CN108084217A - A kind of preparation method of 2,6- dichloros phenyl boric acid - Google Patents
A kind of preparation method of 2,6- dichloros phenyl boric acid Download PDFInfo
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- CN108084217A CN108084217A CN201711442610.7A CN201711442610A CN108084217A CN 108084217 A CN108084217 A CN 108084217A CN 201711442610 A CN201711442610 A CN 201711442610A CN 108084217 A CN108084217 A CN 108084217A
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- Prior art keywords
- dichloro
- reaction
- preparation
- phenyl
- boric acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- DNABCXHXESBMIC-UHFFFAOYSA-N OB(O)OC1=C(Cl)C=CC=C1Cl Chemical compound OB(O)OC1=C(Cl)C=CC=C1Cl DNABCXHXESBMIC-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims abstract description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 125000005620 boronic acid group Chemical class 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 claims abstract description 3
- DKTXXUNXVCHYDO-UHFFFAOYSA-N phenoxyborinic acid Chemical compound OBOC1=CC=CC=C1 DKTXXUNXVCHYDO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 6
- 230000003020 moisturizing effect Effects 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000004821 1,3-dichlorobenzenes Chemical class 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000013517 stratification Methods 0.000 claims description 2
- XNWBABUMAWEJJC-UHFFFAOYSA-N ClC1=C(C(=CC=C1)Cl)[Li] Chemical compound ClC1=C(C(=CC=C1)Cl)[Li] XNWBABUMAWEJJC-UHFFFAOYSA-N 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 2
- SXFRDDSPNXCCNE-UHFFFAOYSA-N (2,3-dichlorophenoxy)boronic acid Chemical class OB(O)OC1=CC=CC(Cl)=C1Cl SXFRDDSPNXCCNE-UHFFFAOYSA-N 0.000 abstract 1
- 125000003963 dichloro group Chemical group Cl* 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000012043 crude product Substances 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229940028001 boric acid antiseptic and disinfectant Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- -1 2,6- dichlorophenyl Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 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 technical field of organic synthesis, more particularly to one kind 2, the preparation method of 6 dichloro phenyl boric acids, the preparation method is with 1,3 dichloro phenylates are raw material, raw material and lithiation reagent occur lithium hydrogen exchange reaction and are made phenyl lithium compound, and phenyl lithium compound and the borate of gained react obtained phenyl boronate；Then 2,6 dichloro-benzenes crude boronic acids are made with dilute hydrochloric acid hydrolysis borate, it is finally purified to obtain 2,6 dichloro phenyl boric acid sterlings；The reaction is by the use of tetrahydrofuran as reaction dissolvent.The advantages of 2,6 dichloro phenyl boric acid preparation method of the invention, is cheap and easy to get using raw material, and reaction condition is mild, and post-processing operation is simple, and production cost is relatively low, high income, reduces reaction cost, is suitble to industrialized production.
Description
Technical field：
The present invention relates to technical field of organic synthesis, and in particular to the preparation method of one kind 2,6- dichloro phenyl boric acids.
Background technology：
The character of 2,6- dichloro phenyl boric acids is white solid, is a kind of very extensive chemical intermediate of purposes, extensively should
For the synthesis of medicine and other fine chemical products.
The content of the invention：
The technical problems to be solved by the invention are to provide the 2,6- dichloros that a kind of purity is high, simple for process and at low cost
The preparation method of phenyl boric acid.
The technical problems to be solved by the invention are realized using following technical solution：
1,3- dichloro phenylate is raw material, and raw material and lithiation reagent occur lithium hydrogen exchange reaction and phenyl lithium compound, institute are made
Phenyl lithium compound and borate react obtained phenyl boronate；Then with the hydrochloric acid hydrolysis boric acid of mass concentration 10%
2,6- dichloro-benzenes crude boronic acids are made in ester, finally purified to obtain 2,6- dichloro phenyl boric acid sterlings；The reaction is made with tetrahydrofuran
For reaction dissolvent.
2. one kind 2, the preparation method of 6- dichloro phenyl boric acids, comprise the following steps：
(1) under nitrogen protection, first 1,3- dichloro-benzenes is put into reaction vessel, adds in tetrahydrofuran, it is cooled to -80~-
50 DEG C, n-BuLi is then added dropwise, mixing control dropping temperature carries out insulation reaction at -80~-50 DEG C after being added dropwise, system
Obtain 2,6- dichlorophenyl lithiums；
(2) butyl borate liquid is added dropwise in the solution of 2,6- dichlorophenyls lithium obtained above, after being added dropwise
Carry out insulation reaction；
(3) the hydrochloric acid stirring of mass concentration 10% is added in into reaction system after reaction, by the pH value tune of reaction solution
To 3~4, then stratification, through extraction, merges organic layer, precipitation, moisturizing rotation butanol obtains 2,6- dichloro-benzenes crude boronic acids；
(4) 2,6- dichloro-benzenes crude boronic acid is obtained into 2,6- dichloro phenyl boric acid sterlings by recrystallization purification.
The molar ratio of 1,3- dichloro-benzenes and n-BuLi is in the step (1)：1:(1.0-1.5), n-BuLi
Concentration be 2.5mol/L.
Step (1) the lithiation reagent dropping temperature is -80~-50 DEG C, and insulation reaction temperature is -80~-50 DEG C, heat preservation
When time is 2 small.
The molar ratio of phenyl lithium and borate is in the step (2)：1:(1.1-2.0).
The reaction temperature of phenyl lithium and borate is -80~-50 DEG C in the step (2), and insulation reaction temperature is -60
~-30 DEG C.
Specific embodiment：
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
(1) lithiumation:Under nitrogen protection, first in 1000mL three-necked flasks, 50g1 is added in, 3- dichloro-benzenes is cooled to -80
~-60 DEG C, 176mL n-BuLis are then added dropwise, process is added dropwise and maintains -80~-50 DEG C, rear insulation reaction 2h is added dropwise.
(2) lithium hydrogen exchanges：117g butyl borate liquid is added dropwise in the solution of phenyl lithium obtained above, is dripped
Insulation reaction is carried out after finishing.The hydrochloric acid stirring of mass concentration 10% is added in into reaction system after reaction, then stands and divides
Layer through extraction, merges organic layer, precipitation, and moisturizing rotation butanol obtains 51.7g 4- phenoxy group phenyl boric acid crude products, yield 80%；
(3) purify：51.7g4- phenoxy group phenyl boric acid crude products are added in 1L three-necked flasks, add 200mL methyl tertiary butyl ether(MTBE)s
Dissolving, precipitation, crystallization, centrifuge to obtain 48.4g4- phenoxy group phenyl boric acid products, yield 75% at cooling.
Embodiment 2
(1) lithiumation:Under nitrogen protection, first in 1000mL three-necked flasks, 50g1 is added in, 3- dichloro-benzenes is cooled to -60
~-50 DEG C, 136mL n-BuLis are then added dropwise, process is added dropwise and maintains -60~-50 DEG C, rear insulation reaction 2h is added dropwise.
(2) lithium hydrogen exchanges：86g butyl borate liquid is added dropwise in the solution of phenyl lithium obtained above, is dripped
Insulation reaction is carried out after finishing.The hydrochloric acid stirring of mass concentration 10% is added in into reaction system after reaction, then stands and divides
Layer through extraction, merges organic layer, precipitation, and moisturizing rotation butanol obtains 38.7g4- phenoxy group phenyl boric acid crude products, yield 60%；
(3) purify：38.7g4- phenoxy group phenyl boric acid crude products are added in 1L three-necked flasks, add 150mL methyl tertiary butyl ether(MTBE)s
Dissolving, precipitation, crystallization, centrifuge to obtain 36.1g4- phenoxy group phenyl boric acid products, yield 56% at cooling.
Embodiment 3
(1) lithiumation:Under nitrogen protection, first in 1000mL three-necked flasks, 50g1 is added in, 3- dichloro-benzenes is cooled to -80
~-60 DEG C, 110mL n-BuLis are then added dropwise, process is added dropwise and maintains -80~-60 DEG C, rear insulation reaction 2h is added dropwise.
(2) lithium hydrogen exchanges：102g butyl borate liquid is added dropwise in the solution of phenyl lithium obtained above, is dripped
Insulation reaction is carried out after finishing.The hydrochloric acid stirring of mass concentration 10% is added in into reaction system after reaction, then stands and divides
Layer through extraction, merges organic layer, precipitation, and moisturizing rotation butanol obtains 45.2g4- phenoxy group phenyl boric acid crude products, yield 70%；
(3) purify：45.2g4- phenoxy group phenyl boric acid crude products are added in 1L three-necked flasks, add 150mL methyl tertiary butyl ether(MTBE)s
Dissolving, precipitation, crystallization, centrifuge to obtain 40.7g4- phenoxy group phenyl boric acid products, yield 63% at cooling.
Embodiment 4
(1) lithiumation:Under nitrogen protection, first in 1000mL three-necked flasks, 50g1 is added in, 3- dichloro-benzenes, it is cooled to -60~
50 DEG C, 204mL n-BuLis are then added dropwise, process is added dropwise and maintains -60~-50 DEG C, rear insulation reaction 2h is added dropwise.
(2) lithium hydrogen exchanges：156.6g butyl borate liquid is added dropwise in the solution of phenyl lithium obtained above, is added dropwise
After carry out insulation reaction.The hydrochloric acid stirring of mass concentration 10% is added in into reaction system after reaction, is then stood
Layering through extraction, merges organic layer, precipitation, and moisturizing rotation butanol obtains 424- phenoxy group phenyl boric acid crude products, yield 65
(3) purify：45.2g 4- phenoxy group phenyl boric acid crude products are added in 1L three-necked flasks, add 150mL methyl tertbutyls
Ether dissolving, precipitation, crystallization, centrifuge to obtain 38.1g4- phenoxy group phenyl boric acid products, yield 59% at cooling.
The basic principles, main features and the advantages of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (6)
1. one kind 2, the preparation method of 6- dichloro phenyl boric acids, it is characterised in that：The preparation method with 1,3- dichloros phenylate be raw material,
Raw material and lithiation reagent occur lithium hydrogen exchange reaction and phenyl lithium compound are made, and phenyl lithium compound and the borate of gained occur instead
Phenyl boronate should be made；Then 2,6- dichloro-benzenes crude boronic acids are made with the hydrochloric acid hydrolysis borate of mass concentration 10%, most
2,6- dichloro phenyl boric acid sterlings are obtained by purifying；The reaction is by the use of tetrahydrofuran as reaction dissolvent.
2. one kind 2, the preparation method of 6- dichloro phenyl boric acids, which is characterized in that comprise the following steps：
(1) under nitrogen protection, first 1,3- dichloro-benzenes is put into reaction vessel, tetrahydrofuran is added in, is cooled to -80~-50 DEG C,
Then n-BuLi is added dropwise, mixing control dropping temperature carries out insulation reaction at -80~-50 DEG C after being added dropwise, and is made 2,6-
Dichlorophenyl lithium；
(2) butyl borate liquid is added dropwise in the solution of 2,6- dichlorophenyls lithium obtained above, is carried out after being added dropwise
Insulation reaction；
(3) the hydrochloric acid stirring of mass concentration 10% is added in into reaction system after reaction, the pH value of reaction solution is transferred to 3~
4, then stratification, through extraction, merges organic layer, precipitation, moisturizing rotation butanol obtains 2,6- dichloro-benzenes crude boronic acids；
(4) 2,6- dichloro-benzenes crude boronic acid is obtained into 2,6- dichloro phenyl boric acid sterlings by recrystallization purification.
3. the preparation method of 2,6- dichloros phenyl boric acid according to claim 2, it is characterised in that：The 1,3- dichloro-benzenes and
The molar ratio of n-BuLi is：1:(1.0-1.5), the concentration of n-BuLi is 2.5mol/L.
4. the preparation method of 2,6- dichloros phenyl boric acid according to claim 2, it is characterised in that：Lithiation reagent dropping temperature
For -80~-50 DEG C, insulation reaction temperature is -80~-50 DEG C, when soaking time is 2 small.
5. the preparation method of 2,6- dichloros phenyl boric acid according to claim 2, it is characterised in that：The phenyl lithium and boric acid
The molar ratio of ester is：1:(1.1-2.0).
6. the preparation method of 2,6- dichloros phenyl boric acid according to claim 2, it is characterised in that：Temperature is added dropwise in the phenyl lithium
It spends for -80~-50 DEG C, insulation reaction temperature is -60~-30 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711442610.7A CN108084217A (en) | 2017-12-25 | 2017-12-25 | A kind of preparation method of 2,6- dichloros phenyl boric acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711442610.7A CN108084217A (en) | 2017-12-25 | 2017-12-25 | A kind of preparation method of 2,6- dichloros phenyl boric acid |
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|---|---|
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|---|---|---|---|
| CN201711442610.7A Pending CN108084217A (en) | 2017-12-25 | 2017-12-25 | A kind of preparation method of 2,6- dichloros phenyl boric acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111474A (en) * | 2018-06-29 | 2019-01-01 | 贾红琴 | The synthetic method of one kind 2,6- dichloro phenyl boric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031461A1 (en) * | 1994-05-17 | 1995-11-23 | Merck & Co., Inc. | Preparation of 2-aryl carbapenems |
| CN103864831A (en) * | 2014-02-14 | 2014-06-18 | 上海工程技术大学 | Aromatic boric acid ester compound and synthetic method thereof |
-
2017
- 2017-12-25 CN CN201711442610.7A patent/CN108084217A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995031461A1 (en) * | 1994-05-17 | 1995-11-23 | Merck & Co., Inc. | Preparation of 2-aryl carbapenems |
| CN103864831A (en) * | 2014-02-14 | 2014-06-18 | 上海工程技术大学 | Aromatic boric acid ester compound and synthetic method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张永强: "取代芳环硼酸化合物的合成进展", 《化工时刊》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111474A (en) * | 2018-06-29 | 2019-01-01 | 贾红琴 | The synthetic method of one kind 2,6- dichloro phenyl boric acid |
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Application publication date: 20180529 |