Structure of the antibiotic botryodiplodin—use of chemical ionization mass spectrometry in organic structure determination

Abstract

The structure assigned to botryodiplodin is based mainly on physical methods including chemical ionization mass spectrometry used for the first time as a tool in organic structure elucidation. SOME physical, chemical, and biological properties of the compound botryodiplodin were reported by Sen Gupta, Chandran, and Divekar who isolated this antibiotic from Botryodiplodia theobromae Pat.2 We assign structure (I) to botryodiplodin based on physical and chemical evidence.The i.r. spectrum of botryodiplodin showed ketone carbonyl absorption at 17 13 cm. -l and hydroxyl absorption a t 3400 cm.-l. Acetylation of botryodiplodin with acetic anhydride and anhydrous pyridine afforded a product (11) with no hydroxyl absorption in its i.r. spectrum but with an added carbonyl absorption band at 1735 cm.-l, indicating the presence of a saturated ester. Hydrolysis of botryodiplodin acetate ( 11) with water at room temperature regenerated botryodiplodin .

Secondary Metabolites of Lasiodiplodia theobromae: Distribution, Chemical Diversity, Bioactivity, and Implications of Their Occurrence

“…Furano-2-ones, furanoles, and pyran-2-ones are often isolated from L. theobromae cultures ( Figure 6 ). (3 R ,4 S )-(-)-Botryodiplodin ( 42 ) was the first compound, belonging to this series, isolated from a liquid culture of a ligninolytic strain of L. theobromae , and reported by [ 24 ] as a new antibiotic product, but its structure and stereostructure were subsequently determined [ 75 , 76 , 77 , 78 ]. Moreover, (±)-botryodiplodin and its stereoisomers were also prepared through numerous synthetic procedures [ 79 ].…”

Chemical ionization mass spectrometry

“…Systematic studies have been made of several classes of compounds: alkanes (6), cycloalkanes (7), alkylbenzenes (5), alkenes and alkynes (0),alkanols (10), esters of monocarboxylic acids (11), esters of diand tricarboxylic acids (12), alkaloids (13), amino acids (14), barbiturates (15), substituted benzophenones (2), aryl ketones (16), steroids (16), and dimeric cyclic ketones (17), Somewhat less extensive studies have been made on several other systems: amines (1), C7Hs isomers (18), RX and RCOR' (X = Cl, Br, I; R = C"H2" + j) (19), RCOOCH0OCH3 (20), RCOOCH2-SCH3 (21), borazine (22), pristane (23), and botryodiplodin (24) Preliminary results have been given of the sequencing of peptides as simple peptides (25,26) and as the phenylthiohydantoin derivatives formed by the Edman degradation (27). Nucleosides also appear to be susceptible to analysis by chemical ionization (28).…”

“…The most common reactant gas for Cl studies has been methane, because it was the first reactant gas tried and because it generally gives information about molecular weight and molecular structure from (M -j-1) + and fragment ions (1, 6-9, 11, 13-15, 17,[23][24][25][26] Chemical ionization mass spectra of compounds are produced by ions formed by ion-molecule reactions. In the basic technique, a small amount of sample is used with a large amount of reactant gas.…”

Formation of DNA-protein cross-links in mammalian cells by levuglandin E2

“…The possibility that LGs might cause DPCs was suggested by the behavior of botryodiplodin (BD) (Gupta et al, 1966;Arsenault et al, 1969;Moreau et al, 1982), a mutagenic (Mould et al, 1981a) mycotoxin isolated from the fungus Botryodiplodia theobromae. BD forms DPCs in eukaryotic cells (Mould et al, 1982 and blocks DNA synthesis in a manner consistent with a DNAdamaging agent (Mould et al, 1981b).…”