Pirimicarb 抗蚜威

抗蚜威

CAS号：23103-98-2
英文名称：pirimicarb
化学名称：2-二甲氨基-5,6-二甲基嘧啶-4-二甲基氨基甲酸酯；2-(Dimethylamino)-5,6-dimethyl-4-pyrimidinyl dimethylcarbamate
其他名称：辟蚜雾，pirimor，灭定威;辟蚜威
分子式：C11H18N4O2
分子量：238.3
理化性质：产品为白色固体，熔点90.5℃。在水中溶解度为2.7g/L，在丙酮、氯仿、乙醇等中溶解度不大，甲醇23g/100ml,乙醇25g/100ml,丙酮40g/100ml, 溶于大多数有机溶剂。

毒性：抗蚜威属中等毒杀虫剂。急性经口毒性LD50（mg/kg）：雄大白鼠148，雌大白鼠127，雄小白鼠79，雌小白鼠81，狗100～200，家禽25～50。大、小白鼠（雄、雌）急性经皮毒性LD50大于1000mg/kg。具有接触毒性和呼吸毒性。在规定浓度下使用，对蜜蜂和天敌低毒。鲤鱼TLm(48h)为40mg/L，水蚤为0.048mg/L。允许残留量；油菜0.2mg/kg，小麦及谷类0.05mg/kg，果树0.05～1.0mg/kg，马铃薯0.05mg/kg，大豆1.0mg/kg，油菜籽0.2mg/kg，蔬菜1.0mg/kg。ADI为0.01mg/kg。如有药剂溅到皮肤上或眼睛内，应立即用清水冲洗，如发生中毒，应立即求医，肌注1～2mg硫酸颠茄碱。

作用特点及杀虫谱：本品是氨基甲酸甲酯类选择性杀蚜虫剂，具有触杀、熏蒸或渗透叶面作用，能防治蚜虫。该药杀虫迅速，施药后数分钟即可杀死蚜虫。是选择性强的杀蚜虫剂，能有效防治除棉蚜以外的所有蚜虫，对有机磷产生抗性的蚜虫亦有效。杀虫迅速，但残效期短。对作物安全，不伤天敌，是综合防治的理想药剂。

适用范围：适用于防治蔬菜、烟草、粮食作物上的蚜虫。

使用方法：

1、防治蔬菜蚜虫 每亩用50%可湿性粉10-18g，对水30-50kg喷雾。

2、防治烟草蚜虫 每亩用50%可湿性粉10-18g，对水30-50kg喷雾。

3、防治粮食及油料作物上的蚜虫 每亩用50%可湿性粉6-8g，对水50-100kg喷雾。

剂型：50%可湿性粉剂，50%可分散粒剂，10%发烟剂，浓乳剂，气雾剂等。

生产方法：

方法一：
N,N-二甲胍的制备 由硫脲与硫酸二甲酯作用，再同二甲胺或二甲胺盐酸盐反应制得N，N-二甲基胍。
α-甲基乙酰乙酸乙酯的制备 将乙酰乙酸乙酯用硫酸二甲酯或碘甲烷甲基化，制得α-甲基乙酰乙酸乙酯。
2-二甲基氨基-5，6-二甲基-4-羟基嘧啶的制备 将14gN,N-二甲基胍（硫酸盐）和4.6g缚酸剂、醇混合后搅拌2h，加入α-甲基乙酰乙酰乙酯和溶剂，搅拌下慢慢升温，于140℃左右反应2h，减压回收溶剂，固体用氯仿溶解并调节pH值7，氯仿浓缩至干，得产品15.7g，含量92。69%,收率93.43%。
2-二甲氨基-5，6-二甲基-4-羟基嘧啶也可以醋酸锌为催化剂，在加压条件下与甲醛反应制得。
抗蚜威的合成 由不对称二甲基胍硫酸盐与α-甲基乙酰乙酸乙酯于60℃反应2h，环合成2-（N,N-二甲氨基）-5,6-二甲基-4-羟基嘧啶，然后在苯中于低温下与光气反应，最后与二甲胺反应得到抗蚜威。

方法二：
在含12.5%光气的35mL苯溶液中，加入7.1g5,6-二甲基-2-二甲氨基-4-羟基嘧啶和4.3g三乙胺的苯溶液（100mL)，于5～8℃反应45min，滴加10mL含3.9g二甲胺的水溶液，搅拌，反应温度小于10℃。然后在10℃搅拌30min以上，加水50mL，至固体全部溶解。分出苯，水洗，加饱和Na2CO3溶液，即得抗蚜威，m.p.88～90℃。

生产情况：江苏山达化工有限公司，无锡禾美农化科技有限公司 ，江阴凯江农化有限公司，

pirimicarb
Insecticide
IRAC 1A; carbamate

NOMENCLATURE
Common name pirimicarb (BSI, E-ISO, ANSI, JMAF); pirimicarbe ((m) F-ISO); pyrimicarbe (France)
IUPAC name 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate
Chemical Abstracts name 2-(dimethylamino)-5,6-dimethyl-4-pyrimidinyl dimethylcarbamate
CAS RN [23103-98-2] EEC no. 245-430-1 Development codes PP062 (ICI) Official codes ENT 27 766; OMS 1330

PHYSICAL CHEMISTRY
Composition Tech. material is 95% pure. Mol. wt. 238.3 M.f. C11H18N4O2 Form White solid. M.p. 91.6 °C V.p. 4 ´ 10-1 mPa (20 °C, by interpolation) KOW logP = 1.7 (unionised) Henry 3.6 ´ 10-5 Pa m3 mol-1 (calc.) S.g./density 1.18 (25 °C); tech. 1.21 (25 ºC) Solubility In purified water 3.0 g/l (20 ºC). In acetone, methanol, xylene >200 g/l (20 ºC). Stability Stable under normal storage conditions for more than 2 years. Hydrolytically stable at pH 4-9 (25 °C). Aqueous solutions are unstable to u.v. light; DT50 <1 d (pH 5, 7 or 9). pKa 4.44 (20 °C), weak base

COMMERCIALISATION
History Aphicide reported by F. L. C. Baranyovits & R. Ghosh (Chem. Ind. (London), 1969, p. 1018). Introduced by ICI Plant Protection Division (now Syngenta AG) and first marketed in 1970. Patents GB 1181657 Manufacturers Jiangsu Eternal; Syngenta

APPLICATIONS
Biochemistry Cholinesterase inhibitor. Mode of action Selective systemic insecticide with contact, stomach, and respiratory action. Absorbed by the roots, and translocated through the xylem. Penetrates the leaves, but is not translocated extensively. Uses A selective aphicide used in a wide range of crops, including cereals and oilseeds (at 125-250 g/ha), potatoes and other vegetables (at 125-375 g/ha), fruit (at 250-750 g/ha), ornamentals and other non-food uses (at 50-500 g/ha). Effective against organophosphorus-resistant Myzus persicae. Formulation types AE; DP; EC; FU; WG; WP. Selected products: 'Aphox' (Syngenta); 'Pirimor' (Syngenta); 'Honolulu' (Rocca); 'Pilly' (Sanonda); 'Pirimisect' (Barclay); 'Tomba' (Cequisa); mixtures: 'Okapi' (+ lambda-cyhalothrin) (Syngenta)

OTHER PRODUCTS
'Abol' (Syngenta); 'Glenroe' (GreenCrop); 'Phantom' (Bayer CropScience); 'Piriflor' (Azot) mixtures: 'Dovetail' (+ lambda-cyhalothrin) (Syngenta); 'Karate K' (+ lambda-cyhalothrin) (Syngenta); 'Adage' (+ deltamethrin) (Bayer CropScience); 'Best' (+ deltamethrin) (Bayer CropScience); 'Evidence' (+ deltamethrin) (Bayer CropScience); 'Kabuto' (+ esfenvalerate) (Philagro); 'Patriot' (+ deltamethrin) (Bayer CropScience) Discontinued products: 'Pronto' * (Atlas Interlates)

ANALYSIS
Product analysis by glc with FID (J. E. Bagness & W. G. Sharples, Analyst (London), 1974, 99, 225; AOAC Methods, 17th Ed., 982.08; CIPAC Handbook, 1998, H, 217). Identity also by glc, tlc, i.r. or nmr (CIPAC Handbook, 1994, F, 406). Residues determined by glc with FID or by colorimetry (Man. Pestic. Residue Anal., 1987, I; D. J. W. Bullock, Anal. Methods Pestic. Plant Growth Regul., 1973, 7, 399). Details available from Syngenta.

MAMMALIAN TOXICOLOGY
Reviews FAO/WHO 38, 39 (see part 2 of the Bibliography). Oral Acute oral LD50 for female rats 142, mice 107, dogs 100-200 mg/kg. Skin and eye Acute percutaneous LD50 for rats >2000, rabbits >500 mg/kg. Non-irritating to skin; mild irritant to eyes (rabbits). Moderate skin sensitiser (guinea pigs, M&K test). Inhalation LC50 (4 h) for female rats 0.86 mg/l. NOEL Chronic NOEL for dogs 3.5 mg/kg daily; for rats 75 mg/kg diet (3.7-4.7 mg/kg daily). Not carcinogenic; no adverse reproductive effects. ADI (JMPR) 0.02 mg/kg b.w. [1982]. Toxicity class WHO (a.i.) II; EPA (formulation) II EC classification T; R25| N; R50, R53

ECOTOXICOLOGY
Birds Acute oral LD50 for poultry 25-50, mallard ducks 28.5, bobwhite quail 20.9 mg/kg. Fish LC50 (96 h) for rainbow trout 79, bluegill sunfish 55, fathead minnow >100 mg/l. Daphnia EC50 (48 h) 0.017 mg/l. Algae EC50 (96 h) 140 mg/l. Other aquatic spp. EC50 (48 h) for Lymnaea stagnalis 19, Gammarus pulex 48, Chironomus riparius 60 mg/l. Bees Not toxic to bees. LD50 (24 h) (oral) 4 mg/bee (tech.); (contact) 53 mg/bee (tech.). Worms LC50 (14 d) >60 mg/kg. Other beneficial spp. Not toxic to Collembola (J. A. Wiles & G. K. Frampton, Pestic. Sci., 47, 273 (1996)).

ENVIRONMENTAL FATE
EHC 64 (WHO, 1986; a review of carbamate insecticides in general). Animals In mammals, the major metabolites are 2-dimethylamino-5,6-dimethyl-4-hydroxypyrimidine, 2-methylamino-5,6-dimethyl-4-hydroxypyrimidine, 2-amino-5,6-dimethyl-4-hydroxypyrimidine and 2-dimethylamino-6-hydroxymethyl-5-methyl-4-hydroxypyrimidine. Soil/Environment For details of degradation in soil, see I. R. Hill, ACS Symp. Series, 1976, 29, 358. DT50 in soil 7-234 d, according to soil type (range o.m. 1.7-51.9%, pH 5.5-8.1).