トリクロロニトロメタン 化学特性,用途語,生産方法
解説
クロロピクリン．一般には，ニトロメタンにさらし粉を作用させると得られるが，クロラールのような有機ハロゲン化合物に硝酸を反応させても得られる．また，水とアルカリの存在下でピクリン酸に塩素を作用させる方法もある．無色の油状液体．沸点112 ℃．エタノール，二硫化炭素，エーテルに可溶．水，鉱酸に安定である．不純物は特異な臭気がある．殺虫殺菌剤などに用いることができる．皮膚，粘膜，呼吸器官などをおかし，呼吸困難から致命症になることもある．LD50 250 mg/kg(ラット，経口)．
用途
農薬(殺虫殺菌剤)
説明
Chloropicrin is a colorless to faint-yellow oily liquid with an
intensely irritating and sharp odor with characteristics of tear
gas. Some common trade names of products containing chloropicrin
include Dolochlor, Aquinite, Nemax, Pic-Chlor, Timberfume,
Profume A, Tri-Clor, and Microlysin. It has
a molecular weight of 164.38, water solubility of 2000 mg l1
at 25°C, and melting and boiling points of 64 and 112°C,
respectively. Chloropicrin is nonflammable and has a vapor
density of 5.7 compared to the vapor density of one assigned to
air. Heating above 234 F results in explosive decomposition of
chloropicrin, leading to the release of toxic gases, including
nitrogen oxides, phosgene, nitrosyl chloride, chlorine, and
carbon monoxide. Chloropicrin is a widely used fungicide that
is primarily used for preplant soil fumigation. Chloropicrin is
used to fumigate stored grain and to treat soil against fungi,
insects, and nematodes either as a stand-alone treatment or in
combination with other fumigants like methyl bromide and
sulfuryl fluoride for enhanced potency. Chloropicrin is also
used to prevent internal decay of wood poles and timber
caused by fungi and insects.
化学的特性
oily colourless liquid
物理的性質
Colorless to pale yellow, oily liquid with a sharp, penetrating odor. Odor threshold concentration
is 0.78 ppm (quoted, Amoore and Hautala, 1983).
使用
Chloropicrin (PS), nitrotrichloromethane, trichloronitromethane, nitrochloroform, is a slightly oily, colorless, pale to transparent liquid that is nearly stable. It is nonflammable, with a boiling point of approximately 235°F (112°C) and slight water solubility. The vapor density is 5.7, which is heavier than air.
定義
ChEBI: A C-nitro compound that is nitromethane in which all three hydrogens are replaced by chlorines. It is a severe irritant, and can cause immediate, severe inflammation of the eyes, nose and throat, and significant injuries to the upper and
lower respiratory tract. Formerly stockpiled as a chemical warfare agent, it has been widely used in the US as a soil fumigant, particularly for strawberry crops. It is not approved for use within the European Union.
毒性
有機ニトロ化合物に塩素を作用させて得る揮発しやすい無色油状液体である。酸化性、腐食性があり、皮膚、粘膜を刺激する有毒物質であるが、その毒性と揮発性を利用して、穀物、果実、種子、土壌などの燻蒸(くんじょう)、殺虫・殺菌剤に使われる。人間に対しては、大気中濃度19ミリグラム／立方メートルで催涙性を示し、2グラム／立方メートルで致命的となる。催涙窒息性の毒ガスに使われたことがあり、アメリカではPS、フランスではAquinite、ドイツではKlopとよばれることがある。
一般的な説明
Chloropicrin mixture is a variable colored liquid usually colorless to yellow. Chloropicrin is noncombustible and the flammability of the mixture will depend on the other component of the mixture. Chloropicrin vapors are heavier than air and Trichloronitromethane is toxic by inhalation.
空気と水の反応
Slowly decomposes in water.
反応プロフィール
CHLOROPICRIN is a powerful irritant affecting all body surfaces, more toxic then chlorine. Trichloronitromethane can be shocked into detonation. When heated to decomposition, Trichloronitromethane emits highly toxic fumes of chlorine gas and nitrogen oxides [Sax, 9th ed., 1996, p. 821]. Trichloronitromethane produces a violent reaction with aniline [Jackson, K. E., Chem. Rev., 1934, 14, p. 269] or strong bases in the presence of alcohols (alkoxides) [Ramsey, B. G., et al., J. Am. Chem. Soc., 1966, 88, p. 3059].
危険性
Very toxic by ingestion and inhalation;
strong eye irritant; pulmonary edema. Questionable
carcinogen.
健康ハザード
Chloropicrin is a strong lachrymator (tear gas) and is severely irritating to eyes, skin and mucosal membranes of the respiratory and gastrointestinal tracts, causing nausea, vomiting, difficulty breathing and respiratory tract inflammation. Because of its high volatility, the main route of human exposure to chloropicrin is inhalation. Damage to the respiratory tract can lead to pulmonary edema and death. Chloropicrin can be absorbed systemically through inhalation, ingestion and the skin. It is severely irritating to the lungs, eyes and skin, causing potentially fatal tissue damage and edema at higher levels. In the atmosphere, it is rapidly degraded and does not deplete the ozone layer.
农业用途
Soil fumigant, Nematicide: Not approved for use in EU countries. A U.S. EPA restricted Use Pesticide (RUP) as telone. Chloropicrin is used in the manufacture of the dye-stuff methyl violet
and in other organic syntheses. It has been used as a chemical warfare gas. It is used as a preplant soil fumigant in seed beds and transplant nurseries for control of verticillium wilt, nematodes, weed seeds and insects. In grain elevators, it is used to control insects and rodents. The top four uses in California are on strawberries, tomatoes, bell peppers, and outdoor nursery plants.
製品名
BROM-O-GAS®[C]; BROZONE®[C]; CHLOR-O-PIC®; DOWFUME®; FUM-A-CIDE® 15[C]; KLOP®; LARVACIDE®[C]; LARVACIDE 100®; METAPICRIN®; NAMFUME®[C]; NEMAX®; OG25®; PESTMASTER® FUMIGANT 1[C]; PICFUME®; PIC-CHLOR® 16; PICRIDE®; PROFUME A®; PS®; TELONE®; TELONE® C[C]; TERR-O-CIDE® 15[C]; TERR-O-GAS®; TIMBERFUME II®; TRI-CLOR®[C]; TRI-CON®; TRI-FORM®; TRIFUME®[C];
職業ばく露
Chloropicrin is an important insecticide and is used in the manufacture of the dye-stuff methyl
violet and in other organic syntheses. It is used as a fumigant insecticide. It is a riot control and tear agent and
has been used as a military poison gas. Some forms of tear
gas also contain chloropicrin. Since tank trucks, tank cars,
and tank vessels carry this throughout the world in large
quantities, it is a potential problem.
発がん性
Chloropicrin was genotoxic in bacterial
test systems.
環境運命予測
Biological. Four Pseudomonas sp., including Pseudomonas putida (ATCC culture 29607)
isolated from soil, degraded chloropicrin by sequential reductive dechlorination. The proposed
degradative pathway is chloropicrin → nitrodichloromethane → nitrochloromethane →
nitromethane + small amounts of carbon dioxide. In addition, a highly water soluble substance
tentatively identified as a peptide was produced by a nonenzymatic mechanism (Castro et al.,
1983).
Photolytic. Photodegrades under simulated atmospheric conditions to phosgene and nitrosyl
chloride. Photolysis of nitrosyl chloride yields chlorine and nitrous oxide (Moilanen et al., 1978;
Woodrow et al., 1983). When aqueous solution of chloropicrin (10
-3 M) is exposed to artificial UV
light (λ <300 nm), protons, carbon dioxide, hydrochloric and nitric acids are formed (Castro and
Belser, 1981).
Chemical/Physical. Releases very toxic fumes of chlorides and nitrogen oxides when heated to
decomposition (Sax and Lewis, 1987). Reacts with alcoholic sodium sulfite solutions and
ammonia to give methanetrisulfonic acid and guanidine, respectively (Sittig, 1985).
代謝経路
Although chloropicrin is stable to hydrolytic degradation, it degrades
rapidly and extensively in soil and under photolytic conditions. The primary
degradation and metabolic pathway in the environment and animal
systems involves step-wise dechlorination reactions, followed by fragmentation
and mineralisation to yield low molecular weight components
and carbon dioxide as terminal residues.
輸送方法
UN1580 Chloropicrin, Hazard Class: 6.1;
Labels: 6.1-Poison Inhalation Hazard, Inhalation Hazard
Zone B.
純化方法
Dry with MgSO4 and fractionally distil. [Beilstein 1 IV 106.] EXTREMELY NEUROTOXIC, u s e appropriate precautions.
不和合性
Chloropicrin decomposes explosively
when heated above 112C. It can be dangerously self-reactive; and, may explode when heated under confinement or
if shocked. Chloropicrin is stable except when it’s heated
to a high temperature; it explosively breaks down, releasing
other poison gases including nitrogen oxides, nitrosyl chloride, chlorine, phosgene, and carbon monoxide. Liquid
chloropicrin (PS) is unstable with high temperatures or
severe shock, particularly when involving containers of
greater than 30 gal capacity. Chloropicrin reacts violently
with aniline, sodium methoxide, and propargyl bromide;
2-bromopropyne and strong oxidizers. Violent reaction with
reducing agents; aniline (especially in presence of heat),
alcoholic sodium hydroxide. Quickly elevated temperatures,
shock, contact with alkali metals or alkaline earth may
cause explosions. It is a strong acid and will react violently
with bases and alkali materials. Liquid attacks some plastics, rubber, and coatings. Chloropicrin reacts with iron,
zinc, light metals including aluminum, magnesium, and
alloys containing these metals. It reacts, sometimes violently, with some types of rubbers and plastics, as well as
some chemicals including common sulfuric acid; and bases.
Contact with metals may evolve explosive hydrogen gas.
廃棄物の処理
Incineration (816C, 0.5 seconds minimum for primary combustion; 1204C, 1.0 second
for secondary combustion) after mixing with other fuel. The
formation of elemental chlorine may be prevented by injection of steam or using methane as a fuel in the process.
Chloropicrin reacts readily with alcoholic sodium sulfite
solutions to produce methanetrisulfonic acid (which is relatively nonvolatile and less harmful). This reaction has been
recommended for treating spills and cleaning equipment.
Although not specifically suggested as a decontamination
procedure, the rapid reaction of chloropicrin with ammonia
to produce guanidine (LD50 5 500 mg/kg) could be used for
detoxification. The Chemical Manufacturers’ Association has suggested two procedures for disposal of Chloropicrin:
(1) Pour or sift over soda ash. Mix and wash slowly into
large tank. Neutralize and pass to sewer with excess water.
(2) Absorb on vermiculite. Mix and shovel into paper boxes.
Drop into incinerator with afterburner and scrubber. In
accordance with 40CFR165, follow recommendations for the
disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by
contacting your local or federal environmental control
agency, or by contacting your regional EPA office.
トリクロロニトロメタン 上流と下流の製品情報
原材料
準備製品