183208-35-7

Basic information

• Product Name: 5-Bromo-7-azaindole
• Synonyms: 5-BROMO-1H-PYRROLO[2,3-B]PYRIDINE;5-BROMO-7-AZAINDOLE;5-BROMO AZAINDOLE;1H-Pyrrolo[2,3-b]pyridine, 5-bromo-;5-Bromo-1H-pyrrolo2,3-büpyridine;3-Bromo-7H-pyrrolo[2,3-b]pyridine;5-Bromo-1H-pyrrolo[2,3-b]pyridine ,97%;5-Bromo-7-azaindole 97%
• CAS NO: 183208-35-7
• Molecular Formula: C₇H₅BrN₂
• Molecular Weight: 197.03
• EINECS: 1308068-626-2
• Product Categories: Heterocycles;CHIRAL CHEMICALS;pyridine;Non-Chiral heterocyclic compounds;Heterocycle-Indole series;Heterocycle-Pyridine series
• Mol File: 183208-35-7.mol
• Article Data: 42

Chemical Properties

• Melting Point: 178.0-178.8°C
• Boiling Point: 357.4±42.0 °C(Predicted)
• Appearance: White to yellow/Crystalline Powder
• Density: 1.77 g/cm³
• Refractive Index: 1.728
• Storage Temp.: Room temperature.
• PKA: 6.25±0.20(Predicted)
• CAS DataBase Reference: 5-Bromo-7-azaindole(CAS DataBase Reference)
• NIST Chemistry Reference: 5-Bromo-7-azaindole(183208-35-7)
• EPA Substance Registry System: 5-Bromo-7-azaindole(183208-35-7)

Safety Data

• Hazard Codes: Xi,Xn
• Statements: 22-41
• Safety Statements: 26-39
• WGK Germany: 3
• HazardClass: IRRITANT
• Hazardous Substances Data: 183208-35-7(Hazardous Substances Data)

Usage

Uses

5-Bromo-7-azaindole is a chemical reagent used in organic syntheses. Used in the synthesis of Venetoclax (A112430), a potent and selective BCL-2 inhibitor that achieves potent antitumour activity while sparing platelets. Also used in other 7-azaindole derivatives such as for PDK1 inihibtors.

InChI:InChI=1/C7H5BrN2/c8-6-3-5-1-2-9-7(5)10-4-6/h1-4H,(H,9,10)

Synthetic route

7-aza-5-bromoindoline (115170-40-6) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With manganese(IV) oxide In dichloromethane for 72h;	100%
With manganese(IV) oxide In toluene for 4h; Reflux;	90%
With activated carbon fiber catalyst In 5,5-dimethyl-1,3-cyclohexadiene at 100℃; for 8h; Solvent;	85.43%

5-bromo-1-(tert-butyl-dimethyl-silanyl)-1H-pyrrolo[2,3-b]pyridine (754214-54-5) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With hydrogenchloride In methanol for 0.133333h;	94%
With tetrabutyl ammonium fluoride In tetrahydrofuran at 25℃; for 0.5h;

2-nitro-3-dimethylaminovinyl-5-bromopyridine → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With sodium at 20 - 60℃; for 1.5h; Temperature; Inert atmosphere;	92.9%

Conditions	Yield
With potassium hydroxide In 1,2-dimethoxyethane at 140℃; for 16h; Industrial scale;	91.5%

5-bromo-3-ethynyl-pyridin-2-ylamine → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With potassium tert-butylate In N,N-dimethyl-formamide at 60 - 85℃; Large scale;	90%
Stage #1: 5-bromo-3-ethynyl-pyridin-2-ylamine With potassium tert-butylate In 1-methyl-pyrrolidin-2-one at 60℃; for 3h; Stage #2: With water In 1-methyl-pyrrolidin-2-one; toluene

(E)-N'-(5-bromo-3-methylpyridin-2-yl)-N-methyl-N-phenylmethanimidamide → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With sodium amide In diethylene glycol dimethyl ether at 10 - 15℃; for 16h; Industrial scale;	87.6%

C9H13Br2NO3 → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With ammonium hydroxide; potassium carbonate; ammonium chloride In tetrahydrofuran at 25 - 60℃; for 4h;	86.8%

4-(2-amino-5-bromopyridin-3-yl)-2-methylbut-3-yn-2-ol (1262985-25-0) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With sodium hydroxide In water; glycerol at 80℃; for 15h; Solvent;	86.6%
With sodium hydroxide In 1-methyl-pyrrolidin-2-one; water at 75 - 81℃; under 262.526 Torr; Inert atmosphere;	75%

2-aminopyrrole (4458-15-5) + bromomalonaldehyde; sodium enolate → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With hydrogen bromide In ethanol Reflux;	85.5%

5-bromo-3-(2-(trimethylsilyl)ethynyl)pyridine-2-amine (905966-34-9) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With sodium hydride In 1-methyl-pyrrolidin-2-one at 80℃; for 1h; Inert atmosphere;	80%
With potassium tert-butylate In 1-methyl-pyrrolidin-2-one at 80℃; for 1h;	70%
Stage #1: 5-bromo-3-(2-(trimethylsilyl)ethynyl)pyridine-2-amine With potassium tert-butylate In tert-butyl alcohol for 12h; Heating / reflux; Stage #2: With hydrogenchloride In water; tert-butyl alcohol at 20℃; for 12h; Heating / reflux; Stage #3: With sodium hydroxide In water; tert-butyl alcohol	60%
Stage #1: 5-bromo-3-(2-(trimethylsilyl)ethynyl)pyridine-2-amine With potassium tert-butylate In tert-butyl alcohol Stage #2: With hydrogenchloride In water; tert-butyl alcohol	56%
With potassium tert-butylate In 1-methyl-pyrrolidin-2-one at 20 - 80℃; for 1h; Product distribution / selectivity;	53%

5-bromo-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one (183208-34-6) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Stage #1: 5-bromo-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one With hydrogenchloride; tin In ethanol; water at 40℃; for 2h; Stage #2: With copper(ll) bromide In chloroform at 60℃; for 2h; Solvent; Temperature; Reagent/catalyst;	77.6%
Stage #1: 5-bromo-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one With borane-THF In tetrahydrofuran at 0 - 20℃; for 0.583333h; Stage #2: With manganese triacetate In acetic acid at 75℃; for 0.75h;	50%
Stage #1: 5-bromo-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one With borane-THF In tetrahydrofuran at 20℃; for 0.833333h; Stage #2: With manganese triacetate; acetic acid at 75℃; for 0.833333h; Further stages.;	50%
Stage #1: 5-bromo-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one With borane-THF In tetrahydrofuran at 0 - 20℃; Stage #2: With manganese(III) triacetate dihydrate; acetic acid In tetrahydrofuran at 75℃;	50%
With hydrogenchloride; borane-THF; manganese triacetate 1.) THF, 0 deg C, 35 min, RT, 2.) H2O, reflux, 3.) acetic acid, 45 min, 75 deg C; Yield given; Multistep reaction;

1-phenylbut-3-yn-1-ol (1743-36-8) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With di-isopropyl azodicarboxylate; diphenyl phosphoryl azide; triphenylphosphine In tetrahydrofuran at 20℃; for 24h;	75%

N-(5-bromo-3-trimethylsilanylethynyl-pyridin-2-yl)-acetamide (875639-46-6) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With tetrabutyl ammonium fluoride In tetrahydrofuran for 15h; Heating / reflux;	67%
With tetrabutyl ammonium fluoride In tetrahydrofuran for 15h; Heating / reflux;	67%

N'-(5-bromo-3-methylpyridin-2-yl)-N-methyl-N-phenylmethanimidamide → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With sodium amide; N-methylaniline for 2h; Reagent/catalyst; Temperature; Inert atmosphere; Reflux;	60%

N'-(5-bromo-3-methyl-pyridin-2-yl)-N,N-dimethyl-formamidine (883052-76-4) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Stage #1: N'-(5-bromo-3-methyl-pyridin-2-yl)-N,N-dimethyl-formamidine With lithium diisopropyl amide In tetrahydrofuran at -30℃; Stage #2: With acetic acid In tetrahydrofuran Product distribution / selectivity;	26%
Stage #1: N'-(5-bromo-3-methyl-pyridin-2-yl)-N,N-dimethyl-formamidine With lithium diisopropyl amide In tetrahydrofuran at -30℃; Stage #2: With acetic acid In tetrahydrofuran Product distribution / selectivity;	26%

(E)-N’-(5-bromo-3-methylpyridin-2-yl)-N,N-dimethylformimidamide → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Stage #1: (E)-N’-(5-bromo-3-methylpyridin-2-yl)-N,N-dimethylformimidamide With lithium diisopropyl amide In tetrahydrofuran at -30℃; for 5 - 6h; Stage #2: With acetic acid In tetrahydrofuran for 0.166667h; Product distribution / selectivity;	26%

5-bromo-1H-pyrrolo[2,3-b]pyridin-2(3H)-one → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridin-2(3H)-one With diborane In tetrahydrofuran at 20℃; for 0.833333h; Inert atmosphere; Stage #2: With manganese triacetate In acetic acid at 75℃; for 0.833333h;	6%

7-Azaindole (271-63-6) + n-pentyl halide → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: 85 percent / bromine / 2-methyl-propan-2-ol; H2O / 24 h / 24.84 °C 2.1: 95 percent / zinc; acetic acid / 5 h / 20 °C 3.1: BH3*THF / tetrahydrofuran / 0.83 h / 20 °C 3.2: 50 percent / Mn(OAc)3*2H2O; acetic acid / 0.83 h / 75 °C View Scheme

3,3,5-Tribromo-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one (183208-32-4) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: 95 percent / zinc; acetic acid / 5 h / 20 °C 2.1: BH3*THF / tetrahydrofuran / 0.83 h / 20 °C 2.2: 50 percent / Mn(OAc)3*2H2O; acetic acid / 0.83 h / 75 °C View Scheme
Multi-step reaction with 2 steps 1.1: 94 percent / zinc; acetic acid / 20 °C 2.1: borane*tetrahydrofurane / tetrahydrofuran / 0.58 h / 0 - 20 °C 2.2: 50 percent / manganese triacetate / acetic acid / 0.75 h / 75 °C View Scheme
Multi-step reaction with 2 steps 1: 94 percent / zinc, acetic acid / 3 h / Ambient temperature 2: 1.) borane-THF complex, 2.) 6N HCl, 3.) manganese(III) acetate / 1.) THF, 0 deg C, 35 min, RT, 2.) H2O, reflux, 3.) acetic acid, 45 min, 75 deg C View Scheme
Multi-step reaction with 2 steps 1.1: zinc; acetic acid / 20 °C 2.1: borane-THF / tetrahydrofuran / 0 - 20 °C 2.2: 75 °C View Scheme

7-Azaindole (271-63-6) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: 85 percent / bromine / 2-methyl-propan-2-ol; H2O / 20 °C 2.1: 94 percent / zinc; acetic acid / 20 °C 3.1: borane*tetrahydrofurane / tetrahydrofuran / 0.58 h / 0 - 20 °C 3.2: 50 percent / manganese triacetate / acetic acid / 0.75 h / 75 °C View Scheme
Multi-step reaction with 3 steps 1: 85 percent / bromine / 2-methyl-propan-2-ol; H2O / 19 h / Ambient temperature 2: 94 percent / zinc, acetic acid / 3 h / Ambient temperature 3: 1.) borane-THF complex, 2.) 6N HCl, 3.) manganese(III) acetate / 1.) THF, 0 deg C, 35 min, RT, 2.) H2O, reflux, 3.) acetic acid, 45 min, 75 deg C View Scheme

C11H15BrN2O (1111638-00-6) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Stage #1: C11H15BrN2O With hydrogenchloride In water for 8h; Heating / reflux; Stage #2: With sodium hydroxide; water

1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: bromine; pyridine / dichloromethane / 2 h / 0 °C 2: 2,3-dicyano-5,6-dichloro-p-benzoquinone / dichloromethane / 1 h 3: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 25 °C View Scheme

5-bromo-1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 2,3-dicyano-5,6-dichloro-p-benzoquinone / dichloromethane / 1 h 2: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 25 °C View Scheme

7-azaindoline (10592-27-5) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: sodium hydride / N,N-dimethyl-formamide; mineral oil / 0.5 h / 0 °C 1.2: 3 h / 0 °C 2.1: bromine; pyridine / dichloromethane / 2 h / 0 °C 3.1: 2,3-dicyano-5,6-dichloro-p-benzoquinone / dichloromethane / 1 h 4.1: tetrabutyl ammonium fluoride / tetrahydrofuran / 0.5 h / 25 °C View Scheme
Multi-step reaction with 2 steps 1: 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione; toluene-4-sulfonic acid / dichloromethane / 1 h / 20 °C 2: manganese(IV) oxide / toluene / 1 h / 90 °C View Scheme

2-amino-3-iodo-5-bromopyridine (381233-96-1) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: lithium hydroxide / dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 / N,N-dimethyl-formamide / 18 h / 70 °C 2: hydrogenchloride / water / 1 h / 50 °C View Scheme
Multi-step reaction with 2 steps 1: copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride; triethylamine / 1 h / 20 °C / Inert atmosphere 2: sodium hydride / 1-methyl-pyrrolidin-2-one / 1 h / 80 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: triethylamine; copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride / tetrahydrofuran / 3 h / 20 °C / Inert atmosphere 2: potassium tert-butylate / 1-methyl-pyrrolidin-2-one / 1 h / 80 °C View Scheme

5-bromo-2-pyridylamine (1072-97-5) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: trifluoroacetic acid; sodium periodate; iodine / acetonitrile / 80 °C 2: lithium hydroxide / dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 / N,N-dimethyl-formamide / 18 h / 70 °C 3: hydrogenchloride / water / 1 h / 50 °C View Scheme
Multi-step reaction with 3 steps 1: trifluoroacetic acid; sodium periodate; iodine / acetonitrile / 80 °C 2: N,N,N',N'-tetramethylguanidine; copper(l) iodide / bis-triphenylphosphine-palladium(II) chloride / toluene / 1 h / 80 °C / Inert atmosphere 3: potassium tert-butylate / 1-methyl-pyrrolidin-2-one / 1 h / 20 - 80 °C View Scheme
Multi-step reaction with 3 steps 1.1: trifluoroacetic acid; N-iodo-succinimide / N,N-dimethyl-formamide / 3 h / 20 - 50 °C 1.2: pH 7 2.1: lithium hydroxide / dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 / 18 h / 70 °C 3.1: hydrogenchloride / water / 1 h / 50 °C View Scheme
Multi-step reaction with 3 steps 1: periodic acid; iodine / acetonitrile / Inert atmosphere 2: copper(l) iodide; bis-triphenylphosphine-palladium(II) chloride; triethylamine / 1 h / 20 °C / Inert atmosphere 3: sodium hydride / 1-methyl-pyrrolidin-2-one / 1 h / 80 °C / Inert atmosphere View Scheme
Multi-step reaction with 3 steps 1: acetic acid; sodium periodate; iodine / 2 h / 80 °C 2: dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; copper(l) iodide; triethylamine / dichloromethane / 30 h / Inert atmosphere; Reflux 3: sodium hydroxide / water; glycerol / 15 h / 80 °C View Scheme

C9H11BrN2O (1356397-50-6) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
With hydrogenchloride In water at 50℃; for 1h; Product distribution / selectivity;
With hydrogenchloride In water at 50℃; for 1h;

5-bromo-3-methyl-pyridin-2-ylamine (3430-21-5) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: toluene-4-sulfonic acid / 1 h / 85 °C 2: 2 h / 110 °C 3: N-methylaniline; sodium amide / 2 h / Inert atmosphere; Reflux View Scheme
Multi-step reaction with 3 steps 1: toluene-4-sulfonic acid / dichloromethane / 16 h / Reflux; Industrial scale 2: toluene / 16 h / 60 °C / Industrial scale 3: sodium amide / diethylene glycol dimethyl ether / 16 h / 10 - 15 °C / Industrial scale View Scheme

2-amino-3,5-dibromopyridine (35486-42-1) → 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: toluene-4-sulfonic acid / 5 h / 95 °C / Industrial scale 2.1: sodium hydride / 1,4-dioxane / 2 h / Industrial scale 2.2: 14 h / 80 °C / Industrial scale 3.1: potassium hydroxide / 1,2-dimethoxyethane / 16 h / 140 °C / Industrial scale View Scheme

5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) + methyl iodide (74-88-4) → 5-bromo-1-methyl-1H-pyrrolo[2,3-b]pyridine (183208-22-2)

Conditions	Yield
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In N,N-dimethyl-formamide at 0 - 20℃; Stage #2: methyl iodide In N,N-dimethyl-formamide at 20℃;	100%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Inert atmosphere; Stage #2: methyl iodide In N,N-dimethyl-formamide at 25℃; for 3h; Inert atmosphere;	99%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In N,N-dimethyl acetamide; mineral oil at 20℃; for 0.5h; Stage #2: methyl iodide In N,N-dimethyl acetamide; mineral oil for 4h;	97%

5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 3-iodo-5-bromo-1H-pyrrolo[2,3-b]-pyridine (757978-18-0)

Conditions	Yield
With N-iodo-succinimide In acetone at 20℃; for 0.333333h;	100%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With potassium hydroxide In dichloromethane at 20℃; for 0.5h; Stage #2: With N-iodo-succinimide In dichloromethane for 15h;	100%
With N-iodo-succinimide In acetone at 20℃; for 0.333333h;	100%

Trichloroacetyl chloride (76-02-8) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 1-(5-bromo-1H-pyrrolo[2,3-b]pyridin-3-yl)-2,2,2-trichloroethanone

Conditions	Yield
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With aluminum (III) chloride In dichloromethane at 20℃; for 0.166667h; Stage #2: trifluoroacetyl chloride In dichloromethane at 20℃;	100%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With aluminum (III) chloride In dichloromethane at 0℃; for 3h; Stage #2: trifluoroacetyl chloride In dichloromethane at 25℃; for 16h;	72%
With aluminum (III) chloride In dichloromethane at 20℃;
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With aluminum (III) chloride at 20℃; for 0.166667h; Inert atmosphere; Stage #2: trifluoroacetyl chloride for 14h;	16.36 g
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With aluminum (III) chloride In dichloromethane at 0℃; for 3h; Stage #2: trifluoroacetyl chloride In dichloromethane at 25℃; for 16h;

(2-trimethylethylsilylethoxy)methyl chloride (76513-69-4) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 5-bromo-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrrolo[2,3-b]pyridine

Conditions	Yield
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In N,N-dimethyl-formamide; paraffin oil at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: (2-trimethylethylsilylethoxy)methyl chloride In N,N-dimethyl-formamide; paraffin oil at 0 - 20℃;	100%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In N,N-dimethyl-formamide at -40℃; for 1h; Stage #2: (2-trimethylethylsilylethoxy)methyl chloride In N,N-dimethyl-formamide at -40℃; for 2h;	87%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: (2-trimethylethylsilylethoxy)methyl chloride In tetrahydrofuran at 20℃; for 2h; Inert atmosphere;	79%

2-bromoacetyl chloride (22118-09-8) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 2-bromo-1-(5-bromo-1H-pyrrolo[2,3-b]pyridin-3-yl)ethanone (875639-57-9)

Conditions	Yield
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With aluminum (III) chloride In dichloromethane for 0.5h; Stage #2: 2-bromoacetyl chloride In dichloromethane for 2h;	100%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With aluminum (III) chloride In dichloromethane at 20℃; for 1h; Stage #2: 2-bromoacetyl chloride In dichloromethane at 20℃;	92%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With aluminum (III) chloride In dichloromethane for 0.5h; Inert atmosphere; Stage #2: 2-bromoacetyl chloride In dichloromethane for 2h;	138 mg

5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) + phenylboronic acid (98-80-6) → 5-phenyl-1H-pyrrolo[2,3-b]pyridine (611205-38-0)

Conditions	Yield
With potassium carbonate; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride In 1,4-dioxane; water at 80℃; for 22.5h; Suzuki Coupling;	99%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In 1,4-dioxane; water at 80℃; for 22.5h; Suzuki coupling;	99%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium carbonate In 1,4-dioxane; water at 80℃; for 22.5h; Inert atmosphere;	99%
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium carbonate In 1,4-dioxane; water at 80℃; for 48h; Inert atmosphere;	82%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In ethanol; toluene at 120℃; for 24h; Suzuki-Miyaura Coupling; Inert atmosphere;	62.93%

cyclopropanemethylamine (2516-47-4) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → N-(cyclopropylmethyl)-1H-pyrrolo[2,3-b]pyridin-5-amine (1248587-76-9)

Conditions	Yield
With dicyclohexyl-(2′,4′,6′-triisopropyl-3,6-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine; chloro[2-(dicyclohexylphosphino)-3,6-dimethoxy-2’,4’,6’-triisopropyl-1,1’-biphenyl] [2-(2-aminoethyl)phenyl]palladium(II); lithium hexamethyldisilazane In tetrahydrofuran at 65℃; for 4h; Inert atmosphere; Sealed vial;	99%

cyclopropylcarbinyl bromide (7051-34-5) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7)

Conditions	Yield
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.25h; Stage #2: cyclopropylcarbinyl bromide In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 2h;	99%

benzyl bromide (100-39-0) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 1-benzyl-5-bromo-1H-pyrrolo[2,3-b] pyridine

Conditions	Yield
With tetra(n-butyl)ammonium hydrogensulfate; potassium hydroxide In acetone at 75℃; Inert atmosphere;	99%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With potassium tert-butylate In N,N-dimethyl acetamide for 0.25h; Cooling with ice; Stage #2: benzyl bromide In N,N-dimethyl acetamide at 20℃; for 1h; Cooling with ice;	0.45 g

1-iodo-butane (542-69-8) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 5-bromo-1-butyl-1H-pyrrolo[2,3-b]pyridine

Conditions	Yield
With tetra(n-butyl)ammonium hydrogensulfate; potassium hydroxide In acetone at 75℃; Inert atmosphere;	99%

piperidine (110-89-4) + carbon monoxide (201230-82-2) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → C13H15N3O

Conditions	Yield
With 2,2,6,6-tetramethyl-piperidine; dicobalt octacarbonyl In tert-Amyl alcohol under 1520.1 Torr; for 48h; Irradiation;	99%

(2,3-difluorophenyl)acetyl chloride (808144-32-3) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 1-(5-bromo-1H-pyrrolo[2,3-b]pyridin-3-yl)-2-(2,3-difluoro-phenyl)-ethanone (849069-12-1)

Conditions	Yield
With aluminum (III) chloride In dichloromethane at 0 - 20℃; for 1.5h;	98%

acetyl chloride (75-36-5) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 1-(5-bromo-1H-pyrrolo[2,3-b]pyridin-3-yl)ethanone (866545-96-2)

Conditions	Yield
With aluminum (III) chloride In dichloromethane at 20℃; Friedel Crafts acylation; Inert atmosphere;	98%
aluminum (III) chloride In dichloromethane at 20℃; for 6h;	93%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With aluminum (III) chloride In dichloromethane at 20℃; for 1h; Stage #2: acetyl chloride In dichloromethane for 5h;	93%

triisopropylsilyl chloride (13154-24-0) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 5-bromo-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (858116-66-2)

Conditions	Yield
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In 1,4-dioxane; N,N-dimethyl-formamide for 0.5h; Stage #2: triisopropylsilyl chloride In 1,4-dioxane; N,N-dimethyl-formamide at 20℃;	97%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In tetrahydrofuran at 0℃; for 0.25h; Schlenk technique; Inert atmosphere; Stage #2: triisopropylsilyl chloride In tetrahydrofuran at 0 - 20℃; Schlenk technique; Inert atmosphere;	94%
With potassium tert-butylate In tetrahydrofuran; N,N-dimethyl-formamide at 0 - 5℃; Solvent;	93.8%

propyl bromide (106-94-5) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 5-bromo-1-propyl-1H-pyrrolo[2,3-b]pyridine (1440956-68-2)

Conditions	Yield
With sodium hydride In N,N-dimethyl acetamide at 20℃; for 2.5h;	97%
Stage #1: 5-bromo-1H-pyrrolo[2,3-b]pyridine With sodium hydride In N,N-dimethyl acetamide; mineral oil at 20℃; for 0.5h; Stage #2: propyl bromide In N,N-dimethyl acetamide; mineral oil for 2h;	97%

bis(pinacol)diborane (73183-34-3) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine (754214-56-7)

Conditions	Yield
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In 1,4-dioxane at 80℃; Inert atmosphere;	95.9%
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate In 1,4-dioxane at 80℃; Inert atmosphere;	95.9%
With potassium acetate; dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2 In 1,4-dioxane at 80℃; for 10h;	94.2%

N-Methyl-N-phenethylamine (589-08-2) + 5-bromo-1H-pyrrolo[2,3-b]pyridine (183208-35-7) → N-methyl-N-phenethyl-1H-pyrrolo[2,3-b]pyridin-5-amine (1248587-68-9)

Conditions	Yield
With RuPhos palladacycle; lithium hexamethyldisilazane; ruphos In tetrahydrofuran at 65℃; for 4h; Inert atmosphere; Sealed vial;	95%

Upstream product

• 183208-34-6 5-bromo-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one 
• 10592-27-5 7-azaindoline 
• 883052-76-4 N'-(5-bromo-3-methyl-pyridin-2-yl)-N,N-dimethyl-formamidine 
• 1743-36-8 1-phenylbut-3-yn-1-ol 
• 35486-42-1 2-amino-3,5-dibromopyridine 
• 872619-43-7 5-bromo-1H-pyrrole[2,3-b]pyrimidine-3-carboxylic acid methyl ester 
• 4458-15-5 2-aminopyrrole 
• 3430-21-5 5-bromo-3-methyl-pyridin-2-ylamine 
• 1210838-82-6 5-bromo-3-ethynyl-pyridin-2-ylamine 
• 1262985-25-0 4-(2-amino-5-bromopyridin-3-yl)-2-methylbut-3-yn-2-ol 
• 1111638-00-6 C₁₁H₁₅BrN₂O 
• 905966-34-9 5-bromo-3-(2-(trimethylsilyl)ethynyl)pyridine-2-amine 
• 875639-46-6 N-(5-bromo-3-trimethylsilanylethynyl-pyridin-2-yl)-acetamide 
• 754214-54-5 5-bromo-1-(tert-butyl-dimethyl-silanyl)-1H-pyrrolo[2,3-b]pyridine 

Downstream Products

• 183208-36-8 5-methoxy-1H-pyrrolo[2,3-b]pyridine 
• 916895-89-1 7-azaserotonin 
• 183208-38-0 3-formyl-5-methoxy-1H-pyrrolo<2,3-b>pyridine 
• 479552-71-1 5-bromo-1-(p-tolylsulfonyl)pyrrolo[2,3-b]pyridine 
• 864681-18-5 1H-pyrrolo[2,3-b]pyridine-5-carboxylic acid ethyl ester 
• 875639-33-1 (3-(1H-pyrrolo[2,3-b]pyridin-5-yl)phenyl)(morpholino)-methanone 
• 923583-55-5 5-Phenylsulfanyl-1H-pyrrolo[2,3-b]pyridine 
• 918511-92-9 5-(pyridin-3-yl)-1H-pyrrolo[2,3-b]pyridine 
• 1036383-51-3 5-methanesulfonyl-1H-pyrrolo[2,3-b]pyridine 
• 849067-96-5 1H-pyrrolo[2,3-b]pyridine-5-carboxylic acid methyl ester 
• 1001070-33-2 1-(benzenesulfonyl)-5-bromo-1H-pyrrolo[2,3-b]pyridine 
• 1111637-68-3 5-bromo-3-fluoro-1H-pyrrolo[2,3-b]pyridine 
• 858117-40-5 (5-bromo-1H-pyrrolo[2,3-b]pyridin-3-yl)(phenyl)methanone 
• 1227611-81-5 (5-bromo-1H-pyrrolo[2,3-b]pyridin-3-yl)-(2,6-dichloro-3-fluorophenyl)methanol 

Relevant articles and documents

Full functionalization of the 7-azaindole scaffold by selective metalation and sulfoxide/magnesium exchange

Filling positions: 7-Azaindoles are important targets in the pharmaceutical industry. All five carbon positions of the azaindole ring system can be functionalized in a predictable manner starting from the appropriately substituted azaindole 1 by directed metalation and halogen/magnesium and sulfoxide/magnesium exchange. The products are fully substituted azaindoles of type 2.

Method for synthesizing 5-bromo-7-azaindole

The invention provides a method for synthesizing 5-bromo-7-azaindole, and belongs to the field of medicinal chemical synthesis. The method comprises the following steps: reacting a raw material 1,1,3,3-tetramethoxypropane 2 with bromine to obtain an intermediate 3, preparing an intermediate 4 from an intermediate 3 under the action of an alkali, and reacting the intermediate 4 with 2-aminopyrroleto obtain the 5-bromo-7-azaindole 1. The method has the advantages of few reaction steps, easily available raw materials, high yield, small pollution, and easiness in amplified production.

Preparation method for 5-bromo-7-azindole

The invention belongs to the technical field of preparation of 5-bromo-7-azindole, in particular to a preparation method for the 5-bromo-7-azindole. The method comprises the following steps: taking 2-amino-5-bromopyridine as a raw material, and performing the steps in sequence: (1) introducing iodine through an iodine reagent; (2) performing a coupling reaction with methylbutynol; and (3) performing a ring-closing reaction under the catalysis of inorganic strong base to prepare the 5-bromo-7-azindole, wherein the catalyst adopted in the coupling reaction in the step (2) is bis(benzonitrile)palladium dichloride or [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloromethane dichloride complex compound. According to the preparation method, cheap 2-amino-5-bromopyridine is taken as the rawmaterial in the step (1); the catalyst with high catalyzing efficiency and a solvent which is easy to treat are adopted; purifying steps in each step are simple; the yield is high; and the and the yield of the finally prepared product, namely, the 5-bromo-7-azindole, can reach over 93 percent.