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Adamsite

Adamsite structure

Adamsite 

structure
  • CAS No:

    578-94-9

  • Formula:

    C12H9AsClN

  • Chemical Name:

    Adamsite

  • Synonyms:

    Phenarsazine,10-chloro-5,10-dihydro-;Phenarsazine,1-chloro-1,6-dihydro-;10-Chloro-5,10-dihydrophenarsazine;Adamsite;5-Aza-10-arsenaanthracene chloride;10-Chloro-5,10-dihydroarsacridine;Diphenylaminechlorarsine;DM;Phenarsazine chloride;Diphenylaminechloroarsine;Adamsit;DM (arsenic compound);5-Chloro-5,10-dihydrophenarsazine;Adamsyte;NSC 86138;10-Chloro-5H-phenarsazinine

  • Categories:

    Organic Chemistry  >  Arsenicals

Description

Adamsite is an odorless crystalline compound with a very low vapor pressure. The color of its crystals varies from bright yellow to dark green, depending on purity. It is readily soluble in some organic solvents, such as acetone and dichloromethane, but is virtually insoluble in water. In vapor form, it appears as a pale yellow fume. Technically, it is an arsenical diphenylaminechlorarsine, which is used as a riot control agent and belongs to a class of chemical warfare agents known as emetic agents or sneeze gases.

Adamsite Basic Attributes

277.58100

277.58

209-433-1

QI287G628L

86138

1698

DTXSID6041890

Canary yellow crystals from carbon tetrachloride|Stable form occurs as orthorhombic crystals|Yellow to green solid

Characteristics

12.03000

2.22610

Diphenylamine chloroarsine is in the form of yellow crystals. The vapors are very irritating to the eyes and mucous membranes and are also nauseating.

1.65

195 °C

410 °C

196.7ºC

In water, 0.65 mg/L at 25 deg C (est)

2X10-13 mm Hg at 20 deg C

LCLo ihl-hmn: 30 g/m3 SCJUAD 4,33,67

None

Henry's Law constant = 3.3X10-8 atm-cu m/mole at 25 °C (est)

Heat of volatilization = 54.8 calories|Specific heat = 0.268 calories|The metastable form melts at 186 °C if monoclinic and 182 °C if triclinic

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

Organometallics

Organometallics, such as DIPHENYLAMINE CHLOROARSINE, are reactive with many other groups. Incompatible with acids and bases. Organometallics are good reducing agents and therefore incompatible with oxidizing agents. Often reactive with water to generate toxic or flammable gases.

Aerosol may collect and stay in confined areas (e.g., sewers, basements, and tanks).

Corrodes iron, bronze, brass

80 °C

Safety Information

I

6.1(a)

UN 1698

Principles and methods for destruction of chemical weapons: ... "Destruction of chemical weapons" means a process by which chemicals are converted in an essentially irreversible way to a form unsuitable for production of chemical weapons, and which in an irreversible manner renders munitions and other devices unusable as such. ... Each State Party shall determine how it shall destroy chemical weapons, except that the following processes may not be used: dumping in any body of water, land burial or open-pit burning. It shall destroy chemical weapons only at specifically designated and appropriately designed and equipped facilities. ... Each State Party shall ensure that its chemical weapons destruction facilities are constructed and operated in a manner to ensure the destruction of the chemical weapons; and that the destruction process can be verified under the provisions of this Convention.|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.

U.S. Army Center for Health Promotion and Preventive Medicine; Detailed Facts About Vomiting Agent Adamsite (DM). Available at: chppm-www.apgea.army.mil/dts/docs/detdm.pdf as of Dec 27, 2007.

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]: Non-combustible, substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic fumes. Some are oxidizers and may ignite combustibles (wood, paper, oil, clothing, etc.). Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. For electric vehicles or equipment, ERG Guide 147 (lithium ion batteries) or ERG Guide 138 (sodium batteries) should also be consulted. (ERG, 2016)

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]: SMALL FIRE: Dry chemical, CO2 or water spray. LARGE FIRE: 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. (ERG, 2016)|Adamsite (DM) is non-combustible.

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: If this material is being used as a weapon, see ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 1698 datasheet. Otherwise 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)

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]: 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. (ERG, 2016)

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]: 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. (ERG, 2016)|Protective Equipment. Protective Gloves: Wear Chemical Protective Glove Set. Eye Protection: Wear chemical goggles; wear a mask/respirator in open areas. Other: Wear additional protective clothing, such as gloves and lab coat with an M9, M17, or M40 mask readily available in closed or confined spaces.|GENERAL INFORMATION: First Responders should use a NIOSH-certified Chemical, Biological, Radiological, Nuclear (CBRN) Self Contained Breathing Apparatus (SCBA) with a Level A protective suit when entering an area with an unknown contaminant or when entering an area where the concentration of the contaminant is unknown. Level A protection should be used until monitoring results confirm the contaminant and the concentration of the contaminant.NOTE:Safe use of protective clothing and equipment requires specific skills developed through training and experience.

Emergency Procedures: Inhalation: remove victim to fresh air; wear a mask/respirator in spite of coughing, sneezing, salivation, and nausea; lift the mask from the face briefly, if necessary, to permit vomiting or to drain saliva from the facepiece; seek medical attention immediately. Eye Contact: don a respiratory protective mask; seek medical attention immediately. Skin Contact: rinse the nose and throat with saline water or bicarbonate of soda solution; wash exposed skin and scalp with soap and water and allow to dry on the skin; dust the skin with borated talcum. Ingestion: seek medical attention immediately; carry on duties as vigorously as possible; this will help to lessen and shorten the symptoms; combat duties usually can be performed in spite of the effects of sternutators.

Irritating to skin and respiratory tract.

Information is unavailable about the carcinogenicity, developmental toxicity, or reproductive toxicity of chronic or repeated exposure to adamsite (DM).

Toxicity

ICt50 Human 22-150 mg.min/cu m; nausea, vomiting: approx 370|Estimated LCt50 of 11,000 mg~min/cu m

LD50 Mouse iv 35 mg/kg|LD50 Rabbit iv 6 mg/kg|LC50 Rat (male) inhalation 3,700 mg/min/cu m, 5 to 90 minute exposure|LC50 Mouse (male) inhalation 22,400 mg/min/cu m, 5 to 90 minute exposure

/AQUATIC SPECIES/ The four arsenic-containing chemical warfare agents (CWA) Adamsite (technical, 10-chloro-9-10-dihydrophenarsazine), Clark 1 (Diphenyl arsine chloride), Clark 2 (Diphenyl arsine cyanide), and Lewisite (2-chloro-ethenyl dichloro arsine) ...also tested in vivo in a dietary exposure study, using juvenile three-spined stickleback (Gasterosteus aculeatus L.) as test organism, with measurement of EROD-activity and studies of liver morphology. The results from the in vivo study indicated small effects, suggesting that a 10-week period of dietary exposure at tested dose levels (1 and 100 ng/mL) affects juvenile three-spined stickleback only to a minor extent.

Adamsite's production may result in its release to the environment through various waste streams; its use as a chemical warfare or riot control agent as well as its use in the formulation of wood treating solutions against marine borers and similar pests(1), will result in its direct release to the environment(SRC).

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 5,750(SRC), determined from a structure estimation method(2), indicates that adamsite is expected to be immobile in soil(SRC). Volatilization from moist soil is not expected to be an important environmental fate process based on an estimated Henry's Law constant 3.3X10-8 atm-cu m/mole(SRC) derived using a fragment constant estimation method(3). Adamsite is not expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 2X10-13 mm Hg at 20 °C(4). Adamsite was reported to hydrolyze slowly under alkaline conditions to bis(diphenylaminoarsine)oxide(5), indicating hydrolysis in moist alkaline soils may be an important environmental fate process. Biodegradation data were not available(SRC, 2008).|AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 5,750(SRC), determined from a structure estimation method(2), indicates that adamsite 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 3.3X10-8 atm-cu m/mole(SRC) derived using a fragment constant estimation method(4). According to a classification scheme(5), an estimated BCF of 263(SRC), from an estimated log Kow of 4.05(6) and a regression-derived equation(7), suggests the potential for bioconcentration in aquatic organisms is high(SRC). Adamsite was reported to hydrolyze slowly under alkaline conditions to bis(diphenylaminoarsine)oxide(8); however, the quantitative rate of this reaction was not reported. Biodegradation data were not available(SRC, 2008).|ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), adamsite, which has a vapor pressure of 2X10-13 mm Hg at 20 °C(2), is expected to exist solely in the particulate-phase in the ambient atmosphere. Particulate-phase adamsite may be removed from air by wet and dry deposition(SRC). Adamsite does not contain chromophores that absorb at wavelengths >290 nm and therefore is not expected to be susceptible to direct photolysis by sunlight(3).

Adamsite does not contain chromophores that absorb at wavelengths >290 nm and therefore is not expected to undergo direct photolysis by sunlight(1). Adamsite was reported to hydrolyze slowly under alkaline conditions to bis(diphenylaminoarsine)oxide(2); however, the quantitative rate of this reaction was not reported.

An estimated BCF of 263 was calculated for adamsite(SRC), using an estimated log Kow of 4.05(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF suggests the potential for bioconcentration in aquatic organisms is high(SRC).

Using a structure estimation method based on molecular connectivity indices(1), the Koc of adamsite can be estimated to be 5750(SRC). According to a classification scheme(2), this estimated Koc value suggests that adamsite is expected to be immobile in soil(SRC).

The Henry's Law constant for adamsite is estimated as 3.3X10-8 atm-cu m/mole(SRC) using a fragment constant estimation method(1). This Henry's Law constant indicates that adamsite is expected to be essentially nonvolatile from water surfaces(2). Adamsite's Henry's Law constant indicates that volatilization from moist soil surfaces is not expected(SRC). Adamsite is not expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 2X10-13 mm Hg at 20 °C(3).

Occupational exposure and exposure to the general population to adamsite should be rare since this compound was primarily used as a chemical warfare agent. (SRC)

Drug Information

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]: 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. (ERG, 2016)

Excerpt from ERG Guide 154 [Substances - Toxic and/or Corrosive (Non-Combustible)]: Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves. 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 calm and warm. Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed. (ERG, 2016)|GENERAL INFORMATION: The effects of exposure to vomiting agents under usual outdoor conditions generally are self-limited, disappearing in 20 minutes to 2 hours, and require no specific therapy other than symptomatic relief. Exposure to large concentrations of adamsite (DM), or exposure to adamsite (DM) within an enclosed space or under adverse weather conditions, may result in more severe adverse health effects, serious illness, or death and may require supportive measures for symptomatic complaints of eye, skin, and airway irritation.

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. /Riot Control Agents/|Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Encourage patient to take deep breaths. Watch for signs of respiratory insufficiency and assist ventilations it necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. 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 ... . /Riot Control Agents/|Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious or is in severe respiratory distress. Early intubation at the first sign of upper airway obstruction may be necessary. Positive-pressure ventilation techniques with a bag-valve-mask device may be beneficial. Monitor cardiac rhythm and treat arrhythmias as 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. Consider vasopressors if patient is hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Treat seizures with diazepam (Valium) or lorazepam (Ativan) ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Riot Control Agents/

/HUMAN EXPOSURE STUDIES/ The speed of effect, toxicity, and persistence of chloracetophenone, diphenylaminochloroarsine, and pelargonic-morpholide were investigated in humans. Subjects were placed in exposure chambers and exposed to 10% chloracetophenone in acetone, 10% diphenylaminochloroarsine in acetone, or pelargonic-morpholide for as long as tolerated, not exceeding the maximum safe doses of 350, 100, and 500 mg/min/cu m, respectively. Subjects were examined before, immediately after, and 2 to 4 days after exposure. Median particle sizes were 0.6 to 1.1 microns. The concentration necessary to produce irritation in 50% of the subjects (ECt50) in 1 minute was 213 mg/min/cu m chloracetophenone and 39 mg/min/cu m pelargonic-morpholide. The 2 minute ECt50 values were 119 mg/min/cu m chloracetophenone, 38 mg/min/cu m diphenylaminochloroarsine, and 29 mg/min/cu m pelargonic-morpholide. The 3 minute ECt50 values were 93 mg/min/cu m chloracetophenone, 19 mg/min/cu m diphenylaminochloroarsine, and 21 mg/min/cu m pelargonic-morpholide. Chloracetophenone caused rhinorrhea and nasal irritation, burning of the throat and eyes, lacrimation, and blurred vision. After exposure, mild to moderate transient conjunctivitis was seen. All symptoms usually disappeared in 10 minutes. Diphenylaminochloroarsine caused burning of the nose, throat, and chest. After exposure, salivation, coughing, and sneezing persisted up to 2 hours. One severe case required treatment with an anesthetic troche. Pelargonic-morpholide caused burning of the nose, throat, and eyes, with rhinorrhea and lacrimation. An uncontrollable cough developed, occasionally followed by nausea. All symptoms were alleviated with fresh air, although some subjects developed a headache. The authors conclude that the compounds produced no permanent adverse effects. Pelargonic-morpholide is the most irritating. Recovery is fastest from pelargonic-morpholide exposure and slowest from diphenylaminochloroarsine exposure.|/SIGNS AND SYMPTOMS/ Vomiting agents typically are disseminated as aerosols. The primary route of absorption is through the respiratory system. Exposure also can occur by ingestion, dermal absorption, or eye impact. The effects of the vomiting agents by any route of exposure are slower in onset and longer in duration than typical riot control agents ... On initial exposure, vomiting agents are irritants. This irritation is delayed for several minutes after contact. As a result of this delay, less early warning properties are present for those exposed. By the time symptoms of irritation occur and personnel consider donning their protective equipment, significant contamination already may have occurred. Systemic signs and symptoms subsequently follow the initial irritation and consist of headache, nausea, vomiting, diarrhea, abdominal cramps, and mental status changes. Symptoms typically persist for several hours after exposure. Death has been reported with excessive exposure.|/SIGNS AND SYMPTOMS/ Ademsite (DM) is a vomiting compound. It is normally a solid, but upon heating, DM first vaporizes and then condenses to form aerosols. It is toxic through inhalation, ingestion, and skin contact. Adamsite is dispersed as an aerosol, irritating to the eyes and respiratory tract but not necessarily to the skin. Under field conditions, vomiting agents can cause great discomfort to the victims; when released indoors, they can cause serious illness or death. Symptoms include irritation of eyes and mucous membranes, coughing, sneezing, severe headache, acute pain and tightness in the chest, nausea, and vomiting. DM has been noted to cause necrosis of corneal epithelium in humans. The human body will detoxify the effects of mild exposures within 30 minutes of evacuation. Severe exposures may take several hours to detoxify and minor sensory disturbances may persist for up to one day.|/SIGNS AND SYMPTOMS/ The majority of exposures occur by inhalation and typically lead to symptoms of ocular, nasal, and respiratory tract irritation. Nonspecific gastrointestinal symptoms (eg, vomiting or diarrhea) might also occur. The effects of adamsite poisoning take minutes to begin and might last for hours ... /A/ rapid onset of manifestations of ... respiratory effects occurs ... /including/ nose or throat irritation, cough, or dyspnea.|For more Human Toxicity Excerpts (Complete) data for ADAMSITE (9 total), please visit the HSDB record page.

10-chloro-5,10-dihydroarsacridine

Adamsite (DM) can affect the body through inhalation, ingestion, skin contact, or eye contact. Ingestion is an uncommon route of exposure.

Short-term effects: Upper respiratory tract irritation in nose and sinuses, burning in throat, chest tightness and pain, uncontrollable and violent coughing and sneezing, greatly increased nasal secretions and oral secretions.


Dermal exposures to low concentrations of adamsite (DM) are likely to produce short-lived skin redness (erythema) and irritation. Exposure to higher concentrations of adamsite (DM) can result in more severe, longer-lasting redness, itching, and swelling possibly followed by blister (vesicle) formation. More severe skin irritation may require symptomatic treatment.


Irritation and burning, tear production (lacrimation), spasmodic blinking (blepharospasm), swelling of the blood vessels that supply the membranes lining the eye (conjunctival injection), necrosis of the corneal epithelium.

Adamsite Use and Manufacturing

Methods of Manufacturing

Prepared by heating diphenylamine with arsenic trichloride: DE 281049 (1914 to I.G. Farben)

Uses

As war gas, dispersed in air in the form of minute particles. For riots in combination with tear gas (chloroacetophenone). In the formulation of wood-treating solutions, against marine borers and similar pests.

Phenarsazine chloride was not toxic enough for the battlefield, but it proved to be too drastic for use against civilian mobs; it was banned for use against civilian populations in the 1930s in the Western nations.|... prepared by all of the belligerent states during World War II. Smoke generators filled with a mixure of /phenarsazine chloride/ and a-chloroacetophenone were also developed.

Vomiting Agents -> NIOSH Emergency Response Categories

Computed Properties

Molecular Weight:277.58
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:1
Exact Mass:276.963947
Monoisotopic Mass:276.963947
Topological Polar Surface Area:12
Heavy Atom Count:15
Complexity:214
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes

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