CN109608903B - Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof - Google Patents

Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof Download PDF

Info

Publication number
CN109608903B
CN109608903B CN201811327162.0A CN201811327162A CN109608903B CN 109608903 B CN109608903 B CN 109608903B CN 201811327162 A CN201811327162 A CN 201811327162A CN 109608903 B CN109608903 B CN 109608903B
Authority
CN
China
Prior art keywords
reaction
acid
condensation product
dye
condensation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811327162.0A
Other languages
Chinese (zh)
Other versions
CN109608903A (en
Inventor
张淑芬
熊伟
唐炳涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN201811327162.0A priority Critical patent/CN109608903B/en
Publication of CN109608903A publication Critical patent/CN109608903A/en
Application granted granted Critical
Publication of CN109608903B publication Critical patent/CN109608903B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/51—Monoazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/08—Azo dyes
    • C09B62/085—Monoazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/523—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl amido or hydroxyalkyl amino sulfonyl group, a quaternised or non-quaternised amino alkyl sulfonyl amido group, or a substituted alkyl amino sulfonyl group, or a halogen alkyl sulfonyl amido or halogen alkyl amino sulfonyl group or a vinyl sulfonylamido or a substituted vinyl sulfonamido group
    • C09B62/527—Azo dyes
    • C09B62/53—Monoazo dyes

Abstract

The invention relates to the field of reactive dyes, in particular to a reactive dye containing benzene sulfonamide and derivatives thereof and a preparation method thereof. A reactive dye substituted with benzenesulfonamide and its derivatives, having the structure of formula i:

Description

Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof
Technical Field
The invention relates to the field of reactive dyes, in particular to a reactive dye containing benzene sulfonamide and derivatives thereof and a preparation method thereof.
Background
Reactive dyes can be covalently bonded to fibers and have high wet fastness, and are now the main dye classes for printing and dyeing cellulose fibers. Azo color bodies have the advantages of cheap and easily-obtained raw materials, simple synthesis, bright color light, complete chromatogram and the like, and about 80 percent of Dyes use azo color precursors, but azo bonds are easily influenced by ultraviolet light, oxygen and the like in the environment and are easy to generate redox reaction so as to have lower light fastness (Dyes and Pigments,1988,9(3): 233-. The following two approaches are mainly used to improve the light stability of dyes: firstly, the chromogens with higher light fastness are adopted, such as: anthraquinones, phthalocyanines, or other types of color bodies; secondly, ultraviolet absorption groups are introduced into dye molecules, or ultraviolet absorbers are added into dyeing auxiliary agents so as to reduce the damage of ultraviolet to the dye and achieve the purpose of improving the light-resistant stability (Coloration Technology,2016,132: 107-113; Advances in the dyeing and Finishing of Technical Textiles,2013,138: 47-77; Colourage,2010,7: 33-39; CN 201310664137). In contrast, the color tone of anthraquinone and phthalocyanine color bodies is generally single, and the full color spectrum of azo color bodies cannot be used (2007 dyeing and dyeing, 3: 10-13). The introduction of UV absorbing groups into the molecular structure of dyes generally reduces the solubility and molar absorption coefficient of the dye (US 5200511; EP 1860162). By introducing hindered amine molecules into the dye structure, the light fastness can be improved by half to one grade (CN 101899225; CN101914300), and by introducing benzophenone molecules into the reactive dye, the light fastness of the dye can be improved by 1-2 grade (Dyes and pigments,1988,9(3): 233-241).
The sulfonamide group is used as a derivative of the sulfonic acid group, so that the color-aiding performance of the sulfonic acid group can be retained, and the strong water solubility of the sulfonic acid group can be eliminated, thereby improving the adsorption capacity of the reactive dye on the fiber. Sulfonamide groups have been introduced as linkers into reactive dye molecules (Dyes and pigments.1999,43(5): 167-172; FR 1352275 a; US3029123A), which mainly use sulfonamide groups to link reactive groups to chromophores, instead of arylamines having carcinogenic properties. Also, sulfonamide groups have been introduced into disperse dyes to improve the adsorption ability of the dyes to hydrophobic fibers such as polypropylene, polylactic acid, and terylene (Chinese Chemical letters, 2007,18(9): 1145-1147); more reports on the introduction of sulfonamide groups into dye molecules have focused on the research on the introduction of sulfonamide groups into para-ester or meta-ester, and the purpose of increasing the degree of exhaustion and fixation of Dyes is achieved by changing the molecular structure of the para-ester or meta-ester to improve the substantivity of the Dyes to fibers (Coloration Technology,2006,122(4): 217-. The benzene sulfonamide is used as the most easily obtained raw material containing a sulfonamide structure, is introduced into the halogenated s-triazine ring, can reduce the electron cloud density on the triazine ring by utilizing the strong electron withdrawing effect of the sulfonamide group, improves the reaction activity of a carbon-halogen bond, and simultaneously achieves the aim of improving the light fastness of the dye. The benzene sulfonamide group is introduced into the reactive dye as a blocking group of a triazine ring, and the reactive dye with high light fastness prepared by using the benzene sulfonamide group is not reported.
Disclosure of Invention
A reactive dye substituted with benzenesulfonamide and derivatives thereof, having the structure of formula I:
Figure BDA0001859036120000021
in the formula I, the compound is shown in the specification,
r is selected from-Cl or-F;
R1selected from-H, methyl, nitrile, sulfonic, trifluoromethyl, methoxy, hydroxy, carboxy, nitro, -Cl, -Br, -F;
R2selected from-H, methyl, aminomethyl, trifluoromethyl, methoxy, hydroxy, nitro, cyano, -Cl, -Br, -F;
R3is selected from-H, -OCH3，-CH3，-CH2CH3；
L is selected from-SO2-，-CO-，-NHCO-，-SO2NH-，-CH2CH2SO2-，-O-CH2CH2SO2-，-NHCH2CH2SO2-，-NHCONHCH2CH2SO2-，-SO2CH2CH2SO2-or-NXSO2-a group wherein X is selected from C1～C4Alkoxy substituted or unsubstituted by carbon atom, phenyl, the substituent of which may be-SO3H. -COOH, -OH, halogen, cyano, aminosulfonyl (H)2NSO2-), ethoxy, cyanomethyl groups;
m is selected from-Cl, or-OSO3R4Wherein R is4Selected from-H, -Na or-K;
a is selected from substituents shown as II-a or II-b;
Figure BDA0001859036120000031
in the formula II-a, the compound is shown in the specification,
n is an integer of 0 to 2;
the residue represented by the formula II-b is one of the following groups:
an H acid residue having the formula:
Figure BDA0001859036120000032
j acid residue of the formula:
Figure BDA0001859036120000033
a gamma acid residue having the formula:
Figure BDA0001859036120000034
a K acid residue of the formula:
Figure BDA0001859036120000035
a chicago acid residue having the formula:
Figure BDA0001859036120000036
further, R1、R2、R3And the position of L is any position of the benzene ring.
Further preferably, R2In the para-position to the sulfonamide group, R1Is at a position of R2Is in an adjacent position or a meta position; r3Is ortho-or meta-to-N ═ N-; the position of L is para or meta to-N ═ N-.
It is still another object of the present invention to provide a method for preparing a reactive dye substituted with benzenesulfonamide and its derivatives, which comprises the following two types of methods:
the method comprises the steps of carrying out condensation reaction on halogenated s-triazine, benzene sulfonamide and amino naphthol sulfonic acid substrates to obtain a condensation product, carrying out diazotization reaction on β -sulfuric ester ethyl sulfone aniline to obtain a diazonium salt solution, carrying out coupling reaction on the condensation product and the diazonium salt solution at the reaction temperature of 0-5 ℃ and the pH of 7-8 to obtain the dye of claim 1;
the second method comprises the steps of carrying out diazotization reaction on β -sulfuric ester ethyl sulfone aniline to obtain a diazonium salt solution, dropwise adding an H acid solution into the diazonium salt solution at a molar ratio of 1:1 at a reaction temperature of 0-5 ℃ for 4H with a pH value of less than 3, carrying out primary coupling reaction to obtain a primary coupling solution, carrying out condensation reaction on halogenated s-triazine, benzenesulfonamide and an arylamine substrate to obtain a condensation product, carrying out diazotization reaction on the condensation product to obtain a condensation product diazonium solution, dropwise adding the condensation product diazonium solution into the primary coupling solution at a reaction temperature of 0-5 ℃ and a pH value of 7-8, and carrying out coupling reaction to obtain the dye.
Preferably, the condensation product is prepared as follows: carrying out first condensation reaction on halogenated s-triazine and benzene sulfonamide or derivatives thereof; then carrying out secondary condensation with an amino naphthol sulfonic acid substrate or an arylamine substrate to obtain a condensation product;
the molar ratio of the first-time condensed halogenated s-triazine to the benzene sulfonamide salt is 1: 1-1: 3, the reaction temperature is 0-5 ℃, the dripping time is 40-50 min, the reaction time is 120min, a first-time condensation product is obtained, the molar ratio of the first-time condensation product to the amino naphthol sulfonic acid substrate or the arylamine substrate is 1: 0.9-1, the reaction temperature is 15-30 ℃, the pH value is 6-7, and the reaction end point is detected by thin-layer chromatography, so that the condensation product is obtained.
Further, the β -sulfate ethylsulfone aniline is a generic term for the structure of the formula:
Figure BDA0001859036120000041
further, β -sulfate ethyl sulfone aniline is one of p- (ethyl- β -hydroxyethyl sulfone sulfate) aniline, 2-methyl, 4- (ethyl- β -hydroxyethyl sulfone sulfate) aniline, p-ester, m-ester, 3- (β -chloroethyl sulfone) aniline, 4-sulfate ethyl sulfone aniline, 3-methoxy, 4-sulfate ethyl sulfone aniline, 4-methoxy-3- (β -sulfate ethyl sulfone) aniline.
Further, the halogenated s-triazine is dissolved in acetone, and the concentration of the acetone solution of the halogenated s-triazine is 0.5 mol/L.
Preferably, after the halogenated s-triazine and the benzene sulfonamide are subjected to a first condensation reaction, unreacted benzene sulfonamide and derivatives thereof are separated out to obtain clear filtrate, the clear filtrate is subjected to a second condensation with an amino naphthol sulfonic acid substrate or an arylamine substrate, and the pH is adjusted to be less than 3 by adding acid in the separation mode.
Further, the pH value of the solution is adjusted to be less than 3, unreacted benzene sulfonamide or substituted benzene sulfonamide is separated out, and the temperature is reduced to ensure that the separation is more complete.
Further, the benzene sulfonamide and the derivatives thereof are firstly added into a sodium hydroxide solution, and the molar ratio of the benzene sulfonamide to the sodium hydroxide is 1:1, the concentration of the sodium hydroxide solution is 0.02 g/L.
Preferably, the halogenated s-triazine is cyanuric chloride and cyanuric fluoride.
Preferably, the amino naphthol sulfonic acid substrate is H acid, J acid, gamma acid, K acid or Chicago acid.
Preferably, the arylamine substrate is 2, 4-diaminobenzene sulfonic acid, 1, 2-diaminobenzene, 1, 3-diaminobenzene, 1, 4-diaminobenzene, 2, 4-diamino-1, 5-disulfonic benzene.
Preferably, the diazotization reaction is a reaction of aromatic primary amine and sodium nitrite at 0-5 ℃ in a strong acid medium to generate diazonium salt, the molar ratio of the aromatic primary amine to the nitrous acid is 1: 1.03-1.1, the strong acid medium is concentrated hydrochloric acid with the mass fraction of 37%, the molar weight of the concentrated hydrochloric acid is 3 times that of the aromatic primary amine, the aromatic primary amine is β -sulfate ethyl sulfone aniline or a condensation product, the condensation product is obtained by condensation reaction of halogenated s-triazine and benzenesulfonamide and then an amino naphthol sulfonic acid substrate,
and (3) detecting whether the hydrochloric acid and the sodium nitrite are sufficient or not by using Congo red test paper and starch-KI test paper in the diazotization reaction, detecting the reaction end point by using an Ellisib reagent, and adding sulfamic acid to destroy redundant sodium nitrite when the diazotization is finished to obtain a diazotization solution.
Preferably, the coupling reaction is monitored by a percolation method to an end point.
The invention has the beneficial effects that: in the prepared reactive dye molecules, benzenesulfonamide and substituted benzenesulfonamide groups are directly connected with halogenated s-triazine molecules, and the electron-withdrawing effect of the dyes reduces the electron cloud density of carbon atoms on a triazine ring, so that the nucleophilic substitution reaction is easy to occur, the reaction activity of the triazine structure is equivalent to that of ethyl sulfone sulfate aniline, the reaction rate of the dyes at 60 ℃ and 90 ℃ is equivalent, and energy-saving dyeing under mild conditions can be realized; and the dye has high light fastness and wide application prospect.
Drawings
FIG. 1 is a graph showing the dyeing curves of the products obtained in examples 1 to 10;
FIG. 2 is a UV-Vis spectrum of the product obtained in example 1;
FIG. 3 is a UV-Vis spectrum of the product obtained in example 2;
FIG. 4 is a UV-Vis spectrum of the product obtained in example 3;
FIG. 5 is a UV-Vis spectrum of the product obtained in example 4;
FIG. 6 is a UV-Vis spectrum of the product obtained in example 5;
FIG. 7 is a UV-Vis spectrum of the product obtained in example 6;
FIG. 8 is a UV-Vis spectrum of the product obtained in example 7;
FIG. 9 is a UV-Vis spectrum of the product obtained in example 8;
FIG. 10 is a UV-Vis spectrum of the product obtained in example 9;
FIG. 11 is a UV-Vis spectrum of the product obtained in example 10;
FIG. 12 is a FT-IR spectrum of the product obtained in example 1;
FIG. 13 is a FT-IR spectrum of the product obtained in example 2;
FIG. 14 is a FT-IR spectrum of the product obtained in example 3;
FIG. 15 is an FT-IR spectrum of the product obtained in example 4;
FIG. 16 is an FT-IR spectrum of the product obtained in example 5;
FIG. 17 is an FT-IR spectrum of the product obtained in example 6;
FIG. 18 is an FT-IR spectrum of the product obtained in example 7;
FIG. 19 is an FT-IR spectrum of the product obtained in example 8;
FIG. 20 is an FT-IR spectrum of the product obtained in example 9;
FIG. 21 is an FT-IR spectrum of the product obtained in example 10;
FIG. 22 is a MS spectrum of the product obtained in example 1;
FIG. 23 is a MS spectrum of the product obtained in example 2;
FIG. 24 is a MS spectrum of the product obtained in example 3;
FIG. 25 is a MS spectrum of the product obtained in example 4;
FIG. 26 is a MS spectrum of the product obtained in example 5;
FIG. 27 is a MS spectrum of the product obtained in example 6;
FIG. 28 is a MS spectrum of the product obtained in example 7;
FIG. 29 is a MS spectrum of the product obtained in example 8;
FIG. 30 is a MS spectrum of the product obtained in example 9;
FIG. 31 is a MS spectrum of the product obtained in example 10.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
TABLE 1 dye structures synthesized in examples 1-42
Figure BDA0001859036120000071
Figure BDA0001859036120000081
Figure BDA0001859036120000091
Figure BDA0001859036120000101
Figure BDA0001859036120000111
Figure BDA0001859036120000121
Example 1
Cyanuric chloride condensation reaction: weighing 3.14g of benzenesulfonamide, adding 40mL of water and 0.8g of sodium hydroxide, heating to 20 ℃, and stirring until the mixture is dissolved to obtain a mixed solution; and (3) dropwise adding 1.84g of cyanuric chloride dissolved in 20mL of acetone into the mixed solution at the temperature of 0-5 ℃, and completing dropwise adding within 40 min. Reacting at 0-5 ℃ until the first condensation reaction is finished, adding 10% hydrochloric acid to adjust the pH of the reaction solution to be less than 3 after the first condensation reaction is finished, precipitating unreacted benzene sulfonamide, and filtering to obtain clear filtrate. And during secondary condensation, adding 4.0g H acid into the reaction filtrate, controlling the reaction temperature to be 25 ℃ and the pH value to be 6-7, and detecting by using a thin-layer chromatography to control the reaction to be at the end point to obtain a condensation product.
Diazotization reaction: weighing 0.01mol of para-ester solid, adjusting the pH value to 5-6, and dissolving in 20mL of water. 0.73g of sodium nitrite was added and dissolved therein. And adding the mixed solution into an acidic aqueous solution which is cooled to 0-5 ℃ and contains 2.5mL of concentrated hydrochloric acid with the mass fraction of 37%, and detecting whether the hydrochloric acid and the sodium nitrite are sufficient or not by using Congo red test paper and starch-KI test paper. After 30min, the reaction end point was detected with elix reagent. When diazotization is finished, sulfamic acid is added into the system to destroy redundant sodium nitrite, and diazo liquid is obtained
Coupling reaction: gradually dropwise adding the diazo solution into a condensation product cyanuric chloride-benzene sulfonamide-bis-H-condensed acid product solution, adjusting the coupling pH to 7-8 by a sodium carbonate solution with the mass fraction of 10% to obtain a coupling reaction system solution,
controlling the coupling temperature to be 0-5 ℃, detecting diazo components and the reaction condition of the coupling components by a ring permeation method at intervals of 10min, wherein the diazo components are diazo liquid, the coupling components are combined reaction system solution, and TLC is combined at the same timeThe progress of the reaction was monitored. After the coupling reaction was completed, the reaction pH was adjusted to about 7, and a buffer salt (Na) was added thereto2HPO3-NaH2PO31 percent, w/v) and then slowly adding potassium acetate solid accounting for about 5 percent of the mass of the coupling reaction system in batches for salting out until a water ring appears in a ring penetration method. And continuously stirring the system for 10min, standing the system for 20min, performing suction filtration, washing a filter cake with 50mL of ethanol for several times, and drying to obtain the dye.
Examples 2 to 3
The structural dyes shown in the examples 2 and 3 can be prepared by respectively replacing the benzene sulfonamide in the example 1 with the p-carboxybenzene sulfonamide and the p-toluene sulfonamide by the same synthetic method.
Example 4
The cyanuric chloride condensation reaction was the same as the reaction procedure of example 1, and 2.15g J acid was used instead of 4.0g H acid in example 1 in the dimerization step.
Diazotization reaction: the preparation method is the same as that of the example 1.
Coupling reaction: gradually dripping the diazo liquid into the secondary condensation product solution, adjusting the coupling pH to 7-8 by using a sodium carbonate solution with the mass fraction of 10%, controlling the coupling temperature to 0-5 ℃, detecting the reaction condition of the diazo component and the coupling component by using a ring infiltration method at intervals of 10min, and simultaneously detecting the reaction process by combining TLC. After the coupling reaction was completed, the reaction pH was adjusted to about 7, and a buffer salt (Na) was added thereto2HPO3-NaH2PO31%, w/v), then slowly adding potassium acetate solid accounting for about 5% of the mass of the reaction system in batches for salting out until a water ring appears in a ring penetration. And continuously stirring the system for 10min, standing the system for 20min, performing suction filtration, washing a filter cake with 50mL of ethanol for several times, and drying to obtain the dye.
Examples 5 to 10
The structural dyes shown in the examples 5-10 can be prepared by the same synthesis method by respectively replacing the benzene sulfonamide in the example 4 with p-carboxylbenzenesulfonamide, p-toluenesulfonamide, p-trifluoromethyl benzenesulfonamide, p-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide and p-bromobenzenesulfonamide.
Example 11
Cyanuric chloride condensation reaction: weighing 3.14g of benzenesulfonamide, adding 40mL of water and 0.8g of sodium hydroxide, heating and stirring until the mixture is dissolved; cyanuric chloride (1.84g, dissolved in acetone) is added dropwise at 0-5 ℃ within 40 min. And (3) reacting at constant temperature until the reaction is finished, and adjusting the pH value of the reaction system to be less than 3 after the reaction is finished to separate out unreacted benzene sulfonamide. And filtering the precipitated unreacted benzene sulfonamide to obtain reaction filtrate. And during secondary condensation, heating the reaction filtrate to 20 ℃, adding 2.15g of gamma acid, controlling the reaction temperature to be 25 ℃ and the pH value to be 6-7, and controlling the reaction to be at the end point.
Diazotization reaction: the preparation method is the same as that of the example 1.
Coupling reaction: gradually dropwise adding the diazo solution into cyanuric chloride-benzene sulfonamide-bis-gamma-condensed acid product solution, adjusting the coupling pH to 7-8 by using a sodium carbonate solution with the mass fraction of 10%, controlling the coupling temperature to 0-5 ℃, detecting the reaction conditions of the diazo component and the coupling component by a permeation ring method at intervals of 10min, and detecting the reaction process by combining TLC. After the coupling reaction was completed, the reaction pH was adjusted to about 7, and a buffer salt (Na) was added thereto2HPO3-NaH2PO31 percent, w/v) and then slowly adding potassium acetate solid accounting for about 5 percent of the mass of the reaction system in batches for salting out until a water ring appears in a ring penetration method. And continuously stirring the system for 10min, standing the system for 20min, performing suction filtration, washing a filter cake with 50mL of ethanol for several times, and drying to obtain the dye.
Examples 12 to 17
The structural dyes shown in examples 12 to 17 can be prepared by the same preparation method as that of example 11 except that the benzenesulfonamide in example 11 is replaced by p-carboxylbenzenesulfonamide, p-toluenesulfonamide, p-trifluoromethylbenzenesulfonamide, p-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, and p-bromobenzenesulfonamide, respectively.
Example 18
Diazotization reaction: the preparation method is the same as that of the example 1, and the para-ester diazonium salt is obtained.
Primary coupling reaction: weighing 4.0g H acid, adding 50mL water to adjust pH to about 6, gradually dripping the H-acid solution into the para-ester diazonium salt, and slowly dripping for about 4H. Controlling the pH value of the primary coupling to be less than 3, controlling the temperature to be 0-5 ℃, detecting the reaction end point by a ring penetration method, and adding a sodium carbonate solution to adjust the pH value of the reaction to be neutral after the coupling reaction is finished to obtain primary coupling solution.
Cyanuric chloride condensation reaction: weighing 3.14g of benzenesulfonamide, adding 40mL of water and 0.8g of sodium hydroxide, heating to 20 ℃, and stirring until the mixture is dissolved; cyanuric chloride (1.84g, dissolved in acetone) is added dropwise at 0-5 ℃ within 40 min. And (5) reacting at constant temperature to the end, and adjusting the pH value of the reaction system to be less than 3 after the reaction is finished to precipitate unreacted benzene sulfonamide. And during secondary condensation, heating the reaction filtrate to 25 ℃, adding 1.8g of 2, 4-diaminobenzene sulfonic acid, controlling the reaction temperature to 25 ℃ and the pH value to be 6-7, and controlling the reaction to the end point.
Diazotization reaction: and (3) cooling the cyanuric chloride-benzene sulfonamide-bis-condensed 2, 4-diaminobenzene sulfonic acid-bis-condensed reaction liquid to 0-5 ℃, and adding 0.72g of sodium nitrite to dissolve in the reaction liquid. And adding the mixed solution into an acidic aqueous solution which is cooled to 0-5 ℃ and contains 2.5mL of concentrated hydrochloric acid, and detecting whether the hydrochloric acid and the sodium nitrite are sufficient or not by using Congo red test paper and starch-KI test paper. After 30min, the reaction end point was detected with elix reagent. At the end of diazotization, a proper amount of sulfamic acid is added into the system to destroy the excess sodium nitrite.
Coupling reaction: gradually dropwise adding the diazo liquid into the primary coupling liquid, adjusting the coupling pH to 7-8 by using a sodium carbonate solution with the mass fraction of 10%, controlling the coupling temperature to 0-5 ℃, detecting the reaction condition of the diazo component and the coupling component by using a permeation ring method at intervals of 10min, and simultaneously detecting the reaction process by combining TLC. After the coupling reaction was completed, the reaction pH was adjusted to about 7, and a buffer salt (Na) was added thereto2HPO3-NaH2PO31 percent, w/v) and then slowly adding potassium acetate solid accounting for about 5 percent of the mass of the reaction system in batches for salting out until a water ring appears in a ring penetration method. And continuously stirring the system for 10min, standing the system for 20min, performing suction filtration, washing a filter cake with 50mL of ethanol for several times, and drying to obtain the dye.
Examples 19 to 22
The structural dyes shown in the embodiments 19 to 22 can be prepared by respectively replacing benzenesulfonamide in the embodiment 18 with p-carboxylbenzenesulfonamide, p-toluenesulfonamide, p-trifluoromethylbenzenesulfonamide and p-nitrobenzenesulfonamide by the same preparation method as that shown in the embodiment 18.
Examples 23 to 25
The structural dyes shown in examples 23 to 25 can be prepared by the same preparation method as that shown in example 18 except that p-chlorobenzenesulfonamide is used to replace benzenesulfonamide in example 18, and 1, 3-diaminobenzene, 1, 2-diaminobenzene, 2, 4-diamino, m-phenylenediamine-4, 6-disulfonic acid is used to replace 2, 4-diaminobenzenesulfonic acid in example 18.
Example 26
The structural dye shown in example 26 was obtained in the same manner as in example 18 except that p-bromobenzenesulfonamide was used in place of benzenesulfonamide in example 18 and 2, 4-diamino, 1, 5-disulfonylbenzene was used in place of 2, 4-diaminobenzenesulfonic acid in example 18.
Example 27
The structural dye shown in example 27 was obtained by using the same preparation method as that shown in example 1 except that cyanuric chloride in example 1 was replaced with cyanuric fluoride and benzenesulfonamide in example 1 was replaced with 4-sulfobenzenesulfonamide.
Examples 28 to 29
The structural dyes shown in examples 28 to 29 were prepared by the same preparation method as example 25 except that 3-hydroxy, 4-methylbenzenesulfonamide and 2, 4-dimethylbenzenesulfonamide were used instead of 4-sulfobenzenesulfonyl in example 27.
Example 30
The same preparation method can be used to prepare dyes with corresponding structures by replacing the benzene sulfonamide in example 1 with 3-methyl, 4-trifluoromethyl benzene sulfonamide and replacing the para-ester in example 1 with para- (ethyl- β -hydroxyethyl sulfone sulfate) aniline.
Example 31
The corresponding structural dye can be prepared by the same preparation method of p- (ethyl- β -hydroxyethyl sulfone sulfate) aniline instead of the para-ester in example 29.
Example 32
Dyes of the corresponding structures were prepared using the same preparation method as that used for 2-methyl, 4-methoxybenzenesulfonamide instead of 3-methyl, 4-trifluoromethylbenzenesulfonamide in example 29.
Example 33
The structural dye of example 33 was prepared by the same method as that for the preparation of 3-hydroxy, 4-methylbenzenesulfonamide instead of benzenesulfonamide in example 1 and 2-methyl, 4- (ethyl- β -hydroxyethyl sulfone sulfate) aniline, i.e., the para-ester in example 1.
Example 34
The structural dye of example 34 was prepared by the same method as that for 3-carboxy, 4-methylbenzenesulfonamide instead of benzenesulfonamide in example 1 and 2-methyl, 4- (ethyl- β -hydroxyethyl sulfone sulfate) aniline instead of the para-ester in example 1.
Example 35
The structural dye shown in example 35 can be prepared by the same preparation method as that of 3-nitro, 4-methylbenzenesulfonamide instead of benzenesulfonamide in example 1 and 2-methyl, 4- (acetylhydroxy sulfate) aniline instead of the para-ester in example 1.
Example 36
The structural dye of example 36 was prepared by the same method as that of 3-chloro, 4-methylbenzenesulfonamide instead of benzenesulfonamide of example 1 and 2-methyl, 4- (acetylaminohydroxy sulfate) aniline instead of the para-ester of example 1.
Example 37
The structural dye of example 37 was obtained by the same production method as that of 3-bromo, 4-methylbenzenesulfonamide instead of benzenesulfonamide in example 1 and 2-methyl, 4- (sulfonamido, β -hydroxyethyl sulfone sulfate) aniline instead of the p-ester in example 1.
Example 38
The structural dye shown in example 38 was obtained by the same production method as that of 3-fluoro, 4-methylbenzenesulfonamide instead of 3-carboxy, 4-methylbenzenesulfonamide used in example 32.
Example 39
The structural dye of example 39 was prepared by the same preparation method as that of 2, 4-methylbenzenesulfonamide instead of 3-carboxy, 4-methylbenzenesulfonamide used in example 32.
Example 40
The same preparation method was used to prepare the structural dye of example 40 by using 3-methoxy, 4-methylbenzenesulfonamide and K acid instead of benzenesulfonamide and H acid in example 1 and using meta-ester instead of para-ester in example 1.
EXAMPLE 41
The dyes of the structures shown in example 41 were obtained by the same procedure except that 3-cyano, 5-methylbenzenesulfonamide, 1-amino, 8-naphthol, 2, 4-dinaphthalenesulfonic acid (Chicago acid) was used instead of benzenesulfonamide and H acid in example 1, and 3- (β -chloroethylsulfone) aniline was used instead of para-ester in example 1.
Example 42
The same procedure was used to prepare the dye of structure 42 by substituting 3-cyano, 5-methylbenzenesulfonamide and K acid for benzenesulfonamide and H acid in example 1 and 3-ethyl, 4-sulfate ethylsulfonanilide for the para-ester in example 1, respectively.
Example 43
The same procedure used to prepare the dye of structure 43 was followed using 3-cyano, 4-methylbenzenesulfonamide instead of 3-cyano, 5-methylbenzenesulfonamide in example 40 and 3-methoxy, 4-sulfate ethylsulfone aniline instead of 2-methyl, 4- (sulfonamido, β -hydroxyethyl sulfone sulfate) aniline in example 35.
Example 44
The dye of example 44 can be obtained by the same preparation method using 3-cyano, 4-aminomethyl benzenesulfonamide, 1-amino, 8-naphthol, 2, 4-dinaphthalenesulfonic acid instead of benzenesulfonamide and H acid in example 1, and 4-methoxy-3- (β -sulfatoethylsulfone) aniline instead of para-ester in example 1.
Testing of dyeing Properties
Taking the example of the 10-branch reactive dye dip dyeing synthesized in examples 1-10, dyeing experiments were carried out, and dyeing curves shown in fig. 1 were used to dye cloth samples with similar color depths, wherein each branch of the dye was dyed under different chromaticity conditions. Meanwhile, in order to compare the dyeing activity of the dye at different temperatures, the color fixing temperatures of 60 ℃, 75 ℃ and 90 ℃ are respectively selected. Taking a proper amount of dye to prepare a dye solution. Accurately weighed 2g of cotton fiber is soaked and dyed in 20mL of dye solutionAnd obtaining a cloth sample. After dyeing, the cloth sample is washed with water and the residual liquid is collected, and the absorbance A is measured1. Placing the washed cloth sample in 0.1% soap solution, boiling at 95 deg.C for 10min, taking out the cloth sample, washing with water, collecting residual liquid, and measuring absorbance A2. Diluting another 1mL of original dye solution to 100mL, and measuring absorbance A0。
① determination of degree of exhaustion, fixation rate and reaction rate
The dye is combined with the fiber through a covalent bond, and the degree of exhaustion, the fixation rate and the reaction rate are calculated through the following formulas:
Figure BDA0001859036120000171
wherein E, F, R is the degree of exhaustion, the fixation rate and the reaction rate (100 percent) respectively; a. the0、A1、A2Respectively is dyeing
Figure BDA0001859036120000181
Figure BDA0001859036120000182
Absorbance of the stock solution, the dyeing residual solution and the soaping residual solution; n is0、n1、n2The dilution times are respectively the corresponding dilution times of the dyeing stock solution, the dyeing residual solution and the soaping residual solution.
② measurement of color fastness
The color fastness to sunlight is determined by GB/T8427-; the color fastness to rubbing is determined by GB/T3920-; the color fastness to washing is determined by GB/T3921-2008, and the solubility of the dye is determined by GB/T21879-2015.
The dyeing results of the above 10 dyes according to the above dyeing conditions are shown in the following table
Table 2 dyeing data of dyes at different fixation temperatures
Figure BDA0001859036120000183
Figure BDA0001859036120000191
The results of the fastness tests of the above 10 dyes according to the above test conditions are shown in Table 3.
TABLE 3 color fastness of dyed cloth sample
Figure BDA0001859036120000192

Claims (9)

1. A reactive dye substituted with benzenesulfonamide and derivatives thereof, having the structure of formula i:
Figure FDA0001859036110000011
in the formula I, the compound is shown in the specification,
r is selected from-Cl or-F;
R1selected from-H, methyl, nitrile, sulfonic, trifluoromethyl, methoxy, hydroxy, carboxy, nitro, -Cl, -Br, -F;
R2selected from-H, methyl, aminomethyl, trifluoromethyl, methoxy, hydroxy, nitro, cyano, -Cl, -Br, -F;
R3is selected from-H, -OCH3，-CH3，-CH2CH3；
L is selected from-SO2-，-CO-，-NHCO-，-SO2NH-，-CH2CH2SO2-，-O-CH2CH2SO2-，-NHCH2CH2SO2-，-NHCONHCH2CH2SO2-，-SO2CH2CH2SO2-or-NXSO2-a group wherein X is selected from C1～C4Alkoxy substituted or unsubstituted by carbon atom, phenyl, the substituent of which may be-SO3H. -COOH, -OH, halogen, cyano, aminosulfonyl (H)2NSO2-), ethoxy, cyanomethyl groups;
m is selected from-Cl, or-OSO3R4Wherein R is4Selected from-H, -Na or-K;
a is selected from substituents shown as II-a or II-b;
Figure FDA0001859036110000012
in the formula II-a, the compound is shown in the specification,
n is an integer of 0 to 2;
the residue represented by the formula II-b is one of the following groups:
an H acid residue having the formula:
Figure FDA0001859036110000021
j acid residue of the formula:
Figure FDA0001859036110000022
a gamma acid residue having the formula:
Figure FDA0001859036110000023
a K acid residue of the formula:
Figure FDA0001859036110000024
a chicago acid residue having the formula:
Figure FDA0001859036110000025
2. the process for preparing a reactive dye substituted with benzenesulfonamide and its derivatives as claimed in claim 1, wherein the process for preparing the dye comprises the following two methods:
the method comprises the steps of carrying out condensation reaction on halogenated s-triazine, benzene sulfonamide and amino naphthol sulfonic acid substrates to obtain a condensation product, carrying out diazotization reaction on β -sulfuric ester ethyl sulfone aniline to obtain a diazonium salt solution, carrying out coupling reaction on the condensation product and the diazonium salt solution at the reaction temperature of 0-5 ℃ and the pH of 7-8 to obtain the dye of claim 1;
the second method comprises the steps of carrying out diazotization reaction on β -sulfate ethyl sulfone aniline to obtain a diazonium salt solution, dropwise adding an H acid solution into the diazonium salt solution at a molar ratio of 1:1 at a reaction temperature of 0-5 ℃ for 4H with a pH value of less than 3, carrying out primary coupling reaction to obtain a primary coupling solution, carrying out condensation reaction on halogenated s-triazine, benzenesulfonamide and an arylamine substrate to obtain a condensation product, carrying out diazotization reaction on the condensation product to obtain a condensation product diazonium solution, dropwise adding the condensation product diazonium solution into the primary coupling solution at a reaction temperature of 0-5 ℃ and a pH value of 7-8, and carrying out coupling reaction to obtain the dye of claim 1.
3. The method of claim 2, wherein the condensation product is prepared by:
carrying out first condensation reaction on halogenated s-triazine and benzene sulfonamide or derivatives thereof; then carrying out secondary condensation with an amino naphthol sulfonic acid substrate or an arylamine substrate to obtain a condensation product;
the molar ratio of the first-time condensed halogenated s-triazine to the benzene sulfonamide salt is 1: 1-1: 3, the reaction temperature is 0-5 ℃, the dripping time is 40-50 min, the reaction time is 120min, a first-time condensation product is obtained, the molar ratio of the first-time condensation product to the amino naphthol sulfonic acid substrate or the arylamine substrate is 1: 0.9-1, the reaction temperature is 15-30 ℃, the pH value is 6-7, and the reaction end point is detected by thin-layer chromatography, so that the condensation product is obtained.
4. The method as claimed in claim 2, wherein the halogenated s-triazine is subjected to a first condensation reaction with benzenesulfonamide to precipitate unreacted benzenesulfonamide and its derivatives, thereby obtaining a clear filtrate, and the clear filtrate is subjected to a second condensation with an aminonaphthol sulfonic acid substrate or an arylamine substrate, wherein the precipitation is carried out by adjusting the pH to be less than 3 with the addition of acid.
5. The process according to claim 2, characterized in that the halogenated s-triazines are cyanuric chloride and cyanuric fluoride.
6. The method of claim 2, wherein the aminonaphthol sulfonic acid based substrate is H acid, J acid, γ acid, K acid, chicago acid.
7. The method according to claim 2, wherein the aromatic amine substrate is 2, 4-diaminobenzene sulfonic acid, 1, 2-diaminobenzene, 1, 3-diaminobenzene, 1, 4-diaminobenzene, 2, 4-diamino-1, 5-disulfonylbenzene.
8. The method according to claim 2, wherein the diazotization reaction is a reaction of aromatic primary amine and sodium nitrite at 0-5 ℃ in a strong acid medium to generate diazo salt, the molar ratio of the aromatic primary amine to the nitrous acid is 1: 1.03-1.1, the strong acid medium is concentrated hydrochloric acid with the mass fraction of 37%, the molar amount of the concentrated hydrochloric acid is 3 times that of the aromatic primary amine, the aromatic primary amine is β -sulfate ethyl sulfone aniline or a condensation product, the condensation product is obtained by condensation reaction of halogenated s-triazine and benzenesulfonamide and then an amino naphthol sulfonic acid substrate,
and (3) detecting whether the hydrochloric acid and the sodium nitrite are sufficient or not by using Congo red test paper and starch-KI test paper in the diazotization reaction, detecting the reaction end point by using an Ellisib reagent, and adding sulfamic acid to destroy redundant sodium nitrite when the diazotization is finished to obtain a diazotization solution.
9. The method of claim 2, wherein the coupling reaction is monitored by a cyclotomic method to an endpoint.
CN201811327162.0A 2018-11-08 2018-11-08 Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof Active CN109608903B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811327162.0A CN109608903B (en) 2018-11-08 2018-11-08 Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811327162.0A CN109608903B (en) 2018-11-08 2018-11-08 Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109608903A CN109608903A (en) 2019-04-12
CN109608903B true CN109608903B (en) 2020-04-14

Family

ID=66003250

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811327162.0A Active CN109608903B (en) 2018-11-08 2018-11-08 Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109608903B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437278A (en) * 2022-02-11 2022-05-06 大连理工大学 Styrene maleic acid copolymerization macromolecular reactive dye and preparation method thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0292618B1 (en) * 1987-05-29 1991-08-28 Agfa-Gevaert N.V. Photographic element incorporating compounds for use in a dye diffusion transfer process
GB9110689D0 (en) * 1991-05-17 1991-07-10 Ici Plc Dyes
TW222298B (en) * 1991-10-23 1994-04-11 Hoechst Ag Fiber reactive dyes which contain a sulfonamido-triazinyl group and one or two groups or the vinyl sulfone series

Also Published As

Publication number Publication date
CN109608903A (en) 2019-04-12

Similar Documents

Publication Publication Date Title
JPS636590B2 (en)
CA1038377A (en) Water-soluble azo dyestuffs, their preparation and utilization
Saeed et al. Synthesis and characterization of high wash fastness novel azo reactive dyes incorporating aromatic bridged diamines
US4855411A (en) Water-soluble, monoazo dyes containing a ureido group and two sulfonyl fiber-reactive groups
KR100383783B1 (en) Dye mixtures of water-soluble fiber-reactive azo dyes, preparation methods and uses thereof
CN110938039A (en) Purple reactive dye based on trisazo multichromosome and preparation and application thereof
CN109608903B (en) Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof
EP1760117B1 (en) Reactive dyestuff compositions and their use
Patel et al. Synthesis of some heteropolyfunctional reactive dyes and their application on silk, wool, and cotton fibers
KR101419324B1 (en) Reddish-yellow Reactive dye composition
JPH0447715B2 (en)
EP0265857B1 (en) Water-soluble monoazodyes containing a ureido group and two sulfonyl fiber-reactive groups, process for their preparation and their use
Wang et al. Design of novel reactive dyes containing cationic groups: Mechanism and application for environmentally friendly cotton dyeing
CN1312225C (en) Fibre-reactive azo dyes, their production and their use
CN110066527B (en) Red reactive dye and preparation method thereof
CN110054910B (en) Black reactive dye composition and preparation method and application thereof
US4845202A (en) Water-soluble disazo compounds containing 3-carboxy or 3-carbamoylpyridium-s-triazinyl groups and fiber-reactive groups of the vinyl sulfone series suitable as dyestuffs
KR890002348B1 (en) Process for the preparation of water-soluble mono azo compounds
KR890001783B1 (en) Process for the preparation of water-solable monoazo compound
CN110903679A (en) Green reactive dye based on monoazo structure of mono H acid and preparation and application thereof
CN104693836B (en) Anthraquinone azo reactive dye
Shabir et al. Synthesis, Characterization and Applications of High Fastness Reactive Dyes on Cotton Fibers.
CN110041729B (en) Orange-red reactive dye and preparation method thereof
CA2405421A1 (en) Dye mixture comprising water-soluble fiber-reactive azo dyes, preparation thereof and use thereof
CN113150576B (en) Ink-jet printing active red dye and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant