CN111943972A - Preparation method of nitrophenylboronic acid - Google Patents
Preparation method of nitrophenylboronic acid Download PDFInfo
- Publication number
- CN111943972A CN111943972A CN202010979862.9A CN202010979862A CN111943972A CN 111943972 A CN111943972 A CN 111943972A CN 202010979862 A CN202010979862 A CN 202010979862A CN 111943972 A CN111943972 A CN 111943972A
- Authority
- CN
- China
- Prior art keywords
- acid
- uniform
- until
- ice water
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0257—Phosphorus acids or phosphorus acid esters
- B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
Abstract
The invention provides a method for preparing nitrobenzene boronic acid, which is characterized by comprising the following steps: under the atmosphere of protective gas, adding phenylboronic acid and an organic solvent into a reaction container, stirring until the mixture is uniform, controlling the temperature of a system to be 0-25 ℃, then adding a catalyst binaphthol phosphate, continuously stirring for 1-2min, then slowly dropwise adding fuming nitric acid into the system, after dropwise addition is finished, keeping the temperature for continuously reacting for 0.5-1h until the reaction is finished, adding ice water into the system, continuously stirring for 5-10 min until the system is uniform, concentrating under reduced pressure, when the volume is reduced to one third, adding the ice water again, continuously stirring until the system is uniform, standing, layering the system, filtering a solid, washing the ice water, and drying in vacuum to obtain the o-nitrobenzoic boronic acid. The method has the advantages of easily controlled reaction, mild reaction, simple post-treatment, high yield and purity, capability of ensuring large-scale production, high yield and purity and suitability for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of nitrophenylboronic acid, and more particularly relates to a preparation method of o-nitrophenylboronic acid.
Background
The o-nitrobenzeneboronic acid is an important chemical intermediate, is an important raw material for synthesizing an organic light-emitting diode, and is also an important intermediate for synthesizing a plurality of medicinal compounds.
The prior art reports that the preparation methods of the nitrobenzeneboronic acid mainly comprise the following methods:
(1) chinese patent CN 103214489A discloses a method for preparing o-nitrobenzeneboronic acid, which comprises the steps of dripping fuming nitric acid containing a small amount of urea into acetic anhydride solution of phenylboronic acid, reacting at low temperature, adding crushed ice into the system after the reaction is finished, concentrating under reduced pressure, adding water, concentrating under reduced pressure, extracting, drying, filtering, concentrating, pulping, recrystallizing, filtering and drying to obtain the acetic anhydride. The method uses excessive nitric acid (the molar weight of the nitric acid is 3 times that of the phenylboronic acid), so that the post-treatment step is very complicated, the whole reaction time is long, the yield is low and is only 42%, and the method is not beneficial to industrial production.
(2) World patent W02011132865A1 discloses a method for preparing o-nitrobenzeneboronic acid, 1-iodine-2-nitrobenzene is dissolved in tetrahydrofuran, cooled to-78 ℃, added with phenylmagnesium chloride slowly and stirred for mixing, added with trimethyl borate, fully stirred after being heated to room temperature, and finally added with hydrochloric acid to terminate the reaction, wherein the molar yield is 89%.
(3) Chinese patent CN 1134170A discloses a method for preparing o-nitrobenzeneboronic acid, under the protection of argon, acetic anhydride is used as a solvent, phenylboronic acid and fuming nitric acid are directly reacted at a low temperature, water is added for many times and concentrated, finally, water is added to form a precipitate, and a product is obtained after filtration and drying. The method also uses excessive fuming nitric acid, so that the post-treatment is very complicated, and more isomers are generated, and the method is not suitable for industrial production.
(4) English literature Journal of Organic Chemistry; vol.79; nb.21; (2014) (ii) a 10568-10580 discloses a method for preparing o-nitrobenzeneboronic acid, which comprises the steps of uniformly mixing 2-nitroaniline and tetrahydroxy diboron in water, sequentially adding hydrogen chloride, sodium nitrite and sodium acetate for reaction to obtain a product, wherein the final reaction molar yield is only 28 percent.
(5) Chinese patent CN 104788484A discloses a method for preparing o-nitrobenzeneboronic acid, which takes acetic anhydride, formic acid acetic anhydride, chloroform, iodoform, dimethyl sulfoxide, dimethyl formamide or acetic acid as solvent, ammonium nitrate, urea, methyl urea, potassium nitrate or sodium nitrite as catalyst, phenyl boronic acid and nitric acid as raw materials, and the product is obtained by low-temperature reaction, ice water cooling, concentration, standing, filtration and ice water washing. In the method, the molar weight of the nitric acid is far greater than that of the phenylboronic acid, so that the post-treatment is complicated, excessive nitric acid exists in the waste liquid, the treatment is very troublesome, and the method has great harm to the environment. In addition, the application omits the reaction or treatment time of each step in the embodiment, in fact, the concentrated nitric acid and water emit heat, and because of the large amount of nitric acid in the system, the concentrated nitric acid cannot be dripped too fast in order to keep the system at a low temperature in the process of dripping the concentrated nitric acid, and a large amount of time is consumed to absorb the released heat, and in addition, the post-treatment time causes great trouble to the post-treatment because a large amount of nitric acid exists in the system, and the nitric acid is very soluble in water, so that a large amount of time is also consumed. Therefore, the method has the advantages of large overall energy consumption and long time consumption, and is not beneficial to large-scale reaction.
Disclosure of Invention
The invention aims to overcome the series of defects existing in the prior art for synthesizing the nitrobenzene boric acid, and provides a method for preparing the nitrobenzene boric acid, which is characterized by comprising the following steps: under the atmosphere of protective gas, adding phenylboronic acid and an organic solvent into a reaction container, stirring until the mixture is uniform, controlling the temperature of a system to be 0-25 ℃, then adding a catalyst, continuously stirring for 1-2min, then slowly dropwise adding fuming nitric acid into the system, after dropwise addition, keeping the temperature, continuously reacting for 0.5-1h until the reaction is finished, adding ice water into the system, continuously stirring for 5-10 min until the system is uniform, carrying out reduced pressure concentration, when the volume is reduced to one third, adding ice water again, continuously stirring until the system is uniform, standing, layering the system, filtering solids, washing with ice water, and carrying out vacuum drying to obtain o-nitrobenzeneboronic acid; the catalyst is a phosphate compound.
According to the preparation method of the nitrobenzene boronic acid of the invention, preferably, the phosphate compound is selected from binaphthol phosphate.
According to the preparation method of the nitrobenzene boronic acid, the protective gas is nitrogen or argon.
According to the preparation method of the nitrobenzene boronic acid of the invention, the protective gas is preferably nitrogen.
According to the preparation method of the nitrobenzene boric acid, the organic solvent is selected from acetic anhydride, methyl acetic anhydride or propionic anhydride.
According to the preparation method of the nitrobenzene boronic acid of the invention, the organic solvent is preferably acetic anhydride.
According to the preparation method of the nitrobenzene boric acid, the molar amount of the fuming nitric acid is not more than that of the benzene boric acid.
According to the preparation method of the nitrobenzene boric acid, the molar ratio of the fuming nitric acid to the benzene boric acid is as follows: 0.8-1: 1.
According to the preparation method of the nitrobenzeneboronic acid, the molar mass ratio of the phenylboronic acid to the catalyst is 1mol (1-5) g.
According to the preparation method of the nitrobenzene boric acid, the dropping time of the fuming nitric acid is 20-40 min.
Further, the invention also provides a new application of the binaphthol phosphate in the catalytic preparation of the nitrobenzene boronic acid.
The main contributions of the present invention with respect to the prior art are the following:
(1) the invention creatively discovers that the binaphthol phosphate can be used for catalyzing and preparing the nitrobenzene boric acid, and the prior art does not have any report that the binaphthol phosphate can be used for catalyzing the reaction.
(2) In the preparation method, the molar quantity of the fuming nitric acid is slightly smaller than that of the phenylboronic acid, so that the fuming nitric acid is not too violent in heat release when being added into a system, the reaction is convenient to control, the fuming nitric acid is also ensured to be completely reacted, excessive nitric acid is not contained in the system, the post-treatment is convenient, the heat of the system is also convenient to control and is not too high, the reaction is easier to control, the reaction is mild, the post-treatment is simple, the yield and the purity are high, the large-batch production can be ensured, the yield and the purity are high, and the preparation method is more suitable for industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions of the embodiments of the present disclosure are clearly and completely described. It is to be understood that the described embodiments are only a few embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the disclosure without any inventive step, are within the scope of protection of the disclosure.
The invention provides a method for preparing nitrobenzene boronic acid, which is characterized by comprising the following steps: under the atmosphere of protective gas, adding phenylboronic acid and an organic solvent into a reaction container, stirring until the mixture is uniform, controlling the temperature of a system to be 0-25 ℃, then adding a catalyst, continuously stirring for 1-2min, then slowly dropwise adding fuming nitric acid into the system, after dropwise addition, keeping the temperature, continuously reacting for 0.5-1h until the reaction is finished, adding ice water into the system, continuously stirring for 5-10 min until the system is uniform, carrying out reduced pressure concentration, when the volume is reduced to one third, adding ice water again, continuously stirring until the system is uniform, standing, layering the system, filtering solids, washing with ice water, and carrying out vacuum drying to obtain o-nitrobenzeneboronic acid; the catalyst is a phosphate compound.
According to the preparation method of the nitrobenzene boronic acid of the invention, preferably, the phosphate compound is selected from binaphthol phosphate.
According to the preparation method of the nitrobenzene boronic acid, the protective gas is nitrogen or argon.
According to the preparation method of the nitrobenzene boronic acid of the invention, the protective gas is preferably nitrogen.
According to the preparation method of the nitrobenzene boric acid, the organic solvent is selected from acetic anhydride, methyl acetic anhydride or propionic anhydride.
According to the preparation method of the nitrobenzene boronic acid of the invention, the organic solvent is preferably acetic anhydride.
According to the preparation method of the nitrobenzene boric acid, the molar amount of the fuming nitric acid is not more than that of the benzene boric acid.
According to the preparation method of the nitrobenzene boric acid, the molar ratio of the fuming nitric acid to the benzene boric acid is as follows: 0.8-1: 1.
According to the preparation method of the nitrobenzeneboronic acid, the molar mass ratio of the phenylboronic acid to the catalyst is 1mol (1-5) g.
According to the preparation method of the nitrobenzene boric acid, the dropping time of the fuming nitric acid is 20-40 min.
Further, the invention also provides a new application of the binaphthol phosphate in the catalytic preparation of the nitrobenzene boronic acid.
Example 1
Under the atmosphere of nitrogen, 1mol of phenylboronic acid and 1.2L of acetic anhydride are added into a reaction container, the mixture is stirred to be uniform, the temperature of the system is controlled to be 0 ℃, then 1g of catalyst binaphthol phosphate is added, the mixture is continuously stirred for 2min, 51g (0.8mol) of fuming nitric acid is slowly dropped into the system, the dropping time is 30min, after the dropping is finished, the temperature is kept to continuously react for 1h until the reaction is finished, 500g of ice water is added into the system, the mixture is continuously stirred for 5min until the system is uniform, the mixture is concentrated under reduced pressure, when the volume is reduced to one third, 200g of ice water is added again, the mixture is continuously stirred until the system is uniform, then the mixture is kept stand, the system is layered, the solid is filtered, washed and dried in vacuum, 130g of o-nitrobenzoic boronic acid is.
Example 2
Under the atmosphere of nitrogen, 1mol of phenylboronic acid and 1.2L of acetic anhydride are added into a reaction container, the mixture is stirred to be uniform, the temperature of the system is controlled to be 10 ℃, 5g of catalyst binaphthol phosphate is added, the mixture is continuously stirred for 1min, 51g (0.8mol) of fuming nitric acid is slowly dropped into the system, the dropping time is 20min, after the dropping is finished, the temperature is kept to continuously react for 40min until the reaction is finished, 500g of ice water is added into the system, the mixture is continuously stirred for 10min until the system is uniform, the mixture is concentrated under reduced pressure, when the volume is reduced to one third, 200g of ice water is added again, the mixture is continuously stirred until the system is uniform, then the mixture is kept stand, the system is layered, and the solid is filtered, washed and dried in vacuum to obtain 130.4g of o-nitrobenzoic boronic acid.
Example 3
Under argon atmosphere, adding 1mol of phenylboronic acid and 1.5L of methyl acetic anhydride into a reaction container, stirring until the mixture is uniform, controlling the temperature of the system to be 25 ℃, then adding 2g of catalyst binaphthol phosphate, continuing to stir for 2min, then slowly dropwise adding 51g (0.8mol) of fuming nitric acid into the system for 40min, after dropwise adding, keeping the temperature for continuing to react for 30min until the reaction is finished, adding 600g of ice water into the system, continuing to stir for 8min until the system is uniform, concentrating under reduced pressure, when the volume is reduced to one third, adding 300g of ice water again, continuing to stir until the system is uniform, standing, layering the system, filtering, washing and drying in vacuum the presence of ice water to obtain 131.1g of o-nitrobenzoic acid, wherein the yield is 98.2% (calculated on fuming nitric acid), and the purity is 99.8%.
Comparative example 1
Under the atmosphere of nitrogen, 1mol of phenylboronic acid and 1.2L of acetic anhydride are added into a reaction container, the mixture is stirred to be uniform, the temperature of the system is controlled to be 0 ℃, 1g of urea is added, the mixture is continuously stirred for 2min, 51g (0.8mol) of fuming nitric acid is slowly dropped into the system, the dropping time is 30min, after the dropping is finished, the temperature is kept to continuously react for 1h until the reaction is finished, 500g of ice water is added into the system, the mixture is continuously stirred for 5min until the system is uniform, the mixture is concentrated under reduced pressure, when the volume is reduced to one third, 200g of ice water is added again, the mixture is continuously stirred until the system is uniform, the mixture is kept stand and layered, solid is filtered, washed by the ice water and dried in vacuum, and 50.6g of o-nitrobenzoic boric acid is obtained.
Comparative example 2
Under the atmosphere of nitrogen, 1mol of phenylboronic acid and 1.2L of acetic anhydride are added into a reaction container, the mixture is stirred to be uniform, the temperature of the system is controlled to be 10 ℃, 5g of potassium nitrate is added, the stirring is continued for 1min, 51g (0.8mol) of fuming nitric acid is slowly dropped into the system, the dropping time is 20min, after the dropping is finished, the temperature is kept for continuing to react for 40min until the reaction is finished, 500g of ice water is added into the system, the stirring is continued for 10min until the system is uniform, the concentration is reduced, when the volume is reduced to one third, 200g of ice water is added again, the stirring is continued until the system is uniform, the system is kept stand and layered, the solid is filtered, washed by the ice water and dried in vacuum, and 58g of o-nitrobenzoic boronic acid is obtained, wherein the yield.
Comparative example 3
Under the argon atmosphere, 1mol of phenylboronic acid and 1.5L of methyl acetic anhydride are added into a reaction container, the mixture is stirred to be uniform, the temperature of the system is controlled to be 25 ℃, then 2g of methyl urea is added, the mixture is continuously stirred for 2min, then 51g (0.8mol) of fuming nitric acid is slowly dropped into the system, the dropping time is 40min, after the dropping is finished, the temperature is kept to continuously react for 30min until the reaction is finished, 600g of ice water is added into the system, the mixture is continuously stirred for 8min until the system is uniform, the mixture is concentrated under reduced pressure, when the volume is reduced to one third, 300g of ice water is added again, the mixture is continuously stirred until the system is uniform, then the mixture is kept stand, the system is layered, and the solid is filtered, washed by the ice water and dried in vacuum, so that 56.8g of o.
Comparative example 5
Under the nitrogen atmosphere, 1mol of phenylboronic acid and 1.2L of acetic anhydride are added into a reaction container, the mixture is stirred to be uniform, the temperature of the system is controlled to be 0 ℃, then 1g of catalyst binaphthol phosphate is added, the mixture is continuously stirred for 2min, then 71g (1.1mol) of fuming nitric acid is slowly dropped into the system, the dropping time is 30min, after the dropping is finished, the temperature is kept to continuously react for 1h until the reaction is finished, 500g of ice water is added into the system, the mixture is continuously stirred for 5min until the system is uniform, the mixture is concentrated under reduced pressure, when the volume is reduced to one third, 200g of ice water is added again, the mixture is continuously stirred until the system is uniform, then the mixture is kept stand, the system is layered, and the solid is filtered, washed and dried in vacuum to obtain 98.4g of o-nitrobenzoic acid.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (8)
1. A preparation method of nitrophenylboronic acid is characterized by comprising the following steps: under the atmosphere of protective gas, adding phenylboronic acid and an organic solvent into a reaction container, stirring until the mixture is uniform, controlling the temperature of a system to be 0-25 ℃, then adding a catalyst, continuously stirring for 1-2min, then slowly dropwise adding fuming nitric acid into the system, after dropwise addition, keeping the temperature, continuously reacting for 0.5-1h until the reaction is finished, adding ice water into the system, continuously stirring for 5-10 min until the system is uniform, carrying out reduced pressure concentration, when the volume is reduced to one third, adding ice water again, continuously stirring until the system is uniform, standing, layering the system, filtering solids, washing with ice water, and carrying out vacuum drying to obtain o-nitrobenzeneboronic acid; the catalyst is a phosphate compound.
2. According to the preparation method of the nitrobenzene boronic acid of the invention, preferably, the phosphate compound is selected from binaphthol phosphate.
3. The method for preparing nitrobenzoic boronic acid according to claim 1, wherein the protective gas is nitrogen or argon, preferably nitrogen.
4. The method for preparing nitrobenzoic boronic acid according to claim 1, wherein the organic solvent is selected from acetic anhydride, methyl acetic anhydride or propionic anhydride.
5. The method of producing nitrobenzoic boronic acid according to claim 1 wherein the molar amount of fuming nitric acid is not greater than the molar amount of phenylboronic acid.
6. The method for preparing nitrobenzoic boronic acid according to claim 1, wherein the molar ratio of fuming nitric acid to phenylboronic acid is: 0.8-1: 1.
7. The method for preparing nitrobenzeneboronic acid according to claim 1, wherein the molar mass ratio of the phenylboronic acid to the catalyst is 1mol (1-5) g.
8. The method for producing nitrobenzoic boronic acid according to claim 1, wherein the dropping time of the fuming nitric acid is 20 to 40 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010979862.9A CN111943972A (en) | 2020-09-17 | 2020-09-17 | Preparation method of nitrophenylboronic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010979862.9A CN111943972A (en) | 2020-09-17 | 2020-09-17 | Preparation method of nitrophenylboronic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111943972A true CN111943972A (en) | 2020-11-17 |
Family
ID=73356916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010979862.9A Pending CN111943972A (en) | 2020-09-17 | 2020-09-17 | Preparation method of nitrophenylboronic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111943972A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2422305A1 (en) * | 1973-05-09 | 1974-11-28 | Monsanto Co | PROCESS FOR THE PRODUCTION OF NITROUND HALOGEN-SUBSTITUTED AROMATIC COMPOUNDS |
| US4034050A (en) * | 1975-01-13 | 1977-07-05 | Sumitomo Chemical Company, Ltd. | Preparation of 5-methyl-2-nitrophenol |
| JPS62277346A (en) * | 1986-02-20 | 1987-12-02 | Sumitomo Chem Co Ltd | Method for nitrating tri-m-cresyl phosphate |
| JPS63208554A (en) * | 1987-02-25 | 1988-08-30 | Sumitomo Chem Co Ltd | Production of 3-methyl-4-nitrophenol |
| CN1134170A (en) * | 1993-11-05 | 1996-10-23 | 普罗格特-甘布尔公司 | Liquid detergents with ortho-substd. phenylboronic acids for inhibition of proteolytic enzyme |
| CN104788484A (en) * | 2015-04-30 | 2015-07-22 | 杭州拜善晟生物科技有限公司 | Synthetic method of 2-nitro phenyl boric acid |
| CN111303003A (en) * | 2018-12-12 | 2020-06-19 | 万华化学集团股份有限公司 | Olive-shaped N-methyl-4-nitrophthalimide crystal and preparation method thereof |
-
2020
- 2020-09-17 CN CN202010979862.9A patent/CN111943972A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2422305A1 (en) * | 1973-05-09 | 1974-11-28 | Monsanto Co | PROCESS FOR THE PRODUCTION OF NITROUND HALOGEN-SUBSTITUTED AROMATIC COMPOUNDS |
| US4034050A (en) * | 1975-01-13 | 1977-07-05 | Sumitomo Chemical Company, Ltd. | Preparation of 5-methyl-2-nitrophenol |
| JPS62277346A (en) * | 1986-02-20 | 1987-12-02 | Sumitomo Chem Co Ltd | Method for nitrating tri-m-cresyl phosphate |
| JPS63208554A (en) * | 1987-02-25 | 1988-08-30 | Sumitomo Chem Co Ltd | Production of 3-methyl-4-nitrophenol |
| CN1134170A (en) * | 1993-11-05 | 1996-10-23 | 普罗格特-甘布尔公司 | Liquid detergents with ortho-substd. phenylboronic acids for inhibition of proteolytic enzyme |
| CN104788484A (en) * | 2015-04-30 | 2015-07-22 | 杭州拜善晟生物科技有限公司 | Synthetic method of 2-nitro phenyl boric acid |
| CN111303003A (en) * | 2018-12-12 | 2020-06-19 | 万华化学集团股份有限公司 | Olive-shaped N-methyl-4-nitrophthalimide crystal and preparation method thereof |
Non-Patent Citations (6)
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nakamura et al. | New stable olefin complexes of cobalt (I) | |
| CN113582874B (en) | Synthesis method of bromoacetonitrile | |
| CN113955792B (en) | Preparation method of copper-cesium halide crystal | |
| CN108906125B (en) | Three dish alkene polymer DTP/ zinc-cadmium sulfide Cd of one kind0.5Zn0.5The preparation method of S composite photo-catalyst | |
| CN111943972A (en) | Preparation method of nitrophenylboronic acid | |
| CN112047969A (en) | Application of phosphate compound in preparation of nitrophenylboronic acid | |
| CN114149324A (en) | Synthesis method of 6-hydroxy-8-chloro ethyl caprylate, 6, 8-dichloro ethyl caprylate and lipoic acid | |
| Firouzabadi et al. | Methyltriphenylphosphonium tetrahydroborate (MePh3PBH4). A stable, selective and versatile reducing agent | |
| CN116063145B (en) | High-purity and high-yield 4-bromofluorobenzene synthesis method | |
| CN114621097B (en) | Method for preparing 2, 4-difluoroaniline by catalytic hydrogenation of 2, 4-difluoronitrobenzene | |
| CN111690004B (en) | Ionic liquid modified silica gel loaded aluminum chloride catalyst | |
| CN113413900B (en) | Copolymer based on carbon nitride and preparation method and application thereof | |
| CN115215782A (en) | Preparation method of 4-bromoindole | |
| CN111662327A (en) | Method for preparing phenyl phosphine dichloride | |
| CN114478154B (en) | Industrial synthesis method of picene | |
| CN116041295B (en) | Preparation method of 3-bromophthalide | |
| CN110452097B (en) | Preparation method of 1-hydroxypyrene | |
| CN108250228B (en) | Preparation method of heterocyclic boric acid compound | |
| CN115536664A (en) | Method for synthesizing furan quinoline derivatives under participation of carbon dioxide | |
| CN115970714A (en) | Composite catalyst and preparation method of mono-substituted cyanuric chloride | |
| CN108586225B (en) | Method for catalytically synthesizing chalcone | |
| CN112552233A (en) | Synthetic method of 2-amino-4-fluoropyridine | |
| CN115490646A (en) | Preparation method of 3-nitro-1,2,4-triazole | |
| CN117720425A (en) | Method for synthesizing Spiro-OMe TAD at low cost | |
| CN112250580A (en) | Preparation method of 2-nitro-2-substituted phenyl propane-1, 3-diol |
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 |