CN112479827B - Method for efficiently preparing binaphthol through liquid ligand cocatalyst - Google Patents
Method for efficiently preparing binaphthol through liquid ligand cocatalyst Download PDFInfo
- Publication number
- CN112479827B CN112479827B CN202011452563.6A CN202011452563A CN112479827B CN 112479827 B CN112479827 B CN 112479827B CN 202011452563 A CN202011452563 A CN 202011452563A CN 112479827 B CN112479827 B CN 112479827B
- Authority
- CN
- China
- Prior art keywords
- binaphthol
- product
- heating
- liquid
- naphthol
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
Abstract
The invention relates to a method for efficiently preparing binaphthol by promoting catalysis of a liquid ligand, which comprises the following steps of 1) adding 2-naphthol, solid cuprous chloride, liquid diazabicyclo DBU and n-butanol solvent into a four-mouth bottle; 2) a thermometer, a heating and stirring device and a reflux condenser pipe are arranged on the four-mouth bottle; 3) stirring at normal pressure, heating to 30-60 ℃ to dissolve the raw materials, introducing air with the flow of 100-500 ml/min for oxidation, and reacting at 50-70 ℃ for 3-12 hours to obtain a reaction mixed solution; 4) adding water into the reaction mixed solution, stirring and heating to 50-90 ℃, washing with water for separating liquid, and removing a wastewater layer to obtain an organic layer; 5) cooling the obtained organic layer to 5-25 ℃, crystallizing, filtering, drying to obtain a white-like binaphthol crude product, distilling the filtrate under reduced pressure, and recovering the n-butanol solvent for recycling; 6) recrystallizing the crude binaphthol product, and drying to obtain a white crystallized binaphthol product. The reaction condition is mild, the product yield is more than 78 percent, and the product purity is higher than 99 percent.
Description
Technical Field
The invention relates to the technical field of production of aromatic compound binaphthol, in particular to a method for efficiently preparing binaphthol by using a liquid ligand as a cocatalyst.
Background
Binaphthol (1, 1' -bi-2-naphtho)ls), also known as 2,2 '-dihydroxy-1, 1' -binaphthyl, formula C20H14O2The binaphthol is a white powder or white needle crystal, has a melting point of 216-218 ℃, is sublimated at a boiling point, is an important fine chemical raw material, has a strong chiral induction effect, and can be used for preparing various chiral catalysts, chiral inducers and resolving agents by using a single enantiomer thereof, so that the binaphthol is widely applied to synthesis and preparation of photoconductive materials, dyes, medicines and luminescent materials.
The method for preparing binaphthol by 2-naphthol oxidation reported at home and abroad and the main technology are as follows:
in 1926, Pummer et al reported that 2-naphthol, Cu (OAc)2Reacting the solution with sodium hydroxide at 280-290 deg.C for two hours to obtain a product with a yield of 52% [ Preparation of conjugated diene dioxide,20,758-]. The method for preparing binaphthol has high temperature requirement and is not beneficial to operation.
In 1977, Feringa et al dissolved 2-naphthol in methanol, added 1-fold amount of copper nitrate and 3-fold amount of alpha-phenylethylamine in methanol and mixed while stirring, and N was introduced thereinto2The reaction was carried out at room temperature for 20 hours, and the yield was 62%. Water as solvent, pyridine copper complex at 100 ℃ for 3min, 70% [ Oxidative Phenol Coupling with copper-Amine Complexes,50, 4447-4450-]. The method is required to be carried out under the condition of nitrogen, other oxidation products can be generated under the condition of oxygen, the requirement is harsh, and the reaction yield is not high.
In 1999, Nakajima et al used copper-amine complex (Cu (OH) Cl-TMEDA) as a catalyst and synthesized binaphthol by air oxidation in the absence of solvent, with a ratio of 2-naphthol to copper-amine complex catalyst of 20:1, a reaction temperature of 50 ℃, a reaction time of 2h, and a yield of 92% [ organic oxidative coupling of 2-naphthol Derivatives catalyzed by a chip-amine complex, 46(11),1814-1815], which is greater than 90%, but can only be used in the preparation of binaphthol in gram order.
In 2003, Chenli et al studied 2-naphthol as the starting material, dichloroethane as the solvent, and CuCl and N-alkyl imidazole complexes for a period of 6h with a yield of 88% [ organic chemistry, 23, 227, 2003 ]. The method adopts dichloroethane as a solvent, is volatile, is not beneficial to solvent recovery, is toxic, is easy to cause liver damage and has high cost.
In 2011, Jinmeihong and the like adopt a solid phase method to prepare binaphthol, and adopt 2-naphthol and CuCl2.2H2The metal salts such as O and the like are put into a ball mill for grinding reaction, which is different from the prior industrial production, the reaction is solvent-free reaction under the action of mechanochemical action in the ball mill, the reaction time is 2h, and the yield is 91 percent (modern chemical industry, 31(6), 35-37, 2011)]. Meanwhile, it is reported that 2-naphthol and ferric trichloride hexahydrate are adopted for grinding reaction in a ball mill, and the method has strict control requirements on reaction equipment and reaction temperature, so that the method cannot be industrialized up to now.
In 2017 and summer chemical (Taicang) Co., Ltd, 2-naphthol is used as a raw material, under the action of a phase transfer catalyst and/or a surfactant, the 2-naphthol is reacted with an iron trichloride aqueous solution and hydrogen peroxide, and an electronic grade product 2, 2' -naphthol is obtained through reaction treatment by a water-insoluble organic solvent, wherein the yield is 95 percent at most [ 201711295324.2 ]. The method for preparing binaphthol has high yield, but generates a large amount of waste water, which brings great difficulty.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for efficiently preparing binaphthol by using a liquid ligand as a cocatalyst, and meeting the requirements of mild reaction conditions, simple and convenient operation, high volume yield and small environmental pollution in production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for efficiently preparing binaphthol by using a liquid ligand as a promoter comprises the steps of preparing binaphthol by using 2-naphthol as a raw material, solid cuprous chloride as a catalyst, liquid diazabicyclo DBU as a ligand and n-butanol as a solvent; the method comprises the following steps:
1) adding 2-naphthol, solid cuprous chloride, liquid diazabicyclo DBU and n-butanol solvent into a four-mouth bottle; the mass ratio of each component is 2-naphthol: n-butanol: cuprous chloride: diazabicyclic DBU ═ 1: (1.5-8.5): (0.005-0.05): (0.005-0.05);
2) a thermometer, a heating and stirring device and a reflux condenser pipe are arranged on the four-mouth bottle;
3) stirring at normal pressure, heating to 30-60 ℃ to dissolve the raw materials, introducing air with the flow of 100-500 ml/min for oxidation, and reacting at 50-70 ℃ for 3-12 hours to obtain a reaction mixed solution;
4) adding water into the reaction mixed solution, stirring and heating to 50-90 ℃, washing with water for separating liquid, and removing a wastewater layer to obtain an organic layer;
5) cooling the obtained organic layer to 5-25 ℃, crystallizing, filtering, drying to obtain a white-like binaphthol crude product, distilling the filtrate under reduced pressure, and recovering the n-butanol solvent for recycling;
6) recrystallizing the crude binaphthol product, and drying to obtain a white crystallized binaphthol product.
Compared with the prior art, the invention has the beneficial effects that:
1) the preparation of binaphthol by CuCl catalytic oxidative coupling is realized by adopting a liquid ligand, the reaction temperature is low, the reaction condition is mild, a ligand DBU is adopted, the product yield is more than 78% after the reaction and the product purity is higher than 99% after the recrystallization;
2) the cheap DBU ligand is adopted, so that the cost of the preparation process of the binaphthol is further reduced;
3) the n-butyl alcohol solvent is adopted, so that the problems of toxicity of halogenated alkane solvents and low yield of alcohol solvents are effectively solved, and the method is more suitable for industrial production;
4) the n-butyl alcohol solvent is adopted, and the water washing treatment is carried out by using a liquid separation mode, so that the operation is simple, the water washing efficiency is improved, the reduction of the wastewater amount is facilitated, and the environmental pollution is reduced;
5) the n-butanol solvent is easy to separate from the product, and the solvent can be recycled by reduced pressure distillation.
Detailed Description
The invention is further illustrated by the following examples:
the following examples describe the invention in detail. These examples are merely illustrative of the best embodiments of the present invention and do not limit the scope of the invention.
A method for efficiently preparing binaphthol by using a liquid ligand as a promoter comprises the steps of preparing binaphthol by using 2-naphthol as a raw material, solid cuprous chloride as a catalyst, liquid diazabicyclo DBU as a ligand and n-butanol as a solvent; the method comprises the following steps:
1) adding 2-naphthol, solid cuprous chloride, liquid diazabicyclo DBU and n-butanol solvent into a four-mouth bottle; the mass ratio of each component is 2-naphthol: n-butanol: cuprous chloride: diazabicyclic DBU ═ 1: (1.5-8.5): (0.005-0.05): (0.005-0.05);
2) a thermometer, a heating and stirring device and a reflux condenser pipe are arranged on the four-mouth bottle;
3) stirring at normal pressure, heating to 30-60 ℃ to dissolve the raw materials, introducing air with the flow of 100-500 ml/min for oxidation, and reacting at 50-70 ℃ for 3-12 hours to obtain a reaction mixed solution;
4) adding water into the reaction mixed solution, stirring and heating to 50-90 ℃, washing with water for separating liquid, and removing a wastewater layer to obtain an organic layer;
5) cooling the obtained organic layer to 5-25 ℃, crystallizing, filtering, drying to obtain a white-like binaphthol crude product, distilling the filtrate under reduced pressure, and recovering the n-butanol solvent for recycling;
6) recrystallizing the crude binaphthol product, and drying to obtain a white crystallized binaphthol product.
[ example 1 ]
Adding 40g of 2-naphthol, 200g of n-butyl alcohol, 0.548g of catalyst solid CuCl and 0.843g of ligand DBU into a 500ml four-neck flask with a heating and stirring device, a thermometer and a reflux condenser device, heating to above 56 ℃ to dissolve the 2-naphthol, introducing air with the flow rate of 300ml/min to oxidize, reacting for 4 hours at 50-70 ℃, adding water into the reaction mixed solution, stirring and heating to 80 ℃, washing with water to separate liquid, removing a waste water layer to obtain an organic layer, cooling to 25 ℃, crystallizing, filtering, drying to obtain a white-like binaphthol crude product, distilling the filtrate under reduced pressure, and recovering the n-butyl alcohol solvent for recycling. And recrystallizing the crude binaphthol product, and drying to obtain 31.40g of binaphthol product, wherein the yield is 78.5%, and the melting point is 217.2-218.6 ℃.
[ example 2 ]
Adding 40g of 2-naphthol, 200g of n-butanol, 0.823g of catalyst solid CuCl and 1.265g of ligand DBU into a 500ml four-neck flask with a heating and stirring device, a thermometer and a reflux condenser device, heating to above 56 ℃ to dissolve the 2-naphthol, introducing air with the flow of 300ml/min to perform oxidation, reacting for 3.5 hours at 50-70 ℃, adding water into the reaction mixed solution, stirring and heating to 80 ℃, performing water washing and liquid separation, removing a waste water layer to obtain an organic layer, cooling to 25 ℃, crystallizing, filtering, drying to obtain a white-like binaphthol crude product, performing reduced pressure distillation on the filtrate, and recovering the n-butanol solvent for recycling. And recrystallizing the crude binaphthol product, and drying to obtain 32.40g of binaphthol product, wherein the yield is 81.0%, and the melting point is 217.2-218.5 ℃.
[ COMPARATIVE EXAMPLE 1 ]
Adding 40g of 2-naphthol, 200g of n-butanol and 0.548g of catalyst solid CuCl into a 500ml four-neck flask with a heating and stirring device, a thermometer and a reflux condenser device, heating to a temperature higher than 50-70 ℃, dissolving the 2-naphthol, introducing air with the flow of 300ml/min for oxidation, reacting at 50-70 ℃ for 24 hours, adding water into the reaction mixed solution, stirring, heating to 80 ℃, washing with water for separating, removing a waste water layer to obtain an organic layer, cooling to 25 ℃, crystallizing, filtering, drying to obtain a white-like binaphthol crude product, distilling the filtrate under reduced pressure, and recycling the n-butanol solvent. And recrystallizing the crude binaphthol product, and drying to obtain 22.40g of binaphthol product, wherein the yield is 56%, and the melting point is 217.2-218.5 ℃.
[ COMPARATIVE EXAMPLE 2 ]
Adding 40g of 2-naphthol, 200g of N-butanol, 0.548g of catalyst solid CuCl and 0.455g of N-methylimidazole into a 500ml four-neck flask with a heating and stirring device, a thermometer and a reflux condenser device, heating to a temperature of above 56 ℃ to dissolve the 2-naphthol, introducing air with the flow rate of 300ml/min to carry out oxidation, reacting at 50-70 ℃ for 8 hours, adding water into the reaction mixed solution, stirring and heating to 80 ℃, washing with water to separate liquid, removing a waste water layer to obtain an organic layer, cooling to 25 ℃, crystallizing, filtering, drying to obtain a white-like binaphthol crude product, distilling the filtrate under reduced pressure, and recovering the N-butanol solvent for recycling. And recrystallizing the crude binaphthol product, and drying to obtain 24.8g of binaphthol product, wherein the yield is 62%, and the melting point is 217.1-218.7 ℃.
[ COMPARATIVE EXAMPLE 3]
Adding 40g of 2-naphthol, 312g of dichloroethane, 0.823g of catalyst solid CuCl and 1.265g of ligand DBU into a 500ml four-neck flask with a heating and stirring device, a thermometer and a reflux condenser device, heating to a temperature of above 56 ℃, dissolving the 2-naphthol, introducing air with the flow of 300ml/min for oxidation, reacting for 14 hours at 50-70 ℃, cooling to 25 ℃, filtering, and drying to obtain a crude binaphthol product. And pulping, washing with water, filtering, washing, drying, recrystallizing and drying the crude product to obtain 32.00g of binaphthol product, wherein the yield is 80%, and the melting point is 217.3-218.9 ℃.
[ COMPARATIVE EXAMPLE 4 ]
Adding 40g of 2-naphthol, 130g of methanol, 0.823g of catalyst solid CuCl and 1.265g of ligand DBU into a 500ml four-neck flask with a heating and stirring device, a thermometer and a reflux condenser device, heating to above 56 ℃ to dissolve the 2-naphthol, introducing air with the flow of 300ml/min to oxidize, reacting at the temperature of 50-60 ℃ for 10 hours, cooling to 25 ℃, filtering and drying to obtain a crude binaphthol product. And pulping and washing the crude product, filtering and washing, drying, recrystallizing and drying to obtain 28.00g of binaphthol product, wherein the yield is 70%, and the melting point is 217.3-218.6 ℃.
The difference between example 1 and comparative example 1 is that the catalyst in example 1 is CuCl and the ligand DBU, while the catalyst in comparative example 1 is only CuCl, and from the experimental results, 31.40g of binaphthol product is obtained in example 1, the yield is 78.5%, the reaction time is moderate, and is 4 h; in comparative example 1, 22.4g of binaphthol was obtained with a yield of only 56%, and the reaction time was long, and the amount of impurities was large, which was not suitable for industrial production.
Comparative example 2 was carried out according to the disclosed technique using 2-naphthol as the starting material, N-butanol as the solvent, CuCl as the catalyst, and N-methylimidazole as the ligand under the described reaction conditions to obtain 24.8g of binaphthol, with a yield of only 62%.
The difference between the example 1 and the comparative example 3 is that the solvent used in the example 1 is n-butanol, and the solvent used in the comparative example 3 is dichloroethane, and from the experimental results, the n-butanol used in the example 1 is used as the solvent, the solvent dosage is small, the water washing treatment is performed by adopting a liquid separation method, and the post-treatment operation is simpler than that of the traditional solid-liquid separation method. In addition, the dichloroethane adopted in comparative example 3 is a solvent, the reaction time is long, the post-treatment operation is complicated, and the dichloroethane is toxic and bad for the environment.
The difference between example 1 and comparative example 4 is that the solvent used in example 1 is n-butanol, while the solvent used in comparative example 4 is methanol, and from the experimental results, the yield is higher and the water washing is more convenient when n-butanol is used as the solvent in example 1, while the yield is lower and the reaction time is longer when methanol is used as the solvent in comparative example 4.
Claims (1)
1. A method for efficiently preparing binaphthol by using a liquid ligand as a cocatalyst is characterized in that 2-naphthol is used as a raw material, solid cuprous chloride is used as a catalyst, liquid diazabicyclo DBU is used as a ligand, and n-butanol is used as a solvent to prepare the binaphthol; the method comprises the following steps:
1) adding 2-naphthol, solid cuprous chloride, liquid diazabicyclo DBU and n-butanol solvent into a four-mouth bottle; the mass ratio of each component is 2-naphthol: n-butanol: cuprous chloride: diazabicyclo DBU ═ 1: (1.5-8.5): (0.005-0.05): (0.005-0.05);
2) a thermometer, a heating and stirring device and a reflux condenser pipe are arranged on the four-mouth bottle;
3) stirring at normal pressure, heating to 30-60 ℃ to dissolve the raw materials, introducing air with the flow of 100-500 ml/min for oxidation, and reacting at 50-70 ℃ for 3-12 hours to obtain a reaction mixed solution;
4) adding water into the reaction mixed solution, stirring and heating to 50-90 ℃, washing and separating liquid, and removing a wastewater layer to obtain an organic layer;
5) cooling the obtained organic layer to 5-25 ℃, crystallizing, filtering, drying to obtain a white-like binaphthol crude product, distilling the filtrate under reduced pressure, and recovering the n-butanol solvent for recycling;
6) recrystallizing the crude binaphthol product, and drying to obtain a white crystallized binaphthol product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011452563.6A CN112479827B (en) | 2020-12-12 | 2020-12-12 | Method for efficiently preparing binaphthol through liquid ligand cocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011452563.6A CN112479827B (en) | 2020-12-12 | 2020-12-12 | Method for efficiently preparing binaphthol through liquid ligand cocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112479827A CN112479827A (en) | 2021-03-12 |
| CN112479827B true CN112479827B (en) | 2022-05-10 |
Family
ID=74941557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011452563.6A Active CN112479827B (en) | 2020-12-12 | 2020-12-12 | Method for efficiently preparing binaphthol through liquid ligand cocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112479827B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6770620B1 (en) * | 2019-09-09 | 2020-10-14 | 第一工業製薬株式会社 | 1,1'-bi-2-naphthol powder |
-
2020
- 2020-12-12 CN CN202011452563.6A patent/CN112479827B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6770620B1 (en) * | 2019-09-09 | 2020-10-14 | 第一工業製薬株式会社 | 1,1'-bi-2-naphthol powder |
Non-Patent Citations (5)
| Title |
|---|
| 1,1′-联-2-萘酚的合成新进展;陈丽 等;《广州化学》;20070930;第32卷(第3期);第59-64页 * |
| A Mild and Convenient Method for the Synthesis of Substituted BINOL;YANG Huameng等;《杭州师范大学学报（自然科学版）》;20130131;第12卷(第1期);第26-29页 * |
| Aerobic oxidative coupling of 2-naphthols by simple copper salts:a highly efficient catalytic system in the absence of ligand or carrier;Shi-Yong Zhang等;《JOURNAL OF CHEMICAL RESEARCH》;20050731;第418-419页 * |
| THE OXIDATIVR CROSS-COUPLING OF SUBSTITUTED 2-HAPETHCLS, PART I: THE SCOPE ARD LIMITATIONS;Martin Hovorka等;《Tehhedron》;19921231;第48卷(第43期);第9503-9516页 * |
| 一种新型2-萘酚氧化偶联合成联萘酚的催化体系;陈丽 等;《有机化学》;20031231;第23卷;增刊第227页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112479827A (en) | 2021-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109320498B (en) | Preparation method of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-alkyl formate | |
| CN107803220B (en) | Supported imidazole ionic liquid catalyst and application thereof in preparation of cyclohexanone and cyclohexanol by catalytic oxidation of cyclohexane | |
| CN102675072A (en) | Method for producing acetophenone through catalytic oxidation of ethylbenzene | |
| CN111662240B (en) | Preparation method of high-purity prothioconazole | |
| Guo | Quaternary ammonium decatungstate catalyst for oxidation of alcohols | |
| CN111777628B (en) | Catalytic wet oxidation catalyst for treating glyphosate wastewater, and synthesis method and application thereof | |
| CN112479827B (en) | Method for efficiently preparing binaphthol through liquid ligand cocatalyst | |
| CN112574003B (en) | Method for efficiently preparing 1, 1' -bi-2-naphthol by solid ligand assisted catalysis | |
| CN101367692B (en) | Method for preparing couplet aromatic hydrocarbons with iodo aromatic hydrocarbons | |
| CN107537529B (en) | Composite catalyst for esterification reaction and bisphenol F synthesis and preparation method thereof | |
| CN112409137B (en) | Method for preparing 1,1' -bi-2-naphthol by inorganic base assisted catalysis | |
| CN113735910B (en) | Method for treating waste rhodium acetylacetonate triphenylphosphine carbonyl agent and rhodium acetylacetonate triphenylphosphine carbonyl catalyst | |
| CN115894178B (en) | Efficient catalytic preparation method of high-purity 1,1' -bi-2-naphthol | |
| CN109499618B (en) | Catalyst for preparing benzoylformic acid and ester compounds thereof, and preparation method and application thereof | |
| CN113999089B (en) | Method for synthesizing 6,6 '-dibromo-1, 1' -bi-2-naphthol by oxidative coupling of 6-bromo-2-naphthol | |
| JP5593002B2 (en) | Method for producing adamantanetriols | |
| CN112645872A (en) | Preparation method of pyridine nitrogen oxide derivative intermediate | |
| CN115894178A (en) | High-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol | |
| CN113999089A (en) | Method for synthesizing 6,6 '-dibromo-1, 1' -bi-2-naphthol by oxidative coupling of 6-bromo-2-naphthol | |
| CN109053541B (en) | Nitrogen-oxygen-containing radical-containing oxygen-free radical sym-terphenyl (triazine) tricarboxylic acid copper complex and application thereof in preparation of menadione | |
| CN117258849A (en) | Novel organic-inorganic hybrid catalytic material, preparation method and application thereof | |
| CN106631690A (en) | Preparation method of 1-adamantanol | |
| CN111004096B (en) | Synthetic method of 2, 6-dichlorobenzaldehyde | |
| WO2010127575A1 (en) | One-step synthesis method of 2,9-dimethyl-4,7-diphenyl-1,10- phenanthroline | |
| CN116730822A (en) | Continuous preparation method of 2-chloro-3-methylbenzoic acid |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |