CN102249963A

CN102249963A - Method for synthesizing 4-methyl-2-amino thiophenol

Info

Publication number: CN102249963A
Application number: CN2011101277766A
Authority: CN
Inventors: 湛雪辉; 李朝辉; 周随安; 姜红宇; 曹芬; 李侠
Original assignee: Changsha University of Science and Technology
Current assignee: Changsha University of Science and Technology
Priority date: 2011-05-18
Filing date: 2011-05-18
Publication date: 2011-11-23

Abstract

The invention relates to a method for synthesizing 4-methyl-2-amino thiophenol. The 4-methyl-2-amino thiophenol is a chelant. The method comprises the following steps of: pre-reacting ammonium salt, a reducing agent and acid for a period of time in a mixed solvent of alcohol and water, and adding a reaction raw material of 4-methyl-2-nitro thiophenol to obtain the 4-methyl-2-amino thiophenol. The synthesis method has the advantage of simple process; and the product is easy to separate and purify and the yield is high.

Description

The synthetic method of the amino thiophenol of a kind of 4-methyl-2-

Technical field

The present invention relates to the synthetic method of the amino thiophenol of a kind of 4-methyl-2-, belong to the technical field that fine chemical product is produced.

Background technology

The complex compound that contains a large amount of cobalts in the waste and old lithium ion battery, mainly the form with cobalt acid lithium exists, if do not recycle, can cause very big harm to environment, wherein cobalt causes red blood cell proliferation disease easily, causes the people intoxicating phenomenons such as poor appetite, nausea,vomiting,diarrhea, hotness to occur.The battery of a heavily about 40g, the about 6g of containing metal cobalt calculates by scrapping 100,000,000 lithium ion batteries every year, and the about 600t of wherein recuperable cobalt is worth about 200,000,000 yuan.Therefore, the cobalt that reclaims in the waste and old lithium ion battery not only has the effect of protecting environment, also has huge economic benefits.

At present, the recovery method of cobalt in waste lithium ion batteries mainly contains the precipitator method, electroreduction method and organic solvent extractionprocess, and it reclaims, and technical process is long, energy consumption is high, efficient is low.The chelating method because of in the heavy metal removal process, produce effect, advantage such as the recyclable recycling of sequestrant obtained widespread use in medicine refinement, mineral floating, wastewater treatment, still, still rarely found at the sequestrant that reclaims the precious metal cobalt.Therefore, the sequestrant of research energy efficient low-consume recovery precious metal cobalt has great importance.

Summary of the invention

The objective of the invention is to be to provide a kind of 4-methyl-2-synthetic method of amino thiophenol.This material is based on can be effectively in conjunction with Co to sulfydryl in the methylbenzene thiophenol ²⁺Performance, a kind of new sequestrant that on the basis of 4-methyl-2-nitro thiophenol, designs, its synthetic method craft is simple, product is easy to separate to purify, the yield height.

The present invention is achieved by the following technical solutions.With 4-methyl-2-nitro thiophenol is the technological process of the synthetic 4-methyl of raw material-amino thiophenol of 2-, it is characterized in that, add ammonium salt, reductive agent and acid in the mixed solvent (alcohol is 1～3 with the volume ratio scope of water) of alcohol and water, wherein alcohol can be methyl alcohol, ethanol or butanols; Ammonium salt is an ionogen, can be ammonium chloride, ammonium sulfate, ammonium nitrate or ammonium phosphate; Reductive agent can be inorganicss such as zinc, iron, tin, also can be organism such as acetoxime, Diacetylmonoxime, cyclohexanone-oxime; Acid provides proton hydrogen, can be formic acid, acetic acid, hydrochloric acid, sulfuric acid or phosphoric acid, and its amount of substance is 0.05～0.15 times of reductive agent amount of substance.Under 50～80 ℃ of temperature of reaction, after reductive agent is lost 0.25～1.5h in advance, add 4-methyl-2-nitro thiophenol, its amount of substance is 0.1～0.5 times of reductive agent amount of substance, react 1～4h down for 60～100 ℃ in temperature of reaction again, making wherein, the nitro Restore All is amino.After the reaction solution cooling, be poured in the distilled water, separate out white precipitate, filter, precipitate three times, precipitate three times with distilled water wash again with corresponding weak acid scrubbing in the reaction system.Get 4-methyl-2-amino thiophenol for-40～60 ℃, pressure for lyophilize 0.5～2h under the-0.8MPa in temperature.

The invention has the advantages that the synthetic method that a kind of new sequestrant is provided, its synthetic method is simple, and product is easy to separate purifies the reaction efficiency height.

Embodiment

In being housed, the 100ml there-necked flask of thermometer, electric mixer, condenser adds 9ml dehydrated alcohol, 6ml distilled water, 0.62g zinc powder, 0.1g ammonium chloride and 0.7ml Glacial acetic acid.After temperature of reaction is 70 ℃ of down pre-erosion 1h, add 0.4g 4-methyl-2-nitro thiophenol, react 3h again after being warmed up to 80 ℃.After having reacted, reaction solution poured into be cooled to room temperature in the beaker, add distilled water 20ml then, separate out white precipitate.With 1mol/L salt acid elution white precipitate three times, remove the zine ion in the precipitation, again with distilled water wash precipitation three times.Is-40～60 ℃, pressure for lyophilize 1h under the-0.8MPa with resultant white precipitate in temperature, obtains the amino thiophenol of 4-methyl-2-.

Claims

1. one kind is the method for the synthetic 4-methyl of raw material-amino thiophenol of 2-with 4-methyl-2-nitro thiophenol, it is characterized in that may further comprise the steps:

A adds ammonium salt, reductive agent and acid in the mixed solvent (alcohol is 1～3 with the volume ratio scope of water) of alcohol and water, wherein alcohol can be methyl alcohol, ethanol or butanols; Ammonium salt is an ionogen, can be ammonium chloride, ammonium sulfate, ammonium nitrate or ammonium phosphate; Reductive agent can be inorganicss such as zinc, iron, tin, also can be organism such as acetoxime, Diacetylmonoxime, cyclohexanone-oxime; Acid provides proton hydrogen, can be formic acid, acetic acid, hydrochloric acid, sulfuric acid or phosphoric acid, and its amount of substance is 0.05～0.15 times of reductive agent amount of substance;

B is under 50～80 ℃ of temperature of reaction, after reductive agent is lost 0.25～1.5h in advance, add 4-methyl-2-nitro thiophenol, its amount of substance is 0.1～0.5 times of reductive agent amount of substance, reacts 1～4h down for 60～100 ℃ in temperature of reaction again, and making wherein, the nitro Restore All is amino;

C, after the reaction solution cooling, be poured in the distilled water, separate out white precipitate, filter, with corresponding weak acid scrubbing precipitation in the reaction system three times,, get 4-methyl-2-amino thiophenol for-40～60 ℃, pressure for lyophilize 0.5～2h under the-0.8MPa in temperature more again with distilled water wash precipitation three times.