Preparation method for weak-base arylamine diazonium salt and method for preparing tertiary amine weak-base arylamine azo dye by weak-base arylamine diazonium salt

Abstract

The invention relates to a preparation method for weak-base arylamine diazonium salt and a method for preparing tertiary amine weak-base arylamine azo dye by the weak-base arylamine diazonium salt, and belongs to the technical field of clean production of the dye. The preparation method comprises the following steps of adding naphthalenesulfonic acid and alkyl nitrite to weak-base arylamine solution in sequence, reacting for 20min to 60min at 0 DEG C to 25 DEG C, and performing solid-liquid separation to obtain weak-base arylamine diazonium salt solid; solvent for dissolving weak-base arylamine is tetrahydrofuran, 1,4-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or ethyl acetate. The preparation method for the weak-base arylamine diazonium salt and the method for preparing the tertiary amine weak-base arylamine azo dye by the weak-base arylamine diazonium salt, disclosed by the invention, have the beneficial effects that no sulfuric acid is used in a process of preparing the weak-base arylamine diazonium salt and the tertiary amine weak-base arylamine azo dye, therefore the environment is protected.

Description

Technical field

[0001] The invention relates to a method for preparing weakly basic aromatic amine diazonium salt and a method for preparing tertiary amine type weakly basic aromatic amine azo dyes, and belongs to the technical field of clean production of dyes. Background technique

[0002] In disperse dyes, azo type accounts for 60%, and the diazo component used to produce azo type disperse dyes usually has weak basic aromatic amines with strong electron withdrawing groups. Because the alkalinity is too weak, the nitrosating agent is not enough to diazotize it. Usually, the nitrosyl sulfuric acid with strong diazotization ability is used. The diazotization mechanism is as follows:

[0003] 2H 2 SO 4 +NaNO 2 →NOHSO 4 +NaHSO 4 +H 2 O

[0004]

[0005] In order to ensure the dissolution and stability of nitrosyl sulfuric acid and diazonium salt, the reaction needs to use concentrated sulfuric acid as a solvent. However, sodium bisulfate is produced during the preparation of nitrosyl...

Examples

Embodiment 1

[0032] A clean preparation method of N,N-diethyl-4-(2,4-dinitrophenylazo)-3-acetamidoaniline dye, the method includes the following steps:

[0033] Diazotization reaction: Dissolve 1.84g of 2,4-dinitroaniline in 60mL of diethylene glycol dimethyl ether, and add 4.32g of 1,5-naphthalene to the 2,4-dinitroaniline solution Disulfonic acid, add 1.72g of tert-butyl nitrite under stirring at 20°C, react at 20°C for 1h, and filter with suction to obtain diazonium salt;

[0034] Coupling reaction: Dissolve 2.06g of N,N-diethyl-3-acetamidoaniline and 2.88g of 1,5-naphthalenedisulfonic acid in 100mL of water and add the weight obtained in the diazotization step at 0°C. Nitrogen salt, adjust the pH to 4-6 with anhydrous sodium carbonate, react for 10 min at 0℃, adjust the pH to neutral, filter with suction, wash, and dry to obtain N,N-diethyl-4-(2,4-dinitro) Phenylazo)-3-acetamidoaniline dye, the yield was 83.50%.

Embodiment 2

[0036] A clean preparation method of N,N-diethyl-4-(2,6-dichloro-4-nitrophenylazo)-3-acetamidoaniline dye, the method includes the following steps:

[0037] Diazotization reaction: Dissolve 2.07g of 2,6-dichloro-4-nitroaniline in 40mL of ethylene glycol dimethyl ether, and add 4.32 to the 2,6-dichloro-4-nitroaniline solution g of 1,5-naphthalenedisulfonic acid, add 1.72g of tert-butyl nitrite with stirring at 25°C, react at 25°C for 0.5h, and filter with suction to obtain the diazonium salt;

[0038] Coupling reaction: Dissolve 2.06g of N,N-diethyl-3-acetamidoaniline and 2.88g of 1,5-naphthalenedisulfonic acid in 100mL of water and add the weight obtained in the diazotization step at 0°C. Nitrogen salt, adjust the pH to 4-6 with anhydrous sodium carbonate, react for 10 min at 0℃, adjust the pH to neutral, filter with suction, wash, and dry to obtain N,N-diethyl-4-(2,6-dichloro -4-nitrophenylazo)-3-acetamidoaniline dye, the yield was 78.77%.

Embodiment 3

[0040] A clean preparation method of N,N-diethyl-4-(2-cyano-4-nitrophenylazo)-3-acetamidoaniline dye, the method includes the following steps:

[0041] Diazotization reaction: Dissolve 1.63 g of 2-cyano-4-nitroaniline in 30 mL of diethylene glycol dimethyl ether, and add 3.17 g of 1 to the 2-cyano-4-nitroaniline solution ,5-Naphthalenedisulfonic acid, add 1.26g of tert-butyl nitrite with stirring at 0℃, react at 0℃ for 20min, and filter with suction to obtain diazonium salt

[0042] Coupling reaction: Dissolve 2.06g of N,N-diethyl-3-acetamidoaniline and 2.88g of 1,5-naphthalenedisulfonic acid in 100mL of water and add the weight obtained in the diazotization step at 0°C. Nitrogen salt, adjust the pH to 4-6 with anhydrous sodium carbonate, react for 10 min at 0°C, adjust the pH to neutral, filter with suction, wash, and dry to obtain N,N-diethyl-4-(2-cyano-4 -Nitrophenylazo)-3-acetamidoaniline dye with a yield of 84.47%.

Technical field

[0001] The invention relates to a method for preparing weakly basic aromatic amine diazonium salt and a method for preparing tertiary amine type weakly basic aromatic amine azo dyes, and belongs to the technical field of clean production of dyes. Background technique

[0002] In disperse dyes, azo type accounts for 60%, and the diazo component used to produce azo type disperse dyes usually has weak basic aromatic amines with strong electron withdrawing groups. Because the alkalinity is too weak, the nitrosating agent is not enough to diazotize it. Usually, the nitrosyl sulfuric acid with strong diazotization ability is used. The diazotization mechanism is as follows:

[0003] 2H 2 SO 4 +NaNO 2 →NOHSO 4 +NaHSO 4 +H 2 O

[0004]

[0005] In order to ensure the dissolution and stability of nitrosyl sulfuric acid and diazonium salt, the reaction needs to use concentrated sulfuric acid as a solvent. However, sodium bisulfate is produced during the preparation of nitrosyl...

Examples

Embodiment 1

[0032] A clean preparation method of N,N-diethyl-4-(2,4-dinitrophenylazo)-3-acetamidoaniline dye, the method includes the following steps:

[0033] Diazotization reaction: Dissolve 1.84g of 2,4-dinitroaniline in 60mL of diethylene glycol dimethyl ether, and add 4.32g of 1,5-naphthalene to the 2,4-dinitroaniline solution Disulfonic acid, add 1.72g of tert-butyl nitrite under stirring at 20°C, react at 20°C for 1h, and filter with suction to obtain diazonium salt;

[0034] Coupling reaction: Dissolve 2.06g of N,N-diethyl-3-acetamidoaniline and 2.88g of 1,5-naphthalenedisulfonic acid in 100mL of water and add the weight obtained in the diazotization step at 0°C. Nitrogen salt, adjust the pH to 4-6 with anhydrous sodium carbonate, react for 10 min at 0℃, adjust the pH to neutral, filter with suction, wash, and dry to obtain N,N-diethyl-4-(2,4-dinitro) Phenylazo)-3-acetamidoaniline dye, the yield was 83.50%.

Embodiment 2

[0036] A clean preparation method of N,N-diethyl-4-(2,6-dichloro-4-nitrophenylazo)-3-acetamidoaniline dye, the method includes the following steps:

[0037] Diazotization reaction: Dissolve 2.07g of 2,6-dichloro-4-nitroaniline in 40mL of ethylene glycol dimethyl ether, and add 4.32 to the 2,6-dichloro-4-nitroaniline solution g of 1,5-naphthalenedisulfonic acid, add 1.72g of tert-butyl nitrite with stirring at 25°C, react at 25°C for 0.5h, and filter with suction to obtain the diazonium salt;

[0038] Coupling reaction: Dissolve 2.06g of N,N-diethyl-3-acetamidoaniline and 2.88g of 1,5-naphthalenedisulfonic acid in 100mL of water and add the weight obtained in the diazotization step at 0°C. Nitrogen salt, adjust the pH to 4-6 with anhydrous sodium carbonate, react for 10 min at 0℃, adjust the pH to neutral, filter with suction, wash, and dry to obtain N,N-diethyl-4-(2,6-dichloro -4-nitrophenylazo)-3-acetamidoaniline dye, the yield was 78.77%.

Embodiment 3

[0040] A clean preparation method of N,N-diethyl-4-(2-cyano-4-nitrophenylazo)-3-acetamidoaniline dye, the method includes the following steps:

[0041] Diazotization reaction: Dissolve 1.63 g of 2-cyano-4-nitroaniline in 30 mL of diethylene glycol dimethyl ether, and add 3.17 g of 1 to the 2-cyano-4-nitroaniline solution ,5-Naphthalenedisulfonic acid, add 1.26g of tert-butyl nitrite with stirring at 0℃, react at 0℃ for 20min, and filter with suction to obtain diazonium salt

[0042] Coupling reaction: Dissolve 2.06g of N,N-diethyl-3-acetamidoaniline and 2.88g of 1,5-naphthalenedisulfonic acid in 100mL of water and add the weight obtained in the diazotization step at 0°C. Nitrogen salt, adjust the pH to 4-6 with anhydrous sodium carbonate, react for 10 min at 0°C, adjust the pH to neutral, filter with suction, wash, and dry to obtain N,N-diethyl-4-(2-cyano-4 -Nitrophenylazo)-3-acetamidoaniline dye with a yield of 84.47%.

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