68837-59-2

Basic information

• Product Name: 4-Bromo-2-methylbenzoic acid
• Synonyms: RARECHEM AL BO 0455;2-METHYL-4-BROMOBENZOIC ACID;4-BROMO-2-METHYLBENZOIC ACID;4-Bromo-o-toluic acid;4-Bromo-2-Methylbenzoic Acid 2-Methyl-4-Bromobenzoic Acid;4-Bromo-2-methylbenzoic acid, 98+%;4-Bromo-2-methylbenz;5-Bromo-2-carboxytoluene
• CAS NO: 68837-59-2
• Molecular Formula: C₈H₇BrO₂
• Molecular Weight: 215.04
• EINECS: 272-437-7
• Product Categories: Aromatic Carboxylic Acids, Amides, Anilides, Anhydrides & Salts;Benzoic acid;C8;Carbonyl Compounds;Carboxylic Acids
• Mol File: 68837-59-2.mol
• Article Data: 4

Chemical Properties

• Melting Point: 180-184 °C
• Boiling Point: 310.1 °C at 760 mmHg
• Flash Point: 141.3 °C
• Appearance: White to off-white crystalline powder
• Density: 1.599 g/cm³
• Vapor Pressure: 0.000264mmHg at 25°C
• Refractive Index: 1.595
• Storage Temp.: Room temperature.
• PKA: 3.63±0.25(Predicted)
• Water Solubility: Insoluble in water.
• BRN: 2249816
• CAS DataBase Reference: 4-Bromo-2-methylbenzoic acid(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Bromo-2-methylbenzoic acid(68837-59-2)
• EPA Substance Registry System: 4-Bromo-2-methylbenzoic acid(68837-59-2)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 22-36/37/38
• Safety Statements: 26-36/37/39-36
• RIDADR: UN 2811 6.1/PG 3
• WGK Germany: 3
• HazardClass: IRRITANT
• PackingGroup: Ⅲ
• Hazardous Substances Data: 68837-59-2(Hazardous Substances Data)

Usage

Chemical Properties

White to brown crystal powde

Uses

A building block which is used in preparation of anthranilic acids possessing antibacterial activity.

InChI:InChI=1/C8H7BrO2/c1-5-4-6(9)2-3-7(5)8(10)11/h2-4H,1H3,(H,10,11)

Synthetic route

4-bromo-2-methylbenzonitrile (67832-11-5) → 4-bromo-2-methylbenzoic acid (68837-59-2)

Conditions	Yield
With potassium hydroxide In water Reflux;	60%
With sulfuric acid; water
With sodium hydroxide
With sulfuric acid; acetic acid In water for 4.5h; Reflux;

4-methyl-4-tribromomethylcyclohexa-2,5-dien-1-one (10087-24-8) → 4-bromo-2-methylbenzoic acid (68837-59-2)

Conditions	Yield
With phosphorus pentabromide

n-butyllithium (109-72-8, 29786-93-4) + 1,4-dibromo-2-methylbenzene (615-59-8) + petroleum ether → 4-bromo-2-methylbenzoic acid (68837-59-2) + 4-bromo-3-methylbenzoic acid (7697-28-1)

Conditions	Yield
at 20℃; anschliessend Behandlung mit CO2;

4-bromo-o-xylene (583-71-1) + nitric acid (7697-37-2) → 4-bromo-2-methylbenzoic acid (68837-59-2)

diazotized 4-amino-2-methyl-benzoic acid → 4-bromo-2-methylbenzoic acid (68837-59-2)

Conditions	Yield
With hydrogen bromide; copper(I) bromide

4-Bromobenzoic acid (586-76-5) + 2,2,6,6-tetramethylpiperidinyl-lithium (38227-87-1) + methyl iodide (74-88-4) → 4-bromo-2-methylbenzoic acid (68837-59-2) + 4-bromo-2-ethylbenzoic acid (644984-78-1) + 3-(2,2,6,6-tetramethylpiperidino)benzoic acid + 4-(2,2,6,6-tetramethylpiperidino)benzoic acid

Conditions	Yield
Stage #1: 4-Bromobenzoic acid; 2,2,6,6-tetramethylpiperidinyl-lithium In tetrahydrofuran; hexane at -78℃; for 4h; Stage #2: methyl iodide In tetrahydrofuran; hexane at -78 - 20℃;	A 12 % Spectr. B 22 % Spectr. C 15 % Spectr. D 12 % Spectr.

4-Bromo-2-methylaniline (583-75-5) → 4-bromo-2-methylbenzoic acid (68837-59-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: durch Austausch von NH2 gegen CN 2: alcoholic NaOH-solution View Scheme

p-cresol (106-44-5) + n-C3H7X → 4-bromo-2-methylbenzoic acid (68837-59-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: AlBr3 / CS2 2: PBr5 View Scheme

methanol (67-56-1) + 4-bromo-2-methylbenzoic acid (68837-59-2) → 4-bromo-2-methyl-benzoic acid methyl ester (99548-55-7)

Conditions	Yield
With hydrogenchloride for 6h; Heating / reflux;	100%
With thionyl chloride at 70℃; for 6h;	100%
With thionyl chloride at 0℃; Inert atmosphere; Reflux;	100%

4-bromo-2-methylbenzoic acid (68837-59-2) → 4-bromo-2-methylbenzoyl chloride (21900-45-8)

Conditions	Yield
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 9h;	100%
With thionyl chloride In toluene for 15h; Reflux;	92%
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane for 0.5h; Cooling with ice;	89%

4-bromo-2-methylbenzoic acid (68837-59-2) → 4-bromo-2-methylbenzyl alcohol (17100-58-2)

Conditions	Yield
With borane-THF In tetrahydrofuran at 0 - 20℃; for 1h;	100%
Stage #1: 4-bromo-2-methylbenzoic acid With borane-THF In tetrahydrofuran at 0 - 20℃; for 3h; Stage #2: With water; sodium hydrogencarbonate In tetrahydrofuran	100%
With borane-THF In tetrahydrofuran at 0 - 20℃; for 2h;	100%

4-bromo-2-methylbenzoic acid (68837-59-2) + diazomethyl-trimethyl-silane (18107-18-1) → 4-bromo-2-methyl-benzoic acid methyl ester (99548-55-7)

Conditions	Yield
In dichloromethane	100%
In tetrahydrofuran; methanol; hexanes at 0 - 20℃; for 1h;	100%
In tetrahydrofuran; methanol at 0 - 20℃; for 1h;	92%

4-bromo-2-methylbenzoic acid (68837-59-2) + methyl iodide (74-88-4) → 4-bromo-2-methyl-benzoic acid methyl ester (99548-55-7)

Conditions	Yield
With sodium hydrogencarbonate In N,N-dimethyl-formamide at 80℃;	100%
With potassium carbonate In N,N-dimethyl-formamide at 20℃;	100%
With sodium hydrogencarbonate In N,N-dimethyl-formamide at 80℃;	100%

4-bromo-2-methylbenzoic acid (68837-59-2) → 4-bromo-2-methyl-benzoic acid methyl ester (99548-55-7)

Conditions	Yield
With hydrogenchloride In methanol	100%
With hydrogenchloride In methanol	100%
With methanol; hydrogenchloride for 3h; Heating / reflux;	86%

4-bromo-2-methylbenzoic acid (68837-59-2) → 4-bromo-2-methylbenzamide

Conditions	Yield
Stage #1: 4-bromo-2-methylbenzoic acid With oxalyl dichloride In dichloromethane at 0 - 20℃; for 2h; Stage #2: With ammonium hydroxide In dichloromethane at 0 - 25℃; for 1h;	100%
With ammonium hydroxide; oxalyl dichloride In dichloromethane	100%
Stage #1: 4-bromo-2-methylbenzoic acid With oxalyl dichloride In dichloromethane at 0 - 20℃; for 2h; Stage #2: With ammonium hydroxide In dichloromethane at 0 - 25℃; for 1h;	100%
Stage #1: 4-bromo-2-methylbenzoic acid With thionyl chloride In dichloromethane for 1h; Stage #2: With ammonium hydroxide	95%
With 4-methyl-morpholine

4-bromo-2-methylbenzoic acid (68837-59-2) + Cyclopropylamine (765-30-0) → 4-bromo-N-cyclopropyl-2-methylbenzamide (345965-99-3)

Conditions	Yield
Stage #1: 4-bromo-2-methylbenzoic acid With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 16h; Stage #2: Cyclopropylamine With triethylamine In dichloromethane at 0 - 20℃; for 2.25h;	99%
Stage #1: 4-bromo-2-methylbenzoic acid With thionyl chloride In dichloromethane; N,N-dimethyl-formamide at 20℃; for 16h; Stage #2: Cyclopropylamine With triethylamine In dichloromethane at 20℃; for 2h;	99%
Stage #1: 4-bromo-2-methylbenzoic acid; Cyclopropylamine With O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; Stage #2: With sodium hydroxide In water at 20℃;	87%

4-bromo-2-methylbenzoic acid (68837-59-2) + N,N-dimethylammonium chloride (506-59-2) → 4-bromo-2-methyl-N,N-dimethylbenzamide (862470-12-0)

Conditions	Yield
Stage #1: 4-bromo-2-methylbenzoic acid With thionyl chloride at 60℃; for 3h; Stage #2: N,N-dimethylammonium chloride With triethylamine In dichloromethane at 0 - 20℃; for 2h;	99%
Stage #1: 4-bromo-2-methylbenzoic acid With thionyl chloride at 60℃; for 3h; Stage #2: N,N-dimethylammonium chloride With triethylamine In dichloromethane at 0 - 20℃; for 2h;	99%
Stage #1: 4-bromo-2-methylbenzoic acid With 1,1'-carbonyldiimidazole In tetrahydrofuran at 20℃; for 0.0833333h; Stage #2: N,N-dimethylammonium chloride With triethylamine In tetrahydrofuran at 20℃; for 3h;

pyrrolidine (123-75-1) + 4-bromo-2-methylbenzoic acid (68837-59-2) + O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate (125700-67-6) + N-ethyl-N,N-diisopropylamine (7087-68-5) → (4-bromo-2-methylphenyl)(pyrrolidin-1-yl)methanone (276678-35-4)

Conditions	Yield
In tetrahydrofuran; water	98%

di-tert-butyl dicarbonate (24424-99-5) + 4-bromo-2-methylbenzoic acid (68837-59-2) → 4-bromo-2-methyl-benzoic acid tert-butyl ester (445003-37-2)

Conditions	Yield
With dmap In tert-butyl alcohol at 20℃; for 18h;	98%
With dmap In tert-butyl alcohol at 20℃; for 18h;	98%
With dmap In tert-butyl alcohol at 20℃; for 12h;	96%

4-bromo-2-methylbenzoic acid (68837-59-2) → 4-bromo-5-iodo-2-methylbenzoic acid (1022983-51-2)

Conditions	Yield
With N-iodo-succinimide; sulfuric acid at 0 - 5℃; for 1h;	98%
With N-iodo-succinimide; sulfuric acid at 0℃;	75%

acrylic acid n-butyl ester (141-32-2) + 4-bromo-2-methylbenzoic acid (68837-59-2) → n-butyl 2-(6-bromo-4-methyl-3-oxo-1,3-dihydroisobenzofuran-1-yl)acetate

Conditions	Yield
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; oxygen; cesium acetate In methanol at 60℃; under 760.051 Torr; for 18h; Schlenk technique; chemoselective reaction;	98%
With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; copper(II) acetate monohydrate In water at 80℃; for 16h; Inert atmosphere; Sealed tube; Green chemistry;	89%

3-Pyrroline (109-96-6) + 4-bromo-2-methylbenzoic acid (68837-59-2) → 4-(2,5-dihydro-pyrrol-1-yl-carbonyl)-3-methyl-bromobenzene (651045-03-3)

Conditions	Yield
With 4-methyl-morpholine; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate In N,N-dimethyl-formamide at 20℃; for 16h;	97%
With 4-methyl-morpholine; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate In N,N-dimethyl-formamide at 20℃; for 16h;	97%

4-bromo-2-methylbenzoic acid (68837-59-2) + ethyl iodide (75-03-6) → ethyl 4-bromo-2-methylbenzoate (220389-34-4)

Conditions	Yield
With sodium carbonate In N,N-dimethyl-formamide at 60℃; for 16h;	97%

ethanol (64-17-5) + 4-bromo-2-methylbenzoic acid (68837-59-2) → ethyl 4-bromo-2-methylbenzoate (220389-34-4)

Conditions	Yield
With thionyl chloride for 3h; Reflux;	96%
With sulfuric acid at 120℃; for 0.0833333h; Microwave irradiation;	79%
With sulfuric acid for 72h; Heating / reflux;
With sulfuric acid for 18h; Heating / reflux;
With hydrogenchloride at 45℃; for 8h;

4-bromo-2-methylbenzoic acid (68837-59-2) + tert-butyl alcohol (75-65-0) → 4-bromo-2-methyl-benzoic acid tert-butyl ester (445003-37-2)

Conditions	Yield
With dmap; di-tert-butyl dicarbonate at 20℃; for 12h;	96%

4-bromo-2-methylbenzoic acid (68837-59-2) + isopropyl alcohol (67-63-0) → isopropyl 2-methyl-4-bromobenzoate (345965-04-0)

Conditions	Yield
With sulfuric acid In benzene for 96h; Heating / reflux;	95%
With sulfuric acid for 96h; Heating / reflux;	95%
	79%
	79%

-butyl vinyl ether (111-34-2) + 4-bromo-2-methylbenzoic acid (68837-59-2) → 4-acetyl-2-methyl benzoic acid (55860-35-0)

Conditions	Yield
Stage #1: -butyl vinyl ether; 4-bromo-2-methylbenzoic acid With 1,3-bis-(diphenylphosphino)propane; potassium carbonate; palladium diacetate In water; butan-1-ol for 5h; Inert atmosphere; Reflux; Stage #2: With hydrogenchloride In water; toluene	95%

aminomethylphosphonic acid diethyl ester (50917-72-1) + 4-bromo-2-methylbenzoic acid (68837-59-2) → diethyl ((4-bromo-2-methylbenzamido)methyl)phosphonate

Conditions	Yield
With 4-methyl-morpholine; 1-hydroxy-7-aza-benzotriazole; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In N,N-dimethyl-formamide at 20℃; for 18h;	95%

4-bromo-2-methylbenzoic acid (68837-59-2) + diethyl (aminomethyl)phosphonate oxalate → diethyl ((4-bromo-2-methylbenzamido)methyl)phosphonate

Conditions	Yield
With 4-methyl-morpholine; 1-hydroxy-7-aza-benzotriazole; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In methanol; N,N-dimethyl-formamide at 20℃; for 18h;	95%

4-bromo-2-methylbenzoic acid (68837-59-2) → ethyl 4-bromo-2-methylbenzoate (220389-34-4)

Conditions	Yield
With concentrated sulfuric acid In ethanol	93%

methanol (67-56-1) + 4-bromo-2-methylbenzoic acid (68837-59-2) → ethyl 4-bromo-2-methylbenzoate (220389-34-4)

Conditions	Yield
With sulfuric acid at 100℃; Inert atmosphere;	92%

4-bromo-2-methylbenzoic acid (68837-59-2) + 2-fluoro-5-methoxyphenylboronic acid → 2′-fluoro-5′-methoxy-3-methylbiphenyl-4-carboxylic acid (1610370-14-3)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium carbonate In water at 130℃; for 0.333333h; Sealed tube; Microwave irradiation;	92%
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium carbonate In water at 130℃; for 0.333333h; Microwave irradiation; Sealed tube;	92%
With tetrakis(triphenylphosphine) palladium(0); tetrabutylammomium bromide; sodium carbonate at 130℃; for 0.333333h; Sealed tube; Microwave irradiation;	92%

4-aminotetrahydropyran (38041-19-9) + 4-bromo-2-methylbenzoic acid (68837-59-2) → 4-bromo-2-methyl-N-(tetrahydropyran-4-yl)benzamide (1350411-41-4)

Conditions	Yield
With 4-methyl-morpholine; benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane; N,N-dimethyl-formamide at 20℃; for 16h; Cooling with ice;	92%

4-bromo-2-methylbenzoic acid (68837-59-2) + N,O-dimethylhydroxylamine*hydrochloride (6638-79-5) → 4-bromo-N-methoxy-N,2-dimethylbenzamide (178313-45-6)

Conditions	Yield
With 4-methyl-morpholine; benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃;	91.6%
With O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 16h;	79%
With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 20℃;	74%

tributyl borane (122-56-5) + 4-bromo-2-methylbenzoic acid (68837-59-2) → 4-butyl-2-methylbenzoic acid

Conditions	Yield
In tetrahydrofuran Suzuki-Miyaura Coupling; Inert atmosphere;	90%

4-bromo-2-methylbenzoic acid (68837-59-2) + 4-methoxyphenylboronic acid (5720-07-0) → 4'-methoxy-3-methyl-4-cyanodiphenyl (104582-73-2)

Conditions

Yield

Stage #1: 4-bromo-2-methylbenzoic acid With resin-bound amine; benzotriazol-1-ol; O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate In N,N-dimethyl-formamide at 20℃; for 18h; Stage #2: 4-methoxyphenylboronic acid With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane for 48h; Suzuki coupling; Heating; Stage #3: With pyridine; trifluoroacetic anhydride In dichloromethane at 20℃; for 16h;

89%

zinc(II) cyanide (557-21-1) + 4-bromo-2-methylbenzoic acid (68837-59-2) → 4-cyano-2-methylbenzoic acid methyl ester (103261-67-2)

Conditions	Yield
tetrakis(triphenylphosphine) palladium(0) In N,N-dimethyl-formamide at 100℃; for 16h; Inert atmosphere;	89%

Upstream product

• 67832-11-5 4-bromo-2-methylbenzonitrile 
• 109-72-8 n-butyllithium 
• 615-59-8 1,4-dibromo-2-methylbenzene 
• 586-76-5 4-Bromobenzoic acid 
• 38227-87-1 2,2,6,6-tetramethylpiperidinyl-lithium 
• 74-88-4 methyl iodide 
• 106-44-5 p-cresol 
• 583-75-5 4-Bromo-2-methylaniline 
• 583-71-1 4-bromo-o-xylene 
• 7697-37-2 nitric acid 
• 10087-24-8 4-methyl-4-tribromomethylcyclohexa-2,5-dien-1-one 

Downstream Products

• 99548-55-7 4-bromo-2-methyl-benzoic acid methyl ester 
• 6968-28-1 4-bromophthalic acid 
• 21900-45-8 4-bromo-2-methylbenzoyl chloride 
• 264927-43-7 4-bromo-2-methyl-5-nitro-benzoic acid 
• 64169-34-2 5-bromophthalide 
• 59247-48-2 isopropyl 4-bromobenzoate 
• 345965-04-0 isopropyl 2-methyl-4-bromobenzoate 
• 651045-03-3 4-(2,5-dihydro-pyrrol-1-yl-carbonyl)-3-methyl-bromobenzene 
• 345964-93-4 4-bromo-2-methyl benzoic acid benzyl ester 
• 276678-35-4 (4-bromo-2-methylphenyl)(pyrrolidin-1-yl)methanone 
• 908247-35-8 (e)-2-methyl-4-(3,3,3-trifluoroprop-1-enyl)benzoic acid 
• 191089-06-2 3-methyl-4-p-carboxybenzeneboronic acid, 
• 345965-99-3 4-bromo-N-cyclopropyl-2-methylbenzamide 
• 65095-33-2 1-(4-bromo-2-methylphenyl)ethan-1-one 

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