3430-18-0

Basic information

• Product Name: 2,5-Dibromo-3-methylpyridine
• Synonyms: 2,5-DIBROMO-3-METHYLPYRIDINE;2,5-DIBROMO-3-PICOLINE;TIMTEC-BB SBB003143;2,5-DIBROMO-3-METHYLPYRIDINE, PURISS, 98%;2-CHLORO-5-HYDROXY-3-PICOLINE;2,5-Dibromo-3-picoline,98%;2,5-Dibromo-3-methyl;2,5-Di BroMo-3-Methyl Pyridnie
• CAS NO: 3430-18-0
• Molecular Formula: C₆H₅Br₂N
• Molecular Weight: 250.92
• EINECS: -0
• Product Categories: Pyridine;Pyridines, Pyrimidines, Purines and Pteredines;Halides;Pyridines;Bromopyridines;Halopyridines;Boronic Acid;C6Heterocyclic Building Blocks;Halogenated Heterocycles;Heterocyclic Building Blocks
• Mol File: 3430-18-0.mol
• Article Data: 11

Chemical Properties

• Melting Point: 43-47 °C(lit.)
• Boiling Point: 114 °C / 6mmHg
• Flash Point: >230 °F
• Appearance: Off-white to beige/Crystalline Powder
• Density: 1.9318 (rough estimate)
• Vapor Pressure: 0.0203mmHg at 25°C
• Refractive Index: 1.6300 (estimate)
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Solubility: soluble in Methanol
• PKA: -1.27±0.20(Predicted)
• CAS DataBase Reference: 2,5-Dibromo-3-methylpyridine(CAS DataBase Reference)
• NIST Chemistry Reference: 2,5-Dibromo-3-methylpyridine(3430-18-0)
• EPA Substance Registry System: 2,5-Dibromo-3-methylpyridine(3430-18-0)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 22-36/38-36/37/38-20/21/22
• Safety Statements: 26-36/37/39-36
• RIDADR: UN 2811 6.1/PG 3
• WGK Germany: 3
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 3430-18-0(Hazardous Substances Data)

Usage

Chemical Properties

Off-white to beige crystalline powder

InChI:InChI=1/C6H5Br2N/c1-4-2-5(7)3-9-6(4)8/h2-3H,1H3

Synthetic route

5-bromo-3-methyl-pyridin-2-ylamine (3430-21-5) → 2,5-dibromo-3-methylpyridine (3430-18-0)

Conditions	Yield
With hydrogen bromide; bromine; sodium nitrite In water at -15℃; for 3h;	94%
With hydrogen bromide; bromine; sodium nitrite In water at -15 - 23℃; for 3h;	94%
Stage #1: 5-bromo-3-methyl-pyridin-2-ylamine With hydrogen bromide; bromine at -15 - -10℃; Stage #2: With sodium nitrite at 15 - 20℃; Temperature;	91.8%

3-methylpyridin-2-ylamine (1603-40-3) → 2,5-dibromo-3-methylpyridine (3430-18-0)

Conditions	Yield
With hydrogen bromide; bromine; sodium nitrite 1.) bromination; 2.) water, -10 deg C, 1.5 h, 0 deg C, 0.5 h; Multistep reaction;
Multi-step reaction with 2 steps 1: N-Bromosuccinimide; ammonium acetate / acetonitrile / 0.42 h / 20 °C / Cooling with ice 2: hydrogen bromide; bromine; sodium nitrite / water / 3 h / -15 °C View Scheme
Multi-step reaction with 2 steps 1: N-Bromosuccinimide; ammonium acetate / acetonitrile / 0.42 h / 0 - 23 °C 2: hydrogen bromide; bromine; sodium nitrite / water / 3 h / -15 - 23 °C View Scheme

2,5-dibromo-3-methylpyridine (3430-18-0) + (R)-(+)-3-(dimethylamino)pyrrolidine → [(R)-1-(5-bromo-3-methyl-pyridin-2-yl)-pyrrolidin-3-yl]-dimethyl-amine

Conditions	Yield
With toluene-4-sulfonic acid at 100℃;	99%

2,5-dibromo-3-methylpyridine (3430-18-0) + dimethyl amine (124-40-3) → N-(5-bromo-3-methyl-2-pyridyl)-N,N-dimethylamine

Conditions	Yield
In water at 150℃; for 1h; Microwave irradiation;	98%
In water at 150℃; for 1h; Microwave irradiation;	98%

2,5-dibromo-3-methylpyridine (3430-18-0) → 5-bromo-2-iodo-3-methylpyridine (376587-52-9)

Conditions	Yield
With sodium iodide In acetyl chloride; acetonitrile for 24h; Reflux;	97%
With acetyl chloride; sodium iodide In acetonitrile for 24h; Reflux;	97%
With acetyl chloride; sodium iodide In acetonitrile for 16h; Reflux;	94.78%

morpholine (110-91-8) + 2,5-dibromo-3-methylpyridine (3430-18-0) → 4-(5-bromo-3-methylpyridin-2-yl)morpholine (566158-47-2)

Conditions	Yield
at 210℃; for 0.166667h; Sealed tube; Microwave irradiation;	97%
at 140℃; for 6h;

2,5-dibromo-3-methylpyridine (3430-18-0) + acetonitrile (75-05-8) → 5-bromo-3-methyl-2-pyridineacetonitrile

Conditions	Yield
Stage #1: acetonitrile With n-butyllithium In tetrahydrofuran at -78℃; for 0.916667h; Stage #2: 2,5-dibromo-3-methylpyridine In tetrahydrofuran at -78 - 20℃; for 2h;	97%
Stage #1: acetonitrile With n-butyllithium In tetrahydrofuran at -78℃; for 1.5h; Inert atmosphere; Stage #2: 2,5-dibromo-3-methylpyridine In tetrahydrofuran at 33℃; for 3h; Temperature;	86%

2,5-dibromo-3-methylpyridine (3430-18-0) + benzyl alcohol (100-51-6) → 2-benzyloxy-5-bromo-3-methylpyridine

Conditions	Yield
Stage #1: benzyl alcohol With sodium hydride In tetrahydrofuran for 1.5h; Reflux; Stage #2: 2,5-dibromo-3-methylpyridine In tetrahydrofuran at 20℃; for 12h; Reflux;	95%

2,5-dibromo-3-methylpyridine (3430-18-0) + sodium methylate (124-41-4) → 2,5-dibromo-3-(methoxymethyl)pyridine

Conditions	Yield
In methanol at 20℃; for 18h;	93%

2,5-dibromo-3-methylpyridine (3430-18-0) + 2-methoxy-ethanol (109-86-4) → 5-bromo-2-(2-methoxy-ethoxy)-3-methyl-pyridine (1288996-83-7)

Conditions	Yield
Stage #1: 2-methoxy-ethanol With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.5h; Stage #2: 2,5-dibromo-3-methylpyridine In dimethyl sulfoxide; mineral oil at 60℃; for 1h;	91%
Stage #1: 2-methoxy-ethanol With sodium hydride In dimethyl sulfoxide; mineral oils at 20℃; for 0.5h; Stage #2: 2,5-dibromo-3-methylpyridine In dimethyl sulfoxide; mineral oils at 60℃; for 1h;	91%

2,5-dibromo-3-methylpyridine (3430-18-0) + 2-{9H-pyrido[2,3-b]indol-9-yl}-9H-carbazole → 9-(5-bromo-3-methylpyridin-2-yl)-2-{9H-pyrido[2,3-b]indol-9-yl}-9H-carbazole

Conditions	Yield
With 1-methyl-1H-imidazole; copper(l) iodide; potassium carbonate In toluene at 120℃; for 16h; Sealed tube; Inert atmosphere;	90%

2,5-dibromo-3-methylpyridine (3430-18-0) + sodium methylate (124-41-4) → 5-bromo-2-methoxy-3-methylpyridine (760207-87-2)

Conditions	Yield
In methanol at 120℃; for 0.666667h;	89%
Stage #1: 2,5-dibromo-3-methylpyridine; sodium methylate In methanol at 120℃; for 0.666667h; Stage #2: With hydrogenchloride In methanol; water at 0℃;	89%
In methanol at 100℃; for 2h; Inert atmosphere;	77.8%

2,5-dibromo-3-methylpyridine (3430-18-0) + Cyclopropylmethanol (2516-33-8) → 5-bromo-2-(cyclopropylmethoxy)-3-methylpyridine (1566224-20-1)

Conditions	Yield
Stage #1: Cyclopropylmethanol With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; for 0.333333h; Stage #2: 2,5-dibromo-3-methylpyridine In N,N-dimethyl-formamide at 60℃;	89%

2,5-dibromo-3-methylpyridine (3430-18-0) + (2R)-methylpiperazine (75336-86-6) → (R)-1-(5-bromo-3-methylpyridin-2-yl)-3-methylpiperazine (878809-59-7)

Conditions	Yield
With potassium carbonate In N,N-dimethyl acetamide at 130℃; for 24h; Large scale;	88%
In N,N-dimethyl acetamide at 130℃; for 16h;
In N,N-dimethyl acetamide at 130℃; for 16h; Product distribution / selectivity;

2,5-dibromo-3-methylpyridine (3430-18-0) + phenylboronic acid (98-80-6) → 5-bromo-3-methyl-2-phenylpyridine (1469759-14-5)

Conditions	Yield
With palladium diacetate; potassium carbonate; triphenylphosphine In methanol; acetonitrile at 50℃; for 24h; Suzuki Coupling; Inert atmosphere; regioselective reaction;	88%

2,5-dibromo-3-methylpyridine (3430-18-0) + phenylmethanethiol (100-53-8) → 2-(benzylthio)-5-bromo-3-methylpyridine

Conditions	Yield
With sodium hydride In tetrahydrofuran at 0 - 20℃; for 4h;	86.9%

2,5-dibromo-3-methylpyridine (3430-18-0) → potassium 6-bromo-5-methylpyridin-3-yltrifluoroborate

Conditions	Yield
Stage #1: 2,5-dibromo-3-methylpyridine With n-butyllithium; Triisopropyl borate In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Inert atmosphere; Stage #2: With potassium hydrogen difluoride In tetrahydrofuran; hexane at 20℃;	85%

N-Methylformamide (123-39-7) + 2,5-dibromo-3-methylpyridine (3430-18-0) → (5-bromo-3-methylpyridin-2-yl)methylamine (245765-66-6)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 100℃; for 3h; Temperature; Reagent/catalyst;	84.2%
Stage #1: N-Methylformamide With potassium tert-butylate In N,N-dimethyl-formamide at 20 - 80℃; for 1.5h; Stage #2: 2,5-dibromo-3-methylpyridine In N,N-dimethyl-formamide for 2h;	70.4%

2,5-dibromo-3-methylpyridine (3430-18-0) + phenylacetylene (536-74-3) → 5-bromo-3-methyl-2-(phenylethynyl)pyridine

Conditions	Yield
With copper(l) iodide; palladium(II) trifluoroacetate; palladium diacetate; diisopropylamine In methanol; acetonitrile for 24h; Reflux; Inert atmosphere; regioselective reaction;	84%

2,5-dibromo-3-methylpyridine (3430-18-0) + 2,3-dichlorobenzeneboronic acid (151169-74-3) → 5-bromo-2-(2,3-dichlorophenyl)-3-methylpyridine

Conditions	Yield
With palladium diacetate; potassium carbonate; triphenylphosphine In methanol; acetonitrile at 50℃; for 24h; Inert atmosphere;	81%

2,5-dibromo-3-methylpyridine (3430-18-0) + carbon monoxide (201230-82-2) + aniline (62-53-3) → 3-methyl-5-bromopyridine-2-N-phenylamide (213771-38-1)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene; palladium diacetate In toluene; acetonitrile at 65℃; under 4137.29 Torr; for 48h; Product distribution / selectivity;	76%
With triethylamine; bis-triphenylphosphine-palladium(II) chloride In acetonitrile at 60℃; under 4137.29 Torr; for 72h; Product distribution / selectivity;	59%

4-morpholinecarboxaldehyde (4394-85-8) + 2,5-dibromo-3-methylpyridine (3430-18-0) → 6-bromo-5-methylpyridine-3-carbaldehyde (885167-81-7)

Conditions	Yield
Stage #1: 2,5-dibromo-3-methylpyridine With isopropylmagnesium chloride In tetrahydrofuran at 0 - 25℃; for 3h; Stage #2: 4-morpholinecarboxaldehyde In tetrahydrofuran at 17 - 25℃; for 1h;	74%
Stage #1: 2,5-dibromo-3-methylpyridine With isopropylmagnesium chloride In tetrahydrofuran at 0 - 20℃; for 3h; Stage #2: 4-morpholinecarboxaldehyde In tetrahydrofuran at 20℃; for 1h;	74%
Stage #1: 2,5-dibromo-3-methylpyridine With isopropylmagnesium chloride In tetrahydrofuran at -78℃; for 0.5h; Inert atmosphere; Stage #2: 4-morpholinecarboxaldehyde In tetrahydrofuran at 0℃; for 2.5h;

2,5-dibromo-3-methylpyridine (3430-18-0) + copper(l) cyanide → 5-bromo-3-methylpyridine-2-carbonitrile (156072-86-5)

Conditions	Yield
In N,N-dimethyl-formamide for 2h; Reflux;	74%
In N,N-dimethyl-formamide for 2h; Reflux;	74%
In water; N,N-dimethyl-formamide	61.3%

2,5-dibromo-3-methylpyridine (3430-18-0) + ethyl 3-[6-cyano-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-3-yl]-propanoate (1415306-66-9) → Ethyl 3-(5-bromo-2’-cyano-3-methyl-2,3’-bipyridine-5’-yl)-propanoate (1415306-74-9)

Conditions	Yield
With potassium phosphate; palladium diacetate; triphenylphosphine In 1,4-dioxane; water at 80℃; for 4h; Inert atmosphere;	74%
Stage #1: 2,5-dibromo-3-methylpyridine With potassium phosphate; palladium diacetate; triphenylphosphine In 1,4-dioxane; water at 20℃; for 0.166667h; Suzuki Coupling; Inert atmosphere; Stage #2: ethyl 3-[6-cyano-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine-3-yl]-propanoate In 1,4-dioxane; water at 80℃; for 2.5h; Suzuki Coupling; Inert atmosphere; regioselective reaction;	74%
With potassium phosphate; triphenylphosphine; palladium diacetate In 1,4-dioxane; water at 20 - 80℃; Inert atmosphere;

2,5-dibromo-3-methylpyridine (3430-18-0) + carbon monoxide (201230-82-2) + N,N',N'-trimethylenediamine (142-25-6) → 5-bromo-3-methyl-pyridine-2-carboxylic acid (2-dimethylamino-ethyl)-methyl-amide + C18H31N5O2

Conditions	Yield
With triethylamine; bis-triphenylphosphine-palladium(II) chloride In toluene; acetonitrile at 55℃; under 517.162 - 5171.62 Torr; for 6h;	A 72% B n/a

2,5-dibromo-3-methylpyridine (3430-18-0) + 9-cyclopentyl-9H-pyrido[4′,3′:4,5]pyrrolo[2,3-d]pyrimidin-2-amine (1169698-48-9) → N-(5-bromo-3-methyl-2-pyridinyl)-9-cyclopentyl-9H-pyrido[4',3':4,5]pyrrolo[2,3-d]pyrimidin-2-amine (1169698-68-3)

Conditions	Yield
With sodium t-butanolate; tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 140℃; for 1h; Microwave irradiation;	71%

4-phenyl-1-piperazine (92-54-6) + 2,5-dibromo-3-methylpyridine (3430-18-0) + carbon monoxide (201230-82-2) → C17H18BrN3O + C28H31N5O2

Conditions	Yield
With triethylamine; bis-triphenylphosphine-palladium(II) chloride In toluene; acetonitrile at 55℃; under 517.162 - 5171.62 Torr; for 6h;	A 70% B n/a

1-methyl-piperazine (109-01-3) + 2,5-dibromo-3-methylpyridine (3430-18-0) + carbon monoxide (201230-82-2) → C12H16BrN3O + C18H27N5O2

Conditions	Yield
With triethylamine; bis-triphenylphosphine-palladium(II) chloride In toluene; acetonitrile at 55℃; under 517.162 - 5171.62 Torr; for 6h;	A 69% B n/a

2,5-dibromo-3-methylpyridine (3430-18-0) → 5-bromo-3-picoline (3430-16-8)

Conditions	Yield
With sodium tetrahydroborate; N,N,N,N,-tetramethylethylenediamine; palladium diacetate; triphenylphosphine In tetrahydrofuran at 25℃; for 0.5h; Inert atmosphere; regioselective reaction;	68%

2,5-dibromo-3-methylpyridine (3430-18-0) + carbon monoxide (201230-82-2) + tert-butylamine (75-64-9) → C16H25N3O2 + 5-bromo-N-(tert-butyl)-3-methylpicolinamide (156072-91-2)

Conditions	Yield
With triethylamine; bis-triphenylphosphine-palladium(II) chloride In toluene; acetonitrile at 55℃; under 517.162 - 5171.62 Torr; for 6h;	A n/a B 67%

2,5-dibromo-3-methylpyridine (3430-18-0) + 2,3-dichlorobenzenethiol (17231-95-7) → 5-bromo-2-(2,3-dichlorophenyl)sulfanyl-3-methyl-pyridine

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 25℃; Heating;	67%

Upstream product

• 3430-21-5 5-bromo-3-methyl-pyridin-2-ylamine 
• 1603-40-3 3-methylpyridin-2-ylamine 

Downstream Products

• 760207-88-3 3-bromo-6-isopropoxy-5-methylpyridine 
• 244139-63-7 C₁₃H₁₇BrN₂O 
• 213771-38-1 3-methyl-5-bromopyridine-2-N-phenylamide 
• 156072-86-5 5-bromo-3-methylpyridine-2-carbonitrile 
• 1003043-34-2 6-bromo-5-methylpyridin-3-yl boronic acid 
• 1575836-59-7 tert-butyl 3'-bromo-1H,5'H-spiro[azetidine-3,7'-furo[3,4-b]pyridine]-1-carboxylate 
• 3430-16-8 5-bromo-3-picoline 
• 1259901-43-3 5-bromo-2-(3,5-dichlorophenyl)-3-methylpyridine 

Relevant articles and documents

Preparation method of 2, 5-dibromo-3-methylpyridine

The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of 2, 5-dibromo-3-methylpyridine. The preparation method comprises the following steps: (1) adding 2-amino-3-methylpyridine and acetic anhydride into a four-neck flask, heating to reflux, and carrying out thin-layer chromatography tracking reaction; (2) when the temperature of a reaction liquid obtained in the step (1) is reduced to 20-25 DEG C, dropwise adding liquid bromine, reacting for 2-3 hours at 50-60 DEG C after dropwise adding of liquid bromine, adding water until all solids are dissolved, dropwise adding a sodium hydroxide solution, continuously reacting for 30 minutes after dropwise adding, and carrying out suction filtration, drying and recrystallization to obtain 2-amino-3-methyl-5-bromopyridine; and (3) adding the obtained 2-amino-3-methyl-5-bromopyridine into a hydrogen bromide solution, dropwise adding a saturated sodium nitrite solution under the catalysis of cuprous bromide, controlling the temperature to be -5 to 10 DEG C, and reacting for 2 to 4 hours to obtain 2, 5-dibromo-3-methylpyridine. The method provided by the invention has the beneficial effects ofmild reaction conditions, high yield, low cost and short process route, and is suitable for industrial production.

A 2, 5 - dibromo -3 - methyl pyridine preparation method (by machine translation)

The invention belongs to the field of organic synthesis, in particular relates to a 2, 5 - dibromo - 3 - methyl pyridine preparation method, comprises the following steps: (1) the 2 - amino - 3 - methyl pyridine and acetic anhydride is added to the four flasks, heating to reflux, thin-layer chromatography the tracking reaction; (2) step (1) of reaction fluids in a temperature drop to 20 - 25 °C when, [...], paused, 50 - 60 °C reaction 2 - 3 h, to all solid-dissolving after adding water, sodium hydroxide solution, after adding continue to reaction 30 min, filtering, drying, recrystallize to get 2 - amino 3 - methyl - 5 - bromo pyridine; (3) the 2 - amino - 3 - methyl - 5 - bromo pyridine is added in a solution of hydrogen bromide, in the catalysis of cuprous bromide, [...] and sodium nitrite solution, temperature control in the - 5 - 10 °C, reaction 2 - 4 h, shall be 2, 5 - dibromo - 3 - methyl pyridine. The method of the invention is beneficial effect: mild reaction conditions, high yield, low cost, the process route is short, it is suitable for industrial production. (by machine translation)

Preparation method for 2,5-dibromo-3-methylpyridine

The invention specifically relates to a preparation method for 2,5-dibromo-3-methylpyridine, which belongs to the field of organic synthesis. The preparation method comprises the following steps: (1) adding 2-amino-3-methylpyridine and acetic anhydride into a four-neck flask, carrying out heating to a reflux state and tracking a reaction via thin-layer chromatogram; (2) as the temperature of a reaction solution in the step (1) drops to 20 to 25 DEG C, adding liquid bromine drop by drop, then carrying out a reaction at 50 to 60 DEG C for 2 to 3 h after completion of the addition, adding water until all the solids are dissolved, then adding a sodium hydroxide solution drop by drop, continuing a reaction for 30 min after completion of the addition, and successively carrying out pumping filtration, drying and recrystallization so as to obtain 2-amino-3-methyl-5-bromopyridine; and (3) adding 2-amino-3-methyl-5-bromopyridine into a hydrogen bromide solution and under the catalysis of cuprous bromide, adding a saturated sodium nitrite solution drop by drop and carrying out a reaction at a temperature of -5 to 10 DEG C for 2 to 4 h so as to obtain 2,5-dibromo-3-methylpyridine. The method provided by the invention has the following beneficial effects: mild reaction conditions, high yield, low cost, short process route and suitability for industrial production.