CN107141322B - Method for chemically synthesizing tetraacetyl geraniol glycoside by using immobilized catalyst - Google Patents
Method for chemically synthesizing tetraacetyl geraniol glycoside by using immobilized catalyst Download PDFInfo
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- CN107141322B CN107141322B CN201610114328.5A CN201610114328A CN107141322B CN 107141322 B CN107141322 B CN 107141322B CN 201610114328 A CN201610114328 A CN 201610114328A CN 107141322 B CN107141322 B CN 107141322B
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- immobilized catalyst
- silica gel
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- 239000003622 immobilized catalyst Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- GLZPCOQZEFWAFX-UHFFFAOYSA-N KU0063794 Natural products CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229930182470 glycoside Natural products 0.000 title claims abstract description 15
- 239000005792 Geraniol Substances 0.000 title claims abstract description 13
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 title claims abstract description 13
- 229940113087 geraniol Drugs 0.000 title claims abstract description 13
- -1 geraniol glycoside Chemical class 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000741 silica gel Substances 0.000 claims abstract description 20
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 5
- 230000001172 regenerating effect Effects 0.000 claims abstract 3
- 239000000499 gel Substances 0.000 claims abstract 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 150000002338 glycosides Chemical class 0.000 claims description 7
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 16
- 229930182478 glucoside Natural products 0.000 abstract description 6
- 150000008131 glucosides Chemical class 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- 238000006994 Koenigs-Knorr glycosidation reaction Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229930182473 O-glycoside Natural products 0.000 description 1
- 150000008444 O-glycosides Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
- C07H15/10—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical containing unsaturated carbon-to-carbon bonds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a method for chemically synthesizing tetraacetyl geraniol glycoside by using an immobilized catalyst, which is characterized in that silicic acid gel is dried and dehydrated to obtain silica gel particles, and silver nitrate reacts with sodium carbonate to make Ag react2And O is crystallized on the inner and outer membranes of the silica gel micropores. The invention also discloses a method for chemically synthesizing tetraacetyl geraniol glycoside by using the immobilized catalyst and a method for regenerating the immobilized catalyst. The method can improve yield of glucoside and reduce cost of chemical synthesis.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis of glucoside substances, and particularly relates to preparation of an immobilized catalyst, chemical synthesis of glucoside substances and regeneration of the immobilized catalyst.
Background
The glucoside compounds are a kind of perfume precursor substances which are abundantly present in plants and can release aroma components under the action of heating, enzymolysis or acid and alkali. In the research of the naturally occurring form and the degradation mechanism, because the content of natural plants is low and the extraction difficulty is high, the chemical synthesis becomes a widely used method.
In order to synthesize the geraniol glycoside, a stereoselective synthesis method is followed, firstly, geraniol is selected as a main raw material, a Koenigs-Knorr method is adopted, glycosylation reaction is carried out on the geraniol and bromo-tetraacetyl sugar, the geraniol-beta-D-tetraacetyl glucopyranoside is synthesized, and then deacetylation reaction is carried out under an alkaline condition, so that the geraniol-beta-D-glucoside is obtained.
In the synthesis reaction of the Koenigs-Knorr method, a catalyst Ag is commonly used2CO3Or Ag2O, also called silver salt method, and a further improved method is a silver carbonate catalyst taking silica gel as a supporter. The method has the advantages that the synthesized product has high purity, is pure O-glycoside, has higher product yield, and has beta-configuration. But has the disadvantages of harsh reaction conditions, strict anhydrous and light-proof conditions, expensive catalyst and long reaction steps.
The silver salt catalyst is used once during synthesis, so that the synthesis cost of the glucoside is high, and the basic research and market application of the stable perfume are limited.
The immobilized catalyst catalyzes chemical synthesis, and the catalyst can be repeatedly used because reactants and products can be effectively separated from the catalyst, so that the synthesis cost is obviously reduced.
The molecular sieve can be used as a catalyst carrier, and the contact area of reactants is enlarged in a chemical reaction by enlarging the specific surface area, so that the synthesis efficiency is effectively improved, and the yield is improved. The microporous silica gel not only has the function of a molecular sieve, but also is a dispersing agent and a curing agent of a catalyst, can effectively reduce the synthesis cost of the glycoside substances, improves the yield, and is a very meaningful attempt.
Disclosure of Invention
The invention aims to overcome the defects that a silver salt catalyst used in the chemical synthesis process of glucoside substances is disposable, the use cost is high, and the contact area of the catalyst and reactants is small, and the synthesis yield is low.
The first aspect of the present invention relates to an immobilized catalyst consisting of microporous silica gel particles and silver oxide.
Preferably, the mass percent of the immobilized catalyst is 55-75% of microporous silica gel particles and 25-45% of silver oxide.
The second aspect of the present invention is a method for preparing an immobilized catalyst, comprising the steps of:
preferably, (1) 5-10% of microporous silica gel particles with the pore diameter of 100-300 meshes are weighed and mixed with 5-15% of silver nitrate by mass concentration;
(2) slowly dripping 2-5% of sodium carbonate under stirring until the volume ratio is 0.5: 1-1.5: 1;
(3) after the dropwise addition is finished, continuously stirring for 10-20 min;
(4) blowing 150-200 ℃ of anhydrous hot air for drying to make Ag2And O is crystallized on the inner and outer membranes of the silica gel micropores.
The third aspect of the invention is the synthesis of tetraacetylgeraniol glycoside catalyzed by immobilized catalyst.
Preferably, the raw materials and the system are subjected to anhydrous treatment, dichloromethane is selected as a solvent, the mass ratio of tetraacetyl bromosugar to geraniol is 1: 1-2: 1, an immobilized catalyst with the sugar content of 0.1-0.5% is added, and the reaction is carried out for 1-10 hours at the temperature of 25-45 ℃. And separating the catalyst from the reaction liquid through a screen, and purifying the reaction liquid through chromatography to obtain the tetraacetylgeraniol glycoside.
The fourth aspect of the present invention is the regeneration of the immobilized catalyst after the reaction.
Preferably, introducing water vapor into the immobilized catalyst after reaction, treating for 30-120 min, and then introducing anhydrous hot air at 150-200 ℃ for drying.
The invention has the beneficial effects that:
1. pore size in the prepared silica gel particlesSilver nitrate reacts with sodium carbonate to generate Ag with the granularity of 100-300 meshes2And O, a crystallization layer is generated on the inner surface of the silica gel hole, so that the catalyst has the functions of a molecular sieve and a dispersing agent, and the specific surface area is enlarged. The yield of the new method reaches 65 percent (bromo-sugar), which is higher than 51.7 percent of the currently reported nitrate + silica gel method, and the improvement of the yield is a very meaningful attempt.
2. The immobilized catalyst is used for catalytic chemical synthesis, and the reactants and the products can be effectively separated from the catalyst, so that the catalyst can be repeatedly used for 3-5 times, and is not used when the yield is lower than 60%, and the preparation cost is greatly reduced by the novel method.
Drawings
FIG. 1 is a flow chart of the synthesis process of tetraacetylgeraniol glycoside according to the present invention.
Detailed Description
Weighing 5% of microporous silica gel particles with the pore diameter of 200 meshes, mixing the microporous silica gel particles with 10% of silver nitrate by mass concentration, slowly dropwise adding 2% of sodium carbonate under stirring until the volume ratio is 1:1, continuously stirring for 15min after dropwise adding is finished, and blowing 180 ℃ of anhydrous hot air for drying to enable Ag to be obtained2And O is crystallized on the inner and outer membranes of the silica gel micropores. The raw materials and the system are subjected to anhydrous treatment, dichloromethane is selected as a solvent, the mass ratio of tetraacetyl bromosugar to geraniol is 1:1, an immobilized catalyst with the sugar content of 0.3% is added, and the reaction is carried out for 5 hours at the temperature of 45 ℃. And separating the catalyst from the reaction liquid through a screen, and purifying the reaction liquid through chromatography to obtain the tetraacetylgeraniol glycoside. Introducing water vapor into the immobilized catalyst after reaction, treating for 60min, and then introducing anhydrous hot air at 180 ℃ for drying.
Claims (2)
1. A method for chemically synthesizing tetraacetyl geraniol glycoside by using an immobilized catalyst is characterized by comprising the following steps: the preparation method of the immobilized catalyst comprises drying and dehydrating silicic acid gel to obtain silica gel particles, and reacting silver nitrate with sodium carbonate to obtain Ag2Crystallizing O on inner and outer membranes of the silica gel micropores, using the immobilized catalyst for synthesizing the tetraacetyl geraniol glycoside, and regenerating the immobilized catalyst after reaction;
the immobilized catalyst consists of 55-75% of microporous silica gel particles and 25-45% of silver oxide;
the method comprises the following steps:
(1) weighing 5-10% of microporous silica gel particles with the pore diameter of 100-300 meshes, and mixing the microporous silica gel particles with silver nitrate with the mass concentration of 5-15%;
(2) slowly dripping 2-5% of sodium carbonate under stirring until the volume ratio is 0.5: 1-1.5: 1;
(3) after the dropwise addition is finished, continuously stirring for 10-20 min;
(4) introducing 150-200 ℃ anhydrous hot air for drying, so that the Ag2O is crystallized on the inner and outer membranes of the silica gel micropores;
the synthesis method of the tetraacetylgeraniol glycoside comprises the following steps: firstly, carrying out anhydrous treatment on the raw materials and the system, selecting dichloromethane as a solvent, adding an immobilized catalyst with the sugar content of 0.1-0.5% into the solvent with the mass ratio of tetraacetyl bromosugar to geraniol of 1: 1-2: 1, reacting for 1-10 h at 25-45 ℃, separating the catalyst from a reaction solution through a screen, and purifying the reaction solution through chromatography to obtain the tetraacetyl geraniol glycoside.
2. The method for chemically synthesizing the tetraacetylgeraniol glycoside by using the immobilized catalyst as claimed in claim 1, wherein the method for regenerating the immobilized catalyst is as follows: introducing water vapor into the reacted catalyst, treating for 30-120 min, and then introducing anhydrous hot air at 150-200 ℃ for drying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610114328.5A CN107141322B (en) | 2016-03-01 | 2016-03-01 | Method for chemically synthesizing tetraacetyl geraniol glycoside by using immobilized catalyst |
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| CN201610114328.5A CN107141322B (en) | 2016-03-01 | 2016-03-01 | Method for chemically synthesizing tetraacetyl geraniol glycoside by using immobilized catalyst |
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| CN107141322A CN107141322A (en) | 2017-09-08 |
| CN107141322B true CN107141322B (en) | 2022-01-11 |
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| CN111253452A (en) * | 2020-03-30 | 2020-06-09 | 山东大学 | Tea aroma precursor glucoside and synthesis method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188589A (en) * | 1995-01-04 | 1996-07-23 | Unitika Ltd | Geranyl-betha-d-galactopyranoside and its production |
| CN101616884A (en) * | 2007-02-16 | 2009-12-30 | 帝斯曼知识产权资产管理有限公司 | The new reaction of primary allylic alcohols |
| CN102120265A (en) * | 2010-01-07 | 2011-07-13 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
-
2016
- 2016-03-01 CN CN201610114328.5A patent/CN107141322B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08188589A (en) * | 1995-01-04 | 1996-07-23 | Unitika Ltd | Geranyl-betha-d-galactopyranoside and its production |
| CN101616884A (en) * | 2007-02-16 | 2009-12-30 | 帝斯曼知识产权资产管理有限公司 | The new reaction of primary allylic alcohols |
| CN102120265A (en) * | 2010-01-07 | 2011-07-13 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
Non-Patent Citations (2)
| Title |
|---|
| 糖苷香料前体的合成及其应用研究;解万翠;《江南大学博士学位论文》;20080331;第26-27页 * |
| 香料前体香叶醇β-D-葡萄糖苷的合成、纯化与表征;王颖等;《食品与机械》;20060531;第22卷(第3期);第47-50页 * |
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