Identification and Related Records
- 【Name】
- 4,4'-Methylenedianiline
- 【Registry number】
- 101-77-9 (CAS DataBase Reference)
- 【Synonyms】
-
4,4'-methylenedianiline
,4'-Methylenebisaniline
4-(4-Aminobenzyl)phenylamine
4,4'-diaminodiphenylmethan
4,4’-diaminoditan
4,4'-methylenebisaniline
4,4'-methylenebis-benzenamin
4,4'-methylenebisbenzenamine
4,4'-Diamino diphenyl methane
DADPM
MDA
- 【EINECS(EC#)】
- 202-974-4
- 【Molecular Formula】
- C13H14N2 (Products with the same molecular formula)
- 【Molecular Weight】
- 198.27
- 【Inchi】
- InChI=1/C13H14N2/c14-12-5-1-10(2-6-12)9-11-3-7-13(15)8-4-11/h1-8H,9,14-15H2
- 【InChIKey】
- YBRVSVVVWCFQMG-UHFFFAOYSA-N
- 【Canonical SMILES】
- C1=CC(=CC=C1CC2=CC=C(C=C2)N)N
101-77-9.mol
Chemical and Physical Properties
- 【Appearance】
- white to yellow or beige flakes or crystals
- 【Density】
- 1.15
- 【Melting Point】
- 88-92℃
- 【Boiling Point】
- 398-399℃ (768 torr)
- 【Vapour】
- 1.52E-06mmHg at 25°C
- 【Flash Point】
- 221℃
- 【Water】
- Slightly soluble.
- 【Solubilities】
- Slightly soluble. <0.1 g/100 mL at 19 oC
- 【Color/Form】
- Crystals from water or benzene
Tan flakes, lumps, or pearly leaflets from benzene
Plates or needles (water); plates (benzene)
Light-brown crystals
Light tan to white crystalline solid
- 【Stability】
- Stable under normal temperatures and pressures.
- 【Storage temp】
- Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.
- 【Spectral properties】
- SADTLER REFERENCE NUMBER: 7846 (IR, PRISM)
Intense mass spectral peaks: 198 m/z (100%), 106 m/z (33%), 182 m/z (19%), 199 m/z (14%)
MASS: 29855 (NIST/EPA/MSDC Mass Spectral Database 1990 version)
IR: 6249 (Coblentz Society Spectral Collection)
UV: 18317 (Sadtler Research Laboratories Spectral Collection)
1H NMR: 11592 (Sadtler Research Laboratories Spectral Collection)
- 【Computed Properties】
- Molecular Weight:198.26366 [g/mol]
Molecular Formula:C13H14N2
XLogP3:1.6
H-Bond Donor:2
H-Bond Acceptor:2
Rotatable Bond Count:2
Exact Mass:198.115698
MonoIsotopic Mass:198.115698
Topological Polar Surface Area:52
Heavy Atom Count:15
Formal Charge:0
Complexity:157
Isotope Atom Count:0
Defined Atom Stereocenter Count:0
Undefined Atom Stereocenter Count:0
Defined Bond Stereocenter Count:0
Undefined Bond Stereocenter Count:0
Covalently-Bonded Unit Count:1
Feature 3D Donor Count:2
Feature 3D Cation Count:2
Feature 3D Ring Count:2
Effective Rotor Count:2
Conformer Sampling RMSD:0.6
CID Conformer Count:3
Safety and Handling
- 【Hazard Codes】
- T:Toxic;N:Dangerousfortheenvironment;
- 【Risk Statements】
- R39/23/24/25;R43;R45;R48/20/21/22;R51/53
- 【Safety Statements 】
- S45;S53;S61
- 【HazardClass】
- 6.1
- 【Safety】
-
Confirmed carcinogen with experimental tumorigenic data. Human poison by ingestion. Poison by subcutaneous and intraperitoneal routes. Human systemic effects by ingestion: rigidity, jaundice, other liver changes. An eye irritant. Mutation data reported. It is not rapidly absorbed through the skin. Combustible when exposed to heat or flame. When heated to decomposition it emits highly toxic fumes of aniline and NOx.
Hazard Codes:
T,
N
Risk Statements: 45-39/23/24/25-43-48/20/21/22-51/53-68
R45:May cause cancer.
R39:Danger of very serious irreversible effects.
R23/24/25:Toxic by inhalation, in contact with skin and if swallowed.
R48:Danger of serious damage to health by prolonged exposure.
R20/21/22:Harmful by inhalation, in contact with skin and if swallowed.
R51/53:Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.
R68:Possible risk of irreversible effects.
Safety Statements: 53-45-61
S53:Avoid exposure - obtain special instructions before use.
S45:In case of accident or if you feel unwell, seek medical advice immediately (show the label whenever possible.)
S61:Avoid release to the environment. Refer to special instructions / safety data sheets.
RIDADR: UN 2651 6.1/PG 3
WGK Germany: 3
RTECS: BY5425000
HazardClass: 6.1
PackingGroup: III
- 【PackingGroup 】
- III
- 【Skin, Eye, and Respiratory Irritations】
- Eye irritant
- 【Cleanup Methods】
- FACILITY AND PROCESS ARE DISCUSSED FOR REMOVAL OF METHYLENEDIANILINE.
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/
- 【Transport】
- UN 2651
- 【Fire Fighting Procedures】
- Combustable when exposed to hear or flame.
- 【Fire Potential】
- Combustable when exposed to hear or flame.
- 【Formulations/Preparations】
- With a diamine assay of 98-99%
Sold in flaked or granular form
- 【DOT Emergency Guidelines】
- /GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Fire or Explosion: Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors, and sewers explosion hazards. Those substances designated with a "P" may polymerize explosively when heated or involved in a fire. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Health: TOXIC; inhalation, ingestion, or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Public Safety: CALL Emergency Response Telephone Number ... 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. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas.
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Protective Clothing: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Evacuation: ... 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.
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Fire: Small fires: Dry chemical, CO2 or water spray. Large fires: Dry chemical, CO2, alcohol-resistant foam or water spray. Move containers from fire area if you can do it without risk. Dike fire control water for later disposal; do not scatter the material. Fire involving tanks or car/trailer loads: Fight fire from maximum distance or use unmanned hose holders or monitor nozzles. Do not get water inside containers. Cool containers with flooding quantities of water until well after fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. ALWAYS stay away from tanks engulfed in fire.
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Spill or Leak: ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area). Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. Prevent entry into waterways, sewers, basements or confined areas. Absorb or cover with dry earth, sand or other non-combustible material and transfer to containers. DO NOT GET WATER INSIDE CONTAINERS.
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ First Aid: Move victim to fresh air. Call 911 or emergency medical service. Give artificial respiration if victim is not breathing. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device. Administer oxygen if breathing is difficult. Remove and isolate contaminated clothing and shoes. In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes. For minor skin contact, avoid spreading material on unaffected skin. Keep victim warm and quiet. Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed. Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.
- 【Reactivities and Incompatibilities】
- Strong oxidizers.
- 【Other Preventative Measures】
- 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/
PRECAUTIONS FOR "CARCINOGENS": Principles that apply to chem or biochem lab also apply to microbiological & cell-culture labs ... Special consideration should be given to route of admin. ... Safest method of administering volatile carcinogen is by injection of a soln. Admin by topical application, gavage, or intratracheal instillation should be performed under hood. If chem will be exhaled, animals should be kept under hood during this period. Inhalation exposure requires special equipment. ... unless specifically required, routes of admin other than in the diet should be used. Mixing of carcinogen in diet should be carried out in sealed mixers under fume hood, from which the exhaust is fitted with an efficient particulate filter. Techniques for cleaning mixer & hood should be devised before expt begun. When mixing diets, special protective clothing &, possibly, respirators may be required. /Chemical Carcinogens/
PRECAUTIONS FOR "CARCINOGENS": When ... admin in diet or applied to skin, animals should be kept in cages with solid bottoms & sides & fitted with a filter top. When volatile carcinogens are given, filter tops should not be used. Cages which have been used to house animals that received carcinogens should be decontaminated. Cage-cleaning facilities should be installed in area in which carcinogens are being used, to avoid moving of ... contaminated /cages/. It is difficult to ensure that cages are decontaminated, & monitoring methods are necessary. Situations may exist in which the use of disposable cages should be recommended, depending on type & amt of carcinogen & efficiency with which it can be removed. /Chemical Carcinogens/
PRECAUTIONS FOR "CARCINOGENS": To eliminate risk that ... contamination in lab could build up during conduct of expt, periodic checks should be carried out on lab atmospheres, surfaces, such as walls, floors & benches, & ... interior of fume hoods & airducts. As well as regular monitoring, check must be carried out after cleaning-up of spillage. Sensitive methods are required when testing lab atmospheres. ... Methods ... should ... where possible, be simple & sensitive. /Chemical Carcinogens/
PRECAUTIONS FOR "CARCINOGENS": Rooms in which obvious contamination has occurred, such as spillage, should be decontaminated by lab personnel engaged in expt. Design of expt should ... avoid contamination of permanent equipment. ... Procedures should ensure that maintenance workers are not exposed to carcinogens. ... Particular care should be taken to avoid contamination of drains or ventilation ducts. In cleaning labs, procedures should be used which do not produce aerosols or dispersal of dust, ie, wet mop or vacuum cleaner equipped with high-efficiency particulate filter on exhaust, which are avail commercially, should be used. Sweeping, brushing & use of dry dusters or mops should be prohibited. Grossly contaminated cleaning materials should not be re-used ... If gowns or towels are contaminated, they should not be sent to laundry, but ... decontaminated or burnt, to avoid any hazard to laundry personnel. /Chemical Carcinogens/
PRECAUTIONS FOR "CARCINOGENS": Doors leading into areas where carcinogens are used ... should be marked distinctively with appropriate labels. Access ... limited to persons involved in expt. ... A prominently displayed notice should give the name of the Scientific Investigator or other person who can advise in an emergency & who can inform others (such as firemen) on the handling of carcinogenic substances. /Chemical Carcinogens/
The worker should immediately wash the skin when it becomes contaminated.
The worker should wash daily at the end of each work shift, and prior to eating, drinking, smoking, etc.
Work clothing that becomes wet or significantly contaminated should be removed or replaced.
Workers whose clothing may have become contaminated should change into uncontaminated clothing before leaving the work premises.
SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.
SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. Quality assurance to ascertain the completeness of the cleaning procedures should be implemented before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at end of shift, but should remain at employee's place of work for cleaning.
SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a POTW is acceptable only after review by the governing authority. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must meet Hazardous Material Criteria for disposal.
- 【Protective Equipment and Clothing】
- 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.
Eyewash fountains should be provided in areas where there is any possbility 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.]
Respirator Recommendations: At concentrations above the NIOSH REL, or where there is no REL, at any detectable concentration: Assigned Protection Factor (APF) Respirator Recommendation APF = 10,000 Any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode. APF = 10,000 Any supplied-air respirator that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxillary self-contained positive-pressure breathing apparatus.
Respirator Recommendations: Escape conditions: Assigned Protection Factor (APF) Respirator Recommendation APF = 50 Any air-purifying, full-facepiece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister having an N100, R100, or P100 filter./Any appropriate escape-type, self-contained breathing apparatus
- 【Specification】
-
4,4'-Methylenedianiline , its cas register number is 101-77-9. It also can be called 4,4'-Diaminodiphenylmethan ; 4,4'-Methylenebis(benzeneamine) ; 4-(4-Aminobenzyl)aniline ; Ancamine TL ; Aniline, 4,4'-methylenedi- ; Benzenamine, 4,4'-methylenebis- ; Bis(4-aminophenyl)methane ; Bis-p-aminofenylmethan ; Curithane ; Dadpm ; Di-(4-aminophenyl)methane ;
Diaminodiphenylmethane ; Methylenebis(aniline) ; Sumicure M ; p,p'-Diaminodifenylmethan ; p,p'-Methylenedianiline ; p-Toluidine, alpha-(p-aminophenyl)- .
- 【Octanol/Water Partition Coefficient】
- log Kow = 1.59
- 【Report】
-
NTP 10th Report on Carcinogens. IARC Cancer Review: Group 2B IMEMDT IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Man . 7 ,1987,p. 56.(World Health Organization, Internation Agency for Research on Cancer,Lyon, France.: ) (Single copies can be ordered from WHO Publications Centre U.S.A., 49 Sheridan Avenue, Albany, NY 12210) ; Animal Sufficient Evidence IMEMDT IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Man . 39 ,1986,p. 347.(World Health Organization, Internation Agency for Research on Cancer,Lyon, France.: ) (Single copies can be ordered from WHO Publications Centre U.S.A., 49 Sheridan Avenue, Albany, NY 12210) ; Animal Inadequate Evidence IMEMDT IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Man . 4 ,1974,p. 79.(World Health Organization, Internation Agency for Research on Cancer,Lyon, France.: ) (Single copies can be ordered from WHO Publications Centre U.S.A., 49 Sheridan Avenue, Albany, NY 12210) . Community Right-To-Know List. Reported in EPA TSCA Inventory.
- 【Disposal Methods】
- SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational exposure 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, aquatic, and plant life; and conformance with environmental and public health regulations.
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/
PRECAUTIONS FOR "CARCINOGENS": HEPA (high-efficiency particulate arrestor) filters ... can be disposed of by incineration. For spent charcoal filters, the adsorbed material can be stripped off at high temp & carcinogenic wastes generated by this treatment conducted to & burned in an incinerator. ... LIQUID WASTE: ... Disposal should be carried out by incineration at temp that ... ensure complete combustion. SOLID WASTE: Carcasses of lab animals, cage litter & misc solid wastes ... should be disposed of by incineration at temp high enough to ensure destruction of chem carcinogens or their metabolites. /Chemical Carcinogens/
PRECAUTIONS FOR "CARCINOGENS": ... Small quantities of ... some carcinogens can be destroyed using chem reactions ... but no general rules can be given. ... As a general technique ... treatment with sodium dichromate in strong sulfuric acid can be used. The time necessary for destruction ... is seldom known ... but 1-2 days is generally considered sufficient when freshly prepd reagent is used. ... Carcinogens that are easily oxidizable can be destroyed with milder oxidative agents, such as saturated soln of potassium permanganate in acetone, which appears to be a suitable agent for destruction of hydrazines or of compounds containing isolated carbon-carbon double bonds. Concn or 50% aqueous sodium hypochlorite can also be used as an oxidizing agent. /Chemical Carcinogens/
PRECAUTIONS FOR "CARCINOGENS": Carcinogens that are alkylating, arylating or acylating agents per se can be destroyed by reaction with appropriate nucleophiles, such as water, hydroxyl ions, ammonia, thiols & thiosulfate. The reactivity of various alkylating agents varies greatly ... & is also influenced by sol of agent in the reaction medium. To facilitate the complete reaction, it is suggested that the agents be dissolved in ethanol or similar solvents. ... No method should be applied ... until it has been thoroughly tested for its effectiveness & safety on material to be inactivated. For example, in case of destruction of alkylating agents, it is possible to detect residual compounds by reaction with 4(4-nitrobenzyl)-pyridine. /Chemical Carcinogens/
Use and Manufacturing
- 【Use and Manufacturing】
- Methods of Manufacturing
... From aniline and formaldehyde; ... By hydrogenolysis of p,p'-diaminobenzophenone with LiAlH4.
Acid-catalyzed reaction of formaldehyde with aniline; distillation from polymeric 4,4'-diaminodiphenylmethane.U.S. Imports
(1972) 1.6X10+6 G
(1974) 1.00X10+6 GU.S. Production
(1972 SALES) 8.57X10+8 G
(1975) 4.10X10+8 G (SALES)
Benzenamine, 4,4'-methylenebis- is listed as a High Production Volume (HPV) chemical (65FR81686). Chemicals listed as HPV were produced in or imported into the U.S. in >1 million pounds in 1990 and/or 1994. The HPV list is based on the 1990 Inventory Update Rule. (IUR) (40 CFR part 710 subpart B; 51FR21438).
Production volumes for non-confidential chemicals reported under the Inventory Update Rule. Year Production Range (pounds) 1986 >100 million - 500 million 1990 >1 million - 10 million 1994 >1 million - 10 million 1998 >1 million - 10 million 2002 >1 million - 10 million
- 【Usage】
- Determination of tungsten & sulfates, as corrosion inhibitor, prepn of azo dyes.
- 【Sampling Procedures】
- NIOSH Method 5029. Analyte: 4,4'-methylenedianiline. Matrix: Air. Sampler: Filter (acid-treated glass fibers, 37 mm). Flow Rate: 1 to 2 l/min. Sample Size: 100 liters. Shipment: Transfer filter to glass vial; extract with 4 ml 0.1 N methanolic potassium hydroxide before shipping. Sample Stability: Stable at least 60 days at 20 deg C.
Biomedical Effects and Toxicity
- 【Pharmacological Action】
- - Substances that increase the risk of NEOPLASMS in humans or animals. Both genotoxic chemicals, which affect DNA directly, and nongenotoxic chemicals, which induce neoplasms by other mechanism, are included.
- 【Biomedical Effects and Toxicity】
- ... Male rats, guinea pigs and monkeys /were/ treated topically with a low (2 mg/kg bw) or high (20 mg/kg bw) dose of 14C-MDA. In rats, 43% and 10% of the low dose was recovered in urine and feces during a 96 hours period; 2% remained in tissues and skin washing removed 25% of dose. The remainder (26%) was recovered by skin extraction and solubilisation. The percentage of dose absorbed decreased by increasing the dose, but the total amount absorbed (approx. 0.225 mg/rat) was similar after both doses. In guinea pigs, 10% and 18% of the low dose was excreted in urine and feces; 1% was recovered in tissue, 41% in the skin wash and 29% from the application area. The percent of dose absorbed decreased following the high dose, but the amounts absorbed (in mg/animal) doubled.
... The percutaneous absorption of MDA /was invesitgated using/ ... full-thickness rat and human skin in vitro. In this study MDA was topically applied (17.7 - 40.6 ug/sq cm in ethanol) to unoccluded skin, using a flow-through diffusion cell. After 72 hours the absorption into the receptor fluid reached 6.1 +/- 2.0% for rat skin and 13.0 +/- 4.3% for human skin related to applied dose. When the skin was occluded, the absorption of MDA was significantly enhanced reaching approx. 13.3% and 33% for rat and human skin, respectively. At the end of each experiment, considerable residual material remained with the skin (about 23-58%).
MDA is absorbed via skin as well as from the gastrointestinal tract.
The disposition of MDA was also examined following iv administration. In rats, 67% and 31% of the low dose (2 mg/kg bw) was recovered in urine and feces by 96 hr after dosing. In monkeys, the radioactivity occurred primarily in the urine (85%) by 168 hr after dosing (2 mg/kg bw). In guinea pigs, however, 35% and 57% of the dose were eliminated in urine and feces, respectively, during 96 hours.
... The in vivo mass balance of (14)C-MDA /was studied/ in rats and rabbits given a single ip dose of the compound. Four male rats, and a male rabbit of each acetylator phenotype were administered 30 mg/kg and 50 mg/kg of (14)C-MDA, respectively. The excretion of radioactivity into the urine and feces was followed daily for 4 days. Since the compound was administered by the intraperitoneal route, the amount of fecal radioactivity provided an indication of biliary excretion. The results show that both species excrete a majority of the radioactivity within two days. In the rat, the main route of excretion is the feces (55.8%) compared to urine (35.0%); whereas the rabbit, regardless of phenotype, excretes about 80% of the radiolabel in the urine. The total recovery of radioactivity from the rat and slow acetylator rabbit is about 10% less than the recovery from the fast acetylator rabbit. This difference in recovery between fast and slow acetylating rabbits is associated with the greater fecal excretion by the fast acetylator rabbit. The residual radioactivity in the organs tends to localize in the liver, kidney, spleen and thyroid at both 24 and 96 hours.
Renal excretion of MDA and its metabolites dominates in rats (after i.v. administration) and monkeys and rabbits. However, after i.p. administration of MDA reported for rats the excretion via the feces as main way.
A single dose of (14)C-ring labeled 4,4'-methylenedianiline (2 or 20 mg/kg) in ethanol/water was applied to the back of rats and the area was covered with a cup. After an exposure of 6 hours, a total of approximately 12% of the applied radioactivity was recovered in the urine, feces, gastrointestinal tract and tissues; 62% was recovered in a wash with soap and water, and 30% remained in the application site (total recoveries from radiotracer studies often exceed 100%). A 24-hour exposure period resulted in a combined 27% of the dose in urine, feces, gastrointestinal tract and tissues, 52% in the wash, and 25% in the application site. After a 96-hour exposure period, 55% of the dose was accounted for by the combined urine, feces, gastrointestinal tract, and tissues, 25% was in the wash and 26% in the application site. The results also showed that after washing, test material which remained within the skin continued to be absorbed. Moreover, occlusion facilitated absorption. When two dose levels were tested, the amount of radioactivity in tissues was higher after the high dose, but the proportion of the applied dose was lower than with the low dose, which suggested a dose-dependent absorption rate. Finally, a greater percentage of the dose was absorbed when the application site was washed with acetone and water 5 minutes after dosing than when washed with soap and water.
The distribution of 4,4'-methylenedianiline (or metabolites) has also been studied in rats and guinea pigs after a single intravenous injection. Rats were injected (14)C-ring-labeled 4,4'-methylenedianiline (2 mg/kg) in ethanol water and sacrifices were conducted 6, 24, or 96 after dosing. After 6 hours, the gastrointestinal tract had the highest amount of radioactivity (24% of the dose); this was followed by the liver (9.5%), skin (3.2%), and blood (2.8%). Twenty-four hours after the injection, the amount of radioactivity had decreased considerably in all tissues, and the liver and gastrointestinal tract had about 4% of the administered dose. Ninety-six hours after dosing, the liver had 4 or more times higher radioactivity (0.9%) than any other tissue. On a per gram basis, the liver had the highest concentration of radioactivity at all times, followed by the lungs at 6 and 24 hours and the spleen at 96 hours. Except for the liver, no preferential accumulation was apparent. The guinea pigs were treated the same as the rats except that sacrifices were conducted only 96 hours after the injection. As a percentage of the applied dose, the liver had the most radioactivity, about 3 times that found in blood. On a per gram basis, radioactivity was most concentrated in the spleen, followed by the liver, and preferential accumulation in these organs was suggested. Total recovery as a percentage of the dose, in blood, tissues, and gastrointestinal tract was 0.55%, 2.4% and 0.61%, respectively.
In monkeys, most of the dose (79%) was excreted in the urine within the first 48 hours; at this time 6.5% of the dose appeared in the feces. Total recovery of radioactivity over a the 168-hour collection period amounted to 94% of the injected dose. As seen in rats, urine was the main route of excretion in monkeys.
In order to estimate human exposure it is useful to determine percutaneous penetration. Previous studies have suggested that both rat and human skin were permeable to MDA, with greater penetration being seen through human skin. In this study no significant difference was seen between the percutaneous penetration of MDA through human or rat skin for three different treatment levels: 0.01, 0.1 and 1mg per skin membrane (0.32 sq cm). The apparent dermal flux was calculated as 0.7 +/- 0.3 and 10.1 +/- 2.0 ug/sq cm/hr for the 0.01 and 0.1 mg treatments, respectively. The permeability constant K(p) was estimated at 1.8 x 10(-3) cm/hr and the lag time at 3.5 +/- 0.5 hr. MDA absorbed into the skin was found to be bioavailable. Experiments also showed that after application of 0.1 mg MDA, 4% penetrated through latex and nitrile gloves, respectively. The potential genotoxicity of MDA in human skin was assessed by DNA (32)P-postlabelling; levels of DNA adducts were detected, following the treatment and penetration of 1mg MDA. [Kenyon, SH et al; Toxicology 196 (1-2): 65-75 (2004)] PubMed Abstract
...Gender affected the disposition of 4,4'-diaminodiphenylmethane (DAPM) metabolites. At 25 mg DAPM/ kg, male rats had greater amounts of DAPM/metabolite in bile and liver, while females had greater amounts in serum and urine. ... [Dugas, TR et al; Journal of Toxicology and Environmental Health. Part A 62 (6): 467-483 (2001)] PubMed Abstract
Five healthy volunteers /were exposed/ dermally for 1 hr to 0.75-2.25 umol MDA dissolved in isopropanol, by use of a patch-test technique. Determination of MDA remaining in the patch units after exposure showed that a median of 28% (range 25-29%) was absorbed. After hydrolyzing MDA has been determined in plasma with an initial peak and a decline after removing the patch. MDA was also detected in hydrolyzed urine. The maximum rate of MDA excretion in urine was found 6-11 hours after the onset of exposure. Within two subjects studied at three doses, the urinary excretion was proportional to the exposure. The elimination half-lives in plasma and urine had medians at 13 and 7 hours, respectively. In eight out of nine exposures, the elimination half-life was longer in plasma than in urine. Slow acetylation seemed to be associated with short elimination half-life in urine. The median of total MDA amount excreted in urine during 48 hours, was 33 nmol for the five subjects exposed to 0.75 umol, which corresponds to roughly 16% (range 2%-26%) of the absorbed dose.
Excretion of metabolites occurs fastest when exposure is via inhalation, dermal absorption will result in slower excretion.
... Given as an ip injection in propylene glycol at a dose of 5 mg DAPM/kg body wt, about 25% appears in the bile within 24 hr in the form of 3 or 4 unidentified metabolites.
Environmental Fate and Exposure Potential
- 【Environmental Fate/Exposure Summary】
- TERRESTRIAL FATE: Based on a classification scheme(1), Koc values ranging from 3825 to 5681(2), indicate that 4,4'-diaminodiphenylmethane is expected to have slight to no mobility in soil(SRC). Volatilization of 4,4'-diaminodiphenylmethane from moist soil surfaces is not expected to be an important fate process(SRC) given an estimated Henry's Law constant of 5.30X10-11 atm-cu m/mole(SRC), based upon its vapor pressure, 2.03X10-7 mm Hg(3), and water solubility, 1.00E+3(4). 4,4'-Diaminodiphenylmethane is not expected to volatilize from dry soil surfaces(SRC) based upon its vapor pressure(3). A 0% of theoretical BOD using activated sludge in the Japanese MITI test(5) suggests that biodegradation will not be an important environmental fate process in soil(SRC).
AQUATIC FATE: Based on a classification scheme(1), measured Koc values ranging from 3825 to 5681(2), indicate that 4,4'-diaminodiphenylmethane is 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 5.30X10-11 atm-cu m/mole(SRC), derived from its vapor pressure, 2.03X10-7 mm Hg(4), and water solubility, 1.00E+3(5). According to a classification scheme(6), BCF values of 3.0 to 14(7) suggest the bioconcentration in aquatic organisms is low(SRC). 4,4'-Diaminodiphenylmethane, present at 100 mg/L, reached 0% of its theoretical BOD in 4 weeks using an activated sludge inoculum at 30 mg/L in the Japanese MITI test(7), suggesting that biodegradation will not be an important fate process in the aquatic environment(SRC).
ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 4,4'-diaminodiphenylmethane, which has a vapor pressure of 2.03X10-7 mm Hg at 25 deg C(2), will exist in both the vapor and particulate phases in the ambient atmosphere. Vapor-phase 4,4'-diaminodiphenylmethane 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 12.8 hours(SRC), calculated from its rate constant of 3.00X10-11 cu cm/molecule-sec at 25 deg C(3). Particulate-phase 4,4'-diaminodiphenylmethane may be removed from the air by wet or dry deposition(SRC). 4,4'-Diaminodiphenylmethane contains chromophores that absorb at wavelengths >290 nm(4) and therefore may be susceptible to direct photolysis by sunlight(SRC).
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