CN112645984B - Half-sandwich ruthenium complex containing phenyl benzoxazole structure and preparation method and application thereof - Google Patents
Half-sandwich ruthenium complex containing phenyl benzoxazole structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a half-sandwich ruthenium complex containing a phenyl benzoxazole structure, a preparation method and application thereof, wherein the ruthenium complex has the following structure:
the preparation method comprises the following steps: at room temperature, phenyl benzoxazole, [ CymRuCl ] 2 ] 2 And sodium acetate are dissolved in methanol, and the reaction is continued after the system is heated; after the reaction is finished, standing and filtering, decompressing and pumping out the solvent, and performing column chromatography separation on the obtained crude product to obtain a red half-sandwich ruthenium complex containing the phenyl benzoxazole structure, and applying the red half-sandwich ruthenium complex to catalyzing oxidation of alkyl pyridine compounds to prepare ketone compounds containing nitrogen heterocycles. Compared with the prior art, the preparation method is simple and green, the catalytic oxidation reaction can be carried out under mild conditions, the catalyst has high stability and is insensitive to air and water.
Description
Technical Field
The invention relates to the field of preparation of complexes, and particularly relates to a half-sandwich ruthenium complex containing a phenyl benzoxazole structure, and a preparation method and application thereof.
Background
The ketone compound based on the nitrogen-containing heterocycle is an important fine chemical intermediate, and has wide application in the fields of drug molecules, compounds with physiological activity, pesticide synthesis and the like.
The Friedel-crafts reaction is a classical method for introducing acyl on an aromatic ring, but the method cannot be applied to pyridine substrates due to the electron withdrawing effect of a nitrogen-containing heterocycle. Therefore, halogenated pyridine is generally adopted to react with a Grignard reagent for preparing the pyridone compound, but the method has high requirements on reaction conditions because the Grignard reagent is used, a solvent does not need to be subjected to anhydrous treatment, and the reaction process needs to be kept in an anhydrous and oxygen-free state.
In recent years, the oxidation of alkylpyridines to prepare corresponding nitrogen-containing heterocyclic ketones has become of great interest. As Maes reports a method for the cocatalytic oxidation of benzylpyridine by iron and copper, the process requires the participation of acid; gao et al report a process for the catalytic oxidation of iodine in the presence of acetic acid; the substrate is limited to 2-or 4-substituted benzylpyridines; lei et al report a chloroacetate-promoted copper-catalyzed process, but this process needs to be carried out at a high temperature of 130 ℃; recently, kang et al developed a class of organic catalysis methods, but required pure oxygen as the oxidant, but the reaction required 24 hours of heating to complete, and used the more toxic benzonitrile as the solvent.
The methods have disadvantages, so that the exploration of a novel efficient catalytic oxidation method of the alkyl pyridine compounds has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a half-sandwich ruthenium complex containing a phenyl benzoxazole structure, which has the advantages of simple and green preparation method, high stability of the catalyst, insensitivity to air and water, and catalytic oxidation reaction which can be carried out under mild conditions, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a half-sandwich ruthenium complex containing a phenylbenzoxazole structure has the following structure:
a preparation method of the half-sandwich ruthenium complex containing the phenylbenzoxazole structure comprises the following steps: at room temperature, phenyl benzoxazole, [ CymRuCl 2 ] 2 And sodium acetate are dissolved in methanol, and the reaction is continued after the system is heated; and after the reaction is finished, standing and filtering, decompressing and pumping the solvent, and performing column chromatography separation on the obtained crude product to obtain the red half-sandwich ruthenium complex containing the phenyl benzoxazole structure.
Further, the phenyl benzoxazole, [ CymRuCl ] 2 ] 2 And sodium acetate in a molar ratio of 1.
Furthermore, the temperature of the system is increased to 45-55 ℃, and the reaction time is 3-6h.
Further, the eluent used for column chromatography separation is a mixed solvent composed of petroleum ether and dichloromethane in a volume ratio of (5-8): 1.
The application of the half-sandwich ruthenium complex containing the phenylbenzoxazole structure is used for catalyzing the oxidation of alkyl pyridine compounds to prepare ketone compounds containing nitrogen heterocycles.
Further, the specific application method comprises the following steps: under the condition of taking ruthenium complex as a catalyst, dissolving alkyl pyridine compounds in dichloromethane for catalytic reaction, and after the reaction is finished, carrying out chromatographic separation on concentrated reaction liquid through a silica gel column to obtain corresponding nitrogen-containing heterocyclic ketone compounds.
Furthermore, the molar ratio of the ruthenium complex to the alkyl pyridine compound is (0.01-0.05): 1.0.
Further, the oxidant is air.
Further, the alkyl pyridine compounds are as follows:
compared with the prior art, the invention has the following advantages:
(1) The preparation method of the half-sandwich ruthenium complex containing the phenyl benzoxazole structure is simple and green, and has excellent selectivity and high yield;
(2) The half-sandwich ruthenium complex containing the phenyl benzoxazole structure has stable physicochemical properties and can stably exist in the air;
(3) The semi-sandwich ruthenium complex can catalyze and synthesize the nitrogen-containing heterocyclic ketone compound at room temperature by taking air as an oxidant, has mild reaction conditions, cheap and easily-obtained substrate, good universality, high catalysis efficiency, few byproducts, lower cost, easy separation of products and no generation of a large amount of waste residues.
Detailed Description
The following examples are given for the detailed implementation and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
Example 1: synthesis of half-sandwich ruthenium complex Ru containing phenyl benzoxazole structure
Phenylbenzoxazoles (1.0 mmol), [ CymRuCl ] were added at room temperature 2 ] 2 (0.5 mmol) and sodium acetate (2.0 mmol) were dissolved in methanol (2.0 mL), and the reaction was continued for 5 hours after the system was warmed to 50 ℃. After the reaction is finished, standing and filtering, and draining the solvent under reduced pressure, the obtained crude product is subjected to column chromatography (petroleum ether/dichloromethane = 6) to obtain a red target product ruthenium (II) complex Ru (yield 81%), and the reaction formula is as follows:
1 H NMR(400MHz,CDCl 3 25 ℃): δ =8.39 (d, J =8.5hz, 1h), 8.27 (d, J =7.5hz, 1h), 7.86 (d, J =8.0hz, 1h), 7.68 (d, J =7.5hz, 1h), 7.64 (t, J =7.5hz, 1h), 7.45 (t, J =7.5hz, 1h), 7.24 (t, J =7.5hz, 1h), 7.09 (t, J =7.5hz, 1h), 5.92 (d, J =6.0hz, 1h), 5.73 (d, J =6.0hz, 1h), 5.38 (d, J =6.0hz, 1h), 5.14 (d, J =6.0hz, 1h), 2.27-2.21 (m, 1H), 2.12 (d, 3.91H), 0.0h, 7.0hz, 1h), theoretical analytical value of J =6.0hz,1h, 10H, 3.76, J =3, J = 0.0hz, 1h, 10H, and analytical values of d, J = 7.27, J =7.0hz,1h 14 B 10 H 19 ClRuNO: c36.40, H4.15, N3.03; experimental values: c36.47, H4.18, N3.00.
Example 2: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines with the catalyst prepared in example 1: dissolving alkyl pyridine compounds (1.0 mmol) and ruthenium complex Ru (0.02 mmol) in 3mL dichloromethane, reacting at room temperature for 8 hours with air as an oxidant, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography, and drying until the mass is unchanged to obtain a corresponding product C 12 H 9 NO (91% yield), which is represented by the formula:
1 H NMR(400MHz,CDCl 3 ,25℃):δ8.70(s,1H),8.00-8.06(m,3H),7.83-7.90(m,1H),754-7.59 (m, 1H), 7.43-7.49 (m, 3H). Theoretical value of elemental analysis C 12 H 9 NO: c78.67, H4.95; n7.65, experimental value: c78.75, H4.92; and N7.60.
Example 3: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines with the catalyst prepared in example 1: dissolving alkyl pyridine compound (1.0 mmol) and ruthenium complex Ru (0.01 mmol) in 3mL dichloromethane, reacting at room temperature with air as oxidant for 6 hours, concentrating the reaction solution, separating by silica gel column chromatography, drying until the mass is unchanged to obtain corresponding product C 13 H 11 NO (83% yield), which is represented by the formula:
1 H NMR(400MHz,CDCl 3 delta 8.61 (s, 1H), 8.00-8.09 (m, 3H), 7.82-7.89 (m, 1H), 7.50-7.57 (m, 1H), 7.33-7.40 (m, 2H), 2.36 (s, 3H) at 25 ℃. Theoretical value of elemental analysis C 13 H 11 NO: c79.16, H5.62; n7.10, experimental value: c79.22, H5.72; and (7.03).
Example 4: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines using the catalyst prepared in example 1: dissolving alkyl pyridine compound (1.0 mmol) and ruthenium complex Ru (0.02 mmol) in 3mL dichloromethane, reacting at room temperature with air as oxidant for 10 hours, concentrating the reaction solution, separating by silica gel column chromatography, drying until the mass is unchanged to obtain corresponding product C 12 H 8 BrNO (93% yield) is represented by the formula:
1 H NMR(400MHz,CDCl 3 25 ℃ delta 8.72 (d, J =3.3Hz, 1H), 8.07 (d, J =7.4Hz, 3H), 7.92 (t, J =7.4Hz, 1H), 7.45-7.52 (m, 3H). Theoretical value of elemental analysis C 12 H 8 BrNO: c54.99, H3.08; n5.34, experimentThe value: c55.03, H3.10; and N5.41.
Example 5: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines with the catalyst prepared in example 1: dissolving alkyl pyridine compounds (1.0 mmol) and ruthenium complex Ru (0.05 mmol) in 3mL dichloromethane, reacting for 7 hours at room temperature with air as an oxidant, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography, and drying until the mass is unchanged to obtain a corresponding product C 12 H 8 BrNO (91% yield) according to the formula:
1 H NMR(400MHz,CDCl 3 25 ℃). Delta.8.66 (d, J =3.2Hz, 1H), 8.15 (d, J =7.0Hz, 3H), 7.84 (t, J =7.0Hz, 1H), 7.40-7.32 (m, 3H). Theoretical value of elemental analysis C 12 H 8 BrNO: c54.99, H3.08; n5.34, experimental value: c55.02, H3.13; and N5.40.
Example 6: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines with the catalyst prepared in example 1: dissolving alkyl pyridine compound (1.0 mmol) and ruthenium complex Ru (0.03 mmol) in 3mL dichloromethane, reacting at room temperature with air as oxidant for 8 hours, concentrating the reaction solution, separating by silica gel column chromatography, drying until the mass is unchanged to obtain corresponding product C 12 H 9 NO (92% yield), according to the formula:
1 H NMR(400MHz,CDCl 3 25 ℃): δ 8.80 (d, J =5.9hz, 2h), 7.81 (d, J =7.2hz, 2h), 7.64 (t, J =7.4hz, 1h), 7.58 (d, J =5.9hz, 2h), 7.51 (t, J =7.9hz, 2h). Theoretical value of elemental analysis C 12 H 9 NO: c78.67, H4.95; n7.65, experimental value: c78.73, H4.99; and N7.62.
Example 7: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines with the catalyst prepared in example 1: dissolving alkyl pyridine compounds (1.0 mmol) and ruthenium complex Ru (0.02 mmol) in 3mL dichloromethane, reacting for 9 hours at room temperature with air as an oxidant, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography, and drying until the mass is unchanged to obtain a corresponding product C 12 H 9 NO (95% yield) according to the formula:
1 H NMR(400MHz,CDCl 3 25 ℃), δ 9.00 (s, 1H), 8.82 (s, 1H), 8.12 (d, J =7.9hz, 1h), 7.82 (d, J =7.4hz, 2h), 7.64 (t, J =7.4hz, 1h), 7.52 (t, J =7.8hz, 2h), 7.46 (q, J =4.9hz, 1h). Theoretical value of elemental analysis C 12 H 9 NO: c78.67, H4.95; n7.65, experimental values: c78.63, H4.97; and (7) N7.69.
Example 8: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines with the catalyst prepared in example 1: dissolving alkyl pyridine compound (1.0 mmol) and ruthenium complex Ru (0.05 mmol) in 3mL dichloromethane, reacting at room temperature with air as oxidant for 6 hours, concentrating the reaction solution, separating by silica gel column chromatography, drying until the mass is unchanged to obtain corresponding product C 13 H 10 FNO (92% yield) according to the formula:
1 H NMR(400MHz,CDCl 3 25 ℃), delta 8.55 (s, 1H), 8.07-8.17 (m, 2H), 7.71-7.78 (m, 1H), 7.52-7.58 (m, 1H), 7.30-7.41 (m, 2H), 2.35 (s, 3H). Theoretical value of elemental analysis C 13 H 10 FNO: c72.55, H4.68; n6.51, experimental value: c72.48, H4.60; and N6.59.
Example 9: catalytic oxidation reaction
Catalyst prepared by example 1Oxidized alkyl pyridine compounds: dissolving alkyl pyridine compound (1.0 mmol) and ruthenium complex Ru (0.03 mmol) in 3mL dichloromethane, reacting at room temperature with air as oxidant for 7 hours, concentrating the reaction solution, separating by silica gel column chromatography, drying until the mass is unchanged to obtain corresponding product C 13 H 7 ClN 2 O (90% yield), which is represented by the formula:
1 H NMR(400MHz,CDCl 3 25 ℃) Δ 8.97 (s, 1H), 8.16-8.22 (m, 2H), 8.06 (d, J =8.5Hz, 2H), 7.48 (d, J =8.5Hz, 2H). Theoretical value of elemental analysis C 13 H 7 ClN 2 O: c64.34, H2.91; n11.54, experimental value: c64.41, H2.98; n11.50.
Example 10: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines with the catalyst prepared in example 1: dissolving alkyl pyridine compound (1.0 mmol) and ruthenium complex Ru (0.01 mmol) in 3mL dichloromethane, reacting at room temperature with air as oxidant for 9 hours, concentrating the reaction solution, separating by silica gel column chromatography, drying until the mass is unchanged to obtain corresponding product C 13 H 11 NO 2 (yield 93%) according to the reaction:
1 H NMR(400MHz,CDCl 3 25 ℃ delta 8.37 (d, J =2.9Hz, 1H), 8.10 (d, J =8.7Hz, 1H), 8.04 (d, J =7.0Hz, 2H), 7.56 (t, J =7.5Hz, 1H), 7.46 (t, J =7.7Hz, 2H), 7.32 (dd, J =7.8Hz,1.9Hz, 1H), 3.93 (s, 3H). Theoretical value of elemental analysis C 13 H 11 NO 2 : c73.23, H5.20; n6.57, experimental value: c73.27, H5.17; and N6.63.
Example 11: catalytic oxidation reaction
Catalytic Oxidation of alkylpyrazoles Using the catalyst prepared in example 1Pyridine compounds: dissolving alkyl pyridine compound (1.0 mmol) and ruthenium complex Ru (0.03 mmol) in 3mL dichloromethane, reacting at room temperature for 6 hours with air as oxidant, concentrating the reaction solution, separating by silica gel column chromatography, drying until the mass is unchanged to obtain corresponding product C 13 H 11 NO 2 (yield 95%) according to the formula:
1 H NMR(400MHz,CDCl 3 25 ℃), δ 8.45 (d, J =2.5hz, 1h), 8.13 (d, J =8.0hz, 1h), 8.00 (d, J =7.0hz, 2h), 7.51 (t, J =7.5hz, 1h), 7.38 (t, J =7.2hz, 2h), 7.20 (d, J =7.8hz, 1h), 3.95 (s, 3H). Theoretical value of elemental analysis C 13 H 11 NO 2 : c73.23, H5.20; n6.57, experimental values: c73.28, H5.23; and N6.68.
Example 12: catalytic oxidation reaction
Catalytic oxidation of alkylpyridines using the catalyst prepared in example 1: dissolving alkyl pyridine compounds (1.0 mmol) and ruthenium complex Ru (0.02 mmol) in 3mL dichloromethane, reacting at room temperature for 8 hours with air as an oxidant, concentrating the reaction solution after the reaction is finished, directly separating by silica gel column chromatography, and drying until the mass is unchanged to obtain a corresponding product C 13 H 11 NO (91% yield) according to the formula:
1 H NMR(400MHz,CDCl 3 delta 8.41 (s, 1H), 8.02-8.11 (m, 3H), 7.71-7.79 (m, 2H), 7.30-7.43 (m, 2H), 2.33 (s, 3H) at 25 ℃. Theoretical value of elemental analysis C 13 H 11 NO: c79.16, H5.62; n7.10, experimental value: c79.20, H5.70; and (7) N7.06.
Example 13: the structure of the half-sandwich ruthenium complex containing the phenyl benzoxazole structure is as follows:
the preparation method of the half-sandwich ruthenium complex comprises the following specific steps:
(1) At room temperature, phenyl benzoxazole, [ CymRuCl 2 ] 2 Dissolving sodium acetate in methanol, heating the system to 50 ℃, and continuing to react for 3 hours; after the reaction is finished, standing and filtering, and decompressing and pumping out the solvent;
(2) And carrying out column chromatography separation on the obtained crude product to obtain a red target product, wherein the eluent is petroleum ether and dichloromethane in a volume ratio of 5.
(3) Phenyl benzoxazole, [ CymRuCl 2 ] 2 And sodium acetate in a molar ratio of 1:0.5:2.5;
the ruthenium complex is used for preparing nitrogen heterocyclic ketone compounds by catalytic oxidation of alkyl pyridine compounds. In the oxidation process, air is used as an oxidant, the reaction temperature is room temperature, the reaction time is 7 hours, and the molar ratio of the ruthenium complex to the alkyl pyridine compound is 1.
Example 14: the structure of the half-sandwich ruthenium complex containing the phenyl benzoxazole structure is as follows:
the preparation method of the half-sandwich ruthenium complex comprises the following specific steps:
(1) At room temperature, phenyl benzoxazole, [ CymRuCl 2 ] 2 And sodium acetate are dissolved in methanol, and the reaction is continued for 4 hours after the temperature of the system is raised to 50 ℃; after the reaction is finished, standing and filtering, and decompressing and pumping out the solvent;
(2) And carrying out column chromatography separation on the obtained crude product to obtain a red target product, wherein the eluent is petroleum ether and dichloromethane in a volume ratio of 7.
(3) Phenyl benzoxazole, [ CymRuCl 2 ] 2 And sodium acetate in a molar ratio of 1:0.5:2.7;
the ruthenium complex is used for preparing nitrogen heterocyclic ketone compounds by catalytic oxidation of alkyl pyridine compounds. In the oxidation process, air is used as an oxidant, the reaction temperature is room temperature, the reaction time is 9 hours, and the molar ratio of the ruthenium complex to the alkyl pyridine compound is 1.
Example 15: the structure of the half-sandwich ruthenium complex containing the phenyl benzoxazole structure is as follows:
the preparation method of the half-sandwich ruthenium complex comprises the following specific steps:
(1) At room temperature, phenyl benzoxazole, [ CymRuCl 2 ] 2 Dissolving sodium acetate in methanol, heating the system to 50 ℃, and continuing to react for 6 hours; after the reaction is finished, standing and filtering, and decompressing and pumping out the solvent;
(2) And carrying out column chromatography separation on the obtained crude product to obtain a red target product, wherein the eluent is petroleum ether and dichloromethane in a volume ratio of 8.
(3) Phenylbenzoxazole, [ CymRuCl 2 ] 2 And sodium acetate at a molar ratio of 1:0.5:3.0;
the ruthenium complex is used for preparing nitrogen heterocyclic ketone compounds by catalytic oxidation of alkyl pyridine compounds. In the oxidation process, air is used as an oxidant, the reaction temperature is room temperature, the reaction time is 6 hours, and the molar ratio of the ruthenium complex to the alkyl pyridine compound is 1.
Claims (8)
1. The application of the half-sandwich ruthenium complex containing the phenylbenzoxazole structure is characterized in that the ruthenium complex has the following structure:
the ruthenium complex is used for catalyzing oxidation of alkyl pyridine compounds to prepare ketone compounds containing nitrogen heterocycles, wherein the alkyl pyridine compounds are as follows:
2. the application of the half-sandwich ruthenium complex containing the phenylbenzoxazole structure according to claim 1, which is characterized in that the preparation method of the ruthenium complex comprises the following steps: at room temperature, phenyl benzoxazole, [ CymRuCl 2 ] 2 And sodium acetate are dissolved in methanol, and the reaction is continued after the system is heated; and after the reaction is finished, standing and filtering, decompressing and pumping out the solvent, and performing column chromatography separation on the obtained crude product to obtain the red half-sandwich ruthenium complex containing the phenylbenzoxazole structure.
3. The use of the half-sandwich ruthenium complex containing phenylbenzoxazole structure according to claim 2, wherein the phenylbenzoxazole, [ CymRuCl ] is 2 ] 2 And the molar ratio of sodium acetate is 1.
4. The application of the half-sandwich ruthenium complex containing the phenylbenzoxazole structure according to claim 2, wherein the temperature of the system is increased to 45-55 ℃, and the reaction time is 3-6h.
5. The application of the half-sandwich ruthenium complex containing the phenylbenzoxazole structure according to claim 2, wherein the eluent used for column chromatography is a mixed solvent of petroleum ether and dichloromethane in a volume ratio of (5-8): 1.
6. The application of the half-sandwich ruthenium complex containing the phenylbenzoxazole structure according to claim 1 is characterized in that the specific application method is as follows: under the condition of taking ruthenium complex as a catalyst, dissolving alkyl pyridine compounds in dichloromethane for catalytic reaction, and after the reaction is finished, carrying out chromatographic separation on concentrated reaction liquid through a silica gel column to obtain corresponding nitrogen-containing heterocyclic ketone compounds.
7. The application of the half-sandwich ruthenium complex containing the phenylbenzoxazole structure according to claim 1, wherein the molar ratio of the ruthenium complex to the alkyl pyridine compound is (0.01-0.05): 1.0.
8. The use of the half-sandwich ruthenium complex containing phenylbenzoxazole structure according to claim 1 wherein the oxidant is air.
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