CN102060790B - Quinoxaline double N-oxide derivative ligand and application thereof in promotion on copper-catalyzed C-O coupling reaction - Google Patents
Quinoxaline double N-oxide derivative ligand and application thereof in promotion on copper-catalyzed C-O coupling reaction Download PDFInfo
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Abstract
The invention discloses a quinoxaline double N-oxide derivative ligand for promoting a copper-catalyzed C-O coupling reaction and application thereof. The novel quinoxaline double N-oxide derivative ligand is characterized by comprising hetero atoms (O or N and the like), wherein the hetero atoms can be coordinated with copper ions to form a transitional hexatomic ring. The ligand can promote the coupling reaction between aryl iodide, aryl bromide or aryl chloride and a phenolic compound. A cheap catalyst system provided by the invention has excellent reaction selectivity and a higher reaction yield coefficient.
Description
Technical field
The present invention relates to a kind of Novel Ligands, specifically a kind of quinoxaline is two
N-oxide derivative part and in the application that promotes copper catalysis C-O linked reaction under the room temperature.
Background technology
Two aryl oxides are prevalent in various natural products, polymer and the pharmaceutical active compounds
[1,2]Because traditional Liv Ullmann etherification reaction needs higher temperature of reaction (125-220 ℃), the copper catalyst of stoichiometry and long reaction times, and yield is lower, and therefore in recent years many explorations are directly, efficiently the research of synthetic two aryl oxides is risen gradually
[3]Adopt the transition metal such as palladium, copper and iron in the C-O linked reaction, to obtain comparatively desirable effect as catalyzer
[4-6]Because palladium catalyst is expensive and higher to air and humidity requirement, so the palladium catalysis method is only used in small-scale production.Copper catalysis Liv Ullmann virtue halogen and phenol/pure linked reaction are used to substitute palladium and catalyze and synthesize the reaction of two aryl oxides.Recently, report is arranged with 1-naphthoic acid, 1,10-phenanthrolene, neocuproine, triphenylphosphine, 2,2,6,6-tetramethyl--3,5-heptadione, tetraethyl orthosilicate,
N, N-two sarcosines, diimide ligand,
β-ketone ester and dipyridyl etc. are as the part of copper catalysis Liv Ullmann linked reaction.But these parts have, and price is high, reaction times bench shortcoming.Therefore, extremely be necessary to develop more efficient, general, gentle part to improve efficient and the suitability of copper catalysis C-O linked reaction under relative mild conditions.
Reference
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Summary of the invention
The object of the invention is to solve the above problems and provide a kind of quinoxaline two
N-oxide derivative part and in the application that promotes copper catalysis C-O linked reaction under the room temperature.The catalyst system of this cheapness has preferably reaction preference and higher reaction yield.
Technical scheme of the present invention
A kind of quinoxaline provided by the invention is two
N-oxide derivative part has all comprised heteroatoms (O or N etc.), can coordinate to form with cupric ion the six-ring of a transition.The coordination of part and metal center is the most important factor that determines whole catalyst system efficient.
A kind of quinoxaline provided by the invention is two
N-oxide derivative part, said quinoxaline is two
N-oxide derivative part can be represented by following logical formula I:
Ⅰ
Wherein:
R
1Be selected from hydrogen, halogen, hydroxyl, C
1-C
6Saturated or the unsaturated C of alkoxyl group, straight or branched
1-C
6Alkyl;
R
2Be selected from hydrogen, hydroxyl, C
1-C
6Saturated or the unsaturated C of alkoxyl group, straight or branched
1-C
6Alkyl, carbalkoxy;
R
3-R
6Be selected from independently of one another hydrogen, halogen, hydroxyl, C
1-C
6Saturated or the unsaturated C of alkoxyl group, straight or branched
1-C
6Alkyl, R
3-R
6Can be identical or different;
A preferred embodiment of above-mentioned part is:
R
1It is hydroxyl;
R
2It is methoxycarbonyl;
R
3-R
6Hydrogen.
Another preferred embodiment of above-mentioned part is:
R
1It is hydroxyl;
R
2It is ethoxycarbonyl;
R
3-R
6Hydrogen.
Above-mentioned a kind of quinoxaline is two
N-oxide derivative part is in the application that promotes copper catalysis C-O linked reaction under the room temperature, namely in room temperature or than under the mild temperature, in non-proton property polar solvent, take mantoquita as catalyzer, and adds mineral alkali reagent and described quinoxaline is two
NIn-oxide derivative part the situation, aryl halide is the linked reaction of aryl iodide, aromatic bromide or aryl chloride compound and phenolic compound.
Described non-proton property polar solvent is the DMF(dimethyl formamide), the DMSO(dimethyl sulfoxide (DMSO)), toluene, CH
3CN is preferably DMF.
Described mantoquita is CuI, CuBr
2, CuCl
22H
2O, CuCl and CuBr are preferably CuI, and consumption is 10mol%.
Described mineral alkali reagent is Cs
2CO
3, K
2CO
3, K
3PO
4, NaOtBu?, KOH and CsOH are preferably Cs
2CO
3
Wherein, the volume mol ratio of non-proton property polar solvent solvent, part, catalyzer mantoquita, mineral alkali reagent, aryl halide and phenols, i.e. solvent: part: catalyzer: mineral alkali reagent: aryl halide: phenols is preferably 1.5ml:0.2mmol:0.1mmol:2.5mmol:1.0mmol:1.1mmol.
Beneficial effect of the present invention
It is two that the present invention discloses a kind of quinoxaline
N-oxide derivative part and in the application that promotes copper catalysis C-O linked reaction under the room temperature.It is characterized in that this Novel Ligands has all comprised heteroatoms (O or N etc.), can coordinate to form with cupric ion the six-ring of a transition.Can promote the linked reaction of aryl iodide under the room temperature, aromatic bromide or aryl chloride compound and phenolic compound.This cheap catalyzing system provided by the invention has outstanding reaction preference and higher reaction yield.
Description of drawings
Fig. 1, quinoxaline are two
N-oxide derivative ligand structure general formula.
Embodiment
Below by embodiment the present invention is further set forth, but do not limit the present invention.
First part The C-O linked reaction of aryl iodide (embodiment 1-14)
Embodiment 1
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of phenyl ether
The structural formula of phenyl ether is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is iodobenzene;
Phenols is phenol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add iodobenzene (0.112 mL, 1.0 mmol), phenol (0.134 mL, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains the colourless oily mater phenyl ether take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography, yield 90%.
1H?NMR?(400MHz,?CDCl
3):?δ?7.36-7.32?(m,?4H),?7.12-7.08?(m,?2H),?7.02-7.00?(m,?4H)?ppm。
Embodiment 2
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2-phenoxy group naphthalene
The structural formula of 2-phenoxy group naphthalene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is iodobenzene;
Phenols is naphthalene-2-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add iodobenzene (0.112 mL, 1.0 mmol), naphthalene-2-alcohol (216.3 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains white solid 2-phenoxy group naphthalene, yield 83% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.36-7.32?(m,?4H),?7.12-7.08?(m,?2H),?7.02-7.00?(m,?4H)?ppm.1H?NMR?(400MHz,?CDCl3):?δ?7.86-7.82?(m,?2H),?7.72-7.70?(m,?1H),?7.48-7.26?(m,?6H),?7.17-7.14?(m,?1H),?7.10-7.08?(m,?2H)?ppm。
Embodiment 3
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
NThe application of-(4-Phenoxyphenyl) ethanamide
NThe structural formula of-(4-Phenoxyphenyl) ethanamide is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is iodobenzene;
Phenols is
N-(4-hydroxyphenyl phenyl) ethanamide;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add iodobenzene (0.112 mL, 1.0 mmol),
N-(4-hydroxyphenyl phenyl) ethanamide (226.7 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 15h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains brown solid take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography
N-(4-Phenoxyphenyl) ethanamide, yield 74%.
1H?NMR?(400MHz,?CDCl
3):?δ?7.92?(br?s,?1H),?7.48-7.45?(m,?2H),?7.32-7.28?(m,?2H),?7.08-7.07?(m,?1H),?6.97-6.94?(m,?4H),?2.15?(s,?3H)?ppm
Embodiment 4
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-methoxyl group-4-phenyl ether
The structural formula of 1-methoxyl group-4-phenyl ether is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is iodobenzene;
Phenols is the 4-mequinol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add iodobenzene (0.112 mL, 1.0 mmol), 4-mequinol (186.2 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 15h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily liquid 1-methoxyl group-4-phenyl ether, yield 99% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.34-7.30?(m,?2H),?7.09-7.05?(m,?1H),?7.03-6.97?(m,?4H),?6.93-6.90?(m,?2H),?3.82?(s,?3H)?ppm。
Embodiment 5
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-methyl 4-phenyl ether
The structural formula of 1-methyl 4-phenyl ether is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-4-toluene;
Phenols is phenol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-4-toluene (141.2 mg, 1.0 mmol), phenol (0.134 mL, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily liquid 1-methyl 4-phenyl ether, yield 72% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.35-7.31?(m,?2H),?7.17-7.15?(m,?2H),?7.10-7.07?(m,?1H),?7.01-6.99?(m,?2H),?6.95-6.93?(m,?2H),?2.35?(s,?3H)?ppm。
Embodiment 6
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
NThe application of-(4-(p-tolyloxy) phenyl) ethanamide
NThe structural formula of-(4-(p-tolyloxy) phenyl) ethanamide is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-4-toluene;
Phenols is
N-(4-hydroxyphenyl) ethanamide;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-4-toluene (141.2 mg, 1.0 mmol),
N-(4-hydroxyphenyl) ethanamide (226.7 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 15h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains brown solid take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography
N-(4-(p-tolyloxy) phenyl) ethanamide, yield 61%.
1H?NMR?(400MHz,?CDCl
3):?δ?7.58?(br?s,?1H),?7.42?(dt,?J?=7.2,?2.0?Hz,?2H),?7.11?(d,?J?=8.0?Hz,?2H),?6.93?(dt,?J?=?7.2,?2.0?Hz,?2H),?6.87?(d,?J?=8.4?Hz,?2H),?2.32?(s,?3H),?2.15?(s,?3H)?ppm。
Embodiment 7
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2-(p-tolyloxy) naphthalene
The structural formula of 2-(p-tolyloxy) naphthalene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-4-toluene;
Phenols is naphthalene-2-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-4-toluene (141.2 mg, 1.0 mmol), naphthalene-2-alcohol (216.3 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 10h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains brown solid 2-(p-tolyloxy) naphthalene, yield 60% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.84-7.81?(m,?2H),?7.70-7.68?(m,?1H),?7.47-7.39?(m,?2H),?7.28-7.25?(m,?2H),?7.20-7.17?(m,?2H),?7.01-6.98?(m,?2H),?2.37?(s,?3H)?ppm。
Embodiment 8
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
NThe application of-(4-(p-tolyloxy) phenyl) ethanamide
NThe structural formula of-(4-(p-tolyloxy) phenyl) ethanamide is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-4-toluene;
Phenols is
N-(4-hydroxyphenyl) ethanamide;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-4-toluene (141.2 mg, 1.0 mmol),
N-(4-hydroxyphenyl) ethanamide (226.7 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 15h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains white solid take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography
N-(4-(p-tolyloxy) phenyl) ethanamide, yield 61%.
1H?NMR?(400MHz,?CDCl
3):?δ?7.42?(d,?J?=?8.8?Hz,?2H),?7.37?(br?s,?1H),?7.11?(d,?J?=?8.0?Hz,?2H),?6.93?(d,?J?=?8.8?Hz,?2H),?6.88?(d,?J?=?8.8?Hz,?2H),?2.32?(s,?3H),?2.16?(s,?3H)?ppm。
Embodiment 9
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
NThe application of-(4-(3,5-dimethyl phenoxy) phenyl) ethanamide
NThe structural formula of-(4-(3,5-dimethyl phenoxy) phenyl) ethanamide is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-3, the 5-3,5-dimethylphenyl;
Phenols is
N-(4-hydroxyphenyl) ethanamide;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-3,5-3,5-dimethylphenyl (0.145 mL, 1.0 mmol),
N-(4-hydroxyphenyl) ethanamide (226.7 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 20h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains light yellow oil matter take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography
N-(4-(3,5-dimethyl phenoxy) phenyl) ethanamide, yield 60%.
1H?NMR?(400MHz,?CDCl
3):?δ?7.44?(d,?J?=8.8?Hz,?2H),?6.95?(d,?J?=8.8?Hz,?2H),?6.72?(s,?1H),?6.59?(s,?2H),?2.27?(s,?6H),?2.17?(s,?3H)?ppm。
Embodiment 10
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
NThe application of-(4-(3,5-dimethyl phenoxy) phenyl) ethanamide
NThe structural formula of-(4-(3,5-dimethyl phenoxy) phenyl) ethanamide is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-3, the 5-dimethyl benzene;
Phenols is naphthalene-2-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-3,5-dimethyl benzene (0.145 mL, 1.0 mmol), naphthalene-2-alcohol (216.3 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 5h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains transparent oily mater take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography
N-(4-(3,5-dimethyl phenoxy) phenyl) ethanamide, yield 95%.
1H?NMR?(400MHz,?CDCl
3):?δ?8.40?(dt,?J?=9.2,?2.8?Hz,?2H),?7.73-7.65?(m,?4H),?7.38?(d,?J?=?3.6?Hz,?1H),?7.33-7.29?(m,?1H),?7.27-7.23?(m,?1H),?6.78?(dd,?J?=?3.4,?0.8?Hz,?1H)?ppm.?13C?NMR?(125?MHz,?CDCl3):?δ?157.3,?155.5,?139.7,?134.5,?130.2,?129.8,?127.8,?127.2,?126.5,?125.3,?124.6,?120.2,?116.9,?114.2,?21.3?ppm。
Embodiment 11
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-nitro-4-phenyl ether
The structural formula of 1-nitro-4-phenyl ether is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-4-oil of mirbane;
Phenols is phenol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-4-oil of mirbane (249 mg, 1.0 mmol), phenol (0.134 mL, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow solid 1-nitro-4-phenyl ether, yield 89% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.20?(d,?J?=9.2?Hz,?2H),?7.46-7.42?(m,?2H),?7.28-7.24?(m,?1H),?7.09?(m,?2H),?7.01?(d,?J?=9.2?Hz,?2H)?ppm。
Embodiment 12
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 4-(2-naphthalene ether) ethyl benzoate
The structural formula of 4-(2-naphthalene ether) ethyl benzoate is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is the 4-iodo ethyl benzoate;
Phenols is naphthalene-2-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 4-iodo ethyl benzoate (276.0 mg, 1.0 mmol), naphthalene-2-alcohol (0.134 mL, 1.5 mmol) and DMF (1.5mL).100 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow solid 4-(2-naphthalene ether) ethyl benzoate, yield 89% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.20?(d,?J?=9.2?Hz,?2H),?7.46-7.42?(m,?2H),?7.28-7.24?(m,?1H),?7.09?(m,?2H),?7.01?(d,?J?=9.2?Hz,?2H)?ppm。
Embodiment 13
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2,4-di-t-butyl-1-(4-nitrophenoxy) benzene
The structural formula of 2,4-di-t-butyl-1-(4-nitrophenoxy) benzene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-4-oil of mirbane;
Phenols is 2,4-DTBP;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-4-oil of mirbane (249 mg, 1.0 mmol), 2,4-DTBP (206.3 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains transparent oily mater 2 take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography, 4-di-t-butyl-1-(4-nitrophenoxy) benzene, yield 96%.
1H?NMR?(400MHz,?CDCl
3):?δ?8.22-8.18?(m,?2H),?7.47-7.46?(m,?1H),?7.24-7.21?(m,?1H),?7.03-6.99?(m,?2H),?6.82-6.80?(m,?1H),?1.36?(s,?9H),?1.35?(s,?9H)?ppm.?
13C?NMR?(125?MHz,?CDCl
3):?δ?163.7,?151.1,?147.9,?142.5,?140.9,?125.9,?124.7,?124.3,?121.0,?117.2,?34.9,?34.7,?31.5,?30.4?ppm。
Embodiment 14
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-methoxyl group-4-(4-nitrophenoxy) benzene
The structural formula of 1-methoxyl group-4-(4-nitrophenoxy) benzene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-iodo-4-oil of mirbane;
Phenols is the 4-methoxyphenol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in flask, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas.Under logical argon shield, add 1-iodo-4-oil of mirbane (206.3 mg, 1.5 mmol), 4-methoxyphenol (186.2 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 6h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains white solid 1-methoxyl group-4-(4-nitrophenoxy) benzene, yield 71% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.17?(d,?J?=9.2?Hz,?2H),?7.02?(d,?J?=9.2?Hz,?2H),?6.97-6.94?(m,?4H),?3.83?(s,?3H)?ppm。
Second section The C-O linked reaction of aromatic bromide (embodiment 15-24)
Embodiment 15
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of phenyl ether
The structural formula of phenyl ether is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is bromobenzene;
Phenols is the 4-methoxyphenol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add bromobenzene (0.105 mL, 1.0 mmol), phenol (0.134 mL, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 20h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains the colourless oily mater phenyl ether take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography, yield 44%.
1H?NMR?(400MHz,?CDCl
3):?δ?7.36-7.32?(m,?4H),?7.12-7.08?(m,?2H),?7.02-7.00?(m,?4H)?ppm。
Embodiment 16
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2-(4-nitrophenoxy) naphthalene
The structural formula of 2-(4-nitrophenoxy) naphthalene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-bromo-4-oil of mirbane;
Phenols is naphthalene-2-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-bromo-4-oil of mirbane (202.0 mg, 1.0 mmol), naphthalene-2-alcohol (216.3 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 2-(4-nitrophenoxy) naphthalene, yield 93% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.24-8.20?(m,?2H),?7.94-7.88?(m,?2H),?7.81-7.78?(m,?1H),?7.56-7.48?(m,?3H),?7.27-7.24?(m,?1H),?7.09-7.05?(m,?2H)?ppm。
Embodiment 17
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-(4-(2 hydroxy naphthalene) phenyl) ethyl ketone
The structural formula of 1-(4-(2 hydroxy naphthalene) phenyl) ethyl ketone is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-(4-bromobenzene) ethyl ketone;
Phenols is naphthalene-2-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-(4-bromobenzene) ethyl ketone (199.0 mg, 1.0 mmol), naphthalene-2-alcohol (216.3 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 15h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains brown solid 1-(4-(2 hydroxy naphthalene) phenyl) ethyl ketone, yield 92% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.99-7.95?(m,?2H),?7.90-7.86?(m,?2H),?7.77-7.75?(m,?1H),?7.53-7.45?(m,?3H),?7.28-7.25?(m,?1H),?7.08-7.05?(m,?2H)?ppm。
Embodiment 18
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
NThe application of-(4-(4-nitrophenoxy) phenyl) ethyl ketone
NThe structural formula of-(4-(4-nitrophenoxy) phenyl) ethyl ketone is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-bromo-4-oil of mirbane;
Phenols is
N-(4-hydroxyphenyl) ethyl ketone;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-bromo-4-oil of mirbane (202.0 mg, 1.0 mmol),
N-(4-hydroxyphenyl) ethyl ketone (226.7 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 11h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow solid take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography
N-(4-(4-nitrophenoxy) phenyl) ethyl ketone, yield 98%.
1H?NMR?(400MHz,?CDCl
3):?δ?8.17?(d,?J?=?9.2?Hz,?2H),?7.69?(br?s,?1H),?7.57?(d,?J?=?8.8?Hz,?2H),?7.03?(d,?J?=?8.8?Hz,?2H),?6.97?(d,?J?=?9.2?Hz,?2H),?2.20?(s,?3H)?ppm。
Embodiment 19
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2-(3-methoxyphenoxy) naphthalene
The structural formula of 2-(3-methoxyphenoxy) naphthalene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-bromo-3-anisole;
Phenols is naphthalene-2 alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-bromo-3-anisole (0.126 mL, 1.0 mmol), naphthalene-2 alcohol (216.3 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 16h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 2-(3-methoxyphenoxy) naphthalene, yield 92% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ7.86-7.83?(m,?2H),?7.74-7.71?(m,?1H),?7.49-7.40?(m,?2H),?7.36-7.35?(m,?1H),?7.29-7.24?(m,?2H),?6.72-6.65?(m,?3H),?3.79?(s,?3H)?ppm。
Embodiment 20
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of N-(4-(4-ethanoyl phenoxy group) phenyl) ethanamide
The structural formula of N-(4-(4-ethanoyl phenoxy group) phenyl) ethanamide is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-(4-bromobenzene) ethyl ketone;
Phenols is
N-(4-hydroxyphenyl) ethanamide;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-(4-bromobenzene) ethyl ketone (199.0 mg, 1.0 mmol),
N-(4-hydroxyphenyl) ethanamide (226.7 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h, 110 ℃ of lower reaction stirred 8h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains white solid N-(4-(4-ethanoyl phenoxy group) phenyl) ethanamide, yield 71% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.05?(br?s,?1H),?7.90?(d,?J?=?8.8?Hz,?2H),?7.54?(d,?J?=?9.2?Hz,?2H),?6.99?(d,?J?=?8.8?Hz,?2H),?6.94?(d,?J?=?8.8?Hz,?2H),?2.56?(s,?3H),?2.17?(s,?3H)?ppm。
Embodiment 21
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of N-(4-(4-ethanoyl phenoxy group) phenyl) ethanamide
The structural formula of N-(4-(4-ethanoyl phenoxy group) phenyl) ethanamide is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-(4-bromobenzene) ethyl ketone;
Phenols is the 4-mequinol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-(4-bromobenzene) ethyl ketone (199.0 mg, 1.0 mmol), 4-mequinol (186.2 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h, 110 ℃ of lower reaction stirred 8h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material N-(4-(4-ethanoyl phenoxy group) phenyl) ethanamide, yield 87% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.92-7.90?(m,?2H),?7.02-7.00?(m,?2H),?6.95-6.91?(m,?4H)?ppm。
Embodiment 22
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-(4-(2,4-di-t-butyl phenoxy group) phenyl) ethyl ketone
The structural formula of 1-(4-(2,4-di-t-butyl phenoxy group) phenyl) ethyl ketone is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-(4-bromobenzene) ethyl ketone;
Phenols is 2,4-DTBP;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-(4-bromobenzene) ethyl ketone (199.0 mg, 1.0 mmol), 2,4-DTBP (206.3 mg, 1.5 mmol) and DMF (1.5 mL).100 ℃ of lower reaction stirred 12h, 110 ℃ of lower reaction stirred 8h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 1-(4-(2,4-di-t-butyl phenoxy group) phenyl) ethyl ketone, yield 87% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.93?(d,?J?=?8.8?Hz,?2H),?7.45?(d,?J?=?2.4?Hz,?1H),?7.18?(d,?J?=?2.4?Hz,?1H),?6.99?(d,?J?=?8.8?Hz,?2H),?7.80?(d,?J?=?8.4?Hz,?1H),?2.57?(s,?3H),?1.38?(s,?9H),?1.34?(s,?9H)?ppm。
Embodiment 23
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-methoxyl group-3-phenyl ether
The structural formula of 1-methoxyl group-3-phenyl ether is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-bromo-3-methyl-phenoxide;
Phenols is phenol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-bromo-3-methyl-phenoxide (0.126 mL, 1.0 mmol), phenol (0.134 mL, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 20h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 1-methoxyl group-3-phenyl ether, yield 55% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.38-7.34?(m,?2H),?7.28-7.22?(m,?1H),?7.15-7.11?(m,?1H),?7.06-7.04?(m,?2H),?6.69-6.67?(m,?1H),?6.62-6.60?(m,?2H),?3.80?(s,?3H)?ppm。
Embodiment 24
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-methoxyl group-3-(4-methoxyl group) phenyl ether
The structural formula of 1-methoxyl group-3-(4-methoxyl group) phenyl ether is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-bromo-3-methyl-phenoxide;
Phenols is the 4-mequinol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-bromo-3-methyl-phenoxide (0.126 mL, 1.0 mmol), 4-mequinol (186.2 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 20h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 1-methoxyl group-3-(4-methoxyl group) phenyl ether, yield 77% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.21-7.17?(m,?1H),?7.01-6.99?(m,?2H),?6.90-6.88?(m,?2H),?6.61-6.59?(m,?1H),?6.53-6.52?(m,?2H),?3.81?(s,?3H),?3.77?(s,?3H)?ppm。
Third part The muriatic C-O linked reaction of aryl (embodiment 25-32)
Embodiment 25
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 1-nitro-2-phenyl ether
The structural formula of 1-nitro-2-phenyl ether is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-chloro-2-oil of mirbane;
Phenols is phenol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-chloro-2-oil of mirbane (236.3 mg, 1.0 mmol), phenol (0.134 mL, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 8h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the question response thing is down to room temperature, and the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 1-nitro-2-phenyl ether, yield 97% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?7.95-7.93?(m,?1H),?7.52-7.48?(m,?1H),?7.40-7.36?(m,?2H),?7.21-7.17?(m,?2H),?7.06-6.99?(m,?3H)?ppm。
Embodiment 26
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
NThe application of-(4-(2-nitro-phenoxy) phenyl) ethanamide
NThe structural formula of-(4-(2-nitro-phenoxy) phenyl) ethanamide is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-chloro-2-oil of mirbane;
Phenols is
N-(4-hydroxyphenyl) ethanamide;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-chloro-2-oil of mirbane (236.3 mg, 1.0 mmol),
N-(4-hydroxyphenyl) ethanamide (226.7 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the question response thing is down to room temperature, and the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains the yellow oily material take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography
N-(4-(2-nitro-phenoxy) phenyl) ethanamide, yield 95%.
1H?NMR?(400MHz,?CDCl
3):?δ?7.93-7.91?(m,?1H),?7.76?(m,?1H),?7.51-7.45?(m,?3H),?7.19-7.15?(m,?1H),?6.98-6.94?(m,?3H),?2.16?(s,?3H)?ppm。
Embodiment 27
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2-(2-nitro-phenoxy) naphthalene
The structural formula of 2-(2-nitro-phenoxy) naphthalene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-chloro-2-oil of mirbane;
Phenols is naphthalene-2-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-chloro-2-oil of mirbane (236.3 mg, 1.0 mmol), naphthalene-2-alcohol (216.3 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the question response thing is down to room temperature, and the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 2-(2-nitro-phenoxy) naphthalene, yield 94% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.01-7.99?(m,?1H),?7.90-7.84?(m,?2H),?7.75-7.73?(m,?1H),?7.54-7.44?(m,?3H),?7.38?(m,?1H),?7.30-7.21?(m,?2H),?7.08-7.06?(m,?1H)?ppm。
Embodiment 28
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2,4-di-t-butyl-1-(2-nitro-phenoxy) benzene
The structural formula of 2,4-di-t-butyl-1-(2-nitro-phenoxy) benzene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-chloro-2-oil of mirbane;
Phenols is 2,4-DTBP;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-chloro-2-oil of mirbane (236.3 mg, 1.0 mmol), 2,4-DTBP (206.3 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the question response thing is down to room temperature, and the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 2 take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography, 4-di-t-butyl-1-(2-nitro-phenoxy) benzene, yield 89%.
1H?NMR?(400MHz,?CDCl
3):?δ?7.95-7.93?(m,?1H),?7.47-7.43?(m,?2H),?7.21-7.18?(m,?1H),?7.14-7.11?(m,?1H),?6.96-6.94?(m,?1H),?6.77-6.75?(m,?1H),?1.42?(s,?9H),?1.35?(s,?9H)?ppm。
Embodiment 29
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 8-(2-nitro-phenoxy) quinoline
The structural formula of 8-(2-nitro-phenoxy) quinoline is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-chloro-2-oil of mirbane;
Phenols is quinoline-8-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-chloro-2-oil of mirbane (236.3 mg, 1.0 mmol), quinoline-8-alcohol (217.8 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the question response thing is down to room temperature, and the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 8-(2-nitro-phenoxy) quinoline, yield 72% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.89?(d,?J?=4.0?Hz,?1H),?8.17?(d,?J?=8.4?Hz,?1H),?8.01?(d,?J?=?8.0?Hz,?1H),?7.62?(d,?J?=?8.4?Hz,?1H),?7.48-7.42?(m,?3H),?7.22-7.16?(m,?2H),?6.97?(d,?J?=?8.4?Hz,?1H)?ppm。
Embodiment 30
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 8-(4-nitrophenoxy) quinoline
The structural formula of 8-(4-nitrophenoxy) quinoline is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-chloro-4-oil of mirbane;
Phenols is quinoline-8-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-chloro-4-oil of mirbane (236.3 mg, 1.0 mmol), quinoline-8-alcohol (217.8 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the question response thing is down to room temperature, and the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 8-(4-nitrophenoxy) quinoline, yield 99% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.89-8.88?(m,?1H),?8.26-8.24?(m,?1H),?8.17?(d,?J?=?8.8?Hz,?2H),?7.77-7.75?(m,?1H),?7.59-7.55?(m,?1H),?7.49-7.46?(m,?1H),?7.44-7.42?(m,?1H),?7.02?(d,?J?=?9.2?Hz,?2H)?ppm。
Embodiment 31
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2-(4-nitrophenoxy) naphthalene
The structural formula of 2-(4-nitrophenoxy) naphthalene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-chloro-4-oil of mirbane;
Phenols is naphthalene-2-alcohol;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-chloro-4-oil of mirbane (236.3 mg, 1.0 mmol), naphthalene-2-alcohol (216.3 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the question response thing is down to room temperature, and the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 2-(4-nitrophenoxy) naphthalene, yield 87% take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography.
1H?NMR?(400MHz,?CDCl
3):?δ?8.24-8.20?(m,?2H),?7.94-7.88?(m,?2H),?7.81-7.78?(m,?1H),?7.56-7.48?(m,?3H),?7.27-7.24?(m,?1H),?7.09-7.05?(m,?2H)?ppm。
Embodiment 32
A kind of quinoxaline is two
N-oxide derivative part is promoting copper catalysis C-O linked reaction to generate
The application of 2,4-di-t-butyl-1-(4-nitrophenoxy) benzene
The structural formula of 2,4-di-t-butyl-1-(4-nitrophenoxy) benzene is as follows:
The present embodiment is used:
Non-proton property polar solvent solvent is DMF;
Quinoxaline is two
N-oxide derivative part is that 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound;
The catalyzer mantoquita is CuI;
Mineral alkali reagent is Cs
2CO
3
Aryl halide is 1-chloro-4-oil of mirbane;
Phenols is 2,4-DTBP;
Add CuI (19.1 mg, 0.1 mmol, 10 mol%) in the dry Shu Lunke pipe with the tetrafluoroethylene valve, 2-methoxycarbonyl-3-hydroxy quinoxaline is two
N-oxide compound (47.2 mg, 0.2 mmol, 20 mol%), Cs
2CO
3(812.5 mg, 2.5 mmol).Reaction flask vacuumized pass into again argon gas (so repeating 3 times).Under logical argon shield, add 1-chloro-4-oil of mirbane (236.3 mg, 1.0 mmol), 2,4-DTBP (206.3 mg, 1.5 mmol) and DMF (1.5 mL).110 ℃ of lower reaction stirred 12h are until starting raw material complete reaction (reaction of TLC tracking monitor).Behind the stopped reaction, the question response thing is down to room temperature, and the brown oil matter that obtains is diluted with ethyl acetate, removes by filter inorganic salt, the rotary evaporation desolventizing.Residue obtains yellow oily material 2 take petrol ether/ethyl acetate as elutriant by purification by silica gel column chromatography, 4-di-t-butyl-1-(4-nitrophenoxy) benzene, yield 91%.
1H?NMR?(400MHz,?CDCl
3):?δ?8.22-8.18?(m,?2H),?7.47-7.46?(m,?1H),?7.24-7.21?(m,?1H),?7.03-6.99?(m,?2H),?6.82-6.80?(m,?1H),?1.36?(s,?9H)?,?1.35?(s,?9H)?ppm。
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. a quinoxaline is two
N-oxide derivative part is in the application that promotes copper catalysis C-O linked reaction, described part for represent with logical formula I the 2-methoxycarbonyl-the 3-hydroxy quinoxaline is two
N-oxide compound:
Wherein: R
1It is hydroxyl; R
2It is methoxycarbonyl; R
3-R
6Hydrogen; It is characterized in that, namely than under the mild temperature, in non-proton property polar solvent, take mantoquita as catalyzer, and add mineral alkali reagent and described quinoxaline is two
NIn-oxide derivative part the situation, the linked reaction of aryl halide and phenolic compound;
Described non-proton property polar solvent is the DMF(dimethyl formamide), the DMSO(dimethyl sulfoxide (DMSO)), toluene, CH3CN;
Described mantoquita is CuI, CuBr
2, CuCl
22H
2O, CuCl and CuBr, consumption are 10mol%;
Described mineral alkali reagent is Cs
2CO
3, K
2CO
3, K
3PO
4, KOH and CsOH;
Wherein, the volume mol ratio of non-proton property polar solvent, part, catalyzer mantoquita, mineral alkali reagent, aryl halide and phenols, i.e. solvent: part: catalyzer: mineral alkali reagent: aryl halide: phenols is 1.5ml:0.2mmol:0.1mmol:2.5mmol:1.0mmol:1.1mmol.
2. a quinoxaline as claimed in claim 1 is two
N-oxide derivative part is characterized in that in the application that promotes copper catalysis C-O linked reaction wherein said aryl halide is aryl iodide, aromatic bromide or aryl chloride compound.
3. a quinoxaline as claimed in claim 2 is two
N-oxide derivative part is characterized in that in the application that promotes copper catalysis C-O linked reaction described non-proton property polar solvent is preferably DMF.
4. a quinoxaline as claimed in claim 3 is two
N-oxide derivative part is characterized in that in the application that promotes copper catalysis C-O linked reaction described mantoquita is preferably CuI, and consumption is 10mol%.
5. a quinoxaline as claimed in claim 4 is two
N-oxide derivative part is characterized in that in the application that promotes copper catalysis C-O linked reaction described mineral alkali reagent is preferably Cs
2CO
3
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|---|---|---|---|---|
| US4343942A (en) * | 1966-11-08 | 1982-08-10 | Research Corporation | Quinoxaline derivatives |
| CN101899003A (en) * | 2010-07-23 | 2010-12-01 | 上海应用技术学院 | Quinoline derivative-N-oxide ligand as well as preparation method and application thereof |
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| US4343942A (en) * | 1966-11-08 | 1982-08-10 | Research Corporation | Quinoxaline derivatives |
| CN101899003A (en) * | 2010-07-23 | 2010-12-01 | 上海应用技术学院 | Quinoline derivative-N-oxide ligand as well as preparation method and application thereof |
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