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41.
2-Aminoaryl ketones undergo condensation with α-methylene ketones in the presence of a catalytic amount of Y(OTf)3 at room temperature under mild conditions to afford the corresponding polysubstituted quinolines in excellent yields. 相似文献
42.
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
43.
Three complexes containing bidentate N-2,3-dimethylphenylglycine, (2,3-HDPG), N-2,4-dimethylphenylglycine, (2,4-HDPG) and N-2-ethylphenylglycine, (2-HEPG) acids have been prepared and characterized. These compounds have the general formula Zn(2,3-DPG)2·2 H2O, Zn(2,4-DPG)2 and Zn(2-EPG)2·2 H2O, respectively. The structure of the complexes as inferred from their chemistries have been found to be compatible with the infrared spectral data. The thermal behaviour of these complexes has been studied from their TG, DTG and DSC diagrams obtained in a dynamic atmosphere of pure air. Heats of dehydration have been calculated from DSC curves. 相似文献
44.
Thazha P Prakash Andrew M Kawasaki Allister S Fraser Guillermo Vasquez Muthiah Manoharan 《The Journal of organic chemistry》2002,67(2):357-369
A versatile synthetic route has been developed for the synthesis of 2'-O-[2-[(N,N-dimethylamino)oxy]ethyl] (abbreviated as 2'-O-DMAOE) modified purine and pyrimidine nucleosides and their corresponding nucleoside phosphoramidites and solid supports. To synthesize 2'-O-DMAOE purine nucleosides, the key intermediate B (Scheme 1) was obtained from the 2'-O-allyl purine nucleosides (13a and 15) via oxidative cleavage of the carbon-carbon bond to the corresponding aldehydes followed by reduction. To synthesize pyrimidine nucleosides, opening the 2,2'-anhydro-5-methyluridine 5 with the borate ester of ethylene glycol gave the key intermediate B. The 2'-O-(2-hydroxyethyl) nucleosides were converted, in excellent yield, by a regioselective Mitsunobu reaction, to the corresponding 2'-O-[2-[(1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl)oxy]ethyl] nucleosides (18, 19, and 20). These compounds were subsequently deprotected and converted into the 2'-O-[2-[(methyleneamino)oxy]ethyl] derivatives (22, 23, and 24). Reduction and a second reductive amination with formaldehyde yielded the corresponding 2'-O-[2-[(N,N-dimethylamino)oxy]ethyl] nucleosides (25, 26, and 27). These nucleosides were converted to their 3'-O-phosphoramidites and controlled-pore glass solid supports in excellent overall yield. Using these monomers, modified oligonucleotides containing pyrimidine and purine bases were synthesized with phosphodiester, phosphorothioate, and both linkages (phosphorothioate and phosphodiester) present in the same oligonucleotide as a chimera in high yields. The oligonucleotides were characterized by HPLC, capillary gel electrophoresis, and ESMS. The effect of this modification on the affinity of the oligonucleotides for complementary RNA and on nuclease stability was evaluated. The 2'-O-DMAOE modification enhanced the binding affinity of the oligonucleotides for the complementary RNA (and not for DNA). The modified oligonucleotides that possessed the phosphodiester backbone demonstrated excellent resistance to nuclease with t(1/2) > 24 h. 相似文献
45.
G.K. Surya Prakash Jinbo Hu Ying Wang George A. Olah 《Journal of fluorine chemistry》2005,126(4):527-532
A fluoride-induced nucleophilic (phenylthio)difluoromethylation method using TMS-CF2SPh has been achieved. This new methodology efficiently transfers “PhSCF2” group into both enolizable and non-enolizable aldehydes and ketones to give corresponding (phenylthio)difluoromethylated alcohols in good to excellent yields. Diphenyldisulfide can also be (phenylthio)difluoromethylated into PhSCF2SPh in high yield. The reaction with methyl benzoate, however, gives only low yield of (phenylthio)difluoromethyl phenyl ketone. The above-obtained PhSCF2-containing alcohols can be further transformed into difluoromethyl alcohols using an oxidation-desulfonylation procedure. This new type of nucleophilic (phenylthio)difluoromethylation methodology may have other potential applications in the medicinal and agrochemical fields. 相似文献
46.
Moriarty RM Rani N Enache LA Rao MS Batra H Guo L Penmasta RA Staszewski JP Tuladhar SM Prakash O Crich D Hirtopeanu A Gilardi R 《The Journal of organic chemistry》2004,69(6):1890-1902
A general and novel solution to the synthesis of biologically important stable analogues of prostacyclin PGI(2), namely benzindene prostacyclins, has been achieved via the stereoselective intramolecular Pauson-Khand cyclization (PKC). This work illustrates for the first time the synthetic utility and reliability of the asymmetric PKC route for synthesis and subsequent manufacture of a complex drug substance on a multikilogram scale. The synthetic route surmounts issues of individual step stereoselectivity and scalability. The key step in the synthesis involves efficient stereoselection effected in the PKC of a benzoenyne under the agency of the benzylic OTBDMS group, which serves as a temporary stereodirecting group that is conveniently removed via benzylic hydrogenolysis concomitantly with the catalytic hydrogenation of the enone PKC product. Thus the benzylic chiral center dictates the subsequent stereochemistry of the stereogenic centers at three carbon atoms (C(3a), C(9a), and C(1)). 相似文献
47.
Masson JF Battaglia TM Davidson MJ Kim YC Prakash AM Beaudoin S Booksh KS 《Talanta》2005,67(5):918-925
The elimination or minimization of non-specific protein adsorption from serum is critical for the use of surface plasmon resonance (SPR) sensors for in vitro and in vivo analysis of complex biological solutions. The ultimate goals in this application are to minimize non-specific adsorption of protein and to maximize analyte signal. A reduction of the non-specific protein adsorption from serum of up to 73% compared to carboxymethylated-dextran 500 kDa (CM-dextran) was achieved following a survey of eight biocompatible polymers and 10 molecular weights of CM-dextran. These coatings minimize non-specific adsorption on the sensor while also serving as immobilization matrices for antibody fixation to the probes. Polymers including polysaccharides: CM-dextrans, CM-hyaluronic acid, hyaluronic acid, and alginic acid were investigated. Humic acid, polylactic acid, polyacrylic acid, orthopyridyldisuldfide–polyethyleneglycol–N-hydroxysuccinimide (OPSS–PEG–NHS), and a synthesized polymer; polymethacrylic-acid-co-vinyl-acetate (PMAVA) were also used. The non-specific protein adsorption reduction was measured over a 14 day period at 0 °C for each polymer. Calibration curves using some of these polymers were constructed to show the performance and low detection limit possibilities of these new antibody supports. For many of the polymers, this is the first demonstration of employment as an antibody support for an optical or surface active sensor. CM-dextran is the polymer offering the largest signal for the antigen detection. However, the biocompatible polymers demonstrate a greater stability to non-specific binding in serum. These biocompatible polymers offer different alternatives for CM-dextran. 相似文献
48.
A solid state copper(II) ion sensor is reported based on the application of electropolymerized undoped (neutral) polycarbazole
(PCz) and polyindole (PIn) modified electrodes. The new sensor shows high selectivity to Cu2+ ions with a detection limit of 10–5 M. PCz and PIn are formed respectively by the anodic oxidation of 50 mM carbazole and 5 mM indole monomers in dichloromethane
containing 0.1 M tetrabutylammonium perchlorate on a platinum electrode using a single compartment cell. Potentiostatic polymerization
of both the monomers are carried out at 1.3 V and 1.0 V vs. Ag/AgCl, respectively. Perchlorate ions were electrochemically
removed from the polymer films by applying – 0.2 V vs. Ag/AgCl. Polymer-coated electrodes are incubated in 1 M KCl solution
for 8 h followed by incubation in distilled water for 2 h before using as a metal ion sensor. The undoped PCz and PIn electrodes
were found to be highly selective and sensitive for Cu2+ ions with little selectivity for Pb2+ and negligible response towards Ag+, Hg2+, Cu+, Ni2+, Co2+, Fe2+, Fe3+ or Zn2+. Potentiometric responses for Cu2+ ions are recorded for both the sensor electrodes together with a double-junction Ag/AgCl reference electrode. Calibration
curves for Cu2+ are reported for both ion sensors. The polymer-modified electrodes were found to be stable for several weeks.
Electronic Publication 相似文献
49.
50.
G. A. Olah G. K. Surya Prakash P. Donald Katherine B. Loker Koop Lammertsma 《Research on Chemical Intermediates》1989,12(2):141-159
In this short review we have shown the importance of protosolvation of onium ions (containing non-bonded pairs of electrons)
in superacid catalyzed reactions. Such activation can result in unusual reactions such as aromatic alkylation with Meerwein’s
salts, aliphatic nitration with nitronium ion, alkylation of saturated hydrocarbons, greatly enhanced activity of acyl cations,
etc. Possibly such phenomena may be operative in hydroxylation reactions using protonated hydrogen peroxide in strong acid
solutions. Even the reactivity of halonium ions could be enhanced by protosolvation. Consequently, electrophilic protosolvation
may play a significant role in strogg acid catalyzed reactions. 相似文献