No abstract

Absorption Spectra of «.^-Unsaturated Cyclic Ketones 1230 trated sulfuric acid and fractionally distilled from metallic sodium.Cyclopentanols.-1-Propylcyclopentanol, m. p. -17.0°, b. p. 72°at 12 mm., d2\ 0.9046, »íod 1.4538, and 1-isopropylcyclopentanol, m. p. 21-22°, b. p. 70°at 15 mm., d"< 0.9135, w"d 1.4560, were prepared, dehydrated over iodine and hydrogenated by standard procedures.A solution of 63 g. of 1-propylcyclopentanol in 70 g. of absolute ethanol was hydrogenated directly to propylcyclopentane over nickel catalyst at 250°under 250 atm. of hydrogen, yielding a two-phase mixture of water, alcohol and propylcycldpentane.1-Allylcyclopentanol was prepared by adding 536 g.(7 moles) of allyl chloride and 504 g. (6 moles) of cyclopentanone in 3000 ml. of dry ether to 146 g. (6 atoms) of magnesium turnings and 1500 ml. of dry ether in a copper

Olefins can be converted by amylsodium to alkenylsodium reagents. This reaction, just observed, is important in a preparative way because the products, when carbonated, yield j3,y-unsaturated acids which, in most cases, have not been prepared hitherto. The work furnishes also a basis for a comparison of the relative hydrocarbo acidities' of the olefins and of the relative acidities a t various positions in an olefin, and shows that an alkyl group reduces this acidity even as it does in aromatic compounds. Finally, this acidity appears to be closely related to the general reactivity of the olefins in reactions where a labile hydrogen atom is involved, because the compounds primarily produced by polymerization of olefins in acid solution can be predicted from the data of relative acidities, as determined by the alkaline reagents.Metalation of Olefins.-The formation of alkeriylsodium compounds takes place so easily that its non-observance in our previous studies now appears surprising. Any interchange that did occur in the past has, however, been extremely slight, since the quantity of olefin present has been very low, the effectiveness of stirring has been much less than a t present and the reaction time has been short. Attention was first directed to this new reaction by a preparation of amylpotassium, analogous to that of amylsodium. The product, after carbonation, contained a trace of unsaturated acids which boiled within the same range as caproic acid. The new products were derived from the reaction shown below between CH?=CHCH (IC) ClHo and KCH=CHCjH7 amylpotassium and 1-pentene, an olefin which happened to be present in the reaction mixture because of a disproportionation in the reaction of amyl chloride with amylpotassium which occurred during the preparation of the latter by addition of aniyl chloride to metallic potassium. Amylsodium was then found to react with the olefin as did amylpotassium provided a sufficient quantity of the hydrocarbon was present and the reaction was given time for completion.Isobutene is readily attacked by amylsodium. The product, after carbonation, is the hitherto unreported P-methylvinylacetic acid, as shown by analysis of the p-bromophenacyl ester derivative, and by isomerization of the acid under the influence of alkali to the known @,@-dimethylacrylic acid. Evidence that a dicarboxylic acid, @-CjE€iiI( + GHie + (1) Morton, Chem. Rm., 35, 1 (1944) H2C=C(-CHoCOzNamcthyleneglutaric acid, H2C=C (CK2COOH)a, the result of dimetalation, is present in a higher boiling fraction, is given by ozone cleavage to formaldehyde stid acetonedicarboxylic acid. By a similar series of reactions propene gives vinylacetic acid, though in smaller yield than the niethylvinylacetic acid. This metalation occurs readily also but a cornparison of. the relative activities of propene and isobutene is difficult to make because propene is so volatile. Propene shows a smaller amount of interchange with benzylsodium than with amylsodium, and this fact accords with the view that the latter is a salt of a weak...