CN106674101A - Method for constructing quinoline compound by means of functionalization of organic antimony catalyzed C-H bond - Google Patents

Method for constructing quinoline compound by means of functionalization of organic antimony catalyzed C-H bond Download PDF

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Publication number
CN106674101A
CN106674101A CN201611141113.9A CN201611141113A CN106674101A CN 106674101 A CN106674101 A CN 106674101A CN 201611141113 A CN201611141113 A CN 201611141113A CN 106674101 A CN106674101 A CN 106674101A
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catalyst
reaction
antimony
vacuum distillation
methyl
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尹双凤
雷健
邱仁华
彭尧
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Hunan University
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Hunan University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/12Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18Halogen atoms or nitro radicals
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D215/00Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20Oxygen atoms
    • C07D215/24Oxygen atoms attached in position 8
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

The invention aims at developing a novel method for preparing a quinoline compound in a manner of high conversion rate and high yield from organic antimony frustrated lewis pair catalyst by means of C-H bond functionalization of imine and unsaturated hydrocarbon at air atmosphere. As air is utilized as an oxidizing agent, the method has the advantages of mild reaction condition, green and environment-friendly preparation process, simple catalyzing system, low cost, excellent conversion rate and yield of target product and capability of recycling catalyst, and has a favorable industrial application prospect.

Description

A kind of method that antimony organic catalysis c h bond sense dough builds quinoline compound
【Technical field】
The present invention relates to organic synthesis field, and in particular to a kind of antimony organic catalysis c h bond sense dough builds quinolate The method of compound.
【Background technology】
In recent years, c h bond sense dough method is because synthesis step is few, Atom economy is high, it is important to build to challenge The advantages of organic functional molecular, become the study hotspot of synthetic organic chemical art.Both at home and abroad Research Team in catalyst, match somebody with somebody The aspect such as body and additive carries out reaction optimization, improves chemo-selective, regioselectivity and the solid of c h bond sense dough Selectivity, and construct serial important organic functional molecular so that the sense dough method of c h bond has obtained development at full speed. But, because c h bond has higher dissociation energy, its thermodynamic stability is higher and chemical reactivity is relatively low, therefore, part It is higher to there is reaction temperature in the catalytic activation method of c h bond, and catalyst system and catalyzing is complicated, needs the oxidant or soda acid addition of equivalent Agent, produces more organic and inorganic wastes, it is difficult to recycling, easily causes the defects such as environmental pollution.On the other hand, C-H The regioselectivity and enantioselectivity of bond activation is difficult to control to, and causes Part Methods to also need to the importing of homing device and take off Remove.Therefore, development more meets the catalyst system and catalyzing of green chemical industry requirement and remains greatly challenge.
2008, Hiyama and Nakao professor of Kyoto University et al. was urged with transition metal Raney nickel and lewis acid Agent system realizes the additive reaction of the disactivation c h bond under temperate condition and unsaturated aromatic hydrocarbon heterocyclic compound.The research Show that by lewis acid coordination activation c h bond its dissociation energy can be reduced, so as to be conducive to oxidative addition to carry out;But should System also needs to couple nickel-metal catalyst for oxidoreduction, it is impossible to realizes simple recycling, is unfavorable for commercial Application. 2006, Canadian Stephan seminar proposed to be obstructed Lewis Acids and Bases to new ideas, is that Lewis acid learning aid has milestone The latest developments of meaning;The lewis acid of wherein big steric hindrance and the lewis base of big steric hindrance interact, and do not occur traditional Neutralization reaction forms Lewis Acids and Bases pair, and is to maintain respective Acidity of Aikalinity, and acidic site and basic site are cooperateed with simultaneously Catalytic effect.Therefore, by the concept of the Lewis Acids and Bases pair that are obstructed, by appropriate design by Louis acid catalysis and oxidoreduction The unified method to single organic metal Lewis acid complex catalyst to realize the green sense dough of inertia c h bond of catalysis It is with certain theory value and industrial application value.
【The content of the invention】
It is an object of the invention to provide a kind of preparation method of quinoline compound, especially a kind of antimony organic are catalyzed C-H The method that key sense dough builds quinoline compound.
To reach above goal of the invention, the present invention provides following technical scheme:
A kind of preparation method of the quinolines with following structure Formulas I,
Comprise the steps of:
Take imine compound, alkynes or alkenes compounds, the antimony organic Lewis Acids and Bases that are obstructed to put catalyst, solvent In reaction vessel, mixing;Under air atmosphere, at reaction temperature is for 50~160 DEG C, continue 6~30h of stirring reaction, instead Room temperature is cooled to after should terminating;Vacuum distillation concentration removes solvent, and with diethyl ether solution crude product is dissolved, and catalyst is recovered by filtration, Vacuum distillation concentration removes ether, and crude product Jing column chromatography obtains final product target product I;
In the structure Formulas I, R1It is hydrogen, chlorine, methyl or methoxyl group;R2It is hydrogen, bromine, methyl or nitro;R3Be hydrogen, chlorine, Bromine, methyl, methoxyl group, the tert-butyl group, isopropyl or nitro;
In above-mentioned preparation method, the described antimony organic Lewis Acids and Bases that are obstructed are to the formula II of catalyst:
Wherein, in addition to two carbon atom bondings of the antimony atoms in compound II in part, also with part in nitrogen Atom forms coordinate bond, and antimony atoms are with fluorine atom into covalent bond;Substituent R wherein in formula II4、R5、R6、R7、R8、R9、 R10、R11Selected from hydrogen, methyl, ethyl, methoxyl group, ethyoxyl, trifluoromethyl or fluorine;The substituent R12、R13、R14、R15It is selected from Hydrogen, methyl, ethyl or fluorine;The substituent R16、R17、R18、R19、R20Selected from hydrogen, methyl, ethyl, trifluoromethyl, aldehyde radical, carboxylic Base, ester group, itrile group, fluorine, chlorine, bromine or iodine.
In above-mentioned preparation method, described imine compound is selected from (E)-N- benzylidene anilines, (E)-N- (4- bromobenzenes Methylene) aniline, (E)-N- (2- methyl benzylidenes) aniline, (E)-N- (2- nitrobenzyl benzylidenes) aniline, (E)-N- (3- Nitro benzylidene) aniline, (E)-N- benzylidenes-2-aminotoluene, (E)-3-monomethylaniline. of-N- benzylidenes, (E)-N- Benzylidene -2- aminoanisoles, (E)-N- benzylidenes -2- chloroanilines, (E)-N- benzylidenes -3- chloroanilines, or (E) - N- benzylidene -4- chloroanilines.
In above-mentioned preparation method, described alkynes compound is selected from phenylacetylene, to Methoxy-phenylacetylene, to tert-butyl benzene Acetylene, p-isopropyl phenylacetylene, to chlorobenzene acetylene, o-methyl-benzene acetylene, a bromobenzene acetylene or ortho-nitrophenyl acetylene.
In above-mentioned preparation method, described alkenes compounds are selected from styrene, to methoxy styrene, to tert-butyl benzene Ethylene, p-isopropyl styrene, to chlorostyrene, o-methyl styrene, a bromstyrol or ortho-nitrophenyl ethylene.
In above-mentioned preparation method, solvent used is selected from dichloromethane, 1,2- dichloroethanes, second in the course of reaction Nitrile, ethylbenzene or toluene.
In above-mentioned synthetic method, the antimony organic is obstructed Lewis Acids and Bases to catalyst, imine compound, alkynes/alkene Mol ratio between hydrocarbon compound is 1:[1~10]:[1~15].
It is provided by the present invention that Lewis Acids and Bases are obstructed to being catalyzed c h bond sense dough by antimony organic according to experimental result The method for building quinoline compound.There is the method superior catalytic performance, wide application range of substrates, gained target product easily to divide From, operation is simple, green safety is reliable, reaction mechanism is novel the features such as.
【Description of the drawings】
It is the synthesis road of the antimony organic catalysis c h bond sense dough structure quinolines that the present invention is provided shown in Fig. 1 Footpath figure.
【Specific embodiment】
Synthetic method of the present invention is described further with reference to the synthesis example of the present invention.
Take imine compoundAlkynesOr alkeneClass Compound, antimony organic are obstructed Lewis Acids and Bases to catalystSolvent is placed in reaction vessel, mixing; Under air atmosphere, at reaction temperature is for 50~160 DEG C, continue 6~30h of stirring reaction, reaction is cooled to room temperature after terminating;Subtract Pressure distillation and concentration removes solvent, and with diethyl ether solution crude product is dissolved, and catalyst is recovered by filtration, and vacuum distillation concentration removes ether, Crude product Jing column chromatography, obtains final product target product I.
With reference to example is specifically prepared, the present invention will be further described:
Preparation example 1
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic force and stir Mix in device and be stirred vigorously, reaction 24 hours is carried out at 100 DEG C.React and room temperature is cooled to after terminating, the complete hydrogen of venting unreacted, Vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing pillar layer separations, Obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 86%, catalyst recovery yield 100%.
Preparation example 2
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN [CH in 25mL reactors2 (2-CH3C6H3)]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL dichloromethane, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 50 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies Separate, obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 82%, catalyst recovery yield 100%.
Preparation example 3
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN [CH in 25mL reactors2 (3-CH3CH2C6H3)]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic It is stirred vigorously in power agitator, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies Separate, obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 83%, catalyst recovery yield 100%.
Preparation example 4
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN [CH in 25mL reactors2 (3-CH3OC6H3)]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic It is stirred vigorously in power agitator, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies Separate, obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 85%, catalyst recovery yield 100%.
Preparation example 5
The freshly prepd antimony organics of 0.50mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN [CH in 25mL reactors2 (3-CH3CH2OC6H3)]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.0mmol phenylacetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 81%, catalyst recovery yield 100%.
Preparation example 6
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN [CH in 25mL reactors2 (4-CF3C6H3)]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic force It is stirred vigorously in agitator, reaction 6 hours is carried out at 100 DEG C.Reaction is cooled to room temperature, the complete hydrogen of venting unreacted after terminating Gas, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies point From obtaining final product target product.Reaction result is:2,4- diphenylquinolines, yield is 84%, catalyst recovery yield 100%.
Preparation example 7
The freshly prepd antimony organics of 1.0mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN [CH in 25mL reactors2 (5-FC6H3)]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.0mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic force and stir Mix in device and be stirred vigorously, reaction 30 hours is carried out at 100 DEG C.React and room temperature is cooled to after terminating, the complete hydrogen of venting unreacted, Vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing pillar layer separations, Obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 83%, catalyst recovery yield 100%.
Preparation example 8
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN [C in 25mL reactors (CH3)2C6H4]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic force and stir Mix in device and be stirred vigorously, reaction 30 hours is carried out at 100 DEG C.React and room temperature is cooled to after terminating, the complete hydrogen of venting unreacted, Vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing pillar layer separations, Obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 82%, catalyst recovery yield 100%.
Preparation example 9
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN [CH in 25mL reactors (CH3CH2)C6H4]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic force It is stirred vigorously in agitator, reaction 24 hours is carried out at 140 DEG C.Reaction is cooled to room temperature, the complete hydrogen of venting unreacted after terminating Gas, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies point From obtaining final product target product.Reaction result is:2,4- diphenylquinolines, yield is 85%, catalyst recovery yield 100%.
Preparation example 10
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors [CF2C6H4]2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic force and stir Mix in device and be stirred vigorously, reaction 24 hours is carried out at 100 DEG C.React and room temperature is cooled to after terminating, the complete hydrogen of venting unreacted, Vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing pillar layer separations, Obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 84%, catalyst recovery yield 100%.
Preparation example 11
The freshly prepd antimony organics of 0.25mmol are added to be obstructed Lewis Acids and Bases to catalyst 2- in 25mL reactors CH3C6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.0mmol phenylacetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 82%, catalyst recovery yield 100%.
Preparation example 12
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst 3- in 25mL reactors CH3CH2C6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in It is stirred vigorously in band magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature, venting unreacted after terminating Complete hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing posts Chromatographic isolation, obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 81%, catalyst recovery yield 100%.
Preparation example 13
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst 3- in 25mL reactors CF3C6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 80%, catalyst recovery yield 100%.
Preparation example 14
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst 4- in 25mL reactors CHOCH2C6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL acetonitriles, put It is stirred vigorously in band magnetic stirring apparatuss, reaction 12 hours is carried out at 80 DEG C.Reaction is cooled to room temperature, venting unreacted after terminating Complete hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing posts Chromatographic isolation, obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 86%, catalyst recovery yield 100%.
Preparation example 15
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst 4- in 25mL reactors COOHC6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and the chloroethene of 2.0mL1,2- bis- Alkane, is placed in band magnetic stirring apparatuss and is stirred vigorously, and reaction 30 hours is carried out at 110 DEG C.Reaction is cooled to room temperature, venting after terminating The complete hydrogen of unreacted, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes second Ether, Jing pillar layer separations, obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 85%, and catalyst is reclaimed Rate 100%.
Preparation example 16
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst 3- in 25mL reactors COOCH2CH3C6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, It is placed in band magnetic stirring apparatuss and is stirred vigorously, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting is not The hydrogen for having reacted, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing pillar layer separations, obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 82%, catalyst recovery yield 100%.
Preparation example 17
The freshly prepd antimony organics of 0.75mmol are added to be obstructed Lewis Acids and Bases to catalyst 3- in 25mL reactors CNC6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.2mmol phenylacetylenes and the chloroethene of 2.0mL1,2- bis- Alkane, is placed in band magnetic stirring apparatuss and is stirred vigorously, and reaction 24 hours is carried out at 160 DEG C.Reaction is cooled to room temperature, venting after terminating The complete hydrogen of unreacted, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes second Ether, Jing pillar layer separations, obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 86%, and catalyst is reclaimed Rate 100%.
Preparation example 18
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst 2- in 25mL reactors ClC6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 84%, catalyst recovery yield 100%.
Preparation example 19
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst 2- in 25mL reactors BrC6H4N(CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:2,4- diphenylquinolines, yield is 83%, catalyst recovery yield 100%.
Preparation example 20
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst 2-IC in 25mL reactors6H4N (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic force and stir Mix in device and be stirred vigorously, reaction 24 hours is carried out at 100 DEG C.React and room temperature is cooled to after terminating, the complete hydrogen of venting unreacted, Vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing pillar layer separations, Obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 85%, catalyst recovery yield 100%.
Preparation example 21
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst C in 25mL reactors6F5N (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic force and stir Mix in device and be stirred vigorously, reaction 24 hours is carried out at 100 DEG C.React and room temperature is cooled to after terminating, the complete hydrogen of venting unreacted, Vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing pillar layer separations, Obtain final product target product.Reaction result is:2,4- diphenylquinolines, yield is 86%, catalyst recovery yield 100%.
Preparation example 22
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol 4- Methoxy-phenylacetylenes and 2.0mL toluene, are placed in It is stirred vigorously in band magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature, venting unreacted after terminating Complete hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing posts Chromatographic isolation, obtains final product target product.Reaction result is:4- (4- methoxyphenyls) -2- phenylchinolines, yield is 87%, catalysis The agent response rate 100%.
Preparation example 23
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol 4- tert-butyl benzenes acetylene and 2.0mL toluene, are placed in It is stirred vigorously in band magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature, venting unreacted after terminating Complete hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing posts Chromatographic isolation, obtains final product target product.Reaction result is:4- (4- tert-butyl-phenyls) -2- phenylchinolines, yield is 84%, catalysis The agent response rate 100%.
Preparation example 24
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol 4- cumenes acetylene and 2.0mL toluene, are placed in It is stirred vigorously in band magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature, venting unreacted after terminating Complete hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing posts Chromatographic isolation, obtains final product target product.Reaction result is:4- (4- isopropyl phenyls) -2- phenylchinolines, yield is 85%, catalysis The agent response rate 100%.
Preparation example 25
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol 4- chlorobenzenes acetylene and 2.0mL toluene, are placed in band magnetic It is stirred vigorously in power agitator, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies Separate, obtain final product target product.Reaction result is:4- (4- chlorphenyls) -2- phenylchinolines, yield is 89%, catalyst recovery yield 100%.
Preparation example 26
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol 2- methyl phenylacetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:4- (2- aminomethyl phenyls) -2- phenylchinolines, yield is 88%, and catalyst is returned Yield 100%.
Preparation example 27
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol 3- bromobenzenes acetylene and 2.0mL toluene, are placed in band magnetic It is stirred vigorously in power agitator, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies Separate, obtain final product target product.Reaction result is:4- (3- bromophenyls) -2- phenylchinolines, yield is 90%, catalyst recovery yield 100%.
Preparation example 28
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene anilines, 1.5mmol 2- nitrobenzene acetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:4- (2- nitrobenzophenones) -2- phenylchinolines, yield is 95%, and catalyst is returned Yield 100%.
Preparation example 29
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- (4- bromobenzene methylene) aniline, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:2- (4- bromophenyls) -4- phenylchinolines, yield is 88%, and catalyst is reclaimed Rate 100%.
Preparation example 30
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- (2- nitrobenzyl benzylidenes) aniline, 1.5mmol phenylacetylenes and 2.0mL toluene, put It is stirred vigorously in band magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting is not anti- The hydrogen answered, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing Pillar layer separation, obtains final product target product.Reaction result is:2- (2- nitrobenzophenones) -4- phenylchinolines, yield is 87%, catalysis The agent response rate 100%.
Preparation example 31
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- (3- nitro benzylidenes) aniline, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in It is stirred vigorously in band magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature, venting unreacted after terminating Complete hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing posts Chromatographic isolation, obtains final product target product.Reaction result is:2- (3- nitrobenzophenones) -4- phenylchinolines, yield is 87%, catalyst The response rate 100%.
Preparation example 32
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2((E)-N- (2- methyl benzylidenes) aniline, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in for SbF, 1.0mmol It is stirred vigorously in band magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature, venting unreacted after terminating Complete hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing posts Chromatographic isolation, obtains final product target product.Reaction result is:2- (2- aminomethyl phenyls) -4- phenylchinolines, yield is 86%, catalyst The response rate 100%.
Preparation example 33
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene -2- aminoanisoles, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in It is stirred vigorously in band magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature, venting unreacted after terminating Complete hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing posts Chromatographic isolation, obtains final product target product.Reaction result is:8- methoxyl group -2,4- diphenylquinolines, yield is 84%, and catalyst is returned Yield 100%.
Preparation example 34
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidenes -2-aminotoluene, 1.5mmol phenylacetylenes and 2.0mL toluene, is placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:8- methyl -2,4- diphenylquinolines, yield is 82%, catalyst recovery yield 100%.
Preparation example 35
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N--3-monomethylaniline .s of benzylidene, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band It is stirred vigorously in magnetic stirring apparatuss, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation remove solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing post colors Spectrum is separated, and obtains final product target product.Reaction result is:7- methyl -2,4- diphenylquinolines, yield is 90%, catalyst recovery yield 100%.
Preparation example 36
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene -4- chloroanilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic It is stirred vigorously in power agitator, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies Separate, obtain final product target product.Reaction result is:Chloro- 2, the 4- diphenylquinolines of 6-, yield is 91%, catalyst recovery yield 100%.
Preparation example 37
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene -3- chloroanilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic It is stirred vigorously in power agitator, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies Separate, obtain final product target product.Reaction result is:Chloro- 2, the 4- diphenylquinolines of 7-, yield is 89%, catalyst recovery yield 100%.
Preparation example 38
The freshly prepd antimony organics of 0.10mmol are added to be obstructed Lewis Acids and Bases to catalyst PhN in 25mL reactors (CH2C6H4)2SbF, 1.0mmol (E)-N- benzylidene -2- chloroanilines, 1.5mmol phenylacetylenes and 2.0mL toluene, are placed in band magnetic It is stirred vigorously in power agitator, reaction 24 hours is carried out at 100 DEG C.Reaction is cooled to room temperature after terminating, and venting unreacted is complete Hydrogen, vacuum distillation removes solvent;Ether dissolution crude product, is recovered by filtration catalyst, and vacuum distillation removes ether, Jing column chromatographies Separate, obtain final product target product.Reaction result is:Chloro- 2, the 4- diphenylquinolines of 8-, yield is 86%, catalyst recovery yield 100%.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art For, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the guarantor of the present invention Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.

Claims (7)

1. a kind of method that antimony organic catalysis c h bond sense dough builds quinoline compound, comprising following step:
Take imine compound, alkynes or alkenes compounds, the antimony organic Lewis Acids and Bases that are obstructed to be placed in anti-catalyst, solvent In answering container, mixing;
Under air atmosphere, at reaction temperature is for 50~160 DEG C, continue 6~30h of stirring reaction, reaction is cooled to after terminating Room temperature;
Vacuum distillation concentration removes solvent, and with diethyl ether solution crude product is dissolved, and catalyst is recovered by filtration, and vacuum distillation concentration is removed Ether, crude product Jing column chromatography, obtains final product target product;
The quinoline compound has following structural formula I:
Wherein, R1It is selected from hydrogen, chlorine, methyl or methoxy;
R2It is selected from hydrogen, bromine, methyl or nitro;
R3It is selected from hydrogen, chlorine, bromine, methyl, methoxyl group, the tert-butyl group, isopropyl or nitro.
2. the method that antimony organic catalysis c h bond sense dough according to claim 1 builds quinoline compound, its feature exists There is following structural formula II to catalyst in, the described antimony organic Lewis Acids and Bases that are obstructed:
Wherein, in addition to two carbon atom bondings of the antimony atoms in part, also coordinate bond is formed with the nitrogen-atoms in part, antimony is former Son is with fluorine atom into covalent bond;The substituent R4、R5、R6、R7、R8、R9、R10、R11Selected from hydrogen, methyl, ethyl, methoxyl group, second Epoxide, trifluoromethyl or fluorine;The substituent R12、R13、R14、R15Selected from hydrogen, methyl, ethyl or fluorine;The substituent R16、 R17、R18、R19、R20Selected from hydrogen, methyl, ethyl, trifluoromethyl, aldehyde radical, carboxyl, ester group, itrile group, fluorine, chlorine, bromine or iodine.
3. the method that antimony organic catalysis c h bond sense dough according to claim 1 builds quinoline compound, its feature exists In described imine compound is selected from (E)-N- benzylidene anilines, (E)-N- (4- bromobenzene methylene) aniline, (E)-N- (2- methyl benzylidenes) aniline, (E)-N- (2- nitrobenzyl benzylidenes) aniline, (E)-N- (3- nitro benzylidenes) aniline, (E)-N- benzylidenes-2-aminotoluene, (E)-3-monomethylaniline. of-N- benzylidenes, (E)-N- benzylidenes-2- methoxybenzenes Amine, (E)-N- benzylidenes -2- chloroanilines, (E)-N- benzylidenes -3- chloroanilines, or, (E)-N- benzylidene -4- chlorobenzenes Amine.
4. the method that antimony organic catalysis c h bond sense dough according to claim 1 builds quinoline compound, its feature exists In, described alkynes compound selected from phenylacetylene, to Methoxy-phenylacetylene, to tert-butyl benzene acetylene, p-isopropyl phenylacetylene, To chlorobenzene acetylene, o-methyl-benzene acetylene, a bromobenzene acetylene or ortho-nitrophenyl acetylene.
5. the method that antimony organic catalysis c h bond sense dough according to claim 1 builds quinoline compound, its feature exists In, described alkenes compounds selected from styrene, to methoxy styrene, p-tert-butylstyrene, p-isopropyl styrene, To chlorostyrene, o-methyl styrene, a bromstyrol or ortho-nitrophenyl ethylene.
6. the method that antimony organic catalysis c h bond sense dough according to claim 1 builds quinoline compound, its feature exists In the solvent is selected from dichloromethane, 1,2- dichloroethanes, acetonitrile, ethylbenzene or toluene.
7. the method that antimony organic catalysis c h bond sense dough according to claim 1 builds quinoline compound, its feature exists In, the antimony organic be obstructed Lewis Acids and Bases between catalyst, imine compound, alkynes or alkenes compounds mole Than for 1:[1~10]:[1~15].
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107602461A (en) * 2017-09-25 2018-01-19 青岛农业大学 A kind of synthetic method of quinolines
CN107739333A (en) * 2017-11-14 2018-02-27 大连理工大学 A kind of preparation method of green quinoline compound

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104529796A (en) * 2014-12-25 2015-04-22 湖南大学 Catalytic synthesis application based on frustrated Lewis acid-base pair

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104529796A (en) * 2014-12-25 2015-04-22 湖南大学 Catalytic synthesis application based on frustrated Lewis acid-base pair

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JING LIU,ET AL.: "Oxidative Povarov Reaction via sp3 C-H Oxidation of N‑Benzylanilines Induced by Catalytic Radical Cation Salt: Synthesis of 2,4-Diarylquinoline Derivatives", 《ORGANIC LETTERS》 *
PARTHASARATHY GANDEEPAN,ET AL.: "Synthesis of Substituted Quinolines by Iron(III)-Catalyzed Three Component Coupling Reaction of Aldehydes, Amines, and Styrenes", 《ASIAN JOURNAL OF ORGANIC CHEMISTRY》 *
YI CHEN,ET AL.: "Synthesis characterization and anti-proliferative activity of heterocyclic hypervalent organoantimony compounds", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107602461A (en) * 2017-09-25 2018-01-19 青岛农业大学 A kind of synthetic method of quinolines
CN107739333A (en) * 2017-11-14 2018-02-27 大连理工大学 A kind of preparation method of green quinoline compound
WO2019095678A1 (en) * 2017-11-14 2019-05-23 大连理工大学 Method for preparing green quinoline compound
CN107739333B (en) * 2017-11-14 2019-09-27 大连理工大学 A kind of preparation method of the quinoline compound of green
US10730838B2 (en) 2017-11-14 2020-08-04 Dalian University Of Technology Green preparation method for quinoline compounds

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