CN111004262A - Synthetic method of p-chlorophenylboronic acid - Google Patents
Synthetic method of p-chlorophenylboronic acid Download PDFInfo
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- CN111004262A CN111004262A CN201911297925.6A CN201911297925A CN111004262A CN 111004262 A CN111004262 A CN 111004262A CN 201911297925 A CN201911297925 A CN 201911297925A CN 111004262 A CN111004262 A CN 111004262A
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- chlorobenzene
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- CAYQIZIAYYNFCS-UHFFFAOYSA-N (4-chlorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Cl)C=C1 CAYQIZIAYYNFCS-UHFFFAOYSA-N 0.000 title claims description 14
- 238000010189 synthetic method Methods 0.000 title claims description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XOBUPLLFOAJDFU-UHFFFAOYSA-N dichloro-(4-chlorophenyl)borane Chemical compound ClB(Cl)C1=CC=C(Cl)C=C1 XOBUPLLFOAJDFU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- XLGLMVCAOMQNJT-UHFFFAOYSA-N boric acid;chlorobenzene Chemical compound OB(O)O.ClC1=CC=CC=C1 XLGLMVCAOMQNJT-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007818 Grignard reagent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- NHDODQWIKUYWMW-UHFFFAOYSA-N 1-bromo-4-chlorobenzene Chemical compound ClC1=CC=C(Br)C=C1 NHDODQWIKUYWMW-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- -1 p-chlorobenzene boric acid Grignard reagent Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LHJSLDBKUGXPMI-UHFFFAOYSA-N tris(2-methylpropyl) borate Chemical compound CC(C)COB(OCC(C)C)OCC(C)C LHJSLDBKUGXPMI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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 Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing p-chlorobenzoic acid, which comprises the steps of taking chlorobenzene as a raw material, reacting the chlorobenzene with boron trichloride through Friedel-crafts reaction under the action of a catalyst to obtain dichloro (4-chlorphenyl) borane, and then carrying out acidic hydrolysis to obtain the p-chlorobenzoic acid. The method takes chlorobenzene as a raw material and adopts Friedel-crafts reaction to synthesize the p-chlorobenzene boric acid, and has the advantages of novel synthetic route, simple and practical operation, easily obtained raw materials, low cost, environmental friendliness and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of p-chlorophenylboronic acid.
Background
P-chlorobenzeneboronic acid is an important drug intermediate, and the traditional preparation method mainly comprises three methods: (1) an organolithium reagent method, (2) a grignard reagent method, and (3) a catalytic boriding method.
The organic lithium reagent method has high yield and few byproducts, but the method has high operation safety and danger and expensive raw materials, and is not suitable for industrial production. The catalytic boronization method is derived after Suzuki coupling reaction is found, has good adaptability to various groups, but the raw materials and the noble metal catalyst are expensive, and the realization of industrial conversion due to the requirement of high-purity compounds still has a plurality of problems to be overcome. At present, the Grignard reagent method is a commonly used method in industry, the preparation of the p-chlorobenzene boric acid Grignard reagent by the Grignard reaction is difficult to initiate, and the solvent cost in the preparation process of some preparation processes which need to use a mixed solvent is too high, and accounts for about 20 to 50 percent. In the production process of p-chlorobenzoic acid, brominated aromatic hydrocarbon is usually used as a raw material, the molecular weight of bromine is much larger than that of chlorine, so that the cost is directly overhigh, and brominated substances not only have larger pollution to the environment, but also generate more magnesium salt solid wastes.
Therefore, how to reduce the cost of the solvent, simplify the process, improve the conversion rate and reduce the amount of solid pollutants is a series of technical problems in industrial production.
Disclosure of Invention
In order to solve the technical problems, the application provides a method for synthesizing p-chlorobenzene boric acid, chlorobenzene is used as a raw material, and Friedel-crafts reaction is adopted to synthesize the p-chlorobenzene boric acid.
The technical scheme of the invention is as follows:
a synthesis method of p-chlorobenzoic acid takes chlorobenzene as a raw material, and reacts with boron trichloride under the action of a catalyst to obtain dichloro (4-chlorphenyl) borane, and the dichloro (4-chlorphenyl) borane is subjected to acid hydrolysis to obtain the p-chlorobenzoic acid, wherein the reaction process comprises the following steps:
preferably, the catalyst is a strong lewis acid; further preferably, the strong lewis acid is one or more of aluminum trichloride, ferric trichloride and aluminum tribromide.
Preferably, the specific preparation steps of the p-chlorobenzoic acid are as follows:
1) under the protection of nitrogen or inert gas, adding chlorobenzene and a catalyst into a reaction container, and continuing to react after boron trichloride gas is introduced at the temperature of 80-120 ℃;
2) and (3) after tracking that the amount of the residual chlorobenzene in the reaction system is less than or equal to 0.5 percent of the total mass of the chlorobenzene added, pouring the substances in the reaction container in the step 1) into strong acid ice water, precipitating a large amount of solids, and performing suction filtration and separation to obtain the product.
Preferably, the molar ratio of feedstock to catalyst is 1: 0.3-1: 0.6.
preferably, the molar ratio of the introduced amount of the boron trichloride to the raw materials is 1: 1.2-1.8.
Preferably, the total reaction time of step 1) is 8 to 10 hours.
Preferably, the reaction pressure in the step 1) is micro-positive pressure, and is 0.01-0.03 MPa.
Preferably, the strongly acidic ice water has pH of 1-2 and temperature of 0-5 deg.C
Preferably, the strong acid is hydrochloric acid.
Preferably, the mass of the strongly acidic ice water is more than 5 times of that of chlorobenzene.
The invention proposes the new process route of synthesizing arylphenylboronic acid through Friedel-crafts reaction for the first time, the invention has the advantages of novel mode, simple and practical operation, easy obtainment of raw materials, low cost, environmental protection and the like, and compared with the mode of synthesizing the p-chlorobenzeboronic acid through the Friedel-crafts reaction and the preparation of the p-chlorobenzeboronic acid by the Grignard reaction method, the method adopts chlorobenzene as a main raw material, is cheap and easy to obtain, greatly reduces the raw material cost, avoids the generation of bromine-containing waste water and the generation of magnesium salt solid waste in the reaction, reduces the treatment cost of the waste water and the solid waste, has no solvent and convenient separation, and is simple to operate, relatively mild in reaction conditions and relatively small in pollution; finally, the defect that the format reaction cannot be produced on a large scale can be effectively avoided through the route, and the requirement of industrial large-scale production can be more favorably met.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The strong acid used in the examples was hydrochloric acid.
Example 1:
under the protection of nitrogen, chlorobenzene (22.5g, 0.2mol) and aluminum trichloride (7.98g, 0.06mol) are added into a 250ml four-mouth bottle, the temperature is raised to 110 ℃, boron trichloride gas (28g, 0.24mol) is slowly introduced, the reaction is continued after the introduction of the gas is completed, the total reaction time is 8 hours, the residual chlorobenzene in a TLC detection reaction system is less than or equal to 0.5 percent of the total mass of the chlorobenzene, substances in the four-mouth bottle are slowly poured into strong acid ice water (the pH is 1-2 and the temperature is 0-5 ℃) which is 5 times of the mass of the chlorobenzene after the reaction is completed, a large amount of solids are generated by stirring, and the product 4-chlorobenzene boric acid is obtained by suction filtration and drying, wherein the yield is 84.6 percent, and the content is.
Example 2:
under the protection of nitrogen, chlorobenzene (33.75g, 0.3mol) and aluminum trichloride (11.97g, 0.09mol) are added into a 250ml four-mouth bottle, the temperature is raised to 120 ℃, boron trichloride gas (42g, 0.36mol) is slowly introduced, the reaction is continued after the introduction of the gas is completed, the total reaction time is 10 hours, the chlorobenzene residual quantity in the reaction system is detected to be less than or equal to 0.5 percent of the total mass of the chlorobenzene, after the reaction is completed, the substances in the four-mouth bottle are slowly poured into strong acid ice water (the pH value is 1-2, the temperature is 0-5 ℃) with 6 times of the mass of the chlorobenzene, a large amount of solid is generated, and the 4-chlorobenzene boric acid is obtained by suction filtration and drying, the yield is 85.5 percent, and the content is 97.2.
Example 3:
under the protection of nitrogen, adding chlorobenzene (22.5g, 0.2mol) and aluminum tribromide (26.6g, 0.1mol) into a 250ml four-mouth bottle, heating to 100 ℃, slowly introducing boron trichloride gas (28g, 0.24mol), continuously reacting after the gas introduction is completed, wherein the total reaction time is 9h, the residual quantity of the chlorobenzene in a TLC detection reaction system is less than or equal to 0.5 percent of the total mass of the chlorobenzene, slowly pouring substances in the four-mouth bottle into strong acid ice water (pH is 1-2 and the temperature is 0-5 ℃) with the mass of 7 times of the chlorobenzene after the reaction is completed, continuously stirring, generating a large amount of solid, and performing suction filtration and drying to obtain 25.3g of 4-chlorobenzene boric acid, wherein the yield is 78.8 percent, and the content is 97.5 percent.
Example 4:
under the protection of nitrogen, chlorobenzene (1687.5g, 15mol) and aluminum trichloride (598.5g, 4.5mol) are added into a 5L four-mouth bottle, the temperature is increased to 110 ℃, boron trichloride gas (2100g, 18mol) is slowly introduced, the continuous reaction is completed after the introduction of the gas is completed, the total reaction time is 10 hours, the chlorobenzene residual quantity in a TLC detection reaction system is less than or equal to 0.5 percent of the total added mass of the chlorobenzene, substances in the four-mouth bottle are slowly poured into strongly acidic ice water (the pH is 1-2 and the temperature is 0-5 ℃) with the mass of 5 times of the chlorobenzene after the reaction is completed, the stirring is continuously carried out, a large amount of solid is generated, and the product 4-chlorobenzene boric acid 2077.0g is obtained through suction filtration and drying, the yield.
Comparative example 1 (example in the application document in application No. 201810797300.5 as comparative example of the present application):
1) under the protection of nitrogen, adding 402g of methyl tertiary butyl ether into a 1L reaction bottle, then adding 382g of p-chlorobromobenzene, and uniformly stirring to obtain a solution A;
2) under the protection of nitrogen, 226g of methyl tetrahydrofuran is added into a 1L reaction bottle, then 205g of triisobutyl borate is added, and the mixture is uniformly stirred to obtain a solution B;
3) under the protection of nitrogen, 313g of tetrahydrofuran, 48.6g of magnesium chips and 0.5g of iodine granules are added into a 2L reaction bottle, the solution B is added under stirring, the temperature is raised to 40-50 ℃ by heating in a water bath, then the solution A is dropwise added at the rate of 3mL/min, and the reaction is carried out for 2.5 hours under heat preservation after the dropwise addition;
4) transferring the reaction mixture to a 3L reaction bottle, slowly dropwise adding 18% dilute hydrochloric acid under stirring until the pH value is 2-3, controlling the temperature below 20 ℃ during the process, then preserving the temperature at 20-30 ℃, and reacting for 3 hours;
5) stopping stirring, standing the reaction mixture for layering, separating an upper organic phase from a lower aqueous phase, extracting the aqueous phase once with 200g of toluene, layering again, combining the organic phases, concentrating the combined organic layers under vacuum of not less than-0.08 MPa and at a temperature of less than or equal to 65 ℃ under reduced pressure, and drying at a temperature of 65-70 ℃ to obtain 248g of p-chlorobenzoic acid in off-white powder, wherein the yield is 79%, and the purity is more than or equal to 99%.
The yield of the comparative example 1 is equivalent to that of the embodiment, wherein a Grignard reagent method is adopted, the problems of difficult initiation and high solvent cost exist, the raw material of the comparative example 1 also adopts brominated aromatic hydrocarbon, the price of the bromobenzene is about 30000 yuan/ton, the solvent is also added in the process, the production cost is about 150000 yuan/ton, the production cost is overhigh, the brominated substances not only have great pollution to the environment, but also generate more solid magnesium salts, and the cost for treating wastewater and solid waste in the comparative example 1 is increased. Compared with the complicated process in the comparison document 1, the obvious process of the invention is simple and easy to operate. The invention is a new process route for synthesizing arylphenylboronic acid by Friedel-crafts reaction, takes chlorobenzene as a raw material, has the price of about 4000 yuan/ton, is low in price and easy to obtain, does not have the addition of a solvent, is convenient to separate, saves the cost of the raw material and the solvent relative to a comparison document 1, is simple and practical to operate, has the production cost of about 60000 yuan/ton, is low in cost, is environment-friendly and the like.
Claims (10)
1. A synthetic method of p-chlorobenzeneboronic acid is characterized in that chlorobenzene is used as a raw material to react with boron trichloride under the action of a catalyst to obtain dichloro (4-chlorphenyl) borane, and the dichloro (4-chlorphenyl) borane is subjected to acid hydrolysis to obtain the p-chlorobenzeneboronic acid, wherein the reaction process is as follows:
2. the method for synthesizing p-chlorobenzoic acid according to claim 1, wherein the catalyst is a strong lewis acid.
3. The method for synthesizing p-chlorophenylboronic acid according to claim 2, wherein the strong Lewis acid is one or more of aluminum trichloride, ferric trichloride and aluminum tribromide.
4. The method for synthesizing p-chlorophenylboronic acid according to claim 1, which is characterized by comprising the following specific preparation steps:
1) under the protection of nitrogen or inert gas, adding chlorobenzene and a catalyst into a reaction container, and continuing to react after boron trichloride gas is introduced at the temperature of 80-120 ℃;
2) and (3) after tracking that the amount of the residual chlorobenzene in the reaction system is less than or equal to 0.5 percent of the total mass of the chlorobenzene added, pouring the substances in the reaction container in the step 1) into strong acid ice water, precipitating a large amount of solids, and performing suction filtration and separation to obtain the product.
5. The method for synthesizing p-chlorophenylboronic acid according to claim 4, wherein the molar ratio of the raw material to the catalyst is 1: 0.3-1: 0.6.
6. the method for synthesizing p-chlorophenylboronic acid according to claim 4, wherein the molar ratio of the introduced amount of boron trichloride to the raw material is 1: 1.2-1.8.
7. The method for synthesizing p-chlorophenylboronic acid according to claim 4, wherein the total reaction time of the step 1) is 8-10 hours.
8. The method for synthesizing p-chlorophenylboronic acid according to claim 4, wherein the reaction pressure in the step 1) is micro-positive pressure of 0.01-0.03 MPa.
9. The method for synthesizing p-chlorophenylboronic acid according to claim 4, wherein the pH of the strongly acidic ice water is 1-2, and the temperature is 0-5 ℃.
10. The method for synthesizing p-chlorophenylboronic acid according to claim 4, wherein the strong acid is hydrochloric acid.
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| CN201911297925.6A CN111004262A (en) | 2019-12-13 | 2019-12-13 | Synthetic method of p-chlorophenylboronic acid |
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| CN201911297925.6A CN111004262A (en) | 2019-12-13 | 2019-12-13 | Synthetic method of p-chlorophenylboronic acid |
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| CN201911297925.6A Pending CN111004262A (en) | 2019-12-13 | 2019-12-13 | Synthetic method of p-chlorophenylboronic acid |
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|---|---|---|---|---|
| GB862222A (en) * | 1958-11-24 | 1961-03-08 | United States Borax Chem | The preparation of dihaloboranes, diaminoboranes, boronic acids and esters thereof |
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| CN106986887A (en) * | 2017-05-11 | 2017-07-28 | 蚌埠中实化学技术有限公司 | A kind of method for preparing 4 ring the third methylene-benzene boric acid |
| CN108690063A (en) * | 2018-07-19 | 2018-10-23 | 济南爱思医药科技有限公司 | A kind of preparation method to chlorophenylboronic acid |
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2019
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| CN106946915A (en) * | 2017-03-16 | 2017-07-14 | 安徽至善新材料有限公司 | A kind of high-purity, method to chlorophenylboronic acid is prepared in high yield |
| CN106986887A (en) * | 2017-05-11 | 2017-07-28 | 蚌埠中实化学技术有限公司 | A kind of method for preparing 4 ring the third methylene-benzene boric acid |
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