Quinalphos 喹硫磷

喹硫磷

CAS号: 13593-03-8
英文名称: Quinalphos
化学名称：O,O-二乙基-O-喹噁啉-2-基硫代磷酸酯; Diethyl O-2-quinoxalinyl phosphorothioate
其他名称：爱卡士；喹噁磷；喹噁硫磷
分子式: C12H15N2O3PS
分子量: 298.3

理化性质 ：纯品为白色无味结晶。m.p.31～32℃,b.p.142℃/3.999×10-2Pa （分解),相对密度1.235(20℃),折射率n25D1.5624，蒸气压3.3466×10-4Pa (20℃)。易溶于苯、甲苯、二甲苯、醇、乙醚、丙酮、乙腈、乙酸乙酯等多种有机溶剂，微溶于石油醚，在水中溶解度为22mg/L(常温）。酸性条件易水解，于120℃分解。

毒性：大白鼠急性经口毒性LD50为62～137mg/kg，大白鼠急性经皮毒性LD50为800～1400mg/kg。对兔皮肤无刺激作用，对兔眼睛有轻度刺激作用。鲤鱼TLm（96h）为3.63mg/L；对蜜蜂有毒，其TLm（24h）为1.59mg/kg。柑桔中最大允许残留量为0.1mg/kg，蔬菜中为0.1mg/kg，棉籽中为1mg/kg（瑞士）。安全间隔期为21天。

作用特点及杀虫谱：广谱性杀虫、杀螨剂，具胃毒和触杀作用，无内吸和熏蒸作用，有一定的杀卵作用。用于防治鳞翅目、红铃虫、棉铃虫、红蜘蛛及蔬菜上的菜青虫等，用于防治水稻螟虫、棉花害虫、蔬菜蚜虫等。对稻瘿蚊有特效，在中晚稻秧田成虫盛发期内开始施药，每隔7～10d施1次，一般2次，每次每百平方米用25%乳油22.5～30mL，对水9～22.5kg喷雾，或用5%颗粒剂180～225g撒施，田间须保持一定量水。防治稻纵卷叶螟、稻蓟马，每百平方米用25%乳油22.5～30mL对水7.5～9kg喷雾。防治二化螟、三化螟、稻飞虱、稻叶蝉等每百平方米用25%乳油15～20mL对水1.13kg喷雾，或用5%颗粒剂每百平方米150～225g均撒。防治棉蚜用25%乳油7.5～9mL,对水7.5kg喷雾。此外还可防治棉蓟马、柑橘潜叶蛾、介壳虫、小绿叶蝉、茶尺蠖等。

剂型：25%乳油；10%高渗乳油。12.5％增效乳油；16％丁硫·喹乳油；15％喹·氯乳油；12.5％增效喹·氰乳油；5%颗粒剂

生产方法 ：O，O-二乙基硫代磷酰氯的制备 先由三氯硫磷与过量的无水乙醇反应生成二氯化物，于25～35℃，停留时间35min，再经水洗、分层得二氯化物。再与过量无水乙醇一起，加入碱粉，控制反应温度为0～5℃，当pH值达9～10时为反应终点。经后处理得乙基氯化物，即O，O-二乙基硫代磷酰氯。
国外多采用五硫化二磷法，由五硫化二磷与乙醇反应制得二乙基二硫代磷酸，再经氯化制得乙基氯化物。后处理过程相对困难。
2-羟基喹噁啉的制备 邻苯二胺与氯乙酸反应，制得2-羟基喹噁啉。缚酸剂可用碳酸铵，于65℃反应1h，得3，4-二氢-2-羟基喹噁啉，收率92%；然后在氢氧化钠存在下，加双氧水于60℃反应5～6h，得2-羟基喹噁啉，两步总收率82%。
喹硫磷的合成 将2-羟基喹噁啉、乙酸乙酯、无水碳酸钾依次加入反应器中，加热搅拌，缓缓加入乙基氯化物，加完后反应一段时间，减压脱溶，加二甲苯，水洗，分层，取样分析。脱二甲苯后原油含量86.0%，收率86.3%。
原料消耗定额：邻苯二胺1200kg/t、氯乙酸1150kg/t、O，O-二乙基硫代磷酰氯800kg/t。

生产情况：四川省化学工业研究设计院；浙江嘉化集团股份有限公司（1000吨/年）；上海农药厂有限公司（1100吨/年）

quinalphos
Insecticide, acaricide
IRAC 1B; organophosphate

NOMENCLATURE
Common name quinalphos (BSI, E-ISO, (m) F-ISO); chinalphos ((m) France)
IUPAC name O,O-diethyl O-quinoxalin-2-yl phosphorothioate
Chemical Abstracts name O,O-diethyl O-2-quinoxalinyl phosphorothioate
CAS RN [13593-03-8] EEC no. 237-031-6 Development codes Bay 77 049 (Bayer); SAN 6538; SAN 6626 (both Sandoz) Official codes ENT 27 394

PHYSICAL CHEMISTRY
Mol. wt. 298.3 M.f. C12H15N2O3PS Form Colourless crystals. M.p. 31-32 ºC B.p. 142 ºC/0.0003 mmHg (decomp.) V.p. 0.346 mPa (20 ºC) KOW logP = 4.44 (23 ºC, 10-100 ppm level) S.g./density 1.235 (20 ºC) Solubility In water 17.8 mg/l (22-23 ºC). In hexane 250 g/l (23 ºC). Readily soluble in toluene, xylene, diethyl ether, ethyl acetate, acetone, acetonitrile, methanol, ethanol. Slightly soluble in petroleum ether (23 °C). Stability A.i. stable 14 d at room temperature; liquid tech. grade less stable but stable under ambient storage conditions, when diluted in non-polar organic solvents and in the presence of stabilising agents. Formulations are stable (shelf life at ave. ann. temp. £25 ºCc. 2 y). Susceptible to hydrolysis; DT50 (25 ºC, 17 ppm and 2.5 ppm) 23 d (pH 3), 39 d (pH 6), 26 d (pH 9).

COMMERCIALISATION
History Insecticide reported by K-J. Schmidt & L. Hammann (Pflanzenschutz-Nachr. (Engl. Ed.), 1969, 22, 314). Introduced by Bayer AG and by Sandoz AG (became Novartis Crop Protection AG); both companies have ceased manufacturing and marketing it. Patents BE 681443; DE 1545817 to Bayer Manufacturers Aimco; Cheminova; Ficom; Gujarat; Sharda; United Phosphorus

APPLICATIONS
Biochemistry Cholinesterase inhibitor. Mode of action Insecticide and acaricide with contact and stomach action. By penetrating the plant tissues through translaminar action, exhibits a systemic effect. Uses Control of many insect pests of the orders Lepidoptera, Coleoptera, Diptera, Hemiptera, etc. For example, used against caterpillars on fruit trees, cotton, vegetables, and peanuts; scales on fruit trees; and the pest complex on rice. Also controls aphids, bollworms, borers, leafhoppers, mealybugs, mites, planthoppers, thrips, etc. on beet, vines, ornamentals, potatoes, soya beans, tea, coffee, cocoa, and other crops. Dose rates 250-500 g/ha of EC and 0.75-1.0 kg/ha of GR. Phytotoxicity Slightly phytotoxic to certain fruit trees. Formulation types DP; EC; GR; UL; EW. Compatibility Not compatible with alkaline substances. Selected products: 'Danulux' (Dhanuka); 'Deviquin' (Devidayal); 'Hilquin' (Hindustan); 'Hubelux' (Sanonda); 'Iguasu' (Rocca); 'Max' (Crop Health); 'Quinaal' (Ramcides); 'Quinatox' (Aimco); 'Quinguard' (Gharda); 'Smash' (RPG); 'Starlux' (Shaw Wallace); mixtures: 'Chintop' (+ beta-cypermethrin) (Agro-Chemie); 'Quick' (+ cypermethrin) (Nagarjuna Agrichem)

OTHER PRODUCTS
'Bayrusil' (Bayer CropScience); 'Ekaquin' (BEC); 'Flash' (Indofil); 'Kinalux' (United Phosphorus); 'Krush' (Biostadt); 'Quinalon' (Papaeconomou); 'Shakthi' (Parry); 'Unifos' (Tecomag) Discontinued products: 'Ekalux' * (Novartis); 'Savall' * (Farm Protection, Novartis); 'Set' * (Cequisa) mixtures: 'Knave' * (+ disulfoton) (Novartis); 'Tombel' * (+ thiometon) (Sandoz)

ANALYSIS
Product analysis by glc or by tlc and subsequent u.v. spectrometric determination of the eluted compound. Residues determined by glc (M. Wisson et al., Anal. Methods Pestic. Plant Growth Regul., 1980, 6,147).

MAMMALIAN TOXICOLOGY
Oral Acute oral LD50 for male rats 71 mg/kg. Skin and eye Acute percutaneous LD50 for male rats 1750 mg/kg. Non-irritating to skin and eyes (rabbits). Inhalation LC50 (4 h) for rats 0.45 mg/l air. NOEL (2 y) (based on cholinesterase inhibition) for rats 3 mg/kg diet. Other No teratogenic effects (rats and rabbits); no mutagenic potential. Cholinesterase inhibitor in rats, mice, and dogs. Toxicity class WHO (a.i.) II; EPA (formulation) II EC classification T; R25| Xn; R21

ECOTOXICOLOGY
Birds Acute LD50 (14 d) for Japanese quail 4.3, mallard ducks 37 mg/kg. Dietary LC50 (8 d) for quail 66, mallard ducks 220 mg/kg. Fish LC50 (96 h) for carp 3.63, rainbow trout 0.005 mg/l. Daphnia LC50 (48 h) 0.66 mg/l. Bees Very toxic to bees. LD50 (oral) 0.07 mg/bee; (topical) 0.17 mg/bee. Worms LC50 (7 d) 188 mg/kg soil; (14 d) 118.4 mg/kg soil.

ENVIRONMENTAL FATE
EHC 63 (WHO, 1986; a general review of organophosphorus insecticides). Animals In rats, following oral administration, rapidly absorbed and metabolised to 2-hydroxyquinoxaline (free and as its conjugates), which are excreted in the urine (c. 87%) and bile (c. 13%) within a short time. Plants In plants, one-third is absorbed by the leaf surface and penetrates into the plant, whilst two-thirds disappears by evaporation within 14 days. The principal metabolite is 2-hydroxyquinoxaline (free and as its conjugates). Soil/Environment In soil, rapidly degraded under aerobic conditions, DT50 c. 3 w. The hydrolysis product 2-hydroxyquinoxaline does not accumulate in the soil, but is further broken down to polar metabolites and CO2. Freundlich K 25-320 mg/kg (o.m. 1.1-35.5%); DT50 21 d (o.m. 2.6%, pH 6.8, 18-22 ºC).