Dehydrohalogenation elimination

Dehydrohalogenations (elimination of HX) can in turn be effected by passing the halide over a solid base such as vacuum-dried hot KOH or f-BuOK adsorbed on some carrier material. Recently, Billups et al. showed that elimination of Mc3SiBr may even be effected at room temperature over solid CsF. Several very interesting strained alkenes have been generated by such techniques, but although these techniques would lend themselves very well for interfacing to matrix isolation we know of no example where this has been achieved. 

Debromination is formally a reduction because a molecule of Br2 (an oxidizing agent) is removed. The reaction with iodide takes place by the E2 mechanism, with the same geometric constraints as the E2 dehydrohalogenation. Elimination usually takes place through an anti-coplanar arrangement, as shown in Mechanism 7-3. Acetone serves as a convenient solvent that dissolves most alkyl halides and sodium iodide. 

Alkyl halides are converted into alkenes by dehydrohalogenation elimination of the elements of hydrogen halide. Dehydrohalogenation involves removal of the halogen atom together with a hydrogen atom from a carbon adjacent to the one... 

In the substitution reaction, the nucleophile replaces the halogen X. In the elimination reaction, the nucleophile acts as a base and removes a proton from carbon-2, the carbon next to the one that bears the halogen X. The halogen X and the hydrogen from the adjacent carbon atom are eliminated, and a new bond (a pi bond) is formed between carbons-1 and -2 The symbol E is used to designate an elimination process. Since in this case a hydrogen halide is eliminated, the reaction is called dehydrohalogenation. Elimination reactions provide a useful way to prepare compounds with double or triple bonds. 

E2 (dehydrohalogenation) elimination to form the most strong base... 

Dehydrohalogenation is the loss of a hydrogen and a halogen from an alkyl halide It IS one of the most useful methods for preparing alkenes by p elimination... 

The regioselectivity of dehydrohalogenation of alkyl halides follows the Zaitsev rule p elimination predominates m the direction that leads to the more highly substi tuted alkene... 

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... 

Double dehydrohalogenation of vicinal dihalides (Section 9 7) Dihalides in which the halogens are on adjacent carbons undergo two elimination processes analogous to those of gemmal dihalides... 

Other Syntheses. Acryhc acid and other unsaturated compounds can also be made by a number of classical elimination reactions. Acrylates have been obtained from the thermal dehydration of hydracryhc acid (3-hydroxypropanoic acid [503-66-2]) (84), from the dehydrohalogenation of 3-halopropionic acid derivatives (85), and from the reduction of dihalopropionates (2). These studies, together with the related characterization and chemical investigations, contributed significantly to the development of commercial organic chemistry. 

Preparation. Thermal elimination of HCl from l-chloro-l,l-difluoroethane (HCFC-142b) [75-68-3] is the principal industrial route to VDF covered by numerous patents (8—19). Dehydrohalogenation of l-bromo-l,l-difluoroethane (20), or 1,1,1-trifluoroethane (HFC-143a) (21—25), or dehalogenation of l,2-dichloro-l,l-difluoroethane (26—28) are investigated alternative routes (see Fluorine compounds, organic-fluorinated aliphatic compounds). 

We have previously seen (Scheme 2.9, enby 6), that the dehydrohalogenation of alkyl halides is a stereospecific reaction involving an anti orientation of the proton and the halide leaving group in the transition state. The elimination reaction is also moderately stereoselective (Scheme 2.10, enby 1) in the sense that the more stable of the two alkene isomers is formed preferentially. Both isomers are formed by anti elimination processes, but these processes involve stereochemically distinct hydrogens. Base-catalyzed elimination of 2-iodobutane affords three times as much -2-butene as Z-2-butene. 

No extensive investigation of mechanism has been undertaken for any of the methods of dehydrohalogenation described. 17-Bromo-20-ketones appear to undergo preferential /ran -elimination. 2-Halo-3-ketones suffer predominant loss of the la (axial) hydrogen, but the geometry of bromine loss is not known. 7>fl -diaxial elimination has sometimes been assumed in configurational assignments, but this is not necessarily correct (see ref. 6). 

By the same token, in base-promoted E2 dehydrohalogenations, the rate of elimination of the halogen as a halide ion is expected to be I > Br > Cl F This element effect has indeed been documented in many instances, a few examples of which are listed in Table I... 

P Elimination (Section 5.8) Reaction in which a double or triple bond is formed by loss of atoms or groups from adjacent atoms. (See dehydration, dehydrogenation, dehydro-halogenation, and double dehydrohalogenation.)... 

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. 

The alkylation reaction is limited to the use of primary alkyl bromides and alkyl iodides because acetylide ions are sufficiently strong bases to cause dehydrohalogenation instead of substitution when they react with secondary and tertiary alkyl halides. For example, reaction of bromocyclohexane with propyne anion yields the elimination product cyclohexene rather than the substitution product 1-propynylcyclohexane. 

AJkynes can be made by dehydrohalogenation of vinylic halides in a reaction that is essentially an E2 process. In studying the stereochemistry of this elimination, it was found that (Z)-2-chloro-2-butenedioic acid reacts 50 times as fast as the corresponding isomer. What conclusion can you draw about the stereochemistry of eliminations in vinylic halides How does this result compare with eliminations of alkyl halides ... 

There have been a number of different synthetic approaches to substituted PTV derivatives proposed in the last decade. Almost all focus on the aromatic ring as the site for substitution. Some effort has been made to apply the traditional base-catalyzed dehydrohalogenation route to PTV and its substituted analogs. The methodology, however, is not as successful for PTV as it is for PPV and its derivatives because of the great tendency for the poly(u-chloro thiophene) precursor spontaneously to eliminate at room temperature. Swager and co-workers attempted this route to synthesize a PTV derivative substituted with a crown ether with potential applications as a sensory material (Scheme 1-26) [123]. The synthesis employs a Fager condensation [124] in its initial step to yield diol 78. Treatment with a ditosylate yields a crown ether-functionalized thiophene diester 79. This may be elaborated to dichloride 81, but pure material could not be isolated and the dichloride monomer had to be polymerized in situ. The polymer isolated... 

The knowledge of the valence tautomerization of benzene oxides to oxepins12 prompted several groups to synthesize oxepins by dehydrohalogenation of 7-oxabicyclo[4.1.0]heptane derivatives. Numerous examples have been described for the base-catalyzed elimination of hydrogen bromide from the 3,4-dibromo-7-oxabicyclo[4.1.0]heptane system. The reaction products are usually obtained as mixtures of oxepin 1 and benzene oxide 2. The 2,7-bis(hydroxy-methyl)oxepin 1 p obtained by this route can be converted to the 2,7-dicarbaldehyde with man-ganese(IV) oxide.23... 

The dehydrohalogenation reaction has been extended to benzannulated oxepins. Elimination of hydrogen bromide from 3-bromo-4-phenyl-2,3-dihydro-l-benzoxepin with 1,5-diazabicyclo-[4.3.0]non-5-ene gives 4-phenyl-1-benzoxepins 15a15 and 15b16 in low yield. 

Hydrogen bromide is eliminated from 10,11-dibromo-l 0,1 l-dihydrodibenz[7>,/]oxepin with potassium tert-butoxide at room temperature to give 10-bromodibenz[i,/]oxepin (17a).160161 When the elimination reaction was performed in boiling toy-butanol the yield increased from 58 to 92%.261 Dehydrohalogenation of 10-chloro-2,3-dimethoxy-10,ll-dihydrodi-benz[/),/]oxepin afforded 2,3-dimethoxydibenz[6,/]oxepin (17b) in 52% yield.162... 

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