Clofentezine 四螨嗪

四螨嗪

CAS号: 74115-24-5
英文名称: Clofentezine
化学名称：3,6-双(2-氯苯基)-1,2,4,5-四嗪；3,6-bis(o-chlorophenyl)-1,2,4,5-tetrazine
其他名称：四螨嗪，阿波罗，螨死净，克芬螨
分子式：C14H8Cl2N4
分子量：303.15

理化性质：纯品为红色晶体，m.p.182.3℃(工业品182～186℃)，蒸气压13×10-3Pa。25℃时溶解度为：二氯甲烷37g/kg，环己烷1.7g/kg，乙醇0.5g/kg，氯仿50g/L，丙酮9.3g/L，苯2.5g/L，己烷1g/L，水<1mg/L。分配系数150 （12600）。对光、热、空气稳定；22℃时水解半衰期为248h (pH=5)、34h (pH=7)、4h(pH=9)，可燃性较低。

毒性LD50：急性经口：大白鼠3200（有效成分），野鸭大于3000，鹌鹑大于7500。大白鼠急性经皮1332以上。对鱼无毒。

作用特点及杀虫谱：四嗪类杀螨剂，胚胎发育抑制剂，属高效、低毒广谱杀螨剂，用于防治苹果和其他果树树冠上的螨虫类，主要杀螨卵，但对幼螨也有一定效果，对成螨无效。药效发挥较慢，持效期50～60d，施药后2～3周可达到最高杀螨效果。用于果树、豌豆、柑橘、观赏植物、棉花等作物，防治全爪螨属和叶螨属害螨，对榆全爪螨（苹果红蜘蛛）的冬卵特别有效。对捕食性螨和有益昆虫安全。一般在开花前后各施1次，每次按100～125mg/L浓度喷施。

剂型：10%、20%可湿性粉剂，25%、50%、20%悬浮剂，以及哒螨酮和四螨嗪复合农药的悬浮剂

生产方法 ：以邻氯苯甲醛与亚硝酸钠及氯气作用，制取（2-ClC6H4CClN)2，或用2-氯苯甲酰氯与N2H4 （经乙醇稀释）反应，再与PCl5反应制取（2-ClC6H4CClN)2。最后与水合肼在相转移催化剂存在下反应制得四螨嗪。

生产情况：江苏省南通宝叶化工有限公司；浙江省杭州庆丰农化有限公司；河北省石家庄市绿丰化工有限公司；河北省张家口长城农化（集团）有限责任公司；
价格：四螨嗪原药价格15.5-16万元/吨（09.08）

clofentezine
Acaricide
IRAC 10A; mite growth inhibitor

NOMENCLATURE
Common name clofentezine (BSI, ANSI, draft E-ISO, (f) draft F-ISO)
IUPAC name 3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine
Chemical Abstracts name 3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine
Other names bisclofentezin* (rejected common name proposal) CAS RN [74115-24-5] EEC no. 277-728-2 Development codes NC 21 314 (Fisons)

PHYSICAL CHEMISTRY
Mol. wt. 303.1 M.f. C14H8Cl2N4 Form Magenta crystals. M.p. 182.3 ºC V.p. 1.3 ´ 10-4 mPa (25 ºC) (gas saturation and glc) KOW logP = 4.1 (25 ºC) Henry 1.97 ´ 10-4 Pa m3 mol-1 (calc.) S.g./density 1.51 (20 °C) Solubility In water 2.5 mg/l (pH 5, 22 ºC). In dichloromethane 37, acetone 9.3, hexane 1, ethanol 0.5 (all in g/l, 25 ºC). Stability The a.i. and formulated products are stable to light, heat and air; on hydrolysis (22 ºC), DT50 248 h (pH 5), 34 h (pH 7), 4 h (pH 9). F.p. Low flammability

COMMERCIALISATION
History Acaricide reported by K. M. G. Bryan et al. (Proc. Br. Crop Prot. Conf. - Pests Dis., 1981, 1, 67) and relationships between chemical structure and biological activity by P. J. Brooker et al. (Pestic. Sci., 1987, 18, 179). Introduced by FBC Limited (now Bayer CropScience) and transferred to Makhteshim-Agan Industries in 2001. Patents EP 5912 Manufacturers Bayer CropScience

APPLICATIONS
Mode of action Specific acaricide with contact action, and long residual activity. Inhibits embryo development. Uses Control of eggs and young motile stages (but not adults) of Panonychus ulmi and Tetranychus spp. on pome fruit and stone fruit (20 g/hl), citrus fruit (12.5-20 g/hl), nuts, vines (20 g/hl), hops, strawberries (200-300 g/ha), cucurbits (100-400 g/ha), cotton (150-250 g/ha), and ornamentals (20-30 g/hl). Has no effect on predatory mites or beneficial insect species. Phytotoxicity May cause slight injury to glasshouse roses. May cause a slight pink deposit on petals of white or pale flowers. Formulation types SC; WP. Compatibility 'Apollo' formulation is compatible with most pesticide products commonly used in orchards, except alkaline and copper products. Selected products: 'Apollo' (Makhteshim-Agan, Bayer CropScience); 'Niagara' (Rocca)

OTHER PRODUCTS
'Apollo Plus' (Makhteshim-Agan); 'Saran' (Makhteshim-Agan); 'Acaristop' (Makhteshim-Agan); 'Apolo' (Makhteshim-Agan); 'Cara' (Makhteshim-Agan); 'Ovation' (Scotts) Discontinued products: 'Panatac' * (AgrEvo)

ANALYSIS
Product analysis by rp hplc (CIPAC Handbook, 1995, G, 18-23) or by visible spectroscopy. Residues in plants and soil determined by hplc. Details available from Bayer CropScience.

MAMMALIAN TOXICOLOGY
Reviews FAO/WHO 47, 49 (see part 2 of the Bibliography). Oral Acute oral LD50 for rats >5200 mg/kg. Skin and eye Acute percutaneous LD50 for rats >2100 mg/kg. Mild eye and skin irritant. Inhalation LC50 (4 h) for rats >9 mg/l air. NOEL (2 y) for rats 40 mg/kg diet; (1 y) for dogs 50 mg/kg diet. ADI (JMPR) 0.02 mg/kg b.w. [1986]. Toxicity class WHO (a.i.) III (company classification); EPA (formulation) III (50 SC)

ECOTOXICOLOGY
Birds Acute oral LD50 for mallard ducks >3000, bobwhite quail >7500 mg/kg. Dietary LC50 (8 d) for mallard ducks and bobwhite quail >2000 mg/kg diet. Fish LC50 (96 h) for rainbow trout >0.015, bluegill sunfish >0.25 mg/l (limits of solubility). Daphnia LC50 (48 h) >1.45 mg/l (limit of solubility). Algae Not toxic to Scenedesmus pannonicus up to limit of solubility. Other aquatic spp. Not toxic to aquatic organisms up to the limit of solubility. Bees Acute LD50 (oral) >20 mg/bee; LC50 (contact) >1500 ppm. Worms Not toxic to earthworms. Other beneficial spp. No known deleterious effects to beneficials, such as predatory mites and predaceous insects.

ENVIRONMENTAL FATE
Animals In mammals, undergoes metabolism by hydroxylation and exchange of the chlorine atoms on the rings for methylthio groups. Following oral administration, excretion occurs within 24-48 hours in the urine and faeces. Plants In metabolism studies, unchanged clofentezine was the major extractable residue. Trace amounts (4%) of 2-chlorobenzonitrile, the major photodegradation product, were also detected. Soil/Environment In soil, the major degradation route leads to 2-chlorobenzoic acid, and finally to CO2. DT50 in soil 65-85 d (15 ºC), 28-56 d (25 ºC), depending upon soil type. However, in laboratory studies, no leaching occurs. In water, 2-chlorobenzonitrile is the major product formed by hydrolysis and photodegradation, with smaller amounts of other compounds. Low solubility in water makes determination of soil adsorption constants difficult.