Classes of reactions

There is one special class of reaction systems in which a simplification occurs. If collisional energy redistribution of some reactant occurs by collisions with an excess of heat bath atoms or molecules that are considered kinetically structureless, and if fiirthennore the reaction is either unimolecular or occurs again with a reaction partner M having an excess concentration, dien one will have generalized first-order kinetics for populations Pj of the energy levels of the reactant, i.e. with... 

A chemical reaction takes place on a potential surface that is determined by the solution of the electronic Schrddinger equation. In Section, we defined an anchor by the spin-pairing scheme of the electrons in the system. In the discussion of conical intersections, the only important reactions are those that are accompanied by a change in the spin pairing, that is, interanchor reactions. We limit the following discussion to these class of reactions. 

Elaborate evaluation procedures were developed for the following mechanistic classes of reactions ... 

At the outset of the development of each module for one of the above mechanistic classes of reactions, a thorough analysis of the literature was performed. On that basis, the developer came up with an evaluation framework that was used to make decisions between various reaction pathways and mechanistic possibilities. 

Turning the argument around reactions that do not involve proton transfer steps will only experience a significant effect of the Lewis acids if a direct interaction exists between catalyst and reactant. The conventional Diels-Alder reaction is a representative of this class of reactions. As long as monodentate reactants are used, the effects of Lewis acids on this reaction do not exceed the magnitude expected for simple salt effects, i.e. there are no indications for a direct interaction between Lewis-acid and substrate. 

Another class of reaction where you can see at once that the disconnection is the reverse of the reaction is Pericychc Reactions. An example would be the Diels-Alder reaction between butadiene and maleic anhydride. Draw the mechanism and the product. 

The technique most often used (i.e., for an atom transfer) is to hrst plot the energy curve due to stretching a bond that is to be broken (without the new bond present) and then plot the energy curve due to stretching a bond that is to be formed (without the old bond present). The transition structure is next dehned as the point at which these two curves cross. Since most molecular mechanics methods were not designed to describe bond breaking and other reaction mechanisms, these methods are most reliable when a class of reactions has been tested against experimental data to determine its applicability and perhaps a suitable correction factor. 

The best way to predict how well a given level of theory will describe a transition structure is to look up results for similar classes of reactions. Tables of such data are provided by Hehre in the book referenced at the end of this chapter. 

Once you are experienced at finding transition structures for a particular class of reactions, you will probably go directly to the technique that has been most reliable for those reactions. Until that time, the checklist above is our best advice for finding a transition structure with the least amount of work for the researcher and the computer. Regardless of experience, it is common to experience quite a bit of trial and error in finding transition structures. Even experienced researchers find that the way they have been regarding a reaction is often much more simplistic than the molecular motions actually involved. 

Transition state theory calculations present slightly fewer technical difficulties. However, the accuracy of these calculations varies with the type of reaction. With the addition of an empirically determined correction factor, these calculations can be the most readily obtained for a given class of reactions. 

In part 2 of this book we have focused attention on some classes of reactions which produce polymers and on some properties of the resulting products. In the final three chapters we shall consider some of the methods that are used to characterize the polymeric products of these syntheses. 

Inorganic Materials. Sol—gel chemistry involves first the formation of a sol, which is a suspension of soHd particles in a Hquid, then of a gel, which is a diphasic material with a soHd encapsulating a solvent. A detailed description of the fundamental chemistry is available in the Hterature (2—4). The chemistry involving the most commonly used precursors, the alkoxides (M(OR) ), can be described in terms of two classes of reactions ... 

Fischer-Tropsch Process. The Hterature on the hydrogenation of carbon monoxide dates back to 1902 when the synthesis of methane from synthesis gas over a nickel catalyst was reported (17). In 1923, F. Fischer and H. Tropsch reported the formation of a mixture of organic compounds they called synthol by reaction of synthesis gas over alkalized iron turnings at 10—15 MPa (99—150 atm) and 400—450°C (18). This mixture contained mostly oxygenated compounds, but also contained a small amount of alkanes and alkenes. Further study of the reaction at 0.7 MPa (6.9 atm) revealed that low pressure favored olefinic and paraffinic hydrocarbons and minimized oxygenates, but at this pressure the reaction rate was very low. Because of their pioneering work on catalytic hydrocarbon synthesis, this class of reactions became known as the Fischer-Tropsch (FT) synthesis. 

Oxo Synthesis. Ad of the synthesis gas reactions discussed to this point are heterogeneous catalytic reactions. The oxo process (qv) is an example of an industriady important class of reactions cataly2ed by homogeneous metal complexes. In the oxo reaction, carbon monoxide and hydrogen add to an olefin to produce an aldehyde with one more carbon atom than the original olefin, eg, for propjiene ... 

The principal class of reactions in the FCC process converts high boiling, low octane normal paraffins to lower boiling, higher octane olefins, naphthenes (cycloparaffins), and aromatics. FCC naphtha is almost always fractionated into two or three streams. Typical properties are shown in Table 5. Properties of specific streams depend on the catalyst, design and operating conditions of the unit, and the cmde properties. 

Polymerization Reactions. Polymerization addition reactions are commercially the most important class of reactions for the propylene molecule and are covered in detail elsewhere (see Olefin polymers, polypropylene). Many types of gas- or liquid-phase catalysts are used for this purpose. Most recently, metallocene catalysts have been commercially employed. These latter catalysts requite higher levels of propylene purity. 

With Unsaturated Compounds. The reaction of unsaturated organic compounds with carbon monoxide and molecules containing an active hydrogen atom leads to a variety of interesting organic products. The hydroformylation reaction is the most important member of this class of reactions. When the hydroformylation reaction of ethylene takes place in an aqueous medium, diethyl ketone [96-22-0] is obtained as the principal product instead of propionaldehyde [123-38-6] (59). Ethylene, carbon monoxide, and water also yield propionic acid [79-09-4] under mild conditions (448—468 K and 3—7 MPa or 30—70 atm) using cobalt or rhodium catalysts containing bromide or iodide (60,61). 

The monochlorotoluenes are stable to the action of steam, alkahes, amines, and hydrochloric and phosphoric acids at moderate temperatures and pressures. Three classes of reactions, those involving the aromatic ring, the methyl group, and the chlorine substituent, are known for monochlorotoluenes. 

Rate data are also available for the solvolysis of l-(2-heteroaryl)ethyl acetates in aqueous ethanol. Side-chain reactions such as this, in which a delocalizable positive charge is developed in the transition state, are frequently regarded as analogous to electrophilic aromatic substitution reactions. In solvolysis the relative order of reactivity is tellurienyl> furyl > selenienyl > thienyl whereas in electrophilic substitutions the reactivity sequence is furan > tellurophene > selenophene > thiophene. This discrepancy has been explained in terms of different charge distributions in the transition states of these two classes of reaction (77AHC(21)119>. 

The distinction between these two classes of reactions is semantic for the five-membered rings Diels-Alder reaction at the F/B positions in (269) (four atom fragment) is equivalent to 1,3-dipolar cycloaddition in (270) across the three-atom fragment, both providing the 47t-electron component of the cycloaddition. Oxazoles and isoxazoles and their polyaza analogues show reduced aromatic character and will undergo many cycloadditions, whereas fully nitrogenous azoles such as pyrazoles and imidazoles do not, except in certain isolated cases. 

Kinds of Catalyzed Organic Reactions A fundamental classification of organic reactions is possible on the basis of the lands of bonds that are formed or destroyed and the natures of eliminations, substitutions, and additions of groups. Here a more pragmatic hst of 20 commercially important lands or classes of reactions will be discussed. In all instances of sohd-catalyzed reactions, chemisorption is a primary step. Often molecules are dissociated on chemisorption into... 

Liquid/hquid reactions of industrial importance are fairly numerous. A hst of 26 classes of reactions with 61 references has been compiled by Doraiswamy and Sharma Heterogeneou.s Reactions, Wiley, 1984). They also indicate the kind of reactor normally used in each case. The reactions range from such prosaic examples as making soap with alkali, nitration of aromatics to make explosives, and alkylation of C4S with sulfuric acid to make improved gasoline, to some much less familiar operations. 

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 " )...

The addition of phenylisocyanate to aldehyde-derived enamines resulted in the formation of aminobutyrolactams (438,439). As aminal derivatives these produets can be hydrolyzed to the linear aldehyde amides and thus furnish a route to derivatives of the synthetically valuable malonaldehyde-acid system. With this class of reactions, a second acylation on nitrogen becomes possible and the six-membered cyclization products have been reported (440). Closely related to the reactions of enamines with isocyanates is the condensation of cyclohexanone with urea in base (441). 

Not all models are physical or pictorial objects. For example, the Sn2 mechanism is a simple model for a particular class of reactions that successfully explains a lot of chemistry. What all of these things have in common is that they use a set of pre-defined objects and rules to approximate real chemical entities and processes. 

FIGURE 18.26 The seven classes of reactions catalyzed by pyridoxal-5-phosphate. 

In addition to simple dissolution, ionic dissociation and solvolysis, two further classes of reaction are of pre-eminent importance in aqueous solution chemistry, namely acid-base reactions (p. 48) and oxidation-reduction reactions. In water, the oxygen atom is in its lowest oxidation state (—2). Standard reduction potentials (p. 435) of oxygen in acid and alkaline solution are listed in Table 14.10- and shown diagramatically in the scheme opposite. It is important to remember that if or OH appear in the electrode half-reaction, then the electrode potential will change markedly with the pH. Thus for the first reaction in Table 14.10 O2 -I-4H+ -I- 4e 2H2O, although E° = 1.229 V,... 

If one replaces one of the two equivalents of P-dicarbonyl with urea, such that the reaction is now carried out with one equivalent of aldehyde 123, one equivalent of P-dicarbonyl 124 and an equivalent of urea 125 in acidic ethanol solution, then dihydropyrimidines 126 are formed. This class of reactions has been named Biginelli reactions and are reviewed in section 10.6... 

It has been established that arynes are formed in the following classes of reaction ... 

The cycloaddition reactions of carbonyl compounds with conjugated dienes cannot be discussed in this context without trying to understand the reaction mechanistically. This chapter will give the basic background to the reactions whereas Chapter 8 dealing with theoretical aspects of metal-catalyzed cycloaddition reactions will give a more detailed description of this class of reactions, and others discussed in this book. 

The [ 2 + 4]-cycloaddition reaction of aldehydes and ketones with 1,3-dienes is a well-established synthetic procedure for the preparation of dihydropyrans which are attractive substrates for the synthesis of carbohydrates and other natural products [2]. Carbonyl compounds are usually of limited reactivity in cycloaddition reactions with dienes, because only electron-deficient carbonyl groups, as in glyoxy-lates, chloral, ketomalonate, 1,2,3-triketones, and related compounds, react with dienes which have electron-donating groups. The use of Lewis acids as catalysts for cycloaddition reactions of carbonyl compounds has, however, led to a new era for this class of reactions in synthetic organic chemistry. In particular, the application of chiral Lewis acid catalysts has provided new opportunities for enantioselec-tive cycloadditions of carbonyl compounds. 

The inverse electron-demand catalytic enantioselective cycloaddition reaction has not been investigated to any great extent. Tietze et al. published the first example of this class of reaction in 1992 - an intramolecular cycloaddition of heterodiene 42 catalyzed by a diacetone glucose derived-titanium(IV) Lewis acid 44 to give the cis product 43 in good yield and up to 88% ee (Scheme 4.31) [46]. 

---