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 PDFInfo
- 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
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- antimony
- vacuum distillation
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic 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
- C07D215/04—Heterocyclic 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
- C07D215/06—Heterocyclic 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic 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
- C07D215/12—Heterocyclic 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic 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
- C07D215/16—Heterocyclic 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
- C07D215/18—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic 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
- C07D215/16—Heterocyclic 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
- C07D215/20—Oxygen atoms
- C07D215/24—Oxygen atoms attached in position 8
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- 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
【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].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611141113.9A CN106674101A (en) | 2016-12-12 | 2016-12-12 | Method for constructing quinoline compound by means of functionalization of organic antimony catalyzed C-H bond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611141113.9A CN106674101A (en) | 2016-12-12 | 2016-12-12 | Method for constructing quinoline compound by means of functionalization of organic antimony catalyzed C-H bond |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106674101A true CN106674101A (en) | 2017-05-17 |
Family
ID=58868192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611141113.9A Pending CN106674101A (en) | 2016-12-12 | 2016-12-12 | Method for constructing quinoline compound by means of functionalization of organic antimony catalyzed C-H bond |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674101A (en) |
Cited By (2)
| 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)
| 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 |
-
2016
- 2016-12-12 CN CN201611141113.9A patent/CN106674101A/en active Pending
Patent Citations (1)
| 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)
| 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)
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Efficient fixation of CO 2 into organic carbonates catalyzed by 2-hydroxymethyl-functionalized ionic liquids | |
| Cheng et al. | Effect of hydrogen bond of hydroxyl-functionalized ammonium ionic liquids on cycloaddition of CO2 | |
| Ye et al. | Cobalt-catalyzed benzylic C–H amination via dehydrogenative-coupling reaction | |
| Leng et al. | Generally applicable and efficient oxidative Heck reaction of arylboronic acids with olefins catalyzed by cyclopalladated ferrocenylimine under base-and ligand-free conditions | |
| Sarkar et al. | Highly efficient synthesis of polysubstituted fluorene via iron-catalyzed intramolecular Friedel–Crafts alkylation of biaryl alcohols | |
| Dutta et al. | Cross dehydrogenative coupling of N-aryltetrahydroisoquinolines (sp 3 C–H) with indoles (sp 2 C–H) using a heterogeneous mesoporous manganese oxide catalyst | |
| Sun et al. | AlCl 3-promoted [3+ 2] annulation of cis-2, 3-disubstituted cyclopropane 1, 1-diesters with isothiocyanates: stereoselective synthesis of densely substituted 2-iminodihydrothiophenes | |
| CN105968137B (en) | Biaryl monophosphorus ligand of a kind of structure containing aphthofurans and its preparation method and application | |
| Guo et al. | Efficient selective catalytic oxidation of benzylic CH bonds by ZIF-67 under eco-friendly conditions | |
| CN106674101A (en) | Method for constructing quinoline compound by means of functionalization of organic antimony catalyzed C-H bond | |
| Mo et al. | The applications of palladacycles as transition-metal catalysts in organic synthesis | |
| CN109675635A (en) | Natural polymer catalyst and preparation method thereof suitable for 2,3,6- oxidation of trimethylphenol | |
| CN103804105A (en) | Synthesis method for biphenyl compounds | |
| CN103553856A (en) | Synthetic method of biphenyl compounds | |
| Song et al. | Fluorine-Containing Furan Derivatives from the Michael Addition of Ethyl 4, 4, 4-Trifluoro-3-oxobutanoate with β-Nitrostyrenes | |
| CN112479898B (en) | Divalent manganese catalyzed arylamine ortho-olefination reaction method | |
| CN111675650B (en) | Preparation method of aromatic vinyl bromide derivative | |
| Meng et al. | Et 3 N-promoted tandem ring-opening reaction of N-tosylaziridines with terminal alkynoates: a straightforward synthesis of functionalized enamines | |
| Bahri et al. | Hydrogen-bond-promoted metal-free hydroamination of alkynes | |
| CN106187723B (en) | A kind of benzyl position is oxidized the method for preparing ketone | |
| Wang et al. | Oxime‐derived palladacycle Immobilized in an Ionic Liquid Brush as an Efficient and Reusable Catalyst for Mozoroki‐Heck Reaction in Neat Water | |
| CN109020814B (en) | Polysubstituted 10-hydroxy phenanthrene and derivative thereof and synthesis method thereof | |
| Khurana et al. | Rapid chemoselective deprotection of benzyl esters by nickel boride | |
| CN107188851A (en) | A kind of method for synthesizing astemizole key intermediate and its derivative | |
| CN110545912A (en) | Method for preparing deuterated ethanol from D2O |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170517 |