Unsaturated Alkyl Halides

Unsaturated alkyl halides react first by ir-complexation (141), followed by C-X oxidative addition, probably on matrix warm-up [but see the preceding point 3, and see ref. (81), which suggests that pyrolysis and radical production can occur on the crucible insulating material to cause reaction]. 

Chlordane Octachlorohexahydromethanoindene Dichloroethene, 1,1 Dichloroethene, 1,2 DCE Heptachlor Hexachlorobutadiene Hexachlorocyclopentadiene Tetrachloroethene Perchloroethylene PCE Toxaphene Chlorinated Camphor Trichloroethene Trichloroethylene TCE Unsaturated Alkyl Halides Vinyl Chloride Uranium Vanadium... 

Chlordane Octachlorohexahydromethanoindene under Unsaturated Alkyl Halides... 

Heptachlor under Unsaturated Alkyl Halides Heptanes under Alkanes and Cyclic Alkanes Heterocyclic Nitrogen Compounds Heterocyclic Oxygen Compounds Heterocyclic Sulfur Compounds... 

Heterocyclic Sulfur Compounds with Two or More Rings Hexachlorobenzene under Ring-Substituted Aromatics Hexachlorobutadiene under Unsaturated Alkyl Halides Hexachlorocyclohexane Lindane under Saturated Alkyl Halides Hexachlorocyclopentadiene under Unsaturated Alkyl Halides Hexachloroethane under Saturated Alkyl Halides Hexadecane under Alkanes and Cyclic Alkanes Hexafluoroethane under Saturated Alkyl Halides Hexamethyldisihzane under Silicon Compounds—Other Significant Hexanes under Alkanes and Cyclic Alkanes Hexylamine under Primary Aliphatic Amines and Diamines... 

Tetracblorobenzene under Ring-Substituted Aromatics Tetracbloroethane, 1,1,2,2 under Saturated Alkyl Halides Tetracbloroethene Percbloroethylene PCE under Unsaturated Alkyl Halides Tetracblorophenol under Halophenols... 

Vinyl Chloride under Unsaturated Alkyl Halides Volatile Organic Compounds... 

Keywords active methylene compound, unsaturated alkyl halide, alumina, potassium tert-butoxide, 4,4-bis-functionalized 1,6-diene, 1,6-diyne... 

All the starting materials were very easily prepared in a single-pot operation by treatment of the alkoxy-allene 96 [70] with lithium organocuprate either in Et20 (for the formation of the Z- vinyl copper intermediate Z-97) or in THF (for the formation of the -vinyl copper intermediate -97) and trapping the resulting alkenyl copper E- and Z-97 with different unsaturated alkyl halides to give 98a-j (Scheme 35) [71]. 

These reactions turned out to be preparatively very useful since they allow the performance of radical cyclization reactions but produce an organozinc halide as a final product (Scheme 9-33) [65-70]. The treatment of an unsaturated alkyl halide 36 (X = Br, I) with a palladium(O) or nickel(O) complex produces, via a one-electron transfer [72], a paramagnetic nickel(I) or palladium(I) salt MLj,(X) (M = Ni, Pd) and a radical 37 which undergoes a smooth cyclization reaction and produces, after recombination with the transition-metal moiety, the nickel(ll) or palladium(II) species 38. After transmetallation with a zinc(II) salt, a stable organozinc cyclopentylmethyl derivative of type 39 is produced. 

Unsaturated alkyl halides, alcohols and ethers can also act as alkylating agents to give products derived by alkylation at one or more reactive sites. Tsukervanik and Yuldashev examined the reaction of vinyl chloride with toluene and anisole in the presence of AICI3 by varying the ratio of reactants. For example, with anisole (equation 90) two products were formed. The diarylated product resulted from reaction of anisole with both reactive centers in vinyl chloride. 

Alkylation with an unsaturated alkyl halide 149 gives an intermediate 150 ready for the tandem sequence. Simple heating at around 200 °C gives a single diastereoisomer of 151 with the creating of two new chiral centres and a typical tandem yield. 

Good, better than SAN. Degrades in UV. Attacked by strong oxidizing acids. Dissolves in esters, ketones and unsaturated alkyl halides. 

McNeely, S.A., The Photobehavior of Unsaturated Alkyl Halides, Ph.D. dissertation. University of North Carolina, Chapel Hill, 1976. 

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