10168-00-0

Basic information

• Product Name: 4-Bromo-3-methylpyridine
• Synonyms: CHEMBRDG-BB 4014100;4-BROMO-3-PICOLINE;4-BROMO-3-METHYLPYRIDINE;4-Bromo-3-methylpyridine HCl;4-Bromo-3-methylpyridine HCl salt;4-Bromo-3-methylpyridine HCl 4-bromo-3-picoline HCI;4-Bromo-5-methylpyridine
• CAS NO: 10168-00-0
• Molecular Formula: C₆H₆BrN
• Molecular Weight: 172.02
• EINECS: -0
• Product Categories: Pyridine;pharmacetical;Pyridines;Boronic Acid;Pyridine Series
• Mol File: 10168-00-0.mol
• Article Data: 9

Chemical Properties

• Boiling Point: 211 ºC
• Flash Point: 82 ºC
• Appearance: /
• Density: 1.494
• Vapor Pressure: 6.97E-05mmHg at 25°C
• Refractive Index: 1.625
• Storage Temp.: Keep Cold
• PKA: 3.58±0.10(Predicted)
• CAS DataBase Reference: 4-Bromo-3-methylpyridine(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Bromo-3-methylpyridine(10168-00-0)
• EPA Substance Registry System: 4-Bromo-3-methylpyridine(10168-00-0)

Safety Data

• Hazard Codes: Xi
• Hazardous Substances Data: 10168-00-0(Hazardous Substances Data)

Usage

General Description

4-Bromo-3-methylpyridine is a synthetic, organic halide. Its molecular formula is C6H6BrN, which indicates the presence of bromine, nitrogen, carbon, and hydrogen atoms, and it has a molecular weight of 172.02 g/mol. This chemical appears as a clear, light yellow to yellow liquid or in crystalline powder form. The compound exhibits insolubility in water and is more dense than water, leading it to sink and likely not to mix well. This chemical is crucially used as a raw material or building block in the pharmaceutical industry and for chemical synthesis. It should be handled carefully as it might cause severe skin burns and eye damage.

InChI:InChI=1/C8H6BrNO/c9-6-2-1-5-3-8(11)10-7(5)4-6/h1-2,4H,3H2,(H,10,11)

Synthetic route

4-bromo-3-methylpyridine 1-oxide (10168-58-8) → 4-bromo-3-methylpyridine (10168-00-0)

Conditions	Yield
With sodium hypophosphite; palladium on activated charcoal In acetic acid at 60℃; for 1.5h;	90%

4-amino-3-methylpyridine (1990-90-5, 953018-16-1) → 4-bromo-3-methylpyridine (10168-00-0)

Conditions	Yield
Stage #1: 4-amino-3-methylpyridine With hydrogen bromide; sodium nitrite In water at -15 - -10℃; for 2.25h; Stage #2: With copper(I) bromide In water at -15 - 20℃; for 5h;	52%

3-Bromopyridine (626-55-1) + lithium diisopropyl amide (4111-54-0) + methyl iodide (74-88-4) → 4-bromopyridin (1120-87-2) + 4-bromo-3-methylpyridine (10168-00-0) + 3-Bromo-4-methylpyridin (3430-22-6)

Conditions	Yield
In tetrahydrofuran at -60℃; Product distribution; Mechanism; temp. change;

3-Bromopyridine (626-55-1) + methyl iodide (74-88-4) → 4-bromo-3-methylpyridine (10168-00-0) + 3-Bromo-4-methylpyridin (3430-22-6)

Conditions	Yield
THF, -60 -> -55.deg C, 1) 15 min, 2) 45 min; Yield given. Multistep reaction. Yields of byproduct given;

3-methyl-4-nitropyridine N-oxide (1074-98-2) → 4-bromo-3-methylpyridine (10168-00-0)

Conditions	Yield
With phosphorus tribromide In ethyl acetate for 0.5h; Heating;

3-picoline-N-oxide (1003-73-2) → 4-bromo-3-methylpyridine (10168-00-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: 80 percent / HNO3; H2SO4 / 2 h / 100 - 105 °C 2: PBr3 / ethyl acetate / 0.5 h / Heating View Scheme

4-bromo-3-methyl-pyridin-1-ol → 4-bromo-3-methylpyridine (10168-00-0)

Conditions	Yield
With sodium hydroxide; phosphorus trichloride In water; 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran
With phosphorus trichloride In dichloromethane at -20 - 20℃; for 0.5h;

4-bromo-3-methylpyridine hydrobromide → 4-bromo-3-methylpyridine (10168-00-0)

Conditions	Yield
With sodium hydroxide In water
With sodium hydroxide In water

4-bromo-3-methylpyridine (10168-00-0) → 4-bromo-3-methylpyridine 1-oxide (10168-58-8)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 15h;	97%
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 5h;	48%

2-chloro-5-methoxyaniline (2401-24-3) + 4-bromo-3-methylpyridine (10168-00-0) → N-(2-chloro-5-methoxyphenyl)-3-methylpyridin-4-amine

Conditions	Yield
With 2-(dicyclohexylphosphino)-2',4',6'-tri-1-propyl-1,1'-biphenyl; palladium diacetate; caesium carbonate In toluene at 100℃; for 16h; Microwave irradiation; Inert atmosphere;	95%

methyl 3-formyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate + 4-bromo-3-methylpyridine (10168-00-0) → methyl 3-formyl-4-(3-methylpyridin-4-yl)benzoate

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium phosphate In 1,4-dioxane; water at 125℃; for 2h; Inert atmosphere; Microwave irradiation; Sealed tube;	92%

2-formylbenzene boronic acid (40138-16-7) + 4-bromo-3-methylpyridine (10168-00-0) → 2-(3-methyl-pyridin-4-yl)-benzaldehyde (1086561-23-0)

Conditions	Yield
With sodium carbonate; tetrakis(triphenylphosphine) palladium(0) In methanol; water; toluene at 90℃; for 15h; Suzuki coupling;	90%

4-bromo-3-methylpyridine (10168-00-0) + N-cyclohexyl-2-bromobenzenecarboxamide (159029-70-6) → 5-cyclohexyl-4-methylbenzo[c][1,6]naphthyridin-6(5H)-one

Conditions	Yield
With palladium(II) trifluoroacetate; norbornene; caesium carbonate; XPhos In toluene at 110℃; for 18h; Inert atmosphere; Sealed tube;	85%

4-bromo-3-methylpyridine (10168-00-0) + 2-trimethylstannylpyridine (13737-05-8) → C11H10N2

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In toluene for 24h; Reflux;	85%

4-bromo-3-methylpyridine (10168-00-0) + trans-3-penten-2-one (3102-33-8) → (+/-)-4-(3-methylpyridin-4-yl)pentan-2-one

Conditions	Yield
With copper(l) iodide; n-butyllithium; Dibutyl sulfide In diethyl ether; hexane at 20℃; for 1h;	82%

allyltributylstanane (24850-33-7) + 4-bromo-3-methylpyridine (10168-00-0) → C9H11N

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride In N,N-dimethyl-formamide at 70℃; for 3h;	81%

2-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde + 4-bromo-3-methylpyridine (10168-00-0) → 2-methyl-4-(3-methylpyridin-4-yl)benzaldehyde

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); caesium carbonate In 1,4-dioxane; water at 100℃; Inert atmosphere;	80%

tert-butyl (2-(3-bromophenyl)propan-2-yl)carbamate (214964-87-1) + 4-bromo-3-methylpyridine (10168-00-0) → tert-butyl (2-(3-(3-methylpyridin-4-yl)phenyl)propan-2-yl)carbamate

Conditions	Yield
Stage #1: tert-butyl [2-(3-bromophenyl)propan-2-yl]carbamate With tetrahydroxydiboron; chloro(2-dicyclohexylphosphino-2’,4’,6’-triisopropyl-1,1‘-biphenyl)[2-(2’-amino-1,1‘-biphenyl’)]palladium(II); potassium acetate; XPhos In ethanol at 80℃; for 5h; Stage #2: 4-bromo-3-methylpyridine With potassium carbonate at 85℃; for 4h;	79%

4-bromo-3-methylpyridine (10168-00-0) + potassium vinyltrifluoroborate → 3-methyl-4-vinylpyridine

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; caesium carbonate In 1,4-dioxane; water at 85℃; for 15h; Inert atmosphere;	79%

4-bromo-3-methylpyridine (10168-00-0) → 3,3'-dimethyl-4,4'-bipyridyl (4479-73-6)

Conditions	Yield
With triphenylphosphine; nickel dichloride; zinc In N,N-dimethyl-formamide at 50℃; for 2h;	67%

4-bromo-3-methylpyridine (10168-00-0) + trimethylsilylacetylene (1066-54-2) → 3-methyl-4-((trimethylsilyl)ethynyl)pyridine (1443684-82-9)

Conditions	Yield
With copper(l) iodide; triethylamine In N,N-dimethyl-formamide at 20 - 110℃; for 24h; Sonogashira Cross-Coupling;	67%

crotonic acid methyl ester (623-43-8) + 4-bromo-3-methylpyridine (10168-00-0) → (+/-)-3-(3-methylpyridin-4-yl)butyric acid methyl ester

Conditions	Yield
With copper(l) iodide; n-butyllithium; Dibutyl sulfide In diethyl ether; hexane at 20℃; for 1h;	65%

4-bromo-3-methylpyridine (10168-00-0) + bis(pinacol)diborane (73183-34-3) → 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (1032358-00-1)

Conditions	Yield
With potassium acetate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In 1,4-dioxane at 110℃; Inert atmosphere;	60%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 110℃; for 3h; Inert atmosphere;	60%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 110℃; for 3h; Inert atmosphere;	60.4%

2-methyl-1-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(trifluoromethyl)phenyl]propan-1-one + 4-bromo-3-methylpyridine (10168-00-0) → 2-methyl-1-[3-(3-methylpyridin-4-yl)-5-(trifluoromethyl)phenyl]propan-1-one

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate In 1,4-dioxane; water at 100℃; for 16h; Suzuki Coupling; Inert atmosphere;	56%

4-bromo-3-methylpyridine (10168-00-0) + 3,4-Dimethoxyphenylboronic acid (122775-35-3) → 4-(3,4-dimethoxyphenyl)-3-methylpyridine

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate In ethanol; toluene at 110℃; for 19h; Inert atmosphere; Sealed tube;	56%

Trimethyl borate (121-43-7) + 4-bromo-3-methylpyridine (10168-00-0) → (3-methylpyridin-4-yl)boronic acid

Conditions	Yield
Stage #1: 4-bromo-3-methylpyridine With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: Trimethyl borate In tetrahydrofuran at 20℃;	56%

2,6-dimethylbenzene boronic acid (100379-00-8) + 4-bromo-3-methylpyridine (10168-00-0) → 4-(2,6-dimethylphenyl)-3-methylpyridine (1323988-24-4)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water Reflux;	52%

C38H38BN3O4 + 4-bromo-3-methylpyridine (10168-00-0) → 5-(3,5-dimethylisoxazol-4-yl)-1-methyl-7-(3-methylpyridin-4-yl)-1H-benzo[d]imidazol-2(3H)-one

Conditions	Yield
Stage #1: C38H38BN3O4; 4-bromo-3-methylpyridine With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water at 90℃; for 16h; Inert atmosphere; Stage #2: With trifluoroacetic acid at 20℃; for 2h;	51%
With tetrakis(triphenylphosphine) palladium(0); potassium hydrogencarbonate In 1,4-dioxane; water at 90℃; for 16h; Inert atmosphere;	51%

[3-(3-ethyl-ureido)-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-isoquinolin-8-ylmethyl]-carbamic acid 2-methoxy-ethyl ester (1401310-97-1) + 4-bromo-3-methylpyridine (10168-00-0) → [3-(3-ethyl-ureido)-5-(3-methyl-pyridin-4-yl)-isoquinolin-8-ylmethyl]-carbamic acid 2-methoxy-ethyl ester (1401309-37-2)

Conditions	Yield
With potassium carbonate; tetrakis(triphenylphosphine) palladium(0) In 1,4-dioxane; water at 90℃; Suzuki Coupling; Inert atmosphere;	42%

{[4-(3-Boranyl-dihydroxy-benzenesulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester + 4-bromo-3-methylpyridine (10168-00-0) → (imino-{4-[3-(3-methyl-pyridin-4-yl)-benzenesulfonyl]-5-methylsulfanyl-thiophen-2-yl}-methyl)-carbamic acid tert-butyl ester (631910-22-0)

Conditions	Yield
Pd(PPh3)4 In ethanol; sodium carbonate; ethyl acetate; toluene	41%

methyl 7-methoxy-2',3',5',6'-tetrahydrospiro[1,3-benzodioxole-2,4'-(4H)-thiopyran]-4-carboxylate (1051493-78-7) + 4-bromo-3-methylpyridine (10168-00-0) → 2-(3-bromopyridine-4-yl)-1-(7-methoxy-2',3',5',6'-tetrahydrospiro[1,3-benzodioxole-2,4'-(4H)-thiopyran]-4-yl)ethanone (1051492-72-8)

Conditions	Yield
Stage #1: methyl 7-methoxy-2',3',5',6'-tetrahydrospiro[1,3-benzodioxole-2,4'-(4H)-thiopyran]-4-carboxylate; 4-bromo-3-methylpyridine With lithium hexamethyldisilazane In tetrahydrofuran at 0 - 20℃; for 12h; Stage #2: With ammonium chloride In tetrahydrofuran; water	40%

8-(benzyloxy)quinoline-5-sulfonyl chloride + 4-bromo-3-methylpyridine (10168-00-0) → 8-benzyloxy-5-[(3-methyl-4-pyridyl)sulfanyl]quinoline

Conditions	Yield
Stage #1: 8-(benzyloxy)quinoline-5-sulfonyl chloride With triphenylphosphine In tetrahydrofuran at 60℃; for 0.833333h; Stage #2: 4-bromo-3-methylpyridine With tris-(dibenzylideneacetone)dipalladium(0); N-ethyl-N,N-diisopropylamine In 1,4-dioxane at 110℃;	38%

8-(N,N-dimethylamino)-3,4-dihydrobenzo[f][1,4]oxazepine-5(2H)-one + 4-bromo-3-methylpyridine (10168-00-0) → 8-(N,N-dimethylamino)-4-(3-methyl-4-pyridyl)-3,4-dihydrobenzo[f][1,4]oxazepine-5(2H)-one

Conditions	Yield
With copper(l) iodide; N,N,N,N,-tetramethylethylenediamine; potassium carbonate In 1,4-dioxane at 120℃; for 16h;	25.4%

Upstream product

• 1990-90-5 4-amino-3-methylpyridine 
• 1074-98-2 3-methyl-4-nitropyridine N-oxide 
• 626-55-1 3-Bromopyridine 
• 74-88-4 methyl iodide 
• 4111-54-0 lithium diisopropyl amide 
• 1003-73-2 3-picoline-N-oxide 
• 10168-58-8 4-bromo-3-methylpyridine N-oxide 

Downstream Products

• 1086561-23-0 2-(3-methyl-pyridin-4-yl)-benzaldehyde 

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