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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    formula CsH1d<U! ^ , and this arose from a consideration of Forster’s work on a hydroxycamphene (Trans., 1901, 79, 644; 1902, 81, 264), to which he assigns the highly probable constitution CH2-CH-CH2 CMe2 CH-CMe-OOH i i This substance was produced by direct steps from 1 : 1-bromonitro- camphane, and Forster pointed out that the origin of the uncertainty in fixing its constitution lies in the several possibilities for the elim¬ ination of hydrogen bromide from the former compound. That an un¬ certainty dependent on an analogous reason can exist with regard to benzoxycamphene is apparent if the structures of 1 : 1-bromonitro- camphane and 1 : 1-chlorobenzoxycamphane—the additive compound of camphor and benzoyl chloride which is assumed to be formed in the production of benzoxycamphene—are placed side by side : ch2-ch- CMe2 CH2*CMe- ■CEL -CEL -CBr-m ch2-ch- CMe, CH2 • C Me—CC1 • 0 • CO • C6H5 The question to be decided was whether benzoxycamphene might not possess a structure similar to that of hydroxycamphene. Hydroxycamphene is stable in presence of alkalis, and does not re¬ act with hydroxylamine (Forster, loc. cit), a behaviour which accords with its constitution, whereby a transformation into camphor would, in the first instance, involve the disruption of a trimethylene ring of the type CMe \/\/ • CH—OOH Such a change is hardly likely to occur under the influence of the agents mentioned. Benzoxycamphene, on the other hand, is hydrolysed by alkalis or hydroxylamine, yielding, how¬ ever, not a hydroxycamphene stable to these reagents, but camphor and camphoroxime respectively; benzoxycamphene, therefore, on hydrolysis gives a hydroxycamphene conforming to Erlenmeyer’s rule, which includes those substances of the type >C!C(OH)-; moreover, Forster has shown that hydroxycamphene, on treatment with bromine with subsequent elimination of hydrogen bromide, affords a bromo- camphor which melts at 78°, has [a]D +19°, and is certainly not an a-bromo-derivative. Benzoxycamphene, however, on treatment with bromine followed by elimination of benzoyl bromide, gave a bromo- camphor which melted at 76°, had [a]D +131°, and was in CHBr all respects identical with a-bromocamphor, c8h14<^0 •