2657-87-6

Basic information

• Product Name: 3,4'-Oxydianiline
• Synonyms: 3,4'-ODA;4-(3-AMINO-PHENOXY)-PHENYLAMINE;3,4'-DPE;3,4'-DIAMINODIPHENYL ETHER;3,4'-DIAMINOPHENYL ETHER;3-(4-aminophenoxy)aniline;3,4'-Oxydianiline(3,4'-ODA);3,4'-DiaminodiphenylEther>99.0%
• CAS NO: 2657-87-6
• Molecular Formula: C₁₂H₁₂N₂O
• Molecular Weight: 200.24
• EINECS: 220-190-0
• Product Categories: Biphenyl & Diphenyl ether;Amines;Miscellaneous;Diphenyl Ethers (for High-Performance Polymer Research);Functional Materials;Reagent for High-Performance Polymer Research;Amine Monomers;Monomers;Primary Amines
• Mol File: 2657-87-6.mol
• Article Data: 6

Chemical Properties

• Melting Point: 67-71 °C(lit.)
• Boiling Point: 206.5 °C1 mm Hg(lit.)
• Flash Point: 209.9 °C
• Appearance: light brown powder
• Density: 1.1131 (rough estimate)
• Refractive Index: 1.6660 (estimate)
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• Solubility: Chloroform, Methanol
• PKA: 4.78±0.10(Predicted)
• CAS DataBase Reference: 3,4'-Oxydianiline(CAS DataBase Reference)
• NIST Chemistry Reference: 3,4'-Oxydianiline(2657-87-6)
• EPA Substance Registry System: 3,4'-Oxydianiline(2657-87-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• RIDADR: UN2811 - class 6.1 - PG 2 - EHS - Toxic solids, organic, n.o.s., HI: all
• WGK Germany: 3
• Hazardous Substances Data: 2657-87-6(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 2657-87-6 differently. You can refer to the following data:
1. 3,4'-Oxydianiline is an ether organic substance and can be used as a pharmaceutical intermediate.
2. 3,4''-Diaminodiphenyl Ether, can be used for the synthesis of asymmetric soluble polyimides. It can also be used as a spacer in the preparation of glycine-based molecular tongs as inhibitors of β-amyloid peptide Aβ1-40 aggregation in vitro.

Synthetic route

4-chlorobenzonitrile (100-00-5) + m-Hydroxyaniline (591-27-5) → 3,4'-diaminodiphenyl ether (2657-87-6)

Conditions	Yield
Stage #1: 4-chlorobenzonitrile; m-Hydroxyaniline With potassium carbonate; sodium hydrogensulfite In N,N-dimethyl-formamide at 100 - 120℃; for 10h; Inert atmosphere; Stage #2: With iron(III) chloride; 5%-palladium/activated carbon; hydrogen at 60 - 80℃; under 3750.38 Torr; for 2h; Autoclave;	96.1%

m-Hydroxyaniline (591-27-5) + p-aminoiodobenzene (540-37-4) → 3,4'-diaminodiphenyl ether (2657-87-6)

Conditions	Yield
With 2-Picolinic acid; potassium phosphate; copper(l) iodide In dimethyl sulfoxide at 80℃; for 24h; Inert atmosphere;	54%

1-nitro-3-(4-nitrophenoxy)benzene (2914-72-9) → 3,4'-diaminodiphenyl ether (2657-87-6)

Conditions	Yield
With hydrogenchloride; tin

4-(3-nitrophenoxy)phenylamine (60732-27-6) → 3,4'-diaminodiphenyl ether (2657-87-6)

Conditions	Yield
With hydrazine

potassium 4-nitrophenolate (1124-31-8) → 3,4'-diaminodiphenyl ether (2657-87-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: copper-powder / 150 °C 2: tin; aqueous hydrochloric acid View Scheme

4-Fluoronitrobenzene (350-46-9) → 3,4'-diaminodiphenyl ether (2657-87-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: copper-powder / 150 °C 2: tin; aqueous hydrochloric acid View Scheme

3-amino-cyclohex-2-enone (5220-49-5) → 3,4'-diaminodiphenyl ether (2657-87-6)

3-amino-4'-nitrodiphenyl ether (22528-34-3) → 3,4'-diaminodiphenyl ether (2657-87-6)

Conditions	Yield
With 0.5% Pd on alumina; hydrogen In N,N-dimethyl-formamide at 30℃; for 7h; Green chemistry;	> 99.9 %Spectr.

3,4'-diaminodiphenyl ether (2657-87-6) + epichlorohydrin (106-89-8) → N,N,N',N'-tetraglycidyl-3,4'-diaminodiphenyl ether (129998-27-2)

Conditions	Yield
With tetra(n-butyl)ammonium hydrogensulfate In water; toluene at 80℃; for 15h;	100%

3,4'-diaminodiphenyl ether (2657-87-6) + indole-2,3-dione (91-56-5) → 3,3'-[oxybis[(3,1)-(4',1')phenylenenitrilo]]bis[1,3-dihydro-2H-indol-2-one]

Conditions	Yield
With acetic acid In ethanol for 28h; Heating;	91%
In water at 20℃; for 45h;	80%
In ethanol Heating;

3,4'-diaminodiphenyl ether (2657-87-6) + 9-anthracene aldehyde (642-31-9) → (E)-N-(anthracen-10-ylmethylene)-3-(4-[(E)-anthracen-10-ylmethyleneamino]phenoxy)benzeneamine (1251936-16-9)

Conditions	Yield
In ethanol Reflux;	88%

3,4'-diaminodiphenyl ether (2657-87-6) + N,N'-bis-Boc-S-methyl-isothiourea (322474-21-5) → 3,4’-bis[2,3-di(tert-butoxycarbonyl)guanidino]diphenylether

Conditions	Yield
With triethylamine; mercury dichloride In dichloromethane at 0 - 20℃;	87%

3,4'-diaminodiphenyl ether (2657-87-6) + 4,4'-(1,1,1,3,3,3-hexafluoroisopropylidene)diphthalic anhydride (1107-00-2) + 2-(4'-aminophenyl)ethyl alcohol (104-10-9) → linear fluorine-containing hydroxy-terminated polyimide

Conditions	Yield
Stage #1: 3,4'-diaminodiphenyl ether; 4,4'-(1,1,1,3,3,3-hexafluoroisopropylidene)diphthalic anhydride; 2-(4'-aminophenyl)ethyl alcohol In 1-methyl-pyrrolidin-2-one at 20℃; for 12h; Stage #2: In para-xylene at 180℃; for 6h; Further stages.;	83%

3,4'-diaminodiphenyl ether (2657-87-6) → 2,3',4,5',6-pentabromo-3,4'-diaminodiphenyl ether

Conditions	Yield
With bromine In acetic acid at 35℃; for 1h;	81%

3,4'-diaminodiphenyl ether (2657-87-6) + tert-butyl N-({[(tert-butoxy)carbonyl]amino}methanethioyl)carbamate (145013-05-4) → 3-amino-{4'-[2,3-di(tert-butoxycarbonyl)]guanidino}diphenyl ether

Conditions	Yield
With triethylamine; mercury dichloride In dichloromethane at 0 - 20℃;	77%
With triethylamine; mercury dichloride In dichloromethane at 25℃; for 12h;	51%

N-tert-butoxycarbonyl-N’-phenylthiourea (1037587-67-9) + 3,4'-diaminodiphenyl ether (2657-87-6) → 3-amino-4'-[2-(tert-butoxycarbonyl)-3-phenylguanidino]diphenyl ether

Conditions	Yield
With triethylamine; mercury dichloride In dichloromethane at 0 - 20℃; for 4h;	76%

3,4'-diaminodiphenyl ether (2657-87-6) + 3-nitro-4-chloro-1,8-naphthalene dicarboxylic acid anhydride (52871-22-4) → C36H18N4O11

Conditions	Yield
In ethanol; N,N-dimethyl-formamide for 0.5h; Heating;	75%

3,4'-diaminodiphenyl ether (2657-87-6) + tert-butyl N-({[(tert-butoxy)carbonyl]amino}methanethioyl)carbamate (145013-05-4) → 3-amino-{4'-[2,3-di(tert-butoxycarbonyl)]guanidino}diphenyl ether + C23H30N4O5

Conditions	Yield
With triethylamine; mercury dichloride In dichloromethane at 0 - 20℃;	A 75% B 25%

2-(3,5-dinitrobenzamido)acetic acid (16533-70-3) + 3,4'-diaminodiphenyl ether (2657-87-6) → C30H22N8O13 (1037570-01-6)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	70%

3,4'-diaminodiphenyl ether (2657-87-6) + benzoyl chloride (98-88-4) → C26H20N2O3 (1037569-97-3)

Conditions	Yield
With (+/-)-propylene oxide In tetrahydrofuran at 20℃;	70%

3,4'-diaminodiphenyl ether (2657-87-6) + -glycin (52071-01-9) → C40H44N6O13 (1037570-05-0)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	69%

3,4'-diaminodiphenyl ether (2657-87-6) + hippuroyl-Gly-Gly (31384-90-4) → C38H38N8O9 (1037570-06-1)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	68%

3,4'-diaminodiphenyl ether (2657-87-6) + 3,5-dinitrobenoyl chloride (99-33-2) → C26H16N6O11 (1037569-98-4)

Conditions	Yield
With (+/-)-propylene oxide In tetrahydrofuran at 20℃;	68%

3,4'-diaminodiphenyl ether (2657-87-6) + 2-thioxo-imidazolidine-1,3-dicarboxylic acid di-tert-butyl ester (173300-83-9) → 3,4’-bis[2,3-di(tert-butoxycarbonyl)-2-iminoimidazolidino]diphenyl ether

Conditions	Yield
With triethylamine; mercury dichloride In dichloromethane at 0 - 20℃;	68%

3,4'-diaminodiphenyl ether (2657-87-6) + N-(4-chloro-3-trifluoromethylphenyl)-N’-(tert-butoxycarbonyl)thiourea → 3-amino-4'-[2-(tert-butoxycarbonyl)-3-(4-chloro-3-trifluoromethyl)guanidino]diphenyl ether

Conditions	Yield
With triethylamine; mercury dichloride In dichloromethane at 0 - 20℃; for 4h;	68%

3,4'-diaminodiphenyl ether (2657-87-6) + 2-hydroxy-3-(morpholinomethyl)benzaldehyde → 2-((3-(4-(2-hydroxy-3-(morpholinomethyl)benzylideneamino)phenoxy)phenylimino)methyl)-6-(morpholinomethyl)phenol

Conditions	Yield
In ethanol Reflux;	68%

3,4'-diaminodiphenyl ether (2657-87-6) + N-[N-(3,5-dinitro-benzoyl)-glycyl]-glycine (1037569-82-6) → C34H28N10O15 (1037570-04-9)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	66%

ethyl-3,3,3-trifluoropyruvate (13081-18-0) + 3,4'-diaminodiphenyl ether (2657-87-6) → 6-(4-aminophenoxy)-3-hydroxy-3-(trifluoromethyl)indolin-2-one (1400992-23-5)

Conditions	Yield
In 1,2-dichloro-benzene at 20 - 150℃; for 0.416667h; Microwave irradiation;	66%

N-(N'-benzoyl-2-aminoethanoyl)-2-aminoethanoic acid (1145-32-0) + 3,4'-diaminodiphenyl ether (2657-87-6) → C34H32N6O7 (1037570-03-8)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	65%

3,4'-diaminodiphenyl ether (2657-87-6) + N-(3,5-dinitro-benzoyl)-glycyl=>glycyl=>glycine (1037569-83-7) → C38H34N12O17 (1037570-07-2)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	65%

Hippuric Acid (495-69-2) + 3,4'-diaminodiphenyl ether (2657-87-6) → C30H26N4O5 (1037570-00-5)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	64%

3,4'-diaminodiphenyl ether (2657-87-6) + 3,4,5-Trimethoxybenzoyl chloride (4521-61-3) → C32H32N2O9 (1037569-99-5)

Conditions	Yield
With (+/-)-propylene oxide In tetrahydrofuran at 20℃;	64%

3,4'-diaminodiphenyl ether (2657-87-6) + (3,4,5-trimethoxybenzoylamino)acetic acid (40915-27-3) → C36H38N4O11 (1037570-02-7)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	63%

3,4'-diaminodiphenyl ether (2657-87-6) + -glycin (52071-02-0) → C44H50N8O15 (1037570-08-3)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	61%

[2-(cyclohexanecarbonylamino)acetylamino]acetic acid (1037569-77-9) + 3,4'-diaminodiphenyl ether (2657-87-6) → C34H44N6O7 (1037569-78-0)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	58%

3,4'-diaminodiphenyl ether (2657-87-6) + N-[N-(3,5-dinitro-benzoyl)-glycyl]-glycine (1037569-82-6) → C23H20N6O8 (1037569-79-1)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; for 15h;	56%

3,4'-diaminodiphenyl ether (2657-87-6) + 5-[(3,4,5-trimethoxybenzoyl)amino]pentanoic acid (32407-06-0) → C42H50N4O11 (1037569-76-8)

Conditions	Yield
With benzotriazol-1-yloxyl-tris-(pyrrolidino)-phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃;	55%

Upstream product

• 2914-72-9 1-nitro-3-(4-nitrophenoxy)benzene 
• 22528-34-3 3-amino-4'-nitrodiphenyl ether 
• 100-00-5 4-chlorobenzonitrile 
• 591-27-5 m-Hydroxyaniline 
• 540-37-4 p-aminoiodobenzene 
• 5220-49-5 3-amino-cyclohex-2-enone 
• 350-46-9 4-Fluoronitrobenzene 
• 1124-31-8 potassium 4-nitrophenolate 
• 60732-27-6 4-(3-nitrophenoxy)phenylamine 

Downstream Products

• 127829-13-4 N,N'-bis(2-oxazolinyl)-3,4'-diaminodiphenyl ether 
• 129998-27-2 N,N,N',N'-tetraglycidyl-3,4'-diaminodiphenyl ether 
• 1037569-98-4 C₂₆H₁₆N₆O₁₁ 
• 1037569-97-3 C₂₆H₂₀N₂O₃ 
• 1037569-99-5 C₃₂H₃₂N₂O₉ 
• 1037569-79-1 C₂₃H₂₀N₆O₈ 

Relevant articles and documents

Method for preparing 3, 4'-diaminodiphenyl ether

The invention discloses a method for preparing 3, 4'-diaminodiphenyl ether, which mainly comprises the following steps: adding m-aminophenol, an acid-binding agent and a solvent into a condensation reaction kettle, stirring, heating under the protection of inert gas, keeping the temperature at 100-120 DEG C, dropwisely adding p-nitrochlorobenzene, keeping the temperature for 2-4 hours after 5-7 hours, and continuing the reaction; after the reaction is finished, filtering to remove inorganic salt, transferring a filtrate into a hydrogenation kettle, adding a noble metal catalyst and a cocatalyst, performing nitrogen replacement, maintaining the temperature at 60-80 DEG C, and introducing hydrogen for catalytic hydrogenation under the hydrogen pressure of not more than 0.5 MPa; after the reaction is finished, filtering out the catalyst, distilling the filtrate, removing the solvent, rectifying, collecting 206-210 DEG C (2-3 mmHg) fraction which is white 3, 4'-diaminodiphenyl ether, and packaging under the protection of nitrogen. The method is short in process step, low in energy consumption and low in production cost, the content of the obtained 3, 4'-diaminodiphenyl ether is largerthan 99.5%, and the total molar yield is larger than 93%.

Orthogonal Cu- and Pd-based catalyst systems for the O- and N-arylation of aminophenols

O- or N-arylated aminophenol products constitute a common structural motif in various potentially useful therapeutic agents and/or drug candidates. We have developed a complementary set of Cu- and Pd-based catalyst systems for the selective O- and N-arylation of unprotected aminophenols using aryl halides. Selective O-arylation of 3- and 4-aminophenols is achieved with copper-catalyzed methods employing picolinic acid or CyDMEDA, trans-N,N′-dimethyl-1,2- cyclohexanediamine, respectively, as the ligand. The selective formation of N-arylated products of 3- and 4-aminophenols can be obtained with BrettPhos precatalyst, a biarylmonophosphine-based palladium catalyst. 2-Aminophenol can be selectively N-arylated with CuI, although no system for the selective O-arylation could be found. Coupling partners with diverse electronic properties and a variety of functional groups can be selectively transformed under these conditions.

Thermoplastic resin composition and a method of molding the same

This invention provides a thermoplastic resin composition comprising a thermoplastic resin and 0.1 to 100 parts by weight, per 100 parts by weight of the thermoplastic resin, of an imide compound prepared, e.g., by dehydration condensation of 1,2,3,4-butanetetracarboxylic acid or a monoanhydride or a dianhydride thereof with a primary amine, and a method of molding the resin composition.