CN115819356B - A method for preparing tetrahydroquinoxaline compounds - Google Patents
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Abstract
本发明公开了一种制备四氢喹喔啉类化合物的方法，其步骤包括：在有机溶剂和碱的存在下，将邻苯二胺类化合物和丙‑2‑炔基硫叶立德盐类化合物在室温下进行反应，得到四氢喹喔啉类化合物。本发明方法工艺简便、产率高且可以克级制备，更重要的是可以同时得到各种位置取代的且具有不同取代基的四氢喹喔啉，且均具有优秀的反应收率，具有良好的工业化应用前景和潜力。
The invention discloses a method for preparing a tetrahydroquinoxaline compound, the steps of which include: reacting an o-phenylenediamine compound and a prop-2-ynylsulfur ylide salt compound at room temperature in the presence of an organic solvent and a base to obtain a tetrahydroquinoxaline compound. The method of the invention has a simple process, a high yield and can be prepared in grams, and more importantly, tetrahydroquinoxaline substituted in various positions and having different substituents can be obtained at the same time, and all have excellent reaction yields, and have good industrial application prospects and potential.
Description
Technical Field
The invention belongs to the fields of organic chemical synthesis and medical intermediates, and particularly relates to a method for preparing tetrahydroquinoxaline compounds.
Background
In the fields of organic chemistry and medical synthesis, quinoxaline compounds are important natural products and key intermediates of drug molecules, and have good biological activities such as antivirus, antibiosis and antiphlogosis, anticancer, insect expelling and the like, so that the quinoxaline compounds are widely focused by chemists as key frameworks for drug construction. To date, various synthetic methods have been developed in the art for quinoxalines. For example, zhang Mo group (Pd(II)-Catalyzed Aerobic Intermolecular 1,2-Diamination of Conjugated Dienes:A Regio-and Chemoselective[4+2]Annulation for the Synthesis of Tetrahydroquinoxalines.Org.Lett.2017,19,2813–2816) reports a method for synthesizing tetrahydroquinoxaline compounds. According to the method, N-dimethyl benzene sulfonyl o-phenylenediamine and conjugated diene are used as raw materials, palladium acetate or copper acetate is used as a catalyst under the condition of oxygen existence, and the corresponding tetrahydroquinoxaline compound is prepared, and the reaction has good reaction yield and substrate universality. Xu Lijin et al chemist (Metal-free tandem cyclization/hydrosilylation to construct tetrahydroquinoxalines,Green Chem.,2018,20,403-410) developed a one-pot tandem reaction, and used o-phenylenediamine and alpha-keto ester as starting materials, and can directly construct tetrahydroquinoxaline compounds under the catalysis of B (C 6F5)3) and the hydrogenation of silane, which is a very simple synthesis process, zhong Fangrui subject group (Intermolecular Vicinal Diaminative Assembly of Tetrahydroquinoxalines via Metal-free Oxidative[4+2]Cycloaddition Strategy,Org.Lett.2020,22,2425–2430) reports [4+2] cyclization reaction of iodobenzene acetate oxidized N, N-di-p-toluenesulfonyl o-phenylenediamine and alkyne, and the tetrahydroquinoxaline compounds can be successfully prepared without metal catalysts, and have very wide application prospects.
As described above, although there have been many methods for synthesizing tetrahydroquinoxaline compounds in the prior art, these methods have disadvantages in that the yield is not ideal and the substrate source is not abundant. Therefore, it is necessary to develop a novel and efficient preparation method of tetrahydroquinoxaline compounds.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a method for preparing tetrahydroquinoxaline compounds. The invention can prepare tetrahydroquinoxaline compounds with quick reaction and high yield, thereby improving the utilization rate of materials and meeting the wide demands in the synthesis of medical intermediates. According to the invention, after alkali is dissolved in an organic solvent, o-phenylenediamine compounds and prop-2-alkynyl sulfolobus ylide compounds are added and uniformly mixed for cycloaddition reaction, so that tetrahydroquinoxaline compounds are obtained.
The invention provides a synthesis method of a tetrahydroquinoxaline medical intermediate compound shown in a formula (III), which comprises the step of performing cycloaddition reaction on an o-phenylenediamine compound shown in the formula (I) and a prop-2-alkynyl sulfotides salt compound shown in the formula (II) at room temperature in the presence of an organic solvent and alkali, so as to obtain the compound shown in the formula (III).
Wherein R 1、R2 is independently selected from H, halogen, alkyl or alkoxy, R 3 is p-toluenesulfonyl (Ts), o-toluenesulfonyl, m-toluenesulfonyl, benzenesulfonyl (Bs), p-chlorobenzenesulfonyl, o-chlorobenzenesulfonyl or m-chlorobenzenesulfonyl, and R 4 is selected from H, C 1-C7 alkyl, cycloalkyl or phenyl.
In the method of the present invention, the halogen atom means a fluorine, chlorine, bromine or iodine atom.
In the process of the present invention, C 1-C7 alkyl refers to an alkyl group having 1 to 7 carbon atoms, which may be straight or branched, and may be, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, isoheptyl, and the like.
In the method of the present invention, the base is an organic base, an alkali metal alkoxide, an alkali metal hydroxide, or an alkali metal carbonate. The base may be any one or a mixture of any more of Et 3 N, DIPEA, DBU, DMAP, DABCO, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide, naOH, KOH, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, and the like. Among them, the base is preferably potassium carbonate, rubidium carbonate or cesium carbonate, and most preferably cesium carbonate.
In the method of the present invention, the organic solvent may be, for example, any one of tetrahydrofuran, 1, 4-dioxane, toluene, dichloroethane, chloroform, acetonitrile, and the like. The amount of the organic solvent is not particularly limited, and for example, an appropriate amount may be determined according to an appropriate reaction progress and easy post-treatment, which may be apparent to those skilled in the art from conventional technical means.
In the method of the present invention, the molar ratio of the compound of formula (I) to the compound of formula (II) is 1:1 to 1:2, for example, may be 1:1, 1:1.5 or 1:2.
In the process of the invention, the molar ratio of the compound of formula (I) to base is from 1:1 to 1:2, for example, it may be 1:1, 1:1.5 or 1:2.
In the process of the invention, the reaction temperature is from 0 to 50 ℃, for example, may be 0 ℃, 25 ℃ or 50 ℃.
In the process of the invention, the reaction time is 8 to 24 hours, for example 8 hours, 16 hours or 24 hours.
In the method, after the reaction is finished, the reaction system can be naturally cooled to room temperature, vacuum concentration is carried out, the residue is subjected to 200-mesh silica gel column chromatography, and a mixture of petroleum ether and ethyl acetate according to the volume ratio of 10:1-3:1 is adopted as eluent to obtain a target compound, namely the compound of formula (III).
As described above, the invention provides a synthetic method of tetrahydroquinoxaline medical intermediate compound, and provides proper selection and combination of reaction substrates, alkali and solvents, so that the target product is obtained in high yield, and the method has good industrial application prospect and potential.
The invention has the following advantages:
the method has simple process, high yield and gram-scale preparation, more importantly, the tetrahydroquinoxaline with various substituted positions and different substituents can be obtained simultaneously, and the method has excellent reaction yield and important application value.
Drawings
FIG. 1 is a 1 H NMR spectrum of a compound represented by formula (III-2) obtained in example 2.
FIG. 2 is a 1 C NMR spectrum of the compound represented by formula (III-2) obtained in example 2.
FIG. 3 is a mass spectrum of the compound represented by formula (III-2) obtained by the preparation of example 2.
FIG. 4 is a 1 H NMR spectrum of the compound represented by formula (III-6) obtained in example 6.
FIG. 5 is a 1 C NMR spectrum of a compound represented by formula (III-6) obtained in example 6.
FIG. 6 is a mass spectrum of the compound represented by formula (III-6) obtained by the preparation of example 6.
Detailed Description
The invention will now be described in further detail with reference to the accompanying drawings, which are given by way of illustration only and are not intended to limit the scope of the invention.
EXAMPLE 1 preparation of the Compound shown in III-1
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the objective formula (III-1) in 88% yield.
The structure of the compound shown in III-1 is characterized by ：1H NMR(500MHz,CDCl3)δ7.83(q,J＝7.5Hz,J＝2.0Hz,1H),7.67(q,J＝7.5Hz,J＝2.0Hz,1H),7.37(d,J＝8.0Hz,2H),7.32(d,J＝8.0Hz,2H),7.21-7.18(m,3H),7.17-7.14(m,3H),5.33(s,1H),4.95(s,1H),3.78(s,2H),2.39(s,3H),2.36(s,3H);13C NMR(125MHz,CDCl3)δ144.8,144.2,135.4,134.4,134.3,129.8,129.7,129.6,129.5,127.6,127.3,125.7,125.4,125.2,123.4,112.7,48.0,21.6,21.5;HRMS(ESI)calcd for C23H23N2O4S2[M+H]+:455.1094,found 455.1086.
The nuclear magnetic spectrum and mass spectrum identification product has the structure shown as the formula III-1.
EXAMPLE 2 preparation of the Compound shown in III-2
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the objective formula (III-1) in 95% yield.
The structure of the compound shown in III-2 is characterized by ：1H NMR(500MHz,CDCl3)δ7.79-7.77(m,1H),7.70-7.68(m,1H),7.34(q,J＝6.5Hz,J＝2.0Hz,2H),7.29-7.28(m,2H),7.20-7.15(m,4H),7.12(d,J＝8.0Hz,2H),5.89(q,J＝15.0Hz,J＝7.5Hz,1H),3.82(s,2H),2.40(s,3H),2.35(s,3H),1.73(d,J＝7.5Hz,3H);13C NMR(125MHz,CDCl3)δ144.6,144.1,135.5,134.6,129.8,129.5,129.4,127.6,127.1,126.7,125.8,125.6,125.1,122.8,42.6,21.6,21.5,13.4;HRMS(ESI)calcd for C24H25N2O4S2[M+H]+:469.1250,found 469.1246.
The nuclear magnetic spectrum and mass spectrum identification product has the structure shown as the formula III-2.
The 1 H NMR spectrum of the compound represented by formula (III-2) is shown in FIG. 1, the 1 C NMR spectrum of the compound represented by formula (III-2) is shown in FIG. 2, and the mass spectrum of the compound represented by formula (III-2) is shown in FIG. 3.
EXAMPLE 3 preparation of the Compound shown in III-3
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the target formula (III-1) in 87% yield.
The structure of the compound shown in III-3 is characterized by ：1H NMR(500MHz,CDCl3)δ7.78-7.77(m,1H),7.69-7.67(m,1H),7.35(d,J＝8.0Hz,2H),7.31(d,J＝8.0Hz,2H),7.19(d,J＝8.0Hz,2H),7.16-7.12(m,4H),5.87(t,J＝15.5Hz,J＝7.5Hz,1H),3.87(s,2H),2.40(s,3H),2.35(s,3H),2.06(q,J＝15.0Hz,J＝7.5Hz,2H),1.50-1.43(m,2H),0.99(t,J＝15.0Hz,J＝7.5Hz,3H);13C NMR(125MHz,CDCl3)δ144.6,144.1,135.5,134.8,132.0,129.8,129.7,129.5,127.6,127.1,126.2,125.8,124.9,122.4,43.1,29.9,22.5,21.6,21.5,13.8;HRMS(ESI)calcd for C26H29N2O4S2[M+H]+:497.1563,found 497.1558.
The nuclear magnetic spectrum and mass spectrum identification product has the structure shown as the formula III-3.
EXAMPLE 4 preparation of the Compounds shown in III-4
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the objective formula (III-1) in 89% yield.
The structure of the compound shown in III-4 is characterized by ：1H NMR(500MHz,CDCl3)δ7.78-7.76(m,1H),7.69-7.67(m,1H),7.35(d,J＝8.5Hz,2H),7.31(d,J＝8.0Hz,2H),7.19(d,J＝8.0Hz,2H),7.16-7.12(m,4H),5.87(t,J＝15.5Hz,J＝7.5Hz,1H),3.86(s,2H),2.40(s,3H),2.35(s,3H),2.07(q,J＝15.0Hz,J＝7.5Hz,2H),1.44-1.41(m,2H),1.37-1.33(m,4H),0.94(t,J＝13.0Hz,J＝6.5Hz,3H);13C NMR(125MHz,CDCl3)δ144.6,144.1,135.5,134.8,132.2,129.8,129.7,129.5,127.6,127.1,126.0,125.9,124.9,122.4,43.1,31.4,28.8,27.8,22.5,21.6,21.5,14.1;HRMS(ESI)calcd for C28H33N2O4S2[M+H]+:525.1876,found 525.1873.
The nuclear magnetic spectrum and mass spectrum identification product has the structure shown as the formula III-4.
EXAMPLE 5 preparation of the Compounds shown in III-5
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the target formula (III-1) in a yield of 90%.
The structure of the compound shown in III-5 is characterized by ：1H NMR(500MHz,CDCl3)δ7.78-7.76(m,1H),7.69-7.67(m,1H),7.35(d,J＝8.0Hz,2H),7.31(d,J＝8.5Hz,2H),7.19(d,J＝8.0Hz,2H),7.16-7.12(m,4H),5.87(t,J＝15.5Hz,J＝7.5Hz,1H),3.86(s,2H),2.40(s,3H),2.35(s,3H),2.09-2.04(m,2H),1.43-1.40(m,2H),1.34-1.31(m,8H),0.91(t,J＝13.5Hz,J＝6.5Hz,3H);13C NMR(125MHz,CDCl3)δ144.6,144.1,135.5,134.8,132.2,129.8,129.7,129.5,127.6,127.1,126.0,125.9,124.9,122.4,43.1,31.8,29.2,29.1,27.9,22.7,21.6,21.5,14.1;HRMS(ESI)calcd for C30H37N2O4S2[M+H]+:553.2189,found 553.2181.
The nuclear magnetic spectrum and mass spectrum identification product has the structure shown as the formula III-5.
EXAMPLE 6 preparation of the Compounds shown in III-6
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the objective formula (III-1) in 88% yield.
The structure of the compound shown in III-6 is characterized by ：1H NMR(500MHz,CDCl3)δ7.81-7.77(m,2H),7.34(d,J＝8.0Hz,2H),7.30(d,J＝8.5Hz,2H),7.20-7.15(m,4H),7.08(d,J＝8.0Hz,2H),5.17(d,J＝10.5Hz,1H),3.84(s,2H),2.40(s,3H),2.33(s,3H),0.97-0.93(m,2H),0.53-0.50(m,2H);13C NMR(125MHz,CDCl3)δ144.6,144.0,137.0,135.1,134.4,129.7,129.4,129.3,128.7,127.7,127.4,125.5,125.3,125.2,123.4,123.1,42.5,21.6,21.5,10.3,7.7;HRMS(ESI)calcd for C26H27N2O4S2[M+H]+:495.1407,found 495.1401.
The nuclear magnetic spectrum and mass spectrum identification product has the structure shown as the formula III-6.
The 1 H NMR spectrum of the compound represented by the formula (III-6) is shown in FIG. 4, the 1 C NMR spectrum of the compound represented by the formula (III-6) is shown in FIG. 5, and the mass spectrum of the compound represented by the formula (III-6) is shown in FIG. 6.
EXAMPLE 7 preparation of the Compounds shown in III-7
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the objective formula (III-1) in 85% yield.
The structure of the compound shown in III-7 is characterized by ：1H NMR(500MHz,CDCl3)δ7.83(q,J＝7.5Hz,J＝2.0Hz,1H),7.73(q,J＝7.5Hz,J＝2.5Hz,1H),7.44-7.41(m,4H),7.36(t,J＝15.0Hz,J＝7.5Hz,1H),7.25-7.24(m,2H),7.22-7.19(m,2H),7.12(d,J＝7.0Hz,2H),7.06-7.02(m,4H),4.09(s,2H),2.44(s,3H),2.35(s,3H);13C NMR(125MHz,CDCl3)δ144.9,143.9,135.2,134.6,134.1,130.9,129.9,129.5,129.3,129.2,128.8,128.4,127.8,127.1,127.0,125.9,125.7,125.1,122.9,43.1,21.7,21.6;HRMS(ESI)calcd for C29H27N2O4S2[M+H]+:531.1407,found 531.1401.
The nuclear magnetic spectrum and mass spectrum identification products have the structure shown in the formula III-7.
Example 8 preparation of the Compounds shown in III-8
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the target formula (III-1) in a yield of 90%.
The structure of the compound shown in III-8 is characterized by ：1H NMR(500MHz,CDCl3)δ7.54(s,2H),7.46(s,2H),7.35(d,J＝8.0Hz,2H),7.28(t,J＝16.5Hz,J＝8.5Hz,2H),7.19(d,J＝8.0Hz,2H),7.12(d,J＝8.5Hz,2H),5.84(q,J＝14.5Hz,J＝7.0Hz,1H),3.76(s,2H),2.40(s,3H),2.35(s,3H),2.26(s,3H),2.24(s,3H),1.68(d,J＝8.0Hz,3H);13C NMR(125MHz,CDCl3)δ144.4,143.9,135.6,134.8,134.5,133.8,129.7,129.3,127.6,127.1,127.0,126.3,126.2,123.5,42.7,21.6,21.5,19.6,19.5,13.4;HRMS(ESI)calcd for C26H29N2O4S2[M+H]+:497.1563,found 497.1555.
The nuclear magnetic spectrum and mass spectrum identification products have the structure shown in the formula III-8.
EXAMPLE 9 preparation of the Compounds shown in III-9
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the objective formula (III-1) in 85% yield.
The structure of the compound shown in III-9 is characterized by ：1H NMR(500MHz,CDCl3)δ8.17(s,1H),8.04(s,1H),7.84-7.81(m,1H),7.76-7.74(m,1H),7.50-7.44(m,2H),7.40-7.37(m,4H),7.18(d,J＝10.0Hz,2H),7.13(d,J＝10.0Hz,2H),5.98(q,J＝18.5Hz,J＝9.0Hz,1H),4.05(s,2H),2.40(s,3H),2.34(s,3H),1.75(d,J＝9.0Hz,3H);HRMS(ESI)calcd for C28H26N2O4S2Na[M+Na]+:541.1226,found 541.1221.
The nuclear magnetic spectrum and mass spectrum identification products have the structure shown in the formula III-9.
EXAMPLE 9 preparation of the Compounds shown in III-9
In a25 mL reaction tube, 0.2mmol of the compound of formula (I), 0.3mmol of the compound of formula (II), 0.4mmol of cesium carbonate and 2mL of tetrahydrofuran were added and reacted overnight. After the reaction, the mixture was concentrated in vacuo, and the residue was subjected to 200-mesh silica gel column chromatography using a mixture of petroleum ether and ethyl acetate in a volume ratio of 5:1 as an eluent to give the compound of the objective formula (III-1) in 86% yield.
The structure of the compound shown in III-10 is characterized by ：1H NMR(500MHz,CDCl3)δ8.09(s,1H),8.05(s,1H),7.37(J＝8.5Hz,2H),7.31(J＝8.5Hz,2H),7.24(J＝8.5Hz,2H),7.17(J＝8.5Hz,2H),5.91(q,J＝14.5Hz,J＝6.0Hz,1H),3.72(s,2H),2.43(s,3H),2.38(s,3H),1.73(d,J＝7.5Hz,3H);13C NMR(125MHz,CDCl3)δ145.2,144.8,134.8,134.1,130.0,129.7,129.2,128.9,127.7,126.7,125.3,121.0,120.1,41.6,21.7,21.6,13.6;HRMS(ESI)calcd for C24H22N2O4S2Br2[M+H]+:624.9461,found 624.9452.
The nuclear magnetic spectrum and mass spectrum identification products have the structures shown in the formula III-10.
Although specific embodiments of the invention have been disclosed for illustrative purposes, it will be appreciated by those skilled in the art that various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will have the scope indicated by the scope of the appended claims.
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| US6924397B2 (en) * | 2003-10-22 | 2005-08-02 | Bristol-Myers Squibb Company | Process for the preparation of α-chloroketones from alkyl esters |
| DE102004023332A1 (en) * | 2004-05-12 | 2006-01-19 | Bayer Cropscience Gmbh | Quinoxaline-2-one derivatives, crop protection agents containing them, and processes for their preparation and their use |
| KR101426966B1 (en) * | 2006-03-14 | 2014-08-06 | 산텐 세이야꾸 가부시키가이샤 | Novel 1,2,3,4-tetrahydroquinoxaline derivative having glucocorticoid receptor binding activity |
| KR102554782B1 (en) * | 2019-01-23 | 2023-07-13 | 아비스코 테라퓨틱스 컴퍼니 리미티드 | 1,2,3,4-Tetrahydroquinoxaline derivatives, preparation methods and applications thereof |
| CN111072577B (en) * | 2019-12-11 | 2023-02-03 | 四川大学 | Novel green synthesis method for efficiently synthesizing quinoxaline derivative through transition metal catalyzed carbene insertion/cyclization reaction |
| AU2020101059A4 (en) * | 2020-06-19 | 2020-07-23 | Adlai Nortye Biopharma Co Ltd | Preparation method of indoleamine 2,3-dioxygenase inhibitor |
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2022
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| A formal [4+2] annulation of diamines and prop-2-ynyl sulfonium salts for the synthesis of tetrahydroquinoxalines;Fei Xia等;《Org. Biomol. Chem.》;20221024;第20卷;第8416页Table 1、第8417页Scheme 2 * |
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