Elimination reactions examples

Figure 3-3. Representative, simple examples of a substitution, an addition, and an elimination reaction showing the number, n, of reaction partners, and the change in n, An, during the reaction.

Simple cyclobutanes do not readily undergo such reactions, but cyclobutenes do. Ben-zocyclobutene derivatives tend to open to give extremely reactive dienes, namely ortho-c]uin(xlimethanes (examples of syntheses see on p. 280, 281, and 297). Benzocyclobutenes and related compounds are obtained by high-temperature elimination reactions of bicyclic benzene derivatives such as 3-isochromanone (C.W. Spangler, 1973, 1976, 1977), or more conveniently in the laboratory, by Diels-Alder reactions (R.P. Thummel, 1974) or by cycliza-tions of silylated acetylenes with 1,5-hexadiynes in the presence of (cyclopentadienyl)dicarbo-nylcobalt (W.G, Aalbersberg, 1975 R.P. Thummel, 1980). 

As a typical example, the catalytic reaction of iodobenzene with methyl acrylate to afford methyl cinnamate (18) is explained by the sequences illustrated for the oxidative addition, insertion, and /3-elimination reactions. 

Double dehydrohalogenation of gemmal dihalides (Section 9 7) An E2 elimination reaction of a gemmal dihalide yields an alkenyl halide If a strong enough base IS used sodium amide for example a second elimination step follows the first and the alkenyl halide IS converted to an alkyne... 

Laboratory syntheses of conjugated dienes can be achieved by elimination reactions of unsaturated alcohols and alkyl halides In the two examples that follow the conjugated diene is produced m high yield even though an isolated diene is also possible... 

True electrophilic substitution is very difficult in pyridopyridazines. For example, the [3,4-d] parent (286) is inert to hot 65% oleum (68AJC1291), and although formation of a 3-bromo derivative (308) was reported in the [2,3-d] series, it seems to have arisen by an addition-elimination reaction via the dibromide (309) (69AJC1745). Attempted chlorination led to ring opening. A similar effect was observed in the [3,4-d] system, where an 8-bromo derivative was obtained (77BSF665), and in iV-oxides of the pyrido[2,3-c]pyridazine and fused pyridazino[3,4-c]isoquinoline series (72JHC351). The formation of (311) from (310)... 

Anions of small heterocyclics are little known. They seem to be involved in some elimination reactions of oxetan-2-ones (80JA3620). Anions of large heterocycles often resemble their acyclic counterparts. However, anion formation can adjust the number of electrons in suitable systems so as to make a system conform to the Hiickel rule, and render it aromatic if flat geometry can be attained. Examples are found in Chapter 5.20. Anion formation in selected large heterocycles can also initiate transannular reactions (see also Section 5.02.7 below). 

Enby 6 is an example of a stereospecific elimination reaction of an alkyl halide in which the transition state requires die proton and bromide ion that are lost to be in an anti orientation with respect to each odier. The diastereomeric threo- and e/ytAra-l-bromo-1,2-diphenyl-propanes undergo )3-elimination to produce stereoisomeric products. Enby 7 is an example of a pyrolytic elimination requiring a syn orientation of die proton that is removed and the nitrogen atom of the amine oxide group. The elimination proceeds through a cyclic transition state in which the proton is transferred to die oxygen of die amine oxide group. 

The products of a eliminations are unstable divalent carbon species called carbenes. They will be discussed in Chapter 10 of Part B. In this chapter, attention will be focused on fi-elimination reactions. Some representative examples of -elimination reactions are given in Scheme 6.1. 

Fluoride-induced /S-elimination reactions of silanes having leaving groups in the position are important processes in synthetic chemistry, as, for, example in the removal of / -trimethylsilylethoxy groups. 

The use of mesyl chloride for the dehydration of C-11 alcohols has already been mentioned, and mesylates can certainly be intermediates at least in the a-series. The preference for a coplanar trans arrangement is demonstrated by the well-known elimination reactions of tosylates of epimeric 20-alcohols (ref. 185, p. 616), although this does not restrict the usefulness of the reaction, and in some cases (sulfonates of 1 la-alcohols, for example) cw-elimination occurs (ref. 216, p. 293 ref. 224, 225, 226). 

The opening of epoxides with neighboring keto groups, accompanied by vinylogous jS-elimination, has already been mentioned (section V). This is an extension of the jS-elimination reactions which occur when a,p- or jS,y-epoxy ketones are opened with acid or base. a,jS-Epoxy ketones give a-substituted a,jS-unsaturated ketones [(162), for example], and j5,y-epoxy ketones give y-substituted a,jS-unsaturated ketones [(163), for example] ... 

Elimination reactions of fluorine compounds are not limited to the removal of simple molecules Frequently, large molecules or combination of smaller ones are formed as by-products, especially in pyrolytic reactions For example perhalo genated acid chlorides lose not only carbon monoxide but also chlorine fluoride [106, 107] (equations 74 and 75)... 

Except for terpene chemistry, the Wagner-Meerwein rearrangement is of limited synthetic importance. It is rather found as an undesired side-reaction with other reactions, for example in the synthesis of alkenes by elimination reactions. 

I Elimination reactions are, in a sense, the opposite of addition reactions. They occur when a single reactant splits into two products, often with formation of a small molecule such as wateT or HBr. An example is the acid-catalyzed reaction of an alcohol to yield water and an alkene. 

The entropy change, AS, is a measure of the change in the amount of molecular randomness, or freedom of motion, that accompanies a reaction. For example, in an elimination reaction of the type... 

The two most common elimination reactions arc dehydroUalogenalion—the loss of HX from an alkyl halide—and dehydration—(he loss of water from an alcohol. Dehydrohalogenation usually occurs by reaction of an alkyl halide with strong base such as potassium hydroxide. For example, bromocvclohexane yields cyclohexene when treated with KOH in ethanol solution. 

One problem with elimination reactions is that mixtures of products are often formed. For example, treatment of 2-bromo-2-methylbutane with KOH in ethanol yields a mixture of two alkene products. What are their likely structures ... 

Elimination reactions are more complex than substitution reactions for several reasons. There is, for example, the problem of regiochemistry. What... 

According to Zaitsev s rule, formulated in 1875 by the Russian chemist Alexander Zaitsev, base-induced elimination reactions generally (although not always) give the more stable alkene product—that is, the alkene with more alkyl substituents on the double-bond carbons. In the following two cases, for example, the more highly substituted alkene product predominates. 

All three elimination reactions--E2, El, and ElcB—occur in biological pathways, but the ElcB mechanism is particularly common. The substrate is usually an alcohol, and the H atom removed is usually adjacent to a carbonyl group, just as in laboratory reactions. Thus, 3-hydroxy carbonyl compounds are frequently converted to unsaturated carbonyl compounds by elimination reactions. A typical example occurs during the biosynthesis of fats when a 3-hydroxybutyryl thioester is dehydrated to the corresponding unsaturated (crotonyl) thioester. The base in this reaction is a histidine amino acid in the enzyme, and loss of the OH group is assisted by simultaneous protonation. 

Elimination reaction, 138. 383-393 biological examples of, 393 summary of, 393-394 Embden-Meyerhof pathway, 1143-1150 see also Glycolysis... 

An elimination reaction is, in a sense, the reverse of an addition reaction. It involves the elimination of two groups from adjacent carbon atoms, converting a saturated molecule into one that is unsaturated. An example is the dehydration of ethanol, which occurs when it is heated with sulfuric acid ... 

Moreover, under well-defined experimental conditions, the organic anion produced may be unstable and undergo isomerisation or/and elimination. Several examples of side-reactions or unexpected formation of new electroactive species at the cathodic interface are listed in the following subsections. 

The phase-transfer catalysis method has also been utilized effectively for addition of dichlorocarbene to olefins,4 as well as for substitution and elimination reactions, oxidations, and reductions.18 The preceding procedure in this volume is another example.13... 

This step is an example of an elimination reaction, a reaction in which two groups or atoms on neighboring carbon atoms are removed from a molecule, leaving a multiple bond (Fig. 18.8). 

The states of reactants and products are often not given for organic reactions, because the reaction may take place at the surface of a catalyst or it may take place in a nonaqueous solvent, as here. The reaction is another example of an elimination reaction and is carried out in hot ethanol, with sodium ethoxide, NaCH CH,0, as the reagent. Some Cl I3CH2CH=CH2 is also formed in this reaction. 

Recently the first examples of complexes between the four-membered amidinato-Group 13 metal(l) heterocycles and transition metal fragments were reported. Complexes of the type CpFe(CO)2[M(X) But(NR)2 ] (M = Al, Ga, In X = Cl, Br R = Pri, Gy) were formed in salt-elimination reactions between Na[CpFe(CO)2] and [But(NR)2]MX2. A series of complexes between the four-membered amidinato-Group 13 metal(l) heterocycles and Group 10 metal(O) fragments have been prepared according to Scheme 35. ... 

It is possible to take advantage of the differing characteristics of the periphery and the interior to promote chemical reactions. For example, a dendrimer having a non-polar aliphatic periphery with highly polar inner branches can be used to catalyse unimolecular elimination reactions in tertiary alkyl halides in a non-polar aliphatic solvent. This works because the alkyl halide has some polarity, so become relatively concentrated within the polar branches of the dendrimer. This polar medium favours the formation of polar transition states and intermediates, and allows some free alkene to be formed. This, being nonpolar, is expelled from the polar region, and moves out of the dendrimer and into the non-polar solvent. This is a highly efficient process, and the elimination reaction can be driven to completion with only 0.01 % by mass of a dendrimer in the reaction mixture in the presence of an auxiliary base such as potassium carbonate. 

The pentacoordinate molecules of trigonal bipyramidal form, like PF5, are a very nice example for the study of the formal properties of stereoisomerizations. They are characterized by an appreciable nonrigidity and they permit the description of kinetics among a reasonable number of isomers, at least in particular cases (see below). Therefore the physical and chemical properties of these molecules have been thoroughly investigated in relation to stereoisomerization. Recent reviews may be found in the literature on some aspects of this problem. Mislow has described the role of Berry pseudorotation on nucleophilic addition-elimination reactions and Muetterties has reviewed the stereochemical consequences of non-rigidity, especially for five- and six-atom families as far as their nmr spectra are concerned. 

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