119-90-4

Usage

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

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

Downstream Products

• 3013-98-7 3,3'-dimethoxy-N,N'-bis-(pyridine-2-thiocarbonyl)-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 
• 14446-33-4 3,3',3'',3'''-tetramethoxy-4',4'''-azo-bis-biphenyl-4-ylamine 

Relevant academic research and scientific papers

Synthetic method for 4,4'-dihalogenated-3,3'-dialkyl(alkoxyl) biphenyl compounds

The invention relates to a synthetic method for 4,4'-dihalogenated-3,3'-dialkyl(alkoxyl) biphenyl compounds. The method employs o-nitro alkyl (alkoxyl) benzene as an initial raw material, 2,2'-dialkyl(alkoxyl) hydrazobenzene is prepared through catalysis hydrogenation in an alkaline environment, hydrochloric acid acidifying rearrangement is carried out, 4,4'-diamino-3,3'-dialkyl(alkoxyl) biphenyl is prepared, finally, a diazotization reaction is carried out and 4,4'-dihalogenated-3,3'-dialkyl(alkoxyl) biphenyl compounds are prepared. The synthetic method is advantaged by cheap and easily available raw materials, mild reaction conditions, simple operation, high safety coefficient, high yield and low cost.

Electrochemical oxidation of o-anisidine, p-anisidine, diphenylamine and o-toluidine at platinum electrode

The oxidation of o-anisidine, p-anisidine, diphenylamine and o-toluidine was carried out at constant potential in non-aqueous system at platinum electrode. The electrolysis was carried out at controlled anodic potential in an electrochemical cell assembly containing reaction mixture, working as well as counter electrode and reference electrode. The oxidative products formed during the electrolysis of aromatic amines at platinum anode are discussed and reported here.

Functionalized Photoreactive Compounds

The present invention concerns functionalized photoreactive compounds of formula (I), that are particularly useful in materials for the alignment of liquid crystals. Due to the adjunction of an electron withdrawing group to specific molecular systems bearing an unsaturation directly attached to two unsaturated ring systems, exceptionally high photosensitivities, excellent alignment properties as well as good mechanical robustness could be achieved in materials comprising said functionalized photoreactive compounds of the invention.

Basic azo dyestuffs of the 3-cyano-2,4,6-triamino pyridine series

The new basic azo dyestuffs of the formula STR1 wherein the symbols have the meaning given in the description, are suitable for dyeing synthetic and naturally occurring substrates which can be dyed with basic dyestuffs.

Pigment compositions for solvent and water-based ink systems and the methods for producing them

This invention is an azo pigment composition containing a water insoluble metal salt of a water soluble polymer; a method of preparing said composition and ink compositions prepared from said azo pigment compositions.

Azo pigment compositions and process for their preparation

This invention is that of an azo pigment composition containing about 1 to 10 percent by weight of a nonionic alkyl polyglycoside dispersing agent. The polyglycosides useful in the invention have the general formulae: wherein: M is an oxygen, sulfur, nitrogen phosphorous or silicon atom; n is an integer from 8 to 18, preferably 8 to 11 and X represents the number average degree of polymerization having a numerical value from about 1 to about 2. These azo pigment compositions are prepared by conducting the azo pigment coupling reaction in the presence of said alkyl polyglycoside. The resulting pigment exhibit superior application properties in water based ink systems.

Synthesis of phthalonitrile resins containing ether and imide linkages

Imide-containing phthalonitrile monomers are prepared from a phthalonitrile and an aromatic dianhydride. The monomer and a method for preparing the monomer is disclosed. These monomers are synthesized into heat resistant polymers and copolymers with aromatic ring structure incorporating imide and ether linkages. The synthesis of the high temperature thermosetting polymers and copolymers is also disclosed.

Triazinyl reactive dyestuffs in which triazinyl group is further substituted with a beta-chloroethylsulfonyl- or vinylsulfonylbutyrylamino moiety

Reactive dyes of the formula STR1 in which D is the radical of an organic dye of the monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthrone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide series, R is hydrogen or substituted or unsubstituted C1-4 -alkyl, X is a substituent which is detachable as an anion, B is a radical of the formula STR2 R1 and R2, independently of each other, are hydrogen or substituted or unsubstituted C1-4 -alkyl or phenyl, A is a substituted or unsubstituted aliphatic or aromatic bridge member, Y is a --CO--Z or --SO2 --Z radical, Z is an aliphatic, aromatic or heterocyclic reactive radical, and n is 1 or 2, are suitable for dyeing or printing cellulose-containing and nitrogen-containing materials and in high dyeing yield produce dyeings and prints having good fastness properties.

Reactive dyestuffs comprising a triazine moiety and a vinylsulfonyl moiety both being linked by a substituted alkylene bridge member

A reactive dye of the formula STR1 in which: F is a radical selected from the group consisting of metal-free or metal-containing monoazo or disazo dyes containing at least one --SO3 H group, anthraquinone dyes, sulfophthalocyanine dyes, formazan dyes, phenazine dyes, oxazine dyes and nitroaryl dyes, R is hydrogen, C1 -C4 alkyl which is unsubstituted or substituted with --COOH or --SO3 H, cyanoethyl, or hydroxyethyl, X is fluorine, chlorine, bromine, --SO3 H, phenylsulfonyl or C1 -C4 -alkylsulfonyl, p is 1 or 2 and A is a radical of the formula STR2 in which: Y is chlorine, bromine, fluorine, --OH, --OSO3 H, --O-acyl, --CN, --COOH, --COO--C1 -C4 -alkyl, --CONH2 or --SO2 --Z, the group designated "alk" is a straight or branched polymethylene radical having 2 to 6 carbon atoms, V is STR3 hydrogen or C1 -C4 -alkyl which is unsubstituted or substituted by C1 -C2 -alkoxy, carboxyl, sulfo, halogen or hydroxy, Z is β-halogenoethyl, vinyl or β-acetoxyethyl, or A is a radical of the formulae STR4 in all of which R' is C1-6 -alkyl or hydrogen, Z is as defined above, o is 0 to 6, and m is 2 to 6.

Triazinyl reactive dyes containing additional fiber reactive groups bound through the sulfonylalkylaminoalkylamino bridge

The invention relates to novel useful reactive dyes of the formula I STR1 in which: F is a radical selected from the group consisting of metal-free or metal-containing monoazo or disazo dyes containing at least one --SO3 H group, anthraquinone dyes, sulfophthalocyanine dyes, formazan dyes, phenazine dyes, oxanine dyes and nitroaryl dyes, R is hydrogen, C1 -C4 alkyl which is unsubstituted or substituted with --COOH or --SO3 H, cyanoethyl, or hydroxyethyl, X is fluorine, chlorine, bromine, --SO3 H, phenylsulfonyl or C1 -C4 -alkylsulfonyl, P is 1 or 2 and A is a radical of the formula STR2 in which: the groups designated "alk" are independently of each other straight or branched polymethylene radicals having 2 to 6 carbon atoms, and Z is β-halogenoethyl, vinyl, β-sulfatoethyl, β-thiosulfatoethyl or βacetoxyethyl.