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Synthetic method of thioamide compound

A technology of thioamide and synthetic method, which is applied in the synthesis of organic compounds and the field of synthesis of pharmaceutical intermediates containing thioamide structural units, can solve the problems of low atom utilization, poor step economy, unfriendly environment, etc., and achieve improvement Effects of atom economy, short reaction time, and production cost reduction

Active Publication Date: 2021-03-19
QUZHOU RES INST OF ZHEJIANG UNIV +1
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These two types of methods are gradually replaced by new multi-component "one-pot" reactions due to the disadvantages of low atom utilization, poor step economy, unfriendly environment, and varying degrees of damage to the human body.
The preparation of thioamides by multi-component reaction is mainly based on the classic Willgerodt-Kindler reaction. Synthesis of thioamide compounds (Chem.Soc.Rev.2013, 42, 7870), although this type of method improves the atom utilization rate and step economy, the raw materials are more expensive and difficult to obtain; the conditions are harsh and the yield is lower The situation is still not improving and the substrates are limited to aromatic compounds

Method used

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  • Synthetic method of thioamide compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] Embodiment 1, a kind of synthetic method of thioamide compound, take iodopropane as raw material:

[0041] Under nitrogen protection, iodopropane (0.67g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), sodium hydroxide (0.47g, 11.7mmol) were added to 5mL N,N-dimethylformamide, and then Cuprous chloride (0.04 g, 0.39 mmol) and ethylenediaminetetraacetic acid (0.23 g, 0.78 mmol) were added, and the reaction was stirred at room temperature for 12 hours.

[0042] After the reaction was completed, 5 mL of deionized water was added to the resulting reaction liquid to quench the reaction liquid, followed by extraction with ethyl acetate (5 mL×3) to obtain an aqueous phase and an organic phase, respectively, and then saturated brine (5 mL×3) The organic phase was washed and dried with anhydrous sodium sulfate, filtered (to remove sodium sulfate), concentrated by rotary evaporation (to remove ethyl acetate), purified by silica gel (100-200 mesh) column chromatography, and purified w...

Embodiment 2

[0043] Embodiment 2, a kind of synthetic method of thioamide compound, take chlorooctane as raw material:

[0044] Under nitrogen protection, chlorooctane (0.58g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), sodium hydroxide (0.47g, 11.7mmol) were added to 5mL N,N-dimethylformamide, Then cuprous chloride (0.04g, 0.39mmol) and ethylenediaminetetraacetic acid (0.23g, 0.78mmol) were added, and the reaction was stirred for 10 hours at a reaction temperature of 40°C.

[0045]After the reaction was completed, 5 mL of deionized water was added to the resulting reaction liquid to quench the reaction liquid, followed by extraction with ethyl acetate (5 mL×3) to obtain an aqueous phase and an organic phase, respectively, and then saturated brine (5 mL×3) The organic phase was washed, dried with anhydrous sodium sulfate, filtered, concentrated by rotary evaporation, purified by silica gel (100-200 mesh) column chromatography, and eluted with a mixture of ethyl acetate / petroleum ether (1:8...

Embodiment 3

[0046] Embodiment 3, a kind of synthetic method of thioamide compound, take bromomethylcyclohexane as raw material:

[0047] Under nitrogen protection, bromomethylcyclohexane (0.69g, 3.9mmol), sublimed sulfur (0.25g, 7.8mmol), sodium hydroxide (0.47g, 11.7mmol) were added to 5mL N,N-dimethylformaldehyde Add cuprous chloride (0.04g, 0.39mmol) and ethylenediaminetetraacetic acid (0.23g, 0.78mmol) to the amide, and stir the reaction for 12 hours at a reaction temperature of 60°C.

[0048] After the reaction was completed, 5 mL of deionized water was added to the resulting reaction liquid to quench the reaction liquid, followed by extraction with ethyl acetate (5 mL×3) to obtain an aqueous phase and an organic phase, respectively, and then saturated brine (5 mL×3) The organic phase was washed, dried with anhydrous sodium sulfate, filtered, concentrated by rotary evaporation, purified by silica gel (100-200 mesh) column chromatography, and eluted with a mixture of ethyl acetate / pet...

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Abstract

The invention discloses a synthesis method of a thioamide compound, which comprises the following steps: under the protection of inert gas, by taking a halide as a substrate, sublimed sulfur as a sulfur source, a copper group metal complex formed by combining copper group metal salt and a ligand as a catalyst, alkali as an accelerant, formamide as a solvent and an amine source, reacting at room temperature to 60 DEG C to obtain the thioamide compound; stirring and reacting the abovef materials for 8-12 hours, and carrying out post-treatment on the reaction product to obtain the thioamide compound. According to the invention, the thioamide compound is synthesized by a three-component one-pot method of halide, sublimed sulfur and formamide; the method has the advantages of mild and safe operation conditions, short reaction time, simplicity and convenience in operation, high product yield and the like.

Description

technical field [0001] The invention relates to a method for synthesizing a class of organic compounds, in particular to the synthesis of a class of pharmaceutical intermediates containing thioamide structural units, and belongs to the field of organic synthesis. Background technique [0002] As an important class of organosulfur functional groups, thioamide fragments are ubiquitous organic structures in important biological and pharmaceutical molecules, such as chlorothionamide, hydroxymethylthiolactam cyclothiidine, N-cyclohexylethyl The base-ETAsV and so on all contain thioamide structure (J.Med.Chem.2011, 54.). In addition, thioamides are also widely used in the construction of many important sulfur-containing heterocycles, such as thiathiazole, thiazoline, thiazolone, etc. (Adv.Synth.Cata1.2017, 359, 4300.) [0003] There are two main categories of traditional methods for the synthesis of thioamides. The first type is to use Lawson's reagent or phosphorus pentasulfide...

Claims

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Application Information

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IPC IPC(8): C07C327/42C07C327/46C07C327/44C07C327/48C07D295/194C07D333/38C07D307/68
CPCC07C327/42C07C327/46C07C327/44C07C327/48C07D295/194C07D333/38C07D307/68C07C2601/14
Inventor 钱超靳浩阮建成周少东陈新志
Owner QUZHOU RES INST OF ZHEJIANG UNIV
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