CN105949119B - A method of polysubstituted 2 (the 1H)-quinolinones compound of synthesis - Google Patents
A method of polysubstituted 2 (the 1H)-quinolinones compound of synthesis Download PDFInfo
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- CN105949119B CN105949119B CN201610475781.9A CN201610475781A CN105949119B CN 105949119 B CN105949119 B CN 105949119B CN 201610475781 A CN201610475781 A CN 201610475781A CN 105949119 B CN105949119 B CN 105949119B
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- 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
- C07D215/22—Oxygen atoms attached in position 2 or 4
Abstract
Polysubstituted 2 (1 are synthesized the present invention relates to a kind ofH) quinolinones compound method.This method is to be added 2 in autoclave（Aryl ethane base）Aniline and diaryl iodonium salt are raw material, after catalyst is added, additive is added, using organic solvent as solvent, it is passed through carbon dioxide, is stirred to react at 40~120 DEG C 6~24 hours, it is cooled to room temperature after reaction, for the unreacted carbon dioxide of slow release to normal pressure, reaction solution obtains crude product after washing, extraction, washing, drying, reduced pressure, purifies to obtain polysubstituted 2 (1H) quinolinones compounds described in series through column chromatography.Synthetic method of the present invention uses multicomponent one kettle way, the disadvantage for overcoming such chemical procedure of conventional synthesis more, cumbersome；And reaction condition is mild, safe operation is simple.Therefore the synthetic method is conducive to industrial production, has a good application prospect in organic, medical and pesticide synthesis.
Description
Technical field
The present invention relates to medication chemistry synthesis technical fields, and in particular to a kind of polysubstituted 2 (1H)-quinolinones of synthesis
The method of compound.
Background technology
2 (1H)-quinolinones and its derivative are a kind of important nitrogen-containing heterocycle compounds, are present in many natural plants
In, as Evodia alkaloid in (McCormick, J.L.；McKee,T.C.；Cardellina,J.H.,II；Boyd,
M.R.J.Nat.Prod.1996,59,469；Yang,S.S.；Cragg,G.M.；Newman,D.J.；Bader,
J.P.J.Nat.Prod.2001,64,265).2 (1H)-quinolinones compounds of difference substitution have different bioactivity
And wide physiology, pharmacological activity, thus had a wide range of applications in chemical industry, medicine and pesticide various aspects.In field of medicaments,
2 (1H)-quinolinones compounds have antitumor, schizophrenia, platelet aggregation-against, positive inotropic action, antiulcer etc.
Effect (D.；Kling,R.C.；Skultety,M.；Leuner,K.；Gmeine,
P.J.Med.Chem.2014,57,4861；Jayashree,B.S.；Thomas,S.；Nayak,Y.Med.Chem.Res.2010,
19,193；Raitio,K.H.；Savinainen,J.R.；J.；Laitinen,J.T.；Poso,A.；T.；Nevalaine,T.J.Med.Chem.2006,49,2022；Rowley,M.；Kulagowski,J.J.；
Watt,A.P.；Rathbone,D.；Stevenson,G.I.；Carling,R.W.；Baker,R.；Marshall,G.R.；
Kemp,J.A.；Foster,A.C.；Grimwood,S.；Hargreaves,R.；Hurley,C.；Saywell,K.L.；
Tricklebank,M.D.；Leeson, P.D.J.Med.Chem.1997,40,4053), such as novel antipsychotic drug A Li piperazines
Azoles (Aripiprazole) treats intermittent claudication drug Cilostazol (Cilostazol) and can be used for treating chronic congestion
Sexual exhaustion drug Vesnarinone (Vesnarinone) is all 2 (1H)-quinolinones compound (Braun, D.E.；Gelbrich,
T.；Kahlenberg,V.；Tessadri,R.；Wieser,J.；Griesser,U.J.Cryst.Growth Des.2009,9,
1054；Roma,G.；Braccio,M.D.；Grossi,G.；Piras,D.；Leoncini,G.；Bruzzese,D.；
Signorello,M.G.；Fossa,P.；Mosti,L.J.Med.Chem.2007,50,2886；Gardner,L.；
M.；Zahid,N.；Uetrecht,J.P.Chem.Res.Toxicol.2005,18,1384).In terms of pesticide, 2 (1H)-quinoline
Ketone compounds are widely used as herbicide, insecticide and bacteria remover etc..Just because of its importance, synthetic method always by
To the extensive concern of people.
The method of conventional synthesis 2 (1H)-quinolinones compound will generally pass through several synthesis steps, and process complexity is numerous
It is trivial, or need harsh reaction condition (McQuaid, L.A.；Lodge,E.C.R.S.D.；Pralong,E.；Calligaro,
J.E.W.D.O.；O'Malley,P.J.J.Med.Chem.1992,35,3423；DeVita,R.J.；Hollings,D.D.；
Goulet,M.T.；Wyvratt,M.J.；Fisher,M.H.；Lo,J.-L.；Yang,Y.-T.；Cheng,K.；Smith,
R.G.Bioorg.Med.Chem.Lett.1999,9,2621).In order to overcome these disadvantages, nearest chemist to develop some mistakes
The cyclization new method for crossing metal catalytic, including：(1) cyclisation of the adjacent Iodoaniline, alkynes and carbon monoxide of palladium chtalyst
React (Kadnikov, D.V.；Larock,R.C.J.Org.Chem.2004,69,6772)；(2) the N- pyridyl group benzene of palladium chtalyst
Amine, interior alkynes and Mo (CO)6[3+2+1] cyclization (Chen, J.；Natte,K.；Spannenberg,A.；Neumann,H.；
Beller,M.；Wu,X.-F.Chem.Eur.J.2014,20,14189)；(3) the N- arylaminos formyl chloride and interior alkynes of iridium catalysis
Cyclization (Iwai, T.；Fujihara,T.；Terao,J.；Tsuji,Y.J.Am.Soc.Chem.2010,132,9602)；
(4) benzamide of rhodium catalysis reacts (Ackermann, L. with the oxidative cyclization of interior alkynes；Lygin,A.V.；Hofman,
N.Angew.Chem.Int.Ed.2011,50,6379)；And three components of the aniline of (5) rhodium catalysis, carbon monoxide and interior alkynes
Oxidative cyclization reacts (Li, X.；Li,X.；Jiao,N.J.Am.Soc.Chem.2015,137,9246).
Although the Study of synthesis method of 2- (1H) -one class compound has been achieved with prodigious progress, some methods are also deposited
Expensive metallic catalyst is being needed, the problems such as using the toxic carbonyl source such as carbon monoxide, need high reaction temperature.Cause
There is still a need for development simplicity, the new synthetic methods of efficient, safety 2 (1H)-quinolinones compounds for this.
Invention content
The present invention provides a kind of methods of polysubstituted 2 (the 1H)-quinolinones compound of synthesis, and principle is with titanium dioxide
Carbon is first under the action of silver salt and alkali with 2- (aryl ethane base) aniline, generates in -2 (1H)-quinolinones compound of 4- hydroxyls
Mesosome, then arylation reaction, polysubstituted 2 (1H)-quinolinones of one-step synthesis occur for diaryl iodonium salt in the presence of alkali
Close object.This method is environmentally friendly using carbon dioxide as carbonyl source, and method is simple, safe operation, has potential practical valence
Value.
The purpose of the present invention is achieved through the following technical solutions：
A method of 2- (aryl second is added in autoclave in polysubstituted 2 (the 1H)-quinolinones compound of synthesis
Alkynyl) aniline and diaryl iodonium salt be raw material, after catalyst be added, additive be added and is passed through two using organic solvent as solvent
Carbonoxide is stirred to react 6~24 hours at 40~120 DEG C, is cooled to room temperature after reaction, slow release unreacted two
For carbonoxide to normal pressure, reaction solution obtains crude product after washing, extraction, washing, drying, reduced pressure, purifies to obtain through column chromatography
Polysubstituted 2 (1H)-quinolinones compounds described in series；
Its reaction is shown below：
Wherein, R1Including methyl, fluorine-based, chloro, bromo or trifluoromethyl；
R2Including methyl, fluorine-based, chloro, bromo, methoxyl group, cyano, dimethyl or trifluoromethyl；
R3And R4Including fluorine-based, chloro, bromo, cyano, methyl, trifluoromethyl, tertiary butyl, nitro or trimethyl.
In the above method, the R1Including 5- methyl, 5- fluorine, 5- chlorine, 5- bromines, 5- trifluoromethyls, 4- fluorine, 4- chlorine, 4- first
Base, 4,6- dichloros or 4- bromines；
The R2Including 2- fluorine, 2- chlorine, 2- bromines, 2- methyl, 3- fluorine, 3- chlorine, 3- bromines, 3- methyl, 3- methoxyl groups, 4- fluorine,
4- chlorine, 4- bromines, 4- methyl, 4- trifluoromethyls, 4- cyano or 2,4- dimethyl；
The R3And R4Including 2- fluorine, 3- fluorine, 2- fluorine, 2- chlorine, 4- chlorine, 2- cyano, 3- methyl, 4- bromines, 4- trifluoromethyls,
4- tertiary butyls, 4- nitros or 2,4,6- trimethyls；
The catalyst is silver salt；The additive is alkali.
In the above method, autoclave uses gap type high-pressure reaction kettle or continuous high pressure reaction kettle；2- (aryl second
Alkynyl) molar ratio of aniline and diaryl iodonium salt is 1：(1~1.5).
In the above method, the silver salt is silver acetate, silver nitrate, silver carbonate, silver chlorate, silver fluoride or silver tetrafluoroborate.
In the above method, the molar ratio of amount and 2- (aryl ethane base) aniline that catalyst is added is (0.1~0.5)：1.
In the above method, the additive is sodium carbonate, potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium tert-butoxide, the tert-butyl alcohol
Lithium, 1,4- diazabicylos [2.2.2] octane, tri- azabicyclics of 1,5,7- [4.4.0] decyl- 5- alkene or 1,8- diazabicylos
[5.4.0] 11 carbon -7- alkene.
In the above method, the molar ratio of amount and 2- (aryl ethane base) aniline that alkali is added is (0.1~1):1.
In the above method, solvent is dimethyl sulfoxide (DMSO).
In the above method, the pressure of carbon dioxide is 0.5~6MPa.
In the above method, product is isolated and purified using column chromatography after reaction；The column chromatography eluent is oil
The mixed solvent of ether and ethyl acetate；Volume ratio between petroleum ether and ethyl acetate is (1~5)：1.
The present invention has the following advantages compared with the prior art and effect：
The synthetic method of polysubstituted 2 (the 1H)-quinolinones compound of the present invention uses multicomponent one kettle way, overcomes traditional conjunction
More, the cumbersome disadvantage at such chemical procedure；And reaction condition is mild, safe operation is simple；As a result of dioxy
Change carbon as carbonyl source, avoids using poisonous and hazardous carbonyl source (such as phosgene and carbon monoxide), it is environmental-friendly；Substrate applicability
Extensively, functional group tolerance is high.Therefore the synthetic method is conducive to industrial production, has in organic, medical and pesticide synthesis good
Good application prospect.
Description of the drawings
Fig. 1 is embodiment 1-12 products therefrom hydrogen spectrograms；
Fig. 2 is embodiment 1-12 products therefrom carbon spectrograms；
Fig. 3 is 13 products therefrom hydrogen spectrogram of embodiment；
Fig. 4 is 13 products therefrom carbon spectrogram of embodiment；
Fig. 5 is 14 products therefrom hydrogen spectrogram of embodiment；
Fig. 6 is 14 products therefrom carbon spectrogram of embodiment；
Fig. 7 is 15 products therefrom hydrogen spectrogram of embodiment；
Fig. 8 is 15 products therefrom carbon spectrogram of embodiment；
Fig. 9 is 16 products therefrom hydrogen spectrogram of embodiment；
Figure 10 is 16 products therefrom carbon spectrogram of embodiment；
Figure 11 is 17 products therefrom hydrogen spectrogram of embodiment；
Figure 12 is 17 products therefrom carbon spectrogram of embodiment；
Figure 13 is 18 products therefrom hydrogen spectrogram of embodiment；
Figure 14 is 18 products therefrom carbon spectrogram of embodiment；
Figure 15 is 19 products therefrom hydrogen spectrogram of embodiment；
Figure 16 is 19 products therefrom carbon spectrogram of embodiment；
Figure 17 is 20 products therefrom hydrogen spectrogram of embodiment；
Figure 18 is 20 products therefrom carbon spectrogram of embodiment；
Figure 19 is 21 products therefrom hydrogen spectrogram of embodiment；
Figure 20 is 21 products therefrom carbon spectrogram of embodiment.
Specific implementation mode
With reference to specific embodiments and the drawings, the present invention is described in further detail, but the embodiment party of the present invention
Formula and the substrate of adaptation are without being limited thereto.
Embodiment 1
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.240 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 85%.
Embodiment 2
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.30 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 86%.
Embodiment 3
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.240 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.10 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 76%.
Embodiment 4
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.240 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.10 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 88%.
Embodiment 5
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver fluoride, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 82%.
Embodiment 6
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of potassium carbonate, 2 milliliters of DMSO are filled with
The CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to room temperature, be slowly vented unreacted CO2。
Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, and organic phase merging is dried over anhydrous sodium sulfate
Afterwards, vacuum distillation removes solvent and obtains target product using column chromatographic isolation and purification.Column chromatography eluent used is body
Product is than being 2：1 petroleum ether：Ethyl acetate mixed solvent, yield 60%.
Embodiment 7
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of 1,8- diazabicylo [5.4.0] ten
One carbon -7- alkene (DBU), 2 milliliters of DMSO are filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring,
It is cooled to room temperature, is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used every time three times
10mL), after organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent and is obtained using column chromatographic isolation and purification
Target product.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 79%.
Embodiment 8
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 24 hours, stop heating and stirring, it is cooling
To room temperature, it is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times,
After organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 89%.
Embodiment 9
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 6 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 51%.
Embodiment 10
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 120 DEG C are stirred to react 8 hours, stop heating and stirring, it is cooling
To room temperature, it is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times,
After organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 43%.
Embodiment 11
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 0.5MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, it is cooling
To room temperature, it is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times,
After organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 29%.
Embodiment 12
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 6MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 89%.
The structural characterization data of embodiment 1-12 products therefroms are (nuclear magnetic spectrogram is as depicted in figs. 1 and 2) as follows：
1H NMR(400MHz,CDCl3):δ=12.00 (s, 1H), 8.05 (d, J=8.0,1H), 7.43 (t, J=8.0,
1H), 7.2 (q, J=4.0,2H), 7.14-6.99 (m, 5H), 6.48 (s, 2H), 2.11 (s, 3H), 1.99 (s, 6H)
13C NMR(100MHz,CDCl3):δ=165.35,158.08,150.55,137.76,133.62,132.06,
130.77,129.76,129.11,128.26,127.08,126.84,123.55,122.17,116.67,116.35,116.07,
20.33,16.83.
IR(KBr):3180,2921,1647,1600,1481,1355,1201,1151cm-1.
MS(EI):M/z (%)=355 [M+],338(100),278,165,162,91,77.
HRMS-ESI(m/z):calcd for C24H21NO2Na(M+Na)+:378.1470,found:378.1464.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 13
In autoclave be added 0.20 mM of 2- ((4- fluorophenyls) acetenyl) aniline, 0.24 mM it is bis- (2,
4,6- trimethylphenyls) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae be bicyclic
[2.2.2] octane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stir
It mixes, is cooled to room temperature, be slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate three times (every time
With 10mL), after organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent and is obtained using column chromatographic isolation and purification
To target product.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 84%.
The structural characterization data of 13 products therefrom of embodiment are (nuclear magnetic spectrogram is as shown in Figure 3 and Figure 4) as follows：
1H NMR(400MHz,CDCl3):δ=12.15 (s, 1H), 8.07 (d, J=8.0,1H), 7.43 (t, J=6.0,
1H), 7.20 (q, J=8.0,2H), 7.00 (q, J=6.0,2H), 6.78 (t, J=8.0,2H), 6.53 (s, 2H), 2.15 (s,
3H),1.99(s,6H).
13C NMR(100MHz,CDCl3):δ=165.31,163.17,160.73,158.37,150.43,137.76,
(133.97,131.40 d, J=8.0), 130.91,129.15,128.21,127.93,123.55,122.30,116.51,
116.07,115.03,114.10,113.89,77.32,20.33,16.78.
IR(KBr):3184,2916,1645,1599,1510,1355,1200,1153,756.
MS(EI):M/z (%)=373 [M+],356(100),336,183,162,91,77.
HRMS-ESI(m/z):calcd for C24H20FNO2Na(M+Na)+:396.1370,found:396.1371.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 14
0.20 mM of 2- ((4- (trifluoromethyl) phenyl) acetenyl) aniline, 0.24 mmoles are added in autoclave
Bis- (2,4,6- trimethylphenyl) the iodine fluoroform sulphonates of that, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae
Bicyclic [2.2.2] octane (DABCO), 2 milliliters of DMSO are filled with the CO of 4MPa2, after 60 DEG C are stirred to react 8 hours, stop heating
And stirring, it is cooled to room temperature, is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate three times
(using 10mL every time), after organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent, pure using column chromatography for separation
Change, obtains target product.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield
83%.
The structural characterization data of 14 products therefrom of embodiment are (nuclear magnetic spectrogram is as shown in Figure 5 and Figure 6) as follows：
1H NMR(400MHz,CDCl3):δ=11.68 (s, 1H), 8.13 (d, J=8.0,1H), 7.51 (t, J=6.0,
1H), 7.30 (t, J=8.0,3H), 7.22 (d, J=8.0,1H), 7.11 (d, J=8.0,2H), 6.46 (s, 2H), 2.10 (s,
3H),1.99(s,6H).
13C NMR(100MHz,CDCl3):δ=150.09,137.71,134.59,131.30,130.05,129.17,
(128.44,123.84 q, J=6.0), 122.58,116.37,115.90,20.13,16.71.
IR(KBr):3134,3088,3005,2887,2229,1638,1602,1321,1285,1200,1155,1121,
758.
MS(EI):M/z (%)=423 [M+],406(100),304,233,190,161,120,91,77.
HRMS-ESI(m/z):calcd for C25H20F3NO2Na(M+Na)+:446.1338,found:446.1339.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 15
0.20 mM of 2- ((4- (4- ethylcyclohexyls) phenyl) acetenyl) aniline, 0.24 are added in autoclave
MM bis- (2,4,6- trimethylphenyl) iodine fluoroform sulphonates, 0.04 mM of silver acetate, 0.02 mM of Isosorbide-5-Nitrae-two
Bicyclic [2.2.2] octane (DABCO) of nitrine, 2 milliliters of DMSO are filled with the CO of 4MPa2, after 60 DEG C are stirred to react 8 hours, stop
Heating and stirring, are cooled to room temperature, are slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate three
Secondary (using 10mL every time), after organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent, using column chromatography for separation
Purifying, obtains target product.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, production
Rate 58%.
The structural characterization data of 15 products therefrom of embodiment are (nuclear magnetic spectrogram is as shown in Figure 7 and Figure 8) as follows：
1H NMR(400MHz,CDCl3):δ=11.31 (s, 1H), 8.08 (d, J=8.0,1H), 7.47 (t, J=8.0,
1H), 7.25-7.20 (m, 2H), 6.88 (q, J=24.0,4H), 6.44 (s, 2H), 2.37-2.31 (m, 1H), 2.08 (s, 3H),
1.96 (s, 6H), 1.85 (q, J=40.0,4H), 1.41-1.25 (m, 5H), 1.09-0.99 (m, 2H), 0.93 (t, J=8.0,
3H).
13C NMR(100MHz,CDCl3):δ=158.10,150.40,146.55,137.40,133.36,130.75,
129.34,129.07,128.92,128.21,128.21,125.59,123.72,122.34,116.86,115.82,44.43,
39.15,34.34,33.20,30.02,20.44,16.91,11.53.
IR(KBr):2922,2852,2362,1730,1646,1355,1262,757.
MS(EI):M/z (%)=423 [M+],337,320,207,72,59(100).
HRMS-ESI(m/z):calcd for C32H36NO2(M+H)+:466.2741,found:466.2744.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 16
In autoclave be added 0.20 mM of 2- ((2,4- 3,5-dimethylphenyls) acetenyl) aniline, 0.24 mM
Bis- (2,4,6- trimethylphenyl) iodine fluoroform sulphonates, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae are double
Ring [2.2.2] octane (DABCO), 2 milliliters of DMSO are filled with the CO of 4MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and
Stirring, is cooled to room temperature, is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate (every three times
It is secondary to use 10mL), after organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent, using column chromatographic isolation and purification,
Obtain target product.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield
52%.
The structural characterization data of 16 products therefrom of embodiment are (nuclear magnetic spectrogram is as shown in Figure 9 and Figure 10) as follows：
1H NMR(400MHz,CDCl3):δ=11.57 (s, 1H), 8.00 (d, J=8.0,1H), 7.44 (t, J=8.0,
1H), 7.25-7.16 (m, 2H), 6.84 (s, 1H), 6.68-6.64 (m, 2H), 6.51 (d, J=20.0,2H), 2.24 (s, 3H),
2.14(s,3H),2.09(s,3H),2.00(s,3H),1.92(s,3H).
13C NMR(100MHz,CDCl3):δ=164.77,159.14,151.34,137.76,136,92,136.78,
133.42,130.65,130.03,129.93,129.07,129.05,128.68,128.52,128.21,125.50,123.57,
122.16,116.84,115.98,21.13,20.41,19.86,17.15,16.74.
IR(KBr):3138,2923,2853,1645,1602,1352,1263,1200,1150,754.
MS(EI):M/z (%)=383 [M+],368,352,248(100),207,91,77.
HRMS-ESI(m/z):calcd for C26H25NO2Na(M+Na)+:406.1777,found:406.1783.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 17
In autoclave be added 0.20 mM of 5- bromo- 2- (phenylene-ethynylene) aniline, 0.24 mM it is bis- (2,4,
6- trimethylphenyls) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae be bicyclic
[2.2.2] octane (DABCO), 2 milliliters of DMSO, is filled with the CO of 4MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stir
It mixes, is cooled to room temperature, be slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate three times (every time
With 10mL), after organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent and is obtained using column chromatographic isolation and purification
To target product.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 55%.
The structural characterization data of 17 products therefrom of embodiment are (nuclear magnetic spectrogram is as is illustrated by figs. 11 and 12) as follows：
1H NMR(400MHz,CDCl3):δ=12.09 (s, 1H), 8.21 (d, J=4.0,1H), 7.43 (d, J=8.0,
1H), 7.10-7.03 (m, 3H), 6.96 (q, J=16.0,3H), 6.45 (s, 2H), 2.09 (s, 3H), 1.96 (s, 6H)
13C NMR(100MHz,CDCl3):δ=156.97,150.12,136.53,133.95,133.76,131.51,
129.52,129.10,128.20,127.12,126.02,118.18,117.87,115.07,20.34,16.82.
IR(KBr):2920,2853,1643,1593,1346,1267,699,637.
MS(EI):M/z (%)=433 [M+],417(100),369,352,219,190,162,91,77.
HRMS ESI(m/z):calcd for C24H20BrNO2Na(M+Na)+:456.0570,found:456.0570.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 18
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of bis- (2,4,6- tri- are added in autoclave
Aminomethyl phenyl) iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] be pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 61%.
The structural characterization data of 18 products therefrom of embodiment are (nuclear magnetic spectrogram is as shown in Figure 13 and Figure 14) as follows：
1H NMR(400MHz,CDCl3):δ=12.14 (s, 1H), 8.37 (s, 1H), 7.53 (d, J=8.0,1H), 7.12-
7.05 (m, 4H), 6.97 (d, J=8.0,2H), 6.47 (s, 2H), 2.10 (s, 3H), 1.97 (s, 6H)
13C NMR(100MHz,CDCl3):δ=165.54,157.63,150.10,139.66,134.19,131.37,
(129.53,129.17,128.25,127.21,125.47,121.42 q, J=12.0), 116.85 (d, J=16.0),
116.31,20.33,16.81.
IR(KBr):3179,3056,2924,2732,1660,1475,1353,1268,1123,848,740,702.
MS(EI):M/z (%)=423 [M+],406(100),230,91,77.
HRMS-ESI(m/z):calcd for C25H21F3NO2(M+H)+:424.1519,found 424.1521.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 19
0.40 mM of 2,4- bis- chloro- 6- (phenylene-ethynylene) aniline, 0.04 mM of vinegar are added in autoclave
Sour silver, 0.20 mM of bis- (2,4,6- trimethylphenyl) iodine fluoroform sulphonates, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae are bicyclic
[2.2.2] octane (DABCO), 2 milliliters of DMSO, is filled with the CO of 4MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stir
It mixes, is cooled to room temperature, be slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate three times (every time
With 10mL), after organic phase merging is dried over anhydrous sodium sulfate, vacuum distillation removes solvent and is obtained using column chromatographic isolation and purification
To target product.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 71%.
The structural characterization data of 19 products therefrom of embodiment are (nuclear magnetic spectrogram is as shown in Figure 15 and Figure 16) as follows：
1H NMR(400MHz,CDCl3):δ=9.32 (s, 1H), 8.08 (d, J=4.0,1H), 7.61 (d, J=4.0,
1H), 7.06-7.00 (m, 3H), 6.90 (d, J=8.0,2H), 6.44 (s, 2H), 2.08 (s, 3H), 1.97 (s, 6H)
13C NMR(100MHz,CDCl3):δ=163.17,156.15,149.84,134.23,132.50,130.64,
130.43,129.12,128.08,127.46,1276.33,127.15,122.62,119.76,118.90,117.61,99.90,
20.30,16.77.
IR(KBr):3029,2922,2855,1647,1436,1341,751,698,563,522.
MS(EI):M/z (%)=423 [M+],408,406(100),303,230,190,91,77.
HRMS-ESI(m/z):calcd for C24H19Cl2NO2Na(M+Na)+:446.0685,found 446.0685.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 20
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of 4-bromo- 4 '-methoxy are added in autoclave
Base diphenyl iodine fluoroform sulphonate, 0.04 mM of silver acetate, bicyclic [2.2.2] octane of 0.02 mM of-two nitrine of Isosorbide-5-Nitrae
(DABCO), 2 milliliters of DMSO are filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to room
Temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, organic
Mutually merge after being dried over anhydrous sodium sulfate, vacuum distillation removes solvent and obtains target product using column chromatographic isolation and purification.
It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 88%.
The structural characterization data of 20 products therefrom of embodiment are (nuclear magnetic spectrogram is as shown in Figure 17 and Figure 18) as follows：
1H NMR(600MHz,DMF-d7):δ=11.98 (s, 1H), 7.64-7.57 (m, 3H), 7.47 (d, J=12.0,
2H), 7.42 (d, J=6.0,2H), 7.31 (t, J=9.0,2H), 7.25 (t, J=9.0,1H), 7.21 (t, J=9.0,1H),
6.95 (d, J=12.0,2H)
13C NMR(150MHz,DMF-d7):δ=157.70,156.05,140.27,133.69,133.30,132.25,
131.45,128.72,128.57,125.78,124.54,123.14,118.89,116.88,116.80,116.61,115.19.
IR(KBr):3062,2922,2853,1703,1665,1613,1486,1353,700.
MS(EI):M/z (%)=347 [M+],228,200,165(100),146,119.
HRMS-ESI(m/z):calcd for C21H14BrNO2Na(M+Na)+:370.0605,found 370.0611.
Infer that the structure of products therefrom is as follows according to data above：
Embodiment 21
0.20 mM of 2- (phenylene-ethynylene) aniline, 0.24 mM of 2- cyano -4 '-first are added in autoclave
Oxygroup diphenyl iodine fluoroform sulphonate, 0.04 mM of silver acetate, 0.02 mM of-two nitrine of Isosorbide-5-Nitrae bicyclic [2.2.2] are pungent
Alkane (DABCO), 2 milliliters of DMSO, is filled with the CO of 1MPa2, after 60 DEG C are stirred to react 8 hours, stop heating and stirring, be cooled to
Room temperature is slowly vented unreacted CO2.Reaction solution is washed with 10mL, then is extracted with ethyl acetate and (is used 10mL every time) three times, is had
Machine mutually merges be dried over anhydrous sodium sulfate after, vacuum distillation removes solvent, using column chromatographic isolation and purification, obtains target production
Object.It is 2 that column chromatography eluent used, which is volume ratio,：1 petroleum ether：Ethyl acetate mixed solvent, yield 80%.
The structural characterization data of 21 products therefrom of embodiment are (nuclear magnetic spectrogram is as illustrated in figures 19 and 20) as follows：
1H NMR(600MHz,DMF-d7):δ=12.11 (s, 1H), 7.76 (d, J=12.0,1H), 7.67 (q, J=6.0,
2H), 7.63 (d, J=6.0,1H), 7.50 (q, J=6.0,3H), 7.33-7.24 (m, 4H), 7.14 (t, J=6.0,1H),
7.06 (d, J=6.0,1H)
13C NMR(150MHz,DMF-d7):δ=162.47,158.50,154.76,139.41,135.20,134.18,
132.05,131.80,130.62,128.13,127.90,124.70,123.39,123.25,122.67,115.96,115.91,
115.89,115.60,101.71.
IR(KBr):2924,2854,2362,2232,1731,1642,1256,698.
MS(EI):M/z (%)=338 [M+],321,310,236,190,165,120(100),92,77.
HRMS-ESI(m/z):calcd for C22H14N2O2Na(M+Na)+:361.0947,found:361.0944.
Infer that the structure of products therefrom is as follows according to data above：
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention
All any modification, equivalent and improvement etc., should be included in the protection of the claims in the present invention made by within spirit and principle
Within the scope of.
Claims (10)
1. a kind of method of polysubstituted 2 (the 1H)-quinolinones compound of synthesis, which is characterized in that in autoclave, be added
2- (aryl ethane base) aniline and diaryl iodonium salt are raw material, and after catalyst is added, additive is added, and are molten with organic solvent
Agent is passed through carbon dioxide, is stirred to react 6~24 hours, is cooled to room temperature after reaction, slow release at 40~120 DEG C
Unreacted carbon dioxide is to normal pressure, and reaction solution obtains crude product after washing, extraction, washing, drying, reduced pressure, through column layer
Analysis purification obtains polysubstituted 2 (1H)-quinolinones compounds described in series；
Its reaction is shown below：
Wherein, R1It is methyl, fluorine-based, chloro, bromo or trifluoromethyl；
R2It is methyl, fluorine-based, chloro, bromo, methoxyl group, cyano or trifluoromethyl；
R3And R4It is fluorine-based, chloro, bromo, cyano, methyl, trifluoromethyl, tertiary butyl or nitro；
The catalyst is silver salt；The additive is alkali.
2. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 1, which is characterized in that
The R1It is 5- methyl, 5- fluorine, 5- chlorine, 5- bromines, 5- trifluoromethyls, 4- fluorine, 4- chlorine, 4- methyl or 4- bromines；
The R2It is 2- fluorine, 2- chlorine, 2- bromines, 2- methyl, 3- fluorine, 3- chlorine, 3- bromines, 3- methyl, 3- methoxyl groups, 4- fluorine, 4- chlorine, 4-
Bromine, 4- methyl, 4- trifluoromethyls or 4- cyano；
The R3And R4It is 2- fluorine, 3- fluorine, 2- fluorine, 2- chlorine, 4- chlorine, 2- cyano, 3- methyl, 4- bromines, 4- trifluoromethyls, the tertiary fourths of 4-
Base or 4- nitros.
3. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 1, which is characterized in that
Autoclave uses gap type high-pressure reaction kettle or continuous high pressure reaction kettle；2- (aryl ethane base) aniline and Diaryl iodonium
The molar ratio of salt is 1：(1~1.5).
4. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 1, which is characterized in that
The silver salt is silver acetate, silver nitrate, silver carbonate, silver chlorate, silver fluoride or silver tetrafluoroborate.
5. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 4, it is characterised in that：
The amount that catalyst is added and the molar ratio of 2- (aryl ethane base) aniline are (0.1~0.5)：1.
6. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 1, it is characterised in that：
The additive is sodium carbonate, potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium tert-butoxide, tert-butyl alcohol lithium, 1,4- diazabicylos
11 carbon -7- alkene of [2.2.2] octane, tri- azabicyclics of 1,5,7- [4.4.0] decyl- 5- alkene or 1,8- diazabicylos [5.4.0].
7. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 6, it is characterised in that：
The amount that alkali is added and the molar ratio of 2- (aryl ethane base) aniline are (0.1~1):1.
8. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 1, it is characterised in that：
Solvent is dimethyl sulfoxide (DMSO).
9. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 1, it is characterised in that：
The pressure of carbon dioxide is 0.5~6MPa.
10. a kind of method of polysubstituted 2 (1H)-quinolinones compound of synthesis according to claim 1, feature exist
In product is isolated and purified using column chromatography after reaction；The column chromatography eluent is the mixed of petroleum ether and ethyl acetate
Bonding solvent；Volume ratio between petroleum ether and ethyl acetate is (1~5)：1.
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| Cu(I)-catalyzed chemical fixation of CO2 with 2-alkynylaniline into 4-hydroxyquinolin-2(1H)-one;Chun-Xiao Guo，等;《Catal. Sci. Technol》;20131213;第4卷;第1570–1577页 * |
| Tomonobu Ishida，等.Efficient Preparation of 4‑Hydroxyquinolin-2(1H)‑one Derivatives with Silver-Catalyzed Carbon Dioxide Incorporation and Intramolecular Rearrangement.《Org. Lett.》.2013,第15卷(第4期),第3710–3713页. * |
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