Double-bond shifts

If a double-bond shift occurs, the number of aldehyde isomers is increased. 

An extremely wide variety of catalysts, Lewis acids, Brmnsted acids, metal oxides, molecular sieves, dispersed sodium and potassium, and light, are effective (Table 5). Generally, acidic catalysts are required for skeletal isomerization and reaction is accompanied by polymerization, cracking, and hydrogen transfer, typical of carbenium ion iatermediates. Double-bond shift is accompHshed with high selectivity by the basic and metallic catalysts. 

Halogenated Butyl Rubber. Halogenation at the isoprene site ia butyl mbber proceeds by a halonium ion mechanism leading to a double-bond shift and formation of an exomethylene alkyl haUde. Both chlorinated and brominated mbber show the predominate stmcture (1) (>80%), by nmr, as described eadier (33,34). Halogenation of the unsaturation has no apparent effect on the isobutylene backbone chains. Cross-linked samples do not crystallize on extension due to the chain irregularities introduced by the halogenated isoprene units. 

Clearly, in the case of (66) two amide tautomers (72) and (73) are possible, but if both hydroxyl protons tautomerize to the nitrogen atoms one amide bond then becomes formally cross-conjugated and its normal resonance stabilization is not developed (c/. 74). Indeed, part of the driving force for the reactions may come from this feature, since once the cycloaddition (of 72 or 73) has occurred the double bond shift results in an intermediate imidic acid which should rapidly tautomerize. In addition, literature precedent suggests that betaines such as (74) may also be present and clearly this opens avenues for alternative mechanistic pathways. 

A peculiar dehydrofluorination occurs when tnfluoromethyl dihydropyndine derivatives are treated with organic bases A double-bond shift and a hydrogen migration convert one tnfluoromethyl group to a difluoromethyl group and aromatize the ring [22] (equation 20)... 

Enamines in which the double-bond shift is sterically prevented afford only the ammonium salts. Their spectra in the C=C stretching vibration region does not differ greatly from that of the free amine spectrum (171). For example, neostrychnine (159) has vc c 1666 cm and its perchlorate at 1665 cm . Salts of quinuclideine (92) and the polycyclic alkaloid trimethylconkurchine have similar properties. 

Both the oxygen and sulfur atoms have two lone pairs while the C/ carbon has ar unpaired electron, and in both cases the double bond shifts from the two carbor atoms to the carbon and the substituent. In acetyl radical, the electron density i centered primarily on the C2 carbon, and the spin density is drawn toward the lattei more than toward the former. In contrast, the density is more balanced between thf two terminal heavy atoms with the sulfur substituent (similar to that in allyl radical with a slight bias toward the sulfur atom. These trends can be easily related to th< varying electronegativity of the heavy atom in the substituent. 

Slow double-bond shifts and little skeletal isomerization H-transfer is minor and nonselective for tertiary olefins only small amounts of aromatics formed from aliphatics at 932°F (500°C)... 

Rapid double-bond shifts, extensive skeletal isomerization, H-transfer is major and selective for tertiary olefins large amounts of aromatics formed from aliphatics at 932°F (50t) O... 

Electrophilic Substitution Accompanied by Double-Bond Shifts... 

This mechanism is exactly analogous to the allylic rearrangement mechanism for nucleophilic substitution (p. 421). The UV spectra of allylbenzene and 1-propenylbenzene in solutions containing NH2 are identical, which shows that the same carbanion is present in both cases, as required by this mechanism. The acid BH protonates the position that will give the more stable product, though the ratio of the two possible products can vary with the identity of BH". It has been shown that base-catalyzed double-bond shifts are partially intramolecular, at least in some cases. The intramolecularity has been ascribed to a conducted tour mechanism (p. 766) in which the base leads the proton from one carbanionic site to the other ... 

No matter which of the electrophilic methods of double-bond shifting is employed, the thermodynamically most stable alkene is usually formed in the largest amount in most cases, though a few anomalies are known. However, there is another, indirect, method of double-bond isomerization, by means of which migration in the other direction can often be carried out. This involves conversion of the alkene to a borane (15-16), rearrangement of the borane (18-11), oxidation and hydrolysis of the newly formed borane to the alcohol (12-28), and dehydration of the alcohol (17-1) ... 

Propargylic acetates, halides, and sulfonates usually react with a double-bond shift to give allenes.34 Some direct substitution product can be formed as well. A high ratio of allenic product is usually found with CH3Cu-LiBr-MgBrI, which is prepared by addition of methylmagnesium bromide to a 1 1 LiBr-Cul mixture.35... 

Epoxides with alkenyl substituents undergo alkylation at the double bond with a double-bond shift accompanying ring opening, leading to formation of allylic alcohols. 

The Stille coupling reaction is very versatile with respect to the functionality that can be carried in both the halide and the tin reagent. Groups such as ester, nitrile, nitro, cyano, and formyl can be present, which permits applications involving masked functionality. For example, when the coupling reaction is applied to l-alkoxy-2-butenylstannanes, the double-bond shift leads to a vinyl ether that can be hydrolyzed to an aldehyde. 

Allylic boranes such as 9-allyl-9-BBN react with aldehydes and ketones to give allylic carbinols. The reaction begins by Lewis acid-base coordination at the carbonyl oxygen, which both increases the electrophilicity of the carbonyl group and weakens the C-B bond to the allyl group. The dipolar adduct then reacts through a cyclic TS. Bond formation takes place at the 7-carbon of the allyl group and the double bond shifts.36 After the reaction is complete, the carbinol product is liberated from the borinate ester by displacement with ethanolamine. Yields for a series of aldehydes and ketones were usually above 90% for 9-allyl-9-BBN. 

Alkylation of cyclohexylidinephenylacetonitrile (89) with 2-chloroethyldimethylamine, using NaH as base, gives nitrile 90. Note that the product results from alkylation of the enolate which results in a double bond shift. This product (90) is transformed to unsaturated amine 91 on heating with HC1. 

The hydrogen atoms are as a whole antibonding with the remaining part in LU MO, so that the charge-transfer to LU from the base easily comes to release these hydrogens. Similar double-bond shift reactions have also been treated 133>. 

Olefins react secondarily for isomerization and hydrogenation (on cobalt sites that are not active for chain growth lower scheme in Figure 9.15). There is a first reversible H-addition (at the alpha- or beta-C-atom of the double bond) to form an alkyl species, and a slow irreversible second H-addition to form the paraffin (lower scheme in Figure 9.15). Thus, double-bond shift and double-bond hydrogenation are interrelated by a common intermediate to produce olefins with internal double bonds or paraffins from the primary FT alpha-olefins. Experimental results1018 are presented in Figures 9.16 and 9.17. 

FIGURE 9.17 Contents of a-olefins in carbon number fractions as referring to secondary double-bond shift. 

With iron, almost no secondary olefin double-bond shift and double-bond hydrogenation are possible (see Figures 9.16, left, and 9.17). Consequently, in... 

Not all acids are equally active isomerization catalysts. With zeolite H-BEA, nearly identical selectivities are achieved when the feed is 1-butene instead of 2-butene (48). In general, even mildly acidic zeolites are excellent catalysts for double-bond shift isomerization. Sulfuric acid also produces nearly identical... 

As to the all-trans yfi-carotene content, the synthetic and fungal preparations are by far the purest [8]. The products from algae and palm oil contain substantial amounts of as-/ -carotene (the central double bond has a cis configuration) and of a-carotene (ring double bond shifted one position). The DSM fermentation process seems to be in a good position here. 

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