Metal nanocluster, preparation method and application thereof, and coupling method of terminal olefin and benzyl alcohol compound

Abstract

The invention relates to a metal nanocluster, a preparation method and application thereof, and a method for coupling terminal olefin and benzyl alcohol compounds. Metal in the metal nanocluster comprises VIII group metal elements, and the diameter of the metal nanocluster is 0.1-10 nm. The metal nanocluster is large in size and can be well used for catalyzing the reaction of olefin and benzyl alcohol compounds.

Description

Technical Field

[0001] The invention relates to a metal nanocluster, a preparation method and application thereof, and a method for coupling terminal olefins with benzyl alcohol compounds. Background Art

[0002] The main methods for synthesizing metal nanoclusters are reduction growth method, seed growth method, alloying method and ligand exchange method. The reduction growth method focuses on reduction, that is, the process of reducing high-valent metals with a reducing agent. The speed of the reduction process and the strength of the reducing agent are crucial to the success of the reaction. Although many nanocluster structures have been obtained, most of them are still in a smaller size. Larger nanoclusters also provide crucial exploration and understanding for material chemists. At present, an important task will be to increase the size of the clusters.

[0003] α-Aryl-2-methylbutenol compounds are important organic synthesis intermediates, commonly used in the synthesis of pharmaceutical intermediates, pesticide intermediates, and flavors and fragrances. However, conventional synthesis requires the use of halogen-containing olefins, or the olefins are transformed in multiple steps and then reacted with other substrates to obtain the target product, which has problems such as long routes and many steps. In direct synthesis methods, catalysts or ligands require special synthesis steps, which is not convenient for large-scale application. Summary of the invention

[0004] The purpose of the present invention is to overcome the problem that the metal nanoclusters in the prior art have poor catalytic performance and cannot be used for the efficient reaction of olefins and benzyl alcohol compounds, and to provide a metal nanocluster and its preparation method and application and a method for coupling terminal olefins with benzyl alcohol compounds. The metal nanocluster has excellent catalytic performance and significantly improves the efficiency of coupling terminal olefins with benzyl alcohol compounds.

[0005] In order to achieve the above object, the first aspect of the present invention provides a metal nanocluster, wherein the metal in the metal nanocluster comprises a metal element of Group VIII, and the diameter of the metal nanocluster is 0.1-10 nm.

[0006] The second aspect of the present invention provides a method for preparing metal nanoclusters, the method comprising: dissolving a Group VIII metal compound in a solvent under an inert gas atmosphere, slowly adding an aromatic boronic acid, and performing dynamic contact reduction.

[0007] The third aspect of the present invention provides a metal nanocluster prepared by the preparation method of the present invention.

[0008] The fourth aspect of the present invention provides an application of the metal nanoclusters described in the first aspect of the present invention and the metal nanoclusters described in the third aspect of the present invention in catalyzing the coupling reaction of terminal olefins and benzyl alcohol compounds.

[0009] The fifth aspect of the present invention provides a method for coupling a terminal olefin with a benzyl alcohol compound, the method comprising: contacting and reacting the terminal olefin and the benzyl alcohol compound in the presence of a catalyst and a sulfonic acid, wherein the catalyst comprises the metal nanoclusters described in the first aspect of the present invention and the metal nanoclusters described in the third aspect of the present invention.

[0010] Through the above technical solution, the present invention has the following beneficial effects:

[0011] The metal nanoclusters of the present invention have a relatively large size and can be well used for catalyzing the reaction of olefins and benzyl alcohol compounds.

[0012] The metal nanoclusters of the present invention do not require complicated catalyst synthesis steps, and only need to use a reducing agent to pre-reduce the Group VIII metal salt. When used, the addition of sulfonic acid can well catalyze the reaction of terminal olefins and benzyl alcohol compounds. That is, the metal nanoclusters of the present application are simple to prepare, have a short synthesis route, and have good atom economy. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is a TEM image of a metal nanocluster prepared according to a preferred embodiment of the present invention. DETAILED DESCRIPTION

[0014] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0015] The present invention provides a metal nanocluster, wherein the metal in the metal nanocluster comprises a metal element of Group VIII, and the diameter of the metal nanocluster is 0.1-10 nm

[0016] The metal nanoclusters having the above-mentioned characteristics of the present invention are relatively large in size and can be well used for catalyzing the reaction of olefins and benzyl alcohol compounds with high catalytic efficiency.

[0017] According to a preferred embodiment of the present invention, the diameter of the metal nanoclusters is 0.5-3 nm. By adopting the above preferred embodiment, the efficiency of the metal nanoclusters in catalyzing the coupling reaction of olefins and benzyl alcohol compounds can be further improved.

[0018] Any metal element of Group VIII can be applied to the present invention. According to a preferred embodiment of the present invention, the metal element of Group VIII is selected from at least one of Ru, Ir, Co and Rh, preferably Ru. By adopting the above preferred embodiment, the efficiency of the metal nanoclusters catalyzing the coupling reaction of olefins and benzyl alcohol compounds can be further improved.

[0019] The invention provides a method for preparing metal nanoclusters, which comprises: dissolving a Group VIII metal compound in a solvent under an inert gas atmosphere, slowly adding an aryl boric acid, and performing dynamic contact reduction.

[0020] The method of the present invention does not require complicated catalyst synthesis steps to prepare metal nanoclusters. It only requires the use of a reducing agent to pre-reduce the Group VIII metal salt, and the addition of sulfonic acid during use can well catalyze the reaction of terminal olefins and benzyl alcohol compounds. That is, the metal nanoclusters of the present invention are simple to prepare, have a short synthesis route, and have good atom economy.

[0021] According to a preferred embodiment of the present invention, the inert gas is selected from at least one of nitrogen, helium and argon.

[0022] According to a preferred embodiment of the present invention, the Group VIII metal compound is a compound of at least one metal selected from Ru, Ir, Co and Rh. The compound may be, for example, a halide, acetate, acetylacetone complex or phosphorus complex corresponding to each element.

[0023] According to a preferred embodiment of the present invention, the Group VIII metal compound is a compound of Ru metal, for example, RuI3, RuCl3, RuBr3, Ru(OAc)3, Ru(acac)3, RuCl2Ph3.

[0024] In the present invention, as long as the purpose of the present invention can be achieved, the optional range of the aryl boronic acid is relatively wide. According to a preferred embodiment of the present invention, the aryl boronic acid is selected from at least one of phenylboronic acid, 3-acyl-4-methylphenylboronic acid, 3-fluorophenylboronic acid and 2,4-difluorophenylboronic acid, preferably phenylboronic acid. By adopting the above preferred embodiment, the size of the metal nanoclusters can be improved, and the efficiency of the metal nanoclusters catalyzing the coupling reaction of olefins and benzyl alcohol compounds can be improved.

[0025] In the present invention, there is no special requirement for the type of the solvent. According to a preferred embodiment of the present invention, the solvent is selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2,2-dimethyltetrahydrofuran, toluene, p-xylene, o-xylene, m-xylene, dichloromethane, chloroform, ether and acetonitrile.

[0026] In the present invention, as long as the purpose of the present invention can be achieved, there is no special requirement for the mass ratio of the solvent, the Group VIII metal compound and the aryl boronic acid. According to a preferred embodiment of the present invention, the mass ratio of the solvent, the Group VIII metal compound and the aryl boronic acid is 80-300:0.1-10:1, preferably 100-200:0.5-5:1.

[0027] In the present invention, the contact reduction conditions can be selected in a wide range, and the dynamic contact method can be stirring, for example.

[0028] According to a preferred embodiment of the present invention, the contact reduction conditions include: a temperature of 5-60°C, preferably 20-35°C.

[0029] According to a preferred embodiment of the present invention, the contact reduction conditions include: time is 0.1-5h, preferably 0.5-1h.

[0030] The present invention provides a metal nanocluster prepared by the preparation method of the present invention. The metal nanocluster has a large size and can be well used for catalyzing the reaction of olefins and benzyl alcohol compounds with high catalytic efficiency.

[0031] The present invention provides an application of the metal nanocluster of the present invention in catalyzing the coupling reaction of terminal olefins and benzyl alcohol compounds.

[0032] The metal nanoclusters of the present invention are used to catalyze the coupling reaction of terminal olefins and benzyl alcohol compounds, which has the effect of high catalytic efficiency.

[0033] The present invention provides a method for coupling a terminal olefin with a benzyl alcohol compound, the method comprising: contacting and reacting the terminal olefin with the benzyl alcohol compound in the presence of a catalyst and a sulfonic acid, wherein the catalyst comprises the metal nanoclusters of the present invention.

[0034] The method of the present invention is used to couple terminal olefins and benzyl alcohol compounds, and has the characteristic of high catalytic efficiency.

[0035] In the present invention, the sulfonic acid has a wide range of selectable acids. According to a preferred embodiment of the present invention, the sulfonic acid is selected from at least one of benzenesulfonic acid, p-toluenesulfonic acid, p-trifluoromethylbenzenesulfonic acid and 2,4,6-trimethylbenzenesulfonic acid. By adopting the above preferred embodiment, the catalytic efficiency of terminal olefins and benzyl alcohol compounds can be further improved.

[0036] In the present invention, as long as the purpose of the present invention can be achieved, there is no particular requirement for the type of the terminal olefin. According to a preferred embodiment of the present invention, the terminal olefin is a conjugated terminal olefin, such as butadiene.

[0037] According to a preferred embodiment of the present invention, the benzyl alcohol compound has a structure as shown in formula (1):

[0038]

[0039] In formula (1), R is selected from at least one of hydrogen, halogen, C1-C10 alkane, C2-C10 olefin, halogenated C1-C10 alkane, C1-C10 alkoxy, and C6-C9 aromatic hydrocarbon. Specific benzyl alcohol compounds may be, for example, benzyl alcohol, 4-methylbenzyl alcohol, 2-methylbenzyl alcohol, and 4-vinylbenzyl alcohol. By adopting the above preferred embodiment, the catalytic efficiency of terminal olefins and benzyl alcohol compounds can be further improved.

[0040] In the present invention, the contact reaction conditions can be selected in a wide range.

[0041] According to a preferred embodiment of the present invention, the conditions of the contact reaction include: a temperature of 30-150°C, preferably 60-120°C.

[0042] According to a preferred embodiment of the present invention, the contact reaction conditions include: time is 0.01-48h, preferably 10-25h.

[0043] According to a preferred embodiment of the present invention, the contact reaction conditions include: the mass ratio of the catalyst, sulfonic acid, terminal olefin and benzyl alcohol compound is 1:1-15:100-800:40-300, preferably 1:2-10:130-450:40-200.

[0044] The present invention will be described in detail below through examples. In the following examples, the product yield parameters are measured by liquid chromatography method (or equipment); the catalyst structure characteristics and metal nanoparticle size are tested using a G2F30 transmission electron microscope (TEM) of FEI Company, USA. All raw materials are commercially available.

[0045] Yield = moles of product / moles of raw material benzyl alcohol × 100%

[0046] Example 1

[0047] In the autoclave, 99.2 mg of RuI3, 15 g of tetrahydrofuran, and 61 mg of phenylboric acid were added, and after nitrogen replacement, the mixture was stirred at room temperature for 20 minutes. The sample was tested using a G2F30 transmission electron microscope (TEM) from FEI Company of the United States. Figure 1, it can be seen from the figure that the diameter of the metal nanoclusters is 0.5-3nm. Then add 158mg of benzenesulfonic acid, 3.1g of benzyl alcohol, and 10g of cooled butadiene, and react at 85℃ for 20 hours. After natural cooling, carefully release the gas in the fume hood, and take the residue for liquid phase analysis to determine the target product. The results show that the yield of α-phenyl-2-methylbutenol can reach 90%.

[0048] Example 2

[0049] In the autoclave, 63.5 mg of CoAc2, 15 g of 2-methyltetrahydrofuran, and 65 mg of phenylboric acid were added, and after nitrogen replacement, the mixture was stirred at room temperature for 20 minutes. The sample was tested using a G2F30 transmission electron microscope (TEM) from FEI Company of the United States. The TEM images and Figure 1 Similarly, it can be seen from the figure that the diameter of the metal nanoclusters is 0.5-3nm. Then add 162mg of p-toluenesulfonic acid, 3.2g of 4-methylbenzyl alcohol, and 10g of cooled butadiene, and react at 85℃ for 20 hours. After natural cooling, carefully release the gas in the fume hood, take the residue and analyze the target product by liquid phase. The results show that the yield of α-(4-methylphenyl)-2-methylbutenol can reach 87%.

[0050] Example 3

[0051] In a 100g autoclave, 100.8mg of Ir(acac)3, 15g of toluene, and 67mg of phenylboric acid were added, and after nitrogen replacement, the mixture was stirred at room temperature for 20 minutes. The sample was tested using a G2F30 transmission electron microscope (TEM) from FEI Company of the United States. The TEM images were as follows: Figure 1 Similarly, it can be seen from the figure that the diameter of the metal nanoclusters is 0.5-3nm. Then add 185mg of 2,4,6-trimethylbenzenesulfonic acid, 3.2g of 2-methylbenzyl alcohol, and 10g of cooled butadiene, and react at 85℃ for 20 hours. After natural cooling, carefully release the gas in the fume hood, and take the residue for liquid phase analysis of the target product. The results show that the yield of α-(2-methylphenyl)-2-methylbutenol can reach 88%.

[0052] Example 4

[0053] Same as Example 1, except that butadiene is replaced by 1-butene. The results show that the yield of α-phenyl-2-methylbutanol can reach 79%.

[0054] Example 5

[0055] Same as Example 1, except that phenylboric acid was replaced with 3-fluorophenylboric acid, and the sample was tested using a G2F30 transmission electron microscope (TEM) from FEI Company of the United States. The TEM images were the same as those of Example 1. Figure 1Similarly, it can be seen from the figure that the diameter of the metal nanoclusters is 0.1-10nm. The results show that the yield of α-phenyl-2-methylbutenol can reach 80%

[0056] Comparative Example 1

[0057] In a 100g autoclave, add 99.2mg of RuI3 and 15g of tetrahydrofuran, replace with nitrogen, and stir at room temperature for 20 minutes. Then add 158mg of benzenesulfonic acid, 3.1g of benzyl alcohol, and 10g of cooled butadiene, and react at 85℃ for 20 hours. After cooling naturally, carefully release the gas in a fume hood, and take the residue for liquid phase analysis to determine the target product. The results show that the yield of α-aryl-2-methylbutenol is 8%.

[0058] Comparative Example 2

[0059] In a 100g autoclave, add 99.2mg of RuI3 and 15g of tetrahydrofuran. After nitrogen replacement, fill with 1MPa H2 and stir at room temperature for 20 minutes. Then add 158mg of benzenesulfonic acid, 3.1g of benzyl alcohol, and 10g of cooled butadiene. React at 85℃ for 20 hours. After natural cooling, carefully release the gas in a fume hood, take the residue and analyze the target product by liquid phase. The results show that the yield of α-phenyl-2-methylbutenol can reach 6%.

[0060] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A metal nanocluster, characterized in that: The metal in the metal nanocluster contains a metal element of Group VIII, and the diameter of the metal nanocluster is 0.1-10 nm.

2. The metal nanocluster according to claim 1, wherein The diameter of the metal nanoclusters is 0.5-3 nm.

3. The metal nanocluster according to claim 1 or 2, wherein: The Group VIII metal element is at least one selected from Ru, Ir, Co and Rh, preferably Ru.

4. A method for preparing metal nanoclusters, characterized in that: The method comprises: dissolving a metal compound of group VIII in a solvent under an inert gas atmosphere, slowly adding arylboronic acid, and performing dynamic contact reduction.

5. The preparation method according to claim 4, wherein: The Group VIII metal compound is a compound of at least one metal selected from Ru, Ir, Co and Rh, preferably a compound of Rh metal; and / or The aromatic boronic acid is selected from at least one of phenylboronic acid, 3-acyl-4-methylphenylboronic acid, 3-fluorophenylboronic acid and 2,4-difluorophenylboronic acid, preferably phenylboronic acid; and / or The solvent is selected from at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2,2-dimethyltetrahydrofuran, toluene, p-xylene, o-xylene, m-xylene, dichloromethane, chloroform, ether and acetonitrile.

6. The preparation method according to claim 4 or 5, wherein: The mass ratio of the solvent, the Group VIII metal compound and the arylboronic acid is 80-300:0.1-10:1, preferably 100-200:0.5-5:1; and / or The contact reduction conditions include: The temperature is 5-60°C, preferably 20-35°C; and / or The time is 0.1-5h, preferably 0.5-1h.

7. A metal nanocluster prepared by the preparation method according to any one of claims 4 to 6.

8. Use of the metal nanocluster according to any one of claims 1 to 3 and the metal nanocluster according to claim 7 in catalyzing the coupling reaction of terminal olefins and benzyl alcohol compounds.

9. A method for coupling a terminal olefin with a benzyl alcohol compound, characterized in that: The method comprises: in the presence of a catalyst and a sulfonic acid, contacting and reacting a terminal olefin and a benzyl alcohol compound, wherein: The catalyst comprises the metal nanoclusters according to any one of claims 1 to 3 and / or the metal nanoclusters according to claim 7; Preferably, The sulfonic acid is selected from at least one of benzenesulfonic acid, p-toluenesulfonic acid, p-trifluoromethylbenzenesulfonic acid and 2,4,6-trimethylbenzenesulfonic acid; and / or The terminal olefin is a conjugated terminal olefin; and / or The benzyl alcohol compound has a structure as shown in formula (1), In formula (1), R is at least one selected from hydrogen, halogen, C1-C10 alkane, C2-C10 alkene, halogenated C1-C10 alkane, C1-C10 alkoxy, and C6-C9 aromatic hydrocarbon.

10. The method according to claim 9, wherein: The conditions of the contact reaction include: The temperature is 30-150°C, preferably 60-120°C; and / or The time is 0.01-48h, preferably 10-25h; and / or The mass ratio of the catalyst, sulfonic acid, terminal olefin and benzyl alcohol compound is 1:1-15:100-800:40-300, preferably 1:2-10:130-450:40-200.

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