Structure of Chlorodesoxypatulinic Acid
BERGEL et al.1 found that the product of the action of ethanolic hydrogen chloride on patulin gave on hydrolysis a crystalline chloro-acid, C7H7O4Cl, now called Chlorodesoxypatulinic acid. Afterwards, Plattner et al.2 observed that the same acid was readily produced by the action of hydrogen chloride on patulin in moist ethereal solution. The expression (I) was originally deduced1 for Chlorodesoxypatulinic acid from its relationship to patulin, for which the structure (II) was assumed3. Recent developments in this Laboratory and in that of Plattner necessitated the abandonment of these views, and led the Swiss group2 to formulate Chlorodesoxypatulinic acid as (III), which was consonant with either of two new structures, (IV)4 and (V)2, put forward for patulin in Cambridge and in Zurich, respectively. We have now accumulated new evidence which requires that (III) in its turn be rejected, and which leads to a new view of the structure of chlorodesoxypatulinic acid which is consistent only with the structure (IV) for patulin.
Welkstoffe und Antibiotika. 12 Mitteilung. Über die Konstitution des Patulins
Das Patulin besitzt nicht die allgemein angenommene Struktur eines Oxymethylen-tetrahydrocomansaure-Lactons I, sein Skelett muss vielmehr demjenigen der Tetrahydro-γ-pyronyl-(3)-essigsaure (VIII) entsprechen, so dass die Formeln II oder (nach Woodward) III wahrscheinlich erscheinen.
CLAVACIN, AN ANTIBIOTIC SUBSTANCE FROM ASPERGILLUS CLAVATUS
In 1942 Wiesner (1) and Waksman, Horning, and Spencer (2) demonstrated that filtrates from cultures of Aspergillus clavatus grown upon synthetic media possess antibiotic activity. These investigators extracted and partially purified the active material (which was named clavacin by Waksman) but did not report its isolation in pure form. As a result of the observations made by Waksman’s group, particularly those on the antibiotic activity toward Gram-negative organisms, we became interested in this antibiotic substance and undertook the investigat,ions of it as part of our work under Contract OEMcmr-155. In the latter part of last year, Raistrick et al. (3) published a report on the isolation and characterization of patulin, an antibiotic substance produced by Penidium pat&urn Bainier and, furthermore, showed that the same compound is produced by P. expansum (4). Subsequent to Raistrick’s first report, Bergel et aE. (5) and Hooper et al. (6) announced the isolation of a crystalline compound from Aspergillus elavatus which on the basis of the data submitted appears to be identical with patulin. Furthermore, Florey, Jennings, and Philpot (7) showed that the same compound is produced by A. giganteus Wehm, and Bergel et al. (5) and Chain, Florey, and Jennings (8) showed that the compound, claviformin, which the latter had previously isolated from P. cZuvij”orme in 1942 (9) is likewise identical with patulin. Although we had isolated a crystalline antibiotic from A. clavatus and prepared the semicarbazone, thiosemicarbazone, 2,4-dinitrophenylhydrazone, and oxime derivatives and a catalytic reduction product