CN110292948B - Application of imines-functionalized imidazole chloride salt as catalyst in preparation of aromatic heterocyclic formate compounds - Google Patents
Application of imines-functionalized imidazole chloride salt as catalyst in preparation of aromatic heterocyclic formate compounds Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
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- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
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- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
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- B01J2231/49—Esterification or transesterification
Abstract
The invention discloses a method for synthesizing aromatic heterocyclic formate compounds, namely the compounds have a molecular formula of [ (ArN = C (CH)3)NCH2CH2NCH2C6H5)CH]Imidazolium chloride salt of Cl (where Ar =2, 6-di-CH (CH)3)2‑C6H3) The aromatic heterocyclic formate compound is synthesized by the carboxylation reaction of the aromatic heterocyclic compound and carbon dioxide under normal pressure as a catalyst. The method is the first example of preparing the aromatic heterocyclic formate compound through the carboxylation reaction of the aromatic heterocyclic compound and carbon dioxide under the catalysis of imidazole salt, and compared with the prior art, the method has the advantages that the catalyst is more green, the synthesis is easier, the reaction condition is mild, and the catalytic activity and the functional group tolerance are equivalent to or better.
Description
The invention discloses a method for synthesizing aromatic heterocyclic formate compounds, which is a divisional application with application number of 2016109319327 and application date of 2016, 10 and 31, and belongs to the technical field of catalyst application.
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for synthesizing aromatic heterocyclic formate compounds by using imidazole chloride salt containing monoamine functionalization as a catalyst.
Background
The aromatic heterocyclic formate compounds are important raw materials or intermediates in organic synthesis, and are also important frameworks in natural products, pesticides or medicines. In recent years, a method for producing an aromatic heterocyclic formate compound by carboxylation of an aromatic heterocyclic compound using carbon dioxide as a C1 source has been rapidly developed.
In 2010, Nolan et al discovered that under the existence of room temperature and potassium hydroxide, N-heterocyclic carbene complexes of gold (I) can catalyze the carboxylation reaction of aromatic heterocyclic compounds and carbon dioxide (1.4 atmospheric pressures), and can be used for synthesizing aromatic heterocyclic formate compounds; subsequently, the group reported that similar copper (I) azaheterocyclic carbene complexes are also capable of catalyzing the carboxylation of heteroaromatic compounds and carbon dioxide (1.4 atmospheres) in the presence of cesium hydroxide at 40 ℃; at the same time, citizens and others have synthesized such compounds using a similar copper (I) azaheterocyclic carbene complex at 80 ℃ in the presence of potassium tert-butoxide (see: i.i.f. boogarts, s.p. Nolan,J. Am. Chem. Soc., 2010, 132, 8858-8859;I. I. F. Boogaerts, G. C. Fortman, M. R. L. Furst, C. S. J. Cazin, S. P. Nolan, Angew. Chem. Int. Ed., 2010, 49, 8674-8677;L. Zhang, J. Cheng, T. Ohishi, Z. Hou, Angew. Chem. Int. Ed., 2010, 49, 8670-8673）。
in the prior art, a transition metal catalyst is used, and the synthesis of the heteroaromatic formic ester compound can be realized by utilizing the activity of metal, but a gold catalyst is expensive, a copper catalyst is toxic, most of the catalysts also need carbon dioxide with certain pressure, and unsafe stress factors exist. So far, no report is found for synthesizing aromatic heterocyclic formate compounds by using monoamine functionalized imidazole chloride salt as a catalyst and carrying out a carboxylation reaction on the aromatic heterocyclic compounds and carbon dioxide under normal pressure.
Disclosure of Invention
The invention aims to provide a method for synthesizing aromatic heterocyclic formate compounds, namely, the compounds have a molecular formula of [ (ArN = C (CH)3)NCH2CH2NCH2C6H5)CH]Imidazolium chloride salt of Cl (where Ar =2, 6-di-CH (CH)3)2-C6H3) In the presence of potassium tert-butoxide, aromatic heterocyclic formate compounds are synthesized by carboxylation reaction of aromatic heterocyclic compounds and carbon dioxide under normal pressure.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for synthesizing aromatic heterocyclic formate compounds comprises the following steps of carrying out normal pressure reaction in inert gas atmosphere by taking imidazole chloride containing monoamine functionalization as a catalyst and taking aromatic heterocyclic compounds and carbon dioxide as raw materials in the presence of alkali; after the reaction is finished, adding halogenated hydrocarbon, and performing esterification reaction to obtain an aromatic heterocyclic formate compound; the chemical structural formula of the imines-containing functionalized imidazole chloride salt is as follows:
in the technical scheme, the aromatic heterocyclic compound is a benzoxazole compound, a benzothiazole compound or a benzimidazole compound; the method has excellent substrate applicability, can not only take conventional aromatic heterocyclic compounds as raw materials, but also catalyze substrates which are difficult to react, such as benzimidazole compounds and benzothiazole compounds, so as to prepare aromatic heterocyclic formate compounds with more structures.
In the technical scheme, the reaction temperature under normal pressure is 50-85 ℃, and the reaction time is 12-24 hours; the esterification reaction temperature is 45-75 ℃ and the time is 0.5-2 hours.
In the above-mentioned solutions, the reaction is carried out in an organic solvent, for exampleN,N-Dimethylformamide (DMF) orN,NDimethylacetamide (DMA), preferably DMF, can dissolve the reaction materials well, making the reaction homogeneous.
In the technical scheme, the halogenated hydrocarbon is iodohydrocarbon, preferably methyl iodide which is a good O-methylation reagent and can ensure that the esterification reaction can be smoothly carried out.
In the technical scheme, the aromatic heterocyclic formate compound is synthesized by a carboxylation reaction of an aromatic heterocyclic compound and carbon dioxide under normal pressure in the presence of potassium tert-butoxide or cesium carbonate as a single-component catalyst and monoamine-containing functionalized imidazole chloride salt, and specifically comprises the following steps: sequentially adding a catalyst, alkali, a solvent and an aromatic heterocyclic compound into a reaction bottle in an inert gas atmosphere; then introducing carbon dioxide gas; stirring and reacting for 12-24 hours at 50-85 ℃ under normal pressure; then adding halogenated hydrocarbon, and carrying out esterification reaction to obtain the aromatic heterocyclic formic ether compound.
In the technical scheme, after the esterification reaction is finished, the reaction liquid is cooled and then is stopped by deionized water, and then is extracted by ethyl acetate, and finally the aromatic heterocyclic formate compound is obtained by column chromatography treatment.
In the technical scheme, the dosage range of the catalyst is 1-5% of that of the aromatic heterocyclic compound according to the molar ratio, and the dosage range of the alkali is 1.0-1.5 times of that of the aromatic heterocyclic compound.
In a preferred technical scheme, when the aromatic heterocyclic compound is a benzoxazole compound, the amount of the base is 1.2 times that of the benzoxazole compound, the amount of the catalyst is 5% that of the benzoxazole compound, and the amount of the halogenated hydrocarbon is 3.0 times that of the benzoxazole compound by mass; the reaction temperature under normal pressure is 80 ℃ and the reaction time is 18 hours; the esterification reaction temperature was 65 ℃ and the time was 1 hour.
The invention also discloses application of the imines-containing functionalized imidazole chloride salt as a catalyst in catalyzing the reaction of aromatic heterocyclic compounds and carbon dioxide; and the application of imidazole chloride salt containing imine functionalization as a catalyst in preparing aromatic heterocyclic formate compounds.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the method avoids the use of a metal catalyst for the first time, adopts the iminium functionalized imidazolium chloride salt as the catalyst, has the characteristics of low price, easy obtainment, environmental protection and stability in the air, and is favorable for large-scale synthesis and use.
2. In the method for synthesizing the aromatic heterocyclic formate compound, the reaction is carried out under normal pressure, so that the safety is effectively ensured, the problem that the prior art considers that the reaction can be effectively carried out only under certain pressure, such as 1.4 atmospheric pressure, is solved, the gas-phase yield of the prepared product reaches 95%, and unexpected technical effects are achieved.
3. In the method for synthesizing the aromatic heterocyclic formate compound, the normal pressure reaction temperature is 50-85 ℃, preferably 65-80 ℃, and most preferably 80 ℃; the prior art considers that the effective temperature of the carboxylation reaction of the aromatic heterocyclic compound and carbon dioxide is at least 100 ℃, the effective temperature is lower than 100 ℃, the conversion cannot be well carried out (the yield is lower than 80%) and even cannot be carried out (no product is produced at 65 ℃), the reaction yield can reach 95% at 80 ℃ and can reach 72% even at 65 ℃ by adopting the technical method of the invention, and unexpected technical effects are obtained.
4. The preparation method disclosed by the invention has universality for various reaction substrates, can efficiently catalyze the carboxylation reaction of the benzoxazole aromatic heterocyclic compound, can smoothly realize the carboxylation reaction of the benzothiazole compound which can not be realized by using the prior art, and obviously improves the substrate universality and the product yield compared with the prior art.
Detailed Description
The invention is further described below with reference to the following examples:
in this example, the molecular formula of the catalyst containing the monoamine functionalized imidazolium chloride salt is [ (ArN = C (CH)3)NCH2CH2NCH2C6H5)CH]Cl (wherein Ar =2, 6-di-CH (CH)3)2-C6H3) The chemical structural formula is as follows:
EXAMPLE Synthesis of benzoxazole-2-carboxylic acid methyl ester by carboxylation of benzoxazole and carbon dioxide
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzoxazole (50.7 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and performing gas chromatography to obtain a product with a yield of 95% and a product with a yield of 90% after column chromatography purification (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent).
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.056 g, 0.5 mmol), DMF (3.0 ml), benzoxazole (50.7 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 88%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.87 (d, J = 7.6 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 7.51 (dd, J 1 = 7.6 Hz, J 2 = 1.5 Hz, 1H), 7.44 (m, 1H), 4.07 (s, 3H)。
EXAMPLE carboxylation of Dibenzoxazole with carbon dioxide Synthesis of benzoxazole-2-carboxylic acid Ethyl ester
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzoxazole (50.7 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, ethyl iodide (120 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing agent) to obtain a yield of 89%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.90 (d, J = 7.6 Hz, 1H), 7.67 (d, J = 8.2 Hz, 1H ), 7.55 (dd, J 1 = 7.6 Hz, J 2 = 1.5 Hz, 1H), 7.44 (m, 1H), 4.57 (q, J = 7.1 Hz, 2H), 1.50 (t, J = 7.1 Hz, 3H)。
EXAMPLES Synthesis of Hexanoxazole-2-carboxylic acid hexyl ester by carboxylation of Tribenzoxazole with carbon dioxide
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzoxazole (50.7 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, 1-iodohexane (222. mu.l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 85%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.90 (d, J = 6.8Hz, 1H), 7.67 (d, J = 6.8Hz, 1H ), 7.55 (dd, J 1 = 6.8 Hz, J 2 = 1.6 Hz, 1H), 7.44 (m, 1H), 4.38 (t, J = 6.8Hz, 2H), 1.70-1.79 (m, 2 H), 1.21-1.38 (m, 6H), 0.79 (t, J = 6.6Hz, 3H)。
EXAMPLE carboxylation of Tetrabenzoxazole with carbon dioxide Synthesis of benzoxazole-2-carboxylic acid methyl ester
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzoxazole (50.7 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 65 ℃ for 18 hours under normal pressure. Methyl iodide (93. mu.l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 72%.
In a reaction flask, catalyst (2.0 mg, 0.005 mmol, 1 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzoxazole (50.7 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, terminating the reaction by using deionized water, extracting a reaction product by using ethyl acetate, and purifying by using column chromatography (taking a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 10 as a developing agent), wherein the yield is 70%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.87 (d, J = 7.6 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 7.51 (dd, J 1 = 7.6 Hz, J 2 = 1.5 Hz, 1H), 7.44 (m, 1H), 4.07 (s, 3H)。
EXAMPLE carboxylation of Pentabenzoxazole with carbon dioxide Synthesis of benzoxazole-2-carboxylic acid methyl ester
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzoxazole (50.7 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 50 ℃ for 18 hours under normal pressure. Methyl iodide (93. mu.l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, terminating the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 54%.
The product is processedDissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.87 (d, J = 7.6 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 7.51 (dd, J 1 = 7.6 Hz, J 2 = 1.5 Hz, 1H), 7.44 (m, 1H), 4.07 (s, 3H)。
EXAMPLE carboxylation of Hexabenzoxazole with carbon dioxide Synthesis of benzoxazole-2-carboxylic acid methyl ester
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), cesium carbonate (0.1955 g, 0.6 mmol), DMF (3.0 ml), benzoxazole (50.7 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 60%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.87 (d, J = 7.6 Hz, 1H), 7.64 (d, J = 8.2 Hz, 1H), 7.51 (dd, J 1 = 7.6 Hz, J 2 = 1.5 Hz, 1H), 7.44 (m, 1H), 4.07 (s, 3H)。
EXAMPLE carboxylation of seven-bromobenzoxazole with carbon dioxide Synthesis of 5-bromobenzoxazole-2-carboxylic acid methyl ester
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), 5-bromobenzoxazole (99.01 mg, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 85%.
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.084 g, 0.75 mmol), DMF (3.0 ml), 5-bromobenzoxazole (99.01 mg, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 88%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 8.02 (d, J = 1.6 Hz, 1H), 7.55 (m, 1H), 7.62 (dd, J1 = 8.8 Hz, J2 = 1.6 Hz, 1H), 4.09 (s, 3H)。
Example Synthesis of methyl 5-chlorobenzoxazole-2-carboxylate by carboxylation of octa 5-chlorobenzoxazole and carbon dioxide
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), 5-chlorobenzoxazole (76.79 mg, 0.5 mmol) were added in this order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction by using deionized water, extracting a reaction product by using ethyl acetate, and purifying by using column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 10 as a developing agent), wherein the yield is 82%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.83 (d, J = 2.1 Hz, 1H), 7.57 (m, 1H), 7.47 (dd, J1 = 8.8 Hz, J2 = 2.1 Hz, 1H), 4.07 (s, 3H)。
EXAMPLE carboxylation of nona-5-methylbenzoxazole with carbon dioxide to synthesize 5-methylbenzoxazole-2-carboxylic acid methyl ester
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), 5-methylbenzoxazole (66.58 mg, 0.5 mmol) were added in this order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 88%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.65 (s, 1H), 7.52 (d, J = 8.8Hz, 1H), 7.35 (d, J = 8.4 Hz, 1H), 4.09 (s, 3H), 2.50 (s, 3H)。
Example Synthesis of methyl 6-methylbenzoxazole-2-carboxylate by carboxylation of Ten 6-methylbenzoxazole and carbon dioxide
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), 6-methylbenzoxazole (58.0 μ l, 0.5 mmol) were added in this order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain 84% yield.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.74 (d, J = 8.4 Hz, 1H), 7.45(s, 1H), 7.29 (d, J = 10.0 Hz, 1H), 4.08 (s, 3H), 2.53 (s, 3H)。
Example Synthesis of benzothiazole-2-carboxylic acid methyl ester by carboxylation of undebenzothiazole and carbon dioxide
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzothiazole (55.0 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing agent) to obtain a yield of 89%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 8.20 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.52 (m, 2H), 4.05 (s, 3H)。
EXAMPLE carboxylation of Dodecabenzothiazole and carbon dioxide to Synthesis Benzothiazole-2-Carboxylic acid methyl ester
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzothiazole (55.0 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 65 ℃ for 18 hours under normal pressure. Methyl iodide (93. mu.l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 52%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 8.20 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.52 (m, 2H), 4.05 (s, 3H)。
EXAMPLE thirteen carboxylation of benzothiazole and carbon dioxide Synthesis of benzothiazole-2-Hexaformate
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), benzothiazole (55.0 μ l, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, 1-iodohexane (222. mu.l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction with deionized water, extracting the reaction product with ethyl acetate, and purifying by column chromatography (using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1: 10 as a developing solvent) to obtain a yield of 80%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 8.20 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.52 (m, 2H), 4.05 (q, J = 7.1 Hz, 2H), 1.31 (t, J = 7.1 Hz, 3H)。
Example Synthesis of methyl 6-methoxybenzothiazole-2-carboxylate by carboxylation of tetradecyl 6-methoxybenzothiazole and carbon dioxide
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), 6-methoxybenzothiazole (82.5 mg, 0.5 mmol) were added in order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, stopping the reaction by using deionized water, extracting a reaction product by using ethyl acetate, and purifying by using column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 10 as a developing agent), wherein the yield is 82%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 8.11 (d, J = 8.8 Hz, 1H), 7.36 (s, 1H), 7.18 (dd, J 1= 8.8 Hz, J 2 = 2.4 Hz, 1H), 4.06 (s, 3H), 3.90 (s, 3H)。
EXAMPLE fifteen reaction of 6-Chlorobenzothiazole with carbon dioxide to synthesize 6-Chlorobenzothiazole-2-carboxylic acid methyl ester
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), 6-chlorobenzothiazole (84.99 mg, 0.5 mmol) were added in this order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 18 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, terminating the reaction by using deionized water, extracting a reaction product by using ethyl acetate, and purifying by using column chromatography (using a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 10 as a developing agent), wherein the yield is 75%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 8.13 (s, 1H), 7.60 (d, J = 8.4 Hz, 1H), 7.56 (d, J = 8.4 Hz, 1H), 4.06 (s, 3H)。
Example Synthesis of methyl 1-methylbenzimidazole-2-carboxylate by carboxylation of hexadeca 1-methylbenzimidazole with carbon dioxide
In a reaction flask, catalyst (9.9 mg, 0.025 mmol, 5 mol%), potassium tert-butoxide (0.0672 g, 0.6 mmol), DMF (3.0 ml), 1-methylbenzimidazole (60.0 μ l, 0.5 mmol) were added in this order under argon protection, carbon dioxide gas was bubbled through, and the reaction was stirred at 80 ℃ for 24 hours under normal pressure. Cooled to 65 ℃, methyl iodide (93 μ l, 1.5 mmol) was added and the reaction stirred at 65 ℃ for 1 hour. Cooling to room temperature, terminating the reaction by using deionized water, extracting a reaction product by using ethyl acetate, and purifying by using column chromatography (taking a mixed solvent with the volume ratio of ethyl acetate to petroleum ether being 1: 10 as a developing agent), wherein the yield is 50%.
The product was dissolved in CDCl3Medium (about 0.4 ml), sealed, and characterized by measurement on a Unity Inova-400 NMR instrument at room temperature.1H NMR (400MHz, CDCl3): 7.78 (m, 1H), 7.61 (m, 1H), 7.33 (m, 1H), 7.32 (m, 1H), 4.00 (s, 3H), 3.88 (s, 3H)。
Claims (7)
1. The application of imidazole chloride salt containing monoamine functionalization as a catalyst in preparing aromatic heterocyclic formate compounds is characterized in that the aromatic heterocyclic formate compounds and carbon dioxide are used as raw materials in preparing the aromatic heterocyclic formate compounds; the chemical structural formula of the imines-containing functionalized imidazole chloride salt is as follows:
2. use according to claim 1, characterized in that: the preparation of the aromatic heterocyclic formate compound comprises the following steps of carrying out normal pressure reaction in an inert gas atmosphere by taking imidazole chloride containing monoamine functionalization as a catalyst and taking an aromatic heterocyclic compound and carbon dioxide as raw materials in the presence of alkali; after the reaction is finished, adding halogenated hydrocarbon, and carrying out esterification reaction to obtain the aromatic heterocyclic formate compound.
3. Use according to claim 2, characterized in that: the normal pressure reaction temperature is 50-85 ℃, and the time is 12-24 hours; the esterification reaction temperature is 45-75 ℃ and the time is 0.5-2 hours.
4. The use according to claim 2, characterized in that it comprises in particular the following steps: sequentially adding a catalyst, alkali, a solvent and an aromatic heterocyclic compound into a reaction bottle in an inert gas atmosphere; then introducing carbon dioxide gas; stirring and reacting for 12-24 hours at 50-85 ℃ under normal pressure; then adding halogenated hydrocarbon, and carrying out esterification reaction to obtain the aromatic heterocyclic formic ether compound.
5. Use according to claim 2, characterized in that: the dosage range of the catalyst is 1 to 5 percent of that of the aromatic heterocyclic compound according to the molar ratio, and the dosage range of the alkali is 1.0 to 1.5 times of that of the aromatic heterocyclic compound.
6. Use according to claim 1, characterized in that: the aromatic heterocyclic compound comprises an oxazole compound, a thiazole compound and an imidazole compound.
7. Use according to claim 6, characterized in that: the aromatic heterocyclic compound comprises an oxazole compound.
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