CN114149389A - Preparation method of naphthoquinone epoxy compound - Google Patents
Preparation method of naphthoquinone epoxy compound Download PDFInfo
- Publication number
- CN114149389A CN114149389A CN202210037030.4A CN202210037030A CN114149389A CN 114149389 A CN114149389 A CN 114149389A CN 202210037030 A CN202210037030 A CN 202210037030A CN 114149389 A CN114149389 A CN 114149389A
- Authority
- CN
- China
- Prior art keywords
- acid
- naphthoquinone
- reaction
- zirconium
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a naphthoquinone epoxy compound, which takes 1, 4-naphthoquinone and derivatives thereof as raw materials and obtains the naphthoquinone epoxy compound through catalytic reaction of a catalyst under the conditions of an acid environment and an oxygen source. The method provides a new idea for naphthoquinone epoxidation, and has excellent selectivity and yield.
Description
Technical Field
The invention relates to the field of preparation of epoxy compounds, in particular to a method for preparing naphthoquinone epoxy compounds by manganese porphyrin metal organic framework catalysis.
Technical Field
1, 4-naphthoquinone-based epoxy compounds are widely distributed in a plurality of natural products as one of quinone compounds, have activities of antibiosis, anti-hyperplasia, antifungal, antitumor and the like, are widely used as medicine and pesticide intermediates, and are also used in the fields of new materials and the like.
The prior epoxidation method of quinone compounds usually adopts NaClO and H under alkaline conditions2O2Or the organic hydroperoxide is taken as an oxidant for epoxidation. The method has certain limitations, such as low reaction yield, narrow substrate range, strong alkaline condition and the like. Therefore, it is of great significance to explore a new method for the epoxidation reaction of the naphthoquinone compound with milder and higher efficiency.
Disclosure of Invention
The invention aims to provide a novel preparation method of naphthoquinone epoxy compound, the invention provides a novel preparation route, manganese porphyrin metal organic framework catalyst is adopted to catalyze and oxidize 1, 4-naphthoquinone derivative to obtain corresponding epoxy compound, the method has mild reaction condition, high selectivity and conversion rate and is environment-friendly.
In order to solve the problems, the invention provides a preparation method of a naphthoquinone epoxy compound, which takes 1, 4-naphthoquinone and derivatives thereof as raw materials and obtains the naphthoquinone epoxy compound through catalytic reaction of a catalyst under the conditions of an acid environment and an oxygen source.
In some preferred embodiments of the present invention, the catalyst is obtained by coordination self-assembly of metal zirconium and a ligand, and the ligand has the structure:
wherein R is1is-COOH, -H, halogen, nitro, amino, R2is-COOH, -H, R3is-COOH, -H, halide, nitryl and amino.
Preferably, R1is-H, R2is-COOH, R3is-H.
OTf is CF3SO3-。
In some preferred embodiments of the present invention, the method for preparing the catalyst comprises the steps of:
the preparation method comprises the following steps of (1) mixing a ligand, a zirconium salt and an organic acid I in a mass ratio of 1: 1-30: and 40-100 parts of the catalyst is added into a reaction container, then an acidic compound and a solvent are added, the reaction is carried out at the temperature of 60-150 ℃, and the catalyst is obtained after the reaction is finished, and is washed, separated, purified and dried, and is marked as Mn @ Mn-PMOF-1 (Zr).
The zirconium salt is a tetravalent zirconium salt such as zirconium tetrachloride, zirconium tetrafluoride, zirconium tetraiodide, zirconium nitrate, or zirconium sulfate, and preferably zirconium tetrachloride.
Further, the organic acid I is benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2, 3-benzenetricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, trimesic acid, preferably benzoic acid.
Further, the acidic compound is an organic acid or an inorganic acid, including acetic acid, hydrochloric acid, sulfuric acid, nitric acid, and the like, preferably acetic acid.
Furthermore, the adding amount of the acidic compound is 1-5% of the mass of the ligand.
Furthermore, the adding amount of the solvent is 100-200% of the mass of the ligand.
Further, the solvent is N, N-Dimethylformamide (DMF) or N, N-Diethylformamide (DEF), preferably N, N-Dimethylformamide (DMF);
further, in the preparation method of the catalyst, after the ligand A, the zirconium salt and the organic acid I are subjected to ultrasonic dissolution assistance, all raw materials can be placed into a reactor, then the reactor is hermetically placed into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, the hydrothermal reaction kettle is placed into an oven to be heated for 24-60 hours, the temperature is controlled at 60-150 ℃ to carry out reaction, then the hydrothermal reaction kettle is cooled to room temperature, N-dimethylformamide is added to carry out rinsing and centrifugation, and the steps are repeated for 1-3 times until a supernatant is colorless, so that a rod-shaped crystal is obtained;
further, the obtained rod-shaped crystal can be further purified, the prepared rod-shaped crystal is sequentially centrifugally washed by DMF and acetone, then is placed in a centrifugal tube filled with 10 ml of acetone, is replaced by fresh acetone for 3-5 times after a period of time (such as 24 hours), is filtered and collected, and is dried in vacuum at 90-150 ℃ for 6-15 hours to obtain a catalyst which is marked as Mn @ Mn-PMOF-1(Zr) for later use.
Further, the adding amount of the catalyst is 1 wt% -10 wt%, preferably 3 wt% -5 wt% of the mass of the 1, 4-naphthoquinone and the derivative thereof.
Further, the structural formula of the 1, 4-naphthoquinone and the derivative thereof is as follows:
wherein R is1Selected from hydrogen, halogen atoms, amino, C1-C4 alkyl, C1-C4 alkoxy, benzoyl, hydroxyethylthio and hydroxyl; r2Hydrogen, halogen atom, amino, alkyl of C1-C4, alkoxy of C1-C4, benzoyl, hydroxyethyl sulfenyl and hydroxyl;
preferably, the 1, 4-naphthoquinone and the derivative thereof are selected from the following structures:
further, the oxygen source comprises one or more of oxygen, peroxide, alcohol, preferably H2O2Tert-butyl peroxide; more preferably, the addition amount of the oxygen source is 100 mol% to 600 mol%, preferably 200 mol% to 500 mol%, of the 1, 4-naphthoquinone and the derivative thereof;
further, the naphthoquinone epoxy compound is prepared in the presence of an organic reagent, wherein the organic reagent is one or more of dichloromethane, acetonitrile, ethanol and water, preferably Dichloromethane (DCM); the adding amount is 1-5 ml, preferably 2-4 ml of organic reagent added to 1mmol of 1, 4-naphthoquinone and derivatives thereof;
further, in the epoxidation reaction, the acidic environment is achieved by adding an acid, which is one or more combinations of acetic acid, hydrochloric acid, sulfuric acid, sulfonic acid, preferably acetic acid;
further preferably, the amount of the acid added is 100 mol% to 1000 mol%, preferably 300 mol% to 500 mol%, of the 1, 4-naphthoquinone and the derivative thereof;
further, the reaction temperature is 0-50 ℃, and preferably 20-30 ℃;
further, the reaction time is 2-5 hours; and after the reaction is finished, filtering and washing the reaction mixture, and removing the organic solvent by rotary evaporation to obtain the target product.
Compared with the prior art, the invention has the advantages that:
the Mn @ Mn-PMOF-1(Zr) catalyst prepared by the invention is used for synthesizing 1, 4-naphthoquinone epoxy compounds by epoxidation, and has the advantages of mild reaction conditions, high selectivity and conversion rate and simple post-treatment.
The invention provides a novel method for preparing naphthoquinone epoxy compound under the catalysis of a metal organic framework, the reaction does not need to be carried out under a strong alkali condition, the conversion rate is high, and the application range of a substrate is wide.
Detailed Description
The following examples further illustrate the process provided by the present invention, but the invention is not limited to the examples listed.
The analysis method comprises the following steps:
gas chromatograph: agilent7820A, column HP-5(30 m.times.320. mu.m.times.0.25 μm), injection port temperature: 240 ℃; the split ratio is 50: 1; carrier gas flow: 1.5 ml/min; temperature rising procedure: keeping at 40 deg.C for 1min, heating to 100 deg.C at 5 deg.C/min, keeping for 2min, heating to 250 deg.C at 30 deg.C/min, and keeping for 5 min. Detector temperature: at 250 ℃ to obtain a mixture.
The raw material sources are as follows:
ligand A: the preparation method is self-made as follows:
(1) 5649.28mg (16mmol) of manganese bis (trifluoromethanesulfonate), 3844.00mg (16mmol) of methyl 4- (4-formylphenyl) benzoate are weighed into a 2000 ml three-necked flask, 288mg (16mmol) of water and 500 ml of dichloroethane are added, heating and refluxing are carried out for 4 hours under nitrogen, after the reaction is finished, cooling is carried out to room temperature, anhydrous sodium sulfate is added to dry the mixture, the organic phase is filtered and rotary evaporation is carried out to obtain compound B.
(2) 2956.55mg (5mmol) of Compound B are weighed into a 500 ml three-necked flask, 100 ml of propionic acid are added, 335.45mg (5mmol) of pyrrole are slowly added dropwise after the solution is refluxed, and the mixture is refluxed for 12 hours in the absence of light. After the reaction was completed, the mixture was cooled to room temperature, and the precipitate was collected by suction filtration and washed with methanol, ethyl acetate, and tetrahydrofuran, respectively. Vacuum drying at 60 ℃ for 5 hours gave compound C.
(3) 2811.06mg (1.1mmol) of Compound C and 1661.00mg (13.2mmol) of MnCl are weighed out2In a 500 ml three-necked flask, 100 ml of DMF was added and refluxed for 6 hours. After the mixture was cooled to room temperature, 150 ml of water was added. The resulting precipitate was filtered and washed with water. The resulting solid was dissolved in chloroform and washed twice with water in a separatory funnel. The organic phase was dried over anhydrous sodium sulfate and rotary evaporated to give compound D.
(4) 2608.43mg (1mmol) of Compound D were weighed into a 250 ml three-necked flask, and 50 ml of a 1:1 volume ratio solution of Tetrahydrofuran (THF) and methanol in a mixed solvent and KOH (2636.70mg, 47mmol) in water (25 ml) were added. The mixture was heated until the solid was completely dissolved and 1M HCl was added dropwise until no further precipitation occurred. The solid was collected by filtration, washed with water and dried to give ligand a.
Manganese bis (trifluoromethanesulfonate): purchased from enokay, 98% pure;
methyl 4- (4-formylphenyl) benzoate: purchased from enokay with a purity of 95%;
zirconium tetrachloride: purchased from alatin with a purity of 98%;
benzoic acid: purchased from alatin with a purity of 99%;
n, N-dimethylformamide: purchased from alatin with a purity of 99%;
hydrogen peroxide: purchased from Annaiji with a purity of 99%;
tert-butyl peroxide: purchased from enokay, 99% pure;
dichloromethane; purchased from Koimei, 99% pure;
acetonitrile: purchased from komi and having a purity of 98%.
2-hydroxy-3-phytyl-1, 4-naphthoquinone: CAS:107421-74-9 was purchased from Ito Kay with a purity of 99%;
2, 3-dihydro-1, 4-naphthoquinone: CAS: 130-15-4, purchased from enokay, 99% pure;
2-amino-3-chloro-1, 4-naphthoquinone: CAS:2797-51-5, purchased from Ito Kay, 99% pure;
2-aminonaphthalene-1, 4-dione: CAS, 2348-81-4, purchased from Ito Kay, 99% pure;
2, 3-dichloro-1, 4-naphthoquinone: purchased from enokay with a purity of 99%.
Catalyst preparation example 1:
ligand A (R)2＝COOH，R1＝H，R3H), zirconium tetrachloride, benzoic acid in a mass ratio of 1: 15: 80, adding acetic acid accounting for 3 percent of the mass of the ligand A and N, N-Dimethylformamide (DMF) accounting for 150 percent of the mass of the ligand A into a reaction vessel, sealing the reaction vessel and placing the reaction vessel into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, heating the reaction vessel in an oven for 48 hours at the temperature of 90 ℃, cooling the reaction vessel to room temperature, adding N, N-rinsing with dimethylformamide, centrifuging, repeating for 3 times until the supernatant is colorless to obtain rod-like crystals;
centrifugally washing the obtained rod-shaped crystal by DMF and acetone in sequence, placing the rod-shaped crystal in a centrifugal tube filled with 10 ml of acetone, replacing the rod-shaped crystal with fresh acetone for 5 times after 24 hours, filtering and collecting the crystal, and performing vacuum drying at 120 ℃ for 9 hours to obtain a catalyst Mn @ Mn-PMOF-1(Zr), which is marked as Mn @ Mn-PMOF-1(Zr) -1 for later use;
catalyst preparation example 2:
ligand a (R2 ═ COOH, R1 ═ H, R3 ═ H), zirconium tetrachloride and benzoic acid were mixed in a mass ratio of 1: 40, adding acetic acid accounting for 1 percent of the mass of the ligand A and N, N-Dimethylformamide (DMF) accounting for 100 percent of the mass of the ligand A into a reaction vessel, sealing the reaction vessel and placing the reaction vessel into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, heating the reaction vessel in an oven for 48 hours at the temperature of 60 ℃, cooling the reaction vessel to room temperature, adding N, N-dimethylformamide for rinsing and centrifuging, and repeating the steps for 3 times until a supernatant is colorless to obtain a rod-shaped crystal;
centrifugally washing the obtained rod-shaped crystal by DMF and acetone in sequence, placing the rod-shaped crystal in a centrifugal tube filled with 10 ml of acetone, replacing the rod-shaped crystal with fresh acetone for 5 times after 24 hours, filtering and collecting the crystal, and performing vacuum drying at 120 ℃ for 9 hours to obtain a catalyst Mn @ Mn-PMOF-1(Zr), which is marked as Mn @ Mn-PMOF-1(Zr) -2 for later use;
catalyst preparation example 3:
ligand A (R2 ═ COOH, R1 ═ H, R3 ═ H), zirconium tetrachloride and benzoic acid were mixed in a mass ratio of 1: 30: 100, adding acetic acid accounting for 5% of the mass of the ligand A and N, N-Dimethylformamide (DMF) accounting for 200% of the mass of the ligand A into a reaction vessel, sealing the reaction vessel and placing the reaction vessel into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, heating the reaction vessel in an oven for 60 hours, controlling the temperature at 150 ℃, cooling the reaction vessel to room temperature, adding N, N-dimethylformamide for rinsing and centrifuging, and repeating the steps for 3 times until a supernatant is colorless to obtain a rod-shaped crystal;
centrifugally washing the obtained rod-shaped crystal by DMF and acetone in sequence, placing the rod-shaped crystal in a centrifugal tube filled with 10 ml of acetone, replacing the rod-shaped crystal with fresh acetone for 5 times after 24 hours, filtering and collecting the crystal, and drying the crystal in vacuum at 150 ℃ for 15 hours to obtain a catalyst Mn @ Mn-PMOF-1(Zr), which is marked as Mn @ Mn-PMOF-1(Zr) -3 for later use;
examples 1 to 10:
weighing the compounds E2-hydroxy-3-phytyl-1, 4-naphthoquinone (452.67mg,1mmol), Mn @ Mn-PMOF-1(Zr) -1(11.90mg,3.00 wt%) and acid (3mmol) in a reaction tube with circulating cooling water, adding a solvent (2mL) under the condition of nitrogen, adding an oxygen source (3mmol) or a normal-pressure oxygen ball, starting stirring, controlling the temperature of circulating water, after the reaction is finished, centrifugally separating, collecting a supernatant, washing with dichloromethane, and removing the organic solvent by rotary evaporation to obtain a target product. The results of the optimization experiments are shown in the following table.
| Examples | Oxygen source | Acid(s) | Organic reagent | Temperature/. degree.C | Conversion rate/% | Selectivity/%) |
| 1 | Hydrogen peroxide | Hydrochloric acid | Ethanol | 20 | 65 | 80 |
| 2 | tert-Butanol peroxide | Hydrochloric acid | Acetonitrile | 20 | 55 | 35 |
| 3 | Oxygen gas | Acetic acid | Ethanol | 20 | 50 | 90 |
| 4 | Hydrogen peroxide | Sulfuric acid | Ethanol | 20 | 45 | 83 |
| 5 | Hydrogen peroxide | Sulfonic acid | Ethanol | 20 | 55 | 80 |
| 6 | Hydrogen peroxide | Acetic acid | DCM | 20 | 93 | 95 |
| 7 | Hydrogen peroxide | Acetic acid | Water (W) | 20 | 47 | 75 |
| 8 | Hydrogen peroxide | Acetic acid | DCM | 0 | 85 | 92 |
| 9 | Hydrogen peroxide | Acetic acid | DCM | 10 | 88 | 93 |
| 10 | Hydrogen peroxide | Acetic acid | DCM | 30 | 97 | 99 |
The reaction route is shown schematically:
example 11:
a1, 4-naphthoquinone-derived epoxy compound was prepared in the same manner as in example 10, except that 2mmol of hydrogen peroxide and 8mmol of acetic acid were added to 2, 3-dihydro-1, 4-naphthoquinone as a raw material, and the reaction temperature was 30 ℃.
Example 12:
a1, 4-naphthoquinone-derived epoxy compound was prepared in the same manner as in example 10, except that 2-amino-3-chloro-1, 4-naphthoquinone was used as a raw material, 5.0mgMn @ Mn-PMOF-1(Zr) -3 and 4mmol of acetic acid were added, and the reaction temperature was 30 ℃.
Example 13:
a1, 4-naphthoquinone-derived epoxy compound was prepared in the same manner as in example 10, except that 2-aminonaphthalene-1, 4-dione was used as a raw material, 5mmol of hydrogen peroxide and 5mmol of acetic acid were added, and the reaction temperature was 30 ℃.
Example 14:
a1, 4-naphthoquinone-derived epoxy compound was prepared in the same manner as in example 10, except that 2, 3-dichloro-1, 4-naphthoquinone was used as a raw material, 25.00mg of Mn @ Mn-PMOF-1(Zr) -2 was added, and the amount of the organic reagent added was 4ml, and the reaction temperature was 30 ℃.
Examples 11-14 the results of the experiments are shown in table 2:
TABLE 2
| Temperature (. degree.C.) | Conversion (%) | Selectivity (%) | |
| Example 11 | 30 | 96 | 97 |
| Example 12 | 30 | 97 | 98 |
| Example 13 | 30 | 97 | 99 |
| Example 14 | 30 | 97 | 98 |
Claims (9)
1. A preparation method of a naphthoquinone epoxy compound is characterized in that 1, 4-naphthoquinone and derivatives thereof are used as raw materials, and the naphthoquinone epoxy compound is obtained through catalytic reaction of a catalyst under the conditions of an acid environment and an oxygen source.
2. The preparation method according to claim 1, wherein the catalyst is obtained by coordination self-assembly of metal zirconium and a ligand, and the ligand has a structure:
wherein R is1is-COOH, -H, halogenSubstituent, nitro group, amino group, R2is-COOH, -H, R3is-COOH, -H, halide, nitryl and amino;
preferably, R1is-H, R2is-COOH, R3is-H;
OTf is CF3SO3-。
3. The method for preparing the catalyst according to claim 1 or 2, comprising the steps of:
the preparation method comprises the following steps of (1) mixing a ligand, a zirconium salt and an organic acid I in a mass ratio of 1: 1-30: and 40-100 parts of the catalyst is added into a reaction container, then an acidic compound and a solvent are added, the reaction is carried out at the temperature of 60-150 ℃, and the catalyst is obtained after the reaction is finished, and is washed, separated, purified and dried, and is marked as Mn @ Mn-PMOF-1 (Zr).
4. The production method according to any one of claims 1 to 3, wherein the zirconium salt is zirconium tetrachloride, zirconium tetrafluoride, zirconium tetraiodide, zirconium nitrate, zirconium sulfate;
preferably, the organic acid is benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2, 3-benzenetricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, trimesic acid, preferably benzoic acid;
preferably, the acidic compound is an organic acid or an inorganic acid, including acetic acid, hydrochloric acid, sulfuric acid, nitric acid, preferably acetic acid;
preferably, the adding amount of the acidic compound is 1-5% of the mass of the ligand;
preferably, the adding amount of the solvent is 100-200% of the mass of the ligand;
preferably, the solvent is N, N-dimethylformamide or N, N-diethylformamide, preferably N, N-dimethylformamide.
5. The process according to any one of claims 1 to 4, wherein the catalyst is added in an amount of 1 to 10 wt%, preferably 3 to 5 wt%, based on the mass of 1, 4-naphthoquinone and its derivatives;
preferably, the structural formula of the 1, 4-naphthoquinone and the derivative thereof is as follows:
wherein R is1Selected from hydrogen, halogen atoms, amino, C1-C4 alkyl, C1-C4 alkoxy, benzoyl, hydroxyethylthio and hydroxyl; r2Hydrogen, halogen atom, amino, alkyl of C1-C4, alkoxy of C1-C4, benzoyl, hydroxyethyl sulfenyl and hydroxyl;
preferably, the 1, 4-naphthoquinone and the derivative thereof are selected from the following structures:
6. the method of any one of claims 1 to 5, wherein the source of oxygen comprises one or more of oxygen, peroxide, alcohol, preferably H2O2Tert-butyl peroxide;
preferably, the amount of the oxygen source added is 100 mol% to 600 mol%, preferably 200 mol% to 500 mol%, of the 1, 4-naphthoquinone and its derivatives.
7. The process according to any one of claims 1 to 6, wherein the naphthoquinone epoxide compound is prepared in the presence of an organic reagent selected from the group consisting of dichloromethane, acetonitrile, ethanol, water, and combinations thereof, preferably dichloromethane; the adding amount is 1-5 ml, preferably 2-4 ml of organic reagent added to 1mmol of 1, 4-naphthoquinone and derivatives thereof.
8. The process according to any one of claims 1 to 7, wherein in the epoxidation reaction the acidic environment is achieved by adding an acid, said acid being one or more combinations of acetic acid, hydrochloric acid, sulfuric acid, sulfonic acid, preferably acetic acid;
preferably, the acid is added in an amount of 100 to 1000 mol%, preferably 300 to 500 mol%, of the 1, 4-naphthoquinone and its derivatives.
9. The method according to any one of claims 1 to 8, wherein the reaction temperature of the epoxidation reaction is 0 to 50 ℃, preferably 20 to 30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210037030.4A CN114149389B (en) | 2022-01-13 | 2022-01-13 | Preparation method of naphthoquinone epoxy compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210037030.4A CN114149389B (en) | 2022-01-13 | 2022-01-13 | Preparation method of naphthoquinone epoxy compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114149389A true CN114149389A (en) | 2022-03-08 |
| CN114149389B CN114149389B (en) | 2023-09-19 |
Family
ID=80449904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210037030.4A Active CN114149389B (en) | 2022-01-13 | 2022-01-13 | Preparation method of naphthoquinone epoxy compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114149389B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0019852A1 (en) * | 1979-05-23 | 1980-12-10 | The Dow Chemical Company | Phosphonium phenoxide catalysts, epoxy resin containing same and process for promoting reaction of epoxides with phenols and/or carboxylic acids |
| US5637739A (en) * | 1990-03-21 | 1997-06-10 | Research Corporation Technologies, Inc. | Chiral catalysts and catalytic epoxidation catalyzed thereby |
| CN1424314A (en) * | 2002-12-24 | 2003-06-18 | 中国科学院兰州化学物理研究所 | Clean eoxidation of alpha-beta-unsaturated carbonyl compound |
| US20110004024A1 (en) * | 2008-03-07 | 2011-01-06 | Alkem Laboratories Limited | Preparation of naphthoquinone compounds using 2,3-dihalonaphthoquinone |
| CN104030975A (en) * | 2014-06-25 | 2014-09-10 | 福州大学 | Mn(III)-Salen catalyst as well as preparation method and application thereof |
| CN107759538A (en) * | 2017-10-30 | 2018-03-06 | 黑龙江八农垦大学 | Naphthoquinones of 2,3 epoxy, 2 nonyl sulfone, 5,8 dimethoxy 1,4 and preparation method thereof and the medicine containing it |
| CN107793380A (en) * | 2017-10-30 | 2018-03-13 | 黑龙江八农垦大学 | Naphthoquinones of 2,3 2 third sulfone of epoxy, 5,8 dimethoxy 1,4 and preparation method thereof and the medicine containing it |
| CN111589421A (en) * | 2020-05-09 | 2020-08-28 | 万华化学集团股份有限公司 | Oxacyclophosphine ligand and preparation method and application thereof |
| CN113828358A (en) * | 2020-06-24 | 2021-12-24 | 万华化学集团股份有限公司 | Mandelic acid oxidation reaction catalyst, preparation method and application thereof |
-
2022
- 2022-01-13 CN CN202210037030.4A patent/CN114149389B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0019852A1 (en) * | 1979-05-23 | 1980-12-10 | The Dow Chemical Company | Phosphonium phenoxide catalysts, epoxy resin containing same and process for promoting reaction of epoxides with phenols and/or carboxylic acids |
| US5637739A (en) * | 1990-03-21 | 1997-06-10 | Research Corporation Technologies, Inc. | Chiral catalysts and catalytic epoxidation catalyzed thereby |
| CN1424314A (en) * | 2002-12-24 | 2003-06-18 | 中国科学院兰州化学物理研究所 | Clean eoxidation of alpha-beta-unsaturated carbonyl compound |
| US20110004024A1 (en) * | 2008-03-07 | 2011-01-06 | Alkem Laboratories Limited | Preparation of naphthoquinone compounds using 2,3-dihalonaphthoquinone |
| CN104030975A (en) * | 2014-06-25 | 2014-09-10 | 福州大学 | Mn(III)-Salen catalyst as well as preparation method and application thereof |
| CN107759538A (en) * | 2017-10-30 | 2018-03-06 | 黑龙江八农垦大学 | Naphthoquinones of 2,3 epoxy, 2 nonyl sulfone, 5,8 dimethoxy 1,4 and preparation method thereof and the medicine containing it |
| CN107793380A (en) * | 2017-10-30 | 2018-03-13 | 黑龙江八农垦大学 | Naphthoquinones of 2,3 2 third sulfone of epoxy, 5,8 dimethoxy 1,4 and preparation method thereof and the medicine containing it |
| CN111589421A (en) * | 2020-05-09 | 2020-08-28 | 万华化学集团股份有限公司 | Oxacyclophosphine ligand and preparation method and application thereof |
| CN113828358A (en) * | 2020-06-24 | 2021-12-24 | 万华化学集团股份有限公司 | Mandelic acid oxidation reaction catalyst, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| HAMID REZA NASIRI等: "Design, Synthesis, and Biological Testing of Novel Naphthoquinones as Substrate-Based Inhibitors of the Quinol/Fumarate Reductase from Wolinella succinogenes", 《J. MED. CHEM.》, vol. 56, pages 9532 * |
| 朱庆英等: "β-环糊精衍生物诱导H2O2水相不对称环氧化trans-查尔酮", 《有机化学》, vol. 36, no. 08, pages 1907 - 1914 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114149389B (en) | 2023-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109776381B (en) | Preparation method of spiro indolone compound in aqueous phase | |
| CN109575014B (en) | Benzimidazo [2,1-a ] isoquinolinone compound and preparation method thereof | |
| CN109956894B (en) | Synthetic method of 3, 3' -disubstituted-2-indolone compound | |
| CN112940002B (en) | Method for synthesizing octatomic bridged ring compound through palladium-catalyzed asymmetric ring addition reaction | |
| CN112264105B (en) | Supported palladium catalyst for synthesis of substituted ketone and bisphenol F | |
| CN114149389A (en) | Preparation method of naphthoquinone epoxy compound | |
| CN111393384A (en) | Application of cuprous complex containing ortho-carborane Schiff base ligand | |
| CN112375105A (en) | Nickel complex containing meta-carborane ligand and preparation method and application thereof | |
| JPS6045621B2 (en) | Method for producing butanone derivatives | |
| CN113318730B (en) | δ-MnO2Catalyst, preparation method and application thereof | |
| CN113511986B (en) | Preparation method of aryl acetonitrile derivative | |
| CN108675999A (en) | A kind of acetic acid copper catalysis preparation 8-（9- sulfoxide group -10- dihydro phenanthrenes）The method of quinoline | |
| CN105669413B (en) | A kind of method that microwave radiation prepares 2- methyl-1,4-naphthaquinone | |
| CN111100085B (en) | Preparation method of 3-aryl-2H-benzo [ beta ] [1,4] benzoxazine-2-one compound | |
| CN107501043A (en) | Method for synthesizing trimesic aldehyde from trimesic acid | |
| CN108083963B (en) | Synthetic method of diarylethene | |
| Rezaei et al. | Microwave Assisted, Solvent Free One Pot Synthesis of Nitriles from Aryl Aldehydes on Melamin Formaldehyde as Solid Support | |
| CN112778351A (en) | Preparation method of beta-dimethylphenyl silicon substituted aromatic nitro compound | |
| CN113801125B (en) | Preparation method of cyclic anhydride | |
| CN112479837B (en) | Method for preparing phenyl propenone compound by catalyzing phenylacetylene with molecular sieve | |
| US5763623A (en) | Process for catalytic epoxidation of olefinic compounds, novel cyclic ketone catalysts useful in said process | |
| CN115557832B (en) | Synthesis method of citronellal | |
| CN109575015B (en) | Sulfonylated indolo [1,2-a ] quinoline compound and preparation method thereof | |
| CN110204456B (en) | Polysubstituted naphthalene derivative and synthesis method thereof | |
| CN115108985B (en) | Synthesis method of 4- (cyclohexylmethyl) -2, 4-dimethylisoquinoline-1, 3 (2H, 4H) -dione |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |