チオりん酸ジエチル4-ニトロフェニル

チオりん酸ジエチル4-ニトロフェニル 用途と合成の方法

• 外観

  うすい黄色〜黄赤色, 澄明の液体

• 性質

  化学式	C10H14NO5PS
  日本語名	パラチオン
  英語名	Parathion
  ＣAS番号	56-38-2
  分子量	291.26g/mol
  融点／凝固点	6 ℃
  沸点	375 ℃

   

  パラチオンはエステル、アルコール、エーテル、ケトン、芳香族炭化水素などに良く溶ける性質を持っています。水への溶解性は24mg/Lと低いです。

  室温では結晶または溶液で、ニンニク類似臭またはフェノール類似臭の独特の臭いを有します。化学的安定性としては、通常の取り扱い条件下では安定です。

  また、パラチオンは120℃で引火し、さらに、200℃以上に加熱されると有毒な気体 (一酸化炭素、窒素酸化物、リン酸化物、イオウ酸化物など) を発生させます。パラチオンを使用・保管する際は、火花や熱源などの着火源から遠ざけ、直射日光を避け冷暗所で保管するようにしてください。

• 溶解性

  水に不溶 (0.0024g/100ml, 25℃)。脂肪族炭化水素以外の殆どの有機溶剤に可溶。アセトン及びトルエンに溶け、水にほとんど溶けない。

• 解説

  パラチオン 。殺虫剤。沸点 157～162℃/0.6mmHg の黄色液体。三塩化リン，硫黄，アルコール，ナトリウム，ニトロフェノールを原料として合成。リンを含み多くの有機溶媒に可溶な化合物。多くの昆虫 (特に二化めい虫) ，だになどに対して強力な殺虫効果があるが，定温動物に対しても強い毒性を示し，急性毒性があまりにも強いので，製造および使用を禁止された。日本ではメイチュウなどイネの害虫防除に大きく貢献したが，人畜毒性が強大で危険なため，1969年で生産中止，1971年で使用禁止。特定毒物であり，環境庁が1997年に公表した〈外因性内分泌攪乱化学物質問題に関する研究班〉の中間報告書で環境ホルモンの候補としてあげられている。ホリドールは商品名。

• 用途

  殺虫剤(販売禁止農薬) (NITE CHRIP)

• 農薬用途

  殺虫剤、ダニ駆除剤

• 説明

  After exposure to parathion ethyl, one case of a bullous contact dermatitis was reported.

• 化学的特性

  Pure parathion is a pale yellow liquid with a faint odor of garlic, while technical parathion is a deep brown to yellow liquid. It is sparingly soluble in water, but soluble in alcohols, aromatic hydrocarbons, esters, ethers, n-hexane, dichloromethane, 2-propanol, toluene,and ketones. Parathion is one of the most acutely toxic pesticides and the US EPA has classifi ed parathion as an RUP, meaning it should only be handled by qualifi ed, trained, and certifi ed workers. In January 1992, the US EPA announced the cancellation of parathion for all uses on fruit, nut, and vegetable crops. Parathion was used for the control of pests of fruits, nuts, and vegetable crops. The only uses retained are those on alfalfa, barley, corn, cotton, sorghum, soybeans, sunfl owers, and wheat. Further, to reduce exposure of agricultural workers, parathion may only be applied to these crops by commercially certifi ed aerial applicators and treated crops may not be harvested by hand. Parathion is a broad spectrum, organophosphate pesticide used to control many insects and mites.

• 物理的性質

  Pale yellow to dark brown liquid with a garlic-like odor. Robeck et al. (1965) reported odor threshold concentrations of 3 and 36 ppm for technical and pure grades, respectively.

• 使用

  Parathion is an organophosphate insecticide used on cotton, rice and fruit trees.

• 一般的な説明

  Light-yellow liquid, Parathion turn solid at 6° C, a deadly poison by all routes. Organic phosphate insecticide, acts as an inhibitor of cholinesterase.

• 空気と水の反応

  Parathion is slightly soluble in water.

• 反応プロフィール

  Pure parathion is a pale yellow liquid with a faint odour of garlic, while the technical parathion is a deep brown to yellow liquid. It is sparingly soluble in water but soluble in alcohols, aromatic hydrocarbons, esters, ethers, n-hexane, dichloromethane, 2-propanol, toluene, and ketones.
  Violent reaction when PARATHION is used as solvent to dissolve endrin. When heated to decomposition Parathion emits very toxic fumes of oxides of sulfur, phosphorus and nitrogen [Lewis, 3rd ed., 1993, p. 984].

• 健康ハザード

  Parathion is highly toxic by all routes of exposure. Parathion, like all organophosphate pesticides, inhibits acetylcholinesterase and alters cholinergic synaptic transmission at neuroeffector junctions (muscarinic effects), at skeletal myoneural junctions, in autonomic ganglia (nicotinic effects), and in the CNS. Exposures to parathion cause symptoms of poisoning that include, but are not limited to, abdominal cramps, vomiting, diarrhea, pinpoint pupils, blurred vision, excessive sweating, salivation and lacrimation, wheezing, excessive tracheobronchial secretions, agitation, seizures, bradycardia or tachycardia, muscle twitching and weakness, and urinary bladder and fecal incontinence. Seizures are much more common in children than in adults. Severe exposures cause loss of consciousness, coma, excessive bronchial secretions, respiratory depression, cardiac irregularity, eventually leading to death. Occupational workers and the general public with health disorders and abnormalities, such as cardiovascular, liver or kidney diseases, glaucoma, or CNS, are at an increased risk of parathion poisoning. Further, high environmental temperatures enhance the severity of parathion poisoning.

• 火災危険

  Combustible material: may burn but does not ignite readily. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.

• 廃棄処分方法

  パラチオンは周辺環境に対する毒性が強いため、環境中に放出してはならない化合物です。パラチオンを廃棄処分する場合は、内容物および容器を都道府県知事の許可を受けた専門の廃棄物処理業者に依頼して廃棄する必要があります。

• 別名

  パラチオンの別名は、エチルパラチオン、ジエチル-パラ-ニトロフェニルチオフォスフェイト、O,O-ジエチル-O-(4-ニトロフェニル)ホスホロチオアートなどがあります。また、ドイツ企業でのパラチオンの商品名はホリドールです。

  厚生労働省による職場の安全データシートや日本国内の大手試薬メーカーのウェブサイトでは、主に「パラチオン」の名称が使用されています。

• 有害性

  パラチオンは、「毒物及び劇物取締法における特定毒物」に指定されている化合物です。パラチオンの危険有害性に関する情報として、発がん性、生殖毒性、神経系および視覚器への毒性、経口・経皮・吸入での急性毒性が確認されています。

  また、パラチオンの水生環境有害性として、急性および長期間の水生生物への強い毒性があります。

• 安全注意情報

  パラチオンは「特定毒物」に指定されており、購入・使用する場合は「毒物劇物取締法に基づく特定毒物研究者指定証」が必要です。パラチオンを使用する際は、厚生労働省が公開している職場のあんぜんサイトに掲載されている安全データシートをよく確認してから作業を開始してください。

  経口・経皮・吸入での急性毒性および眼への刺激・毒性を有する化合物であるため、使用する際には保護眼鏡・保護手袋・呼吸用保護具・保護衣を着用し、眼・皮膚・呼吸器を保護した状態で作業してください。また、パラチオンを取り扱う際の設備対策として、取り扱い場所の近くに洗眼および身体洗浄剤のための設備を設け、よく換気された環境で使用することが推奨されています。

• 使用用途

  パラチオンは、主に農薬として使用されていた有機化合物です。0.05％～0.1％程度の低濃度溶液として稲、小麦、野菜、果樹、綿等に散布して使用されていました。

  ニカメイチュウやシンクイムシ類などの害虫に対して、高い殺虫効果を有します。本剤が害虫体内に吸収されるとコリンエステラーゼ活性が阻害され、神経伝達物質であるアセチルコリンが蓄積し、その結果殺虫効果が発現します。

  しかし、パラチオンは人体およびその他の哺乳類・鳥類・水棲生物・昆虫に対して非常に毒性が高いことから、現在では農薬としての使用は禁止です。日本、アメリカ、ヨーロッパ等にて、主要な農作物に対してパラチオンの残留基準が設定されています。

  現在、試薬メーカーから販売されているパラチオンは、農薬用途ではなく、残留農薬の試験用試薬用途です。残留農薬試験用試薬としてパラチオンを購入し使用する際には、「毒物劇物取締法に基づく特定毒物研究者指定証」が必要です。

• 农业用途

  Insecticide, Acaricide: The U.S. EPA announced in November, 2000, the cancellation of ethyl parathion immediately on seed corn and the eventual phase out for its use in other pesticide products by the end of 2000. By the end of October, 2003, the U.S. EPA phased out its use to control insects and mites on alfalfa, barley, corn, canola, sorghum, soybeans, sunflowers and wheat. Also used to control nuisance birds. Not listed for use in EU countries. Not registered for use in the U.S. There are 25 global suppliers.

• 製品名

  (There are 921 active and canceled/transferred labels registered with the U.S. EPA) ACC 3422®; ALKRON®[C]; ALLERON®; AMERICAN CYANAMID 3422®; APHAMITE®; ARALO®; B 404®; BAY E-605®; BAYER E-605®; BLADAN®; BLADAN F®; COMPOUND 3422®; COROTHION®; CORTHION®; COR-THION®; DANTHION®; DREXEL PARATHION 8E®; E 605®; E 605 F®; ECATOX®; EKATIN WF & WF ULV®; EKATOX®; ETHLON®; ETILON®; FIGHTER®; FOLIDOL®; FOLIDOL E®; FOLIDOL E-605®; FOLIDOL E&E 605®; FOLIDOL OIL®; FOSFERMO®; FOSFERNO®; FOSFEX®; FOSFIVE®; FOSOVA®; FOSTERN®; FOSTOX®; GEARPHOS®; GENITHION®; IDA SEIS-TRES 6-3®; KALPHOS®; KOLODUST®[C]; KYPTHION®; LETHALAIRE G-54®; LIROTHION®; MURFOS®; MURPHOS®; NIRAN®[C]; NIUIF 100®; NITROSTIGMINE®; NOURITHION®; NOVAFOS-M®; OLEOFOS 20®; OLEOPARATHENE®; OLEOPARATHION®; ORTHOPHOS®; PAC®; PACOL®; PARA-KILL®[C]; PARAMAR®; PARA-TOX®[C]; PANTHION®; PARADUST®; PARAPHOS®; PARAWET®; PENNCAP E®; PESTOX PLUS®; PETHION®; PHOSKIL®; PLEOPARAPHENE®; RHODIASOL®; RHODIATOX®; RHODIATROX®; SEIS-TRES 6-3®; SELEPHOS®; SOPRATHION®; STATHION®; SULPHOS®; SUPER RODIATOX®; T-47®; THIOMEX®; THIOPHOS®; THIOPHOS® 3422; TIOFOS®; TOX 47®; TOXOL®; VAPOPHOS®; VITREX®; WOPROPHOS®

• 接触アレルゲン

  One case was reported of a bullous contact dermatitis due to ethylparathion.

• 安全性プロファイル

  A deadly poison by all routes. Human systemic effects by ingestion: general anesthetic; pulmonary effects; and hdney, ureter, bladder effects, true cholinesterase changes. Experimental teratogenic and reproductive effects. Questionable carcinogen with experimental carcinogenic and tumorigenic data. Human mutation data reported. A cholinesterase inhibitor. Parathon, like the other organic phosphorus poisons, acts as an irreversible inhibitor of the enzyme cholinesterase and thus allows the accumulation of large amounts of acetylcholine. When a critical level of cholinesterase depletion is reached, grave symptoms appear. Whether death is actually caused entirely by cholinesterase depletion or by the disturbance of a number of enzymes is not yet known. Recovery is apparently complete if a poisoned animal or human has time to re-form a critical amount of cholinesterase. The organism exposed remains susceptible to relatively low dosages of parathion untd the chohnesterase has regenerated. Small doses at frequent intervals are, therefore, more or less additive. There is no indication that, when recovery from a given exposure is entirely complete, the exposed organism is prejudiced in any way. Combustible when exposed to heat or flame. Violent reaction with endrin. Highly dangerous; shock can shatter the container, releasing the contents A broad spectrum insecticide in agricultural applications. When heated to decomposition it emits highly toxic fumes of NOx, POx, and SOx.

• 職業ばく露

  A severely hazardous pesticide formulation. Those exposed include those engaged in manufacture,formulation and application of this broad spectrum insecticide. This material has also been used as a chemical warfare agent.

• 発がん性

  In an animal bioassay a dose-related increase in the incidence of adrenal cortical adenomas (with a few carcinomas at this site as well) has been observed in one strain of rats in both sexes. The significance of these lesions in aged rats in unclear. Other bioassays in mice and rats had sufficient limitations, such that the IARC deemed them inadequate for evaluation and concluded that there are insufficient data to evaluate the carcinogenicity of parathion for animals and no data for humans.

• 代謝経路

  The structure of parathion is similar to those of methyl parathion (the dimethylphosphoryl analogue) and fenitrothion which has a 3-methyl group on the phenyl ring: consequently the environmental fate and pathways for biotransformation are similar. As the first commercial organophosphorus insecticide, many studies have been conducted on its mechanisms of activation and degradation in a very wide range of organisms. The following is necessarily a selection of only some of the results which have been used to illustrate the principles of its metabolism. The principal metabolic routes of degradation in all media are via de-esterification to give O,O-diethyl phosphorothioate and 4-nitrophenol and by de-ethylation to desethylparathion (a less important route). Activation to the toxic anticholinesterase metabolite paraoxon is also a major metabolic route in soil, plants and animals. Paraoxon is also formed photochemically in the environment; however, it is relatively quickly detoxified in animals and plants by esterase and base-catalysed hydrolysis to 4-nitrophenol and diethyl phosphate. A further detoxification mechanism, which is mainly important in the soil, and possibly in plants and in ruminants, is reduction of the 4nitro group to yield aminoparathion. 4-Nitrophenol is conjugated in plants as the glucoside, in insects as the glucoside and/or sulfate ester and in mammals as the glucuronide and the sulfate ester.

• 代謝

  The principal degradation routes of parathion in animals, plants, and soil are dearylation and dealkylation to give O,O-diethyl hydrogen phosphorothioate, p-nitrophenol, and desethylparathion. Oxidative desulfuration also occurs to form the active methabolite paraoxon, which is quickly detoxified by hydrolysis. DT₅₀ in soil was 65 d.

• 輸送方法

  UN3278 Organophosphorus compound, liquid, toxic, n.o.s., Hazard Class: 6.1; Labels: 6.1-Poisonous materials, Technical Name Required, Potential Inhalation Hazard (Special Provision 5).UN2783 Organophosphorus pesticides, solid, toxic, Hazard Class: 6.1; Labels: 6.1-Poisonous materials. UN3018 Organophosphorus pesticides, liquid, toxic, Hazard Class: 6.1; Labels: 6.1- Poisonous materials.

• 不和合性

  Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Strong oxidizers may cause release of toxic phosphorus oxides. Organophosphates, in the presence of strong reducing agents such as hydrides, may form highly toxic and flammable phosphine gas. Keep away from alkaline materials. Attacks some plastics, rubbers, and coatings. Rapidly hydrolyzed by alkalis.

• 廃棄物の処理

  Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. 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. One manufacturer recommends the use of a detergent in a 5% trisodium phosphate solution for parathion disposal and cleanup problems. For parathion disposal in general, however, the recommended method is incineration (816°C, 0.5 second minimum for primary combustion; 1204°C, 1.0 second for secondary combustion) with adequate scrubbing and ash disposal facilities.