M-Phenylenediamine

log Kow = -0.33

-0.33

0.0

1.0696 at 136 °F (NTP, 1992) - Denser than water; will sink

1.0096 g/cu cm at 58 °C

Density = 1.139

1.14 g/cm³

1.0696 at 136 °F

1.139 @25 °C

WHITE CRYSTALS BECOMING RED ON EXPOSURE TO AIR

Colorless needles

RHOMBIC CRYSTALS FROM ALCOHOL

COLORLESS RHOMBIC NEEDLES

Dark oxidation products /are/ present in compound exposed to moist air.

less than 1 mg/mL at 66 °F (NTP, 1992)

SOL IN WATER, METHANOL, ETHANOL, CHLOROFORM, ACETONE, DIMETHYLFORMAMIDE, METHYL ETHYL KETONE, DIOXANE; SLIGHTLY SOL IN ETHER, CARBON TETRACHLORIDE, ISOPROPANOL, DIBUTYL PHTHALATE. VERY SLIGHTLY SOL IN BENZENE, TOLUENE, XYLENE, BUTANOL.

In water, 2.38X10+5 mg/l at 20 deg

Solubility in water: soluble

280 °F (NTP, 1992)

187 °C c.c.

280 °F

540 to 543 °F at 760 mmHg (NTP, 1992)

284-287 °C

284-287 °C

540-543 °F

287 °C @760 [mm Hg]

145 to 147 °F (NTP, 1992)

145-147 °F

62-63 °C

62-63 °C

145-147 °F

65 °C

Danger

H301: Toxic if swallowed [Danger Acute toxicity, oral]

P203, P261, P262, P264, P264+P265, P270, P271, P272, P273, P280, P301+P316, P302+P352, P304+P340, P305+P351+P338, P316, P318, P321, P330, P333+P317, P337+P317, P361+P364, P362+P364, P391, P403+P233, P405, and P501 (click each P-code to see the statement)

Danger

H301+H311+H331 (23.9%): Toxic if swallowed, in contact with skin or if inhaled [Danger Acute toxicity, oral; acute toxicity, dermal; acute toxicity, inhalation]

P203, P261, P262, P264, P264+P265, P270, P271, P272, P273, P280, P301+P316, P302+P352, P304+P340, P305+P351+P338, P316, P318, P321, P330, P333+P317, P337+P317, P361+P364, P362+P364, P391, P403+P233, P405, and P501 (click each P-code to see the statement)

Chemical: 1,3-Benzenediamine

1,3-Benzenediamine is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of 1,3-Benzenediamine are required to report information about their production and use of this chemical to the EPA under the Toxic Substances Control Act (TSCA). (40 eCFR Part 711)

Status: Active Update: 28-05-2020 https://echa.europa.eu/registration-dossier/-/registered-dossier/14386

1,3-Phenylenediamine: Does not have an individual approval but may be used under an appropriate group standard

The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)

This chemical is combustible. Dust may form explosive mixtures in air (NTP, 1992)

Combustible. Gives off irritating or toxic fumes (or gases) in a fire.

FIRE POINT: 175 °C.

Combustible when exposed to heat or flame.

SYMPTOMS: Symptoms of exposure to this chemical may include skin sensitization reactions, eye irritation and injury, skin irritation, dermatitis, blackened skin and bronchial asthma. Other symptoms may include allergic skin reactions, irritation of the mucous membranes, nose, throat and lungs, coughing, burning sensation, runny nose, sore throat, methemoglobinemia, cyanosis, headache, dizziness, drowsiness, mental confusion, pulmonary edema, kidney and liver damage, central nervous system effects and conjunctivitis. Eye contact may cause discomfort, tearing, blurring of vision, reddening, partial clouding of the cornea and swelling of the eye and surrounding tissue. Dysuria and eosinophiluria may also occur. Exposure may also result in respiratory tract irritation.

In acute studies at lethal doses (650 mg/kg), animals have tremors, convulsions, cyanosis, and methemoglobinemia. In subchronic studies, rats have increased liver weights. Critical Effects are irritation; liver; Confirmed Animal Carcinogen with Unknown Relevance to Humans; [ACGIH] Danger of skin sensitization; [MAK]

ITC/USEPA; Information Review #102 (Draft) m-Phenylenediamine (1979)

TRDB/USEPA; Technical Support Document (Draft) Phenylenediamines (1984)

NIOSH: Current Intelligence Bulletin 2,4-Diaminoanisole #19 (1978)

TSCA CHIPs present a preliminary assessment of 1,4-Benzenediamine's potential for injury to human health & the environment (available at EPA's TSCA Assistance Office: (202) 554-1404 or (800) 424-9065).

USEPA; PHENYLENEDIAMINES; RESPONSE TO INTERAGENCY TESTING COMMITTEE; FED REGIST 47(5) 973 (1982). EVIDENCE IS GIVEN SUPPORTING TESTING OF THE CLASS OF COMPOUNDS PHENYLENEDIAMINES FOR THEIR TOXIC EFFECTS ON HUMAN HEALTH AND THE ENVIRONMENT. THE RESULTS OF TOXICITY TESTING OF 22 COMPOUNDS ARE TABULATED AS ARE THE EFFECTS FOR WHICH TESTING IS BEING CONSIDERED FOR 13 COMPOUNDS, AND THE USES OR POTENTIAL USES OF 47 PHENYLENEDIAMINES.

Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. 1,3-Benzenediamine is included on this list.

Manufacturers and processors of meta-phenylenedimine are required to conduct health efffects, chemical fate and environmental effects testing under TSCA section 4.

Excerpt from ERG Guide 153 [Substances - Toxic and/or Corrosive (Combustible)]:

Use water spray, powder.

Fresh air, rest. Refer for medical attention.

Remove contaminated clothes. Rinse and then wash skin with water and soap. Refer for medical attention .

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

Rinse mouth. Refer for medical attention .

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.

SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.

Recommendable method: Incineration. Peer-review: (Peer-review conclusions of an IRPTC expert consultation (May 1985))

Personal protection: complete protective clothing including self-contained breathing apparatus. Do NOT let this chemical enter the environment. Sweep spilled substance into covered containers. If appropriate, moisten first to prevent dusting. Carefully collect remainder. Then store and dispose of according to local regulations.

Paraoxon (diethyl-p-nitrophenylphosphate) is the toxic, but non-mutagenic metabolite of the organophosphorus ester insecticide parathion. ... A mutagenic synergy when paraoxon was incubated with plant activated m-phenylenediamine (mPDA) or with direct acting 2-acetoxyacetylaminofluorene ... and Salmonella typhimurium tester strains /was discovered/. ... /With/ non-toxic concn of plant activated mPDA and paraoxon a 10-fold incr in the mutant yield of S. typhimurium was observed. The mutagenicity of the plant activated mPDA product required that O-acetyltransferase (OAT) be expressed by the S. typhimurium tester strain. However, the paraoxon dependent mutagenic synergy was observed using the direct acting arylamine metabolite, 2AAAF, with strains YG1024, TA98 and TA98/1,8-DNP6 regardless of their OAT activity. This mutagenic synergy is dependent upon the presence of an activated acetylated form of the arylamine. The data presented here demonstrate that this mutagenic synergy is limited to paraoxon and not to the parent compound (parathion) or to a major metabolite of parathion (p-nitrophenol).

TERRESTRIAL FATE: Based on a recommended classification scheme(1), an estimated Koc value of 16(SRC), determined from a measured log Kow of -0.33(2) and a recommended regression-derived equation(3), indicates that 1,3-benzenediamine is expected to have very high mobility in soil(SRC). However, anilines are expected to bind strongly to humus or organic matter in soils due to the high reactivity of the aromatic amino group(4,5); therefore, mobility may be much lower in some soils(SRC). Volatilization of 1,3-benzenediamine is not expected to be important from moist soil surfaces(SRC) given an estimated Henry's Law constant of 1.3X10-9 atm-cu m/mole(SRC), from its extrapolated vapor pressure, 2.1X10-3 mm Hg(6), and measured water solubility, 2.4X10+5 mg/l(7). 1,3-Benzenediamine is not expected to volatilize from dry soil surfaces based on its extrapolated vapor pressure(6). Limited biodegradation data indicate 1,3-benzenediamine may be resistant to biodegradation in soil; soil microflora did not cleave the benzene ring of 1,3-benzenediamine in 64 days(8).

AQUATIC FATE: Based on a recommended classification scheme(1), an estimated Koc value of 16(SRC), determined from a measured log Kow of -0.33(2) and a recommended regression-derived equation(3), indicates that 1,3-benzenediamine is not expected to adsorb to suspended solids and sediment in water(SRC). However, aromatic amines are recognized as having a strong affinity to organic carbon, suggesting that this compound may bind strongly to suspended organic material in water(4,5). 1,3-Benzenediamine is not expected to volatilize from water surfaces(3,SRC) based on an estimated Henry's Law constant of 1.3X10-9 atm-cu m/mole(SRC), derived from its extrapolated vapor pressure, 2.1X10-3 mm Hg(6), and measured water solubility, 2.4X10+5 mg/l(7). 1,3-Benzenediamine may exist partially in the ionized form at environmental pH's based on pKa values of 2.65 and 4.88 at 25 °C(8). Volatilization of the ionized form is not expected to be an important fate process(SRC). According to a classification scheme(9), BCF values of 1.3 to 4.6 and <1.6 to 24 measured for 1,3-benzenediamine in carp at 2 and 0.2 mg/l, respectively(10), suggest that bioconcentration in aquatic organisms is low(SRC). 1,3-Benzenediamine in the water column may be susceptible to significant photooxidation via hydroxyl and peroxy radicals; half-lives for these photooxidations may be on the order of 19-30 sunlight hours(11). Aqueous screening studies indicate 1,3-benzenediamine may be susceptible to microbial degradation(SRC); 60% degradation was observed after 5 days using an acclimated activated sludge inoculum(12). 1,3-Benzenediamine was reported to be toxic to 3 unacclimated sludges at concns greater than 50 ppm(13).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 1,3-benzenediamine, which has an extrapolated vapor pressure of 2.1X10-3 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase 1,3-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 about 1.9 hours(3,SRC). 1,3-Benzenediamine absorbs light in the environmental spectrum(4), which suggests a potential for direct photolysis in the environment(SRC).

On the basis of the animal and clinical data included in this report, the CIR Expert Panel concludes that m-Phenylenediamine and m-Phenylenediamine Sulfate are safe for use in hair dyes at concentrations of up to 10%.

Safe for use in cosmetics, with qualifications

Blue lips, fingernails and skin. Confusion. Convulsions. Dizziness. Headache. Nausea. Unconsciousness.

MAY BE ABSORBED! Redness. Further see Inhalation.

Redness. Pain.

See Inhalation.

m-Phenylenediamine

Hepatic

6 x 10 ^-3 mg/kg-day

The Koc of 1,3-benzenediamine is estimated as approximately 16(SRC), using a measured log Kow of -0.33(1) and a regression-derived equation(2,SRC). According to a recommended classification scheme(3), this estimated Koc value suggests that 1,3-benzenediamine is expected to have very high mobility in soil(SRC). However, anilines are expected to bind strongly to humus or organic matter in soils due to the high reactivity of the aromatic amino group(4,5); therefore, mobility may be much lower in some soils(SRC).

m-Phenylenediamine (CAS # 108-45-2) commercial grade, was evaluated for dermal carcinogenicity in 24-month skin-painting study with male and female C3H and C57BL/6 mice (40 and 20/sex/group, respectively) exposed daily to doses of 0.6 or 3.0 mg/day. Mice were sacrificed for histologic evaluation at a rate and time determined by incidence of tumor-bearing mice during the course of treatment. Study lethalities and survivors killed at termination of study were necropsied for examination of major organ systems and the brain to determine degree of substance absorption and potential systemic toxicity. Diagnosis of any gross pathology upon these analyses were confirmed histologically. In 24-month study, mortality was significantly higher in the 3 mg, B6 males, however no increased risk of skin tumors was established for either strain or sex of mice in association with treatment.

meta-Phenylenediamine (CAS # 108-45-2) was evaluated for clastogenic effects in male and female Crl:CDBR mice (5-6/sex/group) following gavage dosing (2 doses, 24 hours apart) at concentrations of 0, 16, 33, and 65 mg/kg bodyweight. Five animals/sex/group were sacrificed for harvest of femur bone marrow and 1000 polychromatic erythrocytes/animal at 24 hours (all treatment groups) and 48 hours (0 and 65 mg/kg/day groups) after a second dose. Bone marrow smears were analyzed for treatment-related incidence of micronuclei in polychromatic erythrocytes. At all dose levels, in vivo observations included lethargy, half-closed eyes, and labored and/or rapid breathing. A solitary 65 mg/kg/day male found dead 24 hours after a second dose comprised the study mortality and weight loss in 33 and 65 mg/kg/day treatment groups was statistically significant. Upon cytogenetic evaluation, there was no statistically significant increase in micronucleated polychromatic erythrocytes in any treatment group relative to vehicle control (deionized water). The only statistically significant (p < 0.05; Dunnett's test) finding from all bone marrow smears was a reduction in young, polychromatic erythrocytes.

m-Phenylenediamine (CAS # 108-45-2) was evaluated for acute oral neurotoxicity in Crl:CDBR rats (12/sex/group) administered single gavage doses of 0, 75, 150, and 300 mg/kg (10 ml/kg in sterile water). Bodyweight, feed consumption, clinical signs, functional observational battery performance, fore-, and hindlimb grip strength, foot splay, and motor activity were assessed prior to treatment (baseline values), and at 1 hour, 24 hours, and 4 days post-treatment. Toxicity was demonstrated at all dose levels and generally to a greater extent in females. Females at the 150 and 300 mg/kg dose level, one and eight rats, respectively, were found dead prior to scheduled sacrifice, death occurring from 2-4 days after treatment. All study lethalities were found with pallor and staining. Significant weight loss within one day of dosing and persisting throughout Day 4 was common to 150 and 300 mg/kg treatment groups, while food consumption was adversely affected in a dose-related manner. A rebounding of food consumption and bodyweights was noted thereafter. Clinical signs were apparent from day of dosing and included dose-related pallor in females, and irregular head movements, coloration of urine and a tip-toe gait in males and females. The functional observational battery revealed significant general malaise, postural changes, and palpebral closure. High-dose females also showed diminished arousal. Measurements of fore- and hindlimb grip strength and foot splay were not indicative of a neurotoxicity at any treatment level. Motor activity was significantly depressed following treatment in all treatment groups relative to control (p </= .01), exhibiting a dose-related rate of recovery in the respective groups. Study authors attributed depressed motor activity to a general condition of malaise and reported no evidence of neurotoxicity.

meta-Phenylenediamine (CAS # 108-45-2) was evaluated for subchronic oral neurotoxicity in male and female Crl:CDBR rats (10/sex/group) administered daily gavage doses of 0, 5, 10, and 20 mg/kg for 90 consecutive days. A functional observational battery and motor activity tests were conducted prior to dosing and at weeks 4, 8, and 13 during treatment. Male rats only exhibited minimal dose-related reductions in both horizontal (10 and 20 mg/kg groups) and vertical motor activity (20 mg/kg group) during treatment weeks 4 and 8 relative to controls. Study authors attributed these findings, which were not statistically significant, to general malaise characterized by lethargy rather than a direct effect of treatment on the central nervous system. Neuropathological evaluation at termination of study yielded no anomalies within the nervous system or skeletal muscle.

For more TSCA Test Submissions (Complete) data for 1,3-BENZENEDIAMINE (8 total), please visit the HSDB record page.

Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. 1,3-Benzenediamine is included on this list.

Manufacturers and processors of meta-phenylenedimine are required to conduct health efffects, chemical fate and environmental effects testing under TSCA section 4.

In all experiments concerning the absorption of m-phenylenediamine through the skin, increases in ferrihemoglobin (methemoglobin) concentration of various degrees were observed. ... The delay of the ferrihemoglobin formation /indicates that/ a transformation of the m-phenylenediamine is necessary for ferrihemoglobin formation. ... 6 mg of m-phenylenediamine/kg injected intravenously, ... took more than two hours before the formation of ferrihemoglobin had attained its maximum speed.

m-Phenylenediamine is metabolized in the liver ... as well as being excreted unchanged in the urine.

Groups of seven male Wistar rats were dermally exposed for 24 hr to 556 mumol (14)C-meta-phenylenediamine (MPD; 1,3-diaminobenzene) in either aqueous solution (Group 2) or 4% hydrogen peroxide (Group 3). ... Three N-acetylated metabolites (N-acetyl-1,3-diaminobenzene, N,N'-diacetyl-2,4-diaminophenol and N,N-diacetyl-1,3-diaminobenzene) accounted for 49 and 37% of the urinary excretion of group 2 and 3 rats, respectively, indicating that such metabolites represent important pathways in the metabolism of MPD. Minor exception of at least one highly hydrophilic, unidentified metabolite of MPD was demonstrated. ...

The absorption of m-phenylenediamine ... through dog skin, was studied by determining its concentration in the blood. ... After the gel containing 1.5 g of m-phenylendiamine had been applied to the skin, the m-phenylenediamine concentration in the blood rose quickly. In one hour, it approached the level which was maintained through /to/ the last hour of the dermal contact. ... Three hours after the m-phenylenediamine had been washed off the skin, no detectable concentration was found in the blood.

After the /dog abdominal/ skin was washed, m-phenylenediamine concentration in the blood was observed to decline more rapidly than was the case with p-phenylenediamine and 2,5-diaminotoluene.

META-PHENYLENEDIAMINE IS EXCRETED RAPIDLY, UNCHANGED, WITH LITTLE ABSORPTION.

. Groups of seven male Wistar rats were dermally exposed for 24 hr to 556 mumol (14)C-meta-phenylenediamine (MPD; 1,3-diaminobenzene) in either aqueous solution (Group 2) or 4% hydrogen peroxide (Group 3). The percutaneous absorption and the amount of non-excreted radioactivity were significantly higher in Group 2 rats. Radioactivity associated with DNA purified from the liver and kidneys was demonstrated. Urine was the principal route of excretion, especially in Group 2 rats. Rats in Group 3 excreted significantly more MPD in the faeces than did Group 2 rats. Urinary excretion of material that constituted two of the peaks in the high-performance liquid chromatogram demonstrated first-order elimination kinetics. ...

CIR ingredient: m-Phenylenediamine

Used to make diisocyanates for the production of polyurethane foams and other resins and polymers; Also used as a corrosion inhibitor, curing agent, photographic developer, and intermediate for other chemical products; [CHEMINFO] Used to make dyes, to develop dyes, to dye hair, and to cure epoxy resins; [ACGIH]

Plastic Composites Manufacturing [Category: Industry]

MFR DYES; RUBBER CURING AGENTS; ION EXCHANGE RESINS, DECOLORIZING RESINS, FORMALDEHYDE CONDENSATES; RESINOUS POLYAMIDES, BLOCK POLYMERS, TEXTILE FIBERS, URETHANES, PETROLEUM ADDITIVES, RUBBER CHEMICALS; IN CORROSION INHIBITORS; IN PHOTOGRAPHY; AS REAGENT FOR GOLD & BROMINE

Dyestuff manufacture, detection of nitrite, textile developing agent, laboratory reagent, vulcanizing agent.

IT IS ... EMPLOYED AS CURING AGENT TO HARDEN EPOXY RESINS USED IN CASTING & PLASTIC TOOLING, LAMINATING APPLICATIONS & IN ADHESIVES. IT IS ADDED TO ISOPHTHALOYL CHLORIDE TO PRODUCE POLY-META-PHENYLENE ISOPHTHALAMIDE RESIN, A POLYAMIDE FIBER (NOMEX) USED IN HIGH-TEMP APPLICATIONS, EG PROTECTIVE CLOTHING ...

m-Phenylenediamine: purity 99.5% minimum /with the following constituents:/ water-insoluble matter, 0.1% maximum; moisture content, 0.1% maximum; moisture content, 0.1% maximum; dinitrobenzene, 0.1% maximum; p-Phenylenediamine, 500 mg/kg maximum; o-Phenylenediamine, 200 mg/kg maximum.

In Japan, m-phenylenediamine is available with a minimum purity of 98.5%. ... Dinitrobenzene and phenylenediamine isomers are /found/ as impurities.

(1977) 8.31X10+6 GRAMS (PRINCPL CUSTMS DISTS)

0-135,700 lb (1976-1982)

2023: 10,000,000 - <25,000,000 lb

(1977) AT LEAST 4.54X10+7 GRAMS

(1983) < 20,000,000 lb (estimate)

Production figures for m-phenylenediamine are not available. ... From an analysis of two of its principle uses ... infer that production for the 1976-1977 time period could have been as high as 6 million pounds.

PREPN: PREPARED BY THE REDUCTION OF M-DINITROBENZENE: KUHN, US PATENT 2,768,209 (1956 TO RINGWOOD); FAUST, J PRAKT CHEM 6, 14 (1958); NEILSON ET AL, J CHEM SOC 1962, 371; TALLEE, PELTIER, COMPT REND 259, 400 (1964).

PREPN: REDUCTION OF META-DINITROBENZENE OR NITROANILINE WITH IRON & HYDROCHLORIC ACID. PURIFIED BY CRYSTALLIZATION.

Plastics Material and Resin Manufacturing

1,3-Benzenediamine: ACTIVE