CN105001169A - Synthetic method for 3-aminoquinoxaline-2(1H)-ketone compound - Google Patents

Synthetic method for 3-aminoquinoxaline-2(1H)-ketone compound Download PDF

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CN105001169A
CN105001169A CN201510399965.7A CN201510399965A CN105001169A CN 105001169 A CN105001169 A CN 105001169A CN 201510399965 A CN201510399965 A CN 201510399965A CN 105001169 A CN105001169 A CN 105001169A
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quinoxaline
benzyl
derivative
synthetic method
organic amine
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CN105001169B (en
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崔秀灵
李毅
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Huaqiao University
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Huaqiao University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic 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
    • C07D241/40—Benzopyrazines
    • C07D241/44—Benzopyrazines 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic 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

Abstract

The invention discloses a synthetic method for 3-aminoquinoxaline-2(1H)-ketone compound. A quinoxaline-2(1H)-one derivative, organic amine, and copper acetate are dissolved to dimethyl sulfoxide for reaction for 10 to 25 h at a temperature of 95 to 110 DEG C under a natural ambient condition, and the 3-aminoquinoxaline-2(1H)-ketone compound is obtained through separation and purification. A molar ratio between the quinoxaline-2(1H)-one derivative, organic amine, and copper acetate is 0.9-1.2:2.8-3.3:0.03-0.06. Each millimole quinoxaline-2(1H)-one derivative needs 2-3 mL dimethyl sulfoxide solution. The foregoing quinoxaline-2(1H)-one derivative has a general molecular formula as shown in the specification, wherein R1 is hydrogen, alkyl, aryl, halogen, or alkoxy, and R2 is hydrogen, benzyl, alkyl, or ester base. Raw materials used in the method of the invention is easy to get and gentle in reaction condition. It is unnecessary to add additional additives, a catalytic dosage is small, and a yield is high. A substrate range is wide, reaction specificity is strong, and processing is convenient and environmental friendly.

Description

A kind of synthetic method of 3-aminoquinoxaline-2 (1H)-one compounds
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of synthetic method of 3-aminoquinoxaline-2 (1H)-one compounds.
Background technology
3-aminoquinoxaline-2 (1H)-one compounds is the conventional pharmacophore in medicinal design field, derivative containing this structure parent nucleus has multiple pharmacologically active, be widely used as antineoplastic agent, carcinostatic agent, aldose reductase inhibitor, antiseptic-germicide etc., it is the potential multi-usage lead compound of a class, use in different clinical trials, there is wide development prospect.Chemists are attempting always in recent years.Some systems are successfully applied to this reaction, achieve certain result of study.But there are problems, such as: reactions steps complexity, severe reaction conditions, long reaction time, by product are many, and yield is low, substrate spectrum is narrower, needs unafforested environmental protection reagent such as strong oxidizer etc.
Summary of the invention
The object of the invention is to overcome prior art defect, a kind of synthetic method of 3-aminoquinoxaline-2 (1H)-one compounds is provided.
Concrete technical scheme of the present invention is as follows:
A kind of synthetic method of 3-aminoquinoxaline-2 (1H)-one compounds, by quinoxaline-2 (1H)-one derivative, organic amine and neutralized verdigris are dissolved in dimethyl sulfoxide (DMSO), under air conditions, in 95 ~ 110 DEG C of reactions after 10 ~ 25 hours, through separation and purification, obtain described 3-aminoquinoxaline-2 (1H)-one compounds, wherein quinoxaline-2 (1H)-one derivative, the mol ratio of organic amine and neutralized verdigris is 0.9 ~ 1.2:2.8 ~ 3.3:0.03 ~ 0.06, every mmole quinoxaline-2 (1H)-one derivative needs 2 ~ 3mL dimethyl sulphoxide solution, the general structure of above-mentioned quinoxaline-2 (1H)-one derivative is as follows:
Wherein R 1for hydrogen, alkyl, aryl, halogen or alkoxyl group, R 2for hydrogen, benzyl, alkyl or ester group.
In a preferred embodiment of the invention, described R 1for methyl or Cl, R 2for hydrogen, benzyl, ethyl, ethyl acetate base or 4-methoxy-benzyl.
In a preferred embodiment of the invention, described quinoxaline-2 (1H)-one derivative is quinoxaline-2 (1H)-one, 6, 7-dimethyl-quinoxaline-2 (1H)-one, 6, 7-bis-chloro-quinoxaline-2 (1H)-one, Benzoquinoxalines-2 (1H)-one, 1-benzyl-quinoxaline-2 (1H)-one, 1-ethyl-quinoxaline-2 (1H)-one, 1-ethyl acetate base-quinoxaline-2 (1H)-one, 4-methoxy-benzyl-quinoxaline-2 (1H)-one, 6, 7-dimethyl-1-benzyl-quinoxaline-2 (1H)-one or 6, 7-bis-chloro-1-benzyl-quinoxaline-2 (1H)-one.
In a preferred embodiment of the invention, described organic amine is aliphatic amide.Preferred further, described organic amine is morpholine, piperidines, Pyrrolidine, Tri N-Propyl Amine, Isopropylamine, Isopropylamine, hexahydroaniline, benzylamine, 4-methylbenzylamine, 2-methylbenzylamine, 4-methoxybenzylamine, trifluoromethyl benzylamine, Alpha-Methyl benzylamine, benzhydrylamine or thanomin.
In a preferred embodiment of the invention, quinoxaline-2 (1H)-one derivative, organic amine and neutralized verdigris are dissolved in dimethyl sulfoxide (DMSO), under air conditions, in 100 DEG C of reactions 12 ~ 24 hours.
In a preferred embodiment of the invention, the mol ratio of quinoxaline-2 (1H)-one derivative, organic amine and neutralized verdigris is 1:3:0.05.
In a preferred embodiment of the invention, every mmole quinoxaline-2 (1H)-one derivative needs 2mL dimethyl sulphoxide solution.
In a preferred embodiment of the invention, described separation and purification comprises: drop to room temperature after completion of the reaction, add diluted ethyl acetate, extract with water, after organic phase anhydrous sodium sulfate drying refilters, namely obtain described 3-aminoquinoxaline-2 (1H)-one compounds through column chromatography separating purification.
The invention has the beneficial effects as follows:
1, quinoxaline-2 (1H)-one derivative, organic amine and neutralized verdigris are dissolved in organic solvent by synthetic method of the present invention, under air conditions, in 95 ~ 110 DEG C of reactions after 10 ~ 25 hours, through separation and purification, obtain described 3-aminoquinoxaline-2 (1H)-one compounds, raw material is easy to get, reaction conditions is gentle, without the need to additionally adding additive, catalyzer throwing amount is low, yield high (being up to 98%); Substrate spectrum is wide, and reaction specificity is strong, and aftertreatment is easy and green.
2, the system scope of application of synthetic method of the present invention is comparatively wide, compatible halogen, methyl, methoxyl group, the multiple group such as trifluoromethyl.
Embodiment
Below by way of embodiment, technical scheme of the present invention is further detailed and is described.
Embodiment 1
The preparation of morpholinyl quinoxaline-2 (1H)-one
By quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 44.8mg target product through pillar layer separation, yield is 97%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 10.83 (s, 1H), 7.57 – 7.51 (m, 1H), 7.26 – 7.18 (m, 2H), 7.15 – 7.09 (m, 1H), 4.07 – 4.00 (m, 4H), 3.90 – 3.85 (m, 4H) ppm; 13c NMR (100MHz, CDCl 3): δ 153.4,150.8,133.1,128.5,126.0,125.3,124.3,114.3,66.9,47.3ppm; HRMS (ESI, m/z): calculated for C 12h 13n 3o 2[M+H] +: 232.1086, found:232.1082.
Embodiment 2
The preparation of 6,7-dimethyl-morpholinyl quinoxaline-2 (1H)-one
By 6,7-dimethyl-quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 50.3mg target product through pillar layer separation, yield is 97%.The sign of this compound is as follows: 1hNMR (400MHz, DMSO): δ 12.02 (s, 1H), 7.21 (s, 1H), 6.94 (s, 1H), 3.90 – 3.75 (m, 4H), 3.75 – 3.62 (m, 4H), 2.23 (d, J=2.5Hz, 6H) ppm; 13c NMR (101MHz, DMSO): δ 152.9,151.8,134.6,132.3,131.2,128.2,126.6,115.6,67.0,47.7,20.3,19.9ppm; HRMS (ESI, m/z): calculated for C 14h 17n 3o 2[M+H] +: 260.1399, found:260.1397.
Embodiment 3
The preparation of 6,7-bis-chloro-morpholinyl quinoxaline-2 (1H)-one
By chloro-for 6,7-bis-quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 55.2mg target product through pillar layer separation, yield is 92%.The sign of this compound is as follows: 1h NMR (400MHz, DMSO): δ 12.23 (s, 1H), 7.55 (s, 1H), 7.29 (s, 1H), 3.95 (s, 4H), 3.70 (s, 4H) ppm; 13c NMR (100MHz, DMSO): δ 152.7,152.1,133.3,130.0,126.6,126.5,125.7,116.1,67.0,47.6ppm; HRMS (ESI, m/z): calculated for C 12h 11cl 2n 3o 2[M+H] +: 300.0307, found:300.0303.
Embodiment 4
The preparation of morpholinyl-Benzoquinoxalines-2 (1H)-one
By Benzoquinoxalines-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 43.3mg target product through pillar layer separation, yield is 77%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 9.42 (s, 1H), 7.98 (s, 1H), 7.86 (d, J=7.4Hz, 1H), 7.79 (d, J=7.6Hz, 1H), 7.50 – 7.35 (m, 3H), 4.13 – 4.01 (m, 4H), 3.96 – 3.80 (m, 4H) ppm; 13c NMR (100MHz, CDCl 3): δ 153.1,150.3,132.6,131.0,131.0,128.3,127.8,126.6,125.9,124.9,123.3,109.7,67.0,47.4ppm; HRMS (ESI, m/z): calculated for C 16h 15n 3o 2[M+H] +: 282.1243, found:282.1239.
Embodiment 5
The preparation of 1-benzyl-morpholinyl quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 62.9mg target product through pillar layer separation, yield is 98%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.61 – 7.51 (m, 1H), 7.30 (ddd, J 1=7.5Hz, J 2=6.2Hz, J 3=1.3Hz, 2H), 7.26 – 7.04 (m, 6H), 5.47 (s, 2H), 4.05 – 3.95 (m, 4H), 3.86 (dd, J 1=6.0Hz, J 2=3.5Hz, 4H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.3,150.8,135.5,133.2,130.2,128.9,127.5,127.0,126.7,125.4,123.9,114.1,67.0,47.6,46.1ppm; HRMS (ESI, m/z): calculated for C 19h 19n 3o 2[M+H] +: 322.1556, found:322.1554.
Embodiment 6
The preparation of 1-ethyl-morpholinyl quinoxaline-2 (1H)-one
By 1-ethyl-quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 49.2mg target product through pillar layer separation, yield is 95%.The sign of this compound is as follows: 1h NMR (400MHz, DMSO): δ 7.50 – 7.42 (m, 2H), 7.31 (dd, J 1=8.3Hz, J 2=1.3Hz, 1H), 7.27 – 7.21 (m, 1H), 4.24 (q, J=7.1Hz, 2H), 3.91 – 3.80 (m, 4H), 3.76 – 3.65 (m, 4H), 1.23 (t, J=7.1Hz, 3H) ppm; 13c NMR (100MHz, DMSO) δ 151.7,151.3,133.5,130.3,127.3,126.3,124.3,114.8,67.0,48.0,37.9,13.2ppm; HRMS (ESI, m/z): calculated for C 14h 17n 3o 2[M+H] +: 260.1399, found:260.1396.
Embodiment 7
Prepared by 1-ethyl acetate base-morpholinyl quinoxaline-2 (1H)-one
By 1-ethyl acetate base-quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 62.1mg target product through pillar layer separation, yield is 98%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.59 – 7.52 (m, 1H), 7.26 – 7.22 (m, 2H), 7.01 – 6.93 (m, 1H), 4.99 (s, 2H), 4.25 (q, J=7.2Hz, 2H), 4.01 – 3.93 (m, 4H), 3.88 – 3.80 (m, 4H), 1.31 – 1.24 (m, 3H) ppm; 13c NMR (100MHz, CDCl 3) δ 167.3,152.0,150.2,133.1,123.0,127.1,125.5,124.1,112.7,67.0,62.0,47.5,43.9,14.1ppm; HRMS (ESI, m/z): calculated for C 16h 19n 3o 4[M+H] +: 318.1454, found:318.1451.
Embodiment 8
The preparation of 4-methoxy-benzyl-morpholinyl quinoxaline-2 (1H)-one
By 4-methoxy-benzyl-quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 65.4mg target product through pillar layer separation, yield is 93%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.58 – 7.53 (m, 1H), 7.23 – 7.16 (m, 5H), 6.86 – 6.79 (m, 2H), 5.41 (s, 2H), 4.01 – 3.95 (m, 4H), 3.89 – 3.84 (m, 4H), 3.76 (s, 3H) ppm; 13c NMR (100MHz, CDCl 3): δ 159.0,152.3,150.9,133.2,130.2,128.2,127.5,127.0,125.4,123.8,114.2,114.1,67.0,55.3,47.6,45.6ppm; HRMS (ESI, m/z): calculated for C 20h 21n 3o 3[M+H] +: 352.1661, found:352.1657.
Embodiment 9
The preparation of 6,7-dimethyl-1-benzyl-morpholinyl quinoxaline-2 (1H)-one
By 6,7-dimethyl-1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 54.5mg target product through pillar layer separation, yield is 78%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.38 – 7.27 (m, 3H), 7.24 (dt, J 1=12.0Hz, J 2=4.1Hz, 3H), 6.92 (s, 1H), 5.44 (s, 2H), 3.96 – 3.83 (m, 8H), 2.26 (d, J=9.4Hz, 6H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.2,150.7,135.7,134.7,132.6,131.3,128.8,128.2,127.5,127.4,126.7,114.7,66.9,47.7,46.0,20.2,19.1ppm; HRMS (ESI, m/z): calculated for C 21h 23n 3o 2[M+H] +: 350.1869, found:350.1865.
Embodiment 10
The preparation of 6,7-bis-chloro-1-benzyl-morpholinyl quinoxaline-2 (1H)-one
By chloro-for 6,7-bis-1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, morpholine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 60.1mg target product through pillar layer separation, yield is 77%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.60 (s, 1H), 7.39 – 7.27 (m, 3H), 7.23 – 7.16 (m, 3H), 5.38 (s, 2H), 4.07 – 4.00 (m, 4H), 3.87 – 3.81 (m, 4H) ppm; 13c NMR (101MHz, CDCl 3): δ 151.8,150.6,134.6,132.9,129.4,129.1,128.3,127.9,127.5,127.4,126.7,115.3,66.947.5,46.4ppm; HRMS (ESI, m/z): calculated for C 19h 17c l2n 3o 2[M+H] +: 390.0776, found:390.0773.
Embodiment 11
The preparation of 3-piperidyl-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, piperidines 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 60.0mg target product through pillar layer separation, yield is 94%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.53 (s, 1H), 7.29 (d, J=7.3Hz, 2H), 7.23 (t, J=8.1Hz, 3H), 7.12 (dd, J 1=17.3Hz, J 2=14.4Hz, 3H), 5.47 (s, 2H), 3.89 (d, J=5.3Hz, 4H), 1.72 (s, 6H) ppm; 13cNMR (101MHz, CDCl 3): δ 152.5,151.4,135.7,133.7,130.0,128.8,127.4,126.7,126.6,124.6,123.7,114.0,48.4,46.1,26.1,24.9ppm; HRMS (ESI, m/z): calculated for C 20h 21n 3o [M+H] +: 320.1763, found:320.1761.
Embodiment 12
The preparation of 3-Pyrrolidine base-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, Pyrrolidine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 44.6mg target product through pillar layer separation, yield is 73%.The sign of this compound is as follows: 1hNMR (400MHz, CDCl 3): δ 7.51 – 7.44 (m, 1H), 7.34 – 7.27 (m, 2H), 7.24 (dt, J 1=13.3Hz, J 2=4.3Hz, 3H), 7.17 – 7.10 (m, 1H), 7.03 (dd, J 1=6.1Hz, J 2=1.4Hz, 2H), 5.44 (s, 2H), 3.99 (s, 4H), 1.99 – 1.92 (m, 4H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.8,149.0,135.8,134.9,129.3,128.8,127.4,126.6,125.8,123.8,123.3,113.9,49.7,45.8ppm; HRMS (ESI, m/z): calculatedfor C 19h 19n 3o [M+H] +: 306.1606, found:306.1604.
Embodiment 13
The preparation of 3-Tri N-Propyl Amine base-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, Tri N-Propyl Amine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 24h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 53.4mg target product through pillar layer separation, yield is 91%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.55 (dd, J 1=8.0Hz, J 2=1.3Hz, 1H), 7.35 – 7.26 (m, 3H), 7.25 – 7.04 (m, 5H), 6.44 (s, 1H), 5.50 (s, 2H), 3.59 – 3.49 (m, 2H), 1.74 (dd, J 1=14.5Hz, J 2=7.3Hz, 2H), 1.04 (t, J=7.4Hz, 3H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.7,149.0,135.3,134.5,128.9,128.6,127.6,126.7,126.2,124.1,123.8,114.4,46.2,42.7,22.4,11.6ppm; HRMS (ESI, m/z): calculated for C 18h 19n 3o [M+H] +: 294.1606, found:294.1604.
Embodiment 14
The preparation of 3-isopropylamine base-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, Isopropylamine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 24h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 56.9mg target product through pillar layer separation, yield is 97%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.55 (d, J=7.8Hz, 1H), 7.32 (dd, J 1=11.4, J 2=4.2Hz, 2H), 7.26 – 7.04 (m, 6H), 6.29 (d, J=7.6Hz, 1H), 5.50 (s, 2H), 4.35 (dd, J 1=14.1, J 2=6.7Hz, 1H), 1.33 (d, J=6.5Hz, 6H) ppm; 13c NMR (101MHz, CDCl 3): δ 152.2,148.1,135.4,134.6,128.9,128.5,127.6,126.8,126.2,124.1,123.7,114.4,46.2,42.4,22.5ppm; HRMS (ESI, m/z): calculatedfor C 18h 19n 3o [M+H] +: 294.1606, found:294.1604.
Embodiment 15
The preparation of 3-n-butylamine-based-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, n-Butyl Amine 99 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 24h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 60.2mg target product through pillar layer separation, yield is 98%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.55 (dd, J 1=7.9Hz, J 2=1.2Hz, 1H), 7.38 – 7.26 (m, 3H), 7.25 – 7.16 (m, 3H), 7.15 – 7.02 (m, 2H), 6.41 (s, 1H), 5.50 (s, 2H), 3.57 (td, J 1=7.1Hz, J 2=5.9Hz, 2H), 1.77 – 1.64 (m, 2H), 1.48 (dq, J 1=14.5Hz, J 2=7.3Hz, 2H), 0.99 (t, J=7.4Hz, 3H) ppm; 13cNMR (100MHz, CDCl 3) δ 152.2,149.0,135.3,134.5,128.9,128.6,127.6,126.7,126.2,124.1,123.8,114.4,46.2,40.6,31.3,20.2,13.8ppm; HRMS (ESI, m/z): calculated for C 19h 21n 3o [M+H] +: 3081763, found:308.1761.
Embodiment 16
The preparation of 3-cyclohexylamino-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, hexahydroaniline 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 24h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 32.0mg target product through pillar layer separation, yield is 48%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.54 (dd, J=8.0,1.3Hz, 1H), 7.37 – 7.27 (m, 2H), 7.26 – 7.00 (m, 6H), 6.36 (d, J=8.1Hz, 1H), 5.49 (s, 2H), 4.14 – 4.00 (m, 1H), 2.17 – 2.06 (m, 2H), 1.86 – 1.74 (m, 2H), 1.61 – 0.98 (m, 6H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.2,148.0,135.4,134.6,128.9,128.5,127.6,126.8,126.2,124.1,123.6,114.3,53.4,49.1,46.2,32.8,25.7,24.8ppm; HRMS (ESI, m/z): calculated for C 21h 23n 3o [M+H] +: 334.1919, found:334.1917.
Embodiment 17
The preparation of 3-benzamido group-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, benzylamine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 58.7mg target product through pillar layer separation, yield is 86%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.59 (d, J=7.9Hz, 1H), 7.47 – 7.26 (m, 7H), 7.26 – 7.18 (m, 4H), 7.18 – 7.05 (m, 2H), 6.70 (s, 1H), 5.51 (s, 2H), 4.77 (d, J=5.8Hz, 2H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.1,148.7,138.2,135.3,134.3,128.9,128.8,128.7,128.1,127.6,127.5,126.8,126.4,124.2,124.1,114.4,46.2,45.0ppm; HRMS (ESI, m/z): calculated for C 22h 19n 3o [M+H] +: 342.1606, found:342.1602.
Embodiment 18
The preparation of 3-(4-methylbenzylamine base)-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, 4-methylbenzylamine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 65.4mg target product through pillar layer separation, yield is 92%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.58 (d, J=7.8Hz, 1H), 7.31 (t, J=7.4Hz, 4H), 7.26 – 7.05 (m, 8H), 6.67 (s, 1H), 5.50 (s, 2H), 4.72 (d, J=5.7Hz, 2H), 2.35 (s, 3H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.1,148.7,137.2,135.3,135.1,134.3,129.3,128.9,128.8,128.1,127.6,126.7,126.4,124.2,124.0,114.4,46.2,44.8,21.1ppm; HRMS (ESI, m/z): calculated for C 23h 21n 3o [M+H] +: 356.1763, found:356.1759.
Embodiment 19
The preparation of 3-(2-methylbenzylamine base)-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, 2-methylbenzylamine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 57.5mg target product through pillar layer separation, yield is 81%.The sign of this compound is as follows: 1h NMR (400MHz, CDC l3): δ 7.59 (d, J=7.9Hz, 1H), 7.41 – 7.28 (m, 3H), 7.26 – 7.06 (m, 9H), 6.55 (s, 1H), 5.50 (s, 2H), 4.74 (d, J=5.5Hz, 2H), 2.42 (s, 3H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.0,148.6,136.7,135.9,135.3,134.3,130.5,128.9,128.9,128.8,127.8,127.6,126.8,126.4,126.2,124.2,124.1,114.4,46.2,43.2,19.2ppm; HRMS (ESI, m/z): calculatedfor C 23h 21n 3o [M+H] +: 356.1763, found:356.1759.
Embodiment 20
The preparation of 3-(4-methoxybenzyl amido)-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, 4-methoxybenzylamine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 70.5mg target product through pillar layer separation, yield is 95%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.58 (d, J=7.9Hz, 1H), 7.39 – 7.27 (m, 4H), 7.26 – 7.06 (m, 6H), 6.94 – 6.79 (m, 2H), 6.64 (s, 1H), 5.49 (s, 2H), 4.69 (d, J=5.7Hz, 2H), 3.80 (s, 3H) ppm; 13cNMR (101MHz, CDCl 3): δ 159.1,152.1,148.7,135.3,134.3,130.2,129.5,128.9,128.8,127.6,126.7,126.4,124.2,124.0,114.4,114.1,55.3,46.2,44.5ppm; HRMS (ESI, m/z): calculatedfor C 23h 21n 3o 2[M+H] +: 372.1712, found:372.1708.
Embodiment 21
The preparation of 3-(4-trifluoromethyl benzylamine base)-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, trifluoromethyl benzylamine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 43.4mg target product through pillar layer separation, yield is 53%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.75 – 7.44 (m, 5H), 7.39 – 7.26 (m, 3H), 7.25 – 7.04 (m, 5H), 6.79 (s, 1H), 5.51 (s, 2H), 4.84 (d, J=6.1Hz, 2H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.01 (s), 148.67 (s), 142.57 (s), 135.19 (s), 134.06 (s), 129.69 (q, J=32.4Hz), 128.94 (s), 128.91 (s), 128.16 (s), 127.71 (s), 126.76 (s), 126.52 (s), 125.57 (q, J=3.7Hz), 124.47 (s), 124.30 (s), 122.45 (q, J=270.5Hz), 114.51 (s), 46.25 (s), 44.36 (s) ppm; 19f NMR (376MHz, CDCl 3) δ-62.42 (s, 3F) ppm; HRMS (ESI, m/z): calculated for C 23h 18f 3n 3o [M+H] +: 410.1480, found:410.1475.
Embodiment 22
The preparation of 3-(Alpha-Methyl benzamido group)-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, Alpha-Methyl benzylamine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 54.7mg target product through pillar layer separation, yield is 77%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.52 (d, J=8.0Hz, 1H), 7.46 (d, J=7.5Hz, 2H), 7.38 – 7.26 (m, 5H), 7.25 – 7.04 (m, 6H), 6.69 (d, J=7.8Hz, 1H), 5.50 (t, J=13.3Hz, 2H), 5.41 (dd, J 1=13.5Hz, J 2=6.2Hz, 1H), 1.65 (d, J=6.9Hz, 3H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.0,147.9,143.6,135.3,134.4,128.9,128.7,128.6,127.6,127.2,126.8,126.5,126.4,124.1,124.0,114.3,50.0,46.2,22.2ppm; HRMS (ESI, m/z): calculated for C 23h 21n 3o [M+H] +: 356.1763, found:356.1761.
Embodiment 23
The preparation of 3-(benzhydrylamine base)-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, benzhydrylamine 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 39.2mg target product through pillar layer separation, yield is 47%.The sign of this compound is as follows: 1hNMR (400MHz, CDCl 3): δ 7.50 (d, J=7.8Hz, 1H), 7.32 (ddd, J 1=20.0Hz, J 2=11.5Hz, J 3=7.1Hz, 12H), 7.25 – 6.95 (m, 6H), 6.55 (d, J=8.2Hz, 1H), 5.50 (s, 2H), 1.56 (s, 1H) ppm; 13cNMR (100MHz, CDCl 3): δ 152.0,147.8,141.9,135.3,134.2,128.9,128.6,127.6,127.4,126.8,126.7,124.3,124.1,114.3,58.1,46.3ppm; HRMS (ESI, m/z): calculated for C 28h 23n 3o [M+H] +: 418.1919, found:418.1911.
Embodiment 24
The preparation of 3-ethanol amido-1-benzyl-quinoxaline-2 (1H)-one
By 1-benzyl-quinoxaline-2 (1H)-one 0.2mmol, thanomin 0.6mmol, neutralized verdigris 0.01mmol, dimethyl sulfoxide (DMSO) 2.0mL add in the reaction tubes of 10mL, are placed in the oil bath of 100 DEG C, react 12h under air conditions.Stopped reaction, is cooled to room temperature.Reaction solution diluted ethyl acetate, extracts three times with water, organic phase anhydrous Na 2sO 4drying, filter, obtain 39.0mg target product through pillar layer separation, yield is 66%.The sign of this compound is as follows: 1h NMR (400MHz, CDCl 3): δ 7.55 – 7.48 (m, 1H), 7.30 (dd, J 1=15.4Hz, J 2=7.9Hz, 3H), 7.25 – 7.08 (m, 5H), 6.87 (s, 1H), 5.50 (s, 2H), 4.50 (s, 1H), 3.96 – 3.88 (m, 2H), 3.75 (dd, J 1=9.4Hz, J 2=5.6Hz, 2H) ppm; 13c NMR (100MHz, CDCl 3): δ 152.1,149.9,135.1,133.3,128.9,128.8,127.7,126.7,125.9,124.5,124.4,114.5,63.5,46.3,45.0ppm; HRMS (ESI, m/z): calculatedfor C 17h 17n 3o 2[M+H] +: 296.1399, found:296.1397.
Those skilled in the art are known, when technical parameter of the present invention changes in sub-ranges, still can obtain same as the previously described embodiments or close technique effect, all belong to protection scope of the present invention:
A kind of synthetic method of 3-aminoquinoxaline-2 (1H)-one compounds, by quinoxaline-2 (1H)-one derivative, organic amine (preferred fat amine) and neutralized verdigris are dissolved in dimethyl sulfoxide (DMSO), under air conditions, after 95 ~ 110 DEG C of reactions 10 ~ 25 hours (being preferable over 100 DEG C of reactions 12 ~ 24 hours), through separation and purification, obtain described 3-aminoquinoxaline-2 (1H)-one compounds, wherein quinoxaline-2 (1H)-one derivative, the mol ratio of organic amine and neutralized verdigris is 0.9 ~ 1.2:2.8 ~ 3.3:0.03 ~ 0.06, every mmole quinoxaline-2 (1H)-one derivative needs 2 ~ 3mL dimethyl sulphoxide solution, the general structure of above-mentioned quinoxaline-2 (1H)-one derivative is as follows:
Wherein R 1for hydrogen, alkyl, aryl, halogen or alkoxyl group, R 2for hydrogen, benzyl, alkyl or ester group.
Preferred R 1for methyl or Cl, R 2for hydrogen, benzyl, ethyl, ethyl acetate base or 4-methoxy-benzyl.
The above, be only preferred embodiment of the present invention, therefore can not limit scope of the invention process according to this, the equivalence change namely done according to the scope of the claims of the present invention and description with modify, all should still belong in scope that the present invention contains.

Claims (9)

1. the synthetic method of 3-aminoquinoxaline-2 (1H)-one compounds, it is characterized in that: by quinoxaline-2 (1H)-one derivative, organic amine and neutralized verdigris are dissolved in dimethyl sulfoxide (DMSO), under air conditions, in 95 ~ 110 DEG C of reactions after 10 ~ 25 hours, through separation and purification, obtain described 3-aminoquinoxaline-2 (1H)-one compounds, wherein quinoxaline-2 (1H)-one derivative, the mol ratio of organic amine and neutralized verdigris is 0.9 ~ 1.2:2.8 ~ 3.3:0.03 ~ 0.06, every mmole quinoxaline-2 (1H)-one derivative needs 2 ~ 3mL dimethyl sulphoxide solution, the general structure of above-mentioned quinoxaline-2 (1H)-one derivative is as follows:
Wherein R 1for hydrogen, alkyl, aryl, halogen or alkoxyl group, R 2for hydrogen, benzyl, alkyl or ester group.
2. synthetic method as claimed in claim 1, is characterized in that: described R 1for methyl or Cl, R 2for hydrogen, benzyl, ethyl, ethyl acetate base or 4-methoxy-benzyl.
3. synthetic method as claimed in claim 1, it is characterized in that: described quinoxaline-2 (1H)-one derivative is quinoxaline-2 (1H)-one, 6, 7-dimethyl-quinoxaline-2 (1H)-one, 6, 7-bis-chloro-quinoxaline-2 (1H)-one, Benzoquinoxalines-2 (1H)-one, 1-benzyl-quinoxaline-2 (1H)-one, 1-ethyl-quinoxaline-2 (1H)-one, 1-ethyl acetate base-quinoxaline-2 (1H)-one, 4-methoxy-benzyl-quinoxaline-2 (1H)-one, 6, 7-dimethyl-1-benzyl-quinoxaline-2 (1H)-one or 6, 7-bis-chloro-1-benzyl-quinoxaline-2 (1H)-one.
4. synthetic method as claimed in claim 1, is characterized in that: described organic amine is aliphatic amide.
5. synthetic method as claimed in claim 4, is characterized in that: described organic amine is morpholine, piperidines, Pyrrolidine, Tri N-Propyl Amine, Isopropylamine, Isopropylamine, hexahydroaniline, benzylamine, 4-methylbenzylamine, 2-methylbenzylamine, 4-methoxybenzylamine, trifluoromethyl benzylamine, Alpha-Methyl benzylamine, benzhydrylamine or thanomin.
6. the synthetic method as described in claim arbitrary in claim 1 to 5, is characterized in that: be dissolved in dimethyl sulfoxide (DMSO) by quinoxaline-2 (1H)-one derivative, organic amine and neutralized verdigris, under air conditions, in 100 DEG C of reactions 12 ~ 24 hours.
7. the synthetic method method as described in claim arbitrary in claim 1 to 5, is characterized in that: the mol ratio of quinoxaline-2 (1H)-one derivative, organic amine and neutralized verdigris is 1:3:0.05.
8. the synthetic method as described in claim arbitrary in claim 1 to 5, is characterized in that: every mmole quinoxaline-2 (1H)-one derivative needs 2mL dimethyl sulphoxide solution.
9. the synthetic method as described in claim arbitrary in claim 1 to 5, it is characterized in that: described separation and purification comprises: drop to room temperature after completion of the reaction, add diluted ethyl acetate, extract with water, after organic phase anhydrous sodium sulfate drying refilters, namely obtain described 3-aminoquinoxaline-2 (1H)-one compounds through column chromatography separating purification.
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CN111689951A (en) * 2020-06-11 2020-09-22 西北师范大学 Synthesis method of 1-benzyl-3-alkyl quinoxaline-2 (1H) -ketone
CN111807942A (en) * 2020-08-05 2020-10-23 厦门华厦学院 Preparation method of polysubstituted indanone derivative
CN112679423A (en) * 2021-01-08 2021-04-20 中南大学 Amination reagent and synthesis method and application thereof
CN115385863A (en) * 2022-08-17 2022-11-25 河南师范大学 Synthetic method of 3- (diethoxymethyl) -1-alkyl-2 (1H) -quinoxalinone derivative

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CN109160903A (en) * 2018-09-28 2019-01-08 曲阜师范大学 A kind of photocatalysis preparation method of 3- aminoquinoxaline -2 (1H) -one compound
CN109160903B (en) * 2018-09-28 2021-07-16 曲阜师范大学 Photocatalytic preparation method of 3-aminoquinoxaline-2 (1H) -ketone compound
CN111689951A (en) * 2020-06-11 2020-09-22 西北师范大学 Synthesis method of 1-benzyl-3-alkyl quinoxaline-2 (1H) -ketone
CN111807942A (en) * 2020-08-05 2020-10-23 厦门华厦学院 Preparation method of polysubstituted indanone derivative
CN111807942B (en) * 2020-08-05 2022-11-18 厦门华厦学院 Preparation method of polysubstituted indanone derivative
CN112679423A (en) * 2021-01-08 2021-04-20 中南大学 Amination reagent and synthesis method and application thereof
CN112679423B (en) * 2021-01-08 2022-04-26 中南大学 Amination reagent and synthesis method and application thereof
CN115385863A (en) * 2022-08-17 2022-11-25 河南师范大学 Synthetic method of 3- (diethoxymethyl) -1-alkyl-2 (1H) -quinoxalinone derivative

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