13680-35-8

Basic information

• Product Name: 4,4'-Methylenebis(2,6-diethylaniline)
• Synonyms: 4,4'-METHYLENEBIS(2,6-DIETHYLANILINE);LONZACURE(R) M-DEA;LABOTEST-BB LT00053356;4,4’-methylenebis[2,6-diethyl-benzenamin;4,4’-methylenebis[2,6-diethyl-Benzenamine;4,4'-Methylene-(Bis(2,6-Diethylaniline) (MDEA);4,4'-METHYLENEBIS(2,6-DIETHYLANILINE), 9 9%;Benzenamine, 4,4-methylenebis2,6-diethyl-
• CAS NO: 13680-35-8
• Molecular Formula: C₂₁H₃₀N₂
• Molecular Weight: 310.48
• EINECS: 237-185-4
• Product Categories: Industrial/Fine Chemicals;Miscellaneous;Amine Monomers;Monomers;Primary Amines;Curing Agent for PU Elastomer & Epoxides
• Mol File: 13680-35-8.mol
• Article Data: 2

Chemical Properties

• Melting Point: 88-90 °C(lit.)
• Boiling Point: 205 °C / 0.5mmHg
• Flash Point: 281 °C
• Appearance: Crystalline powder
• Density: 0.90
• Vapor Pressure: 0Pa at 25℃
• Storage Temp.: Keep in dark place,Inert atmosphere,Room temperature
• Solubility: soluble in Toluene
• PKA: 4.88±0.25(Predicted)
• Water Solubility: 440μg/L at 20℃
• CAS DataBase Reference: 4,4'-Methylenebis(2,6-diethylaniline)(CAS DataBase Reference)
• NIST Chemistry Reference: 4,4'-Methylenebis(2,6-diethylaniline)(13680-35-8)
• EPA Substance Registry System: 4,4'-Methylenebis(2,6-diethylaniline)(13680-35-8)

Safety Data

• Hazard Codes: Xn
• Statements: 22-36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• Hazardous Substances Data: 13680-35-8(Hazardous Substances Data)

Usage

Chemical Properties

Crystalline Powder

Uses

LONZACURE(R) M-DEA is an excellent chain extender for polyurethanes (PU) and also a curing agent for epoxides (EP). It provides improved mechanical and dynamic properties which cannot be achieved with standard formulations.

Flammability and Explosibility

Notclassified

Synthetic route

formaldehyd (50-00-0) + 2,6-diethylaniline (579-66-8) + 2-isopropyl-6-methylaniline (5266-85-3) → M-MIPADEA + methylene-1,1-bis(2-isopropyl-6-methylaniline) (16298-38-7) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8)

Conditions	Yield
With sulfuric acid In water; isopropyl alcohol at 60℃; for 5.5h; Product distribution / selectivity;
With sulfuric acid In water; isopropyl alcohol at 60℃; for 5.5h; Product distribution / selectivity;

formaldehyd (50-00-0) + 2,6-diethylaniline (579-66-8) + 2-isopropyl-6-methylaniline (5266-85-3) → M-MIPADEA + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8)

Conditions	Yield
With sulfuric acid In water; isopropyl alcohol at 60℃; for 5.5h; Product distribution / selectivity;

formaldehyd (50-00-0) + 2,6-diethylaniline (579-66-8) → 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8)

Conditions	Yield
Stage #1: 2,6-diethylaniline With hydrogenchloride In water at 50 - 55℃; for 0.5h; Inert atmosphere; Stage #2: formaldehyd In water at 90 - 95℃; for 2h; Temperature;

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) (106246-33-7)

Conditions	Yield
Stage #1: 4,4′-methylenebis(2,6-diethylaniline) With hydrogenchloride In water at 20℃; for 0.25h; Stage #2: With dihydrogen peroxide In water at 45 - 65℃; for 3h;	99.3%
With chlorine; acetic acid at 50 - 55℃; Reagent/catalyst; Temperature;	92.8%

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → bis-(3,5-diethyl-4-aminocyclohexyl)-methane (60469-05-8)

Conditions	Yield
With Ru/Al2O3; hydrogen In cyclohexane at 110℃; under 15001.5 Torr;

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + salicylaldehyde (90-02-8) → [(HOC6H4-o-C(H)=N-2,6-(CH3CH2)2(4-C6H2))2-4-CH2] (849704-38-7)

Conditions	Yield
toluene-4-sulfonic acid In methanol for 12h; Heating / reflux;	95%

3-tert-butyl-2-hydroxybenzaldehyde (24623-65-2) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → [(HO-(3-tert-butyl)C6H3-o-C(H)=N-2,6-(ethyl)2C6H2)2-4-CH2] (937721-14-7)

Conditions	Yield
toluene-4-sulfonic acid In methanol for 12h; Heating / reflux;	95%

maleic anhydride (108-31-6) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → di(3,5-diethyl-4-maleimido-phenyl)methane (105357-12-8)

Conditions	Yield
Stage #1: maleic anhydride; 4,4′-methylenebis(2,6-diethylaniline) In toluene Stage #2: With methanesulfonic acid In toluene for 1.5h; Reflux;	96%

formaldehyd (50-00-0) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → C66H90N6

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 100 - 150℃; for 12h;	99%

quinoline 2-carbaldehyde (5470-96-2) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → C41H40N4

Conditions	Yield
In ethanol at 20℃; for 24h;	50%

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + butanone (78-93-3) → N,N'-di-sec-butyl-4,4'-methylenebis(2,6-diethylbenzeneamine) (910915-05-8)

Conditions	Yield
With amberlyst-15; hydrogen; Pt(S)/C at 22 - 95℃; under 7224.57 Torr; for 3h; sulfonated divinylbenzene/styrene copolymer H ion form; Product distribution / selectivity; Autoclave;	94 %Chromat.
With amberlyst-15; hydrogen; Pt(S)/C In tetrahydrofuran at 22 - 120℃; under 5414.51 - 7224.57 Torr; for 5h; sulfonated divinylbenzene/styrene copolymer H ion form; Product distribution / selectivity; Autoclave;	86 %Chromat.

4-formyl-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (950-81-2) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → CH2[C6H2(C2H5)2NCHC3N2(CH3)2(C6H5)O]2 (1296869-06-1)

Conditions	Yield
With formic acid In methanol for 4h; Reflux; Inert atmosphere;	41.4%

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + butanone (78-93-3) → C25H36N2 + N,N'-di-sec-butylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) (910915-11-6)

Conditions	Yield
With Amberlist-15 In hexanes at 40℃; for 49h; sulfonated divinylbenzene/styrene copolymer H ion form; Heating / reflux;	A n/a B 94.7 %Chromat.

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + butanone (78-93-3) → N-sec-butyl-4,4'-methylenebis(2,6-diethylbenzeneamine) + N,N'-di-sec-butyl-4,4'-methylenebis(2,6-diethylbenzeneamine) (910915-05-8)

Conditions	Yield
With hydrogen; Pt(S)/C In toluene at 22 - 130℃; under 6448.83 Torr; for 19.5h; Product distribution / selectivity; Autoclave;	A 4 %Chromat. B 96 %Chromat.

6-(hydroxymethyl)picolinaldehyde (39621-11-9) + tetrakis(actonitrile)copper(I) hexafluorophosphate (64443-05-6) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → 2C35H40N4O2*2Cu(1+)*2F6P(1-)

Conditions	Yield
Stage #1: 6-(hydroxymethyl)picolinaldehyde; 4,4′-methylenebis(2,6-diethylaniline) In methanol at 20℃; for 0.5h; Stage #2: tetrakis(actonitrile)copper(I) hexafluorophosphate In methanol at 20℃; for 15h;	36%

pyridine-2-carbaldehyde (1121-60-4) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → 4,4'-methylene-N,N'-(2-pyridinylmethylene)-bis(2,6-diethylanil)

Conditions	Yield
With toluene-4-sulfonic acid In ethanol at 20℃; for 48h;	61%
In methanol

phenyl(pyridin-2-yl)methanone (91-02-1) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → 4,4'-methylene-N,N'-(phenyl-2-pyridinylmethlene)-bis(2,6-diethyl-anil)

Conditions	Yield
With tetraethoxy orthosilicate; sulfuric acid at 150℃; for 10h;	73%

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + acetone (67-64-1) → N-isopropylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) + N,N'-diisopropylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) (910915-14-9)

Conditions	Yield
With amberlyst-15 for 24h; sulfonated divinylbenzene/styrene copolymer H ion form; Molecular sieve; Heating / reflux;

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + 1-Chloromethylnaphthalene (86-52-2) → 4′-methylenebis(2,6-diethyl-N-(naphthalen-1-ylmethyl)aniline)

Conditions	Yield
With potassium carbonate In acetonitrile at 83℃; for 24h;

4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) + Phenyl glycidyl ether (122-60-1) → 1-{4-[3,5-diethyl-4-(2-hydroxy-3-phenoxy-propylamino)-benzyl]-2,6-diethyl-phenylamino}-3-phenoxy-propan-2-ol

Conditions	Yield
at 100℃; for 5h;

6-(hydroxymethyl)picolinaldehyde (39621-11-9) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → (6-{[(E)-4-(3,5-Diethyl-4-{[1-(6-hydroxymethyl-pyridin-2-yl)-meth-(E)-ylidene]-amino}-benzyl)-2,6-diethyl-phenylimino]-methyl}-pyridin-2-yl)-methanol

dichloro(1,5-cyclooctadiene)palladium(II) (12107-56-1) + 4-formyl-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (950-81-2) + 4,4’-methylenebis(2,6-diethylaniline) (13680-35-8) → CH2[C6H2(C2H5)2NCHC3N2(CH3)2(C6H5)OPdCl2]2 (1296869-09-4)

Conditions	Yield
In acetic acid under N2, Schlenk techniques; proper 4,4'-methylene bis-(2,6-dialkylaniline), antipyrine-4-carboxaldehyde, PdCl2(COD) added to glacial CH3COOH, reflux (12 h), cooled to room temp.; pptd. (Et2O), solid washed (MeOH, ether); elem. anal.;

Upstream product

• 50-00-0 formaldehyd 
• 579-66-8 2,6-diethylaniline 
• 5266-85-3 2-isopropyl-6-methylaniline 

Downstream Products

• 910915-11-6 N,N'-di-sec-butylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) 
• 910915-05-8 N,N'-di-sec-butyl-4,4'-methylenebis(2,6-diethylbenzeneamine) 
• 106246-33-7 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) 
• 1296869-06-1 CH₂[C₆H₂(C₂H₅)2NCHC₃N₂(CH₃)2(C₆H₅)O]2 
• 105357-12-8 di(3,5-diethyl-4-maleimido-phenyl)methane 
• 937721-14-7 [(HO-(3-tert-butyl)C₆H₃-o-C(H)=N-2,6-(ethyl)2C₆H₂)2-4-CH₂] 
• 910915-14-9 N,N'-diisopropylidene-4,4'-methylenebis(2,6-diethylbenzeneamine) 

Relevant articles and documents

Preparation method of 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline)

The invention discloses a preparation method of 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline). The preparation method comprises the following steps: (1) in a nitrogen protective atmosphere, carrying out reaction on raw materials 2,6-diethylaniline and hydrochloric acid to generate 2,6-diethylaniline hydrochloride, and dropwisely adding formalin to carry out condensation reaction; after the reaction finishes, neutralizing with liquid caustic soda, and carrying out water separation to obtain 4,4'-methylene-bis-(2,6-diethylaniline); (2) dissolving the product in the step (1) in a solvent, and introducing chlorine to carry out chlorination reaction; after the reaction finishes, neutralizing with liquid caustic soda, and carrying out water separation to obtain a 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline) crude product; and (3) dissolving the product in the step (2) in a solvent, decolorizing with activated carbon, cooling to crystallize, filtering, and drying to obtain the final product. The method has the advantages of simple technique, accessible raw materials, low price and high product purity and yield, and can easily implement industrial production.