CN103570753A - Preparation method of arylboronic acid compound - Google Patents
Preparation method of arylboronic acid compound Download PDFInfo
- Publication number
- CN103570753A CN103570753A CN201310561231.5A CN201310561231A CN103570753A CN 103570753 A CN103570753 A CN 103570753A CN 201310561231 A CN201310561231 A CN 201310561231A CN 103570753 A CN103570753 A CN 103570753A
- Authority
- CN
- China
- Prior art keywords
- preparation
- acid compound
- boric acid
- aryl
- compound according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 arylboronic acid compound Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 238000003747 Grignard reaction Methods 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 239000004327 boric acid Substances 0.000 claims description 29
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- 239000007818 Grignard reagent Substances 0.000 claims description 15
- 150000004795 grignard reagents Chemical class 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001502 aryl halides Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UEVKWTASYVIROP-UHFFFAOYSA-N 1-bromo-2-butylbenzene Chemical group CCCCC1=CC=CC=C1Br UEVKWTASYVIROP-UHFFFAOYSA-N 0.000 claims description 4
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical group COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 4
- AITNMTXHTIIIBB-UHFFFAOYSA-N 1-bromo-4-fluorobenzene Chemical compound FC1=CC=C(Br)C=C1 AITNMTXHTIIIBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- ZNOVTXRBGFNYRX-UHFFFAOYSA-N 2-[[4-[(2-amino-5-methyl-4-oxo-1,6,7,8-tetrahydropteridin-6-yl)methylamino]benzoyl]amino]pentanedioic acid Chemical compound C1NC=2NC(N)=NC(=O)C=2N(C)C1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 ZNOVTXRBGFNYRX-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- 150000001720 carbohydrates Chemical class 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002777 nucleoside Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229940125532 enzyme inhibitor Drugs 0.000 abstract 1
- 239000002532 enzyme inhibitor Substances 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 150000003833 nucleoside derivatives Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000003835 nucleoside group Chemical group 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- XLGLMVCAOMQNJT-UHFFFAOYSA-N boric acid;chlorobenzene Chemical compound OB(O)O.ClC1=CC=CC=C1 XLGLMVCAOMQNJT-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a preparation method of an arylboronic acid compound and belongs to the field of organic synthesis. According to the preparation method of the arylboronic acid compound, the arylboronic acid compound is prepared from aryl halohydrocarbon by Grignard reaction and esterification hydrolysis reaction; and the prepared arylboronic acid compound is applied to a hydrocarbon sensor, nucleoside and saccharides selective transporters, an enzyme inhibitor and the like in biology, medical science or materials science. According to the preparation method, a single solvent used in reaction is replaced with a mixed solvent so that the reaction and industrial safety can be improved, and the cost of the raw material can be decreased; in addition, a simple and efficient purification method is provided; and the method is simple in preparation process, mild in reaction conditions, simple and controllable in operation, and suitable for massive industrial production.
Description
Technical field
The present invention relates to a kind of preparation method's of aryl boric acid compound method, belong to organic synthesis field.
Background technology
Aryl boric acid compound is the boronic acid compounds with monocycle, the aryl boric acid of various replacements is important organic synthesis intermediate and medicine, pesticide intermediate, be widely used in Suzuki cross-coupling reaction, amino acid whose asymmetric synthesis, aminocompound catalyzer etc., for example, replace ortho-nitrophenyl boric acid and participate in the synthetic of various heterocycles; Phenylo boric acid is the precursor of the important activity compounds such as substituted diphenylamine derivative, and in biology, medical science or materialogy, the selectivity that aryl boric acid has been used to sensor, nucleosides and the carbohydrate of hydro carbons transports the inhibitor of carrier, enzyme.At present, the universal method of synthesizing aryl boronic acid compounds is Grignard reagent method, by aryl halide and magnesium chips effect, generates Grignard reagent, and then Grignard reagent reacts with boric acid ester and obtains aryl boric acid compound.In the method, select tetrahydrofuran (THF) to make solvent, yet tetrahydrofuran (THF) price is higher, reclaims difficulty.
the industrial production cost that reduces aryl boric acid compound is significant.
Summary of the invention
The object of the invention is to solve the higher problem of solvent cost in above-mentioned synthetic method, a kind of method that adopts mixed solvent low cost to prepare aryl boric acid compound is provided, and a kind of simple and effective purification way is provided.
The technical solution used in the present invention is: a kind of preparation method of aryl boric acid compound be take aryl halide as raw material, through grignard reaction, reacts two steps with esterification catalysis:
(1) under nitrogen protection, under room temperature, in four-hole round-bottomed flask, add 1.0-1.5eq magnesium rod, solvent, the mixed solvent that is 1:3～3:1 by 1.0eq aryl halide and mass ratio mixes, and under nitrogen protection, slowly in the four-hole bottle that contains magnesium rod, adds 1/5 of volume, temperature in flask rises to 30-60 ℃, keep temperature, drip 4/5 of residual volume, control rate of addition, maintain the temperature at 50-60 ℃, obtain Grignard reagent;
(2) in another four-hole round-bottomed flask, add boric acid ester and solvent, be cooled to 0-5 ℃, the above-mentioned Grignard reagent preparing is dripped so far in flask, Grignard reagent dropwises in backward flask and drips dilute hydrochloric acid cancellation reaction, and esterification catalysis has reacted; Separatory drips 1.0-5.0eq inorganic base aqueous solution salify in organic layer, and extraction separatory drips dilute hydrochloric acid in water layer, separates out solid, filters, and is dried to obtain aryl boric acid compound.
When the consumption of described aryl halide is 1.0eq, the consumption of magnesium rod is 1.0-1.5eq, and the consumption of mineral alkali is 1.0-5.0eq.
Described aryl halide is selected from tertiary butyl bromobenzene, para chlorobromobenzene, p-Fluoro bromo benzene.
Described solvent is selected from one or both in toluene, tetrahydrofuran (THF), dimethylbenzene, ether, anhydrous methyl THF.
Described mixed solvent is selected from toluene/tetrahydrofuran (THF), dimethylbenzene/methyltetrahydrofuran, dimethylbenzene/tetrahydrofuran (THF).
Described boric acid ester is selected from trimethyl borate, triisopropyl borate ester, tributyl borate, tri-n-butyl borate.
Described mineral alkali is selected from sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide, sodium bicarbonate, saleratus.
The invention has the beneficial effects as follows: the preparation method of this aryl boric acid compound be take aryl halide as raw material, through grignard reaction, react with esterification catalysis, the aryl boric acid compound of preparation is in biology, medical science or materialogy, and the selectivity that has been used to sensor, nucleosides and the carbohydrate of hydro carbons transports the inhibitor of carrier, enzyme etc.This preparation method changes the related single solvent of reaction into mixed solvent, improved reaction industry security, reduced material cost, and provide a kind of simple and effective method of purification, preparation process is simple, reaction conditions is gentle, simple to operate easy to control, is applicable to large-scale industrial production.
Embodiment
The present invention will be further described by the following examples.
In following examples, the purity of synthesized compound is according to high effective liquid chromatography for measuring.
embodiment 1to tert.-butylbenzene boric acid
under nitrogen protection, under room temperature, in 250 mL four-hole round-bottomed flasks, add magnesium rod 3.23 g(0.13 moL, 1.03 eq), anhydrous tetrahydro furan 37.5 g, dimethylbenzene 12.5 g.Will be to tertiary butyl bromobenzene 26.7 g(0.126 moL, 1.0 eq), and dimethylbenzene/tetrahydrofuran (THF) of 85 g (1:3) mixing, under nitrogen protection, slowly in the four-hole bottle that contains magnesium rod, add 1/5 of about volume, when temperature rising is obviously greater than 15 ℃, illustrate and start to cause, now the temperature in flask approximately can rise to 55～60 ℃ of left and right, keeps temperature, drip remaining to tertiary butyl bromobenzene, control rate of addition, maintain the temperature at 50～60 ℃, grignard reaction is complete; In another 250 mL four-hole round-bottomed flask, add trimethyl borate 13.1 g(0.126 moL, 1.0 eq), with 75 g tetrahydrofuran (THF)s, be cooled to 0～5 ℃, the above-mentioned Grignard reagent preparing is dripped so far in flask, Grignard reagent dropwises in backward flask and drips dilute hydrochloric acid cancellation reaction, and esterification catalysis has reacted; Separatory drips wet chemical salify in organic layer, and extraction separatory drips dilute hydrochloric acid in water layer, separates out solid, filters, and is dried to obtain solid 16.9 g.Purity is 98.1%, and yield is 75.1%.
embodiment 2to chlorobenzene boric acid
Under nitrogen protection, under room temperature, in 250 mL four-hole round-bottomed flasks, add magnesium rod 2.52 g(0.105 moL, 1.05 eq), anhydrous methyltetrahydrofuran 36.5 g, dimethylbenzene 13.5 g.By para chlorobromobenzene 19.2 g(0.1 moL, 1.0 eq), mix with dimethylbenzene/anhydrous methyltetrahydrofuran (1:3) of 85 g, under nitrogen protection, slowly in the four-hole bottle that contains magnesium rod, add 1/5 of about volume, when temperature rising is obviously greater than 15 ℃, illustrates and start to cause, now the temperature in flask approximately can rise to 50～60 ℃ of left and right, keep temperature, drip remaining para chlorobromobenzene solution, grignard reaction is complete; In another 250 mL four-hole round-bottomed flask, add trimethyl borate 10.4 g(0.1 moL, 1.0 eq) and 75 g dimethylbenzene, be cooled to 0～5 ℃, the above-mentioned Grignard reagent preparing is dripped so far in flask, Grignard reagent dropwises rear dropping dilute hydrochloric acid cancellation reaction, and esterification catalysis has reacted; Separatory drips aqueous sodium hydroxide solution salify in organic layer, and extraction separatory drips dilute hydrochloric acid in water layer, separates out solid, filters, and is dried to obtain solid 12.8 g, and purity is 98.7%, and yield is 82.3%.
embodiment 3to fluorobenzoic boric acid
under nitrogen protection, under room temperature, in 250 mL four-hole round-bottomed flasks, add magnesium rod 2.52 g(0.105 moL, 1.05 eq), anhydrous tetrahydro furan 13.5 g, toluene 37.5 g.By p-Fluoro bromo benzene 17.3 g(0.1 moL, toluene/tetrahydrofuran (THF) of 1.0eq) He 85 g (3:1) mixes, under nitrogen protection, slowly in the four-hole bottle that contains magnesium rod, add 1/8 of about volume, when temperature rising is obviously greater than 15 ℃, illustrate and start to cause, now the temperature in flask approximately can rise to 50～60 ℃ of left and right, keeps temperature, drip remaining santochlor solution, grignard reaction is complete; In another 250 mL four-hole round-bottomed flask, add tributyl borate 23.0 g(0.1 moL, 1.0eq) He 75 g toluene, be cooled to 0～5 ℃, the above-mentioned Grignard reagent preparing is dripped so far in flask, Grignard reagent dropwises in backward flask and drips dilute hydrochloric acid cancellation reaction, and esterification catalysis has reacted; Separatory drips sodium bicarbonate aqueous solution salify in organic layer, and extraction separatory drips dilute hydrochloric acid in water layer, separates out solid, filters, and is dried to obtain solid 11.0 g, and purity is 98.9%, and yield is 79.1%.
Claims (7)
1. a preparation method for aryl boric acid compound, is characterized in that: described preparation method be take aryl halide as raw material, through grignard reaction, reacts two steps with esterification catalysis:
(1) under nitrogen protection, under room temperature, in four-hole round-bottomed flask, add magnesium rod, solvent, the mixed solvent that is 1:3～3:1 by aryl halide and mass ratio mixes, and under nitrogen protection, slowly in the four-hole bottle that contains magnesium rod, adds 1/5 of volume, temperature in flask rises to 30-60 ℃, keep temperature, drip 4/5 of residual volume, control rate of addition, maintain the temperature at 50-60 ℃, obtain Grignard reagent;
(2) in another four-hole round-bottomed flask, add boric acid ester and solvent, be cooled to 0-5 ℃, the above-mentioned Grignard reagent preparing is dripped so far in flask, Grignard reagent dropwises in backward flask and drips dilute hydrochloric acid cancellation reaction, and esterification catalysis has reacted; Separatory drips inorganic base aqueous solution salify in organic layer, and extraction separatory drips dilute hydrochloric acid in water layer, separates out solid, filters, and is dried to obtain aryl boric acid compound.
2. the preparation method of a kind of aryl boric acid compound according to claim 1, is characterized in that: when the consumption of described aryl halide is 1.0eq, the consumption of magnesium rod is 1.0-1.5eq, and the consumption of mineral alkali is 1.0-5.0eq.
3. the preparation method of a kind of aryl boric acid compound according to claim 1, is characterized in that: described aryl halide is selected from tertiary butyl bromobenzene, para chlorobromobenzene, p-Fluoro bromo benzene.
4. the preparation method of a kind of aryl boric acid compound according to claim 1, is characterized in that: described solvent is selected from one or both in toluene, tetrahydrofuran (THF), dimethylbenzene, ether, anhydrous methyl THF.
5. the preparation method of a kind of aryl boric acid compound according to claim 1, is characterized in that:
Described mixed solvent is selected from toluene/tetrahydrofuran (THF), dimethylbenzene/methyltetrahydrofuran, dimethylbenzene/tetrahydrofuran (THF).
6. the preparation method of a kind of aryl boric acid compound according to claim 1, is characterized in that: described boric acid ester is selected from trimethyl borate, triisopropyl borate ester, tributyl borate, tri-n-butyl borate.
7. the preparation method of a kind of aryl boric acid compound according to claim 1, is characterized in that: described mineral alkali is selected from sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide, sodium bicarbonate, saleratus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310561231.5A CN103570753A (en) | 2013-11-13 | 2013-11-13 | Preparation method of arylboronic acid compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310561231.5A CN103570753A (en) | 2013-11-13 | 2013-11-13 | Preparation method of arylboronic acid compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103570753A true CN103570753A (en) | 2014-02-12 |
Family
ID=50043529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310561231.5A Pending CN103570753A (en) | 2013-11-13 | 2013-11-13 | Preparation method of arylboronic acid compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103570753A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119367A (en) * | 2014-07-09 | 2014-10-29 | 中国科学技术大学苏州研究院 | Preparation method of aryl boric acid |
| CN106478707A (en) * | 2016-10-14 | 2017-03-08 | 大连九信精细化工有限公司 | A kind of method that utilization continuous flow reactor produces 3 difluoro-methoxy 5 fluorobenzoic boric acid |
| WO2017173668A1 (en) * | 2016-04-08 | 2017-10-12 | 苏州大学张家港工业技术研究院 | Method for preparing phenylboronic acid neopentyl glycol ester |
| CN108690063A (en) * | 2018-07-19 | 2018-10-23 | 济南爱思医药科技有限公司 | A kind of preparation method to chlorophenylboronic acid |
| CN109608341A (en) * | 2018-12-28 | 2019-04-12 | 西南交通大学 | A kind of arylaniline compound and preparation method thereof |
| CN110054642A (en) * | 2019-04-24 | 2019-07-26 | 京博农化科技有限公司 | A kind of preparation method of pair of chlorophenylboronic acid |
| CN110669064A (en) * | 2018-07-03 | 2020-01-10 | 华东师范大学 | A kind of preparation method of arylboronic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168887A (en) * | 1996-06-14 | 1997-12-31 | 美国氰胺公司 | Process for prepn. of 5-bromo-2-fluorobenzeneboronic acid |
| CN1582272A (en) * | 2001-11-30 | 2005-02-16 | 帝人株式会社 | Process for preparing 5-3cyanophenyl-3-formylbenzoic acid compound |
| CN101010351A (en) * | 2004-07-09 | 2007-08-01 | 纳幕尔杜邦公司 | Catalysts for olefin polymerization or oligomerization |
| CN101260117A (en) * | 2008-04-14 | 2008-09-10 | 湖北省化学工业研究设计院 | Industrial method for producing dialkyldimethoxylsilicane by one-step method |
| CN101560396A (en) * | 2009-04-10 | 2009-10-21 | 莱阳市盛华科技有限公司 | Method for synthesizing fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal |
-
2013
- 2013-11-13 CN CN201310561231.5A patent/CN103570753A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1168887A (en) * | 1996-06-14 | 1997-12-31 | 美国氰胺公司 | Process for prepn. of 5-bromo-2-fluorobenzeneboronic acid |
| CN1582272A (en) * | 2001-11-30 | 2005-02-16 | 帝人株式会社 | Process for preparing 5-3cyanophenyl-3-formylbenzoic acid compound |
| CN101010351A (en) * | 2004-07-09 | 2007-08-01 | 纳幕尔杜邦公司 | Catalysts for olefin polymerization or oligomerization |
| CN101260117A (en) * | 2008-04-14 | 2008-09-10 | 湖北省化学工业研究设计院 | Industrial method for producing dialkyldimethoxylsilicane by one-step method |
| CN101560396A (en) * | 2009-04-10 | 2009-10-21 | 莱阳市盛华科技有限公司 | Method for synthesizing fluorine-containing antiform alkyl cyclohexyl biphenyl single liquid crystal |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119367A (en) * | 2014-07-09 | 2014-10-29 | 中国科学技术大学苏州研究院 | Preparation method of aryl boric acid |
| WO2017173668A1 (en) * | 2016-04-08 | 2017-10-12 | 苏州大学张家港工业技术研究院 | Method for preparing phenylboronic acid neopentyl glycol ester |
| US10696696B1 (en) | 2016-04-08 | 2020-06-30 | Soochow University | Method for preparing phenylboronic acid neopentyl glycol ester |
| CN106478707A (en) * | 2016-10-14 | 2017-03-08 | 大连九信精细化工有限公司 | A kind of method that utilization continuous flow reactor produces 3 difluoro-methoxy 5 fluorobenzoic boric acid |
| CN106478707B (en) * | 2016-10-14 | 2018-08-24 | 大连九信精细化工有限公司 | A method of producing 3- difluoro-methoxy -5- fluorobenzoic boric acids using continuous flow reactor |
| CN110669064A (en) * | 2018-07-03 | 2020-01-10 | 华东师范大学 | A kind of preparation method of arylboronic acid |
| CN108690063A (en) * | 2018-07-19 | 2018-10-23 | 济南爱思医药科技有限公司 | A kind of preparation method to chlorophenylboronic acid |
| CN109608341A (en) * | 2018-12-28 | 2019-04-12 | 西南交通大学 | A kind of arylaniline compound and preparation method thereof |
| CN110054642A (en) * | 2019-04-24 | 2019-07-26 | 京博农化科技有限公司 | A kind of preparation method of pair of chlorophenylboronic acid |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103570753A (en) | Preparation method of arylboronic acid compound | |
| Suzuki et al. | Cross-coupling reactions of organoboranes: an easy method for C–C bonding | |
| Jiang et al. | Copper-mediated oxidative difluoromethylenation of aryl boronic acids with α-silyldifluoromethylphosphonates: a new method for aryldifluorophosphonates | |
| CN104327119A (en) | Preparation method of tedizolid phosphate | |
| Mohan et al. | Superparamagnetic copper ferrite nanoparticles catalyzed aerobic, ligand-free, regioselective hydroboration of alkynes: influence of synergistic effect | |
| CN108178770B (en) | A kind of method of synthesizing α-amino boron compound | |
| CN101519411B (en) | Method for preparing phenylboronic acid-2-methyl formate | |
| CN102285937B (en) | Method for synthesizing febuxostat | |
| CN104211723A (en) | Synthesis and application of novel vinyl boronizing reagent | |
| CN107936048A (en) | A kind of preparation method of 2 fluorine, 4 methyl, 3 pyridine boronic acid | |
| CN104892371A (en) | Method for producing glycol dimethyl ether | |
| CN102757455B (en) | Preparation method of cyclopropylboronic acid | |
| CN103044473B (en) | Method for preparing cyclopropylboric acid | |
| CN108084217A (en) | A kind of preparation method of 2,6- dichloros phenyl boric acid | |
| CN103880573A (en) | Preparation method for biphenyl-type compound | |
| CN106167480A (en) | A kind of preparation method of canagliflozin intermediate 2 (4 fluorophenyl) thiophene | |
| CN101016222B (en) | Method of eliminating boric acid group from alkyl biphenyl boric acid compounds | |
| CN104926707A (en) | Synthetic method for pharmaceutical intermediate | |
| CN102850384A (en) | Synthesizing of 4-chloro-7-methoxyindole-2-boric acid | |
| CN103833530A (en) | Preparation method of organic intermediate 3-phenoxyl-1, 2-propylene glycol | |
| CN105294408B (en) | Cation light initiator（2 hydroxy-tetradecyl oxygen phenyl）The preparation method of benzene iodine hexafluoro antimonate | |
| CN113527154B (en) | Method for preparing N-sulfimide | |
| CN102977151B (en) | The preparation method of two (tricyclohexyl phosphine) palladium chloride | |
| CN102653545A (en) | Synthesis method of 2-methyl formate-5-boronic acid pinacol ester thiazole | |
| CN101514141B (en) | Synthetic method for allyl alcohol-like compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140212 |