Carbamates, tests

Glyphosate is a common herbicide that is often monitored in drinking water. Analytical testing is performed by U.S. EPA method 547 using a post-column reaction HPLC system similar to that in carbamate testing (Figure 7.12). 

An efficient chemoenzymatic route for the synthesis of optically active substituted indolines has been recently developed (Scheme 7.27), and also the alkoxycarbonyla-tion process is more efficient than the acylation reaction. Different lipases have been tested in the alkoxycarbonylation of these secondary amines, GALA being found to be the best biocatalyst for 2-substituted-indolines, and CALB for 3-methylindoline. The combination of lipases with a variety of allyl carbonates and TBME as solvent has allowed the isolation of the carbamate and amine derivatives in a high level of enantiopurity [51]. 

Diagnosis of organophosphate poisoning (including methyl parathion) can be confirmed by evaluation of serum (plasma) cholinesterase and erythrocyte cholinesterase. However, cholinesterase inhibition is not specific for organophosphates. For example, carbamate insecticides also result in cholinesterase inhibition, which is usually transitory. Erythrocyte cholinesterase measurement is a specific test for... 

Vandekar M, Reiner E, Svetlicic, et al. 1965. Value of ED50 testing in assessing hazards of acute poisoning by carbamates and organophosphates. Br J Ind Med 22 317-320. 

Oxidative carbonylation generates a number of important compounds and materials such as ureas, carbamates, 2-oxazolidinones, and aromatic polycarbonates. The [CuX(IPr)] complexes 38-X (X = Cl, Br, I) were tested as catalysts for the oxidative carbonylation of amino alcohols by Xia and co-workers [43]. Complex 38-1 is the first catalyst to selectively prepare ureas, carbamates, and 2-oxazolidinones without any additives. The important findings were the identity of the counterion and that the presence of the NHC ligand influenced the conversions. 2-Oxazohdinones were formed from primary amino alcohols in 86-96% yield. Complex 38-1 also catalysed the oxidative carbonylation of primary amines to ureas and carbamates. n-Propylamine, n-butylamine, and t-butylamine were transformed into the... 

Chemical stabilizers have been used to reduce the rate of oxygen-promoted degradation of polysaccharides at T>225°F. Methanol and sodium thiosulfate are the most commonly used (86). Sodium dithio-carbamate, alkanolamines, and thiol derivatives of imidazolines, thiazolines, and other heterocyclic compounds have also been tested for this application. Calcined dolomite (B7) and Cu(l) and Cu(ll) salts (88) have been reported to increase the thermal stability of HEC. 

Burdick and Jackson). All solutions were photolyzed to less than 5% conversion in a standard 3 ml capacity, 1-cm path length quartz cell. Samples were irradiated with a 450-Watt medium pressure, Hanovla mercury lamp focused through an appropriate band-pass filter (280 nm or 254 nm) onto the 1-cm quartz cell with the requisite solution. Test solutions could be purged with either helium or oxygen using a needle valve assembly attached to the tapered quartz cell neck. The loss of carbamate due to photolysis and the amounts of known photoproducts were determined quantitatively by GC using eicosane as an internal standard. The columns were 6 stainless steel containing Carbowax 20M on chromosorb G. 

Many methods have been proposed and are used to study the thermal stability of propellants and to ensure the absence of possible autocatalysed decompositions during storage. None are sufficiently reliable to merit individual description. In practice, stabilisers are added, the usual being diphenylamine for nitrocellulose powders and symmetrical diethyl diphenyl urea (carbamate or centralite) for double base propellants. Provided a reasonable proportion of stabiliser remains, the propellant can be assumed to be free from the possibility of autocatalytic decomposition. The best test of stability is therefore a chemical determination of the stabiliser present. 

Plants, fruits, vegetables, and grains exposed to carbamate nerve agents should be quarantined until tested. 

The topmost layer of unprotected feedstock (e.g., hay or grain) should be destroyed. The remaining material should be quarantined until tested. Carbamate nerve agents are very persistent and forage vegetation could still retain sufficient agent to produce severe effects... 

Currently, there is no information on performance testing of chemical protective clothing against carbamate nerve agents. Evaluation of fabrics used to prevent exposure to carbamate pesticides may provide guidance on selection of appropriate protective clothing. 

Pharmacologically, carbofuran inhibits cholinesterase, resulting in stimulation of the central, parasympathetic, and somatic motor systems. Sensitive biochemical tests have been developed to measure cholinesterase inhibition in avian and mammalian brain and plasma samples and are useful in the forensic assessment of carbamate exposure in human and wildlife pesticide incidents (Bal-lantyne and Marrs Hunt and Hooper 1993). Acute toxic clinical effects resulting from carbofuran exposure in animals and humans appear to be completely reversible and have been successfully treated with atropine sulfate. However, treatment should occur as soon as possible after exposure because acute carbofuran toxicosis can be fatal younger age groups of various species are more susceptible than adults (Finlayson et al. 1979). Carbofuran labels indicate that application is forbidden to streams, lakes, or ponds. In addition, manufacturers have stated that carbofuran is poisonous if swallowed, inhaled, or absorbed through the skin. Users are cautioned not to breathe carbofuran dust, fumes, or spray mist and treated areas should be avoided for at least 2 days (Anonymous 1971). Three points are emphasized at this juncture. First, some carbofuran degradation... 

Carbamate pesticides can easily be converted to A-nitroso derivatives in the presence of sodium nitrite under acidic conditions. The A-nitroso form of carbofuran could possibly be formed in the human stomach (Nelson et al. 1981). Since carbofuran is used routinely on a variety of crops and nitrite is a common component of the human diet and present in human saliva, nitrosation of carbamates under conditions simulating those in the human stomach is possible. Lijinsky and Schmal (1978) tested nitrosocarbofuran and five other nitrosated carbamate pesticides for carcinogenicity in rats. Nitrosocarbofuran, at 16.5 mg/kg BW administered orally once weekly for 23 weeks, was the most toxic compound tested and caused the death of several animals by liver damage early in the experiment. Among survivors, nitrosocarbofuran was the most carcinogenic,... 

Among the strategies used for the development of GST Pl-1 inhibitors is the modification of the GSH backbone to leverage its inherent affinity for GST Pl-1. One approach centered on the incorporation of a carbamate group as an isosteric replacement of the y-carboxylic Glu linkage in GSH. Synthesis and in vitro testing of 42 and 43 showed that this carbamate-replacement approach was not well tolerated [67]. 

The PO mode is a specific elution condition in HPLC enantiomer separation, which has received remarkable popularity especially for macrocyclic antibiotics CSPs and cyclodextrin-based CSPs. It is also applicable and often preferred over RP and NP modes for the separation of chiral acids on the cinchonan carbamate-type CSPs. The beneficial characteristics of the PO mode may arise from (i) the offset of nonspecific hydrophobic interactions, (ii) the faster elution speed, (iii) sometimes enhanced enan-tioselectivities, (iv) favorable peak shapes due to improved diffusive mass transfer in the intraparticulate pores, and last but not least, (v) less stress to the column, which may extend the column lifetime. Hence, it is rational to start separation attempts with such elution conditions. Typical eluents are composed of methanol, acetonitrile (ACN), or methanol-acetonitrile mixtures and to account for the ion-exchange retention mechanism the addition of a competitor acid that acts also as counterion (e.g., 0.5-2% glacial acetic acid or 0.1% formic acid) is required. A good choice for initial tests turned out to be a mobile phase being composed of methanol-glacial acetic acid-ammonium acetate (98 2 0.5 v/v/w). 

---