CN101768036B - Method for preparing heterocyclic aromatic compound replaced by aryl in alcohol solvent - Google Patents
Method for preparing heterocyclic aromatic compound replaced by aryl in alcohol solvent Download PDFInfo
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Abstract
The invention provides a method for preparing a heterocyclic aromatic compound replaced by aryl in an alcohol solvent, belonging to the technical field of catalytic chemistry. The method utilizes Suzuki crossed coupling reaction between a halogenated heterocyclic aromatic compound and aryl boric acid to prepare the heterocyclic aromatic compound replaced by the aryl. The halogenated heterocyclic aromatic compound, the aryl boric acid, alkali and a catalyst are added into glycol or polyethylene glycol (2 to 4mL) according to the molar ratio of 0.5:0.75:1.0:0.00025 to 0.0025; reaction is carried out for 5 to 300 minutes in air under the temperature of 80 DEG C; saturated salt solution is added after the reaction is finished, reaction products are extracted by ethyl acetate, organic phases are merged, drying and filtering are carried out by anhydrous Na2SO4, and then filtering solution is concentrated and separated by column chromatography, so as to obtain the pure heterocyclic aromatic compound replaced by the aryl. The method has the following characteristics: a ligand, a phase transferring agent or an accelerating agent does not need to be added; the protection of inert gases is not needed; the method is friendly to the environment; the using quantity of the palladium catalyst is small, the reaction is quick, the yield is high, and the product separation is simple.
Description
Technical field
The present invention relates to a kind of method of the azepine aromatic compound that the preparation aryl replaces in alcoholic solvent, it belongs to the organic compound technical field of catalytic chemistry.
Background technology
The nitrogen heterocyclic that aryl replaces extensively is present in (Chem. Commun. 2009,3699 in natural product, medicine and multiple organic functional material; Chem. Mater., 2008,20,6254; J. Am. Chem. Soc., 2006,128,16641).The Suzuki linked reaction of palladium catalysis is to form one of the effective means of aryl-azepine aromatic ring structure (Chem. Rev. 1995,95,2457).So far, the method of the azepine aromatic compound that the preparation aryl of bibliographical information replaces generally need to be with promoting air and water sensitive, synthetic difficulty, expensive phosphine part, and the reaction times is grown (Angew. Chem. Int. Ed., 2008,47,4695; Angew. Chem. Int. Ed., 2008,47,928; J. Am. Chem. Soc., 2007,129,3358; Angew. Chem. Int. Ed. 2002,41,23,4500-4503; Org. Lett., 2009,11,345; Org. Lett., 2009,11,381).Thereby development is simple, cheap, preparation method that efficiently reach general aryl substituted nitrogen heterocyclic aromatic compound has the important application prospect.
In recent years, bibliographical information aqueous phase do not need the Suzuki reaction system that part promotes to prepare azepine aromatic compound (Chem. Commun., 2009,6267 that aryl replaces; Eur. J. Org. Chem., 2009,110; Green Chem., 2008,10,868; Chem. Commun., 2007,5069).Yet the method for bibliographical information exists still that catalyst levels is large, reactive behavior is low, long reaction time or the deficiency such as versatility is poor.Have no so far and report that need not part promotes efficiently to activate the universal method that halo azepine aromatic compound is used for Suzuki reaction preparation aryl substituted nitrogen heterocyclic aromatic derivatives.
Summary of the invention
The Suzuki cross-coupling reaction that the purpose of this invention is to provide a kind of simple to operate, cheap, high reactivity and the general palladium catalysis halo azepine aromatic compound that carries out and aryl boric acid in ethylene glycol or two polyoxyethylene glycol prepares the catalysis novel process of the azepine aromatic compound that aryl replaces.
Technical scheme of the present invention is: a kind of method of the azepine aromatic compound that the preparation aryl replaces in alcoholic solvent: in air, at first add 2.0～4.0 mL ethylene glycol or two polyoxyethylene glycol in round-bottomed flask, then add successively 0.00025～0.0025 mmol palladium catalyst, 1.0 mmol alkali, 0.5 mmol halo azepine aromatic compound, 0.75 mmol aryl boric acid, stir at 80 ° of C and carried out the Suzuki cross-coupling reaction 5～300 minutes, after reaction finishes, with 15 ml * 3 ethyl acetate extraction reaction product, merge organic phase, use anhydrous Na
2SO
4Drying is filtered, and filtrate is concentrated, uses column chromatography, and makes the azepine aromatic compound that analytically pure aryl replaces.
In above-mentioned preparation method, described palladium catalyst is selected from palladium or Palladous chloride.
In above-mentioned preparation method, described alkali is selected from potassiumphosphate, sodium hydroxide or potassium hydroxide.
In above-mentioned preparation method, described halo nitrogen heterocyclic is selected from 2-bromopyridine, 2-bromo-5-fluorine pyridine, 2-bromo-5-picoline, 2-bromo-6-picoline, 2-bromo-6-nitropyridine, 3-bromopyridine, 2-amino-3-bromo-5-picoline, 2-amino-5-bromopyridine, 3-bromo-6-methoxypyridine, 2-chlorine piperazine, 3-bromo-quinoline, 2-amino-5-bromo pyrimi piperidine or 5-bromo pyrimi piperidine.
In above-mentioned preparation method, described aryl boric acid is selected from phenylo boric acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2-methoxyphenylboronic acid, 3-methoxyphenylboronic acid, 4-methoxyphenylboronic acid, 4-fluorobenzoic boric acid or 4-chlorobenzene boric acid.
The invention has the beneficial effects as follows: the preparation method of the azepine aromatic compound that this aryl replaces does not use part or promotor, does not need protection of inert gas, reaction medium environmental friendliness, reaction under mild conditions, palladium catalyst consumption are few; substrate is widely applicable; reaction fast, yield is high, product separation is simple, has a wide range of applications at aspects such as synthesizing of natural product, medicine, agricultural chemicals, weedicide and polymer conductive material, liquid crystal material.
Embodiment
The preparation of embodiment 1 2-phenylpyridine
In air, take successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 30 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
The preparation of embodiment 2 2-phenylpyridines
In air, take successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), sodium hydroxide (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 30 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
The preparation of embodiment 3 2-phenylpyridines
In air, take successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassium hydroxide (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 30 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 96%.
The preparation of embodiment 4 2-phenylpyridines
In air, take successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), Palladous chloride (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 30 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 95%.
The preparation of embodiment 5 2-phenylpyridines
In air, take successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL two polyoxyethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 15 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
The preparation of embodiment 6 2-(4-aminomethyl phenyl) pyridine
In air, take successively 2-bromopyridine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 4 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 30 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
The preparation of embodiment 7 2-(2-aminomethyl phenyl) pyridine
In air, take successively 2-bromopyridine (0.5 mmol), 2-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 60 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 94%.
The preparation of embodiment 8 2-(4-p-methoxy-phenyl) pyridine
In air, take successively 2-bromopyridine (0.5 mmol), 4-methoxyphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 40 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
The preparation of embodiment 9 2-(4-fluorophenyl) pyridine
In air, take successively 2-bromopyridine (0.5 mmol), 4-fluorobenzoic boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 20 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
The preparation of embodiment 10 2-(4-chloro-phenyl-) pyridine
In air, take successively 2-bromopyridine (0.5 mmol), 4-chlorobenzene boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 30 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 96%.
The preparation of embodiment 11 2-(4-aminomethyl phenyl)-5-fluorine pyridine
In air, take successively 2-bromo-5-fluorine pyridine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 10 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 96%.
The preparation of embodiment 12 2-methyl-6-phenylpyridines
In air, take successively 2-bromo-6-picoline (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 20 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 92%.
Embodiment 13 2-methyl-6-(4-methyl) preparation of phenylpyridine
In air, take successively 2-bromo-6-picoline (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 15 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 91%.
The preparation of embodiment 14 2-phenyl-5-picolines
In air, take successively 2-bromo-5-picoline (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 35 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
Embodiment 15 2-(4-methyl) preparation of phenyl-5-picoline
In air, take successively 2-bromo-5-picoline (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 60 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 94%.
The preparation of embodiment 16 2-phenyl-5-nitropyridines
In air, take successively 2-bromo-5-nitropyridine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 20 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/49), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
The preparation of embodiment 17 3-phenylpyridines
In air, take successively 3-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 15 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
Embodiment 18 3-(4-methyl) preparation of phenylpyridine
In air, take successively 3-bromopyridine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 15 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
Embodiment 19 3-(3-methyl) preparation of phenylpyridine
In air, take successively 3-bromopyridine (0.5 mmol), 3-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 10 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
Embodiment 20 3-(2-methyl) preparation of phenylpyridine
In air, take successively 3-bromopyridine (0.5 mmol), 2-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 180 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 96%.
Embodiment 21 3-(4-fluorine) preparation of phenylpyridine
In air, take successively 3-bromopyridine (0.5 mmol), 4-fluorobenzoic boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 30 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 96%.
The preparation of embodiment 22 2-amino-3-phenyl-5-picoline
In air, take successively 2-amino-3-bromo-5-picoline (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 240 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 93%.
The preparation of embodiment 23 2-amino-5-phenyl pyridines
In air, take successively 2-amino-5-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL two polyoxyethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 180 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 96%.
The preparation of embodiment 24 2-methoxyl group-5-phenylpyridines
In air, take successively 2-methoxyl group-5-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.00025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 5 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
Embodiment 25 2-methoxyl group-5-(4-fluorophenyls) preparation of pyridine
In air, take successively 2-methoxyl group-5-bromopyridine (0.5 mmol), 4-fluorobenzoic boric acid (0.75 mmol), palladium (0.00025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 12 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
Embodiment 26 2-methoxyl group-5-(2-methyl) preparation of phenylpyridine
In air, take successively 2-methoxyl group-5-bromopyridine (0.5 mmol), 2-methylphenylboronic acid (0.75 mmol), palladium (0.00025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 25 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 96%.
Embodiment 27 2-methoxyl group-5-(4-methoxyl groups) preparation of phenylpyridine
In air, take successively 2-methoxyl group-5-bromopyridine (0.5 mmol), 4-methoxyphenylboronic acid (0.75 mmol), palladium (0.00025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 40 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
Embodiment 28 2-methoxyl group-5-(3-methyl) preparation of phenylpyridine
In air, take successively 2-methoxyl group-5-bromopyridine (0.5 mmol), 3-methylphenylboronic acid (0.75 mmol), palladium (0.00025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 25 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/5), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 95%.
The preparation of embodiment 29 5-phenyl pyrimidines
In air, take successively 5-bromo pyrimi piperidine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0005 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 20 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/20), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
Embodiment 30 5-(4-methyl) preparation of phenyl pyrimidine
In air, take successively 5-bromo pyrimi piperidine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), palladium (0.0005 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 7 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/20), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
Embodiment 31 5-(4-fluorine) preparation of phenyl pyrimidine
In air, take successively 5-bromo pyrimi piperidine (0.5 mmol), 4-fluorobenzoic boric acid (0.75 mmol), palladium (0.0005 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 30 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/20), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 98%.
The preparation of embodiment 32 2-amino-5-phenyl pyrimidines
In air, take successively 2-amino-5-bromo pyrimi piperidine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 7 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1.5/1), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 99%.
The preparation of embodiment 33 3-phenylquinolines
In air, take successively 3-bromoquinoline (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 25 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/20), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 93%.
Embodiment 34 3-(2-methyl) preparation of phenylquinoline
In air, take successively 3-bromoquinoline (0.5 mmol), 2-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 85 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/20), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 80%.
The preparation of embodiment 35 2-phenyl pyrazines
In air, take successively 2-chloropyrazine (0.5 mmol), phenylo boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 45 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/20), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 94%.
Embodiment 36 2-(4-methyl) preparation of phenyl pyrazines
In air, take successively 2-chloropyrazine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 20 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/20), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 94%.
Embodiment 37 2-(4-fluorine) preparation of phenyl pyrazines
In air, take successively 2-chloropyrazine (0.5 mmol), 4-fluorobenzoic boric acid (0.75 mmol), palladium (0.0025 mmol), potassiumphosphate (1.0 mmol) also is transferred in 25 mL round-bottomed flasks, with adding 2 mL ethylene glycol in backward 25 mL round-bottomed flasks.At 80 ° of C lower magnetic force stirring reaction 95 min, thin-layer chromatography is followed the tracks of reaction.Add 15 mL saturated aqueous common salts after reaction finishes and with ethyl acetate (15 mL * 3) extractive reaction product, merge organic phase, anhydrous Na
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate to get thick product, and column chromatography obtains target product, and the elutriant that column chromatography is used is ethyl acetate/petroleum ether (V/V=1/20), and product structure passes through
1H NMR and Mass Spectrometric Identification.Separation yield reaches 88%.
Claims (5)
1. the method for the azepine aromatic compound that the preparation aryl replaces in alcoholic solvent, it is characterized in that: in air, at first add 2.0～4.0 mL ethylene glycol or two polyoxyethylene glycol in round-bottomed flask, then add successively 0.00025～0.0025 mmol palladium catalyst, 1.0 mmol alkali, 0.5 mmol halo azepine aromatic compound, 0.75 mmol aryl boric acid, stir at 80 ° of C and carried out the Suzuki cross-coupling reaction 5～300 minutes, after reaction finishes, with 15 ml * 3 ethyl acetate extraction reaction product, merge organic phase, use anhydrous Na
2SO
4Drying is filtered, and filtrate is concentrated, uses column chromatography, and makes the azepine aromatic compound that analytically pure aryl replaces.
2. according to the method for a kind of azepine aromatic compound that the preparation aryl replaces in alcoholic solvent claimed in claim 1, it is characterized in that: described palladium catalyst is selected from palladium or Palladous chloride.
3. according to the method for a kind of azepine aromatic compound that the preparation aryl replaces in alcoholic solvent claimed in claim 1, it is characterized in that: described alkali is selected from potassiumphosphate, sodium hydroxide or potassium hydroxide.
4. according to the method for a kind of azepine aromatic compound that the preparation aryl replaces in alcoholic solvent claimed in claim 1, it is characterized in that: described halo azepine aromatic compound is selected from 2-bromopyridine, 2-bromo-5-fluorine pyridine, 2-bromo-5-picoline, 2-bromo-6-picoline, 2-bromo-6-nitropyridine, 3-bromopyridine, 2-amino-3-bromo-5-picoline, 2-amino-5-bromopyridine, 3-bromo-6-methoxypyridine, 2-chlorine piperazine, 3-bromo-quinoline, 2-amino-5-bromo pyrimi piperidine or 5-bromo pyrimi piperidine.
5. according to the method for a kind of azepine aromatic compound that the preparation aryl replaces in alcoholic solvent claimed in claim 1, it is characterized in that: described aryl boric acid is selected from phenylo boric acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 2-methoxyphenylboronic acid, 3-methoxyphenylboronic acid, 4-methoxyphenylboronic acid, 4-fluorobenzoic boric acid or 4-chlorobenzene boric acid.
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