Carbamates extraction

Vanadium complexed with tetraphenyl-arsonium chloride and tetramethylene dithio-carbamate, extracted with chloroform... 

At extremely low concentration, silver can be chelated with ammonium pyrrolidine dithio-carbamate, extracted into methyl isobutyl ketone, aspirated into an air-acetylene flame, and measured by AAS. This procedure concentrates the sample, thus extending the detection limits. 

Plant-originated anti-ChEs, such as huperzine A, have been used for thousands of years in the treatment of aging-induced memory impairment (Haviv et al., 2007). In 1877, prior to the discovery of ACh as a neurotransmitter in the brain, physostigmine (eserine)— a carbamate extracted from the seeds of Physostigma venenosum—became the first cholinesterase inhibitor used therapeutically to control increased ocular pressure caused by wide-angle glaucoma (Taylor, 1996). 

An hplc assay was developed suitable for the analysis of enantiomers of ketoprofen (KT), a 2-arylpropionic acid nonsteroidal antiinflammatory dmg (NSAID), in plasma and urine (59). Following the addition of racemic fenprofen as internal standard (IS), plasma containing the KT enantiomers and IS was extracted by Hquid-Hquid extraction at an acidic pH. After evaporation of the organic layer, the dmg and IS were reconstituted in the mobile phase and injected onto the hplc column. The enantiomers were separated at ambient temperature on a commercially available 250 x 4.6 mm amylose carbamate-packed chiral column (chiral AD) with hexane—isopropyl alcohol—trifluoroacetic acid (80 19.9 0.1) as the mobile phase pumped at 1.0 mL/min. The enantiomers of KT were quantified by uv detection with the wavelength set at 254 nm. The assay allows direct quantitation of KT enantiomers in clinical studies in human plasma and urine after adrninistration of therapeutic doses. 

The common impurities found in amines are nitro compounds (if prepared by reduction), the corresponding halides (if prepared from them) and the corresponding carbamate salts. Amines are dissolved in aqueous acid, the pH of the solution being at least three units below the pKg value of the base to ensure almost complete formation of the cation. They are extracted with diethyl ether to remove neutral impurities and to decompose the carbamate salts. The solution is then made strongly alkaline and the amines that separate are extracted into a suitable solvent (ether or toluene) or steam distilled. The latter process removes coloured impurities. Note that chloroform cannot be used as a solvent for primary amines because, in the presence of alkali, poisonous carbylamines (isocyanides) are formed. However, chloroform is a useful solvent for the extraction of heterocyclic bases. In this case it has the added advantage that while the extract is being freed from the chloroform most of the moisture is removed with the solvent. 

To a solution of 20.8 g. (0.3 mole) of hydroxylamine hydrochloride and 20.6 g. (0.5 mole) of sodium hydroxide (98%) in 100 ml. of water is added 22.26 g. (0.25 mole) of ethyl carbamate. After 3 days at room temperature the solution is cooled in an ice bath and carefully neutralized with concentrated hydrochloric acid (Note 1). If necessary (Note 2), the solution is filtered and then extracted with ether the aqueous phase is evaporated on a water bath under reduced [iressurc as rapidly as possible at a temperature not aliove 50 60 . 

Either the iodo carbamate (96) or the iodo amine salt (94) from above can be converted to the aziridine by refluxing about 2.5 g of the respective product in 100 ml of ethanol which contains 10 ml of water and 10 g of potassium hydroxide for ca. 2 hr. The aziridine is then isolated by pouring the basic reaction mixture into 250 ml water and extracting with 200 ml ether. The ether extract is washed several times with water and dried (MgS04). Evaporation of the ether on a steam bath yields 2j5,3j5-iminocholestane (95, 25-95 %) as a clear oil which solidifies on standing mp 103-105°. This aziridine is not easily crystallized. 

The mixture was cooled to 7°C, extracted with two 500-oc portions of ice water to remove pyridine hydrochloride, and the benzene solution of 3-o-methoxyphenoxy-2-hy-droxypropyl chlorocarbonate was added to 500 ml of cold concentrated ammonium hydroxide. The mixture was vigorously stirred at 5°C for 6 hours, then the crude white precipitate of 3-o-methoxyphenoxy-2-hydroxypropyl carbamate was filtered off, dissolved in 1,500 ml of hot benzene and completely dried by codistillation of last traces of water with benzene, treated with decolorizing carbon and filtered while hot. On cooling 160 g of product crystallized as white needles melting at 88° to 90°C. 

Discussion. Small quantities of copper may be determined by the diethyldithio-carbamate method (Section 6.10) or by the neo-cuproin method (Section 6.11), an extraction being necessary in both cases. In another somewhat simpler procedure, the copper is complexed with biscyclohexanone oxalyldihydrazone and the resulting blue colour is measured by a suitable spectrophotometer within the range 570-600 nm (orange filter). The solution measured should contain not more than 100 /tg of copper. 

To a —78 °C solution of (4/C5/ )-2-[(.S )-l-chloro-2-propcnyl]-4,5-dicyclohcxyl-l, 3,2-dioxaborolanc (6) (theoretically 2.0 mmol) in THF are added 0.20 mL (2.0 mmol) of benzaldehydc. The mixture is allowed to reach r.t. overnight and is then treated with 0.30 g (2.0 mmol) of triethanolamine. After stirring for 3 h, 15 mL of sat. aq NH4C1 are added. The phases are separated and the aqueous phase is extracted with three 20-mL portions of diethyl ether. The combined extracts are dried over MgS04 and concentrated. The oily residue is purified by flash chromatography (silica gel, petroleum ether/diethyl ether 6 1) yield 0.26 g (79%) >99% ee [capillary GC of the carbamates obtained with (5 )-(l-isoCyanoethyl)benzene],... 

The reagent sequence is specific for endosulfan and phosphamidon. Other insecticides, e.g. organochlorine insecticides, such as endrin, aldrin, dieldrin, DDT and BHC, organophosphorus insecticides, such as malathion, parathion, dimethoate, quinalphos, phorate and fenitrothion, or carbamate insecticides, such as baygon, car-baryl and carbofuran do not react. Neither is there interference from amino acids, peptides or proteins which might be extracted from the biological material together with the pesticides. 

Belisle AA, Swineford DM. 1988. Simple, specific analysis of organophosphoms and carbamate pesticides in sediments using column extraction and gas chromatography. Environ Toxicol Chem 7 749-752. 

Lippi et. al (87) and Dirstine (88) circumvented titration by converting the liberated fatty acids into copper salts, which after extraction in chloroform are reacted with diethyldithio-carbamate to form a colored complex which is measured photometrically. While the end point appears to be more sensitive than the pH end point determination, the advantages are outweighed by the additional steps of solvent extraction, centrifugation and incomplete extraction when low concentrations of copper salts are present. Other substrates used for the measurement of lipase activity have been tributyrin ( ), phenyl laurate (90), p-nit ro-pheny1-stearate and 3-naphthyl laurate (91). It has been shown that these substrates are hydrolyzed by esterases and thus lack specificity for lipase. Studies on patients with pancreatitis indicate olive oil emulsion is definitely superior to water soluble esters as substrates for measuring serum lipase activity. 

Lord and Pawliszyn" developed a related technique called in-tube SPME in which analytes partition into a polymer coated on the inside of a fused-silica capillary. In automated SPME/HPLC the sample is injected directly into the SPME tube and the analyte is selectively eluted with either the mobile phase or a desorption solution of choice. A mixture of six phenylurea pesticides and eight carbamate pesticides was analyzed using this technique. Lee etal. utilized a novel technique of diazomethane gas-phase methylation post-SPE for the determination of acidic herbicides in water, and Nilsson et al. used SPME post-derivatization to extract benzyl ester herbicides. The successful analysis of volatile analytes indicates a potential for the analysis of fumigant pesticides such as formaldehyde, methyl bromide and phosphine. 

There are a large number of literature references that refer the use of SPE cartridges for the extraction of pesticides from water. There are several comprehensive reviews of the use of SPE, including that by Soriano et al. who discussed the advantages and limitations of a number of sorbents for the analysis of carbamates. Hennion reviewed the properties and uses of carbon based materials for extraction of a wide multiclass range of pesticides. Thorstensen et al. described the use of a high-capacity cross-linked polystyrene-based polymer for the SPE of phenoxy acids and bentazone, and Tanabe et al reported the use of a styrene-divinylbenzene copolymer for the determination of 90 pesticides and related compounds in river water. SPE cartridges are also widely used for the cleanup of solvent extracts, as described below. 

For an individual pesticide (e.g., carbendazim) or a limited class of pesticides (e.g., carbamates, benzoylphenylureas, pyrethroids ), it may be possible to optimize the SPE conditions so that the pesticide(s) are selectively retained on the cartridge. A wash step can be introduced to elute the matrix selectively, thus producing an extremely clean extract. For example, when cleaning up sample extracts for carbendazim analysis, a cation-exchange (SCX) cartridge may be used and the pH carefully controlled to retain the carbendazim firmly, whilst the co-extractives are washed to waste. The carbendazim residues can then be eluted from the column by adjusting the pH. 

SFE. SFE has been established as the extraction method of choice for solid samples. The usefulness of SFE for soil samples has been demonstrated for carbamate,organophosphorus and organochlorine pesticides. However, SFE is more effective in extracting nonpolar than polar residues. In order to obtain a greater extraction efficiency for the polar residues of imidacloprid, the addition of 20% methanol as modifier is required. Extraction at 276 bar and 80 °C with a solvent consisting of supercritical carbon dioxide modified with methanol (5%) for 40 min gives a recovery of 97% (RSD = 3.6%, n = 10). It is possible to use process-scale SFE to decontaminate pesticide residues from dust waste. ... 

The first recommended soil method for oxime carbamates is the method of Honing et al. by HPLC/MS. The LOQ of the method, specifically for aldicarb, methomyl, and oxamyl, is 0.05mgkg. Soil (lOg) is Soxhlet extracted for 16h with acetone-dichloromethane (1 1) using double-thickness cellulose extraction thimbles (80 X 22-mm i.d.). Prior to extraction, the Soxhlet system and the thimbles are cleaned for 14 h by refluxing with methanol. The extracts are removed and concentrated nearly to dryness in a rotary evaporator operating at 35 °C evaporation to dryness... 

Phenolic antioxidants in rubber extracts were determined indirectly photometrically after reaction with Fe(III) salts which form a red Fe(II)-dipyridyl compound. The method was applicable to Vulkanox BKF and Vulkanox KB [52]. Similarly, aromatic amines (Vulkanox PBN, 4020, DDA, 4010 NA) were determined photometrically after coupling with Echtrotsalz GG (4-nitrobenzdiazonium fluoroborate). For qualitative analysis of vulcanisation accelerators in extracts of rubbers and elastomers colour reactions with dithio-carbamates (for Vulkacit P, ZP, L, LDA, LDB, WL), thiuram derivatives (for Vulkacit I), zinc 2-mercaptobenzthiazol (for Vulkacit ZM, DM, F, AZ, CZ, MOZ, DZ) and hexamethylene tetramine (for Vulkacit H30), were mentioned as well as PC and TLC analyses (according to DIN 53622) followed by IR identification [52]. 8-Hydroquinoline extraction of interference ions and alizarin-La3+ complexation were utilised for the spectrophotometric determination of fluorine in silica used as an antistatic agent in PE [74], Also Polygard (trisnonylphenylphosphite) in styrene-butadienes has been determined by colorimetric methods [75,76], Most procedures are fairly dated for more detailed descriptions see references [25,42,44],... 

Urine Extraction of sample with polydithio-carbamate resin and NaOH filtration on cellulose ester membrane neutralization with NaOH ashing dissolution and heating dilution with distilled water ICP/AES (Method P CAM 8310) 0.005 pg/mL 100 NIOSH 1984... 

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