Multi-step

Reaction databases additionally contain information on chemical reactions, giving the reaction participants and reaction conditions of both single- and multi-step reactions. 

CASREACT The CASREACT Eile (The Chemical Absiracts Reaction Search Service) is a chemical reaction database with reaction inlormatioii derived from journal documients from 1974 to the present and from patent documeiiis from 1982 to date. Thie document-based file conlains both 3 million single-step and 3.0 million multi-step reactions (Pcbiniaiy, 2003). 

CASREACT (Chemical Abstracts Reaction Search Service) is a reaction database started in 1985 with more than 6.7 million reactions (3 million single-step and 3.7 million multi-step reactions) (March, 2003) derived from 400 000 documents (journals, patents, etc.). The records contain the following information ... 

Chemln- formRX FIZ CHEMIE GmbH, Germany chemical reactions reaction, biblio., struc- ture 1.0 mio substances, 113859 records, 689029 single-step reactions, 377491 multi-step reactions 250 journals FIZ commercial online quarterly www.mdli.com... 

A further advancement in organic synthesis was the accomplishment of multi-step syntheses comprising 20 and more steps and the synthesis of rather unstable organic compounds. It was now feasible to do an experiment on a milligram scale and to separate and identify products from by-products in order to analyze them separately. The application of selective reagents or reaction conditions allowed the synthesis of enantiomerically or diastereomerically pure compounds. 

The expression template reaction indicates mostly a reaction in which a complexed me) ion holds reactive groups in the correct orientation to allow selective multi-step reactions. T1 template effect of the metal is twofold (i) polymerization reactions are suppressed, since th local concentration of reactants around the metal ion is very high (ii) multi-step reactions are possible, since the metal holds the reactants together. In the following one-step synthesis eleven molecules (three ethylenediamine — en , six formaldehyde, and two ammonia molecules) react with each other to form one single compound in a reported yield of 95%. It is ob vious that such a reaction is dictated by the organizing power of the metal ion (I.I. Creasei 1977),... 

An efficient carboannulation proceeds by the reaction of vinylcyclopropane (135) or vinylcyclobutane with aryl halides. The multi-step reaction is explained by insertion of alkene, ring opening, diene formation, formation of the TT-allylpalladium 136 by the readdition of H—Pd—I, and its intramolecular reaction with the nucleophile to give the cyclized product 137[I08]. 

BARBIER - WIELAND Degradation A multi-step procedure tor chain degradation ot esters... 

A number of alternative multi-step procedures for the synthesis of a-tert-alkyl ketones are known, none of which possess wide generality. A previous synthesis of 2-tert-penty1cyclopentanone involved reaction of N-1-cyclopentenylpyrrol 1 dine with 3-chloro-3-methy1-l-butyne and reduction of the resulting acetylene (overall yield 46 ). However, all other enamines tested afford much lower yields. Cuprate addition to unsaturated ketones may be useful in certain cases. Other indirect methods have been briefly reviewed. ... 

S. V. Ley, l.R. Baxendale, G. Brusotti, M. Caldarelli, A. Massi and M. Nesi, Solid-supported Reagents for Multi-step Organic Synthesis Preparation and Application, II Farmaco 57 321-330 2002. 

Coupling to a mineral surface requires the presence of active hydroxyls on the substrate. The coupling reaction is a multi-step process that proceeds from a state of physisorption through hydrogen bond formation to actual covalent bond formation through condensation of surface hydroxyls with silanols ... 

Caleulating the heat of reaetion is a multi-step proeess. Beginning with the standard heats of formation at 298 K, first ealeulate the standard heat of reaetion, and then ealeulate AH for the aetual system temperature and pressure. The heat of reaetion at 298 K, AHjgg is usually refeiTed to as the standard heat of reaetion. This ean be readily ealeulated from the standard heats of formation of the reaetion eom-ponents. The standard heat of reaetion is expressed as ... 

The nomenclature introduced by Hawthorne and Davis [4] is adopted and gas turbine cycles are referred to as follows CHT, CBT, CHTX, CBTX, where C denotes compressor H, air heater B, burner (combustion) T, turbine X, heat exchanger. R and I indicate reversible and irreversible. The subscripts U and C refer to uncooled and cooled turbines in a cycle, and subscripts 1,2, M indicate the number of cooling steps (one, two or multi-step cooling). Thus, for example, [CHT] C2 indicates an irreversible cooled simple cycle with two steps of turbine cooling. The subscript T is also used to indicate that the cooling air has been throttled from the compressor delivery pres.sure. 

The argument developed in Section 4.2.1.2 can be extended for three or more steps of cooling, to give the same efficiency as the uncooled cycle. Indeed the efficiency will be the same for multi-step cooling, with infinitesimal amounts of air abstracted at an infinite number of points along the compressor to cool each infinitesimal turbine stage at the required pressures. 

But another approach to multi-step cooling [8, 9] involves dealing with the turbine expansion in a manner similar to that of analysing a polytropic expansion. Fig. 4.4 shows gas flow (1 + ijj) at (p,T) entering an elementary process made up of a mixing process at constant pressure p, in which the specific temperature drops from temperature T to temperature T, followed by an isentropic expansion in which the pressure changes to (p dp) and the temperature changes from T to (7 - - dT). 

Fig. 4.4. Temperature-entropy diagram for multi-step cooling—reversible cycle 1CHT]r< m (after Ref. [5 ).

Cycle with multi-step cooling [CHTJicm... 

The two step cooling example given above can in theory be extended to multi-step cooling of the turbine. It is more convenient to treat the turbine expansion as a modification of normal polytropic expansion the analysis is essentially an adaptation of that given in Section 4.2.1.3 for the multi-step cooled turbine cycle. 

Rate-determining step (Section 4.9) Slowest step of a multi-step reaction mechanism. The overall rate of a reaction can be no faster than its slowest step. 

Multiple Gaussian calculations can be performed from a single input file. See Appendix B (page 294) for details on multi-step jobs. 

The various components of an IRC study are often run as a single, multi-step job. 

Many other multisubstrate examples abound in metabolism. In effect, these situations are managed by realizing that the interaction of the enzyme with its many substrates can be treated as a series of uni- or bisubstrate steps in a multi-step reaction pathway. Thus, the complex mechanism of a multisubstrate reaction is resolved into a sequence of steps, each of which obeys the single- and double-displacement patterns just discussed. 

Benzoyl chloride reacts with 2-mercaptoethanol in base to give an ester. When the reaction is monitored carefully, the rapid buildup of an intermediate, X , of molecular formula C9H10O2S, is observed. This is slowly transformed into the ester of the same molecular formula. Although ester formation is known to be a multi-step process, X does not correspond to any of the usual intermediates in ester formation. What is going on here ... 

Replacement of a benzene ring by its isostere, thiophene, is one of the more venerable practices in medicinal chemistry. Application of this stratagem to the NSAID piroxicam, gives tenoxicam, 136, a drug with substantially the same activity, nie synthesis of this compound starts by a multi-step conversion of hydroxy thiophene carboxylic ester 130, to the sulfonyl chloride 133. Reaction of that with N-methylglycinc ethyl ester, gives the sulfonamide 134. Base-catalyzed Claisen type condensation serves to cyclize that intermediate to the p-keto ester 135 (shown as the enol tautomer). The final product tenoxicam (136) is obtained by heating the ester with 2-aminopyridine [22]. 

An on-line supercritical fluid chromatography-capillary gas chromatography (SFC-GC) technique has been demonstrated for the direct transfer of SFC fractions from a packed column SFC system to a GC system. This technique has been applied in the analysis of industrial samples such as aviation fuel (24). This type of coupled technique is sometimes more advantageous than the traditional LC-GC coupled technique since SFC is compatible with GC, because most supercritical fluids decompress into gases at GC conditions and are not detected by flame-ionization detection. The use of solvent evaporation techniques are not necessary. SFC, in the same way as LC, can be used to preseparate a sample into classes of compounds where the individual components can then be analyzed and quantified by GC. The supercritical fluid sample effluent is decompressed through a restrictor directly into a capillary GC injection port. In addition, this technique allows selective or multi-step heart-cutting of various sample peaks as they elute from the supercritical fluid... 

Much effort has been devoted to the development of a multi-step swelling polymerization technique using water as suspension medium [98]. This has resulted in polymers showing similar selectivities but slightly improved mass transfer characteristics compared with the corresponding monolithic polymers. Of particular rele-... 

The incorporation of functionality into an ion slated for use in formulation of an ionic liquid is a usually a multi-step process. Consequently, a number of issues must be considered in planning the synthesis of the ion. The first of these is the choice of the cationic core. The core of a TSIL cation may be as simple as a single... 

The removal of heat within an enclosed space must be considered as a multi-step heat transfer process. Heat passes from the occupants or equipment to the air within the space, and from there to the refrigerant or chilled water. It follows that the temperature differences at each step are a reciprocal function of the air mass flow. Where there is a high latent heat load within the space, the relative humidity will also vary with the air flow - the variation being higher with low air flow. 

Each chapter is summarized by a multi-step Summary Problem that covers all or nearly all of the key concepts in the chapter. You can test your understanding of the chapter by working this problem. A major advantage of the Summary Problems is that they tie together many different ideas, showing how they correlate with one another An experienced general chemistry professor who uses the book always tells his class, If you can answer the Summary Problem without help, you are ready for a test on its chapter. ... 

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