CN111848570B - Hexaacyl reductive cercospora bacteriocin photocatalyst and preparation and application thereof - Google Patents

Hexaacyl reductive cercospora bacteriocin photocatalyst and preparation and application thereof Download PDF

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CN111848570B
CN111848570B CN202010741358.5A CN202010741358A CN111848570B CN 111848570 B CN111848570 B CN 111848570B CN 202010741358 A CN202010741358 A CN 202010741358A CN 111848570 B CN111848570 B CN 111848570B
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饶义剑
袁振波
张艳
刘昌梅
李敏
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Abstract

The invention discloses a hexaacyl reducing cercosporin photocatalyst and preparation and application thereof, belonging to the technical field of catalyst preparation methods and organic synthesis. The catalyst is prepared by adding acid anhydride into a mixture of cercospora sporins, a reducing agent and alkali, stirring at room temperature for 1-3 hours, adding the acid anhydride, continuing to react for 1-3 hours, and performing suction filtration, extraction, concentration and column chromatography purification. The catalyst can catalyze photochemical reactions such as reduction, coupling and the like of halogenated hydrocarbon, and has stronger reaction activity and industrial prospect.

Description

Hexaacyl reductive cercospora bacteriocin photocatalyst and preparation and application thereof
Technical Field
The invention relates to a hexaacyl reducing cercosporin photocatalyst and preparation and application thereof, belonging to the technical field of catalyst preparation methods and organic synthesis.
Background
Cercosporin is a naturally occurring perylenequinone compound. Cercosporin absorbs light energy and produces reactive oxygen species: singlet oxygen (1O2) And superoxide radical (O)2 .-). Therefore, the compound can be used as a novel phototherapy medicine, has wide application prospect in the aspect of photodynamic therapy, and can be used as a photocatalyst in photocatalytic reaction.
However, since the absorption capacity and the redox capacity of cercosporin are intermediate, in order to improve the catalytic activity of the compound, the structure of cercosporin needs to be modified, so that the absorption capacity and the redox capacity of cercosporin are improved, and organic reactions can be better catalyzed. However, no modification of cercosporin has been reported.
Disclosure of Invention
[ problem ] to
Cercosporin can be used as a novel phototherapy medicament, has wide application prospect in the aspect of photodynamic therapy, can be used as a photocatalyst in photocatalytic reaction, but has intermediate light absorption capacity and redox capacity and needs to be improved.
[ solution ]
In order to solve the problem that the photoactivity of cercosporin is not high, the invention provides a hexaacyl reductive cercosporin photocatalyst, cercosporin is used as a raw material, and the hexaacyl reductive cercosporin is directly generated through reduction acylation reaction.
The invention provides a compound, wherein the structural formula of the compound is shown as a formula I:
Figure BDA0002606835970000011
wherein R is selected from methyl, ethyl, propyl, isopropyl, 2-methoxymethyl, trifluoromethyl, trichloromethyl or phenyl.
The invention provides a method for synthesizing the compound, and the synthetic route of the compound is as follows:
Figure BDA0002606835970000021
wherein R is selected from methyl, ethyl, propyl, isopropyl, 2-methoxymethyl, trifluoromethyl, trichloromethyl or phenyl.
In one embodiment of the present invention, the synthesis method specifically comprises the following steps:
(1) adding cercosporal, a reducing agent and alkali into a reaction container, adding acid anhydride into the reaction container, and reacting for 1-3 hours;
(2) adding anhydride into the reaction system, and continuing to react for 1-3 hours;
(3) and (3) adding an extracting agent into the reaction liquid obtained in the step (2) for extraction, then filtering, concentrating the filtrate, and separating to obtain the hexaacyl cercosporin.
In one embodiment of the present invention, the chemical structural formula of cercosporin in step (1) is as follows:
Figure BDA0002606835970000022
in one embodiment of the present invention, the reducing agent in step (1) is any one of magnesium powder, iron powder, zinc powder, and sodium hydrosulfite.
In one embodiment of the present invention, the base in step (1) is any one of N, N-dimethyl-4-aminopyridine, N-diisopropylethylamine, triethylamine, triethylenediamine, sodium carbonate, potassium carbonate, and cesium carbonate.
In one embodiment of the present invention, the molar ratio of cercosporin to reducing agent in step (1) is 1: (4-100).
In one embodiment of the present invention, the molar ratio of cercosporin to base in step (1) is 1: (1-20).
In one embodiment of the present invention, the acid anhydride in step (1) is any one of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, 2-methoxyacetic anhydride, trifluoroacetic anhydride, trichloroacetic anhydride and benzoic anhydride.
In one embodiment of the invention, the molar ratio of cercosporin to anhydride is 1: (10-1000).
In one embodiment of the present invention, the reaction atmosphere comprises any one of oxygen, air and nitrogen.
In one embodiment of the invention, the reaction atmosphere is nitrogen.
In one embodiment of the present invention, the extractant in step (3) is any one of dichloromethane or ethyl acetate.
In one embodiment of the present invention, the specific operations of the filtering in the step (3) are: and filtering the extracted reaction solution, washing the obtained filtrate with distilled water for 2-5 times, collecting an organic phase, drying, and performing suction filtration to obtain a filtrate.
In one embodiment of the present invention, the separation in step (3) is performed by silica gel column chromatography using methanol/dichloromethane (v: v ═ 1:100) as eluent.
The invention provides application of the compound in photocatalytic halohydrocarbon reduction reaction.
The invention provides application of the compound in coupling reaction of photocatalytic halohydrocarbon with water, alcohol, amine and acid.
In one embodiment of the present invention, the alcohol in the coupling reaction includes, but is not limited to, methanol, ethanol, trifluoroethanol, benzyl alcohol, 2-furancarbinol, 2-pyridinecarbinol, and the like.
In one embodiment of the present invention, the amine in the coupling reaction includes, but is not limited to, ethylamine, benzylamine, diethylamine, dibenzylamine, benzamide, p-toluenesulfonamide, and the like.
In one embodiment of the present invention, the acid in the coupling reaction includes, but is not limited to, formic acid, acetic acid, propionic acid, benzoic acid, and the like.
The invention provides application of the compound in phototherapy drugs.
[ advantageous effects ]
1. The hexaacyl reductive cercosporin is directly generated by reduction acylation reaction by using cercosporin as a raw material, and the compound has high photoactivity and can efficiently catalyze the reduction reaction of various photocatalytic halogenated hydrocarbons and the coupling reaction of the halogenated hydrocarbons with water, alcohol, amine and acid.
2. The method for preparing hexaacyl reductive cercosporin has the advantages of simplicity, easily available raw materials, low cost, simple reaction and very good process application prospect, and cercosporin which can be produced in large scale is used as the raw material.
3. The reaction system in the invention has high reaction efficiency, and the yield can reach more than 96 percent at most.
Drawings
FIG. 1 shows a method for synthesizing hexaacyl reducing cercosporin.
FIG. 2 is a hydrogen spectrum of cercosporin synthesized in example 1, which is hexaacetyl reducible.
FIG. 3 is a carbon spectrum of cercosporin synthesized in example 1, which is hexaacetyl reducible.
FIG. 4 is a hydrogen spectrum of cercosporin synthesized in example 2, which is reduced by hexaisobutyryl group.
FIG. 5 is a carbon spectrum of cercosporin synthesized in example 2, which is reduced by hexaisobutyryl group.
Detailed Description
[ example 1 ] preparation of hexaacetyl cercosporin with reducing Properties
Figure BDA0002606835970000041
The reaction formula of this example is shown above, and the specific reaction method is: cercosporin (20mg), acetic anhydride (400. mu.L), magnesium powder (30mg), N-dimethyl-4-aminopyridine (50mg) and a stirrer were added to a reaction vessel and reacted for 2 hours under nitrogen protection. After the reaction was completed, acetic anhydride (400. mu.L) was added again, and the reaction was continued for 2 hours. After completion of the reaction, 20mL of methylene chloride was added to the reaction solution, followed by filtration, and the obtained filtrate was washed three times with 10mL of distilled water. And finally, adding anhydrous magnesium sulfate into the organic phase, drying, performing suction filtration to obtain filtrate, and concentrating by using a rotary evaporator. The product is quickly separated by 200-300 mesh silica gel column chromatography, the eluent is methanol/dichloromethane (v: v ═ 1:100), and the yield of the hexaacetyl reducing cercosporin is 97 percent according to the product mass.
1H NMR(400MHz,CDCl3)δ7.02(s,2H),5.55(s,2H),4.79(s,2H),4.00(s,6H),3.41(dd,J＝13.0,4.1Hz,2H),3.04(dd,J＝13.0,8.6Hz,2H),2.43(d,J＝4.5Hz,12H),1.75(s,6H),0.48(d,J＝6.4Hz,6H)ppm.13C NMR(101MHz,CDCl3)δ170.2,169.0,168.3,154.5,149.6,144.2,130.7,129.6,117.7,116.4,113.5,93.7,70.4,61.8,35.0,21.2,21.0,20.8,18.2ppm。
FIG. 2 is a hydrogen spectrum and FIG. 3 is a carbon spectrum of cercosporin synthesized in this example. The correctness of the structure of the product can be confirmed by FIGS. 2 and 3.
[ example 2 ] preparation of cercosporin
Figure BDA0002606835970000042
The reaction formula of this example is shown above, and the specific reaction method is: cercosporin (20mg), isobutyric anhydride (500. mu.L), magnesium powder (30mg), N-dimethyl-4-aminopyridine (50mg), and a stir bar were added to a reaction vessel and reacted for 2 hours under a nitrogen blanket. After the reaction was completed, isobutyric anhydride (500. mu.L) was added again, and the reaction was continued for 2 hours. After completion of the reaction, 20mL of methylene chloride was added to the reaction solution, followed by filtration, and the obtained filtrate was washed three times with 10mL of distilled water. And finally, adding anhydrous magnesium sulfate into the organic phase, drying, performing suction filtration to obtain filtrate, and concentrating by using a rotary evaporator. The product is quickly separated by 200-300 mesh silica gel column chromatography, the eluent is methanol/dichloromethane (v: v ═ 1:100), and the yield of the hexaisobutyryl cercosporin is 76 percent according to the mass of the product.
1H NMR(400MHz,CDCl3)δ6.96(s,2H),5.53(s,2H),4.89(s,2H),3.98(s,6H),3.46(dd,J＝12.9,4.5Hz,2H),2.88(dtt,J＝9.5,6.4,3.0Hz,6H),2.34(p,J＝7.0Hz,2H),1.46–1.37(m,24H),1.03(dd,J＝8.5,7.0Hz,12H),0.42(d,J＝6.3Hz,6H)ppm.13C NMR(101MHz,CDCl3)δ176.5,175.6,174.8,154.5,149.5,144.8,137.1,131.2,130.9,129.5,118.1,116.0,113.4,93.7,70.0,61.9,35.7,34.1,33.9,33.9,19.2,19.1,19.0,18.8,18.8,18.3ppm。
FIG. 4 is a hydrogen spectrum and FIG. 5 is a carbon spectrum of the reductively produced cercosporin of this example. The correctness of the structure of the product can be confirmed from fig. 4 and 5.
[ example 3 ] preparation of cercosporin under Hexan-butyryl group
Figure BDA0002606835970000051
The reaction formula of this example is shown above, and the specific reaction method is: cercosporin (20mg), butyric anhydride (500. mu.L), magnesium powder (30mg), N-dimethyl-4-aminopyridine (50mg) and a stirrer were added to a reaction vessel and reacted for 2 hours under a nitrogen atmosphere. After the reaction was completed, butyric anhydride (500. mu.L) was added again to continue the reaction for 2 hours. After completion of the reaction, 20mL of methylene chloride was added to the reaction solution, followed by filtration, and the obtained filtrate was washed three times with 10mL of distilled water. And finally, adding anhydrous magnesium sulfate into the organic phase, drying, performing suction filtration to obtain filtrate, and concentrating by using a rotary evaporator. The product is quickly separated by 200-300-mesh silica gel column chromatography, the eluent is methanol/dichloromethane (v: v ═ 1:100), and the yield of the cercosporin n-butyryl is 85 percent according to the mass of the product.
1H NMR(400MHz,CDCl3)δ7.00(s,2H),5.54(s,2H),4.82(s,2H),3.99(s,6H),3.45(dd,J＝12.9,4.3Hz,2H),2.92(dd,J＝12.9,9.2Hz,2H),2.74–2.55(m,8H),2.07(td,J＝7.5,4.3Hz,4H),1.96–1.78(m,8H),1.52(q,J＝7.4Hz,4H),1.10(td,J＝7.4,4.7Hz,12H),0.85(t,J＝7.4Hz,6H)ppm.13C NMR(101MHz,CDCl3)δ172.9,171.9,171.1,154.5,149.5,144.4,136.6,130.9,130.8,129.4,117.9,116.2,113.4,93.7,70.1,61.8,36.3,36.1,35.8,35.5,18.4,18.4,18.3,13.7,13.7,13.5ppm.
[ example 4 ] preparation of hexa-2-methoxyacetyl cercosporin
Figure BDA0002606835970000061
The reaction formula of this example is shown above, and the specific reaction method is: cercosporin (20mg), 2-methoxyacetic anhydride (500. mu.L), magnesium powder (30mg), N-dimethyl-4-aminopyridine (50mg) and a stirrer were added to a reaction vessel and reacted for 2 hours under nitrogen protection. After the reaction was completed, 2-methoxyacetic anhydride (500. mu.L) was added again, and the reaction was continued for 2 hours. After completion of the reaction, 20mL of methylene chloride was added to the reaction solution, followed by filtration, and the obtained filtrate was washed three times with 10mL of distilled water. And finally, adding anhydrous magnesium sulfate into the organic phase, drying, performing suction filtration to obtain filtrate, and concentrating by using a rotary evaporator. The product is quickly separated by 200-300 mesh silica gel column chromatography, the eluent is methanol/dichloromethane (v: v ═ 1:100), and the yield of the hexa-2-methoxyacetyl cercosporin is 83 percent according to the mass of the product.
1H NMR(400MHz,CDCl3)δ7.09(s,2H),5.56(s,2H),4.97–4.81(m,2H),4.44(s,8H),4.01(s,6H),3.79(d,J＝3.1Hz,4H),3.60(d,J＝3.0Hz,12H),3.47(s,2H),3.33(s,6H),2.98(t,J＝10.9Hz,2H),0.51(d,J＝6.3Hz,6H)ppm.
[ example 5 ]
Figure BDA0002606835970000062
The photocatalyst (0.002mmol) prepared in example 1, methyl 4-bromobenzoate (43mg,0.2mmol), N, N-diisopropylethylamine (0.8mmol) and acetonitrile (1mL) were added to a reaction tube and reacted under a nitrogen atmosphere under 23W CFL for 24 hours. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:20), and the yield of the methyl benzoate is 90% according to the product quality.
[ example 6 ]
Figure BDA0002606835970000063
The photocatalyst (0.002mmol) prepared in example 2, methyl 4-bromobenzoate (43mg,0.2mmol), N, N-diisopropylethylamine (0.8mmol) and acetonitrile (1mL) were added to a reaction tube and reacted under a nitrogen atmosphere under 23W CFL for 24 hours. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:20), and the yield of the methyl benzoate is 82% according to the product quality.
[ example 7 ]
Figure BDA0002606835970000071
The photocatalyst (0.002mmol) prepared in example 3, methyl 4-bromobenzoate (43mg,0.2mmol), N, N-diisopropylethylamine (0.8mmol) and acetonitrile (1mL) were added to a reaction tube and reacted under a nitrogen blanket under 23W CFL for 24 hours. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:20), and the yield of the methyl benzoate is 89% according to the product quality.
[ example 8 ]
Figure BDA0002606835970000072
The photocatalyst (0.002mmol) prepared in example 4, methyl 4-bromobenzoate (43mg,0.2mmol), N, N-diisopropylethylamine (0.8mmol) and acetonitrile (1mL) were added to a reaction tube and reacted under a nitrogen blanket under 23W CFL for 24 hours. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:20), and the yield of the methyl benzoate is 86% according to the product quality.
[ example 9 ]
Figure BDA0002606835970000073
The photocatalyst (0.002mmol) prepared in example 1, nickel sulfate hexahydrate (0.02mmol), 4,4 '-dimethoxy-2, 2' -bipyridine (0.02mmol), 4-bromobenzonitrile (36.4mg,0.2mmol), N, N-diisopropylethylamine (0.3mmol), water (8mmol), DMF and acetonitrile (1:1,1mL) were added to a reaction tube, and reacted under 23W CFL irradiation for 24 hours under nitrogen protection. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), and the yield of the 4-hydroxybenzonitrile is 94% according to the product quality.
[ example 10 ]
Figure BDA0002606835970000081
The photocatalyst (0.002mmol) prepared in example 1, nickel sulfate hexahydrate (0.02mmol), 4,4 '-dimethoxy-2, 2' -bipyridine (0.02mmol), 4-bromobenzonitrile (36.4mg,0.2mmol), N, N-diisopropylethylamine (0.3mmol), N-butanol (8mmol), DMF and acetonitrile (1:1,1mL) were added to a reaction tube, and reacted under 23W CFL irradiation for 24 hours under nitrogen protection. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), and the yield of the 4-n-butoxy benzonitrile is 92% according to the product quality.
[ example 11 ]
Figure BDA0002606835970000082
The photocatalyst (0.002mmol) prepared in example 1, nickel sulfate hexahydrate (0.02mmol), 4,4 '-dimethoxy-2, 2' -bipyridine (0.02mmol), 4-bromobenzonitrile (36.4mg,0.2mmol), N, N-diisopropylethylamine (0.3mmol), p-toluenesulfonamide (8mmol), DMF and acetonitrile (1:1,1mL) were added to a reaction tube, and reacted under 23W CFL irradiation for 24 hours under nitrogen protection. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), and the yield of the N- (4-cyanophenyl) -4-methylbenzenesulfonamide is 98% according to the product quality.
[ example 12 ]
Figure BDA0002606835970000083
The photocatalyst (0.002mmol) prepared in example 1, nickel sulfate hexahydrate (0.02mmol), 4,4 '-dimethoxy-2, 2' -bipyridine (0.02mmol), 4-bromobenzonitrile (36.4mg,0.2mmol), N, N-diisopropylethylamine (0.3mmol), benzoic acid (8mmol), DMF and acetonitrile (1:1,1mL) were added to a reaction tube, and reacted under 23W CFL irradiation for 24 hours under nitrogen protection. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), and the yield of the benzoyl-4-cyanobenzene ester is 98% according to the product mass.
Comparative example 1
Figure BDA0002606835970000091
Cercosporin (0.002mmol), methyl 4-bromobenzoate (43mg,0.2mmol), N, N-diisopropylethylamine (0.8mmol) and acetonitrile (1mL) were added to a reaction tube and reacted under 23W CFL irradiation for 24 hours under nitrogen. Detecting the generation of the target product methyl benzoate according to thin layer chromatography.
Comparative example 2
Figure BDA0002606835970000092
Cercosporin (0.002mmol), nickel sulfate hexahydrate (0.02mmol), 4,4 '-dimethoxy-2, 2' -bipyridine (0.02mmol), 4-bromobenzonitrile (36.4mg,0.2mmol), N, N-diisopropylethylamine (0.3mmol), water (8mmol), DMF and acetonitrile (1:1,1mL) were added to the reaction tube and reacted under 23W CFL irradiation for 24 hours under nitrogen protection. And finally, concentrating the reaction liquid by using a rotary evaporator, and quickly separating by using 200-mesh 300-mesh silica gel column chromatography, wherein the used eluent is ethyl acetate/petroleum ether (v: v ═ 1:5), and the yield of the 4-hydroxybenzonitrile is 8% according to the product quality.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. A compound for use in photocatalytic reduction and coupling reactions of halogenated hydrocarbons, said compound having the formula I:
Figure FDA0003184064460000011
wherein R is selected from methyl, ethyl, propyl, isopropyl or 2-methoxymethyl.
2. A method for synthesizing the compound of claim 1, wherein the compound is synthesized by the following steps:
Figure FDA0003184064460000012
wherein R is selected from methyl, ethyl, propyl, isopropyl or 2-methoxymethyl.
3. The method according to claim 2, characterized in that it comprises in particular the steps of:
(1) adding cercosporal, a reducing agent and alkali into a reaction container, adding acid anhydride into the reaction container, and reacting for 1-3 hours;
(2) adding anhydride into the reaction system, and continuing to react for 1-3 hours;
(3) and (3) adding an extracting agent into the reaction liquid obtained in the step (2) for extraction, then filtering, concentrating the filtrate, and separating to obtain the hexaacyl cercosporin.
4. The method of claim 3, wherein the reducing agent in step (1) is any one of magnesium powder, iron powder, zinc powder and sodium hydrosulfite.
5. The method according to claim 3, wherein the base in step (1) is any one of N, N-dimethyl-4-aminopyridine, N-diisopropylethylamine, triethylamine, triethylenediamine, sodium carbonate, potassium carbonate and cesium carbonate.
6. The method according to claim 3, wherein the acid anhydride in step (1) is any one of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, and 2-methoxyacetic anhydride.
7. The method of claim 3, wherein the molar ratio of cercosporin to anhydride is 1: (10-1000).
8. Use of a compound according to claim 1 for photocatalytic halocarbon reduction.
9. The use of a compound of claim 1 for the photocatalytic coupling of halogenated hydrocarbons with water, alcohols, amines, acids, wherein the compound has the formula I:
Figure FDA0003184064460000021
wherein R is selected from methyl, ethyl, propyl or isopropyl.
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