CN1418914A - Yellow dye and preparation process thereof - Google Patents
Yellow dye and preparation process thereof Download PDFInfo
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- CN1418914A CN1418914A CN 02147777 CN02147777A CN1418914A CN 1418914 A CN1418914 A CN 1418914A CN 02147777 CN02147777 CN 02147777 CN 02147777 A CN02147777 A CN 02147777A CN 1418914 A CN1418914 A CN 1418914A
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Abstract
The present invention relates to a yellow dyestuff and its general formula. Said invention also provides its preparation method. Said yellow dyestuff can by synthesized by using di-quaternary ammonium salt containing carboxylic group, p-aminobenzaldehyde (P-N,N-dimethylaminobenzaldehyde) and acetic anhydride solution of cyanoacetic acid through a pot-boiling process. Said yellow dyestuff is easily dissolved in the solvents of water, alcohol and acid, and has good affinity for fibre, can be used for dyeing paper and making ink.
Description
Technical field the present invention relates to a kind of yellow dyes and preparation method thereof.
The basic yellow 96 that background technology BASF Aktiengesellschaft produces is compared, and is a kind of quaternary ammonium salts dyestuff.But basic yellow 96 itself is water-soluble bad, usually needs to add a large amount of auxiliary agents and improves that it is water-soluble, makes it to reach the requirement of use.
Summary of the invention problem to be solved by this invention provides a kind of water-soluble better yellow dyes.
Technical scheme provided by the invention is: a kind of yellow dyes, its general formula are [A-B-A] .2X
-, B is CH in the formula
2CH (OH) CH
2, X is selected from Cl, Br, I, and A is following structural formula:
R wherein
1, R
2=CH
3, C
2H
5, H or CH (CH
3)
2R
3, R
4=H, CH
3, C
2H
5Or CH (CH
3)
2, n=1,2 or 3.
The present invention also provides the preparation method of above-mentioned yellow dyes, and the aceticanhydride solution that will contain bi-quaternary ammonium salt, p-Aminobenzaldehyde (to N, the N-dimethylaminobenzaldehyde) and the cyanoacetic acid of hydroxyl obtains required yellow dyes by the method for the treatment of different things alike is synthetic.
The above-mentioned bi-quaternary ammonium salt that contains hydroxyl can prepare by laxative remedy: will contain the tertiary amine of hydroxyl and the concentrated acid of equivalent (concentrated nitric acid, the vitriol oil, dense hydracid etc.) reaction, the epoxy halogenopropane of gained reaction mixture and equimolar amount (the epoxy haloalkane can be epoxy chloropropane, epoxy bromopropane, epoxy iodopropane etc.) reaction, make the two quaternary ammoniums that contain hydroxyl to its reactive tertiary amine that contains hydroxyl that adds equimolar amount at last, temperature of reaction is controlled at 60-100 ℃.
The preparation of above-mentioned bi-quaternary ammonium salt is carried out in polar aprotic solvent or polar aprotic solvent.
Above-mentioned aceticanhydride and cyanoacetic acid react under 45-65 ℃ of temperature, and the gained reaction solution joins by 1: 2-1: 2.4 (weight ratios) prepare N, and in N-disubstituted amido phenyl aldehyde and the bi-quaternary ammonium salt, 80-100 ℃ of following reaction obtains needed yellow dyes.
Very easily water-soluble, pure, the sour equal solvent of yellow dyes provided by the invention.This class dyestuff does not produce the three wastes when producing and use, meet current strict environmental requirement, and fiber is had avidity preferably, can be used for dying paper and makes ink.The present invention has not only eliminated the pollution in DYE PRODUCTION and the use, and production technique is simple, is easy to industrialization.
Embodiment the present invention with epoxy chloropropane, concentrated hydrochloric acid and hydroxyl aminated compounds at polar aprotic solvent such as alcohols (ethanol, Virahol etc.) and polar aprotic solvent such as N, prepared in reaction bi-quaternary ammonium salt in dinethylformamide (DMF), acetonitrile, methyl-sulphoxide (DMSO), the hexamethylphosphoramide (HMPA) etc.And then the solution that the reaction of cyanoacetic acid and aceticanhydride is obtained joins quaternary ammonium salt and the aminobenzaldehyde (N substituted-amino phenyl aldehyde) for preparing in proportion, and the method for the treatment of different things alike synthesizes required yellow dyes.
Embodiment one: add 100mLN in the 1000mL flask, N-dimethylethanolamine and 200mL Virahol drip the 90mL concentrated hydrochloric acid, and controlled temperature is about 80 ℃.Then, drip the 80mL epoxy chloropropane again.After dropwising, continue reaction 0.5h at 80 ℃.Then, under this temperature, drip 100mL N again, the N-dimethylethanolamine.After dropwising, be warming up to 90 ℃ of reaction 8h.Cooling is filtered, and obtains 270 gram bi-quaternary ammonium salts.
In the 500mL flask, add 109 gram cyanoacetic acids and 290mL aceticanhydride and about 50 ℃, react 1h.Then gained solution is joined be equipped with 270 the gram these routine synthetic bi-quaternary ammonium salts and 199 the gram to N, in the 1000mL single port flask of N-dimethylaminobenzaldehyde, 85-90 ℃ the reaction 6h, obtain required dyestuff.This dyestuff is water-soluble, and its maximum absorption wavelength is 447nm.
Embodiment two: add 100mLN in the 1000mL flask, N-dimethylethanolamine and 200mL ethanol drip the 113mL concentrated hydrochloric acid, and controlled temperature is about 80 ℃.Then, drip the 85.6mL epoxy bromopropane.After epoxy bromopropane dropwises, continue reaction 0.5h at 80 ℃.Under this temperature, then drip 100mL N, the N-dimethylethanolamine.After dropwising, be warming up to 90 ℃ of reaction 8h.Cooling is filtered, and obtains 330 gram bi-quaternary ammonium salts.
In the 500mL flask, add 109 gram cyanoacetic acids and 290mL aceticanhydride and about 50 ℃, react 1h.With gained solution join be equipped with 330 the gram by this routine synthetic bi-quaternary ammonium salt and 199 the gram to N, in the 1000mL flask of N-dimethylaminobenzaldehyde, 85-90 ℃ the reaction 6h, obtain required dyestuff.This dyestuff is water-soluble, and its maximum absorption wavelength is 444nm.
Embodiment three: add 75 gram N in the 1000mL flask, N-dimethyl methyl hydramine and 150mLDMF drip the 90mL concentrated hydrochloric acid, and controlled temperature is about 80 ℃.After dropwising, drip the 80mL epoxy chloropropane again.After epoxy chloropropane dropwises, continue reaction 0.5h at 85 ℃.Under this temperature, continue to drip 75 gram N, N-dimethyl methyl hydramine.After dropwising, under this temperature, continue reaction 9h.Cooling is filtered, and gets 200 gram bi-quaternary ammonium salts.
In the 500mL flask, add 92.4 gram cyanoacetic acids and 254mL aceticanhydride and about 50 ℃, react 1h.With gained solution join be equipped with 200 the gram by this routine synthetic bi-quaternary ammonium salt and 168.7 the gram to N, in the 1000mL flask of N-dimethylaminobenzaldehyde, 85-90 ℃ the reaction 6h, obtain required dyestuff.The maximum absorption wavelength of this dyestuff is 447nm.
Embodiment four: add 145 gram N in the 1000mL flask, N-diisopropyl ethanolamine and 150mL ethanol drip and N, the vitriol oil of N-diisopropyl ethanolamine equivalent, and controlled temperature is about 800 ℃.After dropwising, drip the 80mL epoxy chloropropane again.After epoxy chloropropane dropwises, continue reaction 0.5h at 85 ℃.Under this temperature, continue to drip 145 gram N, the N-diisopropyl ethanolamine.After dropwising, under this temperature, continue reaction 9h.Cooling is filtered, and gets 350 gram bi-quaternary ammonium salts.
In the 500mL flask, add 104 gram cyanoacetic acids and 285mL aceticanhydride and about 60 ℃, react 1h.With gained solution join be equipped with 350 the gram by this routine synthetic bi-quaternary ammonium salt and 189 the gram to N, in the 1000mL flask of N-dimethylaminobenzaldehyde, 90-95 ℃ the reaction 6h, obtain required dyestuff.The maximum absorption wavelength of this dyestuff is 447nm.
Embodiment five: add 100mLN in the 1000mL flask, N-dimethylethanolamine and 200mL ethanol drip and N, the concentrated nitric acid of N-dimethylethanolamine equivalent, and controlled temperature is about 80 ℃.Then, drip the 80mL epoxy chloropropane.After epoxy chloropropane dropwises, continue reaction 0.5h at 80 ℃.Under this temperature, then drip 100mL N, the N-dimethylethanolamine.After dropwising, be warming up to 90 ℃ of reaction 8h.Cooling is filtered, and obtains 250 gram bi-quaternary ammonium salts.
In the 500mL flask, add 101 gram cyanoacetic acids and 278mL aceticanhydride and about 55 ℃, react 1h.With gained solution join be equipped with 250 the gram by this routine synthetic bi-quaternary ammonium salt and 212 the gram to N, in the 1000mL flask of N-diformazan isopropylamino phenyl aldehyde, 88-92 ℃ the reaction 6h, obtain required dyestuff.This dyestuff is water-soluble, and its maximum absorption wavelength is 445nm.
Embodiment six: add 117 gram N in the 1000mL flask, N-diethylethanolamine and 200mL ethanol drip the 90mL concentrated hydrochloric acid, and controlled temperature is about 90 ℃.Then, drip the 80mL epoxy chloropropane.After epoxy chloropropane dropwises, continue reaction 0.5h at 90-95 ℃.Under this temperature, then drip 100mL N, the N-dimethylethanolamine.After dropwising, be warming up to 100 ℃ of reaction 8h.Cooling is filtered, and obtains 285 gram bi-quaternary ammonium salts.
In the 500mL flask, add 97 gram cyanoacetic acids and 268mL aceticanhydride and about 55 ℃, react 1h.With gained solution join be equipped with 285 the gram by this routine synthetic bi-quaternary ammonium salt and 204 the gram to N, in the 1000mL flask of N-diformazan isopropylamino phenyl aldehyde, 88-92 ℃ the reaction 6h, obtain required dyestuff.This dyestuff is water-soluble, and its maximum absorption wavelength is 440nm.
Embodiment seven: add 17.8 kilograms of N in the still of 200L, N-dimethylethanolamine and 30 kilograms of Virahols drip 21.2 kilograms of concentrated hydrochloric acids, and controlled temperature is about 80 ℃.And then drip 18.9 kilograms of epoxy chloropropane.After dropwising, continue reaction 1h at 80 ℃.Then, under this temperature, drip 17.8 kilograms of N again, the N-dimethylethanolamine.After dropwising, be warming up to 90 ℃ of reaction 8h.Cooling is filtered, and obtains 50 kilograms of bi-quaternary ammonium salts.
In the 200L still, add 20 kilograms cyanoacetic acid and 65 kilograms aceticanhydride, at 50 ℃ of reaction 1.5h.With gained solution joined 50 kilograms by this routine synthetic bi-quaternary ammonium salt and 35 kilograms to N, the N-dimethylaminobenzaldehyde at 90 ℃ of reaction 6h, obtains a kind of yellow dyes.This dyestuff is water-soluble, and its maximum absorption wavelength is 447nm.
Claims (7)
1. yellow dyes, its general formula is [A-B-A] .2X
-, B is CH in the formula
2CH (OH) CH
2, X is selected from Cl, Br, I, and A is following structural formula:
R wherein
1, R
2=CH
3, C
2H
5, H or CH (CH
3)
2R
3, R
4=H, CH
3, C
2H
5Or CH (CH
3)
2, n=1,2 or 3.
2. the preparation method of the described yellow dyes of claim 1 will contain the bi-quaternary ammonium salt of hydroxyl, to N, and the aceticanhydride solution of N-disubstituted amido phenyl aldehyde and cyanoacetic acid obtains required yellow dyes by the method for the treatment of different things alike is synthetic.
3. preparation method according to claim 2, it is characterized in that: will contain the tertiary amine of hydroxyl and the concentrated acid reaction of equivalent, the epoxy halogenopropane reaction of gained reaction mixture and equimolar amount, make the bi-quaternary ammonium salt that contains hydroxyl to its reactive tertiary amine that contains hydroxyl that adds equimolar amount at last, temperature of reaction is controlled at 60-100 ℃.
4. preparation method according to claim 3 is characterized in that: the preparation of bi-quaternary ammonium salt is carried out in polar aprotic solvent or polar aprotic solvent.
5. according to claim 2 or 3 described preparation methods, it is characterized in that: described concentrated acid is concentrated nitric acid, the vitriol oil or dense hydracid.
6. according to claim 2 or 3 described preparation methods, it is characterized in that: the epoxy halogenopropane is epoxy chloropropane, epoxy bromopropane or epoxy iodopropane for the epoxy haloalkane.
7. according to claim 2 or 3 described preparation methods, it is characterized in that: aceticanhydride and cyanoacetic acid react under 45-65 ℃ of temperature, the gained reaction solution joins by 1: 2-1: 2.4 prepare N, and in N-disubstituted amido phenyl aldehyde and the bi-quaternary ammonium salt, 80-100 ℃ of following reaction obtains needed yellow dyes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021477779A CN1164685C (en) | 2002-12-05 | 2002-12-05 | Yellow dye and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021477779A CN1164685C (en) | 2002-12-05 | 2002-12-05 | Yellow dye and preparation process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1418914A true CN1418914A (en) | 2003-05-21 |
| CN1164685C CN1164685C (en) | 2004-09-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021477779A Expired - Fee Related CN1164685C (en) | 2002-12-05 | 2002-12-05 | Yellow dye and preparation process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012039286A1 (en) * | 2010-09-22 | 2012-03-29 | 株式会社Adeka | Pigment and colored photosensitive composition |
-
2002
- 2002-12-05 CN CNB021477779A patent/CN1164685C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012039286A1 (en) * | 2010-09-22 | 2012-03-29 | 株式会社Adeka | Pigment and colored photosensitive composition |
| US8664289B2 (en) | 2010-09-22 | 2014-03-04 | Adeka Corporation | Dye and coloring photosensitive composition |
| JP5844267B2 (en) * | 2010-09-22 | 2016-01-13 | 株式会社Adeka | Dye and colored photosensitive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1164685C (en) | 2004-09-01 |
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