 65%.

[0150] Example 24

[0151] Compared with Example 1, Japanese style The molar ratio of the compounds was adjusted to 1:3, and the other steps were the same as in Example 1. The yield of the synthesized quinazolinone compound was 61%.

[0152] By comparing Example 1 with Examples 23 to 24, it can be seen that when the amount of the reaction raw material alcohol is increased, the yield of the quinazolinone compound decreases. This also illustrates that in the reaction system provided by the present invention, the use of a lower equivalent amount of alcohol for the reaction can achieve a higher yield of the quinazolinone compound.

[0153] Comparative Example 1

[0154] Compared with Example 1, the catalyst was replaced with the catalyst of Comparative Preparation Example 1, and the rest were the same as Example 1.

[0155] Comparative Example 2

[0156] Compared with Example 1, the catalyst was replaced with the catalyst of Comparative Preparation Example 2, and the rest were the same as Example 1.

[0157] Comparative Example 3

[0158] Compared with Example 1, the catalyst was replaced by the catalyst of Comparative Preparation Example 3, and the rest were the same as Example 1.

[0159] The yields of the quinazolinone catalysts synthesized in Comparative Examples 1 to 3 are shown in Table 4.

[0160]

[0161] By comparing Example 1 with Comparative Examples 1 to 3, it can be seen that when ruthenium or platinum is used alone as the active component, the yield of the synthesized quinazolinone compounds can only reach 36% and 56%, respectively. Even if the catalysts of Comparative Examples 1 and 2 are physically mixed, the yield of the quinazolinone compounds is at most 66%. When ruthenium and platinum are used as the active components of the catalyst at the same time, a synergistic effect is achieved when the two are presented in the form of an alloy, which can increase the yield of the quinazolinone compounds to more than 93%.

[0162] Comparative Examples 4 to 8

[0163] Compared with Example 1, the catalyst was replaced by the catalysts of Comparative Preparation Examples 4 to 8, and the rest was the same as Example 1.

[0164] Comparative Examples 9 to 11

[0165] Compared with Example 1, the catalyst was replaced by the catalysts of Comparative Preparation Examples 9 to 11, and the rest was the same as Example 1.

[0166] The yields of the quinazolinone compounds synthesized in Comparative Examples 4 to 11 are shown in Table 5.

[0167]

[0168] By comparing Example 1 with Comparative Examples 4 to 8, it can be seen that when the carbon black carrier is replaced with other carbon carriers, whether it is a zero-dimensional, one-dimensional or two-dimensional carbon material, it is not as good as when carbon black is used as a carrier. The yield of the catalyst for catalytic synthesis of quinazolinone compounds is high. This also proves that there is a synergistic effect between the carbon black carrier and the active components ruthenium and platinum, which together achieve the effect of a quinazolinone compound product yield of more than 93%.

[0169] By comparing Example 1 with Comparative Examples 9 to 11, it can be seen that when the carbon black carrier is replaced with other common carriers, such as alumina, zirconia or titanium dioxide, the catalytic performance of the resulting catalyst is greatly reduced, causing the product yield to drop to about 20% or even lower. This also proves that the carbon black carrier has a synergistic effect with the active components ruthenium and platinum, and together they exert an excellent catalytic effect.

[0170] Comparative Examples 12 to 17

[0171] Compared with Example 1, the catalyst was replaced with the catalyst of Comparative Preparation Examples 12 to 17, and the rest was the same as Example 1.

[0172] The yields of the quinazolinone compounds of Comparative Examples 12 to 17 are shown in Table 6.

[0173]

[0174] By comparing Example 1 with Comparative Examples 12 to 17, it can be seen that for the active components of the catalyst, when platinum is replaced by elements such as copper, nickel or cobalt, or when ruthenium is replaced by nickel, platinum, etc., the catalytic effect of the catalyst will be greatly reduced, and can only reach about 30%. This shows that ruthenium and platinum as active components can play a synergistic role in combination, so that the yield of quinazolinone compounds is as high as 93% or more; when other elements are further added on the basis of the combination of ruthenium and platinum, the catalytic effect will be reduced. This fully verifies that when the active components are only ruthenium and platinum, the yield of quinazolinone compounds can be higher and the catalytic effect is excellent.

[0175] Catalyst cycle performance test

[0176] The catalyst used in Example 1 was filtered and dried, and the obtained catalyst was used to continue the synthesis method of Example 1, and repeated 5 times. When repeated use, the reaction temperature and time remained unchanged. The yield of the quinazolinone compound obtained in Example 1 and each repetition was as follows: Figure 10 shown.

[0177] pass Figure 10It can be seen that the catalyst used in Example 1 can still produce quinazolinone compounds with a yield of more than 85% when the reaction is repeated for the fifth time. This also confirms that the catalyst provided by the present invention can maintain high activity when recycled only through simple filtration and drying treatment, and the corresponding catalyst has excellent cyclic stability.

[0178] In summary, in the method for synthesizing quinazolinone compounds by acceptor-free dehydrogenation of alcohols of the present invention, by using the Ru-Pt alloy catalyst, it is possible to efficiently catalyze the reaction of aminobenzamide compounds with alcohols of relatively low equivalents without adding additives such as acid-base additives, oxidants, or hydrogen acceptors, thereby achieving a high yield of quinazolinone compounds. Moreover, the Ru-Pt alloy catalyst can achieve good cycle performance through only a simple washing and drying treatment without the need for activation treatment such as oxidation or reduction, and has important application prospects.

Claims

1. Use of a Ru-Pt alloy catalyst in catalyzing the acceptor-free dehydrogenation of alcohols to synthesize quinazolinone compounds, characterized in that: The Ru-Pt alloy catalyst comprises a carbon black carrier and active components supported on the carbon black carrier, wherein the active components are metal ruthenium and platinum; The molar ratio of the metal ruthenium to platinum is 1:0.5 to 1:0.8; The carbon black carrier includes Ketjen black and / or Cabot black; The Ru-Pt alloy catalyst is prepared by a solvothermal method, which specifically comprises the following steps: (1) Dissolve the ruthenium source and platinum source precursors in a solvent and ultrasonically stir them, and then ultrasonically disperse the carbon black in the solvent; (2) The solution containing the ruthenium source and platinum source precursors obtained in step (1) is mixed with the carbon black dispersion, ultrasonically stirred, treated at 200-250° C., centrifugally washed and dried, and the obtained powder is calcined to obtain the Ru-Pt alloy catalyst.

2. The use according to claim 1, characterized in that The ruthenium source in step (1) is any one of ruthenium chloride, ruthenium acetylacetonate, ruthenium acetate or trichlorohexammineruthenium, or a combination of at least two thereof; The platinum source is any one of chloroplatinic acid, platinum dinitrate, tetraammineplatinum acetate, platinum tetrachloride or platinum acetylacetonate, or a combination of at least two thereof.

3. The use according to claim 2, characterized in that In step (1), the ruthenium source is ruthenium chloride, and the platinum source is platinum acetylacetonate.

4. The use according to claim 1, characterized in that The solvent in step (1) is ethanol; The temperature of the calcination treatment in step (2) is 100-300°C.

5. The use according to claim 1, characterized in that A method for synthesizing quinazolinone compounds by catalytic alcohol receptor-free dehydrogenation, comprising: In the style Japanese style The compound shown is a reaction raw material, and the Ru-Pt alloy catalyst and solvent are added to react to obtain the quinazolinone compound; Mode 、 Mode ; R1 is any one of hydrogen, halogen, alkyl, cycloalkyl, aryl or heteroaryl; R2 and R3 are each independently any one of hydrogen, alkyl, cycloalkyl, aryl or heteroaryl.

6. The use according to claim 5, characterized in that The formula Japanese style The molar ratios of the compounds shown ranged from 1:1.5 to 1:

2.

7. The use according to claim 5, characterized in that No acid or base additive, oxidant or hydrogen acceptor, or a combination of at least two thereof, is added to the reaction system.

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