CN108911997A - A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol - Google Patents
A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol Download PDFInfo
- Publication number
- CN108911997A CN108911997A CN201810862895.8A CN201810862895A CN108911997A CN 108911997 A CN108911997 A CN 108911997A CN 201810862895 A CN201810862895 A CN 201810862895A CN 108911997 A CN108911997 A CN 108911997A
- Authority
- CN
- China
- Prior art keywords
- powder
- fluorophenol
- amino
- preparation
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of medicine intermediate 4- amino -3- fluorophenol, specifically include following steps：Modified granatum powder is prepared by raw material of granatum first, is then hydrolyzed in the dispersion liquid of modified granatum powder by ethyl orthosilicate, and the powder after hydrolysis is calcined, hollow silica powder is made；Then it is mixed to prepare composite catalyst with zinc powder；It finally using 3- fluoro-4-nitrophenol as raw material, under the catalysis of composite catalyst obtained above, is reacted using pressurized with hydrogen, prepares target product 4- amino -3- fluorophenol.This method process is simple, and the catalyst of use is cheap, product purity and high income.
Description
Technical field：
The present invention relates to the preparation fields of medicine intermediate, are specifically related to a kind of medicine intermediate 4- amino -3- fluorobenzene
The preparation method of phenol.
Background technique：
4- amino -3- fluorophenol is the important intermediate of medicine, chemical industry preparation, and preparation method report is less, and the U.S. is learned
Person Benner, Brown etc., Derrenbacker etc., and Japanese scholars Tanaka etc., this grade of tall building are catalyzed with platinum carbon respectively, are carried out
It restores rearrangement reaction and 4- amino -3- fluorophenol is made.It since the technique easily leads to platinum carbon poisoning, is allowed to not apply, and causes
Production cost is excessively high.For Klausener etc. with o-fluoronitrobenzene, aqueous sulfuric acid is raw material, is catalyzed with platinum charcoal, using pressurized with hydrogen
Reaction, prepares fine work 4- amino -3- fluorophenol by porous extractor extraction.The technique solves the problems, such as platinum carbon recovery,
But it can not industrialized production due to using porous extractor.
Chinese patent (201610228793.1) discloses 4- amino -3- fluorophenol and its synthetic method, with a fluorobenzene
Amine is raw material, first progress diazo-reaction, then carries out fluorine solution reaction, white diazosalt solid is obtained, then to white diazonium
Reaction is hydrolyzed in salt solid, and m fluorophenol is made, finally carries out nitration reaction, reduction reaction again, and target product 4- is made
Amino -3- fluorophenol.Although this method product yield is high, the more verbose complexity of reaction process.
Summary of the invention：
The object of the present invention is to provide a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, the present invention is disclosed
Method reaction process it is simple, product yield is high, and low energy consumption.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, includes the following steps：
(1) granatum is shredded, is baked, then ground and powder is made；Powder is impregnated into 3h using sodium hydroxide solution, so
After adopt and be washed with deionized to neutrality, drying, powder obtained is scattered in the ethanol solution of oleic acid, ultrasonic at 35-45 DEG C
1-2h, after treatment are handled, modified granatum powder is made in centrifugal treating after precipitating drying；
(2) it disperses modified granatum powder obtained above in ethyl alcohol, dispersion liquid is made；Positive silicon is added dropwise into dispersion liquid
Acetoacetic ester stirs and reaction solution is made, and places reaction liquid into three-necked flask, triethylamine is added into three-necked flask, and be passed through
Band water nitrogen, is warming up to back flow reaction 15-20h at 120-150 DEG C and is cooled to room temperature after reaction, filters, solid is done
It is dry, and in Muffle furnace, 30-50min is handled under air atmosphere at 500-800 DEG C, after treatment cools to room temperature with the furnace, system
Obtain hollow silica powder；
(3) dehydrated alcohol is added after mixing hollow silica powder obtained above, zinc powder, oleic acid carries out at grinding
Composite catalyst is made in reason；
(4) using 3- fluoro-4-nitrophenol as raw material, under the catalysis of composite catalyst obtained above, using hydrogen plus
Pressure reaction, prepares target product 4- amino -3- fluorophenol.
As a preferred embodiment of the above technical solution, in step (1), the mass concentration of the sodium hydroxide solution is 20-40%.
As a preferred embodiment of the above technical solution, in step (1), the powder, oleic acid mass ratio be 1：(0.001-
0.005)。
As a preferred embodiment of the above technical solution, in step (1), the power of the ultrasonic treatment is 500-1000W.
As a preferred embodiment of the above technical solution, in step (2), the modified granatum powder, ethyl alcohol, ethyl orthosilicate, three
The amount ratio of ethamine is 1g：(20-50)mL：1mL：1mL.
As a preferred embodiment of the above technical solution, in step (4), the dosage of the composite catalyst is the fluoro- 4- nitrobenzene of 3-
The 0.1%-0.3% of phenol quality.
As a preferred embodiment of the above technical solution, in step (4), the temperature of the reaction is 80-120 DEG C, pressure 3-
5MPa。
As a preferred embodiment of the above technical solution, in step (3), hollow silica powder, zinc powder, oleic acid mass ratio be
1：(2-6)：0.02.
The invention has the advantages that：
Target product 4- amino -3- fluorine is made using 3- fluoro-4-nitrophenol as raw material, by catalytic hydrogenation reaction in the present invention
Phenol, the reaction process is simple, and the catalyst used is impregnated using lye first using granatum as raw material, handles colloid
Equal magazines, are then dispersed in the ethanol solution of oleic acid, and the modified granatum powder of oleic acid is made, is then dispersed in preparation two
In the reaction solution of silica, by teos hydrolysis, silica is made on Pomegranate Rind surface, finally in air
It is sintered under atmosphere and hollow silica is made, then it is made with zinc powder mixed grinding, calcium catalyst catalytic activity is high, preparation
It is at low cost；
The conversion ratio of method 3- fluoro-4-nitrophenol disclosed by the invention is 98% or more, and the yield of product is up to
95.2%.
Specific embodiment：
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, includes the following steps：
(1) granatum is shredded, is baked, then ground and powder is made；Powder is impregnated into 3h using sodium hydroxide solution, so
After adopt and be washed with deionized to neutrality, drying, powder obtained is scattered in the ethanol solution of oleic acid, 35-45 DEG C, 500W function
1h, after treatment are ultrasonically treated under rate, modified granatum powder is made in centrifugal treating after precipitating drying；Wherein, powder, oleic acid
Mass ratio be 1：0.001；
(2) it disperses modified granatum powder obtained above in ethyl alcohol, dispersion liquid is made；Positive silicon is added dropwise into dispersion liquid
Acetoacetic ester stirs and reaction solution is made, and places reaction liquid into three-necked flask, triethylamine is added into three-necked flask, and be passed through
Band water nitrogen, is warming up to back flow reaction 15h at 120 DEG C and is cooled to room temperature after reaction, filters, and solid is dry, and
In Muffle furnace, 30min is handled at lower 500 DEG C of air atmosphere, after treatment cools to room temperature with the furnace, and hollow silica is made
Powder；Wherein, modified granatum powder, ethyl alcohol, ethyl orthosilicate, triethylamine amount ratio be 1g：20mL：1mL：1mL；
(3) dehydrated alcohol is added after mixing hollow silica powder obtained above, zinc powder, oleic acid carries out at grinding
Composite catalyst is made in reason；Wherein, hollow silica powder, zinc powder, oleic acid mass ratio be 1：2：0.02；
(4) using 3- fluoro-4-nitrophenol as raw material, under the catalysis of composite catalyst obtained above, using hydrogen plus
Pressure reaction, prepares target product 4- amino -3- fluorophenol；Wherein, the dosage of composite catalyst is 3- fluoro-4-nitrophenol quality
0.1%；The temperature of the reaction is 80 DEG C, pressure 3MPa.
Embodiment 2
A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, includes the following steps：
(1) granatum is shredded, is baked, then ground and powder is made；Powder is impregnated into 3h using sodium hydroxide solution, so
After adopt and be washed with deionized to neutrality, drying, powder obtained is scattered in the ethanol solution of oleic acid, 35-45 DEG C, 1000W
1-2h, after treatment are ultrasonically treated under power, modified granatum powder is made in centrifugal treating after precipitating drying；Wherein, powder,
The mass ratio of oleic acid is 1：0.005；
(2) it disperses modified granatum powder obtained above in ethyl alcohol, dispersion liquid is made；Positive silicon is added dropwise into dispersion liquid
Acetoacetic ester stirs and reaction solution is made, and places reaction liquid into three-necked flask, triethylamine is added into three-necked flask, and be passed through
Band water nitrogen, is warming up to back flow reaction 20h at 150 DEG C and is cooled to room temperature after reaction, filters, and solid is dry, and
In Muffle furnace, 50min is handled at lower 800 DEG C of air atmosphere, after treatment cools to room temperature with the furnace, and hollow silica is made
Powder；Wherein, modified granatum powder, ethyl alcohol, ethyl orthosilicate, triethylamine amount ratio be 1g：50mL：1mL：1mL；
(3) dehydrated alcohol is added after mixing hollow silica powder obtained above, zinc powder, oleic acid carries out at grinding
Composite catalyst is made in reason；Wherein, hollow silica powder, zinc powder, oleic acid mass ratio be 1：6：0.02；
(4) using 3- fluoro-4-nitrophenol as raw material, under the catalysis of composite catalyst obtained above, using hydrogen plus
Pressure reaction, prepares target product 4- amino -3- fluorophenol；Wherein, the dosage of composite catalyst is 3- fluoro-4-nitrophenol quality
0.3%；The temperature of the reaction is 120 DEG C, pressure 5MPa.
Embodiment 3
A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, includes the following steps：
(1) granatum is shredded, is baked, then ground and powder is made；Powder is impregnated into 3h using sodium hydroxide solution, so
After adopt and be washed with deionized to neutrality, drying, powder obtained is scattered in the ethanol solution of oleic acid, 35-45 DEG C, 600W function
1.5h, after treatment are ultrasonically treated under rate, modified granatum powder is made in centrifugal treating after precipitating drying；Wherein, powder, oil
The mass ratio of acid is 1：0.002；
(2) it disperses modified granatum powder obtained above in ethyl alcohol, dispersion liquid is made；Positive silicon is added dropwise into dispersion liquid
Acetoacetic ester stirs and reaction solution is made, and places reaction liquid into three-necked flask, triethylamine is added into three-necked flask, and be passed through
Band water nitrogen, is warming up to back flow reaction 16h at 130 DEG C and is cooled to room temperature after reaction, filters, and solid is dry, and
In Muffle furnace, 35min is handled at lower 550 DEG C of air atmosphere, after treatment cools to room temperature with the furnace, and hollow silica is made
Powder；Wherein, modified granatum powder, ethyl alcohol, ethyl orthosilicate, triethylamine amount ratio be 1g：30mL：1mL：1mL；
(3) dehydrated alcohol is added after mixing hollow silica powder obtained above, zinc powder, oleic acid carries out at grinding
Composite catalyst is made in reason；Wherein, hollow silica powder, zinc powder, oleic acid mass ratio be 1：3：0.02；
(4) using 3- fluoro-4-nitrophenol as raw material, under the catalysis of composite catalyst obtained above, using hydrogen plus
Pressure reaction, prepares target product 4- amino -3- fluorophenol；Wherein, the dosage of composite catalyst is 3- fluoro-4-nitrophenol quality
0.15%；The temperature of the reaction is 90 DEG C, pressure 3.5MPa.
Embodiment 4
A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, includes the following steps：
(1) granatum is shredded, is baked, then ground and powder is made；Powder is impregnated into 3h using sodium hydroxide solution, so
After adopt and be washed with deionized to neutrality, drying, powder obtained is scattered in the ethanol solution of oleic acid, 35-45 DEG C, 700W function
1.5h, after treatment are ultrasonically treated under rate, modified granatum powder is made in centrifugal treating after precipitating drying；Wherein, powder, oil
The mass ratio of acid is 1：0.003；
(2) it disperses modified granatum powder obtained above in ethyl alcohol, dispersion liquid is made；Positive silicon is added dropwise into dispersion liquid
Acetoacetic ester stirs and reaction solution is made, and places reaction liquid into three-necked flask, triethylamine is added into three-necked flask, and be passed through
Band water nitrogen, is warming up to back flow reaction 17h at 130 DEG C and is cooled to room temperature after reaction, filters, and solid is dry, and
In Muffle furnace, 40min is handled at lower 600 DEG C of air atmosphere, after treatment cools to room temperature with the furnace, and hollow silica is made
Powder；Wherein, modified granatum powder, ethyl alcohol, ethyl orthosilicate, triethylamine amount ratio be 1g：30mL：1mL：1mL；
(3) dehydrated alcohol is added after mixing hollow silica powder obtained above, zinc powder, oleic acid carries out at grinding
Composite catalyst is made in reason；Wherein, hollow silica powder, zinc powder, oleic acid mass ratio be 1：4：0.02；
(4) using 3- fluoro-4-nitrophenol as raw material, under the catalysis of composite catalyst obtained above, using hydrogen plus
Pressure reaction, prepares target product 4- amino -3- fluorophenol；Wherein, the dosage of composite catalyst is 3- fluoro-4-nitrophenol quality
0.2%；The temperature of the reaction is 100 DEG C, pressure 4MPa.
Embodiment 5
A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, includes the following steps：
(1) granatum is shredded, is baked, then ground and powder is made；Powder is impregnated into 3h using sodium hydroxide solution, so
After adopt and be washed with deionized to neutrality, drying, powder obtained is scattered in the ethanol solution of oleic acid, 35-45 DEG C, 800W function
1h, after treatment are ultrasonically treated under rate, modified granatum powder is made in centrifugal treating after precipitating drying；Wherein, powder, oleic acid
Mass ratio be 1：0.004；
(2) it disperses modified granatum powder obtained above in ethyl alcohol, dispersion liquid is made；Positive silicon is added dropwise into dispersion liquid
Acetoacetic ester stirs and reaction solution is made, and places reaction liquid into three-necked flask, triethylamine is added into three-necked flask, and be passed through
Band water nitrogen, is warming up to back flow reaction 18h at 140 DEG C and is cooled to room temperature after reaction, filters, and solid is dry, and
In Muffle furnace, 40min is handled at lower 650 DEG C of air atmosphere, after treatment cools to room temperature with the furnace, and hollow silica is made
Powder；Wherein, modified granatum powder, ethyl alcohol, ethyl orthosilicate, triethylamine amount ratio be 1g：30mL：1mL：1mL；
(3) dehydrated alcohol is added after mixing hollow silica powder obtained above, zinc powder, oleic acid carries out at grinding
Composite catalyst is made in reason；Wherein, hollow silica powder, zinc powder, oleic acid mass ratio be 1：5：0.02；
(4) using 3- fluoro-4-nitrophenol as raw material, under the catalysis of composite catalyst obtained above, using hydrogen plus
Pressure reaction, prepares target product 4- amino -3- fluorophenol；Wherein, the dosage of composite catalyst is 3- fluoro-4-nitrophenol quality
0.2%；The temperature of the reaction is 110 DEG C, pressure 4MPa.
Embodiment 6
A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, includes the following steps：
(1) granatum is shredded, is baked, then ground and powder is made；Powder is impregnated into 3h using sodium hydroxide solution, so
After adopt and be washed with deionized to neutrality, drying, powder obtained is scattered in the ethanol solution of oleic acid, 35-45 DEG C, 900W function
2h, after treatment are ultrasonically treated under rate, modified granatum powder is made in centrifugal treating after precipitating drying；Wherein, powder, oleic acid
Mass ratio be 1：0.005；
(2) it disperses modified granatum powder obtained above in ethyl alcohol, dispersion liquid is made；Positive silicon is added dropwise into dispersion liquid
Acetoacetic ester stirs and reaction solution is made, and places reaction liquid into three-necked flask, triethylamine is added into three-necked flask, and be passed through
Band water nitrogen, is warming up to back flow reaction 19h at 140 DEG C and is cooled to room temperature after reaction, filters, and solid is dry, and
In Muffle furnace, 30min is handled at lower 700 DEG C of air atmosphere, after treatment cools to room temperature with the furnace, and hollow silica is made
Powder；Wherein, modified granatum powder, ethyl alcohol, ethyl orthosilicate, triethylamine amount ratio be 1g：40mL：1mL：1mL；
(3) dehydrated alcohol is added after mixing hollow silica powder obtained above, zinc powder, oleic acid carries out at grinding
Composite catalyst is made in reason；Wherein, hollow silica powder, zinc powder, oleic acid mass ratio be 1：5.5：0.02；
(4) using 3- fluoro-4-nitrophenol as raw material, under the catalysis of composite catalyst obtained above, using hydrogen plus
Pressure reaction, prepares target product 4- amino -3- fluorophenol；Wherein, the dosage of composite catalyst is 3- fluoro-4-nitrophenol quality
0.2%；The temperature of the reaction is 110 DEG C, pressure 4.5MPa.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol, which is characterized in that include the following steps：
(1) granatum is shredded, is baked, then ground and powder is made；Powder is impregnated into 3h using sodium hydroxide solution, is then adopted
It is washed with deionized to neutrality, drying, powder obtained is scattered in the ethanol solution of oleic acid, is ultrasonically treated at 35-45 DEG C
Modified granatum powder is made in 1-2h, after treatment, centrifugal treating after precipitating drying；
(2) it disperses modified granatum powder obtained above in ethyl alcohol, dispersion liquid is made；Positive silicic acid second is added dropwise into dispersion liquid
Ester stirs and reaction solution is made, and places reaction liquid into three-necked flask, and triethylamine is added into three-necked flask, and is passed through band water
Nitrogen is warming up to back flow reaction 15-20h at 120-150 DEG C and is cooled to room temperature after reaction, filtering, and solid is dry, and
In Muffle furnace, 30-50min is handled under air atmosphere at 500-800 DEG C, after treatment cools to room temperature with the furnace, be made in
Empty SiO 2 powder；
(3) addition dehydrated alcohol, oleic acid are ground after mixing hollow silica powder obtained above, zinc powder,
Composite catalyst is made；
(4) anti-using pressurized with hydrogen under the catalysis of composite catalyst obtained above using 3- fluoro-4-nitrophenol as raw material
It answers, prepares target product 4- amino -3- fluorophenol.
2. a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol as described in claim 1, it is characterised in that：Step
Suddenly in (1), the mass concentration of the sodium hydroxide solution is 20-40%.
3. a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol as described in claim 1, it is characterised in that：Step
Suddenly in (1), the powder, oleic acid mass ratio be 1：(0.001-0.005).
4. a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol as described in claim 1, it is characterised in that：Step
Suddenly in (1), the power of the ultrasonic treatment is 500-1000W.
5. a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol as described in claim 1, it is characterised in that：Step
Suddenly in (2), the modified granatum powder, ethyl alcohol, ethyl orthosilicate, triethylamine amount ratio be 1g：(20-50)mL：1mL：
1mL。
6. a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol as described in claim 1, it is characterised in that：Step
Suddenly in (4), the dosage of the composite catalyst is the 0.1%-0.3% of 3- fluoro-4-nitrophenol quality.
7. a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol as described in claim 1, it is characterised in that：Step
Suddenly in (4), the temperature of the reaction is 80-120 DEG C, pressure 3-5MPa.
8. a kind of preparation method of medicine intermediate 4- amino -3- fluorophenol as described in claim 1, it is characterised in that：Step
Suddenly in (3), hollow silica powder, zinc powder, oleic acid mass ratio be 1：(2-6)：0.02.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810862895.8A CN108911997A (en) | 2018-08-01 | 2018-08-01 | A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810862895.8A CN108911997A (en) | 2018-08-01 | 2018-08-01 | A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108911997A true CN108911997A (en) | 2018-11-30 |
Family
ID=64393988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810862895.8A Withdrawn CN108911997A (en) | 2018-08-01 | 2018-08-01 | A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108911997A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739505A (en) * | 2014-01-14 | 2014-04-23 | 新泰昊原化工有限责任公司 | Process for preparing ortho-aminophenol by virtue of continuous catalytic hydrogenation |
| CN104250226A (en) * | 2013-06-27 | 2014-12-31 | 爱康药业有限公司 | Method for preparing regorafenib intermediate |
| CN108047064A (en) * | 2017-11-06 | 2018-05-18 | 中国科学院兰州化学物理研究所 | A kind of method that paranitroanisole catalytic hydrogenation prepares paraphenetidine |
-
2018
- 2018-08-01 CN CN201810862895.8A patent/CN108911997A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250226A (en) * | 2013-06-27 | 2014-12-31 | 爱康药业有限公司 | Method for preparing regorafenib intermediate |
| CN103739505A (en) * | 2014-01-14 | 2014-04-23 | 新泰昊原化工有限责任公司 | Process for preparing ortho-aminophenol by virtue of continuous catalytic hydrogenation |
| CN108047064A (en) * | 2017-11-06 | 2018-05-18 | 中国科学院兰州化学物理研究所 | A kind of method that paranitroanisole catalytic hydrogenation prepares paraphenetidine |
Non-Patent Citations (1)
| Title |
|---|
| 周壮 等: "用Pd-Fe/SiO2常压催化加氢合成3-氟-4-氨基苯酚的研究", 《淮阴师范学院学报（自然科学版）》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105669464B (en) | A kind of application of no catalytic hydrogenation in being catalyzed nitro benzene and its derivative hydrogenation reaction | |
| CN108054387B (en) | Preparation method of palladium-mesoporous silica hollow multi-core nano catalytic material | |
| CN101987296B (en) | Method for preparing SiH4 by disproportionating SiH2C12 | |
| CN104307501B (en) | A kind of preparation method of the nano zine oxide as photochemical catalyst | |
| CN106865605A (en) | A kind of Ag TiO2The preparation method of composite aerogel | |
| CN103524306B (en) | A kind of gas-phase catalytic hydrogenation prepares the method for difluoroethanol | |
| CN113398944B (en) | Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof | |
| CN103586048A (en) | Nano-Pd magnetic catalyst, its preparation method, and its use in liquid phase catalysis reaction | |
| CN104001515A (en) | Preparation method and application of loaded-type nickel catalyst | |
| CN101805256A (en) | Application of gold/mesoporous carbon catalyst in glucose selective oxidation reaction to prepare gluconic acid | |
| CN109354480A (en) | The method that convective airflow drying prepares aerogel heat-insulating felt | |
| CN108911997A (en) | A kind of preparation method of medicine intermediate 4- amino -3- fluorophenol | |
| CN106238063A (en) | A kind of glycerine hydrogenation Cu ZnO catalyst preparing propylene glycol and preparation method thereof | |
| CN110292920A (en) | The preparation method of the doping cerium dioxide porous bead of zirconium | |
| CN102259005B (en) | Catalyst for assisting coal natural gas methanation reactor and preparation method thereof | |
| CN106512982A (en) | Preparation method of quadrangle-star-shaped bismuth vanadate catalyst | |
| CN116814084A (en) | Sustained-release sodium sarcosinate and preparation method thereof | |
| CN110433813A (en) | A kind of copper and indium alloy catalyst and the preparation method and application thereof for synthesizing methanol by hydrogenating carbon dioxide | |
| CN105214705A (en) | A kind of partial oxidation of methane is for the cobalt Raney nickel preparation method of the Tungsten Carbides of synthesis gas | |
| CN108786846A (en) | A kind of catalyst and preparation method and application of silicic acid modified zirconia sulfonic acid grafting mesopore silicon oxide | |
| CN104230708A (en) | Preparation method of methyl formate | |
| CN108940283A (en) | A kind of support type efficient hydrogenation catalyst and preparation method thereof | |
| CN109174083A (en) | A kind of particle diameter distribution uniformly aoxidizes the preparation method of platinum particles | |
| CN106179344A (en) | A kind of indoor air purification agent of efficient white light catalysis and preparation method thereof | |
| CN103408434B (en) | Method for synthesizing aniline by directly oxidizing and aminating benzene by one step |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20181130 |