CN109589998B - Novel ZnO/Se/SiO2Preparation method of composite material and application of composite material in preparation of phthalide - Google Patents
Novel ZnO/Se/SiO2Preparation method of composite material and application of composite material in preparation of phthalide Download PDFInfo
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- CN109589998B CN109589998B CN201910038448.5A CN201910038448A CN109589998B CN 109589998 B CN109589998 B CN 109589998B CN 201910038448 A CN201910038448 A CN 201910038448A CN 109589998 B CN109589998 B CN 109589998B
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- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 25
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 25
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 239000011669 selenium Substances 0.000 claims description 46
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 17
- 229910052711 selenium Inorganic materials 0.000 claims description 17
- 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 description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 37
- 239000011787 zinc oxide Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
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Abstract
The invention relates to a novel ZnO/Se/SiO2The preparation method of the composite material and the application of the composite material in preparing phthalide, wherein the preparation method of the phthalide comprises the following steps: dissolving o-methylbenzoic acid in organic solvent, adding ZnO/Se/SiO2The composite material is stirred and reacted for 20 to 24 hours at room temperature, and ZnO/Se/SiO is filtered and recovered2And (4) compounding the materials, concentrating the filtrate to remove the organic solvent to obtain the phthalide.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to novel ZnO/Se/SiO2A preparation method of the composite material and application thereof in preparing phthalide.
Background
The zinc oxide (ZnO) particles have the advantages of large specific surface area, stable chemical properties and the like, and are widely applied to the field of photocatalysts. Selenium (Se) has many excellent physicochemical properties as an intrinsic p-type semiconductor material. At present, no report of ZnO/Se composite material in the aspect of organic reaction catalyst exists. The applicant has recently used zinc nitrate as a zinc source, SiO2As a carrier, preparing a novel ZnO/Se/SiO2The composite material can be used as an oxidant for oxidation reaction, and can be used for further research and development of ZnO/Se/SiO2The invention provides the use of a composite material, ZnO/Se/SiO2The application of the composite material in catalyzing o-methylbenzoic acid to prepare phthalide.
Disclosure of Invention
The invention provides a novel ZnO/Se/SiO2The preparation method of the composite material is characterized by comprising the following steps:
adding into zinc nitrate solution at room temperature under stirringContinuously stirring hydrazine hydrate containing selenium for 20-30min, heating to 170-180 ℃, reacting for 8-12h, naturally cooling to 90 ℃, adding tetraethoxysilane, continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the novel ZnO/Se/SiO2A composite material.
Wherein the concentration of the zinc nitrate solution is preferably 0.1-0.2mmol/mL, and each mmol of zinc nitrate is 1.0-1.5mL of selenium-containing hydrazine hydrate; the selenium-containing hydrazine hydrate contains 6-10mg of selenium per ml of hydrazine hydrate; 150-200 mu L of ethyl orthosilicate is used for each millimole of zinc nitrate; the above reaction is preferably carried out in an autoclave.
Another embodiment of the present invention provides the above novel ZnO/Se/SiO2The application of the composite material in catalyzing o-methylbenzoic acid to prepare phthalide.
Another embodiment of the present invention provides a method for preparing phthalide, which is characterized by comprising the steps of:
dissolving o-methylbenzoic acid in organic solvent, adding the above-mentioned ZnO/Se/SiO2The composite material is stirred and reacted for 20 to 24 hours at room temperature, and ZnO/Se/SiO is filtered and recovered2Concentrating the filtrate to remove organic solvent to obtain phthalide; preference is given to using ZnO/Se/SiO per millimole of o-toluic acid210-15mg of composite material; the organic solvent is preferably one or more of dichloromethane, chloroform, diethyl ether and THF.
Compared with the prior art, the invention has the advantages that: (1) the invention takes zinc nitrate as a zinc source and SiO2As a carrier, preparing a novel ZnO/Se/SiO2The composite material can be used for catalyzing o-methylbenzoic acid to prepare phthalide; (2) ZnO/Se/SiO prepared by the invention2The composite material can be recycled for secondary use.
Drawings
FIG. 1 is an SEM image (right) of product A and a TEM image (left) of product A;
figure 2 is the XRD pattern of product a.
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
Adding hydrazine hydrate containing selenium (10mL, 100mg containing selenium) into zinc nitrate solution (0.1mmol/mL, 100mL) at room temperature under stirring, continuously stirring for 20min, heating to 170 ℃ (high-pressure reaction kettle), reacting for 12h, naturally cooling to 90 ℃, adding tetraethoxysilane (1.5mL), continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and vacuum drying to obtain the ZnO/Se/SiO2Composite material (hereinafter referred to as product a, fig. 1, 2).
Example 2
Adding hydrazine hydrate containing selenium (30mL, 180mg containing selenium) into zinc nitrate solution (0.2mmol/mL, 100mL) at room temperature under stirring, continuously stirring for 30min, heating to 180 ℃ (high-pressure reaction kettle), reacting for 8h, naturally cooling to 90 ℃, adding tetraethoxysilane (4.0mL), continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and vacuum drying to obtain the ZnO/Se/SiO2Composite material (hereinafter referred to as product B, SEM image is consistent with product A).
Example 3
Adding hydrazine hydrate containing selenium (10mL, 100mg containing selenium) into zinc nitrate solution (0.1mmol/mL, 100mL) at room temperature under stirring, continuously stirring for 20min, heating to 170 ℃ (high-pressure reaction kettle), reacting for 12h, naturally cooling to room temperature, filtering, precipitating, washing with deionized water and absolute ethyl alcohol in sequence, and vacuum drying to obtain the ZnO/Se composite material (hereinafter referred to as product C).
Example 4
Adding hydrazine hydrate (10mL) into zinc nitrate solution (0.1mmol/mL, 100mL) at room temperature under stirring, continuously stirring for 20min, heating to 170 ℃ (high-pressure reaction kettle), reacting for 12h, naturally cooling to 90 ℃, adding tetraethoxysilane (1.5mL), continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and vacuum drying to obtain ZnO/SiO2Composite material (hereinafter referred to as product D).
Example 5
Dissolving o-methylbenzoic acid (1mmol) in dichloromethane (8mL), adding product A (15mg), stirring at room temperature for 20 hours, filtering to recover product A, concentrating the filtrate to remove dichloromethane to obtain phthalide (125mg, yield about 93.2%, HPLC purity 92.5%,1H、13c NMR data consistent with the report).
Example 6
Dissolving o-methylbenzoic acid (1mmol) in THF (6mL), adding product B (10mg), stirring at room temperature for 24 hr, filtering to recover product B, concentrating the filtrate to remove THF to obtain phthalide (129mg, yield about 96.2%, HPLC purity 90.2%,1H、13c NMR data consistent with the report).
Example 7
O-methylbenzoic acid (1mmol) was dissolved in dichloromethane (8mL), product C (15mg) was added, and after stirring at room temperature for 20 hours, the reaction solution was checked by HPLC for the o-methylbenzoic acid content to be 86.2%.
Example 8
Dissolving o-methylbenzoic acid (1mmol) in dichloromethane (8mL), adding product D (15mg), stirring at room temperature for 20 hours, and detecting the content of o-methylbenzoic acid in the reaction solution by HPLC (high performance liquid chromatography) to be 97.3%.
Example 9
O-methylbenzoic acid (1mmol) was dissolved in dichloromethane (8mL), the product A recovered in example 1 was added, and after stirring at room temperature for 20 hours, the product A was recovered by filtration, and the filtrate was concentrated to remove dichloromethane, to obtain phthalide (116mg, yield about 86.5%, HPLC purity 89.1%).
Claims (7)
1. The preparation method of phthalide is characterized by comprising the following steps:
dissolving o-methylbenzoic acid in organic solvent, adding ZnO/Se/SiO2The composite material is stirred and reacted for 20 to 24 hours at room temperature, and ZnO/Se/SiO is filtered and recovered2Concentrating the filtrate to remove organic solvent to obtain phthalide;
the ZnO/Se/SiO2The preparation method of the composite material comprises the following steps: adding hydrazine hydrate containing selenium into zinc nitrate solution at room temperature under stirring, continuously stirring for 20-30min, heating to 170-180 ℃, reacting for 8-12h, naturally cooling to 90 ℃, adding tetraethoxysilane, continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the ZnO/Se/SiO2A composite material.
2. The process according to claim 1, wherein ZnO/Se/SiO is used per millimole of o-methylbenzoic acid210-15mg of composite material.
3. The method according to claim 1, wherein the organic solvent is selected from the group consisting of dichloromethane, chloroform, diethyl ether and THF.
4. The method according to claim 1, wherein the concentration of the zinc nitrate solution is 0.1 to 0.2mmol/mL, and 1.0 to 1.5mL of hydrazine hydrate containing selenium is used per mmol of zinc nitrate; the selenium-containing hydrazine hydrate contains 6-10mg of selenium per ml of hydrazine hydrate.
5. The process as claimed in claim 1, wherein the zinc nitrate is used in an amount of 150. mu.L per mmol of zinc nitrate.
6.ZnO/Se/SiO2Application of composite material in preparation of cyclohexanedione by oxidizing cyclohexanediol, and ZnO/Se/SiO2The preparation method of the composite material comprises the following steps: adding hydrazine hydrate containing selenium into zinc nitrate solution at room temperature under stirring, continuously stirring for 20-30min, heating to 170-180 ℃, reacting for 8-12h, naturally cooling to 90 ℃, adding tetraethoxysilane, continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the ZnO/Se/SiO2A composite material.
7.ZnO/Se/SiO2Application of composite material in preparation of phthalide by catalyzing o-methylbenzoic acid, namely ZnO/Se/SiO2The preparation method of the composite material comprises the following steps: adding hydrazine hydrate containing selenium into zinc nitrate solution at room temperature under stirring, continuously stirring for 20-30min, heating to 170-180 ℃, reacting for 8-12h, naturally cooling to 90 ℃, adding tetraethoxysilane, continuously stirring to naturally cool to room temperature, filtering, washing precipitate with deionized water and absolute ethyl alcohol in sequence, and drying in vacuum to obtain the ZnO/Se/SiO2A composite material.
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