CN109135322B - Azo disperse dye compound and synthesis method and application thereof - Google Patents
Azo disperse dye compound and synthesis method and application thereof Download PDFInfo
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- CN109135322B CN109135322B CN201810947334.8A CN201810947334A CN109135322B CN 109135322 B CN109135322 B CN 109135322B CN 201810947334 A CN201810947334 A CN 201810947334A CN 109135322 B CN109135322 B CN 109135322B
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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=
- C09B29/0838—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= specific alkyl-CO-N-, aralkyl CON-, cycloalkyl CON-, alkyl OCON-
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- 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
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- 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
- D06P3/28—Preparing azo dyes on the material
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- 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
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/56—Preparing azo dyes on the material
Abstract
The invention provides an azo disperse dye compound, a synthesis method and application thereof, and specifically comprises the following steps: (1) ugi reaction: carrying out an Ugi four-component reaction on aldehyde, aniline, formic acid and cyclohexyl isonitrile in an organic solvent, filtering the reaction liquid, and washing the reaction liquid with the organic solvent to obtain an Ugi product; (2) and (3) hydrolysis reaction: adding a Ugi product and acid into an alcohol solvent for selective hydrolysis, and neutralizing reaction liquid, extracting by using an organic solvent, concentrating under reduced pressure and drying to obtain a hydrolysate, namely a coupling component for synthesizing the azo disperse dye; (3) coupling reaction: in the presence of organic acid, in a mixed solvent of alcohol and water, coupling the obtained coupling component with 4-nitrophenyl diazonium salt, adjusting the pH value of reaction liquid, filtering, washing, drying and the like on solid to obtain the azo disperse dye compound. The synthesis method can effectively regulate and control the molecular weight and the molecular volume of the dye, introduces amide groups, and greatly improves the dyeing performance on polyester fibers and polyamide fibers.
Description
The technical field is as follows:
the invention relates to an azo disperse dye compound and a synthesis method and application thereof.
Background art:
disperse dyes were first applied to the dyeing of acetate fibers and then developed rapidly with the development of synthetic fibers, particularly polyester fibers (terylene). Disperse dyes are of a wide variety, complete in color spectrum and wide in application, and are now the most important branch in the dye industry. China is the first major producing country of disperse dyes in the world and has strong market competitiveness in the international market. The disperse dye has simple structure and low molecular weight, contains no water soluble group, contains polar group (such as hydroxyl, amino, hydroxyalkylamino, cyanoalkylamino, etc.) in the molecule, still belongs to nonionic dye, and is also the most important dye for dyeing hydrophobic fiber (such as polyester, polyamide, etc.) at present. The disperse dyes have two classification modes, namely, the disperse dyes can be classified into a low-temperature type, a high-temperature type and a medium-temperature type according to application performance; secondly, according to the chemical structure, the disperse dyes can be divided into azo dyes, anthraquinone dyes and heterocyclic dyes, and a small amount of quinophthalone ketones, methines, o-nitroanilides and the like can be obtained. Among them, the azo-type structure of the disperse dyes is the most predominant one, accounting for about 60%. The disperse dye with azo structure has relatively complete color spectrum, and can obtain dyes with different colors and different dyeing properties by changing the electronic effect of the substituent on the diazo component and the coupling component. For example, the introduction of an electron-withdrawing group into the diazo component or the introduction of an electron-donating group into the coupling component can cause the dye to generate a dark color effect; the substituted benzene ring with heterocycle can improve its brilliance and absorption strength. In recent years, the heterocyclic disperse dyes have bright color, high color development intensity, good fastness performance, good deep color effect, high molar extinction coefficient and good dyeing performance, so that the heterocyclic disperse dyes become a field of more researches in the dye world.
At present, with the appearance of superfine polyester fibers, environment-friendly polylactic acid fibers, differential terylene easy-dyeing fibers and novel fibers, the dyeing performance of most of the existing disperse dyes is insufficient. The disperse dye is easy to enter and exit on the fiber, so that the disperse dye has poor washing fastness and poor application performance. The reason for this is that the affinity of the disperse dye with these fibers is poor, and when the temperature is too high, the thermal movement of the dye molecules is accelerated, and the dye molecules migrate from the inside of the fibers to the surface layer of the fibers. The problem of fastness reduction caused by thermal migration of disperse dyes has been generally noted by the industry, and the research on the problem is increasing for the industry at home and abroad.
The main method for improving the affinity between the disperse dye and the fiber is to effectively improve the molecular weight of the disperse dye, and along with the increase of the molecular weight, the Van der Waals force between dye molecules and the fiber is enhanced, and the dyeing performances such as heat migration resistance fastness, sublimation resistance fastness and the like are improved. Therefore, increasing the affinity of the disperse dye for the fiber is expected to fundamentally solve and improve the above-mentioned problems. The development of the disperse dye with novel structure and excellent dyeing performance has important application value.
The invention content is as follows:
the first aspect of the present invention is directed to provide an azo disperse dye compound which has a significant effect on dyeing of polyester fibers and polyamide fibers.
The technical scheme adopted by the invention is as follows:
an azo disperse dye compound has a structural formula shown in formula 1:
in the formula: r1Is H, CH3，R2Is H, Br.
The azo disperse dye compound has the structural characteristics that: the molecular weight and the molecular volume are moderate, and the polyamide contains an amido structural unit (-CONH-). These structural features have an important influence on the improvement of the dyeing properties 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 the characteristic group of amido (-CONH-), the fiber can form hydrogen bonds with hydrogen receiving groups and hydrogen supplying groups in the fiber, is suitable for the structure of the polyester fiber, and enhances the acting force between the polyester fiber and the fiber, thereby improving the dyeing property.
(3) In the synthesis of azo dyes, the groups on the diazo component have a significant influence on the maximum absorption wavelength and the color of the dye. Under the condition that the coupling components are the same, azo dyes with different colors can be obtained by selecting different substituents in the diazo component, thereby providing great convenience for the diversity synthesis of the azo disperse dyes.
The azo disperse dye compound of the invention can be selected from one of the following compounds:
a second aspect of the present invention is to provide a method for producing the aforementioned azo disperse dye compound, characterized by comprising the steps of:
(1) ugi reaction: in an organic solvent, carrying out Ugi four-component reaction on a certain amount of aldehyde, aniline, formic acid and cyclohexyl isonitrile at a certain temperature, filtering reaction liquid, and washing with the organic solvent to obtain a Ugi product;
(2) and (3) hydrolysis reaction: adding a Ugi product and acid with a certain concentration into an alcohol solvent, carrying out selective hydrolysis at a certain temperature, neutralizing reaction liquid, extracting by using an organic solvent, concentrating under reduced pressure, and drying to obtain a hydrolysate, namely a coupling component for synthesizing the azo disperse dye;
(3) coupling reaction: in the presence of organic acid, in a mixed solvent of alcohol and water, coupling the obtained coupling component with 4-nitrophenyl diazonium salt at a certain temperature, adjusting the pH value of a reaction solution, filtering, washing, drying and the like on a solid to obtain the novel disperse dye compound.
The reaction equation involved in the invention is as follows:
in the reaction equation, R is 4-Me and 2-Br
The further setting is that:
in the step (1):
the organic solvent is any one of toluene, methanol, ethanol or acetonitrile.
The mol ratio of the aldehyde to the aniline to the cyclohexyl isonitrile to the formic acid is as follows: 1: 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 (2):
the alcohol solvent is as follows: any one of methanol, ethanol and isopropanol.
The acid is as follows: any one of hydrochloric acid, sulfuric acid and phosphoric acid.
The mass concentration of the acid is as follows: 36.5 percent (hydrochloric acid) and 40 to 60 percent (sulfuric acid).
The molar ratio of Ugi product to acid is: 1:10-20.
The reaction temperature is 60-120 ℃, and the reaction time is as follows: 2-6 h.
The alkali is as follows: and the molar concentration of any one of sodium hydroxide, potassium hydroxide and sodium bicarbonate is 2-8 mol/L.
The organic solvent adopted by the extraction is ethyl acetate or dichloromethane, and the organic phase is washed by saturated saline solution and then dried by anhydrous sodium sulfate.
In the step (3):
the organic acid is: any one of formic acid, acetic acid, sulfonic acid and benzoic acid.
The molar ratio of the coupling component to the 4-nitrophenyldiazonium salt is: 1:1-2.
The reaction temperature is 0-5 ℃, and the reaction time is 24-36 h.
Due to the adoption of the technical scheme, the invention has obvious technical effect. Coupling components with different molecular weights and different molecular volumes can be obtained by changing the substituent or the structure of the initial raw material, so that the molecular volumes and the molecular weights of the novel disperse dye can be effectively controlled, and the dyeing performance and the color fastness of the disperse dye can be regulated and controlled.
The third aspect of the invention aims to provide the use of the azo disperse dye compound in the dyeing of polyester fibers and polyamide fibers, and experiments prove that the polyester fibers and the polyamide fibers are dyed by using the azo disperse dye compound, and a 1:1 standard dyeing sample is subjected to a color fastness test, and the test result shows that the washing fastness of the polyester fiber and polyamide fiber dyeing samples is obviously improved, and particularly the dry heat fastness is obviously improved.
The invention is further described in detail below with reference to the following figures and detailed description:
description of the drawings:
FIG. 1 is a NMR chart of a dye 1a of the present invention;
FIG. 2 is a NMR chart of the dye 1b of the present invention;
FIG. 3 is a graph comparing the absorption spectra of dye 1a of the present invention and disperse orange 3.
FIG. 4 is a graph comparing the absorption spectra of dye 1b and disperse orange 3 of the present invention.
The specific implementation mode is as follows:
example 1: dye 1a
Example 1-1: preparation of dye 1a
(1) Ugi four-component reaction:
to a 250mL round bottom flask were added, in order, anhydrous methanol (150mL), aniline (4.39mL,48.16mmol,1.05eq), p-tolualdehyde (4.9mL, 48.16mmol,1.05eq), formic acid (2.07mL,55.04mmol,1.2eq), and cyclohexylacetonitrile (5.69mL,45.87mmol,1.0 eq). The reaction mixture was heated and stirred in an oil bath at 80 ℃ for 48h, and the reaction was complete by TLC analysis. After cooling the reaction to room temperature, the lower layer was cooled overnight in a refrigerator to yield a white solid. The resulting solid was filtered off with suction (washing with EA: PE: 1:5 solution as filtration) 7.0925g, the filtrate was spin-dried and weighed 4.6563 g. The total amount of the Ugi product obtained was 11.7488g, and the total yield was 73%. The reaction equation is as follows:
and (3) product confirmation:
IR(film)3273,3085,2926,1668,165,1559,700cm-1.
1H NMR(400MHz,CDCl3)δ8.39(s,1H),7.26-7.25,7.26-7.25(m,3H),7.19-7.16(m,2H),7.12(d,J＝8.0Hz,2H),7.06(d,J＝8.0Hz,2H),5.96(s,1H),5.77(br d,J＝8.0Hz,1H),3.88-3.81(m,1H),2.30(s,1H),1.95-1.89(m,2H),1.70-1.57(m,3H),1.39-1.30(m,2H),1.17-1.05(m,3H).
13C NMR(100MHz,CDCl3)δ168.0,163.1,139.4,138.4,131.1,129.6(×2),129.3(×2),128.9(×2),128.2(×2),127.7,63.6,48.8,32.8,25.5,24.8,24.7,21.1.MS(+ESI):m/z(％)＝351(52)[M+H+].
(2) and (3) hydrolysis reaction:
a250 mL round bottom flask was charged with sequentially the Ugi reaction product (7.0925g, 20.26mmol), dry methanol (70mL), and 17.5mL H2O and 17.5mL concentrated H2SO4(98%) was mixed and added dropwise to the flask. The reaction was stirred in an oil bath at 90 ℃ for 2h, spotted and analyzed by TLC to be complete. The reaction solution in the flask was adjusted to pH 7 with 5mol/L NaOH, followed by extraction, washing 2 times with water and ethyl acetate, standing for layer separation, drying the organic phase over anhydrous sodium sulfate, filtration, rotary evaporation, drying and weighing to obtain m 6.0156g, 92% yield. The reaction equation is as follows:
and (3) product confirmation:
IR(film)3300,2930,2854,1647,1504,749cm-1.
1H NMR(400MHz,CDCl3)δ7.33(d,J＝8.4Hz,2H),7.23-7.19(m,4H),6.82(dd,J＝7.6,7.2Hz,1H),6.68(br d,J＝8.0Hz,1H),6.65(dd,J＝8.8,1.2Hz,2H),4.69(s,1H),3.85-3.80(m,1H),2.37(s,3H),1.93-1.81(m,2H),1.72-1.58(m,3H)，1.40-1.29(m,2H),1.22-1.03(m,3H).
13C NMR(100MHz,CDCl3)δ170.2,146.8,138.3,136.0,129.9(×2),129.3(×2),127.3(×2),119.1,113.9(×2),64.1,48.1,33.0,32.8,25.4,24.8,24.7,21.2.MS(+ESI):m/z(％)＝323(100)[M+H+].
(3) and (3) synthesis of a disperse dye:
1. and (3) diazonium salt synthesis: a50 mL round bottom flask was charged with (0.64g,4.65mmol,1.5eq) p-nitroaniline and 4mL H2O and 4mL of concentrated HCl (36.5%) were mixed and added dropwise to the flask and dissolved at 40 ℃ to 60 ℃ (about 2 h). After cooling the solution to room temperature, it was placed in an ice-water bath. Sodium nitrite (0.32g,4.65mmol,1.5eq) was charged with 4mL of H2Dissolving O in the test tube, and placing in ice water bath for 2 min. Mixing the NaNO mentioned above2The aqueous solution is slowly added dropwise, and after the dropwise addition is finished, the reaction is carried out in an ice-water bath for 2 hours.
2. Coupling reaction: in a 100mL round-bottom flask, 10mL of methanol, 2mL of acetic acid and 5mL of water were added and the coupling component (1g, 3.10mmol, 1.0eq) obtained in (2) in example 1-1 was stirred until the coupling component was completely dissolved. And (2) slowly and dropwise adding the 4-nitrophenyldiazonium salt under the ice-water bath condition, stirring for 24 hours at the temperature of 0-5 ℃, and tracking the reaction process by thin-layer spotting. After the reaction is finished, adjusting the pH value to be alkalescent by using 5mol/L sodium hydroxide, filtering, washing by using an organic solvent (EA: PE ═ 1:5), obtaining pure dye 1a by adopting an ethyl acetate recrystallization method, drying and weighing to obtain 1.3934g, wherein the yield is 95%. The reaction equation is as follows:
IR of disperse dye 1a,1H-NMR、13C-NMR and MS data are as follows:
IR(film)3401,2932,1667,1515,1339,1141,860cm-1.
1H NMR(400MHz,CDCl3)δppm 8.34(d,J＝9.2Hz,2H),7.93(d,J＝9.2Hz,2H),7.84(d,J＝9.2Hz,2H),7.35(d,J＝8.0Hz,2H),7.23(d,J＝8.0Hz,2H),6.68(d,J＝8.8Hz,2H),5.89(br d,J＝8.4Hz,1H),5.66(d,J＝3.6Hz,1H),4.85(d,J＝3.6Hz,1H),3.84-3.76(m,1H),2.38(s,3H),1.93(d,J＝12.0Hz,1H),1.78–1.58(m,4H),1.39-1.28(m,2H),1.17-1.10(m,2H),1.03-0.98(m,1H).
13C NMR(100MHz,CDCl3)δ169.1,156.5,150.4,147.7,145.4,138.7,135.3,130.2(×2),127.0(×2),126.0(×2),124.7(×2),122.8(×2),113.5(×2),62.1,48.6,32.9,32.6,25.3,24.7,24.5,21.2.
MS(+ESI):m/z(％)＝588(100),472(35)[M+H+].
examples 1 to 2:
spectral absorption performance: 0.05 g of dye 1a was weighed, dissolved to a constant volume in 50mL of N, N-dimethylformamide, diluted by a certain factor to a concentration of 0.006g/L, and the absorption spectrum curve was measured with a UV-2450 UV-visible spectrophotometer (Shimadzu corporation, Japan) and compared with that of a 0.006g/L dispersed orange 3 solution of the same concentration, as shown in FIG. 3.
From the absorption spectrum curves in the figure, it was found that the maximum absorption wavelength of the dye 1a was shifted by 3nm in the short-wavelength direction from 467nm to 464nm as compared with that of the disperse orange 3. The specific performance indexes are determined as shown in the following table 1-1:
TABLE 1-1 dye absorption Spectroscopy Performance parameters
| Name of dye | Maximum absorption wavelength/nm | Molar extinction coefficient epsilon |
| Disperse orange 3 | 467 | 30777 |
| Dye 1a | 464 | 29393 |
Examples 1 to 3:
and (3) detecting the color fastness performance of the product: the dye 1a prepared in the embodiment and the disperse orange 3 are applied to dyeing of terylene. The test method is as follows, and the dyeing property results are shown in tables 1-2.
The test method comprises the following steps: accurately weighing 0.5000g of dye 1a (or disperse orange 3) and 0.5000g of dispersant MF, putting the materials into a mortar, adding a little water, grinding, transferring a volumetric flask with constant volume to 500mL after 20min to prepare a mother solution with the dye content of 1g/L, sucking the mother solution to prepare dye solutions with different concentrations, dyeing for 180min at 130 ℃ to obtain a dye sample with the color depth value of a 1:1 standard color sample, measuring the washing color fastness by adopting ISO 105-C06:1994(E), measuring the dry heat color fastness by adopting the ISO 105-P01:1993(E) standard, and measuring the rubbing fastness by adopting the GB/T3920-2008 standard.
TABLE 1-2 comparison of color fastness of dyes to polyester dyeing
From the experimental data above: the color fastness properties of the dye 1a and the disperse orange 3 are only slightly improved, but the dry heat fastness achieves the expected effect, the dyeing fastness is greatly improved, and the dye 1a has higher affinity to the fiber and is not easy to migrate from the inside.
Examples 1 to 4:
the dye 1a prepared in the example and the disperse orange 3 are applied to dyeing of polyamide fibers. The test method is as follows, and the dyeing property results are shown in tables 1 to 3.
The test method comprises the following steps: accurately weighing 0.5000g of dye 1a (or disperse orange 3) and 0.5000g of dispersant MF, putting the materials into a mortar, adding a little water, grinding, transferring a volumetric flask with constant volume to 500mL after 20min to prepare a mother solution with the dye content of 1g/L, sucking the mother solution to prepare dye solutions with different concentrations, dyeing for 60min at 100 ℃ to obtain a dye sample with the color depth value of a 1:1 standard color sample, measuring the washing color fastness by adopting ISO 105-C06:1994(E), measuring the dry heat color fastness by adopting the ISO 105-P01:1993(E) standard, and measuring the rubbing fastness by adopting the GB/T3920-2008 standard.
Tables 1-3 comparison of the color fastness Properties of dyes on Polyamide fibers
From the experimental data above: compared with the disperse orange 3, the dye 1a has greatly improved color fastness performance, greatly improves the color fastness of various fibers, and particularly achieves the expected effect of dry heat fastness, which indicates that the dye 1a has higher affinity to the fibers and is not easy to migrate out of the inside.
Example 2: dye 1b
Example 2-1: preparation of dye 1b
(1) Ugi four-component reaction:
to a 250mL round bottom flask were added anhydrous methanol (150mL), aniline (4.39mL,48.16mmol,1.05eq), o-bromobenzaldehyde (5.63mL,48.16mmol,1.05eq), formic acid (2.07mL,55.04mmol,1.2eq), and cyclohexylacetonitrile (5.69mL,45.87mmol,1.0eq), in that order. The reaction mixture was heated in an oil bath at 80 ℃ for 48h and the reaction was complete by TLC analysis. After cooling the reaction to room temperature, the lower layer was cooled overnight in a refrigerator to yield a white solid. The resulting solid was filtered off with suction (washing with EA: PE: 1:5 solution as filtration) 7.8915g, the filtrate was spin-dried and weighed 6.7571 g. The Ugi products were obtained in 14.6486 total in 77% yield. The reaction equation is as follows:
and (3) product confirmation:
IR(film)3347,2929,1692,1663,766,700cm-1.
1H NMR(400MHz,CDCl3)δ8.42(s,1H),7.50(d,J＝6.8Hz,1H),7.31-7.29(m,3H),7.19-7.18(m,3H),7.12-7.06(m,2H),6.32(s,1H),5.78(d,J＝6.8Hz,1H),3.89-3.87(m,1H),2.06-1.92(m,2H),1.75-1.60(m,3H),1.37-1.35(m,2H),1.24-1.09(m,3H).
13C NMR(100MHz,CDCl3)δ.167.6,163.0,138.3,133.5,133.0,131.8,130.2,128.7(×2),128.4(×2),127.9,127.3,125.8,62.5,49.1,32.7(×2),25.5,24.8,24.7.
MS(+ESI):m/z(％)＝415(100)[M+H+].
(2) and (3) hydrolysis reaction:
a250 mL round bottom flask was charged with sequentially the Ugi reaction product (7.8915g, 19.02mmol), dry methanol (70mL), and 17.5mL H2O and 17.5mL concentrated H2SO4(98%) were mixed and added dropwise to the flask. The reaction was heated in an oil bath at 90 ℃ for 2h and analyzed by TLC for completion. The reaction solution in the flask was adjusted to pH 7 with 5mol/L NaOH, extracted, washed 2 times with water and ethyl acetate, allowed to stand for separation, the organic phase was dried over anhydrous sodium sulfate, filtered, rotary evaporated to give a hydrolysate, dried and weighed 7.0243g, 96% yield. The reaction equation is as follows:
and (3) product confirmation:
IR(film)3396,3349,2932,1674,1603,1508,747cm-1.
1H NMR(400MHz,CDCl3)δ7.62(d,J＝8.8Hz,1H),7.49(d,J＝9.2Hz,1H),7.31(d,J＝8.4,7.6Hz,1H),7.21-7.14(m,3H),6.75(dd,J＝7.2,7.2Hz,1H),6.57(d,J＝8.4Hz,1H),6.41(br d,J＝7.2Hz,1H),5.27(s,1H),5.06(br s,1H),5.09(br s,1H),3.86-3.78(m,1H),1.97(d,J＝15.2Hz,1H),1.77-1.70(m,2H),1.60-1.58(m,2H),1.45-1.12(m,5H),1.08-1.02(m,1H).
13C NMR(100MHz,CDCl3)δ169.0,146.1,138.5,133.1,129.8,129.3,128.7(×2),128.5,123.8,118.4,113.5(×2),61.2,48.4,32.8,32.5,25.4,24.5,24.4.
MS(+ESI):m/z(％)＝386(100)[M+].
(3) and (3) synthesis of a disperse dye:
1. preparing a diazonium salt: a50 mL round bottom flask was charged with (0.64g,4.65mmol,1.5eq) 4-nitroaniline and charged with 4mLH2O and 4mL of concentrated HCl (36.5%) were mixed and added dropwise to the flask and dissolved at 40-60 deg.C (about 2 h). After cooling the solution to room temperature, it was placed in an ice-water bath. Sodium nitrite (0.32g,4.65mmol,1.5eq) was charged with 4mL of H2Dissolving O in test tube, placing in ice water bath for 2min, and adding the NaNO2The aqueous solution is slowly added dropwise, and after the dropwise addition is finished, the reaction is carried out in an ice-water bath for 2 hours.
2. Coupling reaction: in a 100mL round-bottom flask, 10mL of methanol, 2mL of acetic acid and 5mL of water, the coupling component (1g, 2.59mmol, 1.0eq) obtained in (2) in example 2-1, were added, stirred until the coupling component was completely dissolved, and the prepared 4-nitrophenyldiazonium salt was slowly dropped dropwise under ice-water bath conditions, and thin-layer spotting followed the progress of the reaction. After the reaction is finished, adjusting the pH value to be alkalescent by using 5mol/L NaOH, filtering, washing by using an organic solvent (EA: PE ═ 1:5), recrystallizing by using ethyl acetate to obtain dye 1b, drying to obtain a crude product 1.017g, wherein the yield is 74%, and the reaction equation is as follows:
the IR of the disperse dye 1b was dispersed,1H-NMR，13C-NMR and MS data are as follows:
IR(KBr)3308,2930,1676,1601,1333,1136cm-1.
1H NMR(400MHz,CDCl3)δppm 8.33(d,J＝8.8Hz,2H),7.91(d,J＝8.8Hz,2H),7.83(d,J＝8.8Hz,2H),7.66(dd,J＝8.0,0.8Hz,1H),7.49(dd,J＝7.6,1.6Hz,1H),7.33(dd,J＝7.6,7.6Hz,1H),7.22(ddd,J＝7.6,7.6,1.2Hz,1H),6.60(d,J＝8.8Hz,1H),6.12(d,J＝4.8Hz,1H),6.10(d,J＝7.6Hz,1H),5.45(d,J＝4.8Hz,1H),3.84-3.75(m,1H),1.99-1.95(m,1H),1.73-1.69(m,2H),1.62-1.57(m,2H),1.46-1.19(m,4H),1.11-1.01(m,1H).
13C NMR(100MHz,CDCl3)δ167.8,156.3,149.7,147.6,145.0,137.6,133.2,130.2,128.9,128.3,126.4,124.7,123.2,122.7,113.3,59.4,48.7,32.7,32.3,25.3,24.4,24.3.
MS(+ESI):m/z(％)＝536(45)[M+H+],538(53)[M+2+H+].
example 2-2:
spectral absorption performance: 0.05 g of dye 1b was weighed, dissolved to a constant volume in 50mL of N, N-dimethylformamide, diluted by a certain factor to a concentration of 0.006g/L, and the absorption spectrum curve was measured with a UV-2450 UV-visible spectrophotometer (Shimadzu corporation, Japan) and compared with that of a 0.006g/L dispersion orange 3 solution of the same concentration. See fig. 4.
From the absorption spectrum curves in the figure, it was found that the maximum absorption wavelength of the dye 1b was shifted by 6nm in the short-wavelength direction from 467nm to 461nm as compared with that of the dispersed orange 3. The specific performance indexes are determined as shown in the following table 2-1:
TABLE 2-1 dye absorption Spectroscopy Performance parameters
| Name of dye | Maximum absorption wavelength/nm | Molar extinction coefficient epsilon |
| Disperse orange 3 | 467 | 30777 |
| Dye 1b | 461 | 34323 |
Examples 2 to 3:
and (3) detecting the color fastness performance of the product: the dye 1b prepared in the embodiment and the disperse orange 3 are applied to dyeing of terylene. The test method is as follows, and the dyeing property results are shown in Table 2-2.
The test method comprises the following steps: accurately weighing 0.5000g of dye 1b (or disperse orange 3) and 0.5000g of dispersant MF, putting the materials into a mortar, adding a little water, grinding, transferring a volumetric flask with constant volume to 500mL after 20min to prepare a mother solution with the dye content of 1g/L, sucking the mother solution to prepare dye solutions with different concentrations, dyeing for 180min at 130 ℃ to obtain a dye sample with the color depth value of a 1:1 standard color sample, measuring the washing color fastness by adopting ISO 105-C06:1994(E) standard, measuring the dry heat color fastness by adopting ISO 105-P01:1993(E) standard, and measuring the rubbing fastness by adopting GB/T3920-2008 standard.
TABLE 2-2 comparison of color fastness of dyes to Dacron dyeing
From the experimental data above: the color fastness properties of the dye 1b and the disperse orange 3 are only slightly improved, but the dry heat fastness achieves the expected effect, the dyeing fastness is greatly improved, and the dye 1b has higher affinity to the fiber and is not easy to migrate from the inside.
Examples 2 to 4:
the dye 1b prepared in this example and disperse orange 3 were used for dyeing polyamide fibers. The test method is as follows, and the dyeing property results are shown in tables 2 to 3.
The test method comprises the following steps: accurately weighing 0.5000g of dye 1b (or disperse orange 3) and 0.5000g of dispersant MF, putting the materials into a mortar, adding a little water, grinding, transferring a volumetric flask with constant volume to 500mL after 20min to prepare a mother solution with the dye content of 1g/L, sucking the mother solution to prepare dye solutions with different concentrations, dyeing for 60min at 100 ℃ to obtain a dye sample with the color depth value of a 1:1 standard color sample, measuring the washing color fastness by adopting ISO 105-C06:1994(E), measuring the dry heat color fastness by adopting the ISO 105-P01:1993(E) standard, and measuring the rubbing fastness by adopting the GB/T3920-2008 standard.
TABLE 2-3 comparison of the color fastness properties of the dyes for dyeing polyamide fibers
From the experimental data above: compared with the disperse orange 3, the dye 1b has greatly improved color fastness performance, greatly improves the color fastness of various fibers, particularly greatly improves the dry heat fastness, and shows that the dye 1b has higher affinity to the fibers and is not easy to migrate out of the inside.
Claims (10)
1. An azo disperse dye compound has a structural formula shown in formula 1:
in the formula: r1Is H, CH3，R2Is H, Br.
2. An azo disperse dye compound according to claim 1, which is selected from one of the following compounds:
3. a process for producing an azo disperse dye compound according to claim 1, comprising the steps of:
(1) ugi reaction: carrying out an Ugi four-component reaction on aldehyde, aniline, formic acid and cyclohexyl isonitrile in an organic solvent, filtering the reaction liquid, and washing the reaction liquid with the organic solvent to obtain an Ugi product;
(2) and (3) hydrolysis reaction: adding a Ugi product and acid into an alcohol solvent to perform selective hydrolysis reaction, and neutralizing reaction liquid, extracting by using an organic solvent, concentrating under reduced pressure and drying to obtain a coupling component for synthesizing the azo disperse dye;
(3) coupling reaction: in the presence of organic acid, in a mixed solvent of alcohol and water, carrying out coupling reaction on the obtained coupling component and 4-nitrophenyl diazonium salt, adjusting the pH value of a reaction solution, filtering, washing and drying a solid to obtain the disperse dye compound shown in the formula 1.
4. The process for producing an azo disperse dye compound according to claim 3, wherein in the step (1): the organic solvent is any one of toluene, methanol, ethanol or acetonitrile; the molar ratio of the benzaldehyde to the aniline to the cyclohexyl isonitrile to the formic acid is as follows: 1: 1-1.2.
5. The process for producing an azo disperse dye compound according to claim 3, wherein in the step (1): the reaction temperature is 40-100 ℃, the reaction conditions are mild, and the reaction time is as follows: 36-48 h.
6. The process for producing an azo disperse dye compound according to claim 3, wherein in the step (2): the alcohol solvent is as follows: any one of methanol, ethanol and isopropanol; the acid is as follows: any one of hydrochloric acid, sulfuric acid and phosphoric acid; the molar ratio of Ugi product to acid is: 1: 10-20; the neutralizing base is: any one of sodium hydroxide, potassium hydroxide and sodium bicarbonate; the organic solvent adopted by the extraction is ethyl acetate or dichloromethane, and the organic phase is washed by saturated saline solution and then dried by anhydrous sodium sulfate.
7. The process for producing an azo disperse dye compound according to claim 3, wherein in the step (2): the reaction temperature is 60-120 ℃, and the reaction time is as follows: 2-6 h.
8. The process for producing an azo disperse dye compound according to claim 3, wherein in the step (3):
the organic acid is: any one of formic acid, acetic acid, sulfonic acid and benzoic acid; the molar ratio of the coupling component to the 4-nitrophenyldiazonium salt is: 1:1-2.
9. The process for producing an azo disperse dye compound according to claim 3, wherein in the step (3): the reaction temperature is 0-5 ℃, and the reaction time is 24-36 h.
10. Use of the azo disperse dye compound of claim 1 for dyeing polyester fibers and polyamide fibers.
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