CN113121579B - Synthesis method of 3- (6-phenylhexyl) phenylboronic acid and derivative thereof - Google Patents
Synthesis method of 3- (6-phenylhexyl) phenylboronic acid and derivative thereof Download PDFInfo
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- LBBKPQIDBPGKNX-UHFFFAOYSA-N [3-(6-phenylhexyl)phenyl]boronic acid Chemical compound OB(O)C1=CC(CCCCCCC2=CC=CC=C2)=CC=C1 LBBKPQIDBPGKNX-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 112
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 62
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 56
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 56
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 37
- 238000004817 gas chromatography Methods 0.000 claims description 36
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 30
- 239000012074 organic phase Substances 0.000 claims description 30
- RAOLIGFNQJMMKW-UHFFFAOYSA-N 6-bromohexylbenzene Chemical compound BrCCCCCCC1=CC=CC=C1 RAOLIGFNQJMMKW-UHFFFAOYSA-N 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 29
- 238000010791 quenching Methods 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000011261 inert gas Substances 0.000 claims description 28
- 238000005070 sampling Methods 0.000 claims description 28
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 27
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 27
- 230000000171 quenching effect Effects 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 26
- -1 3- (6-phenylhexyl) bromobenzene Chemical compound 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 22
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 20
- 239000008346 aqueous phase Substances 0.000 claims description 19
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 18
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 10
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000004042 decolorization Methods 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 27
- 230000015572 biosynthetic process Effects 0.000 abstract description 25
- 239000000376 reactant Substances 0.000 abstract description 19
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000012071 phase Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- JAZNSOPOXXXZQO-UHFFFAOYSA-N [N].CCO Chemical compound [N].CCO JAZNSOPOXXXZQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 2
- DVGPMIRVCZNXMD-UHFFFAOYSA-N 6-phenylhexylbenzene Chemical compound C=1C=CC=CC=1CCCCCCC1=CC=CC=C1 DVGPMIRVCZNXMD-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-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
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of 3- (6-phenylhexyl) phenylboronic acid and derivatives thereof, and relates to the technical field of chemical synthesis. The synthesis method of the 3- (6-phenylhexyl) phenylboronic acid and the derivative thereof comprises the following synthesis steps: s1: synthesizing intermediate H by using a low temperature synthesis step via reactants B and D; s2: synthesizing intermediate I via reactant F and intermediate H using a low temperature synthesis step; s3: the final product is synthesized from reactant G and intermediate I using a low temperature synthesis step. The invention provides a novel synthesis method of 3- (6-phenylhexyl) phenylboronic acid and derivatives thereof, which shortens the reaction steps to three steps, simplifies the materials, recycles the raw materials, improves the reaction yield, has a series of advantages of short reaction time, simple operation, capability of amplifying continuous production, reduction of the reaction cost and the like.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method of 3- (6-phenylhexyl) phenylboronic acid and derivatives thereof.
Background
The organic electroluminescent material is polymer or small molecular organic material capable of emitting light under the action of electric field, and the 3- (6-phenylhexyl) phenylboronic acid compound is an iridium complex, an organic electroluminescent device, a display device and an important raw material and an intermediate of a lighting device, but the conventional synthesis method is mainly adopted for producing the 3- (6-phenylhexyl) phenylboronic acid compound at present, the number of reaction steps is up to seven, the steps are complicated, the materials are complicated, the three wastes are generated, and the yield is lower.
Disclosure of Invention
The present invention is directed to a method for synthesizing 3- (6-phenylhexyl) phenylboronic acid and derivatives thereof, which solves the problems set forth in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions: the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid and the derivative thereof comprises the following synthesis steps:
s1: synthesizing intermediate H by using a low temperature synthesis step via reactants B and D;
s2: synthesizing intermediate I via reactant F and intermediate H using a low temperature synthesis step;
s3: synthesizing a finished product through a reactant G and an intermediate I by utilizing a low-temperature synthesis step;
the chemical reaction process is as follows:
wherein the reactant B is any one or a mixture of more of bromobenzene and aromatic ring bromocompounds, and the chemical formula is as follows:
wherein the R group is any substituent group, the substituent group comprises hydrogen, fluorine, chlorine and methyl, and the reactant D is Br (CH) 2 ) n Br and I (CH) 2 ) n The range of n is 2-12, the reactant F is any one or more of p-dibromobenzene, m-dibromobenzene, o-dibromobenzene and aromatic ring dibromo substituted compound, and the reactant G is any one or more of trimethyl borate, triisopropyl borate and triester borate.
Further, the low-temperature synthesis step in the step S1 is as follows: adding a solvent A and a reactant B into a reaction container, stirring and cooling to a reaction temperature, slowly dripping a reagent C, carrying out heat preservation reaction at the temperature after dripping a reactant D, carrying out heat preservation reaction after slowly returning to the temperature, detecting and analyzing the reaction by a sampling gas chromatography, slowly dripping a reagent E into the system to quench the reaction, separating liquid after returning to the temperature again, extracting the water phase, merging organic phases, washing, drying and concentrating, carrying out reduced pressure distillation on residues, and recovering excessive reactant D and an obtained intermediate H, wherein each 100-400L of solvent A is added with the following components: 40-140mol of reactant B, 40-140mol of reagent C, 80-600mol of reactant D and 5-20L of reagent E.
Further, the low-temperature synthesis step in the step S2 is as follows: adding a solvent A and a reactant F into a reaction container, stirring and cooling to a reaction temperature, slowly dripping a reagent C, carrying out heat preservation reaction at the temperature after dripping an intermediate H, carrying out heat preservation reaction after slowly returning to the temperature, detecting and analyzing the reaction by a sampling gas chromatography, slowly dripping a reagent E into the system to quench the reaction, separating liquid after returning to the temperature again, extracting the water phase, merging organic phases, washing, drying and concentrating, carrying out reduced pressure distillation on residues, and recovering excessive intermediate H and obtained intermediate I, wherein each 100-400L of solvent A is added with the following components: 80-600mol of intermediate H, 40-140mol of reagent C, 40-140mol of reactant F and 5-20L of reagent E.
Further, the low-temperature synthesis step in the step S3 is as follows: adding a solvent A and an intermediate I into a reaction container, stirring and cooling to a reaction temperature, slowly dripping a reagent C, carrying out heat preservation reaction at the temperature after dripping, dripping a reactant G, carrying out secondary heat preservation reaction at the reaction temperature, sampling, slowly dripping a reagent E into a system for quenching reaction after high-pressure liquid chromatography analysis reaction is finished, separating liquid after temperature is returned again, extracting water phase, merging organic phases, washing, drying, decompressing and concentrating after active carbon decoloration treatment, filtering residues, leaching filter cakes, and airing to obtain a finished product compound, wherein each 100-400L of solvent A is added with the following components: 80-600mol of intermediate I, 40-140mol of reagent C, 80-200mol of reactant G and 40-140L of reagent E.
Still further, the solvent A is one or a mixture of more of tetrahydrofuran, diethyl ether, methyl tertiary butyl ether, 2-methyltetrahydrofuran, 2, 5-dimethyltetrahydrofuran, 3-methyltetrahydrofuran and other ether solvents, the reagent C is hexane or tetrahydrofuran solution of organolithium, the organolithium comprises one or a plurality of n-butyllithium, methyllithium, isobutyllithium and tertiary butyllithium, and the reagent E is one or a mixture of a plurality of water, ammonium chloride aqueous solution, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid and phosphoric acid.
Further, the finished product in the step S3 is
Wherein the R group is any substituent comprising hydrogen, fluorine, chlorine and methyl, wherein n ranges from 2 to 12.
Still further, the synthesis process of the low temperature synthesis step needs to be performed under the protection of inert gas, and the reaction vessel is provided with a stirrer and a thermometer.
Still further, the reaction temperature is from-85 ℃ to 0 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the synthesis method provides a novel synthesis method of 3- (6-phenylhexyl) phenylboronic acid and derivatives thereof, the reaction steps are shortened to three steps, materials are simplified, raw materials can be recycled, the reaction yield is improved, and the synthesis method has a series of advantages of short reaction time, simplicity in operation, capability of amplifying continuous production, reduction of reaction cost and the like.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid comprises the following synthesis steps:
s1: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.637 mol) of bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 268ml (0.669 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ for 2 hours after dripping 622g (2.55 mol) of 1, 6-dibromohexane, slowly heating to-20 ℃ for 3 hours, sampling, detecting and analyzing the reaction by gas chromatography, slowly dripping 20ml of hydrogen bromide aqueous solution with the concentration of 10% into the system, quenching the reaction to 0 ℃ after heating to 0 ℃, separating the solution, extracting the water phase with ethyl acetate for 2 times, merging the organic phases, washing with saturated sodium chloride solution for 1 time, drying and concentrating by adopting anhydrous sodium sulfate, distilling the residue under 18-pressure, recovering excessive 1, 6-dibromohexane at 82 ℃, collecting 132g (6-bromohexyl) benzene with the concentration of 98% by adopting gas chromatography, and measuring the purity of the liquid phase by adopting high performance chromatography to 98%;
s2: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.424 mol) of 1, 3-dibromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 178ml (0.445 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ after dripping, reacting for 2 hours, dripping 408g (1.695 mol) of (6-bromohexyl) benzene in the step S1, slowly heating to-20 ℃ and reacting for 3 hours, detecting the analysis reaction by a sampling gas chromatography, slowly dripping 20ml of aqueous solution of hydrogen bromide with the concentration of 10% into the system, quenching the reaction, heating to 0 ℃ for separating liquid, extracting the aqueous phase with ethyl acetate for 2 times, merging the organic phase, washing with saturated sodium chloride solution for 1 time, drying and concentrating by anhydrous sodium sulfate, decompressing and distilling the residue at 18 ℃, recovering excessive (6-bromohexyl) benzene at 123 ℃, collecting 102g of 3- (6-phenylhexyl) at 139 ℃, calculating the total purity of the 3- (6-phenylhexyl) benzene at 76%, and measuring the purity of the product by a gas chromatography of 98% by a high-performance liquid chromatography method, wherein the purity is determined by the high-performance chromatography;
s3: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.315 mol) of 3- (6-phenylhexyl) bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 138.8ml (0.347 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ after dripping for 2 hours, dripping 71.2g (0.378 mol) of triisopropyl borate, continuing to keep the temperature at-80 ℃ for 3 hours, sampling, slowly dripping 32ml of hydrogen bromide aqueous solution with the concentration of 18% into the system for quenching reaction after the reaction by high-pressure liquid chromatography, returning to 0 ℃ for liquid separation, extracting the water phase for 3 times by ethyl acetate, merging organic phases, washing 3 times by adopting saturated sodium chloride solution, drying active carbon for decolorization treatment by adopting anhydrous sodium sulfate, concentrating under reduced pressure, filtering, leaching residues, airing to obtain 78.3- (6-phenylhexyl) phenylboric acid with the yield of 88%, and measuring the purity by high-performance liquid chromatography to 99%;
the chemical reaction process is as follows:
embodiment two:
the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid comprises the following synthesis steps:
s1: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.637 mol) of bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-40 ℃, slowly dripping 268ml (0.669 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-40 ℃ after dripping 622g (2.55 mol) of 1, 6-dibromohexane for 2 hours, slowly heating to-10 ℃ for 2 hours, keeping the temperature for stirring for detecting analysis reaction by a sampling gas chromatography, slowly dripping 20ml of hydrogen bromide aqueous solution with the concentration of 10% into the system for quenching reaction, heating to 0 ℃ for separating liquid, extracting the aqueous phase with ethyl acetate for 2 times, merging the organic phase, washing with saturated sodium chloride solution for 1 time, drying and concentrating by adopting anhydrous sodium sulfate, distilling the residue under the pressure of 18mmHg, recovering excessive 1, 6-dibromohexane at 82 ℃, collecting 117g (6-bromohexyl) benzene with the concentration of 98% by adopting the gas chromatography analysis method, and measuring the purity of the liquid phase by the high-performance chromatography method of 98%;
s2: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.424 mol) of 1, 3-dibromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-40 ℃, slowly dripping 178ml (0.445 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-40 ℃ after dripping, reacting for 2 hours, dripping 408g (1.695 mol) of (6-bromohexyl) benzene in the step S1, slowly heating to-10 ℃ and reacting for 3 hours, detecting the analysis reaction by a sampling gas chromatography, slowly dripping 20ml of aqueous solution of hydrogen bromide with the concentration of 10% into the system, quenching the reaction, heating to 0 ℃ for separating liquid, extracting the aqueous phase with ethyl acetate for 2 times, merging organic phases, washing with saturated sodium chloride solution for 1 time, drying and concentrating by anhydrous sodium sulfate, decompressing and distilling the residue at 18 ℃, recovering excessive (6-bromohexyl) benzene at 123 ℃, collecting at 139 ℃ to obtain 94g of 3- (6-phenylhexyl) bromobenzene, calculating the total purity of which is 98% by a gas chromatography, and measuring the purity of the product by a high-performance liquid chromatography of 98%;
s3: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.315 mol) of 3- (6-phenylhexyl) bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-40 ℃, slowly dripping 138.8ml (0.347 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-40 ℃ after dripping for 2 hours, dripping 71.2g (0.378 mol) of triisopropyl borate, continuing to keep the temperature at-40 ℃ for 3 hours, sampling, slowly dripping 32ml of hydrogen bromide aqueous solution with the concentration of 18% into the system for quenching reaction after the reaction by high-pressure liquid chromatography, returning to 0 ℃ for liquid separation, extracting the water phase for 3 times by ethyl acetate, merging organic phases, washing 3 times by adopting saturated sodium chloride solution, drying active carbon for decolorization treatment by adopting anhydrous sodium sulfate, concentrating under reduced pressure, filtering, leaching residues, airing to obtain 71.2g of 3- (6-phenylhexyl) phenylboric acid, calculating the yield of 80%, and measuring the purity of the product by high-performance liquid chromatography to 99%;
the chemical reaction process is as follows:
embodiment III:
the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid comprises the following synthesis steps:
s1: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.637 mol) of bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-85 ℃, slowly dripping 268ml (0.669 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-85 ℃ for 3 hours after dripping 622g (2.55 mol) of 1, 6-dibromohexane, slowly heating to-20 ℃ for 4 hours, taking out, detecting and analyzing the reaction by a gas chromatography, slowly dripping 20ml of hydrogen bromide aqueous solution with the concentration of 10% into the system, quenching the reaction to-5 ℃, separating the liquid, extracting the water phase with ethyl acetate for 3 times, merging the organic phase, washing with saturated sodium chloride solution for 3 times, drying and concentrating by anhydrous sodium sulfate, recovering excessive 1, 6-dibromohexane at 83 ℃ and collecting 139.7g (6-bromohexyl) benzene with the residue under the pressure of 18mmHg, calculating 86%, and measuring the purity by a high performance liquid chromatography with the purity of 99%;
s2: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.424 mol) of 1, 3-dibromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-85 ℃, slowly dripping 178ml (0.445 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-85 ℃ after dripping, reacting for 3 hours, dripping 408g (1.695 mol) of (6-bromohexyl) benzene in the step S1, slowly heating to-20 ℃ and reacting for 4 hours, detecting and analyzing by a sampling gas chromatography, slowly dripping 20ml of aqueous solution of 10% hydrogen bromide into the system, quenching, heating to-5 ℃ for 3 times, extracting the aqueous phase by ethyl acetate, merging the organic phase, washing 3 times by using saturated sodium chloride solution, drying and concentrating by anhydrous sodium sulfate, decompressing and distilling the residue at 18 ℃, recovering excessive (6-bromohexyl) benzene at 122 ℃, collecting 139 ℃ to obtain 408g (6-bromohexyl) benzene, calculating the 3- (6-phenylhexyl) at 139 ℃, and measuring the purity by using 99% of high-performance liquid chromatography, wherein the purity is 99% by adopting the high-performance liquid chromatography;
s3: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.315 mol) of 3- (6-phenylhexyl) bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-85 ℃, slowly dripping 138.8ml (0.347 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-85 ℃ after dripping for 3 hours, dripping 71.2g (0.378 mol) of triisopropyl borate, continuing to keep the temperature at-85 ℃ for 4 hours, sampling, slowly dripping 32ml of 18% hydrogen bromide aqueous solution with the concentration into the system for quenching reaction after the reaction by high-pressure liquid chromatography, returning the temperature to-5 ℃ for liquid separation, extracting the water phase with ethyl acetate for 3 times, merging organic phases, washing 3 times with saturated sodium chloride solution, drying active carbon for decolorization treatment with anhydrous sodium sulfate, concentrating under reduced pressure, filtering, leaching filter cake water, obtaining 81.9g of 3- (6-phenylhexyl) benzene, calculating the yield of 92%, and measuring the purity of the product by high-performance liquid chromatography to 99%;
the chemical reaction process is as follows:
embodiment four:
the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid comprises the following synthesis steps:
s1: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.637 mol) of bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to 0 ℃, slowly dripping 268ml (0.669 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at 0 ℃ for 1 hour after dripping 622g (2.55 mol) of 1, 6-dibromohexane, slowly heating to-10 ℃ for 2 hours, keeping the temperature for stirring for 2 hours, detecting and analyzing the reaction, sampling gas chromatography, slowly dripping 20ml of aqueous solution of hydrogen bromide with the concentration of 10% into the system for quenching reaction, heating to 0 ℃, separating liquid, extracting the aqueous phase for 1 time by ethyl acetate, merging the organic phases, washing 1 time by saturated sodium chloride solution, drying and concentrating by adopting anhydrous sodium sulfate, decompressing and distilling residues under 18mmHg, recycling excessive 1, 6-dibromohexane at 83 ℃, collecting (6-bromohexyl) benzene at 123 ℃, calculating the yield of 66%, analyzing the product by gas chromatography, and measuring the purity of the product by adopting a high-performance liquid chromatography of 97%;
s2: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.424 mol) of 1, 3-dibromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to 0 ℃, slowly dripping 178ml (0.445 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at 0 ℃ after dripping for reaction for 1 hour, dripping 408g (1.695 mol) of (6-bromohexyl) benzene in the step S1, slowly heating to-10 ℃ for reaction for 2 hours, sampling, detecting and analyzing the reaction by using a gas chromatography, slowly dripping 20ml of aqueous solution with the concentration of 10% of hydrogen bromide into the system for quenching reaction, heating to 0 ℃ for separating liquid, extracting the aqueous phase with ethyl acetate for 1 time, merging organic phases, washing with saturated sodium chloride solution for 1 time, drying and concentrating with anhydrous sodium sulfate, carrying out reduced pressure distillation on the residue at 18mmHg, recovering excessive (6-bromohexyl) benzene at 123 ℃, collecting 80.5g of 3- (6-phenylhexyl) bromobenzene at 140 ℃, calculating the residue at 60%, and measuring the purity of the product by using the gas chromatography as 97%, wherein the purity of the liquid chromatography is determined by using the high-performance chromatography;
s3: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.315 mol) of 3- (6-phenylhexyl) bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to 0 ℃, slowly dripping 138.8ml (0.347 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at 0 ℃ after dripping for 1 hour, dripping 71.2g (0.378 mol) of triisopropyl borate, continuing to keep the temperature at 0 ℃ for 2 hours, sampling, slowly dripping 32ml of hydrogen bromide aqueous solution with the concentration of 18% into the system for quenching reaction, returning to 0 ℃ for separating liquid, extracting the aqueous phase with ethyl acetate for 2 times, merging organic phases, drying with saturated sodium chloride solution for 2 times, concentrating after decolorization treatment with anhydrous sodium sulfate, filtering residues, airing to obtain 62.3g of finished 3- (6-phenylhexyl) phenylboronic acid, calculating the yield to be 70%, and determining the purity of the product by adopting a high performance liquid chromatography to be 98%;
the chemical reaction process is as follows:
fifth embodiment:
the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid comprises the following synthesis steps:
s1: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.637 mol) of bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 268ml (0.669 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ for 2 hours after dripping 976g (4.00 mol) of 1, 6-dibromohexane, slowly heating to-20 ℃ for 3 hours, sampling, detecting and analyzing the reaction by gas chromatography, slowly dripping 20ml of hydrogen bromide aqueous solution with the concentration of 10% into the system, quenching the reaction to 0 ℃, separating the solution, extracting the aqueous phase with ethyl acetate for 2 times, merging the organic phase, washing with saturated sodium chloride solution for 1 time, drying and concentrating by anhydrous sodium sulfate, recovering excessive 1, 6-dibromohexane at 82 ℃ and collecting 136.6g (6-bromohexyl) benzene at 123 ℃, calculating the yield of 89%, and measuring the purity of the product by gas chromatography to 98% by high performance liquid chromatography;
s2: under the protection of inert gas, adding 800ml of tetrahydrofuran and 100g (0.424 mol) of 1, 3-dibromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 178ml (0.445 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ after dripping, reacting for 2 hours, dripping 722g (3.000 mol) of (6-bromohexyl) benzene in the step S1, slowly heating to-20 ℃ and reacting for 3 hours, detecting the analysis reaction by a sampling gas chromatography, slowly dripping 20ml of aqueous solution with the concentration of 10% of hydrogen bromide into the system, quenching the reaction, heating to 0 ℃ for separating liquid, extracting the aqueous phase with ethyl acetate for 2 times, merging the organic phase, washing with saturated sodium chloride solution for 1 time, drying and concentrating by anhydrous sodium sulfate, decompressing and distilling the residue at 18 ℃, recovering excessive (6-bromohexyl) benzene at 123 ℃, collecting and obtaining 722g (6-bromohexyl) in the step S1, calculating the 3- (6-phenylhexyl) at 139 ℃, wherein the purity is 98% by gas chromatography, and the liquid chromatography is determined by the high-performance chromatography;
s3: under the protection of inert gas, adding 800ml of tetrahydrofuran and 120g (0.378 mol) of 3- (6-phenylhexyl) bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 138.8ml (0.347 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ after dripping for 2 hours, dripping 71.2g (0.378 mol) of triisopropyl borate, continuing to keep the temperature at-80 ℃ for 3 hours, sampling, slowly dripping 32ml of hydrogen bromide aqueous solution with the concentration of 18% into the system for quenching reaction after the reaction by high-pressure liquid chromatography, returning to 0 ℃ for liquid separation, extracting the water phase for 3 times by ethyl acetate, merging organic phases, washing 3 times by adopting saturated sodium chloride solution, drying active carbon for decolorization treatment by adopting anhydrous sodium sulfate, concentrating under reduced pressure, filtering, leaching residues, airing to obtain 80g of 3- (6-phenylhexyl) phenylboronic acid, calculating the yield of the product to be 90%, and measuring the purity of the product to be 99% by adopting high-performance liquid chromatography;
the chemical reaction process is as follows:
example six:
the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid comprises the following synthesis steps:
s1: under the protection of inert gas, 1600ml of tetrahydrofuran and 100g (0.637 mol) of bromobenzene are added into a four-port bottle with a stirrer and a thermometer, after stirring and cooling to-80 ℃, 268ml (0.669 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M is slowly dripped, after dripping, 622g (2.55 mol) of 1, 6-dibromohexane is dripped after the reaction is carried out at-80 ℃ for 2 hours, after slowly heating to-20 ℃ for 3 hours, the reaction is detected by sampling gas chromatography, 20ml of hydrogen bromide aqueous solution with the concentration of 10% is slowly dripped into the system for quenching reaction, heating to 0 ℃ for separating liquid, the aqueous phase is extracted for 2 times by ethyl acetate, the organic phase is combined, and washed for 1 time by saturated sodium chloride solution, the residue is dried and concentrated by adopting anhydrous sodium sulfate, the residue is distilled under 18 pressure, 1, 6-dibromohexane is recovered at 82 ℃ for 2 ℃ and 129g of (6-bromohexyl) benzene is obtained after collecting at 123 ℃, the residue is calculated to be 84%, the yield is 98%, the purity is determined by adopting high-performance liquid chromatography with the purity of 98% by adopting the gas chromatography;
s2: under the protection of inert gas, 1600ml of tetrahydrofuran and 100g (0.424 mol) of 1, 3-dibromobenzene are added into a four-port bottle with a stirrer and a thermometer, 178ml (0.445 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M is slowly dripped into the bottle after stirring and cooling to-80 ℃, the mixture is reacted for 2 hours at the temperature of-80 ℃ after dripping, 408g (1.695 mol) of (6-bromohexyl) benzene in the step S1 is dripped into the bottle, the mixture is slowly warmed to-20 ℃ and stirred for 3 hours, the sample gas chromatography is used for detecting and analyzing the reaction, 20ml of hydrogen bromide aqueous solution with the concentration of 10% is slowly dripped into the system for quenching reaction, the mixture is warmed to 0 ℃ for liquid separation, the aqueous phase is extracted for 2 times by ethyl acetate, the organic phase is combined, the mixture is washed 1 time by saturated sodium chloride solution, anhydrous sodium sulfate is dried and concentrated, the residue is decompressed and distilled at the temperature of-80 ℃ for recovering excessive (6-bromohexyl) benzene, 98g is obtained after collecting at 139 ℃, the temperature of 3- (6-phenylhexyl) bromobenzene is calculated to be 73%, the purity is determined to be 98% by gas chromatography, and the purity is determined to be 98% by using high performance chromatography;
s3: under the protection of inert gas, 1600ml of tetrahydrofuran and 100g (0.315 mol) of 3- (6-phenylhexyl) bromobenzene are added into a four-port bottle with a stirrer and a thermometer, 138.8ml (0.347 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M are slowly dripped into the bottle after stirring and cooling to-80 ℃, 71.2g (0.378 mol) of triisopropyl borate is dripped into the bottle after the dripping is finished and is reacted for 2 hours at the temperature of-80 ℃, the stirring and the reaction is continued for 3 hours at the temperature of-80 ℃, 32ml of hydrogen bromide aqueous solution with the concentration of 18% is slowly dripped into the bottle after sampling and high-pressure liquid chromatography analysis reaction is finished, the bottle is returned to the temperature of 0 ℃ for liquid separation, the aqueous phase is extracted for 3 times by ethyl acetate, the organic phase is combined, the bottle is washed for 3 times by saturated sodium chloride solution, the bottle cake yield of 3- (6-phenylhexyl) phenylboronic acid is obtained after the drying and the bottle cake yield of 73g is calculated to 82% after the bottle is decolorized by anhydrous sodium sulfate, and the bottle is leached by water, and the purity of the bottle is 99% by high performance liquid chromatography;
the chemical reaction process is as follows:
embodiment seven:
the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid comprises the following synthesis steps:
s1: under the protection of inert gas, adding 6400mL of tetrahydrofuran and 800g (5.096 mol) of bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 2140mL (5.350 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ for 2 hours after dripping 4973g (20.38 mol) of 1, 6-dibromohexane, slowly heating to-20 ℃ for 3 hours after the reaction, sampling, detecting and analyzing the reaction by gas chromatography, slowly dripping 160mL of hydrogen bromide aqueous solution with the concentration of 10% into the system, quenching the reaction, heating to 0 ℃ for separating the liquid, extracting the aqueous phase for 2 times by ethyl acetate, merging the organic phase, washing 1 time by saturated sodium chloride solution, drying and concentrating by anhydrous sodium sulfate, decompressing and distilling the residue under 18mmHg, recovering excessive 1, 6-dibromohexane at 83 ℃, collecting 1069g (6-bromohexyl) benzene with the concentration of 123 ℃, calculating the yield to 87%, and measuring the purity by gas chromatography to 98% by high performance liquid chromatography;
s2: under the protection of inert gas, adding 6400ml of tetrahydrofuran and 800g (3.39 mol) of 1, 3-dibromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 1425ml (3.56 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ for 2 hours after dripping, dripping 3271g (13.56 mol) of (6-bromohexyl) benzene, slowly returning to-20 ℃ for 3 hours, keeping the temperature for stirring for reaction, sampling and detecting the reaction by using a gas chromatography, slowly dripping 160ml of aqueous solution of 10% hydrogen bromide into the system for quenching reaction, returning to 0 ℃ for separating liquid, extracting the aqueous phase by using ethyl acetate for 2 times, merging the organic phase, washing by using saturated sodium chloride solution for 1 time, drying and concentrating by using anhydrous sodium sulfate, decompressing and distilling the residue at 18 ℃, recovering excessive (6-bromohexyl) benzene at 123 ℃, collecting 817g of 3- (6-phenylhexyl) bromobenzene at 139 ℃, calculating the residue to be 76%, and measuring the purity by using a gas chromatography of 98% by using a high performance liquid chromatography, wherein the purity is 98 mmHg;
s3: under the protection of inert gas, adding 6400mL of tetrahydrofuran and 800g (2.52 mol) of 3- (6-phenylhexyl) bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 1109mL (2.77 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ after dripping for 2 hours, dripping 569g (3.026 mol) of triisopropyl borate, continuing to keep the temperature at-80 ℃ for 3 hours, sampling, carrying out high-pressure liquid chromatography for analysis reaction, slowly dripping 256mL of hydrogen bromide aqueous solution with the concentration of 18%, quenching reaction, returning to 0 ℃ for separating liquid, extracting the aqueous phase with ethyl acetate for 3 times, merging the organic phase, washing with saturated sodium chloride solution for 3 times, concentrating under reduced pressure after decolorization treatment by adopting anhydrous sodium sulfate, filtering residues, airing to obtain 630g of finished 3- (6-phenylhexyl) phenylboronic acid, calculating the yield of 88.5%, and measuring the purity of the product by high-performance liquid chromatography to 99%;
the chemical reaction process is as follows:
example eight:
the synthesis method of the 3- (6-phenylhexyl) phenylboronic acid comprises the following synthesis steps:
s1: under the protection of inert gas, adding 64L of tetrahydrofuran and 8.0kg (50.96 mol) of bromobenzene into a jacketed reaction kettle with a stirrer and a thermometer, stirring, cooling to-80 ℃ by using a liquid nitrogen ethanol solution, slowly dripping 21.4L (53.5 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ for 2 hours after dripping 49.73kg (203.8 mol) of 1, 6-dibromohexane, slowly returning to-20 ℃ for 3 hours, sampling, detecting and analyzing the reaction by using a gas chromatography, slowly dripping 1.6L of hydrogen bromide aqueous solution with the concentration of 10% into the system, quenching the reaction, returning to 0 ℃ for liquid separation, extracting the water phase by using ethyl acetate for 2 times, merging the organic phase, washing by using a saturated sodium chloride solution for 1 time, drying and concentrating by using anhydrous sodium sulfate, distilling the residue under the pressure of 18mmHg, recovering excessive 1, 6-dibromohexane at 83 ℃, collecting and obtaining 10.75kg (6-bromohexyl) benzene at 123 ℃, wherein the calculated temperature is calculated to be 3%, and the purity of the product is 98% by using a gas chromatography, and the purity is determined by using a high-performance liquid chromatography;
s2: under the protection of inert gas, adding 64L of tetrahydrofuran and 8.0kg (33.91 mol) of 1, 3-dibromobenzene into a jacketed reaction kettle with a stirrer and a thermometer, stirring and cooling to-80 ℃ with liquid nitrogen ethanol solution, slowly dripping 14.243L (35.6 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ after dripping for 2 hours, dripping 32.71kg (135.6 mol) of (6-bromohexyl) benzene, slowly heating to-20 ℃ for keeping the temperature and stirring for 3 hours, sampling and detecting and analyzing the reaction by using a gas chromatography, slowly dripping 1.6L of aqueous solution of 10% hydrogen bromide into the system for quenching reaction, heating to 0 ℃ for separating liquid, extracting the aqueous phase with ethyl acetate for 2 times, merging the organic phase, washing 1 time with saturated sodium chloride solution, drying and concentrating with anhydrous sodium sulfate, decompressing and distilling the residue at 18mmHg, recovering excessive (6-bromohexyl) benzene at 123 ℃, collecting and obtaining 3- (6-bromohexyl) benzene at 139 ℃ for 8.25%, and calculating the purity of the liquid phase to be 76.98% by using the high-performance liquid chromatography, wherein the purity is determined by using the gas chromatography;
s3: under the protection of inert gas, adding 64L of tetrahydrofuran and 8.0kg (25.2 mol) of 3- (6-phenylhexyl) bromobenzene into a jacketed reaction kettle with a stirrer and a thermometer, stirring, cooling to-80 ℃ with a liquid nitrogen ethanol solution, slowly dripping 11.09L (27.7 mol) of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ after dripping for 2 hours, dripping 5.688kg (30.26 mol) of triisopropyl borate, continuing to keep the temperature at-80 ℃ for 3 hours, sampling, slowly dripping 2.6L of 18% hydrogen bromide aqueous solution for quenching reaction, returning to 0 ℃ for 3 times, mixing organic phases, washing 3 times with a saturated sodium chloride solution, drying sodium sulfate, decolorizing with active carbon, concentrating under reduced pressure, leaching residues, obtaining 6.32kg of 3- (6-phenylhexyl) phenylboric acid, calculating the yield to 88.9%, and measuring the purity of a filter cake by adopting a high-performance liquid chromatography method to be 99%;
the chemical reaction process is as follows:
comparative example:
the 3- (6-phenylhexyl) phenylboronic acid is synthesized by adopting a traditional synthesis method, the yield is calculated to be 66.8%, the purity is measured to be 96% by adopting a high performance liquid chromatography, and the reaction time is 72 hours.
The experimental results in example three and comparative example were tabulated as shown in table 1: as can be seen from Table 1, the synthesis steps of 3- (6-phenylhexyl) phenylboronic acid are shortened to 3 steps, so that the time consumed by the synthesis is effectively reduced, the synthesis steps are simpler, and raw materials in each synthesis step can be collected and reused, so that the yield and purity of the finished product are higher.
TABLE 1
| Project | Yield (%) | Purity (%) | Reaction time (h) |
| Example 1 | 88.0 | 99 | 24 |
| Example two | 80.0 | 99 | 23 |
| Example III | 92.0 | 99 | 30 |
| Example IV | 70.0 | 98 | 18 |
| Example five | 90.0 | 99 | 24 |
| Example six | 82.0 | 99 | 24 |
| Example seven | 88.5 | 99 | 24 |
| Example eight | 88.9 | 99 | 24 |
| Comparative example | 66.8 | 96 | 72 |
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (1)
1.3- (6-phenylhexyl) phenylboronic acid, which is characterized in that: s1: under the protection of inert gas, adding 800ml of tetrahydrofuran and 0.637mol of bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 0.669mol of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, reacting at-80 ℃ for 2 hours after dripping 4.00mol of 1, 6-dibromohexane, slowly heating to-20 ℃ and stirring for 3 hours, detecting and analyzing the reaction by a sampling gas chromatography, slowly dripping 20ml of hydrogen bromide aqueous solution with the concentration of 10% into the system for quenching reaction, heating to 0 ℃, separating liquid, extracting the aqueous phase with ethyl acetate for 2 times, merging organic phases, washing 1 time by using saturated sodium chloride solution, drying and concentrating by using anhydrous sodium sulfate, recovering the excessive 1, 6-dibromohexane at 82 ℃ under the pressure of 18mmHg, collecting (6-bromohexyl) benzene 136.6g at 123 ℃, calculating the yield of 89%, analyzing the product by gas chromatography to obtain the product with the purity of 98%, and measuring the product with the purity of 98% by a high performance liquid chromatography;
s2: under the protection of inert gas, adding 800ml of tetrahydrofuran and 0.424mol of 1, 3-dibromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to-80 ℃, slowly dripping 0.445mol of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at-80 ℃ after dripping for 2 hours, dripping 3.000mol of (6-bromohexyl) benzene in the step S1, slowly heating to-20 ℃ for 3 hours, keeping the temperature and stirring for reaction, sampling gas chromatography to detect the completion of analysis reaction, slowly dripping 20ml of hydrogen bromide aqueous solution with the concentration of 10% into the system, quenching the reaction, heating to 0 ℃ for separating liquid, extracting the aqueous phase for 2 times by ethyl acetate, merging the organic phase, washing 1 time by using saturated sodium chloride solution, drying and concentrating by using anhydrous sodium sulfate, distilling the residue under reduced pressure at 18mmHg, recovering excessive (6-bromohexyl) benzene at 123 ℃, collecting 112.7g of 3- (6-phenylhexyl) bromobenzene at 139 ℃, calculating the yield of 84%, and measuring the purity of the product by using 98% by gas chromatography as 98% by adopting a high-performance liquid chromatography;
s3: under the protection of inert gas, adding 800ml of tetrahydrofuran and 0.378mol of 3- (6-phenylhexyl) bromobenzene into a four-port bottle with a stirrer and a thermometer, stirring and cooling to the temperature of minus 80 ℃, slowly dripping 0.347mol of n-butyllithium tetrahydrofuran solution with the concentration of 2.5M, keeping the temperature at the temperature of minus 80 ℃ after dripping, reacting for 2 hours, dripping 0.378mol of triisopropyl borate, continuing to react for 3 hours at the temperature of minus 80 ℃, sampling, performing high-pressure liquid chromatography, analyzing the reaction, slowly dripping 32ml of hydrogen bromide aqueous solution with the concentration of 18% into the system, quenching, returning to the temperature of 0 ℃, separating liquid, extracting the aqueous phase with ethyl acetate for 3 times, merging organic phases, washing 3 times by adopting saturated sodium chloride solution, drying active carbon for decolorization treatment by adopting anhydrous sodium sulfate, concentrating under reduced pressure, filtering residues, leaching filter cakes, airing 80g of finished 3- (6-phenylhexyl) phenylboric acid, calculating the yield to be 90%, and measuring the purity of the product by adopting a high-performance liquid chromatography to be 99%;
the chemical reaction process is as follows:
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