Name: 98-33-9|4-Amino-3-methylbenzenesulfonic acid|98%
Brand: Ambeed
SKU: A841581
Price: 6.0 USD
Availability: InStock
Rating: 93 (30 reviews)

1
[ 88-72-2 ]
[ 98-33-9 ]
[ 95-53-4 ]

Yield	Reaction Conditions	Operation in experiment
	With water; sodium hydrogensulfite; sodium sulfite anschliessendes Erhitzen mit wss. Salzsaeure;

Reference： [1]Hunter; Sprung [Journal of the American Chemical Society, 1931, vol. 53, p. 1432,1435, 1440]

2
[ 617-07-2 ]
[ 98-33-9 ]

Yield	Reaction Conditions	Operation in experiment
	With sulfuric acid at 150℃;

Reference： [1]Cazeneuve; Moreau [Bulletin de la Societe Chimique de France, 1898, vol. <3> 19, p. 22]

3
[ 98-33-9 ]
[ 534-52-1 ]

Yield	Reaction Conditions	Operation in experiment
	Diazotization_.Erhitzen der Diazoniumverbindung mit verd. Salpetersaeure;
	With nitrogen oxides; water

Reference： [1]Nevile; Winther [Chemische Berichte, 1880, vol. 13, p. 1947][Journal of the Chemical Society, 1880, vol. 37, p. 631]
[2]Datta; Varma [Journal of the Indian Chemical Society, 1927, vol. 4, p. 323][Chemisches Zentralblatt, 1928, vol. 99, # I, p. 491]

4
[ 98-33-9 ]
[ 31208-76-1 ]

Yield	Reaction Conditions	Operation in experiment
	With nitric acid

Reference： [1]Zincke [Justus Liebigs Annalen der Chemie, 1905, vol. 339, p. 223,224]

5
[ 98-33-9 ]
[ 958990-53-9 ]

Yield	Reaction Conditions	Operation in experiment
	With bromine
40 g	With bromine In N,N-dimethyl-formamide at 20℃; for 4h;	2.1 1) 12mL concentrated sulfuric acid was added to 20mL aqueous solution, heated to 85 ,26g of 2-methylaniline (1) was slowly added and the mixture was heated and stirred for 15 minutes.Swirl to the water. Argon atmosphere, heated to 250 ° C, continued reaction 13h.After the temperature was lowered to room temperature, 200 mL of 10% aqueous sodium hydroxide solution was added,Heated to 90 , 30 minutes after the reaction was cooled and filtered.The filtrate was adjusted to pH = 1 with concentrated sulfuric acid to precipitate a large amount of solid, filtered,45 g of sulfonic acid methylaniline (2) were obtained;The resulting 45 g of product (2) was then treated with 500 mL of N, N-dimethylformamide solution,And 9.0 mL of liquid bromine (dissolved in 50 mL of N, N-dimethylformamide)The reaction was continued for 4 hours at room temperature to give 40 gBrilliant red solid bromosulfonylmethylaniline (3);Then 40 g of product (3) and 350 mL of 11% hydrochloric acid were added to a 500 mL single neck flask,Heated to reflux for 11 hours, cooled to room temperature,Neutralized to pH = 8 with saturated sodium carbonate, extracted with ethyl acetate,Dried over anhydrous sodium sulfate and filtered to give 13.8 gBromo-2-methylaniline (4) as a yellow solid

Reference： [1]Nevile; Winther [Chemische Berichte, 1880, vol. 13, p. 1947][Journal of the Chemical Society, 1880, vol. 37, p. 631]
[2]Current Patent Assignee: SHANGHAI LANGYI FUNCTIONAL MATERIALS CO LTD - CN106810506, 2017, A Location in patent: Paragraph 0045

6
[ 98-33-9 ]
[ 68189-38-8 ]

Yield	Reaction Conditions	Operation in experiment
	With sulfuric acid at 150 - 170℃;
	With chlorosulfonic acid at 160℃;

Reference： [1]Nevile; Winther [Chemische Berichte, 1882, vol. 15, p. 2992] Hasse [Justus Liebigs Annalen der Chemie, 1885, vol. 230, p. 287]
[2]Hasse [Justus Liebigs Annalen der Chemie, 1885, vol. 230, p. 287]

7
[ 98-33-9 ]
2-methyl-4,6,<i>N</i>-trinitro-aniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With nitric acid at -10 - 0℃;

Reference： [1]Zincke; Malkomesius [Justus Liebigs Annalen der Chemie, 1905, vol. 339, p. 221]

8
[ 98-33-9 ]
1-(2-methyl-4,6-dinitro-phenylazo)-[2]naphthylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With nitric acid man behandelt das erhaltene, nicht isolierte 3.5-Dinitro-toluol-diazoniumnitrat-(2) mit β-Naphthylamin;

Reference： [1]Zincke; Malkomesius [Justus Liebigs Annalen der Chemie, 1905, vol. 339, p. 223]

9
[ 98-33-9 ]
5-sulfo-toluene-2-diazonium-betaine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With mixture of gaseous nitrogen oxides; water

Reference： [1]Nevile; Winther [Chemische Berichte, 1880, vol. 13, p. 1947][Journal of the Chemical Society, 1880, vol. 37, p. 631]

10
2,2'-dimethyldianilinium sulfate [ No CAS ]
[ 618-03-1 ]
[ 98-33-9 ]

Yield	Reaction Conditions	Operation in experiment
	With sulfuric acid

Reference： [1]Claus; Immel [Justus Liebigs Annalen der Chemie, 1891, vol. 265, p. 77] Wynne; Bruce [Journal of the Chemical Society, 1898, vol. 73, p. 754]

11
[ 95-53-4 ]
[ 98-33-9 ]

Yield	Reaction Conditions	Operation in experiment
82%	With sulfuric acid for 0.0583333h; microwave irradiation;
	zur Ueberfuehrung;
	With sulfuric acid at 160 - 180℃;

	With sulfuric acid at 220 - 230℃;
	With sulfuric acid; iodine at 150℃;
	With sulfuric acid; iodine at 160 - 165℃;
	With sulfuric acid at 180℃;
	With sulfuric acid In thiophene	15 EXAMPLE 15 EXAMPLE 15 107.2 g (1.0 mol) of o-toluidine are dissolved in 500 ml of sulpholane, and 98.1 g (1.0 mol) of 100% strength H2 SO4 are added to the solution in the course of 8 minutes. During the dropwise addition the temperature increases to 77° C. At the start of the addition of sulphuric acid a suspension is produced, which has turned into a solution by the end of the addition. The reaction water is distilled off at a reaction temperature of 184°-200° C. in the course of 1.5 hours. The suspension is then cooled to 120° C. and its solids are filtered off with suction. The yield of 4-amino-3-methylbenzenesulphonic acid is 93.8%.
45 g	With sulfuric acid In water at 85 - 250℃; for 13h; Inert atmosphere;	2.1 1) 12mL concentrated sulfuric acid was added to 20mL aqueous solution, heated to 85 ,26g of 2-methylaniline (1) was slowly added and the mixture was heated and stirred for 15 minutes.Swirl to the water. Argon atmosphere, heated to 250 ° C, continued reaction 13h.After the temperature was lowered to room temperature, 200 mL of 10% aqueous sodium hydroxide solution was added,Heated to 90 , 30 minutes after the reaction was cooled and filtered.The filtrate was adjusted to pH = 1 with concentrated sulfuric acid to precipitate a large amount of solid, filtered,45 g of sulfonic acid methylaniline (2) were obtained;The resulting 45 g of product (2) was then treated with 500 mL of N, N-dimethylformamide solution,And 9.0 mL of liquid bromine (dissolved in 50 mL of N, N-dimethylformamide)The reaction was continued for 4 hours at room temperature to give 40 gBrilliant red solid bromosulfonylmethylaniline (3);Then 40 g of product (3) and 350 mL of 11% hydrochloric acid were added to a 500 mL single neck flask,Heated to reflux for 11 hours, cooled to room temperature,Neutralized to pH = 8 with saturated sodium carbonate, extracted with ethyl acetate,Dried over anhydrous sodium sulfate and filtered to give 13.8 gBromo-2-methylaniline (4) as a yellow solid

Reference： [1]Li, Hui-Zhang; Xiao, Li-Wei; Li, Hong-Ya; Wang, Kai-Fang; Li, Xu [Journal of Chemical Research - Part S, 2003, # 8, p. 493 - 494]
[2]Ray; Dey [Journal of the Chemical Society, 1920, vol. 117, p. 1407] Davies [Journal of the Chemical Society, 1922, vol. 121, p. 787] Schultz; Lucas [Journal of the American Chemical Society, 1927, vol. 49, p. 301]
[3]Claus; Immel [Justus Liebigs Annalen der Chemie, 1891, vol. 265, p. 77] Gerver [Justus Liebigs Annalen der Chemie, 1873, vol. 169, p. 374]
[4]Nevile; Winther [Chemische Berichte, 1880, vol. 13, p. 1947][Journal of the Chemical Society, 1880, vol. 37, p. 631]
[5]Ray; Dey [Journal of the Chemical Society, 1920, vol. 117, p. 1407]
[6]Davies [Journal of the Chemical Society, 1922, vol. 121, p. 787]
[7]Schultz; Lucas [Journal of the American Chemical Society, 1927, vol. 49, p. 301]
[8]Current Patent Assignee: BAYER AG; SIEMENS AG - US4447368, 1984, A
[9]Current Patent Assignee: SHANGHAI LANGYI FUNCTIONAL MATERIALS CO LTD - CN106810506, 2017, A Location in patent: Paragraph 0045

12
[ 98-33-9 ]
[ 121-60-8 ]
6-sulfanilylamino-toluene-3-sulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; sodium carbonate Erwaermen des Reaktionsprodukts mit wss. Natronlauge;

Reference： [1]Crossley; Northey; Hultquist [Journal of the American Chemical Society, 1938, vol. 60, p. 2217,2219]

13
[ 98-33-9 ]
[ 764-63-6 ]
sodium 4-(3-oxo-1-propenylamino)-3-methylbenzenesulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
43.2%	With sodium hydrogencarbonate In methanol; water

Reference： [1]Tamura, Shinzo; Todoriki, Reiko (nee Imamura) [Chemical and pharmaceutical bulletin, 1980, vol. 28, # 11, p. 3395 - 3400]

14
2,2'-dimethyldianilinium sulfate [ No CAS ]
[ 98-33-9 ]

Yield	Reaction Conditions	Operation in experiment
	at 275℃;

Reference： [1]Singh, Gurdip; Kapoor, Inder Pal Singh; Singh, Jyotsna [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1999, vol. 38, # 9, p. 1114 - 1117]

Yield	Reaction Conditions	Operation in experiment
	With ammonium sulfide

Yield	Reaction Conditions	Operation in experiment
	at 180 - 195℃;

Yield	Reaction Conditions	Operation in experiment
	at 200℃;

18
[ 98-33-9 ]
bromine water [ No CAS ]
[ 30273-41-7 ]
[ 958990-53-9 ]

Reference： [1]Justus Liebigs Annalen der Chemie,1891,vol. 265,p. 77

19
[ 110-86-1 ]
[ 98-33-9 ]
[ 108-24-7 ]
pyridinium 4-(acetylamino)-3-methylbenzenesulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	at 20℃; for 5h;	4.1.65. pyridine 4-acetamido-3-methylbenzenesulfonate(30a) Compound 29a (18.7 g,100 mmol)was dissolved in pyridine andslowly added acetic anhydride (16 mL, 0.162 mol) for 5h at roomtemperature. The solvent was evaporated under pressure, and theresidue was recrystallized with ethanol and dried in vacuum to agrayish white solid 30a. Yield: 88%; 1H NMR (400 MHz, DMSO-d6)d 9.29 (s, 1H), 8.94 (dd, J 6.5, 1.4 Hz, 2H), 8.58 (tt, J 7.8, 1.5 Hz,1H), 8.06 (dd, J 7.7, 6.6 Hz, 2H), 7.44 (s, 1H), 7.38 (s, 2H), 2.21 (s,3H), 2.07 (s, 3H). ESI-MS (m/z): calcd C9H11NO4S [MH] 229.04,found230.
81%	at 20℃; for 2h;	196; XV Into a round-bottom flask were placed 2-aminotoluene-5-sulfonic acid (50.0 g, 267 mmol), and pyridine (300 mL). Acetic anhydride (38 mL, 403 mmol) was added dropwise from an addition funnel and the resulting mixture was allowed to stir for 2 h at rt. The solvents were removed under reduced pressure, to leave a brown solid. Several portions of ethyl alcohol were added to the solid and subsequently removed under reduced pressure, to afford a brown solid which was filtered and washed with several additional portions of ethyl alcohol and dried under vacuum (67.03 g, 81%) 1H NMR (DMSO-d6,) δ 2.08 (s, 3H), 2.22 (s, 3H), 7.39 (s, 2H), 7.45 (s, 1H), 8.02 (t, J= 6 Hz, 2H), 8.53 (t, J= 6Hz, 1H), 8.92 (d, J= 6Hz, 2H), 9.31 (s, 1H).
	at 20℃; for 2h;

Reference： [1]Pan, Chenghao; Nie, Wenwen; Wang, Jiao; Du, Jiamin; Pan, Zhichao; Gao, Jian; Lu, Yang; Che, Jinxin; Zhu, Hong; Dai, Haibin; Chen, Binhui; He, Qiaojun; Dong, Xiaowu [European Journal of Medicinal Chemistry, 2021, vol. 225]
[2]Current Patent Assignee: GLAXOSMITHKLINE PLC - EP1208091, 2006, B1 Location in patent: Page/Page column 9; 20
[3]Chan, Joseph H.; Freeman, George A.; Tidwell, Jeffrey H.; Romines, Karen R.; Schaller, Lee T.; Cowan, Jill R.; Gonzales, Steve S.; Lowell, Gina S.; Andrews III; Reynolds, David J.; St. Clair, Marty; Hazen, Richard J.; Ferris, Rob G.; Creech, Katrina L.; Roberts, Grace B.; Short, Steven A.; Weaver, Kurt; Koszalka, George W.; Boone, Lawrence R. [Journal of Medicinal Chemistry, 2004, vol. 47, # 5, p. 1175 - 1182]

20
[ 98-33-9 ]
[ 100-39-0 ]
sodium 4-(dibenzylamino)-3-methylbenzenesulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate In dichloromethane for 72h; Heating;

Reference： [1]Romines, Karen R.; Freeman, George A.; Schaller, Lee T.; Cowan, Jill R.; Gonzales, Steve S.; Tidwell, Jeffrey H.; Andrews III, Clarence W.; Stammers, David K.; Hazen, Richard J.; Ferris, Robert G.; Short, Steven A.; Chan, Joseph H.; Boone, Lawrence R. [Journal of Medicinal Chemistry, 2006, vol. 49, # 2, p. 727 - 739]

21
[ 98-33-9 ]
[ 329946-22-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: aq. Na₂CO₃ / CH₂Cl₂ / 72 h / Heating 2: thionyl chloride / dimethylformamide / 2 h / 20 °C

Reference： [1]Romines, Karen R.; Freeman, George A.; Schaller, Lee T.; Cowan, Jill R.; Gonzales, Steve S.; Tidwell, Jeffrey H.; Andrews III, Clarence W.; Stammers, David K.; Hazen, Richard J.; Ferris, Robert G.; Short, Steven A.; Chan, Joseph H.; Boone, Lawrence R. [Journal of Medicinal Chemistry, 2006, vol. 49, # 2, p. 727 - 739]

22
[ 98-33-9 ]
[ 329946-24-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: aq. Na₂CO₃ / CH₂Cl₂ / 72 h / Heating 2: thionyl chloride / dimethylformamide / 2 h / 20 °C 3: 1.0 g / ethanol / 0.5 h / 0 °C

Reference： [1]Romines, Karen R.; Freeman, George A.; Schaller, Lee T.; Cowan, Jill R.; Gonzales, Steve S.; Tidwell, Jeffrey H.; Andrews III, Clarence W.; Stammers, David K.; Hazen, Richard J.; Ferris, Robert G.; Short, Steven A.; Chan, Joseph H.; Boone, Lawrence R. [Journal of Medicinal Chemistry, 2006, vol. 49, # 2, p. 727 - 739]

23
[ 98-33-9 ]
2-[4-chloro-2-(3-fluoro-5-trifluoromethyl-benzoyl)-phenoxy]-<i>N</i>-(4-dimethylsulfamoyl-2-methyl-phenyl)-acetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: aq. Na₂CO₃ / CH₂Cl₂ / 72 h / Heating 2: thionyl chloride / dimethylformamide / 2 h / 20 °C 3: 1.0 g / ethanol / 0.5 h / 0 °C 4: 67 percent / H₂ / Pd/C / toluene / 6 h / 2068.59 Torr 5: 42 percent / aq. NaHCO₃ / acetone / 2.5 h / 20 °C

Reference： [1]Romines, Karen R.; Freeman, George A.; Schaller, Lee T.; Cowan, Jill R.; Gonzales, Steve S.; Tidwell, Jeffrey H.; Andrews III, Clarence W.; Stammers, David K.; Hazen, Richard J.; Ferris, Robert G.; Short, Steven A.; Chan, Joseph H.; Boone, Lawrence R. [Journal of Medicinal Chemistry, 2006, vol. 49, # 2, p. 727 - 739]

24
[ 98-33-9 ]
[ 57946-91-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: aq. Na₂CO₃ / CH₂Cl₂ / 72 h / Heating 2: thionyl chloride / dimethylformamide / 2 h / 20 °C 3: 1.0 g / ethanol / 0.5 h / 0 °C 4: 67 percent / H₂ / Pd/C / toluene / 6 h / 2068.59 Torr

Reference： [1]Romines, Karen R.; Freeman, George A.; Schaller, Lee T.; Cowan, Jill R.; Gonzales, Steve S.; Tidwell, Jeffrey H.; Andrews III, Clarence W.; Stammers, David K.; Hazen, Richard J.; Ferris, Robert G.; Short, Steven A.; Chan, Joseph H.; Boone, Lawrence R. [Journal of Medicinal Chemistry, 2006, vol. 49, # 2, p. 727 - 739]

25
[ 95-53-4 ]
[ 98-33-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: H₂SO₄ / 20 °C 2: 275 °C / 60 Torr

Reference： [1]Singh, Gurdip; Kapoor, Inder Pal Singh; Singh, Jyotsna [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1999, vol. 38, # 9, p. 1114 - 1117]

26
[ 98-33-9 ]
[ 19448-38-5 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: chlorosulfonic acid / 160 °C 2: durch Diazotieren, Ueberfuehren der Diazoverbindung ins Hydrazin und Behandeln des letzteren mit Kupfersulfat

Reference： [1]Hasse [Justus Liebigs Annalen der Chemie, 1885, vol. 230, p. 287]

27
[ 98-33-9 ]
3,5-disulfo-toluene-2-diazonium-betaine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: chlorosulfonic acid / 160 °C 2: mixture of gaseous nitrogen oxides
	Multi-step reaction with 2 steps 1: fuming sulfuric acid / 150 - 170 °C 2: benzene; mixture of gaseous nitrogen oxides

Reference： [1]Hasse [Justus Liebigs Annalen der Chemie, 1885, vol. 230, p. 287]
[2]Nevile; Winther [Chemische Berichte, 1882, vol. 15, p. 2992]

28
[ 98-33-9 ]
[ 6291-02-7 ]

Reference： [1]Helvetica Chimica Acta,1976,vol. 59,p. 379 - 387

29
[ 98-33-9 ]
[ 60310-05-6 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: (i) (diazotization), (ii) CuCl 2: PCl₅ 3: HNO₃

Reference： [1]Courtin,A. [Helvetica Chimica Acta, 1976, vol. 59, p. 379 - 387]

30
[ 98-33-9 ]
[ 96-92-4 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: (i) (diazotization), (ii) CuCl 2: PCl₅ 3: HNO₃ 4: H₂O

Reference： [1]Courtin,A. [Helvetica Chimica Acta, 1976, vol. 59, p. 379 - 387]

31
[ 98-33-9 ]
5-Aminotoluol-3-sulfonsaeure [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: (i) (diazotization), (ii) CuCl 2: PCl₅ 3: HNO₃ 4: H₂O 5: H₂, aq. KOH / Pd-C / aq. ethanol

Reference： [1]Courtin,A. [Helvetica Chimica Acta, 1976, vol. 59, p. 379 - 387]

32
[ 98-33-9 ]
[ 108-24-7 ]
[ 121-44-8 ]
[ 244144-50-1 ]

Yield	Reaction Conditions	Operation in experiment
	at 0℃; for 14h;	L Method L; N-Acyl-2-methyl-4-sulphoaniline Triethylamine Salt (1:1) 2-Methyl-4-sulphoaniline (30 g, 0.16 mol) was dissolved in acetic anhydride (50 ml) and stirred in an ice bath. Triethylamine (23 ml, 0.18 mol) was added very slowly with vigorous stirring (and concomittant release of heat). The reaction mixture was left to stir for 14 h, at which point a solid formed; this was filtered to yield the title compound (35 g, 0.11 mol). NMR: 1.15 (t, 9H), 2.05 (s, 3H), 2.45-2.50 (m, 1H), 3.1 (q, 6H), 7.25-7.40 (m, 2H), 7.85 (t, 1H), 9.7 (br s, 1H); MS: 228.

Reference： [1]Current Patent Assignee: ASTRAZENECA PLC - US6667342, 2003, B1 Location in patent: Page column 71

33
[ 98-33-9 ]
[ 33513-42-7 ]
C₁₀H₁₃ClN₂O₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With oxalyl dichloride In dichloromethane at 20℃; for 5h;	1 To a mixture of 2-aminotoluene-5-sulfonic acid (1.0 wt, 1.0 eq. 6.41 mol) in dichloromethane (15 vol) and N,N-dimethylformamid (0.43 wt, 1.1 equiv.,) was added oxalyl chloride (1.53 wt, 2.25 equiv.) over a period of 120 minutes. Additional dichloromethane (1 volume) was added and the resulting mixture stirred at ambient temp 3 hours. IPC of methanol-quenched aliquot (TLC, 8% MeOH-DCM and HPLC normal phase fast LC) showed complete conversion to activated, protected intermediate. Methylene chloride was removed under gentle reflux at atmospheric pressure to approximately 5 volumes and replaced with dimethoxyethane (7.5 vol). The mixture was evaporated under vacuum with a jacket temperature of 65 degrees to approximately 5 volumes and diluted with additional DME (2.5 volumes). The resulting mixture was cooled to 15 degrees and treated with a solution of 28% ammonium hydroxide (2.23 vol., 3 equiv.) added over a period of 15 minutes which results in momentary dissolution of the intermediate followed quickly by precipitation of the protected intermediate. IPC (TLC, normal phase fast LC) showed complete conversion to protected sulphonamide. The intermediate was filtered, and the solid washed with water (2×1 vol), and then placed back in the reactor. The reactor was charged with a solution of LiOH (0.45 wt., 2 equiv) in 9:1 water:methanol (8 vol based on original input). The resulting solution was warmed to 50 degrees for 5 hours or until IPC (TLC and normal phase fast LC) showed complete hydrolysis to a compound of formula (V). Decolorizing carbon (1.0 weight %) and celite (5.0 weight %) was added and the mixture stirred briefly and filtered through filter cloth into reactor B. The solution was cooled to 25 degrees and adjusted to pH 9 with addition 6 N hydrochloric acid (approximately 1.6 vol.) over a period of 15 minutes with vigorous stirring. The solution was maintained at 45 to 55 degrees for a 2 to 4 hour period to allow conversion from the original amorphous precipitate to a crystalline solid, then cooled to 20 degrees and filtered. The resulting crystalline solid was washed with 90% water/methanol (1 volume) followed by water (2×1 volumes) and dried in vacuum oven at 50 degrees with nitrogen sweep for 16 hours.

Reference： [1]Current Patent Assignee: GLAXOSMITHKLINE PLC - US2006/183944, 2006, A1 Location in patent: Page/Page column 4

34
[ 10193-30-3 ]
[ 95-53-4 ]
[ 98-33-9 ]

Yield	Reaction Conditions	Operation in experiment
89.5%	In 1,2-dichloro-benzene	4 2-Methylaniline-4-sulphonic acid EXAMPLE 4 2-Methylaniline-4-sulphonic acid 246.4 g of 2-methylaniline in 460 ml of o-dichlorobenzene were introduced at room temperature into a 1.3 1 enamel autoclave and 225.5 g of 100% sulphuric acid (monohydrate) were added. With stirring at 200° C., constant pressure was attained in the closed autoclave after just under 2 hours. After cooling, 428 g of solid were filtered off with suction and dried. The chromatographic analysis indicated a yield of 89.5% of 2-methylaniline-4-sulphonic acid, in relation to the use of 2-methylaniline. 0.2% of 2-methylaniline-4,6-disulphonic acid was formed.

Reference： [1]Current Patent Assignee: BAYER AG - US4968835, 1990, A

35
strontium nitrate [ No CAS ]
[ 92-70-6 ]
[ 98-33-9 ]
[ 81-16-3 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium hydroxide; calcium chloride; sodium nitrite; In water;	EXAMPLE 1 A solution of 24.2 grams (0.1294 mole) of pure 6-amino-m-toluenesulfonic acid and 1.2 grams (0.0054 mole) of 2-naphthylamine-1-sulfonic acid is prepared in 500 ml of water by adding 57 ml of a 10% solution of sodium hydroxide and adjusting the pH to 11.5. A solution of 35.6 grams of calcium chloride and 1.5 grams of strontium nitrate in 100 ml of water is added thereto and the mixture cooled to 0 C. with ice. The amines are diazotized by adding 35 ml (0.14 mole) of 4 N sodium nitrite, followed by 150 ml (0.411 mole) of 10% hydrochloric acid. The mixture is stirred for about 3 minutes at 0 C., while maintaining excess nitrous acid. 2-Hydroxy-3-naphthoic acid (28.0 grams, 0.1489 mole) is dissolved in 500 ml of water by adding 180 ml of 10% sodium hydroxide.

Reference： [1]Patent: US4217273,1980,A

36
[ 98-33-9 ]
[ 28920-43-6 ]
[ 1122567-33-2 ]

Yield	Reaction Conditions	Operation in experiment
99%	With sodium hydrogencarbonate In 1,4-dioxane; water

Reference： [1]Goodman, Krista B.; Bury, Michael J.; Cheung, Mui; Cichy-Knight, Maria A.; Dowdell, Sarah E.; Dunn, Allison K.; Lee, Dennis; Lieby, Jeffrey A.; Moore, Michael L.; Scherzer, Daryl A.; Sha, Deyou; Suarez, Dominic P.; Murphy, Dennis J.; Harpel, Mark R.; Manas, Eric S.; McNulty, Dean E.; Annan, Roland S.; Matico, Rosalie E.; Schwartz, Benjamin K.; Trill, John J.; Sweitzer, Thomas D.; Wang, Da-yuan; Keller, Paul M.; Krawiec, John A.; Jaye, Michael C. [Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 1, p. 27 - 30]

37
[ 98-33-9 ]
[ 1208317-17-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: pyridine / 2 h / 20 °C 2.1: sodium hydroxide / pyridine / 3 h / 20 °C 2.2: 2 h / -30 - 40 °C 3.1: ammonium hydroxide / tetrahydrofuran / 1 h / 0 - 20 °C 4.1: hydrogenchloride / ethanol; water / 80 °C 5.1: acetic acid / 120 °C

Reference： [1]Sun, Xicheng; Qiu, Jian; Strong, Sarah A.; Green, Louis S.; Wasley, Jan W.F.; Blonder, Joan P.; Colagiovanni, Dorothy B.; Stout, Adam M.; Mutka, Sarah C.; Richards, Jane P.; Rosenthal, Gary J. [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 6, p. 2338 - 2342]

38
[ 98-33-9 ]
[ 252562-03-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: pyridine / 2 h / 20 °C 2.1: sodium hydroxide / pyridine / 3 h / 20 °C 2.2: 2 h / -30 - 40 °C 3.1: ammonium hydroxide / tetrahydrofuran / 1 h / 0 - 20 °C
	Multi-step reaction with 4 steps 1: pyridine / 2 h / 20 °C 2: sodium hydroxide / water / 3 h / 20 °C 3: thionyl chloride / N,N-dimethyl-formamide / 2 h / -40 - 20 °C 4: ammonium hydroxide / water; tetrahydrofuran / 1 h / 0 - 20 °C

Reference： [1]Sun, Xicheng; Qiu, Jian; Strong, Sarah A.; Green, Louis S.; Wasley, Jan W.F.; Blonder, Joan P.; Colagiovanni, Dorothy B.; Stout, Adam M.; Mutka, Sarah C.; Richards, Jane P.; Rosenthal, Gary J. [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 6, p. 2338 - 2342]
[2]Current Patent Assignee: LAUREL THERAPEUTICS LTD - US9138427, 2015, B2

39
[ 98-33-9 ]
[ 14988-21-7 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: pyridine / 2 h / 20 °C 2.1: sodium hydroxide / pyridine / 3 h / 20 °C 2.2: 2 h / -30 - 40 °C
	Multi-step reaction with 3 steps 1: pyridine / 2 h / 20 °C 2: sodium hydroxide / water / 3 h / 20 °C 3: thionyl chloride / N,N-dimethyl-formamide / 2 h / -40 - 20 °C
	Multi-step reaction with 2 steps 1.1: 14 h / 0 °C 2.1: trichlorophosphate / 15.5 h / 0 - 20 °C 2.2: 0.25 h / 0 °C

Multi-step reaction with 2 steps 1.1: 5 h / 20 °C 2.1: sodium hydroxide / 5 h / 20 °C 2.2: -10 °C

Reference： [1]Sun, Xicheng; Qiu, Jian; Strong, Sarah A.; Green, Louis S.; Wasley, Jan W.F.; Blonder, Joan P.; Colagiovanni, Dorothy B.; Stout, Adam M.; Mutka, Sarah C.; Richards, Jane P.; Rosenthal, Gary J. [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 6, p. 2338 - 2342]
[2]Current Patent Assignee: LAUREL THERAPEUTICS LTD - US9138427, 2015, B2
[3]Current Patent Assignee: ASTRAZENECA PLC - US6667342, 2003, B1
[4]Pan, Chenghao; Nie, Wenwen; Wang, Jiao; Du, Jiamin; Pan, Zhichao; Gao, Jian; Lu, Yang; Che, Jinxin; Zhu, Hong; Dai, Haibin; Chen, Binhui; He, Qiaojun; Dong, Xiaowu [European Journal of Medicinal Chemistry, 2021, vol. 225]

40
[ 98-33-9 ]
[ 53297-70-4 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2012,vol. 22,p. 2338 - 2342
[2]Patent: US9138427,2015,B2

41
[ 98-33-9 ]
[ 108-24-7 ]
4-acetamido-3-methylbenzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With pyridine at 20℃; for 2h;	Acetic anhydride (16 ml, 0.16 mol) was added to the solution of 4-amino-3-methylbenzenesulfonic acid (20 g, 0.107 mol) in 80 ml of pyridine. The mixture was stirred at room temperature for 2 hours. Then EtOH (40 ml) was added and the 4-acetamido-3-methylbenzenesulfonic acid was obtained by filtration and washing with EtOH as brown solid (10.3 g, yield 56%).
56%	With pyridine at 20℃; for 2h;	1 Compound 27-2 (0451) Ac2O (16 ml, 0.16 mol) was added to the solution of 27-1 (20 g, 0.107 mol) in 80 ml of pyridine. The mixture was stirred at rt for 2 hours. Then EtOH (40 ml) was added and the solid was isolated by filtration and washed with EtOH to give 27-2 as a brown solid (10.3 g, yield 56%).

Reference： [1]Sun, Xicheng; Qiu, Jian; Strong, Sarah A.; Green, Louis S.; Wasley, Jan W.F.; Blonder, Joan P.; Colagiovanni, Dorothy B.; Stout, Adam M.; Mutka, Sarah C.; Richards, Jane P.; Rosenthal, Gary J. [Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 6, p. 2338 - 2342]
[2]Current Patent Assignee: LAUREL THERAPEUTICS LTD - US9138427, 2015, B2 Location in patent: Page/Page column 303

42
[ 98-33-9 ]
[ 477308-68-2 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: thionyl chloride; N,N-dimethyl-formamide / 28 h / Reflux 1.2: 0.75 h / 20 °C 2.1: hydrogen bromide; sodium nitrite / water / 0.5 h / 5 °C 2.2: 1.33 h / 5 - 70 °C

Reference： [1]Berg, Stefan; Bergh, Margareta; Hellberg, Sven; Hoegdin, Katharina; Lo-Alfredsson, Yvonne; Soederman, Peter; Von Berg, Stefan; Weigelt, Tatjana; Ormoe, Mats; Xue, Yafeng; Tucker, Julie; Neelissen, Jan; Jerning, Eva; Nilsson, Yvonne; Bhat, Ratan [Journal of Medicinal Chemistry, 2012, vol. 55, # 21, p. 9107 - 9119,13]

43
[ 98-33-9 ]
C₁₈H₃₁BN₂O₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: thionyl chloride; N,N-dimethyl-formamide / 28 h / Reflux 1.2: 0.75 h / 20 °C 2.1: hydrogen bromide; sodium nitrite / water / 0.5 h / 5 °C 2.2: 1.33 h / 5 - 70 °C 3.1: n-butyllithium / tetrahydrofuran / 2.5 h / -78 °C / Inert atmosphere

Reference： [1]Berg, Stefan; Bergh, Margareta; Hellberg, Sven; Hoegdin, Katharina; Lo-Alfredsson, Yvonne; Soederman, Peter; Von Berg, Stefan; Weigelt, Tatjana; Ormoe, Mats; Xue, Yafeng; Tucker, Julie; Neelissen, Jan; Jerning, Eva; Nilsson, Yvonne; Bhat, Ratan [Journal of Medicinal Chemistry, 2012, vol. 55, # 21, p. 9107 - 9119,13]

44
[ 98-33-9 ]
C₁₂H₁₉BN₂O₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1.1: thionyl chloride; N,N-dimethyl-formamide / 28 h / Reflux 1.2: 0.75 h / 20 °C 2.1: hydrogen bromide; sodium nitrite / water / 0.5 h / 5 °C 2.2: 1.33 h / 5 - 70 °C 3.1: n-butyllithium / tetrahydrofuran / 2.5 h / -78 °C / Inert atmosphere 4.1: hydrogenchloride / tetrahydrofuran / -78 - 20 °C

Reference： [1]Berg, Stefan; Bergh, Margareta; Hellberg, Sven; Hoegdin, Katharina; Lo-Alfredsson, Yvonne; Soederman, Peter; Von Berg, Stefan; Weigelt, Tatjana; Ormoe, Mats; Xue, Yafeng; Tucker, Julie; Neelissen, Jan; Jerning, Eva; Nilsson, Yvonne; Bhat, Ratan [Journal of Medicinal Chemistry, 2012, vol. 55, # 21, p. 9107 - 9119,13]

45
[ 98-33-9 ]
3-amino-6-[2-methyl-4-(4-methylpiperazin-1-yl)sulfonyl-phenyl]-N-pyridin-3-yl-pyrazine-2-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: thionyl chloride; N,N-dimethyl-formamide / 28 h / Reflux 1.2: 0.75 h / 20 °C 2.1: hydrogen bromide; sodium nitrite / water / 0.5 h / 5 °C 2.2: 1.33 h / 5 - 70 °C 3.1: n-butyllithium / tetrahydrofuran / 2.5 h / -78 °C / Inert atmosphere 4.1: hydrogenchloride / tetrahydrofuran / -78 - 20 °C 5.1: dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH₂Cl₂; silica gel; sodium carbonate / tetrahydrofuran; water / 70 °C

Reference： [1]Berg, Stefan; Bergh, Margareta; Hellberg, Sven; Hoegdin, Katharina; Lo-Alfredsson, Yvonne; Soederman, Peter; Von Berg, Stefan; Weigelt, Tatjana; Ormoe, Mats; Xue, Yafeng; Tucker, Julie; Neelissen, Jan; Jerning, Eva; Nilsson, Yvonne; Bhat, Ratan [Journal of Medicinal Chemistry, 2012, vol. 55, # 21, p. 9107 - 9119,13]

46
[ 109-01-3 ]
[ 98-33-9 ]
[ 486422-38-2 ]

Yield	Reaction Conditions	Operation in experiment
44%	Stage #1: 2-aminotoluene-5-sulfonic acid With thionyl chloride; N,N-dimethyl-formamide for 28h; Reflux; Stage #2: 1-methyl-piperazine In tetrahydrofuran; dichloromethane at 20℃; for 0.75h;

Reference： [1]Berg, Stefan; Bergh, Margareta; Hellberg, Sven; Hoegdin, Katharina; Lo-Alfredsson, Yvonne; Soederman, Peter; Von Berg, Stefan; Weigelt, Tatjana; Ormoe, Mats; Xue, Yafeng; Tucker, Julie; Neelissen, Jan; Jerning, Eva; Nilsson, Yvonne; Bhat, Ratan [Journal of Medicinal Chemistry, 2012, vol. 55, # 21, p. 9107 - 9119,13]

47
[ 98-33-9 ]
[ 638-29-9 ]
3-methyl-4-(pentanoylamino)benzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With triethylamine In ethyl acetate at 20℃; Green chemistry;	General Procedure of Method B General procedure: Primary amino sulfonic acid (2.5 mmol) is suspended in ethyl acetate (50 mL) and then an equivalent amount of acid chloride is added. After the reaction had been stirred intensively for 10 min at room temperature, 10 mmol of triethylamine is added. The mixture is stirred overnight, and then the solvent is removed under reduced pressure. The crude product is washed several times with ethyl acetate and subsequently purified by column chromatography (hexan/ethyl acetate, 1:5 and then methanol).

Reference： [1]Idzik, Krzysztof R.; Noedler, Karsten; Licha, Tobias [Synthetic Communications, 2014, vol. 44, # 1, p. 133 - 140]

48
[ 2736-40-5 ]
[ 98-33-9 ]
4-[(2-ethylbutanoyl)amino]-3-methylbenzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With triethylamine In ethyl acetate at 20℃; Green chemistry;	General Procedure of Method B General procedure: Primary amino sulfonic acid (2.5 mmol) is suspended in ethyl acetate (50 mL) and then an equivalent amount of acid chloride is added. After the reaction had been stirred intensively for 10 min at room temperature, 10 mmol of triethylamine is added. The mixture is stirred overnight, and then the solvent is removed under reduced pressure. The crude product is washed several times with ethyl acetate and subsequently purified by column chromatography (hexan/ethyl acetate, 1:5 and then methanol).

Reference： [1]Idzik, Krzysztof R.; Noedler, Karsten; Licha, Tobias [Synthetic Communications, 2014, vol. 44, # 1, p. 133 - 140]

49
[ 98-33-9 ]
[ 3282-30-2 ]
4-[(2,2-dimethylpropanoyl)amino]-3-methylbenzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With triethylamine In ethyl acetate at 20℃; Green chemistry;	General Procedure of Method B General procedure: Primary amino sulfonic acid (2.5 mmol) is suspended in ethyl acetate (50 mL) and then an equivalent amount of acid chloride is added. After the reaction had been stirred intensively for 10 min at room temperature, 10 mmol of triethylamine is added. The mixture is stirred overnight, and then the solvent is removed under reduced pressure. The crude product is washed several times with ethyl acetate and subsequently purified by column chromatography (hexan/ethyl acetate, 1:5 and then methanol).

Reference： [1]Idzik, Krzysztof R.; Noedler, Karsten; Licha, Tobias [Synthetic Communications, 2014, vol. 44, # 1, p. 133 - 140]

50
[ 98-33-9 ]
[ 79-22-1 ]
4-[(methoxycarbonyl)amino]-3-methylbenzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	In tetrahydrofuran; water at 0 - 20℃; for 48h; Green chemistry;	Method B. General procedure: General procedure of preparing carbamates containing sulfonic groups (without presence of sodium bicarbonate) 1-10. A solution of chloroformate (2.0 mmol) in tetrahydrofuran (30 mL) was slowly added to an ice-water bath cooled solution of primary amine (2.0 mmol) in water (30 mL) (primary amines containing sulfonic groups are very poorly soluble in cold water and must be previously heated till completely dissolve in water and after that cooled to rt.). After the addition was complete, the ice-water bath was removed and the reaction mixture left to stir at room temperature for two days. The solvent was evaporated to give the crude product, which was subsequently purified using column chromatography (hexane/ethyl acetate, 1:5 and then methanol).

Reference： [1]Idzik, Krzysztof R.; Nödler, Karsten; Licha, Tobias [Molecules, 2015, vol. 20, # 4, p. 6856 - 6865]

51
[ 98-33-9 ]
[ 109-61-5 ]
3-methyl-4-[(propoxycarbonyl)amino]benzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With sodium hydrogencarbonate In tetrahydrofuran; water at 0 - 20℃; for 48h; Green chemistry;	Method A. General procedure: General procedure of preparing carbamates containing sulfonic groups (in presence of sodium bicarbonate) 1-10. A solution of chloroformate (2.0 mmol) in tetrahydrofuran (25 mL) was slowly added to an ice-water bath cooled solution of primary amine (2.0 mmol) (primary amines containing sulfonic groups are very poorly soluble in cold water and must previously be heated until completely dissolved in water and after that cooled to rt.) and water solution of sodium bicarbonate (3.0 mmol). After the addition was complete, the ice-water bath was removed and the reaction mixture left to stir at room temperature for two days. After that, aqueous hydrochloric acid was added and the mixture was stirring for 2 h. The solvent was evaporated to give the crude product, which was subsequently purified using column chromatography (hexane/ethyl acetate, 1:5 and then methanol).

Reference： [1]Idzik, Krzysztof R.; Nödler, Karsten; Licha, Tobias [Molecules, 2015, vol. 20, # 4, p. 6856 - 6865]

52
[ 98-33-9 ]
[ 1885-14-9 ]
3-methyl-4-[(phenoxycarbonyl)amino]benzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	In tetrahydrofuran; water at 0 - 20℃; for 48h; Green chemistry;	Method B. General procedure: General procedure of preparing carbamates containing sulfonic groups (without presence of sodium bicarbonate) 1-10. A solution of chloroformate (2.0 mmol) in tetrahydrofuran (30 mL) was slowly added to an ice-water bath cooled solution of primary amine (2.0 mmol) in water (30 mL) (primary amines containing sulfonic groups are very poorly soluble in cold water and must be previously heated till completely dissolve in water and after that cooled to rt.). After the addition was complete, the ice-water bath was removed and the reaction mixture left to stir at room temperature for two days. The solvent was evaporated to give the crude product, which was subsequently purified using column chromatography (hexane/ethyl acetate, 1:5 and then methanol).

Reference： [1]Idzik, Krzysztof R.; Nödler, Karsten; Licha, Tobias [Molecules, 2015, vol. 20, # 4, p. 6856 - 6865]

53
[ 98-33-9 ]
[ 937-62-2 ]
3-methyl-4-[(4-methylphenoxy)carbonyl]amino}benzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With sodium hydrogencarbonate In tetrahydrofuran; water at 0 - 20℃; for 48h; Green chemistry;	Method A. General procedure: General procedure of preparing carbamates containing sulfonic groups (in presence of sodium bicarbonate) 1-10. A solution of chloroformate (2.0 mmol) in tetrahydrofuran (25 mL) was slowly added to an ice-water bath cooled solution of primary amine (2.0 mmol) (primary amines containing sulfonic groups are very poorly soluble in cold water and must previously be heated until completely dissolved in water and after that cooled to rt.) and water solution of sodium bicarbonate (3.0 mmol). After the addition was complete, the ice-water bath was removed and the reaction mixture left to stir at room temperature for two days. After that, aqueous hydrochloric acid was added and the mixture was stirring for 2 h. The solvent was evaporated to give the crude product, which was subsequently purified using column chromatography (hexane/ethyl acetate, 1:5 and then methanol).

Reference： [1]Idzik, Krzysztof R.; Nödler, Karsten; Licha, Tobias [Molecules, 2015, vol. 20, # 4, p. 6856 - 6865]

54
[ 98-33-9 ]
[ 3759-61-3 ]
3-methyl-4-[(naphthalen-1-yloxy)carbonyl]amino}benzenesulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With sodium hydrogencarbonate In tetrahydrofuran; water at 0 - 20℃; for 48h; Green chemistry;	Method A. General procedure: General procedure of preparing carbamates containing sulfonic groups (in presence of sodium bicarbonate) 1-10. A solution of chloroformate (2.0 mmol) in tetrahydrofuran (25 mL) was slowly added to an ice-water bath cooled solution of primary amine (2.0 mmol) (primary amines containing sulfonic groups are very poorly soluble in cold water and must previously be heated until completely dissolved in water and after that cooled to rt.) and water solution of sodium bicarbonate (3.0 mmol). After the addition was complete, the ice-water bath was removed and the reaction mixture left to stir at room temperature for two days. After that, aqueous hydrochloric acid was added and the mixture was stirring for 2 h. The solvent was evaporated to give the crude product, which was subsequently purified using column chromatography (hexane/ethyl acetate, 1:5 and then methanol).

Reference： [1]Idzik, Krzysztof R.; Nödler, Karsten; Licha, Tobias [Molecules, 2015, vol. 20, # 4, p. 6856 - 6865]

55
[ 98-33-9 ]
sodium 4-(acetylamino)-3-methylbenzenesulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: pyridine / 2 h / 20 °C 2: sodium hydroxide / water / 3 h / 20 °C

Reference： [1]Current Patent Assignee: LAUREL THERAPEUTICS LTD - US9138427, 2015, B2

56
[ 98-33-9 ]
[ 39108-47-9 ]
C₁₈H₂₀N₄O₅S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	Stage #1: 2-aminotoluene-5-sulfonic acid With sodium hydroxide In 1-methyl-pyrrolidin-2-one; water Cooling with ice; Stage #2: With hydrogenchloride; sodium nitrite In 1-methyl-pyrrolidin-2-one; water for 2.5h; Cooling with ice; Stage #3: 1-butyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile In 1-methyl-pyrrolidin-2-one; water for 2h; Cooling with ice;	1 Example-1 To 25.0 parts of o-toluidine-4-sulfonic acid tetrahydrate represented by the formula (a-1), 250 parts of water and 50 parts of N-methylpyrrolidone were added, and the mixture was adjusted to pH 7-8 with an aqueous 30% sodium hydroxide solution . The following operation was performed under ice-cooling. 18.4 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. And 64.8 parts of 35% hydrochloric acid was added in small portions to obtain a brown solution, followed by stirring for 2 hours. And 16.7 parts of amide sulfuric acid in 170 parts of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.173 parts of water and 19 parts of N-methylpyrrolidone were added to 19.3 parts of 1-butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-1) And the pH was adjusted to 8 to 9 with a 30% aqueous solution of sodium hydroxide.The following operation was performed under ice-cooling. The pyridone aqueous solution was stirred to give a colorless solution, and the suspension containing the diazonium salt was added dropwise over 2 hours while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of dropwise addition, stirring was continued for another 2 hours to obtain a dark solution. 140 parts of the purified salt were added to the reaction solution and stirred for 5 hours. The yellow solid obtained by filtration was dried at 60 under reduced pressure to obtain 35.8 parts (yield: 91%) of an azo compound represented by the formula (I-36).
91%	Stage #1: 2-aminotoluene-5-sulfonic acid With sodium hydroxide; sodium nitrite In 1-methyl-pyrrolidin-2-one; water for 0.5h; Cooling with ice; Stage #2: With hydrogenchloride In 1-methyl-pyrrolidin-2-one; water for 2h; Stage #3: 1-butyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile With sodium hydroxide In 1-methyl-pyrrolidin-2-one; water for 4h; Cooling with ice;	1 (A-1) yu Shi shown by o-toluidine-4-sulfonic acid tetrahydrate 25.0 parts of water is added into 250 with N-methyl pyrrole [...] 50 after the report, under cold, in order to 30% sodium hydroxide aqueous solution is adjusted to pH7-8. The following operation is carried out to cold. By adding sodium nitrite 18.4 parts stirring 30 minutes. A small amount of gradually adding 35% hydrochloric acid to 64.8 parts brown solution after the bubbling, stirring 2 hours. Will enable acid amide sulfuric acid 16.7 parts dissolved in water 170 parts of adding an aqueous solution formed by the mixing in the reaction solution, can be obtained the suspension containing diazonium salt.(C-1) yu Shi shown by 1-butyl-3-cyano-4-methyl-6-hydroxy-pyridin-2-one 19.3 parts adding water 173 with N-methyl pyrrole [...] 19 after the report, under cold, in order to 30% sodium hydroxide aqueous solution is adjusted to pH8-9.The following operation is carried out to cold. Stirring the aforesaid pyridone solution is colorless solution after the, sides in 30% aqueous sodium hydroxide solution is adjusted to pH8-9, spend 2 hours the suspension containing diazonium salt to pump dropped-. After the end of dropping, to stir 2 hours, to obtain dark solution. The refined salt 140 parts are added to a reaction solution, stirring 5 hours. After filtration of the obtained yellow solid under reduced pressure in order to 60 °C drying, formula (d-1) compound shown in 35.8 parts (yield 91%).
91%	Stage #1: 2-aminotoluene-5-sulfonic acid With sodium hydroxide; sodium nitrite In 1-methyl-pyrrolidin-2-one; water for 0.5h; Cooling with ice; Stage #2: With hydrogenchloride In 1-methyl-pyrrolidin-2-one; water for 2h; Cooling with ice; Stage #3: 1-butyl-6-hydroxy-4-methyl-2-oxo-1,2-dihydropyridine-3-carbonitrile Further stages;	1 To 25.0 parts of o-toluidine-4-sulfonic acid tetrahydrate represented by the formula (a-1), 250 parts of water and 50 parts of N-methylpyrrolidone were added, and the mixture was adjusted to pH 7-8 with an aqueous 30% sodium hydroxide solution . The following operation was carried out under ice-cooling. 18.4 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes.64.8 parts of 35% hydrochloric acid was added in small portions to make a brown solution,And the mixture was stirred for 2 hours.16.7 parts of amide sulfuric acid were dissolved in waterWas added to the reaction solution and stirred,To obtain a suspension containing the diazonium salt.173 parts of water and 19 parts of N-methylpyrrolidone were added to 19.3 parts of 1-butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-1) And adjusted to pH 8 to 9 with a 30% aqueous solution of sodium hydroxide.The following operation was carried out under ice-cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was added dropwise over 2 hours while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, stirring was continued for another 2 hours to obtain a dark solution. 140 parts of purified salt were added to the reaction solution and stirred for 5 hours. The yellow solid obtained by filtration was dried at 60 under reduced pressure to obtain 35.8 parts (yield: 91%) of the compound represented by the formula (d-1).

Reference： [1]Current Patent Assignee: Sumitomo Chemical (w/o Dongwoo Fine-Chem); SUMITOMO CHEMICAL COMPANY LIMITED - KR101644916, 2016, B1 Location in patent: Paragraph 0164-0171
[2]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - TWI515266, 2016, B Location in patent: Page/Page column 58; 59; 60
[3]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - KR101725265, 2017, B1 Location in patent: Paragraph 0195-0202

57
[ 98-33-9 ]
[ 39108-47-9 ]
C₂₆H₃₇N₅O₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: sodium hydroxide / water; 1-methyl-pyrrolidin-2-one / pH 7 - 8 / Cooling with ice 1.2: 2.5 h / Cooling with ice 1.3: 2 h / pH 8 - 9 / Cooling with ice 2.1: thionyl chloride; N,N-dimethyl-formamide / chloroform / 5 h / 50 °C 2.2: 5 h

Reference： [1]Current Patent Assignee: Sumitomo Chemical (w/o Dongwoo Fine-Chem); SUMITOMO CHEMICAL COMPANY LIMITED - KR101644916, 2016, B1

58
[ 98-33-9 ]
C₂₁H₂₇N₅O₅S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: sodium hydroxide; sodium nitrite / water; 1-methyl-pyrrolidin-2-one / 0.5 h / pH 7 - 8 / Cooling with ice 1.2: 2 h 1.3: 4 h / pH 8 - 9 / Cooling with ice 2.1: N,N-dimethyl-formamide; thionyl chloride / acetonitrile / 2 h / 20 - 40 °C 2.2: 1.5 h / 20 °C
	Multi-step reaction with 2 steps 1.1: sodium hydroxide; sodium nitrite / water; 1-methyl-pyrrolidin-2-one / 0.5 h / pH 7 - 8 / Cooling with ice 1.2: 2 h / Cooling with ice 2.1: thionyl chloride / acetonitrile; N,N-dimethyl-formamide / 2 h / 20 - 40 °C 2.2: 1 h / 20 °C

Reference： [1]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - TWI515266, 2016, B
[2]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - KR101725265, 2017, B1

59
[ 98-33-9 ]
C₄₆H₅₆N₁₀O₁₂S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: sodium hydroxide; sodium nitrite / water; 1-methyl-pyrrolidin-2-one / 0.5 h / pH 7 - 8 / Cooling with ice 1.2: 2 h 1.3: 4 h / pH 8 - 9 / Cooling with ice 2.1: N,N-dimethyl-formamide; thionyl chloride / acetonitrile / 2 h / 20 - 40 °C 2.2: 1.5 h / 20 °C 3.1: water; 1-methyl-pyrrolidin-2-one / 0.5 h / Inert atmosphere 3.2: 8 h / 20 °C
	Multi-step reaction with 3 steps 1.1: sodium hydroxide; sodium nitrite / water; 1-methyl-pyrrolidin-2-one / 0.5 h / pH 7 - 8 / Cooling with ice 1.2: 2 h / Cooling with ice 2.1: thionyl chloride / acetonitrile; N,N-dimethyl-formamide / 2 h / 20 - 40 °C 2.2: 1 h / 20 °C 3.1: 1-methyl-pyrrolidin-2-one / 8 h / 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - TWI515266, 2016, B
[2]Current Patent Assignee: SUMITOMO CHEMICAL COMPANY LIMITED; Sumitomo Chemical (w/o Dongwoo Fine-Chem) - KR101725265, 2017, B1

60
[ 98-33-9 ]
[ 53848-17-2 ]

Reference： [1]Patent: CN106810506,2017,A

61
[ 98-33-9 ]
C₂₉H₃₈N₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: bromine / N,N-dimethyl-formamide / 4 h / 20 °C 2: hydrogenchloride / water / 11 h / Reflux 3: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate / 1,4-dioxane / 16 h / 80 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: SHANGHAI LANGYI FUNCTIONAL MATERIALS CO LTD - CN106810506, 2017, A

62
[ 98-33-9 ]
C₆₀H₆₈N₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1: bromine / N,N-dimethyl-formamide / 4 h / 20 °C 2: hydrogenchloride / water / 11 h / Reflux 3: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate / 1,4-dioxane / 16 h / 80 °C / Inert atmosphere 4: 1H-imidazole / acetonitrile / 15 h / 90 °C / Inert atmosphere 5: sodium carbonate; dihydrogen peroxide / 1,4-dioxane / 3.5 h / 20 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: SHANGHAI LANGYI FUNCTIONAL MATERIALS CO LTD - CN106810506, 2017, A

63
[ 98-33-9 ]
C₆₀H₇₂N₄S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 4 steps 1: bromine / N,N-dimethyl-formamide / 4 h / 20 °C 2: hydrogenchloride / water / 11 h / Reflux 3: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate / 1,4-dioxane / 16 h / 80 °C / Inert atmosphere 4: 1H-imidazole / acetonitrile / 15 h / 90 °C / Inert atmosphere

Reference： [1]Current Patent Assignee: SHANGHAI LANGYI FUNCTIONAL MATERIALS CO LTD - CN106810506, 2017, A

64
[ 98-33-9 ]
[ 5593-70-4 ]
4C₇H₈NO₃S^(1-)*Ti⁽⁴⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In ethanol at 30 - 70℃;	1 Example 1 Titanium sulfanilate complexes used in this example were synthesized as follows Dissolve 1.54 g of 4-amino-3-methylbenzenesulfonic acid (III) in 10 mL of ethanol.5 mL of an ethanol solution having a concentration of 0.14 g/mL tetrabutyl titanate (II) was slowly added dropwise at room temperature.Stir at 30-70°C for 3-5 hours,After cooling to room temperature, the solvent is removed by rotary evaporation and the residual solid is the desired product (IV).

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES; Shenzhen Institute of Advanced Technology (in: CAS) - CN108017664, 2018, A Location in patent: Paragraph 0050-0053

65
[ 10196-18-6 ]
[ 98-33-9 ]
Zn⁽²⁺⁾*2C₇H₈NO₃S^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-aminotoluene-5-sulfonic acid With sodium hydroxide In ethanol at 20℃; for 1.5h; Stage #2: zinc(II) nitrate In ethanol at 50 - 70℃;	2 Example 2 Zinc p-aminobenzenesulfonate complexes used in this example were synthesized as follows Dissolve 1.87 g of 4-amino-3-methylbenzenesulfonic acid (III) in 15 mL of ethanol.Add 400mg NaOH solids,After stirring for half an hour at room temperature, add 940 mg of anhydrous zinc nitrate (V).The mixture is stirred at 50 to 70° C. for 3 to 5 hours. After cooling, the solvent is distilled off under reduced pressure. The residual solid is the target product (VI).

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES; Shenzhen Institute of Advanced Technology (in: CAS) - CN108017664, 2018, A Location in patent: Paragraph 0054-0057

66
[ 119-79-9 ]
[ 98-33-9 ]
C₁₇H₁₅N₃O₆S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-aminotoluene-5-sulfonic acid With hydrogenchloride; sodium nitrite In water Stage #2: 5-aminonaphthalene-2-sulfonic acid With sodium carbonate In water	4.1 Example 4 4-amino-3-methyl benzenesulfonic acid (as Ag1-NH2) (18.7 parts) was added in water (200 parts) and 35% hydrochloric acid (40 parts) was added thereto. Subsequently, a 40% aqueous sodium nitrite solution (17.3 parts) was added and the mixture was stirred at 10 to 20° C. to perform diazotization. To the mixture, 1-aminonaphthalene-6-sulfonic acid (as Bg-NH2) (22.3 parts) dissolved in a 15% aqueous sodium carbonate solution, was added. To this solution, a 15% aqueous sodium carbonate solution was added to adjust pH to be 2. The solution was further stirred to complete a coupling reaction. Thereafter, salting out was performed with sodium chloride followed by filtration to obtain the monoazo amino compound (33.7 parts) represented by formula (A12′).

Reference： [1]Current Patent Assignee: NIPPON KAYAKU CO LTD - US2019/48194, 2019, A1 Location in patent: Paragraph 0283-0284

67
[ 119-28-8 ]
[ 98-33-9 ]
C₂₅H₂₃N₅O₈S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: sodium hydroxide / water 1.2: 10 - 20 °C 1.3: pH 2 2.1: sodium hydroxide / water 2.2: 1 h / 10 - 30 °C 2.3: pH 2

Reference： [1]Current Patent Assignee: NIPPON KAYAKU CO LTD - US2019/48194, 2019, A1

68
[ 119-28-8 ]
[ 98-33-9 ]
C₁₇H₁₅N₃O₆S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-aminotoluene-5-sulfonic acid With sodium hydroxide In water Stage #2: With hydrogenchloride; sodium nitrite In water at 10 - 20℃; Stage #3: 8-amino-2-naphthalenesulfonic acid With sodium carbonate In water	14.1 Example 14 4-Amino-3-methyl benzenesulfonic acid (as Ag1-NH2) (18.7 parts) was added in water (300 parts) and completely dissolved by adding a 25% aqueous sodium hydroxide solution. Subsequently, 35% hydrochloric acid (40 parts) was added and a 40% aqueous sodium nitrite solution (17.3 parts) was added. The mixture was stirred at 10 to 20° C. to perform diazotization. To this solution, 1-aminonaphthalene-7-sulfonic acid (as Bg-NH2) (25.3 parts) dissolved in a 15% aqueous sodium carbonate solution was added and further a 15% aqueous sodium carbonate solution was added to adjust pH to be 2. The solution was further stirred to complete a coupling reaction. Thereafter, filtration was performed to obtain the monoazo amino compound (33.7 parts) represented by the following formula (E9′).

Reference： [1]Current Patent Assignee: NIPPON KAYAKU CO LTD - US2019/48194, 2019, A1 Location in patent: Paragraph 0308-0309

69
[ 2494-89-5 ]
[ 108-77-0 ]
[ 98-33-9 ]
N-methyl-N-(4-aminobenzene-2-sulfonic acid)J acid [ No CAS ]
C₃₅H₂₇ClN₈O₁₆S₅^(4-)*4Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: N-methyl-N-(4-aminobenzene-2-sulfonic acid)J acid With sodium hydroxide In water Stage #2: 1,3,5-trichloro-2,4,6-triazine With sodium carbonate In water at 0 - 5℃; Stage #3: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate; 2-aminotoluene-5-sulfonic acid Further stages;	1a-1d a) primary condensation Weigh 1.88 parts of cyanuric chloride, Add 18 parts of water, Crushed ice, Beat for 45 minutes at 0 to 5 °C. At the same time, weighed 4.24 parts of N-methyl-N-(4-aminobenzene-2-sulfonic acid) J acid in 20 parts of water. Adjust the pH to about 6.0 with sodium hydroxide. Make it beaten completely. After the completion of the beating, the above N-methyl-N-(4-aminobenzene-2-sulfonic acid) J acid solution was added dropwise to the cyanuric chloride suspension over 1 hour. After the addition is completed, Adjust the pH of the reaction to 4.0 to 4.5 with sodium carbonate. Reaction for 3 to 4 hours, The free end of N-methyl-N-(4-aminobenzene-2-sulfonic acid) J acid is the end point.b) secondary condensation Weighing 2.81 parts of 4-β-hydroxyethylsulfone aniline sulfate into the above-mentioned primary condensation reaction solution, At the same time, the temperature is raised to 40 to 45 ° C. Sodium carbonate adjusts the pH to 5.5 to 6.0, Maintain this temperature and pH for about 4 hours, The disappearance of 4-β-hydroxyethyl sulfone aniline sulfate by HPLC was the end of the reaction.c) diazotization Weigh 1.87 parts of o-toluidine 4-sulfonic acid, Add 20 parts of water, Stir, 2.7 parts of 30% hydrochloric acid, The ice water bath is cooled to 0 to 5 ° C. Add 0.69 parts of sodium nitrite to make it evenly mixed. Maintain a slight excess of hydrochloric acid and nitrous acid at a temperature of 0 to 5 ° C, Reaction for 1 hour, Then, a small amount of sulfamic acid is used to eliminate a slight excess of nitrous acid, and the diazonium salt is adjusted at 5 to 10 ° C to have a pH of 6 to 6.5.d) coupling Adding c) the diazonium salt to the dimer of b), The coupling reaction is carried out by adjusting the pH of the reaction medium with sodium carbonate at 10 to 15 ° C, and the coupling reaction is carried out. The disappearance of the diazonium salt is the end of the reaction. Then add a stabilizer, The stabilizer is phosphate, The amount added is 1% of the volume of the reaction system, Direct spray drying, 11.94 parts of an orange reactive dye product of the above formula dye (1) was obtained.

Reference： [1]Current Patent Assignee: SINOCHEM HOLDINGS CORPORATION LTD - CN109096793, 2018, A Location in patent: Paragraph 0036-0047

70
[ 98-33-9 ]
C₉H₁₀ClNO₄S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sodium hydroxide / water / 2 h / 50 °C 2: acetic acid; hydrogenchloride; dihydrogen peroxide / water / 40 - 50 °C

Reference： [1]Current Patent Assignee: SHANGHAI BETTERSYN BIOTECH - CN110015963, 2019, A

71
[ 98-33-9 ]
[ 87-63-8 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1: sodium hydroxide / water / 2 h / 50 °C 2: acetic acid; hydrogenchloride; dihydrogen peroxide / water / 40 - 50 °C 3: hydrogenchloride / water; sulfolane / 26 h / 120 °C

Reference： [1]Current Patent Assignee: SHANGHAI BETTERSYN BIOTECH - CN110015963, 2019, A

72
[ 98-33-9 ]
[ 108-24-7 ]
sodium 4-(acetylamino)-3-methylbenzenesulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55 g	With sodium hydroxide In water at 50℃; for 2h;	1 Synthesis of sodium 4-acetamido-3-methylbenzenesulfonate: 40 g of 4-amino-3-methylbenzenesulfonic acid was added to a three-necked flask equipped with a stirrer thermometer.240 g of water, 8.6 g of sodium hydroxide and 26.2 g of acetic anhydride were cooled to 50 ° C, and the reaction was kept for 2 hours to complete the reaction of the starting materials. After completion of the reaction, the mixture was concentrated to dryness under reduced pressure to give a product (yield: 55 g).

Reference： [1]Current Patent Assignee: SHANGHAI BETTERSYN BIOTECH - CN110015963, 2019, A Location in patent: Paragraph 0057-0059

73
[ 98-33-9 ]
6,6'-azo-bis-toluene-3-sulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hypochlorite; sodium carbonate In water for 5h; Cooling with ice;	3.2 Add 11.23g of 2-aminotoluene-5-sulfonic acid and 12.72g of anhydrous sodium carbonate to 120mL of water, and stir to dissolve. 80mL of sodium hypochlorite solution was slowly added in an ice bath; after the dropwise addition, the ice bath was stirred for 5h to obtain a color body solution. The color body solution is filtered after standing, and dried to obtain the color body acid derivative powder

Reference： [1]Current Patent Assignee: HONG KONG POLYTECHNIC UNIVERSITY - CN111117287, 2020, A Location in patent: Paragraph 0117; 0124-0125

74
[ 98-33-9 ]
6,6'-azo-bis-toluene-3-sulfonyl chloride [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: sodium carbonate; sodium hypochlorite / water / 5 h / Cooling with ice 2: oxalyl dichloride; N,N-dimethyl-formamide / dichloromethane / 8 h / 25 °C

Reference： [1]Current Patent Assignee: HONG KONG POLYTECHNIC UNIVERSITY - CN111117287, 2020, A

75
[ 98-33-9 ]
C₃₀H₃₂N₄O₈S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: sodium carbonate; sodium hypochlorite / water / 5 h / Cooling with ice 2.1: oxalyl dichloride; N,N-dimethyl-formamide / dichloromethane / 8 h / 25 °C 3.1: potassium carbonate / acetone / 5 h / 20 °C 3.2: 1 h / 20 °C

Reference： [1]Current Patent Assignee: HONG KONG POLYTECHNIC UNIVERSITY - CN111117287, 2020, A

76
[ 98-33-9 ]
[ 570-24-1 ]

Yield	Reaction Conditions	Operation in experiment
82%	Stage #1: 2-aminotoluene-5-sulfonic acid With acetic acid; zinc(II) oxide at 80℃; for 4h; Stage #2: With nitric acid at 10 - 12℃; for 2h; Stage #3: With hydrogenchloride In water at 100℃; for 1h;	1-3 Example 1 Under mechanical stirring, 60.1g (1.00mol) acetic acid was dropped into a mixture of 93.6g (0.50mol) 4-amino-3-methylbenzenesulfonic acid and 4.2g (0.05mol) zinc oxide. After the addition, The temperature was raised to 80°C for 4h. After the reaction is complete, filter through a pad of diatomaceous earth, transfer the filtrate to an ice water bath, and cool to 10-12°C. Add 63ml of concentrated nitric acid (1.00mol HNO3) dropwise, the addition is completed in about 1.5h, the temperature is controlled at 10-12°C during the dropping, and the reaction is maintained at 10-12°C for 30 minutes after the dropping. After nitrification is complete, The reaction solution was poured into 1.5L ice water, and suction filtered to obtain the nitration product solid (without drying). Put the nitration product solid in the flask, add 150ml concentrated hydrochloric acid (1.80mol HCl), React at 100°C for 1h. After the hydrolysis is completed, it is cooled to room temperature, 150 ml of water is added, a solid is separated out, filtered with suction, and the filter cake is dried to obtain 62.1 g of an orange solid with a yield of 82.0% and a purity of 98.2%.

Reference： [1]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN112159325, 2021, A Location in patent: Paragraph 0015; 0020-0025

77
[ 98-33-9 ]
C₁₅H₁₄ClNO₃S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1: pyridine / 16 h / 25 - 100 °C 2: 1,3,5-trichloro-2,4,6-triazine / propan-2-one / 16 h / Heating