Preparation method of 3,3',4,4'-tetraminodiphenyl sulfide

A technology of tetraamine diphenyl sulfide and dinitrobenzene, which is applied in the field of functional material technology and organic synthesis, and can solve the problems of many by-products, difficulty in industrialization, and complicated operation

Inactive Publication Date: 2014-12-03
BEIJING UNIV OF CHEM TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method has many by-products and requires complicated purification treatment
CN101774953A proposes that substituted benzenesulfenyl chloride reacts with substituted benzene in a chlorinated alkane solvent to generate substituted diphenyl sulfide. The operation of the whole process is complicated, and it is very difficult to realize industrialization
[0005] The present invention provides a 3,3', The preparation method of 4,4'-tetraamine diphenyl sulfide has not yet been published in the literature or patent reports

Method used

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  • Preparation method of 3,3',4,4'-tetraminodiphenyl sulfide
  • Preparation method of 3,3',4,4'-tetraminodiphenyl sulfide
  • Preparation method of 3,3',4,4'-tetraminodiphenyl sulfide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Step 1) Preparation of 4,4'-thiobis(2-nitroaniline)

[0026] Add 40mL of absolute ethanol and 2.7382g (0.0159mol) of 5-chloro-2-nitroaniline to a three-necked flask equipped with a thermometer, dropping funnel, and reflux condenser, stir well, and sulfide 4.85g (0.0119mol) Sodium was dissolved in 30mL of deionized water to make a solution of a certain concentration, and added dropwise to the flask, and after the addition was completed, stirred and reacted at 50°C for 5 hours. After the reaction was completed, the mixture was poured into water, and an orange precipitated solid (1) was precipitated. , filtered, washed and dried to obtain 1.64 g of 4,4'-thiobis(2-nitroaniline).

[0027] Step 2) Preparation of 3,3',4,4'-tetraaminodiphenylsulfide hydrochloride

[0028] 10.09g of stannous chloride dihydrate (SnCl 2 2H 2 O) join in the there-necked flask that 70mL concentrated hydrochloric acid is housed, stir, and the temperature in the flask is maintained on 40 ℃, wait fo...

Embodiment 2

[0032] Preparation of 3,3',4,4'-tetraaminodiphenylsulfide

[0033] Add 40mL of N,N-dimethylformamide (DMF) and 2.85g (0.02mol) of 4-chloro-o-diphenylamine into a three-necked flask equipped with a thermometer, dropping funnel, and reflux condenser and stir evenly. Mix 9.70 g (0.024mol) of sodium sulfide was dissolved in 30mL of deionized water to form a solution of a certain concentration, and was added dropwise to the flask. After the addition was completed, it was stirred and reacted at 50-80°C for 6 hours. After the reaction, the mixture was poured into water. A light pink solid was precipitated, which was filtered, washed and purified to obtain 3,3',4,4'-tetraaminodiphenyl sulfide.

Embodiment 3

[0035] Step 1) Preparation of 4,4'-thiobis(o-dinitrobenzene)

[0036] Add 50 mL of N,N-dimethylformamide (DMF), 2.47 g (0.01 mol) of 5-bromo-2-nitroaniline into a three-necked flask equipped with a thermometer, dropping funnel, and reflux condenser, and stir well , Dissolve 4.85g (0.012mol) of sodium sulfide in 35mL of N,N-dimethylformamide (DMF) to make a solution with a certain concentration, add it dropwise to the flask, and stir at 80°C for reaction After 2 hours, the mixture was poured into water after the reaction, and an orange precipitated solid was precipitated. After filtering, washing and drying, 1.64 g of 4,4'-thiobis(o-dinitrobenzene) was obtained.

[0037] Step 2) Preparation of 3,3',4,4'-tetraaminodiphenylsulfide hydrochloride

[0038]Add 1.04g of 4,4'-thiobis(o-dinitrobenzene), 20mL of ethanol and 0.15g of Pd / C catalyst into a 50mL three-necked flask, blow nitrogen gas, stir in an ice bath, and add 5mL of Hydrazine hydrate. React at 40°C for 7 hours, let sta...

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Abstract

The invention discloses a preparation method of 3,3',4,4'-tetraminodiphenyl sulfide. Orderly through a nucleophilic substitution reaction, a reduction reaction and a neutralization reaction, a desired product is produced from 5-halo-2-nitroaniline, 4-halo-2-nitroaniline or 4-halo-o-dinitrobenzene as a raw material. The preparation method comprises that the raw material and sodium sulfide undergo a nucleophilic substitution reaction to produce a dinitrodiamine intermediate product, then the dinitrodiamine intermediate product and a stoichiometric amount of stannous chloride undergo a reduction reaction to produce hydrochloride of tetramine, then the hydrochloride of tetramine undergoes a neutralization reaction under the action of a sodium hydroxide aqueous solution to produce a crude desired product, and the crude desired product is subjected to column chromatography-based separation purification to form 3,3',4,4'-tetraminodiphenyl sulfide, or comprises that 4-halo-o-diphenylamine as a raw material directly undergoes a nucleophilic substitution reaction to directly produce 3,3',4,4'-tetraminodiphenyl sulfide. The preparation method of 3,3',4,4'-tetraminodiphenyl sulfide has the characteristics of cheap and easily available raw material, short reaction time, simple and easy processes and high yield.

Description

technical field [0001] The invention belongs to the field of functional material technology and organic synthesis, and specifically relates to the preparation of 3,3',4,4'-tetraaminodiphenyl sulfide by a sodium sulfide method. Background technique [0002] Due to the variable valence of the S atom, sulfides can be oxidized to sulfoxides and sulfones by OOH radicals or OH radicals under aqueous or anhydrous conditions (Atmos.Environ.,2012,55:263-270; RSC Advances ,2012,2:6464-6477; J.Chem.Phys.,2013,138:1-4), so the introduction of S atoms into the polymer backbone can significantly improve the oxidation resistance of materials; in addition, the 3d of S atoms The orbital can also significantly reduce the energy of the system and increase the stability of the system. The participation of the 3d orbital in bonding also makes the conductive cation carrier have a high localization effect on the sulfur atom, improving the conductivity of the material; finally, the molecular struct...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C323/37C07C319/20C07C319/14
Inventor 汪中明徐燕燕韩克飞
Owner BEIJING UNIV OF CHEM TECH
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