CN110467524B - Method for preparing 1, 2-dicarbonyl compound through photocatalytic oxidation reaction - Google Patents
Method for preparing 1, 2-dicarbonyl compound through photocatalytic oxidation reaction Download PDFInfo
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Abstract
The invention discloses a method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation reaction, which comprises the following steps: mixing an unsaturated triple bond compound, a coordination catalyst and a solvent to obtain a solution A; and (3) illuminating the solution A in an oxygen-containing environment to obtain the 1, 2-dicarbonyl compound. The reaction can be realized by light irradiation in an oxygen-containing environment, the whole process is simple and efficient, and the reaction conditions are very mild; the traditional iridium and ruthenium complex is not needed to be used as a coordination catalyst, the used catalyst is small in dosage, and the catalytic system is simple and efficient; the reaction can be amplified to gram level, and the potential application of the catalytic process in organic reaction and industrial production is reflected.
Description
Technical Field
The invention relates to the technical field of carbonyl compounds. More particularly, it relates to a method for preparing 1, 2-dicarbonyl compound by photocatalytic oxidation reaction.
Background
1, 2-dione structures are widely found in many natural products and biologically active molecules and therefore play an important role in the field of medicinal chemistry. Meanwhile, due to the two connected carbonyl groups, the derivative can be used as a precursor to obtain a series of nitrogen-containing and oxygen-containing heterocyclic products through a condensation reaction, and is well favored by the majority of synthetic chemists.
There are many methods known in the art for the synthesis of 1, 2-diketones, including: oxidizing olefin by using a strong oxidant such as selenium dioxide or potassium permanganate; oxidation of alpha-halo ketones, alpha-hydroxy ketones; 1, 3-diketone, alpha, beta-epoxypropane and alpha, beta-unsaturated aldehyde ketone; and coupling oxidation of phenyl precursors such as iodobenzene or phenylboronic acid with phenylpropionic acid.
Scientists have focused their attention on the use of alkyne oxidation to obtain 1, 2-dione compounds and have made a series of advances in recent years, in which salts and complexes of noble metals such as palladium, ruthenium and gold can be used as catalysts to react alkynes in DMSO, oxone and K 2 S 2 O 8 And diphenyl sulfoxide to produce 1, 2-ketone, ketoester, ketoamide and other dicarbonyl compounds. However, the noble metal catalysts used in these processes are expensive, the use of excessive amounts of strong oxidants is inconvenient for the work-up, and a large amount of waste is generated.
From the catalyst point of view, the use of noble metal catalysts is avoided, and the tendency of this reaction is to use inexpensive transition metal elements such as copper as catalysts. The group of gaohu xiang takes cuprous iodide as a catalyst and sodium persulfate as an oxidant, and realizes the conversion of diaryl acetylene to diaryl diketone at 140 ℃, but the atom economy of the reaction is greatly reduced by the high-temperature condition used in the reaction and the use of excessive strong oxidant.
From the perspective of the oxidant, the use of strong oxidants such as iodine simple substances, oxone and peroxide is avoided, and the trend of oxidation reaction is replaced by green oxidants. The pyronin group reported the coupling oxidation of amines with terminal alkynes with 2,2,6, 6-tetramethylpiperidinyloxy radical (TEMPO) and cupric bromide as catalysts and oxygen as oxidant simultaneously with the reactants under heating to give the final alpha-ketoamides. In the process, oxygen is used as an oxidant, is activated under the combined action of copper salt and free radicals, and then is added to a substrate molecule, so that the atom economy is good; the Huangguo column project group uses a copper alkynate formed by cuprous chloride and terminal alkyne in situ as a photosensitive unit (lambda max is 476nm), coupling with secondary amine is realized through the action of oxygen, meanwhile, a carbon-carbon triple bond is directly added with activated oxygen to obtain dicarbonyl, and the final product is alpha-ketoamide. And then, in the same subject group, alkynyl sulfonamide and N-alkynyl carbazole are used as substrates, and a substance (lambda max is 460nm) formed by coordination of cuprous chloride and the substrates is used as a photosensitive unit, so that activation of oxygen is realized, and oxygen is added to a carbon-carbon triple bond to obtain a dicarbonyl structure. Univalent copper is used in the two processes, and the univalent copper is not the most stable valence state of copper element, and is easy to deteriorate under the conditions of humidity, oxygen enrichment and the like, so that the experiment is influenced. In contrast, cupric copper is the most stable of copper elements, is convenient to store and preserve, and has a price lower than that of cuprous copper, so that the development of the action of cupric copper and a substrate to generate a photosensitive unit in situ becomes a difficult point in the conversion.
Aiming at the problems, the method overcomes the defects of excessive strong oxidant, noble metal, harsh conditions and the like in the oxidation reaction, realizes the high-efficiency and high-selectivity triple bond oxidation reaction by utilizing the photosensitive unit generated in situ, directly converts the raw materials into the product under the action of the cupric salt without the participation of the traditional photocatalyst, is a reaction with 100 percent atom economy, has wide substrate application range, relatively simpler reaction and greener reaction, and has practical prospect.
Therefore, in order to solve at least one of the problems of excessive strong oxidant, noble metal, harsh conditions and the like in the oxidation reaction, the invention provides a method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation reaction.
Disclosure of Invention
An object of the present invention is to provide a method for producing a 1, 2-dicarbonyl compound by photocatalytic oxidation. The method realizes the oxidation reaction of the carbonyl-induced unsaturated triple bond compound under the illumination condition and in the oxygen-containing environment. The catalytic system of the method is that a coordination catalyst and a substrate form a photosensitive intermediate, and the oxidation reaction of an unsaturated triple bond compound can be efficiently realized by visible light irradiation in an oxygen-containing environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing 1, 2-dicarbonyl compound by photocatalytic oxidation reaction comprises the following steps: mixing an unsaturated triple bond compound, a coordination catalyst and a solvent to obtain a solution A; and (3) illuminating the solution A in an oxygen-containing environment to obtain the 1, 2-dicarbonyl compound.
Preferably, the unsaturated triple bond compound has a structural formula shown as the following formula I:
wherein R is 1 Is phenyl, o-methylphenyl, m-methylphenyl, p-tert-butylphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-methoxyphenyl, p-trifluoromethylphenyl, p-cyanophenyl, p-phenylphenyl, naphthalen-2-yl or thien-2-yl;
R 2 is hydrogen radical and R 3 Is a hydrogen radical;
or R 2 Is hydrogen radical and R 3 Is a fluoro group;
or R 2 Is hydrogen radical and R 3 Is a chlorine group;
or R 2 Is chloro and R 3 Is a hydrogen radical;
or R 2 Is chloro and R 3 Is a fluorine group.
Preferably, the coordination catalyst is a metal salt, and further, the metal salt is an ionic metal salt.
Preferably, the ionic metal salt is an ionic monovalent copper salt or an ionic divalent copper salt.
Preferably, the ionic cuprous salt is cuprous chloride or cuprous bromide.
Preferably, the ionic cupric salt is
Cupric chloride or cupric bromide.
More preferably, the coordination catalyst is
Preferably, the solvent is an organic solvent.
Preferably, the organic solvent is an organic solvent having a coordinating ability; further, the organic solvent having a coordinating ability is an organic solvent having an oxygen coordinating ability or an organic solvent having a nitrogen coordinating ability.
Preferably, the organic solvent having oxygen coordination ability is dimethyl sulfoxide.
Preferably, the organic solvent having nitrogen coordinating ability is acetonitrile.
More preferably, the solvent is acetonitrile.
Preferably, the concentration of the unsaturated triple bond compound in the solution A is 0.1mol/L-1 mol/L.
Preferably, the concentration of the coordination catalyst in the solution A is 1.00X 10 -1 mol/L-3.00× 10 -1 mol/L。
Preferably, the illumination is visible light illumination.
Preferably, the light source for illumination is White light emitting diodes (i.e., White LEDs), White energy saving lamps, or sunlight, more preferably White light emitting diodes.
Preferably, the temperature of the illumination is 10-30 ℃; more preferably, the temperature of the illumination is 20-25 deg.C
Preferably, the illumination time is 4-10 h; more preferably, the illumination time is 6-8 h.
Unless otherwise specified, any range recited herein includes any value between the endpoints and any sub-range defined by any value between the endpoints or any value between the endpoints.
The invention has the following beneficial effects:
(1) the invention realizes the oxidation reaction of triple bond molecules under photocatalysis by using cupric salt as a coordination catalyst for the first time.
(2) The reaction of the invention can be realized by visible light or sunlight irradiation in an oxygen-containing environment, the whole process is simple and efficient, and the reaction conditions are very mild.
(3) The invention does not need the traditional iridium and ruthenium complex as the catalyst, the used catalyst is small in dosage, and the catalytic system is simple and efficient.
(4) The reaction of the invention can be amplified to gram level, which embodies the potential application of the catalytic process in organic reaction and industrial production.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a nuclear magnetic hydrogen spectrum of the product of example 1 of the present invention.
Figure 2 shows the carbon spectrum of the product of example 1 of the invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the present invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are available from published commercial sources unless otherwise specified, and the percentages are by mass unless otherwise specified.
The invention provides a method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation reaction, which comprises the following steps: mixing an unsaturated triple bond compound, a coordination catalyst and a solvent to obtain a solution A; and illuminating the solution A in an oxygen-containing environment to obtain the 1, 2-dicarbonyl compound.
The following describes each step in the synthesis method in detail:
in the above step, the unsaturated triple bond compound is oxidized and added with oxygen molecule to obtain 1, 2-dicarbonyl compound; the structural formula of the unsaturated triple bond compound is shown as the following formula I:
wherein R is 1 Is phenyl, o-methylphenyl, m-methylphenyl, p-tert-butylphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-methoxyphenyl, p-trifluoromethylphenyl, p-cyanophenyl, p-phenylphenyl, naphthalen-2-yl or thien-2-yl;
R 2 is hydrogen radical and R 3 Is a hydrogen radical;
or R 2 Is hydrogen radical and R 3 Is a fluoro group;
or R 2 Is hydrogen radical and R 3 Is a chlorine group;
or R 2 Is chloro and R 3 Is a hydrogen radical;
or R 2 Is chloro and R 3 Is a fluorine group.
The coordination catalyst is used for activating a dicarbonyl raw material substrate in the preparation process; the coordination catalyst can be a metal salt, and further the metal salt is an ionic metal salt; according to the invention, it was found that the reaction cannot be carried out using nonionic metal salts as coordination catalysts. Further, the ionic metal salt is an ionic cuprous salt or an ionic cupric salt, and is more preferably an ionic cupric salt, wherein the ionic cupric salt activates a substrate in the preparation process to form a Cu (I) oxonium salt, and the ionic cupric salt combined with a strong coordination solvent can absorb in a visible light region; while the ionic cuprous salt activates the substrate in each example to form a Cu (0) oxonium salt, but the stability is far less than the former; other divalent metal salts such as
Although palladium acetate can generate an intermediate like cupric salt, the palladium acetate cannot efficiently act with oxygen; wherein the ionic cuprous salt is cuprous chloride orCuprous bromide; the ionic cupric salt is
Copper chloride or bromide; more preferably
(i.e., copper triflate). In the present invention, copper trifluoromethanesulfonate is most preferably used as a coordination catalyst, and the copper salt has a relatively stable anion and is less likely to form a bromine radical cupric salt than other copper salts such as cupric bromide; in addition, copper trifluoromethanesulfonate can coordinate with the starting substrate better.
The solvent is used for dissolving the unsaturated triple bond compound and the coordination catalyst, and the unsaturated triple bond compound, the coordination catalyst and the solvent can generate an intermediate which can absorb light, especially visible light in situ; the solvent is an organic solvent, and further the organic solvent is an organic solvent with coordination capacity, so that the organic solvent with coordination capacity can efficiently dissolve the dicarbonyl compound as the raw material substrate, maintain the activity of the coordination catalyst and facilitate the post-treatment; further, the organic solvent having a coordinating ability is an organic solvent having an oxygen coordinating ability or an organic solvent having a nitrogen coordinating ability; the organic solvent with oxygen coordination capacity is dimethyl sulfoxide; the organic solvent with nitrogen coordination capacity is acetonitrile. A large number of experiments prove that the coordination capacity of the acetonitrile with nitrogen coordination capacity is stronger than that of the dimethyl sulfoxide with oxygen coordination capacity, the solubility of the unsaturated triple bond compound and the coordination catalyst in the acetonitrile is optimal, the boiling point of the acetonitrile is 82 ℃, the boiling point of the acetonitrile is far lower than that of the dimethyl sulfoxide and is 189 ℃, and the post-treatment is convenient.
In addition, the oxygen-containing environment provides oxygen required by the reaction, the invention is preferably carried out in an air environment, and the open system does not need to use an oxygen tank to provide pure oxygen and is convenient to operate.
The reaction can be initiated by illumination, and the reaction is not performed without illumination; the illumination is visible light illumination, wherein the visible light is less harmful to human bodies, and the equipment is simple and easy to operate; further, the light source for illumination is White light emitting diodes (i.e. White LEDs), White energy saving lamps or sunlight, and more preferably White light emitting diodes; white LEDs are more preferable in the invention, are environment-friendly, do not contain mercury, have adjustable voltage and longer service life, do not generate ultraviolet rays and infrared rays, and have more concentrated light paths compared with common light sources.
One possible implementation manner is that the concentration of the unsaturated triple bond compound in the solution A is 0.1mol/L to 1 mol/L; the concentration of the coordination catalyst is 1.00X 10 -1 mol/L-3.00×10 -1 mol/L; the illumination temperature is 10-30 ℃; the illumination time is 4-10 h.
Further, after the illumination, the method further comprises: spin-drying and separating by column chromatography. The method of spin-drying and column separation is not particularly limited, and may be carried out by a conventional technique.
The invention overcomes the defects of excessive strong oxidant, noble metal, harsh conditions and the like in the oxidation reaction, and realizes the oxidation reaction of the carbonyl induced unsaturated triple bond compound under the illumination condition and in the oxygen-containing environment at room temperature. The catalytic system of the method is that a coordination catalyst and a substrate form a photosensitive intermediate, the oxidation reaction of an unsaturated triple bond compound can be efficiently and selectively realized by irradiating with visible light in a solvent with strong coordination capacity under an oxygen-containing environment, and the generated diketone compound has wide application in the fields of sensitization and fluorescent probes. In addition, the reaction does not involve traditional photocatalysts, raw materials are directly converted into products, the reaction is 100% atom economy, the reaction is relatively simpler and more green, and the method has a practical prospect.
Example 1
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To complex the catalyst, 7.2mg of the complex catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2-phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is phenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compounds that are hydrogen radicals),wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. The mixture is pre-stirred for ten minutes, then is illuminated by White LEDs for 8 hours in an air environment at the temperature of 25 ℃, and after the reaction is finished, the mixture is spin-dried and separated by a column. The products are identified to be 1- (2' -benzoylphenyl) -2-phenyl-1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum, and the results are shown in figure 1. The conversion of the starting material was 100% and the yield of the diketone product was 77%.
Examples 2 to 5 and comparative examples 1 to 3
A method for preparing 1, 2-dicarbonyl compound by photocatalytic oxidation reaction, which comprises the same steps as example 1, but differs from the coordination catalyst, the specific results are shown in Table 1:
TABLE 1 product yields obtained for different kinds of coordination catalysts
| Number of | Coordination catalyst | Yield of product |
| Example 2 | Cuprous chloride | 13％ |
| Example 3 | Cuprous bromide | 19％ |
| Example 4 | Copper chloride | 25％ |
| Example 5 | Copper bromide | 33％ |
| Comparative example 1 | |
0％ |
| Comparative example 2 | |
0％ |
| Comparative example 3 | |
6％ |
And (4) conclusion: the zinc salt and the palladium salt can activate the 1- (2' -benzoylphenyl) -2-phenylacetylene substrate, but can not effectively react with oxygen; the molecular copper salt copper acetylacetonate can not activate the substrate; the ionic copper salt can activate the substrate and can effectively act with oxygen; the stability of an intermediate formed by the ionic cuprous salt and a substrate is poor; the stability of an intermediate formed by the ionic cupric salt and the substrate is better; chloride ion and bromide ion can generate free radicals in the reaction to influence the reaction selectivity; copper trifluoromethanesulfonate anion is more stable, is not easy to form free radical to generate side reaction, is easy to be dissociated in organic solution and is easy to be coordinated with a substrate.
Example 6 and comparative example 4
A method for preparing 1, 2-dicarbonyl compound by photocatalytic oxidation reaction, which comprises the same steps as example 1 except that the solvent used is different, the specific results are shown in Table 2:
TABLE 2 product yields obtained with different kinds of solvents
| Numbering | Solvent(s) | Yield of product |
| Comparative example 4 | |
0％ |
| Example 6 | Dimethyl sulfoxide | 26％ |
And (4) conclusion: the reaction cannot be carried out in an ethyl acetate solvent without coordination capacity; dimethyl sulfoxide with oxygen coordination capacity allows the reaction to proceed, but the reaction yield is lower than that of the reaction performed in acetonitrile, a solvent with strong nitrogen coordination capacity.
Examples 7 to 9
A method for preparing 1, 2-dicarbonyl compound by photocatalytic oxidation reaction, which comprises the same steps as example 1 except that the amount of unsaturated triple bond compound is different, the specific results are shown in Table 3:
TABLE 3 product yields obtained with different amounts of unsaturated triple bond compound
And (4) conclusion: after the concentration of the unsaturated triple bond compound is increased, the illumination scattering is increased, the effective collision among molecules is reduced, and the yield is reduced to a certain degree.
Examples 10 to 12
A method for preparing 1, 2-dicarbonyl compound by photocatalytic oxidation reaction, which comprises the same steps as example 1 except that the amount of coordination catalyst used is different, the specific results are shown in Table 4:
TABLE 4 product yields obtained with different amounts of coordination catalyst
| Numbering | Concentration of coordination catalyst (mol/L) | Yield of product |
| Example 10 | 0.1 | 68％ |
| Example 1 | 0.2 | 77％ |
| Example 11 | 0.3 | 70％ |
| Example 12 | 0.6 | 57％ |
And (4) conclusion: the concentration of the coordination catalyst is increased, the light scattering is increased, the effective collision among molecules is reduced, and the yield is reduced.
Examples 13 to 14
A method for preparing 1, 2-dicarbonyl compound by photocatalytic oxidation reaction, which comprises the same steps as example 1 except that a light source is used, and the specific results are shown in Table 5:
TABLE 5 product yields obtained with different light sources
And (4) conclusion: sunlight, a white energy-saving lamp and a white light-emitting diode are used as light sources and can react, but the white energy-saving lamp has weaker light intensity and dispersed light paths compared with the white light-emitting diode, sunlight irradiation is unstable and contains ultraviolet and infrared bands, so the sunlight, the white energy-saving lamp and the white light-emitting diode are not as good as the white light-emitting diode in effect.
Examples 15 to 18
A photocatalytic oxidation process for preparing 1, 2-dicarbonyl compounds is carried out in the same manner as in example 1 except that the temperature of the light is varied, and the specific results are shown in Table 6:
TABLE 6 product yields obtained at different illumination temperatures
| Numbering | Light irradiation temperature (. degree. C.) | Product yield |
| Example 15 | 10～15 | 66％ |
| Example 16 | 16～20 | 72％ |
| Example 17 | 21～25 | 77％ |
| Example 18 | 26～30 | 77％ |
And (4) conclusion: the reaction can be carried out at room temperature with high efficiency, the molecular motion becomes slow at low temperature, effective collision is reduced, the reaction effect is poor, additional heating is required at high temperature, and no practical significance is realized in the reaction.
Examples 19 to 27
A method for preparing 1, 2-dicarbonyl compound by photocatalytic oxidation reaction, which is the same as example 1 except that the light irradiation time is different, is provided, and the specific results are shown in Table 7:
TABLE 7 product yields obtained at different illumination times
| Numbering | Illumination time (h) | Product yield |
| Example 19 | 1 | 14％ |
| Example 20 | 2 | 41％ |
| Example 21 | 3 | 45％ |
| Example 22 | 4 | 54％ |
| Example 23 | 5 | 66 |
| Example 24 | 6 | 68 |
| Example 25 | 7 | 76 |
| Example 1 | 8 | 77 |
| Example 26 | 9 | 75 |
| Example 27 | 10 | 70 |
And (4) conclusion: in the initial stage of the reaction, a coordination catalyst, a substrate and a solvent are required to generate induced coordination, the number of the substrates actually generated in the reaction is small, and the yield is low; the time is prolonged, and the reaction yield is gradually increased; the duration is preferably eight hours, and the yield of the target product is reduced as the reaction time is continuously prolonged.
Example 28
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To complex the catalyst, 7.2mg of the complex catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (4 "-fluorophenyl) -phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-fluorophenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product to be 1- (2 '-benzoylphenyl) -2- (4' -fluorophenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of diketone product was 65%.
Example 29
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (4 "-chlorophenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-chlorophenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product to be 1- (2 '-benzoylphenyl) -2- (4' -chlorphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the raw material was 100%,the yield of diketone product was 64%.
Example 30
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To complex the catalyst, 7.2mg of the complex catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (4 "-bromophenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-bromophenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. The products are identified to be 1- (2 '-benzoylphenyl) -2- (4' -bromophenyl) -1, 2-dione by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 75%.
Example 31
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (4 "-methylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-methylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product to be 1- (2 '-benzoylphenyl) -2- (4' -methylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of diketone product was 84%.
Example 32
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (2 "-methylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is o-methylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. The mixture is pre-stirred for ten minutes, then is illuminated by White LEDs for 8 hours in an air environment at the temperature of 25 ℃, and after the reaction is finished, the mixture is spin-dried and separated by a column. And identifying the product to be 1- (2 '-benzoylphenyl) -2- (2' -methylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 52%.
Example 33
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with a salt of cupric
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (3 "-methylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is m-methylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. The mixture is pre-stirred for ten minutes, then is illuminated by White LEDs for 8 hours in an air environment at the temperature of 25 ℃, and after the reaction is finished, the mixture is spin-dried and separated by a column. The products are identified to be 1- (2 '-benzoylphenyl) -2- (3' -methylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of diketone product was 76%.
Example 34
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2 '-benzoylphenyl) -2- (4' -tert-butylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-tert-butylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. The mixture is pre-stirred for ten minutes, then is illuminated by White LEDs for 8 hours in an air environment at the temperature of 25 ℃, and after the reaction is finished, the mixture is spin-dried and separated by a column. And identifying the product to be 1- (2 '-benzoylphenyl) -2- (4' -tert-butylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of diketone product was 76%.
Example 35
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with a salt of cupric
To coordinate the catalyst, 7.2mg of this coordination catalyst and 0.4mmol of 1- (2 '-benzoylphenyl) -2- (4' -trifluoromethylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-trifluoromethylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound group which is a hydrogen group), wherein the concentration of the complex catalyst is 2.0X 10 - 1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product to be 1- (2 '-benzoylphenyl) -2- (4' -trifluoromethylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 40% and the yield of the diketone product was 25%.
Example 36
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (4 "-phenylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-phenylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product to be 1- (2 '-benzoylphenyl) -2- (4' -phenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 85%.
Example 37
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (2 "-naphthyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is naphthalen-2-yl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product as 1- (2 '-benzoylphenyl) -2- (2' -naphthyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 51%.
Example 38
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To 4mL of acetonitrile was added 7.2mg of the coordination catalyst and 0.4mmol of 1- (2' -benzoylphenyl) -2- (2 "-thienyl) phenylacetylene (i.e. R 1 Is thiophen-2-yl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product to be 1- (2 '-benzoylphenyl) -2- (2' -thienyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 46%.
Example 39
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To complex the catalyst, 7.2mg of the complex catalyst and 0.4mmol of 1- (2 '-p-fluorobenzoylphenyl) -2- (4' -methylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-methylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is fluorine-based), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product as 1- (2 '-p-fluorobenzoylphenyl) -2- (4' -methylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 51%.
Example 40
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2 '-p-chlorobenzoylphenyl) -2- (4' -methylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-methylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated by chlorine radicalsTriple bond compound) in which the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. The products are identified to be 1- (2 '-p-chlorobenzoylphenyl) -2- (4' -methylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 64%.
EXAMPLE 41
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of the coordination catalyst and 0.4mmol of 1- (2 '-benzoyl-4-chlorophenyl) -2- (4' -methylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-methylphenyl, R 2 Is hydrogen radical, R 3 Unsaturated triple bond compound which is hydrogen radical), wherein the concentration of the coordination catalyst is 2.0X 10 -1 mol/L. Pre-stirring for ten minutes, then illuminating with White LEDs at 25 ℃ for 8 hours in an air environment, spin-drying after the reaction is finished, and separating through a column. And identifying the product to be 1- (2 '-benzoyl-4-chlorphenyl) -2- (4' -methylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 68%.
Example 42
A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation, comprising the steps of:
with salts of divalent copper
To coordinate the catalyst, 7.2mg of this coordination catalyst and 0.4mmol of 1- (2 '-p-fluorobenzoyl-4-chlorophenyl) -2- (4' -methylphenyl) phenylacetylene (i.e., R) were added to 4mL of acetonitrile 1 Is p-methylphenyl, R 2 Is chloro, R 3 Unsaturated triple bond compound which is fluorine-based), wherein the concentration of the coordination catalyst is 2.0X 10 - 1 mol/L. Pre-stirringStirring for ten minutes, then illuminating with White LEDs for 8 hours in an air environment at 25 ℃, and after the reaction is finished, spin-drying and separating through a column. And identifying the product as 1- (2 '-p-fluorobenzoyl-4-chlorophenyl) -2- (4' -methylphenyl) -1, 2-diketone by nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum. The conversion of the starting material was 100% and the yield of the diketone product was 60%.
A large number of experiments prove that in the reaction, the yield of the product obtained by the reaction of the unsaturated triple-bond compound containing the electron-withdrawing group is better than that of the unsaturated triple-bond compound containing the electron-withdrawing group, and the yield of the product obtained by the reaction of the unsaturated triple-bond compound with small steric hindrance is better than that of the unsaturated triple-bond compound with large steric hindrance, namely when the unsaturated triple-bond compound is the unsaturated triple-bond compound with the structural formula of R in the formula I 1 Is p-phenylphenyl, R 2 Is hydrogen radical, R 3 When the unsaturated triple bond compound is hydrogen-based, the yield of the obtained product is optimal.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (5)
1. A method for preparing a 1, 2-dicarbonyl compound by photocatalytic oxidation reaction is characterized by comprising the following steps: mixing an unsaturated triple bond compound, a coordination catalyst and a solvent to obtain a solution A; in an oxygen-containing environment, illuminating the solution A to obtain a 1, 2-dicarbonyl compound; the structural formula of the unsaturated triple bond compound is shown as the following formula I:
wherein R is 1 Is phenyl, o-methylphenyl, m-methylphenyl, pMethylphenyl, p-tert-butylphenyl, p-fluorophenyl, p-chlorophenyl, p-bromophenyl, p-methoxyphenyl, p-trifluoromethylphenyl, p-cyanophenyl, p-phenylphenyl, naphthalen-2-yl or thien-2-yl;
R 2 is hydrogen radical and R 3 Is a hydrogen radical;
or R 2 Is hydrogen radical and R 3 Is a fluoro group;
or R 2 Is hydrogen radical and R 3 Is a chlorine group;
or R 2 Is chloro and R 3 Is a hydrogen radical;
or R 2 Is chloro and R 3 Is a fluoro group;
the coordination catalyst is an ionic metal salt; the ionic metal salt is ionic cuprous salt or ionic cupric salt;
the solvent is an organic solvent; the organic solvent is an organic solvent with oxygen coordination capacity or an organic solvent with nitrogen coordination capacity.
2. The photocatalytic oxidation reaction production method for 1, 2-dicarbonyl compound according to claim 1, characterized in that the concentration of the unsaturated triple bond compound in the solution a is 0.1mol/L to 1 mol/L.
3. The photocatalytic oxidation reaction process for producing 1, 2-dicarbonyl compound according to claim 1, wherein the concentration of the coordination catalyst in the solution a is 1.00 x 10 -1 mol/L-3.00×10 -1 mol/L。
4. The photocatalytic oxidation process for producing a 1, 2-dicarbonyl compound according to claim 1, wherein the light irradiation is visible light irradiation.
5. The photocatalytic oxidation reaction production method for a 1, 2-dicarbonyl compound according to claim 1, wherein the temperature of the light irradiation is 10 to 30 ℃; the illumination time is 4-10 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467282A (en) * | 2013-08-29 | 2013-12-25 | 南京大学 | Synthesis method of polysubstitution naphthol and derivative of polysubstitution naphthol |
| CN103664430A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院理化技术研究所 | Method for preparing coupling product through visible light catalysis cross dehydrogenation coupling |
| CN104892377A (en) * | 2015-05-08 | 2015-09-09 | 上海交通大学 | Synthesis method of 1, 2-dione derivatives |
| CN106518634A (en) * | 2016-10-21 | 2017-03-22 | 大连理工大学 | Preparing method of photocatalytic alpha-diketone compound |
-
2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664430A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院理化技术研究所 | Method for preparing coupling product through visible light catalysis cross dehydrogenation coupling |
| CN103467282A (en) * | 2013-08-29 | 2013-12-25 | 南京大学 | Synthesis method of polysubstitution naphthol and derivative of polysubstitution naphthol |
| CN104892377A (en) * | 2015-05-08 | 2015-09-09 | 上海交通大学 | Synthesis method of 1, 2-dione derivatives |
| CN106518634A (en) * | 2016-10-21 | 2017-03-22 | 大连理工大学 | Preparing method of photocatalytic alpha-diketone compound |
Non-Patent Citations (2)
| Title |
|---|
| Combining visible light catalysis and transfer hydrogenation for in situ efficient and selective semihydrogenation of alkynes under ambient conditions;Jian-Ji Zhong等;《Org.Lett.2020》;20151112;第22卷;全文 * |
| Iodine/Water-Mediated Oxidation of o-Alkynylaroyl Compounds and Application of the Products of Oxidation in the Synthesis of Nitrogen Heterocycles;Sakthivel, Karuppusamy等;《European Journal of Organic Chemistry (2013)》;20131231;第16卷;实验部分第2段及表1 * |
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