Examples of reactions

Examples of reactions carried out in fixed-bed catalytic reactors of various types are as follows  

This is a reversible, endothermic reaction carried out adiabatically in a multistage reactor with either axial or radial flow, and interstage heat transfer for temperature adjustment. 

This reaction precedes reaction (D) in the production of styrene. 

Reaction (F) represents one of the uses of methanol (reaction (C)), and is also an example in which reaction selectivity is an important issue. The reaction cannot be allowed to go to ultimate completion, since the complete oxidation of CH3OH would lead to C02 and HzO as products. Similarly, in reaction (D), benzene and other (unwanted) products are produced by dealkylation reactions. 

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Figure 3-13. The reaction scheme comprising the breaking and the making of two bonds and some examples of reactions following this scheme.

Problems 12 2 12 3 and 12 7 offer additional examples of reactions in which only a sin gle product of electrophilic aromatic substitution is possible... 

Diels-Alder Reactions. The important dimerization between 1,3-dienes and a wide variety of dienoplules to produce cyclohexene derivatives was discovered in 1928 by Otto Diels and Kurt Alder. In 1950 they won the Nobel prize for their pioneering work. Butadiene has to be in the j -cis form in order to participate in these concerted reactions. Typical examples of reaction products from the reaction between butadiene and maleic anhydride (1), or cyclopentadiene (2), or itself (3), are <7 -1,2,3,6-tetrahydrophthaHc anhydride [27813-21 -4] 5-vinyl-2-norbomene [3048-64-4], and 4-vinyl-1-cyclohexene [100-40-3], respectively. 

Conversion of CA into cyanuric chloride [108-77-0] (C1CN)3 by PCl is another example of reaction at carbon (78). Cyanuric chloride as an imidoyl chloride reacts as an acid chloride, unlike chloroisocyanurates. 

Particular reactions can occur in either or both phases or near the interface. Nitration of aromatics with HNO3-H2SO4 occurs in the aqueous phase (Albright and Hanson, eds.. Industrial and Laboratoiy Nitration.s, ACS Symposium Series 22 [1975]). An industrial example of reaction in both phases is the oximation of cyclohexanone, a step in the manufacture of caprolactam for nylon (Rod, Proc. 4th Interna-tional/6th European Symposium on Chemical Reactions, Heidelberg, Pergamon, 1976, p. 275). The reaction between butene and isobutane... 

Figure 3 Some interactions between gastrointestinal bacteria and the xenobiotic metabolizing enzyme system of the host. Solid lines, host XME system reactions dotted lines, classes of reactions mediated by gastrointestinal bacteria. Specific examples of reaction classes 1-5 are cited in the text. (Modified from Rowland and Tanaka " )...

Scheme 12.6 gives some examples of reactions in which free-radical rearrangements have been observed. 

The number of examples of reaction with alkyllithium reagents is very limited (14,48). The similarity of the reaetion to Grignard addition suggests that similar products will be obtained. This suggestion is supported by the examples shown in Table 6. 

Examples of reactions that have been carried out in these antimony(III) ionic liquids include the cyclizations of l,2-bis-(9-anthryl)-ethane (Scheme 5.1-12) and 1,2-bis-(l-naphthyl)-ethane (Scheme 5.1-13). A more detailed review of antimony(III) chloride molten salt chemistry has been published by Pagni [4]. 

See Figures I0-93A and I0-93B as limited examples of reaction and other process vessels that require heat transfer for proper processing. Markovitz reports improved heat transfer for the inside of jacketed vessels when the surface has been electropolished, which gives a fine, bright surface. 

Scheme 10.32 Examples of reactions catalyzed by different classes of dehalogenases. HD haloalcohol dehalogenase EH epoxide hydrolase CL p-chlorobenzoyl-CoA ligase CBD p-chlorobenzoyl-CoA dehalogenase.

Several examples of reactions of allylboronates and /f-alkoxy-x-unsubstituted aldehydes ha ve been reported63-64. These reactions do not proceed with exceptional selectivity, however, since the stereocenter of the aldehydic component is remote from the site of the developing C-C bond. 

Two examples of reaction profile diagrams are shown in Fig. 4-5 for the A = I <=s P sequence. The rate constants chosen give values of kss of 0.99 s-1 in case (1) and 0.0099 s l in (2). In the first diagram, step 1 is almost rate-controlling, and in the other, step 2. In Fig. 4-5 note the depth of the well in which the intermediate resides... 

Neutralization agents may be caustic soda (predominantly), ammonia, mono-ethanolamine, and triethanolamine. Examples of reaction equations are as follows ... 

To generate molecular libraries, a series of 5-oxo-2-azabicyclo[2.2.2]octane and triaza analogs were prepared via a stereospecific Diels-Alder reaction by reacting Wang-resin-bound diene 35 with a variety of dienophiles [28]. After removing the solid support with a strong acid, adducts 36 were isolated examples of reactions that have furnished the best yields are reported in Scheme 4.6. 

Fluoboric acid is also an efficacious promoter of cyclic oxo-carbenium ions (Scheme 4.24) bearing an activated double bond which, in the presence of open-chain and cyclic dienes, rapidly undergo a Diels-Alder reaction [91]. Chiral a, -unsaturated ketones bearing a -hydroxy substituents, protected as acetals, react with various dienes in the presence of HBF4, affording Diels-Alder adducts that were isolated as alcohols by hydrolysis of the acetal group by TsOH. Some examples of reactions with isoprene are reported in Table 4.23. The enantios-electivity of the reaction is dependent on the size of the substituent R on the of-carbon high levels of asymmetric induction were observed with R = z-Pr (90 1) and R = t-Bu (150 1) and low levels with R = Me (2.7 1) and R = Ph (3.0 1). Scheme 4.24 shows the postulated reaction mechanism. 

It is thus an example of reaction type A (p. 1175). The sequence shown is genera-lized." In specific cases there are variations in the sequence of the steps, depending on acid or basic catalysis or other conditions. Which step is rate determining also depends on acidity and on the nature of W and of the groups connected to the carbonyl. ... 

Equations (2.22) and (2.23) become indeterminate if ks = k. Special forms are needed for the analytical solution of a set of consecutive, first-order reactions whenever a rate constant is repeated. The derivation of the solution can be repeated for the special case or L Hospital s rule can be applied to the general solution. As a practical matter, identical rate constants are rare, except for multifunctional molecules where reactions at physically different but chemically similar sites can have the same rate constant. Polymerizations are an important example. Numerical solutions to the governing set of simultaneous ODEs have no difficulty with repeated rate constants, but such solutions can become computationally challenging when the rate constants differ greatly in magnitude. Table 2.1 provides a dramatic example of reactions that lead to stiff equations. A method for finding analytical approximations to stiff equations is described in the next section. 

Relationship between Volume 9 and Previous Volumes. Compendium of Organic Synthetic Methods, Voiume 9 presents about 1200 examples of published reactions for the preparation of monofunctional compounds, updating the 10650 in Volumes 1-8. Volume 9 contains about 800 examples of reactions which prepare of difunctional compounds with various functional groups. Reviews have long been a feature of this series and Volume 9 adds almost 90 pertinent reviews in the various sections. Volume 9 contains approximately 1000 fewer entries than Volume 8 for an identical three-year period, primarily for difunctional compunds. Interestingly, there are about 500 fewer citations from the most cited journal (Tetrahedron Letters) than in the previous edition. Whether this represents a trend in the literature or an inadvertent selectivity on my part is unknown, but there has been a clear increase in biochemicai and total synthesis papers which may account for this. 

Years earlier, Nicholas and Ladoulis had found another example of reactions catalyzed by Fe2(CO)9 127. They had shown that Fe2(CO)9 127 can be used as a catalyst for allylic alkylation of allylic acetates 129 by various malonate nucleophiles [109]. Although the regioselectivites were only moderately temperature-, solvent-, and substrate-dependent, further investigations concerned with the reaction mechanism and the catalytic species were undertaken [110]. Comparing stoichiometric reactions of cationic (ri -allyl)Fe(CO)4 and neutral (rj -crotyl ace-tate)Fe(CO)4 with different types of sodium malonates and the results of the Fe2(CO)9 127-catalyzed allylation they could show that these complexes are likely no reaction intermediates, because regioselectivites between stoichiometric and catalytic reactions differed. Examining the interaction of sodium dimethylmalonate 75 and Fe2(CO)9 127 they found some evidence for the involvement of a coordinated malonate species in the catalytic reactions. With an excess of malonate they... 

Other reactions do not go to completion because they reach dynamic equilibrium. While reactant molecules continue to form product molecules, product molecules also interact to re-form reactant molecules. The Haber reaction and many precipitation reactions, described later in this chapter, are examples of reactions that reach d3Tiamic equilibrium rather than going to completion. We treat chemical equilibria in detail in Chapters 16-18. 

To this point the complexes considered have shared the coordination number six and approximate octahedral geometry. It has been argued that they also share the dissociative reaction mode. There are examples of reactions both with and without intermediates of reduced (that is, 5) coordination, but the insensitivity to entering ligands is a consistent feature. It will be interesting, shortly, to see if the dissociative pattern persists in more or less organometallic octahedral systems but first we shall give some attention to the non-labile square planar systems. 

Chiral PTC has been used effectively for making intermediates for drugs. Dolling and coworkers have used 8-R, 9-5, N-(p-trifluoromethylbenzyl) cinchonium bromide to carry out an important asymmetric alkylation, giving 95% ee (Starks, 1987). Nucleophilic epoxidations of enones, Darzens reaction, Michael additions, etc. are some examples of reactions rendered asymmetric through chiral PTCs (Nelson, 1999). 

BATCH HYDROLYSIS OF ACETIC ANHYDRIDE EXAMPLE OF REACTION WITH HEAT EFFECTS UNDER ADIABATIC CONDITIONS... 

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