CN108912001B - Catalytic synthesis method of 1, 3-dicarbonyl compound - Google Patents
Catalytic synthesis method of 1, 3-dicarbonyl compound Download PDFInfo
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- CN108912001B CN108912001B CN201810560723.5A CN201810560723A CN108912001B CN 108912001 B CN108912001 B CN 108912001B CN 201810560723 A CN201810560723 A CN 201810560723A CN 108912001 B CN108912001 B CN 108912001B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Abstract
The invention discloses a catalytic synthesis method of a 1, 3-dicarbonyl compound. According to the catalytic synthesis method, under the participation of sodium carbonate, the aniline compound and bromodifluoroacetic acid ethyl ester are subjected to defluorination reaction to obtain the 1, 3-dicarbonyl compound, and the reaction has good functional group compatibility; the catalytic synthesis method provided by the invention has the advantages that the used medicines can be directly purchased, the operation is simple, the efficiency and the safety are high, the reaction is simple, and the industrial application prospect of the reaction is greatly improved.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis, and particularly relates to a catalytic synthesis method of a 1, 3-dicarbonyl compound.
Background
Halodifluoromethyl compounds are widely used as fluorine reagents, difluorocarbenes, many of which are obtained by cleaving one C-Br bond or two C-Br and C-COOM bonds using difluoroalkylation and difluoromethylation. However, although there has been a great progress in difluoroalkylation and difluoromethylation of difluoro compounds, a method of cleaving four bonds of one carbon atom to form a new source of C has not been reported so far. There are several previously unprecedented challenges: (1) how to cleave four different bonds in a single reaction step also includes how two stable C-F bonds on the same carbon atom (2) can be converted to valuable products using the in situ generated C1.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a catalytic synthesis method of a 1, 3-dicarbonyl compound.
The technical scheme of the invention is as follows:
a catalytic synthesis method of 1, 3-dicarbonyl compounds comprises the following steps:
(1) placing aniline compounds, bromodifluoroacetic acid ethyl ester, sodium carbonate, cobalt (II) acetylacetonate and dry tetrahydrofuran in a pressure-resistant sealed reaction vessel, filling nitrogen, stirring and reacting in an oil bath at 100-150 ℃, and tracking by TLC and GC in the reaction process to determine specific reaction time, wherein the aniline compounds are o-aminobiphenyl, o-aminoalkylbiphenyl or aminoarylbiphenyl;
(2) cooling the material obtained in the step (1) to room temperature, adding ethyl acetate, fully mixing, filtering, washing with ethyl acetate, and finally combining organic phases;
(3) and (3) spin-drying the solvent in the organic phase obtained in the step (2), purifying the product by using a silica gel column, and eluting by using an eluent to obtain the 1, 3-dicarbonyl compound.
In a preferred embodiment of the invention, the ratio of the aniline compound, ethyl bromodifluoroacetate, sodium carbonate, cobalt (II) acetylacetonate and dried tetrahydrofuran is 0.18-0.22 mmol: 0.5-1 mmol: 0.1-0.2 mmol: 0.5-1 mmol: 1-5 mL.
Further preferably, the ratio of the aniline compound, ethyl bromodifluoroacetate, sodium carbonate, cobalt (II) acetylacetonate and dry tetrahydrofuran is 0.2mmol:0.4mmol:0.12mmol:0.5mmol:2 mL.
In a preferred embodiment of the present invention, the reaction temperature of the step (1) is 120 ℃.
In a preferred embodiment of the present invention, the reaction time is 10 to 25 hours.
In a preferred embodiment of the present invention, the eluent is a mixed solution of petroleum ether and ethyl acetate.
Further preferably, the eluent is composed of petroleum ether and ethyl acetate in a volume ratio of 50-100: 1.
The invention has the beneficial effects that:
1. according to the catalytic synthesis method, under the participation of sodium carbonate, the aniline compound and bromodifluoroacetic acid ethyl ester are subjected to defluorination reaction to obtain the 1, 3-dicarbonyl compound, and the reaction has good functional group compatibility;
2. the catalytic synthesis method provided by the invention has the advantages that the used medicines can be directly purchased, the operation is simple, the efficiency and the safety are high, the reaction is simple, and the industrial application prospect of the reaction is greatly improved.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
The reaction formula for this example is shown below:
(1) placing 0.2mmol of aniline, 0.4mmol of ethyl bromodifluoroacetate, 0.12mmol of cobalt acetylacetonate, 0.5mmol of sodium carbonate and 2mL of tetrahydrofuran in a pressure-resistant sealed reaction tube, filling nitrogen, stirring in an oil bath at 120 ℃ for reaction, and tracking by TLC and GC in the reaction process to determine specific reaction time, wherein the reaction time is 12 hours;
(2) cooling the material obtained in the step (1) to room temperature, adding ethyl acetate, fully mixing, filtering, washing with ethyl acetate, and finally combining organic phases;
(3) and (3) drying the solvent in the organic phase obtained in the step (2) in a spinning way, purifying the product by using a silica gel column, and eluting by using an eluent to obtain the 3- ((phenylamino) methylene) pentane-2, 4-dione with the yield of 83 percent, wherein the eluent is a mixed solution of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 100: 1.
Example 2
(1) 0.2mmol of aniline compound, 0.4mmol of ethyl bromodifluoroacetate, 0.02mmol of Cu (OTf)20.024mmol, 1, 10-phenanthroline and 0.5mmol of sodium carbonate are placed in a pressure-resistant sealed reaction tube, nitrogen is filled in the reaction tube, the reaction tube is stirred in an oil bath at 120 ℃ for reaction, TLC and GC are used for tracking in the reaction process to determine specific reaction time, and the reaction time is 20 hours;
the aniline compound is at least one of the following compounds:
(2) cooling the material obtained in the step (1) to room temperature, adding ethyl acetate, fully mixing, filtering, washing with ethyl acetate, and finally combining organic phases;
(3) and (3) spin-drying the solvent in the organic phase obtained in the step (2), purifying the product by using a silica gel column, and eluting by using an eluant to obtain the 1, 3-dicarbonyl compound, wherein the eluant is a mixed solution of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is 100: 1.
The amounts of the substances and the reaction conditions used were experimentally expanded from this example to show that the solution of the invention has good functional group compatibility, and the respective expansion equations are as follows:
the above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (6)
1. A catalytic synthesis method of 1, 3-dicarbonyl compounds is characterized in that: the method comprises the following steps:
(1) placing aniline or aniline compounds, ethyl bromodifluoroacetate, sodium carbonate, cobalt (II) acetylacetonate and dry tetrahydrofuran into a pressure-resistant sealed reaction vessel, filling nitrogen, stirring and reacting in an oil bath at 100-150 ℃, and tracking by TLC and GC in the reaction process to determine specific reaction time, wherein the aniline compounds have one of the following structural formulas:
(2) cooling the material obtained in the step (1) to room temperature, adding ethyl acetate, fully mixing, filtering, washing with ethyl acetate, and finally combining organic phases;
(3) and (3) spin-drying the solvent in the organic phase obtained in the step (2), purifying the product by using a silica gel column, and eluting by using an eluent to obtain the 1, 3-dicarbonyl compound, wherein the specific structural formula is as follows:
2. the catalytic synthesis process of claim 1, wherein: the ratio of the aniline compound, bromodifluoroacetic acid ethyl ester, sodium carbonate, cobalt (II) acetylacetonate and dried tetrahydrofuran is 0.2mmol:0.4mmol:0.12mmol:0.5mmol:2 mL.
3. The catalytic synthesis process of claim 1, wherein: the reaction temperature in the step (1) is 120 ℃.
4. The catalytic synthesis process of claim 1, wherein: the reaction time is 10-25 h.
5. The catalytic synthesis process of claim 1, wherein: the eluent is a mixed solution of petroleum ether and ethyl acetate.
6. The catalytic synthesis process of claim 5, wherein: the eluent is composed of petroleum ether and ethyl acetate in a volume ratio of 50-100: 1.
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| CN201810560723.5A CN108912001B (en) | 2018-06-01 | 2018-06-01 | Catalytic synthesis method of 1, 3-dicarbonyl compound |
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| CN201810560723.5A CN108912001B (en) | 2018-06-01 | 2018-06-01 | Catalytic synthesis method of 1, 3-dicarbonyl compound |
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| CN108912001B true CN108912001B (en) | 2021-03-23 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880675A (en) * | 2014-04-10 | 2014-06-25 | 李娜 | Improved catalyzed synthesis method for 1,4-dicarbonyl compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880675A (en) * | 2014-04-10 | 2014-06-25 | 李娜 | Improved catalyzed synthesis method for 1,4-dicarbonyl compound |
Non-Patent Citations (2)
| Title |
|---|
| 3,3- 二氟-2- 羰基吲哚类化合物的制备及应用;宋秋玲等;《中国医药工业杂志》;20171231;第48卷(第6期);第787-794页 * |
| Synthesis and biological evaluation of new nucleosides derived from trifluoromethoxy-4-quinolones;Kristína Plevová等;《Tetrahedron Letters》;20150716;第56卷(第36期);第5112-5115页 * |
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