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CAS No. : | 87-02-5 | MDL No. : | MFCD00003970 |
Formula : | C10H9NO4S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KYARBIJYVGJZLB-UHFFFAOYSA-N |
M.W : | 239.25 | Pubchem ID : | 6868 |
Synonyms : |
|
Num. heavy atoms : | 16 |
Num. arom. heavy atoms : | 10 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 4.0 |
Num. H-bond donors : | 3.0 |
Molar Refractivity : | 60.23 |
TPSA : | 109.0 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -8.37 cm/s |
Log Po/w (iLOGP) : | 0.09 |
Log Po/w (XLOGP3) : | -0.86 |
Log Po/w (WLOGP) : | 2.46 |
Log Po/w (MLOGP) : | 1.05 |
Log Po/w (SILICOS-IT) : | 0.05 |
Consensus Log Po/w : | 0.56 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.56 |
Log S (ESOL) : | -1.18 |
Solubility : | 15.9 mg/ml ; 0.0664 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.95 |
Solubility : | 27.0 mg/ml ; 0.113 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -2.5 |
Solubility : | 0.764 mg/ml ; 0.00319 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.19 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Diazotization; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; nickel-aluminium at 90℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70.2% | With sodium metabisulfite at 100 - 110℃; | 3 Preparation of 2- (N-phenylamino) -5_naphthol-7-sulfonic acid A, condensation reaction Bottom water added in reactor 275g, then adding 2-amino-5-naphthol-7-sulfonic acid powder 43g, aniline 23g, Na 2 S 2 O 5 80g, then using 14g pH=4-6 to control the reaction of sulfuric acid, then heating to 100-110°C, reflux reaction 10-30 hours to the end point of the reaction, the detection of the liquid phase for 2-amino-5-naphthol-7-sulfonic acid residue ≤ 10% is qualified endpoint. B, materials after treatment The end point of the reaction upon arrival, cooling to 10-50°C, then using the 2g material sulfuric acid acidified pH=4-6, filter pressing or filtered, collecting filter cake 55 kg, yield a filtrate. The filter cake need to re-refining processing, a filtrate collection for the next batch condensation reaction using bottom water. C, refining filter cake Properties in the reactor to 100g, 55g and then adding the above-mentioned filter cake, then using the 10g pH=0-2 sulfating material, stirring 1-3 hours, then filtering or filtering, 50g collecting filter cake, two collecting filtrate. The filter cake is the target product, the measured ammonia value to 70.2%, HPLC purity of 96.2%, J acid residue to 1.9%, double J acid residue to 1.1%, its by-product is 0.8%. The collected filtrate b used for the next batch refined properties of filter cake. |
With sodium disulfite |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With sodium carbonate; sodium chloride In water 1.) 0-5 deg C, 3 h; 2.) 60 deg C; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: N,N'-bis(4-aminophenyl)urea With hydrogenchloride; sodium nitrite In water at 0℃; for 0.333333h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide at 0 - 5℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With sodium hydroxide In tetrahydrofuran at 20℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sodium hydroxide In tetrahydrofuran at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: 2.67 g / imidazole / dimethylformamide / 96 h 2.1: aq. NaNO2; aq. H2SO4 2.2: aq. Na2CO3 / 20 °C / pH 9 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: 2.67 g / imidazole / dimethylformamide / 96 h 2.1: aq. NaNO2; aq. H2SO4 2.2: aq. Na2CO3 / 20 °C / pH 9 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: 2.67 g / imidazole / dimethylformamide / 96 h 2.1: aq. NaNO2; aq. H2SO4 2.2: aq. Na2CO3 / 20 °C / pH 9 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: 2.67 g / imidazole / dimethylformamide / 96 h 2.1: aq. NaNO2; aq. H2SO4 2.2: aq. Na2CO3 / 20 °C / pH 9 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water Stage #2: With hydrogenchloride; sodium nitrite In water at 5℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 0 - 5℃; for 0.5h; | 3 EXAMPLE 3 19.32 g of cyanuric chloride was suspended in an aqueous solution below 0°C for 30 minutes and a solution containing 23.93 g of 6-amino-1-naphthol-3-sulfonic acid was added thereto. The resulting solution was kept at pH 3 and 5°C until the condensation reaction was completed. 30.31 g of 2-amino-naphthol-1,5-disulfonic acid was diazotized in the customary manner, then added to the above reaction solution to conduct the additional condensation reaction at pH 8 and 10°C. To the resulting solution, 23.26 g of 1-amino-3-(N-hydroxyethyl)aminobenzene-4-sulfonic acid was added, and the reaction solution was kept at pH 5 and 50°C for 3 hours to complete the reaction, followed by a diazonium salt corresponding to 28.13 g of 4-sulfatoethylsulfon-1-aminobenzene being added thereto. When the reaction was ended at pH 7 and 10°C, non-solved components were removed by filtering and then the reactant was dried. Subsequently, a deep brown compound of the below formula (λmax= 480 nm) was obtained in an amount of 119 g. | |
In water at 0 - 5℃; for 2h; | 1.C (C); Separately, 6-amino-1-naphthol-3-sulfonic acid (J acid) was dissolved in water so that the pH became 6, and the solution was cooled to 0 to 5°C. Cyanuric chloride was added thereto, and reaction was carried out for 2 hours while maintaining the temperature at from 0 to 5°C, to complete the reaction. Then, at room temperature, a 3-aminobenzenesulfonic acid (metanillic acid) aqueous solution was added thereto, to carry out a condensation reaction at a pH of from 6 to 7 for several hours. | |
With sodium carbonate In water at 0 - 5℃; for 2h; | 2.a (a) 10 parts of cyanuric chloride are added in 70 parts of water at 0°C, and then a solution containing 12 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid are added therein. The pH value of the solution is adjusted to 1∼3 by 15% Na2CO3 aqueous solution: After reaction for 2 hours under 5°C, the solution is afforded by filtration. |
With sodium carbonate In water at 0 - 5℃; for 2h; | 2.a (a) 10 parts of cyanuric chloride are added in 70 parts of water at 0° C., and then a solution containing 12 parts of 2-amino-5-hydroxy-naphthalene-7-sulfonic acid are added therein. The pH value of the solution is adjusted to 13 by 15% Na2CO3 aqueous solution. After reaction for 2 hours under 5° C., the solution is afforded by filtration. | |
In water; acetone at 0 - 5℃; for 2h; | ||
at 0 - 5℃; for 1.5h; | ||
In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; sodium carbonate In water at 5 - 15℃; for 2h; | 1 (The first process) Into 200 parts of water, 17.3 parts of 2-aminobenzenesulfonic acid was charged and neutralized with sodium hydroxide to dissolve, followed by adding 31.3 parts of 35% hydrochloric acid, adjusting the temperature thereof at 5° C. or lower, and diazotizing with 18.1 part of 40% aqueous solution of sodium nitrite to obtain a diazo suspension. Subsequently, 23.9 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid (J Acid) was dispersed in 200 parts of water and dissolved adjusting the pH value to 8.0 to 9.0 with sodium hydroxide, and into the obtained solution, the above obtained diazo suspension was added dropwise at 5 to 10° C. During the dropwise addition, the pH value of the reaction solution was maintained at 8.5 to 9.5 with sodium carbonate. After the completion of the dropwise addition, furthermore, the pH value was adjusted at 8.5 to 9.5 with sodium carbonate, stirring was conducted at a temperature of 10 to 15° C. for 2 hours, and the coupling reaction was completed, followed by salting out by the addition of sodium chloride, and filtering. The thus obtained wet cake was dried to obtain 36.3 parts of a monoazo compound of Formula (23). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water at 20 - 25℃; for 12h; | 5 Example 5 In 300 g Wasser wurden 23,9 g 3-Amino-8-hydroxynaphthalin-6-sulfonsäure eingetragen. Durch Zugabe von 10 gew.-%iger Natronlauge wurde ein pH-Wert von 7-8 eingestellt. Anschließend erfolgte bei 20-25°C die Zugabe von 20,8 g Phthalsäureanhydrid, wobei mit Hilfe von 10 gew.-%iger Natronlauge der pH-Wert auch während der Nachrührzeit über Nacht zwischen 7 und 8 gehalten wurde. Die vollständige Reaktion der 3-Amino-8-hydroxynaphthalin-6-sulfonsäure wurde mit Hilfe der Dünnschichtchromatographie überprüft. Die so hergestellte Lösung der Kupplungskomponente wurde für die Synthese der Farbstoffe ohne Zwischenisolierung eingesetzt |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water at 85℃; for 3h; | 1 36.9g of cyanuric chloride are dissolved in [185ML] of acetone and added to [200G] of ice water at [0C.] At an initial temperature of [0-5C] and, subsequently, at [20C,] 28.7g of [ETHANOLAMINE] are added drop wise with stirring, the pH being maintained at 5.5-6. 5. After 2.5 hours, the temperature is increased to [40-50C] and the pH maintained at 6.5-7. 0 by addition of a total of [164M1 OF] 2N aqueous sodium hydroxide solution. After a further 2 hours the consumption of sodium hydroxide ceases, the reaction mixture is stirred for a further 30 minutes, cooled to room temperature and the white suspension filtered. There are obtained 46.7g of the disubstituted intermediate which are suspended in 300g of water and treated with 47.9g of [L-ACID] (7-amino-4-hydroxy naphthalene-2-sulphonic acid). The resulting beige suspension is heated to [85C] and the pH maintained at 3.0 by addition of a total of [94ML] of 2N aqueous sodium hydroxide solution. After stirring for 3 hours reaction is complete, the pH is adjusted to 5.5 by addition of a further [8ML] of 2N aqueous sodium hydroxide solution, the suspension cooled to room temperature and the precipitated solids filtered. There are obtained 77g of the compound of formula (100a). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water at 45℃; | 4 180 parts of 4-(β-sulfatoethylsulfonyl)aniline are suspended in 440 parts of ice-water and 116 parts of 30% hydrochloric acid and diazotized by dropwise addition of 112 parts of 40% sodium nitrite solution. After excess nitrite has been removed with sulfamic acid, 67 parts of 4-hydroxy-7-(sulfomethylamino)naphthalene-2-sulfonic acid (prepared by reaction of 48 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid with 32 parts of formaldehyde sodium bisulfite in an aqueous medium at pH 5.5-6 and 45° C.) and also 23 parts of 2,4-diaminobenzenesulfonic acid are added, and a first coupling reaction is carried out at pH 1 to 2 below 20° C. to form a mixture of two monoazo dyes as per the formulae (15-4) and (Ga-2). The stated pH range is set and maintained during the coupling reaction by addition of solid sodium bicarbonate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water | 6 156 parts of 2-methoxy-5-(β-sulfatoethylsulfonyl)aniline are suspended in 450 parts of ice-water and 91 parts of 30% hydrochloric acid and diazotized by dropwise addition of 88 parts of 40% sodium nitrite solution. After excess nitrite has been removed with sulfamic acid solution, the diazo suspension obtained is pumped into an aqueous solution of 169 parts of the scarlet monoazo dye of the formula (15-3) [C00032] [00032] [0170] which was obtained by diazotization of 91 parts of 2-amino-5-(β-sulfatoethylsulfonyl)-benzenesulfonic acid with 44 parts of 40% sodium nitrite solution in a sulfuric acid medium and subsequent coupling onto 60 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acid at pH 1.5 to 2. This is followed by the addition of 71 parts of 5-hydroxy-1-(4-sulfophenyl)-1H-pyrazole-3-carboxylic acid and pH 5-6 is set and maintained with sodium carbonate below 25° C. The 60:40 mixture of the two dyes (I-5) and (Gc-5) which has formed after the coupling reaction has ended can be isolated by evaporation under reduced pressure or by spray drying. [C00033] [00033] [0171] The resulting dye mixture of the present invention dyes cotton in reddish shades |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid With sodium nitrite In water Acidic aqueous solution; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water | 10 EXAMPLE 10 [0202] 333 parts of 4-(β-sulfatoethylsulfonyl)aniline are suspended in 850 parts of ice-water and 214 parts of 30% hydrochloric acid and diazotized by dropwise addition of 205 parts of 40% sodium nitrite solution. After excess nitrite has been removed with sulfamic acid solution, the diazo suspension obtained is pumped into an aqueous solution of 339 parts of the scarlet monoazo dye of the formula (15-3) [C00043] [00043] [0203] which was obtained by diazotization of 180.5 parts of 2-amino-5-(β-sulfatoethyl-sulfonyl)benzenesulfonic acid with 87 parts of 40% sodium nitrite solution in an acidic medium and subsequent coupling onto 119 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acid at pH 1.5 to 2. This is followed by the addition of 140 parts each of the two further coupling components (18-2) and (18-3) [C00044] [00044] [0204] and pH 5-6 is set and maintained with sodium carbonate below 25° C. The 50:25:25 mixture of the three dyes (I-1), (II-7) and (II-8) which has formed after the coupling reaction has ended can be isolated by evaporation under reduced pressure or by spray drying. [C00045] [00045] [0205] The resulting dye mixture of the present invention dyes cotton in reddish orange shades. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; at 45℃;pH 5.5 - 6; | EXAMPLE 7 [0195] a) 312 parts of 2-(beta-sulfatoethylsulfonyl)aniline are suspended in 800 parts of ice-water by addition of 165 parts of concentrated sulfuric acid and diazotized by dropwise addition of 195 parts of 40% sodium nitrite solution. After excess nitrite has been removed with sulfamic acid, a mixture of 250 parts of 4-hydroxy-7-(sulfomethyl-amino)naphthalene-2-sulfonic acid and 120 parts of 4-hydroxy-6-(sulfomethyl-amino)naphthalene-2-sulfonic acid (prepared by reaction of 179 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid and 86 parts of 6-amino-4-hydroxynaphthalene-2-sulfonic acid with 171 parts of formaldehyde sodium bisulfite in an aqueous medium at pH 5.5-6 and 45 C.) is added and coupled in a first stage at pH 1 to 2 below 20 C. to form a mixture of two monoazo dyes as per the formulae (15-2) and (II-5). The stated pH range is set (and maintained during the coupling reaction) by addition of solid sodium bicarbonate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; at 45℃;pH 5.5 - 6; | EXAMPLE 4 [0188] 422 parts of 4-(beta-sulfatoethylsulfonyl)aniline are suspended in 1000 parts of ice-water and 270 parts of 30% hydrochloric acid and diazotized by dropwise addition of 260 parts of 40% sodium nitrite solution. After excess nitrite has been removed with sulfamic acid solution, the diazo suspension obtained is admixed with an aqueous solution of 166.5 parts of 4-hydroxy-7-(sulfomethylamino)naphthalene-2-sulfonic acid (obtained by reaction of 119.5 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid with 75 parts of <strong>[870-72-4]formaldehyde sodium bisulfite</strong> in an aqueous medium at pH 5.5-6 and 45 C.) and adjusted to pH 1.5 with solid sodium bicarbonate. After the acidic coupling has ended, this reaction mixture has added to it an aqueous solution of 335 parts of the second coupling component (18-1) and is adjusted to and maintained at pH 5-6 with sodium carbonate below 25 C. [C00035] [00035] [0189] The 50:50 mixture of the two dyes (1-4) and (11-3) which has formed after the coupling reaction has ended can be isolated by evaporation under reduced pressure or by spray drying. [C00036] [00036] [0190] The resulting dye mixture according to the present invention dyes cotton in red shades.; EXAMPLE 11 [0206] 281 parts of 4-(beta-sulfatoethylsulfonyl)aniline are suspended in 700 parts of ice-water and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of 173 parts of 40% sodium nitrite solution. After excess nitrite has been removed with sulfamic acid solution, the diazo suspension obtained is admixed with an aqueous solution of 83 parts of 4-hydroxy-7-(sulfomethylamino)naphthalene-2-sulfonic acid (obtained by reaction of 60 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid with 37.5 parts of <strong>[870-72-4]formaldehyde sodium bisulfite</strong> in an aqueous medium at pH 5.5-6 and 45 C.) and adjusted to pH 1.5 with solid sodium bicarbonate. After the acidic coupling has ended, this reaction mixture has added to it an aqueous solution of 111 parts of 4-amino-phthalene-1-sulfonic acid as the second coupling component and is adjusted to and maintained at pH 5-6 with sodium carbonate below 25 C. After the coupling reaction has ended, the reaction mixture is admixed with 73 parts of the golden yellow azo dye of the formula (Ga-1) and the resulting 42:46:12 mixture of the three azo dyes (I-4), (II-6) and (Ga-1) is isolated by spray drying. [C00046] [00046] [0207] The resulting dye mixture according to the present invention provides orange dyeings and prints on cotton for example under the dyeing conditions customary for reactive dyes. | |
In water; at 45℃;pH 5.5 - 6; | a) 28.1 parts of 4-(beta-sulfatoethylsulfonyl)-aniline are suspended in 70 parts of ice/water and 18 parts of 30% strength hydrochloric acid and diazotized by dropwise addition of 17.5 parts of 40% strength sodium nitrite solution. Following removal of the excess nitrite with amidosulfonic acid solution, the resulting diazo suspension is admixed with an aqueous solution of 33.3 parts of 4-hydroxy-7-(sulfomethyl-amino)-naphthalene-2-sulfonic acid, which has been obtained by reaction of 23.9 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acid with 15 parts of formaldehyde-sodium bisulfite in aqueous medium at a pH of 5.5-6 and at 45 C., and is adjusted to a pH of 1.5 using solid sodium hydrogen carbonate. This is followed by stirring at a pH of 1.5 and at 15-20 C. until the acidic coupling reaction is at an end. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium acetate In tetrahydrofuran; sodium hydroxide; water | 1 Preparation of Compound 1 Example 1 Preparation of Compound 1 4-hydroxy-7-[(5-hydroxy-7-sulfo(2-naphthyl))amino]carbonylamino}naphthalene-2-sulfonic acid disodium salt. To 10.77 g (0.045 moles) of 7-amino-4-hydroxynaphthalene-2-sulfonic acid dissolved in 45 mL of 1 N aqueous NaOH and 50 mL of water was added 3.70 g (0.045 moles) of sodium acetate. The pH of the solution was above 9. The reaction was cooled to under 5° C. in an ice-water bath. Then, 2.23 g (0.045 mole) of triphosgene dissolved in 15 mL of THF was added in three portions. The pH of the reaction fell to 4-5 and was readjusted to 7-8 by the dropwise addition of 1N aqueous NaOH. TLC (6:2:1 ethyl acetate:isopropanol:water) indicated the reaction was incomplete. Another 2.20 grams (0.045 moles) of triphosgene in 10 mL of THF was added portionwise with the pH kept above 7 by the addition of 1N aqueous NaOH. When the reaction was judged complete by TLC, the pH was lowered to 1 with aqueous HCl and the volatiles were removed by rotary evaporation. The solid product was collected by vacuum filtration. This resulted in the recovery of 10.85 g of the desired compound. 7-[(7-(chlorosulfonyl)-5-hydroxy(2-naphthyl))amino]carbonylamino}-4-hydroxynaphthalene-2-sulfonyl chloride. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With sodium hydroxide; sodium acetate In tetrahydrofuran; water | |
With sodium acetate In tetrahydrofuran; sodium hydroxide; water | 1 4-hydroxy-7-[(5-hydroxy-7-sulfo(2-naphthyl))amino]carbonylamino}naphthalene-2-sulfonic acid disodium salt (Compound 4) 4-hydroxy-7-[(5-hydroxy-7-sulfo(2-naphthyl))amino]carbonylamino}naphthalene-2-sulfonic acid disodium salt (Compound 4) To 10.77 g (0.045 moles) of 7-amino-4-hydroxynaphthalene-2-sulfonic acid dissolved in 45 mL of 1 N aqueous NaOH and 50 mL of water was added 3.70 g (0.045 moles) of sodium acetate. The pH of the solution was above 9. The reaction was cooled to under 5° C. in an ice-water bath. Then, 2.23 g (0.045 mole) of triphosgene dissolved in mL of THF was added in three portions. The pH of the reaction fell to 4-5 and was readjusted to 7-8 by the dropwise addition of 1N aqueous NaOH. TLC (6:2:1 ethyl acetate:isopropanol:water) indicated the reaction was incomplete. Another 2.20 grams (0.045 moles) of triphosgene in 10 mL of THF was added portionwise with the pH kept above 7 by the addition of 1N aqueous NaOH. When the reaction was judged complete by TLC, the pH was lowered to 1 with aqueous HCl and the volatiles were removed by rotary evaporation. The solid product was collected by vacuum filtration. This afforded 10.85 g of compound 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; sodium hydrogencarbonate In ice-water | 32 EXAMPLE 32 EXAMPLE 32 A dye mixture according to the invention is prepared by diazotizing a suspension of 281 parts of 4-(β-sulfatoethylsulfonyl)aniline in 650 parts of ice-water and 180 parts of 30% aqueous hydrochloric acid with 173 parts of 40% strength aqueous sodium nitrite solution. 143 parts of 1-amino-8-naphthol-3,6-disulfonic acid is added and the first coupling is carried out at a pH between 1 and 1.3 and at a temperature below 20° C. (the pH is maintained with about 50 parts of sodium bicarbonate). (n a separate reaction, 18.4 parts of cyanuric chloride is suspended in ice-water and acylated with 23.9 parts of 7-amino4-hydroxy-naphthalene-2-sulfonic acid in weakly acidic solution at a temperature of 0 to 20° C. and then further acylated with 8,7 parts morpholin at a pH of 7 to 8 and a temperature of 20 to 40° C. The resulting 7-(4'-chloro-6'-morpholino-1',3', 5'-triazin-2'-yl)amino4-hydroxynaphthalene-2-sulfonic acid coupler solution is added to the above coupling mixture and the pH is raised to 3 to 6 with sodium carbonate at a temperature below 20° C. A deep black dye solution is obtained containing the dye of formulae (A) as mentioned in Example 1, and the dye of formula (F) as shown below in the ratio of 90%:10%. STR16 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60.6% | In water | 5 EXAMPLE 6 4-(5-Hydroxy-7-sulfonaphth-2-yl)-amino-3-nitrophenyl hydroxyethyl sulfone EXAMPLE 6 4-(5-Hydroxy-7-sulfonaphth-2-yl)-amino-3-nitrophenyl hydroxyethyl sulfone 265.7 g of 4-chloro-3-nitrophenyl hydroxyethyl sulfone are added in portions at pH 6.0 to a suspension of 257 g of 2-amino-5-hydroxynaphthalene-7-sulfonic acid (93.2% pure) in 500 ml of water. The mixture is stirred for 16 hours at 80° C., and the reaction product which crystallizes out on cooling to room temperature is filtered off with suction. It is washed with saturated sodium chloride solution to give, after drying, 354 g of 4-(5-hydroxy-7-sulfonaphth-2-yl)-amino-3-nitrophenyl hydroxyethyl sulfone as the sodium salt of melting point 243° C. and 84.2% purity (NO2), corresponding to a yield of 60.6% of theory. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydrogencarbonate In ice-water | 8 EXAMPLE 8 EXAMPLE 8 239 Parts of 2-amino-5-naphthol-7-sulfonic acid in pulverulent form are suspended in 6,000 parts of ice-water. 140 Parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise while stirring thoroughly, while the temperature is maintained at 0° C. and the pH is adjusted and kept at 3.5 to 4.0 by gradually adding sodium bicarbonate. At this pH stirring of the reaction batch is continued for 20 to 30 minutes until no starting compound can be detected any more. This reaction mixture contains the 2-(4',6'-difluoro-1',3',5'-triazin-2'-yl)-amino-5-naphthol-7-sulfonic acid with a yield of 95-98% of theory. The aqueous solution or suspension of this difluorotriazinyl-aminonaphthol sulfonic acid obtained in the synthesis can directly be used for the manufacture of dyestuffs. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water | 3 Dissolving 28.1 parts of 1-aminobenzene-4-β-sulfatoethylsulfone in 1000 parts of ice water, adding 24 parts of 32% HCL aqueous solution therein and stirring the solution adequately, then adding 7.0 parts of sodium nitrite aqueous solution and stirring the solution continuously under the temperature of 05° C. till the diazotization is completed. Then, adding 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid into the reaction solution and stirring the mixed reaction solution till the coupling reaction is completed. At last, adding NaCl to salt-out and filtrating the solution to obtain the following formula (I-3) compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water | 1; 2 Dissolving 36.1 parts of 1-aminobenzene-2-sulfonic acid-4-β-sulfatoethylsulfone in 1000 parts of ice water, adding 24 parts of 32% HCl aqueous solution therein and stirring the solution adequately, then adding 7.0 parts of sodium nitrite aqueous solution and stirring the solution continuously under the temperature of 05° C. till the diazotization is completely. Then, adding 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid into the reaction solution and stirring the mixed reaction solution till the coupling reaction is completed. At last, adding NaCl to salt-out and filtrating the solution to obtain the following formula (I-1) compound.; Dissolving 36.1 parts of 1-aminobenzene-2-sulfonic acid-4-β-sulfatoethylsulfone in 1000 parts of ice water, adding 24 parts of 32% HCl aqueous solution therein and stirring the solution adequately, then adding 7.0 parts of sodium nitrite aqueous solution and stirring the solution continuously under the temperature of 05° C. till the diazotization is completed. Then, adding 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid into the reaction solution and stirring the mixed reaction solution till the coupling reaction is completed. At last, adding NaCl to salt-out and filtrating the solution to obtain the following formula (I-2) compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water | 1; 2 Preparation Example 1 ; Dissolving 36.1 parts of 1-aminobenzene-2-sulfonic acid-4-β -sulfatoethylsulfone in 1000 parts of ice water, adding 24 parts of 32% HCl aqueous solution therein and stirring the solution adequately, then adding 7.0 parts of sodium nitrite aqueous solution and stirring the solution continuously under the temperature of 0~5°C till the diazotization is completely. Then, adding 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid into the reaction solution and stirring the mixed reaction solution till the coupling reaction is completed. At last, adding NaCl to salt-out and filtrating the solution to obtain the following formula (I-1) compound.; Preparation Example 2 ; Dissolving 36.1 parts of 1-aminobenzene-2-sulfonic acid-4-β -sulfatoethylsulfone in 1000 parts of ice water, adding 24 parts of 32% HCl aqueous solution therein and stirring the solution adequately, then adding 7.0 parts of sodium nitrite aqueous solution and stirring the solution continuously under the temperature of 0~5°C till the diazotization is completely. Then, adding 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid into the reaction solution and stirring the mixed reaction solution till the coupling reaction is completed. At last, adding NaCl to salt-out and filtrating the solution to obtain the following formula (I-1) compound. | |
With hydrogenchloride; sodium nitrite In water at 0 - 14℃; for 2h; | 4.4; 4.5; 4.6 (4) sulfonation para-ester diazotization: bottom water in the pan to 2.5 tons, stirring while adding 100% sulfonated para-ester 722 kg, then using the 1.0 tons of ice dropped to 0 °C, then adding 30% hydrochloric acid to 98 kg, slowly adding again 30% wt/wt sodium nitrite solution, pH≤ 2, starch potassium iodide paper blue, stirring 4 hours later, removing excess sodium nitrite obtained diazo liquid sulfonation para position ester;(5) preparation of the acid solution J: adding bottom water in the pan 3 tons, then adding 100% J acid 478.5 kg, then using Na2CO3pH=7.1 adjusting solution, obtained after dissolving J acid solution.(6) acid randoms: in 20s J acid solution to be added to the sulfonated the para-in diazo liquid, keeping temperature 14 °C, stirring 2 hours, after the disappearance of diazo liquid Na2CO3adjusting pH=6.7, more acidic randoms liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water | 3 Preparation Example 3; Dissolving 28.1 parts of 1-aminobenzene-4-β-sulfatoethylsulfone in 1000 parts of ice water, adding 24 parts of 32% HCl aqueous solution therein and stirring the solution adequately, then adding 7.0 parts of sodium nitrite aqueous solution and stirring the solution continuously under the temperature of 0~5°C till the diazotization is completed. Then, adding 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid into the reaction solution and stirring the mixed reaction solution till the coupling reaction is completed. At last, adding NaCl to salt-out and filtrating the solution to obtain the following formula (I-3) compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water at 0 - 5℃; for 0.5h; Stage #2: C10H7N2O6S2(1+) In water at 10℃; Stage #3: 2-(5-amino-2-sulfonic acidphenyl)aminoethanol; C8H9N2O6S2(1+) more than 3 stages; | 3 EXAMPLE 3 19.32 g of cyanuric chloride was suspended in an aqueous solution below 0° C. for 30 minutes and a solution containing 23.93 g of 6-amino-1-naphthol-3-sulfonic acid was added thereto. The resulting solution was kept at pH 3 and 5° C. until the condensation reaction was completed. [0111] 30.31 g of 2-amino-naphthol-1,5-disulfonic acid was diazotized in the customary manner, then added to the above reaction solution to conduct the additional condensation reaction at pH 8 and 10° C. [0112] To the resulting solution, 23.26 g of 1-amino-3-(N-hydroxyethyl)aminobenzene-4-sulfonic acid was added, and the reaction solution was kept at pH 5 and 50° C. for 3 hours to complete the reaction, followed by a diazonium salt corresponding to 28.13 g of 4-sulfatoethylsulfon-1-aminobenzene being added thereto. When the reaction was ended at pH 7 and 10° C., non-solved components were removed by filtering and then the reactant was dried. Subsequently, a deep brown compound of the below formula (λmax=480 nm) was obtained in an amount of 119 g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid With hydrogenchloride; sodium nitrite In water at 0℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water Stage #3: methylamine With sodium hydroxide In water at 20℃; for 12h; | 62 36.1 parts of 1-aminobenzene-4-(β-sulfatoethylsulfone)-2-sulfonic acid and 30 parts of 32% HCl aqueous solution are dispersed in 150 parts of 0° C. water with thorough stirring, followed by the addition of 7.2 parts of sodium nitrite with continuous stirring, until the diazotization is accomplished. Then, 23.9 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid are added therein, and the pH value of the reaction solution is adjusted to 5 by the addition of 12 parts of NaHCO3 with continuous stirring until the coupling reaction is accomplished. Subsequently, 8 parts of NaOH and 3.9 parts of 40% methylamine are added therein to perform reaction for 12 hours at room temperature. The red product of the following formula (65) is obtained by salting-out, filtration and dryness. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | at 20℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water at 8 - 10℃; for 2h; Stage #2: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With sodium carbonate In water at 30 - 35℃; Stage #3: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate; 1,3,5-trichloro-2,4,6-triazine; C18H25N3O5S2; 7-amino-4-hydroxy-2-naphthalenesulfonic acid | 46 (a) 3.19 parts of 1-Naphthol-8-amino-3,6-disulfonic acid was dissolved in alkali solution, and added dropwise into 1.86 parts of cooled dispersion solution of cyanuric chloride. The pH of the reaction solution was adjusted to 13 with sodium hydrogen carbonate, and the temperature of the reaction solution was controlled at 810° C. After reaction for 2 hours, a resulted solution was filtered to obtain a filtrate. (b) 2.8 parts of 4-(β-sulfatoethylsulfone)aniline was dissolved in alkali solution, and added into the solution obtained from (a). The pH of the reaction solution was adjusted to 35 with 15% sodium carbonate, and the temperature of the reaction solution was controlled at 3035° C. After overnight reaction, a solution was obtained. (c) 2.39 parts of 2-amino-5-naphthol-7-sulfonic acid was dissolved in alkali solution, and added dropwise into 1.9 parts of cooled dispersion solution of cyanuric chloride. The pH of the reaction solution was adjusted to 13 with 15% sodium carbonate, and the temperature of the reaction solution was controlled at 510° C. After reaction for 1.5 hours, a resulted solution was filtered to obtain a filtrate. (d) 2.8 parts of 4-(β-sulfatoethylsulfone)aniline was dissolved in alkali solution, and added into the solution obtained from (a). The pH of the reaction solution was adjusted to 35 with 15% sodium carbonate, and the temperature of the reaction solution was controlled at 3035° C. After overnight reaction, a solution was obtained. (e) 20 parts of water was added into a solution with 2.14 parts of compound of formula (4) and 2.5 parts of 32% HCl, followed by completely stirring and dispersion of the reaction solution. Then, 0.76 parts of sodium nitrite was added therein rapidly, and diazotization was performed under 05° C. and completed after 1.5 hours. The resulted solution was added into the solution obtained from (b) and (d), and then the pH of the resulted solution was adjusted to 57 with sodium hydrogen carbonate. After the reaction was performed for 3 hours, a navy blue product of the formula (46) was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium carbonate In water at 5 - 10℃; for 1.5h; Stage #2: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With sodium carbonate In water at 30 - 35℃; Stage #3: C19H27N3O6S2 | 10 (a) 2.39 parts of 2-amino-5-naphthol-7-sulfonic acid was dissolved in alkali solution, and added dropwise into 1.9 parts of cooled dispersion solution of cyanuric chloride. The pH of the reaction solution was adjusted to 13 with 15% sodium carbonate, and the temperature of the reaction solution was controlled at 510° C. After reaction for 1.5 hours, the reaction solution was separated to obtain a filtrate. (b) 2.8 parts of 4-(β-sulfatoethylsulfone)aniline was dissolved in alkali solution, and added into the solution obtained from (a) rapidly. The pH of the reaction solution was adjusted to 35 with 15% sodium carbonate, and the temperature of the reaction solution was controlled at 3035° C. After overnight reaction, a solution was obtained. (c) 30 parts of water was added into a solution with 2 parts of the compound of formula (2) and 3 parts of 32% HCl, followed by completely stirring and dispersion of the reaction solution. Then, 0.7 parts of sodium nitrite was added dropwise therein, and diazotization was performed under 510° C. and completed after 1 hour. (d) The solution obtained form (b) was added into the solution obtained from (c), and the pH of the reaction solution was adjusted to 57 with 15% sodium carbonate. After the coupling reaction was performed for 4 hours, a orange product of the formula (10) was obtained by salt out. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: Benzophenone-3 With sodium carbonate; sodium hydroxide In water at 20℃; for 2.5h; Cooling with ice; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; sodium nitrite In water at 0℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: C14H14N2O7S2 With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water Stage #3: C10H13N2O7S2(1+)*Cl(1-) With sodium carbonate In water | 1 EXAMPLE 1; To 150 parts of 0° C. water, 19.4 parts of compound (R1) obtained from the Preparation Example 1 and 12.6 parts of 32% HCl solution are added. Stirring the solution till the additive dispersed evenly, and then adding 3.7 parts of NaNO2 solution therein rapidly. Controlling the temperature 05° C. to proceed with diazotization for about 1 hour. Then, adding 12 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acid powder and slowly adjusting the reaction pH to 3.5 with 10 parts of NaHCO3 to complete a coupling reaction. Synthesizing 16.3 parts of 2-methoxy-5-methyl-4-(beta-sulfatoethylsulfonyl)aniline by the same method to obtain a diazotizing salt solution, which is added into the above coupling solution. Adjusting the reaction pH to 56 slowly with 5 parts of Na2CO3. After the reaction, obtaining a red product as the following formula (3) through salting-out, filtrating, and drying: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1.5h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water Stage #3: pyridine-4-carboxylic acid With hydrogenchloride; sodium hydroxide more than 3 stages; | 3 EXAMPLE 3; To 150 parts of 0° C. water, 18.1 parts of 1-aminobenzene-4-(β-sulfatoethylsulfone)-2-sulfonic acid and 12.6 parts of 32% HCl solution are added. Stirring the solution till the additive dispersed evenly, and then adding 3.6 parts of NaNO2 solution therein rapidly. Controlling the temperature 05° C. to proceed with diazotization for about 1.5 hours. Then, adding 12 parts of 7-amino-4-hydroxy-Naphthalene-2-sulfonic acid powder and slowly adjusting the reaction pH to 3 with 10 parts of NaHCO3 to complete a coupling reaction. Lowing the temperature to 0° C., adjusting the pH to 13 with 10 parts of 45% NaOH solution, maintaining the same pH value for 15 minutes, and then adjusting the pH to 56 with HCl solution. Adding 6.4 parts of isonicotine acid therein, heating the reaction solution to 60° C., maintaining the temperature for 12 hours to obtain a product (R3) of following structure and lowing the temperature to 20° C. in reserve. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1.5h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water Stage #3: C16H16N3O5S(1+)*Cl(1-) With sodium carbonate In water | 2 EXAMPLE 2; To 150 parts of 0° C. water, 18.1 parts of 1-aminobenzene-4-(β-sulfatoethylsulfone)-2-sulfonic acid and 12.6 parts of 32% HCl solution are added. Stirring the solution till the additive dispersed evenly, and then adding 3.6 parts of NaNO2 solution therein rapidly. Controlling the temperature 05° C. to proceed with diazotization for about 1.5 hours. Then, adding 12 parts of 7-amino-4-hydroxy-Naphthalene-2-sulfonic acid powder and slowly adjusting the reaction pH to 36 with 6 parts of NaHCO3 to obtain a reddish orange coupling solution.Synthesizing 17.5 parts of compound (R2) obtained from Preparation Example 2 by the same method to obtain a diazotizing salt solution, which is added into the above coupling solution. Adjusting the reaction pH to 56 slowly with 5 parts of Na2CO3. After the reaction, obtaining a red product as the following formula (4) through salting-out, filtrating, and drying: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-methoxy-aniline With hydrogenchloride; sodium nitrite In water at 0℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.2% | Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water at 0 - 5℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,5-diaminoanthraquinone With sulfuric acid at 20 - 40℃; Stage #2: With nitrosylsulfuric acid at 22 - 25℃; for 4h; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With hydrogenchloride In water at 0 - 20℃; for 7h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,5-diaminoanthraquinone With sulfuric acid at 20 - 40℃; Stage #2: With nitrosylsulfuric acid at 22 - 25℃; for 4h; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With hydrogenchloride In water at 0 - 20℃; for 7h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With hydrogenchloride; sodium carbonate; sodium nitrite In water at 0 - 5℃; for 1h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water at 0 - 5℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: diphenyl (4'-aminobiphenyl-4-ylamino)(pyridin-3-yl)methylphosphonate With hydrogenchloride; sodium nitrite In water at 0℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 0℃; for 0.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15% | Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid; urea In water at 100℃; for 16h; Inert atmosphere; Stage #2: With hydrogenchloride In water at 100℃; for 17h; Inert atmosphere; | 2-Ureylen-di-N,N´-4-hydroxynaphthalene-2-sulphonic Acid Monosodium Salt (AMI-1) Method A. To a solution of 7-amino-4-hydroxynaphthalene-2-sulphonic acid (2.0 g, 8.36 mmol) in H2O (8 mL) was added urea (0.46 g, 7.73 mmol) and the mixture was stirred for 16 h at 100 ºC. Then, 7-amino-4-hydroxynaphthalene-2-sulphonic acid (2.0 g, 8.36 mmol), H2O (2 mL) and a 10% aqueous solution of HCl (1.52 mL) were added and the mixture was stirred at the same temperature for 17 h. The reaction mixture was acidified with conc. HCl until pH 2 and the precipitate was filtered off. The liquid phase was taken to pH 6.5 using a 50% aqueous solution of NaOH and then saturated with NaCl to obtain additional amounts of the solid. Subsequent crystallization (H2O/acetone) afforded 0.6 g (15%) of a solid identified as 2-ureylendi-N,N´-4-hydroxynaphthalene-2-sulphonic acid monosodium salt AMI-1. 1H-NMR (400.13 MHz, DMSO-d6): d 10.06 (s, 2H, SO3H), 9.05 (s, 2H, NH), 8.01 (d, J = 9.0 Hz, 2H, ArH), 7.90 (d, J = 2.0 Hz, 2H, ArH), 7.60 (dd, J = 9.0, 2.0 Hz, 2H, ArH), 7.46 (s, 2H, ArH), 7.01 (d, J = 1.2 Hz, 2H, ArH), 6.51 (s, 1H, OH) ppm. 13C-NMR (100.62 MHz, DMSO-d6): d 152.7 (s, C=O), 152.6 (s, 2x), 146.7 (s, 2x), 138.0 (s, 2x), 134.2 (s, 2x), 122.7 (d, 2x), 120.4 (s, 2x), 118.5 (d, 2x), 114.2 (d, 2x), 113.8 (d, 2x), 104.5 (d, 2x) ppm. HMRS (ESI-): Calcd. for C21H14N2NaO9S2 ([M-H])-, 525.0044; found, 525.0025. IR (neat): n 3600-3100 (br, OH), 1690 (m, C=O), 1564 (m), 1166 (s, S=O), 1043 (s) cm-1. UV (MeOH): lmax 272, 224 nm. M.p.: > 300 ºC (H2O/acetone). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; sulfuric acid mono-[2-(2-phenylamino-ethanesulfonyl)-ethyl] ester With sodium hydrogencarbonate In water at 0 - 5℃; for 3h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water at 20℃; for 2h; | 1.i 6.2 parts of sulfuric acid mono-[2-(2-phenylamino-ethanesulfonyl)-ethyl] ester wassuspended in 70 parts of water. 14 parts of sodium bicarbonate was added. Thereaction vessel was cooled to 0-5°C using ice. 3.8 parts of cyanuric chloride wasadded. The reaction was stirred at temperature of 0-5°C and pH of 4-4.5 for 3 hours. Thereafter, 4.8 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was addedand the pH was adjusted to 6-6.5 using 15% soda solution. The reaction was stirredat ambient temperature and pH of 6-6.5 for 2 hours. The product (a) obtained wasused in next step without isolation. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-nitro-aniline With hydrogenchloride; sodium nitrite In water at 0℃; for 1.16667h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium carbonate In water at 5 - 6℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-bromo-aniline With hydrogenchloride; sodium nitrite In water at 0℃; for 1.16667h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium carbonate In water at 5 - 6℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-chloro-aniline With hydrogenchloride; sodium nitrite In water at 0℃; for 1.16667h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium carbonate In water at 5 - 6℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With sodium hydroxide In water at 0℃; for 2h; | 4.2.2. General procedure B General procedure: 5-Amino-4-hydroxynaphtalene-2,7-disulfonic acid sodium salt (0.9 eq) was dissolved in iced water (5 mL by mmol of reagent) then pH was adjusted to 9 by adding 30% NaOH solution. The diazonium salt was added to the naphthalene moiety and pH maintained at 9 by addition of 10% NaOH solution. After complete addition of the diazonium salt to the 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid monosodium salt, stirring was maintained at 0 °C for 2 h. Degraded diazonium was removed after extraction with EtOAc and water soluble diazo compounds were recrystallized three times from EtOH/(H2O; pH 2) (1/1). All organic impurities were then extracted by washing with small portions of Et2O. The precipitated compounds were dried under vacuum. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid for 1h; Cooling with ice; Stage #2: trifluoro-[1,3,5]triazine at 5℃; for 0.5h; Stage #3: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate; 2,4-Diaminobenzenesulfonic acid Further stages; | 2 Example 2Preparation of Compound IIa: 23.9 parts of the compound was beaten in ice water for 1 hour,Then 14 parts of trimeric fluorine cyanide at T <5 ,At a pH of 5 to 7,After 30 minutes of addition,Then with 21 parts of the formula in T = 20-40 ,PH = 5.0-10.0 for a second sub-condensation reaction,And then reacted with 56.2 parts of the diazo compound of the formula at T = 5-10 ° C,At a pH of from 6 to 8, to give compound IIa. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 7-amino-4-hydroxy-2-naphthalenesulfonic acid With 4-dimethylamino-benzaldehyde In ethanol; water at 0 - 5℃; for 2 - 3h; Cooling with ice; Stage #2: 2-Amino-5-methylbenzene-1,4-disulfonic acid With hydrogenchloride; sodium nitrite In ethanol; water at 0 - 5℃; for 2h; Cooling with ice; Stage #3: Tau Further stages; | 1.1; 1.2; 1.3 Embodiment 1: Weighing 18.4g (0.1mol) of cyanuric chloride, 30 ml bottom water, 100g ice, 0.5gMF beating 20 min. Weighing 23.9g (0.1mol) J acid, 250 ml bottom water, using 30% liquid caustic soda adjustment of the pH to 6.5-7.0 dissolves clear, to three poly chlorine cyanogen fluid in dropwise, drop increases control pH to 2.0-3.0, temperature 0-5°C. Is omitted with saleratus adjusting pH=3.0-3.5, the temperature 0-5 °C reaction under 2-3h rear, using 4-dimethyl amino formaldehyde of detecting ethanol solution, micro-yellow is the endpoint, as soon as shrinks the fluid, spare. . Weighing 26.7g (0.1mol) 4-methylaniline -2,5-double-sulfonic acid, 30 ml bottom water, 90g ice to beating 20 min, control temperature 0-5°C. Beating is completed by adding 35g31% hydrochloric acid (containing HCl0.3mol), in 10 min in adds by drops 22.3g32% sodium nitrite solution (containing sodium nitrite 0.103mol), every 0.5h excess sodium nitrite is judged whether or not, that is, potassium iodide paper whether to display blue. Reaction 1.5h point control after 4-dimethyl amino formaldehyde of ethanol solution 5s nondiscoloration in, elimination of sodium nitrite spare; (3) coupling reaction In the above-mentioned diazo liquid 30-60min in as soon as adds to shrinks the fluid dripping in, is omitted, a small soda postpone assignment to pH 4.5-5.0 carry out coupling reaction, to control the temperature to 0-10°C, reaction 2h to a terminal point; (4) two reaction Weighing 25g (0.1mol) taurine in added to the liquid, the pH adjustment saleratus for 5.5-6.5, in the temperature 55-60 °C second compression reaction under 12h to end point after, drying the orange reactive dye compounds (I-1), in an aqueous solution of λ max = 480nm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate; trichloroisocyanuric acid With sodium hydrogencarbonate In water at 0 - 5℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water at 40℃; | 1 To a solution of 1-aminobenzene-4-β-sulfonylethylsulfonic acid (28.1 g) dissolved in 200 mL of water using sodium hydrogen carbonate was slowly added dropwise to a solution of 18.4 g of cyanuric chloride in 50 mL of water at 0-5 ° C After adjusting the pH to 2.5 with sodium bicarbonate, stir for 4-5 hours. 6-amino-1-naphthol-3-sulfonic acid was dissolved in 150 ml of water using sodium hydrogencarbonate, and the pH of the solution was adjusted to 5.0 with sodium hydrogencarbonate, and the temperature was adjusted to 40° C and stirred for 4-5 hours to obtain a condensate represented by the following structural formula. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid; C14H15N4O6S2(1-)*Na(1+) With sodium hydroxide In water Stage #2: With 1,3,5-trichloro-2,4,6-triazine In water for 0.0833333h; Cooling with ice; Stage #3: N-ethyl-N-phenylamine In water at 0 - 5℃; for 1h; | 5 Embodiment 5 A red reactive dye, has the following formulae (I) structural formula The above-mentioned type (I) structural formula preparation of reactive dye, comprising the following steps: (A). Dissolving: will 23.9g2-naphthylamine-5-hydroxy-7-sulfonic acid are added to 200g water, using 30% sodium hydroxide solution to adjust the pH=6.5-8.0, after full-soluble to be condensation; (B). One-step condensation: to 1000 ml by adding in a beaker 150g ice crushing, adding 18.8g of cyanuric chloride, assistant the ice rubs 4 drop (volume percentage composition is dioxane 30%, three ethanolamine 30%, chlorofrom 30%, acetic acid 10%). the ice rubs 5 minutes, and 20 minutes dropping step (a) the obtained solution, after is omitted, with 97% of sodium bicarbonate to maintain pH=2.5-3.0, temperature 0-5°C, thermal reaction, TLC plate to 2-naphthylamine-5-hydroxy-7-sulfonic acid completely disappeared to the end point of the reaction, condensation fluid one step; (C) two-step condensation: to the step (b) is added in the resulting one-step condensation fluid 100% amount of N-ethyl aniline 12.1g, for 0-5°C, pH=6.5-7.0 reaction 1 hour, the temperature slowly, about 30 minutes to 40 °C, maintain pH=5.5-6.0 reaction, TLC plate by one step condensation products disappear as the end point of the reaction, to obtain two-step condensation fluid ; (D). Diazotization: will be 100% of the amount of 42.2g the amino-azobenzene-4-sulfonyl amino ethyl sulfate is added to the 1000 ml beaker, add 300 ml water to stir, adding hydrochloric acid solution, the temperature regulation 10-15°C, fast by adding sodium nitrite, to sustain the reaction liquid starch potassium iodide paper blueing, stirring for 2 hours, the elimination of amino sulfonic acid after the completion of reaction of the unreacted nitrous acid, more diazo liquid, spare. (E). Randoms: the step (d) the resulting dizao liquid 15-25 °C is under the conditions of 40 minutes in step (c) in the two-step condensation fluid, and with 15% sodium carbonate aqueous solution to maintain the reaction pH=6.0-7.0, to disappear the diazonium salt for the end point of the reaction, to obtain coincidence. (F) salting-out: to the step (f) the resulting liquid of sodium chloride is added for salting out, wherein the proportion of sodium chloride and coincidence the 0.1g [...] 1 ml, filtration, collection filter cake, drying, crushing dye. |
Yield | Reaction Conditions | Operation in experiment |
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68.5% | With sodium metabisulfite at 100 - 110℃; | 1 Preparation of 2- (N-methylamino) -5_naphthol-7-sulfonic acid A, condensation reaction Properties in the reactor to 70g, then adding 2-amino-5-naphthol-7-sulfonic acid powder 50g, methylamine solution 65g, Na 2 S 2 O 5 25g, then using the 10g pH=7-8 to control the reaction of sulfuric acid, then heating to 100-110°C, reflux reaction 10-30 hours to the end point of the reaction, the detection of the liquid phase for 2-amino-5-naphthol-7-sulfonic acid residue ≤ 10% is qualified endpoint. B, materials after treatment The end point of the reaction upon arrival, cooling to 10-50°C, then using 50g pH=0-2 sulfuric acid dyeworks material, filter pressing or filtered, collecting filter cake 70 kg, yield a filtrate. The filter cake need to re-refining processing, a filtrate collection for the next batch condensation reaction using bottom water. C, refining filter cake Properties in the reactor to 100g, then adding the above-mentioned filter cake 70g, then using the 2g pH=0-2 sulfating material, stirring 1-3 hours, then filtering or filtering, 65g collecting filter cake, two collecting filtrate. The filter cake is the target product, the measured ammonia value is 68.5%, HPLC purity is 96.3%, J acid residue 2.3%, double J acid residue 0.8%, its by-product 0.6%. The collected filtrate b used for the next batch refined properties of filter cake. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 20℃; Stage #2: 1,3,5-trichloro-2,4,6-triazine With triethanolamine; acetic acid In 1,4-dioxane; chloroform; water at 0 - 5℃; for 0.5h; Stage #3: C10H16N2O10S3; 4'-aminoazobenzene-4-sulfonic acid Further stages; | 1 The method for preparing the reactive dyes of the formula (I), comprising the steps of (A). Dissolution: 23.9 g of 2-naphthylamine-5-hydroxy-7-sulfonic acid was added to 200 g of water and adjusted to pH = 6.5 to 7.0 at room temperature with 30% sodium hydroxide solution.(B) .- Step Condensation:To the 1000 ml beaker, 150 g of crushed ice was added, 18.8 g of cyanuric chloride and 4 drops of ice mill were added (30% of dioxane, 30% of triethanolamine, 30% of chloroform, Acetic acid 10%). Ice mill for 5 minutes,The solution of step (a) was added dropwise over 30 minutes, and then ρOH = 2.5 to 3.0, temperature 0 to 5 ° C was maintained with 97% sodium bicarbonate. The TLC plate was treated with 2-naphthylamine-5-hydroxy -7-sulfonic acid completely disappeared as the reaction end point, one step condensate.(C) two-step condensation:To the step (b) - step condensate was added 42.0 g of an intermediate powder of formula (X) at 0 to 5 ° C, pH = 6 • 5 to 7 • 0 for 1 hour, slowly warming up to about 30 minutes 40 ° C, maintain pH = 5 • 5 ~ 6 • 0 Reaction 4 ~ 5 hours, TLC plate with one step condensate disappeared as the reaction end, get two step condensate.(D) Diazotization: 27.7 g of p-aminoazobenzene-4-sulfonic acid was added to a 1000 ml beaker, stirred with 300 ml of water, added with hydrochloric acid solution at a temperature of 10 to 15 ° C, rapidly added to sodium nitrite , The reaction solution was kept to make the starch potassium iodide test paper blue, and the reaction was stirred for 2 hours. After completion of the reaction, the addition of sulfamic acid eliminates unreacted nitrous acid. Get diazonium liquid, spare.() Coupling:The diazonium liquid obtained in step (d) is added dropwise to step (c) at 40 to 25 ° C for 40 minutes, and the reaction is maintained with 15% aqueous sodium carbonate solution ρH- = 6.0 to 7.0, and the diazonium salt disappears Reaction end point, in the coupling solution.(F) salting out:Adding the sodium chloride to the coupling solution of step (f) for salting out, wherein the ratio of sodium chloride to the coupling liquid is 0.1 g: lmL, filtering, collecting the filter cake, drying and pulverizing the finished product dye. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: amino-benzene-1,4-disulfonic acid With hydrogenchloride at 0 - 3℃; for 2h; Stage #2: With sodium nitrite at 3 - 7℃; for 3h; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid Further stages; | 5.1; 5.2; 5.3 1.)Aniline 2,5-bis-sulfonic acid diazonium salt : add 55 parts of hydrochloric acid (in terms of hydrogen chloride) to 251 parts of aniline-2,5-bis-sulfonic acid. Stir for 2h. Add ice to cool to 0-3C. Add 73 parts of sodium nitrite (dubbed 30% solution). Maintain the reaction at 3-7C for 3h to obtain aniline-2,5-bis-sulfonic acid diazonium compound. 2.) Dissolve Jacid : Add 241 parts of J acid in water. Beat for 1h at 15-20C. Adjust ph to 7 using sodium hydroxide. 3.)1st coupling : Add aniline-2,5-bis-sulfonic acid diazonium compound to J acid. Control temperature to 0-3C. React for 4h. Adjust pH to 3.5 using baking soda. After completion of reaction, obtain first conjugate. |
Yield | Reaction Conditions | Operation in experiment |
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With sodium carbonate; In water; at 10℃; for 6h;pH 6 - 9; | 23.9 parts of J acid was dissolved in 200 parts of water, 10% sodium carbonate solution was adjusted to pH 6, fully dissolved, and then added13.5 parts of trifluoroxrimidine at 10 , pH 9 under the conditions of condensation reaction 6h, without J acid is the end point, the preparation of condensation products |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid With hydrogenchloride; sodium nitrite for 1h; Cooling with ice; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate at 0 - 10℃; | 6.1 (1) a diazo, coupling reaction 250 ml beaker, adding 20 parts of ice, 24.3 parts 30% hydrochloric acid, 36.1 parts sulfonated ester, the ice rubs beating 30min, slowly adding 6.97 parts of sodium nitrite to generate the diazonium salt, to be sodium nitrite added completely and then stirring 1h, sulfamic acid to eliminate micro-excessive sodium nitrite; diazonium salt into the dropping 23.9 J acid in a, side drop edge added small soda adjusting pH=3 - 5, after the end of the designing to continue the reaction 2h, while maintaining the system temperature is 0 - 10 °C, diazonium salt completely disappeared. | |
Stage #1: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid With hydrogenchloride; sodium nitrite In water for 1.83333h; Cooling with ice; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water at 0 - 10℃; for 2h; | 4.1 (1) a diazo, coupling reaction 250ml beaker, add 20 parts of ice,24.3 parts of 30% hydrochloric acid,36.1 parts of para-sulfonated ester,Ice mill beating 30min,Was slowly added 6.97 parts of sodium nitrite to form a diazonium salt,Until the sodium nitrite is completely added after stirring 1h,Aminosulfonic acid with the elimination of excessive excess of sodium nitrite;The diazonium salt was slowly added dropwise to 23.9 parts of J acid,While dropping the edge with baking soda pH = 3-5,Continued after the addition reaction 2h, diazonium salt disappeared completely, while maintaining the system temperature is 0-10 . | |
Stage #1: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid With hydrogenchloride In water for 1h; Cooling; Stage #2: With sodium nitrite In water at 0 - 5℃; for 1h; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water at 0 - 5℃; for 6h; | 1.1.A1-1.1.A2 (1) Preparation of J acid monoazo orange reactive dye A1: Add 100% of 36.1 g 4-β-ethylsulfone sulfate aniline-2-sulfonic acid, 200 g ice and 20 mL water into a 1000 mL beaker, and ice-grind for 2 hours. 12.2g industrial hydrochloric acid (30%) was added and the reaction was continued for 1 hour with stirring. After dissolving 100% solid 7.1 g of sodium nitrite in 30 mL of water, it was slowly dripped into the system. During the dripping process, the reaction solution was kept in Congo red test paper and the KI test paper was slightly blue. After the addition is complete, keep the temperature of the reaction system at 0-5°C and continue the reaction for 1 hour. The end point of the reaction is the absence of 4-β-ethylsulfonyl sulfate aniline-2-sulfonic acid as detected by Ehrlich reagent. After the reaction is over, Excess nitrous acid is removed with sulfamic acid to prepare diazonium salt solution of 4-β-ethylsulfone sulfate aniline-2-sulfonic acid;A2: Add 100% of 23.9g 2-amino-5-naphthol-7-sulfonic acid (J acid) to the diazonium salt solution, control the pH of the reaction between 2-3, and keep the temperature at 0-5 , keep the reaction under this condition for 6 hours, detect the absence of diazonium salt and coupling components by the permeation circle method as the end of the reaction, after the reaction is completed, the J acid monoazo orange reactive dye is prepared; |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: C12H13NO9S3 With hydrogenchloride; sodium nitrite for 1h; Cooling with ice; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate at 0 - 10℃; | 8.1 (1) a diazo, coupling reaction 250 ml beaker, adding 20 parts of ice, 24.3 parts 30% hydrochloric acid, 41 parts of 6 - hydroxy ethyl sulfone sulfate -2 - naphthylamine -1 - sulfonic acid the ice rubs beating 50min, slowly adding 6.97 parts of sodium nitrite to generate the diazonium salt, to be sodium nitrite added completely and then stirring 1h, sulfamic acid to eliminate micro-excessive sodium nitrite; diazonium salt into the dropping 23.9 J acid in a, side drop edge added small soda adjusting pH=3 - 5, after the end of the designing to continue the reaction 2h, diazonium salt completely disappeared, while maintaining the system temperature is 0 - 10 °C. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 1-aminobenzene-3-β-sulfatoethylsulfone With hydrogenchloride; sodium nitrite for 1h; Cooling with ice; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate at 0 - 10℃; | 7.1 (1) a diazo, coupling reaction 250 ml beaker, add 20 parts (parts by mass) ice, 24.3 parts 30% hydrochloric acid, 28.1 parts of ester between, the ice rubs beating 30min, 6 . 97 parts of sodium nitrite slowly adding generating diazonium salt, to be sodium nitrite added completely and then stirring 1h, sulfamic acid to eliminate micro-excessive sodium nitrite; diazonium salt into the dropping 23.9 J acid in a, side drop edge added small soda adjusting pH=3 - 5 output from end to continue after the reaction 2h, diazonium salt completely disappeared, while maintaining the system temperature is 0 - 10 °C | |
Stage #1: 1-aminobenzene-3-β-sulfatoethylsulfone With hydrogenchloride; sodium nitrite In water for 1h; Cooling with ice; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water at 0 - 10℃; for 2h; | 1.1 (1) a diazo, coupling reaction In a 250 ml beaker, 20 parts by mass of ice,24.3 parts of 30% hydrochloric acid,28.1 parts of meta-ester,Ice mill beating 30min,6.97 parts of sodium nitrite was slowly added to generate diazonium salt,Until the sodium nitrite is completely added after stirring 1h,Aminosulfonic acid with the elimination of excessive excess of sodium nitrite;The diazonium salt was slowly added dropwise to 23.9 parts of J acid,While dropping while baking with sodium bicarbonate to adjust the pH = 3-5 to complete the reaction after 2h, diazonium salt completely disappeared,While maintaining the system temperature is 0-10 . |
Yield | Reaction Conditions | Operation in experiment |
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With sodium hydroxide; In water; at 30 - 40℃; for 2h;pH 5.5 - 6.5; | (1) will J acid up100% of the 23.9 g was added to 400 mL of water,20% NaOH solution was added with stirring,Adjust the pH value of 6.5, make it dissolved, heated to 30 ,A solution of 13.94 g (99%)<strong>[696-82-2]2,4,6-trifluoro-pyrimidine</strong>Control the pH at 5.5 for 2 hours,Elixi reagent test reaction end point,After the condensation is completed, the reaction solution is used; |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 0 - 15℃; Stage #2: 1,3,5-trichloro-2,4,6-triazine With sodium hydrogencarbonate In water at 0 - 5℃; for 1h; Stage #3: Tau; amino-benzene-1,4-disulfonic acid Further stages; | 1.A; 1.B; 1.C; 1.D Example 1 A reactive yellow dye compound having the formula of formula (I-1) A, J Acid dissolution:Add 100g of water and 50g of ice into a 500ml beaker, put 43.7g of 86% J dry powder into the 500ml beaker, mix with 30% sodium hydroxide solution to adjust the pH value to 6.3-6.5, process control temperature 0-15 ,B, a shrink reaction:In 1000ml beaker add water 50g, ice 50g, into 98% cyanuric chloride 20.7g, stirring to dissolve, the control temperature 0 ~ 2 , the dropwise addition of J acid solution obtained in step A,Adding process control temperature 0 ~ 3 , after adding baking soda to maintain the pH of 1.8-2.2, stirring at 0 ~ 5 incubated for 1 hour to obtain a shrinking reaction solution;C, 2-amino-1,4-benzene disulfonic acid coupling(a) Diazo 2-amino-1,4-benzenedisulfonic acid: To a 500 ml beaker, 50 g of water and 100 g of ice were charged, and 98.5%28.3g of 2-amino-1,4-benzenedisulfonic acid was dissolved, and after stirring uniformly, 11.5g of 35% hydrochloric acid solution was added. After stirring, 7.9g of sodium nitrite with 96% of content was added, the temperature was controlled at 0-5 , pH ≤ 1.2, the reaction was stirred for 1.5 hours, the process requires KI test strips always color.(b) Coupling: After the diazo ending point is reached, the excess sodium nitrite is eliminated with sulfamic acid, and the resulting diazo liquid is addedInto a shrink solution obtained in step B, the pH was adjusted to 6.5-6.8 with baking soda, maintaining the temperature 0 ~ 5 , the reaction was stirred for 2.5 hours,The coupling solution was obtained.D, After the coupling end point, 14 g of 2-aminoethanesulfonic acid (namely, taurine) in an amount of 98% was charged to the step C to obtainOf the coupling solution, stir slowly warming to 40 , and adjusted with baking soda pH 4.0-5.0, the reaction was stirred a small incubation, Continue to heat up to 45 , and adjust the pH to 5.5-6.0 with baking soda, stirring incubated for 1 hour, continue to heat up to 50 , andWith baking soda pH was adjusted to 6.0-6.5, stirring incubated for 10 hours.E, adding hydrochloric acid to adjust the pH of the slurry obtained in Step D to 1.5-1.8, adding potassium chloride salting-out, filtering and drying to obtainThe reactive dye compound of formula (I-1), λmax = 480 nm |
Yield | Reaction Conditions | Operation in experiment |
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A, J Acid dissolution:In 500ml beaker add water 100g, ice 50g, put 86% J acid dry powder 35.7g, stir with 30% sodium hydroxide to adjust the pH to 6.3-6.5, the process control temperature 0 ~ 15 , spare;B, a shrink reaction:In a 1000ml beaker 50g of water and ice 50g, put 98% cyanuric chloride 16.9g, stirring to dissolve, the temperature controlAt 0 ~ 2 C, the dropwise addition of J acid solution obtained in step A, was added to the process control temperature 0 ~ 3 C, after the addition of baking soda to maintain pH1.8-2.2, incubated at 0 ~ 5 incubated for 1 hour to obtain a reduced reaction solution;C, 2-amino-1,4-benzene disulfonic acid coupling(a) Diazo-2-amino-1,4-benzenedisulfonic acid: To a 500 ml beaker, 50 g of water and 100 g of ice were charged and 98% of 2-ammoniaYl-1,4-benzenedisulfonic acid 23.3g dissolved, stir after addition of 30% hydrochloric acid 11g, after mixing was added 96% sodium nitrite6.5g, controlling the temperature at 0 ~ 5 , pH?1.2, stirring reaction for 1.5 hours, the process requires KI test strip always color.(b) Coupling: After the diazo ending point is reached, the excess sodium nitrite is eliminated with sulfamic acid, and the resulting diazo liquid is addedInto a condensate obtained in step B, the pH was adjusted with baking soda 6.5-6.8, maintaining the temperature at 0 ~ 5 , the reaction was stirred 2.5 smallWhen the coupling solution was obtained.D, After the coupling end point, 12.8 g of 98% 2-methylamino-ethanesulfonic acid was charged into the coupling solution prepared in step C,Stir well and then slowly warmed to 40 , and adjusted to pH 4.0-5.0 with baking soda, incubated for 1 hour with stirring, heating was continued to45 , and adjust the pH to 5.5-6.0 with baking soda, stirring the reaction incubated for 1 hour, continue to heat up to 50 , and adjusted with baking soda pHOf 6.0 to 6.5, and the mixture was kept under stirring for 10 hours to obtain a reactive dye compound of the formula (I-2), with lambda max = 470 nm. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 0 - 15℃; Stage #2: 1,3,5-trichloro-2,4,6-triazine With sodium hydrogencarbonate In water at 0 - 5℃; for 1h; Stage #3: amino-benzene-1,4-disulfonic acid; 2,2'-iminobis[ethanol] Further stages; | 3.A; 3.B; 3.C; 3.D Example 3 A reactive yellow dye compound having the formula (I-3): A, J Acid dissolution:Add 100g of water and 50g of ice to a 500ml beaker, put 37.7g of 86% J dry powder into the 500ml beaker, mix with 30% sodium hydroxide to adjust the pH to 6.3-6.5, control the temperature at 0-15 ,B, a shrink reaction:In a 1000ml beaker 50g of water and ice 50g, into 98% cyanuric chloride 17.9g, stirring to dissolve, the temperature controlAt 0 ~ 2 ° C, the dropwise addition of step J acid solution was added to the process control temperature at 0 ~ 3 ° C, after the addition of baking soda to maintainthe pH is 1.8-2.2, incubated at 0 ~ 5 incubated for 1 hour to obtain a reduced reaction solution;C, 2-amino-1,4-benzene disulfonic acid coupling(a) Diazo 2-amino-1,4-benzenedisulfonic acid: 50 g of water and 100 g of ice were put in a 500 ml beaker, and 98% of 2-ammoniaYl-1,4-benzenedisulfonic acid 24.5g dissolved, stir after adding hydrochloric acid 11g 30g, stir 96% sodium nitrite6.8g, the control temperature at 0 ~ 5 , pH ≤ 1.2, the reaction was stirred for 1.5 hours, the process requires KI test strips always color.(b) Coupling: After the diazo end point is reached, the excess sodium nitrite is eliminated with sulfamic acid, and then the weightNitrogen solution was added to a condensate obtained in step B, the pH was adjusted to 6.5-6.8 with baking soda, maintaining the temperature at 0 ~ 5 ° C, the reaction was stirred2.5 hours to give coupling solution.D, After the coupling end point, 10.2% of 98% 2- (2-hydroxy-ethylamino) -ethanol was added to the mixture ofMixing liquid, stirring slowly warming to 40 , and the pH was adjusted to 4.0-5.0 with baking soda, stirring incubated for 1 hour, followed byContinue to heat up to 45 , and adjust the pH to 5.5-6.0 with baking soda, heat the reaction for 1 hour with stirring, continue to heat up to 50 ,The soda was adjusted to pH 6.0-6.5 and stirred for incubation for 10 hours to obtain a reactive dye of formula (I-3) with λmax = 450 nm. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 7-aminonaphthalene-1,3,6-trisulfonic acid With hydrogenchloride; sodium nitrite In water for 1h; Cooling with ice; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water at 0 - 10℃; for 2h; | 2.1 (1) a diazo, coupling reaction 250ml beaker,Add 20 parts of ice,24.3 parts of 30% hydrochloric acid,28.1 parts K acid,Ice mill beating 30min,6.97 parts of sodium nitrite was slowly added to form a diazonium salt,Until the sodium nitrite is completely added after stirring 1h,Aminosulfonic acid with the elimination of excessive excess of sodium nitrite;The diazonium salt was slowly added dropwise to 23.9 parts of J acid,While dropping the edge with baking soda pH = 3-5,Continue to react after adding 2h, diazonium salt disappeared completely,While maintaining the system temperature is 0-10 . |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 2-amino-6-(2-(sulfooxy)ethylsulfonyl)naphthalene-1-sulfonic acid With hydrogenchloride; sodium nitrite In water for 1.83333h; Cooling with ice; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate In water at 0 - 10℃; for 2h; | 3.1 (1) a diazo, coupling reaction 250ml beaker, add 20 parts of ice,24.3 parts of 30% hydrochloric acid,41 parts of 6-hydroxyethyl sulfone sulfate -2-naphthylamine-1-sulfonic acid ice milling beating 50min,Was slowly added 6.97 parts of sodium nitrite to form a diazonium salt,Until the sodium nitrite is completely added after stirring 1h,Aminosulfonic acid with the elimination of excessive excess of sodium nitrite;The diazonium salt was slowly added dropwise to 23.9 parts of J acid solution,While dropping the edge with baking soda pH = 3-5,Continue to react after adding 2h,Diazonium salt disappeared completely,While maintaining the system temperature is 0-10 . |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride; sodium nitrite In water at 0 - 10℃; for 4h; | 1.1 Preparation of compound Ib: 1) Cool 36.1 parts of the compound with ice to T=0-5°C and addInto 3.6 parts of hydrochloric acid, 6.9 parts of sodium nitrite for a diazotization, and then combined with 23.9 parts of the structureCoupling was performed at T=5-8°C, pH=1 to 2, and then 32.5 parts of a compound of structure were cooled with ice to T=0-5° C. and then 3.6 parts of hydrochloric acid was added.6.9 parts of sodium nitrite for secondary diazotization,Finally, the secondary coupling is performed with a conjugate at T=5-10° C., pH=5-7 for 4 h.Compound Ib can be obtained. |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride; sodium nitrite In water at 0 - 10℃; for 4h; | 1.1 Preparation of compound Ia: 1) Cool 36.1 parts of the compound with ice to T=0-5°C.Then add 3.6 parts hydrochloric acid,6.9 parts of sodium nitrite for diazotizationThen with 23.9 parts of the structure as a compound at T=5-8°C,Coupling at pH = 1-2,Then, 34.1 parts of the compound was added to ice and cooled to T=0-5°C.Then add 3.6 parts hydrochloric acid,6.9 parts of sodium nitrite for secondary diazotization,Finally, with the first conjugate at T=5-10°C,Double coupling at pH=5-7,The compound Ia can be obtained after 4h of reaction. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: C11H10Cl2N4O6S2 With sodium hydrogencarbonate; sodium carbonate at 4 - 7℃; Large scale; Stage #2: With sodium hydrogencarbonate at 25℃; for 0.5h; Large scale; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid; 2-amino-1,5-naphthalenedisulfonic acid; 1-amino-8-hydroxy-naphthalene-3,6-disulphonic acid monosodium salt Large scale; Further stages; | 1.2; 1.3; 1.4; 1.5; 1.6 Then add 1242 kilograms of solid paraester (96% amino group content). After stirring thoroughly, Added by soda ash and baking soda (mass ratio 3:7) The formulated mass fraction is 10% mixed alkali solution, Add dropwise to the above condensate, (Drop rates are 500L/10min respectively), Add process control temperature is lower than:TC (with high temperature need to make ice, otherwise affect the reaction), The pH reaches about 1.0, The remaining mixed base adjusts ρΗ = 4.0 for 10-20 minutes. When pH naturally drops to 3.0, Then use a mixture of alkali to maintain ρΗ = 2.8-3.2 (if the mixed alkali is used up, A small amount of baking soda can be used to maintain the pH value) Maintain the temperature 4 ~ 7 °C reaction. A shrinking reaction is over, About 50 kg of baking soda will adjust the pH of the process 2 to 6.5 ~ 7.0, 30 ~ 40 minutes to 25 °C, Hydrolysis for 30 minutes (the pH during hydrolysis is strictly no more than 7.5, If more than 7.5 need to add a small amount of hydrochloric acid back to 7.5 or less). Completion of hydrolysis, Adding a quantity of J acid dry powder (coupling value 90%) 595 kg, Stir until the pH drops below 4.5 Use baking soda to maintain pΗ=4~4.8, Control temperature 25 ~ 30 °C, The reaction was carried out for 1.5 hours to give a bicondensate. Continue to add the amount of H acid dry powder (amino content 85%) 425.5 kg, steam heating to 35 ~ 40°C, adjust and maintain pΗ = 3 ~ 3.8 with baking soda, and react for 3-4 hours until the end point. After the end of the condensation reaction, reduce the temperature to about 13 to 15 °C with about 3,000 kg of ice and add 8 to 12 kg of cyanuric chloride to remove the free H acid in the dilute solution (prevent H acid and sulphonated diazonium salt alone Coupling to generate the bis by-products of the navy blue component, affecting the dye quality), maintaining the pΗ= 3.0-3.8 reaction for 30 min until the yellow reagent appears yellow to give mixed dimers. 124,44 kilograms of sulfonated Tobias acid is put into a glass steel reaction pot containing 2,000 kilograms of water and 3,000 kilograms of ice. The compressed air is turned on and fully beaten for more than one hour to ensure the beating effect of sulphonated turfgrass. Calculate the required amount of HCL based on the measured acid value. After 1 hour, add the quantitative mass fraction of 30% hydrochloric acid 500L, control pΗ=1 to 1.5, control the temperature from 0 to 10 degrees, and then add the dissolved mass fraction of 287.2 kg. 30 to 35% of sodium nitrite solution, diazotized to potassium iodide starch microscopic blue, Congo red test paper blue is good, diazotization reaction for half an hour, and finally eliminate excess nitrous acid with sulfamic acid Sodium, sulphonated diazonium salt solution. The sulfenic acid diazonium salt solution obtained in step 5 is added to the reduced mixture obtained in step 4, Control the temperature from 10 to 15 degrees, Use baking soda to adjust pΗ=6~6.5, Reaction 5 to 6 hours, Get red reactive dyes, The dye solution A was analyzed by HPLC. The molar ratio of the compound of formula I to the compound of formula II is 0.33:0.67. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: C11H10Cl2N4O6S2 With sodium hydrogencarbonate; sodium carbonate at 4 - 7℃; Large scale; Stage #2: With sodium hydrogencarbonate at 25℃; for 0.5h; Large scale; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid at 25 - 30℃; for 1.5h; Large scale; | 1.2; 1.3 Then add 1242 kilograms of solid paraester (96% amino group content). After stirring thoroughly, Added by soda ash and baking soda (mass ratio 3:7) The formulated mass fraction is 10% mixed alkali solution, Add dropwise to the above condensate, (Drop rates are 500L/10min respectively), Add process control temperature is lower than:TC (with high temperature need to make ice, otherwise affect the reaction), The pH reaches about 1.0, The remaining mixed base adjusts ρΗ = 4.0 for 10-20 minutes. When pH naturally drops to 3.0, Then use a mixture of alkali to maintain ρΗ = 2.8-3.2 (if the mixed alkali is used up, A small amount of baking soda can be used to maintain the pH value) Maintain the temperature 4 ~ 7 °C reaction. A shrinking reaction is over, About 50 kg of baking soda will adjust the pH of the process 2 to 6.5 ~ 7.0, 30 ~ 40 minutes to 25 °C, Hydrolysis for 30 minutes (the pH during hydrolysis is strictly no more than 7.5, If more than 7.5 need to add a small amount of hydrochloric acid back to 7.5 or less). Completion of hydrolysis, Adding a quantity of J acid dry powder (coupling value 90%) 595 kg, Stir until the pH drops below 4.5 Use baking soda to maintain pΗ=4~4.8, Control temperature 25 ~ 30 °C, The reaction was carried out for 1.5 hours a dimer was obtained. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: C14H15ClN2O2S With sulfuric acid; acetic acid at 70 - 80℃; for 0.5h; Stage #2: With sodium nitrite In water at 10 - 15℃; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With ammonium bicarbonate In water for 0.166667h; | 2 Example 2 In a 500 ml three-neck flask, 45 g of 98% acetic acid, 20 g of 98% sulfuric acid, and 30 g of 100% of formula (II) were added.1.5g polyoxyethylene sorbitan ester heating temperature 70 ~ 80 °C, stirring for 30 minutes, cooling to 10 ~ 15 °C, 7g 96g of sodium nitrite and 12g of water was added dropwise solution dubbed, obtained diazo components.In a 250ml beaker add 150g water, 24g 100% formula (III), add 12g 30% liquid base to adjust pH = 6.2, then addAfter 3.5 g of 96% ammonium bicarbonate was dissolved at pH=7.0, 1.5 g of activated carbon was added and the mixture was stirred for 10 minutes and filtered to give a coupling component.In a 500ml three-necked bottle, add 100g of ice water, add 2g of sodium ligninsulfonate, stir the solution, add a batch of weightThe nitrogen component was further added dropwise to a batch of coupling components and stirred at 15-25°C for more than 10 hours until the end point reached a temperature of 50-60°C.Add 30% liquid base to adjust the pH = 6.0 ~ 6.5, filtration, filter cake dried at 80 ~ 90 °C, to get 121.2g standard product, the strength of 375%, 0.95 color brilliant, the yield was 4.04. |
Yield | Reaction Conditions | Operation in experiment |
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1.3% | Stage #1: 5-Nitro-2-aminophenol With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1h; Stage #2: With aminosulfonic acid In water for 0.05h; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water at 10℃; for 2h; | 3 Synthesis Example 3. Preparation of Compound 1-3 2-Amino-5-nitrophenol (0.385 g, 2.50 mmol, 1 eq) is dispersed in 5.8 ml of distilled water.After 0.75 g of hydrochloric acid (35%) is added, the temperature is lowered to 0 by adding ice. After adding 0.19 g of sodium nitrite, the mixture is stirred at 5 ° C or lower for 1 hour, then 0.019 g of sulfamic acid is added thereto and stirred for 3 minutes. (0.628 g, 2.62 mmol, 1.05 eq) of 7-amino-4-hydroxynaphthaloene-2-sulfonic acid was added to 9.4 ml of distilled water, And stirred at 10 DEG C or less for 2 hours. The reaction solution was filtered, and the resulting material was purified by silica gel column chromatography to obtain pure compound 1-3 (13 mg, 1.3%) |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride In water for 0.5h; Stage #2: With sodium nitrite In water at 0 - 5℃; for 1h; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid Further stages; | 3' The preparation method of formula (3') is as follows: 1Add parasteric ester, hydrochloric acid, and water in ice for 30 minutes.Add 30% (mass percentage concentration) sodium nitrite solution,After the reaction was maintained for 1 hour at a temperature of T=0 to 5° C., excess sodium nitrite was eliminated with sulfamic acid.When the starch potassium iodide test paper was colorless, the Congo red test paper reached the blue end point, and the diazo solution was obtained.2 Beat the J acid, adjust the pH to 7.0 with caustic soda, and add it to the paradiester diazonium salt to perform a coupling.The reaction was adjusted to pH=2.0-3.0, the reaction was maintained for 4 hours, and one coupling was completed.3 Adjust the pH of a primary conjugate with baking soda to pH=7.0-7.5 and maintain the temperature T=10-15°C. Reaction 4-After 5 hours, the end point arrived and a secondary coupling solution was obtained. The secondary coupling solution was filtered to remove insolubles and spray dried to obtain a dye of formula (3'). |
Yield | Reaction Conditions | Operation in experiment |
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The J acid is 100% discount23.9g is added to 400mL of water,Add 20% NaOH solution under stirring,Adjust the pH to 6.5, dissolve it, raise the temperature to 30C, and add dropwise 13.94g (99%) of <strong>[696-82-2]2,4,6-trifluoropyrimidine</strong>.Controls the condensation reaction to occur at pH 5.5 for 2 hours.The Ehrlich reagent detects the end of the reaction,The condensation reaction solution is used after the condensation is completed |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 2-hydroxy-5-nitroaniline With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 10 - 12℃; for 7h; | 1.c; 2.c c) Preparation of coupling reactant II: Add 15.4 parts of 2-amino-4-nitrophenol to 100 parts of ice water.Stir and cool to 5 ° C,Another 15 parts of 37% hydrochloric acid was added to stir and dissolve.7 parts of sodium nitrite is formulated into a 30% sodium nitrite solution to be added to the above solution for diazotization reaction.Starch-potassium iodide test paper for detecting a slight excess of sodium nitrite,Congo red test paper is blue,The reaction was stirred at 0 to 5 ° C for 1 hour.Ehrlich reagent detects no amino groups,Excess sodium nitrite was removed with sulfamic acid.Another 23.9 parts of 2-amino-5-naphthol-7-sulfonic acid was added to 30 parts of water.The pH was adjusted to 7.0 with 30% sodium hydroxide solution with stirring until it was completely dissolved.An aqueous solution of 2-amino-5-naphthol-7-sulfonic acid is rapidly added to the above diazo solution.Adjust pH=8.0 with 10% sodium hydroxide solution;Stirring coupling reaction at 10-12 ° C for 7 hours,The progress of the reaction can be monitored by TLC or HPLC until the reaction of the raw materials is completed;Then the reaction mixture was adjusted to pH=4.5 with 37% hydrochloric acid;Dialysis,filter,Washed,Drying the monoazo compound represented by the formula (9-1),The monoazo compound has a liquid chromatographic purity of 99%. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 1,3,5-trichloro-2,4,6-triazine; amino-benzene-1,4-disulfonic acid at 0 - 5℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 40 - 45℃; Stage #3: 3-aminobenzenesulfonic acid Further stages; | 1.A; 1.B; 1.C; 1.D A, condensation reaction: One condensation reaction: 184.5 parts of cyanuric chloride is ground to a temperature of 0-5 ° C; 275 parts of aniline-2.5-disulfonic acid is dissolved in a liquid base to adjust the pH to 5.5-6.0.Adding to the cyanuric chloride at a temperature of 0-5 ° C, adjusting the pH to 3.3-3.6 with NaHCO 3 , reacting for 2-4 hours, and detecting the disappearance of aniline-2.5-disulfonic acid by HPLC to obtain a primary condensation solution;Secondary condensation reaction: 239 parts of J acid is added with an appropriate amount of water to dissolve the J acid solution, adjusted to pH 6.5-7.0 with NaOH, added to the primary condensation solution, adjusted to pH 4.5-5.0 with NaHCO3, and heated to 40- At 45 ° C, the reaction is 5-7 hours, the disappearance of J acid by HPLC, the second condensation liquid is obtained, and the temperature is lowered to 10-15 ° C, and is used;B, diazotization reaction: 173 parts of m-aminobenzenesulfonic acid added to water beating, adding hydrochloric acid, cooling to 0-5 ° C, adding sodium nitrite for 30-40 minutes, maintaining the reaction at temperature 0-5 ° C After an hour, the excess sodium nitrite was eliminated with sulfamic acid, and the test was colorless until the starch potassium iodide test paper was tested. The Congo red test paper was tested blue, and the diazobenzenesulfonic acid diazo solution was obtained;C, coupling reaction: the m-aminobenzenesulfonic acid diazo solution is added to the secondary condensation solution at 10-15 ° C, the pH is adjusted to 6.5-7.0 with NaHCO3, the reaction is 6-8 hours, to the diazobenzene The liquid disappeared and the reaction solution was coupled.D. Drying: The coupling reaction solution is spray-dried in a spray drying tower to obtain a compound of the formula (1-4).Secondary condensation reaction: 2-amino-5-naphthol-7-sulfonic acid (aka J acid) water |
Yield | Reaction Conditions | Operation in experiment |
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Step S21: dissolving compound a-1 in water, then adding a 30% hydrochloric acid solution, adding crushed ice to a mass concentration of 8-12%, and adding 30% sodium nitrite solution to adjust the pH in the reaction solution. <2, the potassium iodide test paper is slightly blue after immersion, T=0-10 C, reaction 1-3h, remove excess sodium nitrite with sulfamic acid, and react to obtain the diazo solution described in step S21,Step S22: The compound d is neutralized with a 10%-20% sodium hydroxide solution to pH=6.0-7.0, and all of them are dissolved, and added to the diazo solution in step S21, T=0-10 C, and the reaction is 2-4 h. Reacting the alkaline coupling solution described in step S22;Step S23: dissolving compound e in water, then adding 30% hydrochloric acid solution, adding crushed ice to make a mass concentration of 8-12%, and adding 30% sodium nitrite solution to make pH<2 in the reaction solution. The potassium iodide test paper is slightly blue after immersion, T=0-10 C, the reaction is 1-3 h, and excess sodium nitrite is removed with sulfamic acid to obtain the diazo liquid described in step S22;Step S24: adding the diazo solution obtained in the step S22 to the alkaline coupling solution, adjusting the pH of the solution with a soda ash to 5.5-6.5, T=0-10 C, and maintaining the dye for the chemical structural formula 3-1. The chemical structural formula 3-1 is as follows:Step S25: 10-20% of the salt is added to the dye solution obtained in the step S24, and after the solid is completely precipitated, it is added to a solid-liquid separator for separation, the filtrate is removed, and the filter cake is collected. The filter cake was dissolved in water to a mass concentration of 5-10% to obtain a purified dye solution of the step S25.Step S26: The dye solution purified in the step S25 is desalted and concentrated by a desalting machine to make the wastewater conductivity = 0.5-1 ms/cm, and concentrated to 20-25% to obtain the dye concentrate obtained in the step S26. |
Yield | Reaction Conditions | Operation in experiment |
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Step S21: dissolving compound a in water, then adding a 30% hydrochloric acid solution, adding crushed ice to a mass concentration of 8-12%, and adding 30% sodium nitrite solution to make the pH of the reaction solution <2 After the potassium iodide test paper is immersed, it is slightly blue, T=0-10 C., and the reaction is 1-3 hours. The excess sodium nitrite is removed by using sulfamic acid, and the diazo solution described in step S21 is obtained.Step S22: The compound d is neutralized with a 10%-20% sodium hydroxide solution to pH=6.0-7.0, and all of them are dissolved, and added to the diazo solution in step S21, T=0-10 C, and the reaction is 2-4 h. Reacting the alkaline coupling solution described in step S22;Step S23: dissolving compound e in water, then adding 30% hydrochloric acid solution, adding crushed ice to make a mass concentration of 8-12%, and adding 30% sodium nitrite solution to make pH<2 in the reaction solution. The potassium iodide test paper is slightly blue after immersion, T=0-10 C, the reaction is 1-3 h, and excess sodium nitrite is removed with sulfamic acid to obtain the diazo liquid described in step S22;Step S24: adding the diazo solution obtained in the step S22 to the alkaline coupling solution, adjusting the pH of the solution with a soda ash to 5.5-6.5, T=0-10 C, and maintaining the dye for the chemical structural formula 3-5. The chemical structural formula 3-5 is as follows:Step S25: 10-20% of the salt is added to the dye solution obtained in the step S24, and after the solid is completely precipitated, it is added to a solid-liquid separator for separation, the filtrate is removed, and the filter cake is collected. The filter cake was dissolved in water to a mass concentration of 5-10% to obtain a purified dye solution of the step S25.Step S26: The dye solution purified in the step S25 is desalted and concentrated by a desalting machine to make the wastewater conductivity = 0.5-1 ms/cm, and concentrated to 20-25% to obtain the dye concentrate obtained in the step S26. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 2-methoxy-4-(β-sulfatoethylsulfonyl)-1-aminobenzene With hydrogenchloride; sodium nitrite In water at 0 - 10℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 0 - 10℃; Stage #3: 2-nitro-aniline With hydrogenchloride; sodium nitrite In water at 0 - 10℃; | 4.3 3. Reactive dye component chemical structure formula 3-3 preparation method of dye Step S21: dissolving compound a in water, then adding a 30% hydrochloric acid solution, adding crushed ice to a mass concentration of 8-12%, and adding 30% sodium nitrite solution to make the pH of the reaction solution <2 After the potassium iodide test paper is immersed, it is slightly blue, T=0-10° C., and the reaction is 1-3 hours. The excess sodium nitrite is removed by using sulfamic acid, and the diazo solution described in step S21 is obtained.Step S22: The compound d is neutralized with a 10%-20% sodium hydroxide solution to pH=6.0-7.0, and all of them are dissolved, and added to the diazo solution in step S21, T=0-10 ° C, and the reaction is 2-4 h. Reacting the alkaline coupling solution described in step S22;Step S23: dissolving compound e-2 in water, then adding a 30% hydrochloric acid solution, adding crushed ice to a mass concentration of 8-12%, and adding 30% sodium nitrite solution to make the pH of the reaction solution < 2, the potassium iodide test paper is slightly blue after immersion, T=0-10 ° C, reaction 1-3h, remove excess sodium nitrite with sulfamic acid, and react to obtain the diazo solution described in step S22;Step S24: adding the diazo solution obtained in the step S22 to the alkaline coupling solution, adjusting the pH of the solution with a soda ash to 5.5-6.5, T=0-10 ° C, and maintaining the dye for the chemical structural formula 3-3. The chemical structural formula 3-3 is as follows:Step S25: 10-20% of the salt is added to the dye solution obtained in the step S24, and after the solid is completely precipitated, it is added to a solid-liquid separator for separation, the filtrate is removed, and the filter cake is collected. The filter cake was dissolved in water to a mass concentration of 5-10% to obtain a purified dye solution of the step S25.Step S26: The dye solution purified in the step S25 is desalted and concentrated by a desalting machine to make the wastewater conductivity = 0.5-1 ms/cm, and concentrated to 20-25% to obtain the dye concentrate obtained in the step S26. |
Yield | Reaction Conditions | Operation in experiment |
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With sodium hydroxide In water at 0 - 5℃; for 2h; | 2.2.1. Synthesis of D1, D2, D3 General procedure: In the synthesis of D1, D2 and D3, the same coupling componentwas used, and the diazonium components of dyes D1, D2 and D3 wereprepared using ortho, meta and para-nitroaniline, respectively (seeFig. 1). For example, in the synthesis of D1, the o-nitroaniline wasblended with 40 mL water and 16 mL conc. hydrochloric acid. The resultingsolution was cooled to 0-5 °C and was added to a solution of0.345 g sodium nitrite in 20 mL water over a period of 30 min. Theresulting mixture was stirred at 0-5 °C for 30 min. Then urea was addedto solution until no blue color was apparent on starch/potassium iodidepaper in the range of 2 s. A solution of 0.07 mol of 4-(3-methyl-5-oxo-4,5-dihydropyrazol-1-yl) benzenesulfonic acid and 3 g NaOH in 200 mL water was filtered toremove the solid materials, and the diazo component was added indeionized water at 0-5 °C, pH 8.0. After the resulting mixture wasstirred for 2 h, conc. HCl was added to acid out the coupling product,and the crystalline product was washed and then dried. |
Yield | Reaction Conditions | Operation in experiment |
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140 g | Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; sodium carbonate; sodium nitrite In water at 2 - 4℃; for 1.5h; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydroxide In water at 10℃; Stage #3: In water at 10 - 30℃; for 3h; | <Examples F1 to F25> The reactive dyes were prepared as follows using the compounds of the formulas (a) and (b) purified by the method of Production Example 1 as the starting materials.4-Aminobenzene-beta-D-Sulfatoethylsulfone 112.4 gWas added to 800 g of water and dispersed. Then, 12 g of sodium carbonate was added to dissolve it.It was added to ice-cooling it to approximately 2 ~ 4 then50 g of 35% hydrochloric acid was added, 48 g of a 30% sodium nitrite aqueous solution was added dropwise over about 30 minutes, And diazotized by stirring for 1 hour.After confirming the completion of the diazotization, excess nitrite was removed with sulfamic acid. 2-Amino-5-naphthol-7-sulfonic acid (aka, "J acid")47.8 g was dispersed in 450 g of water and dissolved with 23 g of 25% caustic soda,The mixture was gradually added to the diazo solution and stirred,The primary coupling reaction was completed.The temperature was kept below 10 ° C,The pH was maintained at 1-2.Confirmation of the completion of the first coupling reaction was made until J acid disappears.When J Mountain disappeared, Slowly raise the temperature to 20 ~ 30 The pH was maintained at 6 for at least 3 hours to complete the secondary coupling reaction.The reaction solution was dried to obtain about 140 g of a dye powder (F1) represented by the formula (8). |
Yield | Reaction Conditions | Operation in experiment |
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83% | Stage #1: C8H8FNO2 With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium carbonate In water at 0 - 5℃; for 0.666667h; | 9 first step, diazotization: General procedure: Take 139g of dry 4-aminobenzoyl fluoride as raw material, add to 1L of alcohol, then add 1L of water to dilute, add 40mL of concentrated hydrochloric acid (36%), add a slight excess of 23% NaNO2 solution at 0 °C The diazotization reaction was carried out at 0 to 5 ° C, and the reaction end point was measured using a starch KI test paper.The second step, coupling:Adjusted by NH4Cl with an equimolar ratio of 4-aminobenzoyl fluoride in the diazotization stepThe pH of the medium was weakly acidic to 5.5-6.5, and the diazotization solution obtained in the first step was slowly added thereto at 0 ° C, and reacted at 0 to 5 ° C for 40 minutes. After completion of the reaction, the mixture was subjected to salting out filtration, and the solid was dried at 40 ° C or less to give a dye yield of 88%. |
Yield | Reaction Conditions | Operation in experiment |
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85% | Stage #1: C7H5F2NO With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium carbonate In water at 0 - 5℃; for 0.666667h; | 12 first step, diazotization: General procedure: Take 139g of dry 4-aminobenzoyl fluoride as raw material, add to 1L of alcohol, then add 1L of water to dilute, add 40mL of concentrated hydrochloric acid (36%), add a slight excess of 23% NaNO2 solution at 0 °C The diazotization reaction was carried out at 0 to 5 ° C, and the reaction end point was measured using a starch KI test paper.The second step, coupling:Adjusted by NH4Cl with an equimolar ratio of 4-aminobenzoyl fluoride in the diazotization stepThe pH of the medium was weakly acidic to 5.5-6.5, and the diazotization solution obtained in the first step was slowly added thereto at 0 ° C, and reacted at 0 to 5 ° C for 40 minutes. After completion of the reaction, the mixture was subjected to salting out filtration, and the solid was dried at 40 ° C or less to give a dye yield of 88%. |
Yield | Reaction Conditions | Operation in experiment |
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Stage #1: 1,3,5-trichloro-2,4,6-triazine; 7-amino-4-hydroxy-2-naphthalenesulfonic acid With sodium hydrogencarbonate Cooling with ice; Stage #2: 4,4'-diaminostilbene-2,2'-disulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 2h; Stage #3: With aminosulfonic acid In water for 2h; | 1 Preparation and synthesis of the compound represented by the following formula A ' Take 50ml of ice water and add 0.02mol (3.680g) of melamine chloride to beat for 1h to make it uniformly dispersed. Add 0.02mol (4.785g) of J acid under stirring conditions to adjust the pH of the solution to 3-4. After every 20min during the reaction, 1 ml of a 30% baking soda aqueous solution was added, and the reaction was performed at low temperature for 4 hours. After the reaction, the solution was transparent and pale white, and a primary condensation solution of cyanuric acid and J acid was prepared.Take DSD acid 0.01mol (3.704g), add 50ml ice water to beat for 1h to make the dispersion uniform. Add 1 ml of concentrated hydrochloric acid to it under stirring conditions to stabilize its pH; take 1.4 g of NaNO2 particles to prepare an aqueous solution, and slowly add it to the acidic solution of the above DSD acid, and react at a temperature of 0-5 ° C for 2 h. The solution after the reaction It is a yellow suspension. A 15% sulfamic acid solution was added dropwise to the solution after the above reaction, and the solution was dropped into the solution without air bubbles. The reaction was continued for 10 minutes, and then tested with a starch potassium iodide test paper until the potassium iodide test paper was not micro-blue.The diazotized solution was added to a primary condensation solution of cyanuric acid and J acid under stirring conditions, and the pH of the reaction solution was adjusted to 7 with NaHCO3, and the reaction was performed under ice-bath conditions for 2 hours. Add 2g NaCl per 100ml of the dyeing solution to salt out, suction filter, wash with ethanol 2 to 3 times and then dry. |
Yield | Reaction Conditions | Operation in experiment |
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123 g | Stage #1: 3-methyl-4-aminobenzene-(2-sulfatoethylsulfone) With hydrogenchloride; sodium nitrite In water at 10℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water Stage #3: 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid Further stages; | 15 Preparation Example 1: Synthesis of Compound Represented by Formula 1 General procedure: 28.1 g of 4-aminobenzene- (2-sulfatoethylsulfone) were dispersed in water, followed by diazotization by gradually adding a solution of 7 g of sodium nitrite dissolved in water while maintaining the temperature below 10 ° C under a hydrochloric acid catalyst. ,After adding 31 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, acid coupling was performed at pH 2-3.When the reaction was completed, a solution of 7 g of sodium nitrite dissolved in water while dispersing 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) in water and maintaining the temperature below 10 ° C under a hydrochloric acid catalyst Was slowly added to diazotize, and then added to the acidic coupling solution to be coupled at pH 5-7,After the reaction was completed by spray drying to prepare 131 g of the compound represented by the formula (1). |
Yield | Reaction Conditions | Operation in experiment |
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119 g | Stage #1: 2-methoxy-4-(β-sulfatoethylsulfonyl)-1-aminobenzene With hydrogenchloride; sodium nitrite In water at 10℃; Stage #2: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In water Stage #3: 3-methyl-4-aminobenzene-(2-sulfatoethylsulfone) Further stages; | 14 Preparation Example 1: Synthesis of Compound Represented by Formula 1 General procedure: 28.1 g of 4-aminobenzene- (2-sulfatoethylsulfone) were dispersed in water, followed by diazotization by gradually adding a solution of 7 g of sodium nitrite dissolved in water while maintaining the temperature below 10 ° C under a hydrochloric acid catalyst. ,After adding 31 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, acid coupling was performed at pH 2-3.When the reaction was completed, a solution of 7 g of sodium nitrite dissolved in water while dispersing 36.1 g of 2-aminobenzenesulfonic acid-5- (2-sulfatoethylsulfone) in water and maintaining the temperature below 10 ° C under a hydrochloric acid catalyst Was slowly added to diazotize, and then added to the acidic coupling solution to be coupled at pH 5-7,After the reaction was completed by spray drying to prepare 131 g of the compound represented by the formula (1). |
Yield | Reaction Conditions | Operation in experiment |
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77.1% | (1) Preparation of a condensate: 37.6g (0.204mol) of cyanuric chloride was prepared as a suspension with a mass fraction of 20%, and it was beaten in an ice water bath at 5C for 40 minutes.Accurately weigh 47.8g (0.200mol) of 2-amino-5-naphthol-7-sulfonic acid, configure it as an aqueous solution with a mass fraction of 20%, and adjust its pH to 5.6 6.5, add it to the melamine suspension with beating evenly under the condition of 05,After the dropwise addition, the temperature is maintained at 3 to 5C, the pH value is adjusted to 4.2 with 20% mass fraction of Na2CO3, the reaction is performed for 5 hours, and the end point of the contraction reaction is detected by thin layer chromatography (developing agent: n-butanol: ethanol: ammonia water = 6:2:3). (2) Preparation of diazo salt of o-aminobenzenesulfonic acid: Accurately weigh 34.6g (0.20mol) anthranilic acid, and configure it as a 30% mass solution in water. Stir for 40 minutes until it is evenly mixed and then cool to 0C. Add 22.0g (0.22mol) concentrated hydrochloric acid with a mass fraction of 37.5% and stir for 15min. Afterwards, 13.938g (0.202mol) of sodium nitrite was slowly added dropwise to prepare a 35% mass solution in water. After dropping, the reaction was performed at 5C for 3 hours. After the reaction, excess nitrous acid was eliminated with sulfamic acid. (3) Coupling reaction: Pour the diazonium salt in step (2) into the condensate in step (1), adjust the pH to 4.0-4.5 with a Na2CO3 solution with a mass fraction of 15%, The reaction was carried out at 0 to 2 C for 9 min, and then the reaction was continued at 10 to 15 C for 6 h. The end point of the contraction reaction was detected by thin layer chromatography (developing agent: n-butanol: ethanol: ammonia=4:2:3). (4) Preparation of dicondensate:Accurately weigh 36.8g (0.196mol) 2,4-diaminobenzenesulfonic acid, add it to the coupling solution in step (3), and adjust the pH to 4.5 with a Na2CO3 solution with a mass fraction of 15%. The reaction temperature is 30 ~ 32 , the reaction time is about 4h, thin-layer chromatography is used to detect the end point of the contraction reaction (developing agent: n-butanol: ethanol: ammonia = 4:2:3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4,4'-diamino-2,2'-biphenyldisulfonic acid With sodium hydrogencarbonate In water at 0 - 5℃; for 2.5h; Stage #2: 2,4-Diaminobenzenesulfonic acid With sodium hydrogencarbonate In water at 25 - 30℃; for 5.5h; Stage #3: nicotinic acid; 7-amino-4-hydroxy-2-naphthalenesulfonic acid; 4-aminobenzene-1,3-disulfonic acid Further stages; | 1.1-1.8 (1) Add to crushed ice and water, stir, add, and then add sodium bicarbonate to adjust the pH to 2.5-3.0, and react at 0-5°C for 2.5 hours to obtain the first mixed solution. Among them, the molar ratio of the feed to is 1:0.5; (2) Adding sodium bicarbonate to the first mixed solution to adjust the pH to 5.5-6.0, and reacting at 25-30° C. for 5.5 hours to obtain the second mixed solution. Among them, the molar ratio of feed to is 1:0.96; (3) Add hydrochloric acid and sodium nitrite into the second mixed solution, react at 0-5°C for 1 hour to obtain the third mixed solution, wherein the molar ratio of HCl and sodium nitrite is 1:2.0:1.0; (4) Add to the third mixed solution, add sodium bicarbonate to adjust the pH to 3.5-4.0, and react at 10-15°C for 5.5 hours to obtain the fourth mixed solution. Among them, the molar ratio of feed to is 1:0.96; (5) Add crushed ice and water, then add hydrochloric acid and sodium nitrite, and react at 5-8°C for 1 hour to obtain a fifth mixed solution, wherein the molar ratio of HCl and sodium nitrite is 1:1.0:1.01; (6) Add the fifth mixed solution to the fourth mixed solution, add sodium bicarbonate to adjust the pH value to 6.0-6.3, and react at 15-20°C for 3 to 4 hours to obtain the sixth mixed solution. Wherein, the fourth mixed liquid and the fifth mixed liquid are charged according to a molar ratio of 1:0.99; (7) Add to the sixth mixed solution, add sodium carbonate to adjust the pH value to 5.5-6.0, and react at 75-80°C for 6.5 hours to obtain the seventh mixed solution. Among them, the molar ratio of feed to is 1:2.5; (8) Dry the seventh mixed liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4,4'-diaminostilbene-2,2'-disulfonic acid With sodium hydrogencarbonate In water at 0 - 5℃; for 2h; Stage #2: 2,4-Diaminobenzenesulfonic acid With sodium hydrogencarbonate In water at 25 - 30℃; for 5h; Stage #3: nicotinic acid; 2-[(3-sulfo-4-aminobenzene)sulfonyl]ethoxysulfonic acid; 7-amino-4-hydroxy-2-naphthalenesulfonic acid Further stages; | 2.1-2.8 (1) Add to crushed ice and water, stir, add, then add sodium bicarbonate to adjust the pH to 2.5-3.0, and react at 0-5°C for 2h to obtain the first mixed solution. Among them, the molar ratio of the feed to is 1:0.5; (2) Adding sodium bicarbonate to the first mixed solution to adjust the pH to 5.5-6.0, and reacting at 25-30° C. for 5 hours to obtain a second mixed solution. Among them, the molar ratio of feed to is 1:0.96; (3) Add hydrochloric acid and sodium nitrite into the second mixed solution, react at 0-5°C for 1 hour to obtain the third mixed solution, wherein the molar ratio of HCl and sodium nitrite is 1:2.0:1.0; (4) Add to the third mixed solution, add sodium bicarbonate to adjust the pH to 3.5-4.0, and react at 10-15°C for 6 hours to obtain the fourth mixed solution. Among them, the molar ratio of feed to is 1:0.96; (5) Add crushed ice and water, then add hydrochloric acid and sodium nitrite, and react at 10-15°C for 1.5 hours to obtain the fifth mixed solution, where the molar ratio of HCl and sodium nitrite is 1:1.0:1.01 (6) Add the fifth mixed solution to the fourth mixed solution, add sodium bicarbonate to adjust the pH to 6.0-6.3, and react at 15-20°C for 3 hours to obtain the sixth mixed solution. Wherein, the fourth mixed liquid and the fifth mixed liquid are charged according to a molar ratio of 1:0.99; (7) Add to the sixth mixed solution, add sodium carbonate to adjust the pH to 5.5-6.0, and react at 75-80°C for 7 hours to obtain the seventh mixed solution. Among them, the molar ratio of feed to is 1:2.5; (8) Dry the seventh mixed liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4,4'-diaminostilbene-2,2'-disulfonic acid With sodium hydrogencarbonate In water at 0 - 5℃; for 3h; Stage #2: 2,4-Diaminobenzenesulfonic acid With sodium hydrogencarbonate In water at 25 - 30℃; for 6h; Stage #3: nicotinic acid; 7-amino-4-hydroxy-2-naphthalenesulfonic acid; 4-aminobenzene sulfonic acid Further stages; | 3.1-3.8 (1) Add to crushed ice and water, stir, add, then add sodium bicarbonate to adjust the pH to 2.5-3.0, react at 0-5°C for 3h to obtain the first mixed solution. Among them, the molar ratio of the feed to is 1:0.5; (2) Adding sodium bicarbonate to the first mixed solution to adjust the pH to 5.5-6.0, and reacting at 25-30°C for 6 hours to obtain the second mixed solution. Among them, the molar ratio of feed to is 1:0.96; (3) Add hydrochloric acid and sodium nitrite to the second mixed solution, and react at 0-5°C for 1 hour to obtain the third mixed solution, wherein the molar ratio of HCl and sodium nitrite is 1:2.0:1.1; (4) Add to the third mixed solution, add sodium bicarbonate to adjust the pH to 3.5-4.0, and react at 10-15°C for 6 hours to obtain the fourth mixed solution. Among them, the molar ratio of feed to is 1:0.96; (5) Add crushed ice and water, then add hydrochloric acid and sodium nitrite, and react at 10-15°C for 1.5 hours to obtain the fifth mixed solution, where the molar ratio of HCl and sodium nitrite is 1:1.0:1.01 (6) Add the fifth mixed solution to the fourth mixed solution, add sodium bicarbonate to adjust the pH value to 6.0-6.3, and react at 15-20°C for 4 hours to obtain the sixth mixed solution. Wherein, the fourth mixed liquid and the fifth mixed liquid are charged according to a molar ratio of 1:0.99; (7) Add to the sixth mixed solution, add sodium carbonate to adjust the pH to 5.5-6.0, and react at 75-80°C for 6 hours to obtain the seventh mixed solution. Among them, the molar ratio of feed to is 1:2.5; (8) Dry the seventh mixed liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4,4'-diamino-2,2'-biphenyldisulfonic acid With sodium hydrogencarbonate In water at 0 - 5℃; for 2h; Stage #2: 2,4-Diaminobenzenesulfonic acid With sodium hydrogencarbonate In water at 25 - 30℃; for 5h; Stage #3: nicotinic acid; 7-amino-4-hydroxy-2-naphthalenesulfonic acid; aniline Further stages; | 4.1-4.8 (1) Add to crushed ice and water, stir, add, then add sodium bicarbonate to adjust the pH to 2.5-3.0, and react at 0-5°C for 2h to obtain the first mixed solution. Among them, the molar ratio of the feed to is 1:0.5; (2) Adding sodium bicarbonate to the first mixed solution to adjust the pH to 5.5-6.0, and reacting at 25-30° C. for 5 hours to obtain a second mixed solution. Among them, the molar ratio of feed to is 1:0.96; (3) Add hydrochloric acid and sodium nitrite into the second mixed solution, react at 0-5°C for 1 hour to obtain the third mixed solution, wherein the molar ratio of HCl and sodium nitrite is 1:2.0:1.0; (4) Add to the third mixed solution, add sodium bicarbonate to adjust the pH to 3.5-4.0, and react at 10-15°C for 6 hours to obtain the fourth mixed solution. Among them, the molar ratio of feed to is 1:0.96; (5) Add crushed ice and water, then add hydrochloric acid and sodium nitrite, and react at 10-15°C for 1 hour to obtain a fifth mixed solution, where the molar ratio of HCl and sodium nitrite is 1:2.5:1.01; (6) Add the fifth mixed solution to the fourth mixed solution, add sodium bicarbonate to adjust the pH to 6.0-6.3, and react at 15-20°C for 3 hours to obtain the sixth mixed solution. Wherein, the fourth mixed liquid and the fifth mixed liquid are charged according to a molar ratio of 1:0.99; (7) Add to the sixth mixed solution, add sodium carbonate to adjust the pH to 5.5-6.0, and react at 75-80°C for 6 hours to obtain the seventh mixed solution. Among them, the molar ratio of feed to is 1:2.5; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
14.3 g | In 1-methyl-pyrrolidin-2-one at 140℃; for 21h; | 4 [Synthesis Example 4] Synthesis of pigment (1-4) In the reaction container, 6.9 g of DCSF, 9.09 g of 6-amino-1-naphthol-3-sulfonic acid, and 50 mL of NMP were put, and the mixture was stirred at 140°C for 21 hours. The reaction liquid was put into 200 mL of water, and 100 mL of 35% hydrochloric acid was further added to precipitate the pigment. The solid was taken out by filtration, and after drying, the target pigment (1-4) (14.3g) was obtained as a blue-purple powder |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium tetrahydroborate; acetic acid In methanol for 2h; | 7.a Step (a): Take 19.8 parts of compound (A) and dissolve in 100 parts of methanol and 10 parts of acetic acid,Add 23.92 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid and 3.73 parts of sodium borohydride, stir for 2 hours, and use 4-(dimethylamino)benzaldehyde to determine that the reaction is complete. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84.4% | Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With hydrogenchloride; sodium nitrite at 0 - 5℃; for 1.25h; Stage #2: 4-(4,6-dichloro-1,3,5-triazine-2-ylamino)-N-(pyrimidin-2-yl)benezenesulfonamide With sodium carbonate In water at 0 - 5℃; for 3.75h; | 2.3.2. Diazotization method for dyes (SM1-SM6) General procedure: Homogenized solutions of diazonium components (1.0 mmol) were prepared using 20% hydrochloric acid (HCl), which were then gradually cooled to 0-5 C. A cold solution of sodium nitrite (NaNO 2 ) (1.2 mmol) was added dropwise over a period of 15 min with continuous stirring. Initiation of reaction was indicated by a change in color of reaction mixture. The stirring was continued for about 1 h to get the diazonium salt, shown in Scheme 1 (b). Com- plete formation of diazonium salts was confirmed by TLC using DCM: MeOH (6:4 v/v) as a mobile phase [31] . 2.3.3. Coupling reaction Cyanurated sulfonamide compounds (1.0 mmol) were dissolved in aqueous sodium carbonate solution (20% w/v) and cooled to 0-5 C in an ice bath. The solution was then added dropwise to a cold, freshly prepared diazonium salt solution, with constant stir- ring, over a period of 15 min. The pH of the reaction mixture was adjusted to 7.5-8.5 by adding sodium carbonate (20% w/v) si- multaneously. Reaction mixture was stirred vigorously at this pH for further 3.5 h at a temperature below 5 C as described in Scheme 1 (c). Reaction progress was monitored by TLC analysis us- ing solvent system DCM: MeOH (6:4 v/v). The synthesized dyes were salted out using cold solution of sodium chloride (10% w/v), collected by filtration, washed with 10% NaCl, and air dried [31] . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.1% | Stage #1: 7-amino-4-hydroxy-2-naphthalenesulfonic acid With hydrogenchloride; sodium nitrite at 0 - 5℃; for 1.25h;
Stage #2: 2- |
2.3.2. Diazotization method for dyes (SM1-SM6) General procedure: Homogenized solutions of diazonium components (1.0 mmol) were prepared using 20% hydrochloric acid (HCl), which were then gradually cooled to 0-5 C. A cold solution of sodium nitrite (NaNO 2 ) (1.2 mmol) was added dropwise over a period of 15 min with continuous stirring. Initiation of reaction was indicated by a change in color of reaction mixture. The stirring was continued for about 1 h to get the diazonium salt, shown in Scheme 1 (b). Com- plete formation of diazonium salts was confirmed by TLC using DCM: MeOH (6:4 v/v) as a mobile phase [31] . 2.3.3. Coupling reaction Cyanurated sulfonamide compounds (1.0 mmol) were dissolved in aqueous sodium carbonate solution (20% w/v) and cooled to 0-5 C in an ice bath. The solution was then added dropwise to a cold, freshly prepared diazonium salt solution, with constant stir- ring, over a period of 15 min. The pH of the reaction mixture was adjusted to 7.5-8.5 by adding sodium carbonate (20% w/v) si- multaneously. Reaction mixture was stirred vigorously at this pH for further 3.5 h at a temperature below 5 C as described in Scheme 1 (c). Reaction progress was monitored by TLC analysis us- ing solvent system DCM: MeOH (6:4 v/v). The synthesized dyes were salted out using cold solution of sodium chloride (10% w/v), collected by filtration, washed with 10% NaCl, and air dried [31] . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | Stage #1: para-aminobenzaldehyde With sulfuric acid In lithium hydroxide monohydrate at 80℃; for 0.25h; Stage #2: With NaNO2 In lithium hydroxide monohydrate at 5℃; for 0.5h; Stage #3: 7-amino-4-hydroxy-2-naphthalenesulfonic acid In lithium hydroxide monohydrate; propan-2-one at 0 - 5℃; | 2.1. Synthesis of compound AZDH1 to AZDH4 General procedure: The starting material for the four compounds was prepared by diazotization of p-aminobenzaldehyde. P-amino benzaldehyde (0.6 g, 0.005 mol) was added to 10 ml of 40% aqueous solution of sulphuric acid to form a mixture which was then heated to 80 °C for 15 min while agitating it. About 100 g of ice was intro- duced to lower the temperature of the reaction mixture. Sodium nitrite (0.35 g, 0.005 mol) was introduced drop-wisely for about 30 min while maintaining a < 5 °C temperature. Urea (2 g, 0.05 mole) was then introduced to decompose the excess sodium ni- trite that was produced in the reaction. About 200 ml of iced distilled water was added to obtain an aqueous solution of p- aminobenzaldehyde diazonium salt which was condensed with H- acid, J-acid, Gamma acid and Bronner acid to form compounds AZDH1, AZDH2, AZDH3 and AZDH4 respectively as depicted in Fig. 1 . The yields were 19, 66, 60, 16%, respectively for AZDH1, AZDH2, AZDH3 and AZDH4 while the melting points were ob- tained as 108-110, 118-120, 128-130, and 158-160 0C. prior to synthesis, the compounds were characterized using FTIR, UV and NMR spectroscopy. FTIR-8400S Fourier Transform infrared spec- trophotometer was used to identify the different functional groups present in the synthesized compounds, the UV-absorption of the synthesized compounds was conducted with the V2.30 version UV- 2500 PC series. To determine the molecular weights of the rep- resentative dyes, GC-MS spectroscopy was performed at the Na- tional Research Institute for Chemical Technology (NARICT), Zaria, using the GCMS-QP2010 PLUS Series. The spectra information is presented as Figs. S1 to S2 of supporting information. The analyzed chemical shift data is as thus: AZDH1 OH 8.5 ppm, OH 8.5 ppm, OH 9.01, ppm, NH2 5.79 PPM, CH 7.29 ppm, CH 7.39 ppm, CH 8.10 ppm, CH 8.05 ppm, CH 8.10 ppm, CH 8.05 ppm, CH 9.89. AZDH2 OH 8.5, 9.01, NH2 4.62, CH 6.78, CH 8.10, CH 7.52, CH 8.05, CH 7.03, CH 8.10, CH 7.82, CH 8.05, CH 9.89. AZDH3 OH 8.5, OH 9.01, NH2 4.62, CH 7.15, CH 8.10, CH 7.44, CH 8,05, CH 7.01, CH 8.10, CH 7.90, CH 8.05, CH 9.89 CH AZDH4 OH 8.5, CH 7.94, CH 8.16, CH 8.32, CH 9.02 CH 8.08, CH 7.96, CH 8.19, CH 8.62, CH 7.84, CH 9.80. AZDH4 C 145.3 ppm, C 141.5, C 148.4 ppm, C 153.2 ppm, C 127.7 ppm, C 135.3 ppm, C 134.8, C 126.2 ppm, 122.6 ppm, CH 116.3 ppm, CH 133.0 ppm, CH 132.1 ppm, CH 126.7 ppm, CH 128.8 ppm, CH 130.9 ppm, CH 129.5 ppm, CH 191.0 ppm, AZDH1 1. C 137.1 ppm, C 143.1 ppm, C 138.7 ppm, C 129.8 ppm, C 158.5 ppm, C 137.4 ppm, C 115.0 ppm, C135.3 ppm, C 139.1 ppm, CH 117.2 ppm, CH 108.1 ppm, CH 123.5. CH 120.2 CH 130.2, CH 123.5 ppm, 130.2 CH 191.0, AZDH3 C 135.5 ppm, C 144.6 ppm, C124.9 ppm, C 119.8 ppm, C135.7 ppm, C 139.1 ppm, CH 114.6 ppm, CH 115.6 ppm, CH 118.6 ppm, CH 123.5 ppm, CH 127.4 ppm, C 130.2 ppm, CH 191.0 ppm, AZDH2 C 131.6 ppm C 142.7 ppm, 128.8 ppm, C 158.5 ppm, C 144.3 ppm, C 126.7 ppm, C 128.8 PPM, C 139.1 ppm, CH 107.4 ppm, CH 123.5 ppm, CH 117.5 ppm, CH 130.2 ppm CH 118.4, CH 123.5 ppm, CH 128.5, CH 130.2, CH 191.0 ppm |
Tags: 87-02-5 synthesis path| 87-02-5 SDS| 87-02-5 COA| 87-02-5 purity| 87-02-5 application| 87-02-5 NMR| 87-02-5 COA| 87-02-5 structure
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H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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