CN114539803A - Direct red/direct violet dye compound and preparation method and application thereof - Google Patents

Direct red/direct violet dye compound and preparation method and application thereof Download PDF

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CN114539803A
CN114539803A CN202111484239.7A CN202111484239A CN114539803A CN 114539803 A CN114539803 A CN 114539803A CN 202111484239 A CN202111484239 A CN 202111484239A CN 114539803 A CN114539803 A CN 114539803A
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sodium
amino
direct
sulfonate
hydroxy
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朱国勋
江集楷
李正全
宋化灿
曾耀东
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Institute Of Testing And Analysis Guangdong Academy Of Sciences Guangzhou Analysis And Testing Center China
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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
    • C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
    • C09B29/28—Amino naphthols
    • C09B29/30—Amino naphtholsulfonic acid
    • 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
    • D06P1/02—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 azo dyes

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Abstract

The invention discloses a direct red/direct violet dye compound and a preparation method and application thereof. The preparation method of the direct red/direct violet dye compound comprises the following steps: (1) carrying out diazotization reaction on nitroaniline and polysubstituted naphthol to obtain an intermediate; (2) and (2) dissolving the intermediate prepared in the step (1) in deionized water, reacting for 60-180 minutes at 50-70 ℃ by taking sodium sulfide as a reducing agent, and purifying the product to obtain the direct red/direct violet dye compound. The invention provides a reducing condition with mild condition, environmental protection, simple treatment and strong universality, which is used for modifying the direct dye, selectively reducing the nitro group in the direct dye without damaging azo bonds of the direct dye, and achieving the purpose of prolonging the maximum absorption wavelength of the direct dye.

Description

Direct red/direct violet dye compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of dyes, in particular to a direct red/direct violet dye compound and a preparation method and application thereof.
Background
The nitro in the dye is reduced into amino, which is beneficial to improving the solubility of the dye in acid solution and the dyeing effect, and has important improvement on the performance of the dye. At present, the modification of direct dyes has complex method and large equipment investment, or azo bonds in the direct dyes are damaged when the direct dyes are reduced, so that the structure of dye compounds is damaged. Particularly, when a multi-substituted polyazo direct dye is modified by a nitro reduction structure, the stability of azo double bonds is often the key of reaction control, and has important influences on the yield of the reaction, the purity of the product and the like.
Disclosure of Invention
The invention overcomes the problems in the prior art, and aims to provide a direct red/direct violet dye compound and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a direct red/direct violet dye compound of formula i:
Figure RE-GDA0003584412420000011
wherein: r1Is H, SO3H or SO3Na，R2Is H, SO3Na、SO3H or NH2，R3Is H, SO3H or NH2， R4Is H or NH2，R5Is H or NH2。
Preferably, the direct red/direct violet dye compound is selected from the group consisting of sodium 8-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate, sodium 4-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) naphthalene-1-sulfonate, sodium 7-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate, sodium 6-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate, sodium 5-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) -7 sulfonaphthalene-2-sulfonate, and sodium 2-amino 5-hydroxy-6- ((4- Aminophenyl) diazenyl) -7-sulfo-naphthalene-1-sodium sulfonate.
The invention also provides a preparation method of the direct red/direct violet dye compound, which comprises the following steps:
(1) carrying out diazotization reaction on nitroaniline and polysubstituted naphthol to obtain an intermediate;
(2) and (2) dissolving the intermediate prepared in the step (1) in deionized water, reacting for 60-180 minutes at 50-70 ℃ by taking sodium sulfide as a reducing agent, and purifying the product to obtain the direct red/direct violet dye compound.
The reaction formula of the direct red/direct violet dye compound is shown as a formula II:
Figure RE-GDA0003584412420000021
wherein: r1Is H, SO3H or SO3Na，R2Is H, SO3Na、SO3H or NH2，R3Is H, SO3H or NH2， R4Is H or NH2，R5Is H or NH2。
Preferably, the step (1) of diazotizing p-nitroaniline and polysubstituted naphthol to obtain an intermediate comprises the following specific steps: a) adding dilute hydrochloric acid into paranitroaniline, stirring uniformly, slowly dropwise adding a sodium nitrite solution into the solution, and continuously stirring for reaction after dropwise adding is finished to obtain a paranitroaniline diazonium salt solution for later use; b) mixing the polysubstituted naphthol and the sodium hydroxide, adding a saturated sodium carbonate solution, uniformly stirring, dropwise adding a p-nitroaniline diazonium salt solution, continuously reacting after dropwise adding, centrifuging a product, and drying to obtain an intermediate ((4-nitrophenyl) diazenyl) polysubstituted sodium naphthalenesulfonate).
When hydrochloric acid is added in the step (a), a small amount of ice is added at the same time, so that the reaction is carried out at low temperature (0-5 ℃).
Further preferably, the stirring reaction in step (a) is continued for 50 to 70 minutes, the molar ratio of the paranitroaniline and the hydrochloric acid is 1:2 to 4, the molar ratio of the paranitroaniline and the sodium nitrite is 1:1 to 2, the molar concentration of the dilute hydrochloric acid is 1.0 to 3.0M, and the molar concentration of the sodium nitrite solution is 1.0 to 1.5M.
Further preferably, in step (a), the polysubstituted naphthol is selected from one of sodium 8-amino-4-hydroxynaphthalene-2-sulfonate, sodium 4-amino-5-hydroxynaphthalene-1-sulfonate, sodium 7-amino-4-hydroxynaphthalene-2-sulfonate, sodium 6-amino-4-hydroxynaphthalene-2-sulfonate, sodium 5-amino-4-hydroxy-7-sulfonaphthalene-2-sulfonate and sodium 2-amino-5-hydroxy-7-sulfonaphthalene-1-sulfonate.
Further preferably, the reaction in step (b) is continued for 100-150 minutes, the molar ratio of the paranitroaniline to the polysubstituted naphthol is 1:0.8-1.2, the molar ratio of the polysubstituted naphthol to the sodium hydroxide is 1:1.5-3.0, and the molar ratio of the polysubstituted naphthol to the sodium carbonate is 1: 2.0-5.0.
Preferably, the molar ratio of the intermediate to the sodium sulfide in step (2) is 1: 2-4.
Preferably, the specific steps for purifying the product in step (2) are: the product is treated by salting out to obtain a reduction crude product, and the reduction crude product is refined by ultrasonic pulping to obtain a pure product, namely the direct red/direct violet dye compound.
The method takes (4-nitrophenyl) diazenyl) polysubstituted sodium naphthalenesulfonate as a raw material, sodium sulfide as a reducing agent, deionized water as a solvent, the sodium naphthalenesulfonate reacts for 60 to 180 minutes at a temperature of between 50 and 70 ℃, the reaction is monitored by thin-layer chromatography, a reduced crude product is obtained by salting out a reactant after the reaction reaches an end point, a pure product is obtained by refining by an ultrasonic pulping method, and the product is characterized by nuclear magnetic resonance hydrogen spectroscopy and ultraviolet-visible light absorption spectroscopy.
The invention also protects the application of the direct red/direct violet dye compound in dyeing. The intermediate and the product are subjected to optical performance characterization through ultraviolet-visible absorption spectrum, the testing solvent is a water buffer solution system, the testing concentration is 10ppm, and the maximum absorption wavelength of the reduced product is prolonged by about 20-40nm compared with that of the intermediate through the ultraviolet-visible absorption spectrum.
Compared with the prior art, the invention has the beneficial effects that:
the direct dye provided by the invention has the advantages of mild modification reduction conditions, environmental friendliness, simple treatment and strong universality, can selectively reduce nitro groups in the direct dye, does not damage azo bonds of the direct dye, and achieves the purpose of prolonging the maximum absorption wavelength of the direct dye. The reaction is carried out by a one-pot reaction kettle type reaction, the heating temperature is between 50 ℃ and 70 ℃ for 2-4 hours, the product can be obtained by acid washing or salting out, and the product with the yield of more than 68 percent and the product purity of more than 95 percent can be obtained by simple pulping treatment.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a product (sodium 8-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate) prepared in example 1 of the present invention;
FIG. 2 is a graph showing an ultraviolet-visible light absorption spectrum of an intermediate produced in example 1 of the present invention;
FIG. 3 is a UV-VIS absorption spectrum of a product prepared in example 1 of the present invention;
FIG. 4 is a nuclear magnetic spectrum of a product (4-amino-5-hydroxy-6- ((4-aminophenyl) diazenyl) naphthalene-1-sulfonic acid) prepared in example 2 of the present invention;
FIG. 5 is a graph showing the UV-VIS absorption spectrum of an intermediate produced in example 2 of the present invention;
FIG. 6 is a UV-VIS absorption spectrum of a product obtained in example 2 of the present invention;
FIG. 7 is a nuclear magnetic spectrum of a product (sodium 7-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate) prepared in example 3 of the present invention;
FIG. 8 is a graph showing an ultraviolet-visible light absorption spectrum of an intermediate produced in example 3 of the present invention;
FIG. 9 is a UV-VIS absorption spectrum of a product obtained in example 3 of the present invention;
FIG. 10 is a nuclear magnetic spectrum of a product (sodium 6-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate) prepared in example 4 of the present invention;
FIG. 11 is a graph showing an ultraviolet-visible light absorption spectrum of an intermediate produced in example 4 of the present invention;
FIG. 12 is a UV-VIS absorption spectrum of a product obtained in example 4 of the present invention;
FIG. 13 is a nuclear magnetic spectrum of a product (5-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) -7-sulfonatonaphthalene-2-sulfonic acid sodium sulfonate) prepared in example 5 of the present invention;
FIG. 14 is a graph showing an ultraviolet-visible light absorption spectrum of an intermediate produced in example 5 of the present invention;
FIG. 15 is a UV-VIS absorption spectrum of a product obtained in example 5 of the present invention;
FIG. 16 is a nuclear magnetic spectrum of a product (2-amino-5-hydroxy-6- ((4-aminophenyl) diazenyl) -7-sulfonatonaphthalene-1-sulfonic acid sodium sulfonate) prepared in example 6 of the present invention;
FIG. 17 is a graph showing an ultraviolet-visible light absorption spectrum of an intermediate produced in example 6 of the present invention;
FIG. 18 is a UV-VIS absorption spectrum of a product obtained in example 6 of the present invention;
FIG. 19 is a comparison chart of the intermediate and product colorimetries obtained in examples 1-6.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment used in the present invention is a conventional commercial product in the art unless otherwise specified.
Example 1
Figure RE-GDA0003584412420000051
A preparation method of 8-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sodium sulfonate comprises the following steps:
(1) preparation of intermediate sodium 8-amino-4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sulfonate: weighing paranitroaniline (2.76g, 20mmol) into a 250mL beaker, adding 60mL of 1M dilute hydrochloric acid and 20g of crushed ice, stirring uniformly, slowly dropwise adding 22mL of 1M sodium nitrite solution, and continuously stirring for reacting for 60 minutes after dropwise adding is finished to obtain a paranitroaniline diazonium salt solution for later use. Weighing 8-amino-4-hydroxynaphthalene-2-sodium sulfonate (5.22g, 20mmol) and sodium hydroxide (1.60g, 40mmol) into a 500mL beaker, adding 100mL of 0.6M saturated sodium carbonate solution, stirring uniformly, adding p-nitroaniline diazonium salt solution dropwise, and continuing to react for 120 minutes after dropwise addition is finished to obtain a red-brown suspension. Centrifugation and drying are carried out, thus obtaining 9.0 g of intermediate product 8-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sulfonic acid sodium salt with the yield of 91.8%.
(2) Preparation of sodium 8-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate: weighing 8-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sodium sulfonate (4.1g, 10mmol) into a 250mL round bottom flask, adding 150mL of a sodium sulfide solution with the concentration of 0.2M, uniformly stirring, transferring to a 60 ℃ oil bath for reaction for 120 minutes, stopping the reaction, cooling to room temperature, adding 45mL of dilute hydrochloric acid with the concentration of 1M into the reaction solution, centrifuging to obtain a solid, and pulping by using an ethanol/ethyl acetate mixed solution with the volume ratio of 1:1 to obtain 3.2 g of 8-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sodium sulfonate product with the yield of 83%.
The nuclear magnetic spectrum of the 8-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sodium sulfonate product is shown in figure 1, and the nuclear magnetic data are as follows:1H NMR(500MHz,DMSO-d6)δ8.0(d,J＝8.1Hz,1H),7.9(s,1H),7.8(d,J＝8.8Hz,2H), 7.4(t,J＝7.8Hz,1H),7.4–7.4(m,1H),6.9(d,J＝8.9Hz,2H)。
example 2
Figure RE-GDA0003584412420000061
A process for the preparation of 4-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) naphthalene-1-sulfonic acid comprising the steps of:
(1) preparation of intermediate 4-amino-5-hydroxy-6- ((4-nitrophenyl) diazenyl) naphthalene-1-sulfonic acid: weighing paranitroaniline (2.76g, 20mmol) into a 250mL beaker, adding 60mL of 1M dilute hydrochloric acid and 20g of crushed ice, stirring uniformly, slowly dropwise adding 22mL of 1M sodium nitrite solution, and continuously stirring for reacting for 60 minutes after dropwise adding is finished to obtain a paranitroaniline diazonium salt solution for later use. Weighing 4-amino-5-hydroxynaphthalene-1-sulfonic acid (20mmol) and sodium hydroxide (1.60g, 40mmol) into a 500mL beaker, adding 100mL of 0.6M saturated sodium carbonate solution, stirring uniformly, adding p-nitroaniline diazonium salt solution dropwise, and continuing to react for 120 minutes after dropwise addition is finished to obtain a reddish brown suspension. Centrifugation and drying are carried out, thus obtaining 7.9 g of intermediate 4-amino 5-hydroxy-6- ((4-nitrophenyl) diazenyl) naphthalene-1-sulfonic acid with the yield of 96.4%.
(2) Preparation of 4-amino-5-hydroxy-6- ((4-aminophenyl) diazenyl) naphthalene-1-sulfonic acid: weighing 4-amino 5-hydroxy-6- ((4-nitrophenyl) diazenyl) naphthalene-1-sulfonic acid (10mmol) into a 250mL round-bottom flask, adding 150mL of sodium sulfide solution with the concentration of 0.2M, uniformly stirring, transferring to a 60 ℃ oil bath for reaction for 120 minutes, stopping the reaction, cooling to room temperature, adding 45mL of 1M dilute hydrochloric acid into the reaction solution, centrifuging to obtain a solid, and pulping by using an ethanol/ethyl acetate mixed solution with the volume ratio of 1:1 to obtain 2.7g of 4-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) naphthalene-1-sulfonic acid product with the yield of 70%.
The nuclear magnetic spectrum of 4-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) naphthalene-1-sulfonic acid is shown in figure 4, and the nuclear magnetic data are as follows:1H NMR(500MHz,DMSO-d6)δ15.4(s,1H),7.9(d,J＝9.9Hz,1H),7.8(d,J＝8.7Hz,1H),7.5 (d,J＝8.2Hz,2H),7.3(d,J＝8.1Hz,2H),6.8(d,J＝10.0Hz,1H),6.6(d,J＝8.8Hz,1H)。
example 3
Figure RE-GDA0003584412420000071
The preparation method of the sodium 7-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate comprises the following steps:
(1) preparation of intermediate sodium 7-amino-4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sulfonate: weighing paranitroaniline (2.76g, 20mmol) into a 250mL beaker, adding 60mL of 1M dilute hydrochloric acid and 20g of crushed ice, stirring uniformly, slowly dropwise adding 22mL of 1M sodium nitrite solution, and continuously stirring for reacting for 60 minutes after dropwise adding is finished to obtain a paranitroaniline diazonium salt solution for later use. Weighing 7-amino-4-hydroxynaphthalene-2-sodium sulfonate (5.22g, 20mmol) and sodium hydroxide (1.60g, 40mmol) into a 500mL beaker, adding 100mL of 0.6M saturated sodium carbonate solution, stirring uniformly, adding p-nitroaniline diazonium salt solution dropwise, and continuing to react for 120 minutes after dropwise addition is finished to obtain a red-brown suspension. Centrifugation and drying are carried out, thus obtaining 8.0 g of intermediate product 7-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sodium sulfonate with the yield of 97.6%.
(2) Preparation of sodium 7-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate: weighing 7-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sodium sulfonate (4.1g, 10mmol) into a 250mL round bottom flask, adding 150mL of a sodium sulfide solution with the concentration of 0.2M, uniformly stirring, transferring to a 60 ℃ oil bath for reaction for 120 minutes, stopping the reaction, cooling to room temperature, adding 45mL of dilute hydrochloric acid with the concentration of 1M into the reaction solution, centrifuging to obtain a solid, and pulping by using an ethanol/ethyl acetate mixed solution with the volume ratio of 1:1 to obtain 2.9g of 7-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sodium sulfonate product with the yield of 75%.
The nuclear magnetic spectrum of sodium 7-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate is shown in figure 7, and the nuclear magnetic data are as follows:1H NMR(500MHz,DMSO-d6)δ15.8(s,1H),7.9(d,J＝8.6Hz,1H),7.7(d,J＝8.9Hz,2H),7.3 (d,J＝8.8Hz,2H),7.3(s,1H),6.7(dd,J＝8.6,2.2Hz,1H),6.7(d,J＝2.2Hz,1H)。
example 4
Figure RE-GDA0003584412420000091
A preparation method of 6-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sodium sulfonate comprises the following steps:
(1) preparation of intermediate sodium 6-amino-4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sulfonate: weighing paranitroaniline (2.76g, 20mmol) into a 250mL beaker, adding 60mL of 1M dilute hydrochloric acid and 20g of crushed ice, stirring uniformly, slowly dropwise adding 22mL of 1M sodium nitrite solution, and continuously stirring for reacting for 60 minutes after dropwise adding is finished to obtain a paranitroaniline diazonium salt solution for later use. 6-amino-4-hydroxynaphthalene-2-sulfonic acid sodium salt (5.22g, 20mmol) and sodium hydroxide (1.60g, 40mmol) are weighed into a 500mL beaker, 100mL of saturated sodium carbonate solution with the concentration of 0.6M is added, after uniform stirring, p-nitroaniline diazonium salt solution is added dropwise, and after dropwise addition, reaction is continued for 120 minutes to obtain a red-brown suspension. Centrifugation and drying are carried out, thus obtaining 7.5 g of intermediate 6-amino-4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sulfonic acid sodium salt with the yield of 91.5%.
Nuclear magnetic data for 6-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sulfonic acid is:1H NMR(500MHz, DMSO-d6)δ15.3(s,1H),8.3(d,J＝8.9Hz,2H),7.9(d,J＝9.1Hz,2H),7.4–7.3(m,3H),7.0(dd, J＝8.3,2.5Hz,1H),5.8(s,2H).
(2) preparation of sodium 6-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate: weighing 6-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) naphthalene-2-sodium sulfonate (4.1g, 10mmol) into a 250mL round bottom flask, adding 150mL of a sodium sulfide solution with the concentration of 0.2M, uniformly stirring, transferring to a 60 ℃ oil bath for reaction for 120 minutes, stopping the reaction, cooling to room temperature, adding 45mL of dilute hydrochloric acid with the concentration of 1M into the reaction solution, centrifuging to obtain a solid, and pulping by using an ethanol/ethyl acetate mixed solution with the volume ratio of 1:1 to obtain 2.6g of a 6-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sodium sulfonate product with the yield of 68%.
The nuclear magnetic spectrum of 6-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sodium sulfonate is shown in figure 10, and the nuclear magnetic data are as follows:1H NMR(500MHz,DMSO-d6)δ7.9(d,J＝2.3Hz,1H),7.8–7.8(m,2H),7.7(d,J＝8.4Hz, 1H),7.6(s,1H),7.3(dd,J＝8.4,2.3Hz,1H),7.2(d,J＝8.5Hz,2H)。
example 5
Figure RE-GDA0003584412420000101
The preparation method of 5-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) -7-sulfonic naphthalene-2-sodium sulfonate comprises the following steps:
(1) preparation of intermediate 5-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) -7-sulfonaphthalene-2-sulfonic acid sodium salt: weighing paranitroaniline (2.76g, 20mmol) into a 250mL beaker, adding 60mL of 1M dilute hydrochloric acid and 20g of crushed ice, stirring uniformly, slowly dropwise adding 22mL of 1M sodium nitrite solution, and continuously stirring for reacting for 60 minutes after dropwise adding is finished to obtain a paranitroaniline diazonium salt solution for later use. 5-amino-4-hydroxy-7-sulfonaphthalene-2-sodium sulfonate (6.82g, 20mmol) and sodium hydroxide (1.60g, 40mmol) are weighed into a 500mL beaker, 100mL of saturated sodium carbonate solution with the concentration of 0.6M is added, after uniform stirring, p-nitroaniline diazonium salt solution is added dropwise, and after dropwise addition, reaction is continued for 120 minutes, so that a reddish brown suspension is obtained. Centrifugation and drying are carried out, thus obtaining 7.5 g of intermediate 5-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) -7-sulfonic naphthalene-2-sodium sulfonate with 76.5 percent of yield.
The nuclear magnetic data for sodium 5-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) -7-sulfonaphthalene-2-sulfonate is:1H NMR (500MHz,DMSO-d6)δ15.1(s,1H),8.2(d,J＝8.8Hz,2H),7.8(d,J＝8.7Hz,2H),7.4(s,1H), 7.1(s,1H),6.9(s,1H).
(2) preparation of sodium 5-amino-4-hydroxy-3- ((4-aminophenyl) diazenyl) -7-sulfonaphthalene-2-sulfonate: weighing 5-amino 4-hydroxy-3- ((4-nitrophenyl) diazenyl) -7-sulfonatonaphthalene-2-sodium sulfonate (4.9g, 10mmol) into a 250mL round-bottom flask, adding 150mL of sodium sulfide solution with the concentration of 0.2M, uniformly stirring, transferring to a 60 ℃ oil bath for reaction for 120 minutes, stopping the reaction, cooling to room temperature, adding 45mL of dilute hydrochloric acid with the concentration of 1M into the reaction solution, centrifuging to obtain a solid, and pulping by using an ethanol/ethyl acetate mixed solution with the volume ratio of 1:1 to obtain 3.5g of a 5-amino 4-hydroxy-3- ((4-aminophenyl) -7-sulfonatonaphthalene-2-sodium sulfonate product with the yield of 77%.
The nuclear magnetic spectrum of 5-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) -7-sulfonic naphthalene-2-sodium sulfonate is shown in FIG. 13, and the nuclear magnetic data are as follows:1H NMR(500MHz,DMSO-d6)δ15.2(s,1H),7.7(d,J＝9.0Hz,2H),7.4(s,1H), 7.3(d,J＝10.9Hz,2H),7.1(d,J＝1.5Hz,1H),6.9(s,1H).
example 6
Figure RE-GDA0003584412420000111
The preparation method of the sodium 2-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) -7-sulfonic naphthalene-1-sulfonate comprises the following steps:
(1) preparation of intermediate 2-amino 5-hydroxy-6- ((4-nitrophenyl) diazenyl) -7-sulfonaphthalene-1-sodium sulfonate: weighing paranitroaniline (2.76g, 20mmol) into a 250mL beaker, adding 60mL of 1M dilute hydrochloric acid and 20g of crushed ice, stirring uniformly, slowly dropwise adding 22mL of 1M sodium nitrite solution, and continuously stirring for reacting for 60 minutes after dropwise adding is finished to obtain a paranitroaniline diazonium salt solution for later use. 2-amino-5-hydroxy-7-sulfonaphthalene-1-sodium sulfonate (6.82g, 20mmol) and sodium hydroxide (1.60g, 40mmol) are weighed into a 500mL beaker, 100mL of a 0.6M saturated sodium carbonate solution is added, after uniform stirring, a p-nitroaniline diazonium salt solution is added dropwise, and after dropwise addition, the reaction is continued for 120 minutes to obtain a reddish brown suspension. Centrifugation and drying are carried out, thus obtaining 9.5 g of intermediate 2-amino 5-hydroxy-6- ((4-nitrophenyl) diazenyl) -7-sulfonic naphthalene-1-sodium sulfonate with 96.9 percent of yield.
The nuclear magnetic data of sodium 2-amino 5-hydroxy-6- ((4-nitrophenyl) diazenyl) -7-sulfonaphthalene-1-sulfonate is:1H NMR (500MHz,DMSO-d6)δ15.7(s,1H),8.8(s,1H),8.3(d,J＝8.7Hz,2H),7.9(d,J＝8.8Hz,1H), 7.8(d,J＝8.7Hz,2H),7.5(s,2H),6.8(d,J＝8.8Hz,1H).
(2) preparation of sodium 2-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) -7-sulfonatonaphthalene-1-sulfonate: weighing 2-amino 5-hydroxy-6- ((4-nitrophenyl) diazenyl) -7-sulfonatonaphthalene-1-sodium sulfonate (4.9g, 10mmol) into a 250mL round-bottom flask, adding 150mL of sodium sulfide solution with the concentration of 0.2M, uniformly stirring, transferring to a 60 ℃ oil bath for reaction for 120 minutes, stopping the reaction, cooling to room temperature, adding 45mL of dilute hydrochloric acid with the concentration of 1M into the reaction solution, centrifuging to obtain a solid, and pulping by using an ethanol/ethyl acetate mixed solution with the volume ratio of 1:1 to obtain 3.8g of a 2-amino 5-hydroxy-6- ((4-aminophenyl) -7-sulfonatonaphthalene-1-sodium sulfonate product with the yield of 82%.
The nuclear magnetic spectrum of 2-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) -7-sulfonic naphthalene-1-sodium sulfonate is shown in FIG. 16, and the nuclear magnetic data are as follows:1H NMR(500MHz,DMSO-d6)δ16.0(s,1H),8.8(s,1H),7.9(d,J＝8.8Hz,1H), 7.7(d,J＝8.5Hz,2H),7.3(d,J＝8.5Hz,2H),6.8(d,J＝8.8Hz,1H)。
example 7
The same as example 1, except that:
the stirring reaction is continued for 50 minutes, and the molar ratio of the p-nitroaniline to the hydrochloric acid is 1: and 4, the molar ratio of the paranitroaniline to the sodium nitrite is 1:1, the molar concentration of the dilute hydrochloric acid is 1.0M, and the molar concentration of the sodium nitrite solution is 1.0M. The reaction is continued for 100 minutes, the molar ratio of the paranitroaniline to the 8-amino-4-hydroxynaphthalene-2-sodium sulfonate is 1:0.8, the molar ratio of the 8-amino-4-hydroxynaphthalene-2-sodium sulfonate to the sodium hydroxide is 1:1.5, and the molar ratio of the 8-amino-4-hydroxynaphthalene-2-sodium sulfonate to the sodium carbonate is 1: 2.0. The molar ratio of the intermediate to the sodium sulfide was 1:2. Sodium sulfide is used as a reducing agent, and the reaction is carried out for 180 minutes at 50 ℃, so that the yield is 40%.
Example 8
The same as in example 1, except that:
and continuously stirring and reacting for 70 minutes, wherein the molar ratio of the paranitroaniline to the hydrochloric acid is 1:2, the molar ratio of the paranitroaniline to the sodium nitrite is 1:2, the molar concentration of the dilute hydrochloric acid is 3.0M, and the molar concentration of the sodium nitrite solution is 1.5M. The reaction is continued for 150 minutes, the molar ratio of the p-nitroaniline to the 8-amino-4-hydroxynaphthalene-2-sodium sulfonate is 1:1.2, the molar ratio of the 8-amino-4-hydroxynaphthalene-2-sodium sulfonate to the sodium hydroxide is 1:3, and the molar ratio of the 8-amino-4-hydroxynaphthalene-2-sodium sulfonate to the sodium carbonate is 1: 5. The molar ratio of the intermediate to the sodium sulfide was 1: 4. Sodium sulfide is used as a reducing agent, and the reaction is carried out for 60 minutes at 70 ℃, and the yield is 10%.
Experimental example 1
Ultraviolet-visible light absorption spectrum test and colorimetric experiment results of intermediate and product
The intermediates and products obtained in examples 1 to 6 were weighed and dissolved in deionized water to prepare 100ppm aqueous solutions of standards. Then, 90mL of buffer solutions having different pH (pH 4.01, pH 6.86, pH 9.18) were added to 10mL of the 100ppm aqueous standard solution to prepare 10ppm samples, and the samples were subjected to uv measurement. The test results are summarized in table 1, the spectral patterns of example 1 are shown in detail in fig. 2 and 3, the spectral patterns of example 2 are shown in detail in fig. 5 and 6, the spectral patterns of example 3 are shown in detail in fig. 8 and 9, the spectral patterns of example 4 are shown in detail in fig. 11 and 12, the spectral patterns of example 5 are shown in detail in fig. 14 and 15, and the spectral patterns of example 6 are shown in detail in fig. 17 and 18.
Table 1 summary of the maximum absorption wavelengths of the intermediates and products of examples 1-6
Figure RE-GDA0003584412420000131
Figure RE-GDA0003584412420000141
As shown in Table 1, the maximum absorption wavelength of the product is prolonged compared with that of the intermediate, and the maximum absorption wavelength is increased by about 20-40 nm.
The intermediates and products obtained in examples 1 to 6 were weighed and dissolved in deionized water to prepare 10ppm aqueous solutions, respectively, and colorimetric control was performed, and the results are shown in fig. 19, wherein the intermediates of examples 1, 2, 3, 4, 5 and 6 are shown in fig. 19 from left to right in the order of pink, yellow, red and yellow. In FIG. 19, the products of example 1, example 2, example 3, example 4, example 5 and example 6 are shown from left to right, and the colors are purple, bluish-purple, red, bluish-purple and red in this order. As shown in FIG. 19, the yellow intermediate product is modified to obtain a red product, and the red intermediate product is modified to obtain a purple product.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (10)

1. A direct red/direct violet dye compound of formula i:
Figure FDA0003396832220000011
wherein: r1Is H, SO3H or SO3Na，R2Is H, SO3Na、SO3H or NH2，R3Is H, SO3H or NH2，R4Is H or NH2，R5Is H or NH2。
2. The direct red/direct violet dye compound of claim 1, wherein the direct red/direct violet dye compound is selected from the group consisting of sodium 8-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate, 4-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) naphthalene-1-sulfonate, sodium 7-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate, sodium 6-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) naphthalene-2-sulfonate, sodium 5-amino 4-hydroxy-3- ((4-aminophenyl) diazenyl) -7 sulfonaphthalene-2-sulfonate One of sodium sulfonate and 2-amino 5-hydroxy-6- ((4-aminophenyl) diazenyl) -7-sulfonaphthalene-1-sodium sulfonate.
3. A process for the preparation of a direct red/direct violet dye compound according to claim 1 or claim 2 comprising the steps of:
(1) carrying out diazotization reaction on nitroaniline and polysubstituted naphthol to obtain an intermediate;
(2) and (2) dissolving the intermediate prepared in the step (1) in deionized water, reacting for 60-180 minutes at 50-70 ℃ by taking sodium sulfide as a reducing agent, and purifying the product to obtain the direct red/direct violet dye compound.
4. The preparation method of the direct red/direct violet dye compound according to claim 3, wherein the step (1) of performing diazotization reaction on p-nitroaniline and polysubstituted naphthol to obtain an intermediate comprises the following specific steps: a) adding dilute hydrochloric acid into paranitroaniline, stirring uniformly, slowly dropwise adding a sodium nitrite solution into the solution, and continuously stirring for reaction after dropwise adding is finished to obtain a paranitroaniline diazonium salt solution for later use; b) mixing polysubstituted naphthol and sodium hydroxide, adding saturated sodium carbonate solution, stirring, dripping p-nitroaniline diazonium salt solution, reacting continuously, centrifuging the product, and drying to obtain the intermediate.
5. The method according to claim 4, wherein the step (a) is carried out by stirring for 50-70 min, the molar ratio of p-nitroaniline to hydrochloric acid is 1:2-4, the molar ratio of p-nitroaniline to sodium nitrite is 1:1-2, the molar concentration of dilute hydrochloric acid is 1.0-3.0M, and the molar concentration of sodium nitrite solution is 1.0-1.5M.
6. The method of claim 4, wherein the polysubstituted naphthol in step (a) is selected from the group consisting of sodium 8-amino-4-hydroxynaphthalene-2-sulfonate, 4-amino-5-hydroxynaphthalene-1-sulfonic acid, sodium 7-amino-4-hydroxynaphthalene-2-sulfonate, sodium 6-amino-4-hydroxynaphthalene-2-sulfonate, sodium 5-amino-4-hydroxy-7-sulfonaphthalene-2-sulfonate and sodium 2-amino-5-hydroxy-7-sulfonaphthalene-1-sulfonate.
7. The method for preparing the direct red/direct violet dye compound according to claim 4, wherein the reaction in the step (b) is continued for 100-150 minutes, the molar ratio of the nitroaniline to the polysubstituted naphthol is 1:0.8-1.2, the molar ratio of the polysubstituted naphthol to the sodium hydroxide is 1:1.5-3.0, and the molar ratio of the polysubstituted naphthol to the sodium carbonate is 1: 2.0-5.0.
8. The process according to claim 3, wherein the molar ratio of the intermediate to the sodium sulfide in step (2) is 1: 2-4.
9. The method for preparing a direct red/direct violet dye compound according to claim 3, wherein the step (2) of purifying the product comprises the following steps: the product is treated by salting out to obtain a reduction crude product, and the reduction crude product is refined by ultrasonic pulping to obtain a pure product, namely the direct red/direct violet dye compound.
10. Use of a direct red/direct violet dye compound according to claim 1 for dyeing.
CN202111484239.7A 2021-12-07 2021-12-07 Direct red/direct violet dye compound and preparation method and application thereof Pending CN114539803A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1427516A (en) * 1972-03-09 1976-03-10 Ici Ltd Fungicidal compositions and processes using azonaphthol sulphonic acid derivatives
PL290708A1 (en) * 1991-06-17 1992-12-28 Organika Zachem Zaklady Chemic Method of obtaining novel reactive azo dyes
CN108130759A (en) * 2017-12-22 2018-06-08 浙江理工大学 Realize the method that aryl primary amine dyestuff dyes protein fibre fabric covalent bond

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1427516A (en) * 1972-03-09 1976-03-10 Ici Ltd Fungicidal compositions and processes using azonaphthol sulphonic acid derivatives
PL290708A1 (en) * 1991-06-17 1992-12-28 Organika Zachem Zaklady Chemic Method of obtaining novel reactive azo dyes
CN108130759A (en) * 2017-12-22 2018-06-08 浙江理工大学 Realize the method that aryl primary amine dyestuff dyes protein fibre fabric covalent bond

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"RN：133130-87-7 等", STN, pages 1 - 6 *

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