CN112898233B - Method for preparing amide compound by photocatalytic nitrogen-containing heterocyclic compound - Google Patents
Method for preparing amide compound by photocatalytic nitrogen-containing heterocyclic compound Download PDFInfo
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Abstract
The invention provides a method for preparing amide compounds by photocatalytic nitrogen-containing heterocyclic compounds, which comprises the steps of mixing nitrogen-containing heterocyclic compounds, organic carboxylic acid and tetrahalomethane in a solvent, adding a catalyst, and reacting under the illumination condition to obtain the amide compounds; the invention takes organic carboxylic acid, nitrogen-containing heterocyclic compound containing active hydrogen on nitrogen atom and tetrahalomethane as raw materials, has wide raw material source, low cost and higher safety, and is beneficial to large-scale production; the halogen simple substance is co-produced in the reaction process, the added value is high, the generation of a large amount of waste is avoided, and the method has high atom economy and environmental friendliness; the traditional heating and high-pressure conditions are replaced by the illumination conditions, the reaction conditions are mild, the environmental pollution is reduced, and the reaction cost is reduced; the method has the advantages of good substrate applicability, mild process conditions, environmental protection, simple process, simple and easy operation method, and is beneficial to popularization and application.
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to a method for preparing an amide compound by using a photocatalytic nitrogen-containing heterocyclic compound.
Background
Amide bonds are not only key chemical bonds in proteins, but also basic units for synthesizing many macromolecules. Amide compounds are widely used in pharmaceuticals, pesticides, natural products and functional materials.
The synthesis method of the amide mainly comprises the following steps: firstly, carboxylic acid is taken as a substrate, and reacts with amine in the presence of a coupling reagent, alkali and a solvent to generate amide; the other method is to use acyl halide, acid anhydride and the like to perform nucleophilic addition reaction with organic amine. There are reports in the literature that amides are obtained by catalytic oxidative ammonolysis using aldehydes as starting materials, but this method has disadvantages such as substrate adaptability and long reaction time (Bode JW, Sohn SS. N-heterocyclic carbon-catalyzed redox amines of alpha-functionalized aldehydes with amines [ J ]. Journal of the American Chemical Society,2007,129(45): 13713798-. Bantreil et al used t-butyl hydroperoxide as an oxidant, copper oxide as a catalyst, alcohol and amine hydrochloride reacted at 80 ℃ for 4h to produce amides (Bantreil X, Fleith C, Martinez J, Lamay F. cope-catalyst Synthesis of Benzamides from Alcohols and amides [ J ]. ChemCat Chem,2012,4: 19220152.) Ding et al reported using monovalent copper as a catalyst, TBHP as an oxidant, and aldehyde and amine reacted at room temperature, atmospheric, solventless conditions for 12h to produce amides (Yu L, Luan J, Xu L, Xu Q. Proline and second amine co-Catalyzed condensation of cyclic amides with aldehyde and amine derivatives: a family acids to amides 2-methyl amides [ hydroxyl ] 831, reaction J, Lentices J, et al, hydro. Kawahata et al used aryl Esters or Lactones to hydrolyze tetraalkyl hydroxylamines to form amides (Kawahata N H, Brooks J, Makara G M.A Single Vessel Protocol for the Efficient Formation of amide Bonds from Esters and Lactones [ J ]. Tetrahedron Lett.2002,43(40): 7221. beta. 7223.). Patent CN112110856A discloses a method for preparing 4-chloro-7-methoxyquinoline-6-amide by using 2-amino-4-methoxy-5-cyanobenzoic acid and acetaldehyde as raw materials through a ring closing reaction, a chlorination reaction and a hydrolysis reaction. Patent CN112047854A discloses a process for preparing N-vinyl alkylamides. Patent CN112062688A discloses a preparation method of N, N-diethylacetamide. Patent CN106928083A discloses an amide compound prepared by taking ester and liquid ammonia as raw materials and sodium metal as a catalyst to react in an autoclave at 90-140 ℃. Patent CN108558692A discloses a method for preparing amide compound by reacting azacyclo-carbene, organic acid ester and organic amine in the presence of alkali and inert gas atmosphere. Patent CN101235078A discloses a method for synthesizing amides in the presence of phosphorus oxyhalide, N-lutidine and organic base. Patent CN103492360A discloses a method for preparing hydroxyalkylamides by reacting an ester with a hydroxyalkylamide in an anhydrous solution and under the action of a catalyst. Patent CN106045870A discloses the reaction of triphenylphosphine oxide, oxalyl chloride, organic acid and organic amine in organic solvent to form amide. Patent CN106674040A discloses a method for synthesizing amide by reacting Meldrum's acid with N-substituted arylamine at a reaction temperature of 100-150 ℃. Patent CN104058983A discloses that hydrazine hydrate, 1-benzyl-3-methylimidazole bromide and triphenylphosphine are used as composite catalysts to achieve acylation reaction of carboxylic acid and amine in toluene solvent. Patent CN104418762A discloses a method for synthesizing amides from aldehydes. Patent CN 109810015a discloses that carboxylic acid and amine compound are subjected to grinding reaction in the presence of coupling reagent to obtain amide compound. Patent CN 109761836a discloses a method for preparing amide compounds by grinding reaction of organic carboxylic esters and amine compounds.
In summary, the existing methods for synthesizing amides by reacting carboxylic acids and amines have problems such as low conversion rate, long reaction time, difficulty in separating by-products, use of highly active, expensive and dangerous reagents (such as acyl halides), low atom economy, corrosion of equipment, environmental pollution, etc. Therefore, the development of a green and efficient amide preparation method is urgent.
Disclosure of Invention
The invention provides a method for preparing an amide compound by a photocatalytic nitrogen-containing heterocyclic compound, aims to solve the technical problems of low conversion rate of raw materials, difficult separation of byproducts and the like in an amide preparation process, and provides a preparation method of the amide compound, which has the advantages of high product yield, simple and safe operation process and environmental friendliness.
In order to achieve the purpose, the invention provides a method for preparing an amide compound by a photocatalytic nitrogen-containing heterocyclic compound.
Preferably, the organic carboxylic acid has the structure:
wherein R is 1 Is C 1 ～C 20 Alkyl radical, C 3 ～C 20 Cycloalkyl radical, C 3 ～C 20 Alkylene radical, C 3 ～C 20 Alkynyl radical, C 3 ～C 20 Heterocyclic group, C 5 ～C 12 Heteroaryl or C 6 ～C 20 And one of aryl, the alkyl and the cycloalkyl can be further optionally mono-substituted or multi-substituted by halogen, hydroxyl and alkoxy, which are the same or different.
Preferably, the structure of the nitrogen-containing heterocyclic compound includes:
one or more of the above;
the structure of the amide compound comprises:
one or more of the above;
wherein, R is 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Is H, halogen, alkoxy, C 1 ～C 20 Alkyl radical, C 3 ～C 20 Cycloalkyl radical, C 3 ～C 20 Alkylene radical, C 3 ～C 20 Alkynyl radical, C 3 ～C 20 Heterocyclic group, C 5 ～C 12 Heteroaryl or C 6 ～C 20 One of an aromatic group;
the alkyl and cycloalkyl radicals may be further optionally mono-or polysubstituted, identically or differently, by halogen, hydroxy, alkoxy;
in the structural formula, n is an integer of 1-8.
Preferably, the tetrahalomethane has the structural formula CX 4 Wherein X is one or more of F element, Cl element, Br element and I element.
Preferably, the molar ratio of the organic carboxylic acid to the nitrogen-containing heterocyclic compound to the tetrahalomethane is 1: 0.8-2.5: 0.5-4.0; the addition mass of the metal oxide is 0.5-50% of the mass of the nitrogen heterocyclic compound.
Preferably, the solvent comprises any one or more of toluene, benzene, N-hexane, trifluorotoluene, dichloromethane, dichloroethane, cyclohexane, methanol, ethanol, diethyl ether, isopropanol, butanol, tetrahydrofuran, acetonitrile, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, chloroform, and tetrachloromethane.
Preferably, the metal oxide includes one or more of trimanganese tetroxide, ferroferric oxide, cobaltosic oxide, silver oxide, titanium dioxide, zinc oxide, tin oxide, zirconium dioxide, cadmium sulfide and manganese dioxide.
Preferably, one or more alkali selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, triethylamine, tert-butyl sodium alkoxide, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, barium carbonate, calcium carbonate, lithium hydroxide and barium hydroxide is/are also added into the solvent; the molar ratio of the alkali to the nitrogen-containing heterocyclic compound is as follows: 0-4.0: 1.
Preferably, the illumination is provided by one or more light sources of xenon lamp, light emitting diode, mercury lamp and metal halide lamp.
Preferably, the reaction atmosphere is air or a mixed gas containing oxygen.
Preferably, the reaction further comprises post-treatment, wherein the post-treatment is standing for layering or filtration, and then distillation is carried out.
The scheme of the invention has the following beneficial effects:
1. the method directly adopts the organic carboxylic acid, the nitrogen-containing heterocyclic compound containing active hydrogen on nitrogen atoms and the tetrahalomethane as raw materials, has wide raw material sources, low cost, higher safety and stability and is beneficial to large-scale production;
2. the invention adopts the illumination condition to replace the traditional heating and high-pressure condition, has mild reaction condition, reduces the environmental pollution and reduces the reaction cost;
3. the method co-produces the halogen simple substance in the reaction process, has higher added value, avoids generating a large amount of waste, has higher atom economy and environmental friendliness, is easy to separate the catalyst in the product, can be recycled, and reduces the production cost;
4. the method has the advantages of good substrate applicability, mild process conditions, environmental protection, simple process, simple and easy operation method, and is beneficial to popularization and application.
Drawings
FIG. 1 is a mass spectrum of 1-pyrrolidin-1-octane-1-one obtained in example 1 of the present invention;
FIG. 2 is a mass spectrum of 3-phenyl-1- (pyrrolidinyl) -1-propanone obtained in example 2 of the present invention;
FIG. 3 is a mass spectrum of 2-pyridyl-1-pyrrolidone obtained in example 3 of the present invention;
FIG. 4 is a mass spectrum of 3-pyridyl-1-pyrrolidone obtained in example 4 of the present invention;
FIG. 5 is a mass spectrum of (2-benzoylphenyl) (pyrrolidin-1-yl) methanone obtained in example 5 of the present invention;
FIG. 6 is a mass spectrum of 1-isoquinolinyl-1-pyrrolidone obtained in example 6 of the invention;
FIG. 7 is a mass spectrum of 1-azacyclohexane-1-benzophenone obtained in example 7 of the present invention;
FIG. 8 is a mass spectrum of cyclohexyl-1-pyrrolidone obtained in example 8 of the present invention;
FIG. 9 is a mass spectrum of phenyl-1-pyrrolidone obtained in example 9 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
All percentages in the examples are by mass unless otherwise specified; all parts refer to parts by mass.
Example 1
32.48 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 80.00 parts of trifluorotoluene, 14.20 parts of tetrahydropyrrole (the content is 99.0%), 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.79 parts of sodium carbonate (the content is 99.8%) are added, 29.43 parts of n-octanoic acid (the content is 98.0%) are added, and after stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, the trifluorotoluene solvent is distilled and recovered, so that a reddish black oily bromine and a brown 1-pyrrolidine-1-octane-1-one liquid product serving as a simple substance are obtained.
After the obtained product is separated and purified, the structure is characterized by adopting a mass spectrum characterization mode, and the result is shown in figure 1.
The spectrum of 1-pyrrolidin-1-octane-1-one obtained in example 1 showed that the peak having a mass/charge ratio of 198.1857 was the [ M + H ] ion peak and the theoretical [ M + H ] MS of 1-pyrrolidin-1-octane-1-one was 198.1852.
Example 2
32.40 parts of tetrabromomethane (the content is 97.0 percent) is added into a reactor filled with 80.00 parts of trifluorotoluene, 14.20 parts of tetrahydropyrrole (the content is 99.0 percent) is added, 0.31 part of manganous manganic oxide (the content is 99.5 percent) and 10.67 parts of sodium carbonate (the content is 99.8 percent) are added, 30.34 parts of 3-phenylpropionic acid (the content is 98.0 percent) is added, and after stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, the trifluorotoluene solvent is distilled and recovered to obtain a black-purple oily bromine simple substance and a purple-black 3-phenyl-1- (pyrrolidinyl) -1-acetone liquid product.
After the obtained product is separated and purified, the structure is characterized by adopting a mass spectrum characterization mode, and the result is shown in figure 2.
The spectrum of 3-phenyl-1- (pyrrolidinyl) -1-propanone obtained in example 2 showed that the peak having a mass/charge ratio of 226.1204 was the [ M + Na ] ion peak and the theoretical molecular weight M of 3-phenyl-1- (pyrrolidinyl) -1-propanone was 203.13.
Example 3
34.66 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 80.00 parts of trifluorotoluene, 14.20 parts of tetrahydropyrrole (the content is 99.0%), 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.92 parts of sodium carbonate (the content is 99.8%) are added, 21.87 parts of 2-picolinic acid (the content is 99.0%) are added, and after stirring and reacting for 12 hours under the irradiation of a xenon lamp as a light source, the trifluorotoluene solvent is distilled and recovered to obtain a reddish black oily bromine simple substance and a brownish yellow 2-pyridyl-1-pyrrolidone liquid product.
After the obtained product is separated and purified, the structure is characterized by adopting a mass spectrum characterization mode, and the result is shown in figure 3.
The peak having a mass-to-charge ratio of 177.1027 in the spectrum of 2-pyridyl-1-pyrrolidone obtained in example 3 was an [ M + H ] ion peak, and the theoretical [ M + H ] MS of 2-pyridyl-1-pyrrolidone was 177.1022.
Example 4
34.55 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 100.00 parts of toluene, 14.20 parts of tetrahydropyrrole (the content is 99.0%), 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.85 parts of sodium carbonate (the content is 99.8%) are added, 24.87 parts of nicotinic acid (the content is 99.0%) are added, and the mixture is stirred and reacted for 12 hours under the irradiation of an Led lamp as a light source, and then the toluene solvent is distilled and recovered to obtain a black purple oily bromine simple substance and a black 3-pyridyl-1-pyrrolidone liquid product.
After the obtained product is separated and purified, the structure is characterized by adopting a mass spectrum characterization mode, and the result is shown in figure 4.
The peak having a mass-to-charge ratio of 177.1027 in the spectrum of 3-pyridyl-1-pyrrolidone obtained in example 4 was the [ M + H ] ion peak, and the MS of theoretical [ M + H ] of 3-pyridyl-1-pyrrolidone was 177.1022.
Example 5
32.46 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 100.00 parts of trifluorotoluene, 14.20 parts of tetrahydropyrrole (the content is 99.0%), 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.85 parts of sodium carbonate (the content is 99.8%) are added, 45.70 parts of 2-benzoylbenzoic acid (the content is 99.0%) are added, and after stirring and reacting for 12 hours under the irradiation of a xenon lamp as a light source, the trifluorotoluene solvent is distilled and recovered to obtain a red-black oily bromine simple substance and a brown-yellow (2-benzoylphenyl) (pyrrolidin-1-yl) methanone liquid product.
After the obtained product is separated and purified, the structure is characterized by adopting a mass spectrum characterization mode, and the result is shown in figure 5.
The peak having a mass-to-charge ratio of 280.1338 in the spectrum of (2-benzoylphenyl) (pyrrolidin-1-yl) obtained in example 5 was an [ M + H ] ion peak, and the MS of the theoretical [ M + H ] of (2-benzoylphenyl) (pyrrolidin-1-yl) was 280.1332.
Example 6
32.62 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 100.00 parts of toluene, 14.20 parts of tetrahydropyrrole (the content is 99.0%), 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.63 parts of sodium carbonate (the content is 99.8%) are added, 35.34 parts of isoquinoline carboxylic acid (the content is 98.0%) are added, and after stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, the toluene solvent is distilled and recovered, so that a red-black elementary bromine substance and a brown-black 1-isoquinolyl-1-pyrrolidone liquid product are obtained.
After the obtained product is separated and purified, the structure characterization is carried out by adopting a mass spectrum characterization mode, and the result is shown in figure 6.
The peak having a mass-to-charge ratio of 227.1187 in the spectrum of 1-isoquinolinyl-1-pyrrolidone obtained in example 6 is the [ M + H ] ion peak, and the theoretical [ M + H ] MS of 1-isoquinolinyl-1-pyrrolidone is 227.1179.
Example 7
32.51 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 100.00 parts of trifluorotoluene, 20.24 parts of cyclohexylimine (the content is 98.0%), 0.31 part of mangano-manganic oxide (the content is 99.5%) and 10.62 parts of sodium carbonate (the content is 99.8%) are added, 24.50 parts of benzoic acid (the content is 99.5%) are added, and after stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, the trifluorotoluene solvent is distilled and recovered, so that a bromine simple substance in a red-black oily state and a 1-azacyclohexane-1-benzophenone liquid product in a red-brown color are obtained.
After the obtained product is separated and purified, the structure is characterized by adopting a mass spectrum characterization mode, and the result is shown in figure 7.
The peak having a mass-to-charge ratio of 204.1389 in the spectrum of 1-azacyclohexane-1-benzophenone obtained in example 7 was an [ M + H ] ion peak, and the MS of theoretical [ M + H ] of 1-azacyclohexane-1-benzophenone was 204.1383.
Example 8
32.60 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 100.00 parts of trifluorotoluene, 14.20 parts of tetrahydropyrrole (the content is 99.0%), 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.65 parts of sodium carbonate (the content is 99.8%) are added, 25.89 parts of cyclohexanecarboxylic acid (the content is 99.5%) are added, and after stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, the trifluorotoluene solvent is distilled and recovered, so that a reddish black oily bromine simple substance and a reddish brown cyclohexyl-1-pyrrolidone liquid product are obtained.
After the obtained product is separated and purified, the structure is characterized by adopting a mass spectrum characterization mode, and the result is shown in figure 8.
The peak having a mass-to-charge ratio of 182.1551 in the spectrum of cyclohexyl-1-pyrrolidone obtained in example 8 was the [ M + H ] ion peak, and the MS of theoretical [ M + H ] of cyclohexyl-1-pyrrolidone was 182.1539.
Example 9
Adding 15.51 parts of tetrachloromethane (the content is 99.0%) into a reactor filled with 100.00 parts of trifluorotoluene, adding 14.20 parts of tetrahydropyrrole (the content is 99.0%), adding 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.60 parts of sodium carbonate (the content is 99.8%), adding 24.5 parts of benzoic acid (the content is 99.5%), stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, collecting chlorine generated in the reaction process, and distilling and recovering the trifluorotoluene solvent to obtain a brown phenyl-1-pyrrolidone liquid product.
After the obtained product is separated and purified, the structure is characterized by adopting a mass spectrum characterization mode, and the result is shown in figure 9.
The peak having a mass-to-charge ratio of 176.1072 in the spectrum of phenyl-1-pyrrolidone obtained in example 9 was the [ M + H ] ion peak, and the MS of theoretical [ M + H ] of phenyl-1-pyrrolidone was 176.1070.
Example 10
Adding 32.45 parts of tetrabromomethane (the content is 97.0%) into a reactor filled with 100.00 parts of benzotrifluoride, adding 17.78 parts of morpholine (the content is 98.0%), adding 0.29 part of titanium dioxide (99.0%) and 32.85 parts of sodium carbonate (the content is 99.8%), adding 24.50 parts of benzoic acid (the content is 99.5%), stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, distilling and recovering a benzotrifluoride solvent to obtain a reddish black oily bromine and brown gray 4-morpholinophenyl methanone liquid product.
Example 11
Adding 15.58 parts of tetrachloromethane (the content is 99.0%) into a reactor filled with 100.00 parts of benzotrifluoride, adding 20.23 parts of 1-methylpiperazine (the content is 99.0%), adding 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.60 parts of sodium carbonate (the content is 99.8%), adding 24.50 parts of benzoic acid (the content is 99.5%), stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, collecting chlorine generated in the reaction process, distilling and recovering a benzotrifluoride solvent to obtain a brown gray (4-methyl-1-piperazinyl) phenyl ketone liquid product.
Example 12
32.52 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 100.00 parts of trifluorotoluene, 18.92 parts of 2-aminopyridine (the content is 99.5%), 0.31 part of mangano-manganic oxide (the content is 99.5%) and 10.67 parts of sodium carbonate (the content is 99.8%) are added, 24.50 parts of benzoic acid (the content is 99.5%) are added, and after stirring and reacting for 12 hours under the irradiation of a xenon lamp as a light source, the trifluorotoluene solvent is distilled and recovered to obtain a red-black oily bromine simple substance and a brownish-red 2- (benzoylamino) pyridine liquid product.
Example 13
32.52 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 100.00 parts of trifluorotoluene, 20.24 parts of cyclohexylimine (the content is 99.5%), 0.31 part of mangano-manganic oxide (the content is 99.5%) and 10.69 parts of sodium carbonate (the content is 99.8%) are added, 24.90 parts of nicotinic acid (the content is 99.0%) are added, and after stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, the trifluorotoluene solvent is distilled and recovered, and a reddish black oily bromine and brown 1-azacyclohexane-3-pyridylmethanone liquid product serving as a simple substance is obtained.
Example 14
32.56 parts of tetrabromomethane (the content is 97.0%) is added into a reactor filled with 100.00 parts of trifluorotoluene, 20.24 parts of cycloheximide (the content is 98.0%), 0.31 part of manganous manganic oxide (the content is 99.5%) and 10.68 parts of sodium carbonate (the content is 99.8%), 33.10 parts of n-octanoic acid (the content is 98.0%) are added, and after stirring and reacting for 12 hours under the irradiation of an Led lamp serving as a light source, the trifluorotoluene solvent is distilled and recovered, so that a reddish black oily bromine simple substance and a brownish red 1-azacyclohexane-3-heptyl ketone liquid product are obtained.
Example 15
32.60 parts of tetrabromomethane (the content is 97.0%) are added into a reactor filled with 100.00 parts of trifluorotoluene, 14.20 parts of tetrahydropyrrole (the content is 99.0%), 0.30 part of titanium dioxide (99.0%) and 32.87 parts of sodium carbonate (the content is 99.8%) are added, 31.63 parts of p-chlorobenzoic acid (the content is 99.0%) are added, and after stirring and reacting for 12 hours under the irradiation of an LED lamp serving as a light source, the trifluorotoluene solvent is distilled and recovered, so that a red-black oily bromine simple substance and a khaki (4-chlorophenyl) -1-pyrrolidone liquid product are obtained.
The obtained substituted urea product was weighed and the theoretical yield was calculated from the amount of added starting material and the yield was calculated as shown in table 1.
TABLE 1 EXAMPLES 1-15 yields of amides
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A method for preparing amide compounds by using a photocatalytic nitrogen-containing heterocyclic compound is characterized in that the nitrogen-containing heterocyclic compound, organic carboxylic acid and tetrahalomethane are mixed in a solvent, metal oxide is added, and the mixture reacts under the condition of illumination to prepare the amide compounds; the structure of the nitrogen-containing heterocyclic compound is selected from:
the structure of the amide compound is selected from:
the organic carboxylic acid has the structure:
wherein R is 1 Is C 1 ～C 20 Alkyl radical, C 3 ～C 20 Cycloalkyl radical, C 3 ～C 20 Alkylene radical, C 3 ～C 20 Alkynyl, C 3 ～C 20 Heterocyclyl or C 6 ～C 20 One of aryl, said alkyl and cycloalkyl being optionally further mono-or polysubstituted, identically or differently, by halogen, hydroxy, alkoxy;
the alkyl and cycloalkyl radicals may be further optionally mono-or polysubstituted, identically or differently, by halogen, hydroxy, alkoxy;
in the structural formula, n is an integer of 1-8;
the metal oxide is selected from one or more of trimanganese tetroxide and titanium dioxide;
one or more alkali selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, cesium carbonate, triethylamine, tert-butyl sodium alkoxide, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, barium carbonate, calcium carbonate, lithium hydroxide and barium hydroxide is/are also added into the solvent; the molar ratio of the alkali to the nitrogen-containing heterocyclic compound is as follows: 0-4.0: 1;
the illumination is provided by one or more light sources of a xenon lamp, a light-emitting diode, a mercury lamp and a metal halide lamp; the reaction atmosphere is air or mixed gas containing oxygen.
2. The method of claim 1, wherein the tetrahalomethane has the formula CX 4 Wherein X is one or more of F element, Cl element, Br element and I element.
3. The method according to claim 1, wherein the organic carboxylic acid: a nitrogen-containing heterocyclic compound: the molar ratio of the tetrahalomethane is 1: 0.8-2.5: 0.5-4.0; the addition mass of the metal oxide is 0.5-50% of the mass of the nitrogen heterocyclic compound.
4. The method according to claim 1, wherein the solvent is selected from any one or more of toluene, benzene, N-hexane, trifluorotoluene, dichloromethane, dichloroethane, cyclohexane, methanol, ethanol, diethyl ether, isopropanol, butanol, tetrahydrofuran, acetonitrile, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, chloroform, and tetrachloromethane.
5. The method according to claim 1, wherein the reaction further comprises a post-treatment, wherein the post-treatment is standing for layering or filtration, and then distillation is performed.
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