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排序方式: 共有337条查询结果,搜索用时 171 毫秒
1.
Wang D Schwinden MD Radesca L Patel B Kronenthal D Huang MH Nugent WA 《The Journal of organic chemistry》2004,69(5):1629-1633
The reaction of a variety of methyl esters with dimethylsulfoxonium methylide at 0-25 degrees C affords the chain-extended beta-keto dimethylsulfoxonium ylides. Subsequent treatment with hydrogen chloride in THF proceeds with loss of DMSO to afford the corresponding alpha-chloroketones. This sequence has been utilized to convert the methyl esters of CBZ-protected alanine and valine to the anti N-protected alpha-amino epoxides, which are important pharmaceutical intermediates. When the same protocol is applied to BOC-protected phenylalanine methyl ester, epimerization occurs so that the use of a more reactive aryl ester is required. This chemistry provides a practical route to alpha-chloroketones that avoids the use of toxic and explosive diazomethane. 相似文献
2.
C. D. Kalkar V. M. Raut M. Getahun 《Journal of Radioanalytical and Nuclear Chemistry》1991,155(2):79-90
It is well known that paramagnetic centers are formed when Na2SO4 crystals are exposed to -radiation. The dissolution of such crystals in aqueous ammonium nitrate results in reduction of nitrate to nitrite. Various factors which influence the yield of nitrite are investigated. The yield of nitrite is found to vary with the amount of irradiated Na2SO4 added, the dose absorbed by Na2SO4 crystals, the storing period of the irradiated salt, photoannealing time, concentration of aqueous ammonium nitrate and particle size of the Na2SO4 crystals. The G(NO
2
–
) value under optimum conditions of the conversion of nitrate to nitrite by irradiated Na2SO4 in aqueous ammonium nitrate is 0.009. The efficiency of energy transfer is 1.5%. The mechanism of reduction is based on the reactions of paramagnetic centers with nitrate ions. 相似文献
3.
Soluble complex-formation of mercury(II) thiocyanate has been studied oscillometrically. The titration of mercury(II) nitrate with thiocyanate gives one inflection corresponding to the formation of Hg(SCN)2, while in the reverse titration the formation of Hg(SCN)+ is also indecated. The method is useful for a rapid determination of very small quantities of mercury or thiocyanate in highly dilute solutions. The titrations can be effected in presence of nitric acid provided its total acidity in the system does not exceed about N. Further Work on the mercury(II) -halide and mercury(II)-cyanide reactions is in progress. 相似文献
4.
The concerned diols (general abbreviation, H(2)L) are catechol (H(2)L(1)) and its 3,5-Bu(t)(2) derivative (H(2)L(2)). Esters of the type VO(xsal)(HL), 2, are obtained by reacting H(2)L with VO(xsal)(H(2)O) or VO(xsal)(OMe)(HOMe), where xsal(2-) is the diionized salicylaldimine of glycine (x = g), L-alanine (x = a), or L-valine (x = v). The reaction of VO(acac)(2) with H(2)L and the salicylaldimine (Hpsal) of 2-picolylamine has furnished VO(psal)(L), 3. In the structures of VO(gsal)(HL(1)), 2a, and VO(vsal)(HL(2)), 2f, the HL(-) ligand is O,O-chelated, the phenolic oxygen lying trans to the oxo oxygen atom. The xsal(2-) coligand has a folded structure and the conformation of 2f is exclusively endo. In both 2a and 2f the phenolic oxygen atom is strongly hydrogen bonded (O...O, 2.60 A) to a carboxylic oxygen atom of a neighboring molecule. In VO(psal)(L(2)).H(2)O, 3b, the diionized diol is O,O-chelated to the metal and the water molecule is hydrogen bonded to a phenoxidic oxygen atom (O.O, 2.84 A). The C-O and C-C distances in the V(diol) fragment reveal that 2 is a pure catecholate and 3 is a catecholate-semiquinonate hybrid. In solution each ester gives rise to a single (51)V NMR signal (no diastereoisomers), which generally shifts downfield with a decrease in the ester LMCT band energy. The V(V)/V(IV) and catecholate-semiquinonate reduction potentials lie near -0.75 and 0.35, and 1.10 and 0.70 V vs SCE for 2 and 3, respectively. Molecular oxygen reacts smoothly with 2 quantitatively furnishing the corresponding o-quinone, and in the presence of H(2)L the reaction becomes catalytic. In contrast, type 3 esters are inert to oxygen. The initial binding of O(2) to 2 is proposed to occur via hydrogen bonding with chelated HL(-). 相似文献
5.
The determination of lanthanides by Inductively Coupled Plasma Mass Spectrometry (ICP‐MS) is complicated by several spectral overlaps from M+, MO+ or MOH+ ions formed in the ICP. Especially, it is essential to avoid the spectral interferences from lighter lanthanide and Ba polyatomic ions on middle or heavier lanthanides. To tackle this problem, we have developed a mathematical correction method, which reduces all the spectral overlaps from oxide species of Pr, Nd, Ce and Sm over Gd, Tb, Dy and Ho, and Gd, Tb over Yb and Lu. It can also successfully correct the oxide and hydroxide interference of Ba over Eu. The effectiveness of the proposed the mathematical correction scheme is demonstrated for the USGS Standard Rock samples AGV‐1 and G‐2. The results show that the experimental data obtained by applying the mathematical correction scheme for lanthanides is in good agreement with the reported values, using pneumatic and ultrasonic nebulisation methods, for their ICP‐MS analysis. 相似文献
6.
C. D. Kalkar V. M. Raut V. B. Gaikwad 《Journal of Radioanalytical and Nuclear Chemistry》1994,177(2):345-355
Lyoluminescence of luminol induced by -irradiated NaCl has been studied in aqueous amines. The emission spectra of lyoluminescence are recorded on 400 ASA Kodak film using a Fuess spectrograph. A broad continuous emission band appears in the visible region from 390 to 500 nm. The emission band showed two peaks centered at 430 and 470 nm. The 430 nm peak is more intense in secondary amines while the 470 nm band is more intense in primary amines. The mechanism of light emission is based on the comparative study of lyoluminescence, fluorescence and chemiluminescence of luminol in aqueous amines. 相似文献
7.
Ashok K. Singh Amar Singh Ranjana Gupta Madhu Saxena Bharat Singh 《Transition Metal Chemistry》1992,17(5):413-416
The kinetics of oxidation of three aldoses (glucose, mannose and galactose) byN-bromoacetamide (NBA) in the presence of an alkaline solution of RuO4 as catalyst and Hg(OAc)2 as co-catalyst and as a scavenger for bromide have been investigated. The main products of the oxidation are the corresponding
aldonic acids. The reaction is zero order with respect to aldose and OH−. First order dependence of the reaction on both NBA and RuO4 at low concentrations shifts to zero order at higher concentrations. Addition of acetamide decreases the reaction rate, while
addition of Hg(OAc)2 has the opposite effect. No significant effect of ionic strength was observed. OBr− is postulated as the reactive oxidising species and a mechanism involving co-catalysis by RuO4 and HgII is proposed.
TMC 2588 相似文献
8.
Ashok K. Singh Alka Srivastava Ashutosh Kumar Bharat Singh 《Transition Metal Chemistry》1993,18(4):427-430
Summary The kinetics of iridium(III)-catalysed oxidation of 1,2-ethanediol and 1,4-butanediol by N-bromoacetamide (NBA) in HClO4 in the presence of [Hg(OAc)2] as a scavenger for Br– have been investigated. The reactions are zero-order with respect to both diols, and first-order in NBA at low NBA concentrations, tending to zero order at high concentrations. The order in IrIII decreases from unity to zero at high iridium(III) concentrations. A positive effect on the oxidation rate is observed for [H+] and [HgII] whereas a negative effect is observed for acetamide and [Cl–]. Ionic strength does not influence the oxidation rate. (H2OBr)+ is postulated as the oxidizing species. A mechanism consistent with the observed kinetic data is proposed. 相似文献
9.
Ashish Surya?Prakash?Singh Ashok?Kumar?Singh Bharat?SinghEmail author 《Transition Metal Chemistry》2005,30(5):610-615
Kinetics and mechanism of the Os(VIII) catalysed oxidation of crotonic acid (CA) by KBrO3 in alkaline medium have been investigated. Zero order dependence in [KBrO3] was observed, while first order with respect to CA in its lower concentration range tends to zero order at its higher concentration range. The order in [Os(VIII)] was found to be unity and a positive effect of [OH−] was observed. Variation of the ionic strength (μ) and dielectric constant of the medium and addition of Hg(OAc)2 (used as Br− scavenger) had an insignificant effect on the rate of reaction. Thermodynamic parameters have also been calculated and reported. A suitable mechanism consistent with the observed kinetic results has been suggested and the related rate law deduced. 相似文献
10.
Kinetics of the oxidation of methyl n-propyl ketone and methyl isobutyl ketone by N-bromosuccinimide (NBS) have been studied in perchloric acid media in presence of mercuric acetate. A zero order dependence to N-bromosuccinimide and a first order dependence to both ketones and hydrogen ion concentrations have been observed. Sodium perchlorate, mercuric acetate and succinimide additions have negligible effect while methanol addition has a positive effect on the reaction rate. A solvent isotope effect (k0D2O/K0H2O = 2.3-2.7 and 2.4-2.8 for MeCOn.pr and MeCoi-Bu, respectively) has been observed at 35°. Kinetic investigations have revealed that the order of reactivity is methyl n-propyl ketone > methyl isobutyl ketone. Various thermodynamic parameters have been computed and corresponding 1,2-diketones were found to be the products. A suitable mechanism in conformity with the above observations has been proposed. 相似文献