RCM

The dominance of distiHation-based methods for the separation of Hquid mixtures makes a number of points about RCM and DRD significant. Residue curves trace the Hquid-phase composition of a simple single-stage batch stiHpot as a function of time. Residue curves also approximate the Hquid composition profiles in continuous staged or packed distillation columns operating at infinite reflux and reboil ratios, and are also indicative of many aspects of the behavior of continuous columns operating at practical reflux ratios (12). 

Extractive agent modifies Hquid-phase behavior (activity coefficients) of key components RCM must be of appropriate form for extractive distillation to work. 

The more stmcturaHy, chemically similar components are, the less likely that the separation will be improved by azeotropic distillation (if an MSA-key component azeotrope is being used to alter the RCM) any azeotropes formed between one component and another similar component tend to have similar boiling points, compositions. 

D/B = distillate-to-bottoms ratio, RCM = residue curve map, DRD = distillation region diagram, and MSA = mass separating agent. 

The simplest form of ternary RCM, as exemplified for the ideal normal-paraffin system of pentane-hexane-heptane, is illustrated in Fig. 13-58 7, using a right-triangle diagram. Maps for all other non-azeotropic ternary mixtures are qiiahtatively similar. Each of the infinite number of possible residue curves originates at the pentane vertex, travels toward and then away from the hexane vertex, and terminates at the heptane vertex. 

Although batch distillation is covered in a subsequent separate section, it is appropriate to consider the application of RCM and DRD to batch distulation at this time. With a conventional batch-rectification column, a charge of starting material is heated and fractionated, with a vapor product removed continuously. The composition of the vapor prodiic t changes continuously and at times drastically as the lighter component(s) are exhausted from the stiU. Between points of drastic change in the vapor composition, a cut is often made. Successive cuts can be removed until the still is nearly diy. The sequence, number, and limiting composition of each cut is dependent on the form of... 

Typical values of y range from 1.1 to 1.67, wliich give rcm values of 1.71 to 2.05. Thus, for releases of most diatomic gases (y = 1.4) to tlie atmosphere, upstream pressures over 1.9 bar absolute will result in sonic flow. Note tliat tlie inverse of rent is occasionally used by industry. 

When a mixture of alkenes 1 and 2 or an unsymmetrically substituted alkene 3 is treated with an appropriate transition-metal catalyst, a mixture of products (including fi/Z-isomers) from apparent interchange of alkylidene moieties is obtained by a process called alkene metathesis. With the development of new catalysts in recent years, alkene metathesis has become a useful synthetic method. Special synthetic applications are, for example, ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROM) (see below). 

Acyclic diene molecules are capable of undergoing intramolecular and intermolec-ular reactions in the presence of certain transition metal catalysts molybdenum alkylidene and ruthenium carbene complexes, for example [50, 51]. The intramolecular reaction, called ring-closing olefin metathesis (RCM), affords cyclic compounds, while the intermolecular reaction, called acyclic diene metathesis (ADMET) polymerization, provides oligomers and polymers. Alteration of the dilution of the reaction mixture can to some extent control the intrinsic competition between RCM and ADMET. 

Figure 27.13 Air discharge grilles, (a) Ceiling (Courtesy of Myson RCM Ltd), (b) Wall...

The interest in asymmetric synthesis that began at the end of the 1970s did not ignore the dihydroxylation reaction. The stoichiometric osmylation had always been more reliable than the catalytic version, and it was clear that this should be the appropriate starting point. Criegee had shown that amines, pyridine in particular, accelerated the rate of the stoichiometric dihydroxylation, so it was understandable that the first attempt at nonenzymatic asymmetric dihydroxylation was to utilize a chiral, enantiomerically pure pyridine and determine if this induced asymmetry in the diol. This principle was verified by Sharpless (Scheme 7).20 The pyridine 25, derived from menthol, induced ee s of 3-18% in the dihydroxylation of /rcms-stilbene (23). Nonetheless, the ee s were too low and clearly had to be improved. 

As stated above, olefin metathesis is in principle reversible, because all steps of the catalytic cycle are reversible. In preparatively useful transformations, the equilibrium is shifted to one side. This is most commonly achieved by removal of a volatile alkene, mostly ethene, from the reaction mixture. An obvious and well-established way to classify olefin metathesis reactions is depicted in Scheme 2. Depending on the structure of the olefin, metathesis may occur either inter- or intramolecularly. Intermolecular metathesis of two alkenes is called cross metathesis (CM) (if the two alkenes are identical, as in the case of the Phillips triolefin process, the term self metathesis is sometimes used). The intermolecular metathesis of an a,co-diene leads to polymeric structures and ethene this mode of metathesis is called acyclic diene metathesis (ADMET). Intramolecular metathesis of these substrates gives cycloalkenes and ethene (ring-closing metathesis, RCM) the reverse reaction is the cleavage of a cyclo-... 

Scheme 2 Different modes of the olefin metathesis reaction cross metathesis (CM), ringclosing metathesis (RCM), ring-opening metathesis (ROM), acyclic diene metathesis polymerization (ADMET), and ring-opening metathesis polymerization (ROMP)...

We will focus on the development of ruthenium-based metathesis precatalysts with enhanced activity and applications to the metathesis of alkenes with nonstandard electronic properties. In the class of molybdenum complexes [7a,g,h] recent research was mainly directed to the development of homochi-ral precatalysts for enantioselective olefin metathesis. This aspect has recently been covered by Schrock and Hoveyda in a short review and will not be discussed here [8h]. In addition, several important special topics have recently been addressed by excellent reviews, e.g., the synthesis of medium-sized rings by RCM [8a], applications of olefin metathesis to carbohydrate chemistry [8b], cross metathesis [8c,d],enyne metathesis [8e,f], ring-rearrangement metathesis [8g], enantioselective metathesis [8h], and applications of metathesis in polymer chemistry (ADMET,ROMP) [8i,j]. Application of olefin metathesis to the total synthesis of complex natural products is covered in the contribution by Mulzer et al. in this volume. 

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