CN113171798B - Heterogeneous iron catalyst, preparation method thereof and process for preparing 2-methyl-1, 4-naphthoquinone by catalysis - Google Patents
Heterogeneous iron catalyst, preparation method thereof and process for preparing 2-methyl-1, 4-naphthoquinone by catalysis Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
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- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/04—Preparation of quinones by oxidation giving rise to quinoid structures of unsubstituted ring carbon atoms in six-membered aromatic rings
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a heterogeneous iron catalyst, a preparation method thereof and a process for preparing 2-methyl-1, 4-naphthoquinone by catalysis. The catalyst is characterized in that 4,4 bipyridine and two 3-chloroacetylacetone are connected through quaternary ammonium salt reaction, and carbonyl oxygen atoms and ferric ions are connected through coordination bonds to form a framework structure. The preparation method comprises the following steps: under the inert gas atmosphere, 4-dipyridine and 3-chloracetylacetone are synthesized to react to obtain 4, 4-dipyridine diacetylacetone ion ligand, and then the ligand and ferric salt are heated in a solvent to react under stirring to obtain the heterogeneous iron catalyst. The process of synthesizing 2-methyl-1, 4-naphthoquinone with the complex material as catalyst. The catalyst has the advantages of simple preparation method, good catalyst stability and easy recovery and reuse. The process condition for synthesizing 2-methyl-1, 4-naphthoquinone by catalytic oxidation of 2-methylnaphthalene is mild, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to a heterogeneous iron catalyst, a preparation method thereof and a process for preparing 2-methyl-1, 4-naphthoquinone by catalysis.
Background
2-methyl-1, 4-naphthoquinone (abbreviated as 2-MNQ) is the earliest used vitamin K3 and is also an important intermediate for synthesizing various vitamins K. The compound has anticoagulant effect, and can effectively activate anticoagulant factor in organism; can also be used as an additive for promoting the growth and development of livestock; is also the most important fat-soluble antioxidant in biological systems, can promote the metabolism of high-energy compounds in human bodies, and has the effects of promoting urination and enhancing the detoxification function of livers. There are various methods for preparing 2-MNQ, mainly direct oxidation and indirect oxidation. The direct oxidation method includes reaction paths using 2-methylnaphthalene (Phys. Chem. Phys.,2015,17,23413 to 23422), 2-methyl-1-hydroxynaphthalene (RSC Advances,2016,16,12717), 2-methyl-1-methoxynaphthalene (tetrochelon Lett,2005,46,1091) and the like as raw materials; the indirect oxidation method is relatively few in processes, such as diene synthesis reaction (KINETICS AND CATALYSIS, MAR 2020,61,2,276-282) and the like.
In recent years, lanthanum-doped MCM-41 has been used as a catalyst for liquid-phase oxidation of 2-methylnaphthalene to 2-methyl-1, 4-naphthoquinone (Catalysis Communications (2014) 10-14), and although high conversion of the substrate (95.8%) has been achieved, selectivity is poor (69.3%), lanthanum is a rare earth element, and is expensive, and at the same time, toxic effects of lanthanum are large for organisms.
Among the various preparation methods, the synthetic route using 2-methylnaphthalene as a raw material is the simplest. The oxidant is peracetic acid, hydrogen peroxide or chromic anhydride. In the selection of the oxidizing agent, 2-methylnaphthalene (Med. Chem. Comm,2014,5,923; tetrahedron,1980, 36,123;) is catalytically oxidized with an oxidizing agent made of chromium element, the conversion finally obtained is 42-65%, but the production of chromium-containing wastewater and chromium-containing solid waste during the reaction causes serious pollution to the environment, making it unsuitable for industrial applications, so that the preparation of a green, stable, reusable catalyst is particularly important for industrial demands.
Currently, there are relatively few reports of catalytic oxidation of 2-methylnaphthalene using iron (chem. Eur. J.2010,16,10300-10303; J. Org. Chem.1997,62, 673-678), but the catalyst cannot be recovered.
Disclosure of Invention
The present invention aims to improve the defects of the prior art and provides a heterogeneous iron catalyst, and another aim of the present invention is to provide a preparation method of the catalyst, and a process for preparing 2-methyl-1, 4-naphthoquinone by using the catalyst. Aiming at the problems of large catalyst consumption, low reaction efficiency and serious environmental pollution, the invention provides a novel method for preparing 2-methyl-1, 4-naphthoquinone by oxidizing 2-methylnaphthalene, which has the advantages of mild reaction conditions, higher reaction yield and low catalyst consumption and is environment-friendly.
The technical scheme of the invention is as follows: a heterogeneous iron catalyst is characterized in that 4,4 bipyridine and two 3-chloroacetylacetone are connected through quaternary ammonium salt reaction, carbonyl oxygen atoms and ferric ions are connected through coordination bonds to form a framework structure, and the structural formula is as follows:
the invention also provides a method for preparing the heterogeneous iron catalyst, which comprises the following specific steps: under inert atmosphere, 4-dipyridine and 3-chloroacetylacetone are heated and stirred in acetone (the dosage is ensured to be dissolved), the obtained product is subjected to rotary evaporation, washing and vacuum drying to obtain the (4, 4-dipyridine diacetylacetone ion ligand) double-ion ligand, the double-ion ligand and ferric salt are heated and stirred in a solvent for reaction under inert atmosphere, and the precipitate is filtered, washed and vacuum dried to obtain the heterogeneous iron catalyst.
Preferably, the molar ratio of the 4, 4-dipyridine to the 3-chloroacetylacetone is 1 (1.8-2.5); the ferric salt is ferric nitrate (Fe (NO 3 ) 3 ) Ferric sulfate (Fe) 2 (SO 4 ) 3 ) Or ferric trichloride (FeCl) 3 ) One of them. Preferably, the inert atmosphere is nitrogen or argon.
Preferably, the heating temperature for synthesizing the double-ion ligand is 30-50 ℃, and the synthesis reaction time is 5-15h. Preferably, the solvent used in the washing step of the post-treatment of the zwitterionic ligand is n-hexane, diethyl ether or ethyl acetate.
Preferably, the temperature of the heating reaction of ferric salt and the double-ion ligand is 30-60 ℃; the reaction time is 6-10h; the molar ratio of iron atoms of ferric salt to the double-ion ligand in the reaction of ferric salt and double-ion ligand is 1 (2.5-3.5). Preferably, the solvent in which the iron salt reacts with the di-ionic ligand is methanol or ethanol.
The invention also provides a process for synthesizing 2-methyl-1, 4-naphthoquinone by utilizing the heterogeneous iron catalyst to catalyze and oxidize 2-methylnaphthalene, which comprises the following specific steps: adding 2-methylnaphthalene, an oxidant and a catalyst into an organic solvent, and reacting for 1-10 hours under the condition of specific reaction at 10-60 ℃ to obtain the product 2-methyl-1, 4-naphthoquinone. And finally, centrifugally separating the catalyst, and washing and drying the catalyst by acetonitrile to recycle the catalyst.
Preferably, the organic solvent is acetonitrile; the dosage of the catalyst is 5% -10% of the dosage of the metal Fe in the catalyst which is the material of 2-methylnaphthalene; the oxidant is hydrogen peroxide, and the dosage of the oxidant is 3-9 times of the dosage of the substrate 2-methylnaphthalene.
The beneficial effects are that:
the catalyst provided by the invention has the advantages of simple preparation method, good stability and higher activity. The catalyst has higher activity and high selectivity for preparing 2-methyl-1, 4-naphthoquinone from 2-methylnaphthalene, is easy to recycle, has the advantage of environment-friendly reaction, and is very suitable for industrial production.
Detailed Description
Example 1:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 30 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A1.
Related characterization of 4,4 bipyridine diacetylacetone ionic compounds: FT-IR (v/cm 1): 816,947, 1381.5,1505.6, 2357.7,3025.4,3384.6,3443.9
Elemental analysis (mass fraction): 48.3 percent of C; 11.3% of N; 32.2% of O; fe 3.7%
1 HNMR:8.74(4H,s),7.69(4H,s),2.06(2H,s),0.03(12H,s)
13 CNMR:24.5(4C,s),25.9(4C,s),37.0(2C,s),52.0(4C,s),98.7(2C,s),206.0(4C,s)
The catalysts of the other embodiments below are characterized as above.
Example 2:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 40 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A2.
Example 3:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10h at 50 ℃ under argon atmosphere, after cooling to room temperature, the acetone is removed by rotary evaporation, and then the acetone is washed three times with diethyl ether, the diethyl ether is removed by rotary evaporation and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A3.
Example 4:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 60 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A4.
Example 5:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 6 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A5.
Example 6:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 8 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A6.
Example 7:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) was dissolved in 10ml of acetone, heated and stirred at 50 ℃ under argon atmosphere for 12h, after cooling to room temperature, acetone was removed by rotary evaporation, washed three times with ethyl acetate, ethyl acetate was removed by rotary evaporation and dried under vacuum for use. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A7.
Example 8:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.162g (1 mmol) of anhydrous ferric trichloride was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A8.
Example 9:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and drying in vacuum at 50 ℃ to obtain the catalyst A9.
Example 10:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol and 1.2g (3 mmol) of ligand was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 60 ℃ to obtain the catalyst A10.
Example 11:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol and 1.2g (3 mmol) of ligand was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 70 ℃ to obtain the catalyst A11.
Example 12:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:1.8 (molar ratio) was dissolved in 10ml of acetone, heated and stirred under argon atmosphere at 50 ℃ for 10 hours, after cooling to room temperature, acetone was removed by spin-evaporation, and then washed three times with n-hexane, n-hexane was removed by spin-evaporation, and vacuum drying was performed for use. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A12.
Example 13:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2.5 (molar ratio) was dissolved in 10ml of acetone, heated and stirred under argon atmosphere at 50 ℃ for 10 hours, after cooling to room temperature, acetone was removed by spin-evaporation, and then washed three times with n-hexane, n-hexane was removed by spin-evaporation, and vacuum drying was performed for use. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of ethanol and 1.2g (3 mmol) of the ligand prepared above was added. Stirring at 50 ℃ for 8h under argon atmosphere, filtering, washing with ethanol, and vacuum drying at 80 ℃ to obtain the catalyst A13.
Example 14:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.19993g (0.5 mmolFe) 2 (SO 4 ) 3 ) Anhydrous ferric sulfate was dissolved in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A14.
Example 15:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 5ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A15.
Example 16:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 15ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A16.
Example 17:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 20ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A17.
Example 18:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 30 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A18.
Example 19:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 40 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A19.
Example 20:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 5 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A20.
Example 21:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 15h at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A21.
Example 22:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.0g (2.5 mmol) of the ligand prepared above was added. Under nitrogen atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A22.
Example 23:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.4g (3.5 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 8 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A23.
Example 24:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 6 hours, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A24.
Example 25:
4, 4-bipyridine, 3-chloroacetylacetone were added at 1:2 (molar ratio) is dissolved in 10ml of acetone, heated and stirred for 10 hours at 50 ℃ under argon atmosphere, after cooling to room temperature, acetone is removed by rotary evaporation, and then the acetone is washed three times with n-hexane, n-hexane is removed by rotary evaporation, and vacuum drying is carried out for standby. 0.4g (1 mmol) of ferric nitrate nonahydrate was weighed out in 10ml of methanol, and 1.2g (3 mmol) of the ligand prepared above was added. Under argon atmosphere, stirring at 50 ℃ for 10h, filtering, washing with methanol, and vacuum drying at 80 ℃ to obtain the catalyst A25.
Example 26: the prepared catalyst is used for preparing 2-methyl-1, 4-naphthoquinone.
In a25 ml autoclave, 1mmol of 2-methylnaphthalene, 3mmol of hydrogen peroxide, 1ml of acetonitrile and catalyst A1 were added, and the amount of catalyst was 62mg (addition amount of Fe was 5% =1 mmol 2-methylnaphthalene 5%), and the autoclave lid was screwed. Heating in a kettle sleeve at 30 ℃ for reaction for 5 hours, taking out the high-pressure kettle from the kettle sleeve after the reaction is finished, cooling to room temperature, extracting with diethyl ether, and detecting the conversion rate of 2-methylnaphthalene and the selectivity of 2-methyl-1, 4-naphthoquinone by gas chromatography. Finally, the catalyst is washed by diethyl ether after filtration and can be reused after drying. The reaction formula is as follows:
the process using catalysts A2, A3, A4, A5, A6, A7, A8, A9, a10, a11, a12, a13, a14, a15, a16, a17, a18, a19, a20, a21, a22, a23, a24, a25 was identical to the process flow of A1, and the reaction results are shown in the following tables, respectively:
the reaction temperatures are as in example 26, except that the following are used (the catalyst used is A7):
| temperature (temperature) | Conversion of 2-methylnaphthalene | Selectivity of 2-methyl-1, 4-naphthoquinone |
| 20℃ | 15.3％ | 94％ |
| 40℃ | 20.7％ | 96％ |
| 50℃ | 12.4％ | 82％ |
The reaction times were as in example 26, except that the following were used (the catalyst used was A10):
| time (h) | Conversion of 2-methylnaphthalene | Selectivity of 2-methyl-1, 4-naphthoquinone |
| 1 | 6.8％ | 98％ |
| 2 | 12.4％ | 95％ |
| 3 | 18.9％ | 97％ |
| 4 | 23.7％ | 93％ |
| 6 | 25.7％ | 95％ |
| 8 | 25.73％ | 90％ |
| 10 | 25.9％ | 89％ |
The procedure was as in example 26, except that the following was used, and the hydrogen peroxide amounts were as shown in the following table (the catalyst used was A11):
| hydrogen peroxide amount | Conversion of 2-methylnaphthalene | Selectivity of 2-methyl-1, 4-naphthoquinone |
| 6mmol | 26.2％ | 93％ |
| 9mmol | 26.7％ | 95％ |
The catalyst was prepared in the same manner as in example 26, except that the following was used, and the addition amount of metallic Fe (for example, the addition amount of Fe was 5% =1 mmol 2-methylnaphthalene 5%) was as follows (the catalyst used was a 13):
| fe addition amount | Conversion of 2-methylnaphthalene | Selectivity of 2-methyl-1, 4-naphthoquinone |
| 6％ | 25.8％ | 91％ |
| 7％ | 25.7％ | 97％ |
The recovery and use conditions of the catalyst A3 are shown in the following table:
Claims (9)
1. a heterogeneous iron catalyst is characterized in that 4, 4-bipyridine and two 3-chloroacetylacetone are connected through quaternary ammonium salt reaction, carbonyl oxygen atoms and ferric ions are connected through coordination bonds to form a framework structure, and the structural formula is as follows:
2. a process for preparing a heterogeneous iron catalyst according to claim 1, comprising the specific steps of: and under the inert atmosphere, heating and stirring 4, 4-dipyridine and 3-chloroacetylacetone in acetone for synthesis reaction, and performing rotary evaporation, washing and vacuum drying on the obtained product to obtain a double-ion ligand, heating and stirring the double-ion ligand and ferric salt in a solvent for reaction under the inert atmosphere, and filtering, washing and vacuum drying the precipitate to obtain the heterogeneous iron catalyst.
3. The method according to claim 2, wherein the molar ratio of 4, 4-bipyridine to 3-chloroacetylacetone is 1 (1.8-2.5); the ferric salt is ferric nitrate.
4. The method of claim 2, wherein the inert atmosphere is nitrogen or argon.
5. The method according to claim 2, wherein the heating temperature for the synthesis of the zwitterionic ligand is 30-50 ℃ and the time for the synthesis reaction is 5-15h.
6. The method according to claim 2, characterized in that the solvent used in the washing step of the post-treatment of the zwitterionic ligand is n-hexane, diethyl ether or ethyl acetate.
7. The method according to claim 2, characterized in that the temperature of the heating reaction of the iron salt with the di-ionic ligand is 30-60 ℃; the reaction time is 6-10h; the molar ratio of iron atoms of ferric salt to the double-ion ligand in the reaction of ferric salt and double-ion ligand is 1 (2.5-3.5).
8. The method according to claim 2, characterized in that the solvent for the reaction of the iron salt with the di-ionic ligand is methanol or ethanol.
9. A process for synthesizing 2-methyl-1, 4-naphthoquinone by catalyzing and preparing 2-methylnaphthalene by using the heterogeneous iron catalyst of claim 1, which comprises the following specific steps: adding 2-methylnaphthalene, an oxidant and a catalyst into an organic solvent, and reacting for 3-10 hours at 20-40 ℃ to obtain a product 2-methyl-1, 4-naphthoquinone; wherein the organic solvent is acetonitrile; the dosage of the catalyst is 5% -10% of the dosage of the metal Fe in the catalyst which is the material of 2-methylnaphthalene; the oxidant is hydrogen peroxide, and the dosage of the oxidant is 3-9 times of the dosage of the substrate 2-methylnaphthalene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102249886A (en) * | 2011-05-19 | 2011-11-23 | 南京大学 | Method for preparing beta-methyl naphthoquinone through catalytic oxidation of beta-methylnaphthalene by MCM-41 molecular sieve with iron-containing framework |
| CN106622325A (en) * | 2016-12-13 | 2017-05-10 | 南京工业大学 | Rhenium catalyst and method for catalyzed synthesis of 2-methyl-1,4-naphthoquinone by rhenium catalyst |
| CN110305169A (en) * | 2019-06-27 | 2019-10-08 | 中国科学院青岛生物能源与过程研究所 | A kind of substitution bipyridyl trivalent iron complex and the preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102249886A (en) * | 2011-05-19 | 2011-11-23 | 南京大学 | Method for preparing beta-methyl naphthoquinone through catalytic oxidation of beta-methylnaphthalene by MCM-41 molecular sieve with iron-containing framework |
| CN106622325A (en) * | 2016-12-13 | 2017-05-10 | 南京工业大学 | Rhenium catalyst and method for catalyzed synthesis of 2-methyl-1,4-naphthoquinone by rhenium catalyst |
| CN110305169A (en) * | 2019-06-27 | 2019-10-08 | 中国科学院青岛生物能源与过程研究所 | A kind of substitution bipyridyl trivalent iron complex and the preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Cheng, Yifeng，et al..Solvothermal Synthesis and Crystal Structures of Two Manganese Complexes [Mn(II)(acac-)2(4,4'-bipy)]n (bipy＝4,4'-bipyridine) and [Mn(III)(acac-)3]•4CO(NH2)2.《Chin. J. Chem》.2012,第30卷1063—1068. * |
| Konstanze Moller,et al..Selective Iron-Catalyzed Oxidation of Phenols and Arenes with Hydrogen Peroxide: Synthesis of Vitamin E Intermediates and Vitamin K3.《Chem. Eur. J.》.2010,第16卷10300 – 10303. * |
| S. AMBE,et al..ADDUCTS OF Mn(II), Fe(II), Co(lI), Ni(II) AND Zn(II) ACETYLACETONATES WITH 4,4'-BIPYRIDINE AND PYRAZINE.《J.inorg.nucl.Chem.》.1973,第35卷1109-1115. * |
| 房江华等.Fe(acac)3-Al(i-Bu)3-α，α′-联吡啶催化丙烯腈与苯乙烯共聚合.《分子催化》.2006,第20卷(第4期),335-338. * |
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