CN116355434A - Method for preparing direct dye by replacing benzidine - Google Patents

Method for preparing direct dye by replacing benzidine Download PDF

Info

Publication number
CN116355434A
CN116355434A CN202310089219.2A CN202310089219A CN116355434A CN 116355434 A CN116355434 A CN 116355434A CN 202310089219 A CN202310089219 A CN 202310089219A CN 116355434 A CN116355434 A CN 116355434A
Authority
CN
China
Prior art keywords
fluorenone
diamino
solution
acid
direct dye
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310089219.2A
Other languages
Chinese (zh)
Inventor
朱国勋
邓远强
李正全
宋化灿
曾耀东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute Of Testing And Analysis Guangdong Academy Of Sciences Guangzhou Analysis And Testing Center China
Original Assignee
Institute Of Testing And Analysis Guangdong Academy Of Sciences Guangzhou Analysis And Testing Center China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute Of Testing And Analysis Guangdong Academy Of Sciences Guangzhou Analysis And Testing Center China filed Critical Institute Of Testing And Analysis Guangdong Academy Of Sciences Guangzhou Analysis And Testing Center China
Priority to CN202310089219.2A priority Critical patent/CN116355434A/en
Publication of CN116355434A publication Critical patent/CN116355434A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0018—Monoazo dyes prepared by diazotising and coupling from diazotized aminopolycyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/20—Diazonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • 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
    • C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
    • C09B29/16—Naphthol-sulfonic acids
    • 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/039—Disazo dyes characterised by the tetrazo component
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention discloses a method for preparing direct dye by replacing benzidine. The method uses 2, 7-diamino-9-fluorenone to replace 3,3' -dimethoxy benzidine as a connecting group to prepare direct dye, and the prepared product has similar optical performance with that of a benzidine direct dye compound. The 2, 7-diamino-9-fluorenone has stable structure, difficult decomposition, difficult absorption, safety and low toxicity, can replace benzidine, and realizes the purpose of simply and effectively preparing direct dye with long absorption wavelength.

Description

Method for preparing direct dye by replacing benzidine
Technical Field
The invention relates to the technical field of dye preparation, in particular to a method for preparing a direct dye by using 2, 7-diamino-9-fluorenone to replace 3,3' -dimethoxy benzidine as a connecting group.
Background
Benzidine can be used for preparing disazo salt through one-time diazotization, and the production and the manufacture of a polyazo product are easy to finish. Benzidine is an important raw material for preparing dyes with long absorption wavelength, and many successful commercial dyes are prepared by using benzidine monomers including benzidine, 3 '-dimethylbenzidine, 3' -dimethoxy aniline and the like as raw materials, such as C.I direct yellow 1, C.I direct brown 95, C.I direct blue 168, C.I direct black 91, C.I acid black 29 and the like. However, benzidine-based dyes are degraded to easily reform benzidine, and have serious carcinogenic effects, so that the production and use of dyes made from benzidine have been prohibited.
The diamine monomer can be used for selectively preparing mono-diazonium salt or double-diazonium salt by adjusting the condition of diazotization reaction, and various azo dyes can be prepared by selecting different coupling reagents, so that the preparation method has the advantage of product diversity. On the other hand, the diamine monomer can easily obtain long absorption wavelength products through the conjugation of the monomer, can simplify the synthesis path of the products, and has the advantages of shortening the production route and saving the manufacturing cost. Therefore, the method has important significance in developing safe and low-toxicity diamine monomer to replace benzidine monomer and realizing the synthesis and preparation of direct dye compounds.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a direct dye by using 2, 7-diamino-9-fluorenone to replace 3,3' -dimethoxy benzidine as a connecting group. The method can simply and effectively prepare the direct dye with long absorption wavelength.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a direct dye compound as shown in formula i or formula II:
Figure BDA0004069763220000021
wherein R is 1 Is OH, ONa or NH 2 ，R 2 Is H or NH 2 ，R 3 H, SO of a shape of H, SO 3 H or SO 3 Na，R 4 H, SO of a shape of H, SO 3 H or SO 3 Na，R 5 Is H or SO 3 Na。
Preferably, the direct dye is selected from one of 7-amino-4-hydroxy-3- ((7-amino-9-fluorenone) diazenyl) naphthalene-2-sulfonic acid, 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2-sulfonic acid) -9-fluorenone, 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2, 8-disulfonic acid) -9-fluorenone, 3, 7-diazenyl (1-aminonaphthalene-4-sulfonic acid) -9-fluorenone, 3, 7-diazenyl (1-hydroxynaphthalene-4-sulfonic acid) -9-fluorenone, or a sulfonate thereof.
The invention also provides a preparation method of the direct dye compound, which comprises the following steps:
(1) 2, 7-diamino-9-fluorenone is prepared by reducing 2, 7-binitro-9-fluorenone;
(2) 2, 7-diamino-9-fluorenone is prepared into a diazonium salt intermediate through diazotization reaction;
(3) Diazo coupling is carried out on the diazonium salt prepared in the step (2) and naphthol in alkaline aqueous solution, and the diazonium salt reacts for 20-120 minutes at the temperature of 10-50 ℃ to obtain the direct dye compound.
The preparation reaction formula of the direct dye is shown in a formula III:
Figure BDA0004069763220000031
wherein R is 1 Is OH, ONa or NH 2 ，R 2 Is H or NH 2 ，R 3 Is H or SO 3 H or SO 3 Na，R 4 Is H or SO 3 H or SO 3 Na，R 5 Is H or SO 3 Na。
Preferably, the specific preparation steps of the 2, 7-diamino-9-fluorenone in the step (1) are as follows: a) Adding methanol into 2, 7-binitro-9-fluorenone, uniformly stirring, slowly dripping a reducing agent solution into the mixture, and heating and stirring for reaction after the dripping is finished to obtain a 2, 7-diamino-9-fluorenone solution for later use; b) Evaporating the 2, 7-diamino-9-fluorenone solution to dryness to obtain a crude product, and pulping the crude product by using an organic solvent to obtain the 2, 7-diamino-9-fluorenone.
Further preferably, the amount of methanol used in step (a) is 25mL/g, and the reducing agent is one of ascorbic acid, sodium sulfide, iron powder and zinc powder, more preferably ascorbic acid or sodium sulfide; the molar ratio of the reducing agent to the 2, 7-dinitro-9-fluorenone is 1.0 to 5.0:1, more preferably 3.0 to 4.0:1; the heating temperature is 40-65deg.C, more preferably 55-65deg.C; the reaction time is 1 to 5 hours, more preferably 3 to 4 hours.
Further preferably, the 2, 7-diamino-9-fluorenone solution is evaporated to dryness in step (b) at a temperature of 40 to 60 ℃, more preferably 50 to 55 ℃; the organic solvent is one or a mixture of methanol, ethanol, acetone, petroleum ether and tetrahydrofuran, more preferably a mixture of methanol and petroleum ether, and methanol: the volume ratio of petroleum ether is 1:5-20.
Preferably, the specific steps for preparing the diazonium salt intermediate from the 2, 7-diamino-9-fluorenone in the step (2) are as follows: c) Dissolving 2, 7-diamino-9-fluorenone in an acidic solution for later use; d) Then dropwise adding sodium nitrite solution at low temperature, and continuing to react for a period of time after the completion of the dropwise adding, thus obtaining diazonium salt solution.
Further preferably, the acid used in step (c) is one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid or a mixed acid thereof, more preferably hydrochloric acid or acetic acid; the molar ratio of acid to 2, 7-diamino-9-fluorenone is 3.0 to 5.0:1, more preferably 3.0 to 4.0:1;
it is further preferred that the concentration of the sodium nitrite solution in step (d) is in the range of 0.1 to 2M, more preferably in the range of 0.5 to 1.0M, the molar ratio of sodium nitrite to 2, 7-diamino-9-fluorenone is in the range of 0.5 to 5.0:1, more preferably in the range of 0.75 to 1.5:1 for monoazo salts, more preferably in the range of 2.5 to 4.0:1 for bisazo salts, the reaction temperature is in the range of 0 to 20 ℃, more preferably in the range of 5 to 15 ℃, and the reaction time is in the range of 0.5 to 3 hours, more preferably in the range of 1 to 2 hours.
Preferably, the naphthol in the step (3) is one of 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid and 1-aminonaphthalene-4-sulfonic acid; the molar ratio of diazonium salt to naphthol is 1:0.5-2.5, more preferably 1:0.75-1.5 for monoazo salt, and more preferably 1:2.0-2.5 for disazo salt; the alkaline aqueous solution is one of saturated sodium bicarbonate aqueous solution, saturated sodium carbonate aqueous solution and 0.1-1.0M sodium hydroxide aqueous solution, more preferably saturated sodium carbonate aqueous solution, and the concentration is 0.25-0.5M.
The invention takes 2, 7-binitro-9-fluorenone as raw material, sodium sulfide or ascorbic acid as reducer, methanol as solvent, reacting for 3-4 hours at 55-65 ℃, monitoring the reaction by thin layer chromatography, evaporating the solvent at 50-55 ℃ after the reaction reaches the end point, refining by pulping the mixed solvent of ethanol/petroleum ether to obtain pure 2, 7-diamino-9-fluorenone, and characterizing the product by nuclear magnetic resonance hydrogen spectrum. 2, 7-diamino-9-fluorenone is dissolved in hydrochloric acid or acetic acid aqueous solution, reacts with sodium nitrite solution for 1-2 hours at 5-15 ℃ to prepare monoazo salt or disazo salt, characterization of the azo salt is carried out through nuclear magnetic resonance hydrogen spectrum, and the azo salt and naphthol compound comprise 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid or 1-aminonaphthalene-4-sulfonic acid are coupled to prepare monoazo or disazo direct dye.
The invention also protects the application of the direct dye compound in dyeing. The direct dye prepared by the invention and the product prepared by the control example are subjected to optical performance characterization through an ultraviolet-visible light absorption spectrum, the test solvent is an aqueous buffer solution system, the test concentration is 10ppm, the test concentration can be confirmed through the ultraviolet-visible light absorption spectrum, the 2, 7-diamino-9-fluorenone and the 3,3 '-dimethoxy benzidine have similar effects, the prepared azo compound has a near maximum absorption wavelength and similar absorption peaks, and the 2, 7-diamino-9-fluorenone can replace the 3,3' -dimethoxy benzidine in the application of dye preparation.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the 2, 7-diamino-9-fluorenone provided by the invention has the advantages of mild condition, environment friendliness, simple treatment, simple process, less equipment investment, high yield and low cost. The direct dye compound is prepared by using 2, 7-diamino-9-fluorenone as a linking group, and the product has optical properties similar to those of the biphenyl amine direct dye compound. The 2, 7-diamino-9-fluorenone has stable structure, difficult decomposition, difficult absorption, safety and low toxicity, can replace benzidine, and realizes the purpose of simply and effectively preparing direct dye with long absorption wavelength.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2, 7-diamino-9-fluorenone prepared by the present invention.
FIG. 2 is a nuclear magnetic carbon spectrum of 2, 7-diamino-9-fluorenone prepared by the present invention.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the 2, 7-diamino-9-fluorenone monodiazonium salt prepared by the present invention.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the 2, 7-diamino-9-fluorenone double diazonium salt prepared by the present invention.
FIG. 5 is a nuclear magnetic resonance spectrum of 3,3' -dimethoxybenzidine monodiazonium salt prepared in comparative example 1 according to the present invention.
FIG. 6 is a nuclear magnetic resonance spectrum of a dual nitrogen salt of 3,3' -dimethoxy benzidine prepared in comparative example 2 of the present invention.
FIG. 7 is a graph showing the ultraviolet-visible light absorption spectrum of the product produced in application example 1 of the present invention.
FIG. 8 is a graph showing the ultraviolet-visible light absorption spectrum of the product produced in application example 2 of the present invention.
FIG. 9 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in application example 3 of the present invention.
FIG. 10 is a graph showing the ultraviolet-visible light absorption spectrum of the product produced in application example 4 of the present invention.
FIG. 11 is a graph showing the ultraviolet-visible light absorption spectrum of the product produced in application example 5 of the present invention.
FIG. 12 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 1, which was used in the present invention.
FIG. 13 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 2, which was used in the present invention.
FIG. 14 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 3, which was used in the present invention.
FIG. 15 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 4, which was used in the present invention.
FIG. 16 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 5, which was used in the present invention.
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof.
Example 1
Figure BDA0004069763220000061
The method for preparing 2, 7-diamino-9-fluorenone by reducing ascorbic acid comprises the following steps:
(1) 2, 7-dinitro-9-fluorenone (2.7 g,10 mmol) was weighed into a 250mL round bottom flask, dissolved by adding 70mL methanol, and then transferred to a 60℃oil bath with heating and stirring for 15 minutes; then slowly dripping ascorbic acid solution (5.3 g,30 mmol) into the mixture for five times, continuing to react for 4 hours after the dripping is finished, stopping heating, naturally cooling to room temperature, and performing post-treatment;
(2) Transferring to a rotary evaporator, removing methanol under reduced pressure at 50deg.C to obtain black viscous solid, transferring to a vacuum oven at 50deg.C to thoroughly remove solvent to obtain grey brown solid, pulping with 50mL of mixed solvent (petroleum ether/methanol=10/1, volume ratio), and suction filtering to obtain grey solid 1.7g with 80% yield. Product nuclear magnetism 1 H NMR(500MHz,DMSO-d6)δ7.1(d,J＝7.9Hz,2H),6.7(d,J＝2.2Hz,2H),6.6(dd,J＝7.9,2.3Hz,2H),5.3(s,4H). 13 C NMR(125MHz,DMSO)δ195.36,148.66,135.05,133.74,120.34,119.10,110.1340.25,40.08,39.91,39.75,39.58 (fig. 1, 2).
Example 2
Figure BDA0004069763220000071
The method for preparing 2, 7-diamino-9-fluorenone by reducing sodium sulfide comprises the following steps:
(1) 2, 7-dinitro-9-fluorenone (2.7 g,10 mmol) was weighed into a 250mL round bottom flask, dissolved by adding 70mL methanol, and then transferred to a 60℃oil bath with heating and stirring for 15 minutes; then dropwise adding sodium sulfide nonahydrate solution (9.6 g,40 mmol) into the mixture for five times, continuing to react for 4 hours after the dropwise adding is finished, stopping heating, naturally cooling to room temperature, and carrying out post-treatment;
(2) Transferring to a rotary evaporator, removing methanol under reduced pressure at 50deg.C to obtain black viscous solid, transferring to a vacuum oven at 50deg.C to thoroughly remove solvent to obtain grey brown solid, pulping with 50mL of mixed solvent (petroleum ether/methanol=10/1, volume ratio), and vacuum filtering to obtain grey solid 1.7g with a yield of 60%. Product nuclear magnetism 1 H NMR(500MHz,DMSO-d6)δ7.1(d,J＝7.9Hz,2H),6.7(d,J＝2.2Hz,2H),6.6(dd,J＝7.9,2.3Hz,2H),5.3(s,4H). 13 C NMR (125 MHz, DMSO). Delta. 195.36,148.66,135.05,133.74,120.34,119.10,110.13,40.25,40.08,39.91,39.75,39.58. (FIGS. 1 and 2).
Example 3
Figure BDA0004069763220000072
The method for preparing 2, 7-diamino-9-fluorenone monodiazonium salt by diazotization reaction comprises the following steps:
(1) Weighing 2, 7-diamino-9-fluorenone (2.1 g,10 mmol) in a 100mL beaker, adding 50mL deionized water, stirring and dispersing, then adding concentrated hydrochloric acid (37 wt%,4mL,40 mmol), ultrasonically dissolving, transferring to ice water bath, and cooling to 5 ℃ for standby;
(2) Sodium nitrite (0.56 g,8 mmol) was weighed into 50mL deionized water and then slowly added dropwise to 2, 7-diaminoAnd (3) continuously stirring and reacting the solution in the solution of the-9-fluorenone for 1 hour after the dripping is finished to obtain a solution of 2, 7-diamino-9-fluorenone monoazo salt which is directly used for the next reaction. Nuclear magnetism of 2, 7-diamino-9-fluorenone monodiazonium salt solution 1 H NMR (500 mhz, d2 o) δ8.8 (d, j=13.1 hz, 2H), 8.4 (d, j=8.3 hz, 1H), 7.7 (d, j=8.0 hz, 1H), 7.5 (s, 1H), 7.5 (d, j=8.1 hz, 1H) (fig. 3).
Example 4
Figure BDA0004069763220000081
The method for preparing the 2, 7-diamino-9-fluorenone double nitrogen salt by diazotization reaction comprises the following steps:
(1) Weighing 2, 7-diamino-9-fluorenone (2.1 g,10 mmol) in a 100mL beaker, adding 50mL deionized water, stirring and dispersing, then adding concentrated hydrochloric acid (37 wt%,4mL,40 mmol), ultrasonically dissolving, transferring to ice water bath, and cooling to 5 ℃ for standby;
(2) Sodium nitrite (2.5 g,35 mmol) is weighed and dissolved in 50mL of deionized water, then slowly added dropwise into the 2, 7-diamino-9-fluorenone acid solution, and the mixture is continuously stirred for reaction for 1 hour after the dropwise addition is finished, so that 2, 7-diamino-9-fluorenone double nitrogen salt solution is obtained and is directly used for the next reaction. 2, 7-diamino-9-fluorenone double nitrogen salt solution nuclear magnetism 1 H NMR (500 mhz, d2 o) δ9.1-8.6 (m, 4H), 8.5 (d, j=8.3 hz, 2H) (fig. 4).
Comparative example 1
Figure BDA0004069763220000082
The method for preparing 3,3' -dimethoxy benzidine monodiazonium salt by diazotization reaction comprises the following steps:
(1) Weighing 3,3' -dimethoxy benzidine (2.4 g,10 mmol) in a 100mL beaker, adding 50mL of deionized water, stirring for dispersion, then adding concentrated hydrochloric acid (37 wt%,4mL,40 mmol), ultrasonically dissolving, transferring to ice water bath, and cooling to 5 ℃ for standby;
(2) Sodium nitrite (0.69 g,10 mmol) was weighed and dissolved in 50mL deionized waterThen slowly dropwise adding the mixture into the 3,3 '-dimethoxy benzidine acid solution, and continuing to stir and react for 1 hour after the dropwise adding is finished to obtain 3,3' -dimethoxy benzidine monodiazonium salt solution which is directly used for the next reaction. Nuclear magnetism of 3,3' -dimethoxy benzidine monodiazonium salt solution 1 H NMR (500 mhz, d2 o) δ8.4 (d, j=8.7 hz, 1H), 7.7 (s, 1H), 7.6 (d, j=8.7 hz, 1H), 7.3 (d, j=8.1 hz, 1H), 7.3 (d, j=1.8 hz, 1H), 7.2 (dd, j=8.1, 1.8hz, 1H), 4.2 (s, 3H), 3.9 (s, 3H) (fig. 5).
Comparative example 2
Figure BDA0004069763220000091
The method for preparing the 3,3' -dimethoxy benzidine double nitrogen salt by diazotization reaction comprises the following steps:
(1) Weighing 3,3' -dimethoxy benzidine (2.4 g,10 mmol) in a 100mL beaker, adding 50mL of deionized water, stirring for dispersion, then adding concentrated hydrochloric acid (37 wt%,4mL,40 mmol), ultrasonically dissolving, transferring to ice water bath, and cooling to 5 ℃ for standby;
(2) Sodium nitrite (2.1 g,30 mmol) was weighed and dissolved in 50mL of deionized water, then slowly added dropwise to the 3,3 '-dimethoxybenzidine acid solution, and the reaction was continued for 1 hour after the dropwise addition to obtain a double nitrogen salt solution of 3,3' -dimethoxybenzidine, which was directly used in the next reaction. Nuclear magnetism of 3,3' -dimethoxy benzidine double nitrogen salt solution 1 H NMR (500 mhz, d2 o) δ8.4 (d, j=8.8 hz, 2H), 7.7 (s, 2H), 7.6 (dd, j=8.7, 1.5hz, 2H), 4.2 (s, 6H) (fig. 6).
Application example 1
Figure BDA0004069763220000101
A process for diazotizing coupling to prepare 7-amino-4-hydroxy-3- ((7-amino-9-fluorenonyl) diazenyl)) naphthalene-2-sulfonic acid comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-7-sulfonic acid (2.4 g,10 mmol) in a 500mL beaker, then adding 200mL of saturated sodium carbonate aqueous solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-7-sulfonic acid solution; then, 2, 7-diamino-9-fluorenone monodiazonium salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 3 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the mixture to salt out, and after stirring for 1 hour, the mixture was allowed to stand, centrifuged and dried to obtain 4.1g of a product with a yield of 90%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 551nm (FIG. 7).
Application example 2
Figure BDA0004069763220000102
A process for diazotizing coupling to prepare 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2-sulfonic acid) -9-fluorenone, comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-7-sulfonic acid (4.8 g,20 mmol) in a 500mL beaker, then adding 200mL of saturated sodium carbonate aqueous solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-7-sulfonic acid solution; then, 2, 7-diamino-9-fluorenone double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 4 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solids (45 g,15 wt%) were added to salt out, stirred for 1 hour, then allowed to stand, centrifuged, and dried to give 5.0g of the product in 70% yield.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 540nm (FIG. 8).
Application example 3
Figure BDA0004069763220000111
A process for diazotising a coupling to prepare 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2, 8-disulfonic acid) -9-fluorenone comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid (6.8 g,20 mmol) in a 500mL beaker, then adding 200mL saturated sodium carbonate solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid solution; then, 2, 7-diamino-9-fluorenone double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 4 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solids (45 g,15 wt%) were added to salt out, stirred for 1 hour, then allowed to stand, centrifuged, and dried to give 5.5g of product in 60% yield.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 545nm (FIG. 9).
Application example 4
Figure BDA0004069763220000121
A process for the diazo coupling preparation of 3, 7-diazenyl (1-hydroxynaphthalene-4-sulfonic acid) -9-fluorenone comprising the steps of:
(1) 1-hydroxynaphthalene-4-sulfonic acid (4.9 g,20 mmol) was weighed into a 500mL beaker, then 200mL of saturated sodium carbonate solution was added, and after ultrasonic dissolution, 1-hydroxynaphthalene-4-sulfonic acid solution was obtained; then, 2, 7-diamino-9-fluorenone double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 4 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the mixture to salt out, and after stirring for 1 hour, the mixture was allowed to stand, centrifuged and dried to obtain 5.8g of a product with a yield of 80%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 556nm (FIG. 10).
Application example 5
Figure BDA0004069763220000122
A process for the diazo coupling preparation of 3, 7-diazenyl (1-aminonaphthalene-4-sulfonic acid) -9-fluorenone comprising the steps of:
(1) 1-aminonaphthalene-4-sulfonic acid (4.9 g,20 mmol) was weighed into a 500mL beaker, then 200mL of saturated sodium carbonate solution was added, and after ultrasonic dissolution, 1-aminonaphthalene-4-sulfonic acid solution was obtained; then, 2, 7-diamino-9-fluorenone double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 4 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the solution, and after stirring for 1 hour, the solution was allowed to stand, centrifuged and dried to obtain 2.9g of a product with a yield of 40%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 467nm (FIG. 11).
Comparative example 1 was used
Figure BDA0004069763220000131
A process for diazotizing coupling to prepare 7-amino-4-hydroxy-3- ((3, 3 '-dimethoxy-4' -aminobiphenyl) diazenyl)) naphthalene-2-sulfonic acid comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-7-sulfonic acid (2.4 g,10 mmol) in a 500mL beaker, then adding 200mL of saturated sodium carbonate solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-7-sulfonic acid solution; then, 3' -methoxybenzidine monodiazonium salt solution (100 mL,0.1mol/L,10 mmol) prepared in comparative example 1 was added thereto, and coupling was performed at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the solution, and after stirring for 1 hour, the solution was allowed to stand, centrifuged and dried to obtain 4.5g of a product with a yield of 90%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 558nm (FIG. 12).
Comparative example 2
Figure BDA0004069763220000141
A process for the diazo coupling preparation of 4,4 '-diazenyl (7-amino-4-hydroxynaphthalene-2-sulfonic acid) -3,3' -biphenyl comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-7-sulfonic acid (4.8 g,20 mmol) in a 500mL beaker, then adding 200mL of saturated sodium carbonate solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-7-sulfonic acid solution; then, a double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) of 3,3' -methoxybenzidine prepared in comparative example 2 was added thereto, and the mixture was coupled at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solids (45 g,15 wt%) were added to salt out, stirred for 1 hour, then allowed to stand, centrifuged, and dried to give 5.3g of the product in 70% yield.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 569nm (FIG. 13).
Comparative example 3
Figure BDA0004069763220000142
A process for the diazo coupling preparation of 4,4 '-diazenyl (7-amino-4-hydroxynaphthalene-2, 8-disulfonic acid) -3,3' -biphenyl comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid (6.8 g,20 mmol) in a 500mL beaker, then adding 200mL saturated sodium carbonate solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid solution; then, a double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) of 3,3' -methoxybenzidine prepared in comparative example 2 was added thereto, and the mixture was coupled at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solids (45 g,15 wt%) were added to salt out, stirred for 1 hour, then allowed to stand, centrifuged, and dried to give 5.7g of the product in 60% yield.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 553nm (FIG. 14).
Comparative example 4
Figure BDA0004069763220000151
A process for the diazo coupling preparation of 4,4 '-diazenyl (1-hydroxy-4-naphthalenesulfonic acid) -3,3' -biphenyl comprising the steps of:
(1) 1-hydroxynaphthalene-4-sulfonic acid (4.9 g,20 mmol) was weighed into a 500mL beaker, then 200mL of saturated sodium carbonate solution was added, and after ultrasonic dissolution, 1-hydroxynaphthalene-4-sulfonic acid solution was obtained; then, a double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) of 3,3' -methoxybenzidine prepared in comparative example 2 was added thereto, and the mixture was coupled at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the mixture to salt out, and after stirring for 1 hour, the mixture was allowed to stand, centrifuged and dried to obtain 6.4g of a product with a yield of 80%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 564nm (FIG. 15).
Comparative example 5
Figure BDA0004069763220000161
A process for the diazo coupling preparation of 4,4 '-diazenyl (1-amino-4-naphthalenesulfonic acid) -3,3' -biphenyl comprising the steps of:
(1) 1-aminonaphthalene-4-sulfonic acid (4.9 g,20 mmol) was weighed into a 500mL beaker, then 200mL of saturated sodium carbonate solution was added, and after ultrasonic dissolution, 1-aminonaphthalene-4-sulfonic acid solution was obtained; then, a double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) of 3,3' -methoxybenzidine prepared in comparative example 2 was added thereto, and the mixture was coupled at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the solution, and after stirring for 1 hour, the solution was allowed to stand, centrifuged and dried to obtain 2.8g of a product with a yield of 35%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 419nm (FIG. 16).
The maximum absorption wavelength and the color of the products obtained in the above application examples 1 to 5 and application comparative examples 1 to 5 are shown in Table 1.
TABLE 1 maximum absorption wavelength and color of the products of application examples 1-5/application comparative examples 1-5
Figure BDA0004069763220000162
The products obtained in application examples 1 to 5 and application comparative examples 1 to 5 were weighed and dissolved in deionized water to prepare 10ppm aqueous solutions, and colorimetric control was performed, and the results are summarized in Table 1, and the colors of the application examples and the comparative examples are substantially the same, and the colors of the application examples and the comparative examples are purple, mauve, purple, purplish blue, and orange sequentially with increasing numbers. The application example is similar to the peak type of the ultraviolet-visible light absorption spectrum line of the comparison example, and the maximum absorption wavelength is close, so that the preparation method of the 2, 7-diamino-9-fluorenone and the application of the preparation method to diazotization reaction as a diamine monomer can replace benzidine to prepare azo dye, and the purpose of simply and effectively preparing direct dye with long absorption wavelength is realized.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended 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 such modifications and adaptations are intended to be comprehended within the scope of the invention.

Claims (9)

1. A direct dye compound as shown in formula i or formula II:
Figure FDA0004069763210000011
wherein R is 1 Is OH, ONa or NH 2 ，R 2 Is H or NH 2 ，R 3 H, SO of a shape of H, SO 3 H or SO 3 Na，R 4 H, SO of a shape of H, SO 3 H or SO 3 Na，R 5 Is H or SO 3 Na。
2. The direct dye compound according to claim 1, wherein the direct dye compound is selected from one of 7-amino-4-hydroxy-3- ((7-amino-9-fluorenonyl) diazenyl) naphthalene-2-sulfonic acid, 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2-sulfonic acid) -9-fluorenone, 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2, 8-disulfonic acid) -9-fluorenone, 3, 7-diazenyl (1-aminonaphthalene-4-sulfonic acid) -9-fluorenone, 3, 7-diazenyl (1-hydroxynaphthalene-4-sulfonic acid) -9-fluorenone or a sulfonate thereof.
3. A process for the preparation of a direct dye compound according to claim 1 or 2, comprising the steps of:
(1) 2, 7-diamino-9-fluorenone is prepared by reducing 2, 7-binitro-9-fluorenone;
(2) 2, 7-diamino-9-fluorenone is prepared into a diazonium salt intermediate through diazotization reaction;
(3) Diazo coupling is carried out on the diazonium salt prepared in the step (2) and naphthol in alkaline aqueous solution, and the diazonium salt reacts for 20-120 minutes at the temperature of 10-50 ℃ to obtain the direct dye compound.
4. A process according to claim 3, wherein the specific preparation of 2, 7-diamino-9-fluorenone in step (1) comprises the steps of:
a) Adding methanol into 2, 7-binitro-9-fluorenone, uniformly stirring, slowly dripping a reducing agent solution into the mixture, and heating and stirring for reaction after the dripping is finished to obtain a 2, 7-diamino-9-fluorenone solution for later use;
b) Evaporating the 2, 7-diamino-9-fluorenone solution to dryness to obtain a crude product, and pulping the crude product by using an organic solvent to obtain the 2, 7-diamino-9-fluorenone.
5. The process of claim 4, wherein the reducing agent in step (a) is one of ascorbic acid, sodium sulfide, iron powder, zinc powder; the mol ratio of the reducing agent to the 2, 7-binitro-9-fluorenone is 1.0-5.0:1; the organic solvent in the step (b) is one or a mixture of methanol, ethanol, acetone, petroleum ether and tetrahydrofuran.
6. A process according to claim 3, wherein the diazonium salt intermediate in step (2) is prepared by the steps of:
c) Dissolving 2, 7-diamino-9-fluorenone in an acidic solution for later use;
d) Then dropwise adding sodium nitrite solution at low temperature, and continuing to react for a period of time after the completion of the dropwise adding, thus obtaining diazonium salt solution.
7. The method according to claim 6, wherein the acid used in the step (c) is one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid or a mixed acid thereof; the molar ratio of the acid to the 2, 7-diamino-9-fluorenone is 3.0-5.0:1; the concentration of the sodium nitrite solution in the step (d) is 0.1-2M, the molar ratio of the sodium nitrite to the 2, 7-diamino-9-fluorenone is 0.5-5.0:1, the reaction temperature is 0-20 ℃, and the reaction time is 0.5-3 hours.
8. The process according to claim 3, wherein the naphthol in the step (3) is one of 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid, and 1-aminonaphthalene-4-sulfonic acid; the molar ratio of the diazonium salt to the naphthol is 1:0.5-2.5; the alkaline aqueous solution is one of saturated sodium bicarbonate aqueous solution, saturated sodium carbonate aqueous solution and 0.1-1.0M sodium hydroxide aqueous solution.
9. Use of a direct dye compound according to claim 1 or 2 for dyeing.
CN202310089219.2A 2023-02-09 2023-02-09 Method for preparing direct dye by replacing benzidine Pending CN116355434A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310089219.2A CN116355434A (en) 2023-02-09 2023-02-09 Method for preparing direct dye by replacing benzidine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310089219.2A CN116355434A (en) 2023-02-09 2023-02-09 Method for preparing direct dye by replacing benzidine

Publications (1)

Publication Number Publication Date
CN116355434A true CN116355434A (en) 2023-06-30

Family

ID=86910535

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310089219.2A Pending CN116355434A (en) 2023-02-09 2023-02-09 Method for preparing direct dye by replacing benzidine

Country Status (1)

Country Link
CN (1) CN116355434A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5053302A (en) * 1989-05-15 1991-10-01 Fuji Photo Film Co., Ltd. Electrophotographic photoreceptor containing an azo compound and a charge transporting material
JP2000147808A (en) * 1998-11-09 2000-05-26 Ricoh Co Ltd Photoconductor, organic pigment-dispersed liquid and manufacture of photoconductor by using same, electrophotographic method and apparatus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5053302A (en) * 1989-05-15 1991-10-01 Fuji Photo Film Co., Ltd. Electrophotographic photoreceptor containing an azo compound and a charge transporting material
JP2000147808A (en) * 1998-11-09 2000-05-26 Ricoh Co Ltd Photoconductor, organic pigment-dispersed liquid and manufacture of photoconductor by using same, electrophotographic method and apparatus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JERZY SZADOWSKI: ""Disazo direct dyes containing cyclic amido, keto and amino groups"", DYES AND PIGMENTS, vol. 14, no. 3, pages 217 - 224, XP000141193, DOI: 10.1016/0143-7208(90)87019-Y *

Similar Documents

Publication Publication Date Title
NO135587B (en)
US3947435A (en) Disazo acid compounds containing one sulphonic acid group and one phosphonic or methyl-phosphinic acid group
CN116355434A (en) Method for preparing direct dye by replacing benzidine
CN112341836B (en) Weak acid red bisazo dye and preparation method thereof
CN112322073B (en) Monoazo lake pigment and preparation method thereof
CN110066527B (en) Red reactive dye and preparation method thereof
Szadowski et al. Synthesis and properties of disazo dyes derived from water-soluble derivatives of benzidine and 4, 4'-diaminodiphenylurea
CN109233338B (en) Disperse dye compound and synthesis method and application thereof
CN109135322B (en) Azo disperse dye compound and synthesis method and application thereof
CN113548979A (en) Bisphenol compound containing bisazo and preparation method thereof
JPS6334905B2 (en)
US2741655A (en) Cupriferous azo-dyestuffs
KR950007220B1 (en) Process for the manufacture of copper complex disazo compounds
JPS6111265B2 (en)
CN110041729B (en) Orange-red reactive dye and preparation method thereof
CA1039714A (en) Triazo dyestuff and process for preparing same
US2700669A (en) Hydroxybenzotriazole carboxylic acids
CN115521637B (en) Compound thick and deep bright printing reactive scarlet dye
CN114539803A (en) Direct red/direct violet dye compound and preparation method and application thereof
CN112322068B (en) Monoazo yellow organic pigment and preparation method thereof
CN101735652B (en) Red reactive dye and preparation method thereof
CN101735655B (en) Red reactive dye for wool and preparation method thereof
US447303A (en) Fabriken
CN101735653B (en) Red reactive dye for wool and preparation method thereof
US1716098A (en) Trisazo dye and process of producing the same

Legal Events

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