Heavy ketones synthesis

Although some review articles are now available on the synthesis of heavy ketones," they are restricted to dealing with some selected elements, especially silicon and germanium. We delineate here a more general account of the whole chemistry of stable double bonds between heavier Group 14 and Group 16 elements [i.e., RR M=X (M = Si, Ge, Sn, Pb X = O, S, Se, Te)]. 

The successful synthesis and isolation of a series of heavy ketones (r r2M = X M = Si, Ge, Sn, Pb X = S, Se, Te) using kinetic stabilization (vide infra) and the remarkable progress in the field of theoretical calculations prompted chemists to perform computational calculations on the a and it bond energies as well as on the single and double bond lengths of H2M=X at the higher level of theory.14... 

A variety of preparation methods are known for transient germanium-chalcogen double bond species some of them seemed to be useful also for the synthesis of kinetically stabilized systems. Indeed, the reaction of a germylene with an appropriate chalcogen source was found to be one of the most versatile and general methods for the synthesis of stable germanium-containing heavy ketones (Scheme 21). 

In view of these situations, synthesis and isolation of a kinetically stabilized germanetellone are significant not only for clarifying the character of the Ge-Te double bond by itself but also for elucidating the properties of germanium-containing heavy ketones systematically. 

Synthesis of Alkyl,aryl-Substituted Germanium-Containing Heavy Ketones... 

Heavy ketones have been synthesized by several synthetic methods shown in Scheme 19 (i) the reaction of divalent group 14 element species with chalcogen sources, (ii) the reaction of dihydrometallanes with chalcogen sources, (iii) the dechalcogenation of metal polychalcogenides, (iv) the reaction of dilithiomet-allanes with dihalochalcogenides, and (v) substitution of the chloro group of heavy acyl chlorides. The methods used for the synthesis of heavy ketones are summarized in Tables 3-5. 

The method (i) can be applied to the synthesis of almost all heavy ketones (Tables 3-5). Silanethiones and a silaneselone stabilized by the coordination of a nitrogen group have been synthesized by the method (ii) (Table 4). The method (iii) is effective to the synthesis of kinetically stabilized tricoordinate heavy ketones, although it cannot be applied to the synthesis of double-bond compounds between heavier group 14 elements and tellurium due to the instability of polytellurides (Table 3). The method (iv) can be used only when the unique dilithiometallanes can be generated (Table 3). The synthesis of heavy ketones by the method (v) demands the isolation of the corresponding heavy acyl chlorides as stable compounds (Table 5). 

Production of maleic anhydride by oxidation of / -butane represents one of butane s largest markets. Butane and LPG are also used as feedstocks for ethylene production by thermal cracking. A relatively new use for butane of growing importance is isomerization to isobutane, followed by dehydrogenation to isobutylene for use in MTBE synthesis. Smaller chemical uses include production of acetic acid and by-products. Methyl ethyl ketone (MEK) is the principal by-product, though small amounts of formic, propionic, and butyric acid are also produced. / -Butane is also used as a solvent in Hquid—Hquid extraction of heavy oils in a deasphalting process. 

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