Dodecane-, lithium

Jones and colleagues have prepared 1,4-dicarbonyl compounds by conjugate additions of enolate and related anions to a,P-unsaturated sulfoxides [80,81]. For example, the lithium enolate of acetone dimethylhydrazone (83), in the presence of dimethyl sulfide-copper(I) bromide complex, underwent conjugate addition to 2-phenylsulfinyloct-l-ene (82). Quenching the reaction mixture with dimethyl disulfide gave the doubly protected 1,4-diketone derivative (84), which, on sequential hydrolysis with copper(II) acetate and trifluoroacetic acid gave the dodecane-2,5-dione (85) as the product in 54% yield from (82) (Scheme 5.27). Other examples of the addition of enolate-type species to a,p-unsaturated sulfoxides have also been reported [82.83]. 

A slurry of 2 (0.2472 g, 35.6 mmol of lithium 5.9647 g, 46.5 mmol of naphthalene 1.9765g, 15.4mmol of cobalt chloride) was prepared, and the product washed once with glyme. It was then reacted in 25 ml of glyme with 4.5955 g (22.5 mmol) of phenyl iodide. Quenches were taken periodically by withdrawing 1 ml samples and treating the samples with two drops of IM HCl. The samples were then quantitatively analyzed by GC with use of -dodecane as an internal standard and application of response factor corrections. After 1 min, 59% of the phenyl iodide remained. After 20h (last 3h at reflux), 61% remained. No biphenyl was observed until the reaction mixture was refluxed, after which an 11% yield of that compound was found. 

Percec V, Heck JA, Tomazos D, Ungar G (1993) The influence of the eomplexatimi of sodium and lithium triflate on the self-assembly of tubular-supramolecular architectures displaying a columnar mesophase based on taper-shaped monoesters of oligoethylene oxide with 3,4,5-tris[p-(n-dodecan-l-yloxy)benzyloxy]benzoic acid and of their polymethacrylates. J Chem Soc Perkin Trans 2(12) 2381-2388. doi 10.1039/P29930002381... 

Lee et al. (1968) studied the synergistic use of trioctylphosphine oxide (TOPO) again as the adduct former, but with the chelating agent dibenzoylmethane. Their individual extraction coefficients from 0.02 M Li or 0.88 M KCl when in a 0.1 M KOH solution were 0.025 and 0.010, respectively, and 131 for a mixture of LiCl and KCl. When in p-xylene as a solvent carrier, D was 82.4, in carbon tetrachloride 68.5 and dodecane 49.1, while other solvents greatly reduced the lithium extraction. The selectivity factors ( >u//>Na) for Li/Na were 570 and Li/Cs 12,400 in 3 M NH4OH solutions, and the lithium extraction was only effective at pH values above about 10. 

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