30766-03-1

Basic information

• Product Name: 4-Bromopyridine-2-carboxylic acid
• Synonyms: AKOS BBS-00005794;4-BROMOPICOLINIC ACID;4-BROMOPYRIDINE-2-CARBOXYLIC ACID;4-BROMO-PYRIDINECARBOXYLIC ACID;4-BROMO-2-PYRIDINECARBOXYLIC ACID;IFLAB-BB F1926-0016;AURORA 23242;OTAVA-BB BB7017520050
• CAS NO: 30766-03-1
• Molecular Formula: C₆H₄BrNO₂
• Molecular Weight: 202.01
• EINECS: -0
• Product Categories: blocks;Bromides;Carboxes;Pyridines;Acids and Derivatives;Heterocycles;pharmacetical;Pyridine series;Pyridine;Organohalides;Aromatics Compounds;Aromatics
• Mol File: 30766-03-1.mol
• Article Data: 9

Chemical Properties

• Melting Point: 172-174
• Boiling Point: 347.8 °C at 760 mmHg
• Flash Point: 164.2 °C
• Appearance: Fine needles
• Density: 1.813 g/cm³
• Vapor Pressure: 1.97E-05mmHg at 25°C
• Storage Temp.: -20°C Freezer
• Solubility: Sparingly Soluble in DMSO, Methanol, Water
• PKA: 3.25±0.10(Predicted)
• Water Solubility: Sparingly soluble in dimethyl sulfoxide , methanol and water.
• CAS DataBase Reference: 4-Bromopyridine-2-carboxylic acid(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Bromopyridine-2-carboxylic acid(30766-03-1)
• EPA Substance Registry System: 4-Bromopyridine-2-carboxylic acid(30766-03-1)

Safety Data

• Hazard Codes: Xi
• Statements: 20/21/22
• Safety Statements: 24/25-36/37
• HazardClass: IRRITANT
• Hazardous Substances Data: 30766-03-1(Hazardous Substances Data)

Usage

Chemical Properties

4-Bromopyridine-2-carboxylic acid is fine needles

Uses

Different sources of media describe the Uses of 30766-03-1 differently. You can refer to the following data:
1. 4-Bromopyridine-2-carboxylic acid is a useful synthetic intermediate
2. 4-Bromopicolinic acid is a useful synthetic intermediate. Also used as a intermediate for agrochemical, pharmaceutical and dyestuff field.

InChI:InChI=1/C6H4BrNO2/c7-4-1-2-8-5(3-4)6(9)10/h1-3H,(H,9,10)/p-1

Synthetic route

4-bromo-2-methylpyridine (22282-99-1) → 4-bromo-2-picolinic acid (30766-03-1)

Conditions	Yield
With potassium permanganate In water at 80℃;	33%
Stage #1: 4-bromo-2-methylpyridine With potassium permanganate; water at 20℃; for 6.5h; Heating / reflux; Stage #2: With hydrogenchloride; water pH=4;	22%
Stage #1: 4-bromo-2-methylpyridine With potassium permanganate; water for 6.5h; Heating / reflux; Stage #2: With hydrogenchloride In water pH=4;	22%

4-bromo-2-cyanopyridine (62150-45-2) → 4-bromo-2-picolinic acid (30766-03-1)

Conditions	Yield
Stage #1: 4-bromo-2-cyanopyridine With sodium hydroxide In water Reflux; Stage #2: With hydrogenchloride In water at 130℃; for 0.333333h; pH=1 - 2;	20%

2-methylpyridine N-oxide (931-19-1) → 4-bromo-2-picolinic acid (30766-03-1)

Conditions	Yield
Multi-step reaction with 4 steps 1: 95 percent / H2SO4, fuming HNO3 / 2 h / 100 - 105 °C 2: 85 percent / PCl3 / CHCl3 / 3 h / Ambient temperature 3: 61 percent / AcBr / 6 h / Heating 4: KMnO4 / H2O / Heating View Scheme

2-methyl-4-nitro-pyridine (13508-96-8) → 4-bromo-2-picolinic acid (30766-03-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: 61 percent / AcBr / 6 h / Heating 2: KMnO4 / H2O / Heating View Scheme

2-methyl-4-nitropyridine N-oxide (5470-66-6) → 4-bromo-2-picolinic acid (30766-03-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: 85 percent / PCl3 / CHCl3 / 3 h / Ambient temperature 2: 61 percent / AcBr / 6 h / Heating 3: KMnO4 / H2O / Heating View Scheme
Multi-step reaction with 3 steps 1: iron; acetic acid / 2 h / 20 - 100 °C 2: hydrogen bromide; sodium nitrite / water / 16.5 h / -10 - 20 °C 3: potassium permanganate / water / 6.5 h / 20 °C / Heating / reflux View Scheme
Multi-step reaction with 3 steps 1.1: iron; acetic acid / 2 h / 20 - 100 °C 2.1: hydrogen bromide; sodium nitrite / water / 16.5 h / 0 - 20 °C 3.1: potassium permanganate / water / 6.5 h / 20 °C / Heating / reflux 3.2: pH 4 View Scheme

3-methyl-4-pyridinamine (18437-58-6) → 4-bromo-2-picolinic acid (30766-03-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: hydrogen bromide; sodium nitrite / water / 16.5 h / -10 - 20 °C 2: potassium permanganate / water / 6.5 h / 20 °C / Heating / reflux View Scheme
Multi-step reaction with 2 steps 1.1: hydrogen bromide; sodium nitrite / water / 16.5 h / 0 - 20 °C 2.1: potassium permanganate / water / 6.5 h / 20 °C / Heating / reflux 2.2: pH 4 View Scheme

4-bromopyridin (1120-87-2) → 4-bromo-2-picolinic acid (30766-03-1)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: 3-chloro-benzenecarboperoxoic acid / diethyl ether / 17 h / 20 °C 2.1: triethylamine / acetonitrile / 3.5 h / Schlenk technique; Inert atmosphere; Reflux 3.1: sodium hydroxide / water / Reflux 3.2: 0.33 h / 130 °C / pH 1 - 2 View Scheme

4-bromopyridine-1-oxide (14248-50-1) → 4-bromo-2-picolinic acid (30766-03-1)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: triethylamine / acetonitrile / 3.5 h / Schlenk technique; Inert atmosphere; Reflux 2.1: sodium hydroxide / water / Reflux 2.2: 0.33 h / 130 °C / pH 1 - 2 View Scheme

4-bromo-2-picolinic acid (30766-03-1) + N,0-dimethylhydroxylamine (1117-97-1) → 4-bromo-pyridine-2-carboxylic acid N-methoxy-N-methyl-amide (1005342-94-8)

Conditions	Yield
With triethylamine; HATU In N,N-dimethyl-formamide at 20℃; for 2h;	100%

(5‐chloro‐2‐hydroxyphenyl)boronic acid (89488-25-5) + 4-bromo-2-picolinic acid (30766-03-1) → 4-(5-chloro-2-hydroxyphenyl)picolinic acid

Conditions	Yield
With sodium carbonate In 1,4-dioxane; water at 87 - 88℃; for 29h; Inert atmosphere;	100%

di-tert-butyl dicarbonate (24424-99-5) + 4-bromo-2-picolinic acid (30766-03-1) → tert-butyl 4-bromopyridine-2-carboxylate (1289210-83-8)

Conditions	Yield
With dmap In tetrahydrofuran at 20℃; for 16h;	97.25%

4-bromo-2-picolinic acid (30766-03-1) → (4-bromopyridin-2-yl)-carbamic acid tert-butyl ester (207799-10-8)

Conditions	Yield
	93%
	93%
	93%

5-chloro-2-methoxyphenyl boronic acid (89694-48-4) + 4-bromo-2-picolinic acid (30766-03-1) → 4-(5-chloro-2-methoxyphenyl)picolinic acid

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; water for 16h; Inert atmosphere; Reflux;	92%

methyl 4-aminothiophene-2-carboxylate (89499-43-4) + 4-bromo-2-picolinic acid (30766-03-1) → methyl 4-(4-bromopicolinamido)thiophene-2-carboxylate (1354412-71-7)

Conditions	Yield
With 4-methyl-morpholine; HATU In N,N-dimethyl-formamide at 20℃; for 6h;	90%

4-bromo-2-picolinic acid (30766-03-1) + tert-butyl alcohol (75-65-0) → tert-butyl 4-bromopyridine-2-carboxylate (1289210-83-8)

Conditions	Yield
With pyridine; p-toluenesulfonyl chloride at 0 - 20℃;	89%
With pyridine; p-toluenesulfonyl chloride at 0℃; for 16h;

[{Ir(ppy)2(μ-Cl)}2] + 4-bromo-2-picolinic acid (30766-03-1) → Ir(2-phenylpyridine)2(pyridine-2-carboxylate-Br)

Conditions	Yield
With potassium carbonate In acetone Reflux; Inert atmosphere;	87%

ethanol (64-17-5) + 4-bromo-2-picolinic acid (30766-03-1) → ethyl 4-bromopyridine-2-carboxylate (62150-47-4)

Conditions	Yield
With sulfuric acid at 20 - 70℃; for 12h;	86%
With sulfuric acid at 60℃; for 6h;	73.6%
With sulfuric acid for 3.5h; Schlenk technique; Inert atmosphere; Reflux;	40%

4-bromo-2-picolinic acid (30766-03-1) + 2-phenoxyaniline (2688-84-8) → C18H13BrN2O2

Conditions	Yield
With dmap; benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 25℃; for 6h; Reagent/catalyst; Solvent; Temperature;	86%

4-fluoroboronic acid (1765-93-1) + 4-bromo-2-picolinic acid (30766-03-1) → C12H8FNO2

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 98℃; for 24h; Inert atmosphere;	85.8%
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,4-dioxane; water at 100℃; Suzuki Coupling; Inert atmosphere;
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,4-dioxane; water at 100℃; Suzuki Coupling; Inert atmosphere;
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,4-dioxane; water at 100℃; Suzuki Coupling; Inert atmosphere;

propylamine (107-10-8) + 4-bromo-2-picolinic acid (30766-03-1) → 4-bromo-N-propylpyridine-2-carboxamide (1289051-27-9)

Conditions	Yield
With 1-hydroxy-1H-benzotriazol hydrate; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In acetonitrile at 20℃;	84%

N,O-dimethylhydroxylamine*hydrochloride (6638-79-5) + 4-bromo-2-picolinic acid (30766-03-1) → 4-bromo-pyridine-2-carboxylic acid N-methoxy-N-methyl-amide (1005342-94-8)

Conditions	Yield
Stage #1: 4-bromo-2-picolinic acid With N-ethyl-N,N-diisopropylamine; HATU In N,N-dimethyl-formamide at 10℃; for 0.5h; Stage #2: N,O-dimethylhydroxylamine*hydrochloride In N,N-dimethyl-formamide at 20℃; for 16h;	83%
With 4-methyl-morpholine; benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 12h;	44%
With 4-methyl-morpholine; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In dichloromethane at 0 - 20℃;
With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide at 20℃; for 16h;	5 g

4-bromo-2-picolinic acid (30766-03-1) + 3,4-(methylenedioxy)-benzeneboronic acid (94839-07-3) → C13H9NO4

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 98℃; for 24h; Inert atmosphere;	82.1%

4-bromo-2-picolinic acid (30766-03-1) + N,N-diethylethylenediamine (100-36-7) → 4-bromo-N-(2-(diethylamino)ethyl)picolinamide (1420844-63-8)

Conditions	Yield
Stage #1: 4-bromo-2-picolinic acid With O-(N-succinimidyl)-N,N,N',N'-tetramethyluronium tetrafluoroborate; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 60℃; for 3h; Stage #2: N,N-diethylethylenediamine In N,N-dimethyl-formamide at 20℃; for 2h;	82%

4-bromo-2-picolinic acid (30766-03-1) + 3-(1,3,4-oxadiazol-2-yl)aniline (5378-35-8) → N-(3-(1,3,4-oxadiazol-2-yl)phenyl)-4-bromopicolinamide (1262044-02-9)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine; HATU In N,N-dimethyl-formamide at 20℃; for 1h;	81%

glycine ethyl ester hydrochloride (5680-79-5) + 4-bromo-2-picolinic acid (30766-03-1) → methyl 2-(4-bromopicolinamido)acetate (1289199-67-2)

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 20℃;	79.8%

4-bromo-2-picolinic acid (30766-03-1) + phenylboronic acid (98-80-6) → 4-phenylpyridine-2-carboxylic acid (52565-56-7)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,4-dioxane; water at 90℃; for 8h; Inert atmosphere;	78.9%
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,4-dioxane; water at 100℃; Suzuki Coupling; Inert atmosphere;
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,4-dioxane; water at 100℃; Suzuki Coupling; Inert atmosphere;
With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate In 1,4-dioxane; water at 100℃; Suzuki Coupling; Inert atmosphere;

4-bromo-2-picolinic acid (30766-03-1) + 4-trifluoromethoxyphenylboronic acid (139301-27-2) → C13H8F3NO3

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 98℃; for 24h; Inert atmosphere;	77.7%

3-trifluoromethylaniline (98-16-8) + 4-bromo-2-picolinic acid (30766-03-1) → 4-bromo-N-[3-(trifluoromethyl)phenyl]pyridine-2-carboxamide (1454657-40-9)

Conditions	Yield
Stage #1: 4-bromo-2-picolinic acid With 4-methyl-morpholine; HATU In N,N-dimethyl-formamide for 0.166667h; Stage #2: 3-trifluoromethylaniline In N,N-dimethyl-formamide at 20℃; for 21h; Time;	76%
Stage #1: 4-bromo-2-picolinic acid With 4-methyl-morpholine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide for 0.166667h; Stage #2: 3-trifluoromethylaniline In N,N-dimethyl-formamide at 20℃; for 21h; Reagent/catalyst; Time;	76%

4-bromo-2-picolinic acid (30766-03-1) + methyl iodide (74-88-4) → methyl 4-bromopyridine-2-carboxylate (29681-42-3)

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 20℃; Inert atmosphere;	75.3%

4-bromo-2-picolinic acid (30766-03-1) + tert-butyl alcohol (75-65-0) → (4-bromopyridin-2-yl)-carbamic acid tert-butyl ester (207799-10-8)

Conditions	Yield
With diphenylphosphoranyl azide; triethylamine for 26h; Heating;	74%

O-(tert-butyl)hydroxylamine hydrochloride (39684-28-1) + 4-bromo-2-picolinic acid (30766-03-1) → 4-bromopyridine-2-carboxylic acid tert-butoxyamide (1431470-36-8)

Conditions	Yield
With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 20℃; for 18h;	74%
Stage #1: 4-bromo-2-picolinic acid With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane Stage #2: O-(tert-butyl)hydroxylamine hydrochloride In dichloromethane at 20℃; for 18h;	74%

3-aminoazetidine-1-carboxylic acid tert-butyl ester (193269-78-2) + 4-bromo-2-picolinic acid (30766-03-1) → tert-butyl 3-(4-bromopicolinamido)azetidine-1-carboxylate

Conditions	Yield
With 1-hydroxy-7-aza-benzotriazole; N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide at 20℃;	74%

4-bromo-2-picolinic acid (30766-03-1) + diazomethyl-trimethyl-silane (18107-18-1) → methyl 4-bromopyridine-2-carboxylate (29681-42-3)

Conditions	Yield
In methanol; diethyl ether; ethyl acetate at 0 - 20℃; for 1.5h;	73%
In tetrahydrofuran; ethyl acetate at 0 - 20℃; for 5.08h; Product distribution / selectivity;	62%
Stage #1: 4-bromo-2-picolinic acid; diazomethyl-trimethyl-silane With methanol In tetrahydrofuran at 0 - 20℃; Stage #2: With acetic acid In tetrahydrofuran; methanol; water	60%

(3-bromophenyl)boronic acid (89598-96-9) + 4-bromo-2-picolinic acid (30766-03-1) → C12H8BrNO2

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,2-dimethoxyethane; water at 98℃; for 24h; Inert atmosphere;	71.9%

4-bromo-2-picolinic acid (30766-03-1) + aniline (62-53-3) → 4-bromo-pyridine-2-carboxylic acid phenylamide (1454657-45-4)

Conditions	Yield
Stage #1: 4-bromo-2-picolinic acid With 4-methyl-morpholine; HATU In N,N-dimethyl-formamide for 0.166667h; Stage #2: aniline In N,N-dimethyl-formamide at 20℃; for 66h;	71%
Stage #1: 4-bromo-2-picolinic acid With 4-methyl-morpholine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide for 0.166667h; Stage #2: aniline In N,N-dimethyl-formamide at 20℃; for 66h;	71%

styrene (292638-84-7) + 4-bromo-2-picolinic acid (30766-03-1) → 2-chloro-1-phenylethyl 4-bromopicolinate

Conditions	Yield
With tert-butylhypochlorite In N,N-dimethyl-formamide at 40℃; for 1h; Schlenk technique;	70%

4-bromo-2-picolinic acid (30766-03-1) → 4-bromopyridine-2-carboxamide (62150-46-3)

Conditions	Yield
Stage #1: 4-bromo-2-picolinic acid With 1,1'-carbonyldiimidazole In tetrahydrofuran at 20℃; for 0.25h; Stage #2: With ammonium hydroxide In tetrahydrofuran at 20℃; for 2h;	68%

[Ir(F2PPy)2Cl]2 + 4-bromo-2-picolinic acid (30766-03-1) → Ir(2-(2,4-difluorophenyl)pyridine)2(pyridine-2-carboxylate-4-Br)

Conditions	Yield
With potassium carbonate In acetone Reflux; Inert atmosphere;	68%

Upstream product

• 29681-42-3 methyl 4-bromopyridine-2-carboxylate 
• 22282-99-1 4-bromo-2-methylpyridine 
• 62150-45-2 4-bromo-2-cyanopyridine 
• 14248-50-1 4-bromopyridine-1-oxide 
• 1120-87-2 4-bromopyridin 
• 18437-58-6 3-methyl-4-pyridinamine 
• 5470-66-6 2-methyl-4-nitropyridine N-oxide 
• 13508-96-8 2-methyl-4-nitro-pyridine 
• 931-19-1 2-methylpyridine N-oxide 

Downstream Products

• 64197-01-9 4-bromopyridine-2-carbonyl chloride 
• 1186336-23-1 C₁₆H₁₇BrN₂O₂ 
• 29681-42-3 methyl 4-bromopyridine-2-carboxylate 
• 1415312-56-9 (2R,3R)-3-[(4-bromo-pyridine-2-carbonyl)-amino]-4-(2-chloro-phenyl)-2-hydroxy-butyric acid ethyl ester 
• 62150-48-5 4-bromopicolinohydrazide 
• 62150-47-4 ethyl 4-bromopyridine-2-carboxylate 
• 946000-13-1 tert-butyl N-(4-bromo-2-pyridyl)-N-(methyl)carbamate 
• 1289210-83-8 tert-butyl 4-bromopyridine-2-carboxylate 
• 477252-20-3 2-(4-bromopyridin-2-yl)propan-2-ol 
• 1209459-88-0 4-bromo-pyridine-2-carboxylic acid methyl amide 

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