1911 Encyclopædia Britannica/Ketenes
KETENES, in chemistry, a group of organic compounds which may be considered as internal anhydrides of acetic acid and its substitution derivatives. Two classes may be distinguished: the aldo-ketenes, including ketene itself, together with its mono-alkyl derivatives and carbon suboxide, and the keto-ketenes which comprise the dialkyl ketenes. The aldo-ketenes are colourless compounds which are not capable of autoxidation, are polymerized by pyridine or quinoline, and are inert towards compounds containing the groupings C:N and C:O. The keto-ketenes are coloured compounds, which undergo autoxidation readily, form ketene bases on the addition of pyridine and quinoline, and yield addition compounds with substances containing the C:N and C:O groupings. The ketenes are usually obtained by the action of zinc on ethereal or ethyl acetate solutions of halogen substituted acid chlorides or bromides. They are characterized by their additive reactions: combining with water to form acids, with alcohols to form esters, and with primary amines to form amides.
Ketene, CH2:CO, was discovered by N. T. M. Wilsmore (Jour. Chem. Soc., 1907, vol. 91, p. 1938) among the gaseous products formed when a platinum wire is electrically heated under the surface of acetic anhydride. It is also obtained by the action of zinc on bromacetyl bromide (H. Staudinger, Ber. 1908, 41, p. 594). At ordinary temperatures it is a gas, but it may be condensed to a liquid and finally solidified, the solid melting at −151° C. It is characterized by its penetrating smell. On standing for some time a brown-coloured liquid is obtained, from which a colourless liquid boiling at 126–127° C., has been isolated (Wilsmore, ibid., 1908, 93, p. 946). Although originally described as acetylketen, it has proved to be a cyclic compound (Ber., 1909, 42, p. 4908). It is soluble in water, the solution showing an acid reaction, owing to the formation of aceto-acetic acid, and with alkalis it yields acetates. It differs from the simple ketenes in that it is apparently unacted upon by phenols and alcohols. Dimethyl ketene, (CH3)2C:CO1 obtained by the action of zinc on α-brom-isobutyryl bromide, is a yellowish coloured liquid. At ordinary temperatures it rapidly polymerizes (probably to a tetramethylcylobutanedione). It boils at 34° C (750 mm.) (Staudinger, Ber. 1905, 38, p. 1735; 1908, 41, p. 2208). Oxygen rapidly converts it into a white explosive solid. Diethyl ketene, (C2H5)2C:CO, is formed on heating diethylmalonic anhydride (Staudinger, ibid.). Diphenyl ketene, (C6H5)2C:CO, obtained by the action of zinc on diphenyl-chloracetyl chloride, is an orange-red liquid which boils at 146° C. (12 mm.). It does not polymerize. Magnesium phenyl bromide gives triphenyl vinyl alcohol.