CN112500324B - Method for preparing thioamide compound - Google Patents
Method for preparing thioamide compound Download PDFInfo
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- CN112500324B CN112500324B CN202011464692.7A CN202011464692A CN112500324B CN 112500324 B CN112500324 B CN 112500324B CN 202011464692 A CN202011464692 A CN 202011464692A CN 112500324 B CN112500324 B CN 112500324B
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- C07—ORGANIC CHEMISTRY
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- C07C327/00—Thiocarboxylic acids
- C07C327/38—Amides of thiocarboxylic acids
- C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/44—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
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- C07C327/40—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/42—Amides of thiocarboxylic acids having carbon atoms of thiocarboxamide groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of a saturated carbon skeleton
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/83—Thioacids; Thioesters; Thioamides; Thioimides
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/194—Radicals derived from thio- or thiono carboxylic acids
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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 to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom 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 to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses a method for preparing thioamide compounds, which comprises the following steps: under the protection of inert gas, taking carboxylic ester as a substrate, sublimed sulfur as a sulfur source, alkali as a catalyst, formamide as a solvent and an amine source, and stirring to react for 4-8 hours at the reaction temperature of 60-100 ℃; and carrying out post-treatment on the reaction product to obtain the thioamide compound. The invention synthesizes thioamide compounds by a three-component one-pot method of carboxylic ester, sublimed sulfur and formamide; the method has the technical advantages of mild and safe operation conditions, short reaction time, simple process, simple and convenient operation, no need of special instruments, high product yield and the like.
Description
Technical Field
The invention relates to a synthetic method of an organic compound, in particular to the synthesis of a drug intermediate containing a thioamide structural unit, belonging to the field of organic synthesis.
Background
The thioamide structure is an important structural unit in a C ═ S double-bond compound, widely exists in a drug molecule, and has strong pharmaceutical activity; meanwhile, it is one of the most important precursors for constructing various sulfur-containing heterocycles (such as thiazole, thiazoline, thiazolone and the like) (0rg. Lett.2016, 18, 356.).
The earliest method for the synthesis of thioamides was the sulfurization of carboxamides by means of amides and lawson's reagent or phosphorus pentasulfide (chem.commun.2009, 46, 7122.); this method has the following disadvantages: the lawson reagent or the sulfur and phosphorus reagent used is unstable, the price is expensive, the atom economy is low, the odor is large, and the method is not friendly to the environment.
In recent years, the Willgerodt-Kindler reaction has been increasingly used for producing thioamide compounds, which are synthesized using aryl aldehydes, aryl/alkyl ketones, aryl acetylenes, benzylamines, aryl acetic acids, and the like as substrates (org. lett.2009,11,3064.). Although the method improves the atom utilization rate and the step economy of the reaction, the universality of the substrate is not wide, the reaction conditions of part of the substrate are harsh, the reaction temperature is up to 320 ℃, many raw materials are not easy to obtain, and the practicability of the method is limited by the use of the organic solvent.
Disclosure of Invention
The invention aims to solve the problem of providing a method for preparing thioamide compounds by using carboxylic ester, sublimed sulfur and formamide as reaction raw materials, which has simple process and is green and environment-friendly.
In order to solve the above technical problems, the present invention provides a method for preparing thioamide compounds, comprising:
1) under the protection of inert gas, taking carboxylic ester as a substrate, sublimed sulfur as a sulfur source, alkali (cesium metal alkali) as a catalyst, formamide as a solvent and an amine source, and stirring to react for 4-8 hours at the reaction temperature of 60-100 ℃;
the molar ratio of the carboxylic ester to the sublimed sulfur is 1: 1.5-2.0, and the molar ratio of the carboxylic ester to the alkali is 1: 0.25-0.75;
2) and carrying out post-treatment on the reaction product obtained in the step 1) to obtain the thioamide compound.
As an improvement of the process for producing thioamide compounds of the present invention:
carboxylic acid ester
The formamide is
the-Ar is aryl or substituted aryl;
the-Alkyl is any one of Alkyl, cycloalkyl, epoxyalkyl, substituted Alkyl and alkenyl;
said-R1Is any one of hydrogen radical, methyl and ethyl;
said-R2，-R3Is any one of hydrogen radical, methyl, ethyl, piperidyl and morpholinyl.
As a further improvement of the process for preparing thioamide compounds of the present invention:
the cesium metal base is cesium carbonate, cesium hydroxide or cesium acetate.
As a further improvement of the process for preparing thioamide compounds of the present invention:
the ratio of the volume of formamide to the weight of carboxylate is 5-10 mL/g.
As a further improvement of the process for preparing thioamide compounds of the present invention:
the post-treatment of the step 2) comprises the following steps:
after the reaction is finished, adding water (deionized water) into the reaction product obtained in the step 1) to quench the reaction, extracting with ethyl acetate (extracting with ethyl acetate for three times), washing the organic phase with saturated saline solution (washing for three times), drying the organic phase with anhydrous sodium sulfate, filtering, concentrating the filtrate (removing the solvent, namely ethyl acetate by rotary evaporation) to form a residue, carrying out column chromatography separation on the residue through a silica gel column, collecting an effluent containing a product (target product), and carrying out rotary evaporation on the collected effluent (removing the solvent by rotating an evaporator) to obtain the product (target product).
Description of the drawings: when the reaction solution is quenched, the volume ratio of water to formamide is 1: 1; the volume ratio of ethyl acetate to formamide is 1:1 in each extraction, and the total amount of saturated saline solution is equal to the total amount of ethyl acetate.
The reaction equation of the present invention is as follows:
the method comprises the following specific steps:
under the protection of inert gas (such as nitrogen), adding carboxylic ester, 1.5-2.0 molar equivalent of sublimed sulfur and 0.25-0.75 molar equivalent of alkali into formamide in sequence, and stirring and reacting for 4-8 hours at the reaction temperature of 60-100 ℃. After the reaction was completed, the reaction solution was quenched by adding water (deionized water) having an equal volume to formamide to the obtained reaction solution, followed by extraction three times with ethyl acetate having a volume of 3 times that of formamide, washing the organic phase three times with saturated saline having an equal volume to ethyl acetate, drying the organic phase with anhydrous sodium sulfate, and then filtration. And removing the solvent from the filtrate by using a rotary evaporator to obtain a residue, carrying out column chromatography separation on the residue through a silica gel column, collecting effluent containing the target product, combining the effluent, and removing the solvent by rotating the effluent through the rotary evaporator to obtain the target product.
The preparation method of the thioamide compound has the following technical advantages:
1. the raw material carboxylate (such as benzyl formate) is cheap and easy to obtain, the conversion rate is high, and the production cost can be reduced; the formamide is an amine source and also serves as a solvent, so that the influence caused by solvent doping can be effectively avoided; the sublimed sulfur is adopted as a sulfur source, so that the defects of an organic sulfur source can be overcome, and the atom economy is greatly improved.
2. The cesium metal alkali is used as the catalyst, so that the alkaline environment can be provided, the generation of the thioamide compound can be effectively catalyzed, the reaction temperature is reduced, and the energy cost is saved; meanwhile, a one-pot method is adopted, the intermediate product does not need to be separated, the target product can be directly obtained only by stirring and reacting under normal pressure, the process is greatly simplified, the operation is simple, the safety is high, the equipment investment is small, and the method is suitable for industrial production.
3. The method has the advantages of less three wastes generated in the reaction process, environmental protection and health guarantee of operators; in addition, a series of thioamide compounds can be prepared by the method, so that the method has stronger substrate universality.
4. The technical process is simple, high in yield, less in pollution, safe, environment-friendly, green and mild.
In conclusion, the thioamide compound is synthesized by a three-component one-pot method of carboxylic ester, sublimed sulfur and formamide; the method has the advantages of mild and safe operation conditions, short reaction time, simple process, simple and convenient operation, no need of using special instruments, high product yield and the like. The invention is applicable to both aromatic and aliphatic.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The starting materials are commercially available from the open literature unless otherwise specified.
In the following cases: the petroleum ether used in column chromatography separation is 60-90.
Embodiment 1, a method for preparing thioamide compounds, using benzyl formate as raw material:
benzyl formate (0.53g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), and cesium carbonate (0.32g, 1.0mmol) were added to 2.7mL of formamide under nitrogen, and the reaction was stirred at 80 ℃ for 4 hours.
After the reaction, 2.7mL of deionized water was added to the obtained reaction solution to quench the reaction solution, followed by extraction with ethyl acetate (2.7mL × 3) to obtain an aqueous phase and an organic phase, respectively, and then the organic phase was washed with saturated saline (2.7mL × 3), dried with anhydrous sodium sulfate, filtered (to remove sodium sulfate), concentrated by rotary evaporation (to remove ethyl acetate), purified by column chromatography on silica gel (100-200 mesh), and eluted with a mixture of ethyl acetate/petroleum ether (1:12 volume ratio) as an eluent in an amount of 300mL, and all the eluents were collected and subjected to rotary evaporation concentration treatment; 0.38g of a pale yellow solid was obtained, which was N, N-dimethylthiobenzamide by NMR, in a yield of 70.6%.
Embodiment 2, a method for preparing thioamide compounds, benzyl formate is used as raw material:
benzyl formate (0.53g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), and cesium carbonate (0.44g, 1.4mmol) were added to 4.2mL of N, N-dimethylformamide under nitrogen, and the reaction was stirred at 60 ℃ for 8 hours.
After the reaction is finished, adding 4.2mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (4.2mL multiplied by 3) to obtain an aqueous phase and an organic phase respectively, then washing the organic phase with saturated saline (4.2mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:15 volume ratio) as an eluent, wherein the dosage of the eluent is 350mL, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.55g of pale yellow solid is obtained, which is N, N-dimethyl-thiobenzamide by NMR detection, and the yield is 85.8%.
Embodiment 3, a method for preparing thioamide compounds, using benzyl acetate as raw material:
benzyl acetate (0.59g, 3.9mmol), sublimed sulfur (0.20g, 6.2mmol), and cesium hydroxide (0.26g, 1.8mmol) were added to 4.1mL of N-methylformamide under nitrogen, and the reaction was stirred at 70 ℃ for 7 hours.
After the reaction is finished, adding 4.1mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (4.1mL multiplied by 3) to obtain an aqueous phase and an organic phase respectively, then washing the organic phase with saturated saline (4.1mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:15 volume ratio) as an eluent, wherein the dosage of the eluent is 350mL, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.41g of a pale yellow solid was obtained, which was N-methylthiobenzamide by NMR, in a yield of 70.3%.
Embodiment 4, a method for preparing thioamide compounds, using benzyl acetate as raw material:
benzyl acetate (0.59g, 3.9mmol), sublimed sulfur (0.20g, 6.2mmol), and cesium hydroxide (0.44g, 2.9mmol) were added to 5.3mL of N, N-diethylformamide under nitrogen, and the reaction was stirred at 80 ℃ for 6 hours.
After the reaction, adding 5.3mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5.3mL × 3) to obtain an aqueous phase and an organic phase respectively, washing the organic phase with saturated saline (5.3mL × 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:20 volume ratio) as an eluent, wherein the dosage of the eluent is 400mL, collecting all the eluents, and carrying out rotary evaporation concentration treatment; 0.46g of a brown yellow solid was obtained, which was N, N-diethylthiobenzamide by NMR, in a yield of 60.5%.
Embodiment 5, a method for preparing thioamide compounds, using benzyl propionate as raw material:
benzyl propionate (0.64g, 3.9mmol), sublimed sulfur (0.22g, 7.0mmol), and cesium acetate (0.48g, 2.5mmol) were added to 6.4mL of N-formylmorpholine under nitrogen protection, and the reaction was stirred at 100 ℃ for 4 hours.
After the reaction is finished, adding 6.4mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (6.4mL multiplied by 3) to obtain an aqueous phase and an organic phase respectively, then washing the organic phase with saturated saline (6.4mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:10 volume ratio) as an eluent, wherein the dosage of the eluent is 250mL, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.63g of a bright yellow solid is obtained, which is detected by NMR as thiomorpholine in a yield of 78.2%.
Embodiment 6, a method for preparing thioamide compounds, using benzyl propionate as raw material:
benzyl propionate (0.64g, 3.9mmol), sublimed sulfur (0.22g, 7.0mmol), and cesium acetate (0.48g, 2.5mmol) were added to 3.8mL of N-formylpiperidine under nitrogen protection, and the reaction was stirred at 90 ℃ for 5 hours.
After the reaction is finished, adding 3.8mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (3.8mL multiplied by 3) to obtain an aqueous phase and an organic phase respectively, then washing the organic phase with saturated saline (3.8mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:10 volume ratio) as an eluent, wherein the dosage of the eluent is 250mL, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.60g of a tan solid is obtained, which is detected by NMR to be N-thiobenzylpiperidine with a yield of 75.3%.
Embodiment 7, a method for preparing thioamide compounds, using 4-chlorobenzyl formate as raw material:
4-chlorobenzyl formate (0.66g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:15 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.66g of a yellow solid was obtained, which was detected by NMR to be 4-chloro-N, N-dimethylthiobenzamide, in a yield of 84.3%.
Embodiment 8, a method for preparing thioamide compounds, using 3-fluorobenzyl formate as raw material:
3-Fluorobenzyl formate (0.60g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:15 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.47g of a yellow solid was obtained, which was 3-fluoro-N, N-dimethylthiobenzamide by NMR, in a yield of 65.6%.
Embodiment 9, a method for preparing thioamide compounds, using 4-methylbenzyl formate as raw material:
4-methylbenzyl formate (0.59g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under a nitrogen atmosphere, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:15 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.55g of pale yellow solid is obtained, which is detected to be 4-methyl-N, N-dimethylthiobenzamide by NMR, and the yield is 78.3%.
Embodiment 10, a method for preparing thioamide compounds, using 3-methoxybenzyl formate as a raw material:
under nitrogen protection, 3-methoxybenzyl formate (0.65g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:15 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.53g of a bright yellow solid was obtained, which was 3-methoxy-N, N-dimethylthiobenzamide by NMR, in a yield of 70.1%.
Embodiment 11, a method for preparing thioamide compounds, using 4-trifluoromethyl benzyl formate as raw material:
4-Trifluoromethylbenzyl formate (0.80g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:20 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.73g of a yellow solid was obtained, which was detected by NMR to be 4-trifluoromethyl-N, N-dimethylthiobenzamide, and the yield was 80.2%.
Embodiment 12, a method for preparing thioamide compounds, using 3-aminobenzyl formate as a raw material:
3-aminobenzyl formate (0.59g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline solution (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:4 volume ratio) as an eluent, collecting all eluent, and carrying out rotary evaporation concentration treatment, wherein the dosage of the eluent is 180 mL; 0.40g of a yellow solid was obtained, which was found to be 3-amino-N, N-dimethylthiobenzamide by NMR, in 55.6% yield.
Embodiment 13, a method for preparing thioamide compounds, using 4-hydroxybenzyl formate as raw material:
4-hydroxybenzyl formate (0.59g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:4 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment, wherein the dosage of the eluent is 190 mL; 0.57g of a yellow solid was obtained, which was found to be 4-hydroxy-N, N-dimethylthiobenzamide by NMR, in a yield of 80.5%.
Embodiment 14, a method for preparing thioamide compounds, using 3-cyanobenzyl formate as raw material:
under nitrogen, 3-cyanobenzyl formate (0.63g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:3 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.33g of a brown yellow solid was obtained, which was 3-cyano-N, N-dimethylthiobenzamide by NMR, in 44.6% yield.
Embodiment 15, a method for preparing thioamide compounds, using 4-nitrobenzyl formate as raw material:
4-nitrobenzyl formate (0.71g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline solution (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:4 volume ratio) as an eluent, collecting all eluates, and carrying out rotary evaporation concentration treatment, wherein the dosage of the eluent is 170 mL; 0.30g of a brown yellow solid was obtained, which was detected by NMR to be 4-nitro-N, N-dimethylthiobenzamide, and the yield was 35.8%.
Embodiment 16, a method for preparing thioamide compounds, using formic acid-1-naphthyl ester as raw material:
1-naphthyl formate (0.73g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:8 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.51g of a dark yellow solid is obtained, which is N, N-dimethyl-1-thionaphthamide by NMR, in a yield of 60.3%.
Embodiment 17, a method for preparing thioamide compounds, using 3-pyridine formate as raw material:
3-pyridine formate (0.53g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:2 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.53g of a yellow oil was obtained, which was N, N-dimethyl-3-thiopyridinecarboxamide as determined by NMR, in a yield of 80.2%.
Embodiment 18, a method for preparing thioamide compounds, using formate-2-thiophene ester as raw material:
under nitrogen protection, formic acid-2-thiophene ester (0.56g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:7 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.43g of a yellow solid is obtained, which is detected by NMR to be N, N-dimethyl-2-thiothiophenecarboxamide with a yield of 65.5%.
Embodiment 19, a method for preparing thioamide compounds, using 3-furancarboxylate as raw material:
formic acid-3-furan ester (0.50g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:10 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; 0.50g of a brown-yellow oily substance was obtained, which was N, N-dimethyl-3-thiofurancarboxamide by NMR, and the yield was 80.5%.
Example 20, a method for preparing thioamide compounds, using n-butyl formate as a raw material:
under nitrogen protection, N-butyl formate (0.40g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), and cesium carbonate (0.32g, 1.0mmol) were added to 4mL of N, N-dimethylformamide, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 4mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (4mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (4mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:15 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; this gave 0.43g of a pale yellow oil, which was N, N-dimethyl-N-butane thioamide by NMR, in 83.3% yield.
Embodiment 21, a method for preparing thioamide compounds, using isobutyl formate as raw material:
isobutyl formate (0.40g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 4mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 4mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (4mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (4mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:15 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; this gave 0.39g of a pale yellow oil which was N, N, 2-trimethylpropane thioamide by NMR in 75.9% yield.
Example 22, a method for preparing thioamide compounds using cyclohexylmethylacetate as a raw material:
cyclohexylmethyl acetate (0.61g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline solution (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:10 volume ratio) as an eluent, collecting all eluent, and carrying out rotary evaporation concentration treatment, wherein the dosage of the eluent is 200 mL; this gave 0.47g of a yellow oil, which was N, N-dimethylcyclohexanemethylthioamide by NMR, in a yield of 70.2%.
Example 23, a method for preparing a thioamide compound using tetrahydrofurfuryl alcohol acetate as a raw material:
tetrahydrofurfuryl alcohol acetate (0.56g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:10 volume ratio) as an eluent, collecting all the eluents, and carrying out rotary evaporation concentration treatment; 0.41g of yellow oil was obtained, which was N, N-dimethyloxolane-2-thiocarboxamide by NMR, in a yield of 65.5%.
Embodiment 24, a method for preparing thioamide compounds, taking lauryl acetate as raw material:
lauryl acetate (0.69g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol) and cesium carbonate (0.32g, 1.0mmol) were added to 5mL of N, N-dimethylformamide under nitrogen protection, and the reaction was stirred at 80 ℃ for 8 hours.
After the reaction is finished, adding 5mL of deionized water into the obtained reaction solution to quench the reaction solution, extracting with ethyl acetate (5mL multiplied by 3) to respectively obtain a water phase and an organic phase, washing the organic phase with saturated saline (5mL multiplied by 3), drying with anhydrous sodium sulfate, filtering, carrying out rotary evaporation concentration, purifying by silica gel (100-200 meshes) column chromatography, using a mixed solution of ethyl acetate/petroleum ether (1:10 volume ratio) as an eluent, collecting all the eluent, and carrying out rotary evaporation concentration treatment; this gave 0.51g of a yellow solid which was (E) -N, N-dimethyl-3-phenylprop-2-enesulfamide by NMR in 68.9% yield.
Comparative example 1, cesium carbonate as a catalyst in example 2 was changed as described in the following table 1, and the molar amount was kept constant, and the rest was the same as in example 2.
The final results are shown in table 1 below.
TABLE 1
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (3)
1. A process for the preparation of thioamide compounds, characterized in that:
1) under the protection of inert gas, taking carboxylic ester as a substrate, sublimed sulfur as a sulfur source, alkali as a catalyst, formamide as a solvent and an amine source, and stirring to react for 4-8 hours at the reaction temperature of 60-100 ℃;
the molar ratio of the carboxylic ester to the sublimed sulfur is 1: 1.5-2.0, and the molar ratio of the carboxylic ester to the alkali is 1: 0.25-0.75;
carboxylic acid ester
，
The formamide is
，
Ar is aryl or substituted aryl;
the Alkyl is any one of Alkyl, cycloalkyl, epoxyalkyl, substituted Alkyl and alkenyl;
the R is1Any one of hydrogen radical, methyl and ethyl;
the R is2， R3Any one of hydrogen radical, methyl, ethyl, piperidyl and morpholinyl;
the alkali is cesium carbonate, cesium hydroxide or cesium acetate;
2) carrying out post-treatment on the reaction product obtained in the step 1) to obtain a thioamide compound;
the thioamide compound is as follows:
。
2. the process for producing thioamide compounds as claimed in claim 1, wherein:
the ratio of the volume of formamide to the weight of carboxylate is 5-10 mL/g.
3. The process for producing thioamide compounds as claimed in claim 1 or 2, wherein:
the post-treatment of the step 2) comprises the following steps:
after the reaction is finished, adding water into the reaction product obtained in the step 1) for quenching reaction, extracting by using ethyl acetate, washing an organic phase by using saturated saline solution, drying the organic phase by using anhydrous sodium sulfate, filtering, concentrating a filtrate to form a residue, carrying out column chromatography separation on the residue by using a silica gel column, collecting an effluent containing a product, and carrying out rotary evaporation on the collected effluent to obtain the product.
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| WO2011156220A1 (en) * | 2010-06-08 | 2011-12-15 | Merck Sharp & Dohme Corp. | Novel prolylcarboxypeptidase inhibitors |
| WO2017011232A1 (en) * | 2015-07-10 | 2017-01-19 | Uop Llc | Synthesis of non-cyclic amide and thioamide based ionic liquids |
| CN110590627A (en) * | 2019-10-11 | 2019-12-20 | 温州大学 | Synthesis method of 3-aryl thiopropionamide derivative |
| CN111704575A (en) * | 2020-07-08 | 2020-09-25 | 衡阳师范学院 | Method for synthesizing quinoline-2-thiocarbamide compound under conditions of no catalyst and no additive |
| WO2020219871A1 (en) * | 2019-04-26 | 2020-10-29 | Celgene Corporation | Heterocyclic compounds and their use for treatment of helminthic infections and diseases |
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| WO2011156220A1 (en) * | 2010-06-08 | 2011-12-15 | Merck Sharp & Dohme Corp. | Novel prolylcarboxypeptidase inhibitors |
| WO2017011232A1 (en) * | 2015-07-10 | 2017-01-19 | Uop Llc | Synthesis of non-cyclic amide and thioamide based ionic liquids |
| WO2020219871A1 (en) * | 2019-04-26 | 2020-10-29 | Celgene Corporation | Heterocyclic compounds and their use for treatment of helminthic infections and diseases |
| CN110590627A (en) * | 2019-10-11 | 2019-12-20 | 温州大学 | Synthesis method of 3-aryl thiopropionamide derivative |
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