CN104045661A - Method for preparation of aryl boronic acid and aryl borate by alcohol-promoted boronation reaction of aromatic amine - Google Patents
Method for preparation of aryl boronic acid and aryl borate by alcohol-promoted boronation reaction of aromatic amine Download PDFInfo
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Abstract
The invention discloses a method for preparation of aryl boronic acid and aryl borate by alcohol-promoted boronation reaction of aromatic amine, the aromatic amine which is easy to get and cheap is used as a raw material, a diboron compound is used as a boron source, a nitrite is used as a diazotization reagent, and the aryl boronic acid and aryl borate are obtained by alcohol-promoted reaction at room temperature in no presence of a catalyst. The method has the advantages of simple operation, mild reaction conditions, no presence of a metal catalyst, reduction of the production cost, high product yield, tolerance to different functional groups on aryl, and a wide adaptive range.
Description
Technical field
The invention belongs to the synthesis technical field of aryl boric acid and aryl-boric acid ester, be specifically related to alcohol and promote lower aromatic amine boronation reaction to generate aryl boric acid and aryl-boric acid ester.
Background technology
Aryl boric acid and aryl-boric acid ester are the very useful reaction intermediates of a class, they are widely used in the reaction of transition metal-catalyzed lower generation C-C, C-N, C-O, C-P and C-S key, but also there is the feature of hypotoxicity and high stability, therefore, the synthetic method of aryl boric acid and aryl-boric acid ester also attracts probing into of numerous scientific workers.Make a general survey of the synthetic method development history of aryl boric acid and ester thereof, by initial grignard reagent and lithium reagent method, arriving all can synthesizing aryl boric acid and ester thereof as catalyzer with the compound of palladium, copper, rhodium, iridium and ruthenium again, meanwhile, under nonmetal condition, the method for synthetic this compounds also causes people's extensive concern.Below the synthetic general introduction of aryl boric acid and aryl-boric acid ester:
1) Grignard reagent method (J.Org.Chem.2011,76,9602-9610)
Grignard reagent and tetramethyl ethylene ketone borine (PinBH) are made solvent with tetrahydrofuran (THF) at ambient temperature and can be obtained corresponding aryl-boric acid ester.
2) copper catalysis (Org.Lett.2006,8,261-263)
The linked reaction of tetramethyl ethylene ketone borine and aryl iodide, through experiment, find, no matter be that donor residues or electron withdrawing group can obtain good yield under this condition, it should be noted that, 4-bromo-iodobenzene is under this condition, what obtain is the product of single coupling, and productive rate is 76%, this means that C-I key is faster than C-Br coupling.In addition, containing heteroatomic aryl iodide, also can under this condition, react, the coupled product productive rate obtaining as 2-iodothiophen is 62%.
3) palladium catalysis (Tetrahedron Letters.2000,41,8683 – 8686)
The aryl diazonium salts of palladium catalysis reacts with two valeryl two boron the method for preparing aryl-boric acid ester; With the method can anamorphic zone halogen, the substituent aryl-boric acid ester such as ester group, nitro, productive rate reaches as high as 96%.
4) catalysis (Angew.Chem.Int.Ed.2010,49,1846 – 1849) that nitrous acid tertiary butyl ester participates in
Take acetonitrile as solvent, the boronation effect of arylamines and two valeryl two boron under nitrous acid tertiary butyl ester (t-BuONO) and dibenzoyl peroxide (BPO) effect.The advantage of the method has: the cheap easily preparation of reaction raw materials; This reaction is the reaction of nonmetal participation, has avoided the pollution of metal pair boronation product.
But there is following weak point in aforesaid method: operational hazards, and transition metal is expensive, and temperature of reaction is higher, and substrate is complicated, and some need add superoxide etc.In sum, select a kind of method of easier synthesizing aryl boric acid and aryl-boric acid ester to seem particularly important.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of simple, green aryl boric acid being promoted by alcohol and the synthetic method of aryl-boric acid ester.
Solving the problems of the technologies described above adopted technical scheme is: the aromatic amine shown in formula 1, mineral acid are dissolved in organic solvent completely, then the aqueous solution that adds nitrite, stir, 0～5 ℃ is reacted 30 minutes, add two boron compounds and the alcohol shown in formula 2 or formula 3, the mol ratio of aromatic amine and nitrite, mineral acid, two boron compounds, alcohol is 1:1～2:1～6:2～6:50～100, normal-temperature reaction 0.5～3 hour, separation and purification product, the aryl-boric acid ester shown in a preparation accepted way of doing sth 4 or the aryl boric acid shown in formula 5.
R in formula
1, R
2, R
3, R
4, R
5independently represent separately H, amino, nitro, C
1～C
10alkyl, C
1～C
10alkoxyl group, C
1～C
10trifluoroalkyl, trifluoromethoxy, cyano group, halogen, C
1～C
8thiazolinyl, C
1～C
8alkynyl, C
1～C
10acyl group, C
1～C
10acyloxy, hydroxyl, carboxyl, aldehyde radical, aryl, benzyl, C
1～C
10alkylthio, any one in piperazinyl, preferred R
1, R
2, R
5represent H, R
3represent H or methoxyl group, R
4represent nitro, methyl, methoxyl group or hydroxyl.
Preferred 1:1:3:3:50～100 of mol ratio of above-mentioned aromatic amine and nitrite, mineral acid, two boron compounds, alcohol.
Above-mentioned mineral acid is any one in hydrochloric acid, sulfuric acid, Tetrafluoroboric acid, mistake chloric acid, preferably hydrochloric acid; Alcohol is C
1～C
5primary alcohol, C
3～C
6secondary alcohol, C
4～C
6tertiary alcohol, any one in trifluoroethanol, particular methanol or trifluoroethanol; Two boron compounds are any one in tetrahydroxy two boron, two valeryl two boron, two (neo-pentyl ethylene glycol) two boron, two (hexenyl glycolic acid) two boron, four (tetramethyleneimine also) diboron hexahydride, preferably tetrahydroxy two boron or two valeryl two boron; Nitrite is Sodium Nitrite, potassium nitrite, ammonium nitrite etc.
It is raw material that the present invention adopts aromatic amine cheap and easy to get, two boron compounds of usining are made boron source, nitrite as diazo reagent, under promoting, alcohol can obtain good product yield under room temperature catalyst-free condition, and can tolerate different functional groups, subject range is wider, has overcome the defects such as metal catalyst participation in existing method, high temperature, substrate narrow range and complex operation.
Embodiment
Below in conjunction with embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiment.
Embodiment 1
Take that to prepare the following phenyl-boron dihydroxide of structural formula be example, raw materials used and preparation method is:
Aniline 47mg (0.5mmol), 2.0mL (50mmol) methyl alcohol are added in reaction tubes, treat that aniline dissolves completely, the hydrochloric acid that adds again 0.5mL3mol/L, stir two minutes, 35mg Sodium Nitrite solid is added in 0.25mL distilled water, with syringe, it is slowly added in reaction tubes again, under 0～5 ℃ of condition, stir 30 minutes, then in reaction tubes, add 135mg (1.5mmol) tetrahydroxy two boron, stirring at normal temperature 1 hour, question response finishes, in mixture, add 10mL distilled water, then with 50mL methylene dichloride, divide three extractions, collect organic phase, use anhydrous Na
2sO
4dry, suction filtration, removes methylene dichloride with Rotary Evaporators, obtains white solid phenyl-boron dihydroxide, and its productive rate is 72%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 8.25 (d, J=6.8Hz, 2H), 7.61 (t, J=6.8Hz, 1H), 7.52 (t, J=7.2Hz, 2H);
13cNMR (100MHz, CDCl
3) δ (ppm): 135.66,132.70,127.99.
Embodiment 2
Take that to prepare the following 4-trifluoromethyl phenylo boric acid of structural formula be example, raw materials used and preparation method is:
In embodiment 1, aniline used is replaced with equimolar 4-5-trifluoromethylaniline, and other steps are identical with embodiment 1, obtains white solid 4-trifluoromethyl phenylo boric acid, and its productive rate is 62%, and spectral data is:
1h NMR (400MHz, deuterated acetone) δ (ppm): 8.09 (d, J=8.0Hz, 2H), 7.70 (d, J=8.0Hz, 2H), 7.47 (s, 2H);
13c NMR (100MHz, deuterated acetone) δ (ppm): 135.51,132.25 (d, J
c-F=31.0Hz), 126.82,124.87 (q, J
c-F=3.7Hz).
Embodiment 3
With prepare structural formula following 3,4-dimethylphenyl boronic acid is example, raw materials used and preparation method is:
In embodiment 1, aniline used is with equimolar 3, and 4-xylidine is replaced, and other steps are identical with embodiment 1, obtain white solid 34-dimethylphenyl boronic acid, and its productive rate is 82%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.97 (d, J=6.4Hz, 2H), 7.28 (d, J=8.0Hz, 1H), 2.40 (s, 3H), 2.36 (s, 3H);
13c NMR (100MHz, CDCl
3) δ (ppm): 141.54,136.78,136.00,133.42,129.39,20.20,19.72.
Embodiment 4
Take that to prepare the following 4-methylphenylboronic acid of structural formula be example, raw materials used and preparation method is:
In embodiment 1, aniline used is replaced with equimolar 4-monomethylaniline, and other steps are identical with embodiment 1, obtains white solid 4-methylphenylboronic acid, and its productive rate is 90%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 8.12 (d, J=7.6Hz, 2H), 7.31 (d, J=7.6Hz, 2H), 2.44 (s, 3H);
13c NMR (100MHz, CDCl
3) δ (ppm): 142.91,135.72,128.78,21.9.
Embodiment 5
Take that to prepare the following 4-methoxyphenylboronic acid of structural formula be example, raw materials used and preparation method is:
In embodiment 1, aniline used is replaced with equimolar 4-anisidine, and other steps are identical with embodiment 1, obtains white solid 4-methoxyphenylboronic acid, and its productive rate is 86%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 8.15 (d, J=6.8Hz, 2H), 7.00 (d, J=6.8Hz, 2H), 3.87 (s, 3H);
13c NMR (100MHz, CDCl
3) δ (ppm): 163.23,137.50,113.52,55.17.
Embodiment 6
Take that to prepare the following 4-amino-benzene pinacol borate of structural formula be example, raw materials used and preparation method is:
In embodiment 1, aniline used is replaced with equimolar Ursol D, and tetrahydroxy two boron are replaced with equimolar pair of valeryl two boron, after reaction finishes, in mixture, add saturated sodium bicarbonate aqueous solution to alkalescence, with 50mL methylene dichloride, divide three extractions, collect organic phase anhydrous Na
2sO
4dry, suction filtration, removes methylene dichloride with Rotary Evaporators, with silica gel, carries out column chromatography, and eluent is petrol ether/ethyl acetate=30:1, obtains white solid 4-amino-benzene pinacol borate, and its productive rate is 53%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.61 (d, J=8.0Hz, 2H), 6.65 (d, J=8.0Hz, 2H), 3.82 (s, 2H), 1.35 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 149.3,136.4,114.0,83.2,24.8.
Embodiment 7
To prepare the following 2-of structural formula (4-methoxyl group-phenyl)-5,5-dimethyl-[1,3,2] dioxo bora ring is example, and raw materials used and preparation method is:
In embodiment 1, aniline used is replaced with equimolar 4-anisidine, and tetrahydroxy two boron are replaced with equimolar two (neo-pentyl ethylene glycol) two boron, after reaction finishes, in mixture, add 10mL distilled water, with 50mL methylene dichloride, divide three extractions, collect organic phase anhydrous Na
2sO
4dry, suction filtration, removes methylene dichloride with Rotary Evaporators, with silica gel, carries out column chromatography, eluent is petrol ether/ethyl acetate=70:1, other steps are identical with embodiment 1, obtain white solid 2-(4-methoxyl group-phenyl)-5,5-dimethyl-[1,3,2] dioxo bora ring, its productive rate is 65%, spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.76 (d, J=6.4Hz, 2H), 6.90 (d, J=6.4Hz, 2H), 3.82 (s, 3H), 3.75 (s, 4H), 1.01 (s, 6H);
13c NMR (100MHz, CDCl
3) δ (ppm): 161.89,135.66,113.29,72.40,55.19,32.03,22.06.
Embodiment 8
The preparation 4-piperazinyl phenyl pinacol borate of take is example, and raw materials used and preparation method is:
In embodiment 6, equimolar 1-for Ursol D used (4-amino-benzene) piperazine is replaced, and eluent changes methylene chloride/methanol=25:1 into, other steps are identical with embodiment 6, obtain yellow solid 4-piperazinyl phenyl pinacol borate, its productive rate is 68%, and spectral data is:
1hNMR (400MHz, CDCl
3) δ (ppm): 7.71 (d, J=8.8Hz, 2H), 6.89 (d, J=8.8Hz, 2H), 3.26 (t, J=5.0Hz, 4H), 3.05 (t, J=5.0Hz, 4H), 1.32 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 153.6,136.1,114.5,83.3,49.0,45.6,24.8.
Embodiment 9
Take that to prepare the following 4-oil of mirbane pinacol borate of structural formula be example, raw materials used and preparation method is:
In embodiment 6, Ursol D used is replaced with equimolar 4-N-methyl-p-nitroaniline, and other steps are identical with embodiment 6, obtains white solid 4-oil of mirbane pinacol borate, and its productive rate is 97%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 8.19 (d, J=8.0Hz, 2H), 7.96 (d, J=8.0Hz, 2H), 1.36 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 149.8,135.6,122.3,84.6,24.8.
Embodiment 10
To prepare the following 4-of structural formula (4,4,5,5-tetramethyl--1,3,2-dioxy boron, penta ring-2-yl) ethyl benzoate, be example, raw materials used and preparation method is:
In embodiment 6, Ursol D used is replaced with equimolar PABA ethyl ester, and other steps are identical with embodiment 6, obtain white solid 4-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) ethyl benzoate, its productive rate is 75%, spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 8.02 (d, J=8.0Hz, 2H), 7.86 (d, J=7.6Hz, 2H), 4.38 (q, J=7.1Hz, 2H), 1.39 (t, J=7.2Hz, 3H), 1.35 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 166.6,134.6,132.6,128.5,84.1,61.0,24.8,14.3.
Embodiment 11
Take that to prepare the following 4-hydroxybenzene pinacol borate of structural formula be example, raw materials used and preparation method is:
In embodiment 6, Ursol D used is replaced with equimolar PAP, and other steps are identical with embodiment 6, obtains white solid 4-hydroxybenzene pinacol borate, and its productive rate is 93%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.71 (d, J=8.4Hz, 2H), 6.82 (d, J=8.0Hz, 2H), 5.16 (s, 1H), 1.33 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 158.4,136.7,114.8,83.6,24.8.
Embodiment 12
With prepare structural formula following 3,4-dimethoxy benzene pinacol borate is example, raw materials used and preparation method is:
In embodiment 6, Ursol D used is with equimolar 3, and 4-dimethoxyaniline is replaced, and other steps are identical with embodiment 6, obtain white solid 3,4-dimethoxy benzene pinacol borate, and its productive rate is 96%, spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.42 (dd, J=8.0Hz, J=8.0Hz, 1H), 7.29 (d, J=0.8Hz, 1H), 6.88 (d, J=8.0Hz, 1H), 3.92 (s, 3H), 3.90 (s, 3H), 1.34 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 151.7,148.4,128.5,116.9,110.5,83.6,55.8,55.7,24.8.
Embodiment 13
Take that to prepare the following 4-iodobenzene pinacol borate of structural formula be example, raw materials used and preparation method is:
In embodiment 6, Ursol D used is replaced with equimolar 4-Iodoaniline, and other steps are identical with embodiment 6, obtains white solid 4-iodobenzene pinacol borate, and its productive rate is 78%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.72 (d, J=8.0Hz, 2H), 7.51 (d, J=8.0Hz, 2H), 1.33 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 136.9,136.2,98.8,84.0,24.8.
Embodiment 14
With prepare structural formula following 4,4'-xenyl hypoboric acid two (pinacol ester) is example, raw materials used and preparation method is:
In embodiment 6, Ursol D used is replaced with equimolar p-diaminodiphenyl, and Sodium Nitrite and hydrochloric acid consumption all become original 2 times, other steps are identical with embodiment 6, obtain white solid 4,4'-xenyl hypoboric acid two (pinacol ester), its productive rate is 75%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.88 (d, J=8.0Hz, 4H), 7.62 (d, J=8.0Hz, 4H), 1.36 (
s, 24H);
13c NMR (100MHz, CDCl
3) δ (ppm): 143.6,135.2,126.5,83.8,24.8.
Embodiment 15
Take that to prepare the following 4-Trifluoromethyl phenyl ether pinacol borate of structural formula be example, raw materials used and preparation method is:
In embodiment 6, Ursol D used is replaced with equimolar 4-trifluoro-methoxyaniline, and other steps are identical with embodiment 6, obtains white solid 4-Trifluoromethyl phenyl ether pinacol borate, and its productive rate is 55%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.84 (d, J=8.4Hz, 2H), 7.24 (d, J=8.0Hz, 2H), 1.33 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 151.7 (d, J
c-F=1.0Hz), 136.5,121.7,119.5 (d, J
c-F=69Hz), 84.0,24.8.
Embodiment 16
Take that to prepare the following 4-cyanophenylboronic acid pinacol ester of structural formula be example, raw materials used and preparation method is:
In embodiment 6, Ursol D used is replaced with equimolar 4-cyano-aniline, and other steps are identical with embodiment 6, obtains white solid 4-cyanophenylboronic acid pinacol ester, and its productive rate is 57%, and spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.88 (d, J=8.0Hz, 2H), 7.64 (d, J=8.0Hz, 2H), 1.35 (s, 12H);
13c NMR (100MHz, CDCl
3) δ (ppm): 135.0,131.1,118.8,114.5,84.4,24.8.
Embodiment 17
Take that to prepare the following 4-methylphenylboronic acid pinacol ester of structural formula be example, raw materials used and preparation method is:
By 54mg (0.5mmol) 4-monomethylaniline, 2.0mL (50mmol) ethanol adds in reaction tubes, treat that 4-monomethylaniline dissolves completely, the sulfuric acid that adds again 0.5mL3mol/L, stir two minutes, then 32mg (0.5mmol) ammonium nitrite solid is added in 0.25mL distilled water, with syringe, it is slowly added in reaction tubes, under 0～5 ℃ of condition, stir 30 minutes, in reaction tubes, add two valeryl two boron of 381mg (1.5mmol) again, stirring at normal temperature 3 hours, other steps are identical with embodiment 7, obtain white solid 4-methylphenylboronic acid pinacol ester, its productive rate is 60%, spectral data is:
1h NMR (400MHz, CDCl
3) δ (ppm): 7.73 (d, J=7.6Hz, 2H), 7.20 (d, J=7.2Hz, 2H), 2.38 (s, 3H), 1.35 (s, 12H),
13c NMR (100MHz, CDCl
3) δ (ppm): 141.3,134.8,128.5,83.6,24.8,21.7.
Embodiment 18
In embodiment 17, ethanol used is replaced with equimolar trifluoroethanol, and sulfuric acid is replaced with equimolar Tetrafluoroboric acid, and other steps are identical with embodiment 17, obtains white solid 4-methylphenylboronic acid pinacol ester, and its productive rate is 63%.
Embodiment 19
In embodiment 17, trifluoroethanol used is replaced with the equimolar trimethyl carbinol, and sulfuric acid is replaced with the equimolar chloric acid of crossing, and other steps are identical with embodiment 17, obtain white solid 4-methylphenylboronic acid pinacol ester, and its productive rate is 47%.
Claims (7)
1. an alcohol promotes lower aromatic amine boronation reaction to generate the method for aryl boric acid and aryl-boric acid ester, it is characterized in that: the aromatic amine shown in formula 1 and mineral acid are dissolved in alcohol completely, then the aqueous solution that adds nitrite, stir, 0～5 ℃ is reacted 30 minutes, add again two boron compounds, the mol ratio of aromatic amine and nitrite, mineral acid, two boron compounds, alcohol is 1:1～2:1～6:2～6:50～100, normal-temperature reaction 0.5～3 hour, separation and purification product, obtains aryl-boric acid ester or aryl boric acid;
R in formula 1
1, R
2, R
3, R
4, R
5independently represent separately H, amino, nitro, C
1～C
10alkyl, C
1～C
10alkoxyl group, C
1～C
10trifluoroalkyl, trifluoromethoxy, cyano group, halogen, C
1～C
8thiazolinyl, C
1～C
8alkynyl, C
1～C
10acyl group, C
1～C
10acyloxy, hydroxyl, carboxyl, aldehyde radical, aryl, benzyl, C
1～C
10alkylthio, any one in piperazinyl;
Above-mentioned mineral acid is any one in hydrochloric acid, sulfuric acid, Tetrafluoroboric acid, mistake chloric acid; Alcohol is C
1～C
5primary alcohol, C
3～C
6secondary alcohol, C
4～C
6tertiary alcohol, any one in trifluoroethanol; Two boron compounds are any one in tetrahydroxy two boron, two valeryl two boron, two (neo-pentyl ethylene glycol) two boron, two (hexenyl glycolic acid) two boron, four (tetramethyleneimine also) diboron hexahydride.
2. alcohol according to claim 1 promotes lower arylamine boronation reaction to generate the method for aryl boric acid and aryl-boric acid ester, it is characterized in that: described R
1, R
2, R
5represent H, R
3represent H or methoxyl group, R
4represent any one in nitro, methyl, methoxyl group, hydroxyl.
3. alcohol according to claim 1 promotes lower arylamine boronation reaction to generate the method for aryl boric acid and aryl-boric acid ester, it is characterized in that: the mol ratio of described aromatic amine and nitrite, mineral acid, two boron compounds, alcohol is 1:1:3:3:50～100.
4. according to the alcohol described in claim 1～3 any one, promote lower arylamine boronation reaction to generate the method for aryl boric acid and aryl-boric acid ester, it is characterized in that: described mineral acid is hydrochloric acid.
5. according to the alcohol described in claim 1～3 any one, promote lower arylamine boronation reaction to generate the method for aryl boric acid and aryl-boric acid ester, it is characterized in that: described nitrite is any one in Sodium Nitrite, potassium nitrite, ammonium nitrite.
6. according to the alcohol described in claim 1～3 any one, promote lower arylamine boronation reaction to generate the method for aryl boric acid and aryl-boric acid ester, it is characterized in that: described alcohol is methyl alcohol or trifluoroethanol.
7. according to the alcohol described in claim 1～3 any one, promote lower arylamine boronation reaction to generate the method for aryl boric acid and aryl-boric acid ester, it is characterized in that: two described boron compounds are tetrahydroxy two boron or two valeryl two boron.
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| CN112159422A (en) * | 2020-10-21 | 2021-01-01 | 上海应用技术大学 | Method for catalytic synthesis of phenylboronic acid ester derivative by using iridium catalyst |
| CN113444116A (en) * | 2021-06-04 | 2021-09-28 | 华东师范大学 | System and method for continuous chemical reactions for arylboronic acid ester synthesis under flow via microfluidic chip |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106986886A (en) * | 2017-04-06 | 2017-07-28 | 无锡捷化医药科技有限公司 | A kind of preparation method of the Trifluoromethoxyphen-l pinacol borate of 4 fluorine 3 |
| CN106986886B (en) * | 2017-04-06 | 2019-04-05 | 无锡捷化医药科技有限公司 | A kind of preparation method of the fluoro- 3- Trifluoromethoxyphen-l pinacol borate of 4- |
| CN112159422A (en) * | 2020-10-21 | 2021-01-01 | 上海应用技术大学 | Method for catalytic synthesis of phenylboronic acid ester derivative by using iridium catalyst |
| CN113444116A (en) * | 2021-06-04 | 2021-09-28 | 华东师范大学 | System and method for continuous chemical reactions for arylboronic acid ester synthesis under flow via microfluidic chip |
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