Bifenox 甲羧除草醚 甲羧除草醚

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甲羧除草醚

CAS号:42576-02-3
英文名称:Bifenox
其他名称:甲酯除草醚,芳毒,治草醚,茅丹?茅毒?
分子式:C14H9Cl2NO5
分子量:342.13

理化性质:本品为黄色或浅褐色结晶。,熔点84~86。分解温度290℃,相对密度1.155,30℃时的蒸气压为32mPa,在水中的溶解度为35mg/L,可溶于大多数有机溶剂中。25℃时在乙醇中溶解度<5%,丙酮中为40%,二甲苯中为30%,氯苯中为35%~40%,苯中为4%,水中为0.36mg/L。对光稳定,在土壤中半衰期为7~14d。

毒性:急性口服LD50鼠大于6400mg/kg,急性经皮毒性LD50兔大于20000mg/kg。TLM鲤鱼(48h)为1.22ppm。

作用特点及杀草谱:触杀型芽前土壤处理剂,具有杀草谱广,施药量少,土壤适应性强,不受气温影响等特点。药剂被杂草幼芽吸收,破坏杂草的光合作用。适用于大豆、水稻、高梁、玉米、小麦等作物防除稗草、千金子、鸭跖草、苋菜、本氏蓼、藜、马齿苋、苘麻、苍耳、鸭舌草、泽泻、龙葵、地肤等杂草。如水稻使用于移栽本田,在移栽后4~6d,用7%颗粒剂240~285g/100m2或80%可湿性粉剂22~25g/100m2,制成毒土撒施。施药时灌浅水层,施药后保持水层3~4d。推荐用药量为1~2kg有效成分/hm2。

剂型:制剂有80%可湿性粉剂、10%颗粒剂、21%乳油及水悬剂。

生产方法:制备方法一
水解反应 将772g三氯化苄、0.25g三氯化铁混合手,升温至120℃,再将75g水于一定时间内恒温滴加,滴毕继续搅30min,得苯甲酰氯633g,收率96%。
氯化反应 投入苯甲酰氯281g,铁粉1.4g,硫黄0.56g,于20℃通氯反应2.5h,赶走余氯和氯化氢气体,得间氯苯甲酰氯粗品,收率70%~80%。
酯化反应 将甲醇滴加到间氯苯甲酰氯中,配比为1:1 (mol),于25~68℃范围内反应,反应过程有轻微放热现象,可以调节加料速度,控制反应温度,回流2~3h,反应过程有大量氯化氢逸出,过量的甲醇与残余氯化氢气体用真空排除,得无色间氯苯甲酸甲酯液体,收率98%~99%。硝化反应 将853g间苯甲酸甲酯(纯度94%)和500g 1,2-二氯乙烷混合手,冷却至-10℃,再滴加338g 95%发烟硝酸和816g 96%的硫酸(混酸),约在3h内滴毕,将反应物在-10℃下搅抖2h后,再在0~30℃搅拌3h,倾去有机层(1,2-二氯乙烷),过滤、干燥,得829g 5-氯-2-硝基苯甲酸甲酯,收率76.9%。
缩合反应 将固体碳酸钾1.61mol加入到2,4-二氯苯酚2.49mol及960mL DMF溶液中,升温回流1h,伴有二氧化碳气体逸出。把近1/2的DMF(夹带生成的水)溶剂蒸出后,将5-氯-2-硝基苯甲酸甲酯2.37mol加入温度为95℃的酚盐溶液中。加毕于100℃反应3h,真空蒸出DMF,加1000mL甲醇使粗品溶解,大药冷至65℃,滤出KCl,母液冷冻结晶,得纯甲羧除草醚420g,收率50%。

制备方法二:以苯甲酰氯、氯气、2,4-二氯苯酚为主要原料,进行下列反应而得。1.间氯苯甲酰氯的制备 将苯甲酰氯281g、铁粉1.4g及硫黄0.56g投入反应瓶中。保持温度20℃,通氯氯化,约2.5h。然后通氮气赶除光气和反应生成的氯化氢气体而得。2.间氯苯甲酸甲酯的制备 将甲醇慢慢地加入搅拌下的间氯苯甲酰氯中(酰氯:甲醇=1.0:1.1摩尔比)。在25-68℃之间行酯化反应,回流2-3h,反应过程中有大量氯化氢放出,回收过量的甲醇而得。3.5-氯-2-硝基苯甲酸甲酯的制备 往反应瓶中加入853g间氯苯甲酸甲酯,和500g 1,2-二氯乙烷,冷却至-10℃,滴加338g 95%的发烟硝酸(5.1mol)和816g 96%硫酸(8mol)的混合酸,约3h滴完。在-10℃下搅拌反应2h,再升温至30℃搅拌反应3h。分出有机层,过滤,干燥而得。4.甲酯除草醚的制备 将固体碳酸钾(97%)189g,加入搅拌下的2,4-二氯苯酚(97%)419g及960ml二甲基甲酰胺溶剂中,加热回流1h,伴有二氧化碳放出,约50%的二甲基甲酰胺蒸出之后,将5-氯-2-硝基苯甲酸甲酯(80%)638g加入搅拌下的95%的酚盐中。加完后,在100℃反应3h,脱溶后加甲醇使产品溶解,冷却,滤除氯化钾。滤液冷却结晶而得,熔点84-86℃。

生产情况:如东众意化工有限公司; 盐城市麦迪科化学品制造有限公司;太原市瑞和丰科贸有限公司;施瑞科技(武汉)有限公司

 

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bifenox
Herbicide
HRAC E WSSA 14; diphenyl ether

  Bifenox

NOMENCLATURE
Common name bifenox (BSI, draft E-ISO, (m) draft F-ISO, ANSI, WSSA)
IUPAC name methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate
Chemical Abstracts name methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate
CAS RN [42576-02-3];formerly [12680-11-4] EEC no. 255-894-7 Development codes MC-4379 (Mobil); MCTR-1-79; MCTR-12-79

PHYSICAL CHEMISTRY
Composition ³97% pure. Mol. wt. 342.1 M.f. C14H9Cl2NO5 Form Yellow crystals with a slightly aromatic odour. M.p. 84-86 ºC V.p. 0.32 mPa (30 ºC) KOW logP = 4.5 Henry 1.14 ´ 10-2 Pa m3 mol-1 S.g./density 0.65 g/ml (bulk density) Solubility In water 0.35 mg/l (25 ºC). In acetone 400, chlorobenzene 400, xylene 300, ethanol <50 (all in g/kg, 25 ºC). Slightly soluble in aliphatic hydrocarbons. Stability Thermally stable up to 175 ºC; total decomposition occurs above 290 ºC. Stable in slightly acidic or slightly alkaline media, but rapidly hydrolysed above pH 9. DT50 in saturated aqueous solution, 24 min at 250-400 nm; c. 5 h for a thin film on soil.

COMMERCIALISATION
History Herbicide reported by W. M. Dest et al. (Proc. Northeast. Weed Sci. Conf., 1973, 27, 31). Introduced by Mobil Chemical Co. Agrochemical Division (now Bayer CropScience) and later by Eli Lilly & Co. (agrochemical interests now Dow AgroSciences, who no longer manufacture or market it). Patents GB 1232368; US 3652645; US 3776715 all to Mobil Manufacturers Feinchemie Schwebda

APPLICATIONS
Biochemistry Protoporphyrinogen oxidase inhibitor. Acts by cellular membrane disruption and by inhibition of photosynthesis. Mode of action Selective herbicide, absorbed by the foliage, emerging shoots and roots, with limited translocation from roots and foliage to shoots. Uses Control of annual broad-leaved weeds and some grasses in cereals, maize, sorghum, soya beans, rice, and some other crops at 0.75-1 kg/ha. Applied pre-plant incorporated, pre-emergence, or directed post-emergence. Often used in combination with other herbicides to extend the spectrum of activity. Formulation types SC; EC; GR; WP. Selected products: 'Foxpro' (Feinchemie Schwebda); 'Modown' (Feinchemie Schwebda); 'Tolkan Fox' (Feinchemie Schwebda)

OTHER PRODUCTS
'Athlet' (Feinchemie Schwebda); 'Bifenix' (Feinchemie Schwebda); 'Exel' (Feinchemie Schwebda); 'Foxtar' (Feinchemie Schwebda); 'Foxtril' (Feinchemie Schwebda) mixtures: 'Fizz' (+ ioxynil+ pyraflufen-ethyl) (ioxynil as a salt) (Bayer CropScience); 'Foxpro D+' (+ ioxynil+ mecoprop-P) (Feinchemie Schwebda); 'Foxtril P' (+ ioxynil+ mecoprop-P) (ioxynil and mecoprop-P as potassium salts) (Bayer CropScience); 'Kalao' (+ ioxynil+ mecoprop) (Sipcam Phyteurop); 'Milan' (+ pyraflufen-ethyl) (Nihon Nohyaku, Feinchemie Schwebda) Discontinued products mixtures: 'Sirocco' * (+ MCPA+ mecoprop-P) (Bayer); 'Quickstep' * (+ dicamba) (Novartis)

ANALYSIS
Product analysis is by rplc (CIPAC Handbook, 1995, G, 11-17). Residues determined by glc with MCD. Details available from Bayer CropScience.

MAMMALIAN TOXICOLOGY
Reviews Toxicological Evaluation of the Herbicide Bifenox, J-O. Säfwenberg, Säfwenberg Consulting, Surbrunnsgatan 43 A, S-11348, Stockholm, Sweden. Oral Acute oral LD50 for rats >5000 mg tech./kg, mice 4556 mg/kg. Skin and eye Acute percutaneous LD50 for rabbits >2000 mg/kg. Non-irritating to skin and eyes. Inhalation LC50 for rats >0.91 mg/l air. NOEL (2 y) for rats 80, dogs 145, mice 30 mg/kg b.w. daily. Other Non-mutagenic in mouse lymphoma assay and Ames test. Non-teratogenic. Toxicity class WHO (a.i.) U; EPA (formulation) IV

ECOTOXICOLOGY
Birds Dietary LC50 (8 d) for ducks and pheasants >5000 mg/kg diet. Fish LC50 (96 h) for rainbow trout >0.67, bluegill sunfish >0.27 mg/l. Daphnia LC50 (48 h) 0.66 mg/l. Other aquatic spp. LC50 (96 h) for Palaemonetes pugio (grass shrimp) 569 ppm, for Mysidopsis bahia (mysid shrimp) 0.065 mg/l; (48 h) for Crassostrea virginica (Eastern oyster) 210 mg/l. Bees LD50 (contact) >1000 mg/bee. Worms EC50 and NOEC >1000 mg/kg.

ENVIRONMENTAL FATE
Animals Bifenox is relatively rapidly absorbed and eliminated from the body; 5-(2,4-dichlorophenyl)-2-nitrobenzoic acid was the major urinary metabolite, with no bifenox detected. Bifenox together with 5-(2,4-dichlorophenyl)anthranilate were detected in faeces. Soil/Environment DT50 in soil c. 5-7 d. Duration of residual activity is c. 7-8 w. Degradation is mainly chemical and microbial, and the two metabolites are 5-(2,4-dichlorophenoxy)-2-nitrobenzoic acid and methyl 5-(2,4-dichlorophenoxy)anthranilate. Mobile in soil; Kd 50-300; Koc 500-23 000.