CN111992246B - Supported photocatalyst containing syn- (Me, me) Bimane structure - Google Patents
Supported photocatalyst containing syn- (Me, me) Bimane structure Download PDFInfo
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- CN111992246B CN111992246B CN202010755601.9A CN202010755601A CN111992246B CN 111992246 B CN111992246 B CN 111992246B CN 202010755601 A CN202010755601 A CN 202010755601A CN 111992246 B CN111992246 B CN 111992246B
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- VWKNUUOGGLNRNZ-UHFFFAOYSA-N methylbimane Chemical group CC1=C(C)C(=O)N2N1C(C)=C(C)C2=O VWKNUUOGGLNRNZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 5
- -1 2-methyl ethyl Chemical group 0.000 claims abstract description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 5
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims abstract description 5
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims abstract description 4
- PRCIXKQBKWRGMA-UHFFFAOYSA-N 3,4-dimethyl-1,4-dihydropyrazol-5-one Chemical compound CC1C(C)=NNC1=O PRCIXKQBKWRGMA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229950009390 symclosene Drugs 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- 229940126214 compound 3 Drugs 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229940125904 compound 1 Drugs 0.000 claims description 9
- 229940125782 compound 2 Drugs 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- ZPZDIFSPRVHGIF-UHFFFAOYSA-N 3-aminopropylsilicon Chemical group NCCC[Si] ZPZDIFSPRVHGIF-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- SLZVJHXZTOTIGX-UHFFFAOYSA-N 3-chloropropylsilicon Chemical group [Si]CCCCl SLZVJHXZTOTIGX-UHFFFAOYSA-N 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 9
- 239000003504 photosensitizing agent Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006552 photochemical reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241000662429 Fenerbahce Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B01J35/39—
-
- 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
- C07D487/02—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 two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
Abstract
The invention belongs to the technical field of novel photochemical catalysts, and particularly relates to a supported photocatalyst with a syn- (Me, me) Bimane structure, which is prepared by firstly reacting 2-methyl ethyl acetoacetate with hydrazine hydrate to obtain 3,4-dimethyl-5-pyrazolone, then reacting with trichloroisocyanuric acid, then treating with potassium carbonate to obtain syn- (Me, me) Bimane, brominating the syn- (Me, me) Bimane, and grafting the brominated syn- (Me, me) Bimane onto the surface of silica particles with hydroxyl on the surface through 3-chloropropyltrichlorosilane.
Description
Technical Field
The invention belongs to the technical field of novel photochemical catalysts, and particularly relates to a supported photocatalyst containing a syn- (Me, me) Bimane structure.
Background
syn- (Me, me) Bimane (chemical structure is shown below) is a high-efficiency and low-toxicity luminophor, and has the characteristics of small molecular weight, high fluorescence efficiency, good hydrophilicity and lipophilicity and the like. In addition, the maximum absorption wavelength of syn- (Me, me) Bimane is 356nm, the maximum emission wavelength is 458nm, the emission wavelength is in a visible light band, the corresponding energy of the emission wavelength is 2.707 electron volts, and the electron volts are equivalent to the chemical bond energy of many organic matters, so that the energy of light can be effectively converted into the chemical bond energy, and the photochemical catalyst can be used as a photochemical catalyst for carrying out a photocatalytic reaction.
However, in actual mass production, although the photochemical catalyst is used in a small amount, the unit price is high, and the photochemical catalyst cannot be effectively recycled, so that the production cost is increased, and the photochemical catalyst finally becomes only one component in hazardous waste. In this case, the catalyst can be supported on the particulate matter, and when the catalyst is used, the particulate matter is recovered by a simple means such as filtration and cleaning, and the catalyst can be recovered. When selecting the particles, consideration needs to be given to the combination stability between the particles and the photocatalyst, the optical properties of the particles, the hydrophilicity and lipophilicity of the particles, and the like, so as to adapt to the application field of the photochemical catalyst.
Disclosure of Invention
In order to solve the technical problems, the invention provides a supported photocatalyst containing syn- (Me, me) Bimane structure, and the preparation method comprises the following steps:
(1) Reacting 2-methyl ethyl acetoacetate with hydrazine hydrate to obtain a compound 1, namely 3,4-dimethyl-5-pyrazolone,
(2) Reacting the compound 1 obtained in the step (1) with trichloroisocyanuric acid to obtain a compound 2,
(3) Reacting the compound 2 obtained in the step (2) with potassium carbonate to obtain a compound 3, namely syn- (Me, me) Bimane,
(4) Reacting the compound 3 obtained in the step (3) with N-bromosuccinimide to obtain a compound 4;
(5) Reacting the pretreated silicon dioxide particles with sodium hydride and 3-chloropropyltrichlorosilane to generate 3-chloropropylsilicon-bonded silicon dioxide particles,
(6) Reacting the 3-chloropropyl silicon bonded silica particles obtained in the step (5) with ammonia water to generate 3-aminopropyl silicon bonded silica particles,
(7) And (3) reacting the 3-aminopropyl silicon-bonded silica particles obtained in the step (6) with the compound 4 obtained in the step (4) to obtain silica particles with syn- (Me, me) Bimane structures on the surfaces. The reaction route is as follows:
in the application, the monomer is used as the photochemical reaction substance for grafting and loading to prepare the composite catalyst, and when the photochemical reaction substance exists in a monomer form, compared with a polymer of the photochemical reaction substance, the composite catalyst has better light transmittance, so that the composite catalyst has more obvious advantage in photochemical activity; in the application, silica with good light transmittance is used as a load, and the photochemical activity is basically not influenced; before grafting the photochemical active substance to the surface of the silicon dioxide particles, firstly carrying out hydrogen peroxide treatment on the silicon dioxide to hydroxylate the surface of the silicon dioxide particles, and then chemically bonding the photochemical active monomer with the silicon dioxide through a 3-aminopropyl silicon chain segment, so that the stable combination between the photochemical active substance and the carrier silicon dioxide is ensured, the ideal photocatalytic performance is embodied, and particularly, the supported photocatalyst is applied to an organic solvent system.
Drawings
FIG. 1 is a nuclear magnetic diagram of the hydrogen spectrum of compound 1 in the preparation of bromine-substituted syn- (Me, me) Bimane described below,
FIG. 2 is a nuclear magnetic diagram of the hydrogen spectrum of compound 2 in the preparation of bromine-substituted syn- (Me, me) Bimane described below,
FIG. 3 is a hydrogen nuclear magnetic spectrum of compound 3 in the preparation of bromine-substituted syn- (Me, me) Bimane described below,
FIG. 4 is a nuclear magnetic diagram of the hydrogen spectrum of Compound 4 in the preparation of bromine-substituted syn- (Me, me) Bimane described below.
Detailed Description
Preparation of bromine-substituted syn- (Me, me) Bimane:
(1)
adding 2-methyl ethyl acetoacetate (144.1g, 1.0 mol) into 1L of absolute ethanol, stirring and heating to 50 ℃ under the protection of nitrogen, slowly dropwise adding a hydrazine hydrate aqueous solution (94.0 mL of the solution, wherein the content of hydrazine hydrate is 1.5 mol) with the solute mass fraction of 80% into the solution at the temperature, generating white solids in the dropwise adding process, heating to 80 ℃ after the dropwise adding is finished, refluxing for 5 hours, separating out a large amount of white solids,
adding a small amount of the white solid into dichloromethane, heating until the white solid is dissolved to be clear, and detecting by using a gas chromatograph: the peak area ratio of the raw material 2-methyl ethyl acetoacetate to the product 3,4-dimethyl-5-pyrazolone (compound 1) is less than 3 percent, the reaction is judged to be complete,
at this time, the reaction system obtained above was concentrated to 500mL under reduced pressure,cooling to 10 ℃ under stirring, keeping the temperature at 10 ℃ and stirring for half an hour, carrying out vacuum filtration to obtain a white solid, rinsing the filter cake with absolute ethyl alcohol for 3 times, wherein the dosage of the absolute ethyl alcohol is 50mL each time, and blowing air to the obtained filter cake at 50 ℃ for 3 hours to dry the filter cake to obtain 100.8g of white powdery solid (compound 1) with the yield of 90.0%. 1 H NMR(DMSO-d 6 ,400MHz)：δ＝1.73(s,3H),2.06(s,3H),10.03(bs,2H)ppm.ESI-MS:112.32。
(2)
The compound 1 (50.0 g, 0.45mol) obtained above was added to 500mL of methylene chloride, the resulting mixed system was cooled to 5 ℃ and trichloroisocyanuric acid (34.9 g, 0.15mol) was slowly added to the mixed system while maintaining the temperature, after the addition was completed, the temperature was raised to room temperature (25 ℃ C., the same applies hereinafter) and stirring was carried out for 8 hours, generation of a solid was observed during the stirring,
taking a small amount of clarified liquid in the stirring system, and detecting by using a gas chromatograph: the peak area ratio of the reactant compound 1 to the product compound 2 is less than 0.8 percent, the reaction is judged to be complete,
at this time, the reaction system obtained above was concentrated to 250mL, filtered, the filter cake was rinsed with dichloromethane 3 times, the resulting wash was combined with the filtrate obtained in the previous filtration in this step, concentrated to 100mL, added 250mL of anhydrous ethanol and concentrated to 100mL under reduced pressure, and the operation of "added 250mL of anhydrous ethanol and concentrated to 100mL under reduced pressure" was repeated three times, whereby the dichloromethane solvent was substantially completely replaced with 100mL of anhydrous ethanol, at which time a large amount of solids precipitated, cooled to 0 ℃, and stirred at 0 ℃ for half an hour, filtered, the filter cake was rinsed with anhydrous ethanol 3 times, the amount of anhydrous ethanol used per time was 20mL, and the resulting filter cake was air-dried in an oven at 50 ℃ for 3 hours, yielding compound 2 as a white solid of 49.5g, at a yield of 75.0%. 1 H NMR(CDCl 3 ,400MHz)：δ＝1.67(s,3H),2.12(s,3H),9.12(s,1H)ppm.ESI-MS:147.04。
(3)
Compound 2 (30g, 0.21mol) obtained above was added to 300mL of toluene, heated to 90 ℃ and potassium carbonate (69.0g, 0.5mol) was added thereto in portions (in small portions) with stirring, and each addition was 0.5g, and the addition was completed in 2 hours. The potassium carbonate can release heat and gas violently when being added, so the potassium carbonate must be added in batches for a plurality of times, the mixture is stirred for 1 hour at 90 ℃ after the addition is finished,
standing, taking clear liquid in the stirring system, and detecting by using HPLC: the peak area ratio of the reactant compound 2 is less than 0.5 percent, the reaction is judged to be complete, HPLC detection results show that most of products are syn- (Me, me) Bimane (compound 3), the peak area ratio is more than 92.0 percent, and impurities with the area ratio of about 6.0 percent are identified as isomer anti- (Me, me) Bimane,
at the moment, the reaction liquid is cooled to room temperature, the reaction liquid is filtered, a filter cake is rinsed with dichloromethane for 3 times, the dosage of dichloromethane is 30mL each time, an obtained washing liquid is combined with a filtrate obtained by previous filtering in the step, the filtrate is concentrated to 50mL, a light yellow solid is precipitated, 250mL of absolute ethyl alcohol is added into a mixed system, the mixture is concentrated to 100mL under reduced pressure at 50 ℃, the operation of adding 250mL of absolute ethyl alcohol and concentrating to 100mL under reduced pressure at 50 ℃ is repeated for three times, so that the dichloromethane and toluene solvents are basically completely replaced by 100mL of absolute ethyl alcohol, the obtained mixed system is heated to 75 ℃ and stirred until the light yellow solid is completely dissolved, the temperature is reduced to 40 ℃, the temperature is kept for 1 hour, crystals are slowly precipitated in the heat preservation process, the mixed system is continuously cooled to 10 ℃ and kept at the temperature for half hour, the filtering is rinsed with absolute ethyl alcohol for 3 times, the dosage of absolute ethyl alcohol at each time is 20mL, the obtained filter cake is dried by blowing at 50 ℃ for 3 hours, and the obtained filter cake is dried in an oven, 15.14g of yellow powdery crystals, the compound 3, the yield is obtained, the purity of 8978 xft. 1 H NMR(CDCl 3 ,400MHz)：δ＝1.82(s,6H),2.30(s,6H)ppm.ESI-MS:193.10。
(4)
The compound 3 (10g, 52mmol) obtained above was added to 100mL of dichloromethane, and the temperature was reduced to 0 ℃; dissolving N-bromosuccinimide (9.26g, 52mmol) in 400mL acetone, slowly dropwise adding the acetone solution of N-bromosuccinimide (10 ℃) into the dichloromethane solution of the compound 3 for 2 hours, after the dropwise addition is finished, heating to room temperature and continuously stirring for 12 hours,
taking clear liquid in the stirring system, and detecting by using HPLC: the peak area ratios of the reactant compound 3, the compound 4 and the dibrominated by-products are respectively 15.30 percent, 68.53 percent and 16.17 percent,
the stirred system was concentrated and purified by silica gel column chromatography (300g 400 mesh silica gel, n-hexane/ethyl acetate 3:1 elution) to give 8.43g of a pale yellow solid, compound 4, 60.2% yield, 98.02% HPLC purity. 1 H NMR(CDCl 3 ,400MHz)：δ＝1.85(s,3H),1.90(s，3H)，2.45(s,3H)，4.31(s，2H)ppm.ESI-MS:271.05。
Example 1
Grinding silica particles (200g, adamas, product number 24977) with a ball mill, sieving (200 mesh), immersing 50g of the sieved silica particles in 500mL of aqueous nitric acid solution with 20% solute mass fraction, stirring at room temperature for 24 hours, filtering out the silica particles, rinsing with deionized water for 3 times, wherein the amount of deionized water is 200mL each time, adding 200mL of H to the obtained silica particles 2 O 2 Heating 10% hydrogen peroxide to 80 ℃, stirring for 1 hour, adding 20mL (at room temperature) of saturated ammonium chloride aqueous solution into the obtained mixed system, continuously stirring for half an hour, filtering out silicon dioxide particles, rinsing for 3 times by using deionized water, wherein the dosage of the deionized water is 200mL each time, and putting the obtained silicon dioxide particles into an oven to be dried by blowing air for 12 hours at 60 ℃. The treated silicon dioxide particles can effectively remove residual oil stains on the surfaces of the particles, expose hydroxyl groups on the surfaces of the particles, increase the number of the hydroxyl groups on the surfaces of the particles and promote the reaction efficiency of the next step;
adding 30.0g of the treated silicon dioxide particles into 300mL of anhydrous tetrahydrofuran, cooling to-20 ℃, adding 2g of sodium hydride (the mass percentage of 2g of sodium hydride in the mineral oil is 60%) under the protection of nitrogen, heating the obtained mixed system to 50 ℃, stirring for 1 hour, cooling the obtained reaction system to-20 ℃, dropwise adding 10g of 3-chloropropyltrichlorosilane, heating to 50 ℃ after dropwise adding, stirring for 1 hour, cooling to room temperature, filtering, rinsing the particles obtained by filtering with deionized water for 3 times, wherein the dosage of each deionized water is 200mL, and drying the rinsed particles for 5 hours by blowing at 50 ℃ to obtain 30.5g of colorless transparent silicon dioxide particles with surfaces bonded by 3-chloropropyl silicon;
30.5g of 3-chloropropylsilicon-bonded silica particles obtained in the previous step were added to a 500mL pressure-resistant reaction vessel, and 200mL of NH was added to the pressure-resistant reaction vessel 3 28 percent of concentrated ammonia water by mass, raising the temperature of a pressure-resistant reaction kettle to 70 ℃, stirring for 12 hours, cooling, placing the pressure-resistant reaction kettle in a well-ventilated fume hood for pressure relief, filtering the mixture in the kettle, sequentially rinsing the particles obtained by filtering with 3 percent of solute mass aqueous solution of sodium bicarbonate and deionized water for 3 times respectively, wherein the dosage of the aqueous solution of sodium bicarbonate is 200mL each time and the dosage of the deionized water is 200mL each time, sending the cleaned particles into a blast oven, and drying for 5 hours at 50 ℃ to obtain 30.3g of colorless transparent silicon dioxide particles with 3-aminopropyl silicon bonded surfaces. The reaction formula is as follows:
mixing 100mL of potassium carbonate aqueous solution with solute mass fraction of 5% and 200mL of tetrahydrofuran to obtain a mixed solvent, adding 30.3g of colorless transparent silica particles with 3-aminopropyl silicon bonded on the surface obtained in the previous step into the mixed solvent, adding 2.0g of bromine substituted syn- (Me, me) Bimane into the mixed solvent, namely the prepared compound 4, heating to 70 ℃ under the protection of nitrogen, stirring for 12 hours, filtering, rinsing the obtained particles with tetrahydrofuran and deionized water for 3 times, wherein the amount of tetrahydrofuran is 200mL each time and the amount of deionized water is 200mL each time, and drying the rinsed particles in a blast oven at 50 ℃ for 5 hours to obtain 31.2g of light yellow silica particles with syn- (Me, me) Bimane structures on the surfaces. The reaction formula is as follows:
detection test
1.00g of benzoyl peroxide and 1.00g of n-dodecane (internal standard) were accurately weighed into a 250mL volumetric flask and were made to volume with benzene (HPLC pure) to obtain a constant volume solution. Different amounts of the prepared faint yellow silica particles (hereinafter referred to as "photosensitizer-supported particles") with syn- (Me, me) Bimane structures on the surface or the prepared compound 3 is directly used as a photosensitizer and added into 10mL of the constant volume solution to obtain a photocatalytic system (the addition amount is shown in Table 1), the obtained photocatalytic system is magnetically stirred under the protection of nitrogen, an incandescent lamp is used for continuously irradiating the photocatalytic system (a Philips 60W incandescent lamp) under the stirring state, samples are taken every 2 hours, and the phenol concentration in the photocatalytic system sample is measured by an internal standard method by using GC-FID (gas chromatography-infrared ionization detector), wherein the reaction formula is as follows:
the measurement results are shown in table 1:
TABLE 1
Note: the "blank" in the above table refers to a constant volume solution system without any added photosensitizer, and in the constant volume solution system of the blank, silica is added only in the form of "colorless and transparent silica particles surface-bonded by 3-aminopropyl silicon" prepared in example 1, and the added amount is 485.6mg.
As seen from table 1, it was necessary to use up to 0.025g of unsupported photosensitizer (compound 3) to be comparable in photocatalytic effect to 0.5g of photosensitizer-loaded particles, but according to the reactant dosage ratios in example 1:
(31.2 g-30.3 g) ÷ 271.05g/mol ÷ 31.2g =0.000106mol/g, i.e. 0.000106mol of syn- (Me, me) Bimane structure (i.e. compound 3) carried in each gram of photosensitizer-supporting particle, then 0.5g of photosensitizer-supporting particle carries 0.000053mol of syn- (Me, me) Bimane structure;
whereas the 25mg compound 3 in the above table is 0.025 g/193.1 g/mol =0.00013mol, so that "25mg compound 3" is significantly more than "500mg photosensitizer-loaded particles" in terms of the amount of syn- (Me, me) Bimane structure used, "10mg compound 3" in the above table is comparable to "500mg photosensitizer-loaded particles" in terms of the syn- (Me, me) Bimane structure content, but the photocatalytic performance is significantly less than that of "500mg photosensitizer-loaded particles",
it can be seen that after the silica particles are introduced, not only is the convenient recovery of the photosensitizer achieved, but also the photocatalytic performance is effectively improved, for which the applicant believes that the reason is: the silicon dioxide is an inorganic substance, the constant volume solution is an organic system, after the particles loaded with the photosensitizer are put into the organic system, a syn- (Me, me) Bimane structure loaded on the surfaces of the particles is positioned between the inorganic substance of the silicon dioxide and an organic solvent, and the syn- (Me, me) Bimane structure has hydrophilic and oleophilic amphipathy, so that the solvent can fully enter the loaded structure to infiltrate the surfaces of the photocatalyst particles, and the characteristic has the effect of phase transfer on free radicals generated by illumination, so that the photochemical reaction is more efficient and full.
Claims (5)
1. A supported photocatalyst containing syn- (Me, me) Bimane structure is characterized in that: the preparation method of the supported photocatalyst comprises the following steps,
(1) Reacting 2-methyl ethyl acetoacetate with hydrazine hydrate to obtain a compound 1, namely 3,4-dimethyl-5-pyrazolone,
(2) Reacting the compound 1 obtained in the step (1) with trichloroisocyanuric acid to obtain a compound 2,
(3) Reacting the compound 2 obtained in the step (2) with potassium carbonate to obtain a compound 3, namely syn- (Me, me) Bimane,
(4) Reacting the compound 3 obtained in the step (3) with N-bromosuccinimide to obtain a compound 4;
(5) Reacting the pretreated silicon dioxide particles with sodium hydride and 3-chloropropyltrichlorosilane to generate 3-chloropropylsilicon-bonded silicon dioxide particles,
(6) Reacting the 3-chloropropyl silicon bonded silica particles obtained in the step (5) with ammonia water to generate 3-aminopropyl silicon bonded silica particles,
(7) And (3) reacting the 3-aminopropyl silicon dioxide particles obtained in the step (6) with the compound 4 obtained in the step (4) in the presence of potassium carbonate to obtain silica particles with syn- (Me, me) Bimane structures on the surfaces.
2. The supported photocatalyst comprising syn- (Me, me) Bimane structure according to claim 1, wherein: in the step (4), adding the compound 3 into dichloromethane, and cooling to 0 ℃; and dissolving the N-bromosuccinimide in acetone, slowly dropwise adding the acetone solution of the N-bromosuccinimide into the dichloromethane solution of the compound 3, and heating to room temperature after dropwise adding to continue stirring and reacting.
3. The supported photocatalyst comprising a syn- (Me, me) Bimane structure according to claim 1, wherein: the pretreatment in the step (5) is that firstly, silica particles are put into acid solution to be stirred, then the silica particles are filtered, cleaned and put into hydrogen peroxide to be stirred, after the silica particles are stirred for a period of time in the hydrogen peroxide, ammonium chloride is added into the hydrogen peroxide to be continuously stirred, and finally the silica particles are filtered, cleaned and dried.
4. The supported photocatalyst comprising syn- (Me, me) Bimane structure according to claim 1, wherein: in the step (5), the pretreated silicon dioxide particles are added into anhydrous tetrahydrofuran, the temperature is reduced to-20 ℃, sodium hydride is added into the anhydrous tetrahydrofuran under the protection of nitrogen, the temperature is raised to 50 ℃, the mixture is stirred and reacted, then the temperature is reduced to-20 ℃, 3-chloropropyltrichlorosilane is added into the mixture dropwise, the mixture is heated to 50 ℃ after the dropwise addition, the stirring reaction is carried out, and the mixture is cooled, filtered and washed.
5. The supported photocatalyst comprising syn- (Me, me) Bimane structure according to claim 1, wherein: in the step (7), a potassium carbonate aqueous solution and tetrahydrofuran are mixed to obtain a mixed solvent, the 3-aminopropyl silicon bonded silica particles are added into the mixed solvent, the compound 4 is added into the mixed solvent, and the mixture is heated and stirred to react under the protection of nitrogen, filtered, washed and dried.
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| CN102909070A (en) * | 2012-10-30 | 2013-02-06 | 河南师范大学 | Load type chiral catalyst and preparation method thereof |
| CN106413874A (en) * | 2014-03-11 | 2017-02-15 | Les创新材料公司 | Processes for preparing silica-carbon allotrope composite materials and using same |
| CN110734397A (en) * | 2019-12-02 | 2020-01-31 | 阿里生物新材料（常州）有限公司 | Synthesis method of 4- (difluoromethyl) -2-hydroxypyridine-5-sulfonyl chloride |
| GB2569412B (en) * | 2017-06-04 | 2020-04-01 | Neogi Ishita | Chlorination of pyrazolinones |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102909070A (en) * | 2012-10-30 | 2013-02-06 | 河南师范大学 | Load type chiral catalyst and preparation method thereof |
| CN106413874A (en) * | 2014-03-11 | 2017-02-15 | Les创新材料公司 | Processes for preparing silica-carbon allotrope composite materials and using same |
| GB2569412B (en) * | 2017-06-04 | 2020-04-01 | Neogi Ishita | Chlorination of pyrazolinones |
| CN110734397A (en) * | 2019-12-02 | 2020-01-31 | 阿里生物新材料（常州）有限公司 | Synthesis method of 4- (difluoromethyl) -2-hydroxypyridine-5-sulfonyl chloride |
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