CN111607246A - Azo disperse dye and preparation method and application thereof - Google Patents

Azo disperse dye and preparation method and application thereof Download PDF

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CN111607246A
CN111607246A CN202010610661.1A CN202010610661A CN111607246A CN 111607246 A CN111607246 A CN 111607246A CN 202010610661 A CN202010610661 A CN 202010610661A CN 111607246 A CN111607246 A CN 111607246A
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reaction
mixture
disperse dye
room temperature
azo disperse
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冯高峰
郭小燕
钱红飞
方帅军
周金丽
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University of Shaoxing
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    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • C09B29/0833—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5
    • C09B29/0836—Amino benzenes characterised by the substituent on the benzene ring excepted the substituents: CH3, C2H5, O-alkyl, NHCO-alkyl, NHCOO-alkyl, NHCO- C6H5, NHCOO-C6H5 linked through -N=
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/18—Azo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/19—Nitro dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/26—Polyamides; Polyurethanes using dispersed dyestuffs

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Abstract

The application provides an azo disperse dye and a preparation method and application thereof, belonging to the technical field of monoazo dyes prepared by a coupling method. The azo disperse dye has the following structural formula:
Figure DDA0002561703060000011
wherein R is1Is H or Cl, R2Is H or Cl. The azo disperse dye introduces ester groups and amide groups, improves the interaction between the dye and fibers, and greatly improves the dyeing performance and color fastness on chinlon.

Description

Azo disperse dye and preparation method and application thereof
Technical Field
The application relates to an azo disperse dye, a preparation method and an application thereof, belonging to the technical field of monoazo dyes prepared by a coupling method.
Background
Disperse dyes are the most widespread dye class of the current hydrophobic fiber dyeing dyes. The disperse dyes may be azo type, anthraquinone type, heterocyclic type depending on the type of color body. The azo type disperse dye is the most important type of disperse dye, accounts for about 60 percent, has complete chromatogram, and can obtain different spectral properties and dyeing properties by changing the electronic effect of substituent groups on the diazo component and the coupling component.
Disperse dyes have been developed with the development of synthetic fibers. At present, with the appearance of superfine polyester fibers, environment-friendly polylactic acid fibers, differential terylene easy-to-dye fibers and novel fibers, most of the existing disperse dyes have poor affinity with the fibers, and are easy to generate heat migration after being heated, so that the fibers have poor washing fastness and poor application performance. Therefore, new synthetic methods and strategies are needed to be developed to rapidly obtain novel high-performance disperse dyes with various structures so as to meet the dyeing requirements of the dyes on various fibers.
The magnitude of the acting force between the disperse dye and the fiber fundamentally determines the dyeing performance and the color fastness of the disperse dye. From the analysis of the disperse dye coloring mechanism, the fiber structure and the like, the following methods can be adopted to improve the disperse dye dyeing performance and the color fastness: 1. according to the principle of 'similar compatibility', special functional groups such as ester groups, amide groups and the like are introduced into the disperse dye. Functional groups such as ester groups, amide and the like can form hydrogen bonds with fibers so as to obtain stronger interaction and improve the dyeing property of the fibers; 2. effectively increase the molecular weight of the dye. Along with the increase of molecular weight, the acting force between dye molecules and fibers is increased, and the dyeing properties such as heat migration resistance fastness, sublimation resistance fastness and the like are improved.
The development of a proper synthetic method and a proper synthetic strategy, the effective regulation and control of the molecular weight of the disperse dye and the introduction of a special functional group capable of interacting with fibers are the key points of the development of the high-performance disperse dye. The method has the advantages of simple and easily obtained multi-component reaction raw materials, rapid and efficient reaction, various product skeleton structures and substituent groups, easy regulation and control of molecular weight, and introduction of special groups capable of interacting with fibers, and is an ideal method and strategy for obtaining high-performance disperse dyes.
Disclosure of Invention
The first aspect of the invention aims to provide a novel high-performance azo disperse dye, and the azo disperse dye has a remarkable effect on the dyeing performance and color fastness of chinlon.
An azo disperse dye, which has a structural formula as follows:
Figure BDA0002561703040000021
in the formula: r1Is H, Cl, R2Is H, Cl.
The azo disperse dye has the structural characteristics that: has moderate molecular weight and volume, and contains one ester group and two amide groups (RCOO-, -CONR)2-CONHR). These structural features have an important influence on the improvement of the dyeing properties and color fastness of the novel dyes:
(1) the effective increase of the molecular volume and the molecular weight of the dye improves the contact surface between the dye and the fiber, and enhances the Van der Waals force between the dye and the fiber, thereby improving the affinity between the dye and the fiber, and improving the dyeing performance and the color fastness of the dye.
(2) By introducing characteristic groups such as ester group and amide group, hydrogen bonds can be formed with hydrogen receiving groups and hydrogen supplying groups in the fibers, and the characteristic groups are suitable for the structure of the polyester fibers, so that the acting force between the characteristic groups and the polyester fibers is enhanced, and the dyeing performance can be improved.
(3) In the synthesis of the azo disperse dye, the number of groups on the diazo component and the electronic effect have important influence on the maximum absorption wavelength and the color of the dye. Under the condition that the coupling components are the same, the azo disperse dyes with different colors can be obtained by selecting different substituted diazo components, thereby providing great convenience for the diversity synthesis of the azo disperse dyes.
The novel azo disperse dye can be selected from one of the following compounds:
Figure BDA0002561703040000031
in the preparation process of the azo dye, the preparation of a coupling component is generally carried out firstly, and the preparation process comprises the following two steps:
step one, acid synthesis: 13.0mmol succinic anhydride, 1.0mmol DMAP and 15mL CH are added in turn2Cl210.0mmol triethylamine and 10.0mmol N-ethyl-N-hydroxyethylaniline form a mixed solution, the mixed solution is stirred for 4 hours at room temperature, and after the reaction is finished, the mixed solution is decompressed, concentrated and dried in vacuum.
Step two, a Ugi four-component reaction: and sequentially adding 70mL of anhydrous methanol, 12.0mmol of aniline and 12.0mmol of o-bromobenzaldehyde, transferring the acid synthesized in the step I by using the anhydrous methanol, finally adding 10mmol of cyclohexylacetonitrile, heating and stirring in an oil bath at 80 ℃ for 48 hours, cooling to room temperature after the reaction is finished, cooling to separate out a large amount of white solid, carrying out suction filtration, washing by using ethyl acetate/petroleum ether with the volume ratio of 1:5, and drying.
The following two steps were also carried out to synthesize the disperse dye of formula 1 ba:
(1) synthesis of diazonium salt: dissolving 4.73mmol of sodium nitrite with 5mL of water, placing the solution in an ice water bath for 2min, mixing the 5mL of water with 5mL of 36.5% hydrochloric acid, dropwise adding the mixture into 4.73mmol of 4-nitroaniline, dissolving the mixture at 40-60 ℃, cooling the mixture to room temperature, placing the mixture in the ice water bath, dropwise and slowly adding the aqueous solution of sodium nitrite, and reacting the mixture in the ice water bath for 1h after dropwise adding is finished to obtain the 4-nitrophenyl diazonium salt.
(2) Coupling reaction: adding 30mL of methanol into 3.15mmol of coupling component, heating and stirring in an oil bath at 80 ℃ until the coupling component is completely dissolved, cooling to room temperature, slowly dropwise adding 4-nitrophenyl diazonium salt under the condition of ice-water bath, stirring at 0-5 ℃ for 24 hours, after the reaction is finished, carrying out suction filtration, washing with ethyl acetate/petroleum ether at a volume ratio of 1:5, drying, purifying by adopting column chromatography, eluting with a mixed solvent of ethyl acetate and petroleum ether at a volume ratio of 1:2, and drying.
The synthesis of the disperse dye of formula 1bb also requires the following two steps:
(1) synthesis of diazonium salt: dissolving 4.73mmol of sodium nitrite with 5mL of water, placing the mixture in an ice water bath for 2min to obtain a sodium nitrite aqueous solution, mixing the 5mL of water with 5mL of 36.5% hydrochloric acid, dropwise adding the mixture into 4.73mmol of 2-chloro-4-nitroaniline, dissolving the mixture at 40-60 ℃, cooling the mixture to room temperature, placing the mixture in the ice water bath, dropwise and slowly adding the sodium nitrite aqueous solution, and reacting the mixture in the ice water bath for 1h after dropwise adding is completed to obtain the 2-chloro-4-nitrophenyldiazonium salt.
(2) Coupling reaction: adding 30mL of methanol into 3.15mmol of coupling component, heating and stirring in an oil bath at 80 ℃ until the coupling component is completely dissolved, cooling to room temperature, slowly and dropwise adding 2-chloro-4-nitrophenyl diazonium salt in the ice-water bath, stirring at 0-5 ℃ for 24 hours, after the reaction is finished, carrying out suction filtration, washing with ethyl acetate/petroleum ether in a volume ratio of 1:5, and drying.
The synthesis of the disperse dye of formula 1bc requires the following two steps:
(1) synthesis of diazonium salt: dissolving 4.73mmol of sodium nitrite with 5mL of water, placing the mixture in an ice water bath for 2min to form a sodium nitrite aqueous solution, mixing the 5mL of water with 5mL of 36.5% hydrochloric acid, dropwise adding the mixture into 4.73mmol of 2, 6-dichloro-4-nitroaniline, dissolving the mixture at 40-60 ℃, cooling the mixture to room temperature, placing the mixture in the ice water bath, dropwise and slowly adding the sodium nitrite aqueous solution, and reacting the mixture in the ice water bath for 1h after the dropwise adding is finished to obtain the 2, 6-dichloro-nitrophenyl diazonium salt.
(2) Coupling reaction: adding 30mL of methanol into 3.15mmol of coupling component, heating and stirring in an oil bath at 80 ℃ until the coupling component is completely dissolved, cooling to room temperature, slowly and dropwise adding 2, 6-dichloro-nitrophenyl diazonium salt under the condition of ice-water bath, stirring for 24 hours at 0-5 ℃, carrying out suction filtration after the reaction is finished, washing by using ethyl acetate/petroleum ether with the volume ratio of 1:5, and drying.
The second aspect of the present invention is to provide a preparation method of the azo disperse dye, comprising the following steps:
(1) acid synthesis: in an organic solvent, adding a certain amount of N-ethyl-N-hydroxyethylaniline, succinic anhydride, DMAP and triethylamine into a reaction flask for reaction at room temperature. After the reaction is finished, directly carrying out reduced pressure concentration on the reaction liquid to obtain corresponding carboxylic acid for the next step of Ugi reaction;
(2) ugi reaction (also known as Ugi four-component reaction): in an organic solvent, the acid synthesized in the last step and o-bromobenzaldehyde, aniline and cyclohexyl isonitrile are subjected to an Ugi four-component reaction at a certain temperature. After the reaction is finished, filtering the reaction liquid, and washing the reaction liquid by an organic solvent to obtain a white Ugi product, namely the coupling component of the azo disperse dye.
(3) Coupling reaction: in an organic solvent, the obtained coupling component and a 4-nitrophenyldiazonium compound are coupled at a certain temperature. After the reaction is finished, filtering, washing and drying the solid to obtain the novel disperse dye.
The process can be expressed by the following reaction equation:
Figure BDA0002561703040000051
preferably, the further settings are as follows:
in the step (1):
the organic solvent is any one of dichloromethane, dichloroethane and acetonitrile.
The molar ratio of the N-ethyl-N-hydroxyethyl aniline to the succinic anhydride to the DMAP to the triethylamine is 1: 1.2-1.5: 0.1-0.2: 1-1.5.
The reaction temperature is between room temperature and 50 ℃, and the reaction time is 1-5 h.
In the step (2):
the organic solvent is any one of toluene, methanol, ethanol or acetonitrile.
The molar ratio of the synthetic acid to the o-bromobenzaldehyde to the cyclohexyl isonitrile to the aniline is 1:1.2:1: 1.2.
The reaction temperature is 40-100 ℃, the reaction conditions are mild, and the reaction time is as follows: 36-48 h.
In the step (3):
the molar ratio of the coupling component to the 4-nitrophenyldiazonium salt is: 1: 1.5-1.2.
The reaction temperature is 0-5 ℃, and the reaction time is 24-36 h.
The third aspect of the invention aims to provide an application of the azo compound in dyeing of nylon fabrics, and in the application process, the azo compound can be directly added as disperse red, and can also be used as one component of disperse dye to be mixed with other components for addition. The dyeing process comprises the following steps: weighing an azo compound, fully mixing the azo compound with a dispersant NNO according to the mass ratio of 1:1, and adding water to prepare 1g/L of dye mother liquor; 1g/L of dye mother liquor, 5g/L of ammonium sulfate mother liquor and 5g/L of dispersant NNO solution are taken, water is added to prepare dye liquor, the dye concentration is 0.5 percent (o.w.f), the ammonium sulfate concentration is 1g/L, the NNO concentration is 1g/L, and the bath ratio is 50: 1; putting chinlon into a dye solution at room temperature, starting dyeing at 40 ℃, increasing the temperature to 120 ℃ at a heating rate of 1 ℃/min, then keeping the temperature for 70min, and then cooling to 90 ℃ at full speed; after dyeing is finished, soaping the dyed sample by using a 2g/L standard soap powder aqueous solution, washing for 15min at 95 ℃ in a bath ratio of 50:1, taking out, washing by using tap water, and airing in a natural state.
The preparation method of the invention has the following remarkable technical effects:
firstly, coupling components with different molecular weights and different molecular volumes can be obtained by changing any component (substituent or structure) of initial Ugi four-component reaction, and the molecular volume and molecular weight of the novel disperse dye can be effectively controlled, so that the dyeing property and color fastness of the disperse dye can be regulated and controlled.
Secondly, by the synthesis method of the invention, an ester group and two amide groups are introduced into the novel disperse dye, and the ester group and the amide groups can form interaction with fibers to improve the dyeing performance.
Thirdly, the invention can obtain series of novel disperse dyes with different spectral properties by adopting different diazonium salts, and provides a novel strategy and a novel method for the diversity synthesis of novel high-performance azo disperse dyes.
The invention is further described in detail below with reference to the following figures and detailed description.
Drawings
FIG. 1 is a NMR chart of a coupling component 3b prepared in example 1 in an embodiment;
FIG. 2 is a NMR chart of azo disperse dye 1ba prepared in example 2 in a specific embodiment.
Detailed Description
Example 1: preparation of coupling component 3b
(1) Acid synthesis:
to a 100mL round bottom flask were added succinic anhydride (1.3g, 13.0mmol, 1.3eq), DMAP (122.2mg, 1.0mmol, 0.1eq), CH in that order2Cl2(15mL), triethylamine (1.27mL, 10.0mmol, 1.0eq) and N-ethyl-N-hydroxyethylaniline (1.66mL, 10.0mmol, 1.0 eq). And stirring the reaction mixed solution at room temperature for 4 hours, carrying out thin-layer sample application to track the reaction process, carrying out reduced pressure concentration and vacuum drying on the reaction solution by using a rotary evaporator after the reaction is finished, and directly using the residue in the bottle for the Ugi four-component reaction.
(2) Ugi four-component reaction:
to a 250mL round bottom flask were added anhydrous methanol (70mL), aniline (1.12mL, 12.0mmol, 1.2eq) and o-bromobenzaldehyde (1.39mL, 12.0mmol, 1.2eq) in that order, the acid synthesized in (1) was transferred to the flask with anhydrous methanol, and finally cyclohexylacetonitrile (1.25mL, 10mmol, 1.0eq) was added. And heating and stirring the reaction mixed solution in an oil bath at the temperature of 80 ℃ for 48h, carrying out thin-layer sample application to track the reaction process, cooling the reaction solution to room temperature after the reaction is finished, and cooling in a refrigerator until a large amount of white solid is separated out. And (3) carrying out suction filtration, washing the mixture for multiple times by using an organic mixed solvent (the volume ratio of ethyl acetate to petroleum ether is 1:5), and drying the mixture to obtain 5.98g of white solid 3 b. The reaction equation is as follows:
Figure BDA0002561703040000071
the NMR chart of the coupling component 3b is shown in FIG. 1, which shows1H-NMR、13C-NMR data are as follows:1H NMR(400MHz,CDCl3)ppm 7.52(d,J＝8.0,1.2Hz,1H,Ar-H),7.25-7.18(m,5H,Ar-H),7.05-6.93(m,4H,Ar-H),6.72(d,J＝8.0Hz,2H,Ar-H),6.69(dd,J＝7.6,7.6Hz,1H,Ar-H),6.52(s,1H,COCHN),5.98(d,J＝8.0Hz,1H,NH),4.30-4.19(m,2H,CH2O),3.94-3.84(m,1H,NCH),3.56(t,J＝6.4Hz,2H,CH2CH2N),3.41(q,J＝6.8Hz,2H,CH3CH2N),2.76-2.59(m,2H,OCOCH2),2.43-2.30(m,2H,NCOCH2),2.03(d,J＝16.0Hz,1H,Cy-H),1.92(d,J＝16.4Hz,1H,Cy-H),1.78-1.61(m,3H,Cy-H),1.41-1.25(m,3H,Cy-H),1.18(t,J＝7.2Hz,3H,CH3),1.15-1.07(m,2H,Cy-H).
13C NMR(100MHz,CDCl3)ppm 173.1,171.9,168.3,147.6,139.3,134.4,132.6,132.3,130.0,129.8,129.3(×3),128.9,128.3,127.0,126.3,116.2,112.0(×3),64.0,61.8,49.0,48.8,45.2,32.9,32.8,29.8,29.5,25.5,25.0,24.8,12.3.
example 2: synthesis of disperse dye 1ba
(1) Synthesis of diazonium salt:
4-nitroaniline (0.66g,4.73mmol,1.5eq) was added to a 50mL round-bottomed flask, 5mL of water and 5mL of concentrated hydrochloric acid (36.5%) were mixed and added dropwise to the flask, and the mixture was dissolved at 40-60 ℃ (about 1 h). After cooling the solution to room temperature, it was placed in an ice-water bath. Sodium nitrite (0.33g,4.73mmol,1.5eq) was dissolved in 5mL of water in a small beaker and placed in an ice-water bath for about 2 min. And (3) slowly adding the sodium nitrite aqueous solution dropwise, and reacting in an ice water bath for 1h after the dropwise addition is finished.
(2) Coupling reaction:
in a 150mL round bottom flask, 30mL of methanol and coupling component 3b (2.00g,3.15mmol,1.0eq) were added, heated with stirring in an oil bath at 80 ℃ until the coupling component was completely dissolved, and then the mixture was cooled to room temperature. And (2) slowly and dropwise adding the 4-nitrophenyldiazonium salt synthesized in the step (1) under the condition of ice-water bath, stirring for 24 hours at the temperature of 0-5 ℃, and carrying out thin-layer spotting to track the reaction progress. After the reaction is finished, the mixture is filtered, washed by an organic mixed solvent (the volume ratio of ethyl acetate to petroleum ether is 1:5), and dried to obtain a red solid. Purifying by column chromatography to obtain pure dye 1ba, eluting with mixed solvent of ethyl acetate and petroleum ether at volume ratio of 1:2, drying, and weighing to obtain 1.95 g. The reaction equation is as follows:
Figure BDA0002561703040000081
the NMR chart of disperse dye 1ba is shown in FIG. 2, which shows1H-NMR、13C-NMR data are as follows:
1H NMR(400MHz,CDCl3)ppm 8.36(d,J＝9.2Hz,2H,Ar-H),7.95(d,J＝9.2Hz,2H,Ar-H),7.92(d,J＝9.2Hz,2H,Ar-H),7.52(d,J＝7.6Hz,1H,Ar-H),7.18(br s 4H,Ar-H),7.05-6.97(m,4H,Ar-H),6.49(br s,1H,COCHN),5.80(d,J＝8.4Hz,1H,NH),4.35-4.28(m,2H,CH2O),3.91-3.86(m,1H,NCH),3.71(t,J＝5.6Hz,2H,CH2CH2N),3.55(q,J＝7.6Hz,2H,CH3CH2N),2.71-2.66(m,2H,OCOCH2),2.16-2.90(m,2H,NCOCH2),2.03(d,J＝8.4Hz,1H,Cy-H),1.91(d,J＝10.8Hz,1H,Cy-H),1.76-1.60(m,3H,Cy-H),1.46-1.23(m,3H,Cy-H),1.28(t,J＝7.6Hz,3H,CH2CH3),1.19-1.05(m,2H,Cy-H).
13C NMR(100MHz,CDCl3)ppm 173.0,171.8,168.3,156.6,151.3,147.4,143.8,139.2,134.3,132.7,132.1,130.0,129.9(×2),129.0(×2),128.3,127.1,126.3(×2),124.7(×2),122.6(×2),111.5(×2),64.0,61.4,49.0,48.9,45.8,32.8,32.8,29.7,29.4,25.5,24.9,24.9,12.3.
example 3: synthesis of disperse dye 1bb
(1) And (3) diazonium salt synthesis:
2-chloro-4-nitroaniline (0.82g,4.73mmol,1.5eq) was added to a 50mL round-bottomed flask, 5mL of water and 5mL of concentrated hydrochloric acid (36.5%) were mixed and added dropwise to the flask, and the mixture was dissolved at 40 to 60 ℃. After cooling the solution to room temperature, it was placed in an ice-water bath. Sodium nitrite (0.33g,4.73mmol,1.5eq) was dissolved in 5mL of water in a small beaker and placed in an ice-water bath for about 2 min. And (3) slowly adding the sodium nitrite aqueous solution dropwise, and reacting in an ice water bath for 1h after the dropwise addition is finished.
(2) Coupling reaction:
in a 150mL round bottom flask, 30mL of methanol and coupling component 3b (2.00g,3.15mmol,1.0eq) were added, heated with stirring in an oil bath at 80 ℃ until the coupling component was completely dissolved, and then the mixture was cooled to room temperature. Under the condition of ice-water bath, the 2-chloro-4-nitrophenyldiazonium salt is slowly dripped dropwise, the mixture is stirred for 24 hours at the temperature of 0-5 ℃, and the reaction process is tracked by thin-layer spotting. After the reaction, the mixture is filtered by suction, washed by an organic mixed solvent (the volume ratio of ethyl acetate to petroleum ether is 1:5), dried to obtain a dark red solid, and dried and weighed to obtain 2.14 g.
The reaction equation is as follows:
Figure BDA0002561703040000091
of disperse dye 1bb1H-NMR、13C-NMR data are as follows:
1H NMR(400MHz,CDCl3)ppm 8.40(d,J＝2.0Hz,1H,Ar-H),8.17(dd,J＝8.8,2.4Hz,1H,Ar-H),7.95(d,J＝9.2Hz,2H,Ar-H),7.80(d,J＝8.8Hz,1H,Ar-H),7.51(d,J＝8.0Hz,1H,Ar-H),7.18(br s,3H,Ar-H),7.02-6.96(m,4H,Ar-H),6.81(d,J＝8.8Hz,2H,Ar-H),6.49(s,1H,COCHN),5.84(d,J＝7.6Hz,1H,NH),4.37-4.26(m,2H,CH2O),3.91-3.83(m,1H,NCH),3.71(t,J＝6.4Hz,2H,CH2CH2N),3.55(q,J＝6.8Hz,2H,CH3CH2N),2.72-2.62(m,2H,OCOCH2),2.43-2.33(m,2H,CH2CON),2.01(d,J＝10.8Hz,1H,Cy-H),1.91(d,J＝12.0Hz,1H,Cy-H),1.75-1.60(m,3H,Cy-H),1.39-1.31(m,3H,Cy-H),1.27(t,J＝7.2Hz,3H,CH3),1.13-1.03(m,2H,Cy-H).
13C NMR(100MHz,CDCl3)ppm 172.9,171.8,168.3,153.1,151.7,147.1,144.4,139.2,134.3,134.0,132.7,132.1,130.0,129.9(×2),129.0(×2),128.3,127.1,127.0(×2),126.3,126.0,122.6,118.0,111.5(×3),64.0,61.3,49.0,48.8,45.8,32.9,32.8,29.8,29.4,25.5,25.0,24.8,12.3.
example 4: synthesis of disperse dye 1 bc:
(1) and (3) diazonium salt synthesis:
2, 6-dichloro-4-nitroaniline (0.98g, 4.73mmol,1.5eq) was added to a 50mL round-bottomed flask, 5mL of water and 5mL of concentrated hydrochloric acid (36.5%) were mixed and added dropwise to the flask, and the mixture was dissolved at 40 to 60 ℃. After cooling the solution to room temperature, it was placed in an ice-water bath. Sodium nitrite (0.33g,4.73mmol,1.5eq) was dissolved in 5mL of water in a small beaker and placed in an ice-water bath for about 2 min. And (3) slowly adding the sodium nitrite aqueous solution dropwise, and reacting in an ice water bath for 1h after the dropwise addition is finished.
(2) Coupling reaction:
in a 150mL round bottom flask, 30mL of methanol and coupling component 3b (2.00g,3.15mmol,1.0eq) were added, heated with stirring in an oil bath at 80 ℃ until the coupling component was completely dissolved, and then the mixture was cooled to room temperature. Under the condition of ice-water bath, the 2, 6-dichloro-nitrophenyl diazonium salt is slowly dripped dropwise, the mixture is stirred for 24 hours at the temperature of 0-5 ℃, and the reaction process is tracked by thin-layer spotting. After the reaction, the mixture is filtered by suction, washed by an organic mixed solvent (the volume ratio of ethyl acetate to petroleum ether is 1:5), dried to obtain a dark yellow solid, and dried and weighed to obtain 1.96 g. The reaction equation is as follows:
Figure BDA0002561703040000101
preparation of disperse dye 1bc synthesized in this example1H-NMR、13C-NMR data are as follows:
1H NMR(400MHz,CDCl3)ppm 8.29(s,2H,Ar-H),7.93(d,J＝9.2Hz,2H,Ar-H),7.52(d,J＝8.0Hz,1H,Ar-H),7.18(br s,4H,Ar-H),7.05-6.97(m,5H,Ar-H),6.83(d,J＝9.2Hz,2H,Ar-H),6.49(s,1H,COCHN),5.80(d,J＝8.4Hz,1H,NH),4.36-4.29(m,2H,CH2O),3.89-3.87(m,1H,NCH),3.72(t,J＝6.4Hz,2H,CH2CH2N),3.56(q,J＝7.2Hz,2H,CH3CH2N),2.71-2.66(m,2H,OCOCH2),2.41-2.36(m,2H,CH2CON),2.02(d,J＝10.0Hz,1H,Cy-H),1.90(d,J＝11.2Hz,1H,Cy-H),1.75-1.60(m,3H,Cy-H),1.39-1.22(m,3H,Cy-H),1.27(t,J＝7.2Hz,3H,CH3),1.14-1.05(m,2H,Cy-H).
13C NMR(100MHz,CDCl3)ppm 172.9,171.8,168.3,154.0,151.8,145.2,143.6,139.2,134.3,132.7(×2),132.1(×2),129.9,129.0(×2),128.3,128.0(×2),127.1,126.5,126.3,124.3,124.2(×2),111.5(×2),64.0,61.2,49.0,48.8,45.8,32.9,32.8,29.8,29.4,25.5,25.0,24.8,12.3.
example 5: detection of 1ba, 1bb and 1bc color fastness performance of new dye
The novel disperse dyes 1ba, 1bb and 1bc prepared by the invention and the conventional dyes C.I. disperse red 1 and C.I. disperse red 13 with the same parent structure are applied to dyeing of chinlon, and the color fastness performance of the chinlon is tested. The test method is as follows, and the fastness test results are shown in table 1.
The test method comprises the following steps: respectively and accurately weighing 0.5000g (accurate to +/-0.1 mg) of dye 1ba, 1bb, 1bc, C.I. disperse red 1 and C.I. disperse red 13, fully mixing the dye 1ba, the dye 1bb, the dye 1bc, the C.I. disperse red 13 and a dispersant NNO according to the mass ratio of 1:1, adding a little water, continuously grinding the mixture in a mortar for 30min, transferring the ground dye into a 500mL volumetric flask, adding water to fix the volume, preparing 1g/L of dye mother liquor, and uniformly shaking the dye mother liquor for later use. 5 pieces of chinlon with the weight of 5.0g are sheared, 25mL of 1g/L dye mother liquor, 50mL of 5g/L ammonium sulfate mother liquor, 50mL of 5g/L dispersant NNO solution and 125mL of water are absorbed to prepare 250mL of dye liquor. The dye concentration is 0.5% (o.w.f), the ammonium sulfate concentration is 1g/L, the NNO concentration is 1g/L, and the bath ratio is 50: 1. One portion of each of the above 5 dye stock solutions of 1g/L was prepared. Respectively putting 5 parts of chinlon into 5 parts of dye solution at room temperature, putting a dyeing cup into an oil bath sample dyeing machine, dyeing from 40 ℃, heating to 120 ℃ at a heating rate of 1 ℃/min, then preserving heat for 70min, and then cooling to 90 ℃ at full speed. And (3) after dyeing is finished, soaping the dyed sample by using a 2g/L standard soap powder aqueous solution, washing for 15min at 95 ℃ in a bath ratio of 50:1, taking out, washing with tap water, and airing in a natural state to be tested. The color fastness to washing is determined by adopting ISO 105-C06:1994(E) standard, the color fastness to dry heat is determined by adopting ISO105-P01:1993(E) standard, the rubbing fastness is determined by adopting GB/T3920-2008 standard, and the light fastness is determined by adopting ISO 105-B02 standard.
TABLE 1 comparison of color fastness properties of dyes on polyamide dyeing
Figure BDA0002561703040000121
From the experimental data of table 1: the novel azo disperse dyes 1ba, 1bb and 1bc prepared in the embodiment are detected, the maximum absorption wavelengths λ max are 483, 507 and 436 respectively, and the color is red; the dye is applied to dyeing of chinlon under the same condition, the sublimation staining resistance fastness and the washing resistance fastness of the dye are greatly improved compared with those of disperse red 1 and disperse red 13, and the sublimation staining resistance fastness and the washing resistance fastness of the three new dyes reach the expected effect, so that ester groups and amide groups are introduced into the novel dyes 1ba, 1bb and 1bc, the molecular weight and the molecular size are increased moderately, the acting force and the affinity of the dyes on fibers are enhanced, and the dyes are not easy to migrate out from the inside.
The structural formulae of disperse red 1 and disperse red 13 in table 1 are shown below:
Figure BDA0002561703040000122

Claims (10)

1. an azo disperse dye, wherein the azo disperse dye has the following structural formula:
Figure FDA0002561703030000011
wherein R is1Is H or Cl, R2Is H or Cl.
2. The azo disperse dye according to claim 1, wherein the azo disperse dye has a structural formula
Figure FDA0002561703030000012
The preparation process comprises the following steps:
(1) acid synthesis: 13.0mmol succinic anhydride, 1.0mmol DMAP and 15mL CH are added in turn2Cl210.0mmol of triethylamine and 10.0mmol of N-ethyl-N-hydroxyethylaniline form a mixed solution, the mixed solution is stirred for 4 hours at room temperature, and after the reaction is finished, the mixed solution is decompressed, concentrated and dried in vacuum;
(2) ugi four-component reaction: sequentially adding 70mL of anhydrous methanol, 12.0mmol of aniline and 12.0mmol of o-bromobenzaldehyde, transferring the acid synthesized in the step (1) by using the anhydrous methanol, finally adding 10mmol of cyclohexylacetonitrile, heating and stirring in an oil bath at 80 ℃ for 48 hours, cooling to room temperature after the reaction is finished, cooling to separate out a large amount of white solid, carrying out suction filtration, washing by using ethyl acetate/petroleum ether with the volume ratio of 1:5, and drying;
(3) synthesis of diazonium salt: dissolving 4.73mmol of sodium nitrite with 5mL of water, placing the solution in an ice-water bath for 2min, mixing the 5mL of water with 5mL of 36.5% hydrochloric acid, dropwise adding the mixture into 4.73mmol of 4-nitroaniline, dissolving the mixture at 40-60 ℃, cooling the mixture to room temperature, placing the mixture in the ice-water bath, dropwise and slowly adding an aqueous solution of sodium nitrite, and reacting the mixture in the ice-water bath for 1h after dropwise addition is finished to obtain 4-nitrophenyl diazonium salt;
(4) coupling reaction: adding 30mL of methanol into 3.15mmol of coupling component, heating and stirring in an oil bath at 80 ℃ until the coupling component is completely dissolved, cooling to room temperature, slowly dropwise adding 4-nitrophenyl diazonium salt under the condition of ice-water bath, stirring at 0-5 ℃ for 24 hours, after the reaction is finished, carrying out suction filtration, washing with ethyl acetate/petroleum ether at a volume ratio of 1:5, drying, purifying by adopting column chromatography, eluting with a mixed solvent of ethyl acetate and petroleum ether at a volume ratio of 1:2, and drying.
3. The azo disperse dye according to claim 1, wherein the azo disperse dye has a structural formula
Figure FDA0002561703030000021
The preparation process comprises the following steps:
(1) acid synthesis: 13.0mmol succinic anhydride, 1.0mmol DMAP and 15mL CH are added in turn2Cl210.0mmol of triethylamine and 10.0mmol of N-ethyl-N-hydroxyethylaniline form a mixed solution, the mixed solution is stirred for 4 hours at room temperature, and after the reaction is finished, the mixed solution is decompressed, concentrated and dried in vacuum;
(2) ugi four-component reaction: sequentially adding 70mL of anhydrous methanol, 12.0mmol of aniline and 12.0mmol of o-bromobenzaldehyde, transferring the acid synthesized in the step (1) by using the anhydrous methanol, finally adding 10mmol of cyclohexylacetonitrile, heating and stirring in an oil bath at 80 ℃ for 48 hours, cooling to room temperature after the reaction is finished, cooling to separate out a large amount of white solid, carrying out suction filtration, washing by using ethyl acetate/petroleum ether with the volume ratio of 1:5, and drying;
(3) synthesis of diazonium salt: dissolving 4.73mmol of sodium nitrite with 5mL of water, placing the mixture in an ice water bath for 2min to obtain a sodium nitrite aqueous solution, mixing the 5mL of water with 5mL of 36.5% hydrochloric acid, dropwise adding the mixture into 4.73mmol of 2-chloro-4-nitroaniline, dissolving the mixture at 40-60 ℃, cooling the mixture to room temperature, placing the mixture in the ice water bath, dropwise and slowly adding the sodium nitrite aqueous solution, and reacting the mixture in the ice water bath for 1h after dropwise adding is completed to obtain 2-chloro-4-nitrophenyldiazonium salt;
(4) coupling reaction: adding 30mL of methanol into 3.15mmol of coupling component, heating and stirring in an oil bath at 80 ℃ until the coupling component is completely dissolved, cooling to room temperature, slowly and dropwise adding 2-chloro-4-nitrophenyl diazonium salt in the ice-water bath, stirring at 0-5 ℃ for 24 hours, after the reaction is finished, carrying out suction filtration, washing with ethyl acetate/petroleum ether in a volume ratio of 1:5, and drying.
4. The azo disperse dye according to claim 1, wherein the azo disperse dye has a structural formula
Figure FDA0002561703030000022
The preparation process comprises the following steps:
(1) acid synthesis: 13.0mmol succinic anhydride, 1.0mmol DMAP and 15mL CH are added in turn2Cl210.0mmol of triethylamine and 10.0mmol of N-ethyl-N-hydroxyethylaniline form a mixed solution, the mixed solution is stirred for 4 hours at room temperature, and after the reaction is finished, the mixed solution is decompressed, concentrated and dried in vacuum;
(2) ugi four-component reaction: sequentially adding 70mL of anhydrous methanol, 12.0mmol of aniline and 12.0mmol of o-bromobenzaldehyde, transferring the acid synthesized in the step (1) by using the anhydrous methanol, finally adding 10mmol of cyclohexylacetonitrile, heating and stirring in an oil bath at 80 ℃ for 48 hours, cooling to room temperature after the reaction is finished, cooling to separate out a large amount of white solid, carrying out suction filtration, washing by using ethyl acetate/petroleum ether with the volume ratio of 1:5, and drying;
(3) synthesis of diazonium salt: dissolving 4.73mmol of sodium nitrite with 5mL of water, placing the mixture in an ice water bath for 2min to form a sodium nitrite aqueous solution, mixing the 5mL of water with 5mL of 36.5% hydrochloric acid, dropwise adding the mixture into 4.73mmol of 2, 6-dichloro-4-nitroaniline, dissolving the mixture at 40-60 ℃, cooling the mixture to room temperature, placing the mixture in the ice water bath, dropwise and slowly adding the sodium nitrite aqueous solution, and reacting the mixture in the ice water bath for 1h after the dropwise addition is finished to obtain 2, 6-dichloro-nitrophenyl diazonium salt;
(4) coupling reaction: adding 30mL of methanol into 3.15mmol of coupling component, heating and stirring in an oil bath at 80 ℃ until the coupling component is completely dissolved, cooling to room temperature, slowly and dropwise adding 2, 6-dichloro-nitrophenyl diazonium salt under the condition of ice-water bath, stirring for 24 hours at 0-5 ℃, carrying out suction filtration after the reaction is finished, washing by using ethyl acetate/petroleum ether with the volume ratio of 1:5, and drying.
5. A preparation method of an azo disperse dye is characterized by comprising the following steps:
(1) acid synthesis: reacting N-ethyl-N-hydroxyethyl aniline, succinic anhydride, DMAP and triethylamine in an organic solvent at room temperature to generate corresponding acid, and directly spin-drying reaction liquid under a reduced pressure condition to obtain carboxylic acid for later use;
(2) ugi reaction: in an organic solvent, carrying out Ugi reaction on the synthesized carboxylic acid in the step (1) and o-bromobenzaldehyde, aniline and cyclohexyl isonitrile, filtering the reaction liquid, and washing the reaction liquid with the organic solvent to obtain a Ugi product;
(3) coupling reaction: coupling the Ugi product with 4-nitrophenyldiazonium salt compounds in an organic solvent, filtering, washing and drying to obtain the azo disperse dye.
6. The process for preparing an azo disperse dye according to claim 5, wherein: in the step (1), the organic solvent is any one of dichloromethane, dichloroethane and acetonitrile; the molar ratio of N-ethyl-N-hydroxyethyl aniline, succinic anhydride, DMAP and triethylamine is 1: 1.2-1.5: 0.1-0.2: 1-1.5, the reaction temperature is from room temperature to 50 ℃, and the reaction time is 1-5 h.
7. The process for preparing an azo disperse dye according to claim 5, wherein: in the step (2), the organic solvent is any one of toluene, methanol, ethanol or acetonitrile; the molar ratio of the carboxylic acid to the o-bromobenzaldehyde to the cyclohexyl isonitrile to the aniline is 1:1.2:1:1.2, the reaction temperature is 40-100 ℃, and the reaction time is 36-48 h.
8. The process for preparing an azo disperse dye according to claim 5, wherein: in the step (3), the molar ratio of the Ugi product to the 4-nitrophenyldiazonium salt is 1: 1.5-1.2, the reaction temperature is 0-5 ℃, and the reaction time is 24-36 hours.
9. The application of the azo disperse dye is characterized in that: the azo disperse dye of claim 1 is directly added or used as one of the components of the dye for nylon dyeing.
10. The use of an azo disperse dye according to claim 9, wherein the dyeing process comprises: weighing azo disperse dye, fully mixing the azo disperse dye with a dispersant NNO according to the mass ratio of 1:1, and adding water to prepare 1g/L dye mother liquor; 1g/L of dye mother liquor, 5g/L of ammonium sulfate mother liquor and 5g/L of dispersant NNO solution are taken, water is added to prepare dye liquor, the dye concentration is 0.5 percent (o.w.f), the ammonium sulfate concentration is 1g/L, the NNO concentration is 1g/L, and the bath ratio is 50: 1; putting chinlon into a dye solution at room temperature, starting dyeing at 40 ℃, increasing the temperature to 120 ℃ at a heating rate of 1 ℃/min, then keeping the temperature for 70min, and then cooling to 90 ℃ at full speed; after dyeing is finished, soaping the dyed sample by using a 2g/L standard soap powder aqueous solution, washing for 15min at 95 ℃ in a bath ratio of 50:1, taking out, washing by using tap water, and airing in a natural state.
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