7598-35-8

Usage

Chemical Properties

Light yellow Cryst

Uses

4-Amino-2-bromopyridine is used as medical intermediate.

InChI:InChI=1/C5H5BrN2/c6-5-3-4(7)1-2-8-5/h1-3H,(H2,7,8)

Synthetic route

2-bromo-4-nitropyridine N-oxide (52092-43-0) → 2-bromo-4-aminopyridine (7598-35-8)

Conditions	Yield
With iron In acetic acid at 100℃;	100%
With iron In acetic acid	90%
With iron; acetic acid

2-bromo-4-nitropyridine (6945-67-1) → 2-bromo-4-aminopyridine (7598-35-8)

Conditions	Yield
With titanium for 0.25h;	97%

4-aminopyridine (504-24-5) → 2-bromo-4-aminopyridine (7598-35-8) + 4-amino-3,5-dibromopyridine (84539-34-4)

Conditions	Yield
With N-Bromosuccinimide In tetrachloromethane at 20℃; for 48h; Darkness;	A n/a B 55%

2,4-dibromopyridine (58530-53-3) → 2-amino-4-bromopyridine (84249-14-9) + 2-bromo-4-aminopyridine (7598-35-8)

Conditions	Yield
With ammonium hydroxide at 160℃;

2,4-dibromopyridine (58530-53-3) + ammonium hydroxide → 2-amino-4-bromopyridine (84249-14-9) + 2-bromo-4-aminopyridine (7598-35-8)

Conditions	Yield
at 160℃;

2-bromo-pyridine (109-04-6) + (+-)-2-<4-chloro-phenyl>-5-piperidino-valeronitrile → 2-bromo-4-aminopyridine (7598-35-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: perbenzoic acid / CHCl3 / 72 h / Ambient temperature 2: 77 percent / 96percent H2SO4, 96percent HNO3 / 3 h / 130 °C 3: 90 percent / iron powder / acetic acid View Scheme

2-bromopyridine-N-oxide (14305-17-0) → 2-bromo-4-aminopyridine (7598-35-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 77 percent / 96percent H2SO4, 96percent HNO3 / 3 h / 130 °C 2: 90 percent / iron powder / acetic acid View Scheme
Multi-step reaction with 2 steps 1: concentrated sulfuric acid; nitric acid 2: iron-powder; acetic acid View Scheme
Multi-step reaction with 2 steps 1: concentrated sulfuric acid; nitric acid 2: FeSO4; concentrated aqueous NH3 View Scheme

3-deazauracil (626-03-9) → 2-bromo-4-aminopyridine (7598-35-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: phosphoryl bromide / 130 °C 2: aqueous NH3 / 160 °C View Scheme

2-bromo-4-nitropyridine N-oxide (52092-43-0) + iron (7439-89-6) → 2-bromo-4-aminopyridine (7598-35-8)

Conditions	Yield
In acetic acid
With ammonium chloride In ethanol

2-bromo-4-aminopyridine (7598-35-8) + phenylboronic acid (98-80-6) → 2-phenyl-pyridin-4-ylamine (21203-86-1)

Conditions	Yield
With bis-triphenylphosphine-palladium(II) chloride; potassium phosphate; carbon dioxide In water; acetonitrile at 70℃; under 23257.6 Torr; for 24h; Reagent/catalyst; Pressure; Suzuki Coupling; Inert atmosphere;	99%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate In 1,4-dioxane; water at 110℃; Sealed tube;	61.8%
With tetrakis(triphenylphosphine) palladium(0); sodium hydrogencarbonate In 1,2-dimethoxyethane; water Suzuki Coupling; Reflux; Inert atmosphere;	44%

2-bromo-4-aminopyridine (7598-35-8) + 2,5-hexanedione (110-13-4) → 2-bromo-4-(2,5-dimethyl-1H-pyrrol-1-yl)pyridine (956384-89-7)

Conditions	Yield
With toluene-4-sulfonic acid In toluene for 2h; Heating;	86%

2-bromo-4-aminopyridine (7598-35-8) + 4-fluoro-3-nitro-benzoic acid methyl ester (329-59-9) → 4-(2-bromo-pyridin-4-ylamino)-3-nitro-benzoic acid methyl ester (1227380-68-8)

Conditions	Yield
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 1h; Stage #2: 4-fluoro-3-nitro-benzoic acid methyl ester In tetrahydrofuran; mineral oil at 20℃;	85%
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 1h; Inert atmosphere; Stage #2: 4-fluoro-3-nitro-benzoic acid methyl ester In tetrahydrofuran; mineral oil at 0 - 20℃; Inert atmosphere;	85%
Stage #1: 4-fluoro-3-nitro-benzoic acid methyl ester With sodium hydride In tetrahydrofuran at 0℃; for 1h; Stage #2: 2-bromo-4-aminopyridine In tetrahydrofuran at 0 - 20℃;	85%

2-bromo-4-aminopyridine (7598-35-8) + 2-(5-fluoro-6-methylpyridin-2-yl)-9-(4-methoxybenzyl)-6-phenoxy-9H-purine → N-(2-bromopyridin-4-yl)-2-(5-fluoro-6-methylpyridin-2-yl)-9-(4-methoxybenzyl)-9H-purin-6-amine

Conditions	Yield
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.166667h; Stage #2: 2-(5-fluoro-6-methylpyridin-2-yl)-9-(4-methoxybenzyl)-6-phenoxy-9H-purine In N,N-dimethyl-formamide at 20℃; for 3h;	85%

2-bromo-4-aminopyridine (7598-35-8) + di-tert-butyl dicarbonate (24424-99-5) → 2-bromo-4-[(tert-butoxycarbonyl)amino]pyridine (433711-95-6)

Conditions	Yield
With triethylamine In dichloromethane at 50℃; for 16h; Inert atmosphere;	84%
With sodium hexamethyldisilazane In tetrahydrofuran at 0 - 25℃; Inert atmosphere;	74%
With triethylamine In tetrahydrofuran at 0 - 25℃;	72%
With triethylamine In dichloromethane
Stage #1: 2-bromo-4-aminopyridine With triethylamine In dichloromethane at 20 - 30℃; Stage #2: di-tert-butyl dicarbonate With dmap In dichloromethane at 20 - 30℃; for 16h;	171.2 g

2-bromo-4-aminopyridine (7598-35-8) + 4,4,5,5-tetramethyl-2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,2-dioxaborolane (196212-27-8) → 1,3-bis(4-amino-2-pyridyl)benzene (1369963-51-8)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In tetrahydrofuran; water for 48h; Inert atmosphere; Reflux;	84%

2-bromo-4-aminopyridine (7598-35-8) + ethyl iodide (75-03-6) → 2-bromo-N,N-diethylpyridine-4-amine

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 1h; Reflux;	81.8%

2-bromo-4-aminopyridine (7598-35-8) → 2-Brom-4-(nitroamino)pyridin (15367-12-1)

Conditions	Yield
With sulfuric acid; nitric acid at -10 - -5℃;	79%
With sulfuric acid; nitric acid at 0℃; for 0.333333h;

2-bromo-4-aminopyridine (7598-35-8) + 2,6-dichloro-3,5-dinitrotoluene (51676-76-7) → 2-bromo-N-(3-chloro-2-methyl-4,6-dinitrophenyl)pyridin-4-amine

Conditions	Yield
With sodium hydroxide In tetrahydrofuran; N,N-dimethyl-formamide at 25℃;	79%

2-bromo-4-aminopyridine (7598-35-8) + C10H4Cl2F3N3O → 1-(3-chloropyridin-2-yl)-N-(2-bromopyridin-4-yl)-5-(trifluoromethyl)-1H-pyrazole-4-carboxamide

Conditions	Yield
With sodium hydride In tetrahydrofuran at 20℃; for 12h;	78%

2-bromo-4-aminopyridine (7598-35-8) + chloroacetyl chloride (79-04-9) → N-(2-bromopyridin-4-yl)-2-chloroacetamide

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In dichloromethane at 0 - 20℃; for 3h;	76.5%

2-bromo-4-aminopyridine (7598-35-8) → 2-ethoxy-pyridin-4-ylamine (89943-12-4)

Conditions	Yield
With sodium hydroxide In ethanol; water	76%
With sodium ethanolate at 160℃;

2-bromo-4-aminopyridine (7598-35-8) + 3-pyridylboronic acid (1692-25-7) → [2,3']bipyridinyl-4-ylamine (40963-62-0)

Conditions	Yield
With bis(η3-allyl-μ-chloropalladium(II)); N,N,N′,N′-tetra(diphenylphosphinomethyl)-1,2-ethylenediamine; potassium carbonate In N,N-dimethyl acetamide; butan-1-ol at 110℃; for 24h; Suzuki Coupling; Inert atmosphere;	76%

2-bromo-4-aminopyridine (7598-35-8) + 1-(3-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)-4-isopropylpiperazine → 2-(2-fluoro-4-((4-isopropylpiperazin-1-yl)methyl)phenyl)pyridin-4-amine

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; sodium carbonate In 2-methyltetrahydrofuran; water at 25 - 73℃; for 16h; Inert atmosphere; Large scale;	76%

1-methyl-piperazine (109-01-3) + 2-bromo-4-aminopyridine (7598-35-8) → 2-(4-methylpiperazin-1-yl)pyridin-4-ylamine (876343-33-8)

Conditions	Yield
at 135℃; for 16h; Sealed tube;	75.7%

2-bromo-4-aminopyridine (7598-35-8) + di-tert-butyl dicarbonate (24424-99-5) → 2-bromo-N,N-(di-tert butoxycarbonyl)pyridine-4-amine (1044148-89-1)

Conditions	Yield
With dmap; triethylamine In tetrahydrofuran at 20 - 80℃; for 24h;	75.2%
With sodium hexamethyldisilazane In tetrahydrofuran

2-bromo-4-aminopyridine (7598-35-8) + 2,6-Dichlorobenzoyl chloride (4659-45-4) → N-(2-bromopyridin-4-yl)-2,6-dichlorobenzamide (1258298-00-8)

Conditions	Yield
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.333333h; Stage #2: 2,6-Dichlorobenzoyl chloride In N,N-dimethyl-formamide; mineral oil at 0℃; for 4h;	74%
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.5h; Stage #2: 2,6-Dichlorobenzoyl chloride In N,N-dimethyl-formamide; mineral oil at 0℃; for 4h;	54%
With sodium hydride In N,N-dimethyl-formamide at 0℃;
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.333333h; Inert atmosphere; Stage #2: 2,6-Dichlorobenzoyl chloride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 12h; Inert atmosphere;

2-bromo-4-aminopyridine (7598-35-8) + 9-(4-methoxybenzyl)-2-(6-methylpyridin-2-yl)-6-phenoxy-9H-purine → N-(2-bromopyridin-4-yl)-9-(4-methoxybenzyl)-2-(6-methylpyridin-2-yl)-9H-purin-6-amine

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide for 3h;	71.5%

2-bromo-4-aminopyridine (7598-35-8) + 2,6-dichloro-4-cyanobenzoyl chloride (1258298-06-4) → N-(2-bromopyridin-4-yl)-2,6-dichloro-4-cyanobenzamide (1258298-07-5)

Conditions	Yield
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Stage #2: 2,6-dichloro-4-cyanobenzoyl chloride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃;	70%
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 0.5h; Stage #2: 2,6-dichloro-4-cyanobenzoyl chloride In N,N-dimethyl-formamide; mineral oil at 20℃; for 1h; Inert atmosphere;	59%

2-bromo-4-aminopyridine (7598-35-8) + 2-(3,5-bis-trifluoromethyl-phenyl)-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (69807-91-6) → 4-amino-2-(3,5-bis(trifluoromethyl)phenyl)pyridine

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; methanol; water at 100℃; for 3h; Microwave irradiation;	70%

2-bromo-4-aminopyridine (7598-35-8) + 2,4,6-trichlorobenzoyl chloride (4136-95-2) → N-(2-bromopyridin-4-yl)-2,4,6-trichlorobenzamide (1258298-03-1)

Conditions	Yield
Stage #1: 2-bromo-4-aminopyridine With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; Stage #2: 2,4,6-trichlorobenzoyl chloride In N,N-dimethyl-formamide; mineral oil at 0 - 20℃;	69%

2-Hydroxymethylpyridine (586-98-1) + 2-bromo-4-aminopyridine (7598-35-8) → N-(pyridine-2-methyl)-4-amino-2-bromopyridine (1439400-79-9)

Conditions	Yield
With (phthalocyaninato)iron(II); sodium t-butanolate In toluene at 100℃; for 12h; Inert atmosphere;	68%

2-bromo-4-aminopyridine (7598-35-8) + propionyl chloride (79-03-8) → N-(2-bromopyridin-4-yl)propanamide

Conditions	Yield
With potassium carbonate In acetone at 20℃; for 2h;	67%

2-bromo-4-aminopyridine (7598-35-8) + 2,2,2-trifluoroethanol (75-89-8) → 2-(2,2,2-trifluoroethoxy)pyridin-4-amine (1247075-58-6)

Conditions	Yield
With sodium hydride In 1,4-dioxane for 15h; Reflux;	66.2%

2-bromo-4-aminopyridine (7598-35-8) + 4,4,5,5-tetramethyl-2-(2,4-bis(trifluoromethyl)phenyl)-1,3,2-dioxaborolane (1073353-65-7) → 4-amino-2-(2,4-bis(trifluoromethyl)phenyl)pyridine

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; methanol; water at 100℃; for 3h; Microwave irradiation;	65%

2-bromo-4-aminopyridine (7598-35-8) + (2,6-difluoropyridin-3-yl)boronic acid (136466-94-9) → 2',6'-difluoro-4-amino-2,3'-bipyridine

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water at 70℃; for 18h; Inert atmosphere;	63%

2-bromo-4-aminopyridine (7598-35-8) + Nitrosobenzene (586-96-9) → 2-bromo-(4-phenylazo)pyridine

Conditions	Yield
With pyridine; trimethylphenylammonium hydroxide at 80℃; for 4h;	61%

2-bromo-4-aminopyridine (7598-35-8) → 2,4-dibromopyridine (58530-53-3)

Conditions	Yield
With hydrogen bromide; bromine; sodium nitrite	60%
With sulfuric acid; copper(II) sulfate; potassium bromide; sodium nitrite Diazotization.Reagens 4: Kupfer-Pulver; Reagens 5: Wasser;

Upstream product

• 58530-53-3 2,4-dibromopyridine 
• 52092-43-0 2-bromo-4-nitropyridine N-oxide 
• 6945-67-1 2-bromo-4-nitropyridine 
• 109-04-6 2-bromo-pyridine 
• 14305-17-0 2-bromopyridine-N-oxide 
• 626-03-9 3-deazauracil 
• 7439-89-6 iron 
• 504-24-5 4-aminopyridine 

Downstream Products

• 10386-27-3 2-bromoisonicotinonitrile 
• 58530-53-3 2,4-dibromopyridine 
• 89943-12-4 4-Amino-2-ethoxy-pyridin 
• 861023-90-7 2,3-dibromopyridin-4-amine 
• 861024-31-9 2,3,5-tribromo-[4]pyridylamine 
• 524718-15-8 2-(3,4-dihydro-1H-isoquinolin-2-yl)-pyridin-4-yl-amine 
• 1027052-02-3 6-chloro-2-[(2,4-dimethoxybenzyl)thio]-N-(4-pyridinyl)pyridine-3-carboxamide 
• 433711-95-6 2-bromo-4-[(tert-butoxycarbonyl)amino]pyridine 
• 887310-21-6 N-(2-bromopyridin-4-yl)benzenesulfonamide 
• 75279-37-7 N-(2-bromo-pyridin-4-yl)-N'-phenylurea 
• 357927-50-5 2-bromo-4-fluoro-pyridine 
• 1044148-89-1 4-[di(tert-butoxycarbonyl)amino]-2-bromopyridine 
• 1227380-68-8 4-(2-bromo-pyridin-4-ylamino)-3-nitro-benzoic acid methyl ester 
• 1258298-03-1 N-(2-bromopyridin-4-yl)-2,4,6-trichlorobenzamide 

Relevant academic research and scientific papers

Synthesis of pyridinium betaine azo chromophores

New chromophores have been synthesized and investigated containing as acceptor a quaternized pyridine unit with mobile bromine in the structure conjugated with two donor units - the indan-1,3-dione anion and the dihydroxyethylamino group through a π-conju

Synthesis of 2,4-dibromopyridine and 4,4'-dibromo-2,2'-bipyridine. Efficient usage in selective bromine-substitution under palladium-catalysis

We report an efficient method for preparing 2,4-dibromopyridine and 4,4'-dibromo-2,2'-bipyridine from the corresponding nitroazine N-oxide in one step via a tandem nucleophilic substitution-N-oxide reduction process. The one step preparation of 4,4'-dihalo-2,2'-bipyridines from dihalopyridines via a Stille reaction is also described. 4,4'-Dibromo-2,2'-bipyridine undergoes selective mono- or disubstitution processes under palladium catalysis. This short synthetic procedure is an efficient and reliable process for preparing conjugated pyridine and 2,2'-bipyridine building blocks for applications in coordination chemistry and materials science.

Cyanophenyl derivative

This application relates to a piperazino-substituted novel cyanophenyl derivative in which a substituted carbamoyl or substituted sulfamoyl group having an aryl, heterocyclic or the like group that may have a substituent group is bonded to one nitrogen atom on the piperazine ring. The compound of this application has an anti-androgen action and is useful in preventing or treating prostatic cancer, benign prostatic hyperplasia and the like diseases.

CYANOPHENYL DERIVATIVES

This application relates to a piperazino-substituted novel cyanophenyl derivative in which a substituted carbamoyl or substituted sulfamoyl group having an aryl, heterocyclic or the like group that may have a substituent group is bonded to one nitrogen atom on the piperazine ring. The compound of this application has an anti-androgen action and is useful in preventing or treating prostatic cancer, benign prostatic hyperplasia and the like diseases.

POTASSIUM ION CHANNEL BLOCKERS

The invention provides novel sulphonylurea, sulphonylthiourea and sulphonylguanidine compounds which have the ability to block potassium ion channels regulated by intracellular concentrations of ATP. Methods of synthesis, pharmaceutical compositions and methods for the treatment of conditions such as type II diabetes, cardiac arrhythmias, ischaemic and hypoxic cardiovascular incidents, and cancers are also claimed.

On the Mechanism of the Carbodesilylation of 4- or 5-Substituted 2-(Trimethylsilyl)pyridines

An "ylide mechanism" is proposed for the carbodesilylation of 2-(trimethylsilyl)pyridines with benzaldehyde.In contrast, 3- and 4-(trimethylsilyl)pyridines, react only in the presence of a base catalyst via pyridyl anions with electrophiles.The rates of the uncatalyzed carbodesilylation reactions of 4-substituted 2-(trimethylsilyl)pyridines 2 with benzaldehyde correlate very well with the resonance parameters of the substituents ?0R, whereas the rates of 5-substituted 2-(trimethylsilyl)pyridines 7 correlate with the inductive substituent parameters ?1 in the Taft equation.This is to our knowledge the first direct determination of the resonance parameters ?0R.Key Words: Pyridines, substituted 2-(trimethylsilyl)-, synthesis of, carbodesilylation of / Carbodesilylation / Rate constants

TITANIUM (O) REAGENTS; 4. A SELECTIVE AND EFFICIENT REDUCTION OF NITROPYRIDINE DERIVATIVES

Following the successful applications of a titanium (O) slurry in the deoxygenation of aromatic N-oxides, we attempted to achieve this method for the reduction of a nitro- group in pyridine derivatives.In general, only aminopyridine derivates were formed in 85-98percent yield.The advantage of this excellent reducing agent consists in mild reaction conditions and high yields of products, as well as in the selectivity of the reaction.