CN111793080A - Preparation method of aryl boric acid ester - Google Patents
Preparation method of aryl boric acid ester Download PDFInfo
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- CN111793080A CN111793080A CN202010798487.8A CN202010798487A CN111793080A CN 111793080 A CN111793080 A CN 111793080A CN 202010798487 A CN202010798487 A CN 202010798487A CN 111793080 A CN111793080 A CN 111793080A
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- -1 aryl boric acid ester Chemical class 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004327 boric acid Substances 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 28
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000003254 radicals Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000012074 organic phase Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical group ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 6
- BPAZNZINLQSFMN-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1h-imidazole;dihydrochloride Chemical compound Cl.Cl.CC(C)C1=NCCN1 BPAZNZINLQSFMN-UHFFFAOYSA-N 0.000 claims description 3
- YZTLODREQIMPNK-UHFFFAOYSA-N Cl.Cl.N(=NC(C)(C)C1N(CCN1)CC(O)O)C(C)(C)C1N(CCN1)CC(O)O Chemical compound Cl.Cl.N(=NC(C)(C)C1N(CCN1)CC(O)O)C(C)(C)C1N(CCN1)CC(O)O YZTLODREQIMPNK-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical group Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004821 distillation Methods 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 5
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- KFPMLWUKHQMEBU-UHFFFAOYSA-N 3-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC(S(Cl)(=O)=O)=C1 KFPMLWUKHQMEBU-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 208000003174 Brain Neoplasms Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002777 nucleoside Substances 0.000 description 1
- 125000003835 nucleoside group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
- C07F5/04—Esters of boric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of aryl borate, which mainly comprises the following steps: in the presence of a water-soluble free radical initiator, water is used as a solvent, aryl sulfonyl chloride and diboron acid pinacol ester are used as raw materials for reaction, after the reaction is finished, an organic solvent is used for extraction, an organic phase is collected, and reduced pressure distillation is carried out to obtain the product, namely the aryl boric acid ester. Compared with the prior art that acetonitrile, halogenated alkane, ethyl acetate and other organic solvents are used, the water is used as the solvent, so that the environmental pollution is reduced, the toxicity is reduced, the raw material source is more economical, and the method has the advantages of mild reaction, simple post-treatment, high yield, high purity and the like, and is very suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of aryl borate.
Background
The aryl borate is a borate compound with a single benzene ring or polycyclic aromatic hydrocarbon, various substituted aryl borates are important organic synthesis intermediates and medical and pesticide intermediates, and the aryl borate is widely applied to preparation of bioactive reagents or material research. Substituted aryl borate ester is used as an important organic intermediate and a molecular building block, can participate in various organic chemical reactions to construct a more complex target compound, and is widely applied to Suzuki cross-coupling reaction, asymmetric synthesis of amino acid, an amino compound catalyst and the like. In biology, medicine or materials, aryl boronates have been used in hydrocarbon sensors, selective delivery vehicles for nucleosides and sugars, enzyme inhibitors, and as therapeutics in boron neutron capture therapy in certain brain tumor patients, among others.
The preparation methods of aryl borate compounds are mainly classified into the following methods:
(1) synthesis of aryl boronic acid esters using grignard or lithium reagents
The synthesis of arylboronic acid ester by using the Grignard reagent or the organolithium reagent is carried out at low temperature by reacting the Grignard reagent or the organolithium reagent with diethyl ether solution or boronic acid ester of boron trifluoride, and then esterifying after hydrolysis.
(2) Synthesis of aryl boric acid ester by transition metal catalysis method
Catalysis of the coupling reaction of aryl halides with pinacol ester diborate is the most classical method for the synthesis of such compounds. The method has the biggest advantages of wide applicability, simple and convenient operation and no strict anhydrous and anaerobic conditions. However, there are some disadvantages, such as the use of a noble metal palladium catalyst and the unavailability of a transition metal residue, which is a problem especially marked in the synthesis of drug molecules.
(3) Synthesis of aryl boric acid ester by using aniline as raw material
The reaction does not need metal participation, and the aromatic borate compound can be synthesized by using cheap and easily obtained aniline in one step. The reaction condition is mild, even the reaction can be carried out under the air condition, and the problem of metal residue can be avoided because no metal participates in the reaction.
(4) Synthesis of aryl boric acid ester by photosensitizer catalysis method
The organic photosensitizer is used as a catalyst to catalyze aromatic diazonium salt boronization reaction to synthesize the aryl borate, however, the aromatic diazonium salt compound has unstable structure, is easy to decompose, is not suitable for industrial production and is not easy to store.
(5) Cobalt catalysis method for synthesizing aryl boric acid ester
The cobalt catalysis method takes alkynyl boronic acid pinacol ester and diyne as raw materials, and adopts the cobalt catalysis method in Co2(CO2)8The condensed aryl boric acid ester is synthesized by cycloaddition reaction under catalysis, and the method can react at room temperature and can react with various functional groupsAnd (4) carrying out the following steps. However, the intermediate produced by the coordination of cobalt carbonyl and alkynyl borate in the reaction is sensitive to light, and the cobalt carbonyl can cause partial polymerization of diyne, so that the diyne is lost, and the yield of the cycloaddition reaction is influenced.
(6) Synthesis of aryl boric acid ester by ultraviolet photocatalysis method
The method adopts cheap and easily available aryl sulfonyl chloride as a raw material, can be carried out at room temperature, but has not high yield and is not suitable for industrial production.
Disclosure of Invention
The invention aims to overcome a series of defects existing in the synthesis of aryl borate ester in the prior art, and provides a method for synthesizing the aryl borate ester. In the method, in the presence of a water-soluble free radical initiator, water is used as a solvent, and aryl sulfonyl chloride and boronic acid pinacol ester are used as raw materials to react to obtain aryl borate. Because the water-soluble free radical initiator is used, water can be used as a reaction solvent, and compared with the prior art that organic solvents such as acetonitrile, halogenated alkane, ethyl acetate and the like are used, the water is used as the solvent, so that the environmental pollution and the toxicity are reduced, and the raw material source is more economic. Meanwhile, the technical scheme of the method has the advantages of mild reaction, simple post-treatment, high yield and the like, and is very suitable for industrial production.
Based on solving the problems, the invention provides a preparation method of aryl borate, which is characterized by comprising the following steps: in the presence of a water-soluble free radical initiator, water is used as a solvent, and aryl sulfonyl chloride and diboron acid pinacol ester are used as raw materials to react to obtain the aryl boric acid ester.
According to the preparation method of the aryl borate, it is further preferable that the arylsulfonyl chloride is phenylsulfonyl chloride, p-tolylsulfonyl chloride, o-tolylsulfonyl chloride or m-tolylsulfonyl chloride.
According to the preparation method of the aryl borate, the water-soluble free radical initiator is a water-soluble azo free radical initiator.
According to the preparation method of the aryl borate, the water-soluble azo free-radical initiator is further preferably selected from one or more of 2,2 ' -azobis (2-methylpropylamidine) dihydrochloride, 2 ' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 4 ' -azobis (4-cyanovaleric acid), 2 ' -azobis (N-cyclohexylisobutylamidine) dihydrochloride or 2,2 ' -azobis [2- (dihydroxyethylimidazolidin-2-yl) propane ] dihydrochloride.
According to the preparation method of the aryl borate, the method is preferably carried out at the temperature of 40-100 ℃, and further preferably carried out at the temperature of 50-80 ℃.
According to the preparation method of the aryl borate, the molar ratio of the arylsulfonyl chloride to the water-soluble free radical initiator is preferably 1: 0.1-0.01.
According to the preparation method of the aryl borate, the molar ratio of the arylsulfonyl chloride to the pinacol bisborate is preferably 1: 1-2.
According to the preparation method of the aryl borate, the reaction time is preferably 1-12h, and further preferably 2-10 h.
According to the preparation method of the aryl borate, the method preferably further comprises the steps of extracting with an organic solvent after the reaction is completed, collecting an organic phase, and distilling under reduced pressure to obtain the product.
According to the preparation method of the aryl borate, the organic solvent is preferably one or a combination of ethyl acetate, dichloromethane or chloroform.
The main contributions of the present invention with respect to the prior art are the following:
(1) in the prior art, no record is adopted about the preparation of aryl borate ester by using pinacol ester of diboron and arylsulfonyl chloride as raw materials and using water as a solvent in the presence of a water-soluble free radical initiator.
(2) Because the water-soluble free radical initiator is used, water can be used as a reaction solvent, and compared with the prior art that organic solvents such as acetonitrile, halogenated alkane, ethyl acetate and the like are used, the water is used as the solvent, so that the environmental pollution and the toxicity are reduced, and the raw material source is more economic.
(3) The technical scheme for preparing the aryl borate by adopting the system disclosed by the invention also has the advantages of mild reaction, simple post-treatment, high yield, high purity and the like, and is very 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 preparation method of aryl borate, which is characterized by comprising the following steps: in the presence of a water-soluble free radical initiator, water is used as a solvent, and aryl sulfonyl chloride and diboron acid pinacol ester are used as raw materials to react to obtain the aryl boric acid ester.
According to the preparation method of the aryl borate, it is further preferable that the arylsulfonyl chloride is phenylsulfonyl chloride, p-tolylsulfonyl chloride, o-tolylsulfonyl chloride or m-tolylsulfonyl chloride.
According to the preparation method of the aryl borate, the water-soluble free radical initiator is a water-soluble azo free radical initiator.
According to the preparation method of the aryl borate, the water-soluble azo free-radical initiator is further preferably selected from one or more of 2,2 ' -azobis (2-methylpropylamidine) dihydrochloride, 2 ' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 4 ' -azobis (4-cyanovaleric acid), 2 ' -azobis (N-cyclohexylisobutylamidine) dihydrochloride or 2,2 ' -azobis [2- (dihydroxyethylimidazolidin-2-yl) propane ] dihydrochloride.
According to the preparation method of the aryl borate, the method is preferably carried out at the temperature of 40-100 ℃, and further preferably carried out at the temperature of 50-80 ℃.
According to the preparation method of the aryl borate, the molar ratio of the arylsulfonyl chloride to the water-soluble free radical initiator is preferably 1: 0.1-0.01.
According to the preparation method of the aryl borate, the molar ratio of the arylsulfonyl chloride to the pinacol bisborate is preferably 1: 1-2.
According to the preparation method of the aryl borate, the reaction time is preferably 1-12h, and further preferably 2-10 h.
According to the preparation method of the aryl borate, the method preferably further comprises the steps of extracting with an organic solvent after the reaction is completed, collecting an organic phase, and distilling under reduced pressure to obtain the product.
According to the preparation method of the aryl borate, the organic solvent is preferably one or a combination of ethyl acetate, dichloromethane or chloroform.
Example 1
Adding 100ml of water, 0.1mol of benzenesulfonyl chloride and 0.1mol of pinacol ester diboron into a reaction bottle, fully and uniformly stirring, then adding 0.01mol of 2, 2' -azobis (2-methylpropionamidine) dihydrochloride, slowly raising the temperature to 50 ℃, keeping the temperature for reaction for 10 hours, keeping the reaction process in a stirring state, after the reaction is finished, slowly cooling the system to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, carrying out reduced pressure distillation, and carrying out vacuum drying to obtain white solid pinacol ester phenylboronic acid, wherein the yield is 88.1%, and the purity is 95.6%.
Example 2
Adding 100ml of water, 0.1mol of benzenesulfonyl chloride and 0.2mol of pinacol ester diboron into a reaction bottle, fully and uniformly stirring, then adding 0.01mol of 2, 2' -azobis [2- (2-imidazoline-2-yl) propane ] dihydrochloride, slowly raising the temperature to 100 ℃, keeping the temperature for reacting for 5 hours, keeping the temperature in a stirring state in the whole reaction process, after the reaction is finished, slowly cooling the system to room temperature, extracting for 3 times by using dichloromethane, collecting an organic phase, carrying out reduced pressure distillation and vacuum drying to obtain white solid pinacol ester phenylboronic acid, wherein the yield is 93.5%, and the purity is 95.1%.
Example 3
Adding 100ml of water, 0.1mol of benzenesulfonyl chloride and 0.2mol of pinacol ester diboron into a reaction bottle, fully and uniformly stirring, then adding 0.01mol of 2, 2' -azobis (N-cyclohexyl isobutyl amidine) dihydrochloride, slowly raising the temperature to 80 ℃, keeping the temperature for reacting for 8 hours, keeping the whole reaction process in a stirring state, after the reaction is finished, slowly cooling the system to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, carrying out reduced pressure distillation and vacuum drying to obtain white solid pinacol ester phenylboronic acid, wherein the yield is 90.8%, and the purity is 96.9%.
Example 4
Adding 100ml of water, 0.1mol of p-toluenesulfonyl chloride and 0.15mol of pinacol ester diboron into a reaction bottle, fully and uniformly stirring, then adding 0.001mol of 2, 2' -azobis [2- (dihydroxyethyl imidazoline-2-yl) propane ] dihydrochloride, slowly raising the temperature to 100 ℃, keeping the temperature for reacting for 12 hours, keeping the temperature in a stirring state in the whole reaction process, after the reaction is finished, slowly cooling the system to room temperature, extracting for 3 times by using chloroform, collecting an organic phase, carrying out reduced pressure distillation and vacuum drying to obtain a white solid pinacol ester p-toluenesulfonate, wherein the yield is 93.2%, and the purity is 97.0%.
Example 5
Adding 100ml of water, 0.1mol of p-methylbenzenesulfonyl chloride and 0.2mol of pinacol ester of diboronic acid into a reaction bottle, fully and uniformly stirring, then adding 0.005mol of 2, 2' -azobis (2-methylpropylamidine) dihydrochloride, slowly raising the temperature to 40 ℃, keeping the temperature for reaction for 12 hours, keeping the temperature in a stirring state in the whole reaction process, after the reaction is finished, slowly cooling the system to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, carrying out reduced pressure distillation and vacuum drying to obtain a white solid pinacol ester of p-methylbenzenesulfonic acid, wherein the yield is 89.7%, and the purity is 96.4%.
Example 6
Adding 100ml of water, 0.1mol of o-toluenesulfonyl chloride and 0.2mol of pinacol ester of diboronic acid into a reaction bottle, fully and uniformly stirring, then adding 0.003mol of 2, 2' -azobis (2-methylpropylamidine) dihydrochloride, slowly raising the temperature to 80 ℃, keeping the temperature for reaction for 10 hours, keeping the whole reaction process in a stirring state, after the reaction is finished, slowly cooling the system to room temperature, extracting for 3 times by using ethyl acetate, collecting an organic phase, carrying out reduced pressure distillation and vacuum drying to obtain white solid pinacol ester of o-toluenesulphonic acid, wherein the yield is 90.7%, and the purity is 97.7%.
Example 7
Adding 100ml of water, 0.1mol of o-toluenesulfonyl chloride and 0.2mol of pinacol ester of diboronic acid into a reaction bottle, fully and uniformly stirring, then adding 0.01mol of 2, 2' -azobis [2- (2-imidazoline-2-yl) propane ] dihydrochloride, slowly raising the temperature to 100 ℃, keeping the temperature for reacting for 2 hours, keeping the temperature in a stirring state in the whole reaction process, after the reaction is finished, slowly cooling the system to room temperature, extracting for 3 times by using dichloromethane, collecting an organic phase, carrying out reduced pressure distillation and vacuum drying to obtain white solid pinacol ester of o-toluenesulphonic acid, wherein the yield is 92.5%, and the purity is 95.8%.
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 (9)
1. The preparation method of the aryl borate is characterized by comprising the following steps: in the presence of a water-soluble free radical initiator, water is used as a solvent, and aryl sulfonyl chloride and diboron acid pinacol ester are used as raw materials to react to obtain aryl boric acid ester, wherein the aryl sulfonyl chloride is phenyl sulfonyl chloride.
2. The method of claim 1, wherein the water-soluble free radical initiator is a water-soluble azo free radical initiator.
3. The method of claim 2, wherein the water-soluble azo-based free-radical initiator is selected from the group consisting of 2,2 ' -azobis (2-methylpropionamidine) dihydrochloride, 2 ' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 4 ' -azobis (4-cyanovaleric acid), 2 ' -azobis (N-cyclohexylisobutylamidine) dihydrochloride, and 2,2 ' -azobis [2- (dihydroxyethylimidazolidin-2-yl) propane ] dihydrochloride.
4. The method for preparing aryl borate according to claim 1, wherein the method is carried out at a temperature of 40-100 ℃.
5. The method for preparing aryl borate according to claim 1, wherein the molar ratio of arylsulfonyl chloride to water-soluble radical initiator is 1: 0.1-0.01.
6. The method for preparing aryl borate according to claim 1, wherein the molar ratio of arylsulfonyl chloride to pinacol bisborate is 1: 1-2.
7. The method for preparing aryl borate according to claim 1, wherein the reaction time is 1-12 h.
8. The method of claim 1, further comprising extracting with an organic solvent after the reaction is completed, collecting the organic phase, and distilling under reduced pressure to obtain the final product.
9. The method for preparing arylboronic acid ester according to claim 8, wherein the organic solvent is selected from one or more of ethyl acetate, dichloromethane or chloroform.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030770A (en) * | 2009-09-25 | 2011-04-27 | 北京大学 | Preparation method of aromatic boronic acid ester composite |
| CN105859761A (en) * | 2016-04-26 | 2016-08-17 | 丽水学院 | Synthesis method of aromatic borate compounds |
| CN110885341A (en) * | 2019-12-17 | 2020-03-17 | 北京大学 | Boron esterification reaction method of alkyl bromide without transition metal catalysis |
| WO2020073210A1 (en) * | 2018-10-09 | 2020-04-16 | 南通纺织丝绸产业技术研究院 | Phosphindole derivative, benzophosphindole derivative and preparation method therefor |
| CN114014884A (en) * | 2021-11-29 | 2022-02-08 | 河南省科学院化学研究所有限公司 | Preparation method of aryl nitrogenous heterocyclic borate |
-
2020
- 2020-08-11 CN CN202010798487.8A patent/CN111793080B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030770A (en) * | 2009-09-25 | 2011-04-27 | 北京大学 | Preparation method of aromatic boronic acid ester composite |
| CN105859761A (en) * | 2016-04-26 | 2016-08-17 | 丽水学院 | Synthesis method of aromatic borate compounds |
| WO2020073210A1 (en) * | 2018-10-09 | 2020-04-16 | 南通纺织丝绸产业技术研究院 | Phosphindole derivative, benzophosphindole derivative and preparation method therefor |
| CN110885341A (en) * | 2019-12-17 | 2020-03-17 | 北京大学 | Boron esterification reaction method of alkyl bromide without transition metal catalysis |
| CN114014884A (en) * | 2021-11-29 | 2022-02-08 | 河南省科学院化学研究所有限公司 | Preparation method of aryl nitrogenous heterocyclic borate |
Non-Patent Citations (1)
| Title |
|---|
| 马辉等: "五元含氮杂环硼酸及其酯合成研究进展", 《化学试剂》 * |
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