3365-85-3

Basic information

• Product Name: 4,4''-DIAMINO-P-TERPHENYL
• Synonyms: 4,4’’-diaminoterphenyl;p-Terphenyl, 4,4''-diamine;AKOS AUF02006;4,4''-DIAMINO-P-TERPHENYL;4,4'-DIAMINO-P-TERPHENYL;4,4''-Diamino-(1,1',4',1'')terphenyl;[4-[4-(4-aminophenyl)phenyl]phenyl]amine;4-[4-(4-azanylphenyl)phenyl]aniline
• CAS NO: 3365-85-3
• Molecular Formula: C₁₈H₁₆N₂
• Molecular Weight: 260.33
• EINECS: 1592732-453-0
• Mol File: 3365-85-3.mol
• Article Data: 8

Chemical Properties

• Melting Point: 242-244°C
• Boiling Point: 484.2 °C at 760 mmHg
• Flash Point: 296.3 °C
• Appearance: /
• Density: 1.159 g/cm³
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• Solubility: soluble in Tetrahydrofuran,Acetone
• PKA: 4.59±0.10(Predicted)
• BRN: 2120295
• CAS DataBase Reference: 4,4''-DIAMINO-P-TERPHENYL(CAS DataBase Reference)
• NIST Chemistry Reference: 4,4''-DIAMINO-P-TERPHENYL(3365-85-3)
• EPA Substance Registry System: 4,4''-DIAMINO-P-TERPHENYL(3365-85-3)

Safety Data

• Statements: 20/21/22-45
• Safety Statements: 45-53
• RIDADR: 2811
• PackingGroup: II
• Hazardous Substances Data: 3365-85-3(Hazardous Substances Data)

Usage

General Description

4,4''-DIAMINO-P-TERPHENYL is a chemical compound with the molecular formula C16H14N2. It is also commonly known as 1,4-Bis(4-aminophenyl)benzene or p-Phenylenediamine. 4,4''-DIAMINO-P-TERPHENYL is a white to off-white solid that is insoluble in water but soluble in organic solvents. 4,4''-DIAMINO-P-TERPHENYL is primarily used as a building block in the production of dyes, pigments, and polymers. It is also used in the synthesis of pharmaceuticals, making it an important intermediate in the chemical industry. Additionally, it has potential applications in organic electronic materials and as a component in the manufacture of adhesives and coatings. However, it is important to note that 4,4''-DIAMINO-P-TERPHENYL can be harmful if ingested, inhaled, or absorbed through the skin, and appropriate safety precautions should be taken when working with this compound.

Synthetic route

p,p-dinitro-p-terphenyl (3282-11-9) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
With palladium 10% on activated carbon; hydrazine In ethanol for 6h; Inert atmosphere; Reflux;	100%
With hydrogen; palladium on activated charcoal In tetrahydrofuran for 18h;	99%
With 3% Pd/C; hydrazine In ethanol Heating;	77%

1.4-dibromobenzene (106-37-6) + 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline (214360-73-3) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene for 24h; Schlenk technique; Inert atmosphere; Heating;	52%
With tetrakis(triphenylphosphine) palladium(0); potassium carbonate In water; toluene for 24h; Schlenk technique; Inert atmosphere; Heating;	52%
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate In 1,4-dioxane; water at 110℃; for 48h; Inert atmosphere;	48%

1,4-Phenyldiboronic acid (4612-26-4) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 76 percent / K2CO3 / tetrakis(triphenylphosphine)palladium(0) / tetrahydrofuran / 18 h / Heating 2: 99 percent / H2 / Pd/C / tetrahydrofuran / 18 h View Scheme

para-nitrophenyl bromide (586-78-7) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: 76 percent / K2CO3 / tetrakis(triphenylphosphine)palladium(0) / tetrahydrofuran / 18 h / Heating 2: 99 percent / H2 / Pd/C / tetrahydrofuran / 18 h View Scheme

[1,1';4',1'']terphenyl (92-94-4) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: fuming HNO3 / acetic acid 2: SnCl2, aq. HCl View Scheme
Multi-step reaction with 2 steps 1: HNO3 / acetic acid 2: H2, Py / Raney-Ni / 100 °C / 60800 - 65360 Torr View Scheme

meta-dinitrobenzene (99-65-0) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: N-Bromosuccinimide; sulfuric acid / 60 °C 2: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / tetrahydrofuran / 48 h / Reflux; Inert atmosphere 3: palladium 10% on activated carbon; hydrazine / ethanol / 6 h / Inert atmosphere; Reflux View Scheme

3,5-dinitrobromobenzene (18242-39-2) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / tetrahydrofuran / 48 h / Reflux; Inert atmosphere 2: palladium 10% on activated carbon; hydrazine / ethanol / 6 h / Inert atmosphere; Reflux View Scheme

4-bromo-aniline (106-40-1) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: triethylamine; bis-triphenylphosphine-palladium(II) chloride / 1,4-dioxane / 12 h / 120 °C / Schlenk technique; Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / water; toluene / 24 h / Schlenk technique; Inert atmosphere; Heating View Scheme
Multi-step reaction with 2 steps 1: bis-triphenylphosphine-palladium(II) chloride; triethylamine / 1,4-dioxane / 12 h / 120 °C / Schlenk technique; Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); potassium carbonate / water; toluene / 24 h / Schlenk technique; Inert atmosphere; Heating View Scheme

1.4-dibromobenzene (106-37-6) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: bis(dibenzylideneacetone)-palladium(0); tricyclohexylphosphine; potassium acetate / 1,4-dioxane / Heating 2: potassium carbonate; tetrakis(triphenylphosphine) palladium(0) / tetrahydrofuran; water / Heating 3: hydrazine; 3% Pd/C / ethanol / Heating View Scheme
Multi-step reaction with 3 steps 1.1: potassium acetate; bis(dibenzylideneacetone)-palladium(0); tricyclohexylphosphine / 1,4-dioxane / 4.33 h / 110 °C 2.1: potassium carbonate / tetrahydrofuran; water / 0.33 h / 100 °C 2.2: 5 h / 100 °C 3.1: hydrazine; 3% Pd/C / ethanol / 12 h / 100 °C View Scheme

benzene-1,4-diboronic acid bispinacol ester (99770-93-1) → 4,4''-diamino-p-terphenyl (3365-85-3)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: potassium carbonate / tetrahydrofuran; water / 0.33 h / 100 °C 1.2: 5 h / 100 °C 2.1: hydrazine; 3% Pd/C / ethanol / 12 h / 100 °C View Scheme

4,4''-diamino-p-terphenyl (3365-85-3) + 2-hydroxynaphthalene-1-carbaldehyde (708-06-5) → 1,1'-[(4,4''-p-terphenylene)bis(iminomethyl)]bis(2-naphthol) (1236010-45-9)

Conditions	Yield
With formic acid In methanol; dichloromethane Reflux;	98%

1-bromo-4-tert-butylbenzene (3972-65-4) + 4,4''-diamino-p-terphenyl (3365-85-3) → N4,N4,N4″,N4″-tetrakis(4-(tert-butyl)phenyl)-[1,1′:4′,1″-terphenyl]-4,4″-diamine

Conditions	Yield
With tri-tert-butyl phosphine; potassium tert-butylate; bis(dibenzylideneacetone)-palladium(0) In toluene at 80℃; for 69.5h; Inert atmosphere;	97%

3,5-di-tert-butyl-2-hydroxybenzaldehyde (37942-07-7) + 4,4''-diamino-p-terphenyl (3365-85-3) → 6,6'-[(4,4"-p-terphenylene)bis(iminomethyl)]bis(2,4-di-tert-butylphenol)

Conditions	Yield
With formic acid In methanol; dichloromethane Reflux;	93%

3-tert-butyl-2-hydroxybenzaldehyde (24623-65-2) + 4,4''-diamino-p-terphenyl (3365-85-3) → 6,6'-[(4,4"-p-terphenylene)bis(iminomethyl)]bis(2-tert-butylphenol)

Conditions	Yield
With formic acid In methanol; dichloromethane Reflux;	91%

4,4''-diamino-p-terphenyl (3365-85-3) + Ethoxycarbonyl isothiocyanate (16182-04-0) → 4,4''-bis(N'-ethoxycarbonylthiourea)-[1,1';4',1'']terphenyl (916653-34-4)

Conditions	Yield
In dichloromethane at 20℃; for 24h;	89%

4,4''-diamino-p-terphenyl (3365-85-3) → 4,4''-bis(N'-ethoxycarbonylthiourea)-[1,1';4',1'']terphenyl (916653-34-4)

Conditions	Yield
With Ethoxycarbonyl isothiocyanate In dichloromethane at 20℃; for 24h;	89%

4,4''-diamino-p-terphenyl (3365-85-3) + salicylaldehyde (90-02-8) → 2,2'-[(4,4"-p-terphenylene)bis(iminomethyl)]-diphenol

Conditions	Yield
With formic acid In methanol; dichloromethane Reflux;	84%

bromobenzene (108-86-1) + 4,4''-diamino-p-terphenyl (3365-85-3) → N4,N4”-diphenylamine[1,1':4',1”-terphenyl]-4,4”-diamine

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); tri-tert-butyl phosphine; sodium t-butanolate In toluene for 5h; Inert atmosphere; Reflux;	83.6%

4,4''-diamino-p-terphenyl (3365-85-3) + N,N'-bis-Boc-S-methyl-isothiourea (322474-21-5) → 4,4''-bis-(N',N''-t-butoxycarbonyl)guanidino-[1,1';4',1'']terphenyl

Conditions	Yield
With triethylamine; mercury dichloride In N,N-dimethyl-formamide at 20℃; for 24h;	79%
With triethylamine; mercury dichloride In N,N-dimethyl-formamide at 20℃; for 24h;	79%

4,4''-diamino-p-terphenyl (3365-85-3) → 4,4'-diazidoterphenyl

Conditions	Yield
Stage #1: 4,4''-diamino-p-terphenyl With hydrogenchloride; sodium nitrite In water at 0℃; for 0.5h; Cooling with ice; Stage #2: With sodium azide In water at 0℃; for 2h; Cooling with ice;	78.1%
Stage #1: 4,4''-diamino-p-terphenyl With sodium nitrite In water for 2h; Stage #2: With sodium azide In water for 2h;	45.6%

4,4''-diamino-p-terphenyl (3365-85-3) + 4β-bromo-4-desoxypodophyllotoxin → 4'',4'''-[bis-(4β-N-4-desoxypodophyllotoxin)]-p-terphenyldiamine

Conditions	Yield
With tetra-(n-butyl)ammonium iodide; triethylamine In tetrahydrofuran at 20℃; for 6h;	75%

4,4''-diamino-p-terphenyl (3365-85-3) + ethyl iodide (75-03-6) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → p,p"-bis-diethylamino-p-terphenyl (53693-66-6)

Conditions	Yield
With calcium carbonate In N-methyl-acetamide; water	70%

4-hydroxyphthalic anhydride (27550-59-0) + 4,4''-diamino-p-terphenyl (3365-85-3) → C34H20N2O6

Conditions	Yield
With propionic acid at 150℃; for 10h;	70%

4,4''-diamino-p-terphenyl (3365-85-3) → meri-4,4''-diamino-p-terphenylochinon-diimoniumperchlorat

Conditions	Yield
With potassium dichromate; perchloric acid; acetic acid In water	55.5%

(CO)5CrC(OCH2CH3)CCC6H4CCC(OCH2CH3)Cr(CO)5 + 4,4''-diamino-p-terphenyl (3365-85-3) → [(CO)5CrC(OCH2CH3)CHC(NHC6H4C6H4C6H4NH2)]2C6H4

Conditions	Yield
In tetrahydrofuran Schlenk techniques used, 7c (0.32 mmol) added to THF soln. of 5a (0.16 mmol) in THF under Ar, stirred for 2 h at room temp.; solvent removed under vac., chromd. (SiO2, hexane/AcOEt) under Ar pressure; elem. anal.;	47%

2'-bromospiro[cyclopentane-1,9'-fluorene] (797056-47-4) + 4,4''-diamino-p-terphenyl (3365-85-3) → C86H72N2

Conditions	Yield
With sodium t-butanolate; bis-triphenylphosphine-palladium(II) chloride In xylene at 130℃; for 24h;	41%

2'-bromo(spiro[cyclohexane-1,9'[9H]fluoren]) (797056-48-5) + 4,4''-diamino-p-terphenyl (3365-85-3) → C90H80N2

Conditions	Yield
With sodium t-butanolate; bis-triphenylphosphine-palladium(II) chloride In xylene at 130℃; for 24h;	36%

copper(II) perchlorate hexahydrate + 2,2',2''-triaminotriethylamine (4097-89-6) + 4,4''-diamino-p-terphenyl (3365-85-3) → [(copper(II))2(tris(2-aminoethyl)amine)2(4,4'-p-terphenylenediamine)](perchlorate)4

Conditions	Yield
In N,N-dimethyl-formamide tren (2 mmol) added to soln. of Cu(ClO4)2*6H2O (2 mmol) under stirring, NH2(C6H4)3NH2 (1 mmol) soln. added dropwise; soln. filtered off, Et2O slow diffused into soln., crystd. for one week at room temp., collected, air dried; elem. anal.;	31%

phosgene (75-44-5) + 4,4''-diamino-p-terphenyl (3365-85-3) → terphenyl-4,4''-diisocyanate

Conditions	Yield
In various solvent(s) for 3h; Condensation; Heating;	20%

4,4''-diamino-p-terphenyl (3365-85-3) + α-chlorobenzaldehyde phenylhydrazone (918497-00-4) → C44H30N6

Conditions	Yield
Stage #1: 4,4''-diamino-p-terphenyl; α-chlorobenzaldehyde phenylhydrazone With triethylamine In tetrahydrofuran for 24h; Reflux; Stage #2: With palladium 10% on activated carbon; 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane for 24h;	14%

(tris(3,5-dimethylpyrazol-1-yl)hydroborate)(nitrosyl)diiodomolybdenum-toluene (1/1) + 4,4''-diamino-p-terphenyl (3365-85-3) → [MoNOBH((CH3)2C3HN2)3(NHC6H4)2C6H4]3

Conditions	Yield
With Na In toluene soln. of Mo-complex and ligand in toluene contg. Na was heated under reflux, stirred for 18 h under N2, cooled; filtered, solvent was removed in vacuo, sepd. by column chromy. with CH2Cl2/hexane; elem. anal.;	2%

1,4-bis(thiophen-2-yl)butane-1,4-dione (13669-05-1) + 4,4''-diamino-p-terphenyl (3365-85-3) → C42H28N2S4

Conditions	Yield
With acetic acid In toluene for 48h; Knorr Pyrazole Synthesis; Inert atmosphere; Reflux;
In acetic acid; toluene at 130℃; for 72h; Inert atmosphere;	0.24%

4,4''-diamino-p-terphenyl (3365-85-3) → 1,4-bis[2-(4-hydroxyphenyl)-2-propylene]benzene (4084-45-1)

Conditions	Yield
With hydrogenchloride Diazotization.Einleiten von Wasserdampf;

4,4''-diamino-p-terphenyl (3365-85-3) + phenyl Salicylate (118-55-8) → N,N'-p-terphenyl-4,4''-diyl-bis-salicylamide (117042-61-2)

Conditions	Yield
With 1-Methylnaphthalene

4,4''-diamino-p-terphenyl (3365-85-3) + 2-Methoxybenzoyl chloride (21615-34-9) → 4,4''-Bis-(2-methoxy-benzoylamino)-p-terphenyl (133326-34-8)

Conditions	Yield
With pyridine

Upstream product

• 99770-93-1 benzene-1,4-diboronic acid bispinacol ester 
• 106-37-6 1.4-dibromobenzene 
• 106-40-1 4-bromo-aniline 
• 214360-73-3 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline 
• 18242-39-2 3,5-dinitrobromobenzene 
• 99-65-0 meta-dinitrobenzene 
• 92-94-4 [1,1';4',1'']terphenyl 
• 586-78-7 para-nitrophenyl bromide 
• 4612-26-4 1,4-Phenyldiboronic acid 
• 3282-11-9 p,p-dinitro-p-terphenyl 

Downstream Products

• 17788-93-1 4,4''-bis-cyano[1,1';4',1'']terphenyl 
• 133326-34-8 4,4''-Bis-(2-methoxy-benzoylamino)-p-terphenyl 
• 117042-61-2 N,N'-p-terphenyl-4,4''-diyl-bis-salicylamide 
• 4084-45-1 1,4-bis[2-(4-hydroxyphenyl)-2-propylene]benzene 

Relevant articles and documents

Suzuki cross-coupling method to prepare 4,4″-diamino-p-terphenyl

The synthesis of 4,4″-dinitro-p-terphenyl is accomplished by double Suzuki cross-coupling. The product was reduced catalytically to give 4,4″-diamino-p-terphenyl in 75% overall yield. Copyright Taylor & Francis Group, LLC.

DIAMINE COMPOUND, AND POLYIMIDE PRECURSOR AND POLYIMIDE FILM PREPARED BY USING THE SAME

The present invention disclosed a novel diamine compound including a structure in which a phenylene linker (L) connecting an intramolecular imide ring and the imide ring is bonded to a phenyl ring substituted with -NH-(C=O)- or -O-(C=O)-. A polyimide film prepared by polymerizing the novel diamine compound has not only improved mechanical and thermal properties, but also an excellent refractive index.COPYRIGHT KIPO 2021

MECHANICALLY SHAPED 2-DIMENSIONAL COVALENT ORGANIC FRAMEWORKS

Covalent organic frameworks (COFs) usually crystallize as insoluble powders and their processing for suitable devices has been thought to be limited. Here, it is demonstrated that COFs can be mechanically pressed into shaped objects having anisotropic ordering with preferred orientation between the hk0 and 00/ crystallographic planes. Pellets prepared from bulk COF powders impregnated with LiC1O4 displayed room temperature conductivity up to 0.26 mS cm-1 and stability up to 10.0 V (vs. Li+/Li0). This outcome portends use of COFs as solid-state electrolytes in batteries.