CN108863891B - Synthesis method of 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone - Google Patents
Synthesis method of 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone Download PDFInfo
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- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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Abstract
The invention relates to a synthesis method of 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone, which is characterized in that a substrate 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-ketone and NFSI are dissolved in a solvent, then alkali is added into the solvent, and a reaction mixture is obtained after stirring reaction for 40-180 minutes at room temperature; washing the reaction mixture for 3-6 times by using saturated sodium bicarbonate, and separating to obtain an organic phase; and drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain a yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The method has the advantages of simple reaction process, mild reaction conditions, high yield, convenient operation and short reaction time.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone.
Background
1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone is an important heterocyclic compound and is widely applied to pharmaceutical engineering, natural rubber, resin and aerospace industry, besides, the compound has high heat resistance, so the compound has important application in the field of engineering plastics, and although the compound is widely applied, an environment-friendly and low-cost synthesis method still needs to be continuously explored.
1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, the classical synthesis method of which is a three-component cyclization reaction of tolane, isocyanate or aniline and carbon monoxide catalyzed by a metal such as ruthenium or rhodium, however, this method uses a heavy metal complex as a catalyst, and is environmentally unfriendly and costly. Later, the reaction of phthalic anhydride and aniline catalyzed by magnetite nanoparticles supported on sulfonic acid-silica by G.S. Shankarling et al also yielded 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione in 84% yield, which, although high in yield, required the preparation of the catalyst in advance, which was cumbersome and costly. Furthermore, the arylation of 1-phenyl-1H-pyrrole-2, 5-dione catalyzed by metallic palladium such as palladium acetate or palladium chloride under the action of arylating reagents iodobenzene or arylboronic acid by jafarpor et al can also be used to synthesize the compound, however, the reaction time of the method is as long as 24 hours, the reaction cost is high due to the use of expensive metallic palladium, and the method is not environment-friendly. Yeleswarapu et al, using N- (2-oxo-2-phenylethyl) -N-biphenylacetamide as the starting material, cyclize under the action of a base DBU to give the compound in 67% yield, although the process is simple, the amount of DBU used is 3 equivalents, and byproducts are also formed. In addition, the compound can be produced in 36% yield by S. Zacchino et al using (Z) -4-oxo-2, 3-diphenyl-4- (phenylamino) but-2-enoursolic acid as a raw material and refluxing in an acetic acid solution of sodium acetate, which is low in yield and severe in reaction conditions. In summary, although there are many methods for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, it is particularly necessary to find a synthesis method which has mild reaction conditions, short reaction time, high yield, convenient operation, few reaction by-products, and environmental friendliness.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone, which has the advantages of simple operation, short reaction time, less by-products and high yield.
In order to solve the above problems, the present invention provides a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which is characterized in that: dissolving a substrate 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-ketone and NFSI in a solvent, adding alkali into the solvent, and stirring the mixture at room temperature for 40-180 minutes to obtain a reaction mixture; washing the reaction mixture for 3-6 times by using saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain a yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone; the mass-volume ratio of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-ketone to the solvent is 1: 90-160 parts; the mass ratio of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-ketone to the NFSI to the base is 1: 1-2: 0.1 to 1.2.
The solvent is any one of chloralkane solvent, alcohol solvent and ether solvent.
The chloralkane solvent is any one of dichloromethane, chloroform and carbon tetrachloride.
The alcohol solvent is any one of methanol, ethanol and isopropanol.
The ether solvent is any one of tetrahydrofuran, 1, 4-dioxane and diethyl ether.
The alkali is any one of DBU, DMAP, thiourea, sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide and potassium hydroxide.
The volume ratio of petroleum ether to ethyl acetate in the petroleum ether-ethyl acetate column chromatography is 25: 1.
compared with the prior art, the invention has the following advantages:
1. the compound is prepared by taking 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-ketone as a raw material, taking relatively mild NFSI as an oxidant and DBU as a base and reacting in THF for 40 minutes at room temperature, and thus the compound can be obtained with high yield. The invention is a one-step reaction, the reaction is thorough, the conversion rate is high, and NFSI is a mild oxidant, so the invention has the characteristics of mild reaction condition, short reaction time, few reaction byproducts, environmental friendliness, high yield and convenient operation.
2. The reaction equation of the invention is as follows:
the product obtained is a yellow solid which is obtained by1H NMR test (see FIG. 1), mp 179-180oC; 1H NMR (600 MHz, CDCl3) δ7.54-7.48 (m, 8H), 7.43-7.38 (m, 7H). The results showed agreement with the target molecule.
3. The product of the invention is tested by X-single crystal diffraction (see figure 2 and tables 1-7), and the result shows that the product is a target molecule and has a correct structure.
TABLE 1 Crystal data and Structure
TABLE 2 Primary atomic coordinates and equivalent Isotropic Displacement parameters
TABLE 3 Anisotropic Displacement parameters
TABLE 4 bond Length
TABLE 5 Key Angle
TABLE 6 torsion Angle
TABLE 7 Hydrogen atom coordinates and Isotropic Displacement parameters
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a drawing of the present invention1H NMR chart.
FIG. 2 is an X-ray single crystal diffractogram according to the present invention.
Detailed Description
Example 1 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 86%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 160.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1: 0.1.
the solvent is methanol. The base is DMAP.
The volume ratio (mL/mL) of petroleum ether to ethyl acetate in the petroleum ether-ethyl acetate column chromatography is 25: 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 2 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 89%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 160.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is methanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 3 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 87%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 160.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.5: 0.1.
the solvent is methanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 4 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The rate was 85%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 160.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 2: 0.1.
the solvent is methanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 5 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 84%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 160.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.5.
the solvent is methanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 6 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 83%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 160.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 1.2.
The solvent is methanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 7 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 90%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 150.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is methanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 8 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 92%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is methanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 9 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 89%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 90.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is methanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 10 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 94%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is tetrahydrofuran. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 11 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 91%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is 1, 4-dioxane. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 12 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 88%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is diethyl ether. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 13 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 85%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is ethanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 14 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 83%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is isopropanol. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 15 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 40 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 75%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is dichloromethane. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 16 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 69%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is chloroform. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 17 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 62%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is carbon tetrachloride. The base is DMAP.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 18 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 98%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is tetrahydrofuran. The base is DBU.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 19 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 53%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is tetrahydrofuran. The alkali is sodium carbonate.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 20 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 58%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is tetrahydrofuran. The base is potassium carbonate.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 21 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 68%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is tetrahydrofuran. The base is sodium hydride.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 22 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, in which 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one as a substrate and NFSI are dissolved in a solvent, and then a base is added thereto, followed by stirring at room temperature for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 62%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is tetrahydrofuran. The base is sodium hydroxide.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 23 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 40 minutes to obtain a reaction mixture; washing the reaction mixture for 3 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 64%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is tetrahydrofuran. The alkali is potassium hydroxide.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 24 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature for 180 minutes with stirring to obtain a reaction mixture; washing the reaction mixture for 6 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 73%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
The solvent is tetrahydrofuran. The base is thiourea.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Example 25 a method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione, which comprises dissolving substrates 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one and NFSI in a solvent, adding a base thereto, and reacting the mixture at room temperature with stirring for 100 minutes to obtain a reaction mixture; washing the reaction mixture for 4 times by saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone. The yield thereof was found to be 81%.
Wherein: the mass-to-volume ratio (g/mL) of 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one to the solvent is 1: 120.
The mass ratio (g/g) of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrol-2-one, the NFSI and the alkali is 1: 1.1: 0.1.
the solvent is tetrahydrofuran. The base is thiourea.
Petroleum ether-ethyl acetate column chromatography was the same as in example 1.
The reduced pressure concentration condition refers to reduced pressure distillation by a rotary evaporator under the pressure of 0.075 MPa.
Claims (7)
1. A method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone is characterized in that: dissolving a substrate 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-ketone and NFSI in a solvent, adding alkali into the solvent, and stirring the mixture at room temperature for 40-180 minutes to obtain a reaction mixture; washing the reaction mixture for 3-6 times by using saturated sodium bicarbonate, and separating to obtain an organic phase; drying the organic phase, concentrating under reduced pressure, and performing petroleum ether-ethyl acetate column chromatography to obtain a yellow product 1, 3, 4-triphenyl-1H-pyrrole-2, 5-diketone; the mass-volume ratio of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-ketone to the solvent is 1: 90-160 g/mL; the mass ratio of the 1, 3, 4-triphenyl-1, 5-dihydro-pyrrole-2-ketone to the NFSI to the base is 1: 1-2: 0.1 to 1.2.
2. The method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione as claimed in claim 1, wherein: the solvent is any one of chloralkane solvent, alcohol solvent and ether solvent.
3. The method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione as claimed in claim 2, wherein: the chloralkane solvent is any one of dichloromethane, chloroform and carbon tetrachloride.
4. The method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione as claimed in claim 2, wherein: the alcohol solvent is any one of methanol, ethanol and isopropanol.
5. The method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione as claimed in claim 2, wherein: the ether solvent is any one of tetrahydrofuran, 1, 4-dioxane and diethyl ether.
6. The method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione as claimed in claim 1, wherein: the alkali is any one of DBU, DMAP, thiourea, sodium carbonate, potassium carbonate, sodium hydride, sodium hydroxide and potassium hydroxide.
7. The method for synthesizing 1, 3, 4-triphenyl-1H-pyrrole-2, 5-dione as claimed in claim 1, wherein: the volume ratio of petroleum ether to ethyl acetate in the petroleum ether-ethyl acetate column chromatography is 25: 1.
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| WO2011117254A1 (en) * | 2010-03-22 | 2011-09-29 | Prosidion Limited | Piperidine amides as modulators of the ghrelin receptor |
| US20140031563A1 (en) * | 2012-07-27 | 2014-01-30 | Metacine, Inc. | New compounds for inhibiting differentiation of osteoclast and pharmaceutical composition comprising thereof |
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| WO2011117254A1 (en) * | 2010-03-22 | 2011-09-29 | Prosidion Limited | Piperidine amides as modulators of the ghrelin receptor |
| US20140031563A1 (en) * | 2012-07-27 | 2014-01-30 | Metacine, Inc. | New compounds for inhibiting differentiation of osteoclast and pharmaceutical composition comprising thereof |
Non-Patent Citations (4)
| Title |
|---|
| N-氟代双苯磺酰胺作为氧化剂制备二硫化合物的研究;景丽等;《有机化学》;20171115;第38卷;第692-697页 * |
| Palladium-catalyzed direct arylation of maleimides: A simple route to bisaryl-substituted maleimides;Farnaz Jafarpour et al.;《Tetrahedron》;20170131;第73卷;第1668-1672页 * |
| Ruthenium-catalyzed [2+2+1] Cocyclization of Isocyanates, Alkynes, and CO Enables the Rapid Synthesis of Polysubstituted Maleimides;Teruyuki Kondo et al.;《J. AM. CHEM. SOC.》;20061028;第128卷;第14816-14817页 * |
| Structure-Based Design of Novel Class II c-Met Inhibitors: 1. Identification of Pyrazolone-Based Derivatives;Mark H. Norman et al.;《J. Med. Chem.》;20120209;第55卷;第1858-1867页 * |
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