Interaction of ketones and aldehydes with acid chlorides : the formation of benzoxy-olefines and 1-benzoxy-camphene / by Frederic H. Lees.

  • Lees, F. H. (Frederic Herbert)
Date:
[1903]
Catalogue details

Licence: In copyright

Credit: Interaction of ketones and aldehydes with acid chlorides : the formation of benzoxy-olefines and 1-benzoxy-camphene / by Frederic H. Lees. Source: Wellcome Collection.

    9/14 (page 151)
    50 mm. pressure, gave a colourless oil which contained bromine in quantity, but did not fume. The amount available did not admit of further purification. Taking into consideration the constitution of /3-benzoxyundecylene and the character of the substances formed by decomposition of 1-benzoxycamphene dibromide (p. 153), the product was in all probability a bromo-derivative of methyl nonyl ketone, CnH2iOBr, containing the bromine atom attached to one or other of the carbon atoms adjacent to the carbonyl group. The determination of the exact position of this bromine atom would decide between the two possibilities for the constitution of /Tbenzoxyundecylene (compare p. 146). P-Benzoxynonylene, CH2:C(OBz)'C7H15 or CH3-C(OBz):C*HC6H13. This was prepared from methyl w-heptyl ketone and benzoyl chloride and the yield amounted to somewhat more than 100 per cent, of the ketone employed. It boils at 210—211° under 50 mm. pressure. On analysis : 0-1251 gave 0*3555 C02 and 0-1000 H20. C = 77-5 ; H = 8*9. Ci6H2202 requires C = 78-0; H = 8-9 per cent. 2*062 required NaOH equivalent to 8'6 c.c. of a normal solution* instead of 8*4 c.c., the calculated amount. 13-Benzoxy-y-methylheptylene, CH2:C(0Bz)*CH(CH3)-04H9 or CH3-C(OBz)*C(CH3)-C4H9. This was prepared from methyl sec.-hexyl ketone and benzoyl chloride and the yield amounted to 100 per cent, of the ketone employed. It boils at 197 —200° under 50 mm. pressure. On analysis : 0-1163 gave 0-3288 002 and 0-0896 H20. C = 77*l; H = 8*6. C15H20O2 requires C = 776 ; H = 8'6 per cent. 1*947 required NaOH equivalent to 8'6 c.c. of a normal solution, instead of 8*4 c.c., the calculated amount. fi-Benzoxyhexylene, CH2:C(OBz)-C4H9 or CH3*C(OBz):CH*C3H7. This was prepared from methyl w-butyl ketone and benzoyl chloride. The yield of condensation product was small as compared with that 1 of the higher homologues, but a further amount was obtained by boiling the mixture of unchanged ketone and benzoyl chloride, separated from the higher boiling condensation product, for a further 4 hours. In this way, 13 grams of /3-benzoxyhexylene boiling at 170—175° under 50 mm. pressure were obtained from 19 grams of i ketone: