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]

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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$0-0932 gave 0*2591 C02 and 0*0665 H20. C = 75*8 ; H = 7*9. Ci3Hi602 requires C = 76*5 ; H = 7*8 per cent. 1*919 required NaOH equivalent to 9*7 c.c. of a normal solution, instead of 9*4 c.c., the calculated amount. a-Benzoxy-a-phenylethylene, C6H5*C(OBz)!CH2. This was prepared from acetophenone and benzoyl chloride, and the yield amounted to 80 per cent, of the ketone employed. It boils at 229—230° under 50 mm. pressure. On analysis : 0*1059 gave 0*3097 C02 and 0*0515 H20. C = 79*8; H = 5*4. Ci5Hi202 requires C = 80*3 ; H = 5*4 per cent. 0*8594 required NaOH equivalent to 38*8 c.c. of a decinormal solution, instead of 38*4 c.c., the calculated amount. 1-Benzoxycamphene, C8H14 .CH < OOCOC6H5- Camphor (50 grams) was dissolved in benzoyl chloride (50 grams) and the solution vigorously boiled for 6 hours. The product, when fractionated, yielded first a considerable proportion of unchanged material, and then, at a much higher temperature, a small amount (6 grams) of a nearly colourless oil which distilled at 210—220° under 50 mm. pressure. This operation was repeated several times, and in this way a considerable quantity of the oil was obtained ; this substance, when redistilled, boiled at 215—220° under 50 mm. pressure. Benzoxycamphene is slightly lsevorotatory, having aD — 1°5' in a 25 mm. tube. On analysis : 0*1202 gave 0*3477 C02 and 0*0844 H20. C = 78*9; H = 7*8. 0*0986 „ 0*2850 C02 „ 0*0704 H20. C = 78*8; H = 7*9. Cl7H20O2 requires C = 79*7 ; H = 7’8 per cent. 0*8869 depressed the freezing point of 23 grams of phenol by 1*058°, whence mol. wt. =269. Cl7H20O2 = 256. 2*018 required NaOH equivalent to 7*85 c.c. of a normal solution, instead of 7*9 c.c., the calculated amount. Hydrolysis by Alcoholic Potassium Hydroxide.—An alcoholic solution of 1-benzoxycamphene (10 grams) and potassium hydroxide (3 grams), when boiled for 45 minutes, yielded a mixture of camphor (6 grams) and potassium benzoate. The former was identified by its specific rotation, [a]D-f 38*5°, and by its oxime, which melted at 118°. Action of Hydroxylamine.—This reagent was employed in alcoholic solution in the manner described under /3-benzoxyundecylene. The final products were benzoic acid and camphoroxime, the latter being | J i I j l. i$