The α-diketones may be prepared by boiling the product of the action of alkaline bisulphites on isonitrosoketones with 15% sulphuric acid (H. v. Pechmann, Ber., 1887, 20, p. 3112; 1889, 22, p. 2115), CH3·CO·C:(N·OH)·CH3 → CH3·CO·C:(NHSO3)·CH3 → CH3·CO·CO·CH3; or by the action of isoamyl nitrite on the isonitrosoketones (O. Manasse, Ber., 1888, 21, p. 2177), C2H5·CO·C = (NOH)·CH3 + 11C5HONO = C2H5·CO·CO·CH3 + C5H11OH + N2O. They condense with orthodiamines to form quinoxalines (O. Hinsberg, Ann., 1887, 237, p. 327), and with ammonia and aldehydes to form imidazoles. Diacetyl, CH3·CO·CO·CH3, is a yellowish green liquid, which boils at 87-88°C., and possesses a pungent smell. It combines with sodium bisulphite and with hydrocyanic acid. Dilute alkalis convert it into paraxyloquinone.
The β-diketones form characteristic copper salts, and in alcoholic solution they combine with semicarbazide to form products which on boiling with ammoniacal silver nitrate solution give pyrazoles (T. Posner, Ber., 1901, 34, p. 3975); with hydroxylamine they form isoxazoles, and with phenylhydrazine pyrazoles. Acetyl acetone, CH3·CO·CH2·CO·CH3, may be prepared by the action of aluminium chloride on acetyl chloride, or by condensing ethyl acetate with acetone in the presence of sodium (L. Claisen). It is a liquid of boiling point 136° C. It condenses readily with aniline to give αγ-dimethyl quinoline.
The γ-diketones are characterized by the readiness with which they yield furfurane, pyrrol and thiophene derivatives, the furfurane derivatives being formed by heating the ketones with a dehydrating agent, the thiophenes by heating with phosphorus pentasulphide, and the pyrrols by the action of alcoholic ammonia or amines. Acetonyl acetone, CH3·CO·CH2·CH2·CO·CH3, a liquid boiling at 194° C., may be obtained by condensing sodium aceto-acetate with mono-chloracetone (C. Paal, Ber., 1885, 18, p. 59),
| CH3COCH2Cl + Na·CH·COCH3(COOR) |
| → CH3CO·CH2·CH·COCH3(COOR) |
| → CH3CO·CH2·CH2·COCH3; |
or by the hydrolysis of diaceto-succinic ester, prepared by the action of iodine on sodium aceto-acetate (L. Knorr, Ber., 1889, 22, pp. 169, 2100).
1.5 diketones have been prepared by L. Claisen by condensing ethoxymethylene aceto-acetic esters and similar compounds with β-ketonic esters and with 1.3 diketones. The ethoxymethylene aceto-acetic esters are prepared by condensing aceto-acetic ester with ortho-formic ester in the presence of acetic anhydride (German patents 77354, 79087, 79863). The 1.5 diketones of this type, when heated with aqueous ammonia, form pyridine derivatives. Those in which the keto groups are in combination with phenyl residues give pyridine derivatives on treatment with hydroxylamine, thus benzamarone, C6H5CH[CH(C6H5)·CO·C6H5], gives pentaphenylpyridine, NC5(C6H5)5. On the general reactions of the 1.5 diketones, see E. Knoevenagel (Ann., 1894, 281, p. 25 et seq.) and H. Stobbe (Ber., 1902, 35, p. 1445).
Many cyclic ketones are known, and in most respects they resemble the ordinary aliphatic ketones (see [Polymethylenes]; [Terpenes]).
KETTELER, WILHELM EMMANUEL, Baron von (1811-1877), German theologian and politician, was born at Harkotten, in Bavaria, on the 25th of December 1811. He studied theology at Göttingen, Berlin, Heidelberg and Munich, and was ordained priest in 1844. He resolved to consecrate his life to maintaining the cause of the freedom of the Church from the control of the State. This brought him into collision with the civil power, an attitude which he maintained throughout a stormy and eventful life. Ketteler was rather a man of action than a scholar, and he first distinguished himself as one of the deputies of the Frankfort National Assembly, a position to which he was elected in 1848, and in which he soon became noted for his decision, foresight, energy and eloquence. In 1850 he was made bishop of Mainz, by order of the Vatican, in preference to the celebrated Professor Leopold Schmidt, of Giessen, whose Liberal sentiments were not agreeable to the Papal party. When elected, Ketteler refused to allow the students of theology in his diocese to attend lectures at Giessen, and ultimately founded an opposition seminary in the diocese of Mainz itself. He also founded orders of School Brothers and School Sisters, to work in the various educational agencies he had called into existence, and he laboured to institute orphanages and rescue homes. In 1858 he threw down the gauntlet against the State in his pamphlet on the rights of the Catholic Church in Germany. In 1863 he adopted Lassalle’s Socialistic views, and published his Die Arbeitfrage und das Christenthum. When the question of papal infallibility arose, he opposed the promulgation of the dogma on the ground that such promulgation was inopportune. But he was not resolute in his opposition. The opponents of the dogma complained at the very outset that he was wavering, half converted by his hosts, the members of the German College at Rome, and further influenced by his own misgivings. He soon deserted his anti-Infallibilist colleagues, and submitted to the decrees in August 1870. He was the warmest opponent of the State in the Kulturkampf provoked by Prince Bismarck after the publication of the Vatican decrees, and was largely instrumental in compelling that statesman to retract the pledge he had rashly given, never to “go to Canossa.” To such an extent did Bishop von Ketteler carry his opposition, that in 1874 he forbade his clergy to take part in celebrating the anniversary of the battle of Sedan, and declared the Rhine to be a “Catholic river.” He died at Burghausen, Upper Bavaria, on the 13th of July 1877.