586-77-6

Basic information

• Product Name: 4-Bromo-N,N-dimethylaniline
• Synonyms: P-BROMO-N,N-DIMETHYLANILINE;N,N-DIMETHYL-P-BROMOANILINE;N-(4-BROMOPHENYL)-N,N-DIMETHYLAMINE;4-BROMO-N,N-DIMETHYLANILINE;(4-Bromo-phenyl)-dimethyl-amine;1-Bromo-4-(dimethylamino)benzene;4-(Dimethylamino)phenyl bromide;4-(dimethylamino)phenylbromide
• CAS NO: 586-77-6
• Molecular Formula: C₈H₁₀BrN
• Molecular Weight: 200.08
• EINECS: 209-582-2
• Product Categories: Anilines, Aromatic Amines and Nitro Compounds;Aniline;Miscellaneous;Amines;C8;Nitrogen Compounds;Building Blocks;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks
• Mol File: 586-77-6.mol
• Article Data: 172

Chemical Properties

• Melting Point: 52-54 °C(lit.)
• Boiling Point: 264 °C(lit.)
• Flash Point: >230 °F
• Appearance: White to gray or light blue/Crystalline Solid
• Density: 1.3220
• Vapor Pressure: 0.00996mmHg at 25°C
• Refractive Index: 1.5748 (estimate)
• Storage Temp.: 2-8°C
• Solubility: Chloroform, Methanol
• PKA: 4.23(at 25℃)
• Water Solubility: Soluble in methanol. Insoluble in water.
• Stability: Stable. Incompatible with oxidizing agents, acids, metals.
• BRN: 2206155
• CAS DataBase Reference: 4-Bromo-N,N-dimethylaniline(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Bromo-N,N-dimethylaniline(586-77-6)
• EPA Substance Registry System: 4-Bromo-N,N-dimethylaniline(586-77-6)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 20/21/22-36/38-33-22
• Safety Statements: 26-36-45-37-28A
• RIDADR: 2811
• WGK Germany: 3
• RTECS: BW9300000
• F: 8
• TSCA: Yes
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 586-77-6(Hazardous Substances Data)

Usage

Uses

4-Bromo-N,N-dimethylaniline is used as an internal standard in the determination of iodine present as iodide (as in pharmaceuticals), iodate (as in iodized table salt) and covalently bound to organic compounds (as in milk and vegetables).

Purification Methods

Reflux the aniline for 3hours with two equivalents of acetic anhydride, then fractionally distil it under reduced pressure. [Beilstein 12 IV 1499.]

InChI:InChI=1/C8H10BrN/c1-10(2)8-5-3-7(9)4-6-8/h3-6H,1-2H3

Synthetic route

4-(dimethylamino)benzene-boronic acid (28611-39-4) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With N-Bromosuccinimide In dichloromethane at 20℃; for 0.166667h;	100%
With 2-bromopentane; sodium hydride In dimethyl sulfoxide at 80℃;
Multi-step reaction with 2 steps 1: toluene / 1 h / 20 °C / Inert atmosphere 2: N-Bromosuccinimide / dichloromethane / 0.17 h / 20 °C View Scheme

(4-(N,N-dimethylamino)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (171364-78-6) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With N-Bromosuccinimide In dichloromethane at 20℃; for 0.166667h;	100%

N,N-dimethyl-aniline (121-69-7) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With methanol; tetraethylammonium chloride; bromine In dichloromethane at 35℃; other substituted anilines: regioselectivity of bromination;	99%
With methanol; tetraethylammonium chloride; bromine In dichloromethane at 35℃;	99%
With hexabromocyclopenta-1,3-diene; triethylamine In acetonitrile for 24h; Ambient temperature;	99%

formaldehyd (50-00-0) + 4-bromo-aniline (106-40-1) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With sodium cyanoborohydride; acetic acid at 0 - 65℃; for 3.42h;	99%
With Zr(BH4)2Cl2(dabco)2; zirconium(IV) chloride In methanol; water at 20℃; for 0.1h;	95%
With sodium tetrahydroborate In 2,2,2-trifluoroethanol for 4.3h; Reflux;	94%

carbon dioxide (124-38-9) + 4-bromo-N-methylaniline (6911-87-1) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With phenylsilane; triphenylphosphine In tetrahydrofuran at 120℃; under 3750.38 Torr; for 24h; Autoclave; Green chemistry;	99%
With sodium tetrahydroborate In 1,4-dioxane at 100℃; under 7500.75 Torr; for 24h; Autoclave;	93%
With diphenylsilane; [1,3-bis(2,4,6-trimethylphenyl)imidazol]-2-ylidene In N,N-dimethyl-formamide at 50℃; under 760.051 Torr; chemoselective reaction;	91%

dimethyl sulfoxide (67-68-5) + 4-bromo-aniline (106-40-1) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With formic acid; triethylamine at 150℃; for 12h; Inert atmosphere; Green chemistry;	97%

carbon dioxide (124-38-9) + 4-bromo-aniline (106-40-1) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With diphenylsilane; C21H41N3NiP2 In acetonitrile at 120℃; under 2052.14 Torr; for 24h; Autoclave;	87%
With dimanganese decacarbonyl; phenylsilane; C29H33N2P In acetonitrile at 100℃; under 750.075 Torr; for 15h;	79%
With methanesulfonic acid; hydrogen; tris(acetylacetonato)ruthenium(III); [2-((diphenylphospino)methyl)-2-methyl-1,3-propanediyl]bis[diphenylphosphine] In tetrahydrofuran at 140℃; for 24h; Autoclave; Inert atmosphere;	89 %Chromat.

carbonic acid dimethyl ester (616-38-6) + 4-bromo-aniline (106-40-1) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With 0.72 KNaX-BS zeolite at 150℃; for 1h; Reagent/catalyst;	85%

carbonic acid dimethyl ester (616-38-6) + 4-bromo-aniline (106-40-1) → 4-bromo-N-methylaniline (6911-87-1) + 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With 0.94 HY-BS zeolite at 150℃; for 1h;	A 81% B 16%

methanol (67-56-1) + 4-bromo-aniline (106-40-1) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With Cu1-Mo1/TiO2 In neat liquid at 20℃; for 21h; Catalytic behavior; Inert atmosphere; UV-irradiation;	80%
With triphenylphosphine; 2,3-dicyano-5,6-dichloro-p-benzoquinone In dichloromethane at 20℃; for 0.5h; chemoselective reaction;	60%
With TiO2 supported nano-Pd(0.3) catalyst In water at 20℃; for 5h; Inert atmosphere; Irradiation; Green chemistry;	8 %Chromat.
With zinc oxide-supported iridium catalyst at 150℃; under 3750.38 Torr; for 8h; Inert atmosphere;	38 %Chromat.

N,N-dimethyl-aniline (121-69-7) → 4-bromo-N,N-dimethylaniline (586-77-6) + 2,4-dibromo-N,N-dimethylaniline (64230-27-9)

Conditions	Yield
With dihydrogen peroxide; vanadia; potassium bromide In chloroform; water at 24.84℃; under 760.051 Torr;	A 75% B 12%
With [bis(acetoxy)iodo]benzene; lithium bromide In tetrahydrofuran at 20℃; for 0.5h;	A 73% B 18%
With bromine; acetic acid In tetrachloromethane for 0.0833333h; Ambient temperature; other reagents: bromine, bromodimethylsulfonium bromide, bromodimethylsulfonium bromide/acetic acid;	A 68% B 29%

(4-dimethylamino-phenyl)-phosphonous acid dichloride (29972-74-5) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With pyridine; bromine In dichloromethane at 20℃; for 12h;	67%

N,N-dimethylaniline N-oxide (874-52-2) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
Stage #1: N,N-dimethylaniline N-oxide With dibromo sulfoxide In tetrahydrofuran at -78℃; for 4h; Inert atmosphere; Stage #2: With triethylamine In tetrahydrofuran at -78 - 23℃; for 0.75h; Solvent; Temperature; Inert atmosphere; regioselective reaction;	55%

methanol (67-56-1) + 4-bromo-N-methylaniline (6911-87-1) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With rhodium(III) chloride hydrate; potassium tert-butylate at 130℃; for 24h; Sealed tube; High pressure;	44%

4-bromo-aniline (106-40-1) + methyl iodide (74-88-4) → 4-bromo-N-methylaniline (6911-87-1) + 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With potassium carbonate In tetrahydrofuran at 20℃;	A 26% B 20%
With potassium carbonate In tetrahydrofuran at 20℃;	A 26% B 20%
With potassium carbonate In tetrahydrofuran	A 26% B 20%

formaldehyd (50-00-0) + 2,4,6-tribromoaniline (147-82-0) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With hydrogenchloride; amalgamated zinc; acetic acid

5,5-dibromobarbituric acid (511-67-1) + ethanol (64-17-5) + N,N-dimethyl-aniline (121-69-7) → 4-bromo-N,N-dimethylaniline (586-77-6)

5,5-dibromobarbituric acid (511-67-1) + N,N-dimethyl-aniline (121-69-7) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With ethanol

4-(dimethylamino)phenyl(phenyl)methanol (7494-77-1) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With chloroform; bromine
With diethyl ether; bromine

2-[(4-bromophenyl)(methyl)amino]acetonitrile (157671-45-9) → 4-bromo-N,N-dimethylaniline (586-77-6)

Conditions	Yield
With sulfuric acid

4-bromo-N,N-dimethylaniline (586-77-6) → N,N-dimethyl-aniline (121-69-7)

Conditions	Yield
With 4-methyl-morpholine; tetrahydroxydiboron; 5%-palladium/activated carbon In 1,2-dichloro-ethane at 50℃; for 3h;	100%
With lithium aluminium tetrahydride; di-tert-butyl peroxide In tetrahydrofuran for 3h; Irradiation;	93%
With isopropyl alcohol at 20℃; for 24h; UV-irradiation; chemoselective reaction;	82%

4-bromo-N,N-dimethylaniline (586-77-6) + phenylboronic acid (98-80-6) → N,N-dimethyl-4-biphenylamine (1137-79-7)

Conditions	Yield
With potassium phosphate; naphthidine di(radical cation)s-stabilized Pd nanoparticles In 1,4-dioxane at 80℃; for 8h; Suzuki-Miyaura cross-coupling reaction;	100%
With tetrabutylammomium bromide; potassium carbonate; cyclopalladated N-dodecylferrocenylimine In methanol; water at 20℃; for 18h; Suzuki-Miyaura cross-coupling reaction;	99%
With potassium carbonate In ethanol; water at 50℃; for 4h; Suzuki-Miyaura Coupling;	99%

4-bromo-N,N-dimethylaniline (586-77-6) + methacrylic acid methyl ester (80-62-6) → (E)-3-(4-dimethylaminophenyl)-2-methyl acrylic acid methyl ester (50704-04-6)

Conditions	Yield
With tris(dibenzylideneacetone)dipalladium (0); tri-tert-butyl phosphine; Cy2NMe2 In 1,4-dioxane at 20℃; for 24h; Heck coupling;	100%
With [(C6H5)PdBr2]2[HPtBu3]2 In 1,4-dioxane at 20℃; for 18h; Heck reaction; Inert atmosphere;	97%
With N-Methyldicyclohexylamine; tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butylphosphonium tetraphenylborate In tetrahydrofuran at 30℃; for 25h; Product distribution / selectivity;	87%

sodium cyanide (773837-37-9) + 4-bromo-N,N-dimethylaniline (586-77-6) → 2-[(4-bromophenyl)(methyl)amino]acetonitrile (157671-45-9)

Conditions	Yield
With C47H45Cl2N5Ru2(2+)*2F6P(1-); dihydrogen peroxide; acetic acid In methanol at 60℃; for 10h; Inert atmosphere;	100%
With dihydrogen peroxide; acetic acid In water at 20℃; for 0.583333h;	95%
With oxygen; vanadia; acetic acid In methanol at 60℃; for 2h;	92%

Chloro(chloromethyl)dimethylsilane (1719-57-9) + 4-bromo-N,N-dimethylaniline (586-77-6) → (chloromethyl)[4-(dimethylamino)phenyl]dimethylsilane (60457-97-8)

Conditions	Yield
Stage #1: 4-bromo-N,N-dimethylaniline With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: Chloro(chloromethyl)dimethylsilane	99%

4-bromo-N,N-dimethylaniline (586-77-6) + 4-chlorobenzophenone (134-85-0) → (4'-(dimethylamino)-[1,1'-biphenyl]-4-yl)(phenyl)methanone (94869-73-5)

Conditions	Yield
Stage #1: 4-bromo-N,N-dimethylaniline With lithium Stage #2: With zinc(II) chloride Stage #3: 4-chlorobenzophenone; nickel phosphine amido pincer complex In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 70℃; for 8h; Negishi cross-coupling; Further stages.;	99%

4-bromo-N,N-dimethylaniline (586-77-6) + chlorobenzene (108-90-7) → N,N-dimethyl-4-biphenylamine (1137-79-7)

Conditions	Yield
Stage #1: 4-bromo-N,N-dimethylaniline With lithium Stage #2: With zinc(II) chloride Stage #3: chlorobenzene; nickel phosphine amido pincer complex In tetrahydrofuran; 1-methyl-pyrrolidin-2-one at 70℃; for 12h; Negishi cross-coupling; Further stages.;	99%

2,2,2-trifluoroacetamide (354-38-1) + 4-bromo-N,N-dimethylaniline (586-77-6) → 2,2,2-trifluoro-(4-N,N-dimethyphenyl)acetamide (41116-22-7)

Conditions	Yield
With potassium carbonate; N,N`-dimethylethylenediamine; copper(l) iodide In 1,4-dioxane at 75℃;	99%

sodium cyanide (773837-37-9) + 4-bromo-N,N-dimethylaniline (586-77-6) → 4-cyano-N,N-dimethylaniline (1197-19-9)

Conditions	Yield
With tri-tert-butyl phosphine; [Pd2(dba)5]; zinc In tetrahydrofuran; acetonitrile at 70℃; for 2h;	99%

Diphenylmethane (101-81-5) + 4-bromo-N,N-dimethylaniline (586-77-6) → 4-benzhydryl-N,N-dimethylaniline (13865-57-1)

Conditions	Yield
With KN(SiMe3)2; palladium diacetate; nixantphos In cyclopentyl methyl ether at 24℃; for 12h; Inert atmosphere;	99%
With 15-crown-5; NiXantphos; palladium diacetate; sodium hexamethyldisilazane at 23℃; for 12h; Catalytic behavior; Reagent/catalyst; Glovebox; Inert atmosphere; Sealed tube;	99%

4-fluorodiphenylmethane (587-79-1) + 4-bromo-N,N-dimethylaniline (586-77-6) → {4-[(4-Fluoro-phenyl)-phenyl-methyl]-phenyl}-dimethyl-amine (39768-73-5)

Conditions	Yield
With 15-crown-5; NiXantphos; palladium diacetate; sodium hexamethyldisilazane at 23℃; for 12h; Catalytic behavior; Reagent/catalyst; Glovebox; Inert atmosphere; Sealed tube;	99%

4-bromo-N,N-dimethylaniline (586-77-6) + N-(quinolin-8-yl)-3-(trifluoromethyl)benzamide (331627-96-4) → C25H20F3N3O (1436849-50-1)

Conditions	Yield
With Ru(OAc)2(p-cymene); sodium carbonate; triphenylphosphine In toluene at 130℃; for 15h;	99%

4-bromo-N,N-dimethylaniline (586-77-6) + p-tolylboronic pinacol ester (195062-57-8) → 4-dimethylamino-4'-methylbiphenyl (141082-00-0)

Conditions	Yield
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate; potassium hydroxide In neat (no solvent) at 110℃; for 24h; Suzuki-Miyaura Coupling; Schlenk technique; Inert atmosphere;	99%

4-bromo-N,N-dimethylaniline (586-77-6) + 4-tolylmagnesium chloride (696-61-7) → 4-dimethylamino-4'-methylbiphenyl (141082-00-0)

Conditions	Yield
With C36H52Br2N4NiSi In tetrahydrofuran at 70℃; for 24h; Kumada Cross-Coupling; Inert atmosphere; Schlenk technique;	99%

benzo[c]-[1,2,5]thiadiazole-5,6-dicarbonitrile (54512-79-7) + 4-bromo-N,N-dimethylaniline (586-77-6) → 4,7-bis(4-(dimethylamino)phenyl)benzo[c][1,2,5]thiadiazole-5,6-dicarbonitrile

Conditions	Yield
With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube;	99%
With di-tert-butyl(methyl)phosphonium tetrafluoroborate salt; palladium diacetate; potassium carbonate; Trimethylacetic acid In toluene at 120℃; Inert atmosphere; Sealed tube;

Upstream product

• 511-67-1 5,5-dibromobarbituric acid 
• 64-17-5 ethanol 
• 121-69-7 N,N-dimethyl-aniline 
• 21428-65-9 2,2-dibromo-5,5-dimethylcyclohexane-1,3-dione 
• 71-43-2 benzene 
• 107-10-8 propylamine 
• 151-18-8 2-cyanoethylamine 
• 2052-06-4 4-bromo-N,N-diethylaniline 
• 88799-12-6 4-Brom-N,N-dimethylanilin-Brom-Addukt 
• 29972-74-5 (4-dimethylamino-phenyl)-phosphonous acid dichloride 
• 109-85-3 2-methoxyethylamine 
• 811-93-8 1,1-dimethylethylenediamine 
• 104292-32-2 N-benzyl-N,N-dimethyl-4-bromoanilinium bromide 
• 7446-70-0 aluminium trichloride 

Downstream Products

• 678986-52-2 5-bromo-2-dimethylamino-benzyl alcohol 
• 77265-72-6 5-bromo-2-dimethylamino-benzoic acid 
• 366-29-0 N,N,N',N'-tetramethylbenzidine 
• 92-52-4 biphenyl 
• 1137-79-7 N,N-dimethyl-4-biphenylamine 
• 33733-72-1 (CH₃)2As{p-C₆H₄N(CH₃)2} 
• 510-13-4 1,1-bis(4-dimethylaminophenyl)-1-phenyl-methanol 
• 6947-90-6 N,N-dimethyl-4-(2-phenyl-4H-chromen-4-yl)aniline 
• 109474-56-8 N,N-dimethyl-4-triethylplumbyl-aniline 
• 492-80-8 auramine O 
• 102316-50-7 (4-Dimethylamino-phenyl)-phenyl-[2]pyridyl-methanol 
• 70076-04-9 4-bromo-N,N-dimethyl-3-nitroaniline 
• 861793-69-3 4-bromo-N,N-dimethyl-2,5-dinitro-aniline 
• 829-02-7 4-Bromo-2-nitro-N,N-dimethylbenzeneamine 

Relevant articles and documents

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Photochemical Reaction of N,N-Dimethylanilines with N-Substituted Maleimides Utilizing Benzaldehyde as the Photoinitiator

Photoorganocatalysis constitutes a powerful domain of photochemistry and organic synthesis. The scaffold of pyrrolo[3,4-c]quinolinoles exhibits interesting and potent inhibition against various enzymes, making them really promising pharmaceutical targets. Herein, we describe a photochemical methodology for the reaction of N,N-dimethylanilines with N-substituted maleimides, utilizing benzaldehyde as the photoinitiator. A variety of substituted N,N-dimethylanilines and N-substituted maleimides were converted into the corresponding adducts in moderate to high yields.

Visible light-induced mono-bromination of arenes with BrCCl3

A highly efficient and regioselective bromination of electron-rich arenes and heteroarenes using commercially available BrCCl3as a “Br” source has been developed. The reaction was performed in air under mild conditions with photocatalyst Ru(bpy)3Cl2·6H2O, avoiding the usage of strong acids and strong oxidants. Mono-brominated products were obtained with medium to excellent yields (up to 94%). This strategy has shown good compatibility and highpara-selectivity, which will facilitate the complicated synthesis.

Visible-Light-Induced C(sp2)-C(sp3) Cross-Dehydrogenative-Coupling Reaction of N-Heterocycles with N-Alkyl- N-methylanilines under Mild Conditions

Disclosed herein is a cross-dehydrogenative-coupling reaction of N-heterocycles including 1,2,4-triazine-3,5(2H, 4H)-diones and quinoxaline-2(1H)-ones with N-methylanilines to form C(sp2)-C(sp3) under visible-light illumination and ambient air at room temperature. In this process, easily available Ru(bpy)3Cl2·6H2O serves as the catalyst, and air acts as the green oxidant. This method features high atom economy, environmental friendliness, and convenient operation and provides an efficient and practical access to aminomethyl-substituted N-heterocycles with extensive functional group compatibility in 40-86% yields.