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1.
Vandana Singh Ashutosh TiwariDevendra Narayan Tripathi Tulika Malviya 《Tetrahedron letters》2003,44(39):7295-7297
O-Methylation is of outstanding importance in structural polysaccharide chemistry. A novel method for the methylation of polysaccharides using microwave (MW) irradiation is described. Seed gum from Cyamopsis tetragonolobus (Guar) was fully methylated with dimethyl sulphate and sodium hydroxide using 100% microwave power for 4 min in 68% yield. The completely methylated seed gum thus obtained was hydrolyzed by 70% formic acid followed by 0.5N H2SO4 under full microwave power for 1.16 and 1.66 min, respectively. The partially methylated monosaccharides were separated and identified. 相似文献
2.
Polyphysa peniculus was grown in artificial seawater in the presence of arsenate, arsenite, monomethylarsonate and dimethylarsinic acid. The separation and identification of some of the arsenic species produced in the cells as well as in the growth medium were achieved by using hydride generation–gas chromatography–atomic absorption spectrometry methodology. Arsenite and dimethylarsinate were detected following incubation with arsenate. When the alga was treated with arsenite, dimethylarsinate was the major metabolite in the cells and in the growth medium; trace amounts of monomethylarsonate were also detected in the cells. With monomethylarsonate as a substrate, the metabolite is dimethylarsinate. Polyphysa peniculus did not metabolize dimethylarsinic acid when it was used as a substrate. Significant amounts of more complex arsenic species, such as arsenosungars, were not observed in the cells or medium on the evidence of flow injection–microwave digestion–hydride generation–atomic absorption spectrometry methodology. Transfer of the exposed cells to fresh medium caused release of most cell–associated arsenicals to the surrounding environment. 相似文献
3.
Marie Vahter 《应用有机金属化学》1994,8(3):175-182
Humans are exposed via air, water and food to a number of different arsenic compounds, the physical, chemical, and toxicological properties of which may vary considerably. In people eating much fish and shellfish the intake of organic arsenic compounds, mainly arsenobetaine, may exceed 1000 μg As per day, while the average daily intake of inorganic arsenic is in the order of 10–20 μg in most countries. Arsenobetaine, and most other arsenic compounds in food of marine origin, e.g. arsenocholine, trimethylarsine oxide and methylarsenic acids, are rapidly excreted in the urine and there seem to be only minor differences in metabolism between animal species. Trivalent inorganic arsenic (AsIII) is the main form of arsenic interacting with tissue constituents, due to its strong affinity for sulfhydryl groups. However, a substantial part of the absorbed AsIII is methylated in the body to less reactive metabolities, methylarsonic acid (MMA) and dimethylarsinic acid (DMA), which are rapidly excreted in the urine. All the different steps in the arsenic biotransformation in mammals have not yet been elucidated, but it seems likely that the methylation takes place mainly in the liver by transfer of methyl groups from S-adenosylmethionine to arsenic in its trivalent oxidation state. A substantial part of absorbed arsenate (AsV) is reduced to AsIII before being methylated in the liver. There are marked species differences in the methylation of inorganic arsenic. In most animal species DMA is the main metabolite. Compared with human subjects, very little MMA is produced. The marmoset monkey is the only species which has been shown unable to methylate inorganic arsenic. In contrast to other species, the rat shows a marked binding of DMA to the hemoglobin, which results in a low rate of urinary excretion of arsenic. 相似文献
4.
The influence of humic substances on sorption and methylation processes for inorganic- and organotin species is presented. Four sediment samples from different locations of the Rivers Elbe, Mulde and Spittelwasser, Germany, with different organotin and humic contents were selected to extract the humic and fulvic acids. The various fractions—the original sediment, the humic acid, the fulvic acid and the residual sediment—were analysed for their organotin content. The individual buyltin species show quite different distribution patterns. Monobutyltin is found mostly associated with humic acids. Dibutyltin shows a nonunique behaviour. At low total organotin content, dibutyltin is found bonded to humic and fulvic acids, whereas at high organotin content dibutyltin is distributed more with the residual sediment. Most of the tributyltin remains in the sediment unextracted; only small quantities of it are in the fulvic acid fraction. Tetrabutyltin is only in the humic acid fraction when it binds to humic matter; it mostly remains in the sediment. General observations indicate that ionic butyltin species bind to fulvic acids whereas the non-polar tetrabutyltin is not found in the fulvic acid fractions in any of the samples. The appearance of monomethyl- and dimethyl-tin species in the humic and fulvic acid fractions after the alkaline extraction was surprising. There is a correlation between the humic content of the sample and the formation of methyltin species. Evidence is provided by experiments that humic substances act as methylation agents. 相似文献
5.
6.
A novel methodology in on-line pyrolysis-gas chromatography (Py-GC) for the fast analysis of fatty acids in vegetable oils with minimal sample treatment and the use of non-toxic reagents is described. Pyrolysis at 500 degrees C for 10 s of sub-microgram quantity of vegetable oil dissolved in dimethyl carbonate (DMC) and in the presence of nanopowder titanium silicon oxide resulted in the production of fatty acid methyl esters (FAMEs) as unique products. Pyrolysis performed by means of a resistively heated filament pyrolyser interfaced to a GC-MS apparatus enabled the direct analysis of evolved FAMEs. The DMC/Py-GC-MS analysis was tested on soybean, coconut, linseed, walnut and olive oil and the results compared to the classical BF(3)-methanol as reference methodology. The DMC method exhibited a lower precision and was biased towards lower levels of polyunsaturated fatty acids (PUFA) in comparison to the BF(3)-methanol method, but was more advantageous in terms of reduced sample treatment, waste generation and risk factors of employed chemicals. 相似文献
7.
Summary Multiflorine (1) — a minor lupine alkaloid — treated by methyl lithium or methyl magnesium iodide affords 4S-4-hydroxy-4-methyl-2,3-didehydrosparteine (2) and 2S-2-methyl-4-oxosparteine (3), respectively, as the dominating products. Their steric structure, determined by1H and13C NMR techniques, points to stereospecific preferences of these reactions. The observed nucleophilic 1,2- and 1,4-additions indicate that regiospecificity of the action of MeLi or MeMgI on multiflorine is different from that of the so far known similar alkylation of other enamino ketones.
Die räumliche Struktur von Methylierungsprodukten des Multiflorins
Zusammenfassung Multiflorin (1), ein Lupin-Nebenalkaloid, ergibt bei Umsetzung mit Methyllithium oder Methylmagnesiumiodid 4S-4-Hydroxy-4-methyl-2,3-didehydrospartein (2) und 2S-2-Methyl-4-oxospartein (3) als Hauptprodukte. Ihre NMR-spektroskopisch (1H und13C) aufgeklärte räumliche Struktur weist auf eine Stereoselektivität der erwähnten Reaktionen hin. Die beobachteten nucleophilen 1,2- und 1,4-Additionen zeigen, daß sich die Regiospezifität der Einwirkung von MeLi oder MeMgl auf Multiflorin von jener bis jetzt bekannter Alkylierungen von Enaminoketonen unterscheidet.相似文献
8.
用N,N-二甲基甲酰胺缩二甲醇[(CH3)2NCH(OCH3)2,1]和蝶呤(2-氨基-4- 羟基蝶啶)衍生物在极性有机溶剂中反应一般得到脒化产物:N^2-(N,N-二甲基氨 基亚甲基)-蝶呤衍生物,但是在1,4-二氧六环中进行以上反应时发现,N,N-二甲 基酰胺缩二甲醇(1)不仅是脒化试剂,而且也是蝶呤化合物的甲基化试剂,并且 也依据蝶呤的N^2-位的不同取代基进行选择性的N(3)-或O^4-甲基化反应。 相似文献
9.
Elisabete Curti Douglas de Britto Srgio Paulo Campana‐Filho 《Macromolecular bioscience》2003,3(10):571-576
N,N,N‐trimethylchitosan (TMC) was prepared by reacting purified chitosan with iodomethane, in the presence of sodium hydroxide, water and sodium iodide, at room temperature. The reaction medium was N‐methyl‐2‐pyrrolidone. Different samples of TMC were obtained by adding to the reaction medium a fixed volume (5.5 mL) of aqueous NaOH solutions at different concentrations (15, 20, 30 and 40 wt.‐%) and carrying out the reactions for 9 or 24 h. The features observed in the 1H and 13C NMR spectra of these chitosan derivatives, in respect of the chemical shift, number and relative intensity of the signals, depended strongly on the excess of NaOH and H3CI added to the reaction medium, but when the lowest excess was employed, the characteristics of the derivative were not affected by the reaction time to the same extent. The average degree of quaternization of these N‐methylated derivatives of chitosan ranged from 10.5% to 44.8%, according to the reaction conditions. Increasing the excess of NaOH, in reactions carried out for 9 h, resulted in TMC samples with progressively higher content of trimethylated sites however, the reaction yields were correspondingly lower and O‐alkylation was favored in these cases.
10.
Ernesto Brunet Dulce María Muñoz Susana Mantecón Juan Carlos Rodríguez-Ubis Ramón Asensio 《Tetrahedron letters》2007,48(8):1321-1324
A new method for the preparation of clarithromycin is described through the highly regioselective O-methylation at C(6)-OH of the novel derivative 9-pyrimidyloxime erythromycin A. The facile synthesis of 6,11-O-dimethyl- and 6,11,12-O-trimethyl erythromycin A is also reported. These compounds are useful as standards to assess clarithromycin purity in quality control processes. 相似文献