116-81-4

Basic information

• Product Name: Bromaminic acid
• Synonyms: 1-Amino-4-bromo-9,10-dihydro-9,10-dioxoanthracene-2-sulfonic acid;9,10-Dihydro-1-amino-4-bromo-9,10-dioxoanthracene-2-sulfonic acid;1-AMINO-4-BROMO-9,10-DIOXO-2-ANTHRACENSULFONICACID;1-AMino-4-broMoanthraquinone-2-sulfonic acid, 90+%;BroMaMinic acid, 90+%;1-amino-4-bromo-9,10-dihydro-9,10-dioxo-2-anthracenesulfonicaci;4-Bromo-1-aminoanthraquinone-2-sulfonicacid;BRONAMINE ACID
• CAS NO: 116-81-4
• Molecular Formula: C₁₄H₈BrNO₅S
• Molecular Weight: 382.19
• EINECS: 204-159-9
• Product Categories: ketone;Intermediates of Dyes and Pigments
• Mol File: 116-81-4.mol
• Article Data: 4

Chemical Properties

• Melting Point: ca 280℃
• Appearance: /
• Density: 1.908 g/cm³
• Refractive Index: 1.737
• PKA: -1.56±0.20(Predicted)
• CAS DataBase Reference: Bromaminic acid(CAS DataBase Reference)
• NIST Chemistry Reference: Bromaminic acid(116-81-4)
• EPA Substance Registry System: Bromaminic acid(116-81-4)

Safety Data

• TSCA: Yes
• Hazardous Substances Data: 116-81-4(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 116-81-4 differently. You can refer to the following data:
1. 1-Amino-4-bromoanthraquinone-2-sulfonic acid (bromamine acid) [CAS: 116-81-4] is the most important intermediate for manufacturing reactive and acid dyes.
2. Bromaminic acid is used as a dye.

InChI:InChI=1/C14H8BrNO5S/c15-8-5-9(22(19,20)21)12(16)11-10(8)13(17)6-3-1-2-4-7(6)14(11)18/h1-5H,16H2,(H,19,20,21)

Synthetic route

1-aminoanthraquinone-2-sulfonic acid (83-62-5) → 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4)

Conditions	Yield
With bromine In water at 53 - 55℃; for 1.5h; Temperature; Large scale;	96.6%
With hydrogenchloride; bromine; sodium chloride

C14H8BrNO5S*H2O4S → 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4)

Conditions	Yield
With sodium hydroxide In water at 90℃; for 8h; pH=8;	92%

phosgene (75-44-5) + 2-(3-amino-4-sulfo-benzoyl)-benzoic acid (861600-75-1) → 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4)

Conditions	Yield
man erwaermt das erhaltene Harnstoff-Derivat mit Brom in essigsaurer Loesung und erhitzt das Reaktionsprodukt mit rauchender Schwefelsaeure auf 130-135grad;

1-amino-9,10-anthracenedione (82-45-1) → 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: copper(II) sulfate / 1,2-dichloro-ethane / Large scale 1.2: 3 h / 83 - 85 °C / Large scale 2.1: bromine / water / 1.5 h / 53 - 55 °C / Large scale View Scheme
With sulfuric acid at 120℃; Behandeln des Reaktionsprodukts mit Brom in Wasser;
Multi-step reaction with 3 steps 1: sulfuric acid; sodium sulfate / 1,2-dichloro-benzene / 3 h / 150 °C 2: iodine; bromine / 1,2-dichloro-benzene / 8 h / 80 °C 3: sodium hydroxide / water / 8 h / 90 °C / pH 8 View Scheme

sulfuric acid (7664-93-9) + 1-amino-9,10-anthracenedione (82-45-1) → 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4)

Conditions	Yield
at 120℃; Behandeln der entstandenen Sulfonsaeure mit Bromwasser;

2-(4'-chloro-3'-nitrobenzoyl)benzoic acid (85-54-1) → 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium sulfite / nachfolgend Reduktion 2: man erwaermt das erhaltene Harnstoff-Derivat mit Brom in essigsaurer Loesung und erhitzt das Reaktionsprodukt mit rauchender Schwefelsaeure auf 130-135grad View Scheme

2-amino-6-nitrobenzothiazole (6285-57-0) + 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → 1-amino-4-[(6-nitro-2-benzothiazolyl)amino]-9,10-anthraquinone-2-sulfonic acid (1229115-40-5)

Conditions	Yield
With copper; potassium carbonate; copper(II) sulfate In water at 90℃; for 4h;	98%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid (69166-06-9)

Conditions	Yield
With copper(II) stearate; copper In N,N-dimethyl-formamide at 95℃; for 10h;	96.8%
With alkaline solution; copper
With Fe3O4(att)SiO2-Au/Cu magnetic nanoparticles In water at 90℃; for 2h; Catalytic behavior; Reagent/catalyst; Temperature; Time; Inert atmosphere;

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → sodium 1-amino-4-bromoanthraquinone-2-sulfonate (6258-06-6)

Conditions	Yield
With sodium sulfite In water at 90℃; Large scale;	95.3%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 3-<(hydroxyethyl)sulfonyl>aniline hydrochloride (19076-03-0) → C22H17N2O8S2(1-)

Conditions	Yield
Stage #1: 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid; 3-<(hydroxyethyl)sulfonyl>aniline hydrochloride With sodium hydrogencarbonate; lithium hydroxide In water at 20 - 60℃; Stage #2: With D-glucose; copper(II) sulfate In water at 60℃; for 5h; Stage #3: With sulfuric acid In water at 60℃;	90%
With copper(ll) sulfate pentahydrate; 2,3,4,5,6-pentahydroxy-hexanal; sodium hydrogencarbonate; lithium hydroxide In water at 60℃;	90%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + N-acetyl-p-phenylenediamine (122-80-5) → acid blue 40 sodium salt (6424-85-7)

Conditions	Yield
With copper at 120℃; under 7500.75 Torr; for 0.0833333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	90%

2-aminopyridine (504-29-0) + 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → 1-Amino-9,10-dioxo-4-(pyridin-2-ylamino)-9,10-dihydro-anthracene-2-sulfonic acid

Conditions	Yield
With sodium hydrogencarbonate; copper(II) sulfate; iron(II) sulfate In water at 90℃; for 6h;	85%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 3,5-dimethoxyphenethylamine (3213-28-3) → sodium 1-amino-4-(3,4-dimethoxyphenethylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate

Conditions	Yield
With copper at 100℃; for 0.0833333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	79%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + phenethylamine (64-04-0) → sodium 1-amino-4-(2-phenethylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (18837-50-8)

Conditions	Yield
With copper at 120℃; under 7500.75 Torr; for 0.4h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	75%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + (p-aminostyryl)phosphonic acid → 1-amino-2-sulfo-4-anthraquinone

Conditions	Yield
With sodium hydrogencarbonate; sodium carbonate; copper(l) chloride In water 1) 65-70 deg C, 2 h, 2) 90 deg C, 4 h;	74.5%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + m-aminophenylphosphonic acid (5427-30-5) → 1-amino-2-sulfo-4-(m-phosphonoanilino)anthraquinone

Conditions	Yield
With sodium hydrogencarbonate; sodium carbonate; copper(l) chloride In water at 70℃; for 20h;	56.5%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + p-benzylaniline (1135-12-2) → sodium 1-amino-4-(4-benzylphenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (1052089-06-1)

Conditions	Yield
With copper at 120℃; for 0.0833333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	51%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 3-nitro-aniline (99-09-2) → Sodium; 1-amino-4-(3-nitro-phenylamino)-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonate (100233-15-6)

Conditions	Yield
With copper at 120℃; under 7500.75 Torr; for 0.0833333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	49%

4-aminophenyl phenyl sulfide (1135-14-4) + 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → sodium 1-amino-4-(4-phenylthiophenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (1052089-10-7)

Conditions	Yield
With copper at 120℃; for 0.166667h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	48%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 4-aminodiphenylamine-2-sulfonic acid (91-30-5) → disodium 1-amino-4-[4-phenylamino-3-sulfophenylamino]-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate

Conditions	Yield
With copper at 120℃; for 0.0833333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	46%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + N-phenylphenylene-1,4-diamine (101-54-2) → sodium 1-amino-4-(4-anilinophenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (1007600-12-5)

Conditions	Yield
With copper at 120℃; for 0.0833333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	41%

4-phenoxy-3-sulfoaniline (6375-07-1) + 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → disodium 1-amino-4-[4-phenoxy-3-sulfophenylamino]-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate

Conditions	Yield
With copper at 120℃; for 0.0833333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	35%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 1-amino-naphthalene (134-32-7) → sodium 1-amino-4-(1-naphthylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (1052089-16-3)

Conditions	Yield
With copper at 120℃; under 7500.75 Torr; for 0.0833333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	35%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 2,5-diaminobenzenesulfonic acid (88-45-9) → disodium 1-amino-4-(4-amino-2-sulfophenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (20349-48-8) + disodium 1-amino-4-(4-amino-3-sulfophenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (15827-21-1, 32866-11-8, 116679-68-6)

Conditions	Yield
With copper at 120℃; for 0.333333h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	A 20% B 32%

p-aminophenyl acetate (13871-68-6) + 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → 1-amino-4-((4-(carboxymethyl)phenyl)amino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate

Conditions	Yield
With sodium carbonate; copper(II) sulfate In water for 16h; Reflux;	32%

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + benzylamine (100-46-9) → sodium 1-amino-4-(benzylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate (1052089-14-1)

Conditions	Yield
With copper at 120℃; for 0.166667h; Ullmann reaction; aq. phosphate buffer; Microwave irradiation;	30%

2,5 dichloroaniline (95-82-9) + 1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → 1-amino-4-(2,5-dichloro-anilino)-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonic acid

Conditions	Yield
With ethanol; sodium hydrogencarbonate; copper(l) chloride

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 2-METHYLCYCLOHEXYLAMINE (7003-32-9) → 1-amino-4-(2-methyl-cyclohexylamino)-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonic acid

Conditions	Yield
With pyridine; copper(I) sulfate; sodium carbonate; copper(II) sulfate

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 2-amino-4-trifluoromethylbenzoic acid (402-13-1) → N-(5,8,14-trioxo-11-trifluoromethyl-5,8,13,14-tetrahydro-naphth[2,3-c]acridin-6-yl)-benzamide (6219-97-2)

Conditions	Yield
With potassium acetate; copper; sodium carbonate Reagens 4: H2O; Erhitzen des Reaktionsprodukts mit konz. H2SO4 und mit Benzoylchlorid in Nitrobenzol;
With potassium acetate; sodium carbonate; copper(l) chloride Erhitzen des Reaktionsprodukts mit konz. H2SO4 und mit Benzoylchlorid in Nitrobenzol;
With potassium acetate; copper; sodium carbonate Reagens 4: H2O; Erhitzen des Reaktionsprodukts mit konz. H2SO4 und mit Benzoylchlorid in Nitrobenzol;

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + 2-amino-3-(trifluoromethyl)benzoic acid (313-12-2) → 6-amino-12-trifluoromethyl-13H-naphth[2,3-c]acridine-5,8,14-trione

Conditions	Yield
With water; potassium acetate; copper Erhitzen des Reaktionsprodukts mit konz. H2SO4;
With water; potassium acetate; copper Erhitzen des Reaktionsprodukts mit konz. H2SO4;

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + bornylamine (4481-88-3) → 1-amino-4-bornylamino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonic acid

Conditions	Yield
With copper(I) sulfate; ethanol; sodium carbonate; copper(II) sulfate

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) + potassium anthranilate (37960-65-9) → N-(4-amino-9,10-dioxo-3-sulfo-9,10-dihydro-[1]anthryl)-anthranilic acid (128-82-5)

Conditions	Yield
With water at 120 - 125℃;
With water at 120 - 125℃;

1-amino-4-bromo-9,10-dioxoanthracene-2-sulphonic acid (116-81-4) → 1-amino-2-bromoanthraquinone (3300-23-0)

Conditions	Yield
With sulfuric acid

Upstream product

• 7664-93-9 sulfuric acid 
• 82-45-1 1-amino-9,10-anthracenedione 
• 85-54-1 2-(4'-chloro-3'-nitrobenzoyl)benzoic acid 
• 75-44-5 phosgene 
• 861600-75-1 2-(3-amino-4-sulfo-benzoyl)-benzoic acid 
• 83-62-5 1-aminoanthraquinone-2-sulfonic acid 

Downstream Products

• 4095-85-6 1,4-diamino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonic acid 
• 69166-06-9 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acid 
• 2786-71-2 1-amino-4-anilino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonic acid 
• 102160-11-2 4-phenylamino-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid 
• 1052089-10-7 sodium 1-amino-4-(4-phenylthiophenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate 
• 1052089-06-1 sodium 1-amino-4-(4-benzylphenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate 
• 124515-86-2 sodium 1-amino-4-(3-amino-2,4,6-trimethylphenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate 
• 20349-48-8 disodium 1-amino-4-(4-amino-2-sulfophenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate 
• 15827-21-1 disodium 1-amino-4-(4-amino-3-sulfophenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate 
• 50314-37-9 sodium 1-amino-4-(4-hydroxyphenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate 
• 78510-31-3 sodium 1-amino-4-(4-chlorophenylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate 
• 18837-50-8 sodium 1-amino-4-(2-phenethylamino)-9,10-dioxo-9,10-dihydroanthracene-2-sulfonate 
• 6408-78-2 acid blue 25 

Related news

Catalysis, Kinetics and Reaction EngineeringLigand assisted copper-catalyzed Ullmann cross coupling reaction of Bromaminic acid (cas 116-81-4) with amines☆08/22/2019

Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that...detailed

Relevant articles and documents

Preparation method for bromamine acid

The invention discloses a preparation method for bromamine acid. The preparation method comprises the following steps: 1) taking 1-amino anthraquinone as a raw material and reacting with fuming sulfuric acid and sodium sulfate in a solvent, thereby acquiring a reaction liquor containing sulfonating products, wherein temperature of sulfonating reaction is at 100-150 DEG C and reaction time is 3-10h; 2) cooling the reaction liquor to 60-80 DEG C, adding iodine and anti-foaming agent, slowly dropwise adding bromine for 5-8h, and keeping temperature for 2-3h after the ending of dropwise adding; 3)ending bromination reaction, removing excessive bromine through reduced pressure distillation, adding a certain amount of water, cooling to 50-60 DEG C and filtering, thereby acquiring bromamine acidsulfate; 4) placing bromamine acid sulfate into a large amount of water, heating to 70-90 DEG C, adding sodium hydroxide for regulating pH to 8-9, cooling to 20-30 DEG C and performing suction filtration, thereby acquiring the product bromamine acid. The yield of product is 91% and the purity detected through liquid chromatogram is 99%.

Process for separating off 1-amino-4-bromoanthraquinone-2-sulphonic acid

A process for separating off 1-amino-4-bromoanthraquinone-2-sulphonic acid from the reaction mixture formed by the bromination of 1-aminoanthraquinone-2-sulphonic acid in sulphuric acid, which process comprises adjusting the sulphuric acid concentration of the reaction mixture under the prevailing conditions of temperature and pressure to effect precipitation of 1-amino-4-bromoanthraquinone-2-sulphonic acid as the sulphate and thereafter separating the resultant sulphate precipitate from the reaction mixture.