119-90-4

Basic information

• Product Name: 3,3'-DIMETHOXYBENZIDINE
• Synonyms: o-Dianisidine,3,3′-Dimethoxybenzidine, Fast BlueB;3.3'-Dimethoxybenzidine 1g [119-90-4];4,4'-Diamino-3,3'-dimethoxybiphenyl 3,3'-Dimethoxybenzidine Fast Blue B;3.3'-DiMethoxy;3,3'-Dimethoxybenzidine Solution, 100ppm;3, 3'-Dimethoxybenzidine, pract., 97%;[1,1'-Biphenyl]-4,4'-diamine, 3,3'-dimethoxy-;1’-biphenyl)-4,4’-diamine,3,3’-dimethoxy-(
• CAS NO: 119-90-4
• Molecular Formula: C₁₄H₁₆N₂O₂
• Molecular Weight: 244.29
• EINECS: 204-355-4
• Product Categories: Intermediates of Dyes and Pigments;Biphenyl & Diphenyl ether
• Mol File: 119-90-4.mol
• Article Data: 13

Chemical Properties

• Melting Point: 137-138 °C(lit.)
• Boiling Point: 387.21°C (rough estimate)
• Flash Point: 403 °F
• Appearance: Pink to beige-brown/Crystalline Powder
• Density: 1.1079 (rough estimate)
• Vapor Pressure: 2.49E-06mmHg at 25°C
• Refractive Index: 1.6000 (estimate)
• Storage Temp.: Store at RT.
• Solubility: H2O: slightly soluble
• PKA: 4.71±0.10(Predicted)
• Water Solubility: Soluble in alcohol, benzene, ether, chloroform, acetone, most organic solvents and lipids. Slightly soluble in water.
• Merck: 14,2991
• BRN: 1879884
• CAS DataBase Reference: 3,3'-DIMETHOXYBENZIDINE(CAS DataBase Reference)
• NIST Chemistry Reference: 3,3'-DIMETHOXYBENZIDINE(119-90-4)
• EPA Substance Registry System: 3,3'-DIMETHOXYBENZIDINE(119-90-4)

Safety Data

• Hazard Codes: T
• Statements: 45-22
• Safety Statements: 53-45
• RIDADR: 2811
• WGK Germany: 3
• RTECS: DD0875000
• TSCA: Yes
• HazardClass: 6.1(a)
• PackingGroup: II
• Hazardous Substances Data: 119-90-4(Hazardous Substances Data)

Usage

Description

3,3'-DIMETHOXYBENZIDINE is a chemical compound that is used as a chemical intermediate for the production of dyes and pigments. It is also used in the production of o-dianisidine diisocyanate, which is used in adhesives and as a component of polyurethanes. Additionally, it is used as a dye for paper, plastics, rubber, and textiles, and as a test substance for the detection of metals, thiocyanates, and nitrites.

Uses

Used in Chemical Industry:
3,3'-DIMETHOXYBENZIDINE is used as a chemical intermediate for the production of dyes and pigments. It is also used as a starting material for the production of disazo dyes and pigments.
Used in Adhesives and Polyurethane Industry:
3,3'-DIMETHOXYBENZIDINE is used as a chemical intermediate to produce o-dianisidine diisocyanate, which is used in adhesives and as a component of polyurethane elastomers and resins.
Used in Textile, Paper, Plastics, and Rubber Industry:
3,3'-DIMETHOXYBENZIDINE is used as a dye for various materials, including paper, plastics, rubber, and textiles.
Used in Analytical Chemistry:
3,3'-DIMETHOXYBENZIDINE acts as a reagent to detect metals, thiocyanates, and nitrites.
Properties:
3,3'-DIMETHOXYBENZIDINE is a colorless crystalline compound that turns violet upon standing. It is a known carcinogen. The compound crystallizes dimorphically, with melting points of 133°C (in needle form) and 137-138°C (in flake form). It is sparingly soluble in water but soluble in alcohol, ether, and benzene. The pure compound is stable when exposed to air, but commercial products may turn violet. It is resistant to water but sensitive to oxidizing agents.
Standard (Polyamide):
The standard for 3,3'-DIMETHOXYBENZIDINE in the context of polyamide includes various fastness properties such as ironing fastness, light fastness, perspiration fastness, washing fastness, fading, and staining. The American Association of Textile Chemists and Colorists (AATCC) has established standard ratings for these properties, with ratings ranging from 2 to 5.

Preparation

2-Nitroanisole is reduced (H2-catalyst or iron-formic acid) to o-anisidine or (benzidine-type reaction) to o-dianisidine [119-90-4], both of which are important as dye intermediates.

Synthesis Reference(s)

Journal of the American Chemical Society, 106, p. 7077, 1984 DOI: 10.1021/ja00335a035

Air & Water Reactions

Finely powdered material is a significant dust explosion hazard. Insoluble in water.

Reactivity Profile

o-Dianisidine is a weak base. Reacts exothermically with acids. Sensitive to heat, air and prolonged exposure to light.

Fire Hazard

o-Dianisidine is combustible.

Safety Profile

Confirmed carcinogen with experimental tumorigenic data. Moderately toxic by ingestion. Mutation data reported. Combustible when exposed to heat or flame. When heated to decomposition it emits toxic fumes of NOx.

Carcinogenicity

o-Dianisidine is reasonably anticipated to be a human carcinogen based on sufficient evidence of carcinogenicity from studies in experimental animals.

Standard(Polyamide)

Ironing Fastness

Fading

Stain

InChI:InChI=1/C14H16N2O2/c1-17-13-7-9(3-5-11(13)15)10-4-6-12(16)14(8-10)18-2/h3-8H,15-16H2,1-2H3

Synthetic route

N,N'-bis-(2-methoxy-phenyl)-hydrazine (787-77-9) → 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4)

Conditions	Yield
Stage #1: N,N'-bis-(2-methoxy-phenyl)-hydrazine With hydrogenchloride In water at 30 - 90℃; for 2h; Stage #2: With water; sodium hydroxide pH=9 - 10;	60.3%
acid In 1,4-dioxane Rate constant; nitrogen and carbon kinetic isotope effects, secondary deuterium kinetic isotope effect; various buffers;
With hydrogenchloride

2-Nitroanisole (91-23-6) → 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4)

Conditions	Yield
With sodium hydroxide; palladium; isopropyl alcohol at 50 - 60℃; und Behandeln der abgekuehlten Reaktionsloesung mit wss.Salzsaeure;
Multi-step reaction with 2 steps 1.1: sodium dodecylbenzenesulfonate; 0.8wt% Pd/C; hydrogen; sodium hydroxide; [1,4]naphthoquinone / ethanol / 30 °C / 4500.45 Torr / Autoclave 2.1: hydrogenchloride / water / 2 h / 30 - 90 °C 2.2: pH 9 - 10 View Scheme

2,2'-dimethoxyazobenzene (613-55-8, 18978-15-9, 19129-74-9) → 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4)

Conditions	Yield
With hydrogenchloride; iodine; sulphurous acid

2,2'-dimethoxyazoxybenzene (13620-57-0) → 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 2-methoxy-phenylamine (90-04-0)

hydrogenchloride (7647-01-0) + N,N'-bis-(2-methoxy-phenyl)-hydrazine (787-77-9) → 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4)

3,3',3'',3'''-tetramethoxy-4',4'''-azo-bis-biphenyl-4-ylamine (14446-33-4) + tin dichloride → 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4)

hydrogenchloride (7647-01-0) + iodine (7553-56-2) + sulphurous acid (7782-99-2) + 2,2'-dimethoxyazobenzene (613-55-8, 18978-15-9, 19129-74-9) → 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4)

2-methoxy-phenylamine (90-04-0) → 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 2,2'-dimethoxyazobenzene (613-55-8, 18978-15-9, 19129-74-9)

Conditions	Yield
In N,N-dimethyl-formamide for 3h; Electrolysis;

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 4,4’-dibromo-3,3’-dimethoxy-1,1‘-biphenyl (6161-47-3)

Conditions	Yield
With hydrogenchloride; tert.-butylnitrite; hydrogen bromide In acetonitrile at 65℃;	98%
With hydrogen bromide; copper(I) bromide; sodium nitrite In water; acetonitrile Sandmeyer Reaction; Inert atmosphere; Schlenk technique;	96%
With hydrogen bromide; copper(I) bromide; sodium nitrite In acetonitrile Sandmeyer Reaction;	96%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 2,4-Dihydroxybenzaldehyde (95-01-2) → N,N'-bis-(2,4-dihydroxybenzylidene)-3,3'-dimethoxybenzidine

Conditions	Yield
Microwave irradiation; Green chemistry;	98%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 3-phenylnorbornadiene-2-carbonyl chloride (158198-05-1) → C42H36N2O4

Conditions	Yield
With triethylamine In 1,4-dioxane for 0.166667h; Heating;	95%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 1,1′-bis(2,4-dinitrophenyl)-[4,4′-bipyridine]-1,1′-diium chloride (41168-79-0) → 1,1'-bis(4′-amino-3,3′-dimethoxy-[1,1′-biphenyl]-4-yl)-[4,4′-bipyridine]-1,1′-diium chloride

Conditions	Yield
In methanol; water for 72h; Reflux; Inert atmosphere;	95%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + C34H30N4O2 → C48H40N4O4

Conditions	Yield
In acetic acid Reflux;	93%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 3-diethylaminophenol (91-68-9) → C34H40N6O4

Conditions	Yield
Stage #1: 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine With hydrogenchloride; sodium nitrite In water at 0 - 5℃; for 1h; Stage #2: 3-diethylaminophenol In water at 0 - 5℃; for 2h; pH=5-6;	90.6%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + chloroacetyl chloride (79-04-9) → N,N'-(3,3'-dimethoxybiphenyl-4,4'-diyl)bis(2-chloroacetamide) (2810-43-7)

Conditions	Yield
With sodium hydroxide In water at 20℃; for 4h; Inert atmosphere;	90%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + salicylaldehyde (90-02-8) → N,N'-disalicylidene-3,3'-dimethoxybenzidine (5314-38-5)

Conditions	Yield
In ethanol for 2h; Reflux;	87.3%
With ethanol
In methanol

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 1-amino-4-chloroanthraquinone (2872-47-1) → 1-amino-4-(4'-amino-2,3'-dimethoxybiphenylylamino)anthraquinone (88653-21-8)

Conditions	Yield
With aluminium trichloride In nitrobenzene Ambient temperature;	86%

phosgene (75-44-5) + 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 3,3'-dimethoxy-4,4'-biphenylene diisocyanate (91-93-0)

Conditions	Yield
In various solvent(s) for 1.5h; Condensation; Heating;	85%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 2-hydroxynaphthalene-1-carbaldehyde (708-06-5) → C36H28N2O4 (16196-98-8)

Conditions	Yield
With acetic acid In N,N-dimethyl-formamide at 90℃; for 6h;	85%

thiophene-2-carbaldehyde benzothiazol-2-yl-hydrazone (31350-09-1) + 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → bis-1-(2-methoxyphenyl)-3-thiothenyl-5-(benzthiazole-2-yl)formazane (1268834-71-4)

Conditions	Yield
Stage #1: 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine With hydrogenchloride; sodium nitrite In water Stage #2: thiophene-2-carbaldehyde benzothiazol-2-yl-hydrazone In water; N,N-dimethyl-formamide	81%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 1-(2,4-dinitrophenyl)-4,4'-bipyridinium chloride (71190-35-7) → C34H28N4O2(2+)*2Cl(1-)

Conditions	Yield
In N,N-dimethyl acetamide; water at 95℃; for 120h;	80%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 4,4'-diiodo-3,3'-diethoxylbiphenyl

Conditions	Yield
Stage #1: 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine With sodium nitrite In sulfuric acid; acetic acid; acetonitrile at -5 - 80℃; for 0.5h; Stage #2: With potassium iodide In water at 30 - 40℃; for 2.5h;	79.54%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 4,4'-diiodo-3,3'-dimethoxylbiphenyl (92160-61-7)

Conditions	Yield
Stage #1: 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine With sodium nitrite In sulfuric acid; acetic acid; acetonitrile at -5 - 80℃; for 0.5h; Stage #2: With potassium iodide In water at 30 - 40℃; for 2.5h;	79.39%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + furaldehyde benzthiazolyl-2-hydrazone (31350-07-9) → bis-1-(2-methoxyphenyl)-3-furyl-5-(benzthiazole-2-yl)formazane (1268834-70-3)

Conditions	Yield
Stage #1: 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine With hydrogenchloride; sodium nitrite In water Stage #2: furaldehyde benzthiazolyl-2-hydrazone In water; N,N-dimethyl-formamide	79%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → 4,4'-dichloro-3,3'-dimethoxybiphenyl (66175-54-0)

Conditions	Yield
Stage #1: 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine With sodium nitrite In sulfuric acid; acetic acid; acetonitrile at -5 - 80℃; for 0.5h; Stage #2: With hydrogenchloride; copper(l) chloride In water at 30 - 40℃; for 2.5h;	78.5%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + 4β-bromo-4-desoxypodophyllotoxin → 3'',3'''-dimethoxy-N,N'-bis(4β-4-desoxypodophyllotoxin)benzidine

Conditions	Yield
With tetra-(n-butyl)ammonium iodide; triethylamine In tetrahydrofuran at 20℃; for 6h;	78%

methanol (67-56-1) + formaldehyd (50-00-0) + 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → N,N'-bis(methoxymethyl)dianisidine

Conditions	Yield
With potassium hydroxide In ethanol at 20℃; Mannich Aminomethylation;	78%

5,7-diimino-2,5,6,7-tetrahydro-1H-cyclopenta[cd]phenalene + 3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) → C44H34N4O2

Conditions	Yield
In methanol Heating;	77%

3,3'-dimethoxy-(1,1'-biphenyl)-4,4'-diamine (119-90-4) + (5R,5aS,8aR,9R)-9-(4-Hydroxy-3,5-dimethoxy-phenyl)-5-iodo-5,5a,8a,9-tetrahydro-1,3,6-trioxa-dicyclopenta[b,g]naphthalen-8-one → 3'',3'''-dimethoxy-N,N'-bis(4'-O-demethyl-4β-4-desoxypodophyllotoxin)benzidine

Conditions	Yield
With barium carbonate In acetonitrile	75%

Upstream product

• 13620-57-0 2,2'-dimethoxyazoxybenzene 
• 7647-01-0 hydrogenchloride 
• 7553-56-2 iodine 
• 7782-99-2 sulphurous acid 
• 613-55-8 2,2'-dimethoxyazobenzene 
• 90-04-0 2-methoxy-phenylamine 
• 14446-33-4 3,3',3'',3'''-tetramethoxy-4',4'''-azo-bis-biphenyl-4-ylamine 
• 787-77-9 N,N'-bis-(2-methoxy-phenyl)-hydrazine 
• 91-23-6 2-Nitroanisole 

Downstream Products

• 3013-98-7 3,3'-dimethoxy-N,N'-bis-(pyridine-2-thiocarbonyl)-benzidine 
• 83432-67-1 N,N'-bis-(3,5-dibromo-salicylidene)-3,3'-dimethoxy-benzidine 
• 83310-76-3 N,N'-(3,3'-dimethoxy-biphenyl-4,4'-diyl)-bis-acetamide 
• 34146-19-5 N,N'-bis-(4,4'-bis-dimethylamino-benzhydryl)-3,3'-dimethoxy-benzidine 
• 91-91-8 fast blue B 
• 6161-50-8 3,3'-dimethoxybiphenyl 
• 2373-98-0 3,3'-dihydroxybenzidine 
• 87084-62-6 4,4'-diamino-3'-methoxy-biphenyl-3-ol 
• 13458-23-6 3,3'-dinitro-4,4'-(3,3'-dimethoxy-biphenyl-4,4'-diyldiamino)-bis-benzenesulfonic acid 
• 6404-70-2 4,4'-diamino-5,5'-dimethoxy-biphenyl-2,2'-disulfonic acid 

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