Imazaquin 咪唑喹啉酸

咪唑喹啉酸

CAS No. : 81335-37-7
英文名称：imazaquin
化学名称：(±)2－[4－甲基－4-(1－甲基乙基)－5氧代－1H－咪唑－2－基]－3－喹啉羧酸 ；2-(5-Isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid
其他名称：灭草喹
分子式：C17H17N3O3
分子量：311.3

理化性质： 原药外观浅黄色结晶，熔点：219℃-222℃ ，蒸气压：0.013mpa(60℃) ，溶解度(g/L，25℃): 水 0.06;二氯甲烷　14；甲苯　0.4；二甲基甲酰胺　68； 二甲基亚砜　159。在酸性及中性条件下稳定，遇碱分解。

毒性：原药、制剂大鼠急性经口LD50>4640mg/千克，急性经皮LD50>2150mg/千克。对眼睛轻度刺激、对皮肤无刺激。对大鼠90天饲喂试验50、500、5000mg/千克浓度组，各项检查指标均未见有意义的毒性结果，最大无作用剂量为雌性>380.90mg/千克/天、雄性>417.60mg/千克/天。致突变试验Ames试验、微核试验及小鼠精子畸形试验均为阴性。属低毒农药。

作用特点及杀草谱：是一种咪唑啉酮类高效、选择性除草剂，是侧链氨基酸合成掏剂。主要用于豆田、花生田除草，可有效防除蓼、藜、反枝苋、鬼针草、苍耳、苘麻等阔叶杂草，对臂形草、马唐、野黍、狗尾草属等禾本科杂草也有一定防治效果。灭草喹在土壤中有较长的持效期，对后茬的玉米、棉花、小麦易产生药害。大豆对灭草喹有较好的耐药性。

适用作物主要用于大豆田，也可用于豇豆、烟草、豌豆和苜蓿田。

使用方法：用于东北地区春大豆防除一年生阔叶杂草，施药时期为苗后早期（杂草1～4叶期）或播后苗前喷雾用有效成份112.5～150克/hm2。

剂型：5%、15%、20% 水剂，7.5%咪喹·咪乙烟水剂(豆益)。灭草喹+嗪草酮复剂

生产方法 ：
制备方法一
2-氨基-2，3-二甲基丁腈的制备 将61.36g氰化钠，79g氯化铵溶于400mL28%的氨水中，于室温下滴加1mol甲基异丙基酮，搅拌过夜，分离油层，水层用二氯甲烷萃取，合并油层，干燥，脱溶，得产品。收率90%，纯度94%～95.9%。
2-氨基-2，3-二甲基丁酰胺的制备 将29.7mL浓硫酸在冷却下于25℃以下滴加0.1mol 2-氨基-2，3-二甲基丁腈，然后缓慢升温至100℃，保温反应1h，使氰基水解，再在75℃以下加85mL浓氢氧化铵，即生成2-氨基-2，3-二甲基丁酰胺。用二氯乙烷萃取，有机相干燥、浓缩、重结晶得0.091mol酰胺，收率91%。
喹啉-2，3-二羧酸的制备 将0.01mol 2，3-二氯丁酸二乙酯溶于氯苯，加入等摩尔苯胺，3.6g 33%氢氧化钠，0.14g 四丁基氯化铵，于75～80℃搅拌反应2h，冷却分层，有机相脱溶于0.0046mol相应的二乙酯，收率46%。
将0.02mol该二乙酯溶于40mL甲苯中，常温加到Vilsmeier试剂中，然后加热回流2h，将反应液倒入60mL水中，分层，有机层脱甲苯，残留物重结晶得0.0148mol的喹啉-2，3-二闳酸二乙酯，收率74%，将其在碱性条件下水解，得喹啉-2，3-二羧酸，收率98%。
Vilsmeier试验制备：0.03mol二甲基甲酰胺溶于12mL甲苯中，在20～30℃滴入0.03mol的三氯化磷，保温搅拌60min即成Vilsmeier试剂。
喹啉-2，3-二羧酸酐的制备 由喹啉-2，3-二羧酸分子内脱水制得，脱水剂为光气或醋酐。
咪唑喹啉酸的合成 将40g 2-氨基-2，3-二甲基丁酰胺溶于500mL乙腈中，加入60g 喹啉-2，3-二羧酸酐，于50～60℃反应2h，冷却至常温后滤出固体。将此固体溶于435mL1.5mol/L的氢氧化钠溶液中，于80～85℃加热2h，制得咪唑喹啉酸49g，收率82%。
制备方法二
咪唑喹啉酸也可通过2-甲基喹啉与单质硫和2-氨基-2，3-二甲基丁酰胺一步反应制得相应的2-咪唑酮基衍生物，再经丁基锂作用后，与二氧化碳反应制得咪唑喹啉酸。
这条工艺路线缩短了反应过程，具有潜在应用价值。



生产情况：氰胺公司开发生产，获专利US4798619（1987）。国内生产企业：山东先达化工有限公司（200t/a）；沈阳化工院试验厂；杭州大阳化工有限公司

imazaquin
Herbicide
HRAC B WSSA 2; imidazolinone

NOMENCLATURE
imazaquin
Common name imazaquin (BSI, ANSI, draft E-ISO, WSSA); imazaquine ((m) draft F-ISO)
IUPAC name (RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid
Chemical Abstracts name (?-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinolinecarboxylic acid
CAS RN [81335-37-7] unstated stereochemistry Development codes AC 252 214; CL 252 214 (both Cyanamid); BAS 725 01H (BASF)

imazaquin-ammonium
IUPAC name ammonium (RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylate
Chemical Abstracts name ammonium (?-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinolinecarboxylate
CAS RN [81335-47-9] unstated stereochemistry Development codes BAS 725 03H (BASF)

PHYSICAL CHEMISTRY
imazaquin
Composition Tech. is >95% pure. Mol. wt. 311.3 M.f. C17H17N3O3 Form Tan solid, with slightly pungent odour. M.p. 219-224 ºC (decomp.) V.p. <0.013 mPa (60 ºC) KOW logP = 0.34 (pH 7, 22 ºC) Solubility In water 60-120 mg/l (25 ºC). In toluene 0.4, dimethylformamide 68, dimethyl sulfoxide 159, dichloromethane 14 (all in g/l, 25 ºC). Stability Stable for 3 months at 45 ºC, 2 y at room temperature when stored in the dark. Rapidly degraded on exposure to u.v. light. pKa 3.8

imazaquin-ammonium
Mol. wt. 328.4 M.f. C17H20N4O3 Solubility In water 160 g/l (pH 7, 20 °C). Stability Hydrolysis DT50 >30 d (ARS PPD).

COMMERCIALISATION
History Herbicide reported by P. L. Orwick et al. (Abstr. 1983 Weed Sci. Soc. Annu. Mtg., 36th, 1983, pp. 90, 91), P. K. Martin (ibid., p. 90, No. 46) and H. M. Hackworth et al. (ibid., p. 91). Introduced by American Cyanamid Co. (now BASF AG); registered in US in 1986. Patents US 4798619 Manufacturers BASF; Milenia; Shenyang

APPLICATIONS
Biochemistry Blocks biosynthesis of branched chain amino acids valine, leucine, and isoleucine through inhibition of acetohydroxy acid synthase, thus causing disruption of protein synthesis, which leads to interference in DNA synthesis and cell growth (D. L. Shaner et al., Plant Physiol., 1984, 76, 545). Selectivity in soya beans is attributed to rapid detoxification via ring-opening (B. Tecle et al., Proc. 1997 Br. Crop Prot. Conf. - Weeds, 2,605). Mode of action Selective systemic herbicide, absorbed by the roots and foliage, with translocation in the xylem and phloem throughout the plant, and accumulation in the meristematic regions. Uses Pre-planting, pre-emergence or early post-emergence control of broad-leaved weeds in soya beans, at 70-140 g a.e./ha. Also controls or reduces competition from grasses and sedges. Phytotoxicity Non-phytotoxic to soya beans. Formulation types WG.

imazaquin
Compatibility Compatible with soil-applied grass herbicides. If mixed with post-emergence grass herbicides, reduced activity against grasses will result due to herbicide antagonism. Selected products: 'Scepter 70' (BASF); 'Topgan' (Makhteshim-Agan, Milenia) Formulation types SL.

imazaquin-ammonium
Selected products: 'Scepter' (BASF)

OTHER PRODUCTS
imazaquin
Mixtures: 'Backdraft' (+ glyphosate-isopropylammonium) (BASF); 'Steel' (+ imazethapyr+ pendimethalin) (BASF) Discontinued products mixtures: 'Structure' * (+ imazethapyr+ pendimethalin) (BASF)

imazaquin-ammonium
'Image' (BASF) mixtures: 'Chekway' (+ pendimethalin) (BASF); 'Concord' (+ chlormequat chloride+ ethephon) (BASF); 'Detail' (+ dimethenamid) (BASF); 'Meteor' (+ chlormequat chloride) (BASF); 'Mondium' (+ chlormequat chloride) (BASF); 'One Shot' (+ glyphosate-isopropylammonium) (BASF); 'Satellite' (+ chlormequat chloride+ ethephon) (BASF); 'Squadron' (+ pendimethalin) (BASF); 'Tri-Scept' (+ trifluralin) (BASF) Discontinued products: 'Tone-up' * (BASF) mixtures: 'Scepter OT' * (+ acifluorfen-sodium) (BASF)

ANALYSIS
Product analysis by hplc.

MAMMALIAN TOXICOLOGY
imazaquin
Oral Acute oral LD50 for male and female rats >5000, female mice 2363 mg/kg. Skin and eye Acute percutaneous LD50 for male and female rabbits >2000 mg/kg. Non-irritating to eyes; mildly irritating to skin (rabbits). No skin sensitisation (guinea pigs). Inhalation LC50 (4 h) for rats >5.7 mg/l air. NOEL (90 d) for rats 10 000 mg/kg diet; (2 y) for rats 5000 mg/kg. ADI 0.25 mg/kg b.w. Other Non-carcinogenic, non-mutagenic and non-teratogenic. Toxicity class WHO (a.i.) U; EPA (formulation) III

ECOTOXICOLOGY
imazaquin
Birds Acute oral LD50 for bobwhite quail and mallard ducks >2150 mg/kg. Dietary LC50 (8 d) for bobwhite quail and mallard ducks >5000 mg/kg diet. Fish LC50 (96 h) for channel catfish 320, bluegill sunfish 410, rainbow trout 280 mg/l. Daphnia LC50 (48 h) 280 mg/l. Algae EC50 for Selenastrum 19, for Anabaena 0.09 mg/l. Bees Contact LD50 for honeybees >100 mg/bee. Worms LC50 >23.5 mg/kg soil.

ENVIRONMENTAL FATE
Animals Imazaquin is metabolically inert in rats. Following oral administration, almost all was excreted in the urine as the unchanged compound within 2 days. No accumulation in blood or tissues. Plants Rapidly metabolised by soya bean plants to inactive compounds, formed by opening of the imidazolinone ring at the ring amide (D. L. Shaner & P. A. Robson, Weed Sci., 1985, 33, 469). Soil/Environment Steadily degraded in soil by microbial activity and photolysis, but may remain active in the soil for several weeks to several months, depending on environmental conditions (G. Basham et al., Weed Sci., 1987, 35, 576). DT50 60 d; Koc 20.