molinate
Herbicide
HRAC N WSSA 8; thiocarbamate
NOMENCLATURE
Common name molinate (BSI, E-ISO, (m) F-ISO, JMAF); no name (Germany)
IUPAC name S-ethyl azepane-1-carbothioate; S-ethyl perhydroazepin-1-carbothioate; S-ethyl perhydroazepine-1-thiocarboxylate
Chemical Abstracts name S-ethyl hexahydro-1H-azepine-1-carbothioate
CAS RN [2212-67-1] EEC no. 218-661-0 Development codes R-4572 (Stauffer) Official codes OMS 1373
PHYSICAL CHEMISTRY
Composition Tech. material is 95% pure. Mol. wt. 187.3 M.f. C9H17NOS Form Clear liquid, with an aromatic odour; (tech. is an amber liquid). B.p. 202 °C/10 mmHg V.p. 746 mPa (25 ºC) KOW logP = 2.88 Henry 0.15 Pa m3 mol-1 (calc.) S.g./density 1.063 (20 ºC) Solubility In water 990 (pH 5), 900 (pH 9) (both mg/l, 25 ºC). Miscible with most common organic solvents, e.g. acetone, methanol, ethanol, kerosene, methyl isobutyl ketone, benzene, xylene. Stability Stable for at least 2 years at room temperature and at least 1 month at 120 ºC. Relatively stable to hydrolysis by acids and alkalis (pH 5-9) at 40 ºC. Unstable to light. F.p. >100 ºC
COMMERCIALISATION
History Introduced by Stauffer Chemical Co. (now Syngenta AG). Patents US 3198786; US 3573031 Manufacturers ÉMV; Herbex; Nufarm Ltd; Syngenta
APPLICATIONS
Biochemistry Inhibits lipid synthesis (not ACCase inhibition). Mode of action Selective systemic herbicide, rapidly absorbed by the roots, with translocation acropetally to the leaves. Inhibits germination. Uses Control of germinating broad-leaved and grass weeds, particularly Echinochloa spp., in rice, at 2-4 kg/ha. It is applied either before planting to water-seeded or shallow soil-seeded rice or post-flood, post-emergence in other types of rice culture. Phytotoxicity Non-phytotoxic to rice. Formulation types EC; GR. Selected products: 'Ordram' (Syngenta); 'Sakkimol' (ÉMV)
OTHER PRODUCTS
'Agro-Dram' (AgroSan); 'Molydyn' (Papaeconomou) mixtures: 'Arrosolo' (+ propanil) (Syngenta); 'Arroznox' (+ propanil) (Crystal); 'Mamet SM' (+ simetryn+ MCPB) (MCPB as salt) (Yashima); 'Propanilate' (+ propanil) (Proficol) Discontinued products mixtures: 'Touche' * (+ propanil) (Syngenta)
ANALYSIS
Product analysis by glc with FID (AOAC Methods, 17th Ed., 974.05; CIPAC Handbook, 1983, 1B, 1866); see also method for butylate (ibid., 1983, 1B, 1744). Residues in crops and soil determined by glc or colorimetry after conversion to a suitable derivative. See also G. R. Patchett & G. H. Batchelder, Anal. Methods Pestic., Plant Growth Regul. Food Addit., 1967, 5, 469; G. R. Patchett et al., Anal. Methods Pestic. Plant Growth Regul., 1972, 6, 668. In drinking water, by glc with NPD (AOAC Methods, 17th Ed., 991.07). Analytical methods available from Syngenta.
MAMMALIAN TOXICOLOGY
Oral Acute oral LD50 for male rats 369, female rats 450, mice 795 mg/kg. Skin and eye Acute percutaneous LD50 for rabbits >4640 mg/kg. Moderate eye irritant; mild skin irritant (rabbits). Not a skin sensitiser (guinea pigs). Inhalation LC50 (4 h) for rats 1.36 mg/l. NOEL (90 d) for rats 8, dogs 20 mg/kg daily. Water GV 6 mg/l (TDI 2 mg/kg b.w.). Toxicity class WHO (a.i.) II; EPA (formulation) IV EC classification Xn; R22
ECOTOXICOLOGY
Birds Dietary LC50 (5 d) for mallard ducklings 13 000 mg/kg diet; (11 d) for bobwhite quail >5000 mg/kg. Fish LC50 (96 h) for rainbow trout 13.0, bluegill sunfish 29, goldfish 30 mg/l. At recommended rates, no detectable effects on fish in ditches draining water from treated rice fields in California. Worms LC50 (14 d) 289 mg/kg.
ENVIRONMENTAL FATE
EHC 76 (WHO, 1988; general review of thiocarbamates). Animals In rats, following oral administration, molinate is rapidly metabolised. Within 72 hours, c. 50% is eliminated as the metabolite CO2, 25% excreted in the urine, and 5-20% excreted in the faeces. Plants In plants, molinate is rapidly metabolised to CO2 and naturally-occurring plant constituents. Soil/Environment In soil, microbial breakdown involves hydrolysis to ethyl mercaptan, dialkylamine and CO2. In aerobic soil (pH 4.9-5.9), DT50 8-25 d; in flooded soil, 40-160 d. Soil adsorption K 0.74-2.04 mg/kg in soils with 0.5-2.2% o.m. and pH 5.5-7.8.
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