ニトロアミン

Other Uses -> Explosives

Reactive agents - 3rd degree

1.57 (NIOSH, 2024) - Denser than water; will sink

1.57

Relative density (water = 1): 1.57

1.57 @ 19°C

1.57

Colorless to yellow, crystalline solid

MONOCLINIC CRYSTALS

0.02 % (NIOSH, 2024)

Sol in alc, ether, glacial acetic acid, benzene

In water, 74 mg/L @ 25 °C

Solubility in water: none

0.02%

Explodes (NIOSH, 2024)

Flash point: explodes in air at 187C

explodes in air at 187 °C

Explodes

356 to 374 °F at 760 mmHg (Explodes) (NIOSH, 2024)

187 °C (explodes)

356-374 °F (Explodes)

268 °F (NIOSH, 2024)

130-132 °C

130 °C

268 °F

Danger

H201: (Deleted) Explosive; mass explosion hazard [Danger Explosives]

P210, P230, P240, P250, P260, P261, P262, P264, P270, P271, P280, P301+P316, P302+P352, P304+P340, P316, P319, P321, P330, P361+P364, P370+P380, P372, P373, P401, P403+P233, P405, and P501 (click each P-code to see the statement)

Danger

H201 (100%): (Deleted) Explosive; mass explosion hazard [Danger Explosives]

P210, P230, P240, P250, P260, P261, P262, P264, P264+P265, P270, P271, P272, P280, P301+P316, P302+P352, P304+P340, P305+P351+P338, P316, P319, P321, P330, P332+P317, P333+P317, P337+P317, P361+P364, P362+P364, P370+P380, P372, P373, P401, P403+P233, P405, and P501 (click each P-code to see the statement)

Chemical: Benzenamine, N-methyl-N,2,4,6-tetranitro-

Hazard Traits - Neurotoxicity

Tetryl: Does not have an individual approval but may be used as a component in a product covered by a group standard. It is not approved for use as a chemical in its own right.

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.)

Excerpt from ERG Guide 112 [Explosives - Division 1.1, 1.2, 1.3 or 1.5]:

Gives off irritating or toxic fumes (or gases) in a fire. Finely dispersed particles form explosive mixtures in air. Risk of fire and explosion when exposed to heat or flame. Explosive.

The chemical name for tetryl is 2,4,6-trinitrophenyl-n-methylnitramine. Some commonly used names are nitramine, tetralite, and tetril. Tetryl is an odorless, synthetic, yellow crystal-like solid that is not found naturally in the environment. Under certain conditions, tetryl can exist as dust in air. It dissolves slightly in water and in other liquids. Tetryl was used to make explosives, mostly during World Wars I and II. It is no longer manufactured or used in the United States. Stocks of tetryl are found in storage at military installations and are being destroyed by the Department of Defense (DOD).

Tetryl stains the skin yellow and causes skin sensitization. Severe, prolonged exposures may cause liver injury. [HSDB] Repeated or prolonged inhalation exposure may cause asthma. [ICSC]

BURROWS D, DACRE JC; US NTIS REPORT # ADA010660): 1-96 (1975) THE TOXICITY TO AQUATIC ORGANISMS & THE RELATED CHEMISTRY OF NINE WATERBORNE POLLUTANTS FROM MUNITION PLANTS, ONE OF WHICH WAS TETRYL, WERE REVIEWED.

U.S. Dept Health & Human Services/Agency for Toxic Substances Disease Registry; Toxicological Profile for (Tetryl) (1995) NTIS# PB/95/264271/AS

Excerpt from ERG Guide 112 [Explosives - Division 1.1, 1.2, 1.3 or 1.5]:

Do not attempt to extinguish large fire, evacuate area. In case of fire: keep drums, etc., cool by spraying with water. Combat fire from a sheltered position.

Fresh air, rest. Artificial respiration may be needed. Refer for medical attention.

Remove contaminated clothes. Rinse skin with plenty of water or shower. Wear protective gloves when administering first aid.

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

Refer for medical attention .

Excerpt from NIOSH Pocket Guide for Tetryl:

(General first aid procedures)

Evacuation: If the material is on fire or involved in fire consider evacuation of one mile radius.

Wear positive pressure self-contained breathing apparatus when fighting fires involving this material.

Water may be used on small fires. Do not attempt to extinguish large fires.

Keep solution in the dark.

Protect from shock.

Fireproof. Separated from strong oxidants. Keep in the dark. Keep in a separate building protected from shock, under lock and key.

If tetryl is spilled, the following steps should be taken: 1. Remove all ignition sources. 2. Ventilate area of spill. 3. Attempt to reclaim spilled material; however, do not sweep or burn unless this is supervised by explosives experts.

Both activated carbon amberlite xad-4 removed tnt, hexahydro-1,3,5-trinitro-1,3,5- triazine (rdx), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (hmx) from pink water to a level of less than 1 ppm. Activated charcoal has lower capacity for tnt, and a higher capacity for rdx, hmx, and tetryl, than amberlite xad-4. Decolorization of the effluent with amberlite xad-4 alone was not complete. Both amberlite xad-4 and activated carbon provided similar nitrobody leakage for similar streams.

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.

Tetryl may be disposed of only by explosives experts.

Wastes containing tetryl have been incinerated by grinding and spraying the ground material with water to form a slurry. The types of incineration that have been used to destroy waste munitions such as tetryl include rotary kiln incineration, fluidized bed incineration, and pyrolitic incineration.

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: 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.

Workers whose clothing may have become contaminated should change into uncontaminated clothing before leaving the work premises.

Work clothing that becomes wet or significantly contaminated should be removed and replaced.

For more Preventive Measures (Complete) data for TETRYL (12 total), please visit the HSDB record page.

Dermal (Skin), Immunological (Immune System), Neurological (Nervous System), Respiratory (From the Nose to the Lungs)

Eyes, skin, respiratory system, central nervous system, liver, kidneys

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 2,100(SRC), determined from a structure estimation method(2), indicates that tetryl is expected to have slight mobility in soil(SRC). Volatilization of tetryl from moist soil surfaces is not expected to be an important fate process(SRC) given an estimated Henry's Law constant of 2.7X10-9 atm-cu m/mole(SRC), using a fragment constant estimation method(3). Tetryl 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). Biodegradation of tetryl has been demonstrated in various composing conditions(SRC). A first-order half-life of 1.2 weeks was calculated for tetryl in a manure-hay-sawdust compost(5). Hydrolysis in moist soils may also be an important fate process based upon studies which showed tetryl hydrolyzes at various rates in buffered solutions (63 day half-life at pH 6.88 and 40 °C)(6), and seawater (33 day half-life at pH 8.1 and 25 °C)(7).

AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 2,100(SRC), determined from a structure estimation method(2), indicates that tetryl 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 2.7X10-9 atm-cu m/mole(SRC), developed using a fragment constant estimation method(4). According to a classification scheme(5), an estimated BCF of 4(SRC), from an estimated log Kow of 1.64(6) and a regression-derived equation(7), suggests the potential for bioconcentration in aquatic organisms is low(SRC). The hydrolysis half-life of tetryl in seawater at 25 °C (pH 8.1) is about 33 days(8) and the hydrolysis half-life in buffered solutions at pH 6.88 and 40 °C was 63 days (9). The degradation rate of tetryl in buffered solutions was about an order of magnitude greater when the solutions were exposed to sunlight as compared to the dark solutions(9), suggesting that photolysis in sunlit surface waters in conjunction with hydrolysis may be an important fate process(SRC). Biodegradation of tetryl has been demonstrated in various composting conditions(10) and soil/water slurries(11).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), tetryl, 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 tetryl 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 13 days(SRC), calculated from its rate constant of 1.3X10-12 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Particulate-phase tetryl may be removed from the air by wet and dry deposition(SRC). Tetryl has been shown to undergo photolysis in aqueous solutions and may be susceptible to direct photolysis in the atmosphere(4).

The substance can be absorbed into the body by inhalation of its aerosol, through the skin and by ingestion.

inhalation, skin absorption, ingestion, skin and/or eye contact

Abdominal pain. Cough. Diarrhoea. Headache. Sore throat. Nosebleeds.

Redness. Yellow staining of the skin.

Redness. Pain.

Nausea. See Inhalation.

sensitization dermatitis, itch, erythema (skin redness); edema on nasal folds, cheeks, neck; keratitis (inflammation of the cornea); sneezing; anemia; cough, coryza; irritability; malaise (vague feeling of discomfort), headache, lassitude (weakness, exhaustion), insomnia; nausea, vomiting; liver, kidney damage

The Joliet Army Ammunition Plant, which produced tetryl until production ceased in July 1973, released tetryl to the environment in various wastewater stream emissions generated at the plant(1); wastewater streams were released via drainage ditches with waste waters typically containing 400-460 ppm tetryl(1). In 1963, the US Navy initiated a program in which old liberty ships were loaded with munitions and deliberately sunk in the ocean to dispose of the unwanted munitions(2); tetryl was one of the most common and abundant explosives released in this manner(2).

Because job rotation incr the number of workers at risk, it may favor sensitization and retard "hardening".

Initial medical exam: A complete history and physical exam: The purpose is to detect existing conditions that might place the exposed employee at incr risk, and to establish a baseline for future health monitoring. Persons with a history of asthma ... or known sensitization to tetryl may be at increased risk from exposure. Exam of the resp tract, eyes, liver, central nervous system, and kidneys should be stressed. The skin should be examined for evidence of chronic disorders. ... Tetryl has been shown to cause anemia in humans. A complete blood count should be performed incl a red cell count, a white blood count, a differential count of a stained smear, as well as hemoglobin and hematocrit. The aforementioned medical exam should be repeated on an annual basis.

Using a structure estimation method based on molecular connectivity indices(1), the Koc for tetryl can be estimated to be 2,100(SRC). According to a classification scheme(2), this estimated Koc value suggests that tetryl is expected to have slight mobility in soil(SRC). It was demonstrated that nitroaromatic compounds (including tetryl) adsorb strongly to clay minerals in aqueous suspensions, particularly when exchangeable cations in the clays include ammonium and potassium(3).

/HUMAN EXPOSURE STUDIES/ ...Reported effects from accidental exposures of 11 persons to tetryl. Of those exposed, 2 had died, 1 had a disability, and 8 had no detected permanent disability. ...In addition, 1 worker developed pulmonary pathologic changes, presumably attributable to exposure to tetryl irritation. Irritation of the mucous membranes of the upper resp tract was noteworthy, resulting in sore throats, nosebleeds, and coughing of varying degrees of severity.

/HUMAN EXPOSURE STUDIES/ ... described the typical tetryl dermatitis as presenting the following clinical picture. During the first week of exposure, itching of and around the eyes and irritation of the skin with erythema occurred. Edema often followed and and progressed as long as exposure persisted. The progression of pruritus to erythema to edema was seen about the nasal folds, cheeks and neck soon after the eyelids were affected. This condition was believed to be a sensitization phenomenon rather than a result of local irritation.

/HUMAN EXPOSURE STUDIES/ In a study of 1258 workers affected by tetryl (of 5000 workers at the facility), the presiding symptom in 944 was dermatitis. The dermatitis generally occurred between the second and third week of exposure. ... Also cited /was/ increasing evidence to point toward the probability that systemic changes were quiet possible in exposed workers. Laboratory data cited secondary anemia of a pronounced degree. Other reported symptoms suggestive of systemic illness included headache, irritability, malaise, lassitude, and sleeplessness. Of 1258 cases studied, 3 revealed a previous attack of severe tetryl dermatitis; 2 of these 3 individuals were accidentally re-exposed to tetryl, and a severe reaction promptly recurred.

/SIGNS AND SYMPTOMS/ Workers may experience irritability, easy fatigability, general malaise, headache, lassitude, and sleeplessness but exhibited no abnormal neurological signs /after tetryl exposure/

For more Human Toxicity Excerpts (Complete) data for TETRYL (10 total), please visit the HSDB record page.

Data from composting experiments suggest that biodegradation of tetryl may occur under some conditions(1). When tetryl-contaminated sediment was added to hay-horse feed or sewage sludge-wood chip compost, 90% of the tetryl was removed after 44 days(1). A first-order half-life of 1.2 weeks was calculated for tetryl in a manure-hay-sawdust compost(1). Tetryl was completely biodegraded in a laboratory reactor using a soil slurry amended with molasses over a 3 month operation period(2). Metabolites identified included trinitro-N-methylaniline, trinitrobenzeneamine, dinitrobenzenediamine, nitroaniline and aniline(2). In previous experiments using anoxic conditions and in the absence of co-substrates such as molasses, tetryl and trinitrotoluene (TNT) were not degraded(2).

Seven rabbits orally administered 36 mg/kg/day (range of 32.3-40.0 mg/kg/day) for up to 30 days excreted picramic acid in their urine. Picramic acid was not detected in the urine of two control rabbits (the detection limit was 0.05 mg/L). In addition, the ratio of sulfoconjugates to total sulfates increased with duration of treatment in the treated rabbits, but not in the controls. These data support the hypothesis that tetryl is metabolized to picric acid by removal of the methylnitramine complex, and further metabolized to picramic acid by reduction of a nitro group. The increased sulfoconjugates may be caused by conjugation of picramic acid to sulfates.

Studies in rabbits have shown that after oral administration, tetryl was metabolized to picric acid, which was further metabolized to picramic acid by nitro reduction.

Not produced commercially in the USA; used as an explosive detonator; [HSDB]

Used as an explosive in detonators and primers; as an intermediary detonating agent for other less sensitive, high explosives, and as a booster charge for military devices; it may also be employed as an explosive charge.

Chemical indicator

(1972) NOT PRODUCED COMMERCIALLY IN THE USA

(1975) NOT PRODUCED COMMERCIALLY IN THE USA

Dimethylaniline is nitrated (nitric acid) and oxidized (sulfuric acid, acetone) to form crystallized tetryl.

Tetryl has been produced in a batch process by dissolving dimethylaniline in an excess of concentrated sulfuric acid at 20-30 degree C to give dimethylaniline sulfate. The solution was nitrated with a mixture of nitric and sulfuric acids to produce 2,4-dinitrodimethylaniline and eventually crude tetryl. The crude product was filtered, washed with water, and dissolved in acetone. The acetone was evaporated and the product filtered to yield purified tetryl.

2,4- or 2,6-Dinitrochlorobenzene was reacted with methylamine to form dinitrophenyl methylamine, which was nitrated to form tetryl.

Benzenamine, N-methyl-N,2,4,6-tetranitro-: ACTIVE

Tetryl is not produced commercially in the United States. Prior production was limited to Army ammunition plants such as Joliet Army Ammunition Plant (Illinois), which produced tetryl until 1973.

Aa indicator, 0.1 g in 60 mL alcohol with water to make 100 mL. pH: 10.8 colorless, 13.0 reddish-brown. 1 to 5 drops of solution required for 10 mL liquid. Salt error said to be small.

For use as booster or relay, tetryl is compressed into tablets.

Tetryl was produced by U.S. Army ammunition plants until 1973. It was a military explosive during World War I and World War II.