78137-76-5

Basic information

• Product Name: 4-Bromo-3-nitrophenol
• Synonyms: 4-Bromo-3-nitrophenol;2-Bromo-5-hydroxynitrobenzene;2-Bromo-5-hydroxynitrobenzene, 1-Bromo-4-hydroxy-2-nitrobenzene
• CAS NO: 78137-76-5
• Molecular Formula: C₆H₄BrNO₃
• Molecular Weight: 218
• Mol File: 78137-76-5.mol
• Article Data: 13

Chemical Properties

• Melting Point: 144-145 ºC
• Boiling Point: 281 ºC
• Flash Point: 124 ºC
• Appearance: /
• Density: 1.881
• Vapor Pressure: 0.002mmHg at 25°C
• Refractive Index: 1.652
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• PKA: 7.65±0.10(Predicted)
• CAS DataBase Reference: 4-Bromo-3-nitrophenol(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Bromo-3-nitrophenol(78137-76-5)
• EPA Substance Registry System: 4-Bromo-3-nitrophenol(78137-76-5)

Safety Data

• Hazardous Substances Data: 78137-76-5(Hazardous Substances Data)

Usage

Chemical Properties

brown solid

InChI:InChI=1/C6H4BrNO3/c7-5-2-1-4(9)3-6(5)8(10)11/h1-3,9H

Synthetic route

meta-nitrophenol (554-84-7) → 4-bromo-3-nitrophenol (78137-76-5)

Conditions	Yield
With 1-butyl-3-methylpyridinium tribromide at 20℃;	98%
With 1,3-di-n-butyl-1H-imidazol-3-ium tribromide at 20℃; for 0.133333h; Neat (no solvent); regioselective reaction;	95%
With 1,2-ethanediylbis(triphenylphosphonium) ditribromide In methanol; dichloromethane at 20℃; for 0.0833333h; Solvent; regioselective reaction;	85%
at 120 - 140℃; Einleiten von mit CO2 verduenntem Brom-Dampf;
With hydrogenchloride; carbon dioxide; bromine

4-bromo-3-nitroanizole (5344-78-5) → 4-bromo-3-nitrophenol (78137-76-5)

Conditions	Yield
Stage #1: 4-bromo-3-nitroanizole With boron tribromide In dichloromethane at -78 - 20℃; for 31h; Stage #2: With water In dichloromethane at 0℃;	87%
Stage #1: 4-bromo-3-nitroanizole With boron tribromide In dichloromethane at -78 - 20℃; for 31h; Stage #2: With water In dichloromethane at 0℃;	87%
With boron tribromide In dichloromethane at -78 - 20℃;	83%

4-hydroxy-2-nitroaniline (610-81-1) → 4-bromo-3-nitrophenol (78137-76-5)

Conditions	Yield
With hydrogen bromide Diazotization.Behandlung der Diazoniumsalz-Loesung mit Kupfer-Pulver und wss. HBr;
With sulfuric acid Diazotization.man versetzt mit einer konz. Kaliumbromidloesung und fuegt Kupferpulver hinzu;
Stage #1: 4-hydroxy-2-nitroaniline With hydrogen bromide; sodium nitrite In water at 0 - 10℃; for 1h; Stage #2: With hydrogen bromide; copper(I) bromide at 40 - 45℃; for 1h;	13.1 g

meta-nitrophenol (554-84-7) + bromine (7726-95-6) → 4-bromo-3-nitrophenol (78137-76-5)

Conditions	Yield
at 120 - 140℃;

4-acetamido-3-nitrophenyl acetate (2243-69-8) → 4-bromo-3-nitrophenol (78137-76-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: aqueous hydrobromic acid 2: aqueous HBr / Diazotization.Behandlung der Diazoniumsalz-Loesung mit Kupfer-Pulver und wss. HBr View Scheme

3-nitro-aniline (99-09-2) → 4-bromo-3-nitrophenol (78137-76-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: Diazotization 2: 120 - 140 °C / Einleiten von mit CO2 verduenntem Brom-Dampf View Scheme

4-bromo-3-nitrophenol (78137-76-5) + p-methoxybenzyl chloride (824-94-2) → C14H12BrNO4

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 3h; Inert atmosphere;	100%

4-bromo-3-nitrophenol (78137-76-5) + vinyl zinc chloride (78389-90-9) → 3-nitro-4-vinylphenol

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0) In tetrahydrofuran at 100℃; for 2h;	100%

tetravinylsilane (1112-55-6) + 4-bromo-3-nitrophenol (78137-76-5) → 3-nitro-4-vinylphenol

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0) In tetrahydrofuran at 80℃; for 2h;	100%

4-bromo-3-nitrophenol (78137-76-5) + tri-n-butyl(vinyl)tin (7486-35-3) → 3-nitro-4-vinylphenol

Conditions	Yield
Stage #1: 4-bromo-3-nitrophenol; tri-n-butyl(vinyl)tin With tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane at 80℃; for 4h; Stage #2: With potassium fluoride In 1,4-dioxane at 20℃; for 2h;	100%

4-bromo-3-nitrophenol (78137-76-5) + tert-butyldimethylsilyl chloride (18162-48-6) → (4-bromo-3-nitro)phenoxy-tert-butyl-dimethyl-silane

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 3.5h;	99%

4-bromo-3-nitrophenol (78137-76-5) + benzyl bromide (100-39-0) → 2-Bromo-5-benzyloxy-nitrobenzene (4514-28-7)

Conditions	Yield
With potassium carbonate In acetone; acetonitrile for 17h; Heating;	95%
With potassium carbonate In acetone	91%
With potassium carbonate In acetone; acetonitrile for 17h; Heating / reflux;	78%

triisopropylsilyl chloride (13154-24-0) + 4-bromo-3-nitrophenol (78137-76-5) → (4-bromo-3-nitrophenoxy)(triisopropyl)silane (1380316-20-0)

Conditions	Yield
With 1H-imidazole In N,N-dimethyl-formamide at 18℃; for 20h;	95%

4-bromo-3-nitrophenol (78137-76-5) + 1-Chloro-4-(chloromethyl)benzene (104-83-6) → C13H9BrClNO3

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 3h; Inert atmosphere;	94.8%

4-bromo-3-nitrophenol (78137-76-5) + 2-(bromomethyl)naphthalene (3163-27-7) → 2-Bromo-5-(1-naphthalenylmethoxy)-nitrobenzene

Conditions	Yield
With potassium carbonate In N-methyl-acetamide	92%

4-bromo-3-nitrophenol (78137-76-5) + (4-bromomethyl)-phenoxy-allyl acetate → [4-(4-Bromo-3-nitro-phenoxymethyl)-phenoxy]-acetic acid allyl ester

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 22℃; for 3h;	91%

trifluoromethylsulfonic anhydride (358-23-6) + 4-bromo-3-nitrophenol (78137-76-5) → 4-bromo-3-nitrophenyl trifluoromethanesulfonate

Conditions	Yield
With pyridine In dichloromethane at 0 - 30℃; for 0.5h; Inert atmosphere;	90%

4-bromo-3-nitrophenol (78137-76-5) + (4-tert-butoxycarbonylaminophenyl)boronic acid pinacol ester (330793-01-6) → tert-butyl (4'-hydroxy-2'-nitro-[1,1'-biphenyl]-4-yl)carbamate

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 110℃; for 12h;	72%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane at 110℃; for 12h; Reflux;	72%

4-bromo-3-nitrophenol (78137-76-5) → 3-amino-4-bromophenol (100367-37-1)

Conditions	Yield
With iron(III) oxide; hydrazine hydrate In ethanol for 1.5h; Reflux;	70.9%

(1,3-thiazol-2-yl)methanol (14542-12-2) + 4-bromo-3-nitrophenol (78137-76-5) → 2-((4-bromo-3-nitrophenoxy)methyl)thiazole

Conditions	Yield
With triphenylphosphine; diethylazodicarboxylate In toluene at 0℃; Mitsunobu Displacement; Inert atmosphere; Reflux;	69%

Trimethyl borate (121-43-7) + 4-bromo-3-nitrophenol (78137-76-5) → C6H6BNO5

Conditions	Yield
Stage #1: 4-bromo-3-nitrophenol With n-butyllithium In tetrahydrofuran at -78℃; for 0.5h; Stage #2: Trimethyl borate In tetrahydrofuran at 20℃; for 1h; Stage #3: With hydrogenchloride In tetrahydrofuran for 1h;	53%

1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1Hpyrrole-2-carbonitrile + 4-bromo-3-nitrophenol (78137-76-5) → 5-(4-hydroxy-2-nitrophenyl)-1-methyl-1H-pyrrole-2-carbonitrile

Conditions	Yield
With palladium diacetate; cesium fluoride; catacxium A In 1,4-dioxane; water at 80℃; for 1h; Suzuki Coupling; Inert atmosphere; Sealed tube;	30%

4-bromo-3-nitrophenol (78137-76-5) + chloroacetone (78-95-5) → 1-(4-Bromo-3-nitro-phenoxy)-propan-2-one (78137-77-6)

Conditions	Yield
With potassium carbonate; potassium iodide In N,N-dimethyl-formamide

4-bromo-3-nitrophenol (78137-76-5) + benzyl chloride (100-44-7) → 2-Bromo-5-benzyloxy-nitrobenzene (4514-28-7)

Conditions	Yield
With potassium hydroxide

4-bromo-3-nitrophenol (78137-76-5) → [4-(tert-butyl-dimethyl-silanyloxy)-2-nitro-phenyl]-(2'-nitrophenyl)-amine

Conditions	Yield
Multi-step reaction with 2 steps 1: 99 percent / Et3N / CH2Cl2 / 3.5 h / 20 °C 2: 70 percent / rac-BINAP; Cs2CO3 / Pd2(dba)3 / toluene / 0.5 h / 160 °C / microwave irradiation View Scheme

4-bromo-3-nitrophenol (78137-76-5) → [4-(3-Amino-4-bromo-phenoxymethyl)-phenoxy]-acetic acid allyl ester (1026914-86-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: 91 percent / K2CO3 / dimethylformamide / 3 h / 22 °C 2: 64 percent / Na2S2O4 / tetrahydrofuran; H2O / 4 h / 22 °C View Scheme

4-bromo-3-nitrophenol (78137-76-5) → 4-Oxo-5,6,9,10-tetradehydro-4,5-secofuranoeremophilan-5,1-carbolacton (53820-33-0)

Conditions	Yield
Multi-step reaction with 7 steps 1: K2CO3, KI / dimethylformamide 2: 82 percent / TiCl3 / ethanol 3: 1.)NO(1+) / 1.) diazotation 4: AlH(C4H9)2 / toluene 5: 27 percent / Li / tetrahydrofuran 6: 10 percent / lithium butyl / -100 °C 7: 84 percent / hydrolysis View Scheme

4-bromo-3-nitrophenol (78137-76-5) → 6-amino-5-brom-3-methylbenzofuran (78137-78-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: K2CO3, KI / dimethylformamide 2: 82 percent / TiCl3 / ethanol View Scheme

4-bromo-3-nitrophenol (78137-76-5) → 5-Bromo-3-methyl-benzofuran-6-carbonitrile (78137-79-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: K2CO3, KI / dimethylformamide 2: 82 percent / TiCl3 / ethanol 3: 1.)NO(1+) / 1.) diazotation View Scheme

4-bromo-3-nitrophenol (78137-76-5) → 5-Bromo-3-methyl-benzofuran-6-carbaldehyde (78137-80-1)

Conditions	Yield
Multi-step reaction with 4 steps 1: K2CO3, KI / dimethylformamide 2: 82 percent / TiCl3 / ethanol 3: 1.)NO(1+) / 1.) diazotation 4: AlH(C4H9)2 / toluene View Scheme

4-bromo-3-nitrophenol (78137-76-5) → 1-(5-Bromo-3-methyl-benzofuran-6-yl)-3-(2-methyl-[1,3]dioxolan-2-yl)-propan-1-ol (78137-81-2)

Conditions	Yield
Multi-step reaction with 5 steps 1: K2CO3, KI / dimethylformamide 2: 82 percent / TiCl3 / ethanol 3: 1.)NO(1+) / 1.) diazotation 4: AlH(C4H9)2 / toluene 5: 27 percent / Li / tetrahydrofuran View Scheme

Upstream product

• 554-84-7 meta-nitrophenol 
• 610-81-1 4-hydroxy-2-nitroaniline 
• 5344-78-5 4-bromo-3-nitroanizole 
• 7726-95-6 bromine 
• 2243-69-8 4-acetamido-3-nitrophenyl acetate 
• 99-09-2 3-nitro-aniline 

Downstream Products

• 4514-28-7 2-Bromo-5-benzyloxy-nitrobenzene 
• 1380316-21-1 methyl N-(tert-butoxycarbonyl)-2-nitro-O-(triisopropylsilyl)-L-tyrosinate 
• 1380316-22-2 methyl N-(tert-butoxycarbonyl)-2-nitro-L-tyrosinate 
• 1380316-23-3 methyl N-(tert-butoxycarbonyl)-O-[(1S)-2-methoxy-1-methylethyl]-2-nitro-L-tyrosinate 
• 1380316-26-6 methyl N-(tert-butoxycarbonyl)-O-(2-methoxyethyl)-2-nitro-L-tyrosinate 
• 1380316-20-0 (4-bromo-3-nitrophenoxy)(triisopropyl)silane 
• 100367-37-1 3-amino-4-bromophenol 
• 38383-33-4 2-bromo-5-ethenyl-nitrobenzene 
• 865886-84-6 1-bromo-4-difluoromethoxy-2-nitrobenzene 

Relevant articles and documents

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The invention relates to a method for synthesizing 3-amino-4-bromophenol. The method comprises the following steps of: (1) diazotization reaction: dissolving 3-nitro-4-aminophenol used as a raw material into hydrobromic acid, and dropping a sodium nitrite aqueous solution at 0-10 DEG C for reacting for 1-3 hours to obtain a 3-nitrophenol-4-diazonium brine solution; (2) bromination reaction: dropping the solution obtained in the step (1) into a hydrobromic acid aqueous solution of cuprous bromide, stirring at 40-50 DEG C for reacting, and crystallizing and filtering to obtain a 3-nitro-4-bromophenol solid; and (3) reduction reaction: dissolving the solid obtained in the step (2) into alcohol, adding an iron oxide catalyst, heating up to 50-100 DEG C, and adding a hydrazine hydrate aqueous solution to the mixture for reacting for 2-5 hours to obtain the 3-amino-4-bromophenol. The synthesis method of the 3-amino-4-bromophenol has the advantages of reasonable design, moderate condition, easiness of operation and higher product yield and is suitable for industrial production.

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