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NEW HYPNOTICS 243 the green solid. In the Liebermann reaction a dark green color is imparted to the sulfuric acid.

Vol. 66 aliquot of 5 or 10 cc. is withdrawn, by means of a rubber suction bulb connected to a pipet, and hydrolyzed in 10 cc. of distilled water. Titration with standard acid, using phenolphthalein as an indicator, gives the total alkali. Another 5 or 10 cc. aliquot is added to 10 cc. of dry ether containing 1 cc. of benzyl chloride.8 As the alkyllithium solution is dropped into the benzyl chloride, as rapidly as it drains from the pipet, a yellow color flashes through the liquid. If the RLi solution is concentrated, a white precipitate of lithium chloride forms with the disappearance of the yellow color. The ether solution may become warm enough to boil, but it is not cooled. The mixture is allowed to stand one minute after the addition, then hydrolyzed, and titrated with standard acid. Care must be taken not to overstep the end-point in this titration since the aqueous layer decolorizes before the ether layer.This may be overcome by vigorous shaking near the end point.The benzyl chloride must be dissolved in ether because coupling with the RLi compound takes place much less readily in most other solvents. In analyses of RLi compounds prepared in petroleum ether, the benzyl chloride should be dissolved in a relatively large volume of ether.Lithium «-butoxide did not cleave benzyl chloride under the conditions of the analysis. When these two reagents were refluxed for one minute and then hydrolyzed, no chloride ion was found in the aqueous layer.Reaction of Benzyl Chloride with n-Butyllithium.-To a large excess of benzyl chloride (0.6 mole) in ether was added 250 cc. (0.158 mole) of «-butyllithium. Vigorous refluxing took place, even with a moderate rate of addition. The products isolated were: a small quantity of «-octane, 5 g. (21%) of n-amylbenzene, and 8.2 g. (31%) of bibenzyl. The bibenzyl was identified both by a mixed m. p. determination, and by the 1,3,5-trinitrobenzene-bibenzyl complex (m. p. 103-104°).® Incidentally, no bibenzyl was (8) The benzyl chloride was purified by drying user phosphorus pentoxide and then distilling at reduced pressure.

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