CN104725409A - Borane-pyridine pre-ligand, preparation method and application of borane-pyridine pre-ligand, and preparation method of aryl boric acid ester - Google Patents
Borane-pyridine pre-ligand, preparation method and application of borane-pyridine pre-ligand, and preparation method of aryl boric acid ester Download PDFInfo
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- CN104725409A CN104725409A CN201510067478.0A CN201510067478A CN104725409A CN 104725409 A CN104725409 A CN 104725409A CN 201510067478 A CN201510067478 A CN 201510067478A CN 104725409 A CN104725409 A CN 104725409A
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- boric acid
- boranepyridine
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- -1 aryl boric acid ester Chemical class 0.000 title claims abstract description 51
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000004327 boric acid Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003446 ligand Substances 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 4
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CZYHRTIJLUONKY-UHFFFAOYSA-N 2-(3,5-dimethoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound COC1=CC(OC)=CC(B2OC(C)(C)C(C)(C)O2)=C1 CZYHRTIJLUONKY-UHFFFAOYSA-N 0.000 description 2
- YYAOOIKMZLJELI-UHFFFAOYSA-N CC1=C(C=CC=C1)C.[N].C[N] Chemical compound CC1=C(C=CC=C1)C.[N].C[N] YYAOOIKMZLJELI-UHFFFAOYSA-N 0.000 description 2
- 0 COc1cc(*)ccc1 Chemical compound COc1cc(*)ccc1 0.000 description 2
- CWOMTHDOJCARBY-UHFFFAOYSA-N Cc1cccc(N(C)C)c1 Chemical compound Cc1cccc(N(C)C)c1 CWOMTHDOJCARBY-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HGDYEWOJPHKSMF-UHFFFAOYSA-N CCC(C1)C1c1cccc([O]=C)c1 Chemical compound CCC(C1)C1c1cccc([O]=C)c1 HGDYEWOJPHKSMF-UHFFFAOYSA-N 0.000 description 1
- UTHSCFIYXWSZSS-UHFFFAOYSA-N CN(C)C(C1)C=CC=C1N(C)C Chemical compound CN(C)C(C1)C=CC=C1N(C)C UTHSCFIYXWSZSS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- STSBRNLAXYDNPQ-UHFFFAOYSA-N c(cc1)cc(NB2B(Nc3ccccc33)N3c3ccccn3)c1N2c1ccccn1 Chemical compound c(cc1)cc(NB2B(Nc3ccccc33)N3c3ccccn3)c1N2c1ccccn1 STSBRNLAXYDNPQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 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
-
- 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 provides a borane-pyridine pre-ligand, a preparation method and an application of the borane-pyridine pre-ligand, and a preparation method of aryl boric acid ester. The borane-pyridine pre-ligand is synthesized by the method lower in cost and easy to operate; under the condition of iridium catalysis, the borane-pyridine pre-ligand can be used for efficiently preparing an aryl boric acid ester chemical compound; particularly for substrates with lower activity and strong rich electron replacing groups, the yield is higher; the separation and purification are easier; and the efficiency is more obvious.
Description
Technical field
The invention belongs to technical field of fine, the synthesis of part and the method for efficiently preparing aryl boric acid ester cpds before being specifically related to boranepyridine.
Background technology
Boric acid ester compound is the compound that can be used as such as synthetic drugs/agriculture medicinal intermediate.Prepare the hydrocarbon boronation catalyzed reaction that the most direct method of this compounds is organic compound.Wherein the synthetic method effect of aryl boric acid ester cpds is it is preferred that the catalyst system of iridium catalyst and bipyridyliums part, and the shortcoming of this type of catalyst system is that productive rate is low, especially for the substrate of some strong electron riches.Because the polarity of aryl compound and boronation product thereof is close, and boric acid ester easily trails, if low being easy to of reaction yield causes purifying difficulty below to strengthen, thus improves the cost of synthesis.Thus, the synthetic yield improving aryl boric acid ester cpds has important research and is worth.
Summary of the invention
Part and its preparation method and application and prepare the method for aryl-boric acid ester before the object of the present invention is to provide a kind of boranepyridine, the raw materials cost of synthetic ligands of the present invention is low, simple and easy to get and synthesis is convenient, the yield of aryl boric acid ester cpds is high, be easy to purifying, and Atom economy is high.
For achieving the above object, the technical solution used in the present invention is:
Part before a kind of boranepyridine, before this boranepyridine, part is for having the compound such as formula structure (1) Suo Shi:
Prepare a method for part before boranepyridine, comprise the following steps:
Under nitrogen protection; single pyridine aniline compound and four methylamino-diboranes are reacted 24 ~ 48 hours in 125 ~ 130 DEG C in toluene; the mol ratio of single pyridine aniline compound and four methylamino-diboranes is 2:1 ~ 1.5; pumping toluene under having reacted final vacuum condition and obtain part before boranepyridine, is faint yellow solid.
Described single pyridine aniline compound is for having the compound such as formula structure (2) Suo Shi:
This single pyridine aniline compound (formula (2)) preparation method is as follows: the mixture of phenylenediamine and 2-chloropyridine is heated at 150 ~ 170 DEG C thick material, phenylenediamine in mixture: the mol ratio of 2-chloropyridine is 1:1.1 ~ 1.2, mixture (volume ratio of acetone and water the is generally 1 ~ 2:1) heating for dissolving with acetone and water after room temperature is down to until material, then sodium carbonate adjust ph to 10 ~ 12 are used under room temperature, then extract by ethyl acetate, extract the organic phase (upper strata) obtained and after saturated common salt water washing and anhydrous sodium sulfate drying, obtain single pyridine aniline compound (colorless solid by column chromatography purification successively, formula (2)), the condition of described column chromatography is: the silica gel using 200 ~ 300 order specifications, the mass ratio of silica gel and thing to be purified is 50 ~ 100:1, and eluent is the mixed solution of sherwood oil and ethyl acetate, mixed solution PetroChina Company Limited. ether: the volume ratio of ethyl acetate is 1 ~ 2:1.
Before above-mentioned boranepyridine, part is preparing the application in aryl-boric acid ester.
Prepare a method for aryl-boric acid ester, comprise the following steps:
1) under nitrogen protection, react before aryl compound, connection pinacol borate, 1,5-cyclooctadiene methoxyl group iridium dimer, boranepyridine 8 ~ 48 hours in 80 ~ 125 DEG C after part and ether solvent mixing;
2) removing ether solvent is steamed through revolving after having reacted, then aryl-boric acid ester is obtained with column chromatography purification, the reaction density of described aryl compound is 0.5 ~ 2mol/L, the consumption of described pinacol borate is 0.75 ~ 1.5 times of the amount of substance of described aryl compound, described 1, the dimeric consumption of 5-cyclooctadiene methoxyl group iridium is 0.5 ~ 2% of the amount of substance of described aryl compound, before described boranepyridine, the consumption of part is described 1, 2 ~ 3 times of the dimeric amount of substance of 5-cyclooctadiene methoxyl group iridium, before described boranepyridine, part is for having the compound such as formula structure (1) Suo Shi:
The structure of described aryl-boric acid ester is such as formula shown in (4):
Wherein, R
1and R
3represent alkyl, halogen atom, nitrogen nitrogen dimethyl, methoxyl group, carbonyl, cyano group, thioether or ester group, R
2represent hydrogen atom, alkyl, halogen atom, nitrogen nitrogen dimethyl, methoxyl group, carbonyl, cyano group, thioether or ester group.
Described aryl compound comprises:
The condition of described column chromatography is: the silica gel using 200 ~ 300 order specifications, the mass ratio of silica gel and thing to be purified is 50 ~ 100:1, and eluent is the mixed solution of sherwood oil and ethyl acetate, mixed solution PetroChina Company Limited. ether: the volume ratio of ethyl acetate is 20 ~ 50:1.
Beneficial effect of the present invention is embodied in:
The present invention's lower price and easy-operating method have synthesized part before a kind of pyridyl boron, i.e. part before boranepyridine, itself and iridium catalyst effect, can from simple arene compound by direct C-H bond be converted preparation multiple aryl boric acid ester cpds, especially for the substrate with strong abundant electron substituents group that some activity are lower, aryl boric acid ester cpds productive rate is higher, is easier to separation and purification, can be used for efficiently preparing aryl boric acid ester cpds.
Embodiment
Below in conjunction with embodiment, the present invention is elaborated.
(1) preparation of part before boranepyridine
Before this boranepyridine, part is for having the compound such as formula structure (1) Suo Shi:
Preparation method's example:
1) by phenylenediamine (648mg, 6mmol) with 2-chloropyridine (749mg, mixture 6.6mmol) is heated to thick material (approximately needing 8 ~ 12 hours) at 160 DEG C, be down to after room temperature until material and dissolve (heat can promote to dissolve a little) with the mixture of acetone (3mL) and water (3mL), then sodium carbonate adjust ph to 10 is used under room temperature, then use 8 ~ 10mL ethyl acetate at every turn, extract three times, extract the organic phase obtained and after saturated common salt water washing and anhydrous sodium sulfate drying, (use the silica gel of 200 ~ 300 order specifications by column chromatography successively, silica gel and amount to be purified are than 50 ~ 100:1, eluent is sherwood oil and ethyl acetate, volume ratio 1 ~ 2:1) purifying obtains colorless solid list pyridine aniline compound, through qualification (400MHz nuclear magnetic resonance analyser (CDCl
3, 25 DEG C)),
1hNMR: chemical shift δ 8.16 (dd, J
1=5.0Hz, J
2=0.9Hz, 1H), 7.43 (td, J
1=7.8Hz, J
2=1.8Hz, 1H), 7.19 (d, J=8.0Hz, 1H), 7.09 (td, J
1=8.0Hz, 1.1Hz, 1H), 6.83 (d, J=8.0Hz, 1H), 6.78 (t, J=7.8Hz, 1H), 6.69 (t, J=6.9Hz, 1H), 6.42 (d, J=8.4Hz, 1H), 6.20 (br s, 1H), 3.87 (br s, 2H),
13cNMR: chemical shift δ 158.0,148.7,143.4,138.2,127.6,127.4,126.1,119.3,116.6,114.8,107.6, be specially N-(2-pyridine) phenylenediamine (formula (2)), productive rate is 50% (556mg),
2) under nitrogen protection; by single pyridine aniline compound (278mg; 1.5mmol; formula (2)) and four methylamino-diborane (186mg; 0.94mmol, formula (3)) in toluene (3mL) in 128 DEG C of reactions 45 hours, under having reacted final vacuum condition, (room temperature) pumps toluene and obtains part before boranepyridine; for faint yellow solid, productive rate is 100%.Through qualification (400MH nuclear magnetic resonance analyser (CDCl
3, 25 DEG C)),
1hNMR: chemical shift δ 8.52 (dd, J
1=5.0Hz, J
2=1.3Hz, 2H), 7.66-7.54 (m, 4H), 7.50 (br s, 2H), 7.30 (d, J=8.0Hz, 2H), 7.14 (d, J=7.0Hz, 2H), 7.09 (dd, J
1=7.0Hz, J
2=5.3Hz, 2H), 7.08-6.94 (m, 4H);
13cNMR: chemical shift δ 155.2,148.8,138.0,137.5,135.9,120.8,120.4,119.7,118.7,111.7, product structure is such as formula shown in (1).
Utilize single pyridine aniline compound of other and formula (2) similar also can prepare part before other boranepyridine, but before the boranepyridine shown in formula (1), part is preparing better effects if in aryl-boric acid ester.
(2) preparation of aryl-boric acid ester
Prepare example 1
This example is that milligram rank prepares 3, 5-dimethoxyphenylboronic pinacol ester, specifically comprise the following steps: under nitrogen environment, 1 is added in reaction flask, 3-dimethoxy benzene (69.1mg, 0.5mmol), connection pinacol borate (126.9mg, 0.5mmol, formula (5)), 1, 5-cyclooctadiene methoxyl group iridium dimer (3.4mg, 0.005mmol, 1%, formula (6)), part (4.0mg before boranepyridine, 0.01mmol, 2%, formula (1)) and cyclopentyl-methyl ether (1mL, 1, the reaction density of 3-dimethoxy benzene is 0.5mol/L), 16h is reacted at 100 DEG C, 2. steaming (20 ~ 40 DEG C) is revolved after having reacted except desolventizing (cyclopentyl-methyl ether), (silica gel of 200 ~ 300 order specifications is used by the method for column chromatography, silica gel and amount to be purified are than 50 ~ 100:1, eluent is sherwood oil and ethyl acetate, volume ratio 20 ~ 50:1) purified product, obtain colourless 3,5-dimethoxyphenylboronic pinacol ester solid (125mg, 99%), the nuclear magnetic spectrogram of product is identical with the nuclear-magnetism information reported.
Prepare example 2
This example is that milligram rank prepares 3-methyl-5-nitrogen, nitrogen-dimethylphenyl boronic acid pinacol ester, specifically comprise the following steps: under nitrogen environment, a methyl-nitrogen nitrogen dimethyl benzene (67.6mg is added in reaction flask, 0.5mmol), connection pinacol borate (126.9mg, 0.5mmol, formula (5)), 1, 5-cyclooctadiene methoxyl group iridium dimer (3.4mg, 0.005mmol, 1%, formula (6)), part (4.0mg before boranepyridine, 0.01mmol, 2%, formula (1)) and cyclopentyl-methyl ether (1mL, between the reaction density of methyl-nitrogen nitrogen dimethyl benzene be 0.5mol/L), 24h is reacted at 100 DEG C, 2. steaming (20 ~ 40 DEG C) is revolved after having reacted except desolventizing (cyclopentyl-methyl ether), (silica gel of 200 ~ 300 order specifications is used with column chromatography, silica gel and amount to be purified are than 50 ~ 100:1, eluent is sherwood oil and ethyl acetate, volume ratio 20 ~ 50:1) method purified product, obtain colourless 3-methyl-5-nitrogen, nitrogen-dimethylphenyl boronic acid pinacol ester solid (126mg, 96%), the nuclear magnetic spectrogram of product is identical with the nuclear-magnetism information reported.
In example 3 and example 4, the preparation method of aryl-boric acid ester is substantially identical with example 1,2, and just the reaction times is upper different, and difference is see table 1.
Table 1 four kinds of aryl-boric acid esters compare
The aryl boric acid ester cpds obtained by preparation method of the present invention, can be used for the intermediate of synthetic drugs/agricultural chemicals.This preparation method can be used for preparing a lot of above-mentioned similar product, and can realize gram level even feather weight by altering reactor capacity, realizes suitability for industrialized production.
Claims (8)
1. a part before boranepyridine, is characterized in that: before this boranepyridine, part is for having the compound such as formula structure (1) Suo Shi:
2. prepare a method for part before boranepyridine, it is characterized in that: comprise the following steps:
Under nitrogen protection; single pyridine aniline compound and four methylamino-diboranes are reacted 24 ~ 48 hours in 125 ~ 130 DEG C in toluene; the mol ratio of single pyridine aniline compound and four methylamino-diboranes is 2:1 ~ 1.5, pumps toluene and obtain part before boranepyridine under having reacted final vacuum condition.
3. a kind of method preparing part before boranepyridine according to claim 2, is characterized in that: described single pyridine aniline compound is for having the compound such as formula structure (2) Suo Shi:
4. one kind as claimed in claim 1 before boranepyridine part preparing the application in aryl-boric acid ester.
5. prepare a method for aryl-boric acid ester, it is characterized in that: comprise the following steps:
1) under nitrogen protection, react before aryl compound, connection pinacol borate, 1,5-cyclooctadiene methoxyl group iridium dimer, boranepyridine 8 ~ 48 hours in 80 ~ 125 DEG C after part and ether solvent mixing;
2) removing ether solvent is steamed through revolving after having reacted, then aryl-boric acid ester is obtained with column chromatography purification, the reaction density of described aryl compound is 0.5 ~ 2mol/L, the consumption of described pinacol borate is 0.75 ~ 1.5 times of the amount of substance of described aryl compound, described 1, the dimeric consumption of 5-cyclooctadiene methoxyl group iridium is 0.5 ~ 2% of the amount of substance of described aryl compound, before described boranepyridine, the consumption of part is described 1, 2 ~ 3 times of the dimeric amount of substance of 5-cyclooctadiene methoxyl group iridium, before described boranepyridine, part is for having the compound such as formula structure (1) Suo Shi:
6. a kind of method preparing aryl-boric acid ester according to claim 5, is characterized in that: the structure of described aryl-boric acid ester is such as formula shown in (4):
Wherein, R
1and R
3represent alkyl, halogen atom, nitrogen nitrogen dimethyl, methoxyl group, carbonyl, cyano group, thioether or ester group, R
2represent hydrogen atom, alkyl, halogen atom, nitrogen nitrogen dimethyl, methoxyl group, carbonyl, cyano group, thioether or ester group.
7. a kind of method preparing aryl-boric acid ester according to claim 5, is characterized in that: described aryl compound comprises:
8. a kind of method preparing aryl-boric acid ester according to claim 5, it is characterized in that: the condition of described column chromatography is: the silica gel using 200 ~ 300 order specifications, the mass ratio of silica gel and thing to be purified is 50 ~ 100:1, eluent is the mixed solution of sherwood oil and ethyl acetate, mixed solution PetroChina Company Limited. ether: the volume ratio of ethyl acetate is 20 ~ 50:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108483397A (en) * | 2018-04-13 | 2018-09-04 | 河南师范大学 | The method of one pot synthesis synthesis of cyclic boron hydronitrogen aminodiborane |
| CN108948055A (en) * | 2018-07-20 | 2018-12-07 | 青岛大学 | A kind of 8- methylquinoline is together with two boron compounds and preparation method thereof |
| CN110746448A (en) * | 2018-07-24 | 2020-02-04 | 中国科学院兰州化学物理研究所苏州研究院 | Boron-nitrogen ligand of chiral 1, 2-ethylenediamine skeleton and preparation method and application thereof |
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| CN1639171A (en) * | 2002-03-06 | 2005-07-13 | 三菱丽阳株式会社 | Process for production of heteroaryl-type boron compounds with iridium catalyst |
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|---|---|---|---|---|
| CN1639171A (en) * | 2002-03-06 | 2005-07-13 | 三菱丽阳株式会社 | Process for production of heteroaryl-type boron compounds with iridium catalyst |
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