Another Approach

Paterson s synthesis is based on a short and eflScient asymmetric route to the simplified erythronolide derivative 120 (R=TBS) by using an Evans aldol reaction for the preparation of the C2-C4 and Cg-Cjo fragments. 

The key aldol step was accomplished by adding the dibutylboron enolate of 110 to a racemic aldehyde ( )-109 to give a 1 1 mixture of the two dia-stereomeric adducts 111 and 112. The a-chlorosulfide 113, derived from 112, reacted with the trimethylsilyl enol ether of diethylketone to give only two (114 and 115) out of the four possible diastereomeric products. The sulfone derivatives were converted into a single aldehyde 116 (C7-C13 segment) via an enone 

Paterson s group exploited a useful aldol reaction for macrolide synthesis by using the chiral boron enolate of diethylketone prepared with (—)- or (-1-)-(Ipc)2BOTf/iPr2EtN. 

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In the future it will be difficult to avoid deterioration of certain characteristics such as viscosity, asphaltene and sediment contents, and cetane number. The users must employ more sophisticated technological means to obtain acceptable performance. Another approach could be to diversify the formulation of heavy fuel according to end use. Certain consuming plants require very high quality fuels while others can accept a lower quality. 

Another approach to measurement of surface tension, density, and viscosity is the analysis of capillary waves or ripples whose properties are governed by surface tension rather than gravity. Space limitations prevent more than a summary presentation here readers are referred to several articles [123,124]. 

Another approach is to use the LB film as a template to limit the size of growing colloids such as the Q-state semiconductors that have applications in nonlinear optical devices. Furlong and co-workers have successfully synthesized CdSe [186] and CdS [187] nanoparticles (<5 nm in radius) in Cd arachidate LB films. Finally, as a low-temperature ceramic process, LB films can be converted to oxide layers by UV and ozone treatment examples are polydimethylsiloxane films to make SiO [188] and Cd arachidate to make CdOjt [189]. 

As with most methods for studying ion-molecule kinetics and dynamics, numerous variations exist. For low-energy processes, the collision cell can be replaced with a molecular beam perpendicular to the ion beam [106]. This greatly reduces the thennal energy spread of the reactant neutral. Another approach for low energies is to use a merged beam [103]. In this system the supersonic expansion is aimed at the tluoat of the octopole, and the ions are passed tluough... 

Another approach involves starting with an initial wavefimction Iq, represented on a grid, then generating // /q, and consider that tiiis, after orthogonalization to Jq, defines a new state vector. Successive applications //can now be used to define an orthogonal set of vectors which defines as a Krylov space via the iteration (n = 0,.. ., A)... 

Another approach to mass analysis is based on stable ion trajectories in quadnipole fields. The two most prominent members of this family of mass spectrometers are the quadnipole mass filter and the quadnipole ion trap. Quadnipole mass filters are one of the most connnon mass spectrometers, being extensively used as detectors in analytical instnunents, especially gas clnomatographs. The quadnipole ion trap (which also goes by the name quadnipole ion store, QUISTOR , Paul trap, or just ion trap) is fairly new to the physical chemistry laboratory. Its early development was due to its use as an inexpensive alternative to tandem magnetic sector and quadnipole filter instnunents for analytical analysis. It has, however, staned to be used more in die chemical physics and physical chemistry domains, and so it will be described in some detail in this section. 

Another approach to the fabrication of LB films from prefonned polymers is to fonn a hydrophobic main chain by reacting monomers tenninated by a vinyl group [102, 103, 104, 105 and 106]. The side groups studied also included perfluorinated hydrocarbon chains, which tilt with respect to the nonnal to the plane of the film, whereas the analogous ordinary hydrocarbon chains do not [105]. 

Another approach applies graph theory. The analogy between a structure diagram and a topological graph is the basis for the development of graph theoretical algorithms to process chemical structure information [33-35]. 

Another approach to obtain an overview on chemical information or on information related to specified topies in chemistry, is to use websites that eontain link lists. These link lists arc usually provided by universities and private persons and are classified into subject areas, Table 5-7 gives an sample of the thousands of link lists in chemistry, and in addition some other valuable URLs that deal with chcmoinformatics. 

Another approach employing the autocorrelation coefficients as descriptors was suggested by Gasteiger et al, [22]. They used the neural networks as a working tool for solving a similarity problem. 

Another approach is spin-coupled valence bond theory, which divides the electrons into two sets core electrons, which are described by doubly occupied orthogonal orbitals, and active electrons, which occupy singly occupied non-orthogonal orbitals. Both types of orbital are expressed in the usual way as a linear combination of basis functions. The overall wavefunction is completed by two spin fimctions one that describes the coupling of the spins of the core electrons and one that deals with the active electrons. The choice of spin function for these active electrons is a key component of the theory [Gerratt ef al. 1997]. One of the distinctive features of this theory is that a considerable amount of chemically significant electronic correlation is incorporated into the wavefunction, giving an accuracy comparable to CASSCF. An additional benefit is that the orbitals tend to be... 

Another approach is to run an unrestricted calculation and then project out the spin contamination after the wave function has been obtained (PUHF, PMP2). This gives a correction to the energy but does not affect the wave function. Spin projection nearly always improves ah initio results, but may seriously harm the accuracy of DFT results. 

Another approach to 2-aminothiazole derivatives was recently developed by Zbiral and Hengstberger (667, 700) thus the condensation of )3-acylvinylphosphonium salts (248) with thiourea affords the thiazolyl-methylphosphonium salt (249) via an acyclic intermediate analogous to the Hantzsch s synthesis. Final alkaline hydrolysis of 249 furnishes the 2-aminothiazoles (250) (Scheme 127) (700). 

Molecular fluorescence and, to a lesser extent, phosphorescence have been used for the direct or indirect quantitative analysis of analytes in a variety of matrices. A direct quantitative analysis is feasible when the analyte s quantum yield for fluorescence or phosphorescence is favorable. When the analyte is not fluorescent or phosphorescent or when the quantum yield for fluorescence or phosphorescence is unfavorable, an indirect analysis may be feasible. One approach to an indirect analysis is to react the analyte with a reagent, forming a product with fluorescent properties. Another approach is to measure a decrease in fluorescence when the analyte is added to a solution containing a fluorescent molecule. A decrease in fluorescence is observed when the reaction between the analyte and the fluorescent species enhances radiationless deactivation, or produces a nonfluorescent product. The application of fluorescence and phosphorescence to inorganic and organic analytes is considered in this section. 

Another approach to multielemental analysis is to use a multichannel instrument that allows for the simultaneous monitoring of many analytes. A simple design for a multichannel spectrometer consists of a standard diffraction grating and 48-60 separate exit slits and detectors positioned in a semicircular array around the diffraction grating at positions corresponding to the desired wavelengths (Figure 10.50). 

Another approach to matrix matching, which does not rely on knowing the exact composition of the sample s matrix, is to add a high concentration of inert electrolyte to all samples and standards. If the concentration of added electrolyte is sufficient, any difference between the sample s matrix and that of the standards becomes trivial, and the activity coefficient remains essentially constant. The solution of inert electrolyte added to the sample and standards is called a total ionic strength adjustment buffer (TISAB). 

Another approach to improving resolution is to use thin films of stationary phase. Capillary columns used in gas chromatography and the bonded phases commonly used in HPLC provide a significant decrease in plate height due to the reduction of the Hs term in equation 12.27. 

Capillary Electrochromatography Another approach to separating neutral species is capillary electrochromatography (CEC). In this technique the capillary tubing is packed with 1.5-3-pm silica particles coated with a bonded, nonpolar stationary phase. Neutral species separate based on their ability to partition between the stationary phase and the buffer solution (which, due to electroosmotic flow, is the mobile phase). Separations are similar to the analogous HPLC separation, but without the need for high-pressure pumps, furthermore, efficiency in CEC is better than in HPLC, with shorter analysis times. 

Another approach to optimizing a method is to develop a mathematical model of the response surface. Such models can be theoretical, in that they are derived from a known chemical and... 

To some extent each of these objections is met by the presence of either chemical or crystallite crosslinking in the polymer. Another approach which complements the former is to incorporate rings into the backbone of the chemical chain. As an example, contrast the polyesters formed between ethylene glycol and either suberic or terephthaUc acid. Structures [V] and [VI], respectively, indicate the repeat units in these polymers ... 

Another approach to the control of batching systems is to use a relatively simple scale indicator which does nothing but supply weight data to a controUer such as a PLC, which in turn controls the fiH and discharge system. The communications between the scale and controUer can be serial such as RS-232, or it can be an analogue signal such as 4-20 m A. While this system minimises operator interaction with the scale, it sacrifices speed and accuracy because of the relatively slow communications. 

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