58328-31-7

Basic information

• Product Name: 4,4'-Bis(N-carbazolyl)-1,1'-biphenyl
• Synonyms: 4,4'-Bis(carbazolyl)-1,1'-biphenyl;4,4'-bis(carbazol-9-yl)biphenyl/CBP;4,4'-Di(9H-carbazol-9-yl)-1,1'-biphenyl;CBP,4,4'-Bis(N-carbazolyl)-1,1'-biphenyl;4,4'-Bis(9H-carbazol-9-yl)biphenyl (purified by subliMation);9H-Carbazole,9,9'-[1,1'-biphenyl]-4,4'-diylbis-;4,4'-Bis(N-carbazolyl)-1,1'-biphenyl 97%;4,4'-Bis(N-carbazolyl)-1,1'-biphenyl SynonyMs 4,4'-Bis(9-carbazolyl)-1,1'-biphenyl
• CAS NO: 58328-31-7
• Molecular Formula: C₃₆H₂₄N₂
• Molecular Weight: 484.59
• EINECS: 1312995-182-4
• Product Categories: OLED materials,pharm chemical,electronic;electronic;Electronic Chemicals;Carbazoles;Carbazoles (for Conduting Polymer Research);Electroluminescence;Functional Materials;Reagents for Conducting Polymer Research;White powder;oled materials;fine chemicals, specialty chemicals, intermediates, electronic chemical, organic synthesis, functional materials
• Mol File: 58328-31-7.mol
• Article Data: 25

Chemical Properties

• Melting Point: 281-285 °C
• Boiling Point: 700.8 °C at 760 mmHg
• Flash Point: 377.6 °C
• Appearance: /
• Density: 1.19 g/cm³
• Storage Temp.: -70°C
• Solubility: slightly sol. in Tetrahydrofuran
• CAS DataBase Reference: 4,4'-Bis(N-carbazolyl)-1,1'-biphenyl(CAS DataBase Reference)
• NIST Chemistry Reference: 4,4'-Bis(N-carbazolyl)-1,1'-biphenyl(58328-31-7)
• EPA Substance Registry System: 4,4'-Bis(N-carbazolyl)-1,1'-biphenyl(58328-31-7)

Safety Data

• Hazard Codes: Xi
• Statements: 37/38-41
• Safety Statements: 26-36/39
• WGK Germany: 3
• Hazardous Substances Data: 58328-31-7(Hazardous Substances Data)

Usage

Classification

Carbazole derivatives, Hole-injection layer materials, Hole transport layer materials, Hole blocking layer materials, Phosphorescent host materials, Light-emitting fiodes, Organic electronics, Sublimed materials.

Applications

4,4′-Bis(N-carbazolyl)-1,1′-biphenyl (CBP), is one of the most widely-used host materials for efficient phosphorescent organic light-emitting diodes with high hole mobility. This is due to its electron-rich property from two carbazolyl units. It has been demonstrated that CBP can efficiently host green, yellow and red phosphorescent emitters with triplet energies smaller than that of CBP (ET = 2.6 eV).

Description

4,4′-Bis(N-carbazolyl)-1,1′-biphenyl (CBP), is one of the most widely-used host materials for efficient fluorescent and phosphorescent organic light-emitting diodes with high hole mobility. This is due to its electron-rich property from two carbazolyl units.

Chemical Properties

White to brown powder

Synthetic route

4,4'-diiodobiphenyl (3001-15-8) + 9H-carbazole (86-74-8) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
With copper(I) chloride; potassium carbonate In dimethyl sulfoxide at 140 - 170℃; for 4h;	98%
With potassium carbonate; copper(l) chloride In dimethyl sulfoxide at 140 - 170℃; for 4h;	98%
With copper(l) iodide; caesium carbonate; lithium chloride In N,N-dimethyl-formamide at 150℃; for 48h;	92%

4,4'-dichlorobiphenyl (2050-68-2) + 9H-carbazole (86-74-8) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions

Yield

Stage #1: 9H-carbazole With methylmagnesium chloride In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene at 5℃; for 0.5h; Inert atmosphere; Schlenk technique; Glovebox; Stage #2: 4,4'-dichlorobiphenyl With 2,6-bis(2,4,6-triisopropylphenyl)phenyl(dicyclohexylphosphine) In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene; dodecane at 145℃; for 3h; Reagent/catalyst; Temperature; Inert atmosphere; Schlenk technique; Glovebox; Sealed tube;

98%

4-(4-bromophenyl)bromobenzene (92-86-4) + 9H-carbazole (86-74-8) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
Stage #1: 9H-carbazole With methylmagnesium chloride In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene at 5 - 20℃; for 0.166667h; Inert atmosphere; Stage #2: 4-(4-bromophenyl)bromobenzene With PdCl(π-allyl)(cyclohexyl-(1-methyl-2,2-diphenylcyclopropylphophine)) In tetrahydrofuran; 5,5-dimethyl-1,3-cyclohexadiene at 108 - 112℃; for 0.25h; Inert atmosphere;	97%
With 1-methyl-pyrrolidin-2-one; copper; potassium carbonate at 240℃; for 72h;	55%
With iodine; copper; potassium carbonate Nitrobenzol;
With potassium carbonate In nitrobenzene for 72h; Reflux;

N-(4-bromophenyl)carbazole (57102-42-8) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
Stage #1: N-(4-bromophenyl)carbazole With tert.-butyl lithium In tetrahydrofuran; pentane at -78℃; for 1h; Inert atmosphere; Stage #2: With copper(l) cyanide In tetrahydrofuran; pentane at -78 - 25℃; Inert atmosphere; Stage #3: In tetrahydrofuran; pentane at 25℃; for 3h; Inert atmosphere;	93%

4,4'-dichlorobiphenyl (2050-68-2) + 9H-carbazole (86-74-8) → 3,3'-Bis(9H-carbozol-9-yl)-1,1'-biphenyl (342638-54-4) + 9,9'-(biphenyl-3,4'-diyl)bis(9H-carbazole) (1325751-60-7) + 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
With potassium tert-butylate In toluene at 130 - 140℃; for 48h; Inert atmosphere; Autoclave; regioselective reaction;	A 5% B 2% C 90%

4-(4-bromophenyl)bromobenzene (92-86-4) + 9H-carbazole (86-74-8) → 3,3'-Bis(9H-carbozol-9-yl)-1,1'-biphenyl (342638-54-4) + 9,9'-(biphenyl-3,4'-diyl)bis(9H-carbazole) (1325751-60-7) + 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
With potassium tert-butylate In toluene at 130 - 140℃; for 48h; Inert atmosphere; Autoclave; regioselective reaction;	A 8.5% B 4% C 77%

2,2'-dibromobiphenyl (13029-09-9) + p,p'-diaminobiphenyl (92-87-5) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
With (6-Dipp)PdCl2-SPhos; sodium t-butanolate In neat (no solvent) at 170℃; for 24h; Buchwald-Hartwig Coupling; Inert atmosphere;	76%
With caesium carbonate; L-proline; copper(l) chloride In dimethyl sulfoxide at 150℃; for 48h;	32%

4,4'-diazidobiphenyl (2915-43-7) + 2-Biphenylboronic acid (4688-76-0) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; silver(I) acetate; sodium carbonate In 1,4-dioxane at 80℃; for 12h; Schlenk technique;	70%

N-phenylcarbazole (1150-62-5) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
With tungsten(VI) chloride In dichloromethane Inert atmosphere;	61%

4-(4-bromophenyl)bromobenzene (92-86-4) + N-(trimethylsilyl)-9H-carbazole (74367-40-1) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
With tri-tert-butyl phosphine; caesium carbonate; cesium fluoride; tris-(dibenzylideneacetone)dipalladium(0); carbon dioxide In hexane at 100℃; under 93086.6 Torr; for 48h;	47%

9H-carbazole (86-74-8) + 2-(6-X-hexyloxy)tetrahydro-2H-pyran, X=halide → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: n-BuLi / tetrahydrofuran; hexane / 0 °C 1.2: 53 percent / tetrahydrofuran; hexane / 18 h / 20 °C 2.1: 47 percent / P(t-Bu)3; Cs2CO3; CsF / Pd2dba3; scCO2 / hexane / 48 h / 100 °C / 93086.6 Torr View Scheme

p,p'-diaminobiphenyl (92-87-5) → 3,3'-Bis(9H-carbozol-9-yl)-1,1'-biphenyl (342638-54-4) + 9,9'-(biphenyl-3,4'-diyl)bis(9H-carbazole) (1325751-60-7) + 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: para-dodecylbenzenesulfonic acid; isopentyl nitrite / dimethyl sulfoxide / 0.17 h / 20 °C 1.2: 1 h / 100 °C 2.1: potassium tert-butylate / toluene / 48 h / 130 - 140 °C / Inert atmosphere; Autoclave View Scheme

biphenyl (92-52-4) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: sulfuric acid; iodine; periodic acid / acetic acid; water; tetrachloromethane / 4 h / 80 °C 2: potassium carbonate; copper; 18-crown-6 ether / 1,2-dichloro-benzene / 72 h / Inert atmosphere; Reflux View Scheme
Multi-step reaction with 2 steps 1: iodine; periodic acid / water; acetic acid; sulfuric acid; tetrachloromethane / 4 h / 80 °C 2: potassium carbonate; copper; 18-crown-6 ether / 1,2-dichloro-benzene / 72 h / Inert atmosphere; Reflux View Scheme

2-phenylaniline (90-41-5) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; copper diacetate; Trimethylacetic acid / 1-methyl-pyrrolidin-2-one / 3 h / 120 °C 2: copper; potassium carbonate; 18-crown-6 ether / 1,2-dichloro-benzene / 24 h / Inert atmosphere; Reflux View Scheme

2-Bromobiphenyl (2052-07-5) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran / 2 h / -78 °C / Schlenk technique 1.2: 10 h / -78 - 20 °C / Schlenk technique 1.3: 1 h / 20 °C / pH 6 - 7 / Schlenk technique 2.1: dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; silver(I) acetate; sodium carbonate / 1,4-dioxane / 12 h / 80 °C / Schlenk technique View Scheme

1,2-dibromobenzene (583-53-9) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran / -78 - 0 °C 1.2: 0 °C 2.1: (6-Dipp)PdCl2-SPhos; sodium t-butanolate / neat (no solvent) / 24 h / 170 °C / Inert atmosphere View Scheme

para-diiodobenzene (624-38-4) + 9H-carbazole (86-74-8) → 4,4'-bis(9H-carbazol-9-yl)biphenyl (58328-31-7)

Conditions	Yield
With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; copper(II) choride dihydrate; 18-crown-6 ether; potassium tert-butylate; silver carbonate at 140℃; for 48h;	181 mg

Upstream product

• 92-86-4 4-(4-bromophenyl)bromobenzene 
• 86-74-8 9H-carbazole 
• 3001-15-8 4,4'-diiodobiphenyl 
• 74367-40-1 N-(trimethylsilyl)-9H-carbazole 
• 624-38-4 para-diiodobenzene 
• 2050-68-2 4,4'-dichlorobiphenyl 
• 583-53-9 2,3-dibromobenzene 
• 13029-09-9 2,2'-dibromobiphenyl 
• 92-87-5 p,p'-diaminobiphenyl 
• 2052-07-5 2-Bromobiphenyl 
• 2915-43-7 4,4'-diazidobiphenyl 
• 4688-76-0 2-Biphenylboronic acid 
• 90-41-5 2-phenylaniline 
• 92-52-4 biphenyl 

Relevant articles and documents

Method for synthesizing 4, 4'-bis (9H-carbazole-9-yl) biphenyl compound in one step

The invention relates to a method for one-step synthesis of a 4, 4 '-bis (9H-carbazole- 9-yl) biphenyl compound, which comprises the following steps: adding a carbazole compound, a 1, 4-diiodobenzenecompound, organic alkali, a copper salt catalyst, a silver salt oxidant, a phase transfer catalyst and an organic solvent into a reactor, reacting at 120-140 DEG C for more than 12 hours in an air atmosphere, cooling after completion of the reaction, performing organic solvent rotary evaporation, extracting, washing, drying, filtering, performing organic solvent rotary evaporation, and carrying out column chromatography separation to obtain the 4, 4 '-bis (9H-carbazole -9-yl) biphenyl compound. The method provided by the invention realizes one-step synthesis of the product, and has the advantages of high product yield and low preparation cost.

Preparation method of 4,4'-dicarbazolyl biphenyl

The invention provides a preparation method of 4,4'-dicarbazolyl biphenyl. 4,4'-dichloro biphenyl and carbazole are effectively coupled to generate 4,4'-dicarbazolyl biphenyl under the action of a 2,6-bis(2,4,6-triisopropylphenyl) phenyl-dicyclohexylphosphine coordinated palladium catalyst and an organic magnesium reagent. The method is characterized in that 2,6-bis (2,4,6-triisopropylphenyl) phenyl-dicyclohexylphosphine is used as a supporting ligand of the palladium catalyst.

Rh(III)-Catalyzed C-H Activation of Boronic Acid with Aryl Azide

A Rh(III)-catalyzed C-H activation of boronic acid with aryl azide to obtain unsymmetric carbazoles, 1H-indoles, or indolines has been developed. The reaction constructs dual distinct C-N bonds via sp2/sp3 C-H activation and rhodium nitrene insertion. Synthetically, this approach represents an access to widely used carbazole derivatives. The practical application to CBP and unsymmetric TCTA derivatives has also been performed. Mechanistic experiments and DFT calculations demonstrate that a five-membered rhodacycle species is the key intermediate.