Butyl chloride, olefin elimination from

Simple alkyl chlorides decompose smoothly over a suitable catalyst to an equilibrium mixture of olefinic hydrocarbon and hydrogen chloride for instance, isobutene in equilibrium with t-butyl chloride [33], propylene with isopropyl chloride and ethylene with ethyl chloride [34]. Catalysts were glass wool and a mixture of nickel, cobalt and cadmium chlorides. When a metal is substituted for the chloride catalyst and the equilibrium is disturbed by removal of the olefin, the net result observed is reaction of the HCl with the metal. Mould, Silver and Syrett [35] heated solutions of organochlorine compounds for 6 hours at 473 K in the presence of steel filings which were then washed free of oil and analyzed for inorganic chloride the reactivities thus found are shown in Table 11-9. The order of reactivity is what an organic chemist would expect from reactions involving the elimination of HCl. The thermodynami-... 

The formation of these compounds has been rationalized according to Scheme 6. The reaction of Os (E )-CH=C 11 Ph C1 (C())( P Pr3)2 with n-BuLi involves replacement of the chloride anion by a butyl group to afford the intermediate Os (/i> CH=CHPh ( -Bu)(CO)(P Pr3)2, which by subsequent hydrogen (3 elimination gives OsH ( >CI I=CHPh (CO)( P Pr3)2. The intramolecular reductive elimination of styrene from this compound followed by the C—H activation of the o-aryl proton leads to the hydride-aryl species via the styrene-osmium(O) intermediate Os r 2-CH2=CHPh (CO)(P Pr3)2. In spite of the fact that the hydride-aryl complex is the only species detected in solution, the formation of OsH ( )-CH=CHPh L(CO)(P Pr3)2 and 0s ( )-CH=CHPh (K2-02CH)(C0)(P,Pr3)2 suggests that in solution the hydride-aryl complex is in equilibrium with undetectable concentrations of OsH ( )-CH=CHPh (CO)(P,Pr3)2. This implies that the olehn-osmium(O) intermediate is easily accessible and can give rise to activation reactions at both the olefinic and the ortho phenyl C—H bonds of the... 

Treatment of perfluoro-t-butylmercuric chloride with perfluoropropene in the presence of potassium fluoride (in DMF at 50 °Q yields bis(perfluoro-isopropyl)mercury via displacement of perfluoro-t-butyl anion. Potassium fluoride-initiated reaction of the mercurials (RF)jHg [Rf = (CFgljCF or (CFg)3C] with sulphur in hot DMF gives the corresponding mercaptides [(RFS)aHg]. Displacement of Rf from these mercurials with sodium iodide in a dipolar aprotic solvent occurs readily and, in the absence of electrophilic traps, perfluoro-olefin formation (CFg-CXiCFg X = F or CF3) occurs via j3-elimination of fluoride ion. ... 

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