Rearrangement of Halides

In Chapter 4 you learned that carbocations could be captured by halide anions to give alkyl halides In the present chapter a second type of carbocation reaction has been introduced—a carbocation can lose a proton to form an alkene In the next section a third aspect of carbocation behavior will be described the rearrangement of one carbo cation to another... 

Dehydrohalogenation of alkyl halides (Sections 5 14-5 16) Strong bases cause a proton and a halide to be lost from adjacent carbons of an alkyl halide to yield an alkene Regioselectivity is in accord with the Zaitsev rule The order of halide reactivity is I > Br > Cl > F A concerted E2 reaction pathway is followed carbocations are not involved and rearrangements do not occur An anti coplanar arrangement of the proton being removed and the halide being lost characterizes the transition state... 

The currently accepted mechanism for the Favorskii rearrangement of dihalo ketones involves a cyclopropanone intermediate formed by loss of HX. This is followed by attack of alkoxide synchronous with cyclopropanone fragmentation and departure of halide ion to form the unsaturated ester... 

The rearrangement of arylsubstituted 1,4-dithiadienes, obtained from the Buntes salts derived from phenacyl halides,offers a... 

Yet a final limitation to the Friedel-Crafts reaction is that a skeletal rearrangement of the alkyl carbocation electrophile sometimes occurs during reaction, particularly when a primary alkyl halide is used. Treatment of benzene with 1-chlorobutane at 0 °C, for instance, gives an approximately 2 1 ratio of rearranged (sec-butyl) to unrearranged (butyl) products. 

Several applications of this methodology to the synthesis of racemic a-substituted allylboronates are provided in refs 2-4. It is noted that reagents 6 (X = Br) and 7 are unstable with respect to ailyl rearrangement of the halide ions, either thermally or in tile presence of halide ion, and so care must be exercised in the preparation and handling of a-haloallvlboronates. 

R2NC1, 91, 92 phenyl acetate, Fries rearrangement of, 475 phenyacetyl halides, acylation by, 173 2-phenylbenzoic acid, cycliacylation, 185 phenyl ethers, alkylation of, 149 —, bromination of, 130 —, hydrogen exchange with, 260 —, rearrangement of, 476 phenyl ethyl mercury, mercuridemercuration of, 359, 360... 

Rearrangement of hydroxamic acids and acyl halides (Lossen)... 

Pyrolysis of carboxylic acids Dehydrohalogenation of acyl halides Dehalogenation of a-halo acyl halides Rearrangement of diazo ketones (Wolff)... 

Metallocarboranes and metalloboranes, discussed in 6.5.4, may be prepared from metal halides and carborane anions. Selected examples of complexes formed by thermal—or otherwise—induced polyhedral rearrangements of existing metallocarboranes are given in a few equations, and some other individual compounds are listed in tables. 

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