CN112121858A - Heterogeneous bimetal central metalloporphyrin and preparation method and application thereof - Google Patents
Heterogeneous bimetal central metalloporphyrin and preparation method and application thereof Download PDFInfo
- Publication number
- CN112121858A CN112121858A CN202010884429.7A CN202010884429A CN112121858A CN 112121858 A CN112121858 A CN 112121858A CN 202010884429 A CN202010884429 A CN 202010884429A CN 112121858 A CN112121858 A CN 112121858A
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- China
- Prior art keywords
- porphyrin
- tris
- hydroxyphenyl
- reaction
- stirring
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Links
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 211
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000007787 solid Substances 0.000 claims abstract description 86
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 43
- 239000010703 silicon Substances 0.000 claims abstract description 43
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 32
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- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 31
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 12
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- -1 methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl Chemical group 0.000 claims description 56
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- UFSCWGWFRDOJSB-UHFFFAOYSA-N [Co].ClC1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2C2=CC=C(C=C2)O Chemical compound [Co].ClC1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2C2=CC=C(C=C2)O UFSCWGWFRDOJSB-UHFFFAOYSA-N 0.000 claims description 21
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- 239000000047 product Substances 0.000 claims description 9
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- 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
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
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Abstract
A heterogeneous bimetal central metalloporphyrin catalyst and a preparation method thereof are prepared according to the following method: porphyrin M1(II) porphyrin M2(II), potassium carbonate, potassium iodide and hybrid silicon carrier are placed in N, N-dimethylformamide, stirred and subjected to immobilization reaction in nitrogen atmosphere at 50-200 ℃ in the presence of 1.0 to E120 h; then, carrying out suction filtration and centrifugation on the reaction system to obtain a solid substance; and (3) drying the obtained solid matter at 60-120 ℃ for 8-36 h in vacuum to obtain the heterogeneous bimetallic central metalloporphyrin catalyst. And provides an application of the heterogeneous bimetallic porphyrin catalyst in catalytic oxidation of cycloalkane. The invention has high selectivity of naphthenic alcohol and naphthenic ketone, effectively inhibits the generation of aliphatic diacid, and is a novel efficient and feasible selective catalytic oxidation method of naphthenic hydrocarbon.
Description
(I) technical field
The invention relates to heterogeneous bimetal central metalloporphyrin, a preparation method and application thereof in catalytic oxidation of cycloalkane, belonging to the field of organic catalysis and fine organic synthesis.
(II) background of the invention
The catalytic oxidation of cycloalkane is an important chemical conversion process, and the oxidation products of cycloalkanol and cycloalkanone are not only important organic solvents, but also important fine chemical intermediates, and are widely used for synthesis of fine chemical products such as pesticides, medicines, dyes and the like (WO 2019046316; WO 2019030294; WO 2019069911; CN 108864082; CN 109180556; Journal of Medicinal Chemistry 2019, 62: 1837. multidot. 1858; Russian Journal of General Chemistry 2018, 88: 2646. multidot. 2652, namely world patent 2019046316; world patent 2019030294; world patent 2019069911; Chinese patent 108864082; Chinese patent 109180556; pharmaceutical Chemistry 2019, 62: 1837. multidot. 1858; Russian basic Chemistry 2018, 88: 2646. multidot. 2652). Besides, the cycloalkanol and the cycloalkanone can be further oxidized to prepare aliphatic diacid which is an important precursor for preparing various high molecular materials, for example, the main products of cyclohexane catalytic oxidation, the cyclohexanol and the cyclohexanone can be further oxidized to obtain the important precursor adipic acid for producing the nylon-66 and the nylon-6, and the market demand is very large (Applied Catalysis A, General 2019, 575: 120-&Engineering Chemistry Research 2017, 56: 15030-: 120-131; chemical engineering science 2019,203: 163-172; base application catalysis a, 2018, 554: 71-79; industrial and engineering chemistry studies 2017, 56: 15030-15037). At present, the catalytic oxidation of the cycloalkane in industry is mainly realized by using homogeneous cobalt (II) salt or manganese (II) salt as a catalyst, using molecular oxygen or air as an oxidant, and using an Applied Catalysis A, General 2019, 575: 120-jar 131, Science 2014, 346: 1495-jar 1498, namely basic application Catalysis A,2019, 575: 120-jar 131, Science 2014,346: 1495-1498). Because the reaction temperature is high, the generated cycloalkanol and the cycloalkanone are easy to be deeply oxidized to generate aliphatic diacid, so that a pipeline in the catalytic oxidation process of the cycloalkane is blocked, and the continuous production is not facilitated. The main sources of the above problems are: the intermediate product of oxidation, the naphthenic base hydrogen peroxide, is converted to the target oxidation product of naphthenic alcohol and cycloalkanone by a free radical thermal decomposition path, thereby increasing the uncontrollable property of a reaction system and reducing the selectivity of the naphthenic alcohol and the naphthenic ketone. Thus, O is effectively controlled2In the process of catalytic oxidation of cycloalkane, catalytic conversion of oxidation intermediate product cycloalkyl hydroperoxide is beneficial to improvement of cycloalkane catalytic oxidation selectivity, is a novel process improvement with great application significance in the field of industrial cycloalkane catalytic oxidation, is an urgent need of cycloalkane catalytic oxidation industry, has great production and application values, and also has important theoretical research value.
Metalloporphyrin is used as a model compound of cytochrome P-450 and widely applied to biomimetic Catalysis of various organic synthesis reactions, in particular to oxidation reactions (Polydron 2019, 163: 144-. The metalloporphyrin has an approximately planar molecular structure, so that a metal center with catalytic activity can be exposed in a catalytic system to play a role to the maximum extent, excellent catalytic activity can be shown at 1/1000000-1/100000 of the amount of a substrate substance, the cost of catalytic oxidation of cycloalkane can be obviously reduced, and the metalloporphyrin is one of the preferable catalysts for catalytic oxidation of cycloalkane.
Disclosure of the invention
In order to overcome the defects of the prior art, the invention aims to provide heterogeneous bimetallic central metalloporphyrin, a preparation method thereof and application thereof in catalytic oxidation of cycloalkane, wherein bimetallic central metalloporphyrin is used as a catalyst to catalyze O2Oxidizing cycloalkane and effectively regulating and controlling catalytic conversion of oxidation intermediate product cycloalkyl hydrogen peroxide, and has the advantages of high selectivity of cycloalkyl alcohol and cycloalkyl ketone, low reaction temperature, less by-products, small environmental influence and the like, and the method provided by the inventionThe method has low content of the cycloalkyl hydroperoxide and high safety factor, and is a high-efficiency, feasible and safe method for synthesizing the cycloalkyl alcohol and the cycloalkyl ketone by selective catalytic oxidation of the cycloalkane
The technical scheme of the invention is as follows:
a heterogeneous bimetallic centered metalloporphyrin catalyst having a structure according to formula (I):
in the formula (I), R1、R2、R3、R4、R5Each independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, methoxycarbonyl, benzyl, fluoro, chloro, bromo or iodo, M1Is any one of cobalt (II), manganese (II) and iron (II), M2Is any one of copper (II), zinc (II) and nickel (II).
A preparation method of a heterogeneous bimetal central metalloporphyrin catalyst is prepared by the following steps:
porphyrin M1(II) porphyrin M2(II), potassium carbonate, potassium iodide and a hybrid silicon carrier are placed in N, N-dimethylformamide, stirred and subjected to immobilization reaction for 1.0-120 h (preferably 24-96 h) under the conditions of nitrogen atmosphere and 50-200 ℃ (preferably 80-150 ℃), then a reaction system is subjected to suction filtration and centrifugation to obtain a solid matter, and the obtained solid matter is subjected to vacuum drying for 8-36 h at 60-120 ℃ to obtain the heterogeneous bimetallic central metalloporphyrin catalyst;
the porphyrin M1(II) the mass ratio of the hybrid silicon carrier to the hybrid silicon carrier is 1: 10-40 (preferably 1: 15-30); the porphyrin M2(II) with porphyrin M2(II) the ratio of the amount of substance(s) is 1: 0.5-10 (preferably 1: 1-5); the porphyrin M1(II) substance with Potassium carbonateThe amount ratio of (1: 2-20) (preferably 1: 5-15)); the porphyrin M1(II) the amount of potassium iodide is 1: 0.5-10 (preferably 1: 1-5); the volume usage amount of the N, N-dimethylformamide is 5-15 mL/g based on the mass of the hybrid silicon carrier.
Further, the porphyrin M1(II) is preferably: 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-methoxy) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-ethoxy) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-bromo) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-methyl) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-carboxy) -20- (p-hydroxyphenyl) cobalt porphyrin (II) or 5,10, 15-tris (p-fluorophenyl) -20- (p-hydroxyphenyl) cobalt porphyrin (II) .
Still further, the porphyrin M2(II) is preferably: 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-methoxy) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-ethoxy) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-bromo) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-methyl) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-carboxy) -20- (p-hydroxyphenyl) zinc porphyrin (II) or 5,10, 15-tris (p-fluorophenyl) -20- (p-hydroxyphenyl) zinc porphyrin (II) .
The hybrid silicon carrier of the present invention can be prepared according to the methods reported in the prior literature, and can be specifically referred to Journal of Molecular catalysis a-Chemical 2010,319, 58; european Journal of Organic Chemistry 2012,3625; reactive Functional Polymers 2013,73,192, journal of molecular catalytic chemistry 2010,319, 58; european journal of organic chemistry 2012,3625; reactive and functional polymers 2013,73, 192.
The invention also provides an application of the heterogeneous bimetallic center metalloporphyrin catalyst in catalytic oxidation reaction of cycloalkanes.
The application method comprises the following steps: dispersing heterogeneous bimetallic porphyrin in cycloalkane, sealing a reaction system, heating to 100-130 ℃ under stirring, introducing oxygen to 0.2-3.0 MPa, keeping the set temperature and oxygen pressure, stirring for reaction for 3-24 h, and then carrying out post-treatment on reaction liquid to obtain the product cycloalkanol and cycloalkanone.
In the method, cycloalkane is used as a reaction raw material, heterogeneous bimetallic central metalloporphyrin is used as a catalyst, and molecular oxygen is used as an oxidant;
the mass ratio of the heterogeneous bimetallic central metalloporphyrin to the cycloparaffin is 1: 100-10000, preferably 1: 400-850;
the stirring speed is 100-1500 rpm, preferably 600-1200 rpm;
the reaction temperature is 100-150 ℃, and preferably 110-130 ℃;
the reaction pressure is 0.2-3.0 MPa, preferably 0.6-1.6 MPa;
the reaction time is 2.0-48 h, preferably 3.0-24 h.
The post-treatment method comprises the following steps: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3And the using amount of the peroxide is 2.5-25% of the amount of the cycloparaffin substance, the peroxide generated by reduction is stirred for 30min at room temperature (20-30 ℃), and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.
The technical conception of the invention is as follows: the invention takes heterogeneous bimetallic center metalloporphyrin as a catalyst, catalyzes molecular oxygen to oxidize cycloalkane under the condition of no solvent, not only obviously improves the selectivity of cycloalkanol and cycloalkanone, but also improves the conversion rate of cycloalkane, and realizes the inhibition of aliphatic diacid in the oxidation process of cycloalkane. Therefore, the heterogeneous bimetallic porphyrin is used as a catalyst to catalyze molecular oxygen to oxidize cycloalkane under the condition of no solvent, so that the method has the potential of solving the problem that cycloalkanol and cycloalkanone are easy to deeply oxidize to generate aliphatic diacid in the catalytic oxidation process of cycloalkane in the industry, has important industrial application value and theoretical research value, and has certain reference value for improving the selectivity of other catalytic oxidation systems.
The invention has the following beneficial effects: the invention takes heterogeneous bimetallic central metalloporphyrin as a catalyst, has novel structure, simple synthetic route and wide application, has high selectivity of cycloalkanol and cycloalkanone in catalytic oxidation reaction of cycloalkane, and effectively inhibits the generation of aliphatic diacid; the aliphatic diacid has low selectivity, and is beneficial to the continuous oxidation of the naphthenic hydrocarbon and the separation of products; has the potential of solving the problem that naphthenic alcohol and cycloalkanone are easy to deeply oxidize to generate aliphatic diacid in the catalytic oxidation process of the cycloalkane in industry. The invention is a new efficient and feasible selective catalytic oxidation method of cycloalkanes.
(IV) description of the drawings
FIG. 1 is an XPS spectrum of a hybrid silicon support;
FIG. 2 is an XPS spectrum of a heterogeneous bimetallic central metalloporphyrin;
FIG. 3 is an infrared spectrum of a hybrid silicon support (a), heterogeneous bimetallic central metalloporphyrin (b).
(V) detailed description of the preferred embodiments
The invention will be further illustrated with reference to specific examples, without limiting the scope of the invention thereto.
Examples 1-26 are syntheses of the heterogeneous bimetallic central metalloporphyrin catalysts;
examples 27-53 are the use of the heterogeneous bimetallic central metalloporphyrin catalyst in catalytic oxidation of cycloalkanes;
examples 54-57 are comparative experiments in which the heterogeneous bimetallic central metalloporphyrin catalyst was used in catalytic oxidation of cycloalkanes;
example 58 is a scale-up experiment of the use of the heterogeneous bimetallic central metalloporphyrin catalyst in catalytic oxidation of cycloalkanes.
The preparation method of the hybrid silicon carrier of the present invention can be found in Journal of Molecular catalysis A-Chemical 2010,319, 58; european Journal of Organic Chemistry 2012,3625; the Reactive Functional Polymers 2013,73 and 192 are specifically as follows: dissolving 12.04g of 3-chloropropyltriethoxysilane and 41.67g of tetraethoxysilane in 150mL of absolute ethyl alcohol to prepare a solution I; dissolving 17.12g of water and 20.0mL of 1M tetrahydrofuran solution of tetrabutylammonium fluoride in 100mL of absolute ethanol to prepare a solution II; and (3) quickly pouring the solution I into the solution II, violently shaking for 10s, standing, and aging for 6.0d at room temperature. The obtained solid was washed with absolute ethanol (3X 150mL) and then dried under vacuum at 80 ℃ for 10 hours to obtain 46.58g of white solid powder (hybrid silicon carrier).
The metalloporphyrins used in the present invention are all referred to Journal of the American Chemical Society 2017,139: 18590-18597; journal of the American Chemical Society 2018,140:6383-6390 synthesis. All reagents used were commercially available analytical grade.
Example 1
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature under a nitrogen atmosphere for 10min, then stirring the reaction mixture, raising the temperature to 50 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.3089 g. The XPS spectrum of the hybrid silicon carrier is shown in the attached figure 1, the XPS spectrum of the heterogeneous bimetallic central metalloporphyrin is shown in the attached figure 2, and the infrared spectra of the hybrid silicon carrier (a) and the heterogeneous bimetallic central metalloporphyrin (b) are shown in the attached figure 3.
Example 2
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooling to room temperature, suction filtering, transferring to 10mL centrifuge tube, centrifuging for 10min, taking off the solid layer, washing with dry DMF (10X 8mL) until the supernatant is clear, washing with distilled water (2X 8mL) until the supernatant is clear, and dryingThe upper layer was clear by dry acetone washing (5X 8mL), and the lower solid was removed and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.6039g。
Example 3
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature under a nitrogen atmosphere for 10min, then stirring the reaction mixture, raising the temperature to 200 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.7573g。
Example 4
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 12.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.2796g。
Example 5
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl)Phenyl) porphyrin zinc (II), 0.1866g (1.35mmol) K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reacting for 96.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.7845g。
Example 6
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 120.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.8039g。
Example 7
In a 50mL single-port reaction tube, 1.1840g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooling to room temperature, suction filtering, transferring to 10mL centrifuge tube, centrifuging for 10min, taking off the solid layer, washing with dry DMF (10X 8mL) until the supernatant is clear, washing with distilled water (2X 8mL) until the supernatant is clear, and dryingThe upper layer was clear by dry acetone washing (5X 8mL), and the lower solid was removed and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.4085g。
Example 8
In a 50mL single-port reaction tube, 3.5520g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.7123g。
Example 9
In a 50mL single-port reaction tube, 4.7360g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.8235g。
Example 10
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.0592g (0.075mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl)Phenylphenyl) porphyrin zinc (II), 0.1866g (1.35mmol) K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.4215g。
Example 11
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.5918g (0.75mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.7764g。
Example 12
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of cobalt (II) 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin, 1.1835g (1.5mmol) of zinc (II) 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin, 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooling to room temperature, suction filtering, transferring to a 10mL centrifuge tube, centrifuging for 10min, taking off the solid in the lower layer, washing with dry DMF (10X 8mL) until the upper layer is clear, washing with distilled water (2X 8mL) until the upper layer is clear,the dry acetone wash (5X 8mL) was applied until the supernatant was clear, the solid was removed and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.9016g。
Example 13
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.0415g (0.3mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.4023g。
Example 14
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.3110g (2.25mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.7011g。
Example 15
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II) were placedPhenylphenyl) porphyrin zinc (II), 0.4146g (3.0mmol) K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.7934g。
Example 16
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0125g (0.075mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature under a nitrogen atmosphere for 10min, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.5467g。
Example 17
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.1245g (0.75mmol) KI in 20mL N, N-dimethylformamide, stirring under nitrogen atmosphere at room temperature for 10min, then stirring the reaction mixture and raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooling to room temperature, suction filtering, transferring to a 10mL centrifuge tube, centrifuging for 10min, removing the solid from the lower layer, washing with dry DMF (10X 8mL) until the upper layer is clear, washing with distilled water (2X 8mL) until the upper layer is clearThe supernatant was clarified by dry acetone washing (5X 8mL), and the solid was removed and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.6839g。
Example 18
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.2490g (1.5mmol) KI in 20mL N, N-dimethylformamide, stirring under nitrogen atmosphere at room temperature for 10min, then stirring the reaction mixture and raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.7452g。
Example 19
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 10mL of N, N-dimethylformamide, stirring at room temperature under a nitrogen atmosphere for 10min, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.4958g。
Example 20
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20-(p-hydroxyphenyl) porphyrin zinc (II), 0.1866g (1.35mmol) K2CO3And 0.0500g (0.3mmol) of KI in 30mL of N, N-dimethylformamide, stirring at room temperature under a nitrogen atmosphere for 10min, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.6113g。
Example 21
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1386g (0.15mmol) of 5,10, 15-tris (p-bromophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2772g (0.3mmol) of 5,10, 15-tris (p-bromophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II), 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Br-Porp&Zn)0.7041g。
Example 22
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1098g (0.15mmol) of 5,10, 15-tris (p-amino) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2196g (0.3mmol) of 5,10, 15-tris (p-amino) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooling to room temperature, suction filtering, transferring to a 10mL centrifuge tube, centrifuging for 10min, taking off the solid in the lower layer, washing with dry DMF (10X 8mL) until the upper layer is clear, washing with distilled water (2X 8mL) until the upper layer is clear,the dry acetone wash (5X 8mL) was applied until the supernatant was clear, the solid was removed and dried at 80 ℃ for 12.0 h. Obtaining the brownish red solid powder (Si @ p-NH)2-Porp.Co&Zn)0.5883g。
Example 23
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1098g (0.15mmol) of 5,10, 15-tris (p-methyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2196g (0.3mmol) of 5,10, 15-tris (p-methyl) -20- (p-hydroxyphenyl) porphyrin zinc (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining a brownish red solid powder (Si @ p-CH)3-Porp.Co&Zn)0.5746g。
Example 24
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 0.2385g (0.3mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin copper (II) and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Cu)0.6178g。
Example 25
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1179g (0.15mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin manganese (II), 0.2400g (0.3mmol) of 5,10, 15-tris (p)-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin zinc (II), 0.1866g (1.35mmol) K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Zn)0.5939g。
Example 26
In a 50mL single-port reaction tube, 2.0000g of hybrid silicon carrier, 0.1184g (0.15mmol) of iron (II) 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin, 0.2370g (0.3mmol) of nickel (II) 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin, and 0.1866g (1.35mmol) of K2CO3And 0.0500g (0.3mmol) of KI in 20mL of N, N-dimethylformamide, stirring at room temperature for 10min under a nitrogen atmosphere, then stirring the reaction mixture, raising the temperature to 120 ℃, and stirring for reaction for 72.0 h. Cooled to room temperature, filtered with suction, transferred to a 10mL centrifuge tube, centrifuged for 10min to remove the supernatant solid, washed with dry DMF (10X 8mL) until the supernatant is clear, washed with distilled water (2X 8mL) until the supernatant is clear, washed with dry acetone (5X 8mL) until the supernatant is clear, removed the supernatant solid, and dried at 80 ℃ for 12.0 h. Obtaining brownish red solid powder (Si @ p-Cl-Porp&Ni)0.6112g。
Example 27
In a 100mL stainless steel autoclave with a Teflon liner, 0.0200g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; moving and fetching10mL of the resulting solution was analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.57%, cyclohexanol selectivity 48.9%, cyclohexanone selectivity 42.8%, cyclohexyl hydroperoxide selectivity 5.3%, adipic acid selectivity 2.1%, glutaric acid selectivity 0.9%.
Example 28
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.57%, the cyclohexanol selectivity is 51.6%, the cyclohexanone selectivity is 43.7%, the cyclohexyl hydroperoxide selectivity is 2.9%, the adipic acid selectivity is 1.1%, and the glutaric acid selectivity is 0.7%.
Example 29
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0600g of Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.08%, cyclohexanol selectivity 48.2%, cyclohexanone selectivity 46.0%, cyclohexyl hydroperoxide selectivity 3.4%, adipic acid selectivity 1.5%, glutaric acid selectivity 0.9%.
Example 30
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 0.2 MPa. Stirring and reacting at 120 ℃ and 0.2MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.57%, cyclohexanol selectivity 36.1%, cyclohexanone selectivity 38.9%, cyclohexyl hydroperoxide selectivity 16%, adipic acid selectivity 7.6%, glutaric acid selectivity 1.3%.
Example 31
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 0.6 MPa. Stirring and reacting at 120 ℃ and 0.6MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.97%, the cyclohexanol selectivity is 40.7%, the cyclohexanone selectivity is 34.0%, the cyclohexyl hydroperoxide selectivity is 20.9%, the adipic acid selectivity is 3.7%, and the glutaric acid selectivity is 0.6%.
Example 32
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, and stirring was carried outHeating to 120 deg.C, and introducing oxygen to 1.2 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.2MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.72%, cyclohexanol selectivity 51.7%, cyclohexanone selectivity 44.0%, cyclohexyl hydroperoxide selectivity 2.3%, adipic acid selectivity 1.2%, glutaric acid selectivity 0.8%.
Example 33
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 3.0 MPa. Stirring and reacting at 120 ℃ and 3.0MPa oxygen pressure for 8.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.96%, cyclohexanol selectivity 43.0%, cyclohexanone selectivity 42.6%, cyclohexyl hydroperoxide selectivity 9.0%, adipic acid selectivity 4.1%, glutaric acid selectivity 1.3%.
Example 34
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 100 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 100 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) Reduced and generated by stirring for 30min at room temperatureA peroxide. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 3.63%, the cyclohexanol selectivity is 40.9%, the cyclohexanone selectivity is 39.1%, the cyclohexyl hydroperoxide selectivity is 11.0%, the adipic acid selectivity is 6.5%, and the glutaric acid selectivity is 2.5%.
Example 35
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 110 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 110 ℃ under 1.0MPa of oxygen pressure at 800rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.78%, cyclohexanol selectivity 45.7%, cyclohexanone selectivity 36.7%, cyclohexyl hydroperoxide selectivity 9.6%, adipic acid selectivity 5.8%, glutaric acid selectivity 2.2%.
Example 36
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 130 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 130 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 6.13 percent, cyclohexanol selectivity of 51.6 percent, cyclohexanone selectivity of 44.3 percent, cyclohexyl hydroperoxide selectivity of 2.3 percent, adipic acid selectivity of 1.1 percent and glutaric acid selectivity of 0.7 percent.
Example 37
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring and reacting at 120 ℃ and 1.0MPa oxygen pressure for 3.0h at 800 rpm. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 1.28%, cyclohexanol selectivity 30.4%, cyclohexanone selectivity 28.6%, cyclohexyl hydroperoxide selectivity 29.1%, adipic acid selectivity 7.6%, glutaric acid selectivity 4.3%.
Example 38
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 12.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.86%, the cyclohexanol selectivity is 51.6%, the cyclohexanone selectivity is 44.1%, the cyclohexyl hydroperoxide selectivity is 2.5%, the adipic acid selectivity is 1.1%, and the glutaric acid selectivity is 0.7%.
Example 39
At 100mL in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0400g of Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 24.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 5.93%, cyclohexanol selectivity 51.6%, cyclohexanone selectivity 44.3%, cyclohexyl hydroperoxide selectivity 2.3%, adipic acid selectivity 1.1%, glutaric acid selectivity 0.7%.
Example 40
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.89%, cyclohexanol selectivity 50.3%, cyclohexanone selectivity 41.5%, cyclohexyl hydroperoxide selectivity 4.8%, adipic acid selectivity 2.3%, glutaric acid selectivity 1.1%.
EXAMPLE 41
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. Stirring at 120 deg.C, 1.0MPa oxygen pressure, 1200rpmThe time is 8.0 h. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.68%, the cyclohexanol selectivity is 51.1%, the cyclohexanone selectivity is 43.9%, the cyclohexyl hydroperoxide selectivity is 2.7%, the adipic acid selectivity is 1.3%, and the glutaric acid selectivity is 1.0%.
Example 42
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 100rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.89%, the cyclohexanol selectivity is 42.6%, the cyclohexanone selectivity is 34.7%, the cyclohexyl hydroperoxide selectivity is 14.0%, the adipic acid selectivity is 7.3%, and the glutaric acid selectivity is 1.4%.
Example 43
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 14.0240g (200mmol) of cyclopentane, the reaction vessel was sealed, stirred and heated to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. Remove 10mLCarrying out gas chromatography analysis on the obtained solution by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cyclopentane was 4.23%, the selectivity for cyclopentanol was 43.9%, the selectivity for cyclopentanone was 46.0%, the selectivity for cyclopentyl hydroperoxide was 6.2%, the selectivity for glutaric acid was 2.3%, and the selectivity for succinic acid was 1.6%.
Example 44
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 19.6380g (200mmol) of cycloheptane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion rate of cycloheptane is 29.41 percent, the selectivity of cycloheptanol is 47.9 percent, the selectivity of cycloheptanone is 45.6 percent, the selectivity of cycloheptyl hydroperoxide is 4.7 percent, the selectivity of pimelic acid is 1.8 percent, and no generation of adipic acid is detected.
Example 45
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn is dispersed in 22.4410g (200mmol) of cyclooctane, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclooctane conversion rate 40.67%, cyclooctanol selectivity 48.5%, cyclooctanone selectivity 46.2%, cyclooctyl hydrogen peroxideThe selectivity was 3.2%, the selectivity to suberic acid was 2.1%, and no pimelic acid formation was detected.
Example 46
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 33.6640g (200mmol) of cyclododecane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The conversion of cyclododecane was 47.32%, the selectivity for cyclododecanol was 50.7%, the selectivity for cyclododecanone was 45.3%, the selectivity for cyclododecyl hydroperoxide was 3.3%, the selectivity for dodecanedioic acid was 0.7%, and the formation of undecanedioic acid was not detected.
Example 47
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0400g Si @ p-OCH3-Porp.Co&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.67%, cyclohexanol selectivity 50.6%, cyclohexanone selectivity 43.7%, cyclohexyl hydroperoxide selectivity 3.5%, adipic acid selectivity 1.3%, glutaric acid selectivity 0.9%.
Example 48
Stainless steel with polytetrafluoroethylene inner container in 100mLIn a high-pressure reaction kettle, 0.0400g of Si @ p-CH3-Porp.Co&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.89%, cyclohexanol selectivity 49.4%, cyclohexanone selectivity 43.8%, cyclohexyl hydroperoxide selectivity 4.0%, adipic acid selectivity 1.9%, glutaric acid selectivity 0.9%.
Example 49
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0400g of Si @ p-Br-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 5.13%, the cyclohexanol selectivity is 49.1%, the cyclohexanone selectivity is 45.3%, the cyclohexyl hydroperoxide selectivity is 3.0%, the adipic acid selectivity is 1.7%, and the glutaric acid selectivity is 0.9%.
Example 50
In a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, 0.0400g Si @ p-NH is added2-Porp.Co&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After the reaction is finishedAfter completion, ice water was cooled to room temperature, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.73%, cyclohexanol selectivity 48.1%, cyclohexanone selectivity 45.7%, cyclohexyl hydroperoxide selectivity 3.7%, adipic acid selectivity 1.8%, glutaric acid selectivity 0.7%.
Example 51
In a 100mL stainless steel autoclave with a polytetrafluoroethylene inner container, 0.0400g Si @ p-Cl-Porp&Cu was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.03%, cyclohexanol selectivity 44.8%, cyclohexanone selectivity 40.3%, cyclohexyl hydroperoxide selectivity 6.7%, adipic acid selectivity 5.6%, glutaric acid selectivity 2.6%.
Example 52
In a 100mL stainless steel autoclave with a polytetrafluoroethylene liner, 0.0400g Si @ p-Cl-Porp&Zn was dispersed in 16.8320g (200mmol) cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the resulting solution was removed as aPerforming gas chromatography with benzene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.33%, cyclohexanol selectivity 46.9%, cyclohexanone selectivity 40.5%, cyclohexyl hydroperoxide selectivity 5.4%, adipic acid selectivity 4.6%, glutaric acid selectivity 2.6%.
Example 53
In a 100mL stainless steel autoclave with a Teflon liner, 0.0400g Si @ p-Cl-Porp&Ni was dispersed in 16.8320g (200mmol) of cyclohexane, the reaction vessel was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 3.43%, cyclohexanol selectivity 40.0%, cyclohexanone selectivity 39.6%, cyclohexyl hydroperoxide selectivity 11.0%, adipic acid selectivity 8.1%, glutaric acid selectivity 1.3%.
Example 54 (comparative experiment)
In a 100mL stainless steel autoclave having a polytetrafluoroethylene inner vessel, 0.0020g (0.0030mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-methoxyphenyl) zinc (II) porphyrin and 0.0020g (0.0030mmol) of 5,10, 15-tris (p-chlorophenyl) -20- (p-methoxyphenyl) cobalt (II) porphyrin were dispersed in 16.8320g (200mmol) of cyclohexane, the autoclave was sealed, the temperature was raised to 120 ℃ with stirring, and oxygen was introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and subjected to liquid phase chromatography using benzoic acid as an internal standardAnd (4) performing chromatographic analysis. The cyclohexane conversion rate is 3.76%, the cyclohexanol selectivity is 34.8%, the cyclohexanone selectivity is 35.3%, the cyclohexyl hydroperoxide selectivity is 14.1%, the adipic acid selectivity is 10.4%, and the glutaric acid selectivity is 5.3%.
Example 55 (comparative experiment)
0.0400g of Si @ p-Cl-Porp.Zn is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 2.43%, the cyclohexanol selectivity is 9.0%, the cyclohexanone selectivity is 18.7%, the cyclohexyl hydroperoxide selectivity is 65.8%, the adipic acid selectivity is 4.5%, and the glutaric acid selectivity is 2.0%.
Example 56 (comparative experiment)
0.0400g of Si @ p-Cl-Porp.Co is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. The cyclohexane conversion rate is 3.61%, the cyclohexanol selectivity is 33.3%, the cyclohexanone selectivity is 36.7%, the cyclohexyl hydroperoxide selectivity is 12.7%, the adipic acid selectivity is 14.0%, and the glutaric acid selectivity is 3.3%.
Example 57 (comparative experiment)
0.0400g of Si @ p-Cl-Porp. Cu is dispersed in 16.8320g (200mmol) of cyclohexane in a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container, the reaction kettle is sealed, the temperature is raised to 120 ℃ by stirring, and oxygen is introduced to 1.0 MPa. The reaction was stirred at 800rpm for 8.0h at 120 ℃ under 1.0MPa of oxygen pressure. After completion of the reaction, the reaction mixture was cooled to room temperature with ice water, and 1.3115g (5.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. The resulting reaction mixture was made to 100mL with acetone as the solvent. 10mL of the obtained solution is transferred, and gas chromatography analysis is carried out by taking toluene as an internal standard; 10mL of the resulting solution was removed and analyzed by liquid chromatography using benzoic acid as an internal standard. Cyclohexane conversion 4.20%, cyclohexanol selectivity 39.5%, cyclohexanone selectivity 30.2%, cyclohexyl hydroperoxide selectivity 15.0%, adipic acid selectivity 11.2%, glutaric acid selectivity 4.1%.
Example 58 (amplification experiment)
0.4000g of Si @ p-Cl-Porp.Co is put into a 1.00L stainless steel high-pressure reaction kettle with a polytetrafluoroethylene inner container&Zn was dispersed in 168.3200g (2.00mol) cyclohexane, the reaction vessel was sealed, stirred and heated to 120 ℃ and oxygen was introduced to 1.0 MPa. The reaction was stirred at 120 ℃ under 1.0MPa of oxygen pressure and 600rpm for 8.0 h. After completion of the reaction, ice water was cooled to room temperature, and 13.1145g (50.00mmol) of triphenylphosphine (PPh) was added to the reaction mixture3) The resulting peroxide was reduced by stirring at room temperature for 30 min. Distilling, recovering 154.45g of cyclohexane, and ensuring the conversion rate to be 7.85%; vacuum rectification is carried out to obtain 11.65g of cyclohexanol, the selectivity is 46.9%, 9.96g of cyclohexanone and the selectivity is 48.0%.
Claims (10)
1. A heterogeneous bimetallic centered metalloporphyrin catalyst, wherein the heterogeneous bimetallic centered metalloporphyrin has the structure shown in formula (I):
in the formula (I), R1、R2、R3、R4、R5Each independently is: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1-naphthyl, 2-naphthyl, methoxy, ethoxy, hydroxy, mercapto, amino, methylamino, ethylamino, dimethylamino, 1-hydroxyethyl, nitro, cyano, carboxy, methoxycarbonyl, benzyl, fluoro, chloro, bromo or iodo, M1Is any one of cobalt (II), manganese (II) and iron (II), M2Is any one of copper (II), zinc (II) and nickel (II).
2. The method for preparing the heterogeneous bimetallic central metalloporphyrin catalyst according to claim 1, wherein the heterogeneous bimetallic central metalloporphyrin catalyst is prepared by the following method:
porphyrin M1(II) porphyrin M2(II), potassium carbonate, potassium iodide and a hybrid silicon carrier are placed in N, N-dimethylformamide, stirred and subjected to immobilization reaction for 1.0-120 h under the condition of nitrogen atmosphere and temperature of 50-200 ℃; then, carrying out suction filtration and centrifugation on the reaction system to obtain a solid matter, and carrying out vacuum drying on the obtained solid matter at the temperature of 60-120 ℃ for 8-36 h to obtain the heterogeneous bimetallic central metalloporphyrin catalyst;
the porphyrin M1(II) the mass ratio of the hybrid silicon carrier to the hybrid silicon carrier is 1: 10-40; the porphyrin M1(II) with porphyrin M2(II) the amount of substance is 1: 0.5-10; the porphyrin M1(II) the mass ratio of potassium carbonate to potassium carbonate is 1: 2-20; the porphyrin M1(II) the amount of potassium iodide is 1: 0.5-10; the volume usage amount of the N, N-dimethylformamide is 5-15 mL/g based on the mass of the hybrid silicon carrier.
3. The method of preparing a heterogeneous bimetallic central metalloporphyrin catalyst of claim 2, wherein said porphyrin M is M1(II) and a hybrid silicon carrier in a mass ratio of 1: 15-30, wherein the porphyrin M is1(II) with porphyrin M2(II) in a ratio of 1: 1-5, wherein the porphyrin is present in an amount ofM1The mass ratio of (II) to potassium carbonate is 1: 5-15, and the porphyrin M1The ratio of (II) to potassium iodide is 1: 1-5.
4. The method of preparing a heterogeneous bimetallic central metalloporphyrin catalyst according to claim 2 or 3, characterized in that the porphyrin M is M1(II) is 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 5,10, 15-tris (p-methoxy) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 5,10, 15-tris (p-ethoxy) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 5,10, 15-tris (p-bromo) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 5,10, 15-tris (p-methyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II), 5,10, 15-tris (p-carboxy) -20- (p-hydroxyphenyl) porphyrin cobalt (II) or 5,10, 15-tris (p-fluorophenyl) -20- (p-hydroxyphenyl) porphyrin cobalt (II) Cobalt (II).
5. The method of preparing a heterogeneous bimetallic central metalloporphyrin catalyst according to claim 2 or 3, characterized in that the porphyrin M is M2(II) is 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-methoxy) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-ethoxy) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-bromo) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-methyl) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-carboxy) -20- (p-hydroxyphenyl) zinc porphyrin (II) or 5,10, 15-tris (p-fluorophenyl) -20- (p-hydroxyphenyl) zinc porphyrin (II) Zinc (II).
6. Use of the heterogeneous bimetallic central metalloporphyrin catalyst of claim 1 in catalytic oxidation of cycloalkanes.
7. The application of claim 6, wherein the method of applying is: dispersing the heterogeneous bimetal central metalloporphyrin of claim 1 in cycloalkane, sealing a reaction system, heating to 100-130 ℃ under stirring, introducing oxygen to 0.2-3.0 MPa, keeping the set temperature and oxygen pressure, stirring for reaction for 3-24 h, and then carrying out post-treatment on the reaction liquid to obtain the product cycloalkanol and cycloalkanone;
the mass ratio of the heterogeneous bimetallic central metalloporphyrin to the cycloparaffin is 1: 100-10000;
the stirring speed is 100-1500 rpm;
the reaction temperature is 100-150 ℃;
the reaction pressure is 0.2-3.0 MPa;
the reaction time is 2.0-48 h;
the cycloalkane is: one or a mixture of at least two of cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane and cyclododecane in any proportion.
8. The use of claim 7, wherein the mass ratio of heterogeneous bimetallic central metalloporphyrin to cycloparaffin is 1: 400-850, the stirring speed is 600-1200 rpm, the reaction temperature is 110-130 ℃, the reaction pressure is 0.6-1.6 MPa, and the reaction time is 3.0-24 h.
9. The use of claim 7, wherein the porphyrin M is1(II) is: 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-methoxy) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-ethoxy) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-bromo) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-methyl) -20- (p-hydroxyphenyl) zinc porphyrin (II), 5,10, 15-tris (p-carboxy) -20- (p-hydroxyphenyl) zinc porphyrin (II) or 5,10, 15-tris (p-fluorophenyl) -20- (p-hydroxyphenyl) zinc porphyrin (II) (ii) a The porphyrin M2(II) is: 5,10, 15-tris (p-chlorophenyl) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-methoxy) -20- (p-hydroxyphenyl) cobalt porphyrin (v), 5,10, 15-tris (p-ethoxy) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-bromo) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-methyl) -20- (p-hydroxyphenyl) cobalt porphyrin (II), 5,10, 15-tris (p-carboxy) -20- (p-hydroxyphenyl) cobalt porphyrin (II) or 5,10, 15-tris (p-fluorophenyl) -20- (p-hydroxyphenyl) cobalt porphyrin (II) .
10. The use of claim 7, wherein the post-processing method is: after the reaction is finished, adding triphenylphosphine PPh into the reaction solution3And the using amount of the peroxide is 2.5-25% of the amount of the cycloparaffin substance, the peroxide generated by reduction is stirred for 30min at room temperature (20-30 ℃), and the crude product is distilled, rectified under reduced pressure and recrystallized to obtain an oxidation product.
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