The constitution of umbellulone. Pt. III / by Frank Tutin.

  • Tutin, Frank.
Date:
1908
Catalogue details

Licence: Attribution 4.0 International (CC BY 4.0)

Credit: The constitution of umbellulone. Pt. III / by Frank Tutin. Source: Wellcome Collection.

Provider: This material has been provided by The Royal College of Surgeons of England. The original may be consulted at The Royal College of Surgeons of England.

    4/12 (page 253)
    (Californian laurel). It was shown by them to possess the formula C49H440, an(j be a bicyclic ketone containing an ethylenic linking in the a/3-position with respect to the carbonyl group. In the first communication-by the present author, the behaviour of umbellulone on oxidation with potassium permanganate was studied. When submitted to this treatment, it gave a saturated keto-acid, um- bellulonic acid, C9H1403, which on distillation passes into an un- saturated lactone, C9H1202. The latter, on oxidation, yielded umbellu- laric acid, a polymethylenedicarboxylic acid, possessing the formula CsH1204. These changes may be represented as follows : Umbellulone. C1 IT C°2H / ^uu2±l \ COCHg \^^io\c(OH):CHJ C00H Umbellulonic acid. Enolic modification. C6H10<>O --V C„H1c<co2h c:ch2 ou2±i Lactone. Umbellularic acid. It was stated regarding umbellularic acid, that its general properties, especially its great stability, “ indicate that it is one of the tetra-, penta-, or hexa-methylenedicarboxylic acids.” It was not, however, at that time considered necessary to state in detail the reasons for concluding that it could not be a trimethylene compound. Since the hexamethylenedicarboxylic acids are all known, and the oxidation products of umbellulone are not identical or stereoisomeric with those of pinene, it was concluded that umbellularic acid was most probably a metliylpentamethylenedicarboxylic acid. From these results, together with other considerations (loc. cit.), it was concluded that umbellulone was most probably represented by the following formula : CH2 CH CO l/CHg-CHMe | . CH CMe==CH Umbellulonic and umbellularic acids respectively, would then have the following constitutions : cit-co2h /\ MeCH CH2 ch2--ch-co-ch3 Umbellulonic acid. ch-co2h MeCH CH2 ch2-ch-co2h Umbellularic acid. This conclusion is in harmony with the observation, recorded in the author’s second paper (loc. cit.), that when the x’ing contained in umbellulonic acid is opened by the addition of two atoms of hydrogen, S-hydroxy-a-isopropyl-rt-hexoic acid is obtained. Although, as stated above, the reasons for concluding that umbellularic acid was not a trimethylene compound were not detailed