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Preparation method of quinoxalin-2-one derivative and product purification method

A derivative, quinoxalone technology, applied in the field of organic compound synthesis, can solve the problems of high cost, expensive, unfavorable industrialization, etc., and achieve the effect of low cost, high yield, and cheap synthesis system

Inactive Publication Date: 2016-04-27
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] The above-mentioned synthetic method has the advantage of high synthetic efficiency, but this method requires relatively expensive ligand 1,10-phenanthroline; in addition, the substrate N-methyl-N-(2-iodophenyl)- 2-chloroacetamide is relatively expensive, so the cost of using the above-mentioned synthetic method is higher, which is unfavorable for industrialization popularization

Method used

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  • Preparation method of quinoxalin-2-one derivative and product purification method
  • Preparation method of quinoxalin-2-one derivative and product purification method
  • Preparation method of quinoxalin-2-one derivative and product purification method

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preparation example Construction

[0028] The preparation method of quinoxalone derivatives comprises the following steps: taking N-methyl-N-phenyl trifluoropropionamide or its derivatives as substrate, adding TBN in the substrate, the mol ratio of substrate and TBN is 1:4; and the amount of further TBN is 4 equivalents; then dissolve with acetonitrile solution as solvent, and in molecular sieve, The amount of molecular sieve is 100 mg; and in the base Cs 2 CO 3 / acid HOAc in an air atmosphere, the preferred Cs 2 CO 3 The amount of HOAc / HOAc is 2 equivalents; the crude product is obtained by heating at 100°C for 24 hours, and its chemical reaction formula is as follows:

[0029]

[0030] Among them, R in the general formula of the substrate is one of methyl, methoxy, acetyl, nitro, fluorine, chlorine, bromine, hydrogen; R' is methyl, ethyl, isopropyl, phenyl One of , benzyl and hydrogen.

[0031] After the reaction finishes cooling, the crude product obtained by the above method is purified and purif...

specific Embodiment 1

[0037] Specific embodiment one: 43.4 milligrams (0.2mmol) N-methyl-N-phenyltrifluoropropionamide, 82.4 milligrams (0.8mmol) TBN, 130.4 milligrams (0.4mmol) Cs 2 CO 3 , 24 mg (0.4 mmol) HOAc, 100 mg Molecular sieves were added to the reaction test tube, and then 2mL CH 3 CN, heated at 100°C for 24 hours, cooled after the reaction, filtered, and the filtrate was deacidified to obtain a crude product. The crude product was chromatographed on a silica gel column, washed with a mixed eluent prepared with ethyl acetate and petroleum ether, and detected by TLC , Combine the effluents containing the product, distill off the solvent with a rotary evaporator, and dry in vacuo to obtain 26.6 mg of 1-methylquinoxalin-2-one as a yellow liquid, with a yield of 83%. 1 HNMR (500MHz, CDCl 3 )δ7.45-7.39(m,3H),7.25-7.22(m,2H),3.29(s,3H); 13 CNMR (125MHz, CDCl 3 )δ144.5, 138.9, 130.1, 129.7, 128.2, 127.0, 124.9, 110.6, 36.7; LRMS (EI, 70eV) m / z (%): 160 (M + ,100),132(36),106(15),91(50),77...

specific Embodiment 2

[0039] Specific example two: 47 mg (0.2 mmol) N-methyl-N-(2-fluorophenyl) trifluoropropionamide, 82.4 mg (0.8 mmol) TBN, 130.4 mg (0.4 mmol) Cs 2 CO 3 , 24 mg (0.4 mmol) HOAc, 100 mg Molecular sieves were added to the reaction test tube, and then 2mL CH 3 CN, heated at 100°C for 24 hours, cooled after the reaction, filtered, and the filtrate was deacidified to obtain a crude product. The crude product was chromatographed on a silica gel column, washed with a mixed eluent prepared with ethyl acetate and petroleum ether, and detected by TLC , combined the effluents containing the product, distilled off the solvent with a rotary evaporator, and dried in vacuo to obtain 34.2 mg of 1-methyl-7-fluoroquinoxalin-2-one as a yellow solid, with a yield of 96%. 1 HNMR (500MHz, CDCl 3 )δ7.52-7.47(m,1H),7.38-7.35(m,1H),7.30-7.25(m,2H),3.34(s,3H); 13 CNMR (125MHz, CDCl 3 )δ158.2 (d, J=250.6Hz), 144.9, 131.9, 129.5, 127.4, 125.5, 117.3 (d, J=19.4Hz), 110.2, 36.1; LRMS (EI, 70eV) m / z (%)...

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Abstract

The invention discloses a preparation method of a quinoxalin-2-one derivative and a product purification method. The preparation method comprises the following steps: using N-methyl-N-phenyltrifluoropropionamide or its derivative as a substrate, adding tert-butyl nitrite into the substrate, using an acetonitrile solution as a solvent, and heating to carry out a reaction in the environment of a buffer solution prepared from a 4 Angstrom molecular sieve, cesium carbonate and acetic acid so as to prepare a crude product. Then, the crude product undergoes purification. The purification method comprises the following steps: filtering the crude product and removing acid to obtain residue; carrying out silica-gel column chromatography on the residue, leaching with an eluate and collecting an eluant; merging product-containing eluants; condensing the merged eluant to remove the solvent; and finally carrying out vacuum drying to obtain a target product. The invention has advantages of simple technological process, low cost and high yield.

Description

technical field [0001] The invention belongs to the field of organic compound synthesis, and specifically relates to a preparation method of quinoxalone derivatives and a method for purification and purification of products thereof, in particular to 1-methylquinoxalin-2-one. Background technique [0002] Quinoxalone is an important synthetic intermediate, widely exists in many natural products, and is also a ubiquitous structural unit in many biologically active compounds. [0003] Literature Bao, W.-L. (J.Org.Chem.2010, 75, 5768) discloses the synthesis of quinoxalone compounds through a copper-catalyzed coupling reaction, and the method includes a preparation process and a purification process. [0004] Its preparation process is as follows: [0005] With N-phenyl-N-(2-iodophenyl)-2-chloroacetamide as substrate (0.5mmol), add CuI (10mol%), TsNH 2 (0.6mmol), 1,10-phenanthroline (20mol%), CsCO 3 (2mmol), using dioxane (2mL) as a solvent, and reacting at 100°C for 18h unde...

Claims

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Application Information

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IPC IPC(8): C07D241/44
CPCC07D241/44
Inventor 张兴国王方胡伯伦张小红邓辰亮
Owner WENZHOU UNIVERSITY
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