Substituted urea herbicides

Herbicides Substituted urea herbicides Diuron, neburon, phenobenzuron and isoproturon Adsorption LiChrosorb SI 60 Water saturated with dichloromethane (the role of water being to block the most active silanol sites thereby... 

The amine group of 3-arninoben2otrifluoride can be replaced by Cl, Br, I, F, CN, or OH groups by standard dia2oti2ation reactions. Phosgenation gives 3-trifluoromethylphenyhsocyanate [329-01-1/, which can then be converted to the selective herbicide fluometuron [2164-17-2] a substituted urea. Application. 

Pesticide Solvent. The majority of organic fungicides, insecticides, and herbicides (qv) are soluble in DMSO, including such difficult-to-solvate materials as the substituted ureas and carbamates (see Fungicides, agricultural Insect control technology Pesticides). Dimethyl sulfoxide forms cosolvent systems of enhanced solubiUty properties with many solvents (109). 

Mechanism of action can be an important factor determining selectivity. In the extreme case, one group of organisms has a site of action that is not present in another group. Thus, most of the insecticides that are neurotoxic have very little phytotoxicity indeed, some of them (e.g., the OPs dimethoate, disyston, and demeton-5 -methyl) are good systemic insecticides. Most herbicides that act upon photosynthesis (e.g., triaz-ines and substituted ureas) have very low toxicity to animals (Table 2.7). The resistance of certain strains of insects to insecticides is due to their possessing a mutant form of the site of action, which is insensitive to the pesticide. Examples include certain strains of housefly with knockdown resistance (mutant form of Na+ channel that is insensitive to DDT and pyrethroids) and strains of several species of insects that are resistant to OPs because they have mutant forms of acetylcholinesterase. These... 

The recommended field application rates for terrestrial weed control usually range between 0.28 and 1.12 kg paraquat cation/ha (0.25 and 1.0 pounds/acre), between 0.56 and 2.24 kg paraquat dichloride/ha (0.5 and 2.0 pounds/acre) — both applied as an aerosol — and between 0.1 and 2.0 mg/L for aquatic weed control, although sensitive aquatic plants may be affected between 0.019 and 0.372 mg/L (Ross etal. 1979 Summers 1980 Bauer 1983 Dial and Bauer 1984). Paraquat is frequently used in combination with other herbicides (Fletcher 1974 Summers 1980). Water solutions of the dichloride salt, which usually contain 240 g/L, have been successfully mixed with 2,4-D, substituted ureas, dalapon, amitrol, and various triazines (Anonymous 1963, 1974). 

Aliphatic hydrocarbons, triazine, substituted urea type and phenoxyacetic acid types of herbicides, Fluazifop and Fluazifop-butyl herbicides, ethylene diamine tetracetic acid salts in soil, aliphatic and polyaromatic hydrocarbons, phthalate esters, various organosulphur compounds, triazine herbicides, optical whiteners, mixtures of organic compounds and organotin compounds in non-saline sediments, aromatic hydrocarbons, humic and fulvic acids and mixtures of organic compounds in saline sediments and non-ionic surfactants and cobalamin in sludges. 

This technique has been applied to the determination of chlorinated insecticides, carbamate insecticides and substituted urea type herbicides in soil and chloroaliphatic hydrocarbons in non-saline sediments. Separation is usually achieved on thin layers of silica gel or alumina. 

Another growing technique is super-critical fluid chromatography. Recent references to soil analysis include the following applications aliphatic hydrocarbons, polyaromatic hydrocarbons, polychlorobiphenyls, dioxins, alkyl and aryl phosphates, chloro, organophosphorus, triazine, substituted urea, phenoxy acetic acid, Dacthal herbicides and insecticides and mixtures of herbicides and pesticides and mixtures of organic compounds. 

The gas chromatographic procedure described by Cohen and Wheals [80] has been applied to the determination of various substituted urea herbicides in soil in amounts down to l-50pg kgr1. 

The method based on immunosorbents coupled on-line with liquid chromatography-atmospheric pressure chemical ionization mass spectrometry [109], discussed in section 9.4.2.1, has been applied to the determination of substituted urea type herbicides. Supercritical fluid extraction with methanol modified carbon dioxide has been applied to the determinants of sulfonyl urea herbicides in soil [261],... 

Abbott and Wagstaff [251] of the Laboratory of the Government Chemist UK have described a thin layer chromatographic method for the identification of 12 acidic herbicides and 19 nitrogenous herbicides (carbamates, substituted ureas and triazine). 

More than 25 different substituted urea herbicides are currently commercially available [30, 173]. The most important are phenylureas and Cycluron, which has the aromatic nucleus replaced by a saturated hydrocarbon moiety. Benzthiazuron and Methabenzthiazuron are more recent selective herbiddes of the class, with the aromatic moiety replaced by a heterocyclic ring system. With the exception of Fenuron, substituted ureas (i.e., Diuron, Fluometuron, Fig. 10, Table 3) exhibit low water solubilities, which decrease with increasing molecular volume of the compound. The majority of the phenylureas have relatively low vapor pressures and are, therefore, not very volatile. These compounds show electron-donor properties and thus they are able to form charge transfer complexes by interaction with suitable electron acceptor molecules. Hydrolysis, acylation, and alkylation reactions are also possible with these compounds. 

Senesi and Testini [147,156] and Senesi et al. [150,153] showed by ESR the interaction of HA from different sources with a number of substituted urea herbicides by electron donor-acceptor processes involves organic free radicals which lead to the formation of charge-transfer complexes. The chemical structures and properties of the substituted urea herbicides influence the extent of formation of electron donor-acceptor systems with HA. Substituted ureas are, in fact, expected to act as electron donors from the nitrogen (or oxygen) atoms to electron acceptor sites on quinone or similar units in HA molecules. 

In the search for more effective post-emergent herbicides, many laboratories have measured the inhibition of photosystem II in chloroplasts i.e., the Hill reaction. In a continuing investigation of this system, ( ) Corwin Hansch s group at Pomona College, in cooperation with BASF in Germany, analyzed two sets of phenyl substituted ureas 17 1,1-dimethyl-3-phenyl, and 38... 

A group of substituted ureas used as herbicides has a profound inhibiting effect on the photosynthetic mechanism in plants. The relatively advanced... 

RG Luchtefeld. Multiresidue method for determining substituted urea herbicides in foods by liquid chromatography. J Assoc Off Anal Chem 70 740-745, 1987. 

JH Onley, G Yip. Analysis of a single crop extract for substituted urea herbicides and metabolites, chlorinated insecticides and amitrolc. J Assoc Off Anal Chem 52 526-532, 1969. 

SE Katz. Determination of the substituted urea herbicides linuron, monuron, diuron, neburon and fenuron in surface waters. J Assoc Off Anal Chem 49 452-456, 1966. 

CE McKone, RJ Hance. Gas chromatography of some substituted urea herbicides. J Chromatogr 36 234 -237, 1968. 

Cohen and Wheals [334] determined ten hydrolysable carbamate and substituted urea herbicides in soil in amounts down to 0.001-0.05 ppm. In this method, a solution of the herbicide-containing extract of the soil is spotted onto a silica gel G plate and developed with hexane acetone (5 1). The plate is sprayed with 1-fluoro-l,4-dinitrobenzene in acetone and heated to 190 °C to produce the 2,4-dinitrophenyl derivative of the herbicide amine moiety acetone extracts of the areas of interest are subjected to gas chromatography. 

Triazine (e.g., atrazine, simazine) and substituted urea (e.g., diuron, monuron) herbicides bind to the plastoquinone (PQ)-binding site on the D1 protein in the PS II reaction center of the photosynthetic electron transport chain. This blocks the transfer of electrons from the electron donor, QA, to the mobile electron carrier, QB. The resultant inhibition of electron transport has two major consequences (i) a shortage of reduced nicotinamide adenine dinucleotide phosphate (NADP+), which is required for C02 fixation and (ii) the formation of oxygen radicals (H202, OH, etc.), which cause photooxidation of important molecules in the chloroplast (e.g., chlorophylls, unsaturated lipids, etc.). The latter is the major herbicidal consequence of the inhibition of photosynthetic electron transport. 

Masabni et al (1996) identified a Ser264 to Thr (threonine) mutation in a resistant biotype of common purslane. This conferred a high level of resistance to atrazine and also to linuron, a substituted urea herbicide. This was the first report of a Ser264 to Thr substitution in higher plants selected under field conditions. Previously, this mutation had only been selected through tissue culture in tobacco and potato (Sigematsu et al, 1989 Smeda etal, 1993). 

Table 6.4 shows first-order rate coefficients and tx/2 values for degradation of a number of pesticides in soils (Rao and Davidson, 1982). The k and t1/2 values calculated from field data are based on the disappearance of the parent compound (solvent extractable). Table 6.4 also includes k and t1/2 values calculated on mineralization (14C02 evolution) and parent-compound disappearance from laboratory studies. The t1/2 values were smaller for field than for laboratory studies. Rao and Davidson (1980) attribute this to the multitude of factors that can affect pesticide disappearance in the field while only one factor is studied in the laboratory. Rao and Davidson (1982) suggested that pesticides be classified into three groups based on values (Table 6.5) nonpersistent (t1/2 < 20 days), moderately persistent (20 < t1/2 < 100 days), and persistent (/1/2 > 100 days). Most chlorinated hydrocarbons are grouped as persistent, while carboxyl-kanoic acid herbicides are nonpersistent. The s-triazines, substituted ureas, and carbamate pesticides are moderately persistent. 

In addition to the most popular chlorophenoxy herbicides, the group includes a variety of other chemical classes—e.g., amides, bipyridyls, carbamates, dinitrophenols, substituted ureas and triazines. Most of the chemicals tested are animal teratogens, as are many of the fungicides in this miscellaneous group (ref. 185. p. 578 and 586). 

Table 15.8 Substituted urea herbicides with different substituents...

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