Lithium unsaturated hydrocarbons

A broad scope is documented for the preparation of suspensions of 2-alkenylpotassium lithium toV-butoxide complexes from unsaturated hydrocarbons by means of butyllithium/ potassium /erf-butoxidc (Schlosser Lochmann base LICKOR reagents )38-45,432 456. Examples are given in Section D.1.3.3.3.3.2.1. 

III. LITHIUM COMPLEXES OF UNSATURATED HYDROCARBONS A. The Li(C2H2)i,2 and LI2C2H2 Compounds... 

A series of investigations was performed on the structure of the complexes formed by unsaturated hydrocarbons with lithium dissolved in a solid argon matrix. The structures proposed for these complexes are based on assignment of the perturbations observed in the IR spectra of the free hydrocarbons and their isotopically enriched species. 

Recently, it was found that the triangular skeleton can be easily destroyed in reactions which most likely include an electron transfer step. For example, the reduction of gem-dichloro[3]triangulane 66 with lithium in f-butanol (which is the standard method for the synthesis of cyclopropanes) unexpectedly gave 50% of unsaturated hydrocarbon (equation 45)88. An even more complex mixture of hydrogenolysis products was obtained in the reduction of dichloride 67. ... 

In 1968 Peterson published his results about the reaction of a-silylated carbanions with carbonyl compounds to achieve /3-hydroxyalkyl-silanes. He found that instantaneous elimination affords unsaturated hydrocarbons ( Peterson olefmation )180 Thus, the lithiated trimethyl-benzyl-silane (274) plus benzophenone (135) give via lithium l,l,2,-triphenyl-2-TMS-ethanolate (275) 1,1,2-triphenyl-ethene (276)180 ... 

Note Highly polar solvent sweet, ethereal odor soluble in water flammable, burns with a luminous flame highly toxic by ingestion, inhalation and skin absorption miscible with water, methanol, methyl acetate, ethyl acetate, acetone, ethers, acetamide solutions, chloroform, carbon tetrachloride, ethylene chloride, and many unsaturated hydrocarbons immiscible with many saturated hydrocarbons (petroleum fractions) dissolves some inorganic salts such as silver nitrate, lithium nitrate, magnesium bromide incompatible with strong oxidants hydrolyzes in the presence of aqueous bases and strong aqueous acids. Synonyms methyl cyanide, acetic acid nitrile, cyanomethane, ethylnitrile. 

G. Tsitsishvili Interaction of LP with molecules of unsaturated hydrocarbons and CO is very sensitive to the presence of water molecules in a zeolite and to column temperature increase. On a zeolite containing hydrophilic lithium cations, with most of the substitutions corresponding to Li" in open positions Sn and Sm, the adsorption heat of the studied compounds is lower than with the sodium form. In lithium forms with a high percentage of lithium ions, the Li" in nonhydrated positions influence adsorbate molecules, causing an increase of adsorption heat in comparison with NaX zeolite. Migration of Li" ions from Si to other positions is also possible. 

Whereas alkylphosphonic diesters react readily with lithium or organomagnesium reagents with the formation of the metallated phosphonate carbanions, the reactions between such esters and the metals themselves result, by contrast, in dealkylation of the ester groups involving both C-0 and P-0 cleavage traces of unsaturated hydrocarbons, even including alkynes and aromatics, are thought to be formed by radical-induced reactions. 

Liquid Elh.r-like odor Poisonous Burns with a lumi nous name Flash pt 12 8 C <55 F) dl 0.78745. d 0 7l38 mp —45. bpw, 81 6° njf I 34604. ng 1.33934 Dido.Inc constant al 20° — 38.8. Surface tension at 20" - 29 04 dyncs/cm. Misc with water, methannl. melhyl acetate, elhyl acetate, acetone, ether, acetamide solutions, chlornform. carbon tetrachloride, ethylene chloride and many unsaturated hydrocarbons. Immiscible with many saturated hydrocarbons (petroleum fractions). Dissolves some in organic salts, eg., silver nitrate, lithium nitrate, magnesium bromide Constant boiling mixture with water contains 16% HjO and bp 76° LDm orally in rats 3800 mg/kg (Smyth)... 

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