Potassium-Graphite

Potassium Graphite. Potassium, mbidium, and cesium react with graphite and activated charcoal to form intercalation compounds CgM, C24M, C gM, C gM, and C qM (61,62). Potassium graphite [12081 -88-8] 8 P gold-colored flakes, is prepared by mixing molten potassium with graphite at 120—150°C. 

With special techniques for the activation of the metal—e.g. for removal of the oxide layer, and the preparation of finely dispersed metal—the scope of the Refor-matsky reaction has been broadened, and yields have been markedly improved." The attempted activation of zinc by treatment with iodine or dibromomethane, or washing with dilute hydrochloric acid prior to use, often is only moderately successful. Much more effective is the use of special alloys—e.g. zinc-copper couple, or the reduction of zinc halides using potassium (the so-called Rieke procedure ) or potassium graphite. The application of ultrasound has also been reported. ... 

Allylic sulfones and a, /5-unsaturated sulfones are known to be in equilibrium314-319. Allylic sulfones, such as 242, isomerize to a, /5-unsaturated sulfones 243 upon treatment with a catalytic amount of potassium t-butoxide in dry THF. The a, /5-unsaturated sulfones can be converted to the corresponding olefins upon desulfonation with sodium amalgam320 or aluminium amalgam294,321. Since treatment of allylic sulfones with potassium-graphite gives 2-alkenes, alkylation of allylic sulfones and subsequent desulfonation is a useful process for the synthesis of olefins, as shown in Scheme 6. 

A particular case of a [3C+2S] cycloaddition is that described by Sierra et al. related to the tail-to-tail dimerisation of alkynylcarbenes by reaction of these complexes with C8K (potassium graphite) at low temperature and further acid hydrolysis [69] (Scheme 24). In fact, this process should be considered as a [3C+2C] cycloaddition as two molecules of the carbene complex are involved in the reaction. Remarkable features of this reaction are (i) the formation of radical anion complexes by one-electron transfer from the potassium to the carbene complex, (ii) the tail-to-tail dimerisation to form a biscarbene anion intermediate and finally (iii) the protonation with a strong acid to produce the... 

Potassium graphite reduction of the dichloro precursors under an atmosphere of N2 in THF according to Scheme 101 allowed access to new families of Group 4 bimetallic "side-on-bridged" dinitrogen complexes... 

HEAVY ALKYNE ANION RADICALS The Only example of Compounds of this type, the anion radical of the valence isomer of distannyne 51-K, was recently synthesized by Power by the reduction of chlorostannylene 52 with potassium graphite in THF (Scheme 2.39). ... 

The story of the heavy analogs of 6jt-electron cyclopentadienyl anions has culminated in the latest synthesis of a compound containing three heavier group 14 elements (two Si and one Ge) in the ring. This aifionic species 69 Li+ was prepared by the reduction of the disilagermacyclopentadiene precursor 70 with potassium graphite KCg followed by the exchange of countercation from K+ to Li+ by treatment with LiBr (Scheme 2.66). ... 

Use of potassium graphite or caesium graphite to generate methylborylene is uneventful, while use of sodium-potassium alloy (1 5 mol) caused an explosion in 2 out of 5 attempts. 

Catalysts and reaction conditions used are generally similar to those used for olefin isomerization. Catalysts reported are sodium-organosodium catalysts prepared in situ by reaction of a promoter such as o-chloro-toluene or anthracene with sodium 19-24), alkali metal hydrides 20,21), alkali metals 22), benzylsodium 26), and potassium-graphite 26). These catalysts are strong bases that can react with alkylaromatics to replace a benzylic hydrogen [Reaction (2)]. 

Hydrogenation using Raney nickel is carried out under mild conditions and gives cis alkenes from internal alkynes in yields ranging from 50 to 100% [356, 357, 358, 359, 360]. Half hydrogenation of alkynes was also achieved over nickel prepared by reduction of nickel acetate with sodium borohydride (P-2 nickel, nickel boride) [349,361,362] or by reduction with sodium hydride [49], or by reduction of nickel bromide with potassium-graphite [363]. Other catalysts are palladium on charcoal [364], on barium sulfate [365, 366], on... 

Reduction of a,/3-unsaturated to saturated ketones was further achieved by electrolysis in a neutral medium using copper or lead cathodes (yields 55-75%) [766], with lithium in propylamine (yields 40-65%) [876], with potassium-graphite clathrate CgK (yields 57-85%) [807], and with zinc in acetic acid (yield 87%) [688]. Reduction with amalgamated zinc in hydrochloric acid (Clemmensen reduction) usually reduces both functions [877]. 

Alkene formation can also be achieved using potassium/graphite (C8K) or sodium naphthalenide for reduction.172 The reductant prepared in this way is more efficient at... 

Avdeev VV, Zharikov OV, Nalimova VA, Pal nichenko AV, Semenenko KN (1986) Superconductivity of the layered potassium-graphite compounds CgK and C4K. Pis ma Zh Eksp Teor Fiz 43 376—378... 

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