The quest for new antibiotic substances produced by microorganisms has stimulated investigations on comparatively simple synthetic compounds, particularly those having structural features common to several of the natural antibiotics. Geiger and Conn2 have called attention to the structural feature, -CH=C-C=0 common to I both penicillic acid and clavacin and have postulated that the antibacterial activity of both compounds is very likely closely associated with this grouping. The fact that both clavacin, penicillic

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PART I. THE CARBONYL GROUPSince the report by Whitman, Wintersteiner, and Schwenk (1) on the reduction of estrone to a mixture of alpha-and beta-estradiol by a nickel-aluminum (Raney) alloy in alkaline solution there has appeared in the literature, as far as we could determine, but one instance (2) of the use of this reduction method. During the course of other investigations, we have had the opportunity to study further the reducing action of this alloy. This first paper represents the results we have obtained with compounds containing the carbonyl group.Compounds of this type usually take up hydrogen quite easily when treated with nascent hydrogen, or with hydrogen in the presence of a catalyst, to give the corresponding alcohols. Occasionally, even reduction to the hydrocarbon has been observed. A more general method of obtaining the hydrocarbon is by the Clemmensen reduction, which, however, has not always given satisfactory results (3, 4). Alternative methods for accomplishing the transformation of carbonyl compounds to the hydrocarbons are the Wolff -Kishner reduction and catalytic hydrogenation.We have found that with many carbonyl compounds our reduction method gives results comparable to those obtainable by the Clemmensen reduction. However, unlike the Clemmensen reduction, our reduction method is not specific, in that it converts carbonyl compounds to either the corresponding carbinol or the hydrocarbon, the extent of the reduction depending solely on the structure of the carbonyl compound. Carbonyl compounds of the general formula I

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N,N-Diethyl-N'-(2,2-dibutylhexyl)-ethylenediamine.-A mixture of 21 g. (0.1 mole) of 2,2-dibutylhexylamine, 14 g. (0.1 mole) of diethylaminoethyl chloride and 11 g. of anhydrous sodium carbonate in 50 cc. of dry xylene was refluxed with stirring for sixty-five hours. The cooled reaction product was poured into water, the xylene layer separated, and the solvent removed in vacuo.The brown oily residue was distilled; yield 29 g.; b. p. 155-156°( 2 mm.); n23d 1.4540. The analytical sample showed the following constants:

Recently there has been described from these laboratories (1) a simplified procedure for carrying out the Willgerodt rearrangement of aryl methyl ketones to the aryl acetic acids using morpholine and sulfur in place of the conventional ammonium polysulfide. In the course of other investigations we have had the opportunity to apply this modification of the Willgerodt reaction to a number of ketones not previously studied. In the meantime, the reaction has been used successfully by other investigators (2) with slight modification.We have now established that the reaction is much more general than previously reported. Under the proper conditions amino and hydroxy substituted aryl-aliphatic ketones can be converted into the corresponding aryl-aliphatic acids in yields ranging from 40-60%. Halógena ted aryl ketones give the corresponding acetic acids in yields of 50%. In addition, ketones such as phenyl «-propyl and phenyl «-butyl ketones react to give the -phenyl aliphatic acids in yields of 36% and 14% respectively.With carboxy or carbalkoxy substituted ketones, an interesting series of reactions takes place. When such ketones are heated with sulfur and an excess of morpholine, the keto group undergoes the normal Willgerodt rearrangement to the thioacetmorpholide with the simultaneous aminolysis of the carboxy or carbalkoxy group to the morpholide. For example, o-acetyl benzoic acid and