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Dianisidine

Dianisidine structure

Dianisidine 

structure
  • CAS No:

    119-90-4

  • Formula:

    C14H16N2O2

  • Chemical Name:

    Dianisidine

  • Synonyms:

    [1,1′-Biphenyl]-4,4′-diamine,3,3′-dimethoxy-;Fast Blue B Base;Benzidine,3,3′-dimethoxy-;3,3′-Dimethoxy[1,1′-biphenyl]-4,4′-diamine;Amacel Developed Navy SD;Azogene Fast Blue B;Blue Base Irga B;Blue Base NB;Blue BN Base;Cellitazol B;Cibacete Diazo Navy Blue 2B;C.I. Disperse Black 6;Diacel Navy DC;o-Dianisidine;3,3′-Dimethoxybenzidine;Fast Blue Base B;Fast Blue DSC Base;Hiltonil Fast Blue B Base;Kayaku Blue B Base;Lake Blue B Base;Mitsui Blue B Base;Naphthanil Blue B Base;Setacyl Diazo Navy R;4,4′-Bi-o-anisidine;3,3′-Dimethoxy-4,4′-diaminodiphenyl;Dianisidine;4,4′-Diamino-3,3′-dimethoxy-1,1′-biphenyl;3,3′-Dimethoxybenzidene;NSC 3168;3,3′-Dimethoxy-4,4′-diaminobiphenyl;3,3′-Dimethoxy-biphenyl-4,4′-diamine;59777-10-5

  • Categories:

    Organic Chemistry  >  Amides

Description

Colorless crystals that turn a violet color on standing. [Note: Used as a basis for many dyes.]


3,3'-dimethoxybenzidine appears as colorless crystals or a light brown powder. Turns violet on standing. Carcinogen.|COLOURLESS CRYSTALS.|Colorless crystals that turn a violet color on standing.|Colorless crystals that turn a violet color on standing. [Note: Used as a basis for many dyes.]


3,3'-dimethoxybenzidine appears as colorless crystals or a light brown powder. Turns violet on standing. Carcinogen.|3,3'-Dimethoxybenzidine is a member of biphenyls.|3,3'-Dimethoxybenzidine is used as an intermediate in the production of dyes and pigments. No information is available on the acute (short-term), chronic (long-term), reproductive, developmental, or carcinogenic effects of 3,3'-dimethoxybenzidine in humans. Animal studies have reported effects on the liver, kidneys, spleen, and bladder, and endocrine effects, gastritis, intestinal hemorrhage, and weight loss from chronic oral exposure. Increased incidences of tumors in several organs have been reported in rats orally exposed to 3,3'-dimethoxybenzidine or its salt. EPA has classified 3,3'-dimethoxybenzidine as a Group B2, probable human carcinogen.|Dianisidine is a colorless, highly toxic, crystalline compound that turns violet when exposed to air. Dianisidine is used exclusively as an intermediate for the production of dyes and pigments. Exposure to this substance causes skin irritation and sensitization. Dianisidine is reasonably anticipated to be a human carcinogen based on evidence of carcinogenicity in experimental animals. (NCI05)|Highly toxic compound which can cause skin irritation and sensitization. It is used in manufacture of azo dyes.

Dianisidine Basic Attributes

244.29

244.29

1879884

204-355-4

MJY508JZXV

1582

3168

2811|2431|3077

DTXSID3025091

C44365

LEAFLETS OR NEEDLES FROM WATER|Colorless crystals that turn a violet color on standing.

2922299090

Characteristics

70.5

1.81

Pink to beige-brown Crystalline Powder

1.2±0.1 g/cm3

137 °C

356 °C

403 °F

1.619

soluble in alcohol, benzene, ether, chloroform, acetone, most organic solvents and lipids. Slightly soluble in water.

Store at RT.

negligible

8.5

Oral-Rat  LD50: 1920 mg/kg

Open flame, high heat and combustible; react with oxidant; burning produces toxic nitrogen oxide fumes

The finely powdered carcinogen is a significant dust explosion hazard.

WEAK BASE

HAS GENERAL CHARACTERISTICS OF PRIMARY AROMATIC AMINES

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

Ethers

3,3'-DIMETHOXYBENZIDINE is a weak base. Reacts exothermically with acids. Sensitive to heat, air and prolonged exposure to light.

Combustible Solid

The vapour is heavier than air and may travel along the ground; distant ignition possible.

Safety Information

II

6.1(a)

2811

3

45-22

53-45

DD0875000

T

Treasury is ventilated at low temperature and dry; stored separately from oxidants and food additives

P201-P308 + P313

H302-H350

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number U091, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.|A good candidate for liquid injection incineration at a temperature range of 650 to 1,600 °C and a residence time of 0.1 to 2 seconds. A good candidate for rotary kiln incineration at a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases, and hours for solids. A good candidate for fluidized bed incineration at a temperature range of 450 to 980 °C and residence times of seconds for liquids and gases, and longer for solids.|PRECAUTIONS FOR "CARCINOGENS": There is no universal method of disposal that has been proved satisfactory for all carcinogenic compounds & specific methods of chem destruction ... published have not been tested on all kinds of carcinogen-containing waste. ... summary of avail methods & recommendations ... /given/ must be treated as guide only. /Chemical Carcinogens/|PRECAUTIONS FOR "CARCINOGENS": ... Incineration may be only feasible method for disposal of contaminated laboratory waste from biological expt. However, not all incinerators are suitable for this purpose. The most efficient type ... is probably the gas-fired type, in which a first-stage combustion with a less than stoichiometric air:fuel ratio is followed by a second stage with excess air. Some ... are designed to accept ... aqueous & organic-solvent solutions, otherwise it is necessary ... to absorb soln onto suitable combustible material, such as sawdust. Alternatively, chem destruction may be used, esp when small quantities ... are to be destroyed in laboratory. /Chemical Carcinogens/|For more Disposal Methods (Complete) data for 3,3'-DIMETHOXYBENZIDINE (7 total), please visit the HSDB record page.

... Can react with oxidizing materials.|Oxidizers.

USEPA/ECAO; Health and Environmental Effects Profile for 3,3'-Dimethoxybenzidine (1987) EPA/600/X-87/101, NTIS No. PB89-119515|DHHS/NTP; Toxicology & Carcinogenesis Studies of 3,3'-Dimethoxybenzidine dihydrochloride in F344/N Rats (Drinking Water Studies) Technical Report Series No. 372 (1990) NIH Publication No. 90-2827|National Toxicology Program. Eleventh Report on Carcinogens (2005). The Report on Carcinogens is an informational scientific and public health document that identifies and discusses substances (including agents, mixtures, or exposure circumstances) that may pose a carcinogenic hazard to human health. 3,3'-Dimethoxybenzidine (119-90-4) is listed as reasonably anticipated to be a human carcinogen. /3,3'-Dimethoxylbenzidine and Dyes Metabolized to 3,3'-Dimethoxylbenzidine/[Available from, as of July 31, 2009: http://ntp.niehs.nih.gov/ntp/roc/eleventh/profiles/s073dmob.pdf]

This chemical is combustible. (NTP, 1992)|Combustible. Gives off irritating or toxic fumes (or gases) in a fire.

|Danger|H302: Harmful if swallowed [Warning Acute toxicity, oral]|P201, P202, P264, P270, P281, P301+P312, P308+P313, P330, P405, and P501|H302 (100%): Harmful if swallowed [Warning Acute toxicity, oral]|Aggregated GHS information provided by 49 companies from 4 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.|Warning|P201, P202, P260, P264, P270, P281, P301+P312, P308+P313, P314, P330, P405, and P501

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]: As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. SPILL: Increase, in the downwind direction, as necessary, the isolation distance shown above. FIRE: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2016)

SMALL SPILLS AND LEAKAGE: If a spill of this chemical occurs, FIRST REMOVE ALL SOURCES OF IGNITION, then you should dampen the solid spill material with acetone and transfer the dampened material to a suitable container. Use absorbent paper dampened with acetone to pick up any remaining material. Seal your contaminated clothing and the absorbent paper in a vapor-tight plastic bag for eventual disposal. Solvent wash all contaminated surfaces with acetone followed by washing with a soap and water solution. Do not reenter the contaminated area until the Safety Officer (or other responsible person) has verified that the area has been properly cleaned. STORAGE PRECAUTIONS: You should protect this chemical from exposure to light. Keep the container tightly closed under an inert atmosphere, and store under refrigerated temperatures. (NTP, 1992)

Skin: Wear appropriate personal protective clothing to prevent skin contact. Eyes: Wear appropriate eye protection to prevent eye contact. Wash skin: The worker should immediately wash the skin when it becomes contaminated. The worker should wash daily at the end of each work shift. Remove: Work clothing that becomes wet or significantly contaminated should be removed and replaced. Change: Workers whose clothing may have become contaminated should change into uncontaminated clothing before leaving the work premise. Provide: Eyewash fountains should be provided in areas where there is any possibility that workers could be exposed to the substance; this is irrespective of the recommendation involving the wearing of eye protection. Facilities for quickly drenching the body should be provided within the immediate work area for emergency use where there is a possibility of exposure. [Note: It is intended that these facilities provide a sufficient quantity or flow of water to quickly remove the substance from any body areas likely to be exposed. The actual determination of what constitutes an adequate quick drench facility depends on the specific circumstances. In certain instances, a deluge shower should be readily available, whereas in others, the availability of water from a sink or hose could be considered adequate.] (NIOSH, 2016)|USE GLOVES AND GOGGLES TO AVOID CONTACT WITH SKIN AND EYES. USE EFFECTIVE FUME REMOVAL DEVICE OR OTHER RESPIRATORY PROTECTION.|PRECAUTIONS FOR "CARCINOGENS": ... Dispensers of liq detergent /should be available./ ... Safety pipettes should be used for all pipetting. ... In animal laboratory, personnel should ... wear protective suits (preferably disposable, one-piece & close-fitting at ankles & wrists), gloves, hair covering & overshoes. ... In chemical laboratory, gloves & gowns should always be worn ... however, gloves should not be assumed to provide full protection. Carefully fitted masks or respirators may be necessary when working with particulates or gases, & disposable plastic aprons might provide addnl protection. ... gowns ... /should be/ of distinctive color, this is a reminder that they are not to be worn outside the laboratory. /Chemical Carcinogens/|Wear appropriate personal protective clothing to prevent skin contact.|Wear appropriate eye protection to prevent eye contact.|For more Personal Protective Equipment (PPE) (Complete) data for 3,3'-DIMETHOXYBENZIDINE (8 total), please visit the HSDB record page.|(See protection codes)

Combustible when exposed to heat or flame.

The finely powdered carcinogen is a significant dust explosion hazard.

WATER, CARBON DIOXIDE, DRY CHEMICAL.

PRECAUTIONS FOR "CARCINOGENS": A high-efficiency particulate arrestor (HEPA) or charcoal filters can be used to minimize amt of carcinogen in exhausted air ventilated safety cabinets, lab hoods, glove boxes or animal rooms ... Filter housing that is designed so that used filters can be transferred into plastic bag without contaminating maintenance staff is avail commercially. Filters should be placed in plastic bags immediately after removal ... The plastic bag should be sealed immediately ... The sealed bag should be labelled properly ... Waste liquids ... should be placed or collected in proper containers for disposal. The lid should be secured & the bottles properly labelled. Once filled, bottles should be placed in plastic bag, so that outer surface ... is not contaminated ... The plastic bag should also be sealed & labelled. ... Broken glassware ... should be decontaminated by solvent extraction, by chemical destruction, or in specially designed incinerators. /Chemical Carcinogens/

PRECAUTIONS FOR "CARCINOGENS": Smoking, drinking, eating, storage of food or of food & beverage containers or utensils, & the application of cosmetics should be prohibited in any laboratory. All personnel should remove gloves, if worn, after completion of procedures in which carcinogens have been used. They should ... wash ... hands, preferably using dispensers of liq detergent, & rinse ... thoroughly. Consideration should be given to appropriate methods for cleaning the skin, depending on nature of the contaminant. No standard procedure can be recommended, but the use of organic solvents should be avoided. Safety pipettes should be used for all pipetting. /Chemical Carcinogens/|PRECAUTIONS FOR "CARCINOGENS": In animal laboratory, personnel should remove their outdoor clothes & wear protective suits (preferably disposable, one-piece & close-fitting at ankles & wrists), gloves, hair covering & overshoes. ... clothing should be changed daily but ... discarded immediately if obvious contamination occurs ... /also,/ workers should shower immediately. In chemical laboratory, gloves & gowns should always be worn ... however, gloves should not be assumed to provide full protection. Carefully fitted masks or respirators may be necessary when working with particulates or gases, & disposable plastic aprons might provide addnl protection. If gowns are of distinctive color, this is a reminder that they should not be worn outside of lab. /Chemical Carcinogens/|PRECAUTIONS FOR "CARCINOGENS": ... Operations connected with synth & purification ... should be carried out under well-ventilated hood. Analytical procedures ... should be carried out with care & vapors evolved during ... procedures should be removed. ... Expert advice should be obtained before existing fume cupboards are used ... & when new fume cupboards are installed. It is desirable that there be means for decreasing the rate of air extraction, so that carcinogenic powders can be handled without ... powder being blown around the hood. Glove boxes should be kept under negative air pressure. Air changes should be adequate, so that concn of vapors of volatile carcinogens will not occur. /Chemical Carcinogens/|PRECAUTIONS FOR "CARCINOGENS": Vertical laminar-flow biological safety cabinets may be used for containment of in vitro procedures ... provided that the exhaust air flow is sufficient to provide an inward air flow at the face opening of the cabinet, & contaminated air plenums that are under positive pressure are leak-tight. Horizontal laminar-flow hoods or safety cabinets, where filtered air is blown across the working area towards the operator, should never be used ... Each cabinet or fume cupboard to be used ... should be tested before work is begun (eg, with fume bomb) & label fixed to it, giving date of test & avg air-flow measured. This test should be repeated periodically & after any structural changes. /Chemical Carcinogens/|For more Preventive Measures (Complete) data for 3,3'-DIMETHOXYBENZIDINE (13 total), please visit the HSDB record page.

PRECAUTIONS FOR "CARCINOGENS": Procurement ... of unduly large amt ... should be avoided. To avoid spilling, carcinogens should be transported in securely sealed glass bottles or ampoules, which should themselves be placed inside strong screw-cap or snap-top container that will not open when dropped & will resist attack from the carcinogen. Both bottle & the outside container should be appropriately labelled. ... National post offices, railway companies, road haulage companies & airlines have regulations governing transport of hazardous materials. These authorities should be consulted before ... material is shipped. /Chemical Carcinogens/|PRECAUTIONS FOR "CARCINOGENS": When no regulations exist, the following procedure must be adopted. The carcinogen should be enclosed in a securely sealed, watertight container (primary container), which should be enclosed in a second, unbreakable, leakproof container that will withstand chem attack from the carcinogen (secondary container). The space between primary & secondary container should be filled with absorbent material, which would withstand chem attack from the carcinogen & is sufficient to absorb the entire contents of the primary container in the event of breakage or leakage. Each secondary container should then be enclosed in a strong outer box. The space between the secondary container & the outer box should be filled with an appropriate quantity of shock-absorbent material. Sender should use fastest & most secure form of transport & notify recipient of its departure. If parcel is not received when expected, carrier should be informed so that immediate effort can be made to find it. Traffic schedules should be consulted to avoid ... arrival on weekend or holiday ... /Chemical Carcinogens/

... CAN CAUSE SKIN IRRITATION ...

NIOSH recommends that o-dianisidine-based dyes be regulated as a potential human carcinogen. /o-Dianisidine-based dyes/|NIOSH considers o-dianisidine to be a potential occupational carcinogen.|NIOSH usually recommends that occupational exposures to carcinogens be limited to the lowest feasible concentration.

Personal protection: particulate filter respirator adapted to the airborne concentration of the substance. Personal protection: chemical protection suit. Vacuum spilled material with specialist equipment.

Separated from oxidants and food and feedstuffs. Well closed.

A harmful concentration of airborne particles can be reached quickly on spraying or when dispersed, especially if powdered.

This substance is probably carcinogenic to humans.

NO open flames.

See EFFECTS OF LONG-TERM OR REPEATED EXPOSURE. AVOID ALL CONTACT!

Use ventilation (not if powder), local exhaust or breathing protection.

Protective gloves. Protective clothing.

Wear face shield or eye protection in combination with breathing protection.

Listed as a hazardous air pollutant (HAP) generally known or suspected to cause serious health problems. The Clean Air Act, as amended in 1990, directs EPA to set standards requiring major sources to sharply reduce routine emissions of toxic pollutants. EPA is required to establish and phase in specific performance based standards for all air emission sources that emit one or more of the listed pollutants. 3,3'-Dimethoxybenzidine is included on this list.

| 0 - Materials that, under emergency conditions, would offer no hazard beyond that of ordinary combustible materials.| 1 - Materials that must be preheated before ignition can occur. Materials require considerable preheating, under all ambient temperature conditions, before ignition and combustion can occur.| 0 - Materials that in themselves are normally stable, even under fire conditions.| 1 - Materials that, under emergency conditions, can cause significant irritation.

3,3'-Dimethoxybenzidine is used as an intermediate in the production of dyes and pigments. No information is available on the acute (short-term), chronic (long-term), reproductive, developmental, or carcinogenic effects of 3,3'-dimethoxybenzidine in humans. Animal studies have reported effects on the liver, kidneys, spleen, and bladder, and endocrine effects, gastritis, intestinal hemorrhage, and weight loss from chronic oral exposure. Increased incidences of tumors in several organs have been reported in rats orally exposed to 3,3'-dimethoxybenzidine or its salt. EPA has classified 3,3'-dimethoxybenzidine as a Group B2, probable human carcinogen.

U091; A toxic waste when a discarded commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or a manufacturing chemical intermediate.

Persons in charge of vessels or facilities are required to notify the National Response Center (NRC) immediately, when there is a release of this designated hazardous substance, in an amount equal to or greater than its reportable quantity of 100 lb or 45.4 kg. The toll free number of the NRC is (800) 424-8802; In the Washington D.C. metropolitan area (202) 426-2675. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV. D.3.b).

U091; As stipulated in 40 CFR 261.33, when 3,3'-dimethoxybenzidine, as a commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or a manufacturing chemical intermediate, becomes a waste, it must be managed according to federal and/or state hazardous waste regulations. Also defined as a hazardous waste is any container or inner liner used to hold this waste or any residue, contaminated soil, water, or other debris resulting from the cleanup of a spill, into water or on dry land, of this waste. Generators of small quantities of this waste may qualify for partial exclusion from hazardous waste regulations (40 CFR 261.5(e)).

Toxicity

moderately toxic

LD50 Rat oral 1920 mg/kg

Carcinogenesis studies were conducted by administering 3,3'-dimethoxybenzidine dihydrochloride (greater than 97.5% pure) in drinking water /@ 0, 80, 170, or 330 ppm/ to groups of F344/N rats of each sex for 21 months. ... Average amount of 3,3'-dimethoxybenzidine dihydrochloride consumed per day was approximately 6, 12, or 21 mg/kg for low, mild, or high dose male rats and 7, 14, or 23 mg/kg for low, mid, or high dose female rats. ... Increased incidences of several nonneoplastic lesions were observed in exposed rats, including hematopoietic cell proliferation in the spleen and cystic and centrilobular degeneration and necrosis of the liver. ... There was clear evidence of carcinogenic activity of 3,3'-dimethoxybenzidine dihydrochloride for male F344/N rats, as indicated by benign and malignant neoplasms of the skin, Zymbal gland, preputial gland, oral cavity, intestine, liver, and mesothelium. Increased incidences of astrocytomas of the brain may have been related to chemical administration. There was clear evidence of carcinogenic activity of 3,3'-dimethoxybenzidine dihydrochloride for female F344/N rats, as indicated by benign and malignant neoplasms of the Zymbal gland, clitoral gland, and mammary gland. Increases in neoplasms of the skin oral cavity, large intestine, liver, and uterus/cervix were also considered to be related to chemical administration of 3,3'-dimethoxybenzidine dihydrochloride. /3,3'-Dimethoxybenzidine dihydrochloride/

3,3'-Dimethoxybenzidine's production and use as a chemical intermediate in the production of azo dyes(1) may result in its release to the environment through various waste streams(SRC). 3,3'-Dimethoxybenzidine is apparently not produced in the US any longer but may still be imported into the country(1).

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 230(SRC), determined from a log Kow of 1.81(2) and a regression-derived equation(3), indicates that 3,3'-dimethoxybenzidine is expected to have moderate mobility in soil(SRC). The first pKa of 3,3'-dimethoxybenzidine is estimated as 4.2(SRC), using an estimation method based on perturbed molecular orbital theory and linear free energy (LFER) methods(4). This estimated pKa indicates that 3,3'-dimethoxybenzidine will partially exist in the protonated form under acidic conditions and cations have greater adsorption to soils than neutral molecules(SRC). Furthermore, 3,3'-dimethoxybenzidine is an aromatic amine which may form covalent bonds with humic materials resulting in relatively immobile quinone-like complexes(5). Volatilization of the neutral species of 3,3'-dimethoxybenzidine from moist soil surfaces is not expected to be an important fate process(SRC) based upon an estimated Henry's Law constant of 4.7X10-11 atm-cu m/mole(SRC), developed using a fragment constant estimation method(6). The conjugate acid of 3,3-dimethoxybenzidine will not volatilize since cations are non-volatile(SRC). 3,3'-Dimethoxybenzidine is not expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 1.2X10-7 mm Hg(SRC), determined from a fragment constant method(7). No data were found regarding the biodegradation of 3,3'-dimethoxybenzidine in soils; however, screening studies using sewage sludge inoculum suggest biodegradation will occur slowly in the environment(8,9). Structurally similar compounds such as benzidine are shown to be rapidly oxidized by Fe(III) and other cations which are frequently found in soil(10), which suggest that 3,3'-dimethoxybenzidine may also be degraded by a similar process(SRC).|AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 230(SRC), determined from a log Kow of 1.81(2) and a regression-derived equation(3), indicates that 3,3'-dimethoxybenzidine is expected to adsorb to suspended solids and sediment(SRC). The frist pKa of 3,3'-dimethoxybenzidine is estimated as 4.2(SRC), using an estimation method based on perturbed molecular orbital theory and linear free energy (LFER) methods(4). This estimated pKa indicates that 3,3'-dimethoxybenzidine will partially exist in the protonated form under acidic conditions and cations have greater adsorption to suspended solids and sediment than neutral molecules(SRC). Volatilization of the free base from water surfaces is not expected(3) based upon an estimated Henry's Law constant of 4.7X10-11 atm-cu m/mole(SRC), developed using a fragment constant estimation method(5). The conjugate acid of 3,3'-dimethoxybenzidine will not volatilize since cations are non-volatile(SRC). According to a classification scheme(6), an estimated BCF of 5(SRC), from its log Kow(2) and a regression-derived equation(7), suggests the potential for bioconcentration in aquatic organisms is low(SRC). No information on the biodegradation of 3,3'-dimethoxybenzidine in natural waters was found(SRC), but this compound was reported to be resistant to biodegradation in the Japanese MITI test(8), suggesting biodegradation in waters will most likely occur slowly(SRC). Structurally similar compounds such as benzidine are shown to be rapidly oxidized by Fe(III) and other cations which are frequently found in environmental waters(9), which suggest that 3,3'-dimethoxybenzidine may also be degraded by a similar process(SRC).|ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 3,3'-dimethoxybenzidine, which has an estimated vapor pressure of 1.2X10-7 mm Hg at 25 °C(SRC), determined from a fragment constant method(2), is expected to exist in both the vapor and particulate phases in the ambient atmosphere. Vapor-phase 3,3'-dimethoxybenzidine is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 3 hours(SRC), calculated from its rate constant of 1.3X10-10 cu cm/molecule-sec at 25 °C (SRC)determined using a structure estimation method(3). Since 3,3'-dimethoxybenzidine absorbs light greater than 290 nm(4), it may be susceptible to direct photolysis in the environment(SRC). Particulate-phase 3,3'-dimethoxybenzidine may be removed from the air by wet and dry deposition(SRC).

The rate constant for the vapor-phase reaction of 3,3'-dimethoxybenzidine with photochemically-produced hydroxyl radicals has been estimated as 1.3X10-10 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 3 hours at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). The first pKa of 3,3'-dimethoxybenzidine is estimated as 4.2(SRC), using an estimation method based on perturbed molecular orbital theory and linear free energy (LFER) methods(2). This estimated pKa indicates that 3,3'-dimethoxybenzidine will partially exist in the protonated form under acidic conditions(SRC). 3,3'-Dimethoxybenzidine absorbs light greater than 290 nm(3) and may be susceptible to photolysis in the environment(SRC). Other than the protonation of the 2 amine groups, 3,3'-dimethoxybenzidine is not expected to undergo hydrolysis due to a lack of hydrolyzable functional groups(4).

An estimated BCF of 5 was calculated for 3,3'-dimethoxybenzidine(SRC), using a log Kow of 1.81(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC).

The Koc of 3,3'-dimethoxybenzidine is estimated as 230(SRC), using a measured log Kow of 1.81(1) and a regression-derived equation(2). According to a classification scheme(3), this estimated Koc value suggests that 3,3'-dimethoxybenzidine is expected to have moderate mobility in soil(SRC). The first pKa of 3,3'-dimethoxybenzidine is estimated as 4.2(SRC), using an estimation method based on perturbed molecular orbital theory and linear free energy (LFER) methods(4). This estimated pKa indicates that 3,3'-dimethoxybenzidine will partially exist in the protonated form under acidic conditions and cations have greater adsorption to soils than neutral molecules(SRC). Furthermore, 3,3'-dimethoxybenzidine is an aromatic amine which may form covalent bonds with humic materials resulting in relatively immobile quinone-like complexes(5).

The first pKa of 3,3'-dimethoxybenzidine is estimated as 4.2(SRC), using an estimation method based on perturbed molecular orbital theory and linear free energy (LFER) methods(1). This estimated pKa indicates that 3,3'-dimethoxybenzidine will partially exist in the protonated form under acidic conditions and cations will not volatilize from water or soil surfaces(SRC). The Henry's Law constant for the neutral species (free base) of 3,3'-dimethoxybenzidine is estimated as 4.7X10-11 atm-cu m/mole(SRC) using a fragment constant estimation method(2). This Henry's Law constant indicates that 3,3'-dimethoxybenzidine is expected to be essentially nonvolatile from water surfaces(3). 3,3'-Dimethoxybenzidine's Henry's Law constant(2) indicates that volatilization from moist soil surfaces is not expected(SRC). 3,3'-Dimethoxybenzidine is not expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 1.2X10-7 mm Hg(SRC), determined from a fragment constant method(4).

Processes in which dried dye is handled have the greatest potential for employee exposure during the manufacture or repackaging of benzidine-based dyes. ... During use of benzidine-based dyes, the greatest potential for exposure would be expected to be among dye-weighers who handle dry powders. /Benzidine-based dyes/|Human exposure ... is possible through inhalation of dye particles from equipment, vent systems; & skin absorption from finished dyed product, textile processing, mixing operations, or packaging processes.|Workers potentially exposed to DMOB /3,3'-dimethoxybenzidine/ are dye makers and o-dianisidine diisocyanate prodn workers. However, current prodn processes for DMOB and dyes made from DMOB are generally closed systems with minimal risk to workers.|It has been estimated that approximately 1,000 workers are exposed to /3,3'-Dimethoxybenzidine/ during dye manufacturing and that perhaps as many as 15,000 workers are exposed in the various dye application industries.|NIOSH (NOES Survey 1981-1983) has statistically estimated that 2,482 workers (866 of these are female) are potentially exposed to 3,3'-dimethoxybenzidine in the US(1). Occupational exposure to 3,3'-dimethoxybenzidine may occur through inhalation and dermal contact with this compound at workplaces where 3,3'-dimethoxybenzidine is used(SRC).

Drug Information

O-DIANISIDINE HAS BEEN FOUND IN URINE OF WORKERS EXPOSED TO THIS CMPD.|(14)C-labeled 3,3'-dimethoxybenzidine was absorbed through rat skin after application of an acetone soln, and only 29% had disappeared from the application site in 24 hr. It was found in the tissues and excreta.|The carcinogenic aromatic amine 3,3'-dimethoxybenzidine was rapidly metabolized in the rat. Thirty min after iv admin of (14)C-3,3'-dimethoxybenzidine less than 2% of the dose could be recovered from the animal as the parent cmpd. Extensive biliary excretion (70%) resulted in the accumulation of 50% in the intestinal tract. Three days after either oral or iv dosing, 50% of the admin radiolabel had been excreted in the feces and 30-40% excreted in the urine while 45% of the remaining radiolabel was present in the liver in the form of covalently bound metabolites.|... In 1954 /results from laboratory tests indicated/ that skin is principal portal of entry of benzidines. ... It was considered likely that the hydrochloride salt could be absorbed percutaneously. /Benzidines/|For more Absorption, Distribution and Excretion (Complete) data for 3,3'-DIMETHOXYBENZIDINE (6 total), please visit the HSDB record page.

BISAZOBIPHENYL DYE DERIVED FROM 3,3'-DIMETHOXYBENZIDINE WAS METABOLIZED TO 3,3'-DIMETHOXYBENZIDINE IN BOTH THE DOG AND RAT. THE N-ACETYL DERIV OF 3,3'-DIMETHOXYBENZIDINE WAS IDENTIFIED IN URINE FROM RATS TREATED WITH DYE DERIVED FROM 3,3'-DIMETHOXYBENZIDINE.|... AFTER ADMIN OF A DOSE OF 1 G O-DIANISIDINE TO 2 DOGS, 0.4% FREE DIAMINE & ... 5% OF A METABOLITE WITH PROPERTIES SIMILAR TO ... 3,3'-DIHYDROXYBENZIDINE WERE EXCRETED IN URINE.|The carcinogenic aromatic amine 3,3'-dimethoxybenzidine was rapidly metabolized in the rat. GC/MS studies of urine and bile demonstrated the presence of 8 previously unidentified metabolites formed via-N-acetylation, hydroxylation, O-demethylation, and glucuronidation.|The conventional Ames assay metabolising system was confirmed to be deficient in its ability to N-acetylate. This may render the test less sensitive to compounds which normally have an acetylation step during their in vivo activation to carcinogens. The addition of acetyl-coenzyme A to the S9 mix in the Ames assay increased the mutagenicity of benzidine in Salmonella typhimurium strains TA98 and TA1538 4-5-fold. This was consistent with the observation that benzidine is N-acetylated prior to deoxyribonucleic acid binding in vivo in rat liver. Two 3,3'-disubstituted benzidines, o-tolidine and o-dianisidine, were also tested. A smaller increase in o-tolidine mutagenicity, compared to that observed with benzidine, occurred with the addition of acetyl-coenzyme A. However, the production of acetylated metabolites from o-tolidine was only 37% of that from benzidine. The mutagenicity of o-dianisidine was unaffected by acetyl-coenzyme A. Acetylation of o-dianisidine was only 16% of that observed with benzidine, and the N-acetyl derivatives of o-dianisidine showed lower mutagenicity than the parent amine.|For more Metabolism/Metabolites (Complete) data for 3,3'-DIMETHOXYBENZIDINE (12 total), please visit the HSDB record page.

Exposure Routes: inhalation, skin absorption, ingestion, skin and/or eye contact Symptoms: Irritation skin Target Organs: Skin, kidneys, liver, thyroid, liver (NIOSH, 2016)|Carcinogens, Mutagens

EYES: First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop. SKIN: IMMEDIATELY flood affected skin with water while removing and isolating all contaminated clothing. Gently wash all affected skin areas thoroughly with soap and water. IMMEDIATELY call a hospital or poison control center even if no symptoms (such as redness or irritation) develop. IMMEDIATELY transport the victim to a hospital for treatment after washing the affected areas. INHALATION: IMMEDIATELY leave the contaminated area; take deep breaths of fresh air. IMMEDIATELY call a physician and be prepared to transport the victim to a hospital even if no symptoms (such as wheezing, coughing, shortness of breath, or burning in the mouth, throat, or chest) develop. Provide proper respiratory protection to rescuers entering an unknown atmosphere. Whenever possible, Self-Contained Breathing Apparatus (SCBA) should be used; if not available, use a level of protection greater than or equal to that advised under Protective Clothing. INGESTION: DO NOT INDUCE VOMITING. If the victim is conscious and not convulsing, give 1 or 2 glasses of water to dilute the chemical and IMMEDIATELY call a hospital or poison control center. Be prepared to transport the victim to a hospital if advised by a physician. If the victim is convulsing or unconscious, do not give anything by mouth, ensure that the victim's airway is open and lay the victim on his/her side with the head lower than the body. DO NOT INDUCE VOMITING. IMMEDIATELY transport the victim to a hospital. OTHER: Since this chemical is a known or suspected carcinogen you should contact a physician for advice regarding the possible long term health effects and potential recommendation for medical monitoring. Recommendations from the physician will depend upon the specific compound, its chemical, physical and toxicity properties, the exposure level, length of exposure, and the route of exposure. (NTP, 1992)|(See procedures)


Fresh air, rest.


Remove contaminated clothes. Rinse and then wash skin with water and soap.


First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Basic treatment: Establish a patent airway. Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with normal saline during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patent can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Aniline and related compounds/|Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious. Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start an IV with D5W /SRP: "To keep open", minimal flow rate/. Use lactated Ringer's if signs of hypovolemia are present. Watch for signs of fluid overload. Administer 1% solution methylene blue if patient is symptomatic with severe hypoxia, cyanosis, and cardiac compromise not responding to oxygen. ... . For hypotension with signs of hypovolemia, administer fluid cautiously. Consider vasopressors if hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Treat seizures with diazepam (Valium) ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Aniline and related compounds/

NO EPIDEMIOLOGICAL DATA ON OCCURRENCE OF CANCER IN WORKERS EXPOSED TO O-DIANISIDINE ALONE APPEAR IN LITERATURE. MOST WORKERS EXPOSED ... HAVE ALSO BEEN EXPOSED TO RELATED AMINES SUCH AS BENZIDINE, WHICH HAS BEEN STRONGLY ASSOCIATED WITH OCCURRENCE OF URINARY BLADDER CANCER IN MAN.

3,3' Dimethoxybenzidine

The substance can be absorbed into the body by inhalation, through the skin and by ingestion.|inhalation, skin absorption, ingestion, skin and/or eye contact

irritation skin; In Animals: kidney, liver damage; thyroid, spleen changes; [potential occupational carcinogen]


Cough.


Redness.

Skin, kidneys, liver, thyroid, liver

Dianisidine Use and Manufacturing

Methods of Manufacturing

The methyl ether of o-nitrophenol is reduced by zinc dust and caustic soda to the hydrazo cmpd which is then rearranged with hydrochloric acid.

Uses

o-Dianisidine (3,3'-DIMETHOXYBENZIDINE) is a colorless or Light purple to brown, highly toxic, crystalline compound that turns violet when exposed to air. manufacture of azo dyes and pigments. o-Dianisidine 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. o-Dianisidine is used for the detection of Au, Co, Cu, SCN-, V; determination of Au, NO2-, Ce(IV) (spectrophotometrically). Ortho Dianisidine may be used in a novel automated method, used to measure the total antioxidant response (TAR) against potent free radical reactions. It may also be used along with glucose oxidase and peroxidase in the determination of blood and urinary glucose. o-Dianisidine is used as a redox indicator. 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. Exposure to this substance causes skin irritation and sensitization. Dianisidine is reasonably anticipated to be a human carcinogen based on evidence of carcinogenicity in experimental animals. (NCI05)

Production

(1967) 368,000 lbs

ESSENTIALLY 100% AS A CHEM INT FOR DYES AND PIGMENTS

IT IS AVAILABLE COMMERCIALLY AS FREE BASE (TECHNICAL AND 99% GRADES) AND AS ITS DIHYDROCHLORIDE.

[1,1'-Biphenyl]-4,4'-diamine, 3,3'-dimethoxy-: ACTIVE|3,3'-Dimethoxybenzidine is apparently not produced in the US any longer but may still be imported into the country.

THIN-LAYER CHROMATOGRAPHY.|NIOSH Method 5031. Dyes, Benzidine, o-Toluidine, o-Anisidine. HPLC UV detection.|OSW Method 8270B. Determination Semivolatile Organic compounds by Gas Chromatography/Mass Spectrometry (GC/MS): Capillary Column Technique.|EPA Method 1625. Semivolatile Organic Compounds by Isotope Dilution GCMS.|For more Analytic Laboratory Methods (Complete) data for 3,3'-DIMETHOXYBENZIDINE (6 total), please visit the HSDB record page.

Hazardous Air Pollutants (HAPs)|Health Hazards -> Carcinogens, Mutagens

Computed Properties

Molecular Weight:244.29
XLogP3:2.2
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:3
Exact Mass:244.121177757
Monoisotopic Mass:244.121177757
Topological Polar Surface Area:70.5
Heavy Atom Count:18
Complexity:236
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes

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