[ CAS No. 535-87-5 ] {[proInfo.proName]}

Name: 535-87-5|3,5-Diaminobenzoic acid|98%
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Quality Control of [ 535-87-5 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 535-87-5 ]

Product Details of [ 535-87-5 ]

CAS No. :	535-87-5	MDL No. :	MFCD00007807
Formula :	C₇H₈N₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	UENRXLSRMCSUSN-UHFFFAOYSA-N
M.W :	152.15	Pubchem ID :	12062
Synonyms :

Calculated chemistry of [ 535-87-5 ]

Physicochemical Properties

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	3.0
Molar Refractivity :	42.21
TPSA :	89.34 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	No
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-7.08 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.04
Log Po/w (XLOGP3) :	0.21
Log Po/w (WLOGP) :	0.57
Log Po/w (MLOGP) :	-0.7
Log Po/w (SILICOS-IT) :	-0.22
Consensus Log Po/w :	-0.02

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.56

Water Solubility

Log S (ESOL) :	-1.25
Solubility :	8.49 mg/ml ; 0.0558 mol/l
Class :	Very soluble
Log S (Ali) :	-1.65
Solubility :	3.44 mg/ml ; 0.0226 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-1.04
Solubility :	14.0 mg/ml ; 0.092 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.08

Safety of [ 535-87-5 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 535-87-5 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 535-87-5 ]
Downstream synthetic route of [ 535-87-5 ]

[ 535-87-5 ] Synthesis Path-Upstream 1~7

1
[ 99-34-3 ]
[ 535-87-5 ]

Yield	Reaction Conditions	Operation in experiment
98.8%	With sodium hydroxide In water at 25 - 30℃;	M-Dinitrobenzoic acid 51 g (0.24 mol), 300 mL water added to 1L of Stainless steel high pressure reactor, after stirring it evely, the pH adjusted to 7-8 by using sodium hydroxide aqueous solution with a mass percentage concentration of 20percent, then 0.25g of Ni- Yb-Al three-way catalyst was added, after nitrogen replacement three times, controlled the hydrogen gas pressure at 0.2MPa, maintained the temperature at 25 ~ 30 degrees, reaction does not depressurize until the pressure is substantially reduced. Then recovered the catalyst through filtration, adjusted the filtrate to pH 3 with concentrated hydrochloric acid, precipitated the solid, filtration, washed with water and dried under vacuum to obtain the product 3,5-diamino benzoic acid 36.5g, The yield was 98.8percent and the HPLC purity was 98.9percent. The retention time was in accordance with the standard control.
75%	Stage #1: With sulfuric acid In water at 98℃; Stage #2: With sodium carbonate In water	EXAMPLE 4 3,5-DI NITRO BENZOIC ACID TO 3,5-DI AMINO BENZOIC ACID Fresh cycle: In a 2-Liter-4-neck round bottom flask equipped with stirrer, condenser, thermometer, addition port arranged in suitable heating / cooling system was charged 700 ml water, heated to 80°C. Charged 20 ml 50percent H2S04 to get pH 2.0 and immediately charged 60 g G-CAT start up with continuous stirring at 80°C. First lot of 15.3 g Nitro 20 g G-CAT was charged to the reaction mass in 10 min. The reaction mass was maintained for 5-10 min at 98-100°C. Remaining lots of nitro G-CAT was charged in four equal lots in similar manner as followed for first lot. Reaction mass was maintained at 98-100°C for 60 min. Then 160.0 ml 25percent Na2C03 was charged to adjust pH 8.5 in 30 min to adjust pH 8.5. Then it is decanted collected in separate flask for further processing. 400 ml hot water wash given to solid inorganic by-product, remaining in the flask under stirring at 98°-100°C, to get 335 g of dry cake of solid inorganic by-product 0.34percent amine content, and appearance was black. The decanted mass is then cooled to 30-35°C and charged 49 ml 50percent Sulphuric acid (H2S04) slowly in 1.0 hrs to get pH 3.5 to 4.0. Liquid layer was then filtered and crystalline material was washed with 150 ml water to get 42 g off white with purity 98.56percent. with melting range 234°C. Total filtrate i.e. reaction medium and washings was collected recycled in subsequent batches.
75%	Stage #1: at 98℃;	EXAMPLE 4 3,5-DI NITRO BENZOIC ACID TO 3,5-DI AMINO BENZOIC ACIDFresh cycle: In a 2-Liter-4-neck round bottom flask equipped with stirrer, condenser, thermometer, addition port arranged in suitable heating/cooling system was charged 700 ml water, heated to 80° C. Charged 20 ml 50percent H2SO4 to get pH 2.0 and immediately charged 60 g G-CAT start up with continuous stirring at 80° C. First lot of 15.3 g Nitro 20 g G-CAT was charged to the reaction mass in 10 min. The reaction mass was maintained for 5-10 min at 98-100° C. Remaining lots of nitro G-CAT was charged in four equal lots in similar manner as followed for first lot. Reaction mass was maintained at 98-100° C. for 60 min. Then 160.0 ml 25percent Na2CO3 was charged to adjust pH 8.5 in 30 min to adjust pH 8.5. Then it is decanted collected in separate flask for further processing. 400 ml hot water wash given to solid inorganic by-product, remaining in the flask under stirring at 98°-100° C., to get 335 g of dry cake of solid inorganic by-product 0.34percent amine content, and appearance was black. The decanted mass is then cooled to 30-35° C. and charged 49 ml 50percent Sulphuric acid (H2SO4) slowly in 1.0 hrs to get pH 3.5 to 4.0. Liquid layer was then filtered and crystalline material was washed with 150 ml water to get 42 g off white with purity 98.56percent.with melting range 234° C. Total filtrate i.e. reaction medium and washings was collected recycled in subsequent batches.First recycle: In the same set up as described above, 700 ml reaction medium generated in fresh cycle was charged, heated to 90° C. Charged 20 ml 50percent H2SO4 to get pH 2.0 and immediately charged 60 g G-CAT start up with continuous stirring at 90-100° C. First lot of 15.3 g Nitro 20 g G-CAT was charged to the reaction mass in 10 min. The reaction mass was maintained for 5-10 min at 98-100° C. Remaining lots of nitro G-CAT was charged in four equal lots in similar manner as followed for first lot. Reaction mass was maintained at 98-100° C. for 60 min. Then 165.0 ml 25percent Na2CO3 was charged in 30 min to adjust pH 8.5. Then it is decanted collected in separate flask for further processing. 400 ml hot water wash given to solid inorganic by-product, remaining in the flask under stirring at 98°-100° C., to get 340 g of dry cake of solid inorganic by-product 0.34percent amine content, and appearance was black. The decanted mass is then cooled to 30-35° C. and charged 58 ml 50percent Sulphuric acid (H2SO4) slowly in 1.0 hrs to get pH 3.5 to 4.0. Liquid layer was then filtered and crystalline material was washed with 150 ml water to get 63 g off white with purity 98.26percent.with melting range 230° C. Total filtrate i.e. reaction medium and washings was collected recycled in subsequent batches.Fifth recycle: In the same set up as described above, 700 ml reaction medium generated in fourth cycle was charged, heated to 90° C. Charged 20 ml 50percent H2SO4 to get pH 2.0 and immediately charged 60 g G-CAT start up with continuous stirring at 90-100° C. First lot of 15.3 g Nitro 20 g G-CAT was charged to the reaction mass in 10 min. The reaction mass was maintained for 5-10 min at 98-100° C. Remaining lots of nitro G-CAT was charged in four equal lots in similar manner as followed for first lot. Reaction mass was maintained at 98-100° C. for 60 min. Then 170.0 ml 25percent Na2CO3 was charged in 30 min to adjust pH 8.5. Then it is decanted collected in separate flask for further processing. 400 ml hot water wash given to solid inorganic by-product, remaining in the flask under stirring at 98°-100° C., to get 370 g of dry cake of solid inorganic by-product 0.53percent amine content, and appearance was black. The decanted mass is then cooled to 30-35° C. and charged 53 ml 50percent Sulphuric acid (H2SO4) slowly in 1.0 hrs to get pH 3.5 to 4.0. Liquid layer was then filtered and crystalline material was washed with 150 ml water to get 70 g off white with purity 97.05percent.with melting range 233° C. Total filtrate i.e. reaction medium and washings was collected recycled in subsequent batches.Tenth recycle: In the same set up as described above, 700 ml reaction medium generated in ninth cycle was charged, heated to 90° C. Charged 20 ml 50percent H2SO4 to get pH 2.0 and immediately charged 60 g G-CAT start up with continuous stirring at 90-100° C. First lot of 15.3 g Nitro 20 g G-CAT was charged to the reaction mass in 10 min. The reaction mass was maintained for 5-10 min at 98-100° C. Remaining lots of nitro G-CAT was charged in four equal lots in similar manner as followed for first lot. Reaction mass was maintained at 98-100° C. for 60 min. Then 180.0 ml 25percent Na2CO3 was charged in 30 min to adjust pH 8.5. Then it is decanted collected in separate flask for further processing. 400 ml hot water wash given to solid inorganic by-product, remaining in the flask under stirring at 98°-100° C., to get 340 g of dry cake of solid inorganic by-product 0.65percent amine content, and appearance was black. The decanted mass is then cooled to 30-35° C. and charged 56 ml 50percent Sulphuric acid (H2SO4) slowly in 1.0 hrs to get pH 3.5 to 4.0. Liquid layer was then filtered and crystalline material was washed with 150 ml water to get 67 g off white with purity 92.65percent with melting range 230° C. Total filtrate i.e. reaction medium and washings was collected recycled in subsequent batches.Fifteenth recycle: In the same set up as described above, 700 ml reaction medium generated in fourteen Recycle was charged, heated to 90° C. Charged 20 ml 50percent H2SO4 to get pH 2.0 and immediately charged 60 g G-CAT start up with continuous stirring at 90-100° C. First lot of 15.3 g Nitro 20 g G-CAT was charged to the reaction mass in 10 min. The reaction mass was maintained for 5-10 min at 98-100° C. Remaining lots of nitro G-CAT was charged in four equal lots in similar manner as followed for first lot. Reaction mass was maintained at 98-100° C. for 60 min. Then 195.0 ml 25percent Na2CO3 was charged in 30 min to adjust pH 8.5. Then it is decanted collected in separate flask for further processing. 400 ml hot water wash given to solid inorganic by-product, remaining in the flask under stirring at 98°-100° C., to get 330 g of dry cake of solid inorganic by-product 0.66percent amine content, and appearance was black. The decanted mass is then cooled to 30-35° C. and charged 59 ml 50percent Sulphuric acid (H2SO4) slowly in 1.0 hrs to get pH 3.5 to 4.0. Liquid layer was then filtered and crystalline material was washed with 150 ml water to get 65 g off white with purity 95percent with melting range 232° C. Total filtrate i.e. reaction medium and washings was collected recycled in subsequent batches.Twentieth recycle: In the same set up as described above, 700 ml reaction medium generated in nineteen cycles was charged, heated to 90° C. Charged 20 ml 50percent H2SO4 to get pH 2.0 and immediately charged 60 g G-CAT start up with continuous stirring at 90-100° C. First lot of 15.3 g Nitro 20 g G-CAT was charged to the reaction mass in 10 min. The reaction mass was maintained for 5-10 min at 98-100° C. Remaining lots of nitro G-CAT was charged in four equal lots in similar manner as followed for first lot. Reaction mass was maintained at 98-100° C. for 60 min. Then 200.0 ml 25percent Na2CO3 was charged in 30 min to adjust pH 8.5. Then it is decanted collected in separate flask for further processing. 400 ml hot water wash given to solid inorganic by-product, remaining in the flask under stirring at 98°-100° C., to get 315 g of dry cake of solid inorganic by-product 0.68percent amine content, and appearance was black. The decanted mass is then cooled to 30-35° C. and charged 63 ml 50percent Sulphuric acid (H2SO4) slowly in 1.0 hrs to get pH 3.5 to 4.0. Liquid layer was then filtered and crystalline material was washed with 150 ml water to get 65 g off white with purity 98percent with melting range 230° C. Total filtrate i.e. reaction medium and washings was collected recycled in subsequent batches.Twenty-Fifth recycle: In the same set up as described above, 700 ml reaction medium generated in twenty-fourth cycles was charged, heated to 90° C. Charged 20 ml 50percent H2SO4 to get pH 2.0 and immediately charged 60 g G-CAT start up with continuous stirring at 90-100° C. First lot of 15.3 g Nitro 20 g G-CAT was charged to the reaction mass in 10 min. The reaction mass was maintained for 5-10 min at 98-100° C. Remaining lots of nitro G-CAT was charged in four equal lots in similar manner as followed for first lot. Reaction mass was maintained at 98-100° C. for 60 min. Then 195.0 ml 25percent Na2CO3 was charged in 30 min to adjust pH 8.5. Then it is decanted collected in separate flask for further processing. 400 ml hot water wash given to solid inorganic by-product, remaining in the flask under stirring at 98°-100° C., to get 330 g of dry cake of solid inorganic by-product 0.53percent amine content, and appearance was black. The decanted mass is then cooled to 30-35° C. and charged 68 ml 50percent Sulphuric acid (H2SO4) slowly in 1.0 hrs to get pH 3.5 to 4.0. Liquid layer was then filtered and crystalline material was washed with 150 ml water to get 66 g off white with purity 97.12percent with melting range 231° C. Total filtrate i.e. reaction medium and washings was collected recycled in subsequent batches.

Reference： [1] Patent: CN105949076, 2016, A, . Location in patent: Paragraph 0025; 0026; 0031; 0036; 0040; 0045; 0053
[2] Journal of the Iranian Chemical Society, 2014, vol. 11, # 6, p. 1587 - 1592
[3] Synthetic Communications, 2000, vol. 30, # 20, p. 3639 - 3644
[4] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2000, vol. 39, # 9, p. 709 - 711
[5] Synthetic Communications, 2003, vol. 33, # 2, p. 281 - 289
[6] Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2009, vol. 48, # 9, p. 1315 - 1318
[7] Patent: WO2011/48535, 2011, A1, . Location in patent: Page/Page column 40-42
[8] Patent: US2012/203031, 2012, A1, . Location in patent: Page/Page column 12-14
[9] Justus Liebigs Annalen der Chemie, 1856, vol. 99, p. 104
[10] Zeitschrift fuer Chemie, 1865, p. 51
[11] Justus Liebigs Annalen der Chemie, 1870, vol. 154, p. 326 Anm. 2
[12] Justus Liebigs Annalen der Chemie, 1870, vol. 154, p. 326 Anm. 2
[13] Journal of the American Chemical Society, 1956, vol. 78, p. 3210,3215
[14] The Journal of biological chemistry, 1958, vol. 233, # 1, p. 184 - 188
[15] Journal and Proceedings of the Royal Society of New South Wales, 1940, vol. 74, p. 74,79, 373
[16] Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 2011, vol. 41, # 6, p. 590 - 597

2
[ 99-34-3 ]
[ 618-84-8 ]
[ 535-87-5 ]

Reference： [1] Advanced Synthesis and Catalysis, 2011, vol. 353, # 8, p. 1306 - 1316

3
[ 401-99-0 ]
[ 535-87-5 ]

Reference： [1] Photochemistry and Photobiology, 2005, vol. 81, # 6, p. 1539 - 1543

4
[ 65-85-0 ]
[ 535-87-5 ]

Reference： [1] Justus Liebigs Annalen der Chemie, 1870, vol. 154, p. 326 Anm. 2
[2] Justus Liebigs Annalen der Chemie, 1856, vol. 99, p. 104

5
[ 4277-02-5 ]
[ 535-87-5 ]

Reference： [1] Chemische Berichte, 1882, vol. 15, p. 2721

6
[ 81417-03-0 ]
[ 535-87-5 ]

Reference： [1] Chemische Berichte, 1882, vol. 15, p. 2721

7
[ 368-53-6 ]
[ 535-87-5 ]

Reference： [1] Photochemistry and Photobiology, 2005, vol. 81, # 6, p. 1539 - 1543

[ 535-87-5 ] Synthesis Path-Downstream 1~29

1
[ 67-56-1 ]
[ 535-87-5 ]
[ 1949-55-9 ]

Yield	Reaction Conditions	Operation in experiment
96%	With hydrogenchloride
94%	With thionyl chloride ice-NaCl cold bath, 45 min, 40 deg C, 4 h;
89%	With sulfuric acid at 90℃; for 6h; Cooling with ice; Reflux;	2 3.1.2. Methyl 3,5-diaminobenzoate (7) 3,5-Diaminobenzoic acid 6 (1.52 g, 10 mmol) was dissolved in 20 mL 10% sulfuric acid-methanol solution under an ice water bath, then refluxed at 90 °C for 6 h. After cooling, the solution was concentrated in vacuo, extracted with ethyl acetate, neutralized with saturated sodium bicarbonate solution, the extract was dried over anhydrous Na2SO4, ethyl acetate evaporated, and the residue was distilled in vacuo to give compound 7 (1.48 g, 8.9 mmol, 89%). 1H NMR (400 MHz, CD3OD) d 6.76e6.73 (m, 2H, ArH), 6.32e6.31 (m,1H, ArH), 3.82 (s, 3H, CH3O-).

89%	With sulfuric acid at 90℃; for 6h; Cooling with ice;	1.2.2 1.2.2 Synthesis of Compound A2: Add 1.52g A120mlCH3OH, 2ml concentrated sulfuric acid in sequence in a single-necked flask under ice-water bath, stir and dissolve and reflux for 6h at 90 ° C, stop the reaction and distill off the methanol, add the appropriate amount of ethyl acetate After extraction, washing with water and saturated sodium bicarbonate solution three times, ethyl acetate was rotary evaporated to give 21.48g of black solid product, yield 89%
85%	Stage #1: 3.5-diaminobenzoic acid With hydrogenchloride In methanol at 0℃; for 2h; Stage #2: methanol In methanol for 4h; Heating;
85%	With hydrogenchloride for 4h; Heating;
76%	With sulfuric acid at 90℃; for 24h;
65%	With sulfuric acid for 48h; Heating;
49.4%	With sulfuric acid at 90℃; for 32h;
	With sulfuric acid
	With thionyl chloride	IV.2 Step 2: Step 2: Synthesis of methyl 3,5-bis(2′-decyltetradecanamido)benzoate [0132] 3,5-Diaminobenzoic acid (Sigma-Aldrich) was esterified using a known procedure (Electrochimica Acta 2001, 46, 3955-3962) with thionyl chloride and anhydrous methanol to give the corresponding methyl ester, methyl 3,5-diaminobenzoate. Methyl 3,5-diaminobenzoate (260.8 mg, 1.9 mmol) was dissolved in dry tetrahydrofuran (5 mL) in a 100 mL vessel under inert atmosphere. Triethylamine (0.7 mL, 4.99 mmol) was then added and the solution was cooled to 0° C. A solution of 2-decyltetradecanoyl chloride from Step 1 in dry tetrahydrofuran (10 mL) was then added slowly, dropwise. The reaction was then allowed to warm slowly to room temperature. After stirring overnight, the reaction was quenched with water and the tetrahydrofuran was removed by rotary evaporation. The crude product residue was then dissolved in diethyl ether (50 mL) and washed with deionized water (20 mL). The ether layer was separated and concentrated to give methyl 3,5-bis(2′-decyltetradecanamido)benzoate as a pale pink solid (1.17 g).
	With thionyl chloride	3.2 3,5-diaminobenzoic acid (Sigma-Aldrich) was esterified with thionyl chloride and absolute methanol using a known method (Electrochimica Acta 2001, 46, 395-3-362) to give the corresponding methyl ester, i.e., 3,5-diaminobenzoate.3,5-diaminobenzoate (260.8 mg, 1.9 mmol) was dissolved in dry tetrahydrofuran (5 mL) under an inert atmosphere in a 100 mL vessel.After which triethylamine (0.7 mL, 4.99 mmol) was added and the solution was cooled to 0 & lt; 0 & gt; C.A solution (10 mL) of 2-decyltetradecanoyl chloride in step 1 dissolved in dry tetrahydrofuran was then slowly added dropwise.The reaction was then slowly warmed to room temperature.After stirring overnight, the reaction was quenched with water and the tetrahydrofuran was removed by rotary evaporation.The crude product residue was then dissolved in diethyl ether (50 mL) and washed with deionized water (20 mL).The ether layer was separated and concentrated to give methyl 3,5-bis (2'-decyltetradecanoyl) benzoate as a pale pink solid (1.17 g).
	With sulfuric acid
	With sulfuric acid for 5h;

Reference： [1]Kraft, Arno; Osterod, Frank [Journal of the Chemical Society. Perkin transactions I, 1998, # 6, p. 1019 - 1025]
[2]Huang, Danwen; Matile, Stefan; Berova, Nina; Nakanishi, Koji [Heterocycles, 1996, vol. 42, # 2, p. 723 - 736]
[3]Yang, Qinglai; He, Changyu; Zhang, Zhen; Tan, Lianjiang; Liu, Bingya; Zhu, Zhenggang; Shao, Zhifeng; Gong, Bing; Shen, Yu-Mei [Polymer, 2016, vol. 90, p. 351 - 362]
[4]Current Patent Assignee: SHANGHAI JIAO TONG UNIVERSITY - CN104693258, 2017, B Location in patent: Paragraph 0103; 0106
[5]Ho, Yong Lee; Seong, Ryong Nam; Hong, Jong-In [Journal of the American Chemical Society, 2007, vol. 129, # 5, p. 1040 - 1041]
[6]Nam, Seong Ryong; Lee, Ho Yong; Hong, Jong-In [Tetrahedron, 2008, vol. 64, # 46, p. 10531 - 10537]
[7]Hou, Jiaxin; Liao, Jinglun; Feng, Yancong; Feringa, Ben L.; Chen, Jiawen; Li, Hao; Zhou, Guofu [ChemPlusChem, 2020, vol. 85, # 6, p. 1104 - 1110]
[8]Page, Daniel; Roy, Rene [Bioorganic and Medicinal Chemistry Letters, 1996, vol. 6, # 15, p. 1765 - 1770]
[9]Ma, Jing-Jing; Liu, Wei-Sheng [Dalton Transactions, 2019, vol. 48, # 32, p. 12287 - 12295]
[10]Yoshiizumi, Kazuya; Nakajima, Fumio; Dobashi, Rika; Nishimura, Noriyasu; Ikeda, Shoji [Bioorganic and Medicinal Chemistry Letters, 2004, vol. 14, # 11, p. 2791 - 2795]
[11]Current Patent Assignee: XEROX CORP - US2013/158135, 2013, A1 Location in patent: Paragraph 0132
[12]Current Patent Assignee: XEROX CORP - CN103159639, 2016, B Location in patent: Paragraph 0190
[13]Liao, Jinglun; Feng, Yancong; Zhang, Jingxing; Li, Hao; Zhou, Guofu [Journal of Molecular Liquids, 2022, vol. 349]
[14]Mondal, Debashis; Ahmad, Manzoor; Panwaria, Prakash; Upadhyay, Avisikta; Talukdar, Pinaki [Journal of Organic Chemistry, 2022, vol. 87, # 1, p. 10 - 17]

2
[ 24424-99-5 ]
[ 535-87-5 ]
[ 133887-83-9 ]

Yield	Reaction Conditions	Operation in experiment
96%	With triethylamine In methanol
94%	In 1-methyl-pyrrolidin-2-one at 0 - 20℃; Inert atmosphere;
94%	In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Inert atmosphere;	1.2 2. Synthesis of compound 2 Using 3,5-diaminobenzoic acid (1.65 g, 10.9 mmol) and di-tert-butyldicarbonate (5.2 g, 23.9 mmol), and n-methyl-2-pyrrolidone (NMP, 50 mL) as a solvent The reaction was carried out at room temperature under a nitrogen atmosphere for 12 hours, and the reactant cooled in cold water was added to obtain a precipitate, and then the precipitate was filtered to remove the residual solvent. Then, the filtered precipitate was extracted with ethyl acetate. It was dried in vacuum at 80° C. for more than 24 hours to obtain 3,5-di-tertiary-butoxycarbonylaminobenzoic acid (Compound 2) in a powder form with a yield of 94%.

87%	With sodium hydroxide In <i>tert</i>-butyl alcohol at 20℃; for 16h;
83%	With triethylamine In dichloromethane at 25℃; for 24h;	9.1 Step 1: Synthesis of Compound 9a The synthesis of Compound 9a was performed as described in the literature (Synthesis, 1986, 48.). 3,5-diaminobenzoic acid (0.45 g, 2.96 mmol) and di-tert-butoxy dicarbonate ((t-Boc)2O, 0.57 g, 8.9 mmol) with triethylamine (NEt3; 2.1 mL, 10.6 mmol) in DCM, 60 mL) were stirred at room temperature (25° C.) for overnight (24 hours). The resulting solution was extracted with water, dried with Na2SO4 to give Compound 9a (N-Boc-3,5-diaminobenzoic acid) (0.87 g, yield 83%) as a brown powder. Chemical formula of Compound 9a: C17H24N2O6. 1H NMR (500 MHz, CDCl3) δ 7.87 (s, 1H, ArH), 7.70 (s, 2H, ArH), 6.90 (bs, 2H, NH), 1.52 (s, 18H, CH3).
	With sodium hydroxide In water; <i>tert</i>-butyl alcohol Cooling with ice;	10a (Example 10a) Synthesis of compound (1)-1a by a consecutive method In a 1000-ml three-neck flask, 10 g (65.7 mmol) of 3,5-diaminobenzoic acid, 150 ml of t-butanol and 150 ml of a 1N NaOH aqueous solution were added and stirred, ant it was confirmed that the compound was dissolved. 29.4 g (134.7 mmol) of di-t-butyl dicarbonate were dropped thereto and stirred while cooling with ice. After confirming the disappearance of the raw materials by HPLC, 300 ml of toluene were added therto. After neutralizing this solution by adding hydrochloride acid thereto, the solution was separated. After adding 200 ml of water and separating the solution, 6.7 g (65.7 ml) of triethylamine were added to the oil layer and stirred under a nitrogen atmosphere. To this reaction solution, 7.5 g (65.7 mmol) of methanesulfonyl chloride were added and stirred for 30 minutes while cooling with ice. To this reaction solution, a solution prepared by mixing 7.7 g (65.7 mmol) of 3-ethynylaniline and 6.7 g (65.7 mmol) of triethylamine in 10 ml of toluene was dropped. After confirming the disappearance of the raw materials by HPLC, 200 ml of water was added and the solution was separated. To the obtained toluene layer, 22.1. g (230 mmol) of methanesulfonic acid were added and stirred at room temperature. After confirming the disappearance of the raw materials, the solution was neutralized with a sodium bicarbonate aqueous solution and washed with distilled water. The obtained organic layer was condensed using an evaporator, thereby obtaining 7.74 g of compound (1)-1a (yield: 47%). The properties of the obtained compound were the same as those of the compound obtained in Example 3a.
	In methanol at 20℃; for 24h;

Reference： [1]Kumar, Anil; Meijer [Chemical Communications, 1998, # 16, p. 1629 - 1630]
[2]Location in patent: experimental part Kwon, Se Jin; Chae, Boknam; Kim, Joo Young; Jung, Woo-Sik; Lee, Seung Woo [Molecular Crystals and Liquid Crystals, 2012, vol. 563, p. 1 - 9]
[3]Current Patent Assignee: KOREA INSTITUTE OF INDUSTRIAL TECHNOLOGY - KR2021/129538, 2021, A Location in patent: Paragraph 0043-0046; 0054-0056
[4]Thoma, Gebhard; Streiff, Markus B.; Katopodis, Andreas G.; Duthaler, Rudolf O.; Voelcker, Nicolas H.; Ehrhardt, Claus; Masson, Christophe [Chemistry - A European Journal, 2006, vol. 12, # 1, p. 99 - 117]
[5]Current Patent Assignee: INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE - US2018/169262, 2018, A1 Location in patent: Paragraph 0157-0159
[6]Current Patent Assignee: FUJIFILM HOLDINGS CORP. - EP2202220, 2010, A1 Location in patent: Page/Page column 61
[7]Redko, Boris; Albeck, Amnon; Gellerman, Gary [New Journal of Chemistry, 2012, vol. 36, # 11, p. 2188 - 2191]

3
[ 64-17-5 ]
[ 535-87-5 ]
[ 1949-51-5 ]

Yield	Reaction Conditions	Operation in experiment
91%	With thionyl chloride; In ethanol; at 0℃;Inert atmosphere; Reflux;	In a two-neck round bottom flask, thionyl chloride (SOCl2; 1.0 eq.)was added dropwise to dry ethanol under nitrogen at 0C. Afterwards, 25 (3.0 eq.) was added in3 portions and the resulting mixture was stirred at reflux overnight. The ethanol and unreacted SOCl2were evaporated, remaining residue was dissolved in water and alkalized with sat. aqueous solutionof NaHCO3. The cloudy mixture was extracted with ethyl acetate, collected organic phases werewashed with water and dried over a MgSO4. Brown crystals were obtained (91% yield).

Reference： [1]Organic Letters,2011,vol. 13,p. 212 - 215
[2]Journal of Organic Chemistry,2001,vol. 66,p. 2978 - 2989
[3]Molecules,2019,vol. 24
[4]Chemistry - A European Journal,2001,vol. 7,p. 686 - 699

4
[ 535-87-5 ]
[ 19094-48-5 ]

Yield	Reaction Conditions	Operation in experiment
		To an ice -cooled stirred suspens ion of 3,5 -diaminobenzoic acid (6.0 g, 39.5 mmol) in concentrated sulfuric acid (60.0 ml) mixed with water (30.0 ml), sodium nitrite (6.5 g, 94.00 mmol) was slowly added. The color of the originally red suspension changed to orange. After 2 hours, urea ( 6.0 g, 100.00 mmol) was added, and then the solution was added slowly to an ice cooled solution of potassium iodide (40.0 g) in water (40.0 ml). After 3 hours at room temperature, water (300.0 ml) was added, and a black -brown solid was collected by filtra tion. This solid was dissolved in ethyl acetate, and the solution was washed with aqueous NaS 2O3 until the I2 had disappeared. Ethyl acetate was removed to give a brown solid in the amount of 7.1 g. This product was used for the next step without any fur ther purification.
	With potassium iodide; urea; sodium nitrite; In sulfuric acid; water; ethyl acetate;	Step 1: 3,5-Diiodobenzoic acid (YZ-I-89) To an ice-cooled stirred suspension of 3,5-diaminobenzoic acid (6.0 g, 39.5 mmol) in concentrated sulfuric acid (60.0 ml) mixed with water (30.0 ml), sodium nitrite (6.5 g, 94.00 mmol) was slowly added. The color of the originally red suspension changed to orange. After 2 hours, urea (6.0 g, 100.00 mmol) was added, and then the solution was added slowly to an ice cooled solution of potassium iodide (40.0 g) in water (40.0 ml). After 3 hours at room temperature, water (300.0 ml) was added, and a black-brown solid was collected by filtration. This solid was dissolved in ethyl acetate, and the solution was washed with aqueous NaS2O3 until the I2 had disappeared. Ethyl acetate was removed to give a brown solid in the amount of 7.1 g. This product was used for the next step without any further purification.

Reference： [1]Tetrahedron,2002,vol. 58,p. 3999 - 4005
[2]New Journal of Chemistry,2011,vol. 35,p. 2130 - 2135
[3]ChemPlusChem,2015,vol. 80,p. 1259 - 1266
[4]Organic and Biomolecular Chemistry,2011,vol. 9,p. 4440 - 4443
[5]Journal of Polymer Science, Part A: Polymer Chemistry,2013,vol. 51,p. 1315 - 1322
[6]Journal of the American Chemical Society,2012,vol. 134,p. 8718 - 8728
[7]Patent: WO2009/80799,2009,A2 .Location in patent: Page/Page column 57-58
[8]Patent: US2010/331509,2010,A1

5
[ 535-87-5 ]
[ 1107-00-2 ]
polymer, inherent viscosity 0.76 dl/g; monomer(s): 3,5-diaminobenzoic acid; 4,4\-(hexafluoroisopropylidene)diphthalic anhydride [ No CAS ]

Reference： [1]Macromolecules,2003,vol. 36,p. 5885 - 5890

6
[ 535-87-5 ]
[ 28920-43-6 ]
[ 248602-44-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium carbonate In tetrahydrofuran; water at 20℃;
72%	With sodium hydrogencarbonate In 1,4-dioxane at 0 - 20℃; for 9h;
	With sodium hydrogencarbonate In water	4.a a) a) Synthesis of 3,5-di(Fmoc-Amino)benzoic Acid The compound was synthesised from 3,5-diaminobenzoic acid and Fmoc-chloride using sodium bicarbonate as base in a mixture of water and a suitable organic solvent. NMR analytical data were in accordance with the structure.

Reference： [1]Wang, Minghui; Feng, Xiaoqian; Gao, Ruixuan; Sang, Peng; Pan, Xin; Wei, Lulu; Lu, Chao; Wu, Chuanbin; Cai, Jianfeng [Journal of Medicinal Chemistry, 2021, vol. 64, # 14, p. 9894 - 9905]
[2]Douat-Casassus, Celine; Darbre, Tamis; Reymond, Jean-Louis [Journal of the American Chemical Society, 2004, vol. 126, # 25, p. 7817 - 7826]
[3]Current Patent Assignee: GENERAL ELECTRIC CO - US6548048, 2003, B1

7
[ 535-87-5 ]
[ 121-44-8 ]
[ 4263-52-9 ]
3-[bis-(2-sulfo-ethyl)-amino]-5-(2-sulfo-ethylamino)-benzoic acid; compound with triethyl-amine [ No CAS ]

Reference： [1]Tetrahedron Letters,2006,vol. 47,p. 8279 - 8284

8
[ 368-53-6 ]
C₁₄H₁₃F₃N₄O [ No CAS ]
C₁₄H₁₄N₄O₃ [ No CAS ]
C₂₁H₁₉F₃N₆O₂ [ No CAS ]
[ 535-87-5 ]

Reference： [1]Photochemistry and Photobiology,2005,vol. 81,p. 1539 - 1543

9
[ 535-87-5 ]
[ 1949-55-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	With sulfuric acid In methanol at 90℃; for 6h;
60%	With thionyl chloride In methanol	19 Methyl 3,5-diaminobenzoate Methyl 3,5-diaminobenzoate Thionyl chloride (3.7 g) was added dropwise under ice cooling to a solution of 5.0 g (33 mmol) of 3,5-diaminobenzoic acid in 250 ml of methanol, followed by stirring at room temperature for 2 hours and then stirring under heating and reflux for additional 6 hours. After the solvent was distilled out under reduced pressure, the residue was neutralized with aqueous ammonia and then extracted with methylene chloride. The extract was dried over sodium sulfate and then dried up under reduced pressure, whereby 3.3 g of white powder were obtained (yield: 60%). IR(KBr)cm-1: 3389, 3314, 3219, 1705, 1602, 771.

Reference： [1]Yang, Qinglai; Bai, Ling; Zhang, Yuanqing; Zhu, Fangxia; Xu, Yuhong; Shao, Zhifeng; Shen, Yu-Mei; Gong, Bing [Macromolecules, 2014, vol. 47, # 21, p. 7431 - 7441]
[2]Current Patent Assignee: MITSUI CHEMICALS,INC. - US5852011, 1998, A

10
[ 88-21-1 ]
[ 535-87-5 ]
[ 292827-49-7 ]

Yield	Reaction Conditions	Operation in experiment
		Preparation Example 9 ; Dissolving 17.3 parts of 1-aminobenzene-2-sulfonic acid in 1000 parts of ice water, adding 24 parts of 32% HCl aqueous solution therein and stirring the solution adequately, then adding 7.0 parts of sodium nitrite aqueous solution and stirring the solution continuously under the temperature of 0~5C till the diazotization is completed. Then, adding 15.2 parts of 3,5-diaminobenzoic acid powders into the reaction solution and stirring the mixed reaction solution till the coupling reaction is completed. At last, adding NaCl to salt-out and filtrating the solution to obtain the following formula (II-1) compound.
		PREPARATION EXAMPLE 3Dissolving 17.3 parts of 1-aminobenzene-2-sulfonic acid in 200 parts of ice water, adding 24 parts of 32% HCl aqueous solution therein and stirring the solution adequately, then adding 7 parts of sodium nitrite aqueous solution and stirring the solution continuously under the temperature of 05 C. till the diazotization is completed. After that, adding 15.2 parts of 3,5-diaminobenzoic acid powders into the reaction solution and stirring the reaction mixture till the coupling reaction is completed. At last, adding NaCl to salt-out and filtrating the solution to obtain the following formula (III-2) compound.

Reference： [1]Patent: EP1930379,2008,A2 .Location in patent: Page/Page column 14-15
[2]Patent: US2008/282484,2008,A1 .Location in patent: Page/Page column 6

11
[ 2494-89-5 ]
[ 535-87-5 ]
C₂₃H₂₄N₆O₁₄S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; water; sodium nitrite at 0 - 5℃; Stage #2: 3.5-diaminobenzoic acid With sodium hydrogencarbonate In water at 10 - 15℃;	2 PREPARATION EXAMPLE 2; 33.8 parts of 1-aminobenzene-4-β-sulfatoethylsulfone are prepared and dissolved in 200 parts of ice water, and followed by stirring in 16 parts of 32% HCl aqueous solution. Subsequently the reacting solution undergoes diazotization by the addition of 8.7 parts of sodium nitrite aqueous solution under a temperature of 0 to 5° C. To this mixture 9.1 parts of powdered 3,5-diaminobenzoic acid are then added, and the pH is adjusted gradually to 3.5 by the addition of sodium bicarbonate. Under a temperature of 10-15° C., it is stirred till coupling reaction has completed. The solution is salted out with NaCl and filtered to obtain compound (3).
	Stage #1: 2-(p-aminophenylsulfonyl)ethyl hydrogen sulfate With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: 3.5-diaminobenzoic acid With sodium hydrogencarbonate In water at 10 - 15℃;	2 Preparation example 2; 33.8 parts of 1-aminobenzene-4-β-sulfatoethylsulfone are prepared and dissolved in 200 parts of ice water, and followed by stirring in 16 parts of 32% HCl aqueous solution. Subsequently the reacting solution undergoes diazotization by the addition of 8.7 parts of sodium nitrite aqueous solution under a temperature of 0 to 5°C. To this mixture 9.1 parts of powdered 3,5-diaminobenzoic acid are then added, and the pH is adjusted gradually to 3.5 by the addition of sodium bicarbonate. Under a temperature of 10-15°C, it is stirred till coupling reaction has completed. The solution is salted out with NaCl and filtered to obtain compound (3).

Reference： [1]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - US7387647, 2008, B2 Location in patent: Page/Page column 15-16
[2]Current Patent Assignee: EVERLIGHT CHEMICAL INDUSTRIAL CORPORATION - EP1669415, 2006, A1 Location in patent: Page/Page column 14

12
[ 535-87-5 ]
[ 6258-06-6 ]
sodium 1-amino-4-(3-amino-5-carboxyphenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With disodium hydrogenphosphate; sodium dihydrogenphosphate In water at 120℃; for 0.333333h; Microwave heating; Aqueous phosphate buffer;	2 To a 5 mL microwave reaction vial equipped with a magnetic stirring bar were added a bromo-substituted phenyl derivative or another mono-, bi- or tricyclic bromo-substituted compound (e.g. bromaminic acid sodium salt) (0.20 mmol) and the appropriate aniline derivative or other amino-substituted compound (0.40 mmol), followed by a buffer solution of Na2HPO4 (pH 9.6) (4 mL) and NaH2PO4 (pH 4.2) (1 mL). A catalytic amount (e.g. 0.002-0.003 g) of finely powdered elemental copper (or copper(I)-salt, or copper(II)-salt, respectively) was added. The mixture was capped and irradiated in the microwave oven (e.g. 40-100 W) for 1-30 min at 40-150 °C. Then the reaction mixture was cooled to rt, and the product was purified using the following procedure. The contents of the vial were filtered to remove the elemental copper. Then ca. 200 mL of water was added to the filtrate and the aqueous solution was extracted with chloroform (200 mL). The extraction procedure was repeated until the chloroform layer became colorless (2-3 times). Then the aqueous layer was reduced by rotary evaporation to a volume of 10-20 mL, which was subsequently submitted to flash column chromatography using RP-18 silica gel and water as an eluent. The polarity of the eluent was then gradually decreased by the addition of methanol in the following steps: 20, 40, 60, 80, and 100 %. Fractions containing blue product were collected. For some compounds the last step of purification (RP-18 flash chromatography) had to be repeated two to three times to obtain pure product (≥ 95% purity as determined by LC-MS). The pooled product-containing fractions were evaporated under vacuum to remove the methanol, and the remaining water was subsequently removed by lyophilization to yield the products (30-90%) as blue powders; Example 2 Sodium 1-amino-4-(3-amino-5-carboxyphenylamino)-9,10-dioxo-9,10-dihydroanthracene 2-sulfonate. Reaction conditions: according to the general procedure A: 20 min, 120 °C, 100 W; pressure up to 10 bar. Analytical data: mp > 300 °C, blue powder. 1H-NMR: δ 5.29 (bs, 2H, 3'-NH2), 6.53 (dd, 1H, 6'-H), 7.03 (d, 1H, 2'-H), 7.08 (d, 1H, 4'-H), 7.83 (m, 2H, 6-H, 7-H), 7.96 (s, 1H, 3-H), 8.26 (m, 2H, 5-H, 8-H), 10.13 (br, 2H, 1-NH2), 12.04 (s, 1H, 4-NH). 13C-NMR: δ 109.05 (C-9a), 110.75 (C-4a), 110.93, 112.33, 112.51 (C-2', C-4', C-6'), 123.40 (C-3), 126.07 (C-5), 126.15 (C-8), 132.86 (C-6), 133.17 (C-7), 133.83 (C-10a), 134.29 (C-8a), 139.11 (C-1'), 142.12 (C-4), 142.94 (C-2, C-5'), 144.35 (C-1), 149.77 (C-3'), 172.50 (COOH), 181.78 (C-9), 182.14 (C-10). LC-MS (m/z): 471 [M-Na+NH4+]+, 454 [M-Na]+, 452 [M-Na]-. Purity by HPLC-UV (254 nm)-ESI-MS: 95%.
	With disodium hydrogenphosphate; sodium dihydrogenphosphate; copper In water at 100 - 120℃; Microwave irradiation;
	With copper Phosphate buffer; Microwave irradiation;

Reference： [1]Current Patent Assignee: UNIVERSITY OF BONN - EP1967513, 2008, A1 Location in patent: Page/Page column 34-35; 38
[2]Location in patent: experimental part Baqi, Younis; Lee, Sang-Yong; Iqbal, Jamshed; Ripphausen, Peter; Lehr, Anne; Scheiff, Anja B.; Zimmennann, Herbert; Bajorath, Jürgen; Müller, Christa E. [Journal of Medicinal Chemistry, 2010, vol. 53, # 5, p. 2076 - 2086]
[3]Location in patent: experimental part Baqi, Younis; Hausmann, Ralf; Rosefort, Christiane; Rettinger, Jürgen; Schmalzing, Günther; Müller, Christa E. [Journal of Medicinal Chemistry, 2011, vol. 54, # 3, p. 817 - 830]

13
[ 132178-37-1 ]
[ 535-87-5 ]
[ 1092173-28-8 ]

Yield	Reaction Conditions	Operation in experiment
70%	With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; Inert atmosphere;

Reference： [1]Zou, Yekui; Yin, Jun [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 20, p. 5664 - 5667]

14
[ 13148-65-7 ]
[ 535-87-5 ]
[ 1208535-53-8 ]

Reference： [1]Tetrahedron Letters,2010,vol. 51,p. 653 - 656

15
[ 535-87-5 ]
[ 116-81-4 ]
sodium 1-amino-4-(3-amino-5-carboxyphenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With copper Heating; aq. phosphate buffer; Microwave irradiation;

Reference： [1]Location in patent: experimental part Baqi, Younis; Atzler, Kerstin; Köse, Meryem; Glänzel, Markus; Müller, Christa E. [Journal of Medicinal Chemistry, 2009, vol. 52, # 12, p. 3784 - 3793]

16
[ 535-87-5 ]
[ 17352-25-9 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 3 steps 1.1: sulfuric acid; urea; sodium nitrite / water / 2 h / 0 °C 1.2: 5 h / 25 °C 2.1: borane-THF 3.1: pyridinium chlorochromate / dichloromethane / 25 °C

Reference： [1]Li, Sinan; Moorefield, Charles N.; Shreiner, Carol D.; Wang, Pingshan; Sarkar, Rajarshi; Newkome, George R. [New Journal of Chemistry, 2011, vol. 35, # 10, p. 2130 - 2135]

17
[ 14615-72-6 ]
[ 535-87-5 ]
C₄₉H₄₀N₂O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In methanol; at 20℃; for 0.333333h;	To a heterogeneous solution of 3,5-diamino benzoic acid (0.23 g, 1.50 mmol) in MeOH(2 mL) was added a solution of aldehyde 7 (1.00 g, 3.15 mmol) in MeOH (20 mL). Afterstirring at room temperature for 20 min, the reaction flask was cooled in an ice bath and NaBH4 (0.096 g, 2.53 mmol) was added. The reaction was allowed to stir at room temperature overnight, after which TLC in 5% MeOH, 1% Et3N in CH2Cl2 confirmed its completion. The reaction was cooled to 0 C and distilled H2O (5 mL) was added. The DMSO, SO3.pyr,DIPEA, solution was neutralized with 2N HCl (6.4 mL) and extracted with CH2Cl2 (3X, 30 mL). The organic layers were combined and dried over MgSO4 and rotary evaporated to afford a green foam. The crude product was purified by silica gel column in 5% MeOH and 1% Et3N in CH2Cl2 to afford 0.98 g (92%) of a gold foam product.

Reference： [1]Beilstein Journal of Organic Chemistry,2013,vol. 9,p. 2320 - 2327

18
[ 616-02-4 ]
[ 535-87-5 ]
[ 143659-09-0 ]

Yield	Reaction Conditions	Operation in experiment
92%	Stage #1: citraconic acid anhydride; 3.5-diaminobenzoic acid In acetone at 25℃; for 2h; Stage #2: With 1,1,1,3,3,3-hexamethyl-disilazane; zinc(II) chloride In N,N-dimethyl-formamide; toluene for 5h; Reflux;	3,5-Di-(3-methylmaleimido)benzoic acid (12) To a solution of 3,5-diaminobenzoic acid (1.0 g, 6.58 mmol) in acetone (40 mL) was added citraconic anhydride (1.8 mL, 19.74 mmol) and the resulting mixture was stirred at 25° C. for 2 hours after which solvents were evaporated under reduced pressure. The crude solid was triturated in Et2O, filtered under reduced pressure and used in the next step without further purification. The dimaleamic acid (500 mg, 1.33 mmol) was dissolved in DMF (5 mL) and then toluene (40 mL) was added, followed by ZnCl2 (544 mg, 3.99 mmol) and HMDS (1.13 mL, 5.98 mmol). The resulting mixture was heated to reflux for 5 hours after which the solvents were evaporated. The title compound 12 was obtained as an off-white solid after precipitation with 0.1 M HCl (417 mg, 1.22 mmol, 92%). 1H NMR (300 MHz, DMSO-d6) δ 7.94 (d, J=1.8 Hz, 2H), 7.62 (t, J=1.8 Hz, 1H), 6.83 (q, J=1.8 Hz, 2H), 2.08 (d, J=1.8 Hz, 6H); 13C NMR (75 MHz, DMSO-d6) δ 170.4, 169.5, 166.2, 146.2, 132.8, 132.2, 128.2, 127.8, 126.0, 11.0; HRMS (ESI) Calculated for C17H13N2O6 [M+H]+: 341.0768. Found: 341.0770. m.p.: 254° C. (dec.).

Reference： [1]Current Patent Assignee: UNIVERSITY OF OTTAWA - US8835641, 2014, B2 Location in patent: Page/Page column 27

19
[ 88-21-1 ]
diazo 4-sulfatoethylsulfone-1-aminobenzene [ No CAS ]
[ 535-87-5 ]
C₂₉H₂₈N₈O₁₇S₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		(1) Diazotization of aniline-2-sulfonic acid: 9.6 g of aniline-2-sulfonic acid was added into 40 mL of water, the resulting mixture was well stirred and cooled to 0 C. to 5 C. with ice, 6.5 g of 31% (w/w) hydrochloric acid was then added, then 13.1 g of 30% (w/w) sodium nitrite solution was slowly added dropwise at 0 C. to 5 C., the pH of the mixture was controlled at 1.0 to 1.2, the reaction took 1.5 to 2 hours during which the potassium iodide test paper maintained a blue color, and excess sodium nitrite was eliminated with sulfamate acid to obtain a diazonium salt solution of aniline-2-sulfonic acid; (0031) (2) Diazotization of Para Base Ester: 31.4 g of Para Base Ester (i.e. p-((beta-sulfato ethyl sulfonyl) aniline) was added into 50 mL of water, the resulting mixture was well stirred and then cooled to 0 C. to 5 C. with ice, 11.5 g of 31% hydrochloric acid and 26 g of 30% sodium nitrite solution were added at 0 C. to 5 C., then the reaction was carried out for 1 hour while maintaining a temperatue of 0 C. to 5 C., a pH of ?1.2, and KI test paper in a blue color, and finally excess sodium nitrite was eliminated with sulfamic acid to give a diazonium salt solution of Para Base Ester; (0032) (3) the first coupling reaction: 8.5 g of 3,5-diaminobenzoic acid was added into 30 mL of water, after stirring well, the pH of the mixture was adjusted to 8.0 to 8.5 with sodium bicarbonate, stirred the mixture for 2 hours until 3,5-diaminobenzoic acid almost dissolved, then the diazonium salt solution of aniline-2-sulfonic acid obtained according to step (1) was added to the solution within 15min to 30 min, the temperature was maintained at ?5 C. with ice, the pH was adjusted to 5.8 to 6.2, and this was followed by reacting for 3 hours until 3,5-diaminobenzoic acid almost disappeared to give a solution of the first coupling reaction; (0033) (4) the second coupling reaction: the diazonium salt solution of Para Base Ester obtained according to step (2) was rapidly added drop-wise to the solution of the first coupling reaction obtained according to step (3), the pH of the mixture was controlled at 0.8 to 1.1 and the temperature was at 9 C. to 13 C., the resulting mixture was stirred until completely clear, then the pH was slowly adjusted to 5.5 to 6.5 with sodium bicarbonate, the temperature was controlled at 10 C. to 15 C., then coupling reaction was carried out for 8 hours with the pH maintained at 5.5 to 6.5, and the resulting slurry was dried to obtain a dye compound of formula (I-1) with a hydrazone structure in the form of free acid, whose NMR spectrum and COSY spectrum were respectively shown in FIG. 1 and FIG. 2. The fabric dyed with the dye displayed a yellow hue. (0034) Analysis of the spectra: (0035) There are two groups of peaks at 3.70 ppm to 4.04 ppm, which can be clearly attributed to the hydrogen atoms of methylene attached to the sulfur atom of sulfonyl group (SO2-CH2) , and the hydrogen atoms of methylene attached to the oxygen atom of hydrogen sulfate (HOSO2-O-CH2) in the reactive group (i.e. beta-sulfato ethyl sulfonyl). The integral value is 8, which indicates that there are two reactive groups (i.e. beta-sulfato ethyl sulfonyl). (0036) The peaks at 7.37 ppm to 8.20 ppm are attributed to the hydrogen atoms in the aromatic region, which can be divided into two parts: (0037) There are signals for four hydrogens at 7.30 ppm to 7.63 ppm, and the hydrogen-hydrogen related COSY spectrum and coupling constants indicate that: the signal at 7.38 ppm is split twice by the adjacent hydrogen atoms with chemical shifts of 7.44 ppm and 7.91 ppm, and the signal at 7.44 ppm is split twice by the adjacent hydrogen atoms with chemical shifts of 7.38 ppm and 7.63 ppm, indicating that the ring has the characteristic of 1,2-disubstituted structure, and the peaks can be attributed to hydrogen atoms of the component of formula (a). (0038) There are 4 sets of hydrogen signals at 7.92 ppm to 8.19 ppm, and the COSY spectrum indicates that: the hydrogen atom with a chemical shift of 7.91 ppm and the hydrogen atom with a chemical shift of 7.98 ppm are adjacent, and the hydrogen with a chemical shift of 8.01 ppm and the hydrogen with a chemical shift of 8.20 ppm are adjacent, indicating that each ring has the characteristic of para-disubstituted structrue. Thus, the peaks can be attributed to the hydrogen atoms on the rings of the components of formula (b) and formula (c), respectively. (0039) There should be two groups and a total of eight reactive hydrogen atoms in the structure of the yellow reactive dye, wherein, the reactive hydrogen atom of sulfonic group in the diazo component of formula (a), the reactive hydrogen atoms of hydrogen sulfates in the diazo components of formulas (b) and (c), and the reactive hydrogen atom of carboxylic acid group in the coupling component are very easy to be deuterated and combined in the water peak of solvent. Another group of hydrogen atoms attached to nitrogen atoms are present in the f...

Reference： [1]Patent: US2015/232668,2015,A1 .Location in patent: Paragraph 0030-0040

20
[ 88-21-1 ]
[ 535-87-5 ]
C₈H₉NO₆S₂ [ No CAS ]
C₂₉H₂₀N₈O₁₇S₅^(4-)*4Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Weigh 17.3 g of o-aminobenzenesulfonic acid placed in 500 ml beaker, respectively, add 80 grams of water and 40 grams of ice beating, cooling to 0 C. After half an hour, 12.25 g of hydrochloric acid at a concentration of 31% (w / w) was added and a solution of sodium nitrite (6.91 g of sodium nitrite) in a concentration of 30% (w / w) was added dropwise to an anthranilic acid Solution, the control temperature of 2 , pH = 2 diazotization reaction. After diazotization of o-aminobenzenesulfonic acid, a diazo solution was obtained.Weigh 15.2 grams of 3,5-diaminobenzoic acid placed in water, stirring half an hour later added to the diazo liquid, the control temperature of 5 C, pH = 2 for the first coupling reaction, the reaction is complete after a coupling .Also called 56.2 grams of para-ester placed in 500 ml beaker, respectively, add 200 grams of water and 80 grams of ice beating, cooling to 0 . After half an hour, 24.52 g of hydrochloric acid at a concentration of 31% (w / w) was added and a 30% w / w solution of sodium nitrite (containing 13.88 g of sodium nitrite) was added dropwise at a controlled temperature of 2C , PH = 2, followed by diazotization 2 hours laterThe reaction was terminated to obtain a para ester diazo solution.A second coupling was carried out by adding a para ester diazonium solution to the primary conjugate at a temperature of 5 C and pH = 6.0. After completion of the reaction, the insoluble matter was removed by filtration through a filter paper and dried in an oven to obtain a brown reactive dye represented by the formula (a).The resulting compound is dyed on a cotton cloth by a dyeing method commonly used for reactive dyes.

Reference： [1]Patent: CN104059000,2016,B .Location in patent: Paragraph 0095; 0096; 0097; 0098; 0099; 0100; 0101

21
[ 535-87-5 ]
[ 96-75-3 ]
C₈H₉NO₆S₂ [ No CAS ]
C₂₉H₁₉N₉O₁₉S₅^(4-)*4Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Weigh 21.7 grams of p-nitroaniline sulfonic acid placed in 500 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.25 g of hydrochloric acid at a concentration of 31% (w / w) was added and a 30% (w / w) concentration of sodium nitrite solution (containing 6.91 g of sodium nitrite) was added dropwise to p- Sulfonic acid solution, the control temperature is 2 ,PH = 2 for diazotization.After diazotization of p-nitroaniline-o-sulfonic acid, a diazonium solution was obtained. 15.15 g of 3,5-diaminobenzoic acid was weighed in water, stirred for half an hour and then added to the above diazo solution to control the temperature at 5 C and then adjusted to pH 2.5 with baking soda for the first coupling reaction, After completion of the reaction, a primary conjugate was obtained.Also called 28.16 grams of para-ester placed in 250 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.26 g of hydrochloric acid was added at a concentration of 31% (w / w), and a solution of sodium nitrite (containing 6.94 g of sodium nitrite) in a concentration of 30% (w / w) was added dropwise at a controlled temperature of 2C , PH = 2, and the diazotization reaction was completed after 2 hours to obtain p-ester diazo solution. A second coupling reaction was carried out by adding p-diazotized diazonium solution to the primary conjugate at a temperature of 8 C and adjusting the pH to 4 with baking soda. After the completion of the reaction, the secondary conjugate was obtained.Also called 28.18 grams of para-ester placed in 250 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.33 g of hydrochloric acid was added at a concentration of 31% (w / w), and a solution of sodium nitrite (containing 6.95 g of sodium nitrite) in a concentration of 30% (w / w) was added dropwise at a controlled temperature of 2 C , PH = 2, and the diazotization reaction was completed after 2 hours to obtain p-ester diazo solution.A third coupling reaction was carried out by adding p-diazonium azide to the secondary conjugate at a control temperature of 15 C and adjusting the pH to 5.5 with baking soda. After completion of the reaction, the insoluble matter was removed by filtration through a filter paper and dried in an oven to obtain a brown reactive dye as in the formula (I-3).The resulting compound is dyed on a cotton cloth by a dyeing method commonly used for reactive dyes.

Reference： [1]Patent: CN104059000,2016,B .Location in patent: Paragraph 0087; 0088; 0089; 0090; 0091; 0092; 0093; 0094

22
[ 535-87-5 ]
[ 96-75-3 ]
C₈H₉NO₉S₃ [ No CAS ]
C₈H₉NO₆S₂ [ No CAS ]
C₂₉H₁₈N₉O₂₂S₆^(5-)*5Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Weigh 21.8 gramsP-nitroaniline-o-sulfonic acidPlaced in 500 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.20 g of hydrochloric acid at a concentration of 31% (w / w) was added and a 30% w / w solution of sodium nitrite (containing 6.92 g of sodium nitrite) was added dropwise to p-nitroaniline Sulfonic acid solution, the control temperature is 2 ,PH = 2 for diazotization.After diazotization of p-nitroaniline-o-sulfonic acid, a diazonium solution was obtained. 15.2 g of 3,5-diaminobenzoic acid was weighed and placed in water. After stirring for half an hour, the solution was added to the above diazo solution. The temperature was controlled at 6 C and the pH was adjusted to 2.5 with baking soda. After completion of the reaction, a primary conjugate was obtained.Another 36.1 grams of sulfonated para-ester placed in 250 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.22 g of hydrochloric acid at a concentration of 31% (w / w) was added and a 30% w / w solution of sodium nitrite (containing 6.93 g of sodium nitrite) was added dropwise at a controlled temperature of 2 C , PH = 2, and the diazotization reaction was completed 2 hours later, and a sulfonated para ester diazonium solution was obtained. The second coupling reaction was carried out by adding the sulfonated para ester diazo solution to the primary conjugate at a temperature of 9 C and adjusting the pH to 4.5 with baking soda. After the completion of the reaction, the secondary conjugate was obtained.Also called 28.1 grams of para-ester placed in 250 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.31 g of hydrochloric acid was added at a concentration of 31% (w / w), and a solution of sodium nitrite (6.94 g of sodium nitrite) in a concentration of 30% (w / w) was added dropwise at a controlled temperature of 2C , PH = 2, and the diazotization reaction was completed after 2 hours to obtain p-ester diazo solution.A third coupling reaction was carried out by adding p-diazonium azide to the secondary conjugate at a temperature of 16 C and adjusting the pH to 6.0 with baking soda. After the completion of the reaction, insolubles were removed by filtration through a filter paper and dried in an oven to obtain a brown reactive dye of the formula (I-1).The resulting compound is dyed on a cotton cloth by a dyeing method commonly used for reactive dyes.

Reference： [1]Patent: CN104059000,2016,B .Location in patent: Paragraph 0071; 0072; 0073; 0074; 0075; 0076; 0077; 0078

23
[ 535-87-5 ]
[ 96-75-3 ]
[ 25781-90-2 ]
[ 41162-51-0 ]
C₂₉H₂₀N₉O₁₄S₄^(3-)*3Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Weigh 21.7 grams of p-nitroaniline sulfonic acid placed in 500 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.25 g of hydrochloric acid at a concentration of 31% (w / w) was added and a 30% (w / w) concentration of sodium nitrite solution (containing 6.91 g of sodium nitrite) was added dropwise to p- Sulfonic acid solution, the control temperature is 2 ,PH = 2 for diazotization.After diazotization of p-nitroaniline-o-sulfonic acid, a diazonium solution was obtained. 15.15 g of 3,5-diaminobenzoic acid was weighed in water, stirred for half an hour and then added to the above diazo solution at a control temperature of 6 C and then adjusted to pH 2.5 with baking soda for the first coupling reaction, After completion of the reaction, a primary conjugate was obtained.Also called 36.17 grams of sulfonated para-ester placed in 250 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.26 g of hydrochloric acid was added at a concentration of 31% (w / w), and a solution of sodium nitrite (containing 6.94 g of sodium nitrite) in a concentration of 30% (w / w) was added dropwise at a controlled temperature of 2C , PH = 2, and the diazotization reaction was completed 2 hours later, and a sulfonated para ester diazonium solution was obtained. The second coupling reaction was carried out by adding the sulfonated para ester diazo solution to the primary conjugate at a temperature of 9 C and adjusting the pH to 4.5 with baking soda. After the completion of the reaction, the secondary conjugate was obtained.Also called 28.18 grams of para-ester placed in 250 ml beaker, were added 100 grams of water and 50 grams of ice beating, cooling to 0 C. After half an hour, 12.33 g of hydrochloric acid was added at a concentration of 31% (w / w), and a solution of sodium nitrite (containing 6.95 g of sodium nitrite) in a concentration of 30% (w / w) was added dropwise at a controlled temperature of 2 C , PH = 2, and the diazotization reaction was completed after 2 hours to obtain p-ester diazo solution.A third coupling reaction was carried out by adding p-diazonium azide to the secondary conjugate at a temperature of 16 C and adjusting the pH to 6.0 with baking soda. After the reaction was completed, the pH was adjusted to pH 13 to de-esterify. After the pH was stabilized for 2 hours, the insoluble matter was removed by filtration through a filter paper and dried in an oven to obtain a brown reactive dye of the formula (I-2).The resulting compound is dyed on a cotton cloth by a dyeing method commonly used for reactive dyes.

Reference： [1]Patent: CN104059000,2016,B .Location in patent: Paragraph 0079; 0080; 0081; 0082; 0083; 0084; 0085; 0086

24
[ 535-87-5 ]
[ 88-44-8 ]
C₁₄H₁₂N₄O₅S^(2-)*2Na⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		In a 250 ml beaker, 5 g of water and 60 g of ice were added, and 18.7 g of 100% 4-methyl-2-sulfonic acid-aniline was added under stirring, followed by beating at 0 C. for 1 hour, then 12 g of 30% hydrochloric acid was added, and then Under the liquid surface, 7.11 g (97%) of industrial product sodium nitrite (made into a 30% sodium nitrite solution) was added, and the temperature was controlled at 5C. The KI test paper was slightly blue,Congo red paper dark blue, after the completion of the addition of sodium nitrite solution to maintain the temperature 5 C, KI test paper micro-blue reaction for 1 hour, before coupling with a small amount of sulfamic acid to eliminate the slight excess of nitrous acid.Seven, a couplingThe above-prepared diazonium salt was added to 149 g of 3,5-diamino-benzoic acid solution.After the addition of diazonium salt, slowly adjust pH=5-5.5 with baking soda 8.5g.At the same time, 12g of ice was added to control the temperature at 10C for one coupling, and the reaction was continued for 2 hours until the diazonium salt disappeared.

Reference： [1]Patent: CN104592786,2017,B .Location in patent: Paragraph 0042; 0053; 0054; 0055; 0056; 0126; 0129-0132

25
[ 618-58-6 ]
[ 535-87-5 ]

Yield	Reaction Conditions	Operation in experiment
92%	With ammonium hydroxide In water at 20℃; for 9h; Green chemistry;

Reference： [1]Avudaiappan; Palmurukan; Unnikrishnan; Sreekumar [New Journal of Chemistry, 2020, vol. 44, # 4, p. 1477 - 1484]

26
[ 1927-94-2 ]
[ 535-87-5 ]
3,5-bis[(E)-3-chloro-2-hydroxybenzylidene]amino}benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	In methanol for 3h; Reflux;	2.1.3 Synthesis of imines 2a-6h General procedure: Imines 2a-2h, 3a-3h, 4a-4h, 5a-5h, and 6a-6h were synthesized according to Krtk etal.(2020). Briefly, 1 mmol of amino compound (2, 4, 5, 6) was dissolved in 7 ml of MeOH and then appropriate aldehyde (1.1 mmol) was added in one portion. In the case of imines 3a-3h, 3,5-diaminobenzoic acid 3 (1 mmol) was dissolved in 10 ml of MeOH and 2.2 mmol of appropriate aldehyde was added. The reaction mixture was refluxed for 3 hours. After additional 12 hours of stirring at room temperature, the reaction mixture was stored at -20°C for 1 h. The precipitate formed was filtered off and washed successively by MeOH and diethyl ether thoroughly. If necessary, the products were crystallized from tetrahydrofuran/MeOH to obtain pure Schiff bases.

Reference： [1]Krátký, Martin; Konečná, Klára; Brokešová, Kateřina; Maixnerová, Jana; Trejtnar, František; Vinšová, Jarmila [European Journal of Pharmaceutical Sciences, 2021, vol. 159]

27
[ 535-87-5 ]
[ 215124-03-1 ]
3,5-bis[(E)-5-chloro-2-hydroxy-3-iodobenzylidene]amino}benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
92%	In methanol for 3h; Reflux;	2.1.3 Synthesis of imines 2a-6h General procedure: Imines 2a-2h, 3a-3h, 4a-4h, 5a-5h, and 6a-6h were synthesized according to Krtk etal.(2020). Briefly, 1 mmol of amino compound (2, 4, 5, 6) was dissolved in 7 ml of MeOH and then appropriate aldehyde (1.1 mmol) was added in one portion. In the case of imines 3a-3h, 3,5-diaminobenzoic acid 3 (1 mmol) was dissolved in 10 ml of MeOH and 2.2 mmol of appropriate aldehyde was added. The reaction mixture was refluxed for 3 hours. After additional 12 hours of stirring at room temperature, the reaction mixture was stored at -20°C for 1 h. The precipitate formed was filtered off and washed successively by MeOH and diethyl ether thoroughly. If necessary, the products were crystallized from tetrahydrofuran/MeOH to obtain pure Schiff bases.

28
[ 2631-77-8 ]
[ 535-87-5 ]
3,5-bis[(E)-2-hydroxy-3,5-diiodobenzylidene]amino}benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	In methanol; for 3h;Reflux;	General procedure: Imines 2a-2h, 3a-3h, 4a-4h, 5a-5h, and 6a-6h were synthesized according to Krtk etal.(2020). Briefly, 1 mmol of amino compound (2, 4, 5, 6) was dissolved in 7 ml of MeOH and then appropriate aldehyde (1.1 mmol) was added in one portion. In the case of imines 3a-3h, 3,5-diaminobenzoic acid 3 (1 mmol) was dissolved in 10 ml of MeOH and 2.2 mmol of appropriate aldehyde was added. The reaction mixture was refluxed for 3 hours. After additional 12 hours of stirring at room temperature, the reaction mixture was stored at -20C for 1 h. The precipitate formed was filtered off and washed successively by MeOH and diethyl ether thoroughly. If necessary, the products were crystallized from tetrahydrofuran/MeOH to obtain pure Schiff bases.

Reference： [1]European Journal of Pharmaceutical Sciences,2021,vol. 159

29
[ 535-87-5 ]
[ 88-64-2 ]
C₁₅H₁₅N₅O₆S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2-amino-4-acetylaminobenzene sulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 20℃; Stage #2: 3.5-diaminobenzoic acid With sodium carbonate; sodium hydroxide In water at 5 - 25℃;	1.1; 1.2 (1) Diazotization: Put 23.0g (0.1mol) 4-acetamido-2-aminobenzenesulfonic acid into 100g water and 100g ice to make a slurry for about 1h, then add 20g 31% hydrochloric acid (containing HCl 0.17mol), Add 24g 30% sodium nitrite solution (containing 0.104mol sodium nitrite) within 20-30min, Control pH=0.5-2.0, temperature T=0-20°C for diazotization reaction for 1 to 2 hours, and use 4-dimethylaminobenzaldehyde in ethanol to detect the end point (that is, the color does not change within 5s). After the diazonium end point is reached, use sulfamic acid to eliminate excess sodium nitrite, and the obtained 4-acetamido-2-aminobenzenesulfonic acid diazonium solution is stored for later use. (2) Coupling: First add 15.2g (0.1mol) 3,5-diaminobenzoic acid to 200g water for beating, adjust pH=8.0-9.0 with soda ash, temperature 20-25°C , Add the 0.1mol 4-acetamido-2-aminobenzenesulfonic acid diazonium solution obtained in step (1) to the beaten 3,5-diaminobenzoic acid solution, and use 30% liquid caustic so as to control the pH at 5- 5.5. Control the temperature at 5-10°C, react for 0.5-2.5h, use HPLC to control the free 3,5-diaminobenzoic acid below 3% to reach the end point, and obtain the color base shown in the following formula (A), mass spectrum as shown in picture 2.
	Stage #1: 2-amino-4-acetylaminobenzene sulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 20℃; Stage #2: 3.5-diaminobenzoic acid With sodium carbonate; sodium hydroxide In water at 5 - 25℃;	1.1-1.2 Diazotization: Put 23.0g (0.1mol) 4-acetamido-2-aminobenzenesulfonic acid into 100g water,Beat in 100g ice for about 1h, then add 20g 31% hydrochloric acid (containing HCl 0.17mol),Add 24g 30% sodium nitrite solution (containing 0.104mol sodium nitrite) within 20-30min,Control pH = 0.5-2.0, temperature T = 0-20 for diazotization reaction for 1 to 2 hours,The end point was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (that is, the color did not change within 5s).After the end of diazonium is reached, use sulfamic acid to eliminate excess sodium nitrite,The obtained 4-acetamido-2-aminobenzenesulfonic acid diazonium liquid is stored for later use.Put 56.2g (0.2mol) of para-ester (p-hydroxyethyl sulfone sulfate aniline) into 200g of water,Beat in 200g ice for about 1h, then add 35g 31% hydrochloric acid (containing HCl 0.3mol),Add 48g of 30% sodium nitrite solution (containing 0.208mol of sodium nitrite) within 20-30min,Control pH = 0.5-2.0, temperature T = 0-20 for diazotization reaction for 1 to 2 hours,Use 4-dimethylaminobenzaldehyde in ethanol to detect the end point (that is, the color does not change within 5 seconds).After the end of diazonium is reached, use sulfamic acid to eliminate excess sodium nitrite,The obtained para-ester diazonium liquid is stored for later use.(2) Coupling:First, 15.2g (0.1mol) of 3,5-diaminobenzoic acid is added to 200g of water for beating.Adjust pH=8.0-9.0 with soda ash, temperature 20-25, and add 0.1mol obtained in step (1) 4-Acetylamino-2-aminobenzenesulfonic acid diazonium solution is added to the beaten 3,5-diaminobenzoic acid solution, the pH is controlled at 5-5.5 with 30% liquid caustic soda, and the temperature is controlled at 5-10°C.After reacting for 0.5-2.5 hours, use HPLC to control the free 3,5-diaminobenzoic acid below 3% to reach the end point, and obtain the chromophore shown in the following formula (A). The mass spectrum is shown in Figure 2.
	Stage #1: 2-amino-4-acetylaminobenzene sulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 20℃; Stage #2: 3.5-diaminobenzoic acid With sodium carbonate; sodium hydroxide In water at 5 - 25℃;	1.1-1.2 Diazotization: Put 23.0g (0.1mol) 4-acetamido-2-aminobenzenesulfonic acid into 100g water,Beat in 100g ice for about 1h, then add 20g 31% hydrochloric acid (containing HCl 0.17mol),Add 24g 30% sodium nitrite solution (containing 0.104mol sodium nitrite) within 20-30min,Control pH = 0.5-2.0, temperature T = 0-20 for diazotization reaction for 1 to 2 hours,The end point was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (that is, the color did not change within 5s).After the end of diazonium is reached, use sulfamic acid to eliminate excess sodium nitrite,The obtained 4-acetamido-2-aminobenzenesulfonic acid diazonium liquid is stored for later use.Put 56.2g (0.2mol) of para-ester (p-hydroxyethyl sulfone sulfate aniline) into 200g of water,Beat in 200g ice for about 1h, then add 35g 31% hydrochloric acid (containing HCl 0.3mol),Add 48g of 30% sodium nitrite solution (containing 0.208mol of sodium nitrite) within 20-30min,Control pH = 0.5-2.0, temperature T = 0-20 for diazotization reaction for 1 to 2 hours,The end point was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (that is, the color did not change within 5s).After the end of diazonium is reached, use sulfamic acid to eliminate excess sodium nitrite,The obtained para-ester diazonium liquid is stored for later use.(2) Coupling:First, 15.2g (0.1mol) of 3,5-diaminobenzoic acid is added to 200g of water for beating.Adjust pH=8.0-9.0 with soda ash, temperature 20-25, and add 0.1mol obtained in step (1)4-Acetylamino-2-aminobenzenesulfonic acid diazonium solution is added to the beaten 3,5-diaminobenzoic acid solution, the pH is controlled at 5-5.5 with 30% liquid caustic soda, and the temperature is controlled at 5-10°C.React for 0.5-2.5h, use HPLC to control the free 3,5-diaminobenzoic acid below 3% to reach the end point, and obtain the chromophore represented by the following formula (A),The mass spectrum is shown in Figure 2.

Stage #1: 2-amino-4-acetylaminobenzene sulfonic acid With hydrogenchloride; sodium nitrite In water at 0 - 20℃; Stage #2: 3.5-diaminobenzoic acid With sodium carbonate; sodium hydroxide In water at 5 - 25℃;

1.1-1.2 Diazotization: Put 23.0g (0.1mol) 4-acetamido-2-aminobenzenesulfonic acid into 100g water,Beat in 100g ice for about 1h, then add 20g 31% hydrochloric acid (containing HCl 0.17mol),Add 24g 30% sodium nitrite solution (containing 0.104mol sodium nitrite) within 20-30min,Control pH = 0.5-2.0, temperature T = 0-20 for diazotization reaction for 1 to 2 hours,The end point was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (that is, the color did not change within 5s).After the end of diazonium is reached, use sulfamic acid to eliminate excess sodium nitrite,The obtained 4-acetamido-2-aminobenzenesulfonic acid diazonium liquid is stored for later use.Put 56.2g (0.2mol) of para-ester (p-hydroxyethyl sulfone sulfate aniline) into 200g of water,Beat in 200g ice for about 1h, then add 35g 31% hydrochloric acid (containing HCl 0.3mol),Add 48g of 30% sodium nitrite solution (containing 0.208mol of sodium nitrite) within 20-30min,Control pH = 0.5-2.0, temperature T = 0-20 for diazotization reaction for 1 to 2 hours,The end point was detected with an ethanol solution of 4-dimethylaminobenzaldehyde (that is, the color did not change within 5s).After the end of diazonium is reached, use sulfamic acid to eliminate excess sodium nitrite,The obtained para-ester diazonium liquid is stored for later use.(2) Coupling:First, 15.2g (0.1mol) of 3,5-diaminobenzoic acid was added to 200g of water for beating, adjusted to pH=8.0-9.0 with soda ash, and the temperature was 20-25. The 0.1mol obtained in step (1)4-acetyl Amino-2-aminobenzenesulfonic acid diazonium solution is added to the beaten 3,5-diaminobenzoic acid solution, the pH is controlled at 5-5.5 with 30% liquid caustic soda, the temperature is controlled at 5-10, and the reaction is 0.5- For 2.5 hours, control the free 3,5-diaminobenzoic acid below 3% by HPLC to reach the end point, and obtain the color base shown in the following formula (A), and the mass spectrum is shown in Figure 2.

Reference： [1]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD; ZHEJIANG KEYONG CHEMICAL ENG - CN112574592, 2021, A Location in patent: Paragraph 0189-0191; 0193-0195
[2]Current Patent Assignee: ZHEJIANG KEYONG CHEMICAL ENG; ZHEJIANG LONGSHENG GROUP CO., LTD - CN112679984, 2021, A Location in patent: Paragraph 0082-0088
[3]Current Patent Assignee: ZHEJIANG LONGSHENG GROUP CO., LTD; ZHEJIANG KEYONG CHEMICAL ENG - CN112679987, 2021, A Location in patent: Paragraph 0189-0195
[4]Current Patent Assignee: ZHEJIANG KEYONG CHEMICAL ENG; ZHEJIANG LONGSHENG GROUP CO., LTD - CN112679988, 2021, A Location in patent: Paragraph 0190-0196

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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. 535-87-5 ] {[proInfo.proName]}

Quality Control of [ 535-87-5 ]

Related Doc. of [ 535-87-5 ]

Product Details of [ 535-87-5 ]

Calculated chemistry of [ 535-87-5 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 535-87-5 ]

Application In Synthesis of [ 535-87-5 ]

[ 535-87-5 ] Synthesis Path-Upstream 1~7

[ 535-87-5 ] Synthesis Path-Downstream 1~29

Related Functional Groups of [ 535-87-5 ]

Aryls

Amines

Carboxylic Acids

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 535-87-5 ]