Phenthoate 稻丰散

稻丰散

CAS号: 2597-03-7
英文名称：Phenthoate
化学名称：O,O-二甲基-S-(苯基乙酸乙酯)二硫代磷酸酯;甲基乙酯磷;
其他名称：爱乐散;稻芬妥胺酚拉明;益而散
分子式: C12H17O4PS2
分子量: 320.36

理化性质：纯品为白色结晶，具芳香味。m.p.17～18℃, 蒸气压5.333×10-3Pa (40℃)，相对密度1.226 (20℃)，折射率n20D1.5550。易溶于丙酮、苯等多种有机溶剂，在水中溶解度为11mg/L。在酸性与中性介质中稳定，碱性条件下易水解。工业品为黄褐色芳香味液体，相对密度1.21～1.23 (20℃)。

毒性：急性毒性：LD50300～400mg/kg(大鼠经口)；350～400mg/kg(小鼠经口)；72mg/kg(野兔经口)；218mg/kg (野鸡经口);300mg/kg(鹌鹑经口) ，对人畜毒性中等。
水生生物平均忍度限量：鲤鱼2.0ppm/48小时，金鱼2.4ppm/48小时



作用特点及杀虫谱：高效、广谱性有机磷杀虫、杀卵、杀螨剂。具有触杀和胃毒作用，无内吸作用。此外，还具有残效期长、速效性强、对作物安全的特点。可用于防治水稻、棉花、蔬菜、柑橘、果树、茶叶、油料等作物的大螟、二化螟、三化螟、叶蝉、飞虱等多种害虫。如防治二化螟、三化螟在卵孵高峰期，用50%乳油15～30mL/100m2对水7.5～10.5kg喷雾。同样浓度和剂量也可用于防治稻飞虱、叶蝉、棉铃虫、菜青虫、小菜蛾、蚜虫、棉叶蝉、斜纹夜蛾、蓟马等。用于防治稻、棉、蔬菜、果树、油料等作物上的多种害虫。

剂型：50％稻丰散乳油

生产方法：方法1：在苯乙酸中添加红磷（用量为苯乙酸重量的6%），于85℃左右通氯至反应液相对密度达到1.29-1.30（50/4℃）。然后加入95%的乙醇（按摩尔比，用量是苯乙酸的1.7倍），于60-80醇化，得到含量为99%以上的α-氯代苯乙酸酯。将α-氯代苯乙酸乙酯至85℃，滴加O，O-二甲基二硫代磷酸钠盐，用NaHCO3调节pH为7-8，反应3-3.5h即生成稻丰散。制和的稻丰散含量为62%以上，收率43%以上。原料消耗定额：五硫化二磷1080kg/t、甲醇780kg/t、工业酒精（95%）700kg/t、碳酸氢钠1140kg/t、氰苄（＞97%）1040kg/t、硫酸（＞95%）1000kg/t、液氯（＞99%）1630kg/t。

方法2：也可以采用α-溴代苯乙酸酯与O，O-二甲基二硫代磷酸钠水溶液在甲苯中反应，添加相转移催化剂，在65℃反应4h时，可得含量92%的稻丰散。

α-溴代苯乙酸乙酯的制备 在30℃下，将95%以上三氯化磷70mol慢慢滴入到192mol苯乙酸和40L的二氯乙烷混合液中，滴毕，回流反应30min,继续搅拌1h。再在回流状态下于1～1.5h内滴加250mol的无水乙醇，滴毕，继续搅拌反应1h为酯化结束。反应液经碱洗、萃取、中和、水洗、脱去溶剂后得棕红色液体α-溴代苯乙酸乙酯45kg，含量91%以上，收率87.7%。

O，O-二甲基二硫代磷酸（简称甲基硫代物）的制备 通常采用P2S5与CH3OH作用，甲醇适当过量，反应温度55～60℃，为强放热反应，操作时要特别注意安全。反应过程较复杂，同时发生一系列副反应。O，O-二甲基二硫代磷酸的收率和含量75%～80%。
采用适当催化剂，在（55±2）℃反应，收率和含量可达90%左右。
O，O-甲基二硫代磷酸盐的制备 O，O-二甲基二硫代磷酸与碳酸钠（铵）或碳酸氢钠在常温下反应，控制终点pH值成盐。

稻丰散的合成 将用Na2CO3处理的160mol O，O-二甲基二硫代磷酸钠水溶液，加甲苯30L，升温至40～45℃，加入相转移催化剂，在0.5～1h内滴加100mol的α-溴代苯乙酸乙酯，滴毕，于65℃下保温反应4h，经碱洗、中和、水洗、脱去溶剂后得红黄色油状稻丰散原油，含量92%，收率88%。

生产情况：稻丰散1961年由意大利蒙特卡蒂尼公司开发成功并投入产业化。现在国外主要有意大利蒙特卡蒂尼公司和日本日产化学工业株式会社生产。国内主要由江苏腾龙生物药业有限公司和湖南省常德市农药有限公司生产（似乎已停产），生产龙头企业江苏腾龙生物药业有限公司生产能力2000吨/年

phenthoate
Insecticide, acaricide
IRAC 1B; organophosphate

NOMENCLATURE
Common name phenthoate (BSI, E-ISO, (m) F-ISO); PAP (JMAF)
IUPAC name S-a-ethoxycarbonylbenzyl O,O-dimethyl phosphorodithioate
Chemical Abstracts name ethyl a-[(dimethoxyphosphinothioyl)thio]benzeneacetate
Other names dimephenthoate CAS RN [2597-03-7] EEC no. 219-997-0 Development codes L 561 (Agrimont); S-2940 (Sumitomo) Official codes OMS 1075; ENT 27 386

PHYSICAL CHEMISTRY
Mol. wt. 320.4 M.f. C12H17O4PS2 Form Colourless crystals; (tech., reddish-yellow liquid). M.p. 17-18 ºC B.p. 186-187 °C/5 mmHg V.p. 5.3 mPa (40 ºC) KOW logP = 3.69 S.g./density 1.226 (20 ºC) Solubility In water 10 mg/l (25 °C). Readily soluble in methanol, ethanol, acetone, hexane, xylene, benzene, carbon disulfide, chloroform, dichloromethane, acetonitrile, tetrahydrofuran; in n-hexane 116, kerosene 340 (both in g/l, 25 °C) Stability Decomposes 180 °C. In water, stable under neutral and acidic conditions; degrades under alkaline conditions. F.p. 165-170 ºC

COMMERCIALISATION
History Introduced by Montecatini S.p.A. (now Isagro S.p.A.). Patents GB 834814; US 2947662 Manufacturers Agrochem; Aimco; Hanwha; Nissan; Sharda

APPLICATIONS
Biochemistry Cholinesterase inhibitor. Mode of action Non-systemic insecticide and acaricide with contact and stomach action. Uses Control of Aphididae (aphids), Coccidae & Diaspididae (scale insects), Cicadellidae (leafhoppers), Fulgoridae (lantern bugs), Pseudococcidae (mealybugs), Tingidae (lace bugs), Pyrrhocoridae (cotton stainers, red bugs) and Pentatomidae (shield bugs), Thripidae (thrips), Aleyrodidae (whitefly), Noctuidae (bollworms, stem borers), in citrus fruit, pome fruit, olives, Japanese persimmons, chestnuts, mulberries, cotton, cereals, maize, rice, coffee, tea, sunflowers, sugar cane, tobacco, vegetables, cucurbits, and ornamentals, at 40-75 g/hl, 500-1000 g/ha. Also used for mosquito control (adults and larvae). Phytotoxicity Phytotoxic to some varieties of grape, fig, and peach, and red-skinned varieties of apple. Formulation types DP; EC. Compatibility Not compatible with pesticides which are alkaline in reaction. Selected products: 'Cidial' (Isagro); 'Aimsan' (Aimco); 'Elsan' (Nissan); 'Guard' (Crop Health); 'Vifel' (Vipesco)

OTHER PRODUCTS
'Tanone' (Isagro); 'Amaze' (Biostadt); 'Genocide' (Agrochem) mixtures: 'Rogodial' (+ dimethoate) (Isagro); 'Vicidi-M' (+ etofenprox) (Vipesco); 'Viphensa' (+ fenobucarb) (Vipesco) Discontinued products: 'Papthion' * (Sumitomo)

ANALYSIS
Product analysis by glc (B. Bazzi et al., Anal. Methods Pestic. Plant Growth Regul., 1976, 8, 159). Residues determined by glc (B. Bazzi et al., loc. cit.; Man. Pestic. Residue Anal., 1987, I, 6, S19; Anal. Methods Residues Pestic., 1988, Part I, M11; A. Ambrus et al., J. Assoc. Off. Anal. Chem., 1981, 64, 733). Details available from Isagro.

MAMMALIAN TOXICOLOGY
Reviews FAO/WHO 42, 43 (see part 2 of the Bibliography). Oral Acute oral LD50 for male rats 270, female rats 249, mice 350, dogs >500, guinea pigs 377, rabbits 72 mg/kg. Skin and eye Acute percutaneous LD50 for rats >5000, male mice 2620 mg/kg. Non-irritating to skin and eyes (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC50 (4 h) for rats 3.17 mg/l air. NOEL (104 w) for dogs 0.29 mg/kg daily. ADI (JMPR) 0.003 mg/kg b.w. [1984]. Toxicity class WHO (a.i.) II EC classification Xn; R21/22

ECOTOXICOLOGY
Birds Acute oral LD50 for pheasants 218, quail 300 mg/kg. Fish TLm (48 h) for carp 2.5, goldfish 2.4 ppm. Bees Toxic to bees. LD50 0.306 mg/bee.

ENVIRONMENTAL FATE
EHC 63 (WHO, 1986; a general review of organophosphorus insecticides). Animals In mammals, phenthoate is degraded with almost equal facility by hydrolysis of the carboethoxy moiety, cleavage of the P-S or C-S bond and removal of the methoxy group by either direct demethylation or hydrolytic cleavage of the P-O bond. The following metabolites were identified in either urine or faeces: demethyl phenthoate, demethyl phenthoate acid, demethyl phenthoate oxon acid, O,O-dimethyl phosphorodithioic and phosphorothioic acids. Plants In plants, there is oxidation to the phosphorothioate, followed by hydrolysis. Phosphoric acid, dimethyl and monomethyl phosphate have been identified as metabolites. Soil/Environment DT50 £1 d in both upland and submerged soil. The degradation product is phenthoate acid.