128-93-8

Basic information

• Product Name: 1-Methylamino-4-bromo anthraquinone
• Synonyms: 1-BROMO-4-METHYLAMINO-ANTHRAQUINONE;1-METHYLAMINO-4-BROMO ANTHRAQUINONE;4-BROMO-1-(METHYLAMINO)ANTHRAQUINONE;1-bromo-4-(methylamino)-10-anthracenedione;1-bromo-4-(methylamino)-anthraquinon;1-Bromo-4-methylamino-9,10-anthracenedione;1-Methylamine-4-Bromoanthraquinone;1-methylamino-4-bromanthrachinon
• CAS NO: 128-93-8
• Molecular Formula: C₁₅H₁₀BrNO₂
• Molecular Weight: 316.15
• EINECS: 204-920-5
• Product Categories: Intermediates of Dyes and Pigments
• Mol File: 128-93-8.mol
• Article Data: 5

Chemical Properties

• Melting Point: 195.5°C
• Boiling Point: 510.058 °C at 760 mmHg
• Flash Point: 262.274 °C
• Appearance: /
• Density: 1.5512 (rough estimate)
• Vapor Pressure: 1.6E-10mmHg at 25°C
• Refractive Index: 1.6320 (estimate)
• PKA: 1.41±0.20(Predicted)
• CAS DataBase Reference: 1-Methylamino-4-bromo anthraquinone(CAS DataBase Reference)
• NIST Chemistry Reference: 1-Methylamino-4-bromo anthraquinone(128-93-8)
• EPA Substance Registry System: 1-Methylamino-4-bromo anthraquinone(128-93-8)

Safety Data

• Hazardous Substances Data: 128-93-8(Hazardous Substances Data)

Usage

Safety Profile

An eye irritant. When heated to decomposition it emits toxic fumes of NOx and Br

InChI:InChI=1/C15H10BrNO2/c1-17-11-7-6-10(16)12-13(11)15(19)9-5-3-2-4-8(9)14(12)18/h2-7,17H,1H3

Synthetic route

1-(methylamino)anthraquinone (82-38-2) → 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8)

Conditions	Yield
With hydrogen bromide; 3-chloro-benzenecarboperoxoic acid In methanol at 30 - 32℃; for 0.166667h; Reagent/catalyst; regioselective reaction;	87%
With pyridine; bromine
With aluminium trichloride; bromine; nitrobenzene
With bromine In acetic acid
Stage #1: 1-(methylamino)anthraquinone With acetic acid for 0.5h; Stage #2: With bromine at 15 - 50℃; for 19h;	4.27 g

1-bromo-4-nitro-anthraquinone (780038-86-0) + methylamine (74-89-5) → 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8)

Conditions	Yield
With pyridine at 60℃;

1-(methylamino)anthraquinone (82-38-2) → 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 1-methylamino-2-bromoanthraquinone (6374-84-1)

Conditions	Yield
With hydrogen bromide; bromine In acetic acid; propionic acid at 0℃; for 1h; Yield given. Yields of byproduct given;
With hydrogen bromide; bromine In acetic acid; propionic acid at 0℃; for 1h; Product distribution; without HBr; other N-substituted 1-aminoanthraquinone;

1-chloroanthracene-9,10-dione (82-44-0) → 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: copper (II)-acetate; aqueous pyridine / 130 °C 2: pyridine; bromine View Scheme

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 1-amino-3-methylbenzene (108-44-1) → solvent blue 63 (6408-50-0)

Conditions	Yield
With copper(II) sulfate; sodium hydroxide at 100℃; for 7h; Temperature;	92%

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 1-(methylamino)-4-[(4-methylphenyl)amino]anthraquinone (128-85-8)

Conditions	Yield
With sodium acetate In p-toluidine	82%
With sodium acetate In p-toluidine	82%

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 1-(methylamino)anthraquinone (82-38-2) + 4,4'-bi(1-methylaminoanthraquinone) (106508-56-9)

Conditions	Yield
With copper In N,N-dimethyl-formamide for 2h; Heating;	A n/a B 57%

acetamide (60-35-5) + 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 1-acetylamino-4-methylaminoanthraquinone (77817-44-8)

Conditions	Yield
With sodium acetate; copper (I) acetate; copper In chlorobenzene for 4h; Heating;	37%

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 4-Amino-2',4'-dinitroazobenzene (76788-23-3) → 1-Methylamino-4-<4-(2,4-dinitrophenylazo)phenylamino>anthraquinone (76788-10-8)

Conditions	Yield
With sodium acetate; copper (I) acetate; copper In various solvent(s) Heating;	19%

naphthalen-1-yl-acetyl chloride (5121-00-6) + 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → [1]naphthyl-acetic acid-[(4-bromo-9,10-dioxo-9,10-dihydro-[1]anthryl)-methyl-amide]

Conditions	Yield
With toluene

2-bromoacetyl chloride (22118-09-8) + 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → bromo-acetic acid-[(4-bromo-9,10-dioxo-9,10-dihydro-[1]anthryl)-methyl-amide]

Conditions	Yield
With xylene

1-amino-5-cyanopentane (2432-74-8) + 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 6-(4-methylamino-9,10-dioxo-9,10-dihydro-[1]anthrylamino)-hexanenitrile

Conditions	Yield
With copper diacetate; nitrobenzene

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 1-aminopyrene (1606-67-3) → 1-methylamino-4-pyren-1-ylamino-anthraquinone

Conditions	Yield
With pentan-1-ol; copper diacetate; sodium acetate at 140℃;

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 5-Aminosalicylic Acid (89-57-6) → 2-hydroxy-5-(4-methylamino-9,10-dioxo-9,10-dihydro-[1]anthrylamino)-benzoic acid

Conditions	Yield
With potassium acetate; copper diacetate; copper weiteres Reagens: Amylalkohol;

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 3-aminosalicylic acid (570-23-0) → 2-hydroxy-3-(4-methylamino-9,10-dioxo-9,10-dihydro-[1]anthrylamino)-benzoic acid

Conditions	Yield
With potassium acetate; copper diacetate; copper weiteres Reagens: Amylalkohol;

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 3-aminobenzenemethanol (1877-77-6) → 1-(3-hydroxymethyl-anilino)-4-methylamino-anthraquinone

Conditions	Yield
With 1-ethoxyethanol; potassium acetate; copper diacetate

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 4-hydroxy-1-aminoanthraquinone (116-85-8) → 4-hydroxy-4'-methylamino-1,1'-imino-di-anthraquinone

Conditions	Yield
With copper chloride; potassium acetate; nitrobenzene

2-aminotetralin (2954-50-9) + 1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 1-methylamino-4-(1,2,3,4-tetrahydro-[2]naphthylamino)-anthraquinone

Conditions	Yield
With potassium acetate at 190℃;

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + sodium methylate (124-41-4) → 1-methoxy-4-methylamino-anthraquinone (54559-02-3)

Conditions	Yield
With methanol; sodium acetate; copper (I) acetate at 85℃; im Rohr;

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 2,4-dibromo-1-(methylamino)anthracene-9,10-dione (33278-77-2)

Conditions	Yield
With bromine; acetic acid

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 1-methylamino-4-hydroxyanthraquinone (6373-16-6)

Conditions	Yield
With sulfuric acid

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 6-bromo-3-methyl-2,7-dioxo-2,7-dihydro-3H-naphtho[1,2,3-de]quinoline-1-carbonitrile (116387-59-8)

Conditions	Yield
With nitrobenzene; ethyl 2-cyanoacetate

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 1-bromo-4-(methyl-nitroso-amino)-anthraquinone

Conditions	Yield
With acetic acid; sodium nitrite

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) → 6-methylamino-2,2-dioxo-3H-2λ6-anthra[1,9-cd][1,2,6]thiadiazin-7-one

Conditions	Yield
With pentan-1-ol; copper (I?)-acetate; potassium acetate; SULFAMIDE

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + indole-2,3-dione (91-56-5) → 1-(4-methylamino-9,10-dioxo-9,10-dihydro-[1]anthryl)-indoline-2,3-dione

Conditions	Yield
With sodium acetate; copper (I) acetate; nitrobenzene

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + acetic anhydride (108-24-7) → 1-(Ν-methyl)acetamido-4-bromoanthraquinone (6374-83-0)

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + ethyl acetoacetate (141-97-9) → 1-acetyl-6-bromo-3-methyl-3H-naphtho[1,2,3-de]quinoline-2,7-dione (109943-21-7)

Conditions	Yield
With sodium acetate
With sodium acetate

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + ethyl 3-oxo-3-phenylpropionate (94-02-0) → 1-benzoyl-6-bromo-3-methyl-3H-naphtho[1,2,3-de]quinoline-2,7-dione (477579-25-2)

Conditions	Yield
With sodium acetate at 195℃;
With sodium carbonate In xylene at 140 - 150℃; for 8h;
With sodium carbonate In xylene at 140 - 150℃; for 8h;

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + p-toluidine (106-49-0) → 1-(methylamino)-4-[(4-methylphenyl)amino]anthraquinone (128-85-8)

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + toluene-4-sulfonamide (70-55-3) → N-(4-methylamino-9,10-dioxo-9,10-dihydro-[1]anthryl)-toluene-4-sulfonamide

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + ethanolamine (141-43-5) → disperse blue 3 (86722-66-9)

Conditions	Yield
With copper diacetate
With sodium acetate; copper In toluene at 80℃; for 3h;

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + 2,2'-iminobis[ethanol] (111-42-2) → 1-[bis-(2-hydroxy-ethyl)-amino]-4-methylamino-anthraquinone

Conditions	Yield
With copper diacetate at 130℃;

1-bromo-4-(methylamino)-9,10-anthracenedione (128-93-8) + chloroacetyl chloride (79-04-9) → chloro-acetic acid-[(4-bromo-9,10-dioxo-9,10-dihydro-[1]anthryl)-methyl-amide] (39774-39-5)

Conditions	Yield
With benzene

Upstream product

• 82-38-2 1-(methylamino)anthraquinone 
• 82-44-0 1-chloroanthracene-9,10-dione 
• 780038-86-0 1-bromo-4-nitro-anthraquinone 
• 74-89-5 methylamine 

Downstream Products

• 6374-83-0 1-(Ν-methyl)acetamido-4-bromoanthraquinone 
• 109943-21-7 1-acetyl-6-bromo-3-methyl-3H-naphtho[1,2,3-de]quinoline-2,7-dione 
• 477579-25-2 1-benzoyl-6-bromo-3-methyl-3H-naphtho[1,2,3-de]quinoline-2,7-dione 
• 86722-66-9 disperse blue 3 
• 6373-16-6 1-methylamino-4-hydroxyanthraquinone 
• 14254-18-3 3-{[9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthryl]aminopropyl}trimethylammonium methyl sulphate 
• 1220-94-6 1-amino-4-(methylamino)anthraquinone 
• 6408-50-0 solvent blue 63 
• 128-85-8 1-(methylamino)-4-[(4-methylphenyl)amino]anthraquinone 
• 25264-26-0 1-{[3-(dimethylamino)propyl]amino}-4-(methylamino)anthraquinone 
• 82-38-2 1-(methylamino)anthraquinone 
• 68227-28-1 1-Butylamino-4-methylamino-anthraquinone 
• 106508-56-9 4,4'-bi(1-methylaminoanthraquinone) 
• 76788-10-8 1-Methylamino-4-<4-(2,4-dinitrophenylazo)phenylamino>anthraquinone 

Relevant articles and documents

Picosecond Fluorescence Lifetimes of Anthraquinone Derivatives. Radiationless Deactivation via Intra- and Intermolecular Hydrogen Bonds

Radiationless deactivations from the S1(1CT) states of seven 1- and 2-substituted aminoanthraquinones were investigated by measuring picosecond fluorescence lifetimes and fluorescence quantum yields in benzene, acetonitrile, and ethanol.The S1(1CT) states of all derivatives were largely deactivated in ethanol.Deuterium isotope effects of the solvents on the nonradiative rate constants knr(in EtOH)/knr(in EtOD) = 9.0 (1-NH2 (2)), 2.1 (2-NH2 (5)), and 1.7 (2-piperidino (7)) were observed.The fluorescence quantum yield in ethanol was not affected by temperature (278-343 K).In benzene the excited 1-aminoanthraquinones were deacvated faster than 2-aminoanthraquinones.These observations were interpreted in terms of the radiationless deactivations od S1(1CT) through the intra- and intermolecular hydrogen bonds.

Efficient, facile metal free protocols for the bromination of commercially important deactivated aminoanthracene-9,10-diones

Highly efficient, mild synthetic protocols were developed for the oxidative bromination of deactivated aminoanthracene-9,10-diones by using H2O2-HBr and m-CPBA-HBr in methanolic medium. Both the protocols offer excellent bromine atom economy, good conversion (100%) along with high yield (82–93%) and high purity of desired product. The N-alkylated amines undergo regio-selective bromination to give selective p-bromo product. The commercial availability of all the starting materials, simple reaction procedure and ease of work up, and easily amenable for scale up demonstrated commercial feasibility of both the protocols.

Process for preparing substituted aminoanthraquinones

Substituted aminoanthraquinone compounds, which are used for dye stuffs or intermediate thereof, represented by the formula (II) STR1 wherein R3 represents a C1 -C6 alkyl group which may be substituted, X represents a hydrogen atom, --COR1 or --SO2 R2 wherein R1 and R2 each represents a substituted or unsubstituted C1 -C4 alkyl or C6 -C12 aryl group, and Y and Z represent independently a hydrogen atom, a halogen atom, a nitro group or a C1 -C4 alkyl group, is prepared by allowing anthraquinone compounds represented by the formula STR2 wherein X, Y and Z are as defined above, to react with alkylating agents in organic solvents in the presence of organic quaternary ammonium salts and alkalies.