The synthesis of 2:4:6-trimethoxyphenyl-3:4-dimethoxystyryl ketone / by Frank Tutin and Frederic W. Caton.

  • Tutin, Frank.
Date:
[1910?]
Catalogue details

Licence: In copyright

Credit: The synthesis of 2:4:6-trimethoxyphenyl-3:4-dimethoxystyryl ketone / by Frank Tutin and Frederic W. Caton. Source: Wellcome Collection.

    6/12 page 2065
    from the reaction mixture only a small amount of 2-hydroxy-4 : 6-di- metlioxyacetophenone, unchanged phloroglucinol trimethyl ether, and a hydroxydiacetyldimethoxyhenzene, C12H14O5, no matter how the conditions of the experiment were varied. A quantity (11*5 grams) of phloroglucinol trimethyl ether was dissolved in carbon disulphide, 6 grams of acetyl chloride added, and then 10 grams of powdered aluminium chloride gradually introduced. After heating the mixture for one hour the solvent was decanted, and the residue decomposed with ice and hydrochloric acid. The product so obtained was dissolved in ether and shaken with a solution of potassium hydroxide, which removed the greater part of the material. The neutral product remaining in the ether consisted almost entirely of unchanged phloroglucinol trimethyl ether. The alkaline extracts were acidified, and the precipitated product was crystallised, first from ether, and then from alcohol, when it formed long, slender prisms, melting at 127—128° : 0*1090 gave 0*2407 COg and 0*0583 H2O. C = 60*2; H=:5*9. 0*1130 „ 0*2491 002 „ 0*0595 H2O. 0 = 60*1; H = 5*9. 0*1316 „ 0*2924 002, „ 0*0714 H2O. 0 = 60*6; H = 6*0. OH’0(>H2(OMe)2(0O*0H3) requires 0 = 61*2; H = 6*l per cent. OH-06H(OMe)2(0O-0H3)2 „ 0 = 60*5; H = 5*9 OH*06(OMe)2(0O*0H3)3 „ 0 = 60*0; H=:5*7 These analyses indicate that the substance under consideration was a hydroxydiacetyldimethoxybenzene, 0H*0gH(0Me)2(00*0H3)2, and this conclusion was subsequently confirmed by the analysis of its benzoyl derivative. No direct proof of the constitution of the diketone was obtained, but it would appear most probable that it is represented as follows: OH /\C0-CH, CO-CH, This formula is preferred to the other possible one, as it is known that 2:4: 6-trimethoxyacetophenone, which must first be formed, readily yields 2-hydroxy-4 : 6-dimethoxyacetophenone in the presence of aluminium chloride, and a second acetyl group, when entering the nucleus of the latter ketone, would assuredly enter the para- position with respect to the hydroxyl group. Hydroxydiacetyldimethoxybenzene is sparingly soluble in ether, and moderately so in alcohol. It did not lose either of the methyl groups when treated with anhydrous ferric chloride or with aluminium chloride, and attempts to introduce a third acetyl group into the nucleus of it Avere unsuccessful.
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