CN109675635B - Non-covalent polymer catalyst suitable for 2,3, 6-trimethylphenol oxidation and preparation method thereof - Google Patents
Non-covalent polymer catalyst suitable for 2,3, 6-trimethylphenol oxidation and preparation method thereof Download PDFInfo
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- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
- C07C46/08—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring with molecular oxygen
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- C08G79/14—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing two or more elements other than carbon, oxygen, nitrogen, sulfur and silicon
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention discloses a catalyst suitable for preparing 2,3, 5-trimethyl-p-benzoquinone by catalytic oxidation of 2,3, 6-trimethylphenol, which belongs to the technical field of catalyst preparation, and is prepared from Co (Salphen) and bipyridyl compounds, wherein the bipyridyl compounds comprise two para-position pyridyl groups, and a Co atom in the Co (Salphen) and a nitrogen atom in the bipyridyl compounds are connected through a coordination bond to form a non-covalent polymer catalyst; the preparation method of the catalyst is simple and can be realized by using O2The catalyst is used for catalyzing 2,3, 6-trimethylphenol to be oxidized into 2,3, 5-trimethyl-p-benzoquinone at room temperature and normal pressure by using an oxidant, the limitations that most heterogeneous reactions need hydrogen peroxide and high temperature are overcome, and the conversion rate of a substrate and the selectivity of a product can be well maintained in the process of recycling the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, relates to a catalyst suitable for preparing 2,3, 5-trimethyl-p-benzoquinone by catalytic oxidation of 2,3, 6-trimethylphenol, and particularly relates to a non-covalent polymer catalyst suitable for oxidizing 2,3, 6-trimethylphenol and a preparation method thereof.
Background
2,3, 5-trimethyl-p-benzoquinone is an important intermediate for synthesizing vitamin E, and the synthesis of 2,3, 5-trimethyl-p-benzoquinone mainly has two ways, namely a sulfonation-oxidation method and a one-step catalytic oxidation method. The sulfonation-oxidation method has serious environmental pollution and is gradually eliminated; the one-step catalytic oxidation method has mild conditions, is environment-friendly and has wide development prospect.
At present, the 2,3, 5-trimethyl-p-benzoquinone is mainly prepared by catalytic oxidation of 2,3, 6-trimethylphenol, and most of catalysts are small molecules such as CuCl2And Co (Salen), O2The catalyst is an oxidant, and although the catalyst has better conversion rate and selectivity, the stability of micromolecules is poor, the product and the catalyst are difficult to separate due to the dissolution of the micromolecule catalyst in the reaction process, so that the catalyst is difficult to recycle, the catalyst wastewater pollutes the environment, and the industrial production of the 2,3, 5-trimethyl-p-benzoquinone is greatly restricted, so that the problem of searching for the catalyst with good cycle performance and good catalytic performance is urgently solved at present.
Compared with covalent polymers, the non-covalent polymer has the advantages of simple synthesis, definite structure and the like, but the application of the non-covalent polymer in heterogeneous catalysis is limited due to poor stability. The stability of the coordination bond is between the non-covalent bond and the covalent bond, and the non-covalent polymer constructed by taking the coordination action as the driving force has better stability and has good potential in heterogeneous catalysis.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a non-covalent polymer catalyst suitable for oxidizing 2,3, 6-trimethylphenol and a preparation method thereof, wherein the catalyst is used for catalytically oxidizing 2,3, 6-trimethylphenol into 2,3, 5-trimethyl-p-benzoquinone in the presence of oxygen, has high selectivity, can be repeatedly utilized, and has high substrate conversion rate and good selectivity of a target product.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a non-covalent polymer catalyst suitable for 2,3, 6-trimethylphenol oxidation, which is prepared from Co (Salphen) and a bipyridine compound, wherein the bipyridine compound comprises two para-position pyridyl groups, and a Co atom in the Co (Salphen) and a nitrogen atom in the bipyridine compound are connected through a coordination bond to form the non-covalent polymer catalyst.
Preferably, the bipyridine compound is 4, 4-bipyridine, and the prepared non-covalent polymer catalyst is named as: the structure of the SuP-CSU-1 is as follows:
preferably, the bipyridine compound is 1, 2-bis (4-pyridyl) ethylene, and the prepared non-covalent polymer catalyst is named as: the structure of the SuP-CSU-2 is as follows:
preferably, the bipyridine compound is 1, 4-di (p-pyridyl) benzene, and the obtained non-covalent polymer catalyst is named as: the structure of the SuP-CSU-3 is as follows:
as a general inventive concept, the present invention also provides a method for preparing the non-covalent polymer catalyst, comprising the steps of:
(1) synthesis of bis-saltphen: absolute ethyl alcohol is used as a solvent, the mass ratio of salicylaldehyde to o-phenylenediamine is 2-3: 1, and N is2Protecting, stirring the reaction mixture for 3-24 h at 25-80 ℃, filtering, and recrystallizing to obtain the required target product; wherein the structure of Salphen is as follows:
(2) synthesis of co (salphen): dropwise adding a methanol solution of cobalt acetate into a tetrahydrofuran solution of bis-Salphen, wherein the mass ratio of the bis-Salphen to the cobalt acetate is 1: 2-3, stirring the reaction mixture at 25-80 ℃ for 3-24 h, filtering and drying to obtain a required target product; wherein the structure of BiCo (Salphen) is as follows:
(3) synthesis of SuP-CSU: DMF is taken as a solvent, the mass ratio of the Co (Salphen) and the bipyridyl compounds is 1:1, and N is2And (3) protecting, stirring the reaction mixture at 30-100 ℃ for 24-48 h, cooling to room temperature, filtering, and extracting with methanol and tetrahydrofuran for 24-48 h to obtain the non-covalent polymer catalyst.
The invention also provides application of the non-covalent polymer catalyst, which takes methanol as a solvent to catalyze the oxidation of 2,3, 6-trimethylphenol into 2,3, 5-trimethyl-p-benzoquinone under the condition of oxygen.
Furthermore, the feeding mass ratio of the catalyst to the 2,3, 6-trimethylphenol is 1: 3-10.
Further, the reaction temperature is 25-65 ℃, the oxygen pressure is 0.1-5 MPa, and the catalytic oxidation reaction time is 1-36 h.
The reaction process for catalyzing the oxidation of 2,3, 6-trimethylphenol into 2,3, 5-trimethyl-p-benzoquinone comprises the following steps:
the reaction process in the above formula uses methanol as solvent and oxygen as oxidant.
In order to realize heterogeneous catalytic oxidation of 2,3, 6-trimethylphenol, the invention adopts Co (Salphen) and bipyridyl compound to react to prepare a non-covalent polymer catalyst, and the polymer takes methanol as a solvent and O as a solvent2The high-selectivity oxidation of the 2,3, 6-trimethylphenol can be realized under the condition of an oxidant, the high-efficiency separation of the catalyst can be realized through simple filtration or centrifugation, and the catalyst can be recycled.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) the catalyst prepared by the invention takes methanol as a solvent, oxygen as an oxidant, 2,3, 6-trimethylphenol is oxidized at 25-65 ℃ and 0.1-5 Mpa to generate 2,3, 5-trimethyl-p-benzoquinone, the catalytic reaction is carried out for 1-36 h, the reaction conversion rate is 5-99%, the selectivity of the 2,3, 6-trimethylphenol is more than 99%, and the catalyst can be repeatedly used, so that the catalyst has a good industrial application prospect.
(2) The preparation method of the catalyst is simple and can be realized by using O2The catalyst is used for catalyzing 2,3, 6-trimethylphenol to be oxidized into 2,3, 5-trimethyl-p-benzoquinone at room temperature and normal pressure by using an oxidant, the limitations that most heterogeneous reactions need hydrogen peroxide and high temperature are overcome, and the conversion rate of a substrate and the selectivity of a product can be well maintained in the process of recycling the catalyst.
Drawings
FIG. 1 shows a scheme for the synthesis of Salphen1H NMR chart.
FIG. 2 shows a scheme of Salphen1C NMR chart.
FIG. 3 shows the mass spectrum of Co (Salphen).
FIG. 4 shows FT-IR chart of Co (salphen).
FIG. 5 shows the UV spectrum of Co (Salphen).
FIG. 6 is a UV diagram of 4, 4-bipyridine.
FIG. 7 is a FT-IR chart of Sup-CSU-1.
FIG. 8 shows the UV pattern of Sup-CSU-1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The invention is further described with reference to the following figures and specific examples.
Example 1
The invention provides a preparation method of a non-covalent polymer catalyst suitable for oxidizing 2,3, 6-trimethylphenol, which comprises the following steps:
(1) synthesis of bis-saltphen: in a 500ml three-neck flask, 3-diaminobenzidine (1g,4.67mmol) and 150ml methanol are added, under nitrogen protection, salicylaldehyde (2.74g,22.4mmol) is dissolved in 100ml methanol and added dropwise to the reaction solution, the mixture is stirred for 24h at room temperature, filtered and washed with methanol to obtain a crude product, and THF is recrystallized to obtain the desired Salphen compound, wherein the bis-Salphen has the following structure:
(2) synthesis of co (salphen): adding Salphen (251mg,0.4mmol) and 100ml THF into a 250ml three-neck flask, ultrasonically dissolving, dropwise adding a methanol (30ml) solution of cobalt acetate tetrahydrate (238mg,0.95mmol) into a double-Salphen THF solution under the protection of nitrogen, stirring for 24h at room temperature, filtering, and washing with methanol and water to obtain a required Co (Salphen) compound; wherein the structure of BiCo (Salphen) is as follows:
(3) synthesis of SuP-CSU-1: adding Co (salphen) (500mg, 0.67mmol) and 4, 4-bipyridine (105mg, 0.67mmol) into a 100ml three-neck flask, under the protection of nitrogen, injecting 50ml DMF into a syringe, stirring for 24h at 100 ℃, cooling to room temperature, filtering, and extracting with methanol and THF to obtain the required SuP-CSU-1, wherein n is 10-1000, and the structure is as follows:
example 2
The invention provides a preparation method of a non-covalent polymer catalyst suitable for oxidizing 2,3, 6-trimethylphenol, which comprises the following steps:
(1) synthesis of bis-saltphen: adding 3, 3-diaminobenzidine (1g,4.67mmol) and 150ml of methanol into a 500ml three-neck flask, dissolving salicylaldehyde (2.74g,22.4mmol) in 100ml of methanol under the protection of nitrogen, dropwise adding the mixture into the reaction solution, stirring for 24 hours at room temperature, filtering, washing with methanol to obtain a crude product, and recrystallizing with THF to obtain the required Salphen compound;
(2) synthesis of co (salphen): adding Salphen (251mg,0.4mmol) and 100ml THF into a 250ml three-neck flask, dissolving by ultrasonic wave, dropwise adding a methanol (30ml) solution of cobalt acetate tetrahydrate (238mg,0.95mmol) into a Salphen THF solution under the protection of nitrogen, stirring for 24h at room temperature, filtering, and washing with methanol and water to obtain a required Co (Salphen) compound;
(3) synthesis of SuP-CSU-2: adding Co (salphen) (500mg, 0.67mmol) and 1, 2-bis (4-pyridyl) ethylene (122mg, 0.67mmol) into a 100ml three-neck flask, under the protection of nitrogen, injecting 50ml of DMF into a syringe, stirring for 24h at 100 ℃, cooling to room temperature, filtering, and extracting with methanol and THF to obtain the required SuP-CSU-2, wherein n is 10-1000, and the structure is as follows:
example 3
The invention provides a preparation method of a non-covalent polymer catalyst suitable for oxidizing 2,3, 6-trimethylphenol, which comprises the following steps:
(1) synthesis of bis-saltphen: adding 3, 3-diaminobenzidine (1g,4.67mmol) and 150ml of methanol into a 500ml three-neck flask, dissolving salicylaldehyde (2.74g,22.4mmol) in 100ml of methanol under the protection of nitrogen, dropwise adding the mixture into the reaction solution, stirring for 24 hours at room temperature, filtering, washing with methanol to obtain a crude product, and recrystallizing with THF to obtain the required Salphen compound;
(2) synthesis of co (salphen): adding Salphen (251mg,0.4mmol) and 100ml THF into a 250ml three-neck flask, dissolving by ultrasonic wave, dropwise adding a methanol (30ml) solution of cobalt acetate tetrahydrate (238mg,0.95mmol) into a Salphen THF solution under the protection of nitrogen, stirring for 24h at room temperature, filtering, and washing with methanol and water to obtain a required Co (Salphen) compound;
(3) synthesis of SuP-CSU-3: adding Co (salphen) (500mg, 0.67mmol) and 1, 4-di (p-pyridyl) benzene (156mg, 0.67mmol) into a 100ml three-neck flask, under the protection of nitrogen, injecting 50ml of DMF into a syringe, stirring for 24h at 100 ℃, cooling to room temperature, filtering, and extracting with methanol and THF to obtain the required SuP-CSU-3, wherein n is 10-1000, and the structure is as follows:
example 4
The reaction of 2,3, 6-trimethylphenol oxidation to 2,3, 5-trimethylp-benzoquinone is catalyzed by SuP-CSU-1:
20mg of Sup-CSU-1, 68.1mg of 2,3, 6-trimethylphenol, 2ml of methanol, O2The reaction is carried out for 36 hours at 30 ℃ under 0.1Mpa, the conversion rate of 2,3, 6-trimethylphenol is 99 percent, and the selectivity of 2,3, 5-trimethyl-p-benzoquinone is 99 percent.
Example 5
The reaction of 2,3, 6-trimethylphenol oxidation to 2,3, 5-trimethylp-benzoquinone is catalyzed by SuP-CSU-2:
20mg of Sup-CSU-2, 68.1mg of 2,3, 6-trimethylphenol, 2ml of methanol, O2The reaction is carried out for 36 hours at 30 ℃ under 0.1Mpa, the conversion rate of 2,3, 6-trimethylphenol is 99 percent, and the selectivity of 2,3, 5-trimethyl-p-benzoquinone is 99 percent.
Example 6
The reaction of 2,3, 6-trimethylphenol oxidation to 2,3, 5-trimethylp-benzoquinone is catalyzed by SuP-CSU-3:
20mg of Sup-CSU-3, 68.1mg of 2,3, 6-trimethylphenol, 2ml of methanol, O2The reaction is carried out for 36 hours at 30 ℃ under 0.1Mpa, the conversion rate of 2,3, 6-trimethylphenol is 99 percent, and the selectivity of 2,3, 5-trimethyl-p-benzoquinone is 99 percent.
Example 7
The reaction of 2,3, 6-trimethylphenol oxidation to 2,3, 5-trimethylp-benzoquinone is catalyzed by SuP-CSU-1:
20mg of Sup-CSU-1, 68.1mg of 2,3, 6-trimethylphenol, 2ml of methanol, O2The reaction is carried out at 1Mpa and 30 ℃ for 3 hours, the conversion rate of 2,3, 6-trimethylphenol is 99 percent, and the selectivity of 2,3, 5-trimethyl-p-benzoquinone is 99 percent.
Example 8
The catalyst after the reaction of example 7 was centrifuged and washed, and then continuously subjected to catalytic oxidation:
68.1mg of 2,3, 6-trimethylphenol, methanol 2ml, O20.1Mpa, 30 ℃ for 36h, the catalyst is circulated for the first time, the conversion rate of 2,3, 6-trimethylphenol is 99 percent, and the selectivity of 2,3, 5-trimethyl-p-benzoquinone is 99 percent.
Example 9
The catalyst after the reaction of example 8 was centrifuged and washed, and then continuously subjected to catalytic oxidation:
68.1mg of 2,3, 6-trimethylphenol, methanol 2ml, O20.1Mpa, reaction at 30 ℃ for 36h, second circulation of the catalyst, 99 percent of conversion rate of 2,3, 6-trimethylphenol and 99 percent of selectivity of 2,3, 5-trimethyl-p-benzoquinone.
Example 10
The catalyst after the reaction of example 9 was centrifuged and washed, and then continuously subjected to catalytic oxidation:
68.1mg of 2,3, 6-trimethylphenol, methanol 2ml, O20.1Mpa, 30 ℃ for 36h, the catalyst is circulated for the third time, the conversion rate of 2,3, 6-trimethylphenol is 99 percent, and the selectivity of 2,3, 5-trimethyl-p-benzoquinone is 99 percent.
Example 11
The catalyst after the reaction of example 9 was centrifuged and washed, and then continuously subjected to catalytic oxidation:
68.1mg of 2,3, 6-trimethylphenol, methanol 2ml, O20.1Mpa, 30 ℃ for 36h, the catalyst is circulated for the fourth time, the conversion rate of 2,3, 6-trimethylphenol is 98 percent, and the selectivity of 2,3, 5-trimethyl-p-benzoquinone is 99 percent.
Example 12
The catalyst after the reaction of example 9 was centrifuged and washed, and then continuously subjected to catalytic oxidation:
68.1mg of 2,3, 6-trimethylphenol, methanol 2ml, O2The reaction is carried out for 36 hours at 30 ℃ under 0.1Mpa, the catalyst is circulated for the fifth time, the conversion rate of 2,3, 6-trimethylphenol is 96 percent, and the selectivity of 2,3, 5-trimethyl-p-benzoquinone is 99 percent.
FIG. 1 shows a scheme for the synthesis of Salphen1H NMR chart, solvent is deuterated CDCl3From the figure canTo yield: the number of the hydrogen species is 9, the number ratio of the hydrogen species is approximately 1:1:1:2:2:2:2:2:2, and the target compound corresponds to the total number of the hydrogen species.
FIG. 2 shows a scheme of Salphen13C NMR chart, solvent is deuterated CDCl3From the figure, it can be derived: the number of carbon species is 13, and the target compound corresponds to the number.
Fig. 3 is a mass spectrum of co (salphen), and the mode is a positive ion mode, and can be obtained from the following chart: the highest peak molecular weight 744.0035 corresponds to the theoretical molecular weight 744.06, indicating correct synthesis of the target compound.
FIG. 4 is an infrared chart of Co (Salphen), from which: the peak at 1610nm is C ═ N bond, helping to demonstrate the correct synthesis of co (salphen).
FIG. 5 is a UV map of Co (Salphen), from which: pi-pi due to aromatic rings at 270nm, N-pi transition at 406nm due to C-N bonds, and d-pi charge transfer at 476nm due to Co-O bonds.
FIG. 6 is a UV diagram of 4, 4-bipyridine, from which it can be derived: at 270nm, pi-pi may be attributed to aromatic rings.
FIG. 7 is an infrared map of SuP-CSU-1, from which can be derived: the peak at 1608nm is a small blue shift of the C ═ N bond compared to Co (salphen), which indirectly explains the occurrence of coordination between pyridine N and Co.
FIG. 8 is a UV map of SuP-CSU-1, from which it can be derived: a certain red shift of the C-N bond N-pi transition and the d-pi charge transfer of the Co-O bond occurs, probably due to the coordination of pyridine N to Co.
Claims (8)
1. A non-covalent polymer catalyst suitable for the oxidation of 2,3, 6-trimethylphenol, which is prepared from Co (salphen) and bipyridines compound, wherein the bipyridines compound comprises two pyridyl groups at para positions, and a Co atom in the Co (salphen) and a nitrogen atom in the bipyridines compound are connected through a coordination bond to form the non-covalent polymer catalyst;
wherein the structure of the bi-Co (Salphen) is as follows:
the bipyridine compound is any one of 4, 4-bipyridine, 1, 2-di (4-pyridyl) ethylene and 1, 4-di (p-pyridyl) benzene.
2. The non-covalent polymeric catalyst suitable for the oxidation of 2,3, 6-trimethylphenol according to claim 1, wherein the bipyridine compound is 4, 4-bipyridine and the resulting non-covalent polymeric catalyst is designated as: the structure of the SuP-CSU-1 is as follows:
3. the non-covalent polymer catalyst suitable for the oxidation of 2,3, 6-trimethylphenol according to claim 1, wherein the bipyridyl compound is 1, 2-bis (4-pyridyl) ethylene, and the resulting non-covalent polymer catalyst is named: the structure of the SuP-CSU-2 is as follows:
4. the non-covalent polymer catalyst suitable for the oxidation of 2,3, 6-trimethylphenol according to claim 1, wherein the bipyridine compound is 1, 4-di (p-pyridyl) benzene, and the obtained non-covalent polymer catalyst is named as: the structure of the SuP-CSU-3 is as follows:
5. the method for preparing the non-covalent polymer catalyst according to any of claims 1 to 4, comprising the steps of:
(1) synthesis of bis-saltphen: absolute ethyl alcohol is used as a solvent, the mass ratio of salicylaldehyde to o-phenylenediamine is 2-3: 1, and N is2Protecting, stirring the reaction mixture for 3-24 h at 25-80 ℃, filtering, and recrystallizing to obtain the required target product; wherein the structure of Salphen is as follows:
(2) synthesis of co (salphen): dropwise adding a methanol solution of cobalt acetate into a tetrahydrofuran solution of bis-Salphen, wherein the mass ratio of the bis-Salphen to the cobalt acetate is 1: 2-3, stirring the reaction mixture at 25-80 ℃ for 3-24 h, filtering and drying to obtain a required target product; wherein the structure of BiCo (Salphen) is as follows:
(3) synthesis of SuP-CSU: DMF is taken as a solvent, the mass ratio of the Co (Salphen) and the bipyridyl compounds is 1:1, and N is2And (3) protecting, stirring the reaction mixture at 30-100 ℃ for 24-48 h, cooling to room temperature, filtering, and extracting with methanol and tetrahydrofuran for 24-48 h to obtain the non-covalent polymer catalyst.
6. The use of the non-covalent polymer catalyst according to any of claims 1 to 4, wherein the non-covalent polymer catalyst catalyzes the oxidation of 2,3, 6-trimethylphenol to 2,3, 5-trimethylbenzoquinone under oxygen conditions with methanol as a solvent.
7. The use of the non-covalent polymer catalyst according to claim 6, wherein the mass ratio of the catalyst to 2,3, 6-trimethylphenol is 1: 3-10.
8. The use of the non-covalent polymer catalyst according to claim 6, wherein the reaction temperature is 25-65 ℃, the oxygen pressure is 0.1-5 MPa, and the catalytic oxidation reaction time is 1-36 h.
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