Syntheses in the epinephrine series. [Pt. I] / by Frank Tutin, Frederic W. Caton and Archie C.O. Hann.

  • Tutin, Frank.
Date:
[1909]
Catalogue details

Licence: Attribution 4.0 International (CC BY 4.0)

Credit: Syntheses in the epinephrine series. [Pt. I] / by Frank Tutin, Frederic W. Caton and Archie C.O. Hann. Source: Wellcome Collection.

Provider: This material has been provided by The Royal College of Surgeons of England. The original may be consulted at The Royal College of Surgeons of England.

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    except) with one molecule of water, and melt respectively at 181° and 126—127°. Ex PERIMENTAL. ia-Chloro-^-hydroxyaceto'phenone. Kunckell and Johannssen {Ber., 1898, 31, 167) prepared to-chloro- p-hydroxyacetophenone by the action of chloroacetyl chloride and excess of aluminium chloride on anisole, but, when they attempted to obtain it directly from phenol, the experiment resulted in the formation of phenyl chloroacetate, and subsequently of to-chloro- p-hydroxyacetophenone chloroacetate. With the object of obtain- ing from phenol the acetate corresponding with the last-mentioned compound, the present authors treated phenyl acetate with chloro- acetyl chloride and aluminium chloride. Thirteen grams of phenyl acetate and an equal weight of chloro- acetyl chloride were dissolved in carbon disulphide, and treated with 17 grams of powdered aluminium chloride. After heating the mixture for six hours, the solvent was removed, and ice and dilute hydrochloric acid were added. The product was then extracted with ether, when, on removing the solvent, a light green oil was obtained, which became partly solid when stirred with light petroleum. The solid was drained on a tile, after which it was recrystallised from benzene, when colourless needles, melting at 73—74°, were obtained: 0T869 gave 0-3850 COg and 0'0729 HoO. C = 56-2; H = 4-3. CjoHgOgCl requires C = 56-5; H = 4-2 per cent. That this compound was T^-hydroxyacetophenone chloroacetate was evident from the fact that, on treatment with ammonia, it yielded p-hydroxyacetophenone and the base, NHa-CO-CHg-NH-CHg-CO-NHa, which was obtained by Heintz bv the action of ammonia on ethyl chloroacetate {Annalen, 1868, 148, 177). It is evident, therefore, that the acetyl group had wandered into the para-position, its place being taken by the chloroacetyl radicle. In view of the statements of Behn (D.R.-P. 95901), we attempted to obtain w-chloro-p-hydroxyacetophenone directly from phenol by means of aluminium chloride, but with the use of nitrobenzene as a solvent. Although this operation was successful, the yield was so small that we returned to the original method of Kunckell and Johannssen (Zoc. cit.'), using, however, an improved means of isolating the product. Twenty grams of anisole and 24 grams of chloroacetyl chloride were dissolved in carbon disulphide, and 60 grams of aluminium chloride gradually introduced. After heating for about four hours.
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