CN109422700A - A kind of synthetic method of N- acetyl group quinoxaline -2- amide and its derivative - Google Patents

A kind of synthetic method of N- acetyl group quinoxaline -2- amide and its derivative Download PDF

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CN109422700A
CN109422700A CN201710740529.0A CN201710740529A CN109422700A CN 109422700 A CN109422700 A CN 109422700A CN 201710740529 A CN201710740529 A CN 201710740529A CN 109422700 A CN109422700 A CN 109422700A
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quinoxaline
amide
derivative
acetyl group
formula
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刘运奎
鲍汉扬
刘潋滟
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Jiang University Of Technology
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Jiang University Of Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D241/00Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/40Benzopyrazines
    • C07D241/44Benzopyrazines 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 carbon atoms of the hetero ring

Abstract

The invention discloses the synthetic methods of a kind of N- acetyl group quinoxaline -2- amide and its derivative: using quinoxaline -2- formaldehyde shown in formula I or formula III as starting material; it is dissolved in the mixed solvent; under copper catalyst and oxidant effect; it is reacted 3~12 hours in 40~80 DEG C, gained reaction solution is post-treated to respectively obtain N- acetyl group quinoxaline -2- amide and its derivative shown in formula II or formula IV;The copper catalyst is copper trifluoromethanesulfcomposite, copper acetate or copper chloride;The oxidant is one of tertbutanol peroxide aqueous solution of ammonium persulfate, potassium peroxydisulfate, the chloro- 5,6- dicyano -1,4- benzoquinones of 2,3- bis- or 70%wt or more than one mixture;The mixed solvent is the mixed solution of the acetonitrile that volume ratio is 5~100:1 and water;The ratio between the amount of substance of quinoxaline -2- formaldehyde shown in the catalyst and the oxidant, formula I is 0.01~0.3:1~1.2:1.

Description

A kind of synthetic method of N- acetyl group quinoxaline -2- amide and its derivative
(1) technical field
The present invention relates to a kind of synthetic methods of organic compound, relate in particular to a kind of N- acetyl group quinoxaline -2- The synthetic method of amide and its derivative.
(2) background technique
Quinoxaline is a kind of important benzopyrazines heterocyclic compounds with armaticity.Many quinoxaline derivant tools There are anticancer, antibacterial isoreactivity.There are also many quinoxaline derivants significant effect in clinical trial, the quinoxalines of some functionalization Derivative is expected to be used as organic semiconductor, chemical switch and Supramolecular Receptors.Quinoxaline can aggregate into high polymer, aromatic heterocycle High polymer has heat-resisting, the high good characteristics such as plastic, high-intensitive and corrosion-resistant.Phenyl replaces the quinoxaline of hydrogen, the introducing of phenyl It is greatly improved the thermal stability of polymer, quinoxaline derivant can also be used in synthetic dyestuffs, since quinoxaline derivant is being cured Medicine, pesticide, dyestuff etc. have a wide range of applications, so its study on the synthesis receives much attention.On the other hand, aryl amides Close the important as precursors that object is synthesis of natural product, drug, pesticide, high molecular polymer.Based on quinoxaline derivatives and aryl The related synthetic technology of the extensive use of amides compound, research and development quinoxalinyl amide has broad prospect of application.
Currently, the amide synthetic method generallyd use is: carboxylic acid forms under the action of activating reagent active intermediate first Body, such as active ester, carboxylic acid halides and acid anhydrides, then the intermediate is again acylated amine.But such method is in Atom economy It goes up no advantage and to have pollution and toxicant using some, be unfavorable for industrial application.Chemists go back in recent years Developed the method for some novel synthesizing amides: 1. provide a group centered on nitrogen with formamide, with aldehyde and first Amide reacts purposed amide class compound.The method is free radical process, needs higher temperature and needs large excess of uncle Butylhydroperoxide.2. the pure and mild amide using equivalent has directly generated amide compound under the catalytic action of ruthenium complex. The method needs to use noble ruthenium, and needs ligand to be used sufficiently complex.3. being urged using manganese Metal complex and hydrogen peroxide Change oxidation phenylacetylene and ammonium reaction forms amide, has more than 80% yield.The hydrogen peroxide that the method uses is too dangerous.Mirror In above-mentioned problem, the synthetic route that a kind of raw material is simple and easy to get, the reaction time is short, easy to operate, reaction is mild is developed Come synthesize N- acetyl group quinoxaline -2- amides compound be very it is necessary to.
(3) summary of the invention
For the deficiencies in the prior art, the present invention is intended to provide a kind of prepare N- acetyl group quinoxaline -2- amide And its method of derivative, the shortcomings that overcoming the prior art, with the expensive noble metal of base metal substitution, with quinoline simple and easy to get Quinoline -2- formaldehyde replaces carboxylic acid, is amine source using cheap itrile group class compound and realization is reacted under the conditions of relatively mild.
The synthetic method of a kind of N- acetyl group quinoxaline -2- amide and its derivative, the method specifically press following step It is rapid to carry out:
It is dissolved in the mixed solvent as starting material using quinoxaline -2- formaldehyde shown in formula I, is made in copper catalyst and oxidant Under, reacted 3~12 hours in 40~80 DEG C, gained reaction solution is post-treated to obtain N- acetyl group quinoxaline-shown in formula II 2- amide and its derivative;The copper catalyst is copper trifluoromethanesulfcomposite, copper acetate or copper chloride;The oxidant was One in ammonium sulfate, potassium peroxydisulfate, the chloro- 5,6- dicyano -1,4- benzoquinones of 2,3- bis- or 70%wt tertbutanol peroxide aqueous solution Kind or more than one mixture;The mixed solvent is the mixed solution of the acetonitrile that volume ratio is 5~100:1 and water;Institute The ratio between amount of substance of quinoxaline -2- formaldehyde shown in the catalyst stated and the oxidant, formula I for 0.01~0.3:1~ 1.2:1
In Formulas I or formula II:
R1For H, CH3、CH2CH3、OCH3、OCH2CH3, Cl or Br;
R2For H, CH3、CH2CH3、OCH3、OCH2CH3、F、Cl、Br、
n1~n2Represent the number of substituent group, n1For 1~4, n2It is 1~5.
Further, the additional amount of the mixed solvent is with the amount of the substance of quinoxaline -2- formaldehyde shown in the formula I It is calculated as 10~12ml/mmol.
Further, the preferably described reaction temperature is 60 DEG C, and the reaction time is 6 hours.
Further, the ratio between the preferably described catalyst and the amount of substance of quinoxaline -2- formaldehyde shown in oxidant, formula I For 0.2:1:1.
Further, the preferably described copper catalyst is copper trifluoromethanesulfcomposite.
Further, the preferably described oxidant is ammonium persulfate.
Further, the preferably described mixed solvent is the mixed solution that volume ratio is 100:1 acetonitrile and water.
Further, recommend the post-processing approach of the reaction solution are as follows: after reaction, be added into gained reaction solution The column chromatography silica gel of 100-200 mesh is simultaneously evaporated under reduced pressure removing solvent, gained crude product is carried out silica gel column chromatography separation, and with body Product is than being that the petroleum ether of 10:1 and the mixture of ethyl acetate are eluted as eluant, eluent, and TLC tracks elution process, and collection contains There is the eluent of target product, merges the eluent solvent is evaporated off and obtain N- acetyl group quinoline shown in the formula II Quinoline -2- amide and its derivative.
The synthetic method of a kind of N- acetyl group quinoxaline -2- amide and its derivative, the method specifically press following step It is rapid to carry out:
It is dissolved in the mixed solvent as starting material using quinoxaline -2- formaldehyde shown in formula III, is made in copper catalyst and oxidant Under, reacted 3~12 hours in 40~80 DEG C, gained reaction solution is post-treated to obtain N- acetyl group quinoxaline-shown in formula IV 2- amide and its derivative;The copper catalyst is copper trifluoromethanesulfcomposite, copper acetate or copper chloride;The oxidant was One in ammonium sulfate, potassium peroxydisulfate, the chloro- 5,6- dicyano -1,4- benzoquinones of 2,3- bis- or 70wt% tertbutanol peroxide aqueous solution Kind or more than one mixture;The mixed solvent is the mixed solution of the acetonitrile that volume ratio is 5~100:1 and water;Institute The ratio between amount of substance of quinoxaline -2- formaldehyde shown in the catalyst stated and the oxidant, formula III for 0.01~0.3:1~ 1.2:1
In formula III or formula IV:
R3For H, CH3、CH2CH3、OCH3、OCH2CH3, Cl or Br;R4For H, Cl or CH3
N represents the number of substituent group, and n is 1~4.
Further, the additional amount of the mixed solvent is with the substance of quinoxaline -2- formaldehyde shown in the formula III Amount is calculated as 10~12ml/mmol.
Further, preferably, the reaction temperature is 60 DEG C, the reaction time is 6 hours.
Further, the preferably described catalyst and the substance of quinoxaline -2- formaldehyde shown in the oxidant, formula III The ratio between amount is 0.2:1:1.
Further, the preferably described copper catalyst is copper trifluoromethanesulfcomposite.
Further, the preferably described oxidant is ammonium persulfate.
Further, the preferably described mixed solvent is the mixed solution that volume ratio is 100:1 acetonitrile and water.
Further, recommend the post-processing approach of the reaction solution are as follows: after reaction, be added into gained reaction solution The column chromatography silica gel of 100-200 mesh is simultaneously evaporated under reduced pressure removing solvent, gained crude product is carried out silica gel column chromatography separation, and with body Product is than being that the petroleum ether of 10:1 and the mixture of ethyl acetate are eluted as eluant, eluent, and TLC tracks elution process, and collection contains There is the eluent of target product, merges the eluent solvent is evaporated off and obtain N- acetyl group quinoline shown in the formula IV Quinoline -2- amide and its derivative.
Raw material quinoxaline -2- the formaldehyde that the present invention uses, those skilled in the art side according to disclosed in existing literature Method is voluntarily prepared, such as document [Jarikote, Dilip V.et al, Bioorganic&Medicinal Chemistry, 2011,19,826-835] etc..
Compared with prior art, the beneficial effects of the present invention are:
The present invention passes through quinoline -2- formaldehyde under copper trifluoromethanesulfcomposite/potassium peroxydisulfate catalyst system effect, using acetonitrile as amine Source, water are oxygen source, and N- acetylquinoline -2- amide is made and its derivative, raw material are simple and easy to get;Catalyst is cheap and easy to get, it is low It is malicious efficient, and assisted without extra ligand;Reaction condition is milder, saves energy consumption;It is few to generate waste;In addition, also having The features such as yield is high, and atom economy type is good, and substrate universality is strong, easy to operate.
(4) specific implementation method
Invention is further described in detail combined with specific embodiments below, but protection scope of the present invention is not limited to This:
The tertbutanol peroxide aqueous solution of 70%wt of the present invention is bought by An Naiji Reagent Company.
The synthetic method for the raw material quinoxaline -2- formaldehyde that the present invention uses:
(1) acetophenone compounds (20mmol) and 100mL ether are added in the round-bottomed flask of 250mL, are dripped under ice bath Liquid feeding bromine (22mmol, 1.07mL) is added dropwise rear solution and rufous is presented, remove ice bath, stirs 1 hour at room temperature, reddish brown Color gradually takes off, and uses NaS after reaction2O3Solution washes away extra bromine, is extracted with ether, anhydrous Na2SO4It is dry, mistake Filter, vacuum distillation remove solvent, and the alpha-brominated propiophenone of gained crude product is not required to be further purified, and can be directly used in next step.
(2) by alpha-brominated propiophenone (20mmol), HClO obtained by step (1)4-SiO4(2.6g) and 100 mL acetonitriles are added In the round-bottomed flask of 250mL, under magnetic stirring, corresponding o-phenylenediamine is dissolved in 20mL acetonitrile, is added drop-wise to round bottom burning In bottle, stirs, detected with TLC at room temperature, until fully reacting (it is generally necessary to 2-3 days), filtering, wash filter residue with methylene chloride, The column chromatography silica gel of 100-200 mesh is added into filtrate and is evaporated under reduced pressure removing solvent, gained crude product is subjected to silica gel column layer Analysis separation, and eluted using volume ratio for the petroleum ether of 20:1 and the mixture of ethyl acetate as eluant, eluent, collect elution TLC tracks elution process to liquid simultaneously, and solvent is evaporated off in the obtained eluent containing target product and obtains the production of 2- methyl-quinoxaline Object sterling.
(3) selenium dioxide (18mmol, 2g), Isosorbide-5-Nitrae-dioxane of 80mL and 5mL water are added in round-bottomed flask, heating Selenium dioxide is dissolved, 2- methyl-quinoxaline obtained by step (2) is then added, is heated to 105 DEG C, is flowed back 5 hours.TLC detection Reaction uses diatomite drainage after reaction, washs filter residue with methylene chloride, merging filtrate is added a large amount of water, uses methylene chloride Extraction, merge organic layer simultaneously the column chromatography silica gel of 100-200 mesh is added and is evaporated under reduced pressure removing solvent, by gained crude product into The separation of row silica gel column chromatography, and washed using volume ratio for the petroleum ether of 30:1 and the mixture of ethyl acetate as eluant, eluent De-, collecting eluent, TLC tracks elution process simultaneously, and solvent is evaporated off in the obtained eluent containing target product and obtains quinoline Quinoline -2- aldehyde products sterling.
Embodiment 1
By 0.3mmol 3- phenyl-quinoxaline -2- formaldehyde (70.2mg), 0.3mmol ammonium persulfate (68.5 mg) and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) is added in 15mL heavy wall pressure resistance reaction tube, adds 3mL acetonitrile and 30 μ L water Make solvent.Then, two spoon column chromatography silica gel (100-200 are added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1's with volume ratio The mixture of petroleum ether and ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, and collection contains target product Eluent, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 89%.Characterize number According to:1H NMR(500MHz,CDCl3):δ10.26(s,1H),8.23(dd,J1=8.5Hz, J2=1.0Hz, 1H), 8.19 (dd, J1=8.5Hz, J2=1.0Hz, 1H), 7.96-7.93 (m, 2H), 7.91-7.87 (m, 1H), 7.68-7.66 (m, 2H), 7.54- 7.53(m,3H),2.55(s,3H);13C NMR(125MHz, CDCl3):δ172.2,162.9,154.4,143.1,142.0, 138.9,138.3,132.9,131.1,129.42, 129.37,129.3,128.9,128.3,25.3.
Embodiment 2
By 0.3mmol 3- phenyl-quinoxaline -2- formaldehyde (70.2mg), the chloro- 5,6- dicyano-of 0.3mmol 2,3- bis- Isosorbide-5-Nitrae-benzoquinones (68.1mg) and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) are added in 1 5mL heavy wall pressure resistance reaction tube, then 3mL acetonitrile and 30 μ L water as solvent are added.Then, magnetic agitation 6 hours at 60 DEG C, two spoons are added into gained reaction solution Column chromatography silica gel (100-200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, And eluted using volume ratio for the petroleum ether of 10:1 and the mixture of ethyl acetate as eluant, eluent, TLC tracking elute into Journey collects the eluent containing target product, merges the eluent solvent is evaporated off and obtain target product.The substance is white Solid, yield 40%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.26(s,1H),8.23(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.19(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.96-7.93 (m, 2H), 7.91-7.87 (m, 1H), 7.68–7.66(m,2H),7.54–7.53(m,3H),2.55(s,3H);13C NMR(125MHz, CDCl3):δ172.2, 162.9,154.4,143.1,142.0,138.9,138.3,132.9,131.1,129.42, 129.37,129.3,128.9, 128.3,25.3.
Embodiment 3
By 0.3mmol 3- phenyl-quinoxaline -2- formaldehyde (70.2mg), 0.3mmol potassium peroxydisulfate (81 mg) and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) is added in 15mL heavy wall pressure resistance reaction tube, adds 3mL acetonitrile and 30 μ L water Make solvent.Then, two spoon column chromatography silica gel (100-200 are added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1's with volume ratio The mixture of petroleum ether and ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, and collection contains target product Eluent, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 83%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.26(s,1H),8.23(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.19(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.96-7.93 (m, 2H), 7.91-7.87 (m, 1H), 7.68–7.66(m,2H),7.54–7.53(m,3H),2.55(s,3H);13C NMR(125MHz, CDCl3):δ172.2, 162.9,154.4,143.1,142.0,138.9,138.3,132.9,131.1,129.42, 129.37,129.3,128.9, 128.3,25.3.
Embodiment 4
By the tertiary fourth of peroxidating of 0.3mmol 3- (4- chlorphenyl)-quinoxaline -2- formaldehyde (80.4mg), 0.6mmol 70% Alcohol solution and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) are added in 15mL heavy wall pressure resistance reaction tube, add 3mL second Nitrile and 30 μ L water as solvent.Then, two spoon columns chromatography silicon is added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Glue (100-200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and with volume Mixture than petroleum ether and ethyl acetate for 10:1 is eluted as eluant, eluent, and TLC tracks elution process, and collection contains The eluent of target product, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 56%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.26(s,1H),8.23(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.19(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.96-7.93 (m, 2H), 7.91-7.87 (m, 1H), 7.68–7.66(m,2H),7.54–7.53(m,3H),2.55(s,3H);13C NMR(125MHz, CDCl3):δ172.2, 162.9,154.4,143.1,142.0,138.9,138.3,132.9,131.1,129.42, 129.37,129.3,128.9, 128.3,25.3.
Embodiment 5
By 0.3mmol 3- (4- chlorphenyl)-quinoxaline -2- formaldehyde (80.4mg), 0.6mmol ammonium persulfate (68.5mg) It is added in 15mL heavy wall pressure resistance reaction tube with 0.06mmol copper chloride (6mg), adds 3mL acetonitrile and 30 μ L water as solvent. Then, two spoon column chromatography silica gels (100-200 mesh) is added into gained reaction solution, and leads to for magnetic agitation 6 hours at 60 DEG C Cross vacuum distillation remove solvent, by gained crude product carry out silica gel column chromatography separation, and with volume ratio for 10:1 petroleum ether and The mixture of ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, collects the eluent containing target product, Eluent described in merging is evaporated off solvent and obtains target product.The substance is white solid, yield 23%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.26(s,1H),8.23(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.19(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.96-7.93 (m, 2H), 7.91-7.87 (m, 1H), 7.68–7.66(m,2H),7.54–7.53(m,3H),2.55(s,3H);13C NMR(125MHz, CDCl3):δ172.2, 162.9,154.4,143.1,142.0,138.9,138.3,132.9,131.1,129.42, 129.37,129.3,128.9, 128.3,25.3.
Embodiment 6
By 0.3mmol 3- (4- chlorphenyl)-quinoxaline -2- formaldehyde (80.4mg), 0.6mmol ammonium persulfate (68.5mg) It is added in 15mL heavy wall pressure resistance reaction tube with 0.06mmol copper acetate (12mg), adds 3mL acetonitrile and 30 μ L water as solvent. Then, two spoon column chromatography silica gels (100-200 mesh) is added into gained reaction solution, and leads to for magnetic agitation 6 hours at 60 DEG C Cross vacuum distillation remove solvent, by gained crude product carry out silica gel column chromatography separation, and with volume ratio for 10:1 petroleum ether and The mixture of ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, collects the eluent containing target product, Eluent described in merging is evaporated off solvent and obtains target product.The substance is white solid, yield 16%.Characterize data:1H NMR(500MHz,CDCl3):δ10.26(s,1H),8.23(dd,J1=8.5Hz, J2=1.0Hz, 1H), 8.19 (dd, J1= 8.5Hz,J2=1.0Hz, 1H), 7.96-7.93 (m, 2H), 7.91-7.87 (m, 1H), 7.68-7.66 (m, 2H), 7.54- 7.53(m,3H),2.55(s,3H);13C NMR(125MHz, CDCl3):δ172.2,162.9,154.4,143.1,142.0, 138.9,138.3,132.9,131.1,129.42, 129.37,129.3,128.9,128.3,25.3.
Embodiment 7
By the chloro- quinoxaline -2- formaldehyde (57.8mg) of 0.3mmol 3-, 0.3mmol ammonium persulfate (68.5 mg) and 0.003mmol copper trifluoromethanesulfcomposite (1.1mg) is added in 15mL heavy wall pressure resistance reaction tube, adds 3mL acetonitrile and 30 μ L water Make solvent.Then, two spoon column chromatography silica gel (100-200 are added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1's with volume ratio The mixture of petroleum ether and ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, and collection contains target product Eluent, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 38%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.21(s,1H),8.16(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.11(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.99-7.89 (m, 2H), 2.66 (s, 3H);13C NMR (125MHz,CDCl3):δ172.0,162.8,145.2,143.1,140.1,138.5,134.0, 131.7,129.4,128.4, 25.4.
Embodiment 8
By the chloro- quinoxaline -2- formaldehyde (57.8mg) of 0.3mmol 3-, 0.3mmol ammonium persulfate (68.5 mg) and 0.03mmol copper trifluoromethanesulfcomposite (10.9mg) is added in 15mL heavy wall pressure resistance reaction tube, adds 3mL acetonitrile and 30 μ L water Make solvent.Then, two spoon column chromatography silica gel (100-200 are added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1's with volume ratio The mixture of petroleum ether and ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, and collection contains target product Eluent, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 59%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.21(s,1H),8.16(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.11(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.99-7.89 (m, 2H), 2.66 (s, 3H);13C NMR (125MHz,CDCl3):δ172.0,162.8,145.2,143.1,140.1,138.5,134.0, 131.7,129.4,128.4, 25.4.
Embodiment 9
By the chloro- quinoxaline -2- formaldehyde (57.8mg) of 0.3mmol 3-, 0.3mmol ammonium persulfate (68.5 mg) and 0.09mmol copper trifluoromethanesulfcomposite (32.6mg) is added in 15mL heavy wall pressure resistance reaction tube, adds 3mL acetonitrile and 30 μ L water Make solvent.Then, two spoon column chromatography silica gel (100-200 are added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1's with volume ratio The mixture of petroleum ether and ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, and collection contains target product Eluent, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 70%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.21(s,1H),8.16(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.11(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.99-7.89 (m, 2H), 2.66 (s, 3H);13C NMR (125MHz,CDCl3):δ172.0,162.8,145.2,143.1,140.1,138.5,134.0, 131.7,129.4,128.4, 25.4.
Embodiment 10
By 0.3mmol quinoxaline -2- formaldehyde (47.5mg), 0.36mmol ammonium persulfate (68.5mg) and 0.06mmol tri- Fluorine copper methane sulfonate (21.7mg) is added in 15mL heavy wall pressure resistance reaction tube, adds 3mL acetonitrile and 30 μ L water as solvent.It connects , two spoon column chromatography silica gels (100-200 mesh) is added into gained reaction solution, and passes through for magnetic agitation 6 hours at 60 DEG C Vacuum distillation removes solvent, gained crude product is carried out silica gel column chromatography separation, and be the petroleum ether and second of 10:1 with volume ratio The mixture of acetoacetic ester is eluted as eluant, eluent, and TLC tracks elution process, collects the eluent containing target product, is closed And the eluent is evaporated off solvent and obtains target product.The substance is white solid, yield 75%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.31(s,1H),9.66(s,1H),8.20(dd,J1= 8.5Hz,J2=1.0Hz, 1H), 8.14 (dd, J1=8.5Hz, J2=1.0Hz, 1H), 7.94-7.87 (m, 2H), 2.69 (s, 3H);13C NMR(125MHz,CDCl3):δ171.8,162.0,144.4,143.5,141.5,139.9, 132.7,131.4, 129.8,129.5,25.4.
Embodiment 11
By 0.3mmol quinoxaline -2- formaldehyde (47.5mg), 0.30mmol potassium peroxydisulfate (68.5mg) and 0.06mmol tri- Fluorine copper methane sulfonate (21.7mg) is added in 15mL heavy wall pressure resistance reaction tube, adds 3mL acetonitrile and 0.6mL water as solvent.It connects , two spoon column chromatography silica gels (100-200 mesh) is added into gained reaction solution, and passes through for magnetic agitation 6 hours at 60 DEG C Vacuum distillation removes solvent, gained crude product is carried out silica gel column chromatography separation, and be the petroleum ether and second of 10:1 with volume ratio The mixture of acetoacetic ester is eluted as eluant, eluent, and TLC tracks elution process, collects the eluent containing target product, is closed And the eluent is evaporated off solvent and obtains target product.The substance is white solid, yield 52%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.31(s,1H),9.66(s,1H),8.20(dd,J1= 8.5Hz,J2=1.0Hz, 1H), 8.14 (dd, J1=8.5Hz, J2=1.0Hz, 1H), 7.94-7.87 (m, 2H), 2.69 (s, 3H);13C NMR(125MHz,CDCl3):δ171.8,162.0,144.4,143.5,141.5,139.9, 132.7,131.4, 129.8,129.5,25.4.
Embodiment 12
By 0.3mmol 6- methylquinoline -2- formaldehyde (47.5mg), 0.30mmol potassium peroxydisulfate (68.5 mg) and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) is added in 15mL heavy wall pressure resistance reaction tube, adds 3mL acetonitrile and 0.003mL Water as solvent.Then, two spoon column chromatography silica gel (100- are added into gained reaction solution for magnetic agitation 6 hours at 40 DEG C 200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1 with volume ratio Petroleum ether and the mixture of ethyl acetate eluted as eluant, eluent, TLC tracks elution process, and collection contains target product Eluent, merge the eluent solvent be evaporated off and obtain target product.The substance is white solid, yield 41%.Characterization Data:1H NMR(500MHz,CDCl3):δ10.31(s,1H),9.66(s,1H),8.20(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.14(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.94-7.87 (m, 2H), 2.69 (s, 3H);13C NMR (125MHz,CDCl3):δ171.8,162.0,144.4,143.5,141.5,139.9, 132.7,131.4,129.8,129.5, 25.4.
Embodiment 13
By 0.3mmol 3- (3- bromophenyl)-quinoxaline -2- formaldehyde (93.6mg), 0.30mmol ammonium persulfate (68.5mg) It is added in 15mL heavy wall pressure resistance reaction tube with 0.06mmol copper trifluoromethanesulfcomposite (21.7mg), adds 3mL acetonitrile and 30 μ L Water as solvent.Then, two spoon column chromatography silica gel (100- are added into gained reaction solution for magnetic agitation 6 hours at 80 DEG C 200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1 with volume ratio Petroleum ether and the mixture of ethyl acetate eluted as eluant, eluent, TLC tracks elution process, and collection contains target product Eluent, merge the eluent solvent be evaporated off and obtain target product.The substance is white solid, yield 75%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.32(s,1H),8.22(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.20(dd,J1=8.0Hz, J2=1.0Hz, 1H), 7.99-7.95 (m, 1H), 7.94-7.90 (m, 1H), 7.83 (t, J=2.0Hz, 2H), 7.86-7.64 (m, 1H), 7.57-7.54 (m, 1H), 7.39 (t, J=8.0Hz, 1H), 2.57 (s,3H);13C NMR(125MHz,CDCl3):δ172.2,162.6,152.9, 143.0,141.5,139.1,133.2, 132.3,131.8,131.6,129.6,129.5,129.4,127.7,122.4, 25.4.
Embodiment 14
By 0.3mmol 3- (3- bromophenyl)-quinoxaline -2- formaldehyde (93.6mg), 0.30mmol ammonium persulfate (68.5mg) It is added in 15mL heavy wall pressure resistance reaction tube with 0.06mmol copper trifluoromethanesulfcomposite (21.7mg), adds 3mL acetonitrile and 30 μ L Water as solvent.Then, two spoon column chromatography silica gel (100- are added into gained reaction solution for magnetic agitation 3 hours at 60 DEG C 200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1 with volume ratio Petroleum ether and the mixture of ethyl acetate eluted as eluant, eluent, TLC tracks elution process, and collection contains target product Eluent, merge the eluent solvent be evaporated off and obtain target product.The substance is white solid, yield 55%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.32(s,1H),8.22(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.20(dd,J1=8.0Hz, J2=1.0Hz, 1H), 7.99-7.95 (m, 1H), 7.94-7.90 (m, 1H), 7.83 (t, J=2.0Hz, 2H), 7.86-7.64 (m, 1H), 7.57-7.54 (m, 1H), 7.39 (t, J=8.0Hz, 1H), 2.57 (s,3H);13C NMR(125MHz,CDCl3):δ172.2,162.6,152.9, 143.0,141.5,139.1,133.2, 132.3,131.8,131.6,129.6,129.5,129.4,127.7,122.4, 25.4.
Embodiment 15
By 0.3mmol 3- (3- bromophenyl)-quinoxaline -2- formaldehyde (93.6mg), 0.30mmol ammonium persulfate (68.5mg) It is added in 15mL heavy wall pressure resistance reaction tube with 0.06mmol copper trifluoromethanesulfcomposite (21.7mg), adds 3mL acetonitrile and 30 μ L Water as solvent.Then, two spoon column chromatography silica gel (100- are added into gained reaction solution for magnetic agitation 12 hours at 60 DEG C 200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1 with volume ratio Petroleum ether and the mixture of ethyl acetate eluted as eluant, eluent, TLC tracks elution process, and collection contains target product Eluent, merge the eluent solvent be evaporated off and obtain target product.The substance is white solid, yield 71%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.32(s,1H),8.22(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.20(dd,J1=8.0Hz, J2=1.0Hz, 1H), 7.99-7.95 (m, 1H), 7.94-7.90 (m, 1H), 7.83 (t, J=2.0Hz, 2H), 7.86-7.64 (m, 1H), 7.57-7.54 (m, 1H), 7.39 (t, J=8.0Hz, 1H), 2.57 (s,3H);13C NMR(125MHz,CDCl3):δ172.2,162.6,152.9, 143.0,141.5,139.1,133.2, 132.3,131.8,131.6,129.6,129.5,129.4,127.7,122.4, 25.4.
Embodiment 16
By 0.3mmol 3- (2- fluorophenyl)-quinoxaline -2- formaldehyde (75.6mg), 0.30mmol ammonium persulfate (68.5mg) It is added in 15mL heavy wall pressure resistance reaction tube with 0.06mmol copper trifluoromethanesulfcomposite (21.7mg), adds 3mL acetonitrile and 30 μ L Water as solvent.Then, two spoon column chromatography silica gel (100- are added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C 200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and be 10:1 with volume ratio Petroleum ether and the mixture of ethyl acetate eluted as eluant, eluent, TLC tracks elution process, and collection contains target product Eluent, merge the eluent solvent be evaporated off and obtain target product.The substance is white solid, yield 92%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.29(s,1H),8.24–8.18(m,2H),7.97– 7.89 (m, 2H), 7.78-7.75 (m, 1H), 7.55-7.50 (m, 1H), 7.40-7.37 (m, 1H), 7.17 (t, J=4.0Hz, 1H), 2.58(s,3H);13C NMR(125MHz,CDCl3):δ172.2,162.4,161.0, 159.1,149.0,143.4,142.4, (138.9,132.9,131.43,131.35,130.4 d, J=2.5Hz), 129.4 (d, J=3.75Hz), 126.8 (d, J= 15.0Hz), 124.7 (d, J=2.5Hz), 115.2 (d, J=10.0Hz), 25.3.
Embodiment 17
By 0.3mmol 3- (4- ethylphenyl)-quinoxaline -2- formaldehyde (78.7mg), 0.30mmol ammonium persulfate (68.5mg) and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) are added in 15mL heavy wall pressure resistance reaction tube, add 3mL second Nitrile and 30 μ L water as solvent.Then, two spoon columns chromatography silicon is added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Glue (100-200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and with volume Mixture than petroleum ether and ethyl acetate for 10:1 is eluted as eluant, eluent, and TLC tracks elution process, and collection contains The eluent of target product, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 75%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.28(s,1H),8.20(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.16(dd,J1=8.5Hz, J2=1.0Hz, 1H), 7.93-7.90 (m, 1H), 7.87-7.84 (m, 1H), 7.61 (d, J=8.0Hz, 2H), 7.36 (d, J=8.0Hz, 2H), 2.77 (q, J=7.5Hz, 2H), 2.56 (s, 3H), 1.31 (t, J=7.5Hz, 3H);13C NMR(125MHz,CDCl3):δ172.2,163.1, 154.2,145.7,143.0,142.0, 138.7,135.5,132.7,130.9,129.3,129.2,128.9,127.9, 28.7,25.4,15.2.
Embodiment 18
By 0.3mmol 3- (4- methoxyphenyl)-quinoxaline -2- formaldehyde (79.3mg), 0.30mmol ammonium persulfate (68.5mg) and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) are added in 15mL heavy wall pressure resistance reaction tube, add 3mL second Nitrile and 30 μ L water as solvent.Then, two spoon columns chromatography silicon is added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Glue (100-200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and with volume Mixture than petroleum ether and ethyl acetate for 10:1 is eluted as eluant, eluent, and TLC tracks elution process, and collection contains The eluent of target product, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 78%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.23(s,1H),8.19(dd,J1=8.5Hz, J2= 1.0Hz,1H),8.15(dd,J1=8.0Hz, J2=1.5Hz, 1H), 7.94-7.90 (m, 1H), 7.87-7.84 (m, 1H), 7.66 (d, J=8.5Hz, 2H), 7.05 (d, J=8.5Hz, 2H), 3.90 (s, 3H), 2.58 (s, 3H);13C NMR(125MHz, CDCl3):δ172.3,163.2,160.8,153.8,143.1,141.9,138.6, 132.8,130.8,130.6,130.4, 129.29,129.27,113.9,55.4,25.4.
Embodiment 19
By the bromo- 3- phenyl-quinoxaline -2- formaldehyde (117.6mg) of 0.3mmol 2,7- bis-, 0.30mmol ammonium persulfate (21.7mg) is added into 15mL heavy wall pressure resistance reaction tube in (68.5mg) and 0.06mmol copper trifluoromethanesulfcomposite, adds 3mL second Nitrile and 30 μ L water as solvent.Then, two spoon columns chromatography silicon is added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Glue (100-200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and with volume Mixture than petroleum ether and ethyl acetate for 10:1 is eluted as eluant, eluent, and TLC tracks elution process, and collection contains The eluent of target product, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 85%.
Characterize data:1H NMR(500MHz,CDCl3):δ9.99(s,1H),8.53(s,1H),8.49(s,1H), 7.67– 7.65(m,2H),7.56–7.51(m,3H),2.52(s,3H);13C NMR(125MHz,CDCl3): δ171.8,162.8, 156.1,143.6,141.9,138.0,137.4,133.4,133.1,130.1,129.9,128.9, 128.4,128.1, 25.3.
Embodiment 20
By 0.3mmol 2,7- dimethyl -3- phenyl-quinoxaline -2- formaldehyde (78.7mg), 0.30mmol ammonium persulfate (68.5mg) and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) are added in 15mL heavy wall pressure resistance reaction tube, add 3mL second Nitrile and 30 μ L water as solvent.Then, two spoon columns chromatography silicon is added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Glue (100-200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and with volume Mixture than petroleum ether and ethyl acetate for 10:1 is eluted as eluant, eluent, and TLC tracks elution process, and collection contains The eluent of target product, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 67%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.37(s,1H),7.96(s,1H),7.90(s,1H), 7.64–7.62(m,2H),7.52–7.51(m,3H),2.56–2.55(m,9H);13C NMR(125MHz, CDCl3):δ172.3, 163.0,153.6,144.3,142.13,142.08,140.6,138.6,137.9,129.1, 128.8,128.3,128.14, 128.05,25.4,20.7,20.4.
Embodiment 21
By the chloro- 3- phenyl-quinoxaline -2- formaldehyde (90.9mg) of 0.3mmol 2,7- bis-, 0.30mmol ammonium persulfate (68.5mg) and 0.06mmol copper trifluoromethanesulfcomposite (21.7mg) are added in 15mL heavy wall pressure resistance reaction tube, add 3mL second Nitrile and 30 μ L water as solvent.Then, two spoon columns chromatography silicon is added into gained reaction solution for magnetic agitation 6 hours at 60 DEG C Glue (100-200 mesh), and solvent is removed by vacuum distillation, gained crude product is subjected to silica gel column chromatography separation, and with volume Mixture than petroleum ether and ethyl acetate for 10:1 is eluted as eluant, eluent, and TLC tracks elution process, and collection contains The eluent of target product, merges the eluent solvent is evaporated off and obtain target product.The substance is white solid, yield 83%.
Characterize data:1H NMR(500MHz,CDCl3):δ10.01(s,1H),8.34(s,1H),8.30(s,1H), 7.67–7.65(m,2H),7.56–7.52(m,3H),2.52(s,3H);13C NMR(125MHz,CDCl3): δ171.9, 162.8,156.1,143.5,141.6,137.8,137.5,137.4,136.0,129.94,129.87,129.7, 128.9, 128.4,25.3。

Claims (10)

1. the synthetic method of a kind of N- acetyl group quinoxaline -2- amide and its derivative, it is characterised in that: the method is specific It carries out as follows:
It is dissolved in the mixed solvent as starting material using quinoxaline -2- formaldehyde shown in formula I, under copper catalyst and oxidant effect, It is reacted 3~12 hours in 40~80 DEG C, gained reaction solution is post-treated to obtain N- acetyl group quinoxaline -2- amide shown in formula II And its derivative;The copper catalyst is copper trifluoromethanesulfcomposite, copper acetate or copper chloride;The oxidant is persulfuric acid One of ammonium, potassium peroxydisulfate, the chloro- 5,6- dicyano -1,4- benzoquinones of 2,3- bis- or tertbutanol peroxide aqueous solution of 70%wt Or more than one mixture;The mixed solvent is the mixed solution of the acetonitrile that volume ratio is 5~100:1 and water;It is described Catalyst and the oxidant, formula I shown in quinoxaline -2- formaldehyde the ratio between the amount of substance for 0.01~0.3:1~ 1.2:1
In Formulas I or formula II:
R1For H, CH3、CH2CH3、OCH3、OCH2CH3, Cl or Br;
R2For H, CH3、CH2CH3、OCH3、OCH2CH3、F、Cl、Br、
n1~n2Represent the number of substituent group, n1For 1~4, n2It is 1~5.
2. the synthetic method of N- acetyl group phenanthridines -6- amide as described in claim 1 and its derivative, it is characterised in that: institute The additional amount for the mixed solvent stated is calculated as 10~12ml/ with the amount of the substance of quinoxaline -2- formaldehyde shown in the formula I mmol。
3. the synthetic method of N- acetyl group phenanthridines -6- amide as described in claim 1 and its derivative, it is characterised in that: institute State n1It is 1 or 2, n2It is 1.
4. the synthetic method of N- acetyl group phenanthridines -6- amide as described in claim 1 and its derivative, it is characterised in that: institute The ratio between the catalyst stated and the amount of substance of quinoxaline -2- formaldehyde shown in oxidant, formula I are 0.2:1:1.
5. the synthetic method of N- acetyl group phenanthridines -6- amide and its derivative as described in one of Claims 1 to 4, feature It is: the post-processing approach of the reaction solution are as follows: after reaction, the column chromatography of 100-200 mesh is added into gained reaction solution Silica gel is simultaneously evaporated under reduced pressure removing solvent, gained crude product is carried out silica gel column chromatography separation, and be the petroleum of 10:1 with volume ratio The mixture of ether and ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, collects the elution containing target product Liquid, merges the eluent solvent is evaporated off and obtain N- acetyl group quinoxaline -2- amide and its derivative shown in the formula II Object.
6. the synthetic method of N- acetyl group quinoxaline -2- amide and its derivative shown in a kind of formula III, it is characterised in that: described Method specifically carry out as follows:
It is dissolved in the mixed solvent as starting material using quinoxaline -2- formaldehyde shown in formula III, is acted in copper catalyst and oxidant Under, it is reacted 3~12 hours in 40~80 DEG C, gained reaction solution is post-treated to obtain N- acetyl group quinoxaline -2- shown in formula IV Amide and its derivative;The copper catalyst is copper trifluoromethanesulfcomposite, copper acetate or copper chloride;The oxidant is over cure Sour ammonium, potassium peroxydisulfate, the chloro- 5,6- dicyano -1,4- benzoquinones of 2,3- bis- or 70%wt tertbutanol peroxide aqueous solution in one Kind or more than one mixture;The mixed solvent is the mixed solution of the acetonitrile that volume ratio is 5~100:1 and water;Institute The ratio between amount of substance of quinoxaline -2- formaldehyde shown in the catalyst stated and the oxidant, formula III for 0.01~0.3:1~ 1.2:1
In formula III or formula IV:
R3For H, CH3、CH2CH3、OCH3、OCH2CH3, Cl or Br;R4For H, Cl or CH3
N represents the number of substituent group, and n is 1~4.
7. the synthetic method of N- acetyl group phenanthridines -6- amide as claimed in claim 6 and its derivative, it is characterised in that: institute The additional amount for the mixed solvent stated is calculated as 10~12ml/ with the amount of the substance of quinoxaline -2- formaldehyde shown in the formula III mmol。
8. the synthetic method of N- acetyl group phenanthridines -6- amide as claimed in claim 6 and its derivative, it is characterised in that: institute The n stated is 1.
9. the synthetic method of N- acetyl group phenanthridines -6- amide as claimed in claim 6 and its derivative, it is characterised in that: institute The ratio between amount of substance of quinoxaline -2- formaldehyde shown in the catalyst and the oxidant, formula III stated is 0.2:1:1.
10. such as the synthetic method of N- acetyl group phenanthridines -6- amide as claimed in one of claims 6 to 9 and its derivative, feature It is: the post-processing approach of the reaction solution are as follows: after reaction, the column chromatography of 100-200 mesh is added into gained reaction solution Silica gel is simultaneously evaporated under reduced pressure removing solvent, gained crude product is carried out silica gel column chromatography separation, and be the petroleum of 10:1 with volume ratio The mixture of ether and ethyl acetate is eluted as eluant, eluent, and TLC tracks elution process, collects the elution containing target product Liquid, merges the eluent solvent is evaporated off and obtain N- acetyl group quinoxaline -2- amide and its derivative shown in the formula IV Object.
CN201710740529.0A 2017-08-25 2017-08-25 A kind of synthetic method of N- acetyl group quinoxaline -2- amide and its derivative Pending CN109422700A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422699A (en) * 2017-08-25 2019-03-05 浙江工业大学 A kind of synthetic method of alpha-keto amide class compound
CN110204486A (en) * 2019-06-21 2019-09-06 江南大学 A kind of synthetic method of quinoline

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422680A (en) * 2017-08-25 2019-03-05 浙江工业大学 A kind of synthetic method of N- acetylquinoline -2- amide and its derivative
CN109422701A (en) * 2017-08-25 2019-03-05 浙江工业大学 A kind of synthetic method of quinokysalines and its derivative

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422680A (en) * 2017-08-25 2019-03-05 浙江工业大学 A kind of synthetic method of N- acetylquinoline -2- amide and its derivative
CN109422701A (en) * 2017-08-25 2019-03-05 浙江工业大学 A kind of synthetic method of quinokysalines and its derivative

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109422699A (en) * 2017-08-25 2019-03-05 浙江工业大学 A kind of synthetic method of alpha-keto amide class compound
CN110204486A (en) * 2019-06-21 2019-09-06 江南大学 A kind of synthetic method of quinoline

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