244205-40-1

Basic information

• Product Name: 2-Bromophenylboronic acid
• Synonyms: 2-broMoborate;o-BBBA;2-Bromophenylboronic acid >=95.0%;Boronic acid,B-(2-bromophenyl)-;2-BROMOPHENYLBORONIC ACID;2-BROMOBENZENEBORONIC ACID;AKOS BRN-0929;RARECHEM AH PB 0074
• CAS NO: 244205-40-1
• Molecular Formula: C₆H₆BBrO₂
• Molecular Weight: 200.83
• EINECS: -0
• Product Categories: Boronate Ester;Boronic Acid;Potassium Trifluoroborate;Pyridines;blocks;BoronicAcids;Bromides;B (Classes of Boron Compounds);Boronic Acids;Aryl;Boronic Acids;Boronic Acids and Derivatives
• Mol File: 244205-40-1.mol
• Article Data: 5

Chemical Properties

• Melting Point: 113 °C(lit.)
• Boiling Point: 329.17 °C at 760 mmHg
• Flash Point: 152.877 °C
• Appearance: White to off-white/Powder
• Density: 1.671 g/cm³
• Vapor Pressure: 7.27E-05mmHg at 25°C
• Refractive Index: 1.598
• Storage Temp.: Refrigerator (+4°C)
• Solubility: Acetonitrile (Slightly), Chloroform (Slightly), DMSO (Slightly), Methanol (Spari
• PKA: 8.25±0.58(Predicted)
• Water Solubility: Soluble in methanol. Slightly soluble in water.
• BRN: 8542615
• CAS DataBase Reference: 2-Bromophenylboronic acid(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Bromophenylboronic acid(244205-40-1)
• EPA Substance Registry System: 2-Bromophenylboronic acid(244205-40-1)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 36/37/38-22
• Safety Statements: 37/39-26
• WGK Germany: 3
• HazardClass: IRRITANT
• Hazardous Substances Data: 244205-40-1(Hazardous Substances Data)

Usage

Chemical Properties

White to off-white powder

Uses

2-Bromobenzeneboronic acid is a boronic acid derivative that is widely used in organic synthesis for carbon-carbon bond formation. In Suzuki coupling, aryl halides and boronic acid aryl or vinyl esters or boronic acids are coupled using Pd(PPh3)4.

Application

2-Bromophenylboronic Acid is used as an inhibitor of the hormone sensitive lipase.Catalyzes the formation of amide bonds from amines and carboxylic acids.Used to promote greener amidations of carboxylic acids and amines in catalytic amounts. This technology avoids the requirement of preactivation of the carboxylic acid or use of coupling reagents.It is also an important intermediate for Organic Light-Emitting Diod ( OLED) .

Preparation

2-Bromophenylboronic acid synthesis: take 2-bromoaniline as raw material, synthesize the intermediate 1-Bromo-2-iodobenzene through diazotization and iodination, and then carry out magnesium iodide exchange with isopropylmagnesium bromide to synthesize o-bromophenylmagnesium bromide, It is then subjected to substitution reaction with trimethyl borate to synthesize methyl o-bromophenylboronic acid, and then hydrolyzed to synthesize 2-bromophenylboronic acid.

InChI:InChI=1/C6H6BBrO2/c8-6-4-2-1-3-5(6)7(9)10/h1-4,9-10H

Synthetic route

potassium (2-bromophenyl)trifluoroborate → (2-bromophenyl)boronic acid (244205-40-1)

Conditions	Yield
With iron(III) chloride; water In tetrahydrofuran at 20℃; for 0.5h;	91%

Trimethyl borate (121-43-7) + 1,2-dibromobenzene (583-53-9) → (2-bromophenyl)boronic acid (244205-40-1)

Conditions

Yield

With LiC(CH3)3; HCl In tetrahydrofuran; diethyl ether (under Ar, Schlenk); soln. of o-dibromobenzene, THF-Et2O cooled to -115°C, LiC(CH3)3 (-78°C) added, stirred for 35 min at -115°C, treated with B(OCH3)3 in Et2O (-78°C), stirred for 2 h at -115-105°C; quenched with EtOH/HCl at -115°C, warmed to room temp., extd. with Et2O, organic layer washed with brine, H2O, dried over MgSO4, solvent removed by rotary evaporator, residue refluxed in H2O for 2 h, filtered,recrystd. from H2O; elem. anal.;

66%

diisopropyl (2-bromophenyl)boronate → (2-bromophenyl)boronic acid (244205-40-1)

Conditions	Yield
With hydrogenchloride In tetrahydrofuran; hexane; toluene at 20℃; for 0.5h;

1,2-dibromobenzene (583-53-9) → (2-bromophenyl)boronic acid (244205-40-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: triisopropyl borate; n-butyllithium / toluene; tetrahydrofuran; hexane / 2.08 h / -70 - 20 °C 2: aq. HCl / toluene; tetrahydrofuran; hexane / 0.5 h / 20 °C View Scheme

C8H10BBrO2 → (2-bromophenyl)boronic acid (244205-40-1)

Conditions	Yield
With hydrogenchloride; water In tetrahydrofuran; diethyl ether; ethanol; pentane at -115 - 20℃;	0.55 g

1-Bromo-2-iodobenzene (583-55-1) → (2-bromophenyl)boronic acid (244205-40-1)

Conditions	Yield
Stage #1: 1-Bromo-2-iodobenzene With isopropylmagnesium chloride In tetrahydrofuran at -42℃; for 2h; Inert atmosphere; Stage #2: With Triisopropyl borate In tetrahydrofuran at 20℃; Inert atmosphere; Stage #3: With sodium hydroxide In tetrahydrofuran; water for 1h; Inert atmosphere;

Trimethyl borate (121-43-7) + 1-Bromo-2-iodobenzene (583-55-1) → (2-bromophenyl)boronic acid (244205-40-1)

Conditions	Yield
Stage #1: 1-Bromo-2-iodobenzene With lithium acetate; 1-propylmagnesium chloride; 3-butyl-1-methylimidazolium acetate In tetrahydrofuran at 0 - 10℃; for 4h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran at 10℃; for 3h; Inert atmosphere; Stage #3: With acetic acid at 15℃; for 0.333333h; Inert atmosphere;	86.83 g

2,2-Dimethyl-1,3-propanediol (126-30-7) + (2-bromophenyl)boronic acid (244205-40-1) → 2,2-dimethylpropane-1,3-diyl [2-bromophenyl] boronate (884010-16-6)

Conditions	Yield
In toluene for 1h; Heating;	100%
In dichloromethane at 20℃; for 3.5h;	100%
In benzene Reflux;
In diethyl ether at 20℃; Inert atmosphere; Molecular sieve;

di(4-methyl)phenylthiosulfonate (2943-42-2) + (2-bromophenyl)boronic acid (244205-40-1) → 1-bromo-2-(4-methylphenylsulfanyl)benzene (15861-49-1)

Conditions	Yield
With sodium hydrogencarbonate; copper(II) sulfate In methanol at 20℃; for 24h; Inert atmosphere;	100%
With sodium hydrogencarbonate; copper(II) sulfate In methanol at 20℃; for 24h; Inert atmosphere;	95%

(2-bromophenyl)boronic acid (244205-40-1) + 1-bromo-4-fluoro-2-iodobenzene → 2,2′-dibromo-5-fluoro-1,1′-biphenyl

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 110℃; Inert atmosphere;	100%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; ethanol; water at 90℃; Inert atmosphere;	93%

bis(6-bromopyridin-2-yl)amine (1195970-59-2) + (2-bromophenyl)boronic acid (244205-40-1) → bis[6-(2-bromophenyl)pyridine-2-yl]amine

Conditions	Yield
Stage #1: bis(6-bromopyridin-2-yl)amine With tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane for 0.166667h; Stage #2: (2-bromophenyl)boronic acid In 1,2-dimethoxyethane; ethanol for 0.25h; Stage #3: With sodium carbonate In 1,2-dimethoxyethane; ethanol; water Reflux;	100%

4,4'-dichlorophenyl thiosulfonate (1146-44-7) + (2-bromophenyl)boronic acid (244205-40-1) → 2-bromophenyl 4-chlorophenylsulfide (24535-55-5)

Conditions	Yield
With sodium hydrogencarbonate; copper(II) sulfate In methanol at 20℃; for 19h; Inert atmosphere;	100%

3-bromo-4-iodotoluene (71838-16-9) + (2-bromophenyl)boronic acid (244205-40-1) → 2,2′-dibromo-4-methyl-1,1′-biphenyl

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 110℃; Inert atmosphere;	100%

3-bromo-4-iodoanisole (466639-53-2) + (2-bromophenyl)boronic acid (244205-40-1) → 2,2′-dibromo-4-methoxy-1,1′-biphenyl

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 110℃; Inert atmosphere;	100%

4-toluenesulfonic acid 2-amino-3-iodo-5-methylphenyl ester (863301-13-7) + (2-bromophenyl)boronic acid (244205-40-1) → 2-amino-2'-bromo-5-methyl-3-(4-toluenesulfonyloxy)-1,1'-biphenyl (863301-14-8)

Conditions	Yield
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In ethanol; water; benzene Suzuki-Miyaura cross-coupling reaction; Heating;	99%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; benzene for 2h; Suzuki-Miyaura cross-coupling reaction; Heating;	99%

naphthalene-1,8-diamine (479-27-6) + (2-bromophenyl)boronic acid (244205-40-1) → 2-(2-bromophenyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine (927384-42-7)

Conditions	Yield
In toluene for 2h; Heating;	99%
In toluene byproducts: H2O; refluxed with azeotropic removal of H2O;	98%
In toluene Reflux; Dean-Stark;	95%

4-amino-3-(4-chloro-phenoxy)-5-iodo-benzoic acid methyl ester (931414-13-0) + (2-bromophenyl)boronic acid (244205-40-1) → 6-amino-2'-bromo-5-(4-chloro-phenoxy)-biphenyl-3-carboxylic acid methyl ester (931414-14-1)

Conditions	Yield
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In toluene at 85℃; for 3h; Suzuki coupling;	99%

5-amino-4-iodo-2-methylphenol 4-methylbenzenesulfonate ester (1025389-16-5) + (2-bromophenyl)boronic acid (244205-40-1) → 2-amino-2'-bromo-5-methyl-1,1'-biphenyl-4-ol 4-methylbenzenesulfonate ester (1025389-21-2)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; benzene for 3h; Suzuki-Miyaura coupling; Inert atmosphere; Reflux;	99%

10-chlorobenzo[h]nquinoline (408328-57-4) + (2-bromophenyl)boronic acid (244205-40-1) → 10-(2-bromophenyl)benzo[h]quinoline (1416448-67-3)

Conditions	Yield
With palladium diacetate; cesium fluoride; Triphenylphosphine oxide In 1,4-dioxane; water at 20℃; for 0.0333333h;	99%

trifluoromethanesulfonic acid 2-nitronaphthalen-1-yl ester (253270-06-3) + (2-bromophenyl)boronic acid (244205-40-1) → C16H10BrNO2

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 1h; Reflux;	99%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; water; toluene for 1h; Reflux;	97%

8-bromo-5,12-bis(4-(tert-butyl)phenoxy)-2-(2,6-diisopropylphenyl)-1H-benzo[5,10]anthra[2,1,9-def]isoquinoline-1,3(2H)-dione (165550-66-3) + (2-bromophenyl)boronic acid (244205-40-1) → C60H54BrNO4

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; water at 95℃; for 12h; Schlenk technique; Inert atmosphere;	99%

n-butyldiethanolamine (102-79-4) + (2-bromophenyl)boronic acid (244205-40-1) → 2-(2'-bromophenyl)-6-butyl-1,3,6,2-dioxazaborocan (1008106-85-1)

Conditions	Yield
In toluene at 50℃; for 2h; Product distribution / selectivity;	98.6%
In toluene at 50℃; for 2h;	98%
In toluene at 50℃; for 2h;	98%
In toluene at 50℃; for 2h;	58%

n-butyldiethanolamine (102-79-4) + (2-bromophenyl)boronic acid (244205-40-1) → 2-(2'-bromophenyl)-6-butyl[1,3,6,2]dioxazaborocan

Conditions	Yield
In toluene at 50℃; for 2h;	98.6%

(2-bromophenyl)boronic acid (244205-40-1) + 3-(1-benzenesulfonyl-1H-indol-3-yl)-4-bromo-1-methyl-pyrrole-2,5-dione (386235-52-5) → 2-methyl-8-(benzenesulfonyl)benzo[a]pyrrolo[3,4-c]carbazole-1,3(2H,8H)-dione (876017-32-2) + 3-(1-benzenesulfonyl-1H-indol-3-yl)-4-(2-bromophenyl)-1-methylpyrrole-2,5-dione (876017-30-0)

Conditions	Yield
With palladium diacetate; potassium carbonate In 1,4-dioxane; water at 100℃; for 9h;	A 1% B 98%

benzaldehyde (100-52-7) + (2-bromophenyl)boronic acid (244205-40-1) → (S)-o-bromobenzhydrol (143880-86-8)

Conditions	Yield
Stage #1: (2-bromophenyl)boronic acid With diethylzinc In toluene at 60℃; for 0.25h; Inert atmosphere; Stage #2: With C46H38NOP In toluene at 20℃; for 0.25h; Inert atmosphere; Stage #3: benzaldehyde optical yield given as %ee; enantioselective reaction; Further stages;	98%

C28H18BrN (1313017-94-5) + (2-bromophenyl)boronic acid (244205-40-1) → C34H22BrN

Conditions	Yield
tetrakis(triphenylphosphine) palladium(0) In 1,2-dimethoxyethane for 11h; Inert atmosphere; Reflux;	98%

ethyl 4-bromo-6-methoxy-1,5-naphthyridine-3-carboxylate (724788-64-1) + (2-bromophenyl)boronic acid (244205-40-1) → ethyl 4-(2-bromophenyl)-6-methoxy-1,5-naphthyridine-3-carboxylate (1310359-66-0)

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate In 1,4-dioxane; water for 2h; Suzuki-Miyaura coupling; Reflux;	98%

1-bromo-2-naphthaldehyde (3378-82-3) + (2-bromophenyl)boronic acid (244205-40-1) → C17H11BrO

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 90℃; for 24h; Suzuki Coupling; Inert atmosphere;	98%

2-iodo-1-(4-methoxyphenyl)-9-methyl-9H-carbazole + (2-bromophenyl)boronic acid (244205-40-1) → C26H20BrNO

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 80℃; for 2h; Suzuki Coupling;	98%

carbon monoxide (201230-82-2) + diphenyl acetylene (501-65-5) + (2-bromophenyl)boronic acid (244205-40-1) → 2,3-diphenyl-1H-inden-1-one (1801-42-9)

Conditions	Yield
With sodium carbonate; chloro(1,5-cyclooctadiene)rhodium(I) dimer In 1,4-dioxane; water at 80℃; under 760.051 Torr; for 20h;	97%

N-methyliminodiacetic acid (4408-64-4) + (2-bromophenyl)boronic acid (244205-40-1) → 2-bromophenylboronic acid MIDA ester

Conditions	Yield
In dimethyl sulfoxide; benzene for 13h; Heating;	97%
In dimethyl sulfoxide; benzene treatment of boronic acid deriv. with amine deriv. in benzene-DMSO (10:1); chromy. (silica gel);	97%
In dimethyl sulfoxide; toluene for 20h; Reflux;	96%

(S)-2-bromo-6a,7,8,9-tetrahydro-5H-pyrido[3,2-e]pyrrolo[1,2-a][1,4]diazepine-6,11-dione (1411774-31-6) + (2-bromophenyl)boronic acid (244205-40-1) → (S)-2-(2-bromophenyl)-6a,7,8,9-tetrahydro-5H-pyrido[3,2-e]pyrrolo[1,2-a][1,4]diazepine-6,11-dione (1411774-42-9)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 100℃; for 4h; Suzuki Coupling; Inert atmosphere;	97%

N-benzyl hydroxylalmine (622-30-0) + (2-bromophenyl)boronic acid (244205-40-1) → N-benzyl-2-bromoaniline (71687-81-5)

Conditions	Yield
With trichloroacetonitrile In tert-butyl alcohol at 28℃;	97%

2,2,2-trifluoro-N-phenyl-acetimidoyl chloride (61881-19-4) + (2-bromophenyl)boronic acid (244205-40-1) → 6‐(trifluoromethyl)phenanthridine (1269183-17-6)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate In toluene at 120℃; for 12h; Inert atmosphere;	97%

2,2,2-trifluoro-N-phenyl-acetimidoyl chloride (61881-19-4) + (2-bromophenyl)boronic acid (244205-40-1) → (Z)-N-(1-(2-bromophenyl)-2,2,2-trifluoroethylidene)aniline

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate In toluene at 60℃; for 6h; Inert atmosphere;	97%

2-methylimidazole (693-98-1) + (2-bromophenyl)boronic acid (244205-40-1) → C10H9BrN2 (1233883-52-7)

Conditions	Yield
With Cu-exchanged fluoroapatite; air In methanol at 20℃; for 5h;	96%

2,3-dibromopyridine (13534-89-9) + (2-bromophenyl)boronic acid (244205-40-1) → 3-bromo-2-(2-bromophenyl)pyridine (1312012-32-0)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium hydroxide In tetrahydrofuran; water at 70℃; for 4h; Suzuki-Miyaura Coupling; Schlenk technique; Inert atmosphere; chemoselective reaction;	96%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; potassium hydroxide In tetrahydrofuran; water for 72h; Inert atmosphere; Reflux;	92%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; potassium hydroxide In tetrahydrofuran; water for 72h; Reflux;	92%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; potassium hydroxide In tetrahydrofuran; water at 70℃; for 18h; Schlenk technique;	85%

Upstream product

• 121-43-7 Trimethyl borate 
• 583-55-1 1-Bromo-2-iodobenzene 
• 583-53-9 2,3-dibromobenzene 

Downstream Products

• 38527-58-1 1-bromo-2-(furan-2-yl)benzene 
• 106851-53-0 2-(2’-bromophenyl)thiophene 
• 59142-47-1 (2-bromophenyl)phenylmethanol 
• 61613-22-7 2-bromodiphenylamine 
• 931414-14-1 6-amino-2'-bromo-5-(4-chloro-phenoxy)-biphenyl-3-carboxylic acid methyl ester 
• 5041-48-5 3-butyl-2-phenyl-1H-inden-1-one 
• 150192-43-1 3-phenyl-2-(trimethylsilyl)-1H-inden-1-one 
• 101445-80-1 1-oxo-2-phenyl-1H-indene-3-carboxylic acid methyl ester 
• 200057-24-5 1-oxo-3-phenyl-1H-indene-2-carboxylic acid methyl ester 
• 751-38-2 1,2,3,4-tetraphenylnaphthalene 
• 1801-42-9 2,3-diphenyl-1H-inden-1-one 
• 13304-52-4 2-methyl-3-phenylinden-1-one 
• 10408-73-8 3-methyl-2-phenyl-inden-1-one 
• 866236-26-2 N,N'-bis(2,6-diisopropylphenyl)-1,7-di(2-bromophenyl)-3,4:9,10-perylene tetracarboxdiimide 

Relevant articles and documents

Easily accessible 2-(2-bromophenyl)-4,4,5,5-tetramethyl-[1,3,2] dioxaborolane for Suzuki-Miyaura reactions

A simple and direct method has been developed for the preparation of the title compound from 1,2-dibromobenzene. Suzuki-Miyaura reactions of this compound with substituted bromoaryls proceeded smoothly to give 2-bromobiphenyl derivatives in moderate to excellent yields. Instead of converting each of the bromoaryl compounds to the corresponding arylmetals followed by reacting with 2-iodobromobenzene, the advantage of this protocol is that the substituted bromoaryls were used directly to couple with the title compound.

Preparation method of monohalogenated phenylboronic acid

The invention relates to the technical field of chemical synthesis, and particularly discloses a preparation method of monohalogenated phenylboronic acid. The preparation method comprises the following steps of: by taking dihalogenated benzene as a raw material and a mixture of lithium salt and alkaline ionic liquid as a catalyst, carrying out Grignard exchange with R1MgCl to generate monohalogenated phenyl magnesium chloride, reacting with B (OR) 3 to generate monohalogenated phenyl borate, and hydrolyzing under acidic conditions to obtain monohalogenated phenylboronic acid. The HPLC (High Performance Liquid Chromatography) content of the monohalogenated phenylboronic acid prepared by the method is greater than 99.5%; the total yield of the product is greater than 80%, the contents of monohalogenated phenylboronic acid and phenyldiboronic acid impurities of another halogen are both less than 0.003%, the requirements of modern fine chemical synthesis are completely met, the raw materials are easily available, the operation is simple, the safety is high, and the industrial production of monohalogenated phenylboronic acid is realized.

Supramolecular structures and spontaneous resolution: The case of ortho-substituted phenylboronic acids

The solid state structures of a number of ortho-substituted arylboronic acids, ortho-bromophenyl, ortho-phenylphenyl, pentamethylphenyl, and 10-bromo-9-anthryl, were determined by X-ray diffraction techniques. All boronic acids investigated form dimers in the solid state, but the interconnection of dimers to ribbons differs from that of the parent phenylboronic acid. Pentamethylphenylboronic acid only uses one hydrogen bond but an additional OH-π interaction for connection of dimers, while all others investigated employ two hydrogen bonds for interconnection of dimers to ribbons. 10-Bromo-9-anthrylboronic acid is found to undergo spontaneous resolution of its enantiomers to a racemic conglomerate upon crystallization. The Royal Society of Chemistry.