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

Chemical Properties

o-Dianisidine, crystallizes dimorphically, rarely in needles, with mp 133°C , often in flakes with mp 137-138°C . It forms colorless crystals, but commercial products have a tinge of violet. It is sparingly soluble in water but soluble in alcohol, ether, and benzene. One gram of ethyl acetate dissolves 0.285 g of o-dianisidine at 73°C . The pure compound is stable upon exposure to air, but commercial products turn violet. o-Dianisidine is resistant to water but sensitive to oxidizing agents.

Uses

Different sources of media describe the Uses of 119-90-4 differently. You can refer to the following data:
1. o-Dianisidine is used almost exclusively as a chemical intermediate for producing dyes and pigments. In 1971, the Society of Dyers and Colourists reported its use in the production of 89 dyes (see Dyes Metabolized to o-Dianisidine, below). o-Dianisidine is also used as a chemical intermediate to produce o-dianisidine diisocyanate for use in adhesives and as a component of polyurethanes. Other uses are as a dye for paper, plastics, rubber, and textiles and as a test substance for detection of metals, thiocyanates, and nitrites (IARC 1974, HSDB 2009).
2. o-Dianisidine is a starting material for the production of disazo dyes and pigments. Like benzidine and o-tolidine, o-dianisidine forms colors with numerous oxidizing agents, e.g., copper, cobalt, and gold ions. o-Dianisidine is quantitatively determined by titration with nitrite using potassium iodide and starch paper as the indicator. o-Dianisidine can be detected in the urine using potassium 1,2-naphthoquinone4-sulfonate after extraction. A rapid and easy method is based on the color formed with cyanogen bromide. Its detection limit is 0.05 mg/kg. The free o-dianisidine base and the dihydrochloride are marketed in moist forms with a 10-30% water content.
3. o-Dianisidine is used as a redox indicator. It is used as an intermediate for the preparation of azo dyes, pigments and o-dianisidine diisocyanate, which finds application in adhesives, polyurethane elastomers and resins. It is also used in various industries like leather, paper, plastics, rubber, and textiles. It acts as a reagent to detect metals, thiocyanates, and nitrites.

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

General Description

Colorless crystals or a light brown powder. Turns violet on standing. Carcinogen.

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.

Properties and Applications

red light navy blue light to dark. And C.I.Azoic Diazo Component 48 the same chemical structure. Standard(Polyamide) Ironing Fastness Light Fastness Persperation Fastness Washing Fastness Fading Stain Fading Stain Fading Stain AATCC 2 5 5 5 5

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

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

Downstream Products

• 83310-76-3 N,N'-(3,3'-dimethoxy-biphenyl-4,4'-diyl)-bis-acetamide 
• 29398-96-7 N,N'-bis-(2,4-dinitro-phenyl)-3,3'-dimethoxy-benzidine 
• 83432-66-0 N,N'-bis-(5-bromo-2-hydroxy-benzylidene)-3,3'-dimethoxy-benzidine 
• 92415-69-5 3,3'-Dimethoxy-biphenyl-4,4'-diamine; compound with 1,3-dinitro-benzene 
• 92415-59-3 3,3'-Dimethoxy-biphenyl-4,4'-diamine; compound with 1,3,5-trinitro-benzene 
• 6404-70-2 4,4'-diamino-5,5'-dimethoxy-biphenyl-2,2'-disulfonic acid 
• 106-34-3 quinhydrone 
• 14446-33-4 3,3',3'',3'''-tetramethoxy-4',4'''-azo-bis-biphenyl-4-ylamine 
• 861533-46-2 4-(4-carboxy-3-hydroxy-phenyl)-2-hydroxy-benzoic acid 
• 47659-36-9 4,4'-Dibenzoyl-biphenyl-3,3'-diol 

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