Volume 1

Recent advances in organic chemistry / by Alfred W. Stewart.

  • Alfred Walter Stewart
Date:
1931
Catalogue details

Licence: Attribution-NonCommercial 4.0 International (CC BY-NC 4.0)

Credit: Recent advances in organic chemistry / by Alfred W. Stewart. Source: Wellcome Collection.

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    during autoxidation—the so-called keten oxides. These have compositions corresponding to— and they are prepared by passing oxygen through ethereal solutions of ketens at ordinary temperatures. On heating with water, diphenyl-keten oxide yields benzilic acid— (C6H5)2C-CO] +nH20 = w(C6H5)2C(OH) . COOH n Rather unexpectedly, the action of methyl alcohol on diphenyl- keten oxide produces diphenyl-methoxy-acetic acid (I.) while aniline gives a quantitative yield of anilido-diphenylacetic acid (II.). (I.) (C6H5)2C—COOH (II.) (C6H5)2C—COOH OCH3 NH. C6H5 In this last case, the production of the anilide of benzilic acid is what might have been expected to occur. 3. The Grignard Reaction.— Only one or two applications of the Grignard reaction to ketens have been made. Keten,1 when treated with methyl-magnesium iodide, produces acetone. This reaction may be regarded as due to an attack on the carbonyl radicle such as is usually found with ketonic compounds and the Grignard reagent; or it may be brought into line with the rest of the keten reactions by assuming that the Grignard reagent attaches itself to the ethylenic bond, as shown below : CH2 : CO+CH3 . Mg . I = I. Mg . CH2. CO . CH3 I. Mg . CH2 . CO . CH3+H20 = CH3. CO . CH3-fI. Mg . OH Diphenyl-keten, when treated with phenyl-magnesium bromide, yields triphenyl-vinyl alcohol, (C6H5)2C : C(OH) . C6H5. 4. Addition of Ketens to Double Bonds.—The extraordinary activity of the ethylenic bond in the keten molecule is mani¬ fested by the readiness with which the ketens react with many