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CN-122010823-A - Synthesis method of 4-mercaptoethylpyridine compound

CN122010823ACN 122010823 ACN122010823 ACN 122010823ACN-122010823-A

Abstract

The invention provides a method for synthesizing a 4-mercaptoethylpyridine compound, which takes 4-vinylpyridine and potassium sulfide as raw materials to obtain a target product 4-mercaptoethylpyridine under an acidic condition. The reaction method has the advantages of cheap and easily obtained starting materials, high yield and simple method, and has high industrial application value.

Inventors

  • HU XIANGPING
  • Chen Xiushuai

Assignees

  • 中国科学院大连化学物理研究所

Dates

Publication Date
20260512
Application Date
20241111

Claims (8)

  1. 1. A process for synthesizing 4-mercaptoethylpyridine includes such steps as reaction of 4-vinyl pyridine with potassium sulfide under acidic condition, regulating pH value to 7-14 (preferably 8-12, more preferably 9-10) with alkali, and distillation.
  2. 2. The method according to claim 1, wherein the 4-mercaptoethylpyridine compound has the following structure:
  3. 3. the synthesis method according to claim 1 or 2, wherein the reaction equation is shown as:
  4. 4. The synthesis method according to claim 1, wherein the reaction is carried out in a solvent selected from at least one or more of water, toluene, benzene, methanol, ethanol, isopropanol, butanol, methylene chloride, ethylene dichloride, carbon tetrachloride, ethyl acetate, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide, and N, N-dimethylformamide; one or more of the above alcohol compounds are preferable, and methanol is more preferable.
  5. 5. The synthesis method according to claim 1, wherein the acid is one or more selected from the group consisting of p-toluenesulfonic acid, benzenesulfonic acid, benzoic acid, acetic acid, oxalic acid, hydrochloric acid, sulfuric acid and nitric acid, preferably one or more selected from the group consisting of benzoic acid and hydrochloric acid.
  6. 6. The synthesis according to claim 1,4 or 5, wherein the molar ratio of 4-vinylpyridine to potassium sulphide is 1:1-20, preferably 1:1-10, more preferably 1:1-5; The molar ratio of 4-vinylpyridine to acid is from 1:1 to 10, preferably from 1:1 to 8, more preferably from 1:1 to 5; the reaction solvent is used in an amount of 1 to 50mL, preferably 1 to 10mL, per millimole of 4-vinylpyridine.
  7. 7. A synthesis process according to claim 1, wherein the reaction temperature is from 25℃to 180℃and preferably from 50℃to 120℃and more preferably from 50℃to 100 ℃. The reaction time is 1 to 24 hours, preferably 5 to 15 hours, more preferably 5 to 12 hours.
  8. 8. The method for synthesizing the polypeptide according to any one of claims 1 to 7, wherein the method is specifically as follows: Adding 4-vinyl pyridine, potassium sulfide and a reaction solvent into a reaction bottle according to a proportion, adding acid, raising the temperature to 50-180 ℃, reacting for 1-24 hours, cooling, filtering, regulating the pH value of the filtrate by using alkaline water (regulating the pH value to 7-14, preferably 8-12, more preferably 9-10), removing the water layer, distilling the solvent from the organic layer under reduced pressure, and continuously distilling the product 4-mercaptoethylpyridine under reduced pressure.

Description

Synthesis method of 4-mercaptoethylpyridine compound Technical Field The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of a 4-mercaptoethylpyridine compound. Background 4-Mercaptoethylpyridine is a chemical product with high added value, can be used for synthesizing bisphenol A and other many fine organic chemical intermediates, and has wide application in the fields of high polymer materials, surfactants, medicines, pesticides and the like. The production process of 4-mercaptoethylpyridine mainly has two routes at present, wherein the first route is that 4-vinyl pyridine reacts with thiourea under the acidic condition, and then is neutralized by alkali to obtain the target product 4-mercaptoethylpyridine [ CN1206220C ], the reaction yield of the route reaches 80 percent at most. The second route is that 4-vinyl pyridine and hydrogen sulfide generate 4-mercaptoethylpyridine [ CN1283627C ] under the catalysis of alkali, the reaction yield of the route reaches 95%, although the yield is good, the taste of the hydrogen sulfide gas is bad, a pressure container is needed in the reaction process, the potential safety hazard of the reaction is increased, and the reaction cost is indirectly improved. In order to enrich the synthesis method of 4-mercaptoethylpyridine, the method for synthesizing the 4-mercaptoethylpyridine compound under the acidic condition can greatly improve the yield of the 4-mercaptoethylpyridine, improve the production efficiency and is environment-friendly. Disclosure of Invention The invention aims to provide a synthesis method of a 4-mercaptoethylpyridine compound, which has the advantages of simple operation, easily available raw materials, high reaction activity, great improvement of production efficiency, reduction of reaction cost and high industrial application value. The invention provides a method for synthesizing a 4-mercaptoethylpyridine compound, which comprises the specific steps of adding 4-vinylpyridine, potassium sulfide and a reaction solvent into a reaction bottle according to a proportion, then adding acid, raising the temperature to 50-180 ℃, reacting for 1-24 hours, cooling, filtering, regulating the pH value of filtrate by using alkaline water, removing a water layer, distilling an organic layer under reduced pressure to remove the solvent, and continuously distilling the product 4-mercaptoethylpyridine under reduced pressure. The acid is selected from one or more of p-toluenesulfonic acid, benzenesulfonic acid, benzoic acid, acetic acid, oxalic acid, hydrochloric acid, sulfuric acid, and nitric acid, preferably benzoic acid and hydrochloric acid. The reaction solvent is at least one selected from water, toluene, benzene, methanol, ethanol, isopropanol, butanol, dichloromethane, dichloroethane, carbon tetrachloride, ethyl acetate, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl sulfoxide or N, N-dimethylformamide. Alcohols are preferred, and methanol is more preferred. The molar ratio of 4-vinyl pyridine to potassium sulfide is 1-20:1, preferably 1-10:1, more preferably 1-5:1; The molar ratio of 4-vinylpyridine to acid is from 1:1 to 10, preferably from 1:1 to 8, more preferably from 1:1 to 5; The reaction conditions are as follows: the reaction temperature is 25 ℃ to 180 ℃, preferably 50 ℃ to 120 ℃, more preferably 50 ℃ to 100 ℃; The reaction time is 1 to 24 hours, preferably 5 to 15 hours, more preferably 5 to 12 hours. The reaction method has the advantages of cheap and easily obtained starting materials, good yield, high purity, high efficiency and simple method, and has high industrial application value. The invention has the following advantages: 1. The starting materials are readily available and inexpensive. 2. The reaction condition is mild, the yield is high, and the efficiency is high. 3. The method greatly reduces the reaction cost, is environment-friendly and green, and is suitable for industrial production. Drawings FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 4-mercaptoethylpyridine prepared in example 1; FIG. 2 is a nuclear magnetic resonance carbon spectrum of 4-mercaptoethylpyridine prepared in example 1. Detailed Description The following examples further illustrate the invention, but are not intended to limit it. Nuclear magnetic resonance was measured by Bruker400 Nuclear magnetic resonance, and gas chromatography was Agilent 7820A. Example 1 10.5G (0.1 mol) of 4-vinylpyridine and 11.26g (0.1 mol) of potassium sulphide, 100mL of methylene chloride are added into a reaction bottle, 17.2g (0.1 mol) of p-toluenesulfonic acid is then added, the temperature is raised to 50 ℃, the reaction is carried out for 5 hours, the reaction is cooled to room temperature, solid residues are removed by filtration, the pH of the filtrate is adjusted to 9-10 by using 2mol/L NaOH aqueous solution, then the liquid is separated, the aqueous layer is extracted by 20mL of x 3 methylene chlo