N,N-Dimethyl-p-phenylenediamine

136.19

136.19

508105

202-807-5

7GZH2FMK7X

1493

2811

DTXSID6025149

Reddish-violet crystals|Needles from benzene

2921590090

29.3

1.25 (est)

black crystalline

1.036 g/cm³ @ Temp: 20 °C

53 °C

262 °C

130 °C

1.607

H2O: 11 g/L (20 ºC);soluble in alcohol, chloroform, ether

2-8°C

7.51X10-3 mm Hg at 25 deg C (est)

4.69 (NTP, 1992) (Relative to Air)

Henry's Law constant = 3.03X10-8 atm-cu m/mol at 25 °C (est)

pKa = 6.59 at 25 °C (conjugate acid)

Stable in air when pure|Degraded by light and air|White to grayish-white, hygroscopic crystalline powder. Freely soluble in water; soluble in alcohol /N,N-Dimethyl-p-phenylenediamine dihydrochloride/|Hydroxyl radical reaction rate constant = 2.013X10-10 cu cm/molec-sec at 25 °C (est)

No rapid reaction with air. No rapid reaction with water.

Amines, Aromatic

DIMETHYL-P-PHENYLENEDIAMINE neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides. Incompatible with strong oxidizers, strong acids and acid anhydrides. Also incompatible with alkalis (NTP, 1992).

II

6.1

UN 2811 6.1/PG 2

3

23/24/25-36/37/38

28-45-36/37/39-26

ST0874000

T

Toxic/Keep Cold

Stable. Incompatible with acid chlorides, acid anhydrides, strong acids, strong oxidizing agents. Combustible.

P261-P280-P301 + P310-P311

H301 + H311 + H331

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal and plant life; and conformance with environmental and public health regulations.|Product: Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a licensed professional waste disposal service to dispose of this material. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. Contaminated packaging: Dispose of as unused product.

Acid chlorides, Acid anhydrides

When heated to decomposition, it emits toxic fumes of nitrogen oxides. (EPA, 1998)

|Danger|H300 (10.42%): Fatal if swallowed [Danger Acute toxicity, oral]|P261, P264, P270, P271, P280, P301+P310, P302+P352, P304+P340, P311, P312, P321, P322, P330, P361, P363, P403+P233, P405, and P501|Aggregated GHS information provided by 48 companies from 5 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.|H301: Toxic if swallowed [Danger Acute toxicity, oral]|H300: Fatal if swallowed [Danger Acute toxicity, oral]|P261, P262, P264, P270, P271, P280, P301+P310, P302+P350, P304+P340, P310, P311, P321, P322, P330, P361, P363, P403+P233, 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)

(Nonspecific -- Phenylenediamine). Do not touch material; stop leak if it can be done without risk. Keep unnecessary people away. Isolate area and deny entry. Stay upwind and out of low areas. For small spills, use shovel to place material into clean, dry container and cover; move containers from spill area. For large spills, dike far ahead to collect for later disposal. (EPA, 1998)

For emergency situations, wear a positive pressure, pressure-demand, full facepiece self-contained breathing apparatus (SCBA) or pressure- demand supplied air respirator with escape SCBA and a fully-encapsulating, chemical resistant suit. (EPA, 1998)|Hand protection: Handle with gloves.|Respiratory protection: Where risk assessment shows air-purifying respirators are appropriate use a full-face particle respirator type N100 (US) or type P3 (EN 143) respirator cartridges as a backup to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).|Eye protection: Face shield and safety glasses. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).|Skin and body protection: Complete suit protecting against chemicals, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.

Not flammable or combustible.

Suitable extinguishing media Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide. Special protective equipment for firefighters Wear self contained breathing apparatus for fire fighting if necessary.

Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Methods and materials for containment and cleaning up: Pick up and arrange disposal without creating dust. Sweep up and shovel. Keep in suitable, closed containers for disposal.

Precautions for safe handling: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Provide appropriate exhaust ventilation at places where dust is formed.

N,N-Dimethyl-p-phenylenediamine is a severe skin irritant in man.

Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Dimethyl-p-phenylenediamine is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 10 or 10,000 lbs. Extremely hazardous substances that are solids are subject to either of two threshold planning quantities ... The lower quantity applies only if the solid exists in powdered form and has a particle size less than 100 microns; or is handled in solution or in molten form; or meets the criteria for a National Fire Protection Association (NFPA) rating of 2, 3 or 4 for reactivity. If the solid does not meet any of these criteria, it is subject to the upper ... threshold planning quantity ... .

IDENTIFICATION AND USE: N,N-Dimethyl-p-benzenediamine forms colorless needles or reddish-violet crystals. It is used in microscopy, as a reagent in some chemical and biochemical tests, as a base for production of methylene blue, and as a photodeveloper. It is also used in laboratories to screen bacterial culture plates for Neisseria gonorrheae. HUMAN EXPOSURE AND TOXICITY: N,N-Dimethyl-p-benzenediamine is a severe skin irritant. There have been occasional reports of positive patch tests. In human erythrocytes it produced ferrihemoglobin (methemoglobin), diminished glutathione, and thioethers. ANIMAL STUDIES: Studies on the carcinogenic activity of N,N-Dimethyl-p-benzenediamine in rats gave no indications that the substance has carcinogenic potential. The substance was shown to be a severe skin irritant in the rabbit and caused systemic toxicity after absorption through the skin. Subcutaneous injection of N,N-Dimethyl-p-benzenediamine at 25 mg/100 g in rats produced focal necrosis and myofibrillar contracture in skeletal muscles. In the red muscle fibers, band-shaped injury foci accompanied by rapid and intensive plasma cell infiltration was observed. In the white muscle fibers, nodular foci were accompanied by slow, mild plasma cell infiltration. N,N-Dimethyl-p-benzenediamine is not embryotoxic, fetotoxic or teratogenic in rats. It was positive in bacterial mutagenicity assay with Salmonella typhimurium strains TA100 and TA98 with or without activation, and in vitro in CHO cell cytogenetics-sister chromatid exchange assay with or without activation. It was negative in vitro in CHO cell cytogenetics-chromosome aberrations assay with or without activation. Phenolic metabolites and a nitrosamine have been found in the urine and the feces following the oral administration of N,N-Dimethyl-p-benzenediamine to rats.

LD50 Rats oral 171 mg/kg bw|LD50 Rats oral 67 mg/kg bw

N,N-Dimethyl-p-benzenediamine's production and use as a chemical intermediate and reagent(1) may result in its release to the environment through various waste streams(SRC).

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 38(SRC), determined from a structure estimation method(2), indicates that N,N-dimethyl-p-benzenediamine is expected to have very high mobility in soil(SRC). The pKa of N,N-dimethyl-p-benzenediamine is 6.59(3), indicating that this compound will exist partially in the cation form in the environment and cations generally adsorb more strongly to soils containing organic carbon and clay than their neutral counterparts(4). Aromatic amines are expected to bind strongly to humus or organic matter in soils due to the high reactivity of the aromatic amino group(5,6); therefore, mobility may be much lower in some soils(SRC). N,N-Dimethyl-p-benzenediamine is not expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 7.91X10-3 mm Hg(SRC), determined from a fragment constant method(7). Volatilization of the neutral species of N,N-dimethyl-p-benzenediamine from moist soil surfaces is not expected to be an important fate process(SRC) given an estimated Henry's Law constant of 3.0X10-8 atm-cu m/mole(SRC), using a fragment constant estimation method(7). N,N-Dimethyl-p-benzenediamine is not expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 7.9X10-3 mm Hg at 25 °C(SRC), determined from a fragment constant method(2). Biodegradation data in soil were not available(SRC, 2014).|AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 38(SRC), determined from a structure estimation method(2), indicates that N,N-dimethyl-p-benzenediamine is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is not expected(3) based upon an estimated Henry's Law constant of 3.0X10-8 atm-cu m/mole(SRC), developed using a fragment constant estimation method(4). N,N-Dimethyl-p-benzenediamine in the water column may be susceptible to photo-oxidation via hydroxyl and peroxy radicals; half-lives for these photo-oxidations may be on the order of 19-30 sunlight hours(5). According to a classification scheme(6), an estimated BCF of 3(SRC), from an estimated log Kow of 1.25(2) and a regression-derived equation(2), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Biodegradation data in water were not available(SRC, 2014).|ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), N,N-dimethyl-p-benzenediamine, which has an estimated vapor pressure of 7.9X10-3 mm Hg at 25 °C((SRC), determined from a fragment constant method(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase N,N-dimethyl-p-benzenediamine 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 2 hrs(SRC), calculated from its rate constant of 2.0X10-10 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). N,N-Dimethyl-p-benzenediamine contains chromophores that absorb at wavelengths >290 nm(4) and, therefore, may be susceptible to direct photolysis by sunlight(SRC).

The rate constant for the vapor-phase reaction of N,N-dimethyl-p-benzenediamine with photochemically-produced hydroxyl radicals has been estimated as 2.0X10-10 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 2 hours at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). N,N-Dimethyl-p-benzenediamine is not expected to undergo hydrolysis in the environment due to the lack of functional groups that hydrolyze under environmental conditions(3). N,N-Dimethyl-p-benzenediamine contains chromophores that absorb at wavelengths >290 nm(3) and, therefore, may be susceptible to direct photolysis by sunlight(SRC). As a class, aromatic amines react relatively rapidly in sunlit natural waters via reaction with photochemically-produced hydroxyl radicals and peroxy radicals(4); typical half-lives for hydroxyl radical and peroxy radical reactions are on the order of 19-30 sunlight hours(4).

An estimated BCF of 23 was calculated for N,N-dimethyl-p-benzenediamine(SRC), using an estimated log Kow of 1.25(1) and a regression-derived equation(2). According to a classification scheme(2), this BCF suggests the potential for bioconcentration in aquatic organisms is low.

Using a structure estimation method based on molecular connectivity indices(1), the Koc for the unprotonated form of N,N-dimethyl-p-benzenediamine can be estimated to be 38(SRC). According to a classification scheme(2), this estimated Koc value suggests that N,N-dimethyl-p-benzenediamine is expected to have very high mobility in soil. However, aromatic amines are expected to bind strongly to humus or organic matter in soils due to the high reactivity of the aromatic amino group(3,4); therefore, mobility may be much lower in some soils(SRC). The pKa of N,N-dimethyl-p-benzenediamine is 6.59(5), indicating that this compound will exist partially in the cation form in the environment and cations generally adsorb to organic carbon and clay more strongly than their neutral counterparts.

The Henry's Law constant for N,N-dimethyl-p-benzenediamine is estimated as 3.0X10-8 atm-cu m/mole(SRC) using a fragment constant estimation method(1). N,N-Dimethyl-p-benzenediamine is not expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 7.91X10-3 mm Hg(SRC), determined from a fragment constant method(3).

NIOSH (NOES Survey 1981-1983) has statistically estimated that 50 workers (50 of these are female) are potentially exposed to N,N-dimethyl-p-benzenediamine in the US(1). Occupational exposure to N,N-dimethyl-p-benzenediamine may occur through inhalation and dermal contact with this compound at workplaces where N,N-dimethyl-p-benzenediamine is produced or used(SRC).

The contribution of the radical cation versus the quinonediimine on redox and addition reactions was studied in human red blood cells exposed to N,N-dimethyl-p-phenylenediamine (99989) (DMPD). A direct reaction occurred between DMPD and oxyhemoglobin under the formation of ferrihemoglobin (methemoglobin) and the N,N-dimethyl-p-phenylenediamine radical cation (DMPP.+). Quinonediimine could not be excluded as the ultimate ferrihemoglobin forming oxidant. Addition of excess DMPD shifted the reaction towards the radical side, increasing ferrihemoglobin formation. This showed that the radical was the responsible oxidant. Reactions with glutathione occurred predominantly with the quinonediimine. In corresponding reactions with N,N,N',N'-tetramethyl-p-phenylenediamine radical cation, the disproportionation reaction of DMPD.+ was very fast. The formation of glutathione disulfide was negligible. Two isomeric glutathione adducts represented the main reaction products. DMPD in human erythrocytes produced many equivalents of ferrihemoglobin, diminished glutathione, and produced both thioethers. DMPD and glutathione disappearance as well as thioether appearance occurred only after a marked lag phase. At increasing concentrations of ferrihemoglobin, higher steady state concentrations of the radical were attained. Preformed ferrihemoglobin in red cells accelerated DMPD and glutathione disappearance significantly; ferrihemoglobin complexing cyanide completely prevented this effect. The authors emphasize the metabolic competency of blood for the biotransformation of aromatic amines.|Phenolic metabolites and a nitrosamine have been found in the urine and the feces following the oral administration of N,N-dimethyl-p-phenylenediamine to rats.

Lowest toxic dose with skin effect is 14 mg/kg. Irritant to skin and eyes. (EPA, 1998)

Warning: Dimethyl-p-phenylenediamine is an irritant of the skin and eyes, and is a skin sensitizer. Signs and Symptoms of Dimethyl-P-Phenylenediamine Exposure: Signs and symptoms of acute exposure to dimethyl-p-phenylenediamine may include irritation of skin and eyes, optic neuritis, lenticular opacities, methemoglobinemia, hypoglycemia, hyper-excitability, and convulsions. Emergency Life-Support Procedures: Acute exposure to dimethyl-p-phenylenediamine exposure may require decontamination and life support for the victims. Emergency personnel should wear protective clothing appropriate to the type and degree of contamination. Air-purifying or supplied-air respiratory equipment should also be worn, as necessary. Rescue vehicles should carry supplies such as plastic sheeting and disposable plastic bags to assist in preventing spread of contamination. Inhalation Exposure: 1. Move victims to fresh air. Emergency personnel should avoid self-exposure to dimethyl-p-phenylenediamine. 2. Evaluate vital signs including pulse and respiratory rate and note any trauma. If no pulse is detected, provide CPR. If not breathing, provide artificial respiration. If breathing is labored, administer 100% humidified oxygen or other respiratory support. 3. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures. 4. Transport to a health care facility. Dermal/Eye Exposure: 1. Remove victims from exposure. Emergency personnel should avoid self-exposure to dimethyl-p-phenylenediamine. 2. Evaluate vital signs including pulse and respiratory rate and note any trauma. If no pulse is detected, provide CPR. If not breathing, provide artificial respiration. If breathing is labored, administer 100% humidified oxygen or other respiratory support. 3. Remove contaminated clothing as soon as possible. 4. If eye exposure has occurred, eyes must be flushed with lukewarm water for at least 15 minutes. 5. Wash exposed skin areas thoroughly with soap and water. 6. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures. 7. Transport to a health care facility. Ingestion Exposure: 1. Evaluate vital signs including pulse and respiratory rate and note any trauma. If no pulse is detected, provide CPR. If not breathing, provide artificial respiration. If breathing is labored, administer 100% humidified oxygen or other respiratory support. 2. DO NOT induce vomiting or attempt to neutralize. 3. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures. 4. Give the victims water or milk: children up to 1 year old, 125 mL (4 oz or 1/2 cup); children 1 to 12 years old, 200 mL (6 oz or 3/4 cup); adults, 250 mL (8 oz or 1 cup). Water or milk should be given only if victims are conscious and alert. 5. Activated charcoal may be administered if victims are conscious and alter. Administer charcoal slurry, aqueous or mixed with saline cathartic or sorbitol. Usual charcoal dose: 30 to 100 g in adults and 15 and 30 g in children (1 to 2 g/kg in infants). Administer one dose of a cathartic, mixed with charcoal or given separately. 6. Promote excretion by administering a saline cathartic or sorbitol to conscious and alert victims. Children require 15 to 30 g (1/2 to 1 oz) of cathartic; 50 to 100 g (1-3/4 to 3-1/2 oz) is recommended for adults. 7. Transport to a health care facility. (EPA, 1998)

/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Aromatic hydrocarbons and related compounds/|/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). 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 pulmonary edema and treat if necessary ... . 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 0.9% saline (NS) 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 patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Aromatic hydrocarbons and related compounds/|/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Consider drug therapy for pulmonary edema ... . Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias if necessary ... Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... .Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Aromatic hydrocarbons and related compounds/

/SIGNS AND SYMPTOMS/ N,N-Dimethyl-p-phenylenediamine is a severe skin irritant in man. There have been occasional reports of positive patch tests.|/CASE REPORTS/ Three cases of allergic contact dermatitis due to N,N-dimethyl-para-phenylenediamine in a bacteriology laboratory are presented. This chemical, a dye closely related to the common contact allergen para-phenylenediamine, is used in laboratories to screen bacterial culture plates for Neisseria gonorrheae. The three patients had strongly positive patch test reactions to N,N-dimethyl-para-phenylenediamine, but had negative reactions to para-phenylenediamine.

N,N-dimethyl-p-phenylenediamine

1,4-Benzenediamine, N1,N1-dimethyl-: ACTIVE

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