CN111841647B - Ferrocene derived nickel catalyst and application thereof in generating N1-substituted pyrazole derivatives - Google Patents
Ferrocene derived nickel catalyst and application thereof in generating N1-substituted pyrazole derivatives Download PDFInfo
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- CN111841647B CN111841647B CN201910353773.0A CN201910353773A CN111841647B CN 111841647 B CN111841647 B CN 111841647B CN 201910353773 A CN201910353773 A CN 201910353773A CN 111841647 B CN111841647 B CN 111841647B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to the field of pesticides and medicines, in particular to a ferrocene derived nickel catalyst and application thereof in catalyzing and generating N1-substituted pyrazole derivatives. The catalyst has a structure shown as a formula I; the catalyst is applied to catalyzing and generating N1-substituted pyrazole derivatives. The catalyst disclosed by the invention is simple, cheap and stable to prepare, has a wide application range when being applied to catalyzing pyrazole compounds and halogen-containing aromatic rings or heterocycles, and is simple to prepare, high in yield and mild in reaction conditions.
Description
Technical Field
The invention relates to the field of pesticides and medicines, in particular to a ferrocene derived nickel catalyst and application thereof in catalyzing and generating N1-substituted pyrazole derivatives by utilizing the catalyst.
Background
Pyrazole is an important member in a nitrogen-containing heterocyclic ring system, has a unique structure, and derivatives thereof have unique biological activity and play an important role in the aspects of pesticides, medicines and the like. In particular, the pyrazole derivatives generated by N1-substitution have wide application in the fields of pesticide and medicine, such as the currently used insecticides, i.e. pyrifenoxan (pyrolan), pyrazole herbicides, i.e. metazachlor (metazachlor); celecoxib (celecoxib) and the like for the pharmaceutical treatment of rheumatism, rheumatoid and osteoarthritis.
At present, the literature reports that the N1-substituted pyrazole derivatives are synthesized from beta-keto ester and hydrazine derivatives, and the method is convenient and easy but has a complex process, so that the method is not beneficial to reaction diversification. In 2017, adrian Huang, kellie WO et al propose a method for generating N1-substituted pyrazole derivatives without catalysts, and the method has narrow applicability range of reaction substrates and is only suitable for synthesizing pyrazole compounds substituted by 3-position strong electron-withdrawing groups and aromatic rings or heterocyclic rings substituted by chlorine or individual bromine. Therefore, it is necessary to develop a catalyst for catalytically synthesizing N1-substituted pyrazole derivatives, which is highly efficient, inexpensive and readily available.
Disclosure of Invention
The invention aims to provide a ferrocene derived nickel catalyst and application thereof in catalyzing and generating N1-substituted pyrazole derivatives by utilizing the catalyst.
In order to realize the above, the invention adopts the technical scheme that:
a ferrocene derived nickel catalyst has a structure shown as a formula I:
a preparation method of a ferrocene derived nickel catalyst comprises the step of reacting a nickel dibromo complex with 2,4,6-trimethyl-phenyl magnesium bromide to generate the catalyst.
The nickel dibromo-complex is formed by the reaction of 1-bis- (di-phenyl-phosphine) -ferrocene and nickel bromide.
The catalyst can be directly prepared from a commercially available complex and 2,4,6-trimethyl-phenyl magnesium bromide, or prepared by firstly preparing the complex and then reacting the complex with 2,4,6-trimethyl-phenyl magnesium bromide; the method comprises the following steps:
(1) 10mmol of nickel bromide was placed in a dry three-necked round bottom flask, 60mL of absolute ethanol was added, followed by 10mmol of 1, 1-bis- (di-phenyl-phosphine) -ferrocene.
(2) After heating to reflux under nitrogen for 30 minutes, the mixture was cooled to room temperature under ice bath.
(3) Suction filtration, washing with cold absolute methanol and ether sequentially for 3 times.
(4) Washing with dichloromethane, collecting washing liquid, and spin-drying to obtain solid represented by formula (I).
(5) 8mmol of (I) and 40mL of dried tetrahydrofuran are added to a dry round-bottom flask under the protection of nitrogen, and 8mmol of 2,4, 6-trimethylphenyl magnesium bromide is added dropwise at 0 ℃.
(6) After the completion of the dropwise addition, the temperature was raised to room temperature, and the reaction was carried out for 30 minutes.
(7) Distilling the solvent under reduced pressure, adding 30mL of cold absolute ethyl alcohol, filtering, and washing with cold absolute ethyl alcohol and petroleum ether for 3 times respectively.
(8) Washing with dichloromethane, collecting washing liquid, and spin-drying to obtain light brown solid, i.e. the catalyst.
Or repeating the operations (5) to (8) by utilizing a commercially available nickel dibromo complex to obtain the catalyst.
Use of a ferrocene-derived nickel catalyst: the catalyst is applied to catalyzing and generating N1-substituted pyrazole derivatives.
Further, a pyrazole compound, a halogen substituted aromatic ring or heterocyclic ring, an alkaline substance and the catalyst are heated and refluxed for 1 to 9 hours in an organic solvent under the condition of nitrogen; the pyrazole compound, halogen substituted aromatic ring or heterocycle, alkaline substance and the catalyst 1:1.0-1.1 (mol: mol).
And cooling the reaction liquid after the reaction to room temperature, filtering, distilling the filtrate under reduced pressure, and separating residual liquid through a column to obtain the N1-substituted pyrazole derivative.
The halogen-substituted aromatic ring is a halogen-substituted benzene ring or benzyl halide; the halogen-substituted heterocycle is a halogen-substituted picolyl compound.
The alkaline substance is sodium methoxide, potassium tert-butoxide or ethanol; the solvent is tetrahydrofuran.
A preparation method of N1-substituted pyrazole derivatives comprises the steps of putting a pyrazole compound, a halogen substituted aromatic ring or heterocyclic ring, a basic substance and a catalyst in an organic solvent, and heating and refluxing for 1-9 hours under the condition of nitrogen; the pyrazole compound, the halogen-substituted aromatic ring or heterocyclic ring, the basic substance and the catalyst 1:1.0-1.1 (mol: mol).
And cooling the reaction liquid after the reaction to room temperature, filtering, distilling the filtrate under reduced pressure, and separating residual liquid through a column to obtain the N1-substituted pyrazole derivative.
The alkaline substance is sodium methoxide, potassium tert-butoxide or sodium ethoxide; the solvent is tetrahydrofuran; the reaction temperature is 20-100 ℃.
The halogen-substituted aromatic ring is a halogen-substituted benzene ring or benzyl halide; the halogen-substituted heterocycle is a halogen-substituted picolyl compound.
The invention has the advantages that:
the catalyst has the advantages of low cost, simple preparation process, high catalyst ring efficiency, good stability, wide application range and mild reaction conditions.
The catalyst is obtained by derivation of commercial products, and the catalyst is used for catalyzing and synthesizing the N1-substituted pyrazole derivatives; the catalyst has the advantages of high catalytic efficiency, simple preparation process, mild reaction conditions, stability in air (the catalyst still has catalytic activity after being placed for 3 months without change in appearance), low cost and wide application range.
The catalyst can be suitable for synthesizing halogen substituted heterocycle with lower catalytic activity and pyrazole compounds, and the solvent used in the preparation and catalytic processes of the catalyst is green, environment-friendly, nontoxic or low-toxic.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The preparation process of the catalyst comprises the following steps:
process for preparing catalyst
In the examples of the present invention, all the drugs are measured in millimoles (mmol) and all the solvents are measured in milliliters (mL) unless otherwise specified. The products are verified by LC-MS, and the detection conditions are acetonitrile: water =50, 80 after 10 minutes, flow rate 0.8mL/min,30 ℃,12min, rp-C 18 And (3) a column.
Example 1:
preparation of the catalyst:
1) Preparation of a complex of the formula
10mmol of nickel bromide was placed in a dry three-necked round bottom flask, 60mL of absolute ethanol was added, followed by 10mmol of 1, 1-bis- (di-phenyl-phosphine) -ferrocene. After heating to reflux under nitrogen for 30 minutes, it was cooled to 0 ℃ under ice bath. Suction filtration, washing with cold absolute ethanol and diethyl ether respectively for 3 times. Finally, washing with dichloromethane, collecting washing liquid, and concentrating under reduced pressure to obtain the nickel dibromo-complex with the yield of 85.3%.
2) Preparation of a catalyst of the formula
Under nitrogen, 8mmol of nickel dibromo complex and 40mL of dried tetrahydrofuran were added to a dry round-bottom flask, and 8mmol of 2,4, 6-trimethylphenyl magnesium bromide was added dropwise at 0 ℃. After the completion of the dropwise addition, the temperature was raised to room temperature, and the reaction was carried out for 30 minutes. Spin-dry the solvent, add 30mL cold absolute ethanol, pump-filter, wash 3 times each with cold absolute ethanol, petroleum ether sequentially. Finally, washing with dichloromethane, collecting washing liquid, and spin-drying to obtain the ferrocene-derived nickel catalyst with the yield of 92.3%.
Meanwhile, the catalyst is prepared by utilizing the existing commercially available nickel dibromo complex and 2,4,6-trimethylphenyl magnesium bromide according to the record of the step 2).
Example 2:
a100 mL round-bottomed flask was charged with 0.68g of pyrazole, 1.26g of benzyl chloride, 0.90g of the ferrocene-derived nickel catalyst prepared in the above example, 1.52g of potassium tert-butoxide, and 70mL of tetrahydrofuran, and the mixture was heated under stirring and reflux for 5 hours under nitrogen. The reaction solution was filtered, and the filtrate was distilled under reduced pressure, and the residue was subjected to column chromatography (ethyl acetate: petroleum ether =1:4 (v/v)) to give 1.38g of a colorless liquid with a yield of 80.1%.
Example 4:
1.36g of 3-trifluoromethylpyrazole, 2.00g of benzyl chloride, 0.45g of the ferrocene-derived nickel catalyst prepared in the above example, 1.40g of potassium tert-butoxide and 60mL of tetrahydrofuran are placed in a 100mL round-bottom flask and heated under reflux with stirring under nitrogen for 7 hours. The reaction solution was filtered, and the filtrate was distilled under reduced pressure, and the residue was subjected to column chromatography (ethyl acetate: petroleum ether =1:2 (v/v)) to give 2.31g of a pale yellow liquid with a yield of 96.0%.
Example 4:
a100 mL round-bottom flask was charged with 0.82g of 3-methylpyrazole, 1.83g of benzyl chloride, 0.45g of the ferrocene-derived nickel catalyst prepared in the above example, 1.68g of potassium tert-butoxide, and 50mL of tetrahydrofuran, and heated under reflux for 8 hours under nitrogen. Filtration was carried out, and the residue obtained after the distillation of the filtrate under reduced pressure was subjected to column chromatography (ethyl acetate: petroleum ether =1:2 (v/v)) to obtain 1.56g of a yellow liquid with a yield of 83.4%.
Example 5:
in a 100mL round bottom flask were placed 0.68g of pyrazole, 1.27g of benzyl chloride, 0.45g of the ferrocene-derived nickel catalyst prepared in the above example after standing for 3 months, 0.54g of sodium methoxide, and 50mL of tetrahydrofuran, and the mixture was heated under reflux with stirring under nitrogen for 9 hours. The reaction solution was filtered, and the filtrate was distilled under reduced pressure, and the residue was subjected to column chromatography (ethyl acetate: petroleum ether =1:4 (v/v)) to give 0.98g of a colorless liquid with a yield of 56.4%.
Example 6:
a100 mL round-bottom flask was charged with 0.68g of pyrazole, 1.61g of benzyl chloride, 0.45g of the ferrocene-derived nickel catalyst prepared in the above example, 1.40g of potassium tert-butoxide, and 50mL of tetrahydrofuran, and heated under reflux for 6 hours under nitrogen with stirring. The reaction solution was filtered, and the filtrate was distilled under reduced pressure, and the residue was subjected to column chromatography (ethyl acetate: petroleum ether =1:4 (v/v)) to give 1.64g of a colorless liquid with a yield of 78.9%.
Example 7:
1.36g of 3-trifluoromethylpyrazole, 1.66g of benzyl chloride, 0.45g of the ferrocene-derived nickel catalyst prepared in the above example, 1.40g of potassium tert-butoxide and 60mL of tetrahydrofuran were placed in a 100mL round-bottomed flask and heated under reflux with stirring under nitrogen for 7 hours. The reaction solution was filtered, and the filtrate was distilled under reduced pressure, and the residue was subjected to column chromatography (ethyl acetate: petroleum ether =1:2 (v/v)) to give 2.50g of a pale yellow liquid with a yield of 90.8%.
Example 8:
a100 mL round-bottom flask was charged with 0.82g of 3-methylpyrazole, 1.89g of p-chlorobenzyl chloride, 0.45g of the ferrocene-derived nickel catalyst prepared in the above example, 1.65g of potassium tert-butoxide, and 50mL of tetrahydrofuran, and heated under reflux for 5 hours under nitrogen. Filtration was carried out, and the filtrate was distilled under reduced pressure, and the residue was subjected to column chromatography (ethyl acetate: petroleum ether =1:2 (v/v)) to give 1.90g of a pale yellow liquid with a yield of 85.7%.
Claims (9)
2. Use of a ferrocene-derived nickel catalyst as claimed in claim 1 wherein: the nickel dibromo-complex reacts with 2,4,6-trimethyl-phenyl magnesium bromide to generate the catalyst.
3. Use of a ferrocene-derived nickel catalyst according to claim 2, wherein: the nickel dibromo-complex is formed by the reaction of 1-bis- (di-phenyl-phosphine) -ferrocene and nickel bromide.
4. Use of a ferrocene-derived nickel catalyst according to claim 1, wherein: a pyrazole compound, a halogen substituted aromatic ring or heterocyclic ring, an alkaline substance and the catalyst are heated and refluxed for reaction for 1 to 9 hours in an organic solvent under the condition of nitrogen; the pyrazole compound, the halogen-substituted aromatic ring or heterocyclic ring, the basic substance and the catalyst 1:1.0-1.1 (mol: mol).
5. Use of a ferrocene-derived nickel catalyst according to claim 4, wherein: and cooling the reaction liquid after the reaction to room temperature, filtering, distilling the filtrate under reduced pressure, and separating residual liquid through a column to obtain the N1-substituted pyrazole derivative.
6. Use of a ferrocene-derived nickel catalyst according to claim 4, wherein: the alkaline substance is sodium methoxide, potassium tert-butoxide or ethanol; the solvent is tetrahydrofuran.
7. A preparation method of N1-substituted pyrazole derivatives is characterized by comprising the following steps: a pyrazole compound, a halogen substituted aromatic ring or heterocycle, an alkaline substance and a catalyst are put in an organic solvent and heated and refluxed for reaction for 1 to 9 hours under the condition of nitrogen; the pyrazole compound, the halogen-substituted aromatic ring or heterocyclic ring, the basic substance and the catalyst 1:1.0-1.1 (mol: mol);
the catalyst structure is shown as a formula I:
the formula I is shown.
8. The process for the preparation of N1-substituted pyrazole derivatives according to claim 7, wherein: and cooling the reaction liquid after the reaction to room temperature, filtering, distilling the filtrate under reduced pressure, and separating residual liquid through a column to obtain the N1-substituted pyrazole derivative.
9. The process for the preparation of N1-substituted pyrazole derivatives according to claim 7, wherein: the alkaline substances are sodium methoxide, potassium tert-butoxide and sodium ethoxide; the solvent is tetrahydrofuran; the reaction temperature is 20-100 ℃.
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