CN101475546A - Catalytic synthesis process of benzofurane derivatives - Google Patents

Catalytic synthesis process of benzofurane derivatives Download PDF

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CN101475546A
CN101475546A CNA2009100664923A CN200910066492A CN101475546A CN 101475546 A CN101475546 A CN 101475546A CN A2009100664923 A CNA2009100664923 A CN A2009100664923A CN 200910066492 A CN200910066492 A CN 200910066492A CN 101475546 A CN101475546 A CN 101475546A
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alkyl
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nitro
carboxyl
carbalkoxy
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王芒
刘军
刘颖杰
袁红娟
梁德强
刘群
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Northeast Normal University
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Abstract

The invention belongs to a synthesizing method by organic synthetic chemistry, and relates to a method for catalytically synthesizing benzfuran derivatives. The method uses ketene dithioacetals and a quinine compound as raw materials, methyl cyanide and methylene dichloride as solvents, boron triflouride, or copper halide and the boron triflouride, or halogen acid, such as hydrobromic acid and hydriodic acid as a catalyst. The method comprises the following steps: adding certain amount of the ketene dithioacetals and the quinine compound into an organic solvent; adding the catalyst into the solvent according to the proportion at room temperature; and obtaining the benzfuran derivatives. The yield is between 20 and 88 percent in terms of different reactions, and the synthesized benzfuran compound has a rich functional group to be further modified. Therefore, the invention can introduce a reformable and modifiable ethylthio structure unit into alpha-mother nucleus furan nucleus, and provides a simple and universal method for further synthesizing novel benzfuran compound library with potential bioactivity. The method has the advantages of few steps, accessible raw materials and catalyst, low cost, mild reaction condition, simple operation, and easy industrialization.

Description

A kind of process for catalytic synthesis of benzofuran derivative
Technical field
The invention belongs to the technical study field of Synthetic Organic Chemistry, relating to a kind of is raw material with quinone and dithio keteal compounds, the synthetic method of catalysis synthesizing new benzofuran derivative.
Background technology
The cumarone structural unit extensively is present in the natural product, and wherein many being proved has good pharmaceutical use, as: ((a) Tetrahedron 2000,57,5585 such as antimycotic, antitumor; (b) J.Nat.Prod.2002,65,820.).In addition, as useful organic synthesis intermediate, cumarone is applied to making up complex compound more.Therefore, research and development are from raw material inexpensive, that be easy to get, and the functionalized cumarone of synthetic benzofuran derivative, the especially potential using value of tool is the research emphasis in synthetic method field simply, efficiently, enjoys the favor of organic chemist.The synthetic method of relevant benzofuran compounds is a lot, wherein, the method of constructing the furan nucleus in the cumarone parent nucleus via the ring-closure reaction of fisher's formula precursor compound is the most common, as under transition metal-catalyzed, phenyl allyl ether class (Angew.Chem.Int.Ed.2004,43,6144.) and α-alkynyl phenol type substances ((a) J.Am.Chem.Soc.2005,127,15024; (b) ring-closure reaction Org.Lett.2005,7,2707.) is the method for studying very deeply for preparing benzofuran compounds.Some synthetic methods in addition, such as the addition reaction (Tetrahedron Lett.2007,48,431.) of salicylic aldehyde and monochloromethyl ketone, the photochemical catalysis rearrangement reaction (Angew.Chem.Int.Ed.1999 of α-styryl furans, 38,2558.) also be effective synthesis path etc.For many years, this seminar is engaged in design and the study on the synthesis based on the organic micromolecule compound of functionalized dithio keteal intermediate always.In the recent period, we have found the α position C-C linked reaction of the catalytic functionalized dithio keteal of a kind of mantoquita, and successfully this method are applied in coumarin kind compound synthetic (Adv.Syn.Catal.2009,351 (1), early view.).The present invention then designs from functionalized dithio keteal and quinones, the synthetic similar thing of cumarone under cheap metal commonly used, non-metallic catalyst catalysis, thereby can introduce the α position of parent nucleus furan nucleus for the alkylthio structural unit of transforming, modifying, the active novel benzofuran compounds of tool potential source biomolecule storehouse is synthetic to provide easy a, method in common in order further to carry out.
Summary of the invention
The objective of the invention is: set up a kind ofly, utilize easy, the efficient novel method of the synthetic benzofuran derivative of simple metal, non-metallic catalyst catalysis from raw material inexpensive, that be easy to get.
Positively effect of the present invention is: the method that a kind of easy novel benzofuran compounds of preparation is provided.Institute's synthetic benzofuran compounds has the abundant functional group for further modification.This method synthesis step few (step), raw material and catalyzer are easy to get, and be cheap, and the reaction conditions gentleness is simple to operate, is easy to technology, industrialization.
Used starting raw material dithio keteal of the present invention and quinones are represented with following general formula:
Figure A200910066492D00061
The dithio keteal quinone
A kind of process for catalytic synthesis of benzofuran derivative institute of the present invention synthetic benzofuran derivative is represented with following general formula:
Figure A200910066492D00062
Benzofuran derivative
Wherein, R 1Be various C 1-C 6Alkyl; Be connected with nitro, cyano group, sulfonic group, carboxyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The methylene radical that the alkoxyl group of alkyl replaces; Benzyl; Be connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on the phenyl ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The benzyl that the alkoxyl group of alkyl replaces;
Wherein, R 2Be nitro; Cyano group; Sulfonic group; Carboxyl; Alkyl is C 1-C 4The acyl group of alkyl; Benzoyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The sweet-smelling formacyl that the alkoxyl group of alkyl replaces; Enoyl-; Be connected with C on two keys 1-C 4Alkyl, phenyl and be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The aryloxy carbonyl of alkyl, and C 1-C 4The enoyl-of the phenyl that the alkoxyl group of alkyl replaces; Alkyl is C 1-C 4The carbalkoxy of alkyl; Carbobenzoxy; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The aryloxy carbonyl of alkyl, and C 1-C 4The aryloxy carbonyl that the alkoxyl group of alkyl replaces; Benzenesulfonyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylsulfonyl that the alkoxyl group of alkyl replaces; Be connected with various C on basic carbonyl of amine (ammonia) and the amido 1-C 4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The amido carbonyl of the alkoxy substituted phenyl of alkyl;
Wherein, R 3Be hydrogen atom; Halogen atom such as chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Carboxyl; Alkyl is C 1-C 4The acyl group of alkyl; Benzoyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The sweet-smelling formacyl that the alkoxyl group of alkyl replaces; Alkyl is C 1-C 4The alkoxyl group of alkyl; Alkyl is C 1-C 4The carbalkoxy of alkyl; Carbobenzoxy; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy carbonyl that the alkoxyl group of alkyl replaces; Phenoxy group; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy that the alkoxyl group of alkyl replaces; Thiophenyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylthio that the alkoxyl group of alkyl replaces; Benzenesulfonyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylsulfonyl that the alkoxyl group of alkyl replaces; Aminocarboxyl; Be connected with various C on the amido 1-C 4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The amido carbonyl of the alkoxy substituted phenyl of alkyl;
Wherein, R 4Be hydrogen atom; Halogen atom such as chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Carboxyl; Alkyl is C 1-C 4The acyl group of alkyl; Benzoyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The sweet-smelling formacyl that the alkoxyl group of alkyl replaces; Alkyl is C 1-C 4The alkoxyl group of alkyl; Alkyl is C 1-C 4The carbalkoxy of alkyl; Carbobenzoxy; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy carbonyl that the alkoxyl group of alkyl replaces; Phenoxy group; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy that the alkoxyl group of alkyl replaces; Thiophenyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylthio that the alkoxyl group of alkyl replaces; Benzenesulfonyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylsulfonyl that the alkoxyl group of alkyl replaces; Aminocarboxyl; Be connected with various C on the amido 1-C 4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The amido carbonyl of the alkoxy substituted phenyl of alkyl;
Wherein, R 5Be hydrogen atom; Halogen atom such as chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Carboxyl; Alkyl is C 1-C 4The acyl group of alkyl; Benzoyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The sweet-smelling formacyl that the alkoxyl group of alkyl replaces; Alkyl is C 1-C 4The alkoxyl group of alkyl; Alkyl is C 1-C 4The carbalkoxy of alkyl; Carbobenzoxy; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy carbonyl that the alkoxyl group of alkyl replaces; Phenoxy group; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy that the alkoxyl group of alkyl replaces; Thiophenyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylthio that the alkoxyl group of alkyl replaces; Benzenesulfonyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylsulfonyl that the alkoxyl group of alkyl replaces; Aminocarboxyl; Be connected with various C on the amido 1-C 4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The amido carbonyl of the alkoxy substituted phenyl of alkyl;
In addition, R 4And R 5Between the various and ring substituents of dotted line representative, as: work as R 4, R 5When representative and phenyl, quinone is 1, the 4-naphthoquinones; 1, the hydrogen atom on the phenyl ring of 4-naphthoquinones can be replaced by following atom or group respectively, as: chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Hydroxyl; Carboxyl; Various C 1-C 6The carbalkoxy of alkyl; Various C 1-C 6Alkyl; Various C 1-C 6The alkoxyl group of alkyl; Various C 1-C 6The alkylthio of alkyl; Benzyl; Be connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The benzyl that the alkoxyl group of alkyl replaces; Phenyl; Be connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on the phenyl ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The phenyl that the alkoxyl group of alkyl replaces;
Technical scheme of the present invention is as follows:
With dithio keteal and quinones is raw material, and the method for the synthetic benzofuran derivative of catalysis comprises following experiment condition and step:
Solvent for use is in the reaction: acetonitrile, methylene dichloride.
Catalyst system therefor is in the reaction: boron trifluoride; Copper halide and boron trifluoride; Haloid acid is as Hydrogen bromide, hydroiodic acid HI.
In certain organic solvent of as above mentioning (4.0-8.0 milliliters), add above-mentioned dithio keteal (1.0 mmole) and quinones (1.5 mmole).Under the stirring at room, add the above-mentioned a certain class catalyzer of mentioning (0.02-0.1 mmole), (above quantity can be amplified in proportion).Finish, continue under the room temperature to stir 10 minutes-24 hours, separate obtaining benzofuran derivative through aftertreatment.Productive rate is looked differential responses between 20-88%, sees the embodiment in the embodiment for details.
Embodiment
Embodiment 1:
In 50 milliliters of round-bottomed flasks, add 0.192 gram (1.0 mmole) 3,3-diformazan sulfenyl acrylic acid ethyl ester, 0.162 gram (1.5 mmole) para benzoquinone.Under the stirring at room, add the acetonitrile solution (concentration: 0.025mol/L, 0.1 mmole) of 4.0 milliliters of boron trifluoride diethyl etherate that prepare in advance.Continue to stir 0.5 hour to 3,3-diformazan sulfenyl acrylic acid ethyl ester react completely (thin-layer chromatography TLC monitoring).In reaction mixture impouring 20 ml waters, be neutralized to neutrality with saturated sodium bicarbonate.With dichloromethane extraction (10 milliliters * 3).Merge organic phase, with anhydrous magnesium sulfate drying.After steaming desolventized, (elutriant: petroleum ether/ethyl ether=9/1) get white solid was 2-methylthio group-3-ethoxycarbonyl-5-hydroxyl benzofuran 0.126 gram to residuum, productive rate 50% through the silica gel column chromatography separation.React formula as follows:
Figure A200910066492D00091
Embodiment 2:
In 50 milliliters of round-bottomed flasks, add 0.192 gram (1.0 mmole) 3,3-diformazan sulfenyl acrylic acid ethyl ester, 0.237 gram (1.5 mmole) 1,4-naphthoquinones, and 0.005 gram (0.02 mmole) cupric bromide.Under the stirring at room, add the acetonitrile solution (concentration: 0.025mol/L, 0.1 mmole) of 4.0 milliliters of boron trifluoride diethyl etherate that prepare in advance.Continue to stir 10 minutes to 3,3-diformazan sulfenyl acrylic acid ethyl ester react completely (thin-layer chromatography TLC monitoring).In reaction mixture impouring 20 ml waters, be neutralized to neutrality with saturated sodium bicarbonate.With dichloromethane extraction (10 milliliters * 3).Merge organic phase, with anhydrous magnesium sulfate drying.After steaming desolventized, (elutriant: petroleum ether/ethyl ether=9/1) get white solid was 2-methylthio group-3-ethoxycarbonyl-5-hydroxyl aphthofurans 0.266 gram to residuum, productive rate 88% through the silica gel column chromatography separation.React formula as follows:
Figure A200910066492D00092
Embodiment 3:
In 50 milliliters of round-bottomed flasks, add 0.145 gram (1.0 mmole) 3,3-diformazan sulfenyl third rare nitrile, 0.237 gram (1.5 mmole) 1,4-naphthoquinones, and 0.005 gram (0.02 mmole) cupric bromide.Under the stirring at room, add the acetonitrile solution (concentration: 0.025mol/L, 0.1 mmole) of 4.0 milliliters of boron trifluoride diethyl etherate that prepare in advance.Continue to stir 9.0 hours to 3,3-diformazan sulfenyl third rare nitrile react completely (thin-layer chromatography TLC monitoring).In reaction mixture, add 4.0 milliliters of ether, separate out a large amount of precipitations.It is 2-methylthio group-3-itrile group-5-hydroxyl aphthofurans 0.133 gram that filtration under diminished pressure gets faint yellow solid, productive rate 57%.React formula as follows:
Figure A200910066492D00101
Embodiment 4:
In 50 milliliters of round-bottomed flasks, add 0.190 gram (1.0 mmole) 4,4-diethyl sulfenyl-3-fourth is rare-2-ketone, 0.162 gram (1.5 mmole) para benzoquinone, and 0.011 gram (0.05 mmole) cupric bromide.Under the stirring at room, add the dichloromethane solution (concentration: 0.025mol/L, 0.1 mmole) of 4.0 milliliters of boron trifluoride diethyl etherate that prepare in advance.Continue to stir 24 hours, have precipitation to separate out in the reaction process.Treat 4,4-diethyl sulfenyl-3-fourth is rare-2-ketone consumption (thin-layer chromatography TLC monitoring) fully, 4.0 milliliters of ether of adding are separated out a large amount of precipitations in reaction mixture.It is 2-ethylmercapto group-3-ethanoyl-5-hydroxyl benzofuran 0.113 gram that filtration under diminished pressure gets faint yellow solid, productive rate 48%.React formula as follows:
Figure A200910066492D00102
Embodiment 5:
In 50 milliliters of round-bottomed flasks, add 0.162 gram (1.0 mmole) 4,4-diformazan sulfenyl-3-fourth is rare-2-ketone, 0.162 gram (1.5 mmole) para benzoquinone.Under the stirring at room, add the acetonitrile solution (concentration: 0.025mol/L, 0.1 mmole) of 4.0 milliliters of pre-configured Hydrogen bromides (47% aqueous solution).Continue stirring 24 hours to 4,4-diformazan sulfenyl-3-fourth is rare-2-reactive ketone (thin-layer chromatography TLC monitoring) fully.In reaction mixture impouring 20 ml waters, be neutralized to neutrality with saturated sodium bicarbonate.With dichloromethane extraction (10 milliliters * 3).Merge organic phase, with anhydrous magnesium sulfate drying.After steaming desolventized, (elutriant: petroleum ether/ethyl ether=9/1) get white solid was 2-methylthio group-3-ethanoyl-5-hydroxyl benzofuran 0.151 gram to residuum, productive rate 68% through the silica gel column chromatography separation.React formula as follows:
Figure A200910066492D00103
Embodiment 6:
In 50 milliliters of round-bottomed flasks, add 0.252 gram (1.0 mmole) 3,3-diethyl sulfenyl-1-phenyl-2-third rare-1-ketone, 0.396 gram (1.5 mmole) 2,3-two bromo-1,4-benzoquinones, and 0.005 gram (0.02 mmole) cupric bromide.Under the stirring at room, add the acetonitrile solution (concentration: 0.025mol/L, 0.1 mmole) of 4.0 milliliters of boron trifluoride diethyl etherate that prepare in advance.Continue to stir 10 hours to 3,3-diethyl sulfenyl-1-phenyl-2-third rare-1-reactive ketone is (thin-layer chromatography TLC monitoring) fully.In reaction mixture impouring 20 ml waters, be neutralized to neutrality with saturated sodium bicarbonate.With dichloromethane extraction (10 milliliters * 3).Merge organic phase, with anhydrous magnesium sulfate drying.After steaming desolventized, (elutriant: petroleum ether/ethyl ether=10/1) get white solid was 2-ethylmercapto group-3-benzoyl-5-hydroxyl aphthofurans 0.277 gram to residuum, productive rate 50% through the silica gel column chromatography separation.React formula as follows:

Claims (3)

1, a kind of process for catalytic synthesis of benzofuran derivative is characterized in that:
With dithio keteal and quinones is raw material; Solvent for use is in the reaction: acetonitrile, methylene dichloride; Catalyst system therefor is in the reaction: boron trifluoride; Copper halide and boron trifluoride; Haloid acid is as Hydrogen bromide, hydroiodic acid HI;
In 4.0-8.0 milliliters of organic solvents that certain is as above mentioned, add above-mentioned dithio keteal 1.0 mmoles and quinones 1.5 mmoles, under the stirring at room, add above-mentioned a certain class catalyzer 0.02-0.1 mmole of mentioning, above quantity can be amplified in proportion, finish, continue under the room temperature to stir 10 minutes-24 hours, separate obtaining benzofuran derivative through aftertreatment.Productive rate is looked differential responses between 20-88%.
2, according to the process for catalytic synthesis of the described benzofuran derivative of claim 1, it is characterized in that: in 50 milliliters of round-bottomed flasks, add 1.0 mmoles 3,3-diformazan sulfenyl acrylic acid ethyl ester, 1.5 mmoles 1,4-naphthoquinones, and 0.02 mmole cupric bromide; Under the stirring at room, add concentration and be the acetonitrile solution of the boron trifluoride diethyl etherate that 0.1 mmole of 0.025mol/L prepares in advance, continue to stir 10 minutes to 3,3-diformazan sulfenyl acrylic acid ethyl ester reacts completely; In reaction mixture impouring 20 ml waters, be neutralized to neutrality with saturated sodium bicarbonate, with dichloromethane extraction, merge organic phase, with anhydrous magnesium sulfate drying, after steaming desolventizes, residuum separates through silica gel column chromatography, with petroleum ether/ethyl ether=9/1 elutriant wash-out, getting white solid is 2-methylthio group-3-ethoxycarbonyl-5-hydroxyl aphthofurans 0.266 gram, productive rate 88%.
3, benzofuran derivative is characterized in that its general formula is expressed as follows:
Figure A200910066492C00021
Wherein, R 1Be various C 1-C 6Alkyl; Be connected with nitro, cyano group, sulfonic group, carboxyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The methylene radical that the alkoxyl group of alkyl replaces; Benzyl; Be connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on the phenyl ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The benzyl that the alkoxyl group of alkyl replaces;
Wherein, R 2Be nitro; Cyano group; Sulfonic group; Carboxyl; Alkyl is C 1-C 4The acyl group of alkyl; Benzoyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The sweet-smelling formacyl that the alkoxyl group of alkyl replaces; Enoyl-; Be connected with C on two keys 1-C 4Alkyl, phenyl and be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The aryloxy carbonyl of alkyl, and C 1-C 4The enoyl-of the phenyl that the alkoxyl group of alkyl replaces; Alkyl is C 1-C 4The carbalkoxy of alkyl; Carbobenzoxy; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The aryloxy carbonyl of alkyl, and C 1-C 4The aryloxy carbonyl that the alkoxyl group of alkyl replaces; Benzenesulfonyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylsulfonyl that the alkoxyl group of alkyl replaces; Be connected with various C on amine, aminocarboxyl and the amido 1-C 4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The amido carbonyl of the alkoxy substituted phenyl of alkyl;
Wherein, R 3Be hydrogen atom; Halogen atom; Nitro; Cyano group; Sulfonic group; Carboxyl; Alkyl is C 1-C 4The acyl group of alkyl; Benzoyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The sweet-smelling formacyl that the alkoxyl group of alkyl replaces; Alkyl is C 1-C 4The alkoxyl group of alkyl; Alkyl is C 1-C 4The carbalkoxy of alkyl; Carbobenzoxy; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy carbonyl that the alkoxyl group of alkyl replaces; Phenoxy group; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy that the alkoxyl group of alkyl replaces; Thiophenyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylthio that the alkoxyl group of alkyl replaces; Benzenesulfonyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylsulfonyl that the alkoxyl group of alkyl replaces; Aminocarboxyl; Be connected with various C on the amido 1-C 4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The amido carbonyl of the alkoxy substituted phenyl of alkyl;
Wherein, R 4Be hydrogen atom; Halogen atom; Nitro; Cyano group; Sulfonic group; Carboxyl; Alkyl is C 1-C 4The acyl group of alkyl; Benzoyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The sweet-smelling formacyl that the alkoxyl group of alkyl replaces; Alkyl is C 1-C 4The alkoxyl group of alkyl; Alkyl is C 1-C 4The carbalkoxy of alkyl; Carbobenzoxy; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy carbonyl that the alkoxyl group of alkyl replaces; Phenoxy group; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy that the alkoxyl group of alkyl replaces; Thiophenyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylthio that the alkoxyl group of alkyl replaces; Benzenesulfonyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylsulfonyl that the alkoxyl group of alkyl replaces; Aminocarboxyl; Be connected with various C on the amido 1-C 4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The amido carbonyl of the alkoxy substituted phenyl of alkyl;
Wherein, R 5Be hydrogen atom; Halogen atom; Nitro; Cyano group; Sulfonic group; Carboxyl; Alkyl is C 1-C 4The acyl group of alkyl; Benzoyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The sweet-smelling formacyl that the alkoxyl group of alkyl replaces; Alkyl is C 1-C 4The alkoxyl group of alkyl; Alkyl is C 1-C 4The carbalkoxy of alkyl; Carbobenzoxy; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy carbonyl that the alkoxyl group of alkyl replaces; Phenoxy group; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The aryloxy that the alkoxyl group of alkyl replaces; Thiophenyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylthio that the alkoxyl group of alkyl replaces; Benzenesulfonyl; Be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The arylsulfonyl that the alkoxyl group of alkyl replaces; Aminocarboxyl; Be connected with various C on the amido 1-C 4Alkyl, phenyl and on phenyl ring, be connected with fluorine, chlorine, bromine, iodine, hydroxyl, nitro, cyano group, sulfonic group, carboxyl, C 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The amido carbonyl of the alkoxy substituted phenyl of alkyl;
In addition, R 4And R 5Between the various and ring substituents of dotted line representative, work as R 4, R 5When representative and phenyl, quinone is 1, the 4-naphthoquinones; 1, the hydrogen atom on the phenyl ring of 4-naphthoquinones can be replaced by following atom or group respectively: chlorine, bromine, iodine; Nitro; Cyano group; Sulfonic group; Hydroxyl; Carboxyl; Various C 1-C 6The carbalkoxy of alkyl; Various C 1-C 6Alkyl; Various C 1-C 6The alkoxyl group of alkyl; Various C 1-C 6The alkylthio of alkyl; Benzyl; Be connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on the aromatic ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The benzyl that the alkoxyl group of alkyl replaces; Phenyl; Be connected with fluorine, chlorine, bromine, iodine, nitro, cyano group, sulfonic group, carboxyl, C on the phenyl ring 1-C 4Alkyl, C 1-C 4The carbalkoxy of alkyl, and C 1-C 4The phenyl that the alkoxyl group of alkyl replaces.
CNA2009100664923A 2009-01-20 2009-01-20 Catalytic synthesis process of benzofurane derivatives Pending CN101475546A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104447649A (en) * 2014-10-29 2015-03-25 辽宁大学 Methylnaphtho-[1,2-b] furan amide compound, and pharmaceutical acceptable salt, preparation method and application of methylnaphtho-[1,2-b] furan amide compound
CN106518760A (en) * 2016-11-22 2017-03-22 东北师范大学 4-Aminoquinoline compound and preparation method thereof
CN110003187A (en) * 2019-05-10 2019-07-12 南京工业大学 Polyfluoroalkyl substituted benzofuran compound and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104447649A (en) * 2014-10-29 2015-03-25 辽宁大学 Methylnaphtho-[1,2-b] furan amide compound, and pharmaceutical acceptable salt, preparation method and application of methylnaphtho-[1,2-b] furan amide compound
CN104447649B (en) * 2014-10-29 2016-08-17 辽宁大学 Methyl naphtho-[1,2-b] amide compounds and pharmaceutically acceptable salt and its preparation method and application thereof
CN106518760A (en) * 2016-11-22 2017-03-22 东北师范大学 4-Aminoquinoline compound and preparation method thereof
CN106518760B (en) * 2016-11-22 2019-06-25 东北师范大学 A kind of 4- aminoquinoline compounds and preparation method thereof
CN110003187A (en) * 2019-05-10 2019-07-12 南京工业大学 Polyfluoroalkyl substituted benzofuran compound and preparation method thereof
CN110003187B (en) * 2019-05-10 2021-11-05 南京工业大学 Polyfluoroalkyl substituted benzofuran compound and preparation method thereof

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