The preparation method of p-aminophenyl-β-hydroxyethyl sulfide

Abstract

The invention discloses a p-aminophenyl-beta-hydroxyethyl sulfide preparation method comprising the steps that: (1) under the effect of a catalyst, sodium sulfide, sodium hydrosulfide and nitro chlorobenzene are mixed, such that nucleophilic substitution reaction, and nitro reduction reaction are carried out; and post-treatment is carried out, such that sodium p-aminothiophenol is obtained; (2) sodium p-aminothiophenol is subjected to a reaction with ethylene oxide, such that p-aminophenyl-beta-hydroxyethyl sulfide is obtained. According to the invention, a mixed solution of sodium sulfide and sodium hydrosulfide is used for replacing a polysulfide solution for carrying out the substitution and reduction reactions, such that the nucleophilic reagent SH<-> has high concentration at the beginning, and the substitution reaction can be smoothly carried out, side reaction can be inhibited, and yield can be improved. Ethylene oxide is used for replacing 2-chloroethanol in a condensation reaction with sodium p-aminothiophenol, such that production process is reduced, and production cost is reduced.

Description

technical field

[0001] The invention belongs to the field of preparation of dye intermediates, in particular to a preparation method of p-aminophenyl-β-hydroxyethyl sulfide. Background technique

[0002] Vinylsulfone-type reactive dyes (that is, domestic KN-type reactive dyes), with many varieties and complete chromatograms, are widely used in the dye industry. p-Aminophenyl-β-hydroxyethyl sulfide is an important component of vinylsulfone-type reactive dyes. intermediate. At present, it is mainly used for the synthesis of reactive blue 19 and its para-isomers. According to related reports, reactive blue 19 and its corresponding reactive group in the para-position of imino can be used as KN type reactive dyes (C.I. reactive blue 19 Research on the performance of its para-isomers - 1. Research on hydrolysis performance, Lu Rongwen, Li Huiping, Zhang Zhuxia, Gao Kunyu, Dyestuffs and Dyeing, 2006 No. 02), and compound use is more beneficial to improve the application performanc...

Examples

Embodiment 1

[0029] Add 240mL of water into a 500mL four-neck flask, add 95.8g of sodium sulfide (industrial product) and 59.5g of sodium hydrosulfide (industrial product) under stirring, and raise the temperature to 40-60°C. Continue to stir until the sodium sulfide and sodium hydrosulfide are completely dissolved, add 0.8 g of activated carbon, stir for half an hour to decolorize, and collect the filtrate by suction filtration for later use.

[0030] Add 200mL of water, 100g of p-nitrochlorobenzene, and 0.6g of N-methylpyrrolidone into a 1000mL four-neck flask, stir and heat to 92-96°C, then add the above-mentioned filtrate dropwise at this temperature, and drop it in about 1.5 hours. Finally, continue to stir and keep warm for 7 hours until the end of the reaction. After the reaction is over (the reaction solution is tested by HPLC: the HPLC content of p-aminothiophenate sodium is 90.5%, and the HPLC content of the by-product p-chloroaniline is 2.5%), the reaction device is changed to a...

Embodiment 2

[0033]Add 240mL of water into a 500mL four-necked flask, add 114.4g of sodium sulfide (industrial product) and 73.2g of sodium hydrosulfide (industrial product) under stirring, and raise the temperature to 40-60°C. Continue to stir until the sodium sulfide and sodium hydrosulfide are completely dissolved, add 0.8 g of activated carbon, stir for half an hour to decolorize, and collect the filtrate by suction filtration for later use.

[0034] Add 200mL of water, 100g of p-nitrochlorobenzene, and 0.9g of N-ethylpyrrolidone into a 1000mL four-neck flask, stir and heat to 100-105°C, then add the above-mentioned filtrate dropwise at this temperature, and drop it in about 1.5 hours. Finally, continue to stir and keep warm for 6 hours until the end of the reaction. After the reaction is over (the reaction solution is tested by HPLC: the HPLC content of p-aminothiophenate sodium is 91.0%, and the HPLC content of the by-product p-chloroaniline is 2%), the reaction device is changed to ...

Embodiment 3

[0037] Add 240mL of water into a 500mL four-necked flask, add 104g of sodium sulfide (industrial product) and 66g of sodium hydrosulfide (industrial product) under stirring, and raise the temperature to 40-60°C. Continue to stir until the sodium sulfide and sodium hydrosulfide are completely dissolved, add 0.8 g of activated carbon, stir for half an hour to decolorize, and collect the filtrate by suction filtration for later use.

[0038] Add 200mL of water, 100g of p-nitrochlorobenzene, and 1g of N-methylpyrrolidone into a 1000mL four-neck flask, stir and heat to 95-98°C, then add the above-mentioned filtrate dropwise at this temperature for about half an hour, and finally Continue to stir and keep warm for 8 hours until the end of the reaction. After the reaction (the reaction liquid is tested by HPLC: the HPLC content of p-aminothiophenate sodium is 92%, and the HPLC content of the by-product p-chloroaniline is 3%), the reaction device is changed to a distillation device, a...

technical field

[0001] The invention belongs to the field of preparation of dye intermediates, in particular to a preparation method of p-aminophenyl-β-hydroxyethyl sulfide. Background technique

[0002] Vinylsulfone-type reactive dyes (that is, domestic KN-type reactive dyes), with many varieties and complete chromatograms, are widely used in the dye industry. p-Aminophenyl-β-hydroxyethyl sulfide is an important component of vinylsulfone-type reactive dyes. intermediate. At present, it is mainly used for the synthesis of reactive blue 19 and its para-isomers. According to related reports, reactive blue 19 and its corresponding reactive group in the para-position of imino can be used as KN type reactive dyes (C.I. reactive blue 19 Research on the performance of its para-isomers - 1. Research on hydrolysis performance, Lu Rongwen, Li Huiping, Zhang Zhuxia, Gao Kunyu, Dyestuffs and Dyeing, 2006 No. 02), and compound use is more beneficial to improve the application performanc...

Examples

Embodiment 1

[0029] Add 240mL of water into a 500mL four-neck flask, add 95.8g of sodium sulfide (industrial product) and 59.5g of sodium hydrosulfide (industrial product) under stirring, and raise the temperature to 40-60°C. Continue to stir until the sodium sulfide and sodium hydrosulfide are completely dissolved, add 0.8 g of activated carbon, stir for half an hour to decolorize, and collect the filtrate by suction filtration for later use.

[0030] Add 200mL of water, 100g of p-nitrochlorobenzene, and 0.6g of N-methylpyrrolidone into a 1000mL four-neck flask, stir and heat to 92-96°C, then add the above-mentioned filtrate dropwise at this temperature, and drop it in about 1.5 hours. Finally, continue to stir and keep warm for 7 hours until the end of the reaction. After the reaction is over (the reaction solution is tested by HPLC: the HPLC content of p-aminothiophenate sodium is 90.5%, and the HPLC content of the by-product p-chloroaniline is 2.5%), the reaction device is changed to a...

Embodiment 2

[0033]Add 240mL of water into a 500mL four-necked flask, add 114.4g of sodium sulfide (industrial product) and 73.2g of sodium hydrosulfide (industrial product) under stirring, and raise the temperature to 40-60°C. Continue to stir until the sodium sulfide and sodium hydrosulfide are completely dissolved, add 0.8 g of activated carbon, stir for half an hour to decolorize, and collect the filtrate by suction filtration for later use.

[0034] Add 200mL of water, 100g of p-nitrochlorobenzene, and 0.9g of N-ethylpyrrolidone into a 1000mL four-neck flask, stir and heat to 100-105°C, then add the above-mentioned filtrate dropwise at this temperature, and drop it in about 1.5 hours. Finally, continue to stir and keep warm for 6 hours until the end of the reaction. After the reaction is over (the reaction solution is tested by HPLC: the HPLC content of p-aminothiophenate sodium is 91.0%, and the HPLC content of the by-product p-chloroaniline is 2%), the reaction device is changed to ...

Embodiment 3

[0037] Add 240mL of water into a 500mL four-necked flask, add 104g of sodium sulfide (industrial product) and 66g of sodium hydrosulfide (industrial product) under stirring, and raise the temperature to 40-60°C. Continue to stir until the sodium sulfide and sodium hydrosulfide are completely dissolved, add 0.8 g of activated carbon, stir for half an hour to decolorize, and collect the filtrate by suction filtration for later use.

[0038] Add 200mL of water, 100g of p-nitrochlorobenzene, and 1g of N-methylpyrrolidone into a 1000mL four-neck flask, stir and heat to 95-98°C, then add the above-mentioned filtrate dropwise at this temperature for about half an hour, and finally Continue to stir and keep warm for 8 hours until the end of the reaction. After the reaction (the reaction liquid is tested by HPLC: the HPLC content of p-aminothiophenate sodium is 92%, and the HPLC content of the by-product p-chloroaniline is 3%), the reaction device is changed to a distillation device, a...

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