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.

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    mixture boiled for 6 hours. After removing some of the alcohol, water was added and the liquid extracted with ether, the ethereal solution was washed first with water and then with dilute sodium carbonate solution to remove benzoic acid ; it was then dried with anhydrous potassium carbonate and the ether removed. The product was an oil which soon formed a crystalline paste ; this was drained on a porous tile and the dry, crystalline substance recrystallised from dilute alcohol, from which it separated as long needles melting at 46°. On analysis : 0*1062 gave 0-2788 C02 and 0-1206 H20. C = 71-6; H=12-6. CnH23ON requires C = 71 4 ; H = 12-4 per cent. This substance is therefore methylnonylketoxime, which melts at 46°. The aqueous solution, from which the oxime had been extracted by ether, when acidified with sulphuric acid and warmed for some time on the water-bath, gave, on cooling, a quantity of benzoic acid. Action of Bromine.—To a solution of /3-benzoxyundecylene (10 grams) in dry carbon disulphide (20 c.c.) at 0°, dry bromine (6 grams), also dissolved in dry carbon disulphide (20 c.c.), was slowly added in the dark. The bromine was instantly absorbed without any formation of hydrogen bromide, and as soon as the whole had been decolorised the carbon disulphide was removed in a current of dry air. The product was a thick, light yellow oil and weighed 16 grams. In order to remove the last traces of carbon disulphide prior to analysis, a small portion was allowed to remain in a vacuum over solid paraffin for some time. On opening the desiccator, it was observed that the substance showed a tendency to lose hydrogen bromide; it was therefore analysed without delay : 0*3608 gave 0*273 AgBr. Br = 32*2. Oi8H2602Br2 requires Br = 37*0 per cent. It is thus seen that /3-benzoxyundecylene forms a dibromide, which, however, is somewhat unstable. Action of Heat on the Dibromide.—The dibromide was distilled under 50 mm. pressure; decomposition rapidly ensued, and fractions boiling below 170° and at 170—190° were collected. The former, on redistillation under the ordinary pressure, came over at 220—230° as a heavy, strongly fuming liquid. When mixed with alcohol, much heat was developed, and when boiled with water it slowly dissolved, forming a clear solution, from which a quantity of benzoic acid separated on cooling. This fraction would thus seem to be benzoyl bromide. The fraction which distilled at 170—190°, on redistillation under ' < !•