90-20-0|4-Amino-5-hydroxynaphthalene-2,7-disulfonic acid| Ambeed

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1
[ 108-77-0 ]
[ 90-20-0 ]
[ 7538-88-7 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide
	With sodium hydroxide In lithium hydroxide monohydrate at 0 - 5℃; for 1.5h;
	With sodium hydroxide; phosphoric acid disodium salt In lithium hydroxide monohydrate at 0℃; for 2h;	1.a Example 1 19 parts of cyanuric chloride are mixed vigorously and thoroughly with 50 parts of ice/water and 5 parts of disodium hydrogen phosphate, with the addition of a wetting agent. To the resulting suspension there is added, dropwise, a neutral solution of 32 parts of 1-AMINO-8-HYDROXYNAPHTHALENE-3, 6-DISULFONIC acid (H acid) in such a manner that the pH of the reaction mixture does not exceed 3. Afterwards, the pH is maintained at 3 for a further 2 hours by adding sodium hydroxide solution.

	With wetting agent In lithium hydroxide monohydrate at 0℃; for 1h;	1.a 19 parts of cyanuric chloride are dispersed in 75 parts of ice and 75 parts of water with the addition of a wetting agent. A neutral solution of 32.0 parts of 1-amino-8-naphthol-3,6- disulfonic acid in 350 parts of water is added to the resulting dispersion. After a few hours, the pH value of the reaction mixture is adjusted to from 4 to 5.5 by adding aqueous sodium hydroxide solution.
	With anhydrous sodium carbonate In lithium hydroxide monohydrate at 0 - 20℃; for 1 - 2h;	2.a Example 2; (a) 19.45 parts of cyanuric chloride is dispersed in 150 parts of 0°C water, and then 31.5 parts of 1-naphthol-8-amino -3,6-disulfonic acid powder is added therein. The pH value of the reaction solution is adjusted to 3 by 15% of Na2CO3 aqueous solution. The temperature of the aqueous solution is raised smoothly to 20°C and then maintained for 1∼2 hours.
	With hydrogenchloride In lithium hydroxide monohydrate at 0 - 5℃;	1.a EXAMPLE 1; (a) 40 parts of a neutral solution of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (H-acid) in 200 parts of water are added drop wise at pH 2-2.5 and 0-5° C. to a fine suspension of 23.5 parts of cyanuric chloride in 100 parts by volume of water and 100 parts of ice. The mixture is adjusted to pH 2.5 by means of hydrochloric acid. During the addition the reaction temperature is maintained at 0-5° C. by cooling. After the addition is finished the pH is maintained at pH 2 with a soda ash solution (20%) until the reaction is complete.
	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In lithium hydroxide monohydrate Stage #2: With sodium hydroxide In lithium hydroxide monohydrate	1.c c) 19 parts of [CYANURIC] chloride are dispersed in 75 parts of ice and 75 parts of water, with addition of a wetting agent. To the resulting dispersion there is added a neutral solution of 31.9 parts of [1-AMINO-8=NAPHTHOL-3, 6-DISULFONIC] acid in 350 parts of water. After a few hours, the pH of the reaction mixture is adjusted to a value from 4 to 5.5 by addition of aqueous sodium hydroxide solution.
	With anhydrous sodium carbonate In lithium hydroxide monohydrate at 0 - 20℃; for 1 - 2h;	2.a Example 2; (a) 19.45 parts of cyanuric chloride is dispersed in 150 parts of 0°C water, and then 31.5 parts of 1-naphthol-8-amino -3,6-disulfonic acid powder is added therein. The pH value of the reaction solution is adjusted to 3 by 15% of Na2CO3 aqueous solution. The temperature of the aqueous solution is raised smoothly to 20°C and then maintained for 1∼2 hours.
	With anhydrous sodium carbonate In lithium hydroxide monohydrate at 0 - 5℃; for 2h;	1.a (a) 18.8 parts of cyanuric chloride are dispersed in 200 parts of 0° C. water, followed by the addition of a solution containing 31.9 parts of 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid. Next, the pH value of the reaction solution is adjusted to a range of 1 to 3 by the addition of 15% Na2CO3 (aq), and its temperature is maintained below 5° C. to perform reaction for 2 hours. Finally, the reaction solution is filtered and the filtrate is reserved.
	With anhydrous sodium carbonate In lithium hydroxide monohydrate; propan-2-one at 0 - 5℃; for 5h;
	With anhydrous sodium carbonate In lithium hydroxide monohydrate; propan-2-one at 0 - 5℃;
	In lithium hydroxide monohydrate at 0 - 5℃; for 0.5h;
	In lithium hydroxide monohydrate; propan-2-one at 0 - 5℃; for 2h;
	In lithium hydroxide monohydrate; propan-2-one at 0 - 5℃; for 3h;	Red dye A solution of 1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid, H-acid (38.8 g, 0.1 mol M.I. 388), in water at pH 6.5, was added to a stirred, freshly prepared, suspension of cyanuric chloride (18.45 g, 0.1 mol) in aqueous acetone 0e5 C and the cold mixture stirred for 3 h, after which reaction was essentially complete. The resulting solution of N-dichlorotriazinyl H-acid was filtered to remove a small amount of insoluble material. Concurrently, diazotisation of 2-aminonaphthalene-1,5-disulphonic acid (52 g, 0.1 mol, M.I. 520) was accomplished with sodium nitrite (6.9 g, 0.1 mol) and hydrochloric acid (0.25 mol, strength 35%) at 3e4 C. The resulting suspension of diazonium salt was added to the freshly prepared solution of N-dichlorotriazinyl H-acid at pH 6e6.5 and at 8e10 C. After 60 min the reaction was essentially completed and product was salted out by slowly adding sodium chloride (15% w/v) to the stirred solution and dried under reduced pressure. Rf 0.53. R.T. (h.p.l.c.) 1.89 min. Yield 108 g, 65%. M.I. 1808. E.a. strength 45%.
	at 0 - 5℃; for 1.5h;
	at 0 - 5℃;
	With anhydrous sodium carbonate In lithium hydroxide monohydrate; propan-2-one at 0 - 5℃;
	With Sodium hydrogenocarbonate In lithium hydroxide monohydrate; propan-2-one at -5℃; for 3h;	1 2.6.1. Synthesis of 6-(4,6-dichloro-1,3,5-triazin-2-ylamino)-7-hydroxynaphthalene-2-sulfonic acid (1) and 4-(4,6-dichloro-1,3,5-triazin-2-ylamino)-5-hydroxynaphthalene-2,7-disulfonic acid (4) General procedure: Cyanuric chloride (0.97g, 53mmol) was stirred in a mixture of acetone (20ml) and water (5ml) for 1h to form a fine suspension at-5°C. A neutral solution of 6-amino-7-hydroxy-2-naphthalenesulfonic acid (1.2g, 50mmol) and/or 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (1.4g, 50mmol) in NaHCO3 solution (10%, 3ml) was added in such a way that the temperature did not exceed above-5°C. The reaction mixture was stirred for up to 3h while maintaining the pH at 6.9-7.0. The solid formed was filtered, washed with water and crystallized from ethanol to give compounds 1 and 4.
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydroxide In lithium hydroxide monohydrate for 0.5h; Stage #2: 1,3,5-trichloro-2,4,6-triazine With Sodium hydrogenocarbonate In lithium hydroxide monohydrate at 0 - 5℃; for 0.5h; Cooling with ice;	1.1; 2.1; 3.1 Example 1 (1) H acid dissolution: 0.1 mol of H acid was dispersed in 300 g of water, and then the pH of the solution was adjusted with 20% sodium hydroxideThe whole to between 6-6.5, all dissolved, stirring 0.5h, spare;Cyanuric chloride dispersion: 0.103mol of cyanuric chloride, dispersed in 200g ice water, dispersed 0.5h,Make it evenly distributed;Condensation: the dissolved H acid solution, slowly dropping into the cyanuric chloride dispersion, in the drop process,Do not control the pH, control the temperature 0-5 , after dropping, with sodium bicarbonate dry powder to adjust the pH value of 1.8-2.2.Control the temperature and pH until the reaction ends. TLC (chromatography) detection endpoint.Filtration: the reaction solution of the condensation solution with medium-speed filter paper to remove excess cyanuric chloride, the filtration process,Keep the temperature 0-5 ° C. After filtering, heat preservation, spare.
	In lithium hydroxide monohydrate at 4 - 5℃; for 3.33333h; Cooling with ice;	1.1 step 1)Shrink: Beat 18.8g of cyanuric chloride and ice, 0.1g of dispersing agent MF in a beaker for 45 minutes;Add 40g H acid (1-amino-8-naphthol-3,6-disulfonic acid) to another beaker, add 100g of water, and add liquid alkali with stirring.(30%) adjust PH6.3-6.5, the solution is ready;The prepared H acid solution is slowly added to the cyanuric chloride beating solution.Keep the pH 3.0- after the slowing process3.5, the dropping time is 50 minutes, the temperature is 4-5 degrees,Stirring was continued for 2.5 hours after the addition was completed.Liquid phase detection endpoint,The free H acid is controlled to be 0.5% or less.
	With sodium hydroxide In lithium hydroxide monohydrate at 0 - 5℃;	2.1 The first step is the condensation of cyanuric chloride with H acid. Cyanuric chloride (9.2g, 0.05mol, Zhejiang Longsheng Dyestuff Chemical Co., Ltd., 98%) and 100mL water (containing 1%Emulsifier TX-100, Nantong Yongle Chemical Co., Ltd., 98%) mixed, cooled to 0-5 ° C, adjusted with 5% concentration of NaOHpH = 5-6. H acid (16.0g, 0.05mol, Zhejiang Longsheng Dyestuff Chemical Co., Ltd., wet cake, solid content 85.48%) and water(200 mL) was mixed and dissolved by adding 10% NaOH (pH < 7). Slowly add the H acid solution to the upper part at 0-5 ° C.In the aqueous suspension of cyanuric chloride, during the period, the concentration of 5% NaOH is continuously added to adjust the pH=5-6, and the reaction is kept for 2-3 hours.The resulting product was an aqueous solution of Compound 7.
45.3 g	With sodium hydroxide In lithium hydroxide monohydrate at 0 - 5℃; for 2h;	2 Example 2 (Dye Compound I-2): Add 31.9 grams of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid to 100 grams of water, adjust the pH to 6.5-7.0 with a 30% by weight aqueous NaOH solution to dissolve the materials, cool to 5°C, and then add to the In 19 g of cyanuric chloride suspension dispersed in 70 g of ice water, the temperature was maintained at 0-5° C. and stirred for 2 hours, and the insoluble matter was filtered out to obtain 45.3 g of the primary condensation product represented by the following formula A2.
	With anhydrous sodium carbonate In lithium hydroxide monohydrate; propan-2-one at 0 - 5℃; for 4h;	2.1.2 The coupling components preparation For 1-h, cyanuric chloride (1g, 0.005mol) was soaked in 25ml acetone at a temperature of less than 5° Celsius. Over the course of 1h, a little amount of a neutral solution of 1-naphthaol-8-amino-3,6 disulphonic acid (H-acid 1.7g, 0.005mol) in Na2CO3 aqueous solution (10 O/O w/v) was added in small amounts. The pH was kept neutral by adding Na2CO3 solution (1°/o w/v) at the same time to the reaction mixture, which was then agitated at 0.5°C for another 4h to yield a clear solution. The finished product was subsequently put to immediate use according to Scheme 2 .

Reference： [1]Current Patent Assignee: Novartis (w/o Sandoz); NOVARTIS AG - DE485185, 1929, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 16, p. 1050][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 16, p. 1050]
[2]Current Patent Assignee: CLARIANT AG - US6365719, 2002, B1 Location in patent: Example 1
[3]Current Patent Assignee: HUNTSMAN CORP - WO2004/85545, 2004, A1 Location in patent: Page 15
[4]Current Patent Assignee: HUNTSMAN CORP - WO2006/51053, 2006, A1 Location in patent: Page/Page column 15
[5]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - EP1887046, 2008, A2 Location in patent: Page/Page column 9
[6]Current Patent Assignee: HUNTSMAN CORP - US2010/159140, 2010, A1 Location in patent: Page/Page column 6
[7]Current Patent Assignee: HUNTSMAN CORP - WO2004/13235, 2004, A1 Location in patent: Page 28
[8]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2008/39614, 2008, A1 Location in patent: Page/Page column 5
[9]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2011/15378, 2011, A1 Location in patent: Page/Page column 5
[10]Location in patent: experimental part Patel, Divyesh R.; Patel, Keshav C. [Journal of the Serbian Chemical Society, 2011, vol. 76, # 2, p. 177 - 188]
[11]Location in patent: experimental part Patel, Divyesh R.; Patel, Keshav C. [Dyes and Pigments, 2011, vol. 90, # 1, p. 1 - 10]
[12]Location in patent: experimental part Bhatti, Khalid Pervez; Zuber, Muhammad [Journal of the Chemical Society of Pakistan, 2011, vol. 33, # 2, p. 263 - 268]
[13]Location in patent: experimental part Javadi, Marzieh S.; Mokhtari, Javad [Journal of the Chinese Chemical Society, 2012, vol. 59, # 6, p. 793 - 801]
[14]Pasha, Khalid; Taylor, John A. [Dyes and Pigments, 2013, vol. 96, # 2, p. 397 - 402]
[15]Ahmad; Bhatti; Bhatti; Hussain; Abbas; Shahid [Asian Journal of Chemistry, 2013, vol. 25, # 8, p. 4532 - 4536]
[16]Saeed, Qurat-Ul-Ain; Bhatti, Ijaz Ahmad; Abbas, Muhammad [Journal of the Chemical Society of Pakistan, 2013, vol. 35, # 3, p. 666 - 672]
[17]Parekh, Nikhil M.; Maheria, Kalpana C. [Research on Chemical Intermediates, 2014, vol. 40, # 3, p. 1003 - 1019]
[18]Rizk; Ibrahim; El-Borai [Dyes and Pigments, 2015, vol. 112, p. 86 - 92]
[19]Current Patent Assignee: SHANGHAI BESTON COLOR TECHNOLOGY CO LTD - CN106280534, 2017, A Location in patent: Paragraph 0082; 0083; 0084; 0085; 0095-0098; 0108-0111
[20]Current Patent Assignee: SHANGHAI ANOKY DIGITAL TECH; DONGYING ANOKY TEXTILE MAT; SHANGHAI ANOKY GROUP CO., LTD.; JIANGSU ANOKY CHEMICALS; YANTAI ANOKY FINE CHEMICALS - CN108467607, 2018, A Location in patent: Paragraph 0090; 0092; 0093; 0094
[21]Current Patent Assignee: DONGHUA UNIVERSITY; SHANGHAI UNIVERSITY OF ENGINEERING SCIENCES; EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN109825108, 2019, A Location in patent: Paragraph 0082-0085
[22]Current Patent Assignee: ARGUS SHANGHAI TEXTILE AUX - CN112662199, 2021, A Location in patent: Paragraph 0077-0079
[23]Adalikwu, Stephen A.; Agwamba, Ernest C.; Asogwa, Fredrick C.; Benjamin, Innocent; Ekoja, Paulworship; Eno, Ededet A.; Louis, Hitler; Orosun, Muyiwa M.; Unimuke, Tomsmith O. [Journal of the Indian Chemical Society, 2022, vol. 99, # 7]

2
[ 90-20-0 ]
[ 100-34-5 ]
[ 2203-16-9 ]

Yield	Reaction Conditions	Operation in experiment
	With alkali
	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.

Reference： [1]Brode [Industrial and Engineering Chemistry, 1926, vol. 18, p. 709][Chemisches Zentralblatt, 1926, vol. 97, # II, p. 1340]
[2]Chen, Weiguo; Gao, Pu; Jiang, Hua; Cui, Zhihua [Dyes and Pigments, 2019, vol. 168, p. 300 - 310]

3
[ 90-20-0 ]
[ 148-25-4 ]

Reference： [1]Patent: DE68721,
    Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 3,p. 464
[2]Patent: DE68721,
    Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 3,p. 464
[3],1933,vol. 3,p. 453,455
    Chemisches Zentralblatt,1935,vol. 106,p. 593

4
[ 90-20-0 ]
diluted alkaline solution [ No CAS ]
[ 148-25-4 ]

Reference： [1]Patent: DE68721,
Fortschr. Teerfarbenfabr. Verw. Industriezweige,vol. 3,p. 464

5
[ 785-30-8 ]
[ 90-20-0 ]
[ 54-21-7 ]
Direct Red 155 [ No CAS ]

Reference： [1]Revue Roumaine de Chimie,2004,vol. 49,p. 345 - 349

6
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: C₁₁H₁₀ClN₅O₅S₂ With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water	3.c (c) 19.5 parts of the filter cake obtained from the above (b) step and 25 parts of 32% HCl aqueous solution are added to 150 parts of 0°C water and then the solution is stirred thoroughly, followed by the rapid addition of 3.6 parts of sodium nitrite aqueous solution. Diazotization is carried out for 1.5 hours at 0~5°C, followed by the addition of 16.0 parts of 1-naphthol-8-amino -3,6-disulfonic acid powder. The pH value is adjusted slowly to 3 by 10 parts of sodium bicarbonate. After completion of the reaction, the filter cake is obtained by salting-out and filtration.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - EP1887046, 2008, A2 Location in patent: Page/Page column 10

7
[ 90-20-0 ]
[ 832724-65-9 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: C₁₁H₁₀ClN₅O₅S₂ With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water	37.c (c) 19.5 parts of the filter cake obtained from the above (b) step and 25 parts of 32% HCl aqueous solution are added to 150 parts of 0°C water and then the solution is stirred thoroughly, followed by the rapid addition of 3.6 parts of sodium nitrite aqueous solution. Diazotization is carried out for 1.5 hours at 0~5°C, followed by the addition of 8.0 parts of 1-naphthol-8-amino -3,6-disulfonic acid powder. The pH value is adjusted slowly to 3 by 10 parts of sodium bicarbonate to accomplish the coupling reaction. After completion of the reaction, the dark blue product of the following formula (37) is obtained by salting-out, filtration and dryness.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - EP1887046, 2008, A2 Location in patent: Page/Page column 18

8
diazo 4-sulfatoethylsulfone-1-aminobenzene [ No CAS ]
C₁₀H₁₃N₂O₈S₂⁽¹⁺⁾*Cl^(1-) [ No CAS ]
[ 130-23-4 ]
[ 90-20-0 ]
C₁₈H₁₇N₃O₁₂S₄ [ No CAS ]
[ 131413-68-8 ]
C₂₀H₂₁N₃O₁₄S₄ [ No CAS ]
C₂₀H₂₁N₃O₁₄S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydrogencarbonate at 25℃;	4.a EXAMPLE 4 EXAMPLE 4 [0072] a) A mixture of 141 parts of 4-(-sulfatoethylsulfonyl)aniline and 171 parts of 2,5-dimethoxy-4-(-sulfatoethylsulfonyl)aniline is diazotized as described in example 2a. 159 parts of 1-amino-8-naphthol-3,6-disulfonic acid and also 159 parts of 1-amino-8-naphthol-4,6-disulfonic acid are added and coupled in a first step at pH 1 to 1.3 at below 25 C. to form a mixture of red monoazo dyes conforming to the general formula (1). The stated pH range is set and maintained during the coupling reaction by means of sodium bicarbonate.

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - US2003/229952, 2003, A1 Location in patent: Page 7

9
[ 111150-46-0 ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide In water at 0 - 5℃;	1 To another beaker 3.9 g (82%, 0.01 mol) of 1-naphthol-8-amino-3,6-disulfonic acid and 40 mL of water were added. This solution was neutralized (pH=7) with 2.5 mL of 4N NaOH aqueous solution and the 1-naphthol-8-amino-3,6-disulfonic acid was completely dissolved. This aqueous solution was transferred to a dropping funnel and was added dropwise to the diazo component aqueous solution of 4-aminophenyl vinylsulfone while keeping the temperature at 0 to 5° C. to complete the first coupling. [0035] 1H-NMR (300 MHz, DMSO-d6) δ11.76 (1H, br), 10.58 (2H, br), 7.957.92 (4H, m), 7.52 (1H, s), 7.36 (1H, s, 1 Hz), 7.27 (1H, br), 4.003.95 (2H, t, 6 Hz, 9 Hz), 3.683.63 (2H, t, 6 Hz, 9 Hz).

Reference： [1]Current Patent Assignee: KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY - US2004/143106, 2004, A1 Location in patent: Page 3-4

10
[ 1421264-46-1 ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide In water at 0 - 5℃;	1 To the 40 mL of water in a beaker 3.9 g (82%, 0.01 mol) of 1-naphthol-8-amino-3,6-disulfonic acid was added. This solution was neutralized (pH=7) with 2.5 mL of 4N NaOH aqueous solution and the 1-naphthol-8-amino-3,6-disulfonic acid was completely dissolved. This aqueous solution was transferred to a dropping funnel and was added dropwise to the diazo component aqueous solution of 4-aminophenyl vinylsulfone while keeping the temperature at 0 to 5° C. to complete the first coupling reaction. [0027] 1H-NMR (300 MHz, DMSO-d6) δ10.62 (2H, br), 7.89 (4H, br), 7.52 (1H, s), 7.407.36 (1H, d, 12 Hz), 7.187.10 (1H, dd, 9 Hz, 6 Hz), 6.366.30 (1H, d, 18 Hz), 6.216.18 (1H, d, 9 Hz)

Reference： [1]Current Patent Assignee: KOREA RESEARCH INSTITUTE OF CHEMICAL TECHNOLOGY - US2004/143106, 2004, A1 Location in patent: Page 3

11
[ 90-20-0 ]
[ 100442-99-7 ]

Yield	Reaction Conditions	Operation in experiment
74%	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With hydrogen bromide; sodium nitrite In water at 0 - 5℃; for 2h; Stage #2: With aminosulfonic acid In water Stage #3: With hydrogen bromide; copper(I) bromide In water at 0 - 90℃; for 1.16667h;	31.1 Example 31 Preparation of: Stage 1: Preparation of 1-bromo-8-hydroxynaphthalene-3, 6-disulfonic acid 1-Amino-8-hydroxynaphthalene-3, 6-disulfonic acid (72% strength, 44.4 g, 0. 1mol) was stirred in a mixture of water (340mis) and 48% hydrobromic acid (20mis). The suspension was cooled to 0-5°C and sodium nitrite (7.6g, 0. 11 mol) was added in small portions. The mixture was stirred for 2 hours at 0-5°C and then the excess nitrous acid was destroyed by the addition of sulfamic acid solution. Further 48% hydrobromic acid (70mis) was added and the mixture cooled to 5°C. A solution of copper (I) bromide (14.4g, 0. 1mol) in 48% hydrobromic acid (30mis) and water (20mis) was then added dropwise at 0-5°C. The mixture was stirred for 10 minutes at 5°C and then the temperature was slowly raised to and maintained at 90°C for 1 hour. The reaction mixture was cooled to room temperature and sodium chloride added (30% w/v). The product was collected by filtration and washed with 20% sodium chloride solution. The dried product (56g) contained 49% sodium chloride. Yield 74%.

Reference： [1]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - WO2005/58807, 2005, A1 Location in patent: Page/Page column 24

12
[ 90-20-0 ]
[ 108-24-7 ]
[ 134-34-9 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide In water at 15 - 30℃;	1 PREPARATION EXAMPLE 1; 15 parts of 1-amino-8-naphthol-3,6-disulfonic acid are dissolved in 280 parts of water. For fully dissolve of 1-amino-8-naphthol-3,6-disulfonic acid, the pH of the solution is adjusted to 7.07.2 by adding 45% NaOH solution into the above solution. Then 7.6 parts of acetic anhydride is added and stirred at 15 to 30° C. until the acetylation reaction is completed. 13.5 parts of 2-naphthylamino-1-sulfonic acid and 4.6 parts of sodium nitrite are dissolved in 150 parts of water, then it is further added into a solution that consists of 300 parts of ice water and 35.5 parts of 32% HCl solution. The mixture is subsequently stirred at room temperature until the diazotization reaction is completed. Follow-up to this mixture, the aforementioned acetylated solution is added and stirred at room temperature until the coupling reaction is completed. The reaction mixture is further stirred for two hours at 70 to 80° C. while the pH is kept at 10-13 by adding dropwise a 45% NaOH solution for deacetylation reaction to complete. Lastly NaCl is added, and a pH of 6.8-7.2 is maintained with 32% HCl solution. Compound (P-1) is obtained after filtration.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2005/203286, 2005, A1 Location in patent: Page/Page column 9

13
[ 110-91-8 ]
[ 2494-89-5 ]
[ 108-77-0 ]
[ 87-02-5 ]
[ 90-20-0 ]
7-(4'-chloro-6'-morpholino-1',3', 5'-triazin-2'-yl)amino4-hydroxynaphthalene-2-sulfonic acid [ No CAS ]

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

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - US6015439, 2000, A

14
[ 110-91-8 ]
[ 90-20-0 ]
[ 112291-51-7 ]
[ 81-16-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; In water;	EXAMPLE 1 31.9 g of 1-hydroxy-8-aminonaphthalene-3,6-disulphonic acid are dissolved in 400 ml of water under neutral conditions. At 0 to 5 C., 8.8 ml of trifluorotriazine are added, and the pH is maintained at 4.0 to 4.5 by adding 20% strength sodium carbonate solution. After 5 minutes, 9 g of morpholine are added, and the pH is maintained at 7 using 20% strength sodium carbonate solution. After 15 minutes at 10 C., the reaction is complete. The solution thus obtained of the compound of the formula STR9 is further reacted as follows: A diazonium salt suspension obtained by diazotisation of 22.3 g of 2-aminonaphthalene-1-sulphonic acid prepared in the usual manner is added to the reaction product obtained at 0 to 5 C.

Reference： [1]Patent: US5239063,1993,A

15
[ 675-14-9 ]
[ 90-20-0 ]
[ 70233-72-6 ]

Yield	Reaction Conditions	Operation in experiment
	In ice-water	6 EXAMPLE 6 EXAMPLE 6 While stirring thoroughly 135 parts of 2,4,6-trifluoro-1,3,5-triazine are added dropwise at 0° C. to a suspension of 319 parts of ground 1-amino-8-naphthol-3,6-disulfonic acid in 4,000 parts of ice-water. The pH is kept at 3.5 to 4.0 by slowly adding pulverulent sodium bicarbonate. After 30 minutes the reaction is complete. The titrimetrically determined yield of 1-(4',6'-difluoro-1',3',5'-triazin-2'-yl)-amino-8-naphthol-3,6-disulfonic acid is more than 95% of theory.
	With sodium hydroxide In water	1 EXAMPLE 1 STR5 EXAMPLE 1 STR5 319 parts of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid are suspended in 2000 parts by volume of water at 15°, and with the addition of 100 parts by volume of 10 N sodium hydroxide solution dissolved at pH 6. To this solution are added 1500 parts of ice; and there are subsequently added dropwise at 0°, with thorough stirring, 135 parts of 2,4,6-trifluoro-1,3,5-triazine. The pH value falls rapidly to 4.5 and is held at this value by the continuous addition of 2 N sodium hydroxide solution. After completion of the addition, stirring is maintained for a further 5 minutes, and the content is determined by titration. Result: content of uncondensed 8-amino-1-hydroxynaphthalene-3,6-disulphonic acid under 1%; yield of 1-(4',6'-difluoro-1',3',5'-triazin-2'-yl)-amino-8-hydroxynaphthalene-3,6-disulphonic acid=97%.
42.1 g	With sodium hydroxide In water at 0 - 5℃; for 2h;	3 Example 3 (Dye Compound I-4): Add 31.9 grams of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid to 100 grams of water, adjust the pH to 6.5-7.0 with a 30% by weight NaOH aqueous solution to dissolve the materials, and cool to 5°C.Then add it to the already dispersed in 70 grams of ice waterIn 13.5 g of cyanuric cyanide suspension, the temperature was maintained at 0-5° C. and stirred for 2 hours, and the insoluble matter was filtered out to obtain 42.1 g of the primary condensation product represented by the following formula A3.

Reference： [1]Current Patent Assignee: SANOFI - US4361698, 1982, A
[2]Current Patent Assignee: BASF SE - US4189570, 1980, A
[3]Current Patent Assignee: ARGUS SHANGHAI TEXTILE AUX - CN112662199, 2021, A Location in patent: Paragraph 0092-0095

16
[ 88-44-8 ]
[ 90-20-0 ]
1,3-phenylenediamine-4-sulphonic acid sodium salt [ No CAS ]
2-(2'-sulphophenylamino)-4,6-difluoro-1,3,5-triazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		EXAMPLE 2 31.4 Parts of 8-amino-naphthol-3,6-disulphonic acid are condensed with cyanuric chloride at 0 C. and pH 1 to 2. To the suspension of the primary condensation product is added an aqueous solution of 21 parts of the sodium salt of 2,4-diaminobenzenesulphonic acid and condensation is effected at a pH of 4 to 5. When the condensation is complete, the secondary condensation product is coupled at pH 6 to 6.5 with the diazo compound obtained from 18.7 parts of 2-amino-5-methylbenzenesulphonic acid. The red dye solution is then added to a suspension of 2-(2'-sulphophenylamino)-4,6-difluoro-1,3,5-triazine prepared by condensing 17.3 parts of 2-aminobenzenesulphonic acid with 13.5 parts of 2,4,6-trifluoro-1,3,5-triazine at 0 C.

Reference： [1]Patent: US4507236,1985,A

17
[ 90-20-0 ]
[ 130-23-4 ]

Yield	Reaction Conditions	Operation in experiment
		102 EXAMPLE 102 EXAMPLE 102 If the 6.38 parts of 1-amino-8-naphthol-3,6-disulfonic acid in Example 101 are replaced by 6.38 parts of 1-amino-8-naphthol-4,6-disulfonic acid and in other respects the procedure followed is the same as that described above, an isomeric dyestuff with similar properties is obtained.
		205 EXAMPLE 205 EXAMPLE 205 If, in Example 204, the 6.38 parts of 1-amino-8-naphthol-3,6-disulfonic acid are replaced by 6.38 parts of 1-amino-8-naphthol-4,6-disulfonic acid and in other respects the procedure followed is the same as that described in Example 204, an isomeric dyestuff with similar properties is obtained.

Reference： [1]Current Patent Assignee: SANOFI - US4242258, 1980, A
[2]Current Patent Assignee: SANOFI - US4242258, 1980, A

18
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2,5-dimethoxyphenyl-4-(2-sulfatoethyl)sulfonyl aniline With hydrogenchloride; sodium nitrite In water at 0℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water at 20℃;	126.a a) 24 parts of 2,5-dimethoxy-4-(β-sulfatoethylsulfonyl)aniline are suspended in60 parts of ice-water and 13 parts of 30% strength hydrochloric acid and diazotized by dropwise addition of 12.5 parts of 40% strength sodium nitrite solution. After removal of the excess nitrite with amidosulfonic acid, 21.5 parts of 1-amino-8- hydroxynaphthalene-3,6-disulfonic acid are added and coupling is carried out in a first stage at a pH of 1 -1.5 below 200C to give a red monoazo dye of the formula (15-2)The pH range indicated is set, and maintained during the coupling reaction, by addition of solid sodium hydrogen carbonate. After the end of the first coupling an EPO aqueous solution is added of 12.1 parts of the yellow monoazo dye of the formula (24-1),which was prepared by diazotizing 7.4 parts of 2-aminobenzene-1 ,4-disulfonic acid with 5.1 parts of 40% strength sodium nitrite solution in an acidic medium and subsequent coupling onto 3.1 parts of 1 ,3-diaminobenzene in an aqueous medium at a pH of 1.5-2.5.

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - WO2007/39573, 2007, A2 Location in patent: Page/Page column 65-66

19
[ CAS Unavailable ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: C₂₇H₂₁N₅O₈S₂ With hydrogenchloride; sodium nitrite In water at 5℃; for 2h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydroxide; sodium acetate In water at 20℃; for 3h;	2.c Example 2 c) 24.3 parts of the bisazo dyestuffs of part b) above are stirred into a mixture of 70 parts of water and 12.2 parts of 30% HCI. 50.0 parts of ice are added, followed by 11.0 parts by volume of 4N [NAN02] solution. The resulting dark brown suspension is stirred for 2 hours at [5°C] before destroying the excess of sodium nitrite with aminosulfonic acid. The suspension of diazonium salt is then slowly poured into a solution of 13.6 parts of [1-AMINO-8-HYDROXYNAPHTHALENE-3,] 6- disulfonic acid (H acid) in 50 parts of water and 4.7 parts of 30% [NAOH.] By the simultaneous addition of 21.7 parts of sodium acetate, the pH is brought to 4.5- 5.0. The resulting mixture is then stirred at room temperature for 3 hours resulting in a dark violet suspension. The trisazo dyestuff is recovered by filtration and dried.

Reference： [1]Current Patent Assignee: CLARIANT AG - WO2003/99937, 2003, A1 Location in patent: Example 2

20
[ 2494-89-5 ]
[ 90-20-0 ]
[ 82572-37-0 ]

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: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water	60 28.1 parts of 4-β-sulfatoethylsulfone-aniline and 25.6 parts of 32% HCl aqueous solution are added into 300 parts of 0° C. water with thorough stirring to form a dispersion solution, followed by the addition of 7.2 parts of sodium nitrite with continuous stirring at a temperature in the range of 0° C. to 5° C. until the diazotization is accomplished. Then, 31.9 parts of 4-amino-5-hydroxy-2,7-napthalenedisulfonic acid powder are added into the above solution, and the pH value of the reaction solution is adjusted to 2-3 by the addition of 10 parts of NaHCO3 with continuous stirring until the coupling reaction is accomplished.
	Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; sodium nitrate In water at 0 - 5℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water for 6h;	28.1 g of 1-aminobenzene-4-beta-sulfatoethylsulfone was dispersed in 200 mL of water for about 1 hour. 10 mL of 35% hydrochloric acidAfter cooling to 0-5 ° C, 6.9 g of sodium nitrite is dissolved in 30 ml of water and slowly added. About 3-4 hours reactionThen, 34.1 g of 8-amino-1-naphthol-3,6-disulfonic acid was added to 400 mL of water, and then sodium hydrogen carbonate was added to dissolve the solution.Slowly add to the reaction solution. At this time, the pH was kept below 3.0, and when the dropwise addition was completed, the pH was adjusted to 3.0 with sodium hydrogencarbonateAfter 6 hours of reaction, the compound having the following structure is obtained.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2009/176972, 2009, A1 Location in patent: Page/Page column 16
[2]Current Patent Assignee: RIFA CO LTD - KR101565868, 2015, B1 Location in patent: Paragraph 0027; 0028

21
[ 1123208-56-9 ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: C₁₈H₂₅N₃O₄S₂ With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water	61 20.6 parts of the compound (4) are dispersed in 150 parts of ice water, and then 25.6 parts of 32% HCl aqueous solution are added therein with thorough stirring, followed by the addition of 7.1 parts of sodium nitrite with continuous stirring at a temperature in the range of 0° C. to 5° C. until the diazotization is accomplished. Subsequently, 31.9 parts of 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid powder are added therein, and the pH value of the reaction solution is adjusted to 2-3 by the addition of 6 parts of NaHCO3 with continuous stirring until the coupling reaction is accomplished.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2009/176972, 2009, A1 Location in patent: Page/Page column 17

22
[ 2494-89-5 ]
[ 108-77-0 ]
[ 1189818-84-5 ]
[ 87-02-5 ]
[ 90-20-0 ]
C₆₆H₆₀Cl₂N₁₈O₃₁S₁₀ [ No CAS ]

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.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US7598357, 2009, B1 Location in patent: Page/Page column 28-29

23
[ 93052-36-9 ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: C₁₅H₁₃ClN₆O₆S₂ With hydrogenchloride In water at 10 - 15℃; for 0.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium carbonate In water	22 EXAMPLE 22; 9.4 parts of 2,4-diamino-1-benzene sulfonic acid are dissolved in 100 parts of water, where sodium carbonate is also applied for adjusting the pH of the resulting solution to 5.0-5.7. The aforementioned resulting solution is then added slowly to a solution consisting of 9.31 parts of cyanuric chloride and 100 parts of ice water, under 0-5° C., 15% sodium carbonate solution (aq) is utilized to adjust the pH to 5.06.5, thereafter, the solution is stirred until the reaction is completed. 8.65 parts of 3-aminobenzenesulfonic acid is added to the reactant solution, the temperature is elevated and maintained at 3540° C., also the pH is adjusted and maintained at 5.0-6.5 by the addition of sodium bicarbonate, thereafter, the solution is stirred until the reaction is completed. The temperature of the resulting solution is chilled to 0-5° C. by the addition of ice, soon after, 3.55 parts of sodium nitrite is added and stirred for 10 minutes, and rapidly 16.2 parts of 32% HCl(aq) is further added and stirred for 30 minutes under 1015° C. Lastly, 0.6 parts of achromatic agent is added and stirred for 10 minutes. 15.79 parts of 1-amino-8-hydoxynaphthyl-3,6- disulfonic acid is added to the reactant solution, where sodium carbonate is used to adjust the pH of the resulting solution to 2.5-3.0, then the resulting solution is stirred until the reaction is completed. 11.34 parts diazonium salt solution of 2-aminonaphthalene sulfonic acid is added to the reactant solution where sodium carbonate is used to adjust the pH to 8.0-8.5, and again the solution is stirred until the reaction is completed. Continue with the resulting solution, where 9.3 parts of nicotinic acid is further added, which is then heated to 85100° C. with the pH being maintained at 5.05.5 until the reaction is completed. Compound (22) can be obtained after salting out and filtration.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2005/203286, 2005, A1 Location in patent: Page/Page column 12

24
[ 97987-08-1 ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-amino-4-[4-(2-chloroethylsulfonyl)butyrylamino]benzenesulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 3℃; for 1h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With hydrogenchloride In water	1.b; 1.c (b) The amine obtained according to (a) is dissolved in 400 parts of water to give a neutral pH, and 25 parts of a 4N sodium nitrite solution are added. A mixture of ice and 25 parts of concentrated hydrochloric acid is added dropwise at from 0 to 3°C to the solution obtained. Stirring is carried out at that temperature for 1 hour. Excess nitrite is then eliminated using sulfamic acid.(c) To the diazo solution according to (b) there is added a solution of 31.9 parts of 1-amino- 8-hydroxynaphthalene-3,6-disulfonic acid (H-acid) in 500 parts of water, which is adjusted to pH 4 using hydrochloric acid. During the coupling reaction, the pH is maintained at from 3 to 3.5 with sodium acetate. A monoazo dye is obtained which, in the form of the free acid, corresponds to formula

Reference： [1]Current Patent Assignee: HUNTSMAN CORP - WO2006/34967, 2006, A1 Location in patent: Page/Page column 13

25
[ 108-77-0 ]
[ 90-20-0 ]
[ 25926-16-3 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water Stage #2: With acetic anhydride In water at 5℃; Stage #3: 1,3,5-trichloro-2,4,6-triazine more than 3 stages;	2 EXAMPLE 2; 15.6 parts of 1-amino-3,6-disulfo-8-hydroxy-naphthalene are added to 20 parts of water, and for fully dissolve the pH is adjust to 6.5-7.0, follow up the temperature of the solution is lower to 5° C. and 6.7 parts of acetic anhydride are then added and stirred till the reaction is completed. On the other hand 11.2 parts of 2-amino-naphthyl sulfonic acid undergoes diazotization by the practice known methods, and the aforementioned solution is then poured into this diazotized solution where then the pH is adjusted to 78. After confirming the completion of the reaction, the pH is further adjusted to 1213 and the temperature is elevated to 7090° C., after the reaction has completed 50 parts of sodium chloride are added and the pH is adjusted to 6.87.2 and filtered after. The wet cake is dissolved in 1,000 parts of water, and immediately after it is poured into 8.7 parts of cyanuric chloride solution which are readily dissolved in 30 parts of ice water prior while maintaining the pH at 67 and at temperatures of 58° C. After the reaction is completed 11.6 parts of 4-amino-2-(2-hydroxyethyl)amino benzene sulfonic acid are further added while maintaining the pH at 57 and elevating the temperature to 4060° C. After the reaction has completed 6.8 parts of 3-carboxypyridinium are mixed with the aforementioned reacting solution while maintaining the pH at 57 and at temperatures of 80100° C., where then it is cooled down to 710° C. after the reaction has completed. 18 parts of 2-sulfonic acid-4-(2-sulfatoethylsulfonyl)aniline are then undergoes diazotization by the practiced known method and the diazotized salt is added to the afore solution where the pH is adjust to 6.0. After the reaction has completed, the obtained solution is filter and dried to obtain the dyestuff of the following formula (2), and after dyed a pink-red dyed material with fine properties can be obtained.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2006/230552, 2006, A1 Location in patent: Page/Page column 20

26
[ 94625-55-5 ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: C₁₁H₁₀ClN₅O₅S₂ With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water	3.c (c) 19.5 parts of the filter cake obtained from the above (b) step and 25 parts of 32% HCl aqueous solution are added to 150 parts of 0°C water and then the solution is stirred thoroughly, followed by the rapid addition of 3.6 parts of sodium nitrite aqueous solution. Diazotization is carried out for 1.5 hours at 0~5°C, followed by the addition of 16.0 parts of 1-naphthol-8-amino -3,6-disulfonic acid powder. The pH value is adjusted slowly to 3 by 10 parts of sodium bicarbonate. After completion of the reaction, the filter cake is obtained by salting-out and filtration.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2008/39614, 2008, A1 Location in patent: Page/Page column 6

27
[ 94625-55-5 ]
[ 90-20-0 ]
[ 832724-65-9 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: C₁₁H₁₀ClN₅O₅S₂ With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water	37.c (c) 19.5 parts of the filter cake obtained from the above (b) step and 25 parts of 32% HCl aqueous solution are added to 150 parts of 0°C water and then the solution is stirred thoroughly, followed by the rapid addition of 3.6 parts of sodium nitrite aqueous solution. Diazotization is carried out for 1.5 hours at 0~5°C, followed by the addition of 8.0 parts of 1-naphthol-8-amino -3,6-disulfonic acid powder. The pH value is adjusted slowly to 3 by 10 parts of sodium bicarbonate to accomplish the coupling reaction. After completion of the reaction, the dark blue product of the following formula (37) is obtained by salting-out, filtration and dryness.

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US2008/39614, 2008, A1 Location in patent: Page/Page column 13-14

28
[ 90-20-0 ]
[ 500870-50-8 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With potassium hydroxide In water Stage #2: With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1h; Stage #3: With hydrogenchloride; tin(ll) chloride In water at 10 - 20℃;	7.1 Stage 1-Preparation of: 8-Amino-1-naphthol-3,6-disulphonic acid (H-Acid) (1 equiv) is dissolved in water with the addition of caustic liquor until alkaline to brilliant yellow indicator paper. Sodium nitrite (1.1 equiv) is then added and the solution then charged to a stirred mixture of ice and hydrochloric acid. After stirring at 0-5° C. for 1 hr the excess nitrous acid is destroyed by the addition of sulphamic acid. The precipitated diazonium salt is isolated by filtration and the damp paste added to a stirred, cooled (<10° C.) mixture of tin(II)chloride (excess) and hydrochloric acid (1 ml per gram of tin chloride). On completion of the addition the slurry is stirred at room temperature for overnight. The product is isolated by filtration and purified by washing in ethanol before being re-isolated by filtration and dried.

Reference： [1]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - US2011/14435, 2011, A1 Location in patent: Page/Page column 13

29
[ 90-20-0 ]
[ CAS Unavailable ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: C₂₁H₃₀N₄O₆S With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 2h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydroxide In water at 0 - 5℃;	1 Example 1To an aqueous suspension of 11.68 grams of p-acetamidobenzenesulfonyl chloride cooled to 15-20° C. is added 8.15 grams of 3-(2-(2-hydroxyethoxy)ethoxy)propylamine at a rate sufficient to keep the temperature below 20° C. Aqueous sodium hydroxide solution is added as needed to keep the pH at >7. After 2 hours of stirring, the reaction is complete and 50 ml of concentrated hydrochloric acid is added, and the mixture refluxed until the infrared spectrum indicated that the acetyl group has been cleaved. The mixture is cooled to 0-5° C. and 3.58 grams of sodium nitrite is added to the mixture and stirred for 2 hours. The resulting diazonium salt is added to a cooled solution of 6.85 grams of 2-methoxy-5-methylaniline in dilute aqueous hydrochloric acid resulting in a deep orange red product. This product is further diazotized at 0-5° C. by adding 3.58 grams of sodium nitrite with additional hydrochloric acid as necessary to keep the pH at <2. The mixture is stirred for 2 hours. The resulting diazonium salt is added to a cooled (0-5° C.) aqueous solution of H-acid in water containing sufficient sodium hydroxide to dissolve the H-acid. The pH of the reaction mixture is kept at 10-12 during the addition of the diazonium salt by adding sodium hydroxide solution as necessary. This resulted in a solution of the deep violet colored product represented as Formula BA4 herein. The product has a λmax of 569 nm in water.

Reference： [1]Current Patent Assignee: MILLIKEN & COMPANY - US2012/101265, 2012, A1 Location in patent: Page/Page column 25

30
[ 90-20-0 ]
[ 108-24-7 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
1594 g	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid; acetic anhydride With sodium hydroxide In water at 10 - 30℃; for 1h; Stage #2: With hydrogenchloride In water	1.a a) Acetylation of H-acid 191 .9 g (0.5 mol) 4-amino-5-hydroxy-naphthalene-2,7-disulphonic acid (83%, CAS-No. 90-20-0) are suspended in 500 ml water and dissolved at pH 7 by addition of 48.6 ml aqueous NaOH (30%). 92.1 g acetic acid anhydride are slowly added within 10 minutes. The reaction mixture is cooled to 10°C by addition of 250.0 g ice. A pH-level of 7 is adjusted by addition of 1 18.3 ml aqueous NaOH (30%). 56.2 ml aqueous NaOH (30%) are added subsequently. A pH-level of 10.5 is maintained for 1 hour at a temperature of 30°C by addition of 4.8 ml aqueous NaOH (30%). By addition of 32.9 ml aqueous HCI (32%) the solution is adjusted to a pH-level of 7.2. After cooling to 20°C with 180 g ice, 1594 g solution of acetylated H-acid (ca. 0.5 mol) is obtained.

Reference： [1]Current Patent Assignee: BASF SE - WO2013/160328, 2013, A1 Location in patent: Page/Page column 28

31
[ 90-20-0 ]
[ CAS Unavailable ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydroxide In water at 20℃; Stage #2: C₁₁H₁₀Cl₂N₄O₁₀S₃ With sodium carbonate In water at 5 - 30℃; for 6h;	2.a; 2.b 6.1 g (0.019 mol) of 1 -amino-8-hydroxy-3,6-disulfonaphthalene (H-Acid) are suspended into 100 ml of water at 20°C. The pH is adjusted to 6.0 - 7.0 by addition of an aqueous sodium hydroxyde solution (30%), and the mixture is then stirred until H-Acid is completely dissolved. (b) The solution obtained according to step (a) of this Example 2 is added to a solution prepared in accordance with Example 1 (c) at pH 2.0 and a temperature of 5 - 10°C. The pH is then raised slowly to pH 4.0 by addition of an aqueous sodium carbonate solution (20%). Once pH 4 is reached, the temperature is raised to 25 - 30°C and the mixture is stirred at this temperature for 6 hours, while the pH is kept constant by addition of an aqueous sodium carbonate solution (20%). After completion of the reaction, the solution is kept as it is until further use. The pH is raised to 7.0 - 7.5 by addition of an aqueous sodium carbonate solution (20%), before submitting the solution to the procedure described in step (d).

Reference： [1]Current Patent Assignee: ARCHROMA TEXTILES SARL - WO2013/186029, 2013, A1 Location in patent: Page/Page column 29

32
[ 90-20-0 ]
[ CAS Unavailable ]
[ 1515947-57-5 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium nitrite In water at 0 - 5℃; for 0.166667h; Stage #2: With hydrogenchloride; aminosulfonic acid In water at 0 - 5℃; for 0.5h; Stage #3: C₂₄H₃₂N₆O₆S₂ at 0 - 5℃;	iii) 6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid was added into 70 parts of water. The pH was adjusted to 5-6 using 15% soda solution. The reactionvessel was cooled to 0-5°C using ice. 4.3 milliliters of 5M sodium nitrite solution was added into the reaction mixture. After stirring for 10 mm, 20.7 parts of 37% hydrochloric acid was added. The reaction was stirred at 0-5°C for 0.5 h and then 0.2 parts of sulfamic acid was added.The solution of product (a) obtained above was cooled down to 0-5°C using ice. Thediazonium salt was added into this coupler solution slowly while maintaining the pHto 5-6.5. The reaction was stirred until completion to yield the intermediate (b).

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - WO2013/189815, 2013, A1 Location in patent: Page/Page column 201

33
[ 90-20-0 ]
[ 1515946-80-1 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium nitrite In water at 0 - 5℃; for 0.166667h; Stage #2: With hydrogenchloride; aminosulfonic acid In water at 0 - 5℃;	1.ii 6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid was added into 70parts of water. The pH was adjusted to 5-6 using 15% soda solution. The reactionvessel was cooled to 0-5°C using ice. 4.3 milliliters of 5M sodium nitrite solution was10 added into the reaction mixture. After stirring for 10 min, 20.7 parts of 37%hydrochloric acid was added. The reaction was stirred at 0-5°C for 0.5 h and then0.2 parts of sulfamic acid was added.The solution of product (a) obtained above was cooled to 0-5°C using ice. Thediazonium salt was added into this coupler solution slowly while maintaining the pH to15 5-6.5. The reaction was stirred until completion to yield the intermediate (b).

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - WO2013/189814, 2013, A1 Location in patent: Page/Page column 143; 144

34
[ 90-20-0 ]
[ 1516880-77-5 ]
[ 1516880-78-6 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium nitrite In water at 0 - 5℃; for 0.166667h; Stage #2: With hydrogenchloride; aminosulfonic acid In water at 0 - 5℃; for 0.5h; Stage #3: 1-(sulfatoethyl sulfonylethyl)-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonamide In methanol; water at 0 - 5℃;	124 6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (a) was added into 70parts of water. The reaction vessel was cooled to 0-5 °C using ice. 1 .5 parts of sodium nitrite was added into the reaction mixture. After stirring for 10 mm, 20.7 parts of 37% hydrochloric acid was added. The reaction was stirred at 0-5 °C for 0.5 h and then 0.2 parts of sulfamic acid was added.7.66 parts of I -(sulfatoethyl sulfonyl ethyl)-6-hydroxy-4-methyl-2-oxo-1 ,2-dihydropyridine-3-carbonamide (h) was dissolved in water/methanol mixture. The reaction vessel was cooled to 0-5 °C using ice. The diazonium salt was added into the coupler solution slowly while maintaining the pH at in the slightly acidic range. The reaction was stirred until completion to yield the intermediate (i).

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - WO2013/189813, 2013, A1 Location in patent: Page/Page column 262; 263

35
[ 90-20-0 ]
[ 28141-13-1 ]
[ 1516880-75-3 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium nitrite In water at 0 - 5℃; for 0.166667h; Stage #2: With hydrogenchloride; aminosulfonic acid In water at 0 - 5℃; for 0.5h; Stage #3: 3-cyano-1-ethyl-6-hydroxy-4-methyl-2-pyridone In methanol; water at 0 - 5℃;	1 6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (a) was added into 70parts of water. The reaction vessel was cooled to 0-5 °C using ice. 1 .5 parts of sodiumnitrite was added into the reaction mixture. After stirring for 10 mm, 20.7 parts of 37%hydrochloric acid was added. The reaction was stirred at 0-5 °C for 0.5 h and then 0.2parts of sulfamic acid was added.3.6 parts of I -Ethyl-6-hydroxy-4-methyl-2-oxo-1 ,2-dihydropyridine-3-carbonitrile (e) was dissolved in water/methanol mixture. The reaction vessel was cooled to 0-5 °C using ice. The diazonium salt was added into the coupler solution slowly while maintaining the pH at in the slightly acidic range. The reaction was stirred untilcompletion to yield the intermediate (f).

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - WO2013/189813, 2013, A1 Location in patent: Page/Page column 259

36
[ 151407-77-1 ]
[ 90-20-0 ]
[ 1516880-05-9 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium nitrite In water at 0 - 5℃; for 0.166667h; Stage #2: With hydrogenchloride; aminosulfonic acid Stage #3: 1-(4-[β-sulfatoethylsulfonyl]-phenyl)-5-hydroxy-3-methyl-1H-pyrazole In water for 2h;	2 Synthesizing procedure for Example 28.0 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (a) was dissolved in 50 parts of water. 5.1 parts of sodium nitrite solution was added into the reaction mixture. The reaction vessel was cooled down to 0-5 °C using ice-salt mixture. After 10 mins 7.5 parts of 37% hydrochloric acid was added to the reaction mixture. The reaction mixture was stirred for 1-2 hrs. After completion 0.2 parts of sulfamic acid was addedinto the reaction mixture.8.7 parts of coupling component (b) was suspended in 50 parts of water. The diazocomponent was added. The reaction mixture was stirred for 2 hrs. After completion,16.1 parts of the product (c) was obtained by addition of salt and followed by filtration.
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 1-(4-[β-sulfatoethylsulfonyl]-phenyl)-5-hydroxy-3-methyl-1H-pyrazole With aminosulfonic acid In water for 2h;	1 8.0 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid (a) was dissolved in 50 parts of water. The reaction vessel was cooled to 0-5 & lt; 0 & gt; C using an ice-salt mixture.After 10 minutes, 7.5 parts of 37% hydrochloric acid was added to the reaction mixture. The reaction mixture was stirred for 1 to 2 hours. After completion, 0.2 part of sulfamic acid was added to the reaction mixture.8.7 parts of coupling component (b) was suspended in 50 parts of water. The pH was adjusted to 4.5. Diazo component was added. The reaction mixture was stirred for 2 hours. After completion, salt addition followed by filtration yielded 16.1 parts of product

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - WO2013/189813, 2013, A1 Location in patent: Page/Page column 260; 261
[2]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - KR2015/32668, 2015, A Location in patent: Paragraph 0513-0516

37
[ 90-20-0 ]
[ CAS Unavailable ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: sodium salt of (4-β-sulphatoethyl)sulphonylaniline With hydrogenchloride; sodium nitrite In water at 4 - 6℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water Further stages;	A-1 Example A-1 10 parts 2-[(4-Aminophenyl)sulfonyl]ethyl sodium sulfate (Parabase-ester) were mixed with 9 parts water, 3 parts ice and 3.9 parts hydrochloric acide 30 % at 4 to 6 °C. The mixture was diazotized with 4.8 parts of 40.5 %ic sodium nitrit solution. To this parabase-ester diazotation 5.7 parts 1-amino-3,6-disulfo-8-hydroxy-naphthalene (H-acid) were added in potions. The product of the 1st coupling reaction was transferred to a vessel containing 7 parts of water. During this transfer the pH was kept between pH 4.8 and 5.5 using 1.9 parts of sodium carbonate. After the 2nd coupling the pH was adjusted to pH 8 to 9 and the mixture was stirred until vinylisation was completed. Then the product was isolated via filtration.
	Stage #1: sodium salt of (4-β-sulphatoethyl)sulphonylaniline With hydrogenchloride; sodium nitrite In water at 4 - 6℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium carbonate In water	A-1 Example A-1 10 parts 2-[(4-Aminophenyl)sulfonyl]ethyl sodium sulfate (Parabase-ester) " were mixed with 9 parts water, 3 parts ice and 3.9 parts hydrochloric acide 30 % at 4 to 6 °C. The mixture was diazotized with 4.8 parts of 40.5 %ic sodium nitrit solution. To this parabase-ester diazotation 5.7 parts 1-amino-3,6-disulfo-8-hydroxy-naphthalene (H-acid) were added in potions. The product of the 1st coupling reaction was transferred to a vessel containing 7 parts of water. During this transfer the pH was kept between pH 4.8 and 5.5 using 1.9 parts of sodium carbonate. After the 2nd coupling the pH was adjusted to pH 8 to 9 and the mixture was stirred until vinylisation was completed. Then the product was isolated via filtration. The resulting product has the following structure: (A-1 ) and dyes cotton in navy blue shades.
	Stage #1: sodium salt of (4-β-sulphatoethyl)sulphonylaniline With hydrogenchloride; sodium nitrite In water at 4 - 6℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium carbonate In water Stage #3: In water	A-1 10 parts 2-[(4-Aminophenyl)sulfonyl]ethyl sodium sulfate (Parabase-ester) were mixed with 9 parts water, 3parts ice and 3.9 parts hydrochloric acide 30 % at 4 to 6 °C. The mixture was diazotized with 4.8 parts of 40.5 %ic sodiumnitrit solution. To this parabase-ester diazotation 5.7 parts 1-amino-3,6-disulfo-8-hydroxy-naphthalene (H-acid) wereadded in potions. The product of the 1st coupling reaction was transferred to a vessel containing 7 parts of water. Duringthis transfer the pH was kept between pH 4.8 and 5.5 using 1.9 parts of sodium carbonate. After the 2nd coupling thepH was adjusted to pH 8 to 9 and the mixture was stirred until vinylisation was completed. Then the product was isolatedvia filtration.

	Stage #1: sodium salt of (4-β-sulphatoethyl)sulphonylaniline With hydrogenchloride; sodium nitrite In water at 4 - 6℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium carbonate In water Stage #3: In water	A-1 10 parts 2-[(4-Aminophenyl)sulfonyl]ethyl sodium sulfate (Parabase-ester) were mixed with 9 parts water, 3parts ice and 3.9 parts hydrochloric acide 30 % at 4 to 6 °C. The mixture was diazotized with 4.8 parts of 40.5 %ic sodiumnitrit solution. To this parabase-ester diazotation 5.7 parts 1-amino-3,6-disulfo-8-hydroxy-naphthalene (H-acid) wereadded in potions. The product of the 1st coupling reaction was transferred to a vessel containing 7 parts of water. Duringthis transfer the pH was kept between pH 4.8 and 5.5 using 1.9 parts of sodium carbonate. After the 2nd coupling thepH was adjusted to pH 8 to 9 and the mixture was stirred until vinylisation was completed. Then the product was isolatedvia filtration.
	Stage #1: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid; sodium salt of (4-β-sulphatoethyl)sulphonylaniline With hydrogenchloride; sodium nitrite In water at 4 - 6℃; Cooling with ice; Stage #2: With sodium carbonate In water	A.A-1 Example A-1 10 parts 2-[(4-Aminophenyl)sulfonyl]ethyl sodium sulfate (Parabase-ester) were mixed with 9 parts water, 3 parts ice and 3.9 parts hydrochloric acide 30 % at 4 to 6 °C. The mixture was diazotized with 4.8 parts of 40.5 %ic sodium nitrit solution. To this parabase-ester diazotation 5.7 parts 1-amino-3,6-disulfo-8-hydroxy-naphthalene (H-acid) were added in potions. The product of the 1st coupling reaction was transferred to a vessel containing 7 parts of water. During this transfer the pH was kept between pH 4.8 and 5.5 using 1.9 parts of sodium carbonate. After the 2nd coupling the pH was adjusted to pH 8 to 9 and the mixture was stirred until vinylisation was completed. Then the product was isolated via filtration. The resulting product has the following structure: (A-1 ) and dyes cotton in navy blue shades.

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - EP2725070, 2014, A1 Location in patent: Paragraph 0088
[2]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - WO2014/63822, 2014, A1 Location in patent: Page/Page column 20-21
[3]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - EP2725069, 2014, A1 Location in patent: Paragraph 0088; 0089
[4]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - EP2725068, 2014, A1 Location in patent: Paragraph 0084; 0085
[5]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD - WO2014/63824, 2014, A1 Location in patent: Page/Page column 30-31

38
[ 2272-40-4 ]
[ 90-20-0 ]
C₁₉H₁₄ClN₅O₇S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate In water at 25 - 30℃;	Condensation reaction of cyanuric chloride General procedure: Cyanuric chloride(1.90 g, 0.0103 mol) was introduced into 20 g of ice cubes with 2mL of water and the mixture was stirred at a temperature of 0-5 °C. After stirring for 30 min, 4a-g (0.01 mol) was added. The temperature of the mixture was maintained at 0-5 °C and pH was maintained at 4-5 using 10% Na2CO3 aqueous solution. The reaction mixture was stirred for about 1 h until no chromogenic reactionto the Erich reagent was detectable. And then 4.0 g (0.01 mol,85.6%) H-acid was added and the reaction was performed at 25-30 C and pH 5-5.5 using 10% Na2CO3 aqueous solution. The reaction mixture was stirred for about 3-4 h to give the solution of 6a-g product and TLC was used to monitor the completion of the reaction (n-PrOH:i-BuOH:EtOAc:H2O, 2:4:1:3, v/v).

Reference： [1]Shan, Bin; Tong, Xing; Xiong, Wei; Qiu, Wenzhu; Tang, Bingtao; Lu, Rongwen; Ma, Wei; Luo, Yi; Zhang, Shufen [Dyes and Pigments, 2015, vol. 123, p. 44 - 54]

39
1-aminonaphthalene-3,6,8-trisulphonic acid trisodium salt [ No CAS ]
[ 148-25-4 ]
[ 90-20-0 ]
C₁₀H₉NO₇S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		As the preferredembodiment, the said step 70) specifically includes: preheat concentratedliquid caustic soda through a heat exchanger to 180. Then, feed into the alkali-fusion kettle.Respectively preheat methanol and concentrated amino T acid solution beforepumping them into the alkali-fusion kettle.React the caustic soda, methanol and amino T acid solution at 200 and2.8 MPa. After the reaction is complete,pass the material through a dilution kettle and add water to dilute. Obtain dilute methanol and dlutedalkali-fused compound; Condense throughdistillation to recover dilute methanol, and recover residual methanol from thediluted alkali-fused compound by making it pass through a strippingcolumn; Send dilute methanol to themethanol distillation section to recover methanol, and the recovered methanolis used for the alkali-fusion reaction;feed diluted alkali-fused compound into a buffer tank. In this step, thedilute methanol obtained after the reaction undergoes recovery. And therecovered dilute methanol is to be used again for the alkali-fusionreaction. Recycling the methanolsolution greatly reduces the amount of methanol required for the production ofH-acid and thus it helps reduce costs. As the preferredembodiment, the said step 80) specifically includes: Undergoing acidtreatment: cool the dilute methanol obtained from step 40) and the 98%concentrated sulfuric acid mixture to formulate the set concentration of thesulfuric acid, and send to the second dilute sulfuric acid buffer tank; Undergoing isolation:send the diluted alkali-fused compound of step 70), the H-acid filtrate and thedilute sulfuric acid from the second dilute sulfuric acid buffer tank into theisolation kettle and undergo isolation.After cooling the produced sulfur dioxide, undergo liquefactionrecovery. Undergoing cooling andfiltration: the isolated material goesthrough a cooling kettle to be cooled to 50.use a filter equipment to filter, wash with water. Obtain H-acid filtercake, filtrate and the mother liquor.Store filtrate in a filtrate tank to be used again for isolation; send the mother liquor to a wastewatertreatment system.

Reference： [1]Patent: CN105693560,2016,A .Location in patent: Paragraph 0064; 0065; 0066; 0067

40
[ 91-20-3 ]
[ 148-25-4 ]
[ 90-20-0 ]
C₁₀H₉NO₇S₂ [ No CAS ]

Reference： [1]Patent: CN105693560,2016,A

41
[ 18791-02-1 ]
[ 90-20-0 ]
[ 118-03-6 ]
C₂₃H₁₁BrN₃O₁₇S₅^(5-)*5Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 7-aminonaphthalene-1,3,6-trisulfonic acid With hydrogenchloride; potassium iodide; sodium nitrite In water at 0 - 5℃; for 2h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water at 10 - 15℃; for 2h; Stage #3: 2,3-dibromo-propionyl chloride Further stages;	1 Preparation method Maoist red reactive dyes, comprising the steps of a, K acid diazotization [0062] added to the kettle water, K acid 19. 2g, stir, add crushed ice and 30% hydrochloric acid solution and 30% aqueous sodium nitrite Solution, the reaction solution at a temperature of _5 ° C, pH potassium iodide starch test paper blue LEACHABLE state under conditions, react for 2 hours After sulfamate eliminate excess nitrous acid was K diazonium salt, to be coupled; Preparation of an aqueous acid solution [0063] b, H [0064] The solid material 17g H acid added to the kettle, add water, 30% NaOH solution to adjust pH to about 7, H acid Completely dissolved to give an aqueous solution of H acid to be coupled; [0065] c, the coupling reaction: [0066] K is a step of preparing an acid diazonium salt was slowly added in step b H prepared aqueous acid, the reaction temperature process 10-15 ° C, pH = 5-6 for 2 hours, the acid process to detect J diazonium salt remaining in the reaction vessel to control the reaction end point, No reaction was complete the remaining diazonium salt, completion of the coupling process, the coupling solution was to be condensed.d, the condensation reaction: [0068] d-1: Preparation of condensate: Weigh bromo propionyl chloride 12. 82g, acetone 1. 3g, so bromo propionyl chloride in acetone carve Scattered evenly to give bromo propionyl chloride and acetone mixture, to prepare condensation. [0069] d-2: The coupling step c cooling liquid to 0-10 ° C, bromo propionyl chloride and acetone solution of d-1 step of preparing a mixture of Washed with Na2C03 to maintain pH = 6-7, and reacted for 4 hours to obtain a condensed liquid. [0070] e, alkali treatment: [0071] The condensation step d with 30% NaOH aqueous solution was adjusted to pH 11~12, the reaction temperature is 5~10 ° C, heat 2 Hours, to obtain a compound of formula (I). [0072] f, removing insolubles: f, removing insolubles: [0073] The product of Step added to the solid-liquid separator, separation, removal of sludge, the filtrate is collected in the tank. [0074] g, shading and intensity: [0075] The step f stained material, then the shade, according to staining intensity adjustment; [0076] h, Drying: [0077] The color was added to the feed step g liquid preheater, adjust the inlet temperature of 210 ° C, with 95-100 ° C outlet temperature Of spray-dried to obtain the final product.

Reference： [1]Current Patent Assignee: TIANJIN DEK CHEMICAL CO., LTD. - CN102433024, 2016, B Location in patent: Paragraph 0059

42
[ 108-77-0 ]
[ 18791-02-1 ]
[ 90-20-0 ]
[ 103-69-5 ]
1,3-phenylenediamine-4-sulphonic acid sodium salt [ No CAS ]
C₃₀H₂₁BrClN₈O₁₁S₃^(3-)*3Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
120 g	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water at 0 - 10℃; for 0.5h; Cooling with ice; Stage #2: N-ethyl-N-phenylamine With sodium hydrogencarbonate In water at 30 - 40℃; Stage #3: 2,3-dibromo-propionyl chloride; 1,3-phenylenediamine-4-sulphonic acid sodium salt Further stages;	2 Exaample 2 A.20 g of cyanuric chloride and 100 g of ice were mixed with 50 g of water for 1 hour, 43 g of H acid and 150 g of water were mixed, and the pH of the H acid solution was adjusted to 6.5 to 7.0 with 13 g of baking soda. And then to be finished after the end of cyanuric chloride, the dissolved H acid to cyanuric chloride for 30 minutes, the condensation temperature is maintained at 0-10 , pH = 1.0-3.0, H acid added after the end of incubation reaction 30 min, with 10 g of sodium bicarbonate up to adjust the pH = 1.5-2.5, reaction to H acid completely disappeared as a shrink end.B. Two-fold reaction.Ethyl aniline was added at a rate of 14 g, and then the temperature was raised to 30-40 ° C and the pH was adjusted to 5.0-7.0 with 15 g of sodium bicarbonate. The temperature and pH were allowed to react for 1-2 hours until the final product Completely disappeared for the end of the second reduction.C. Acylation.30g between the two plus 150g water mixed stirring dissolved, and then start dropping 40g2.3-dibromo propionyl chloride, dropping time control in 1-3 hours, the temperature control at 0-30 , and with 10g baking soda control pH = 5.0 -8.0. After the dropwise addition, the pH value is maintained and the reaction is carried out for 1 to 2 hours, so that the double-elimination completely disappears as the acylation end point.D. Diazo reaction.8g of sodium nitrite plus 20g of water mixed stirring dissolved, and then between the two acylated liquid cooling to 5-20 , adding 30g of hydrochloric acid to make the material pH ≤ 1.0, and then start dropping sodium nitrite solution, 30-50 minutes drop , And then keep the temperature and control the pH between 0.5-1.5, and the reaction time of 1 hour for the diazo endpoint, after the arrival of the end of the addition of 0.5g sulfamic acid balance excessive sodium nitrite.E. Alkali reaction.The reaction of the two cool down to 5-20 ° C, and then add the reaction between the two acylated diazonium salt, after the addition, with 20g baking soda to adjust the material pH = 5.0-8.0 alkaline reaction 1-3 hours , The reaction between the two acyl diazonium salt disappeared as alkali end point.F. Degreasing reaction.And then the reaction of alkali material is heated to 50-70 ° C, and 8g soda ash adjusted pH = 8.0-9.0 reaction 1-2 hours, and then 15g hydrochloric acid callback pH = 5.0-6.5, which is type (1-2 ) Of the original slurry, steam drying available dry powder (1-2) 120g.

Reference： [1]Current Patent Assignee: ZHEJIANG YIDE CHEMICAL - CN105542511, 2016, A Location in patent: Paragraph 0085; 0086; 0087; 0088; 0089; 0090; 0091-0103

43
[ 108-77-0 ]
[ 18791-02-1 ]
[ 90-20-0 ]
[ 103-69-5 ]
1,3-phenylenediamine-4-sulphonic acid sodium salt [ No CAS ]
C₃₀H₂₂Br₂ClN₈O₁₁S₃^(3-)*3Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
115 g	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water at 0 - 10℃; for 0.5h; Cooling with ice; Stage #2: N-ethyl-N-phenylamine With sodium hydrogencarbonate In water at 30 - 40℃; Stage #3: 2,3-dibromo-propionyl chloride; 1,3-phenylenediamine-4-sulphonic acid sodium salt Further stages;	1 Example 1 A.20 g of cyanuric chloride and 100 g of ice were beaten with 50 g of water for 1 hour, 43 g of H acid and 150 g of water were mixed, and the pH of the H acid solution was adjusted to 6.5 to 7.0 with 13 g of baking soda. And then to be finished after the end of cyanuric chloride, the dissolved H acid to cyanuric chloride for 30 minutes, the condensation temperature is maintained at 0-10 , pH = 1.0-3.0, H acid added after the end of incubation reaction 30 min, with 10 g of sodium bicarbonate up to adjust the pH = 1.5-2.5, reaction to H acid completely disappeared as a shrink end.B. Two-fold reaction.Ethyl aniline was added at a rate of 14 g, and then the temperature was raised to 30-40 ° C and the pH was adjusted to 5.0-7.0 with 15 g of sodium bicarbonate. The temperature and pH were allowed to react for 1-2 hours until the final product Completely disappeared for the end of the second reduction.C. Acylation.30g between the two plus 150g water mixed stirring dissolved, and then start dropping 40g2.3-dibromo propionyl chloride, dropping time control in 1-3 hours, the temperature control at 0-30 , and with 10g baking soda control pH = 5.0 -8.0. After completion of the dropwise addition, the pH was maintained and the reaction was allowed to proceed for 1-2 hours to completely eliminate the acylation end point.D. Diazo reaction.8g of sodium nitrite plus 20g of water mixed stirring dissolved, and then between the two acylated liquid cooling to 5-20 , adding 30g of hydrochloric acid to make the material pH ≤ 1.0, and then start dropping sodium nitrite solution, 30-50 minutes drop Finished, and then heat and control the pH value of 0.5-1.5 between the reaction 1 hour for the diazo endpoint, the end of the arrival of the addition of 0.5g sulfamic acid balance excessive sodium nitrite.E. Alkali reaction.The reaction of the two cool down to 5-20 ° C, and then add the reaction between the two acylated diazonium salt, after the addition, with 20g baking soda to adjust the material pH = 5.0-8.0 alkaline reaction 1-3 hours (1-1), and steam drying is carried out to obtain 115g of the dry powder type (1-1). The formula (1-1) can be used as a raw material.

Reference： [1]Current Patent Assignee: ZHEJIANG YIDE CHEMICAL - CN105542511, 2016, A Location in patent: Paragraph 0057; 0058; 0061; 0062; 0063; 0064; 0065-0073

44
[ 2494-89-5 ]
[ 90-20-0 ]
remazol black B [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; sodium nitrite In water at 5 - 10℃; for 4h; Large scale; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water at 8 - 16℃; Large scale;	7,000 kilograms of water in the reaction pot,Open mixing,A well-weighed para-ester was added (96% by mass) (4-ethylsulfosulfanilide) 5854 kg,After the addition was complete, the mixture was stirred for about 1 hour,Adding about 3000 kg to 4000 kg of ice,Ice grinding about 0.5 hours.Then, 2400 kg of metered hydrochloric acid (31%) was added,Add the right amount of ice,Liquid sodium nitrite solution (1438 kg of industrial sodium nitrite (96%), about 3500 kg of water dissolved)Keep Congo red test paper bright blue,KI starch test paper micro blue drop,About 2 hours plus finished.After the addition,The reaction was stirred at 5 ° C to 10 ° C for about 2 hours,The excess sodium nitrite is then removed with the para ester,To be coupled.3900 kg of dry powder of H acid (1-amino-8-naphthol-3,6-disulfonic acid) was placed in a diazo pot,About 30 minutes to 45 minutes plus finished.After the addition, maintain 8 ° C ~ 16 ° C reaction of about 4 hours,Plus crushed ice to 3 ° C ~ 5 ° C,With baking soda dry powder to adjust the pH to 5. 0.Maintain the pH = 4. 5 ~ 5. 0 reaction for about 1 hour,To obtain a dye slurry,The slurry was spray dried into a spray tower to obtain component (1-1).
	Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With sulfuric acid; sodium nitrite In water at 15℃; for 3h; Cooling with ice; Large scale; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With aminosulfonic acid In water at 15℃; for 4h; Large scale; Stage #3: With sodium hydroxide In water for 1h; Large scale;	2 (1) diazotization: Weigh the para-ester 6000kg (off hundred),Was added to 9,000 kg of water in a stirred diazo pot,Beat for 1 hour.Adding 4000kg ice to cool, then adding 2135kg mass concentration of 98% sulfuric acid, and then beating for 1 hour.Cooling to about 10 ,From the liquid surface as soon as possible by adding sodium nitrite solution (100% 1492kg, dubbed 30% solution), temperature 15 .Timely measurement of acidity and sub-sodium overdose, Congo red paper into the case of dark blue for additional sodium hypochlorite, faster.In the guarantee of sufficient sulfuric acid and sub-sodium under the premise of maintaining 1 hour; (2) acid coupling: coupling pot to add the end of ice water 6000kg, input fold 3500kgH acid, stirring beating 1h.Then, the aminosulfonic acid was added to the diazonium salt prepared in the step (1), and then the solution was added to the H acid after being beaten twice, and the weight of the weight was 50% Nitrogen salt, keep the temperature 15 , keep 1h, then add the remaining diazonium salt and then continue to maintain 3h, get acid coupling solution; (3) basic coupling: in the above (2) acidic coupling solution by adding 10% sodium hydroxide solution to adjust the pH 5, pH maintained constant stirring reaction 1h; (4) cooling: cooling the above-mentioned (3) coupling fluid cooling coil to 6-8 ° C and slowing the agitation speed to 18 rpm to cause the precipitation of part of the sodium sulfate in the solution; (5) Filtration: The above-mentioned (4) cooling material is rapidly filtered, the precipitated sodium sulfate is filtered out, the filtrate is collected, and the filter material such as sodium sulfate is collected as soon as possible; (6) Post-treatment: The collected filtrate of the above (5) was subjected to spray drying to obtain 10130 kg of high-intensity active black dye 2.The strength of the high-intensity active black dye 2 was 153%.
	Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 3.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water at 10 - 15℃; for 3h;	1.1; 1.2 (1) To 31.53g Add dispersant to p-(β-hydroxyethyl sulfone sulfate) aniline (that is, p-ester). After beating for 1 hour to confirm that no fine particles are present, add 13.65g of 30% hydrochloric acid, stir for 30 minutes, and cool to At 5°C, slowly add 21.7g of 30% sodium nitrite solution, control the temperature at 0-5°C and stir for 2 hours, ensure that the reaction solution can make the Congo red test paper blue, and the starch potassium iodide test paper shows Slightly blue, with no yellow intersection with the Ehrlich reagent as the end point of the reaction, add a small amount of sulfamic acid to remove the excess sodium nitrite, so that the starch potassium iodide test paper does not appear blue, and the para-ester diazonium solution is obtained;(2) Add 34.1g of 1-amino-8-naphthol-3,6-disulfonic acid (i.e. H acid) into water, beating for 1 hour, and after confirming that no fine particles are present, add it to the above-mentioned para-ester diazonium The reaction was stirred in the liquid for 2 hours, the temperature was controlled at 10-15°C, the pH was 1.0, and the p-nitroaniline diazonium salt was used for detection. The complete disappearance of free H acid was the end of the reaction to obtain a coupling reaction liquid; a coupling liquid In the early stage, it is purple-red, and there is a blue component in the middle and late stages;

Reference： [1]Current Patent Assignee: ZHEJIANG RUIHUA CHEMICAL - CN104194394, 2016, B Location in patent: Paragraph 0044; 0045; 0046
[2]Current Patent Assignee: ZHEJIANG JIHUA GROUP CO LTD - CN106118122, 2016, A Location in patent: Paragraph 0035; 0036; 0037; 0038; 0039; 0040; 0041; 0042
[3]Current Patent Assignee: HUBEI HWALLE DYESTUFF IND - CN113667324, 2021, A Location in patent: Paragraph 0044-0047

45
[ 2494-89-5 ]
[ 90-20-0 ]
C₂₆H₂₅N₅O₁₉S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: hydrogenchloride; sodium nitrate / water / 0 - 5 °C 1.2: 6 h / pH 3 2.1: hydrogenchloride; sodium nitrate / water / 0 - 5 °C 2.2: pH 6 - 7
150 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: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydroxide In water at 10℃; Stage #3: at 10 - 30℃; for 3h;	<Examples A1 to A25> Using the compound of formula (a) and (b) purified by the method of Preparation 1 as a starting material, a reactive dye was prepared as follows.4-Aminobenzene-beta-D-Sulfatoethylsulfone118.2 g was added to 500 g of water and dispersed,22 g of sodium carbonate was added to dissolve. Ice was added and the mixture was cooled to about 2-4 DEG C, then 50 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.63.8 g of 1-amino-8-naphthol-3,6-disulfonic acid (aka, "H acid") was dispersed in 450 g of water and 23 g of 25%And 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.Completion confirmation of the primary coupling reaction was made until H acid was eliminated. When H-acid 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 liquid was dried to obtain about 150 g of a dye powder (A1) represented by the formula (3).

Reference： [1]Current Patent Assignee: RIFA CO LTD - KR101565868, 2015, B1
[2]Current Patent Assignee: KYUNG-IN SYNTHETIC CORPORATION - KR101960807, 2019, B1 Location in patent: Paragraph 0170-0179

46
[ 2494-89-5 ]
[ 88-21-1 ]
[ 90-20-0 ]
C₂₄H₁₇N₅O₁₆S₅^(4-)*4Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Weigh 30.35 g p-ester (that is, (beta- ethyl sulfone sulfate) aniline) in 500 ml beaker, add the right amount of water, ice, an ice mill beating, was added 12.72 g concentration after half an hour to 31 % (w / w) hydrochloric acid, then 30% (w / w) concentration of sodium nitrite solution (containing sodium nitrite 7.46 g) was added dropwise to a solution of p-ester, controlling the temperature 0-5 re nitriding.Until after the end of the diazo-ester obtained diazo solution weighed 32.86 g H acid was added to the diazonium solution, controlling the temperature 5 ~ 10 reaction was stirred for 10 hours, then treated with sodium bicarbonate to adjust the pH of 2 to 2.5 acidic the coupling reaction was complete to give the acid conjugate.Another weighed 17.82 g anthranilic acid in 250 ml beaker, add the right amount of water, ice, an ice mill beating, was added 13.31 g concentration of 31% (w / w) hydrochloric acid after half an hour, and then 30% (w / w) concentration of sodium nitrite solution (containing sodium nitrite 7.11 g) was added dropwise, controlling the temperature 0-5 diazotization reaction, the reaction 2 hours after the end of diazotization to give the anthranilic acid diazo solution.Anthranilic acid was added to the acid diazo conjugate, the control pH of 6 to 7, the temperature 5 ~ 10 for the second coupling.2 hours after the end of the second coupling, insolubles were filtered off with filter paper, and dried with an oven, such as to give the formula (I-1) navy blue reactive dyes.

Reference： [1]Patent: CN103992659,2016,B .Location in patent: Paragraph 0069; 0070; 0071; 0072; 0073; 0074

47
[ 88-21-1 ]
[ 90-20-0 ]
[ 25781-90-2 ]
C₂₄H₁₆N₅O₁₂S₄^(3-)*3Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Weigh 30.35 g p-ester (that is, (beta- ethyl sulfone sulfate) aniline) in 500 ml beaker, add the right amount of water, ice, an ice mill beating, liquid caustic soda was added to adjust the pH to half an hour 12, the temperature control at 0-5 deg.] C, was added at a concentration of 12.72 g 31% (w / w) hydrochloric acid pH stable after one hour, and then 30% (w / w) concentration of sodium nitrite solution (sodium nitrite 7.46 g) was added dropwise to a solution of p-ester, controlling the temperature 0-5 diazotization.Until after the end of the diazo-ester obtained diazo solution weighed 32.86 g H acid was added to the diazonium solution, controlling the temperature 5 ~ 10 reaction was stirred for 10 hours, then treated with sodium bicarbonate to adjust the pH of 2 to 2.5 acidic the coupling reaction was complete to give the acid conjugate.Another weighed 17.82 g anthranilic acid in 250 ml beaker, add the right amount of water, ice, an ice mill beating, was added 13.31 g concentration of 31% (w / w) hydrochloric acid after half an hour, and then 30% (w / w) concentration of sodium nitrite solution (containing sodium nitrite 7.11 g) was added dropwise, controlling the temperature 0-5 diazotization reaction, the reaction 2 hours after the end of diazotization to give the anthranilic acid diazo solution.Anthranilic acid was added to the acid diazo conjugate, the control pH of 6 to 7, the temperature 5 ~ 10 for the second coupling.2 hours after the end of the second coupling, liquid caustic soda to adjust pH to 12-13 were degreased, after two hours until pH stabilized insoluble matter was removed by filtration using a filter paper, and dried to give navy blue oven as defined in formula (I-3) of reactive dyes.

Reference： [1]Patent: CN103992659,2016,B .Location in patent: Paragraph 0076; 0077; 0078; 0079; 0080; 0081

48
[ 2494-88-4 ]
[ 90-20-0 ]
[ 98-44-2 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-aminobenzene-3-β-sulfatoethylsulfone With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water at 15 - 20℃; for 8h; Stage #3: amino-benzene-1,4-disulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 10℃; for 4.5h;	3 Preparation Example 3 Weigh 29.51 g meta-ester (that is, between (β- ethyl sulfone sulfate) aniline) in 500 ml beaker, add the right amount of water, ice, an ice mill beating, was added 12.36 g concentration after half an hour to 31 % (w / w) hydrochloric acid, then 30% (w / w) concentration of sodium nitrite solution (containing sodium nitrite 7.25 g) was added dropwise to a solution of meta-ester, controlling the temperature 0-5 re nitriding.Meta diazo ester to be obtained after the diazo solution, weighed 31.9 grams H acid was added to the diazonium solution, controlling the temperature 15 ~ 20 The reaction was stirred for 8 hours, and then adjust pH3 ~ 3.5 acidic complete coupling reaction to give Acid conjugate.Another weighed 25.3 g aniline-2,5-disulfonic acid in 250 ml beaker, add the right amount of water, ice, an ice mill beating, 5.8 grams of a 31% (w / w) hydrochloric acid after half an hour, then 30% (w / w) concentration of sodium nitrite solution (containing 6.9 g of sodium nitrite) was added dropwise, controlling the temperature 0-5 diazotization reaction, two hours after the end of diazotization.The aniline-2,5-disulfonic acid was added to the acid diazo conjugate, the control pH of 6 to 7, the temperature of 5 ~ 10 for the second coupling.2 hours after the end of the second coupling, insolubles were filtered off with filter paper, and dried with an oven to give a compound of formula (I-6).

Reference： [1]Current Patent Assignee: ZHEJIANG RUIHUA CHEMICAL - CN103992659, 2016, B Location in patent: Paragraph 0082; 0083; 0084; 0085; 0086; 0087

49
[ 108-77-0 ]
[ 88-21-1 ]
[ 90-20-0 ]
[ 107-15-3 ]
KPR-6 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		1) 100 parts of cyanuric chloride was subjected to ice-milling for 30 minutes at a control temperature of T = 0 C, and 100 parts of H acid was dissolved in 20% of soda water, adjusted to pH 7.5 and dispersed in 1 hour into ice- Cyanuric chloride.2) The step 1)The resulting mixture was adjusted to pH 3.0 with 20% pure alkali water and the reaction temperature was set at 2 . The reaction was terminated for 3 hours and the disappearance of H acid was detected at the end point to obtain a primary condensate.3) 100 parts of o-aminobenzenesulfonic acid was ice ground for 30 minutes. First, 100 parts of hydrochloric acid was added, then 103 parts of sodium nitrite was added to carry out diazo reaction, and the starch potassium iodide test paper blue, Congo red test paper dark blue, control reaction temperature 5 , 3 hours to reach the end of the reaction, the elimination of excess sodium nitrite with sulfamic acid, diazo liquid.4) The diazo solution obtained above was added to the primary condensation solution, stirred for 1 hour, mixed with sodium chloride for 30 minutes, adjusted to pH 7.0 with 20% pure alkali water, reacted for 5 hours, controlled temperature T = 15 , The salt disappears to give the coupling solution.5) 50 parts of ethylenediamine was added to the coupling solution1 part of phase transfer catalyst, heated to 50 C, with 20% soda ash adjusted PH = 6.0, 8 hours reaction, detection of conjugate disappeared secondary condensate.6) The secondary condensate is filtered and concentrated by a nanofiltration apparatus, and concentrated until the dialysate is the same as the concentrated volume.7) According to customer requirements,The concentrated solution is standardized, the shade and intensity are adjusted to the design requirements, spray dried by a spray drying tower, and the dried product is directly packaged to obtain a red reactive dye, and its structural formula is as follows: The red reactive dye prepared in this example is subjected to a dyeing test , The test results shown in Table 1.

Reference： [1]Patent: CN105273437,2016,A .Location in patent: Paragraph 0038; 0039; 0040; 0041; 0042; 0043-0047

50
[ 90-20-0 ]
[ 10312-55-7 ]
C₁₈H₁₃N₃O₁₁S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80.2%		Diazo reaction: All operating temperatures of the diazo reaction step are controlled at 10 C. The procedure is as follows:First, 2 parts by weight of sodium nitrite was mixed with 4 parts by weight of dilute hydrochloric acid at a concentration of 25% to obtain a solution of nitrous acidLiquid, reserve;1 part by weight of the amino compound of PTA was mixed with 4 parts of dilute hydrochloric acid at a concentration of 25%, and nitriteAcid solution, stirring and reacting for 5 hours to obtain diazonium salt;To the obtained diazonium salt, 90 parts by weight of urea having a concentration of 30% was added, and the reaction time was 1 hour to remove the polyNitrous acid, to obtain said diazonium salt.The diazonium salt obtained in Example 4 was used to react with the coupling component to prepare an azo dye: Formulation of a 15%1-amino-8-naphthol-3,6-disulfonic acid solution, pH adjusted to 7.5 with sodium carbonate, slowly dropping into the diazonium salt,The crystals were filtered and dried at 60 C for 2 hours to give azo dyes of the formula (IV) with a purity of 96% and a yield of 80.2%.

Reference： [1]Patent: CN103664684,2016,B .Location in patent: Paragraph 0051; 0052; 0053; 0054; 0055; 0056

51
[ 90-20-0 ]
[ 1584676-17-4 ]
[ 1584676-20-9 ]

Yield	Reaction Conditions	Operation in experiment
83.3%	Stage #1: bis(2-hydroxyethyl) 2-aminoterephthalate With hydrogenchloride; cis-nitrous acid In water at 5℃; for 5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium carbonate for 1h;	2.4 Diazo Reaction: All operating temperatures of the diazo reaction step are controlled at 5 ° C. The procedure is as follows:First, 2 parts by weight of sodium nitrite was mixed with 4 parts by weight of dilute hydrochloric acid at a concentration of 25% to obtain a solution of nitrous acidLiquid, spare1 part by weight of the amino compound of BHET was mixed with 4 parts of dilute hydrochloric acid at a concentration of 25%, and nitriteAcid solution, stirring and reacting for 5 hours to obtain diazonium salt;Further, 100 parts by weight of urea having a concentration of 30% was added to the resulting diazonium salt, and the reaction time was 1 hour to removeExcess nitrous acid, to obtain the diazonium salt.Formulation of a 20%1-amino-8-naphthol 3,6-disulfonic acid solution, adjust the pH value with sodium carbonate to 8. 5, by adding diazonium salt, reaction 1 hour,The sodium chloride was added, crystallized, filtered, and dried at 60 ° C for 1 hour to give azo dyes of the formula (II) with a purity of 95%The rate was 83.3%.

Reference： [1]Current Patent Assignee: JIANGNAN UNIVERSITY - CN103664684, 2016, B Location in patent: Paragraph 0029; 0030; 0031; 0032; 0033; 0034

52
[ 675-14-9 ]
[ 90-20-0 ]
[ 26878-11-5 ]
[ 88-64-2 ]
[ 24605-36-5 ]
C₃₅H₂₆FN₁₁O₂₀S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
52.1%		2.75g of aniline-2,5-bis-sulfonic acid monosodium salt, dissolved in water, under the conditions of good stirring, slowly dropping 1.39g of trifluoro cyanide in -5 ~ 0 reaction 20min or so, control pH3-4, the reaction is completed After the filter, the filtrate, a shrink product;3.19 g of H acid was added to 20 mL of water to dissolve and the pH was adjusted to 4-5; a shrunken product was added dropwise to the H acid solution and incubated at 25 C in a water bath to perform a diastolic reaction. The end point was measured with Elich.2.30 g of 4-acetylamino-2-aminobenzenesulfonic acid was added to 20 mL of water, adjusted to pH 7-8 and dissolved with 0.75 g of sodium nitrite to give 4-acetylamino-2-aminobenzenesulfonic acid containing sodium nitrite.In the beaker, add a small amount of ice, then add 3mL concentrated hydrochloric acid, stirring; containing sodium nitrite 4-acetamido-2-aminobenzenesulfonic acid solution quickly into the concentrated hydrochloric acid solution in the ice bath reaction; with Congo red test paper And starch potassium iodide test paper were instantly blue; and then continue to respond for 30min, with elixir reagent detection end point; after the end of the reaction by adding sulfamic acid decomposition of excess nitrous acid, diazonium salt solution.2.54 g of 1- (4'-sulfonic acid phenyl) -3-methyl-5-pyrazolone was dissolved in 50 mL of water, adjusted to pH 7-8, and the above diazonium salt solution was added dropwise to maintain the pH 7-8 The reaction mixture was cooled to 90 C for 5 hours. After the reaction, the reaction solution was cooled to a solution of 8% sodium hydroxide in the above mixed solution, and the reaction solution was cooled to At room temperature, adjusted to pH 7-8 with concentrated hydrochloric acid to give the intermediate solution containing pyrazolone.Add about 10g of ice and 3mL concentrated hydrochloric acid in the beaker, stir well; in the above-mentioned pyrazolone-containing intermediates solution by adding 0.75g sodium nitrite dissolved, and its rapid into the concentrated hydrochloric acid solution, with Congo red Test paper and starch potassium iodide test paper were instantly blue; and then continue to respond for 30min, with elixir reagent detection end; adding sulfamic acid decomposition of excess nitrite, which was containing pyrazolone structure diazonium salt solution.The pH of the above-mentioned dichroic solution was adjusted to 7-8, and the above-mentioned solution containing the pyrazolone-containing diazonium salt was added dropwise to the shrink product to carry out the coupling reaction, and the end point was measured by the bleeding test.After the end of the reaction, the pH 7 was adjusted, and the high-light fastness azo-type red reactive dyes containing the monofluorotriazine structure was obtained by salting out, filtering and washing the filter cake and the yield was 52.1%.

Reference： [1]Patent: CN106167626,2016,A .Location in patent: Paragraph 0062; 0063; 0064; 0065; 0066; 0067; 0068; 0069

53
[ 108-77-0 ]
[ 90-20-0 ]
[ 26878-11-5 ]
[ 88-64-2 ]
[ 24605-36-5 ]
C₃₅H₂₆ClN₁₁O₂₀S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58.7%		Example 11.75 g of cyanuric chloride and an appropriate amount of crushed ice at 0 C with stirring; 2.75 g of aniline-2,5-bis sulfonic acid monosodium salt, 40 mL of water was added to adjust pH 6.0; aniline-2,5-bis Solution was added to the trichloro cyanide slurry to carry out a shrinkage reaction, keep the pH 4-5, reaction 3h, with elixir reagent detection end point, that was a shrink product.3.19 g of H acid was added to 20 mL of water and the pH was adjusted to 4-5. A shrunken product was added dropwise to the H acid solution and the mixture was incubated at 35 C for 35 C to maintain pH 4-5 for about 4 h. Test the end point, that is, shrink products.2.30 g of 4-acetamido-2-aminobenzenesulfonic acid was added to 20 mL of water, adjusted to pH 7-8 and dissolved with 0.75 g of sodium nitrite to give 4-acetylamino-2-aminobenzenesulfonic acid containing sodium nitrite.In the beaker, add a small amount of ice, then add 3mL concentrated hydrochloric acid, stirring; containing sodium nitrite 4-acetylamino-2-aminobenzenesulfonic acid solution quickly into the concentrated hydrochloric acid solution in the ice bath reaction, with Congo red test paper and Starch potassium iodide test paper are instantly blue.And then continue to respond for 30min, with elixir reagent detection end point; after the end of the reaction by adding sulfamic acid decomposition of excess nitrous acid, diazonium salt solution.2.54 g of 1- (4'-sulfonic acid phenyl) -3-methyl-5-pyrazolone was dissolved in 50 mL of water, adjusted to pH 7-8, and the above diazonium salt solution was added dropwise maintaining pH 7-8, The reaction solution was cooled to room temperature, and the reaction solution was cooled to room temperature. After the reaction was carried out, the reaction solution was cooled to room temperature, and the reaction solution was cooled to room temperature. The reaction solution was cooled to room temperature, Hydrochloric acid to adjust pH7-8, to obtain the structure of the intermediate containing pyrazolone solution.Add about 10 g of ice and 3 mL of concentrated hydrochloric acid in a beaker and stir the reaction in an ice bath; add 0.75 g of sodium nitrite to the solution containing the pyrazolone solution and quickly pour it into a concentrated hydrochloric acid solution and use a Congo red test paper and Starch potassium iodide test paper are instantly blue; and then continue to respond for 30min, with elixir reagent detection end point; after the end of the reaction by adding sulfamic acid decomposition reaction process generated excess nitrite, that is, the weight of the pyrazolone structure Nitrogen salt solution.Adjusting the pH of the product solution to 7-8, dropping the solution containing the pyrazolone structure diazonium salt into the shrink product to carry out the coupling reaction, detecting the end point with the bleeding experiment; adjusting the product solution pH 7, The filtrate was washed and dried to obtain high gloss fastness azo red reactive dyes containing monochlorotriazine. The yield was 58.7%.

Reference： [1]Patent: CN106167626,2016,A .Location in patent: Paragraph 0045; 0046; 0047; 0048; 0049; 0050; 0051; 0052

54
[ 108-77-0 ]
[ 90-20-0 ]
[ 26878-11-5 ]
[ 88-64-2 ]
C₂₉H₂₀Cl₂N₁₀O₁₄S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60.7%	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water at 0℃; for 3h; Stage #2: 2-amino-4-acetylaminobenzene sulfonic acid With sodium nitrite In water Cooling with ice; Stage #3: 1-(4'-sulfophenyl)-3-methylpyrazol-5-one Further stages;	8 Example 8 1.86 g of cyanuric chloride and an appropriate amount of crushed ice at 0 ° C with beating; 3.19 g of H acid was added to 20 mL of water; the H acid solution was added to the triprichchlorochlorine slurry for a shrinkage reaction, maintaining pH 5-6, TheUse Ehrlich to detect the end point, that is, a shrink product.2.30 g of 4-acetamido-2-aminobenzenesulfonic acid was added to 20 mL of water, adjusted to pH 7-8 and dissolved with 0.75 g of sodium nitrite to give 4-acetylamino-2-aminobenzenesulfonic acid containing sodium nitrite.In the beaker, add a small amount of ice, then add 3mL concentrated hydrochloric acid, stir.4-acetylamino-2-aminobenzenesulfonic acid solution containing sodium nitrite was rapidly poured into a concentrated hydrochloric acid solution and reacted in an ice bath. The test was carried out with Congo red test paper and starch potassium iodide test paper. Li Xi reagent detection end; adding sulfamic acid decomposition of excess nitrous acid, get diazonium salt solution.2.54 g of 1- (4'-sulfonic acid phenyl) -3-methyl-5-pyrazolone was dissolved in 50 mL of water, adjusted to pH 7-8, and the above diazonium salt solution was added dropwise maintaining pH 7-8, The reaction solution was cooled to room temperature and adjusted with concentrated hydrochloric acid. The reaction mixture was stirred at room temperature for 5 hours. The reaction solution was cooled to room temperature and adjusted with concentrated hydrochloric acid. PH 7-8 to give an intermediate solution containing a pyrazolone structure.Add about 10 g of ice and 3 mL of concentrated hydrochloric acid in a beaker and stir well. To dissolve the above-mentioned solution containing the pyrazolone-containing intermediate, add 0.75 g of sodium nitrite and pour it into the concentrated hydrochloric acid solution quickly. Red test paper and starch potassium iodide test paper are instantly blue; and then continue to respond for 30min, with elixir reagent detection end point; after the end of the reaction by adding sulfamic acid decomposition of excess nitrite, which was containing pyrazolone structure diazonium salt solution TheThe pH of the aforementioned shrinkage product solution was adjusted to 7-8.The above-mentioned pyrazolone-containing diazonium salt solution was dropped into a shrunk product to carry out coupling reaction, and the end point was measured by the bleeding experiment.After the completion of the reaction, the product solution was adjusted to pH 7, and the high color fastness azo type red reactive dyes containing the dichlorotriazine structure was obtained by salting out, suctioning and washing the filter cake, and the yield was 60.7%.

Reference： [1]Current Patent Assignee: DALIAN UNIVERSITY OF TECHNOLOGY - CN106167626, 2016, A Location in patent: Paragraph 0055; 0056; 0057; 0058; 0059; 0060; 0061

55
[ 2494-89-5 ]
[ 90-20-0 ]
C₁₈H₁₅N₃O₁₃S₄^(2-)*2Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride In water for 0.5h; Cooling with ice; Stage #2: With sodium nitrite In water for 1h; Stage #3: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate at 0 - 10℃; for 2h;	7.1 250 ml beaker, 20 parts of ice, 24.3 parts of 30% hydrochloric acid, 28.1 parts of p-bit ester,Ice mill beating 30min, 6.97 copies of sodium nitrite slowly added to generate diazonium salt,Until the addition of sodium nitrite and then stir lh,Amino acid was removed with sulfamic acid; 31.9 parts of H acid was slowly added dropwise to the diazonium salt,After the addition of 2h, the diazonium salt completely disappeared while maintaining the temperature of the system at 0-10 ° C.
	Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; sodium nitrite for 1h; Cooling with ice; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate at 0 - 10℃;	2.1 (1) heavy nitrogen, coupling reaction 250 ml beaker, adding 20 parts of ice, 24.3 parts 30% hydrochloric acid, 28.1 parts ester, 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; will be 31.9 parts H acid slowly dropping in the added to the diazonium salt, to continue the reaction after adding 2h, diazonium salt completely disappeared, while maintaining the system temperature is 0 - 10 °C.

Reference： [1]Current Patent Assignee: TAIXING JINYUN DYESTUFF CO., LTD. - CN106590026, 2017, A Location in patent: Paragraph 0110-0112
[2]Current Patent Assignee: TAIXING JINYUN DYE - CN106634038, 2017, A Location in patent: Paragraph 0089; 0090; 0091

56
[ 2494-88-4 ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1-aminobenzene-3-β-sulfatoethylsulfone With hydrogenchloride In water for 0.5h; Cooling with ice; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium nitrite In water for 1h; Stage #3: With sodium hydrogencarbonate at 0 - 10℃;	6.1 250 ml of a 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 copies of sodium nitrite slowly added to generate diazonium salt,Until the sodium nitrite completely added and then stirring lh, with sulfamic acid to eliminate micro-excess sodium nitrite;31.9 parts of H acid was added to the diazonium salt and the reaction was continued until the diazonium salt disappeared completely,While maintaining the system temperature at 0-1 0 ° C.
	Stage #1: 1-aminobenzene-3-β-sulfatoethylsulfone With hydrogenchloride; sodium nitrite for 1h; Cooling with ice; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate at 0 - 10℃;	1.1 (1) diazo,Coupling reaction 250 ml of a beaker, 20 parts by mass of ice was added,24.3 parts 30% hydrochloric acid,28.1 parts of meta-ester,Ice cream beating30min,6.97 parts of sodium nitrite slowly added to the formation of diazonium salt,Until the sodium nitrite completely added and then stir 1h,Elimination of slightly excess sodium nitrite with sulfamic acid;31.9 parts of H acid was added to the diazonium salt,After the addition, the reaction is continued until the diazonium salt is completely eliminatedLoss, while maintaining the system temperature of 0-10 .
	Stage #1: 1-aminobenzene-3-β-sulfatoethylsulfone With hydrogenchloride; sodium nitrite In water for 1.5h; Cooling with ice; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water at 0 - 10℃;	6.1 (1) diazo, coupling reaction 250ml 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;31.9 parts of H acid were added to the diazonium salt,After the addition continued reaction to the diazonium salt disappeared completely,While maintaining the system temperature is 0-10 .

Reference： [1]Current Patent Assignee: TAIXING JINYUN DYESTUFF CO., LTD. - CN106590026, 2017, A Location in patent: Paragraph 0091-0093
[2]Current Patent Assignee: TAIXING JINYUN DYE - CN106634038, 2017, A Location in patent: Paragraph 0070; 0071; 0072
[3]Current Patent Assignee: TAIXING JINYUN DYESTUFF CO., LTD. - CN106833013, 2017, A Location in patent: Paragraph 0108-0110

57
[ 108-77-0 ]
[ 90-20-0 ]
[ 2944-29-8 ]
[ 62-53-3 ]
[ 1797428-49-9 ]

Yield	Reaction Conditions	Operation in experiment
91.3%	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium carbonate In water at 0 - 5℃; for 1h; Stage #2: aniline In water at 25 - 30℃; for 3h; Stage #3: 1,4-bis((4-aminophenyl)amino)anthrancene-9,10-dione Further stages;	1 the condensation reaction of cyanuric chloride: into a beaker added the 1.90 g (0.0103mol) of cyanuric chloride, 20g crushed ice and 2mL H2O, mechanical stirring beating for 30min, and then gradually added the drops of 4.0g (0.01mol, 85.6%) H acid, carry on reaction at 0 ~ 5 ° C with mechanical stirring, and during the reaction the pH value of solution is controlled between 4~5 with 10% sodium carbonate solution. After reaction till 1h, the end point of the contraction reaction is measured with the Ehrlich reagent. After completion of the reaction, added the 0.93 g (0.01mol) of aniline, the temperature increased at 25 ~ 30 ° C, control the pH value at 5 ~ 6 reaction, insulation reaction for 3h after that, determination of reaction end point by thin layer chromatography (developing agent is n-butanol: isopropanol: ethyl acetate: water = 2: 4: 1: 3). After completion of the reaction, the obtained tirethylene material is placed in an ice bath. Diazotization reaction: into the 2.10g (0.005mol) 1, 4-Bis (p-aminophenylamino) anthraquinone added 20mL of water, and then added the 2.5mL of concentrated hydrochloric acid (37%), stirring dissolved, cooling at 0 ~ 5 ° C, and quickly adding 0.73g sodium nitrite, and then carry on reaction for 30min, by Ehrlich reagent test the reaction end point, after the reaction is completed, added a small amount of sulfamic acid to remove excess sodium nitrite, the prepared diazonium salt is placed in an ice-water bath as spare. Coupling reaction: the above prepared 1, 4-Bis (p-aminophenylamino) anthraquinone diazonium salt is gradually added to the spare tirethylene, by using 10% sodium carbonate solution control the pH at 7 ~ 8 reaction, stir evenly, raise the temperature at 20 ° C, reaction ends at 24 hours. Add 10 ~ 20g anhydrous potassium acetate, pumping filter, and wash with anhydrous ethanol 3 times, dry, and then obtained Anthraquinone azo reactive dyes, yield is 91.3%.

Reference： [1]Current Patent Assignee: DALIAN UNIVERSITY OF TECHNOLOGY - CN104693836, 2017, B Location in patent: Paragraph 0048-0051

58
[ 90-20-0 ]
[ 98-59-9 ]
[ 6860-97-5 ]

Yield	Reaction Conditions	Operation in experiment
77%	With sodium acetate; sodium hydroxide In water at 70℃; Darkness;	3 Synthesis of Tosyl-H-Acid of formula (IX) 42.6g of H-Acid (75%, MW 319.3g/mol, CAS 90-20-0) 0.1 mol were suspended with 40 ml water in a flask. The grey suspension was heated to 70°C and the pH was adjusted to a value of 3 with 10.8g of a 30% solution of sodium hydroxide. 22.3g of p-Toluenesulfonylchloride 99% were slowly added to the dark solution maintaining the pH to a value of 3 using 21 g of a 30% solution of sodium hydroxide. The pH was then set to a value of 6 using 20g of sodium acetate. The reaction mixture was then concentrated in the rotary evaporator and cooled down to room temperature. The obtained product was collected by filtration and washed with 20ml Methanol. Tosyl-H-Acid was then obtained in a 77% yield

Reference： [1]Current Patent Assignee: DFI CHEM - WO2017/92872, 2017, A1 Location in patent: Page/Page column 19

59
[ 108-77-0 ]
[ 88-21-1 ]
[ 90-20-0 ]
[ 88-53-9 ]
C₂₆H₁₅Cl₂N₇O₁₃S₄^(4-)*4Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		first condensation reaction [0043] In 1000mL beaker, add 184g (1mol) cyanuric chloride, 150g of ice water and carried out beating for 1h. then 222 g (1 mol) of 98% CLT acid (2-amino-4-methyl-5-chlorobenzenesulfonic acid) was dissolved in 30% liquid caustic soda , adjusted pH= 6.0 and controlled the temperature =10 C. The CLT acid solution was added to the cyanuric chloride for beating solution, after adding completion the reaction was reacted for 2h under the pEta = 3.0-3.5, and the temperature ? 5 C conditions to obtain first condensate; [0044] 2nd condensation reaction [0045] the 1009g (1mol) H acid dissolved with 30% caustic soda to pH = 7.0, then first condensate was added , warmed to 40 C, and completion the reaction was reacted for 3h under the pH = 3.0-3.5, temperature = 40 conditions to obtain second condensate; [0046] diazo reaction [0047] In 500mL beaker, 137g (1mol) p-aminobenzoic acid, 100g of ice water was added and carried out beating for 1h. then 31% hydrochloric acid (containing HC1 40g (1.1mol)) was added and stirred for 10min. A 30% sodium nitrite solution containg sodium nitrite 70g (1.01mol) was added within 20mins, control pH ? 1.2, temperature ? 5 C, after the addition the pH was maintained at pEta= 1.0-1.2, temperature at T? 5 C and reacted for 2h. Control potassium iodide test strips Micro-blue, remove the excess sodium nitrite with sulfamic acid to give 4- aminobenzoic acid diazo liquid standby; [0048] Coupling reaction [0049] the second condensate at temperature of 10 C was added to the 4- aminobenzoic acid diazo liquid solution, after stirring evenly adjust pH =5.5 by using Sodium bicarbonate, control temperature ? 5 C and reacted for 5h. that is to obtain Red reactive dye compound (1-1),

Reference： [1]Patent: CN105038312,2017,B .Location in patent: Paragraph 0051-0060

60
[ 90-20-0 ]
[ 17405-00-4 ]
[ 696-82-2 ]
C₂₁H₁₃F₂N₅O₉S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		(1) 34.1 parts of H acid was dissolved in 200 parts of water,Add 10% sodium carbonate solution to adjust the pH to 7,Total dissolved, then 13.5 parts of trifluoropyrimidine at 20 C,Condensed at pH 5 for 3 to 4 hours,No H acid when the end point, obtained condensation products; 2) take 13.7 parts of para-amino benzoic acid diazonium salt, and the condensation product obtained in step (1) at 15 C, a pH of 7Under the conditions of coupling reaction 5h, to obtain compound B.

Reference： [1]Patent: CN106398303,2017,A .Location in patent: Paragraph 0018-0019; 0024-0025; 0028-0030

61
[ 90-20-0 ]
[ 696-82-2 ]
C₁₄H₉F₂N₃O₇S₂ [ No CAS ]
C₁₄H₁₀F₂N₄O₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; In water; at 20℃; for 4h;pH 5 - 7;	(1) 34.1 parts of H acid was dissolved in 200 parts of water,Add 10% sodium carbonate solution to adjust the pH to 7,Total dissolved, then 13.5 parts of trifluoropyrimidine at 20 C,Condensed at pH 5 for 3 to 4 hours,No H acid when the end point, obtained condensation products;

Reference： [1]Patent: CN106398303,2017,A .Location in patent: Paragraph 0018; 0024; 0025; 0028; 0029

62
[ 90-20-0 ]
[ 4346-59-2 ]
[ 696-82-2 ]
C₂₁H₁₅F₂N₅O₈S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		(1) 34.1 parts of H acid was dissolved in 200 parts of water,Add 10% sodium carbonate solution to adjust the pH to 7,Total dissolved, then 13.5 parts of trifluoropyrimidine at 20 C,Condensed at pH 5 for 3 to 4 hours,No H acid when the end point, obtained condensation products; (2) take 12.3 parts of para-amino-anisidine diazonium salt, and the condensation product obtained in step (1) at 15 C, a pH of 6Under the conditions of coupling reaction 5h, to give compound A.

Reference： [1]Patent: CN106398303,2017,A .Location in patent: Paragraph 0018-0019; 0024-0026; 0028-0029

63
[ 90-20-0 ]
[ 2149564-89-4 ]
[ 2149564-91-8 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: C₁₂H₁₆N₂O₆S₂ With hydrogenchloride; sodium nitrite In water Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate In water for 3h;	1-(2) Synthesis of Intermediate 1-b 4-Amino-5-hydroxy-naphthalene-2,7-disulfonic acid (32 g)Was dissolved in water in a neutral solution. The solution was dropwise added to an aqueous solution containing 36 g of Intermediate 1-a dissolved in water at a temperature of 5 ° C or lower over about 30 minutes, and then the mixture was adjusted to pH 3.5 with sodium hydrogencarbonate for about 3 hours To give intermediate 1-b. (Yield: 90%)

Reference： [1]Current Patent Assignee: OH YOUNG - KR2017/121986, 2017, A Location in patent: Paragraph 0128-0133

64
[ 108-77-0 ]
[ 90-20-0 ]
[ 25781-90-2 ]
[ 103-69-5 ]
1,3-phenylenediamine-4-sulphonic acid sodium salt [ No CAS ]
C₃₈H₂₇Cl₂N₁₂O₁₂S₄^(3-)*3Na⁽¹⁺⁾ [ No CAS ]

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 carbonate In water at 0 - 5℃; for 1.5h; Stage #2: N-ethyl-N-phenylamine With sodium carbonate at 35 - 40℃; for 4h; Stage #3: 1,3,5-trichloro-2,4,6-triazine; 1-amino-4-vinylsulphonylbenzene; 1,3-phenylenediamine-4-sulphonic acid sodium salt Further stages;	4 Example 4: Prepare a dye of the formula: The condensation solution obtained in e) in Example 1, ie, dye (1) solution, was adjusted to pH = 10 with sodium hydroxide,The reaction was maintained at 40-50 ° C and the reaction was followed by HPLC until the disappearance of the condensate was completed.The solution was further adjusted to pH 7.0 with 30% hydrochloric acid solution and directly dried to give 17.5 parts of a red reactive dye product of the above formula (4). a) cyanuric chloride and H acid condensation reaction Weigh 1.88 parts cyanuric chloride,Add 18 parts of water, crushed ice,Beating at 0 ~ 5 for 30 minutes.3.41 parts of 1-amino-8-naphthol-3,6-disulfonic acid was weighed simultaneously in 15 parts of water,With sodium carbonate pH = 6 ~ 7, so that it completely dissolved.After the beating is finished, the above H acid solution is dripped into the cyanuric chloride suspension within 1 hour.After the addition was completed, the reaction was adjusted to pH 2-3 with sodium carbonate, and the reaction was terminated with no free 1-amino-8-naphthol-3,6-disulfonic acid. b) Second condensation reaction Weigh 1.21 parts of N-ethylaniline was added to the first condensation reaction solution, while warming to 35 ~ 40 ,Sodium carbonate to adjust the pH to 5 ~ 5.5,Maintain the temperature and pH value of about 4 hours, HPLC detection to N-ethyl aniline disappear is the end of the reaction. c) Cyanuric chloride and sodium 2,4-diaminobenzene sulfonate condensation, diazotization Weigh 1.88 parts cyanuric chloride, add 18 parts of water, crushed ice,Beating at 0 ~ 5 for 30 minutes.Meanwhile, 2.1 parts of sodium 2,4-diaminobenzenesulfonate was weighed out in 15 parts of water to dissolve completely.After the beating is finished, the above solution of 2,4-diaminobenzenesulfonic acid is added to the cyanuric chloride suspension.In this condition,To free 2,4-diaminobenzenesulfonic acid is the end point,Condensation of cyanuric chloride and sodium 2,4-diaminobenzenesulfonate. Measure 2.7 parts of 30% hydrochloric acid,Was added to the above cyanuric chloride and sodium 2,4-diaminobenzene sulfonate condensate,At 0 to 5 ° C, 0.7 part of sodium nitrite was added,Under this condition to maintain a slight excess of hydrochloric acid and nitrite,Reaction for 2 hours, with a small amount of sulfamic acid to eliminate excessive nitrous acid,Cyanuric chloride and 2,4-diamino benzene sulfonate condensate diazonium salt. e) Condensation 2.81 parts of 2 - [(4-aminophenyl) sulfonyl] ethyl hydrogen sulfate was weighed out,Added to the above d) conjugate,Heated to 40 ~ 50 ,With sodium carbonate to adjust the pH of the reaction medium = 6 ~ 7,To detect two components disappear as the reaction end.Then add the stabilizer, direct spray drying, the product was red dye 17 parts.

Reference： [1]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - CN104710835, 2017, B Location in patent: Paragraph 0045; 0046; 0047; 0048-0061; 0062-0064

65
[ CAS Unavailable ]
[ 90-20-0 ]

Yield	Reaction Conditions	Operation in experiment
65.86%	With sulfuric acid; water at 90℃; for 5h;	1.4 Example 1 Step 4: Hydrolysis The solution obtained in the previous step was adjusted to a sulfuric acid concentration of 50% by weight with concentrated sulfuric acid, and the reaction was heated to 90° C. with stirring. After 5 hours of reaction, the progress of the reaction was monitored with a liquid phase until the reaction system stopped without raw materials, and the temperature was reduced to 5° C. H acid.Product yield: 65.86%.

Reference： [1]Current Patent Assignee: BEIJING RISUN TECH - CN107759496, 2018, A Location in patent: Paragraph 0025; 0032-0033; 0042-0043; 0051-0052

66
[ 108-77-0 ]
[ 90-20-0 ]
[ CAS Unavailable ]
[ CAS Unavailable ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
86.4%	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 1-amino-2-sulfonic acid-4-(3-amino-2,4,6-trimethyl-5-sulfoamidophenyl)anthraquinone monosodium salt In water at 0 - 5℃; for 4h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water at 28 - 35℃; Stage #3: sodium 7-aminonaphthalene-1,3,6-trisulphonate Further stages;	3 preparation of 1-amino-4-((3-amino-2,4,6-trimethyl-5-sulfophenyl)amino)anthraquinone-2-sulfonate sodium salt into a 500mL three-necked flask add 200mL water, add 0.11 mol of M acid, stir and heat up at 50-55°C, adjust the pH at 7-8 with 30% liquid caustic soda, the material is completely dissolved. Into this material again add 0.10mol of Bromamine acid, use baking soda to adjust the pH at about 8-9, add 0.5g of cuprous chloride as a catalyst, after that in about 1.5 hours, the temperature rises at 75°C, insulation reaction for 20 h, detection endpoint (TLC, TLC), after that heat filter, cool, dry, and then obtained 49 color-base. [0052] (2) Preparation of a condensate: 18.6 g (0.lmol) of cyanuric chloride is formulated into a 20% mass aqueous suspension, beating 0.5h at 0 ~ 5 °C in ice water bath, obtained Beating a homogeneous cyanuric chloride suspension, in step (1) 52.61 g (0.099 mol) of 1-Amino-2-sulfonic acid-4-(3-amino-2, 4, 6-trimethyl-5-sodium sulfonate phenylamino)anthraquinone sodium salt is configured to a mass fraction of 15 % of water solution, adjust the pH at 5.8-6.5, solution as a clear blue solution, at 0-5°C condition within 1h it is added drop-wise to the cyanuric chloride suspension that is evenly beaten, after the addition is completed, the temperature is maintained at 5°C, pH value is 4~4.5 and carry on reaction for 3h, thin layer chromatography detects the end of a reaction, and then obtained a condensate liquid. [0053] (3) Preparation of a Di-condensate 33.42 g (0.098 mol) of 1-amino-8-naphthol-3, 6-disulfonic acid dry powder is added to the condensate liquid of step (2), adjust the pH at 3.5 ~ 4.0, slowly warm up to 28 ~ 35 °C, maintain this pH and temperature conditions and carry on reaction for 4-6 hours, thin layer chromatography for the end of the Di-condensate reaction, obtained Di-condensate liquid. [0054] (4) Preparation of Diazonium salt: 37.61g (0.098mol) of Sodium 2-Naphthylamine-3,6,8-trisulfonic acid is formulated as a 20% by mass aqueous solution, stir for 0.5 hour until the mixture is evenly cooled at 0 ~ 5 °C, a one-time solution of 9.8g (0.098mol) of a 37.5% hydrochloric acid solution is added, stir 10min, after that a solution of 6.969 g (0.101 mol) of sodium nitrite is slowly added drop-wise within 1h, after the drop is complete, the reaction is continued for 1.5 hours, after the reaction is completed, sulfamic acid is used to eliminate excess nitrous acid, and obtained Diazonium salt. [0055] (5) Coupling reaction: in step (3) the Di-condensate liquid cool down at 0 ~ 5 °C, the diazonium salt in step (4) is added to the Di-condensate solution at once, slowly adjust the pH at 6-6.5 with saturated NaHC03 solution, at this pH and under 0 ~ 5 °C conditions maintain for 5-10min, after that, continue the reaction for 3 hours at room temperature, after the reaction is completed, add about 10% sodium chloride solution, salting out, filtering, drying at a temperature of 65°C, obtained purple reactive dyes, yield is 88.20%, the maximum absorption wavelength of this dye is 532nm, (as shown in example 3 in Fig.1), Molar extinction coefficient is 15180L/mol*cm.

Reference： [1]Current Patent Assignee: DONGHUA UNIVERSITY - CN107722667, 2018, A Location in patent: Paragraph 0050-0055

67
[ 108-77-0 ]
[ 88-21-1 ]
[ 90-20-0 ]
1-amino-2-sulfonic acid-4-(3-amino-2,4,6-trimethyl-5-sulfoamidophenyl)anthraquinone monosodium salt [ No CAS ]
C₄₂H₂₇ClN₉O₁₈S₅^(5-)*5Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84.23%		preparation of 1-Amino-2-sulfonic acid-4-(3-amino-2, 4, 6-trimethyl-5-sodium sulfonate phenylamino) anthraquinone sodium salt 49 color-Base: into a 500mL three-necked flask add 200mL water, add 0.11 mol of M acid, stir and heat up at 50-55C, adjust the pH at 7-8 with 30% liquid caustic soda, the material is completely dissolved. Into this material again add 0.10mol of Bromamine acid, use baking soda to adjust the pH at about 8-9, add 0.5g of cuprous chloride as a catalyst, after that in about 1.5 hours, the temperature rises at 75C, insulation reaction for 20 h, detection endpoint (TLC, TLC), after that heat filter, cool, dry, and then obtained 49 color-base. [0038] (2) Preparation of a condensate: 18.6 g (0.lmol) of cyanuric chloride is formulated into a 20% mass aqueous suspension, beating 0.5h at 0 ~ 5 C in ice water bath, obtained Beating a homogeneous cyanuric chloride suspension, in step (1) 52.61 g (0.099 mol) of 1-Amino-2-sulfonic acid-4-(3-amino-2, 4, 6-trimethyl-5-sodium sulfonate phenylamino)anthraquinone sodium salt is configured to a mass fraction of 15 % of water solution, adjust the pH at 5.8-6.5, solution as a clear blue solution, at 0-5C condition within 1h it is added drop-wise to the cyanuric chloride suspension that is evenly beaten, after the addition is completed, the temperature is maintained at 5C, pH value is 4~4.5 and carry on reaction for 3h, thin layer chromatography detects the end of a reaction, and then obtained a condensate liquid. [0039] (3) Preparation of a Di-condensate 33.42 g (0.098 mol) of 1-amino-8-naphthol-3, 6-disulfonic acid dry powder is added to the condensate liquid of step (2), adjust the pH at 3.5 ~ 4.0, slowly warm up to 28 ~ 35 C, maintain this pH and temperature conditions and carry on reaction for 4-6 hours, thin layer chromatography for the end of the Di-condensate reaction, obtained Di-condensate liquid. [0040] (4) Preparation of Diazonium salt: 16.95 g (0.098mol) of orthanilic acid is formulated as a 20% by mass aqueous solution, stir for 0.5 hour until the mixture is evenly cooled at 0 ~ 5 C, a one-time solution of 9.8g (0.098mol) of a 37.5% hydrochloric acid solution is added, stir 10min, after that a solution of 6.969 g (0.101 mol) of sodium nitrite is slowly added drop-wise within 1h, after the drop is complete, the reaction is continued for 1.5 hours, after the reaction is completed, sulfamic acid is used to eliminate excess nitrous acid, and obtained Diazonium salt. [0041] (5) Coupling reaction: in step (3) the Di-condensate liquid cool down at 0 ~ 5 C, the diazonium salt in step (4) is added to the Di-condensate solution at once, slowly adjust the pH at 6-6.5 with saturated NaHC03 solution, at this pH and under 0 ~ 5 C conditions maintain for 5-10min, after that, continue the reaction for 3 hours at room temperature, after the reaction is completed, add about 10% sodium chloride solution, salting out, filtering, drying at a temperature of 65C, obtained purple reactive dyes, yield is 84.23%, the maximum absorption wavelength of this dye is 524nm, (as shown in example 1 in Fig.1), Molar extinction coefficient is 14460L/mol*cm.

Reference： [1]Patent: CN107722667,2018,A .Location in patent: Paragraph 0034-0041

68
[ 108-77-0 ]
[ 90-20-0 ]
[ CAS Unavailable ]
[ CAS Unavailable ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
86.4%	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 1-amino-2-sulfonic acid-4-(3-amino-2,4,6-trimethyl-5-sulfoamidophenyl)anthraquinone monosodium salt In water at 0 - 5℃; for 4h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid In water at 28 - 35℃; Stage #3: sodium 3‐aminonaphthalene‐1,5‐disulfonate Further stages;	2 preparation of 1-amino-4-((3-amino-2,4,6-trimethyl-5-sulfophenyl)amino)anthraquinone-2-sulfonate sodium salt base was prepared by adding 200 mL of water to a 500 mL three-necked flask, adding 0.11 mol of M acid, stirring and heating to 50-55° C., adjusting the pH to 7-8 with 30% liquid caustic soda, and the material was completely dissolved. Add 0.10 mol of bromine to the material, adjust the pH to approximately 8-9 with baking soda, add 0.5 g of cuprous chloride as a catalyst, and then heat up to 75°C for about 1.5 h.At 20 h, the end point was detected (TLC, thin layer chromatography), followed by hot filtration, cooling, and drying to give 49 color.(2) Preparation of a Condensate: 18.6 g (0.1 mol) of cyanuric chloride was placed into an aqueous suspension with a mass fraction of 20%, and beaten in an ice-water bath at 0-5° C. for 0.5 h to obtain uniform pulping. Cyanuric chloride suspension, step (1)52.61g (0.099mol) 1-Amino-2-sulfonic acid-4-(3-amino-2,4,6-trimethyl-5-sulfonic acid sodium phenylamino) phosphonium sodium salt was formulated as a mass fraction 15% aqueous solution, adjust the pH value of 5.8 to 6.5, the solution is a blue clear solution, and it is added dropwise to the beryllium cyanurate suspension that is uniformly beaten at 0-5°C for 1 hour, and the temperature is kept after the dropwise addition is completed. 5 °C, pH value of 4 ~ 4.5 reaction 3h, thin layer chromatography to detect the end of a contraction reaction, to obtain a liquid.Preparation of a bicondensate: Add 33.42 g (0.098 mol) of 1-amino-8-naphthol-3,6-disulfonic acid dry powder to a solution of step (2) and adjust the pH to From 3.5 to 4.0, the temperature was slowly increased to 28-35°C. The pH and temperature conditions were maintained for 4-6 h. Thin-layer chromatography was used to measure the endpoint of the 2-shrink reaction to obtain a double-cone.4) Preparation of diazonium salt:29.72 g (0.098 mol) of sodium 2-naphthylamine-4,8-disulfonate is formulated as a 20% by mass aqueous solution.Stir for 0.5 hour until the mixture is uniformly cooled to 0-5°C.9.8g (0.098mol) of 37.5% hydrochloric acid solution was added in one portion, stirred for 10 minutes, and then 6.969g (0.101mol) of aqueous sodium nitrite was slowly added dropwise over 1 hour. After the addition, the reaction was continued for 1.5 hours. After the reaction, the reaction was complete. Excess nitrous acid is eliminated with sulfamic acid to give a diazonium salt.(5) Coupling reaction: cool down the dilute solution in step (3) to 0-5°C, add the diazonium salt in step (4) to the dilute solution in one go, and slowly adjust the pH value with saturated NaHCO3 solution. 66.5, maintain the pH value and 05°C for 5-10min, then continue the reaction at room temperature for 3 hours. After the reaction is finished, add about 10% sodium chloride solution, salt out, filter at 65°C. Dry at a temperature of °C to obtain a purple reactive dye with a yield of 86.40%. The maximum absorption wavelength of the dye isAt 536 nm (Example 2 in Figure 1), the molar extinction coefficient was 15010 L/mol*cm.

Reference： [1]Current Patent Assignee: DONGHUA UNIVERSITY - CN107722667, 2018, A Location in patent: Paragraph 0042-0049

69
[ 90-20-0 ]
[ 98-42-0 ]
C₁₇H₁₃N₃O₁₁S₃^(2-)*2Na⁽¹⁺⁾ [ No CAS ]

Reference： [1]Journal of the Chemical Society of Pakistan,2018,vol. 40,p. 283 - 287

70
[ 108-77-0 ]
[ 90-20-0 ]
[ 25781-90-2 ]
4-chloro-3-(ethenesulfonyl)aniline [ No CAS ]
2Na⁽¹⁺⁾*C₂₉H₁₉Cl₂N₇O₁₁S₄^(2-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 1-amino-4-vinylsulphonylbenzene With sodium carbonate In water Cooling with ice; Stage #2: With sodium hydrogencarbonate In water Heating; Stage #3: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid; 4-chloro-3-(ethenesulfonyl)aniline Further stages;	1 The preparation method of the red reactive dye comprises the following steps: (a). Para-ester dissolution: 28.9 g of 100% para-ester was added to a beaker, beaten with 200 ml of water, and adjusted to pH=5-5.5 with a 15% aqueous sodium carbonate solution to completely dissolve the para-ester, and set aside. (b). One-step condensation reaction: 200g of crushed ice, 100% of cyanuric chloride and 3 drops of ice-milling aid were added to another beaker, stirred for 3 minutes, and the step (a) solution was added dropwise for 5-10 minutes. After that, the industrial sodium hydrogencarbonate adjusts the reaction pH to 2.5 to 3.0, and the heat retention reaction for 4 to 6 hours, and the thin layer chromatography detects the complete reaction of the para-ester to the end point. Get a shrink; spare. (c). The two-step condensation reaction: adding 33.07 g of a 100% amount of H acid powder to the reaction liquid of the step (b), adjusting the pH of the industrial sodium carbonate to 4.5 to 5, and stirring the reaction for 5 to 6 hours under the condition of raising the temperature to 20 to 30 ° C; A shrinkage of the TLC plate completely reacted to the end point. Get two things; spare. (d). Diazotization: Add 100% of 4-chloro-3-(β-hydroxyethylsulfone sulfate) aniline 31.55g to another beaker, add 200g of crushed ice, and cool down to 0~5 °C, add Industrial hydrochloric acid 15.8g, rapid addition of industrial sodium nitrite 7.33g diazotization, keeping the starch potassium iodide test paper slightly blue, stirring reaction for 2 hours, after the reaction is completed, add sulfamic acid to eliminate unreacted nitrous acid, and set aside. (e) Coupling: the diazonium salt prepared in the step (d) is added dropwise to the condensate prepared in the step (c), and the 15% sodium carbonate solution is controlled to have a pH of 6.0 to 6.5, thin layer chromatography. Analysis of the dimer is completely coupled to the end point, resulting in a conjugate; (f) Alkali treatment: The reaction liquid of the step (e) is heated to 50 to 55 ° C, the industrial sodium carbonate is adjusted to pH = 9 to 9.5, and the reaction is stirred for 4 to 5 hours. The complete reaction of the conjugate in the step (e) of the thin layer chromatography analysis is the end point, and the pH of the industrial hydrochloric acid is adjusted to 6 to 6.5. The finished dye is obtained by salting out, filtering, beating and spray drying.

Reference： [1]Current Patent Assignee: TIANJIN DEK CHEMICAL CO., LTD. - CN104277490, 2019, B Location in patent: Paragraph 0016-0025

71
[ 108-77-0 ]
[ 90-20-0 ]
[ 25781-90-2 ]
4-chloro-3-(β-hydroxyethylsulfonyl)aniline [ No CAS ]
2Na⁽¹⁺⁾*C₂₉H₂₁Cl₂N₇O₁₂S₄^(2-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 1,3,5-trichloro-2,4,6-triazine; 1-amino-4-vinylsulphonylbenzene With sodium carbonate In water Cooling with ice; Stage #2: With sodium hydrogencarbonate In water Heating; Stage #3: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid; 4-chloro-3-(β-hydroxyethylsulfonyl)aniline Further stages;	2 The preparation method of the red reactive dye comprises the following steps: (a). Para-ester dissolution: 28.9 g of 100% para-ester was added to a beaker, beaten with 200 ml of water, and adjusted to pH=5-5.5 with a 15% aqueous sodium carbonate solution to completely dissolve the para-ester, and set aside. (b). One-step condensation reaction: 200g of crushed ice, 100% of cyanuric chloride and 3 drops of ice-milling aid were added to another beaker, stirred for 3 minutes, and the step (a) solution was added dropwise for 5-10 minutes. After that, the industrial sodium hydrogencarbonate adjusts the reaction pH to 2.5 to 3.0, and the heat retention reaction for 4 to 6 hours, and the thin layer chromatography detects the complete reaction of the para-ester to the end point. Get a shrink; spare. (c). The two-step condensation reaction: adding 33.07 g of a 100% amount of H acid powder to the reaction liquid of the step (b), adjusting the pH of the industrial sodium carbonate to 4.5 to 5, and stirring the reaction for 5 to 6 hours under the condition of raising the temperature to 20 to 30 ° C; A shrinkage of the TLC plate completely reacted to the end point. Get two things; spare. (d). Diazotization: Add 100% of 4-chloro-3-(β-hydroxyethylsulfone sulfate) aniline 31.55g to another beaker, add 200g of crushed ice, and cool down to 0~5 °C, add Industrial hydrochloric acid 15.8g, rapid addition of industrial sodium nitrite 7.33g diazotization, keeping the starch potassium iodide test paper slightly blue, stirring reaction for 2 hours, after the reaction is completed, add sulfamic acid to eliminate unreacted nitrous acid, and set aside. (e) Coupling: the diazonium salt prepared in the step (d) is added dropwise to the condensate prepared in the step (c), and the 15% sodium carbonate solution is controlled to have a pH of 6.0 to 6.5, thin layer chromatography. Analysis of the dimer is completely coupled to the end point, resulting in a conjugate; (f) Alkali treatment: The reaction liquid of the step (e) is heated to 50 to 55 ° C, the industrial sodium carbonate is adjusted to pH = 9 to 9.5, and the reaction is stirred for 4 to 5 hours. The complete reaction of the conjugate in the step (e) of the thin layer chromatography analysis is the end point, and the pH of the industrial hydrochloric acid is adjusted to 6 to 6.5. The finished dye is obtained by salting out, filtering, beating and spray drying.

Reference： [1]Current Patent Assignee: TIANJIN DEK CHEMICAL CO., LTD. - CN104277490, 2019, B Location in patent: Paragraph 0028-0037

72
[ 58557-61-2 ]
[ 90-20-0 ]
[ 3577-63-7 ]
C₂₆H₁₅Br₂N₆O₁₆S₄^(5-)*5Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
522.63 kg	Stage #1: 2-amino-5-sulfo-benzoic acid With hydrogenchloride; sodium nitrite In water at 0 - 10℃; for 2h; Large scale; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With sodium hydrogencarbonate; sodium carbonate In water at 10 - 20℃; for 2h; Large scale; Stage #3: C₉H₉Br₂N₂O₄S^(1-)*Na⁽¹⁺⁾ Large scale; Further stages;	2 A reactive dye for navy blue hair having the following structural formula: The preparation method of the reactive dye for the navy blue hair comprises the following steps:a, H acid dissolution: add 800 liters of bottom water to the reaction tank, then add 200.00 kg of H acid, stir evenly, adjust the pH = 6-8 with sodium carbonate to obtain H acid solution, set aside;b,Diazotization of 2-amino-5-sulfonic acid benzoic acid:500 liters of bottom water and 127.42 Kg of 2-amino-5-sulfonic acid benzoic acid were added to the reaction tank, and the mixture was uniformly stirred. 300 kg of crushed ice, 85.57 liters of 30% hydrochloric acid solution and 41.07 Kg of sodium nitrite were added. At 0-10 ° C, pH < 2, the reaction for 2 hours, the excess nitrous acid was eliminated with sulfamic acid to obtain a solution of 2-amino-5-sulfonic acid diazonium salt, which was to be coupled.c, a coupling reaction:The H acid solution was added dropwise to a solution of 2-amino-5-sulfonic acid benzoic acid diazonium salt, and the dropping process was T=10-20 ° C, and the pH was adjusted to 2.5-3.5 with baking soda. After the dropwise addition, the reaction was carried out for 2 hours to obtain a coupling solution. The second coupling reaction is to be carried out.d, di-diactivation diazotization reaction:Add 500 liters of bottom water to the reaction tank, and 234.46 Kg of the second activated material, stir evenly, add 300 Kg of crushed ice, 85.53 liters of 30% hydrochloric acid solution and 41.81 Kg of sodium nitrite. At 0-10 ° C, pH < 2, the reaction for 2 hours, the excess nitrous acid was eliminated with sulfamic acid to obtain a solution of the di-activated diazonium salt to be coupled.e, secondary coupling reactionThe m-diactivator diazonium salt solution was added dropwise to the primary coupling solution, and the dropping process was T=20-30 ° C, and the pH was adjusted to 6-8 with soda ash. After the dropwise addition, the reaction was carried out for 2 hours to obtain a secondary coupling liquid.f, removing insoluble matter: the e-step secondary coupling liquid is added to the solid-liquid separator, separating, removing the waste residue, collecting the filtrate in the storage tankin.g, adjust the color and intensity:The material obtained in step f is dyed, and then the color light and intensity are adjusted according to the dyeing result; the coloring liquid;h, dry:The color liquid of the g step was added to the liquid preheater, the inlet temperature was adjusted to 210 ° C, and spray drying was carried out at an outlet temperature of 95-100 ° C to obtain 522.63 Kg of the dye compound.

Reference： [1]Current Patent Assignee: TIANJIN DEK CHEMICAL CO., LTD. - CN109233331, 2019, A Location in patent: Paragraph 0062-0080

73
[ 90-20-0 ]
[ 39638-06-7 ]
[ 2815314-40-8 ]

Yield	Reaction Conditions	Operation in experiment
81%	Stage #1: 3-aminobenzoyl fluoride With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With ammonium chloride In water at 0 - 5℃; for 0.666667h;	8 first step, diazotization: Take 139g of dry 3-aminobenzoyl fluoride as raw material.Add to 1L of alcohol, then add 1L of water to dilute,Add 40 mL of concentrated hydrochloric acid (36%),Add a slight excess of 23% NaNO2 solution at 0 °C.Diazotization reaction at 0-5 ° C,The reaction endpoint was determined using a starch KI test paper.The second step, a coupling:Taking the equimolar ratio of 3-aminobenzoyl fluoride in the diazotization step, adjusting the pH of the medium to a weak acidity of 5.5-6.5 with NH4Cl, and slowly adding the diazotized solution obtained in the first step at 0 ° C,The reaction was carried out at 0-5 ° C for 40 min.The third step, the second coupling:According to the same method, the reaction liquid of the previous step is added to a medium which adjusts the pH of the medium to a weakly alkaline 7.5-8.5 with Na2CO3.Add the same amount of 3-aminobenzoyl fluoride as in the second step (primary coupling).The reaction was carried out at 0-5 ° C for 40 min. After the reaction is finished, the salting out is filtered.The solid was dried below 40 ° C to give a dye yield of 81%.

Reference： [1]Current Patent Assignee: NANJING FORESTRY UNIVERSITY - CN109971209, 2019, A Location in patent: Paragraph 0093-0099

74
[ 2494-89-5 ]
[ 108-77-0 ]
[ 88-21-1 ]
[ 87-02-5 ]
[ 90-20-0 ]
[ 88-63-1 ]
C₄₃H₂₇ClN₁₂O₂₃S₇^(6-)*6Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
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).

Reference： [1]Patent: CN110903678,2020,A .Location in patent: Paragraph 0050-0060

75
[ 556-18-3 ]
[ 90-20-0 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
19%	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: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic 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

Reference： [1]Adeyinka, Adedapo S.; Agwamba, Ernest C.; Benjamin, Innocent; Louis, Hitler; Owen, Aniekan E.; Udoikono, Akaninyene D.; Unimuke, Tomsmith O. [Journal of Molecular Structure, 2022, vol. 1264]

76
[ 59-67-6 ]
[ 108-77-0 ]
[ 90-20-0 ]
[ 117-61-3 ]
[ 88-63-1 ]
[ 146764-47-8 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
76%	Stage #1: 4,4'-diaminobiphenyl-2,2'-disulfonic acid With hydrogenchloride; NaNO₂ In lithium hydroxide monohydrate at 0 - 5℃; for 1.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With Sodium hydrogenocarbonate In lithium hydroxide monohydrate at 10 - 15℃; for 6h; Stage #3: pyridine-3-carboxylic acid; 1,3,5-trichloro-2,4,6-triazine; 2,4-Diaminobenzenesulfonic acid; Sulfanilic acid Further stages;	2 (1) stirring will be added in water and crushed ice, keeping temperature is 05 , adding sodium nitrite to react 1.5 hours after adding hydrochloric acid to obtain the first mixed solution, wherein, the mol ratio of hydrochloric acid and sodium nitrite is 1: 1.0:1.01, hydrochloric acid selects the hydrochloric acid of concentration 30%;(2) adding sodium bicarbonate to the first mixed solution obtained in step (1) to adjust the pH to 2.53.0, and reacting at 1015° C. for 6 hours to obtain the second mixed solution, wherein the molar ratio of is 1:2.02;(3) will be added into crushed ice and water and stirred, then add sodium bicarbonate to adjust pH value to 3.03.5, react 3 hours at 510 to obtain the third mixed solution, wherein, with the molar ratio of charging as 1:0.99;(4) adding in the third mixed solution obtained in step (3), adding sodium bicarbonate to adjust the pH value to 5.56.0, and reacting at 2025 for 6 hours to obtain the fourth mixed solution, wherein, the feed intake of The molar ratio is 1:0.96;(5) hydrochloric acid and sodium nitrite are added in the 4th mixed solution that step (4) obtains, react 1.5 hours at 0-5 and obtain the 5th mixed solution, wherein, the molar ratio of HCl, sodium nitrite is 1 :2.0:1.0;(6) adding the second mixed solution obtained in step (2) to the fifth mixed solution obtained in step (5), adding sodium bicarbonate to adjust the pH value to 6.0-6.5, and reacting at 10-15 ° C for 4 hours to obtain the first mixed solution Six mixed solutions, wherein, the second mixed solution and the fifth mixed solution feeding are 1:1.03 according to the molar ratio of feeding;(7) will be added in the sixth mixed solution obtained in step (6), add sodium carbonate to adjust the pH value to 5.56.0, and react at 7580 for 6 hours to obtain the seventh mixed solution, wherein, the molar ratio of feeding to is 1:2.5;(8) drying the seventh mixed solution obtained in step (7) to obtain the product reactive dye blue.

Reference： [1]Current Patent Assignee: SUZHOU AOYUANSHENG NEW MATERIAL TECH - CN112175413, 2022, B Location in patent: Paragraph 0080-0092

77
[ 2494-89-5 ]
[ 59-67-6 ]
[ 108-77-0 ]
[ 90-20-0 ]
[ 88-63-1 ]
[ 81-11-8 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
78%	Stage #1: 4,4′-diaminostilbene-2,2′-disulfonic acid With hydrogenchloride; NaNO₂ In lithium hydroxide monohydrate at 0 - 5℃; for 1.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With Sodium hydrogenocarbonate In lithium hydroxide monohydrate at 10 - 15℃; for 5h; Stage #3: 2-(4-aminophenylsulfonyl)-ethylhydrogen sulfate; pyridine-3-carboxylic acid; 1,3,5-trichloro-2,4,6-triazine; 2,4-Diaminobenzenesulfonic acid Further stages;	3 (1) stirring will be added in water and crushed ice, maintaining temperature is 05 , adding sodium nitrite to react 1.5 hours after adding hydrochloric acid to obtain the first mixed solution, wherein, the molar ratio of HCl and sodium nitrite is 1 : 1.0: 1.01, the hydrochloric acid selects the hydrochloric acid of concentration 30% for use;(2) adding sodium bicarbonate to the first mixed solution obtained in step (1) to adjust the pH value to 2.53.0, and reacting at 1015° C. for 5 hours to obtain the second mixed solution, wherein the molar ratio of is 1:2.02;(3) will be added into crushed ice and water and stirred, then add sodium bicarbonate to adjust pH value to 2.53.0, react 4 hours at 510 DEG C to obtain the third mixed solution, wherein, the molar ratio of feeding with is 1:1.01;(4) adding in the third mixed solution obtained in step (3), adding sodium bicarbonate to adjust the pH value to 5.56.0, and reacting at 2025 for 5 hours to obtain the fourth mixed solution, wherein, the feed intake of The molar ratio is 1:0.96;(5) hydrochloric acid and sodium nitrite are added in the 4th mixed solution that step (4) obtains, react 1.5 hours at 0-5 and obtain the 5th mixed solution, wherein, the mol ratio of HCl and sodium nitrite is 1: 2.0:1.0;(6) adding the second mixed solution obtained in step (2) to the fifth mixed solution obtained in step (5), adding sodium bicarbonate to adjust the pH value to 6.0-6.5, and reacting at 10-15 ° C for 3 hours to obtain the first mixed solution Six mixed solutions, wherein, the second mixed solution and the fifth mixed solution feeding are 1:1.03 according to the molar ratio of feeding;(7) will be added in the sixth mixed solution obtained in step (6), add sodium carbonate to adjust the pH value to 5.56.0, and react at 7580 for 6 hours to obtain the seventh mixed solution, wherein, the molar ratio of feeding to is 1:2.5;(8) drying the seventh mixed solution obtained in step (7) to obtain the product reactive dye blue.

Reference： [1]Current Patent Assignee: SUZHOU AOYUANSHENG NEW MATERIAL TECH - CN112175413, 2022, B Location in patent: Paragraph 0093-0105

78
[ 59-67-6 ]
[ 108-77-0 ]
[ 90-20-0 ]
[ 88-63-1 ]
[ 121-47-1 ]
[ 81-11-8 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: 4,4′-diaminostilbene-2,2′-disulfonic acid With hydrogenchloride; NaNO₂ In lithium hydroxide monohydrate at 0 - 5℃; for 1.5h; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With Sodium hydrogenocarbonate In lithium hydroxide monohydrate at 10 - 15℃; for 6h; Stage #3: pyridine-3-carboxylic acid; 1,3,5-trichloro-2,4,6-triazine; 2,4-Diaminobenzenesulfonic acid; 3-aminobenzenesulfonic acid Further stages;	4 (1) It will be added to water and crushed ice to stir, maintain the temperature of 0 ~ 5 °C, add hydrochloric acid after adding sodium nitrite to react for 1.5 hours to obtain the first mixed solution, wherein the molar ratio of HCl and sodium nitrite is 1:1.0:1.01, and the hydrochloric acid is selected at a concentration of 30%;(2) To step (1) to the first mixed solution obtained by adding sodium bicarbonate to adjust the pH value to 2.5 ~ 3.0, reaction at 10 ~ 15 °C for 6 hours to obtain a second mixed solution, wherein the molar ratio of the feeding with the feeding is 1:2.02;(3) Will be added to crushed ice and water stirring, will be added, and then add sodium bicarbonate to adjust the pH value to 2.5 ~ 3.0, at 0 ~ 5 °C reaction for 3 hours to obtain a third mixed solution, wherein, with the dosing molar ratio of 1:0.99;(4) The third mixture obtained in step (3) was added, and then sodium bicarbonate was added to adjust the pH value to 5.5 to 6.0, and the fourth mixed solution was obtained by reacting at 20 to 25 °C for 5 hours, wherein the molar ratio of the feeding with the feeding was 1:0.96;(5) The hydrochloric acid and sodium nitrite were added to the fourth mixed solution obtained in step (4), and the fifth mixed solution was obtained by reacting at 0-5 °C for 1.5 hours, wherein the molar ratio of HCl and sodium nitrite was 1:2.0:1.0;(6) Step (2) to obtain the second mixture added to step (5) to obtain the fifth mixture, add sodium bicarbonate to adjust the pH value to 6.0 ~ 6.5, reaction at 10 ~ 15 °C for 3 hours to obtain the sixth mixed solution, wherein the second mix and the fifth mixture are fed in accordance with the molar ratio of 1:1.03;(7) The sixth mixture obtained by adding step (6), adding sodium carbonate to adjust the pH value to 5.5 ~ 6.0, reaction at 75 ~ 80 ° C for 6 hours to obtain the seventh mixed solution, wherein, the molar ratio of the feeding with is 1:2.5;(8) The seventh mixture obtained in step (7) is dried to obtain the product reactive dye blue.

Reference： [1]Current Patent Assignee: SUZHOU AOYUANSHENG NEW MATERIAL TECH - CN112175413, 2022, B Location in patent: Paragraph 0106-0118

79
[ 59-67-6 ]
[ 108-77-0 ]
[ 88-21-1 ]
[ 90-20-0 ]
[ 117-61-3 ]
[ 88-63-1 ]
[ CAS Unavailable ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: 4,4'-diaminobiphenyl-2,2'-disulfonic acid With hydrogenchloride; NaNO₂ In lithium hydroxide monohydrate at 0 - 5℃; Stage #2: 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid With Sodium hydrogenocarbonate In lithium hydroxide monohydrate at 10 - 15℃; for 5.5h; Stage #3: pyridine-3-carboxylic acid; 1,3,5-trichloro-2,4,6-triazine; 2-amino-1-benzenesulfonic acid; 2,4-Diaminobenzenesulfonic acid Further stages;	1 (1) stirring will be added in water and crushed ice, maintaining temperature is 05 , adding sodium nitrite to react 1.5 hours after adding hydrochloric acid to obtain the first mixed solution, wherein, the molar ratio of HCl and sodium nitrite is 1 : 1.0: 1.01, the hydrochloric acid selects the hydrochloric acid of concentration 30% for use;(2) adding sodium bicarbonate to the first mixed solution obtained in step (1) to adjust the pH value to 2.53.0, and reacting at 1015° C. for 5.5 hours to obtain the second mixed solution, wherein, the molar ratio of feeding to is 1:2.02;(3) will be added into crushed ice and water and stirred, then add sodium bicarbonate to adjust pH value to 3.03.5, react 3.5 hours at 510 to obtain the third mixed solution, wherein, the molar ratio of feeding with is 1:0.99;(4) adding in the third mixed solution obtained in step (3), adding sodium bicarbonate to adjust the pH value to 5.56.0, and reacting at 2025° C. for 5.5 hours to obtain the fourth mixed solution, wherein the feeding of the The molar ratio is 1:0.96;(5) hydrochloric acid and sodium nitrite are added in the 4th mixed solution that step (4) obtains, react 1.5 hours at 0-5 and obtain the 5th mixed solution, wherein, the mol ratio of HCl and sodium nitrite is 1: 2.0:1.0;(6) adding the second mixed solution obtained in step (2) to the fifth mixed solution obtained in step (5), adding sodium bicarbonate to adjust the pH value to 6.0-6.5, and reacting at 10-15 ° C for 3.5 hours to obtain the first mixed solution Six mixed solutions, the second mixed solution and the fifth mixed solution feeding are 1:1.03 according to the molar ratio of feeding;(7) will be added in the sixth mixed solution obtained in step (6), add sodium carbonate to adjust the pH value to 5.56.0, react at 7580 for 7 hours to obtain the seventh mixed solution, wherein, with the molar ratio of feeding is 1:2.5;(8) drying the seventh mixed solution obtained in step (7) to obtain the product reactive dye blue.

Reference： [1]Current Patent Assignee: SUZHOU AOYUANSHENG NEW MATERIAL TECH - CN112175413, 2022, B Location in patent: Paragraph 0067-0079

CAS No. :	90-20-0	MDL No. :	MFCD00035728
Formula :	C₁₀H₉NO₇S₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	APRRQJCCBSJQOQ-UHFFFAOYSA-N
M.W :	319.31	Pubchem ID :	7009
Synonyms :

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:

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
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

[ CAS No. 90-20-0 ] {[proInfo.proName]}

Quality Control of [ 90-20-0 ]

Related Doc. of [ 90-20-0 ]

Product Details of [ 90-20-0 ]

Safety of [ 90-20-0 ]

Application In Synthesis of [ 90-20-0 ]

[ 90-20-0 ] Synthesis Path-Upstream 1~1

[ 90-20-0 ] Synthesis Path-Downstream 1~79

Precautionary Statements-General

Prevention

Response

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Disposal

Physical hazards

Health hazards

Environmental hazards

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