Subject alkane formation

Formation of a C-C bond to a cyclopropane ring at the expense of a C-Si bond is also achieved by acetylation of trimethylsilylcyclopropanes. Cyclopropyltrimethylsilane was converted to acetylcyclopropane (5) in 60% yield when treated with a mixture of acetyl chloride and aluminum(III) chloride in dichloromethane. "- Other compounds subjected to the same reaction conditions involve various (n- -3)-trimethylsilylbicyclo[n.l.0]alkanes. Some of these compounds undergo ring opening and give no cyclopropane whereas others afford complex reaction mixtures. Thus, when cxo-6-trimethylsilylbicyclo[3.1.0]hexane was acetylated as outlined above a 55 35 6 4 mixture of 6-acetylbicyclo[3.1.0]hexane (6), l-(2-chlorocyclopen-tyl)-propan-2-one (7), 2-acetyl-l-chlorocyclohexane (8), and l-(cyclopent-l-enyl)propan-2-one (9), respectively, was isolated in 94% total yield. 

Epoxides were involved as intermediates when 1-cyclopropyl-1-[tris(methylsulfanyl)meth-yl]alkan-l-ols were subjected sequentially to butyllithium (1 equivalent) and CUCIO4 4MeCN (2 equivalents) and underwent rearrangement to thioesters with the carbonyl /i to the cyclopropane ring, e.g. formation of 7. A l-cyclopropyl-2-diazoalkanol reacted in a similar fashion on treatment with rhodium(II) acetate. ... 

The mechanism of stoichiometric CH borylation by complexes of this type has been the subject of several recent studies designed, in particular, to probe the underlying factors responsible for the unique ability of boryl systems to bring about alkane functionalization [37-39,50,51]. The thermodynamics of B-C bond formation have previously been noted to be favourable [50,51], and... 

The photochemical aspects of carbonyl photochemistry remain important subjects of research. Wagner and Thomas have used CIDNP to elucidate radical formation from a,a,a-trifluoroacetophenone. Irradiation of benzophenone and its derivatives in the presence of molecules with abstractable hydrogen atoms can give rise to intensely fluorescent compounds. This effect may interfere with the observation of nanosecond-domain kinetics.Quantum yields and kinetic isotope effects in nanosecond flash studies of the reduction of benzophenone by aliphatic amines have been measured by Inbar et Rate constant data are given in Tables 13 and 14. Winnik and Maharaj have studied the reaction of benzophenone with n-alkanes through hexane to hexatriacontane is 3.9 0.2kcal for all chain lengths.The effects of substituents on the benzophenone on these reactions have also been examined. The reactions of phenylacetophenone when used as polymerization initiator have been reviewed by Merlin and Fouassier. ... 

---