3652-89-9

Basic information

• Product Name: 4-BroMo-9H-carbazole
• Synonyms: 4-BroMo-9H-carbazole;4-broMocarbazole;4-BroMo-9H-carbazole (4BC);9H-Carbazole, 4-broMo-;Carbazole, 4-bromo-
• CAS NO: 3652-89-9
• Molecular Formula: C₁₂H₈BrN
• Molecular Weight: 246.10262
• EINECS: -0
• Product Categories: OLED
• Mol File: 3652-89-9.mol
• Article Data: 43

Chemical Properties

• Melting Point: 104-105℃
• Boiling Point: 409.2±18.0 °C(Predicted)
• Appearance: /
• Density: 1.617±0.06 g/cm3 (20 ºC 760 Torr)
• Storage Temp.: Sealed in dry,Room Temperature
• PKA: 16.04±0.30(Predicted)
• CAS DataBase Reference: 4-BroMo-9H-carbazole(CAS DataBase Reference)
• NIST Chemistry Reference: 4-BroMo-9H-carbazole(3652-89-9)
• EPA Substance Registry System: 4-BroMo-9H-carbazole(3652-89-9)

Safety Data

• Hazardous Substances Data: 3652-89-9(Hazardous Substances Data)

Usage

Chemical Properties

White powder.

Uses

4-BROMO-9H-CARBAZOLE is a useful research chemical.

Synthesis

Under nitrogen protection,Add 357.6g m-dibromobenzene (99%, 1.5mol) into a 500mL reaction flask,26.1g o-bromoaniline (99%, 0.15mol),0.084g palladium(II) acetate (99%, 0.375mmol),0.18g 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl (99%, 0.375mmol),58.2g sodium tert-butoxide (99%, 0.6mol),After feeding,Warm up to 130°C,Stirring speed 600rpm,Incubate for 24hr,After the reaction,Vacuum distillation to recover unreacted m-dibromobenzene,Add water and ethyl acetate to extract the residue,The organic layer was desolvated to obtain the crude product which was crystallized in ethanol to obtain 34.3 g of 4-BroMo-9H-carbazole.The content is 99.6% and the yield is 92.5%.

Synthetic route

C12H9Br2N → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; 1,8-diazabicyclo[5.4.0]undec-7-ene; triethylamine at 150℃; for 3h; Temperature; Reagent/catalyst; Inert atmosphere;	94.6%

1,3-dibromobenzene (108-36-1) + 2-bromoaniline (615-36-1) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
With palladium diacetate; sodium t-butanolate; XPhos at 130℃; for 24h; Temperature; Suzuki Coupling; Inert atmosphere;	92.5%

2-bromo-2′-nitro-1,1′-biphenyl (17613-47-7) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
With triphenylphosphine In 1,2-dichloro-benzene for 12h; Reflux;	87%
With triphenylphosphine In 1,2-dichloro-benzene at 170℃; for 12h; Inert atmosphere;	87%
With triphenylphosphine In 1,2-dichloro-benzene at 180℃; for 18h; Inert atmosphere;	86%

4-Nitro-9H-carbazole (57905-76-7) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Stage #1: 4-Nitro-9H-carbazole With acetic acid; zinc In ethanol; water at 40℃; for 2h; Inert atmosphere; Stage #2: With hydrogen bromide; sodium nitrite In water for 0.5h; Cooling with ice; Stage #3: With copper(I) bromide In water for 2h;	72%
Stage #1: 4-Nitro-9H-carbazole With acetic acid; zinc In ethanol; water at 40℃; for 2h; Inert atmosphere; Stage #2: With hydrogen bromide In ethanol; water for 0.5h; Inert atmosphere; Further stages;	72%

2'-bromo-6'-nitro-1,2-dihydro-1,1'-biphenyl → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
With triphenylphosphine In 1,2-dichloro-benzene for 24h; Reflux;	60%
With triphenylphosphine In 1,2-dichloro-benzene for 24h; Reflux;
With triethyl phosphite at 160 - 165℃; for 14h;

C12H8BrN3 → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
With water; palladium diacetate at 110℃; Microwave irradiation;	52%
With tetrabutylammonium tricarbonylnitrosylferrate In 1,2-dichloro-ethane at 100℃; for 1h; Inert atmosphere; Schlenk technique; Microwave irradiation;	37%

5-bromo-1,2,3,4-tetrahydrocarbazole (78863-98-6) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
With chloranil; xylene

cyclohexanone (108-94-1) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: aqueous sulfuric acid 2: tetrachloro-<1,4>benzoquinone; xylene View Scheme

3-bromophenylhydrazine (40887-80-7) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: aqueous sulfuric acid 2: tetrachloro-<1,4>benzoquinone; xylene View Scheme

o-nitroiodobenzene (609-73-4) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: palladium diacetate; potassium carbonate; triphenylphosphine / ethanol; water; toluene / 18 h / 100 °C / Inert atmosphere 2: triphenylphosphine / N,N-dimethyl acetamide / 14 h / 180 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: potassium carbonate / tetrakis(triphenylphosphine) palladium(0) / water; tetrahydrofuran / 80 °C 2: triphenylphosphinepalladium / 1,2-dichloro-benzene / 24 h / Reflux View Scheme
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); sodium carbonate / toluene; water / 8 h / 80 °C / Inert atmosphere 2: triphenylphosphine / 1,2-dichloro-benzene / 8 h / 180 °C / Inert atmosphere View Scheme

(2-bromophenyl)boronic acid (244205-40-1) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: palladium diacetate; potassium carbonate; triphenylphosphine / ethanol; water; toluene / 18 h / 100 °C / Inert atmosphere 2: triphenylphosphine / N,N-dimethyl acetamide / 14 h / 180 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: potassium carbonate / tetrakis(triphenylphosphine) palladium(0) / water; tetrahydrofuran / 80 °C 2: triphenylphosphinepalladium / 1,2-dichloro-benzene / 24 h / Reflux View Scheme
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / tetrahydrofuran; water / 12 h / Reflux 2: triphenylphosphine / 1,2-dichloro-benzene / 12 h / Reflux View Scheme

2-nitrophenyl bromide (577-19-5) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / tetrahydrofuran; water / 12 h / Reflux 2: triphenylphosphine / 1,2-dichloro-benzene / 12 h / Reflux View Scheme
Multi-step reaction with 2 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / tetrahydrofuran; water / 12 h / 90 °C / Inert atmosphere 2: triphenylphosphine / 1,2-dichloro-benzene / 12 h / 170 °C / Inert atmosphere View Scheme
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / tetrahydrofuran; water / 24 h / 95 °C 2: triphenylphosphine / 1,2-dichloro-benzene / 24 h / 180 °C View Scheme

2-bromoaniline (615-36-1) → 4-bromo-9H-carbazole (3652-89-9)

Conditions

Yield

Multi-step reaction with 3 steps 1.1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / toluene; water / 20 h / 95 °C / Inert atmosphere; Schlenk technique 2.1: sodium nitrite / water; acetic acid / 1 h / 0 °C / Inert atmosphere; Schlenk technique 2.2: 1 h / 0 - 20 °C / Inert atmosphere; Schlenk technique 3.1: tetrabutylammonium tricarbonylnitrosylferrate / 1,2-dichloro-ethane / 1 h / 100 °C / Inert atmosphere; Schlenk technique; Microwave irradiation View Scheme

2’-bromo-[1,1’-biphenyl]-2-amine (54147-91-0) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sodium nitrite / water; acetic acid / 1 h / 0 °C / Inert atmosphere; Schlenk technique 1.2: 1 h / 0 - 20 °C / Inert atmosphere; Schlenk technique 2.1: tetrabutylammonium tricarbonylnitrosylferrate / 1,2-dichloro-ethane / 1 h / 100 °C / Inert atmosphere; Schlenk technique; Microwave irradiation View Scheme
Multi-step reaction with 2 steps 1.1: acetic acid; sodium nitrite / water / 2 h / 0 °C 1.2: 25 °C 2.1: water; palladium diacetate / 110 °C / Microwave irradiation View Scheme

phenylboronic acid (98-80-6) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); sodium hydroxide / tetrahydrofuran; water / 80 - 90 °C 2: triphenylphosphine / 1,2-dichloro-benzene / 24 h / Reflux View Scheme
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); sodium hydroxide / tetrahydrofuran; water / 24 h / 80 °C 2: triethyl phosphite / 14 h / 160 - 165 °C View Scheme
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); sodium hydroxide / tetrahydrofuran; water / 80 - 90 °C 2: triphenylphosphine / 1,2-dichloro-benzene / 24 h / Reflux View Scheme

1-bromo-2-iodo- 3-nitrobenzene (32337-96-5) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); sodium hydroxide / tetrahydrofuran; water / 80 - 90 °C 2: triphenylphosphine / 1,2-dichloro-benzene / 24 h / Reflux View Scheme
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); sodium hydroxide / tetrahydrofuran; water / 24 h / 80 °C 2: triethyl phosphite / 14 h / 160 - 165 °C View Scheme
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); sodium hydroxide / tetrahydrofuran; water / 80 - 90 °C 2: triphenylphosphine / 1,2-dichloro-benzene / 24 h / Reflux View Scheme

2-iodophenylamine (615-43-0) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: sodium carbonate; palladium diacetate / ethylene glycol; water / 48 h / 90 °C 2.1: acetic acid; sodium nitrite / water / 2 h / 0 °C 2.2: 25 °C 3.1: water; palladium diacetate / 110 °C / Microwave irradiation View Scheme

4-bromo-1,2,3,9-tetrahydrocarbazole → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
With chloranil at 110℃; for 4h; Concentration;	40.2 g

aniline (62-53-3) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 5 steps 1: magnesium oxide / toluene / 4 h / 110 °C / Inert atmosphere 2: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate / N,N-dimethyl acetamide / 8 h / 80 °C 3: sodium tetrahydroborate / tetrahydrofuran / 2 h / 20 °C 4: hydrogen bromide; ferric(III) bromide / 4 h / 20 °C 5: chloranil / 4 h / 110 °C View Scheme
Multi-step reaction with 3 steps 1.1: triethylamine / 8 h / Reflux 2.1: iron(III) chloride; pyrographite; hydrazine hydrate / ethanol / 6 h / 70 - 80 °C 3.1: sulfuric acid; acetic acid / 15 °C 3.2: 1 h / 15 - 20 °C 3.3: 2 h / Reflux View Scheme

1,3-cylohexanedione (504-02-9) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 5 steps 1: magnesium oxide / toluene / 4 h / 110 °C / Inert atmosphere 2: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate / N,N-dimethyl acetamide / 8 h / 80 °C 3: sodium tetrahydroborate / tetrahydrofuran / 2 h / 20 °C 4: hydrogen bromide; ferric(III) bromide / 4 h / 20 °C 5: chloranil / 4 h / 110 °C View Scheme

3-phenylaminocyclohex-2-enone (24706-50-1) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 4 steps 1: (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; caesium carbonate / N,N-dimethyl acetamide / 8 h / 80 °C 2: sodium tetrahydroborate / tetrahydrofuran / 2 h / 20 °C 3: hydrogen bromide; ferric(III) bromide / 4 h / 20 °C 4: chloranil / 4 h / 110 °C View Scheme

1,2,3,9-tetrahydro-4H-carbazol-4-one (15128-52-6) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 3 steps 1: sodium tetrahydroborate / tetrahydrofuran / 2 h / 20 °C 2: hydrogen bromide; ferric(III) bromide / 4 h / 20 °C 3: chloranil / 4 h / 110 °C View Scheme

1-Bromo-2-iodobenzene (583-55-1) + 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nitrobenzene (190788-59-1) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / water; toluene; 1,4-dioxane / 12 h / Reflux 2: triphenylphosphine / 1,2-dichloro-benzene / 24 h / Reflux View Scheme

2-Chloronitrobenzene (88-73-3) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: copper / 10 h / 200 °C 2.1: triethyl phosphite / 2 h / 150 °C 3.1: zinc; acetic acid / ethanol; water / 2 h / 40 °C / Inert atmosphere 3.2: 0.5 h / Cooling with ice 3.3: 2 h View Scheme
Multi-step reaction with 3 steps 1.1: copper / 12 h / 200 °C 2.1: triethyl phosphite / 2 h / 160 °C / Inert atmosphere 3.1: zinc; acetic acid / ethanol; water / 2 h / 40 °C / Inert atmosphere 3.2: 0.5 h / Inert atmosphere View Scheme

1‐bromo‐3‐fluoro‐2‐nitrobenzene (886762-70-5) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: triethylamine / 8 h / Reflux 2.1: iron(III) chloride; pyrographite; hydrazine hydrate / ethanol / 6 h / 70 - 80 °C 3.1: sulfuric acid; acetic acid / 15 °C 3.2: 1 h / 15 - 20 °C 3.3: 2 h / Reflux View Scheme

3-bromo-N1-phenylbenzene-1,2-diamine → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Stage #1: 3-bromo-N1-phenylbenzene-1,2-diamine With sulfuric acid; acetic acid at 15℃; Stage #2: With sodium nitrite In water at 15 - 20℃; for 1h; Stage #3: With copper In water for 2h; Reflux;	46.4 g

2-nitrophenyl bromide (577-19-5) + (2-bromophenyl)boronic acid (244205-40-1) → 4-bromo-9H-carbazole (3652-89-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / toluene; ethanol; water / 110 °C / Inert atmosphere 2: triphenylphosphine / 1,2-dichloro-benzene / 180 °C / Inert atmosphere View Scheme

4-bromo-9H-carbazole (3652-89-9) + 2,4,6-trichlorobenzoyl chloride (4136-95-2) → 9-(2,4,6-trichlorobenzoyl)-4-bromo-9H-carbazole

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 0 - 23℃; for 2h; Inert atmosphere;	100%

4-bromo-9H-carbazole (3652-89-9) + diphenylamine (122-39-4) → N,N-diphenyl-9H-carbazol-4-amine

Conditions	Yield
With tris(dibenzylideneacetone)dipalladium(0) chloroform complex; lithium hexamethyldisilazane; tri tert-butylphosphoniumtetrafluoroborate In tetrahydrofuran at 65℃; for 12h; Inert atmosphere;	99%
With tributylphosphine; palladium diacetate; sodium t-butanolate In toluene at 110℃; for 16h; Inert atmosphere;	58.4%

4-bromo-9H-carbazole (3652-89-9) + di-tert-butyl dicarbonate (24424-99-5) → tert-butyl 4-bromo-9H-carbazole-9-carboxylate

Conditions	Yield
Stage #1: 4-bromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 2h; Inert atmosphere; Stage #2: di-tert-butyl dicarbonate In N,N-dimethyl-formamide for 1h;	98%
With dmap In tetrahydrofuran at 20℃; for 12h; Inert atmosphere;	84%
With N-ethyl-N,N-diisopropylamine In acetonitrile at 25℃; for 2h; Inert atmosphere;	77%

4-bromo-9H-carbazole (3652-89-9) + iodobenzene (591-50-4) → 4-bromo-9-diphenyl-9H-carbazole (1097884-37-1)

Conditions	Yield
Stage #1: 4-bromo-9H-carbazole; iodobenzene With copper(l) iodide; potassium carbonate In N,N-dimethyl-formamide for 0.5h; Inert atmosphere; Stage #2: With copper(l) iodide; 1-(2-pyridyl)-3-(2-pyridyl)-1,3-propanedione In N,N-dimethyl-formamide at 110℃; Inert atmosphere;	97%
With dibenzo-18-crown-6; copper; potassium carbonate at 150℃; for 24h;	95%
With 18-crown-6 ether; copper; potassium carbonate In 1,2-dichloro-benzene at 140℃; for 16h; Sealed tube;	92%

4-bromo-9H-carbazole (3652-89-9) + methyl iodide (74-88-4) → 4-bromo-9-methyl-9H-carbazole

Conditions	Yield
Stage #1: 4-bromo-9H-carbazole With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 0.5h; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran; mineral oil at 0 - 20℃; for 18h; Inert atmosphere;	96%
Stage #1: 4-bromo-9H-carbazole With sodium hydride In tetrahydrofuran at 0 - 20℃; for 0.5h; Stage #2: methyl iodide In tetrahydrofuran at 0 - 20℃; for 18h;	92.7%
Stage #1: 4-bromo-9H-carbazole With sodium hydride In tetrahydrofuran at 20℃; for 0.5h; Stage #2: methyl iodide In tetrahydrofuran at 0 - 20℃; for 18h;	92.7%
Stage #1: 4-bromo-9H-carbazole With sodium hydride In tetrahydrofuran at 20℃; for 0.5h; Stage #2: methyl iodide In tetrahydrofuran at 0 - 20℃; for 18h;	92.7%
Stage #1: 4-bromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: methyl iodide In N,N-dimethyl-formamide at 0 - 20℃; for 12h; Inert atmosphere; Schlenk technique;	85%

4-bromo-9H-carbazole (3652-89-9) + 4-bromo-1,1'-biphenyl (92-66-0) → C24H16BrN

Conditions	Yield
Stage #1: 4-bromo-9H-carbazole; 4-bromo-1,1'-biphenyl With copper(l) iodide; potassium carbonate In N,N-dimethyl-formamide for 0.5h; Inert atmosphere; Stage #2: With copper(l) iodide; 1-(2-pyridyl)-3-(2-pyridyl)-1,3-propanedione In N,N-dimethyl-formamide at 110℃; Inert atmosphere;	96%

chloro-trimethyl-silane (75-77-4) + 4-bromo-9H-carbazole (3652-89-9) → 4-(trimethylsilyl)-9H-carbazole

Conditions	Yield
Stage #1: 4-bromo-9H-carbazole With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 1h; Inert atmosphere; Stage #2: chloro-trimethyl-silane In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Inert atmosphere;	95%

4-bromo-9H-carbazole (3652-89-9) + 2-iodonaphthalene (612-55-5) → C22H14BrN

Conditions	Yield
With dibenzo-18-crown-6; copper; potassium carbonate at 150℃; for 24h;	95%

4-bromo-9H-carbazole (3652-89-9) + phenylhydrazine (100-63-0) → 4-bromo-9-diphenyl-9H-carbazole (1097884-37-1)

Conditions	Yield
With copper(l) iodide; caesium carbonate In acetonitrile at 0℃; for 4h; Schlenk technique;	95%

4-bromo-9H-carbazole (3652-89-9) + 2-(dibenzo[b,d]thiophen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane → 4-(1-dibenzo[b,d]thienyl)carbazole

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene at 70℃; for 19.5h; Inert atmosphere;	93%

4-bromo-9H-carbazole (3652-89-9) + phenylboronic acid (98-80-6) → 4-phenyl-9H-carbazole (1201561-34-3)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 3h; Reflux;	91%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; toluene for 3h; Reflux;	91%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In ethanol; water; toluene for 3h; Reflux;	91%
With palladium diacetate; potassium carbonate; tris-(o-tolyl)phosphine In ethanol; water; toluene for 8h; Inert atmosphere; Reflux;	63%

4-bromo-9H-carbazole (3652-89-9) + 9,9-dimethyl-9H-fluoren-2-yl-2-boronic acid (333432-28-3) → C27H21N

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 12h; Inert atmosphere; Reflux;	90%

4-bromo-9H-carbazole (3652-89-9) + bis(pinacol)diborane (73183-34-3) → 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

Conditions	Yield
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 120℃; for 6h;	89%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; tricyclohexylphosphine In N,N-dimethyl-formamide at 130℃; for 12h;	83%
With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; tricyclohexylphosphine In N,N-dimethyl-formamide at 130℃; for 12h;	83%

4-bromo-9H-carbazole (3652-89-9) + p-methoxybenzyl chloride (824-94-2) → C20H16BrNO

Conditions	Yield
Stage #1: 4-bromo-9H-carbazole With sodium hydride In tetrahydrofuran; mineral oil Stage #2: p-methoxybenzyl chloride In tetrahydrofuran; mineral oil	88%

4-bromo-9H-carbazole (3652-89-9) + 4-iodo-biphenyl (1591-31-7) → C24H16BrN

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); tert-butylphosphine; sodium t-butanolate In toluene at 60℃; for 12h;	87%
With copper(l) iodide; copper; potassium carbonate In 1,2-dichloro-benzene for 12h; Inert atmosphere; Reflux;	71%

4-bromo-9H-carbazole (3652-89-9) + dimethyl 2-phenyl-1,1-cyclopropanedicarboxylate (3709-20-4) → dimethyl 2-(2-(4-bromo-9H-carbazol-9-yl)-2-phenylethyl)malonate

Conditions	Yield
With scandium tris(trifluoromethanesulfonate) In dichloromethane at 0 - 20℃; for 12h; Sealed tube; regioselective reaction;	86%

3-bromo-9-phenyl-9H-carbazole (1153-85-1) + 4-bromo-9H-carbazole (3652-89-9) → C30H19BrN2

Conditions	Yield
Stage #1: 3-bromo-9-phenyl-9H-carbazole; 4-bromo-9H-carbazole With copper(l) iodide; potassium carbonate In N,N-dimethyl-formamide for 0.5h; Inert atmosphere; Stage #2: With copper(l) iodide; 1-(2-pyridyl)-3-(2-pyridyl)-1,3-propanedione In N,N-dimethyl-formamide at 110℃; Inert atmosphere;	84%

4-bromo-9H-carbazole (3652-89-9) + 2-diazo-2-phenylacetic acid isopropyl ester (264882-04-4) → isopropyl (R)-2-(4-bromo-9H-carbazol-9-yl)-2-phenylacetate

Conditions	Yield
With copper(l) iodide; C36H24N4; sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate In tert-butyl methyl ether; toluene at 30℃; Molecular sieve; Inert atmosphere; Schlenk technique; enantioselective reaction;	83%

bromobenzene (108-86-1) + 4-bromo-9H-carbazole (3652-89-9) → 4-bromo-9-diphenyl-9H-carbazole (1097884-37-1)

Conditions	Yield
With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium t-butanolate In toluene at 110℃;	82%
With 18-crown-6 ether; copper; potassium carbonate In water for 10h; Reflux;	79%
With dibenzo-18-crown-6; potassium acetate; copper In N,N-dimethyl-formamide at 120℃; for 4h;	77%
With dibenzo-18-crown-6; potassium acetate; copper In N,N-dimethyl-formamide at 120℃; for 4h;	77%

4-bromo-9H-carbazole (3652-89-9) + C14H5(2)H4ClN2 → C26H12(2)H4BrN3

Conditions	Yield
Stage #1: 4-bromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide Inert atmosphere; Stage #2: C14H5(2)H4ClN2 In N,N-dimethyl-formamide Inert atmosphere;	79.1%
Stage #1: 4-bromo-9H-carbazole With sodium hydride In N,N-dimethyl-formamide for 1h; Inert atmosphere; Stage #2: C14H5(2)H4ClN2	79.1%

4-bromo-9H-carbazole (3652-89-9) + 9-phenanthrenylboronic acid (68572-87-2) → C26H17N

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water; toluene Reflux;	78%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In 1,4-dioxane; water; toluene Reflux;	78%

4-bromo-9H-carbazole (3652-89-9) + 2-bromobenzoic acid chloride (7154-66-7) → (2-bromophenyl)(9H-carbazol-4-yl)methanone (1346645-51-9)

Conditions	Yield
Stage #1: 4-bromo-9H-carbazole With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Inert atmosphere; Stage #2: 2-bromobenzoic acid chloride In tetrahydrofuran; hexane at -78 - 20℃; Inert atmosphere;	77%
Stage #1: 4-bromo-9H-carbazole With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Inert atmosphere; Stage #2: 2-bromobenzoic acid chloride In tetrahydrofuran; hexane at -78 - 20℃; for 2h;	77%
Stage #1: 4-bromo-9H-carbazole With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Inert atmosphere; Stage #2: 2-bromobenzoic acid chloride In tetrahydrofuran; hexane at -78 - 20℃; for 2h;	77%

4-bromo-9H-carbazole (3652-89-9) + N-[1,1"-biphenyl]-4-yl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-[1,1-biphenyl]-4-amine (952431-30-0) → C42H30N2

Conditions	Yield
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0) In ethanol; water; toluene for 12h; Inert atmosphere; Reflux;	75%

4-bromo-9H-carbazole (3652-89-9) + C31H20BrN → C43H27BrN2

Conditions	Yield
With bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In toluene at 95℃; for 24h;	75%

N-phenyl-9H-carbazol-3-boronic acid (854952-58-2) + 4-bromo-9H-carbazole (3652-89-9) → 9-phenyl-9H,9'H-3,4'-bicarbazole (1407183-66-7)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; water; toluene at 80℃; for 8h; Inert atmosphere;	74%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,2-dimethoxyethane; water; toluene at 80℃; for 8h; Inert atmosphere;	74%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 4h; Inert atmosphere; Reflux;	63%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In tetrahydrofuran; water for 4h; Reflux; Inert atmosphere;	59%

4-bromo-9H-carbazole (3652-89-9) + N-biphenylyl-N-(Naphthylphenyl)aminophenyl boronic acid pinacol ester → C46H32N2

Conditions	Yield
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0) In ethanol; water; toluene for 12h; Inert atmosphere; Reflux;	72%

Upstream product

• 108-36-1 1,3-dibromobenzene 
• 615-36-1 2-bromoaniline 
• 886762-70-5 2?bromo?6?fluoronitrobenzene 
• 57905-76-7 4-Nitro-9H-carbazole 
• 88-73-3 2-Chloronitrobenzene 
• 583-55-1 1-Bromo-2-iodobenzene 
• 190788-59-1 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nitrobenzene 
• 15128-52-6 1,2,3,9-tetrahydro-4H-carbazol-4-one 
• 24706-50-1 3-phenylaminocyclohex-2-enone 
• 504-02-9 1,3-cylohexanedione 
• 62-53-3 aniline 
• 615-43-0 2-iodophenylamine 
• 32337-96-5 1-bromo-2-iodo-3-nitro-benzene 
• 98-80-6 phenylboronic acid 

Downstream Products

• 1325725-59-4 1-(3,5-bis(trifluoromethyl)phenyl)-3-((S)-3,3-dimethyl-1-((R)-2-(9-methyl-9H-carbazol-4-yl)pyrrolidin-1-yl)-1-oxobutan-2-yl)thiourea 
• 1097884-37-1 4-bromo-9-diphenyl-9H-carbazole 
• 1370555-65-9 (9-phenyl-9H-carbazol-4-yl)boronic acid 

Relevant articles and documents

Preparation method of 4-bromocarbazole

The invention discloses a preparation method of 4-bromocarbazole, and belongs to the technical field of chemistry. According to the preparation method of 4-bromocarbazole, o-bromoaniline and m-dibromobenzene are subjected to a C-N coupling and C-C coupling cascade reaction under the action of a catalyst, a ligand and alkali, 4-bromocarbazole is synthesized in one step through a one-pot method, m-dibromobenzene is a reactant and also serves as a reaction solvent at the same time, and residual m-dibromobenzene can be recycled after the reaction is finished. According to the preparation method, o-bromoaniline and m-dibromobenzene, which are cheap and easy to obtain, are used as raw materials, the product 4-bromocarbazole is obtained by one step through a one-pot method cascade reaction, and compared with the prior art, the step of nitro reduction cyclization is avoided, namely the reaction step is shortened, and the preparation method has the advantages of low production cost, environmental friendliness and the like.

4-bromocarbazole preparation method

The invention discloses a 4-bromocarbazole preparation method. The method includes: in a reaction bottle, mixing 2-bromo-6-fluoronitrobenzene with aniline, adding triethylamine, starting stirring, performing reflux reaction for 8h, after reaction is finished, adding water to perform quenching reaction, and carrying out suction filtration to obtain brownish red solid namely 2-nitro-3-bromo-1,1'-biphenyl; mixing 2-nitro-3-bromo-1,1'-biphenyl with ethyl alcohol, adding ferric trichloride and activated carbon, starting stirring, dropwise adding 80% hydrazine hydrate, then stirring for 6h under a reflux state, and performing filtering, extracting, layering, washing and distilling to obtain off-white solid namely 2-amino-3-bromo-1,1'-biphenyl. By adoption of cheap and easily-acquirable raw materials, a target compound is obtained through three-step reaction of fluorine nucleophilic substitution, reduction and diazonium cyclization, and the total yield of products is high. In addition, a process is simple in operation, suitable for large-scale production and beneficial to product market competitiveness.

4-bromo-9H-carbazole synthesizing method

The invention discloses a 4-bromo-9H-carbazole synthesizing method and belongs to the field of organic synthesis. According to the method, o-chloronitrobenzene is utilized as a starting material, 2,2'-dinitrobiphenyl is synthesized through high-temperature coupling reaction under copper powder catalysis, then 4-nitro carbazole is obtained through triethyl phosphite ring closure reaction, diazoniumsalt is prepared from 4-nitro carbazole through zinc powder reduction and diazotization reaction under the acid condition, and then the diazonium salt reacts with cuprous bromide to synthesize a product of 4-bromo-9H-carbazole. According to the method, the raw materials are easy to obtain, the production cost is low, and the yield can reach 70% or more; the method has easiness in industrial production and provides basis for industrialization of 4-bromo-9H-carbazole and follow-up derivatives of 4-bromo-9H-carbazole.