CN102942429A - Method for preparing aza or thia aryl biaryl compound by aid of palladium and carbon catalysts - Google Patents
Method for preparing aza or thia aryl biaryl compound by aid of palladium and carbon catalysts Download PDFInfo
- Publication number
- CN102942429A CN102942429A CN2012104864615A CN201210486461A CN102942429A CN 102942429 A CN102942429 A CN 102942429A CN 2012104864615 A CN2012104864615 A CN 2012104864615A CN 201210486461 A CN201210486461 A CN 201210486461A CN 102942429 A CN102942429 A CN 102942429A
- Authority
- CN
- China
- Prior art keywords
- mmol
- bromo
- air
- boric acid
- round
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
A method for preparing aza or thia aryl biaryl compound by aid of reusable palladium and carbon catalysts in the air belongs to the technical field of the catalytic chemistry and is used for preparing the aza or thia aryl biaryl compound through cross coupling reaction of halogenated aromatic benzoheterocyclic compounds and Suzuki of arylboronic acid. The method is characterized in that halogenated aromatic benzoheterocyclic compounds, arylboronic acid, alkalis and catalysts are filled into 4mL alcohol-water mixed solution as the mole ratio to be 0.5:0.75:1.0: (0.0005-0.0075), are magnetically stirred in the air with reaction temperature to be 50-100 DEG C and react for 5-120min, saturated salt water is filled after the reaction is completed, ethyl acetate is used for extracting reaction products, organic phases are merged, and the analytically pure biaryl compound is obtained after vacuum concentration and column chromatography. The method has the advantages that the palladium and carbon catalysts are inexpensive, easy to obtain and reusable and can be separated from product easily, reaction medium environment is good due to the fact that the reaction is carried out in the air, and the method is simple to operate, fast and efficient and has wide application prospect in the fields such as synthesized natural products, dyestuff, medicines and organic functional materials.
Description
Technical field
The present invention relates to a kind of in air the reusable method for preparing azepine or thia aryl biaryl compound of palladium catalyst, it belongs to the organic compound technical field of catalytic chemistry.
Background technology
Azepine or thia aryl biaryl compound extensively are present in (J. Am. Chem. Soc., 2006,128,16641 in natural product, dyestuff, medicine and the organic functional material; Chem. Commun., 2009,3699; Chem. Mater., 2008,20,6254).The method for preparing azepine or thia aryl biaryl compound of bibliographical information, normally under the protection of rare gas element, use Suzuki cross-coupling reaction (Angew. Chem. Int. Ed., 2005 of the auxiliary homogeneous palladium catalysts catalysis of part, 44,4442; Angew. Chem. Int. Ed., 2006,45,3484; J. Am. Chem. Soc., 2007,129,3358).But the synthetic method of bibliographical information exists still that precious metals palladium catalyst can not reclaim and reuse, part is synthetic numerous and diverse and with high costs and need the deficiency such as inert atmosphere protection.Therefore, development is simply efficient, easy to operate, palladium catalyst can conveniently reclaim and reusable heterogeneous catalysis system prepares azepine or thia aryl biaryl compound has important application prospect.
Palladium carbon (Pd/C) is the most frequently used heterogeneous palladium catalyst, have cheap and easy to get, stable in the air, easily reclaim and the advantage such as reusable, be widely used in the organic synthesis.In recent years, have bibliographical information reacts to prepare azepine or thia aryl biaryl compound with palladium carbon catalysis Suzuki method (Tetrahedron Lett., 1994,35,3277; Eur. J. Org. Chem., 2003,4080; Chem. Commun., 2007,5069; Adv. Synth. Catal., 2010,352,718-730; Chem. Rev., 2011,111,2251).Yet many deficiencies such as the method for bibliographical information still exists needs to use part to air and water sensitive, needs protection of inert gas, catalyst levels is large, long reaction time or versatility are poor.Up to now, the report for preparing azepine or thia aryl biaryl compound there are no palladium carbon catalysis in air without the water Suzuki reaction of part.
Summary of the invention
The Suzuki cross-coupling reaction that the purpose of this invention is to provide a kind of simple to operate, environmental friendliness, efficiently reaches the good palladium carbon catalysis halo heteroaromatic ring compounds that carries out of versatility and aryl boric acid in alcohol-water mixed solution prepares the catalysis novel process of azepine or thia aryl biaryl compound, the used palladium-carbon catalyst of this catalyst system can be by simple filtered and recycled, and can recycle at least 3 times.
Technical scheme of the present invention is: a kind of in air the reusable method for preparing azepine or thia aryl biaryl compound of palladium catalyst, at first, in air, in round-bottomed flask, add successively halo heteroaromatic ring compounds 0.5 mmol, aryl boric acid 0.75 mmol, alkali 1.0 mmol, palladium catalyst carbon 0.0005～0.0075 mmol, then, adding alcohol is solvent 4 mL of 1:1-3:1 with water volume ratio, carried out the Suzuki cross-coupling reaction 5～120 minutes at 50～100 ° of C, reaction process is followed the tracks of by tlc, after question response is complete, stop to stir, add saturated aqueous common salt 15 mL termination reactions, merge organic phase with ethyl acetate 15 ml extractive reaction products 4 times, vacuum concentration makes analytically pure biaryl compound by column chromatography for separation.
Among the above-mentioned preparation method, described solvent is selected from ethanol-water solution or isopropanol-water solution.
Among the above-mentioned preparation method, described alkali is selected from salt of wormwood, yellow soda ash, cesium carbonate or potassiumphosphate.
Among the above-mentioned preparation method, described halo azepine aromatic compound is selected from 2-bromopyridine, 2-bromo-4-picoline, 2-bromo-5-picoline, 2-bromo-5-methoxypyridine, 2-bromo-5-fluorine pyridine, 2-bromo-6-picoline, 2-bromo-6-methoxypyridine, 2-bromo-6-fluorine pyridine, 2-bromo-6-acetylpyridine, 3-bromopyridine, 3-bromo-6-methoxypyridine, 2-bromoquinoline, 3-bromoquinoline, 2-bromothiophene, 3 bromo thiophene, 5-bromo pyrimi piperidine or 2-chloropyrazine.
Among the above-mentioned preparation method, described aryl boric acid is selected from phenylo boric acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 4-bromobenzene boric acid, 3-chlorobenzene boric acid, 4-fluorobenzoic boric acid, 4-(9-carbazyl) phenylo boric acid, N-phenyl-3-carbazole boric acid or 4-triphenylamine boric acid.
The invention has the beneficial effects as follows: this method for preparing azepine or thia aryl biaryl compound does not need protection of inert gas, need not use part or promotor, the reaction medium environmental friendliness, reaction conditions is gentle, substrate is widely applicable, quick and high efficient reaction, the palladium-carbon catalyst consumption is few and recyclable and reuse.The method has a wide range of applications in the fields such as dyestuff, medicine and organic functional material.
Embodiment
The preparation of embodiment 1 2-phenylpyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 30 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 98%.
The preparation of embodiment 2 4-methyl-2-phenylpyridine
In air, take by weighing successively 2-bromo-4-picoline (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 30 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 88%.
The preparation of embodiment 3 5-methyl-2-phenylpyridine
In air, take by weighing successively 2-bromo-5-picoline (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 30 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 98%.
The preparation of embodiment 4 5-methoxyl group-2-phenylpyridine
In air, take by weighing successively 2-bromo-5-methoxypyridine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 20 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 97%.
The preparation of embodiment 5 5-fluoro-2-phenylpyridines
In air, take by weighing successively 2-bromo-5-fluorine pyridine (0.5 mmol), phenylo boric acid (0.75 mmol), potassiumphosphate (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.100 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 15 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 95%.
The preparation of embodiment 6 6-methyl-2-phenylpyridine
In air, take by weighing successively 2-bromo-6-picoline (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 35 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 91%.
The preparation of embodiment 7 6-methoxyl group-2-phenylpyridine
In air, take by weighing successively 2-bromo-6-methoxypyridine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 10 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 99%.
The preparation of embodiment 8 6-fluoro-2-phenylpyridines
In air, take by weighing successively 2-bromo-6-fluorine pyridine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 15 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 94%.
The preparation of embodiment 9 6-ethanoyl-2-phenylpyridine
In air, take by weighing successively 2-bromo-6-acetylpyridine (0.5 mmol), phenylo boric acid (0.75 mmol); salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg); be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 20 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 99%.
Embodiment 10 2-(4-aminomethyl phenyls) preparation of pyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 20 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 98%.
Embodiment 11 2-(3-aminomethyl phenyls) preparation of pyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), meta-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 25 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 99%.
Embodiment 12 2-(2-aminomethyl phenyls) preparation of pyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), ortho-, meta-or p-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, afterreaction was complete in 24 hours.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 90%.
Embodiment 13 2-(4-fluorophenyls) preparation of pyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), p-fluorobenzoic boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, afterreaction was complete in 6 hours.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 92%.
The preparation of embodiment 14 3-phenylpyridines
In air, take by weighing successively 3-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, afterreaction was complete in 2.5 hours.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 90%.
Embodiment 15 3-(4-aminomethyl phenyls) preparation of pyridine
In air, take by weighing successively 3-bromopyridine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, afterreaction was complete in 2 hours.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 91%.
The preparation of embodiment 16 2-methoxyl group-5-phenylpyridine
In air, take by weighing successively 2-methoxyl group-5-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 10 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 93%.
Embodiment 17 2-methoxyl group-5-(4-aminomethyl phenyl) preparation of pyridine
In air, take by weighing successively 2-methoxyl group-5-bromopyridine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 8 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 99%.
Embodiment 18 2-methoxyl group-5-(2-aminomethyl phenyl) preparation of pyridine
In air, take by weighing successively 2-methoxyl group-5-bromopyridine (0.5 mmol), ortho-, meta-or p-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 20 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 96%.
Embodiment 19 2-methoxyl group-5-(4-fluorophenyl) preparation of pyridine
In air, take by weighing successively 2-methoxyl group-5-bromopyridine (0.5 mmol), 4-fluorobenzoic boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 15 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 91%.
The preparation of embodiment 20 5-phenyl pyrimidines
In air, take by weighing successively 5-bromo pyrimi piperidine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 40 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 97%.
Embodiment 21 5-(4-aminomethyl phenyls) preparation of pyrimidine
In air, take by weighing successively 5-bromo pyrimi piperidine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 60 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 93%.
Embodiment 22 5-(4-fluorophenyls) preparation of pyrimidine
In air, take by weighing successively 5-bromo pyrimi piperidine (0.5 mmol), 4-fluorobenzoic boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, afterreaction was complete in 2 hours.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 91%.
The preparation of embodiment 23 2-phenylquinolines
In air, take by weighing successively 2-bromoquinoline (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 15 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 92%.
The preparation of embodiment 24 2-(4-aminomethyl phenyl) quinoline
In air, take by weighing successively 2-bromoquinoline (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 12 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 94%.
The preparation of embodiment 25 2-(4-fluorophenyl) quinoline
In air, take by weighing successively 2-bromoquinoline (0.5 mmol), 4-fluorobenzoic boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, afterreaction was complete in 3 hours.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 90%.
The preparation of embodiment 26 3-phenylquinolines
In air, take by weighing successively 3-bromoquinoline (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 25 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 89%.
The preparation of embodiment 27 2-phenyl thiophene
In air, take by weighing successively 2-bromothiophene (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 20 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 84%.
The preparation of embodiment 28 3-phenyl thiophene
In air, take by weighing successively 3 bromo thiophene (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, afterreaction was complete in 12 hours.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 79%.
The preparation of embodiment 29 2-phenyl pyrazines
In air, take by weighing successively 2-chloropyrazine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, afterreaction was complete in 2 hours.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 82%.
Embodiment 30 2-(4-aminomethyl phenyls) preparation of pyrazine
In air, take by weighing successively 2-chloropyrazine (0.5 mmol), 4-methylphenylboronic acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 90 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 91%.
The preparation of embodiment 31 2-phenylpyridines
In air, take by weighing successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), yellow soda ash (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 120 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 92%.
The preparation of embodiment 32 2-phenylpyridines
In air, take by weighing successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), cesium carbonate (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 60 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 94%.
The preparation of embodiment 33 2-phenylpyridines
In air, take by weighing successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), potassiumphosphate (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 120 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 96%.
The preparation of embodiment 34 2-phenylpyridines
In air, take by weighing successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% isopropanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 60 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 92%.
Embodiment 35 2-[4-(9-carbazyls) phenyl] preparation of pyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), the 4-(9-carbazyl) phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 30 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 95%.
Embodiment 36 2-(9-phenyl-3-carbazyl) preparation of pyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), 9-phenyl-3-carbazyl boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 30 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 96%.
Embodiment 37 2-(4-diphenylamino) preparation of phenylpyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), 4-triphenylamine boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 30 min afterreactions are complete.Stop to stir, add 15 mL saturated aqueous common salt termination reactions, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 93%.
Embodiment 38 2-(4-bromophenyls) preparation of pyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), 4-bromobenzene boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% isopropanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, stopped reaction behind 60 min adds 15 mL saturated aqueous common salts, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 86%.
Embodiment 39 2-(4-chloro-phenyl-s) preparation of pyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), 4-chlorobenzene boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% isopropanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, stopped reaction behind 60 min adds 15 mL saturated aqueous common salts, with ethyl acetate (4 * 15 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product, and product structure passes through
1H NMR,
13C NMR and Mass Spectrometric Identification, its separation yield reaches 84%.
Embodiment 40 palladium-carbon catalysts are reused effect in preparation 2-phenylpyridine
In air, take by weighing successively 2-bromopyridine (0.5 mmol), phenylo boric acid (0.75 mmol), salt of wormwood (1.0 mmol), palladium carbon (5% Pd/C, 16 mg), be transferred in the 25 mL round-bottomed flasks, then, in round-bottomed flask, add 4 mL, 75% ethanol-water solution.80 ° of C magnetic agitation, utilize thin-layer chromatography to follow the tracks of reaction process, 30 min afterreactions are complete, stop to stir, and are cooled to room temperature.Reacting liquid filtering is isolated palladium carbon.Use successively 10 ml ethanol and 10 ml deionized water wash palladium carbon.Filtrate adds 15 mL saturated aqueous common salts, with ethyl acetate (4 * 25 ml) extraction and merging organic phase, anhydrous Mg
2SO
4Drying is filtered, and uses Rotary Evaporators to concentrate and obtains thick product, through column chromatography for separation, obtains analytically pure target product.Palladium carbon after the washing places air, naturally dries.Palladium carbon after drying is used for next time reaction as catalyzer, and the catalyst recirculation result of use is shown in table 1.
Table 1. Pd/C recycles effect
| The catalyzed reaction number of times | For the first time | For the second time | For the third time |
| Product yield (%) | 98 | 95 | 86 |
Above embodiment is the further description of the present invention being done in conjunction with optimal technical scheme, can not assert that implementation of the present invention only limits to these explanations.Concerning the general technical staff of the technical field of the invention, under the prerequisite that does not break away from design of the present invention, can also make simple deduction and replacement, all should be considered as protection scope of the present invention.
Claims (5)
1. reusable method for preparing azepine or thia aryl biaryl compound of palladium catalyst in air, it is characterized in that: at first, in air, in round-bottomed flask, add successively halo heteroaromatic ring compounds 0.5 mmol, aryl boric acid 0.75 mmol, alkali 1.0 mmol, palladium catalyst carbon 0.0005～0.0075 mmol, then, adding alcohol is solvent 4 mL of 1:1-3:1 with water volume ratio, carried out the Suzuki cross-coupling reaction 5～120 minutes at 50～100 ° of C, reaction process is followed the tracks of by tlc, after question response is complete, stop to stir, add saturated aqueous common salt 15 mL termination reactions, merge organic phase with ethyl acetate 15 ml extractive reaction products 4 times, vacuum concentration makes analytically pure biaryl compound by column chromatography for separation.
According to claimed in claim 1 a kind of in air the reusable method for preparing azepine or thia aryl biaryl compound of palladium catalyst, it is characterized in that: described solvent is selected from ethanol-water solution or isopropanol-water solution.
According to claimed in claim 1 a kind of in air the reusable method for preparing azepine or thia aryl biaryl compound of palladium catalyst, it is characterized in that: described alkali is selected from salt of wormwood, yellow soda ash, cesium carbonate or potassiumphosphate.
According to claimed in claim 1 a kind of in air the reusable method for preparing azepine or thia aryl biaryl compound of palladium catalyst, it is characterized in that: described halo heteroaromatic ring compounds is selected from the 2-bromopyridine; 2-bromo-4-picoline; 2-bromo-5-picoline; 2-bromo-5-methoxypyridine; 2-bromo-5-fluorine pyridine; 2-bromo-6-picoline; 2-bromo-6-methoxypyridine; 2-bromo-6-fluorine pyridine; 2-bromo-6-acetylpyridine; the 3-bromopyridine; 3-bromo-6-methoxypyridine; the 2-bromoquinoline; the 3-bromoquinoline; the 2-bromothiophene; 3 bromo thiophene; 5-bromo pyrimi piperidine or 2-chloropyrazine.
According to claimed in claim 1 a kind of in air the reusable method for preparing azepine or thia aryl biaryl compound of palladium catalyst, it is characterized in that: described aryl boric acid is selected from phenylo boric acid, 2-methylphenylboronic acid, 3-methylphenylboronic acid, 4-methylphenylboronic acid, 4-bromobenzene boric acid, 3-chlorobenzene boric acid, 4-fluorobenzoic boric acid, 4-(9-carbazyl) phenylo boric acid, N-phenyl-3-carbazole boric acid or 4-triphenylamine boric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104864615A CN102942429A (en) | 2012-11-26 | 2012-11-26 | Method for preparing aza or thia aryl biaryl compound by aid of palladium and carbon catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104864615A CN102942429A (en) | 2012-11-26 | 2012-11-26 | Method for preparing aza or thia aryl biaryl compound by aid of palladium and carbon catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102942429A true CN102942429A (en) | 2013-02-27 |
Family
ID=47725450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012104864615A Pending CN102942429A (en) | 2012-11-26 | 2012-11-26 | Method for preparing aza or thia aryl biaryl compound by aid of palladium and carbon catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102942429A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058908A (en) * | 2014-07-02 | 2014-09-24 | 魏建华 | Olefin typed coupling reaction method for naphthene typed compounds |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136157A (en) * | 1996-05-14 | 2000-10-24 | Labwell Ab | Method for organic reactions |
| WO2001066248A2 (en) * | 2000-02-22 | 2001-09-13 | University Of New Orleans Research And Technology Foundation | C-c and c-n coupling catalyst comprising transition metal and carbene |
| US20040029714A1 (en) * | 2000-06-26 | 2004-02-12 | Parlevliet Floris Jacobus | Process for regenerating pd catalysts |
| CN101643378A (en) * | 2009-09-02 | 2010-02-10 | 中国农业大学 | Method for synthesizing aryl-linking compound |
-
2012
- 2012-11-26 CN CN2012104864615A patent/CN102942429A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136157A (en) * | 1996-05-14 | 2000-10-24 | Labwell Ab | Method for organic reactions |
| WO2001066248A2 (en) * | 2000-02-22 | 2001-09-13 | University Of New Orleans Research And Technology Foundation | C-c and c-n coupling catalyst comprising transition metal and carbene |
| US20040029714A1 (en) * | 2000-06-26 | 2004-02-12 | Parlevliet Floris Jacobus | Process for regenerating pd catalysts |
| CN101643378A (en) * | 2009-09-02 | 2010-02-10 | 中国农业大学 | Method for synthesizing aryl-linking compound |
Non-Patent Citations (2)
| Title |
|---|
| ANTONIO ARCADI等: "A Mild and Versatile Method for Palladium-Catalyzed Cross-Coupling of Aryl Halides in Water and Surfactants", 《EUR. J. ORG. CHEM.》 * |
| 袁艳琴等: "双水相体系中Pd /C催化Suzuki偶联反应的研究", 《化学试剂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058908A (en) * | 2014-07-02 | 2014-09-24 | 魏建华 | Olefin typed coupling reaction method for naphthene typed compounds |
| CN104058908B (en) * | 2014-07-02 | 2015-12-30 | 魏建华 | A kind of Olefination linked reaction method of naphthenic compounds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Cobalt-catalyzed cross-dehydrogenative coupling reactions of (benz) oxazoles with ethers | |
| Kowsari et al. | Ultrasound promoted synthesis of quinolines using basic ionic liquids in aqueous media as a green procedure | |
| Tu et al. | A robust hydrophilic pyridine-bridged bis-benzimidazolylidene palladium pincer complex: Synthesis and its catalytic application towards Suzuki–Miyaura couplings in aqueous solvents | |
| Roopan et al. | Fe nano particles mediated C–N bond-forming reaction: Regioselective synthesis of 3-[(2-chloroquinolin-3-yl) methyl] pyrimidin-4 (3H) ones | |
| Liu et al. | Palladium-catalyzed ligand-free and aqueous Suzuki reaction for the construction of (hetero) aryl-substituted triphenylamine derivatives | |
| Sarkar et al. | A novel recyclable organocatalytic system for the highly asymmetric Michael addition of aldehydes to nitroolefins in water | |
| Fu et al. | An efficient, eco-friendly and sustainable tandem oxidative amidation of alcohols with amines catalyzed by heteropolyanion-based ionic liquids via a bifunctional catalysis process | |
| CN105801595A (en) | Method for catalytically preparing 4,5-dihydropyran[c]chromene derivative | |
| CN102659662A (en) | A synthetic method of 3-R-3-hydroxy-2-oxindole compound | |
| CN101638352B (en) | Aryl-replaced nitrogen heterocyclic compound preparation method | |
| CN111229311A (en) | Supported imidazole ionic liquid catalyst and method for synthesizing 2-amino-3-cyano-4H-pyran compounds | |
| Dong et al. | Knoevenagel condensation catalysed by poly (vinyl chloride) supported tetraethylenepentamine (PVC-TEPA) | |
| CN103408573B (en) | Boric acid derivatives and its preparation method and application | |
| CN102942429A (en) | Method for preparing aza or thia aryl biaryl compound by aid of palladium and carbon catalysts | |
| CN102964190A (en) | Method for preparing biaryl compounds in pure water | |
| CN101948366A (en) | Method for preparing 4-(diphenylamino)biaryl compound in water phase | |
| Li et al. | Water‐Soluble and Recyclable Cyclopalladated Ferrocenylimine for Suzuki Coupling Reaction | |
| CN107501118B (en) | The synthetic method of N- substitution Carbox amide | |
| CN101768036B (en) | Method for preparing heterocyclic aromatic compound replaced by aryl in alcohol solvent | |
| CN105732518B (en) | A kind of method that trisulfonic acid radical ion liquid catalyst prepares pyrimidone derivatives | |
| CN101792414B (en) | Method for preparing 2-(3'-quinolyl) propenol | |
| CN102491968A (en) | Method for preparing carbazolyl biaryl compound in aqueous phase | |
| Liu et al. | Amide as an efficient ligand in the palladium-catalyzed Suzuki coupling reaction in water/ethanol under aerobic conditions | |
| CN105294776A (en) | Method for preparing symmetric dimer of nitrogen heterocyclic ring aromatic compound | |
| CN111777564A (en) | Method for synthesizing quinazolinone compound through photocatalytic alcohol oxidation in aqueous phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130227 |